Nov. 15, 1949 N. E.

SEARLE 2,487,832
PROCESS FOR PREPARING 'ANISOLE

Filed Nov. 2, 1946

FIG.1.
DIMETHYL ETHERk ‘ PHENOL
i

CA TALYST
CHAMBER

ANISOLE

F|G.2.
METHYL ALCOHOL‘ 4 PHENOL

>
r

D'METHYL CATALYST
ETHER \/ ' CHAMBER

‘I
ANISOLE

INVENTOR.
NORMAN E. SEARLE

ATTO
vPatented Nov. 15, 1949 2,487,832

' UNITED STATES PATENT OFFICE

PROCESS FOR PREPARING ANISOLE
Norman E. Searle, Wilmington, Del., assignor to
E. I. du Pont de Nemours & Company, Wil
mington, Del., a corporation of Delaware
Application November 2, 1946, Serial No. 707,483
4 Claims. (Cl. 260-612)
1 2
This invention relates to the manufacture of based on the concept of preparing anisole by the
anisole and more particularly to processes for the reaction of phenol and dimethyl ether and the
manufacture of anisole from‘ phenol and dimethyl . discovery'that the reaction can be attained by
ether, which processes comprise the steps of leading dimethyl ether and phenol into a re
leading phenol and dimethyl ether into a reac action zone and contacting the reaction while in
tion zone and in the reaction zone contacting the mixture and in the vapor phase with a suitable
phenol and the dimethyl ether in admixture in catalyst.
the vapor phase with a solid dehydrating cata In bringing together dimethyl ether and
lyst at a temperature of about 200 to 400° C. phenol, it is preferred to control the amounts so
It is an object of the invention to provide 10 that there is present at the time of contact of
methods for the manufacture of anisole. A fur the reactants with the catalyst at least one-half
ther object is to provide practical commercial mole of dimethyl ether for each mole of phenol.
continuous vapor phase processes for the manu Preferably,,there is led into the reaction zone
facture of anisole in which phenol and dimethyl from‘ 1 to 2 moles of dimethyl ether for each mole
other are continuously brought together as re 15 of phenol.
actants in the vapor phase and contacted with Various methods, which will be apparent to one
a dehydrating catalyst. A still further object is skilled in the art, may be used for bringing the
to provide methods for the manufacture of reactants, phenol and dimethyl ether, into ad
anisole in relatively high yield by reacting phenol mixture and heating them to the reaction tem
and dimethyl ether in the vapor phase in the 20 perature so that on contact with a suitable cata
presence of a catalyst, separating unreacted di lyst anisole will be produced. For example, the
methyl ether, and returning it for admixture mixing and heating may be carried out by vapor
with phenol and methyl alcohol. Other objects izing the phenol and then leading the gaseous
will appear hereinafter. phenol and gaseous dimethyl ether separately
The foregoing and other objects of the inven I into a common feed pipe in which the vapors are
tion are attained by leading phenol into a re mixed. The mixed vapors may then be heated
action zone, leading dimethyl ether into the same to the temperature applied in the reaction zone
reaction zone, and in the reaction zone contact prior to contact with the catalyst, or, alter
ing said phenol and said dimethyl ether, in ad natively, a part of the reaction zone itself may
mixture in the vapor phase with a solid dehy be used as a preheating vessel. Other methods
hydrating catalyst at a temperature of about 200v of heating and effecting mixture of the reactants
to 400° C. will be apparent, such as preheating the re
The nature of this invention will be better actants ‘to the required reaction temperature be
understood by reference to the accompanying fore mixing or dissolving gaseous dimethyl ether
drawings wherein: 35 in molten phenol under pressure and then
Figure 1 is a ?owsheet showing a procedure for vaporizing the solution and heating to the de
carrying out the processes of the invention. sired temperature.
Figure 2, also a ?owsheet, illustrates a simpli Catalysts suitable for use in the conversion of
?ed and preferred procedure in which unreacted dimethyl ether and phenol to anisole are of the
dimethyl ether is recycled. 40 type vknown in catalytic practice as dehydrating
Dimethyl ether for use in the preparation of catalysts. In practicing the processes of this in- '
anisole according to the processes of this inven vention, the class of dehydrating catalyst is
tion may be obtained by any of the well-known further restricted to include only those dehydrat
methods of manufacture. The dimethyl ether ing catalysts which are solid at the reaction
may be prepared, for example, by reaction of temperature. Perhaps the most common solidv
methyl alcohol with sulfuric acid or by the con dehydrating catalysts are the activated aluminas
version of methyl alcohol to dimethyl ether by which are generally prepared by the heat treat
contact of gaseous methyl alcohol with a suit ment of aluminum hydroxide. .The activated
able catalyst such as activated alumina or silicic aluminas comprise a preferred type of solid de
acid gel. 50 hydrating catalyst for use in the processes of
