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Patented Dec. 24, 1946
2,413,255 .
' > , UNITED ‘STATE
s“ PATENT OFFICE
2,413,255
-
.
.
- PROCESS FOR REFINING STYRENE AND
METHYL STYRENE
,
'
Frank J. Soday, Baton Ronge,;La., assignor to
The United Gas Improvement Company, a cor
poration of Pennsylvania
‘
-
No Drawing. Application May 1"],v 1943,
Serial No. 487,345
7 Claims.
.
1
(01. 260-669) ‘
2
alkaline earth metals.
_ .
.
Examples of such metals are lithium, sodium,
potassium, rubidium, caesium, barium, strontium
removal of impurities from styrene and substi- _‘
tuted styrene by the application thereto of one or
and calcium. Due to the availability and low cost '
of sodium and potassium, however, these metals
more metals of group Ia andv group 11a of the pe
riodic table, as well as certain active alloys there- ‘
are preferred for the use set forth herein. .
,
Alloys of these metals, such as'NaPbio, NaHg‘r,
.
NaCa5, NaZnm, KNa and the like,- also may be
‘ An object'of the present invention is the re
I moval of certain impurities from styrene and sub
stituted styrene by treatment with one or more!
?nely divided'alkali or alkaline earth metals, or
and y
\
‘
More particularly, this invention pertains to the
of.
,
obtained by the use of ?nely divided alkali
This invention relates to the re?ning of styrene
type compounds.
i
w
employed for the removal of undesired impurities
from styrene and substituted styrene. In general,
10
the alloys of the respective metals react with the
impurities present in styrene and substituted
styrene fractions at a slower rate than-the corre
active alloys thereof. Another object of the in
vention is the provision of certain methods where- '
sponding metals.
by styrene and substituted styrene and particu
larly light oil styrene and substituted styrene
'
In general, therefore, it may be said that very‘
?nely divided metals in groups Ia and 11a of the,
' periodic system, and their\ reactive alloys, may be
fractions, maybe puri?ed in a continuous manner
by the application of alkali or alkaline earth met
als without undue loss of unsaturated hydrocar
bons in the ‘form of soluble or insoluble polymers.
Other objects and. advantages of the‘ invention
will be apparent to those skilled in the art upon
an, inspection of the following description and
used to re?ne styrene and substituted styrene.
The styrene and substituted styrene which may
be re?ned by this method may-be obtained from
any desired ‘source such as synthetically, for
‘example by the removal of the elements-of chlo
rine or. hydrogen chloride from chlorinated ethyl
.
benzene or'substituted ethyl b'en'zenesfby the .
Styrene and substituted styrene fractions, par 25 partialv hydrogenation of certain phenyl or sub
ticularly light oil fractions, frequently contain ' s‘tituted-phenyl acetylenes; by the dehydrogena
substantial quantities of impurities, such as acet
‘tion of ethyl benzene or substituted ethyl ben
claims.
ylenic hydrocarbons and compounds; ' oxygenated '
zenes; by the dehydration of’ phenyl ethyl alcohol
compounds such as aldehydes and peroxides; sul 30 or methyl phenyl carbinol, or substituents there
fur compounds; and other impurities, which in
of ;- and by the pyrolysis of petroleum or petro
terfere with the use of suchmaterials in most, if , leum hydrocarbons in‘the gaseous phase at tem
.peratures above 1000° F., and more particularly
not all, industrial applications.
Thus, for example, a 60% light oil styrene frac
above 1300° F., followed by condensation and
‘ tion obtained by the pyrolysis of petroleum in the 35 fractionation; and by the pyrolysis of other car
gas phase at temperatures substantially above
procedures also may _
bonaceous materials. Other
’
1300° F., followed by'condensation and fractiona
be employed for the production of styrene or sub
tion', was found to contain,0.2% phenyl acetylene,
stituted styrene which may be ‘ re?ned by the
0.1% sulfur, and 0.02% aldehydes, as well as cer
methods to be more particularly described herein.
tain other oxygenated impurities. This ‘styrene 40
The styrene fractions which may be re?ned by ,
styrene obtained therefrom‘ by the use of suitable
concentrating methods‘, such as a 98% styrene
my process may have any ‘desired, boiling point,
although I generally prefer to employ fractions ‘
boiling mainly in the range of 125 to 160° 0., and
concentrate, is unsuited for the production of
more particularly from 140 to 150° C. 1 Excellent -
resins of good quality due to the inhibiting action,
results are obtained by the ‘use of styrene frac
tlons boiling mainly in the range of l43eto148° C.
fraction, as well as the more highly concentrated
~ and other undesirable properties, of the impuri
ties contained therein.
As a result of extensive experimentation, I have
discovered that styrene and substituted styrene,
particularly light oil styrene and substituted
The substituted styrenes which may be re?ned
by my process may be‘ represented by the follow
" ing formula
50
styrene fractions, may be re?ned by the applica
tion in ?nely divided form'ofat least'one metal -
of group In and group 11a of the periodic table, as
well as certain active alloys thereof, in a continu-
ous operation. Particularly desirable results are
(d) 1|
3
in which at least one of the group a, ‘b, and d
is an alkyl group, such as methyl, ethyl, propyl,
butyl, or amyl, the remaining groups being‘hy
drogen, and n denotes that from up to five of such
substituents may be present on the benzene ring.
