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vPatented
1946
-‘ . 2,413,254
umrso fsrarss PATENT 'QFFHCQE
A
.
2,413,254
'
I
'
.
HYDROGARBON MATERIAL WITH AN AL
KALI 0R
EARTH METAL
Frank J. Soday, Swarthmore, Pa, assignor to
The United Gas Improvement Company, a cor
poration of Pennsylvania
No Drawing. Application
'
24, 1942, ‘
Serial No. 470,078
'
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was... (crate-.611) _.
v
1
2
v
This invention relates to the puri?cation of
unsaturated hydrocarbons.
More particularly, this invention is concerned
.
. may be re?ned by the application in ?nely di
vided form‘of at least one metal or group Ia and
group no of the periodic table, as well as certain
active alloys thereof. Particularly desirable re
with the removal of certain impurities from un
saturated hydrocarbons, or mixtures thereof.
An object of. the present invention is the re
sults are obtained by the use of ?nely divided al
kali and alkaline earth metals.
moval of certain impurities from unsaturated hy-~
drocarbons by ‘the application of at least one
Examples’ of such metals are lithium, sodium,‘
potassium, rubidium, caesium, barium, strontium
, v?nely divided metal of groups In and 11a of the
and calcium- Due to the availability and low cost -'
of sodium and potassium, however, these metals
periodic system, or active alloys thereof. Another
object of the invention is the re?ning of oleilnes,
or fractions or mixtures containing at least one
ole?ne, under conditions designed to. reduce the
losses incurred in such operations. Other objects
and advantages of the invention will be apparent
to those skilled in the art upon an inspection 0
the speci?cation and claims.
.
are preferred for the use set forth herein.
Alloys of these metals, such as,NaPb1o,‘NaI-lg4,
NaCas, NaZmz, Ella, and th‘eiike, also maybe
employed-for the removal of undesired impurities
fromunsaturated hydrocarbons. Ingeneral, the
alloys of the respective metals react with the im
purities present in such materials at a slower rate
'
Unsaturated hydrocarbons and unsaturated
hydrocarbon fractions,- particularly those ob
4 than the corresponding metals.
Mind that a solution of sodium, or a suspension
or emulsion of very finely divided sodium, or a
solution, suspension, or emulsion of one or more
tained by the pyrolysis of petroleum or of petrol
eum hydrocarbons, frequently contain substan
tial proportions of impurities which interfere with
their use in most, if not all, industrial applica
t ons.
sodium alloys or active compounds, is a particu
larly desirable agent for the removal of certain
undesirable impurities iromunsaturated hydro
.
Thus, unsaturated hydrocarbons obtained by
carbons. Excellent'results are obtained by the
.use of a" suspension of very finely divided sodium.
the pyrolysis of petroleum may contain impurities
The alkali metals, particularly sodium and po
tassium. are very active catalysts for the poly
_ such as acetylenes, aldehydes, peroxides, phenolic -
compounds, other oxygen-containing compounds,
sulfur-containing compounds, such as disul?des
merization of ' unsaturatedhydrocarbons, Thus,
and mercaptans, nitrogen-containing com 30 practically all of the early work on the prepara
tion of synthetic rubber from isoprene, both‘in
pounds, and thellike. These compounds may be
present in proportions ranging from traces to
this country and abroad, was based on the use‘ of
several percent depending, among other things,
sodium and/or potassium as the catalyst. Con-Y
sequently, the use of such an active catalyst, par
upon the boiling range of the particular fraction
or mixture in question, the characteristics of the 35 ticularly in ?nely divided (and hence most active)
form, for the re?ning of unsaturated hydrocar
petroleum or petroleum fraction from which it
was obtained, and the cracking ‘temperature, as
bons would be expected to result in the‘conversi‘on
of the greater portion, if not all, of the unsatur
well as other pyrolysis conditions, employed. .
The removal of one or more impurities from .
ated hydrocarbon to polymers.
.
v.
-
_
unsaturated hydrocarbons or unsaturated hydro 40 It should be emphasized that the success of the
re?ning operations is dependent upon rigid ad
carbon vfractions is complicated generally by the
ease with which such materials may be polymer
Y herence to certain operating conditions such as
ized. The application of the re?n'ing techniques‘
customarilyemployed for the removal of impuri
temperature, reaction time, concentration, and so
forth, which (will be discussed in considerable‘
ties from hydrocarbons or hydrocarbon fractions 45
detail.
