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Патент USA US2407044

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Patented Sept. 3, 1946
2,407,044
UNITED STATES PATENT‘ OFFICE
2,407,044
MANUFACTURE OF PHENOLS
Daniel Tyrer, Stockton-on-Tees, England
No Drawing. Application April 6, 1943, Serial No.
482,065. In Great Britain March 31, 1942
5 Claims.
(Cl. 260-628)
1
This invention relates to the manufacture of
phenols from salts of mono sulphonic acids.
The customary process for the manufacture of
phenol from benzene sulphonic acid involves fus
ing the sodium salt of benzene sulphonic acid
with caustic soda at a temperature of 300-350" C‘.
The reaction may be represented by the equation:
2
relatively low temperature of 370-420” C. giving
excellent results.
,
According to the present ‘invention, therefore,
a process for the manufacture of phenols com
‘ prises preparing a solid mixture of a salt of the
mono-sulphonic acid of the phenol desired and
an inorganic base which is infusible at temper
atures up to 420° C. and is capable of forming
with sulphur dioxide a sulphite stable at such
The product is dissolved in Water and the phenol 10 temperatures, and producing the phenol by sub
jecting the solid mixture to a temperature rang
is recovered by treating the sodium phenate with
ing from 370-420" C. while passing therethrough
a suitable acid. However, this process is some
what expensive owing to the cost of the caustic
steam free from acidic gases.
The ‘term “phenols” is used herein to denote
alkali, and to the fact that the latter has to be
simple hydroxyl-substituted aromatic or hetero
used in an amount considerably in excess of th
cyclic compounds which are free from other sub
theoretical quantity.
‘
‘
‘
stituents and obtainable from the corresponding
An object of the present invention is to pro
mono-sulphonates by exchanging the sulpho
vide a simple, less costly and e?icient process for
group for hydroxyl, and which, both in the form
the manufacture of phenols from mono-sul
phonic acids in good yield with the aid of cal 20 of the hydroxyl compounds and the correspond
ing sulphonates, do not readily decompose or lead
cium hydroxide or other inorganic base, instead
to side reactions at the reaction temperature
of caustic alkali.
required for the present process. Among the
It has been proposed to manufacture phenols
more especially suitable phenols there may be
by heating a mixture of a sulphonate correspond
mentioned " the hydroxy-benzenes, hydroxy
ing with the phenol desired and calcium hy
naphthalenes and hydroxy-pyridines.
droxide to form the calcium phenate, and then
The passage of the steam through the solid
liberating the phenol by decomposing the phenate
mixture and the progress of the reaction are
in a current of steam containing an acidic di
oxide gas, such as sulphur. dioxide or carbon
dioxide, capable of reacting with the phenate.
1 0
However, at the high temperature of 425-500° C.
required in this process there is a considerable
formation of undesired lay-products.
I have unexpectedly found that the mono
sulphonic acid salts, which are convertible by
the exchange of sulpho-groups for hydroxyl
groups into “phenols” as hereinafter de?ned,
assisted by bringing the mixture into the form
of solid agglomerated masses containing the sul
phonic acid salt and the base in a state of very
intimate contact. ‘Thus, for example, if sodium
benzene sulphonate is merely ?xed in the form
of ‘a dry powder with dry calcium hydroxide,
35
and'the mixture is heated'at 400° C. in a cur-‘
rent of steam the ‘liberation of phenol ‘is some
what slow. If, however; the reactants are more
intimately admixed by ?rst mixing them with a
slowly decompose when heated alone ‘in steam
small‘ amount of Water to form a“ slurry, and
at 400-500° C. to yield the corresponding free
phenol with the liberation of sulphur dioxide. m. evaporating the watersufliciently, while stirring,
to produce'a solid granular mass which Will not
I have further discovered that this decomposi
soften on heating due to the ‘presence of resid
tion is greatly accelerated by the presence of an
ual
water, the rate of phenol formation is very
inorganic base,‘ such as calcium hydroxide, which
much higher.
is infusible at the reaction temperature and is 45 While the above method of bringing the re
capable'of forming‘with the liberated sulphur
actants into a state of intimate contact by pre
dioxide a sulphite stable at that temperature.
