United States Patent Office 2,715,145

Patented Aug. 9, 1955

: 2
The decomposition of the material which boils at
2,715,145 higher temperatures than the boiling points of phenol
MANUEFACTURE OF PESENOL and acetophenone may be achieved by heating said mate
rial to temperatures at which pyrolysis takes place. These
Thomas Bewey, Epsom, Bertram Eraest Wictor Bowen, temperatures may vary within wide limits according to
Totabridge, Kent, Peter Lioned Brainwyche, London, the composition of the mixture and the pressure during
and Geoffrey William Jackson, Southborough, Kent, the heat treatment. Generally speaking, temperatures
England, assignors, by aesae assignments, to Hercules from 200 to 400 C. have been found to give good re
Powder Company, a corporation of Delaware Sults. It is expedient to carry out the decomposition at
No Drawing. Application May 29, 1950, O
as low a temperature as possible and effect it at reduced
Seria No. 165,101 pressure. The products resulting from this decomposi
tion comprise phenol and alphamethylstyrene. Fre
Claims priority, application Great Britain June 3, 1949 quently the formation of isopropylbenzene during the
8 Claims. (C. 260-621) heat treatment has also been observed. The desired
decomposition may be promoted by the addition to the
This invention refers to improvements in the process residue of acids such as Sulphuric acid, phosphoric acid
for the manufacture of phenol and relates in particular or Sulphonic acids. Small catalytic amounts of these
to the manufacture of phenol by the decomposition of acids added to the residue allow the decomposition to be
isopropyl benzene peroxides by means of acidic Sub effected at lower temperatures than in the absence of
stances which exert a catalytic action. Such acidic Sub added acids. Acid washed activated earth, such as,
stances are for instance aqueous mineral acids, strong fuller's earth have also proved useful for promoting the
organic acids, hydrogen ion exchange materials and acid decomposition. It is preferred to effect the decomposition
treated activated earths. The products of this decompo of the material with boiling points which are higher than
sition reaction are mainly phenol and acetone with alpha those of phenol and acetophenone after the compounds
methyl styrene and some acetophenone. This inven with a lower boiling point have been removed from the
tion is based on the discovery that besides the named mixture produced by the acid decomposition of the per
compounds a residue with a boiling point which is higher oxides. This removal may be complete in which case
than that of phenol and acetophenone is formed and a it is convenient to remove the products resulting from the
major proportion of this residue, which may amount to decCraposition of the higher boiling material from the
from 2 to 10% or more of the peroxides brought into 30
still as they are formed. It is however possible to carry
contact with the acidic catalyst consists of para alpha out the decomposition with a material which still contains
cumyl phenol, and one of its objects is to improve the Some of the compounds with lower boiling points such as
yield of phenol and, also, other compounds of economic phenol and acetophenone.
value. The removal of the compounds with lower boiling
By the expressions peroxides or peroxidic compounds points, Such as acetone, phenol, alphamethylstyrene and
in this specification are to be understood the hydroper acetophenone from the mixture resulting from the decom
oxide as well as the peroxide of isopropyl benzene. position of the isopropylbenzene peroxides may be
It is expedient to effect the acid decomposition reac achieved by various methods. For instance, the acetone
tion with a solution of said peroxides in an inert Solvent may be removed first by distillation and after its removal
and to use isopropyl benzene as Such solvent. With ad the remaining mixture may be subjected to distillation
vantage, therefore, the solution which results from the 40 preferably under diminished pressure. Another alterna
oxidation of isopropyl benzene by means of molecular tive is to remove the acetone in conjunction with the phe
oxygen at elevated temperatures and wherein only a nol by treating the decomposition reaction mixture with
part of the isopropyl benzene is converted into the cor Water, preferably at temperatures between 50 and 100°
responding peroxides whilst the remainder Serves as C., by which means acetone and phenol are dissolved
solvent for the peroxides, is brought into contact with whereas acetophenone and methyl styrene with the un
the acidic catalysts effecting the decomposition of the reacted isopropyl benzene, if present, remain undissolved.
peroxides. In this case, in addition to the above-named The acetone may be recovered from the aqueous solution
decomposition products unchanged isopropyl benzene is in the Well-known way, while acetophenone, isopropyl
present in the acid decomposition mixture. 5
benzene, if any, and methyl styrene are recovered from
According to this invention the process for the manu the water extracted residue by fractional distillation, pref.