,
'
Unsaturated hydrocarbons which may be re
which are preponderantly saturated and/or aro'-_
?ned by methods to be more particularly de-_
matic in character, such as gasoline, kerosene,
scribed herein ‘include hydrocarbons containing
light petroleum distillates, coal tar fractions, and
' at least one double bond such as ole?nes, for ex
the like, to unsaturated hydrocarbons or unsatur
ated hydrocarbon ‘fractions frequently leads to 50 ample, aliphatic, cyclic, and aromatic ole?nes;
dioleilnes such as aliphatic, ‘cyclic and aromatic
the conversion of a substantial proportion, or all.
diole?nes; and mixtures containing one or more
of such materials to inferior types of polymers.
of the foregoing, classes of'hydrocarbons.
As a result of extensive experimentation, I have
The process is particularly applicable to the re
discovered that unsaturated hydrocarbons and
unsaturated hydrocarbon fractions and mixtures % ?ning of ole?nes, such as aliphatic-de?nes.
a
.
‘
I
- amazes
. .
3
be re?ned then is passed‘ upward
A desirable source of ole?nes. to be re?ned by
methods to be more particularly described herein
._._
column of liquid at a rate suilicient to insure the
is the by-product obtained upon the concentra- ~ a removal of the desired quantity and type of- im
purities present at the temperature employed.
tion of diole?nes, such as butadiene. Thus. they
Other methods of contacting _-the material to
ole?ne fraction obtained upon the concentration '
'be treated and the re?ning agent also may be
of a butadiene fraction usually contains substan
employed if desired. Thus, the unsaturated-hy
tial, and generally contains predominating. Pro
- drocarbonv may be passed through a horizontal
7 portions of‘ isob'utylene. Such fractions may be
‘ re?ned readily by the process disclosed herein.
treating unit, such as a pipe or bank of pipes,
A preferred embodiment of this-invention is 10. containing a suspension of the desired're?nins
agent, or otherwise.
The suspending liquid employed for the re- '
the re?ning of isobutylene or of unsaturated hy
drocarbon fractions in which isobutylene is the.
?ning agent may be of any desired type, pro
vided that it does not reactwith the reagent or
prepondering unsaturated hydrocarbon present.
Buchfractions also may contain minor.proportions of one or more diole?nes.
' the material to be treated to any substantial
.
extent, and provided that it does not introduce
any additional
impurities into the material to
_
be treated.
I ?nd . that hydrocarbons
and hy
,
drocarbon fractions‘ are particularly
desirable.
While the re?ning operations may be rrigged‘
‘
f
added
' out m the absence 0 em
any 10
inhibitors’ I prefer to
p y
e
polym
_
on .
1
one or more
p0ly- of the unsaturated hydrocarbons in the form of
‘polymers, as well as to increase the limits of the _>
merization inhibitors in order to reduce the loss
permissible reaction variables.
materials for use as suspending mediums for
refining agents of the type described herein.
Excellent results have been obtained by the use
.
of aromatic hydrocarbons and aromatic hydro
Excellent results may be obtained when one or
carbon fractions for ‘this purpose.
'
more inhibitors selected from a list comprising
(1). secondary aryl amines such as phenyl beta 25 It is to be understood, of course, that the ma-‘
terial to be treated may dissolve to some extent
naphthylamine, diphenyl-p-phenylene dlamine,
isopropoxydiphenyl
amine,
aldol-alpha-naph- ' . in the suspending medium, consequently the
' suspending medium actually employed in the op
thylamine (and polymers thereof), symm. di
beta-naphthylhp-phenylene diamine, trimethyl
dihydroquinoline (and polymers thereof),'and
eration of the process usually comprises a mix
30 ture of the material to be treated and the sus
pending medium initially introducedv into the
the ditolylamines;' (2) phenolic compounds, such
as p-tertiary but? catechol and alkylated poly
system.
ketone, such" as
I cetone‘,‘
n
_
,
.
‘
-
The unsaturated hydrocarbon being treated
- droxy phenols; a d (3) reaction products of a
also may serve as a suspending medium for the .
and/or an aldehyde,‘
such as formaldehyde vand acetaldehyde. with an 35 re?ning agent without the addition of any other
' amine, such as aniline, are used in the re?ning ‘ material, if desired. Thus, the unsaturated hy
drocarbon or unsaturated hydrocarbon fraction
operations disclosed ‘herein.