paring a solid granular mass is the preferred
In contradistinction to the prior proposal‘ re
method, it is to be understood that other methods
ferred to above, I have found that the phenol
may be used. For example, a moist mixture of
can be produced by introducing steam directly 50 the reactants may be pelleted or briquetted under
into the mixture of sulphonate and base without
pressure. In making up the mixture in granu
the need of any preformation of phenate or any
lated, pelleted or briquetted form a binding agent
acidic dioxide gas to decompose a phenate,‘ and
may be used, provided that it has no deleterious
that under these conditions the undesirably high
temperatures of 425-500” C. are not required, a
effect on the reaction.
In‘carrying out the process to make phenol
2,407,044
3
4
itself by heating an intimate mixture of sodium
benzene sulphonate and calcium hydroxide in a
current of steam a temperature of about 400° C.
is satisfactory, and at a temperature of 400-420°
C. the rate of phenol formation is about 12 times
greater than when the sulphonate is heated with
potassium, sodium, barium or calcium. There
may also be mentioned trisodium phosphate,
borax, sodium silicate or tricalcium silicate. If
desired, a mixture of diiferent bases may be used.
In general any base capable of combining strong
ly with sulphur dioxide may be used, and the
reaction will generally be more rapid the stronger
the base. Especially rapid is the reaction be‘
tween barium hydroxide and sodium benzene
sulphonate in presence of sodium chloride, the
speed of reaction being practically as rapid as
in the case of the potassium sulphonate referred
to above. A fairly good speed of reaction is also
obtained in the case of the sodium sulphonate
with barium carbonate in the presence of sodium
out calcium hydroxide.
It will be understood that the reaction should
be conducted in the absence of air in order to
prevent oxidation of the phenol produced, and
the introduction of steam secures this object.
As the sulphonate there may be used the sul
phonic acid salt of any metal forming a base
which is as strong as or stronger than the base
used for the reaction, for example, potassium,
sodium, lithium, calcium, strontium, barium,
chloride or with sodium carbonate alone.
magnesium, lead or zinc, or a mixture of sul
salt is especially suitable. Thus, when a granu
lated mixture of potassium benzene sulphonate ‘LU
general the proportion of the base in relation to
the sulphonate need not exceed, or greatly ex
ceed, the theoretical quantity, which is one equiv
alent of the base per molecular proportion of
and calcium hydroxide prepared by evaporating
the sulphonate. However, when the proportion
a slurry of these reactants as described above
is heated in a slow current of steam at 400° C.
or somewhat over, so copius a formation of phe
quantity there is a greater tendency for side
phonates of different metals.
The potassium
nol occurs that the phenol separates from the
condensate as an oily layer. In the case of some
In
of the base used is at or near the theoretical
reactions to occur. In the case of calcium hy
droxide an excess over the theoretical quantity
has practically no effect on the reactivity of the
mixture, and in practice it is advisable to use
only a small excess, advantageously an excess
steam is increased when they are used in ad
of about 50 per cent., the total quantity of cal
mixture with a benzene sulphonate of a different
metal. For example, a mixture of the sodium 30 cium hydroxide then amounting to about 30 per
cent. of the weight of the sodium benzene sul
and potassium sulphonates in equimolecular pro
benzene sulphonates the speed of reaction in
portions reacts about 16 times faster at about
400° C‘. than the sodium sulphonate alone, and
phonate.
In order to reduce the risk of the formation of
undesired products, it is advisable to prevent the
a mixture of 2 mols of the sodium sulphonate
and 1 mol of the potassium sulphonate about 10 35 reactants from coming into contact with cata
lytically active surfaces tending to promote de
times faster. In some cases a mixture of the
composition of the products.
sulphonates of different metals reacts more rap
The rate at which the steam is introduced is
idly than either of the sulphonates used alone.
not of critical importance, but in order to obtain
For example, a mixture of 1 equivalent of the
sodium sulphonate with 1 equivalent of the bari 40 the product in association with as little water
as possible it is advisable not to introduce the
um sulphonate gives a more speedy reaction than
steam at a rate higher than is required for satis
either of these sulphonates used alone.