,
adherence to certain operating conditions such
‘as temperature, reaction time, concentration,
and so forth, which will be discussed in consider
able detail.
V
In addition, the use of polymerization in
Examples of such substituted styrenes are the _ -, hibitors, as well as the method employed for con
methyl styrenes, and particularly the nuclear~
ductingthe re?ningoperations, also has a very
substituted ‘methyl styrenes.
_
considerable in?uence upon the results‘obtained.
Of particular interest is the mixture. of nu
'
While the re?ning operations maybe carried
clear-substituted methyl styrenes obtained 10 .out in the absence of any added polymerization
among other ways, by the pyrolysis of petroleum '
inhibitors, I prefer to employ‘ one or more poly
at temperatures above 1300“ F. These fractions
merization inhibitors in order to reduce the loss
may have any desired boiling range, although I
of styrene-type compound in the form of poly
generally prefer to ' employ fractions boiling
mers, as well as to broaden the permissible limits
mainly in the range of 160 to 180°_ 0., and more.
of certain of the reaction variables.
.particularly in the range of 165 to 175° C. Ex; 1,5, Inhibitors which are particularly effective
cellent results are obtained by the use of frac-v
agents for retarding the rate of polymerization of
tions boiling mainly in the range of 167 to 173° C. ‘.- stynene-typ'e compounds ' when re?ned with
A preferred embodiment ‘of this invention is ‘
‘very ?nely divided metals in groups Ia and 11a
the continuous re?ning of a mixture, of styrene 20 of the periodic system, their reactive alloys. and
and methyl styrene, such as a light oil fraction
reactive derivatives, may be classi?ed in the fol
boiling mainly in the range of 125.to 180° 0.,
lowing groups. 1
I
followed by the separation of the styrene and
l. Amines and nitrogen-containing inhibitors,
methyl styrene, if desired, and/or the concen
particularly aryl amines such as:
tration of the styrene and/or methyl styrene. 25
Alpha-naphthylamine,
For convenience in the speci?cation and claims,
Thiodlaryl amines,
the term “styrene-type compound" will be used
p-Phenylene diamine,
to denote styrene, substituted styrene, and mix
o-Phenylene diamine,
.2,4-diamino diphenylamine
tures thereof.
1
The. fractions containing styrene-type com-' 30
Phenyl hydrazine,
'
I
pounds also may be initially concentrated to any
Benzamide,
V
desired extent prior to re?ning, and such con
Cyclohexyl naphth’yl amine, and
centration ,may be carried out by any desired
Polybutyl amines.
method.- This
ay include concentration by
fractionation, azeotropic distillation, solvent ex
I'articularly desirable results may be obtained
traction, a combination of solvent extraction and
by the use of secondary aryl amines having the
fractionation methods, and the formation-of '
complexes between the diole?ne and some active '
following general formula
'
compound, followed by the removal of the un
reactedportion of the fraction and the decom- ' 40
position of the complex. Other concentrating
' methods also may be amp loyed if desired.
In addition, other re?ning methods also may
in which R1 is a substituted or an unsubstituted
aryl such as phenyl or naphthyl, aralkyl such as
tolyl or methyl phenyl, cyclopara?lnic such as
be applied to styrene-type compounds and frac- '
cyclobutyl, cyclopentyl, or cyclohexyl, cyclo
‘tions thereof to remove at least a portion of one‘ 45 ole?nic such as cyclobutenyl, cyclopentyl, or cy
or more impurities present prior to re?ning by
methods to be more particularly described here
in. Thus, such fractions may be contacted with
acids or acidic solutions or materials to remove
clohexenyl, .hydroaromatic such as ,dihydro
phenyl, or tetrahydrophenyl, or naphthenic such
as methyl cyclohexyl, ring or group, and in which
materials present.
aralkyl, cyclopara?lnlc, cycloole?nic, hydroarop
R is a substituted or an unsubstituted alkyLesuch
a portionv of certain impurities or undesirable ' 50 as, ‘methyl, ethyl, propyl, butyl or amyl, aryl,
'
Such concentrating and/or partial re?ning
operations also may be applied to styrene-type
~ ‘compounds subsequent to the re?ning operations
matic, or naphthenic ring or group such as given
in the case of R1. Included ‘are secondary
amines such as for examples
'
to be more particularly described herein.
.
v I ?nd that a solution of sodium, or a suspension
or emulsion of "very ?nely divided. sodium, or a
solution,‘ suspension, or emulsion of one or more
?nely divided sodium alloys, is a particularly
desirable agent for the continuous removal of
certain undesirable impurities from styrene
type 'compounda- Excellent results are obtained
by the use ,of a suspension of very finely divided
sodium.