In general, I prefer to employ less than 10% .. may (be introduced into the desired tower or
vessel, together with the ?nely divided. re?ning
by weight, of polymerization inhibitor, based on
agent, after which the material to be treated‘is
the unsaturated hydrocarbon ‘or unsaturated hy-v
passed ‘into the suspension of the re?ning agent
drocarbon fraction in batch treating ‘processes,
and the maximum total volume of suspending I in the unsaturated hydrocarbon at the desired
temperature, the. charging rate and more par-.
liquid in the treating system at any one time in
ticularly the operating pressure being adjusted to
the casezof continuous treating processes. Good
results also have been obtained by the use of less 45 ‘maintain the treating agent at the desired level
in the vessel.
_
than 5% inhibitor and even 2% inhibitor in cer-q
tain cases, particularly when one or more of the
It is to be understood, of course, that the por-‘
inhibitors listed in the preceding paragraph are
tion of the‘ material to be treated which has
‘been dissolved in the suspending medium or which
employed.
-
While the re?ning operations ‘may be carried 50 has been employed as the suspending medium in
out in a satisfactory manner in a batchwise .
the substantial absence of other liquid materials,
manner, I prefer to conduct such operations in a
does not necessarily remain in the treating zone
continuous or semi-continuous system in order
throughout the entire treating cycle. Rather,
to reduce the proportion of unsaturated hydro
this material is in a state of‘ dynamic equilibrium
carbon lost in the form of polymers, as well as to
with the‘material being treated, a portion of it
secure greater economy in the use of the reagent.
volatilizing continuously and being removed from
'The preferred re?ning method disclosed herein
the system, the material volatilized in this man
‘ differs fundamentally from all methods described
ner being replaced by the solution ‘of a corre
spondingquantity of freshly added material to
drocarbons in that the material in question is 60 be treated. The major portion of the material treated with a metal of group IA or group'IIA,
to be treated, of course, bubbles up through the
_or an active alloy of such metals, in ?nely di
suspending medium without dissolving therein.
vided or solution form in a continuous system
' The thickness of the layer of reagent through
preferably in the presence of one or more poly
which the material to be treated is preferably
merization inhibitors. By the use of a continu 65
passed depends upon a number of factors, such
ous system, particularly in conjunction with the
heretofore for'the re?ning of unsaturated hy
. as thequantity and type of impurities present, .
‘
use of an‘ inhibitor, the loss of unsaturated by
drocarbons due toside reactions or to polymeri- ,
zation is very markedly reduced, or almost com
pletely'eliminated.
70
Although the process may be carried outin
any-desiredmannerHI prefer. to conduct it in a
vertical vessel or tower in which a certain height
of a liquid suspension or solution of the active
re?ning agent is maintained. The material to 75
the extent to which such impurities are to be re- I
moved, the type and degree of dispersion of the
treating agent employed,‘ the reaction tempera
ture, the concentration of the treating agent in
the suspending medium. and the like. In gen
eral,'however, I prefer to employ a layer of re
agent at least one foot thick and, more prefer
ably, at least two feet thick. ‘ Excellent. results , ‘
2,413,954
are obtained by the use of a layer of reagent at
,at subatmo'spheric pressures, thereby reducing
least four feet thick.
the concentration of the unsaturated hydrocars
_
It will be recognized that, other things being
equal, the depthoi‘ reagent employed in the treat
ing vessel controls the contact time between the
material to be re?ned and the re?ning reagent.
The degree of dispersion of the treating agent
bon ‘present in the re?ning system at a given
reaction temperature. This serves to reduce the
quantity of unsaturated hydrocarbonlconverted
to polymers in the process, consequently, it is a
preferred embodiment of this invention.
The temperature at which the process is con
also has a very profound effect upon the degree
ducted also has a very considerable bearing up
of re?ning obtained. In thecase'of sodium, I
prefer to employ a subdivided mass in which at 10 on the degree to which the unsaturated hydro
least the maJority of the particles present .have
carbon is re?ned and the, losses incurred due to
polymerization. Although the optimum reaction
a diameter of not more than 0.05’; and, more
temperature to be employed is dependent large-l
preferably, not more than 0.03"; Excellent re
1y upon other factors, such as the concentration
sults are obtained when at least the majority of the particles present‘ have a diameter of not more 15 of both the unsaturated hydrocarbon and the re
?ning agent in the reaction zone, I generally pre
than 0.02". '_
fer to conduct the re?ning operations at temper
This subdivision may be carried out in any
atures below 100° C. and. more particularly, be
desired manner. Thus. in the case of sodium, a
low 80° C. ,Excellent results are obtained by consolution of this material in liquid ammonia may
be introduced into an inert liquid, such as xylene, 20 ducting the re?ning operations at temperatures
below 70° C.
-'
at room temperature or at elevated temperatures.