factory removal of the phenol. A higher rate
In the case of metal sulphonates which react
than this has no advantageous effect on the
more slowly than the potassium sulphonates the
reaction may be accelerated by the presence of 45 speed of the reaction. In general a suitable rate
is 400 grams of steam per hour per 100 grams of
another substance. for example, a salt, which is
sulphonate, but it may vary widely without
otherwise inert. For example, the incorporation
affecting the reaction, and in the case of a phenol
with a mixture of sodium benzene sulphonate
which is not very readily volatilised it will be of
and calcium hydroxide of potassium chloride,
potassium sulphate or other potassium salt which 60 advantage to introduce the steam at a somewhat
higher rate.
is stable under the reaction conditions consid
The pressure of the steam in the reaction ves
erably increases the speed of reaction. Other
sel may be below or above that of the atmosphere,
substances which similarly accelerate the reac
but in general atmospheric pressure is most suit
tion are sodium chloride, borax. sodium hydrox
ide (in small quantities)‘, zinc chloride or a mix 55 able. The pressure does not materially affect the
reaction, except in certain cases. For example,
ture of barium carbonate and sodium chloride.
some sulphonates have a tendency to swell and
Mixtures of sodium chloride with a potassium
produce a frothy mass. This effect. which hin
salt or with any of the other substances named
ders the reaction can be counteracted by in
above are also useful. By the use of such sub
stances. especially a potassium salt, the speed 60 creasing the pressure of the steam.
The particular reaction temperature within
of reaction in a current of steam can be made
the aforesaid range of 370-420° C. depends to
to approach that of the potassium sulphonate re
some extent on the particular sulphonate and
ferred to above. Even a small addition of potas
base used. In the case of sodium benzene sul
sium chloride to the sodium sulphonate appreci
ably accelerates the reaction. The maximum ac v65 phonate and calcium hydroxide practically no
reaction occurs below about 400° C., but the re
celeration appears to be obtained with 0.75
action proceeds fairly rapidly at 410° C., which
equivalent of potassium chloride, when the re
temperature is also suitable with most of the
action is about. 15 times faster than with the
other mixtures referred to above. In the case of
sodium sulphonate alone.
In addition to calcium hydroxide, which may 70 pyridine-B-sulphonate a somewhat lower tem
perature, for example 3'75-385° (3., is satisfactory.
be introduced in the form of calcium oxide, other
It is generally advantageous to introduce the
suitable bases for reaction with the sulphonate
steam in a preheated condition so as to provide
are metal hydroxides, oxides or carbonates, for
example, the hydroxides of barium, magnesium,
heat for the reaction.
lead, zinc or cadmium, and the carbonates of 75
Among the various methods of carrying out the
1.2540104‘;
"
5
e
process‘ described 'above’thetpreferredmethod i
wnate, :andalso zany reaction "acceleratonzsuch as
‘in. potassium ‘salt, which may ‘have been added.
‘_. to. heatin steam atmixture of. a ‘potassium sul
phonateand:calciumchydroxide or of¢a¢sodium 1
sulphonate with potassium chlorideand calcium
t ::.It.is desirable; especially when the reaction is
not carried beyond the stage of a 9.0 per cent con
hydroxide.
~5._-;;.version, .to'gtreat the residue. in order to recover
. Although the speed of. the reactions as measev
.thezyaluable;constituents thereof, or,~more ad
ured byrtbe rateof the formation of phenol in‘.
relation to the weight'of unconvertedsulphonate
yantageously, to :convert the residue into. a fresh
.reactionrmixture; suitable for a further reaction.