'
_
-
\ in which R and R1 have the same meaning as be
fore.
.
.
Secondary amines containing'one or more aryl
- The alkali metals, particularly sodium and 65 or substituted aryl groups are preferred, such as:
' potassium, are very active catalysts for the poly
1 Diphenyl-p-phenylene diamine,
merization of styrene-type compounds. Con
sequently, the use‘ of such an active catalyst,
particularly in ?nely_-divided (and hence most .
active) v~forin, for the re?ning of styrene-type
compounds would be expected to result in the
‘ converslonof the greater portion, if not all, of
such compounds present to polymers. _
- It s ould be emphasized that the success of
the re
Phenyl-beta-naphthylamine,
Isopropoxydiphenyl amine,
Aldoll-alpha-naphthyl' amine (and polymers
thereof),
_
.
,
Symmetrical di beta naphthyl-p-phenylenedh
amine,
.
Trimethyl‘ ~dihydroquinol1ne (and polymers
thereof), and
Hg operations'is dependent upon rigid 75~- Ditolylamines,
and mixtures thereof. ,
' ‘
.
acraaes
' a
metal of group Ia or group IIa, or an active
2. Phenolic compounds, such as:
alloy of such metals, in ?nely divided or solution I
p-Tertiary butyl ca'techol,
,
' Dihydroxybenzenes (and substitution prod
ucts thereof) ,
Pyrogallol
.
\
(and
,
'
of one or more polymerization inhibitors. By the
products 5 use of a continuous system, particularly in con
junction with the use of an inhibitor, the lossJof
substitution
thereof),
_ form ina continuous system and in the presence
'
styrene-type compound due to side reactions ‘or >
<
Pyrocatechol,
to ‘polymerization is very markedly reduced, or
Resorcinol,
almost completely eliminated.
Xylenols,
~
- As pointed out previously, this is of particula
Catechol, Y
Trihydroxybenzene
thereof),
Nitrosophenol,
(and
importance in the case of styrene-type compounds
which are quite susceptible to polymerization
when placed in contact with certain active metals,
as well as active alloys thereof. Thus, sodium
15 isv a very active catalyst for the polymerization of
substituents "
‘
' Diaminophenoi,
Alpha-naphthol,
, Dihydroxynaphthalene,
Hydroxy quinollne,_
‘
styrene-type compounds,~ and has been suggested
as a catalyst for the conversion of styrene to
resinous polymers in numerous references. The
use of this material in very ?nely divided form in
20 a continuous system for the re?ning of styrene
'
Hydroxy tetrahydroquinoline,
Polyhydric phenols,
Polyhydroxy'phenanthrene, and
typ'e compounds, therefore, ‘must be carried out
within well defined limits in order to prevent
4-nitroso-2-methyl phenol.
3. Compound inhibitors, such as:
Acyl-substituted amino phenols,
- undue loss of styrene-type coinpounds due to
polymerization.
or other active metals, or alloys, must be attrib
uted largely to the continuoous nature of opera
tion, resulting in‘ a minimum contact time be
tween the styrene-type compound and the re
actant.
Although the process may-be carried out in any
o-Amino phenol, and
5-amino-2-hydroxytoluene.
4. Miscellaneous inhibitors, such as:
Hydroquinone,
>
The success of the preferred
re?ning method employing ?nely divided sodium,
25
4-cyclohexyl amino phenol,
p-Amino phenol,
Quinol,
.
5 ‘
»
desired manner, I prefer to conduct it in a ver
tical vessel or tower in which a certain height
V
Nitroso naphthols,
of a liquid suspension or solution of the active
Quinhydrone,
'
Reaction product of an aldehyde and an 35 re?ning agent is maintained.‘ The material to be
re?ned then is passed upward in the vapor and/ or
‘amine,
liquid phase‘ through this column of reagent at
1
p-Amino acetophenone,
Dihydroxy anthraquinone, andv
a ratesu?icient to insure the remova1 of the de—
sired quantity and type of impurities present at
Reaction product of a ketone' with an
amine.
the temperature employed. The re?ned mate- 1
_ rial preferably is taken off at the top in. the vapor
I
phase, temperature and pressure conditions being
Excellent results maybe obtained when one or
more inhibitors selected from a list comprising
.
adjusted for this purpose.
‘
Other methods of contacting the material to be
(1) secondary aryl amines such as phenyl beta- -
naphthylamine, diphenyl-p-phenylene diamine, 45 treated and the re?ning agent also may be em}
isopropoxydiphenyl amine, aldol-alpha-naphthyl
amine (and polymers. thereof)‘, symm. di-beta-
ployed if desired. Thus, the unsaturated 'hydro- _
carbon may be passed through a horizontal treat
naphthyl-p-phenylene diamine, trimethyl dihy
in: unit, such as a pipe or bank of pipes, partially
or completely ?lled with a suspension of the de-_
droquinoline (and polymers thereof), and the di
tolylamines; (2) phenolic compounds, such as p
50 sired re?ning agent, or otherwise. .