The rate at which the material to be re?ned is ~
The almost instantaneous volatilization of the
passed through the reagent has a very consider
ammonia present results in the dispersion of the
able e?ect upon the degree to which the impuri
sodium present in the xylene in an extremely
?nely divided state. Another method comprises 25 ties present are removed, although this is de
pendent to some extent upon other variables
spraying molten sodium into an inert liquid such
such as the concentration of re?ning agent in the
as xylene or solvent naphtha. By suitable varis
suspending medium and the temperature, at
ations in the type and degree of ?neness or in the
.
dispersing ability of the spray nomle employed, .
. which the re?ning operations are being conduct
or both, sodium of almost any desired degree of 30 ed. While it is dif?cult to establish exa'ct'limits
for optimum throughputs under all conditions,
?neness may be obtained at will.
' Anothersatisfactory method comprises melting
~ I generally prefer not to exceed a throughput of
the sodium under the surface of a suitable liquid,
such as xylene, followed by violent agitation, such
material to be treated on an hourly basis of
more than four times the weight of'suspendirm
inert liquid
treated, upon'an hourly basis, are passed through
as with a turbo-mixer, and cooling with agita 35 medium ‘employed and more preferably, not
more than twice the weight of the suspending
tion. Other methods which may be used include
medium. Excellent results are obtained when
extrusion through ?ne ori?ces, and the genera
not more than equal quantities of material to be
tion of ‘an are between sodium electrodes in an
'
_
_
.
Although almost any desired concentration of 40 the suspending medium.
It will be recognized that the contact time be
treating agent in the suspending medium may be
tween the material to be treated and the reagent
employed, depending upon the type and concen
is determined both by the thickness of'the layer
tration of the unsaturated“ hydrocarbon in the .
of reagent employed and by the rate at which the
diluted fraction to be re?ned, the temperature,
the depth of reagent employed, and the like, I 45 material to be treated is passed through the re-,
generally prefer to employ a reagent containing
agent.
-
_
-
20% by weight of the treating agent. Excellent
The method employed 'for introducing the ma
terial to be re?ned into the re?ning agent also
results are obtained when less than 15 % by weight '
has some in?uence upon the extent to which the
less than 30% and more particularly less than
of the treating agent is‘ suspended in the sus 50 unsaturated hydrocarbon or unsaturated hydro
carbon -fraction is re?ned. In general, it may be
(pending medium. '
’
said that a ?ne stream or jet of the liquid or gas
It is to be understood, ofvc'ourse, that the term
eous material to be re?ned is desired. This may
suspending medium refers to the actual-suspend;
be accomplished by introducing the material to
ing agent employed during the treating opera
tion, and includes any of the material being 55 be treated into the reagent by ‘means of suitable
ori?ces, jets, nozzles, or other subdividing means.
treated which may dissolve in such agent.
Porous objects or materials also may be employed
The concentration vof the unsaturated hydro
for this purpose, such as porous ceramic or glass
carbon to be treated also has a considerable in
diffusing blocks or units‘.,
'
?uence upon the method of operating the process.
I generally prefer to employ such proportion of do As the re?ning agent may show some tendency _
to settle out in the bottom of the treating vessel
suspending medium that the actual concentra
or_unit, the jets or nozzles by means of which the
tion of the unsaturated hydrocarbon in the re
material to be treated is introduced into the unit
action zone is less than 80% and, more prefer
' may be so arranged as to prevent any undue setably, less than 70%. Excellent results are ob‘
- tained when the actual concentration of unsat 65 tling of this material. In vertical vessels, this
may be accomplished by locating these units in
urated hydrocarbon in the reaction zone ‘is less
than 60%.
»
»
'
'
. such a way as to impinge the inlet stream or
streams upon the bottom of the treating vessel.
The inlet Jets also may be arranged tangentially
and-superatmospheric pressures.
‘
70 to'impart a swirling or circular motion to the
In many cases, particularly when a fairly high
treating reagent, if desired. Another method
The process may be carried out‘ at any desired
pressure, such as atmospheric, subatmospheric,
ly concentrated fraction is re?ned with a sus
pension or ~ solution of a ?nely divided active
comprises locating the inlet jet or jets directly 7
in the bottom of the reactor, or ‘tangentially in
the sides of the reactor, or both, to prevent any
metal. or alloy of the type described herein; it is
highly advantageous to conduct such operations 75 settling in the bottom of the reacting vessel and
I 2,418,954
7
.
to impart any desired circular or other motion to
the treating medium.