present at any time remains substantially cone; ;-.: Onemethod is to extractthe residue with water,
stant throughout the reaction, it: will be under: ' :;filter to; remove the insoluble calcium compounds,
stood that the rate at which the phenol is pro’
.treatpthe, ?ltrate .i with sui?cient fresh sulphonic
duced in relation to the weight of the initial re
. acidztopiorm alkali sulphonate, boil the solution
action mixture diminishes as the sulphonate fis
-to.expe1, the sulphur dioxideproduced by the re
consumed. When about 90-95 per cent. of the
actionpadd the necessary quantity of calcium hy
sulphonate ‘has reacted‘the rate of phenol. pro- 15 droxide, and evaporate the whole to produce a
duction becomes too slow to be of practical value
»<:solidigranularrzmass providing . a fresh batch of
and his generally advisable not to proceed be
:reactiongxmixture. .Thegsulphur dioxide expelled
' yond the stage of .a 90 per cent. conversion and.
imayberecovered, andzused in any desired man
to recover the unchanged sulphonate from the." ...ner.-.,:.J~For. example, it;may be .used for the manu
residue as‘hereinafter described- If the reactionxizo ifalctul'eilclf Sulphuric :acid for makingthe sul
is conducted as a continuous process by‘charging
. ' phonic acid.
fresh reaction mixture into the reaction vessel.‘
‘ .v If‘ thegysulphonic acid ‘.used for preparingythe
and removing the reaction residue the initial'
high rate of phenol production can be substan
sulphonate; contains some. sulphuric .acid, the
greater partof the lattermay be removed by add
ing to the mixedsolution sufficient calcium hy
tially maintained.
"'
The vapours‘issuing from the reaction vessel: .-‘.1;‘.droxide,- or;.-;for example, recovered calcium sul
may be wholly condensed to form‘ a mixture of . ._ ..phite'to-precipitate-the sulphuric acid as. calcium
the phenol and water or partially condensed to;
csulphate; The precipitated calcium sulphate need
obtain the phenol in a more concentrated formr. .wllOl'?bB removed immediately, if only a small quan
Phenol itself forms an azeotropic mixture
v‘301:.tii'lyiof;sulphuric acid'is present, its removal being
water containing approximately 9 per cent oi‘: .:.:performed.aiter.the next reaction when the resi
phenol and boiling slightly below 100° C. In the,‘v
, dueisextracted ‘with water.
case of‘ phenol, therefore, partial. condensatio
to obtain an enrichment in phenol is only use
If, on the other
hand,zthe quantity of sulphuric acid present is ap
preciable the, precipitated calcium sulphate is ad
ful when the ratio of Water to phenol in the; .g vantageouslyremoved by ?ltration. In this case
vapours is less than 10:1. With a substantially“ JIZJ‘SBCOI‘ld ?ltration ltoiremove the precipitated cal
higher ratio of water to phenol partial condensa
.oium sulphatecan be avoided by adding the sul
tion may be effected so as to obtain a secondar,
phonic:acid:;suitably.diluted directly to the pow
condensate containing approximately 9 per cent:
dered :reaotionzresidue or to an aqueous slurry
of phenol. In the case of some other phenolsitps-i? z-thereof.v Thesulphuric acid will thus be automat
is possible by partial condensation .to obtain the
ically removed, or at least prevented from accu
phenol almost free. from water. In other cases
mulating, provided it is not present in excess of
the phenol may be recovered ‘from the concenthe equivalent quantity relatively to the calcium
trated phenol-water mixture in“ a substantially
compounds in the reaction residue. The quantity
pure state by known methods, for example by 45 of the sulphonic acid used will, of course, be pro
simple. distillation. When the phenol is only .. ‘ portional tothe amount of decomposable alkali
slightly soluble. in water the separation-may be. ; .. compounds. present.
>
performed by simple physical meansrand the.
i. Shouldtherfresh sulphonic acid only be avail
secarated phenol may be recti?ed by distillation. .1 -..able. in the form of the calcium salt, when an
When the phenol is appreciably,‘ soluble in water. .5"? alkali sulphonate is required for the reaction, the
it may ‘be extracted by means ‘of a suitable sol-, .i.
vent. and recovered in a substantially .pure state
‘from. the extract solution by. distillation.