- _
Phenols; and (3) reaction produ'cts‘of a ketone,
The suspending liquid employed for the re
?ning agent may be'of any desired‘type. Pref- '
such as acetone, 'and/ or an aldehyde,suchasform
erabLv, it does not react with the reagent or the '
.7 tertiary butyl catechol and alkylated polyhydroxy
material to be treated to any substantial extent,‘
aldehyde and acetaldehyde, with an amine, such
as aniline, are employed in the re?ning process 55 and preferably it does- not introduce ‘any addi
described.
.
.tional impurities into the material to be treated.
_
I ?nd that hydrocarbons and hydrocarbon frac- >
In general, I prefer to employ less than 10% , by
weight, of polymerization inhibitor, based on the
tions are particularly desirable materials for use.
as suspending mediums for re?ning agents of
treating system at any one time in the continuous co the type described herein. Excellent 'resultshaye
been obtained by the use of aromatic hydrocar
treating system. Good results also have been ob
bons and aromatic hydrocarbon fractions for this
tained by the use of less than 5% inhibitor, and
maximum total volume of suspending liquid in the
purpose, particularlythose having initial boiling~
. even less than 2% inhibitor, in certain cases, par~
ticularly when one or more of the inhibitors listed
in the preceding paragraph are employed.
points above 180° Q.‘ and more preferably above _ I
65 200° C.‘
.
.
' As pointed out previously, the ‘refining opera
tions are carried out in a continuous or semi
continuous system in order to reduce the propor
tion of styrene-type compound lost in the form of
polymers, as well as to secure greater economy in 70
pending medium actually employed in the opera
tion of the process usually 'comprises a mixture of /
the use of the reagent.
the material to be treated and~the suspending
'
‘
' The re?ning method disclosed herein di?ers
fundamentally from all methods described here
‘It is to be-understood, of course, that the ma
terial to be treated may dissolve to ‘some extent
in the suspending medium,/c0nsequent1y the sus
medium initially introduced into the system. _
The material being treatedalso may serve as ‘
tofore for the re?ning of styrene-type compounds
a suspending ‘medium for the re?ning agent with
in that the material in question is treated with a 75 out the addition of any other material, if desired.
r 2,413,255
Thus, a light oil styrene fraction may be intro
include extrusion through ?ne ori?ces, and the.
generation of an arcbetween sodium electrodes
duced into the desired tower or vessel, together
in an inert liquid.
‘
with the ?nely divided re?ning agent, after which
the styrene fraction is passed into the suspension
Although almost any desired concentration of 4
of the re?ning agent in the said styrene fraction 5 treating agent in the suspending medium may,
at the desired temperature, the charging rate
be employed. depending upon the type and con
and more particularly the operating pressure be
centration of the styrene-type compound, or
ing adjusted to maintain the treating agent at
the desired level in the vessel.
'
fraction thereof, to be re?ned, the temperature,
tion of the material to be treated which has been
dissolved in the suspending mediumor which has
less than 30%, and more particularly less than
20%, by weight of the treating agent. Excellent
been employed as the suspending medium in‘ the -
results are obtained when less than 15% by
weight of the treating agent is suspended in the
the depth of reagent employed, and the like, 'I
It is to be understood. of course, that the por 10 generally prefer to employ a reagent containing
substantial absence of other liquid materials,
does not necessarily remain in the treating zone
throughout the entire treating cycle. Rather,
suspending medium.
this material is in a state of dynamic equilibrium
It is to be understood, of course, that the term
vsuspending medium refers to the actual sus
vwith the material being treated, a portion of .it
pending agent employed during the treating op
volatilizing continuously and being removed from
the system, the material volatilized in this man
ner being replaced by the solution of a corre
eration, and . includes any of ,material being‘
20 treated which may dissolve in such agent.
The concentration of the styrene-type‘ com
sponding quantity of freshly added material to
be treated. The major portion of the material
- pound to~~be treated also has a considerable in
?uence upon the method of operating the proc
ess. Thus, with a highly concentrated styrene
type compound, such as 98% styrene, the reagent
should preferably contain a fairly low concentra
tion of active agent to minimize losses due to
to be treated, of course, passes upward through
the suspending medium without dissolving
therein.
I
~
The thickness of the layer of reagent through
which the material to be treated is preferably
polymerization.
‘
. I generally preferato'employ a fraction of such '
passed depends upon a number of factors, such
concentration, and with such proportion of sus
as the quantity and type of impurities present,
pending r'nediumythat the actual concentration
the extent to which such'impurities 'are to be
removed, the type and degree of dispersion of ‘ of styrene-type compound in the reaction zone
is less than 80%, and more preferably, less than
the treating agent employed, the reaction tem
- 70%] Excellent results are obtained when the
perature, the concentration of the treating agent
in the suspending medium, and the like. In gen 35 actual concentration of styrene-type compound
in the reaction zone is lessthan 65%.
eral, however, I prefer to employ a layer of re
The concentration of styrene-type compound
agent at ‘least one foot thick and, more prefer
also may be reduced by the addition thereto of
ably, at least two feet thick. Excellent results
a suitable solvent, such as a hydrocarbon ‘or hy
.40 drocarbon fraction, prior to introduction into the -
are obtained by the use of a layer of reagent at a
least four feet thick.