facture of phenol by the decomposition by means of erably under reduced pressure. A further alternative con
acidic catalysts of isopropylbenzene peroxides comprises sists in Subjecting the reaction mixture originating from
increasing the yield of phenol by decomposing the mate the decomposition reaction after said mixture has been
rial contained in the peroxidic acidic catalyst decomposi 55
Separated from the acidic catalysts to fractional distilla
tion mixture and boiling at temperatures higher than tion preferably under reduced pressure, whereby first the
phenol and acetophenone. acetone and Subsequently isopropyl benzene, if present,
The oxidation of the isopropyl benzene, the decom then alpha methyl styrene, phenol and acetophenone are
position of the peroxidic compounds formed thereby and recovered in the consecutive distillation fractions. When
the recovery of the resulting products may be carried out the reaction products are recovered from the decomposi
in accordance with the processes described and claimed 60
tion reaction mixture by fractional distillation it is pre
in the pending United States applications Serial No. ferred to carry out the fractionation beyond the removal
738,726-filed April 1, 1947, now U. S. Patent 2,547,938 therefrom of phenol so as to collect at least the major
issued April 10, 1951; Serial No. 5178-filed January part of the acetophenone present. The fractional distilla
29, 1948, now U. S. Patent 2,628,983 issued February tion of the phenol and acetophenone is preferably carried
17, 1953; Serial No. 45,326-filed August 20, 1948; out under reduced pressure avoiding a temperature in the
and Serial No. 86,258-filed April 8, 1949, now U. S.
Patent 2,663,743 issued December 22, 1953. kettle of the still of more than 200° C. and preferably
The decomposition of the peroxidic compounds may rising to a temperature not above 160° C. In this way it
be effected by reacting them with an acidic catalyst after is possible to obtain the various fractions in a pure state.
they have been isolated from the oxidation reaction mix By the decomposition of the higher boiling material ac
ture or while the said peroxidic compounds are dissolved cording to the present invention, considerable additional
in unreacted isopropyl benzene. quantities of phenol and of alphamethylstyrene are ob
 2,715,145
e A.
tained. In some cases isopropyl benzene was also recov alpha methyl styrene and 185 parts consisting mainly of
ered amongst the decomposition products. The Separa isopropyl benzene.
tion of these reaction products may be effected by frac Example 3
tional distillation, preferably under diminished pressure
or the phenol may be extracted therefrom by means of 5 157 parts of the residue as obtained in Example 1 were
water or aqueous alkaline solutions whilst the separation heated with 1.6 parts by weight of concentrated Sulphuric
of alphamethylstyrene from the isopropyl benzene, if acid to 263 C. final temperature. 108.7 parts of distillate
present, is effected by distillation. The phenol, when were obtained, containing 41.2 parts of phenol, 23.1 parts
added to the phenol produced as the main product of the of methyl styrene and 44 parts of a fraction consisting
acid decomposition of the isopropyl benzene peroxides mainly of isopropyl benzene.
and recovered from the decomposition mixture prior to Example 4
the collection of the material with the high boiling points
increases the economic value of the whole process of phe sopropyl benzene was oxidised with gaseous oxygen to
nol production from isopropyl benzene. In addition, the
alphamethylstyrene is a further valuable compound. It : yield a product containing 25% by weight of peroxides.
may be reconverted to isopropyl benzene by hydrogena This material was concentrated by removal of the bulk
tion, for example, with a nickel catalyst and may then of the unchanged isopropyl benzene in a climbing film
be recycled to the oxidation process for the production of evaporator, and the concentrate containing 65% by
isopropyl benzene peroxides. If any isopropyl benzene weight of the peroxide decomposed with 40% w/w sul
is found among the decomposition products this can be phuric acid in a continuous reactor under conditions of
also returned to the oxidation process. efficient stirring. The decomposer product was freed from
The following examples illustrate the manner in which acids by washing with 12% w/v sodium carbonate solu
the process of the invention is carried out in practice: tion and fractionally distilled to remove as successive
fractions acetone, isopropylbenzene plus alpha-methyl
Example I 2 5 styrene, phenol and acetophenone. The high boiling
residue from the last distillation (amounting to 21% of
1,000 lbs. of isopropyl benzene were oxidised with oxy the weight of phenol recovered) was decomposed by heat
gen at 130 C. until the reaction mixture contained about ing up to 360° C. with an added 0.25% by weight of sul
25% isopropyl benzene peroxides. This mixture was phuric acid. From 165 parts by weight of the residue were
stirred vigorously with an aqueous Sulphuric acid con 30 obtained in this way 116 parts of a distillate and 47 parts
taining in 100 grams about 45 grams of H2SO4, at 30 of an undistilable tar. The distillate was found to con
C. whereby the peroxides were converted into acetone tain 35 parts of isopropy benzene, 35 parts of methyl
and phenol. The oil layer leaving the decomposer was styrene, 34 parts of phenol and 5 parts of acetophenone,
washed successively with small amounts of water and/or together with minor amounts of water and hydrocarbons
aqueous sodium carbonate solution to remove acid and boiling below isopropyl benzene.