Phenol for use in the processes of the inven this invention. Other solid dehydrating catalysts
tion may be obtained by any conventional means, ' suitable for use in the processes of the invention
‘the usual commercial phenol being of satisfac are, for example, the oxides of thorium, tungsten,
tory quality. titanium, zirconium, molybdenum, and chromium
The invention,'as illustrated by Figure 1, is 55 either alone or together with promoters such as
 2,487,888
3
the oxides of aluminum, magnesium, zinc, and the eiliuent gases and recycled, thus forming a
potassium carbonate. Heat treated clays, such as continuous operation. The separation of the
kaolin, are also recognized in the art as dehydrat ingredients of the eiiluent gases leaving the reac
ing catalysts and are effective in promoting the tion zone may be effected in any of the ways
reaction of dimethyl ether and phenol accord well known and used in the art for separating
ing to the processes of this invention. chemicals of this type. Most advantageously,
The best conversions are obtained by keeping the e?iuent gases are passed into a rectifying
the temperature in the reaction zone between column by means of which the low boiling di
the limits of 200 and 400° C. It will be appre methyl ether is readily separated from the re
ciated that the optimum temperature within the 10 maining constituents of the gases and may be
limits prescribed will vary with the particular returned directly for admixture with phenol and
catalyst used and the particular adjustment of methyl alcohol prior to reaction to form addi
other process variables such as the relative pro tional anisole. After effecting such a separation
portions of the ingredients and the ?ow rates. of dimethyl ether, the other constituents of the
The contact of reactants with the catalyst 15 eiiluent gases may be separated by subsequent
may be effected in any of the ways known and distillation processes.
practiced in catalytic operations. For example, Alternatively, the effluent gases from the re
the gaseous reactants may be passed downward action chamber may be cooled su?iciently to
or upward thru‘ a‘reaction vessel packed with a condense all the compounds therein except the
granular catalyst mass, such catalyst mass being 20 dimethyl ether and the gaseous dimethyl ether
composed entirely of active catalyst or a com withdrawn for recycle, the condensed material
bination of carrier and active catalyst. The ac being separated subsequently by batch or con
tivity of the catalyst may be varied thruout the tinuous distillation processes, or, if it is desired,
catalyst zone or zones as desired. Alternatively, the effluent gases from the reaction chamber
the catalyst chamber or chambers may contain 25 may be cooled so that substantially the whole
trays for supporting catalyst beds, the trays be of the gases is condensed and the liquid so ob
ing so placed that the gases follow a circuitoustained passed into a fractionating system for
route in passing thru the reaction zone and are separation of the constituents so that the di
subjected to extended contact with the catalyst methyl ether and unused phenol may be recycled
The reaction also may be effected by 30 and the product, anisole, recovered.
following the so-called “?uid catalyst” method The invention maybe more fully understood by
in which the reactant gases are passedthru a reference to the following examples: '
?nely powdered catalyst, the ?ow rate of the
gases being so regulated as to maintain the Example 1
catalyst mass in an ebullient or apparent boiling 35 This example illustrates the process shown in
condition. In the latter type of operation the Figure 1. ' '
catalyst chamber may be so designed that no Molten phenol and dimethyl ether were con
substantial amounts of catalyst are carried along tinuously mixed in the proportions of 54 parts
with the ‘effluent gases or circulating catalyst by weight per minute of phenol and 68 parts by
system may be used in which the catalyst is 40 weight per minute of dimethyl ether and this mix
separated from the eiiluent gases in a vessel such ture was constantly passed into a tube containing
as a cyclone separator, collected and recycled 3880 parts by weight of an activated alumina cat
to the reaction vessel for mixture with incoming alyst of 8-14 mesh size. The temperature of the
dimethyl ether and phenol. catalyst mass was maintained between about 345
Figure 2 illustrates a preferred embodiment 45 and 355° C. The ei?uent from the catalyst tube
of the invention in which phenol, recycled di was condensed and the condensate was fraction
methyl ether, and methyl alcohol are led con > ally distilled to recover the anisole produced. The
tinuously in admixture in a gaseous phase into anisole recovered by operating at 2 hours under
contact with a solid catalyst at a temperature of the above conditions was'2180 parts by weight,
about 200 to 400° C. In this embodiment, un to had a boiling point of 154-1550 C., and a refrac