,
It will be recognized that, .other things being
equal, the depth of reagent employed in the
treating vessel controls the contact time be
tween the material to be re?ned and the re?ning
reagent.
.
re?ning
The degree of dispersion of the treating agent
,also has a very profound effect upon the degree
of re?ning obtained. In the case of sodium, I
prefer to employ a subdivided mass in which at
7
_
L
pressure, such as atmospheric, subatmospheric,
and superatmospheric pressures.
45
_
system.
The processamay be carried out at any desired
,
‘
'
In. many cases, particularly when a styrene
type compound in a'fairly highly concentrated
form is refined with a suspension or solution of
a finely divided active metal, or alloy, of the type '
_ described herein in a higher-boiling solvent, it
least the majority of the particles present have 50 'isihighly advantageous to conduct such opera
tions at subatmospheric pressures, thereby reduc
a diameter of not more than 0.05" and, more
ing the concentration of styrene-type compound ‘
present in the re?ning system at a given reac
tion temperature. This serves to reduce the
- 55 quantity of styrene-type compound converted to
than 0.02".
.
I
polymers in the process, consequently it is a pre~
This subdivision may be carried out in any de
ferred embodiment of this invention.
_ sired manner. Thus, in the case of sodium, a ' The temperature at which the process is con
solution of this material in; liquid amomnia may
ducted also has a very considerable bearing upon
be introduced into an inert liquid, such as xylene,
at room temperature or at elevated temperatures. 60 vthe degree to which the styrene-type compound
preferably, not more than 0.03".
Excellent re
sults are obtained when at least the majority of
the particles present have a diameter of not more
The almost instantaneous volatilization of the
ammonia present results in the dispersion of the
sodium present in the xylene in an extremely
finely divided state. Another‘method comprises
is refined and the lossesincured due to polymer
ization. Although the optimum reaction tern-r
perature vto - be employed is dependent largely
upon other factors, such as theconcentration of
_ spraying molten sodium into an inert liquid such 65 both'thé styrene-type. compound and the re?n
as'xylene or solvent naphtha. By suitable vari- . _ing agent in the reaction zone, I generally prefer
. ations in the type and degree of ?neness and/or
to conduct the re?ning operations at tempera
dispersing ability of the spray nozzle employed,
sodium of almost any desired degree of ?neness
may be obtained at will.
‘ ,
Another satisfactory’method comprises melt
‘ - ing the sodium under the surface of a suitable
liquid, such as xylene, followed by violent agita
tion, such as with a turbo-mixer, and cooling with
tures below 100°C. and more particularlykbelow
- 85° C. Excellent results are obtained by conduct
70 ing the re?ning operations at temperatures below‘
'75? C.
'
' The rate at which the material to be re?ned
is passed through the reagent has a very consid-'
erable effect upon the degree to which the im
agitation. Other methods which may be used 75puritiesl present are removed, although this is
2,418,255
.9.
i0
.
‘dependent to some extent upon other variables
such as the concentration of re?ning agent in‘
' the suspending medium and .the'temperature at
Y which the re?ning operations are being con
you?’
- in the gaseous ‘state upward-through the column '
was found to maintain the'system in the desired _' degree of agitation. ‘
- The re?ning agent.
particularly‘ when ?nely
ducted. While it is di?icult to establish exact 5 divided sodium is employed for this purpose.
limits for optimum throughputs under all condi- >
usually actsboth as a reactant and as a poly
tions, 1 generally prefer not to exceed a through-
merizing'l agent for the" removal of undesired im
put of material to bevtreated on an ‘hourly basis
purities. Thus, in the ‘case of light ‘oil styrene
of more than four times the weight of suspend- 1 fractions containing acetylenes, aldehydes, and
lag medium employed and more preferably not 10 other impurities, the sodium usually will react .
more than twice the weight of the, suspending
with at least a portion of the acetylenes present
medium. Excellent results are obtained when
to form the corresponding sodium'acetyildes, and
not more than equal quantities of material to be
.may react with certain of the oxygenated deriva
Vtreated. upon an hourly-basis. are passed through
tlves to form corresponding metallic derivatives. _
the suspending medium.
_
15 At least a portion of the acetylenic hydrocarbons
' _ It will be recognized that the contact time 116present also are polymerized to form polymers,
' tween the material to be treated and the reagent 1 I or copolynrers with other unsaturated hydro
is determined both by the thickness of the layer
carbons present, which frequently are insoluble
of reagent employed and by the rate at which
in nature. Certain of the omgenated derivatives,
the material to be treated is passed through the 20 such as aldehydes, also may be polymerized to
reagent.
'
,
form polymers which may be insoluble in type.’ '
The method employed for introducingthe material to be re?ned into the re?ning agent also
has some in?uence upon the extent to which the
styrene-type compound is re?ned.