Any desired combination of these methods also
may be employed, such as the use of a jet or jets
directly impinging upon the bottom of the reac-'
tor in conjunction with the'use of a tangential
jet or jets to prevent the active agent from
a
8
carbon dioxide to form unsaturated acids, oi‘
otherwise.
'
A convenient method for the disposal of the
insoluble polymers comprises treatment with
carbon dioxide, suitably in the presence of traces
of moisture, followed by ?ltration.
As the cost of the treating process is largely a -
function ‘of the quantity of the reactive agent
reactor and to maintain the reaction medium in . employed in the re?ning operations, the efficient
10 utilization of such agent is of considerable im
any desiredstate of agitation. ‘
.
settling out and depositing on the walls of the
The reaction medium also may be maintained
in the desired. degree of agitation by the use of
suitable stirring or mixing devices, or by the use
portance. A desirable method for insuring op
timum utilization of the treating agent is to carry
methods also may be used in conjunction with
one or more of the methods discussed previously
to maintain the system in the desired degree of
material to be treated. '
out the operations in a continuous countercur
rent manner, the reagent moving through the
of circulating pumps, or by a combination of these
methods, or otherwise. One or more of these 15 system in a manner countercurrent to that of the
dispersion.
This may be illustrated by means of a consider
ation of a simple continuous countercurrent sys
tem comprising two treating towers or 'vessels.
It should be pointed out, howeventhat the use 20 The material to be treated is passed into the ?rst
tower, which contains a partially exhaustedre
of such agitation methods is not required in most
agent. This serves‘to remove a substantial por
cases. Thus, excellent results have been secured
by conducting the re?ning operations in a tower, - tion of the impurities present, after which the
partially re?ned material passes into the second
the material to be treated being introduced into
the bottom of the tower by means of a small ori 25 tower, which contains a fresh, or more highly
concentrated, reagent. This serves ‘to remove the
?ce. The passage of the fraction being treated
impurities present to the desired extent. The
> in the gaseous state upward through the column
process is continued until the reagent in the ?rst
usually is su?lcient to maintain the system in the
tower is almost, or completely, exhausted, after
desired degree of agitation.
. The re?ning agent, particularly when ?nely di 30 which it is discarded and the partially exhausted
reagent from the second column substituted for
vided sodium is employed for this purpose, usu
it. Fresh reagent then is added to the second
ally acts both as a reactant and as a polymeriz
column.
,
ing agent for the removal of undesired impuri
In this manner the material to-be treated and
ties. Thus, in the case of unsaturated hydrocar
the treating agent pass through the system
bon fractions containing acetylenes, aldehydes,
countercurrent to each other, the ?rst continu
and other impurities, the sodium usually will re
ously and the second in a discontinuous manner.
act with at least a portion of the acetylenes‘ pres
This may be modi?ed such as by the continuous
ent to form sodium acetylides, and may react
addition of fresh reagent to the second tower, the
with certain of the oxygenated derivatives to
At 40 continuous transfer of partially exhausted re- ‘
_ form corresponding metallic derivatives.
agent to the ?rsttower, and the continuous with
least a portion of‘ the acetylenic hydrocarbons
drawal of more completely exhausted, or ex- ‘
present also are polymerized to form polymers,
hausted, reagent ‘from the ?rst tower. A com
or copolymers with other unsaturated hydrocar-'
pletely continuous countercurrent treating sys- '
bons present, which polymers frequently are in
soluble in nature. Certain of the oxygenated de 45 tem thus is achieved. _
Any desired modi?cation of these methods may
rivatives, such as aldehydes, also may be poly
be employed, and any number of treating towers
merized to form polymers which may be insolu
ble in type.
~
.
As a result, the re?ning of unsaturated hydro
carbons with a suspension of ?nely divided so
dium usually is characterized by the gradual ac
cumulation-of insoluble polymers in the re?ning '
medium, This may be removed in any desired
manner, such as by ?ltration, which may be car
ried out continuously during the re?ning opera
tion, or may be carried out in a batchwise man
ner after the termination of the re?ning step.
or units may be used. It will be observed that
,in each of the cases discussed, the incoming
50 material to be re?ned is contacted with partially
exhausted reagent (maximum concentration of
- impurities-minimum concentration of reagent),
while theoutgoing material to be re?ned is con
tacted with fresh or morehighly concentrated
reagent (minimum concentration of impurities
maximum concentration ‘of reagent). Thus the
two objectives to be sought, namely, practically
As the removal of the insoluble polymers also - complete, or complete, utilization of the reagent
and substantial, or practically complete, removal
is attended by some loss or re?ning agent, even
when the latter is in a very ?ne state of subdivi 60 of impurities from the material to be re?ned, are
achieved.