reacted dimethyl ether leaving the reaction tive index of
chamber is separated from anisole and is returned 25.5
as the aforementioned recycled dimethyl ether n—5~-1.5150
and methyl alcohol is introduced into the sys
tem in substantially the amount required to re 55 which compares closely with the boiling point and
place dimethyl ether consumed in the reaction; '- refractive index of a known sample of anisole.
that is, in amount corresponding substantially to
2 moles of methyl alcohol per mole of dimethyl Example 2
ether consumed. v This example is illustrative of the process
In practicing the embodiment illustrated by» 60 shown in Figure 2 in which unreacted dimethyl
Figure 2, it is preferred that the sum of the ether is recycled, and mixed with phenol and
amounts of dimethyl ether and methyl alcohol make-up methyl alcohol. The rates and condi
employed be in excess of the amount of said tions given in this example were maintained sub
mixture stoichiometrically required to react with stantially constant over a 4.43-hour period of op
phenol to form anisole, and still more preferably 65 eration to obtain representative data.
the sum of the amounts of recycled, dimethyl A mixture of molten phenol and methyl alcohol
ether and methyl alcohol correspond to about was prepared containing 5.9 parts by weight of
' two to four times the total amount required to phenol for each part by weight of methyl alcohol.
react with phenol to form anisole. This mixture was then mixedv continuously at the
The gases leaving the catalyst chamber, ac 70 rate of 90 parts by weight per minute with gaseous
cording to the process illustrated in Figure 2, dimethyl ether, the dimethyl ether being supplied
contain principally anisole, unreacted dimethyl at the rate of 51 parts by weight per minute. This
ether, and smaller amounts of unreacted phenol rate of addition of dimethyl ether corresponds
and water. According to the process of the substantially to the rate at which unreacted di
invention the dimethyl ether is separated from 75 methyl ether issued from the catalyst tube.
 2,487,882
The above mixture, consisting of phenol, di activated alumina catalyst at a. temperature of
methyl ether, and methyl alcohol, was passed into about 200 to 400° 0., whereby anisole is formed,
a catalyst tube containing 3880~parts by weight and continuously separating unreacted dimethyl
of activated alumina. The temperature in the ether from the anisole. -
catalyst tube was maintained at about 335-345° C. 4. A continuous process for the manufacture
Unreacted dimethyl ether was separated from the of anisole which comprises leading phenol, re
'e?luent from the catalyst tube by condensing the cycled dimethyl ether, and methyl alcohol into a
effluent and then heating it su?lciently to distill reaction zone in proportions such that the sum
off the dimethyl ether. There was recovered from of the recycled dimethyl ether and the methyl al
the remaining e?luent by‘fractional distillation a 10 cohol is in excess of the stoichiometric amount to
_ total of 4110 parts by weight of anisole, boiling at react with phenol to form anisole, in the reaction
154-155° C. zone continuously contacting, the phenol, re
I claim: . . cycled dimethyl ether, and methyl alcohol in ad
1. A process for the manufacture of anisole mixture in the vapor phase with an activated
which comprises leading phenol into a reaction 15 alumina catalyst at a temperature of about 200 to
zone, leading dimethyl ether into the same reac 400° 0., whereby anisole is formed, continuously
tion zone, and in the reaction zone contacting separating unreacted dimethyl ether from the
said phenol and said dimethyl ether in admix anisole, and returning the separated dimethyl
ture in the vapor phase with a solid dehydrating etger as the aforementioned recycled dimethyl
catalyst at a temperature of about 200 to 400° C. 20 et er. -
2. A process for the manufacture of anisole NORMAN E. SEARLE.
which comprises leading phenol and dimethyl
ether intov a reaction zone in the proportions of REFERENCES CITED
at least one-half mole of dimethyl ether for each ' The following. references are of record in the
mole of phenol and in the reaction zone contact 25 file of this patent:
ing the phenol and the dimethyl ether in ad
mixture in the vapor phase with a solid dehydrat Hennion, "Jour. Amer. Chem. Soc.”, vol. 55
ing catalyst at a temperature of about 200 to v (1933), pages 2858-2860.
400° C. ' Sowa, "Jour. Amer. Chem. Soc", vol. 57 (1935),
3. A continuous process for the manufacture of pages 709-711. ".
anisole which comprises leading phenol and di 30 . Cullinane, “Journal Chem. Soc. (London) "
methyl ether into a reaction zone in the propor (1945), pages 821-3. _
tions of at least one-half mole of dimethyl ether Senderens, “Comptes Rendus", vol. 146 (1908),
for each mole of phenol, in the reaction zone con pages 1211-1213.
tinuously contacting the phenol and dimethyl 35 Kolka et al., “Jour. Am. Chem. 800.," vol. 61
ether in admixture in the vapor phase with an (1939); pages 1463-5.