_ As a result, the re?ning or styrene-type com
- pounds witha suspension of ?nely divided sodium
is characterized by the gradual accumulation
In general, 25 of insoluble polymers in the re?ning medium.
.it may be said that a ?ne stream or jet of the
liquid or gaseous material to be re?ned is do-
This may be removed in any desired manner,
such as by ?ltration, which may be carried out ‘
continuously during the. re?ning - operation, or
siredv This may be accomplished by introducing
the material to be treated into. the reagent by
may be carried out in a batchwise manner after
means of suitable ori?ces, jets, nozzles, or other 30' the termination of the re?ning step,
_
,
subdividing means. Porous objects or materials
As the removal of the insoluble polymers also
also may be employed for this Purpose, Such as
is attended by some loss of re?ning agent, even
'
porous ceramic or glass diffusing blooksor units
when the latter is in a/ very ?ne‘ state of sub;
,
As the re?ning agent may show some tendency
division, it isadvisable in many cases to continue
to settle out in the bottom of the treating vessel 35 the re?nmg operations 'until the re?ning agent
or unit, the jets or nozzles by means of which
has been largely or completely exhausted before
the material to 'be treated is introduced into the »
unit may be so arranged as to prevent any undue ,
?ltering.
’
'
.
'
.
-
The solidor semi-solid ?ltered products may
settling of this material, In vertical vessels, this
be treated to recover any desired materials or ,
may 'be accomplished bylocating these units in 40 they may be disposed of in any suitable manner.
such away as to impinge the inlet stream or
Thus, any unchanged re?ning agent,‘ such ‘as
streams upon the bottom of the treating vessel.
sodium, may be recovered by melting and coalesc
The inlet jets also may be, aranged tangentially
ing operations, or by amalgamation with mercury,
to impart a swirling or circular motion to the
treating reagent, if desired.
or otherwise. - Certain of vthe reaction products,
Another method _ 45 such as sodium acetylide‘s, may be decomposed '
comprises locating the inlet jet or jets directly
with water to regenerate the corresponding
in the bottom of the reactor, or tangentially in
the sides of the reactor, or both, to prevent any
acetylenes or they ‘may be reacted with carbon '
' dioxide to form unsaturated acids, or otherwise.
‘ settling in the .bottom of the reacting vessel
A convenient method for the disposal of the
‘and/or to impart any desired circular or other 50 insoluble polymers ' comprises treatment with .‘
' motion to the treating medium.
carbon dioxide, suitably in the presence of traces
Any desired combination of these methods also
of moisture, iollowed by ?ltration.
may be employed, such as the use of a jet or jets
As the cost of the treating process is largely
.- directly impinging upon the bottom of the reactor
a function of the quantity ‘or the reactive agent
in conjunction with the use of a tangential jet or 55 employed in the re?ning operations, the e?icient
jets to prevent‘ the active agent from settling out‘
utilization of such agent is-of considerable im
_ and depositing on the walls of the 'eactor and/or
to maintain the reaction medium 11 any desired
portance. _A desirable method for insuring
optimum utilization oi.’ the treating agent is to
state of‘ agitation.
,
i
I
carry out the operations in a continuous counter
The reaction medium also-may be maintained 60 current manner, the reagent moving through the‘
in the desired degree of agitation by the use of
system in a manner countercurrent to that of
7 suitable stirring or mixing devices, or by the use
the material tobe treated.
.
'
'
‘
'
of circulating pumps, or by a .combination of
This may be illustratedby means of a consider
these methods, or otherwise. One or more of
ation of a simple continuousicountercurrent sys
these methods also may be used in conjunction 65
_ tom comprising two treating towers or vessels. ,
" v.with one or more of-the methods discussed pre- -
viously to maintain the system in‘ the desired
degree of dispersion.‘
_
,
v
_>
The material to be treated is passed into the ?rst
tower, ‘which contains a partially exhausted re
-
agent. This serves to remove a substantial por
tion of the impurities present, after which the
of suchngitationomethods is notlrequired in most ' 70 partially re?ned material passes into the second
.It should be pointed out, however,'that-the use
cases.v Thus, excellent results have been secured
by conducting the re?ning operations in a tower.
thematerial to be treated being introduced into
tower, whichcontains a iresh,~or more highly
concentrated; reagent. This serves to remove the
impurities present to the desired extent. ,The
the bottom of the tower by means of a small
process is continued until the reagent in the ?rst
I ‘ori?ce! The passage of the fraction being treated 75_'tower is ‘almost, ‘or completely exhausted, after
‘ 9,418,205
11
»
12
'
'
passed‘ continuously into the bottomofa 2" steel
column containing very ?nely divided- sodium
which it is discarded and the partially exhausted -
reagent from the second column substituted for it.
Fresh reagent then is added to the second column.
suspended in a mixture of amyl-substituted
naphthalenes at a temperature of 60° C. The
In this manner the material to be treatedand
the treating agent pass through the system
operation was carried out under reduced pressure,
countercurrent to each other, the ?rst continu-__
which was adjusted ‘to maintain the treatins
mixture at the desired level. The re?ned styrene
fraction obtained as a result of such operations
ously and the second in a discontinuous manner.