then fed to a continuous still from the top of which a We claim:
mixture containing 81% acetone, 8% isopropyl benzene 1. In the process for the manufacture of phenol by
and 11% low boiling compounds, including a little water, the decomposition of isopropyl benzene peroxides with
was removed. The liquid leaving the bottom of the still an acidic catalyst whereby there is formed a decomposi
was fed into a vacuum still operated at 100 mm. in this tion reaction mixture comprising acetone, alpha methyl
still 684 lbs. of isopropyl benzene were distilled off from styrene, phenol, acetophenone and para alpha cumyl
the mixture containing as impurities 0.08% alpha-methyl phenol, and wherein the acetone, alpha methylstyrene,
styrene and 0.29% phenol. The liquid leaving at the phenol and acetophenone are substantially separated from
base of the said vacuum still is further fractionated in a said decomposition reaction mixture to leave a residue
second vacuum still, the kettle temperature of which was containing said para alpha cumyl phenol, the improve
kept below 160° C. The first fractions contained another ment which comprises pyrolyzing said residue at a tem
14 lbs. of isopropyl benzene and 25 lbs. of alphamethyl perature between about 200 and about 400° C. to form
styrene, and, as second fraction, were obtained 129 Ibs. additional quantities of phenol and alpha methyl styrene.
of 98-99% pure phenol. Finally, a fraction containing 2. Process as set forth in claim 1 wherein the pyrolysis
acetophenone and phenol was distilled off. 36.2 lbs. of of the residue is promoted by the addition thereto of an
residue remained in the kettle. acidic catalyst.
This residue was heated to an initial kettle temperature 3. Process as set forth in claim 1 wherein the pyrolysis
of 240 C. at normal pressure in a gas fired still fitted of the residue is carried out under diminished pressure.
with a fractionating column. The temperature at the 4. Process as set forth in claim 1 wherein the phenol
top of the column was kept at about 200 C. and the tem 55 and alpha methyl styrene formed by the pyrolysis of the
perature in the kettle was finally allowed to rise to 400 residue are distilled off as they are formed.
C. The distillate from this decomposition of the residue 5. Process as set forth in claim 4 wherein the phenol
contained 11 lbs. of phenol and 8 lbs. of alpha methyl and alpha methyl styrene subsequently are separated by
styrene and 8 lbs. of a fraction consisting mainly of iso fractional distillation.
propyl benzene. This distillate was worked up in the 6) 6. Process as set forth in claim 4 wherein the phenol
usual way in order to recover the phenol as pure ma and alpha methyl styrene. Subsequently are separated by
terial. The distillate can with advantage be returned to extraction of the phenol with a material selected from the
the distillation system, for instance to the still in which group consisting of water and aqueous alkalies.
the isopropyl benzene is separated from the reaction 7. In the process for the manufacture of phenol by the
products. decomposition of an isopropyl benzene peroxide with
an acidic catalyst whereby there is formed a decomposi
Example 2 tion reaction mixture comprising acetone and para-o-
cumyl phenol, and wherein the acetone and phenol are
936 parts of a residue as obtained in Example I was substantially separated from said decomposition reaction
continuously fed into a still kettle fitted with a fractionat mixture to leave a residue containing said para-a-cumy
ing column whilst the vapours were continuously removed, phenol, the improvement which comprises pyrolyzing said
the temperature at the top of the column being kept at residue at a temperature between about 250 and about
180°-200° C. The temperature in the kettle was allowed 400 C. to form additional quantities of phenol.
to rise to 405 C. 715 parts of a distillate were obtained 8. In the process for the manufacture of phenol by the
which contained 242 parts of phenol and 228 parts of decomposition of an isopropylbenzene peroxide with an
 2,715,145
5 6
acidic catalyst whereby there is formed a decomposition References Cited in the file of this patent
reaction mixture comprising acetone, phenol and para-az UNITED STATES PATENTS
cumylphenol, and wherein the acetone and phenol are sub 2,113,951 Shuman ---------------- Apr. 12, 1938
stantially separated from said decomposition reaction
mixture to leave a residue containing said para-or-cumyl OTHER REFERENCES
phenol, the improvement which comprises heating said Hocket al., Berichte Der Deutsches Chemisches Gesell
residue to temperatures at which pyrolysis takes place to schaft, volume 77, B, pages 257-264 (1944).
form additional quantities of phenol.