'
1
sion, it is advisable in many cases to continue
As the limiting factor affecting the utilization
the re?ning operations until the re?ning agent
has been largely ‘or. completely exhausted before.
of the reagent is' the proportion of insoluble
polymers and/or residues which can be con
?ltering.
I
65 tained therein without seriously impairing its
The solid or semi-solid ?ltered products ‘may
?owing properties, or thepassage of the gaseous
be treated to_-recover any desired materials or
material to be treated therethrough, it frequently
they may be?disposed of in any suitable manner.
happens that the quantity of insoluble material
, Thusf‘any‘ unchanged re?ning agent, such as
present is insu?lcient to interfere seriously with
the operation of the process when the re?ning
may be recovered by melting'and coa
agent present has been almost completely, ex
lescing?‘ operations, or by amalgamation with
hausted. In this case, the operation of the unit
ni'er'curyj‘or otherwise. Certain of the reaction
may be continued by the addition thereto of an
prfdtii'icts, such ‘as sodium acetylides, may be de
additional quantity of the re?ning agent, and
composedl'with water to ‘regenerate the corre
sponding'i'acids or they may be reacted with 75 this process may be continued until the concen
’
' $418,254
tration or insoluble niai'erial ‘in the reagent
Iclaim:
renders it too viscous to be used further- in the _ '
process in a satisfactory manner. " '
_.
.
ing acetylenic and-aldehyde material, comprising I
have a tendency to stabilize the sodium suspen- ?nely divided sodium in certain cases. _ As this ' l
_
- 1. A process for re?ning unsaturated hydrocar-v
bon material having from one to two double bonds
terial being contaminated with impurity includ
' sion andact to reduce the rate of settling of the '
materials to a fresh reagent.
@
permolecule, said unsaturated hydrocarbon ma
In this connection, it is well to point out that
_ the insoluble products ‘formed during the reaction
is desirable, the incomplete removal of insoluble
products from the reagent may be indicated, or
even the addition of a certain quantity of such
10
,
passing said unsaturated hydrocarbon material
at a temperature below 100° C. through a disper
> sion 'of a ?nely divided material selected from the
10 group consisting of metals of group IA and group
_ ‘ _
HA of the periodic system and alloys thereof, said
dispersion being at, least one foot in thickness in
Soluble polymers also usually .are formed in > the direction'of flow of said unsaturated hydro
carbon material and containing less than 30% by
small amounts during the re?ning operations. As
weight of said ?nely divided material, maintain-_
certain. of these soluble polymers are converted
ing the concentration of said unsaturated hydro- on prolonged contact with‘the re?ning agent to
carbon material in the reaction zone below 80%
viscous or insoluble products, their removal from. , by
weight of the total material present, while
the suspending medium, suitable at the end; maintaining
the rate of ?ow per hour of said un
of a re?ning cycle and prior to'the return of the
suspendingv agent to ‘the system, maybe -indi-. 20 saturated hydrocarbon material through said dis-,
persion at less than fourv times the weight of dis
cated. On the other hand, certain of these
persion medium employed, and removing said un
soluble polymers are sufficiently stable to actas a I
suspending medium for the refining agent.
An example of procedure which may be con
saturated hydrocarbon material less contami- '
nated with impurity including acetylenic and
aldehy'dematerial from said reaction zone, suffi
ciently rapidly to prevent a large loss of said on
‘ saturated hydrocarbonimaterial due to the poly
1 venientiy followed ‘in the practice of my inven
tion is as follows:
Example 1
meriz‘ation thereof.
,
,
_ 2._A process for re?ning unsaturated hydro
A light oil fraction containing approximately
carbon material having from one to’ two double
25% isobutylene, as well as approximately 1% 30 bonds per molecule, said unsaturated hydrocar- '
acetylenic hydrocarbons, 0.05% aldehydes, and
other impurities} was passed continuously in the
gaseous stateinto a xylene suspension of ?nely
divided sodium contained in a’steel column 2"
in diameter at a temperature of 50° 0.
Under the operating conditions chosen, the
re?ning agent comprised a. 10% suspension of,
?nely divided sodium in a suspending. medium
bon material being contaminated with impurity
‘including acetylenic ‘material, which comprises
continuously passing said unsaturated hydrocar-'
bon material ‘at a temperature below 80? 0.
through a dispersion of a ?nely divided material
‘selected from the group consisting of metals of
group IA and group 115 of the periodic system and
alloys thereof. said dispersion containing less than '
containing ‘approximately 90% xyleneand 10%: ' 20% by ‘weight thereof of said ?nely divided ma- ’
' isobutylene fraction.