. ‘
If desired, the vapours issuing from the reac~= . tion vessel may be used. to preheat to some extent
the steam introduced into-the vessel. the/vapours .:
being subseouently wholly or partially condensed ‘ ‘
as described above.v Residual steam may be re-,‘ .,
calcium sulphonate is added to the aqueous ex
tract of. the reaction residue in an amount suffi
cient to react with the alkali sulphite and alkali
hydroxide present, the alkali hydroxide having
been formedby reaction of a part of the alkali
{sulphite withcalcium hydroxide duringthe ex
traction of the residue with water.
. An‘ alternative procedure is to separate the al
turned to the reaction vessel for re-use. Fur‘ Kali sulphite from the aqueous extract.‘ of the
‘ thermore, the'aqueous condensate,».afterrseparat- 6"‘ reaction residue by crystallisation, and use the
ing the ‘bulk’ of the phenol therefrom, may be i . residual liquor containing unchanged sulphonate
used for generating steam required for the proc_.
for making a fresh batch of reaction mixture.
ess, small residual quantities of the phenol being
The _separated alkah Sulphlte may be usfed for
recovered either by being volatilised and so re-‘ 65 "gllgngégependent' manufacture of alkah sul
‘ turned into the system or by‘being concentrated
as aresidue in the still.
,
In the latter case an
alkali hydroxide may be added to bindthe' phenol
as phenolate, if ‘desired.
_
_
'
_
_
_ .
.
'
.
.
.
If, instead. of calcium hydroxlde, sodium car
bonate, for example, is used as the basesthe re
action residue will be wholly soluble in water.
i
The resulting sodium. sulphite may be separated
The sohd residue ‘remamm? in the reactlon '70 from theaqueous solution ofthe residueby crys
vessel may be‘ treated 111 VarlOuS Ways-
when; . .htallisation and used in part for the manufacture
calcium hydroxide is used as the base, the residue,
will generally contain alkali sulphite (containing
. the metal of the sulphonate), calcium sulphite, ‘
of fresh sulphonate, Wh?e the ‘mother liquor is
introduced into a, fresh batch,
It will be evident from the above description
calcium hydroxide andunchangedalkali sulphoe . 75.. that the only rawmaterial consumed :in the proc
7
aqueous extract by ?ltration su?icient benzene
sulphonic acid is added to the mixture to pro
hydroxide or similar base. The alkali combined
duce 100 parts of sodium benzene sulphonate of
with or added to the sulphonic acid can be wholly
which about 10 per cent constitutes the un
recovered.
changed sulphonate left in the reaction vessel.
Owing to the repeated working up of the re
The mixture is then boiled to expel the sulphur
action residue to form fresh reaction mixture the
dioxide set free. Any sulphuric acid present in
latter will become progressively contaminated
the benzene sulphonic acid introduced is for the
with impurities. Thus, the whole of the residue
most part precipitated as calcium sulphate by
may be discarded after a certain time, or the
accumulation of impurities may be retarded by 10 the calcium compounds present in the residue.
The mixture is then ?ltered, and 30 parts of
removing a small portion of the residue after
calcium hydroxide are added to the ?ltrate,
each reaction. The material so discarded or re
which is then suitable for the preparation of a
moved may be treated in any suitable manner to
second batch of reaction mixture.
recover any of the useful constituents, such as
The quantity of phenol recovered depends on
15
potassium salts.
the extent of the conversion, but with a 90 per
The above description is mainly concerned with
ess, apart from the sulphonic acid, is the calcium
the manufacture of phenol from benzene sulpho
nates, but the invention is also applicable to other
phenols of the kind hereinbefore de?ned, for ex
cent conversion approximately 45 parts of phenol
are obtained representing a yield of about 96 per
cent.