This may be modi?ed such as by the continuous
addition of fresh reagent to the second tower, the
. was water-white and was substantially free of
to the ?rst tower, and the continuous withdrawal
phenylacetylene, aldehydes, and other impurities.
The impurities'present, particularly the acet
of more completely exhausted, vor exhausted'
ylenes and the aldehydes, were converted both to
continuous transfer of partially exhausted reagent
reagent from the ?rst tower. A completely con
tinuous countercurrent treating system thus is
achieved.
sodium derivatives and to insoluble polymers.
In the speci?cation and in the claims, the fol
15' lowing terms have the indicated meanings.
‘
Any desired modi?cation of these methods may
be employed, and any number of treating. towers
The term "metals of group Ia and group 11::
of the periodic system” is intended to mean lith
or‘ units may be used. It will be observed that
in each of the cases discussed, the incoming ma
terial to be re?ned is contacted with ‘partially.
ium, sodium, potassium, rubidium, caesium, bar
2.0
exhausted reagent (maximum concentration of
impuritiesq-min‘imum concentration of reagent),
ium, strontium, and calcium, as well'as active '
alloys containing one or more of ‘such metals as
an essential ingredient.
_
.
The term “?nely divided" is intended to' mean
while the outgoing material to be re?ned ‘is con
a material reduced ‘to such a state of ?neness
that the 'preponderating part is composed of par
tacted with fresh or more highly concentrated
- reagent (minimum concentration of impurities--, 25 ticles having a diameter of less than 0.05". as
well as‘materials in the colloidal or dissolved
maximum concentration'of reagent). Thus the
two objectives to be sought, namely, practically
While reagents and procedures of a particular
complete, or complete, utilization of the ‘reagent
and substantial, or practically complete, removal - nature have been speci?cally described, it_ is to
of impurities from the material to be re?ned, are 30 be understood that ‘these are given by way of
illustration. JTherefore, changes, omissions. ad
As the limiting factor a?ecting the utilization
ditions, substitutions, and/or modi?cations may
of the reagent is theproportion of insoluble poly
be made within the scope of the claims without
form.
achieved.
'
-
.
-
~
,
Y
’
‘departing from the spirit of the'invention, which
mers and/or residues which can be contained
therein without seriously impairing its ?owing ' is intended‘ to be limited only \as. required by the
properties, or the passage of the gaseous mate
prior art.
rial to be treated 'therethrough, it frequently
happens that the quantity of insoluble material
present is-insuf?cient to interfere seriously with
I
claim:
.
‘
_
l. A process for re?ning a hydrocarbon selected
from the grouplconsisting of styrene and methyl
the operation of the process when the re?ning 40 styrene and contained in a hydrocarbon mixture
which alsoicontains impurity including acetylenic
agent present has been almost completely ex
hausted. In this case, the operation of the unit
material, comprising passing said mixture at a
temperature below 100° 0. through a dispersion
may be continued by the addition thereto of an
additional quantity of the re?ning agent, and
of a ?nely. divided metal selected from’the group
this process may be continued until the concen ‘5 consisting'of metals'orgroupla and group 11a
of the periodic system, said dispersion‘ being at
tration of insoluble material inv the reagent ren
dersit too viscous to be used further in the proc
es in a satisfactory manner.
‘
least .one foot. in thickness in the direction of
.?ow of said mixture andcontaining less than
"
30% by weight of said ?nely divided metal, main
In this connection, itis well to point out that
' the insoluble products-formed during the reaction 5° taining the concentration of said selected hydrohave a tendency to stabilize the sodium suspen
carbon in_the reaction zone less than 80% by
weight of the total material present, while main
sion and act to reduce the rate. of settling of the
taining the rate of ?ow per hour of said mixture
' ?nely divided sodium in certain cases. As this is _
desirable; the incomplete removal of insoluble '
through said dispersion less than four'times the '
products from the reagent may be indicated, or 55 weight of, dispersion 'medium’employed, and re
moving said mixture‘less contaminated with-im
even the addition of a certain quantity of, such
lpurityincluding acetylenic material from said
materials to a fresh reagent. _
‘
,
reaction zone sumciently' rapidly to prevent a
Soluble polymers also usually are f‘rmed in
small amounts .during ‘the. re?ning operations, - .largekloss of said selected hydrocarbon due to the .
As certain of these soluble and/or~ liquid polymers 60polymerization thereof. . '
may be converted on prolonged contact with the ‘
re?ning agent to viscous and/or insoluble prod
ucts, their removal from the suspending medium‘,
suitably at the end of a re?ning cycle and prior
to the return of the suspending‘agent to the sys
tem, may be indicated. On the other hand, cer
tain of these soluble polymers are su?lciently
stable to act as a suspending medium for the
re?ning agent.
-
.
-
.