The height of re?ning
terialland being atleast two feet in thickness in
agentemployed was approximately 6 feet.
the direction of ?ow of said unsaturated hydro
The re?ning operation was continued for a
carbon material, maintaining the concentration
period of 30 hours, the isobutylene-fraction being ' of said unsaturated hydrocarbon material in the
charged at; the rate of approximately 1000 grams 45 reaction zone less than I10% by weight of the total
material present, while maintaining a rate of
The product obtained was water-white in color
?ow per hour, of said unsaturated hydrocarbon
and contained only 0.002% acetylenes. ~The alde
- material through said dispersion of less than
hydes present had been removed completely.
twice the weight of dispersion medium employed,
The product was in a high state of purity and
and continuously'removing said unsaturated .hy
50
could be used for the production of polybutene or
drocarbon material less contaminated with impur
synthetic rubber, suitably by copolymerization
ity including acetylenic material from said reac
with relatively small proportions of one or more
tion zone suf?ciently rapidly to prevent a large
diole?nes.
,
loss of said unsaturated hydrocarbon material due
In the speci?cation and in the claims, the fol
to polymerization thereof.
.
lowing terms have the indicated meanings.
-3._ A process for re?ning unsaturated hydrocar
The term "a metal of group IA and group 11A
material having from one to two double bonds
of‘ the periodic system” is intended to mean one > bon
per molecule, 'said unsaturated hydrocarbon ma
of a gr'oup consisting of lithium, sodium, potas
terial being contaminated with impurity includ
sium, rubidium, caesium, barium, strontium. and
60 ing aldehyde material, whichcomprises continu-' ‘
ously passing said unsaturated hydrocarbon ma
’
The term “alkali
metal” is employed as ‘de?ne ' terialat a temperature below 80° C- through a
itive of the group of metals consisting of lithium,
dispersion of ,a ?nely divided material selected . I
per hour.
calcium.
v
,
'
_
1
I
-
sodium, potassium, rubidium,- and caesium.
The term “?nely divided” is intended to mean
a material reduced to such a state of ?neness that
from the group consisting of metals of group'IA
and group 11A of the periodic system and alloys
the preponderatingpart is composed of particles
thereof, said dispersion containing less than ‘20%.
tions, substitutions, and/or modi?cations may be
material present,- while maintaining a rate of ?ow
per hour of said‘unsaturated hydrocarbon mate
75 rial througb said dispersion of less than twice the
by weight thereof of said ?nely divided material
having a diameter of less than 0.05", as well as
and being at least two feetin thickness in the
materials in the colloidal or dissolved form.
direction of ?ow of said unsaturated hydrocarbon
While reagents and procedures of a particular
nature have been speci?cally described, it is to 70 material, maintaining the concentration of said
unsaturated hydrocarbon material in ,the' reac-_.
be understood that these are given by way of
tion
zone less than 70% by weight of the total
illustration. Therefore, changes, omissionaaddi
made within the scope of the claims without de
parting from the spiirtof the invention. /
8,418,854
11 .
.
weight of dispersion medium employed, and con
tinuously removing said unsaturated hydrocarbon
material less contaminated with impurity includ
za'tion thereof.
"1. A process for the puri?cation of isobutylene
contained in admixture with impurity including
acetylenic material. which comprises continuously
ing aldehyde material from said reaction zone
sumciently rapidly to prevent a large loss ofsaid
unsaturated hydrocarbon material due to poly
nierization thereof.
12
_ loss of aliphatic ole?ne material due to polymeri
passing said admixture in vapor phase at a tem
perature. below 100° C. through a dispersion of
‘
4. A process for re?ning ole?ne material con
?nely divided sodium,_ said dispersion being at
tained in a mixture including‘acetylenic mate-'
least one foot in thickness in the direction of ?ow
rial, which comprises continuouslypassing said 10 of said admixture and containing less than 30%
mixture ‘in vapor phase under temperature con
by weight thereof of said ?nely divided sodium,
_ ditlons below 100° 0. through a dispersion of a
maintaining the concentration of said‘isobutylene
?nely divided alkali metal, said dispersion con
taining less than 30% by weight thereof of said
v?nely divided alkali metal and being at least one
foot in thickness in the the direction of ?ow of
in the‘reaction zone‘ less than 80% by‘ weight of
the total material present, while maintaining the
rate of ?ow per hour ofsaid admixture through
, said mixture, maintaining the concentration of
of dispersion medium employed, and continuously
said dispersion at less than four times the weight -
said ole?ne material in the reaction zone less
removingisobutylene in vapor phase less con
than 80% by weight of the total material present,
taminated with said impurity including acetylenic
while maintaining the 'rate of ?ow per hour of
said mixture through said dispersion at less than
‘four times the weight of dispersion medium em-.
material from said reaction zone su?iciently
rapidly to- prevent a large loss of said isobutylene
due to polymerization thereof.