Although this example describes a batch proc
ample, oc- 0r ?-naphthol or p-hydroxy-pyridine, 20
ess, it will be understood that by obvious modi
as illustrated in Examples 3, 4 and'5 below. In
?cations it can be carried out as a continuous
the case of a-naphthol, the sodium a-sulphonate
process.
mixed with calcium hydroxide and an addition of
Example 2
potassium chloride gives a smooth and rapid re
action at 400° C. with steam, and a yield of about 25
27.5 parts of calcium hydroxide are added to
77-83 per cent. calculated on the sulphonate
a strong aqueous solution of 100 parts of potas
which reacts. The (Jr-naphthol is volatilised by
sium benzene sulphonate, and the mixture is
the steam. In the case of ?-naphthol, the reac
converted into a solid granular mass and further
tion of the sodium p-sulphonate with calcium hy
treated as described in Example 1. The only
droxide in the presence of potassium chloride and 30 diiference from Example 1 is that the stage of
steam proceeds more slowly than with the sodium
90 per cent conversion is reached after heating
a-sulphonate, but the yield is somewhat better,
for about one hour at the reaction temperature.
amounting to about 85-90 per cent of the sul
The yield of phenol is approximately the same
phonate which reacts. In the case of ?-hydroxy
as that obtained in Example 1, and the treat
pyridine, the reaction of the potassium-B-sul
ment of the residue is the same.
phonate or the sodium-e-sulphonate (with the
addition of potassium chloride) with calcium
hydroxide is su?iciently rapid at a temperature of
Example 3
An aqueous solution of 100 parts of sodium
370-385° C. but it is necessary to introduce the
naphthalene-a-sulphonate is mixed with 24 parts
steam at a higher rate as the product is more 40 of potassium chloride and 24 parts of calcium
hydroxide. The mixture is evaporated to pro
di?icult to volatilise.
The following examples illustrate the inven
duce a solid granular mass, and the latter is
tion, the parts being by weight:
Example 1
30 parts of potassium chloride is added to a
strong aqueous solution of 100 parts of sodium
benzene sulphonate, and 30 parts of calciiun
hydroxide are added to the resulting solution.
The whole is then evaporated with suitable agi
tation or stirring to produce an intimate mixture
of the constituents in the form of a loose gran
ular mass. The granular mass is charged into
a reaction vessel in which it can be brought to a
reaction temperature of 400-420° C., and a slow 55
heated at 390-410° C. in a current of preheted
steam. The issuing vapours are condensed to
give a mixture of u-naphthol and water. After
about 2 hours the reaction is about 90' per cent
complete, and after cooling the solid residue is
discharged from the reaction vessel.
The said residue is extracted with hot water,
and treated with su?‘icient calcium naphthalene
a-sulphonate to produce, together with the un
changed sulphonate, 100 parts of sodium naph
thalene-a-sulphonate. The whole is then ?ltered
to remove the insoluble calcium compounds, and
24 parts of calcium hydroxide are added to the
?ltrate for preparing a fresh batch of reaction
current of steam, preferably preheated to about
mixture.
440° C., is passed through the mass. The steam
The condensate is extracted with benzene, the
is introduced at the rate of 400 parts per hour,
extract is distilled to remove the benzene, and
and the rate of introduction is later reduced as
the reactants are consumed. The vapours is 60 the crude a-naphthol is puri?ed by fractional dis
tillation under reduced pressure. Alternatively
suing from the reaction vessel are condensed to
the condensate may be ?rst treated with caustic
form a mixture of phenol and water which sepa
soda solution to disslove the a-naphthol, the in
rates into two layers. The reaction is stopped
soluble matter separated from the solution, and
when the rate of phenol formation has become
very low. This occurs after heating for about 65 the latter acidi?ed and the precipitated naphthol
collected. There are thus obtained approxi
21/2 hours, when about 90 per cent of the sul
mately 45 parts of a product which may be fur
phonate will have reacted.
The phenol is recovered by extracting the
ther puri?ed by distillation under reduced
phenol-water mixture with benzene, distilling
the extract to remove and recover the benzene, 70
pressure.
Example 4
and rectifying the residual phenol by distillation.
The solid residue which remains in the reac
tion vessel is discharged after cooling and ex
tracted with su?icient hot water to dissolve all
the alkali salts present. Before separating the
100 parts of sodium naphthalene-p-sulphonate,
24 parts of calcium hydroxide and 24 parts of
potassium chloride are mixed with water to form
a paste, and the latter is evaporated to produce
2,407,044
9
.
a solid granular mass. The latter is heated ‘at
390-410" C. in a current of steam. The issuing
vapours are condensed to give a mixture of #
naphthol and water. After about 4 hours the
reaction is about 90 per cent complete. The
solid residue and the condensate are worked up
10
capable of forming with sulphur dioxide 2. sul
phite stable at such temperatures, and producing
the phenol by subjecting the solid mixture to a
temperature ranging from 370-420° C. while pass
ing therethrough steam free from acidic gases.