I _‘
low 75° C. througha dispersion of a ?nely divided _
alkali metal, said- dispersion containing‘ less than
20% by weight thereof of said ?nely divided metal
and being at least two feet in thickness in the di
rection of?ow' of said fraction, maintaining the
70 concentration of said styrene in the reaction zone
The process may be more completely‘ illustrate
by means of the following example. _
2. IA‘PX'OOGSS for re?ning styrene contained in
admixture with- impurity including acetylenic ma
terial in a light oil styrene fraction‘, which com
prises passing said fraction at a temperature be
_
(Example
A 60% light oil styrene fraction containing’
less ‘than 65% by weight of the total material pres
ent, while maintaining a rate of now perhour of
. said fraction through said dispersion of less than
four times the weight of dispersion medium em
0.2% phenyiacetylene and,0.02% aldehydes, ‘was 76 ployed, and removing 'saidstyrene fraction less
/
- 2,418,255
.
l3
14
.
'
.
‘
contaminated with impurity including acetylenic
one foot inthlckness in the direction of flow of
material from said reaction zone su?lciently rap
idly to prevent a large loss of said styrene due to
said mixture, maintaining the concentration of
polymerization thereof.
65% by weight of the total material present,
said methyl styrene in the reaction zone less than
while maintaining the rate ,of ?ow per hour of said
3. A process for re?ning methyl styrene con
mixture through said dispersion at less than four
times the weight of dispersion medium employed,
ylenic material in a light oil methyl styrene frac
and removing said methyl styrene in vapor phase
tion, which comprises passing said fraction at a
‘less contaminated with impurity including acet
temperature below 75° C. through a dispersion of
a ?nely divided alkali metal, said dispersion con 10 ylenic material from said reaction zone su?lciently
rapidly to prevent a large loss of said methyl
taining less than 20% by weight thereof of said
styrene due to polymerization thereof.
‘
?nely divided metal and being at least two feet
tained in admixture with impurity including acet-,
6. A process for the puri?cation of styrene con
in thickness in the direction of ?ow of said frac
tained in admixture with impurity including acet
tion, maintaining the concentration of said methyl
styrene in the reaction" zone less than 65% by 15 ylenic material, which comprises passing said ad
mixture at a temperature below 85° 0. through a
weight of the total material present, while main
dispersion of ?nely divided sodium, said dispersion
taining a rate of flow per hour of said fraction
being at least one foot in thickness in thedirec
through said dispersion of less than four times
tion of ?ow of said admixture and containing less
the weight of’ dispersion medium employed, and
removing said methyl styrene fraction less con 20 than_30% by weight thereof of said ?nely divided
sodium, maintaining the concentration of said
taminated with impurity including acetylenic ma
styrene in the reaction zone less than 65% by
terialv from said reaction zone sumciently rapidly
weight of the total material present, while main; ~
to prevent a large loss of said methyl styrene due
to polymerization thereof.
‘
,
.
4. A process for re?ning styrene contained in a
hydrocarbon mixture contaminated with impurity
including acetylenic‘ material, which comprises
taining the rate of flow per hour of said admix- '
ture through said dispersion at less than four
times the weight of dispersion medium employed,
- and removing styrene less contaminated with im
purity including acetylenic material from said re
action zone ,su?iciently rapidly to prevent a large
loss
of said styrene due to polymerization thereof.
divided alkali metal, said dispersion conta
30'
7. A process for the puri?cation of methyl
less than 30% by weight thereof of said ?nely di
styrene contained in admixture with impurity in
vided metal and being at least one vfoot in thick
cluding acetylenic material, which comprises
ness in the direction of flow of said mixture, main
passing said admixture at a temperature below
taining the concentration of said styrene in the
reaction zone less than 65% by weight of the total 35 85° C. through a dispersion of ?nely divided so
dium, said dispersion being at least one foot in
material present, while maintaining the rate of
thickness in the direction of ?ow of said admix
?ow per hour of said mixture through said dis
ture and containing less. than 30% by weight
persion'at' less than four times the weight of dis
thereof of said ?nely divided sodium, maintaining
persion medium employed, and removing said
styrene in vapor phase less contaminated with im 40 the concentration of said methyl styrene in the
reaction zone less than 65% by weight of the total
purity including acetylenic material from said re-~
material present, while maintaining the rate of
action zone sumciently rapidly to prevent a large
?owper hour of said admixture through said dis
loss of said styrene due to polymerization thereof. ‘
persion at less than four times the weight of dis
5. A process for re?ning methyl styrene con
tained in a hydrocarbon mixture contated 45 persion medium employed, and removing methyl
styrene less contaminated with impurity includ»
with impurity including acetylenic material,
ing acetylenic material from said reaction zone
which comprises passing said mixture under tem
suf?ciently rapidly to prevent a large loss of said
perature conditions below 100° C. through a, dis
methyl styrene due to polymerization thereof.
persion of a ?nely divided alkali metal, said dis
passing said mixture under temperature condi
tions below 100° (2.‘. through a dispersion of a ?nely
persion containing less than 30% by weight vthere
' of of said
ly divided metal
being at least
"1 J. sonar. .
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