8. A process for the recovery of isobutylene
from a mixture containing the same and contain
ployed, and continuously removing said ole?ne
material less contaminated with impurityinclud
ing acetylenic material from said reaction zone
su?iciently rapidly to prevent a large loss of said,
ole?ne material due to polymerization thereof.
5. A process for the recovery of aliphatic ole?ne
‘material from a mixture containing the same and
ing impurity including acetylenic material. which
comprises continuously passing said mixture in
vapor phase at a temperature below ‘10° vC.
through a reaction zone containing a dispersion -
of ?nely dividedsodium at least the majority of
containing impurity including acetylenic mate 30 the particles of which have a- diameter, of not
rial, which comprises continuously passing said '
more than 0.05", said dispersion containing less
than 30% by weight thereof of said'?nely divided
_mixture in vapor phaseunder temperature cori-v
ditions below 80° 0. through a dispersion of finely
' soduim ‘and being at least one vfoot in thickness
divided sodium, said dispersion containing less
. in the direction of ?ow of said mixture. maintain
than 20% by weight thereof of said ?nely divided. as ing the concentration ofsaid isobutylene in said
sodium and being at least two feet in thickness
reaction zone less than 80% by-weight of the total
in the direction of ?ow of said mixture, maln
material present. while maintaining a rateof ?ow
talning the concentration of aliphatic ole?ne
" per hour of said mixture through said dispersion
material in the reaction zone less than 70% by
of less than four times the weight of dispersion
weight of the total material present, while main (0 medium employed. and continuously removing
taining a rate of flow per hour of said mixture
' isobutylene in vapor phase and less contaminated
through said dispersion of less .than twice the
with said impurity including acetylenic' material
weight of dispersion medium employed, and con
from said reaction zone ‘su?lciently rapidly to
tinuously removing said aliphatic ole?ne material
prevent a, large loss of said isobutylene due to‘
in vapor phase less contaminated with impurity 45 polymerization thereof.
including acetylenic material from said reaction
9. A process for the puri?cation of a light oil
zone su?lciently rapidly to prevent a large loss of
isobutylene fraction containing isobutylene to
said aliphatic ole?ne material due to polymeriza
gether with impurity at least a portion of which
tion thereof.
is in the form of acetylenic material, which com
6. A process for the puri?cation of aliphatic 50 prises continuously passingsald fraction in vapor
ole?ne material contained in admixture with im
phase at a temperature below 80° ‘C. upwardly
purity including aldehyde material, which com
through‘ a reaction zone containing a dispersion
prises continuously passing said admixture in
‘ of ?nely divided sodium at least the majority of
vapor phase at a temperature below 80° 0. through I the particles of which have a diameter of not
a reaction zone containing a dispersion of ?nely 55 more than 0.03", said dispersion containing less
divided sodium, said dispersion containing less
than 20% by weight thereof of said ?nely divided
than 20% by weight thereof of said ?nely divided
sodium and being at least two feet in thickness in
sodium and being at least two feet in thickness
the direction of flow of said fraction, maintaining
in the direction of ?ow of _said admixture, main
the concentration of said isobutylene in said re
taining the concentration of aliphatic ole?ne 60 action zone less than 70% by weight of the total
material present while maintaining a rate of ?ow
material in said reaction zone less than 70%
‘by weight of the total material present, while
per hour of said, fraction .throughsaid dispersion
maintaining _a rate of ?ow per hour of said ad
mixture through said dispersion of less than twice
dium' employed: and continuously removing said
of less than twice the weight of dispersion me
the ‘weight of dispersion medium employed, and 65 fraction in vapor phase from the top of said
continuously removing said aliphatic ole?ne ma
reaction zone less ‘contaminated with impurity
terial in vapor phase less contaminated with im- -
including acetylenic material suiliciently rapidly
purity including aldehyde material from said re
action zone su?iciently rapidly to prevent a large
to prevent a large loss of said isobutylene due to
polymerization thereof.
70
'
FRANK J. SODAY.
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