2. A process for the manufacture of phenols
as described in Example 3. Approximately 50
which comprises, bringing a mixture of a salt of
parts of crude ,e-naphthol are obtained which
the mono-sulphonic acid corresponding to the
may be puri?ed by distillation under reduced
phenol desired and an inorganic base, which is
pressure.
10 infusible at temperatures up to 420° C. and is ca
Example 5
pable of forming with sulphur dioxide a sulphite
stable at such temperatures, into the form of
To an aqueous solution of 100 parts of sodium
solid agglomerated masses containing the said salt
pyridine-5~si1lphonate are added 30 parts of po
and base in a state of very intimate contact,
tassium chloride and 30 parts of calcium hydrox 15 and
producing the phenol by subjecting the solid
ide. The mixture is evaporated, while stirring,
mixture to a temperature ranging from 370-420"
to produce a solid granular mass. The gran
C. while passing therethrough steam free from
ular mass is heated at a temperature 0f'375
acidic gases.
385° C. in a current of steam which is passed
3. A process for the manufacture of phenols
through the mass at the rate of 1200 parts by 20
which comprises, preparing a solid mixture of a
weight per hour. The issuing vapour is partially
salt of the mono-sulphonic acid corresponding to
condensed in a small packed tower in which the
the phenol desired and calcium hydroxide, and
condensate scrubs the rising vapour and the
producing the phenol by subjecting the solid
uncondensed vapour is returned to the steam
mixture to a temperature ranging from 370-420"
inlet of the reaction vessel. The condensation 25 C. while passing therethrough steam free from
is so controlled that only about one tenth of the
acidic gases.
'
total steam is condensed and the remainder is
4.
A
process
for
the manufacture. of phenols
returned to the reaction vessel. The hot con
which comprises, preparing a solid mixture of a
densate so obtained consists of a mixture of mol-‘
potassium salt of the mono-sulphonic acid corre
ten-p-hydroxy-pyridine and water which latter 30 i sponding
to the phenol desired and an inorganic
contains some of the p-hydroxy-pyridine in so
base
which
is infusible at temperatures up to 420°
lution. The operation is continued until the
C. and is capable of forming with sulphur diox
quantity of ?-hydroxy-pyridine present in the
ide a sulphite stable at such temperatures, and
condensed vapor becomes insigni?cant, that is
producing the phenol by subjecting the solid
to say after about 4 hours. At the end or this 35 mixture to a temperature ranging from 370-420"
period about 90-95 per cent of the sodium pyri
C. while passing therethrough steam free from
dine-p-sulphonate will have undergone reaction.
acidic gases.
The water is removed from the aqueous con
5. A process for the manufacture of phenols
densate by distillation, and approximately 42
which comprises, preparing a solid mixture of a
parts of crude e-hydroxy-pyridine remain behind.
sodium salt of the mono-sulphonic acid of the
The crude product is puri?ed by distillation to
phenol desired, an inorganic base which is in
yield 38 parts of the puri?ed product. About 2
fusible at temperatures up to 420° C. and is ca
parts of e-hydroxy-pyridine remain in the solid
pable of forming with sulphur dioxide a sulphite
reaction residue and may be recovered therefrom
stable at such temperatures, and a reaction ac
by known methods, If desired.
45 celerator selected from the group consisting of
I claim:
potassium chloride and potassium sulphate, and
1. A process for the manufacture of phenols
producing the phenol by subjecting the solid mix
which comprises, preparing a solid mixture of a
ture to a temperature ranging from 370-420" C.
salt of the mono-sulphonic acid corresponding to
passing therethrough steam free from acid
the phenol desired and an inorganic base which 50 while
ic gases.
is infusible at temperatures up to 420° C., and is
DANIEL TYRER.
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