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Патент USA US2410583

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Nov. 5, E946.
A. J. L. HUTCHINSON
l
2,410,583
SEPARATION oF HYDRATE -FoRMING> COMPONENTS 0F GAsEoUs MIXTURES
Filed July l0, 1945
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2 Sheets-Sheet 1
ov. 5, 1946.
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A. J. l.. vl-«zUTcl-nNsoN
29430533
SEPARATION OF HYDRATE-FORMING~ COMPONENTS OF GASEOUS MIXTURES
Filed July l0, 1943
2 Sheets-Sheet 2
v
Patented Nov. 5, 1946
2,410,583
UNITED STATES PATENT ortica
2,410,583
SEPARATION 0F HYDRATE-FORMING COM
PONENTS 0F GASEOUS MIXTURES
Arthur J. L. Hutchinson, San Marino, Calif., as
signor to The Fluor Corporation,> Ltd., Los
Angeles, Calif.,
a corporation of California
Application July 1o, 194s, serial No. 494,164
10 Claims. (ol. 26o-_676)
2
This invention has to do with improved proc
esses for the separation from normally gaseous
mixtures containing one or more hydrate-form
hydrate-forming zone, and thus maintained in a
state of continuous circulation between the two
zones.
ing components, of one or more components in
Another object of the invention is to provideA
capable of forming hydrates, or at least which
do not form hydrates under the conditions of
treatment in the process. More particularly the
invention is directed to the separation from hy
for a high degree of separation of the inert com
ponents from the gas, by the formation of a hy
drate phase characterized by `its readiness of
formation, stability and low vapor pressure, all
drocarbon gases such as natural gas or reñnery
of
which properties tend to permit segregation
tail gas, of undesirable or inert gases, of which l()
out
of the gas of the maximum percentages of
nitrogen and hydrogen may be taken as typical.
its hydrate-forming components. In this respect,
the invention contemplates treatment of the hy
drocarbon in the presence of an additive, to pro
This application is a continuation-in-part of
Hutchinson application Serial No. 392,186, filed
May 6, 1941, on Fractionation of hydrate-forming
duce what may be referred to generally as a
mixed hydrate of the hydrocarbons and additive, l
hydrocarbons, and Hutchinson application Serial
No. 407,036, ñled August 14, 1941, on System for
characterized by its readiness of formation and
considerably lower vapor pressure, and therefore
greater stability, than the pure hydrate of the
forming and storing hydrocarbon hydrates.
Generally speaking, the present process in
volves phase segregation of hydrate-forming hy
drocarbon components, from inert or- non-hy
same hydrocarbon at the same temperature.
20
drate-forming components, by converting the
former to their solid hydrates and separating the
non-hydrated fluid phase.
The invention broadly contemplates the use of
any suitable additive. capable of forming with
hydrate-'forming hydrocarbons, a mixed hydrate,
One basically dis
or hydrate complex, as hereinafter designated,
tinctive aspect of the process, is the method
whereby the hydrates may be subjected to con 25 the mixed hydrate having the property of sub
stantially lower vapor pressure than the vapor
tinuous dissociation in a single zone receiving a
pressure
of the hydrate of the hydrocarbon com
stream of the hydrates, with the end result that
ponent of the mixed hydrate. Suitable additives
fall within the general class of halogenated hy
the raw gas being Atreated undergoes continuous
separation into two continuously ñowing streams
of
its
hydrocarbon ' and
inert
components. 30 drocarbons which are liquid at 0° C. and are
Specifically, the invention contemplates subject
ing the gas in a conversion zone and in the pres
ence of water, to pressure and temperature con
ditions causing hydration of the component or
components to be hydrated, separating the non 36
hydrated gas, and continuously transferring the
hydrates to a suitable decomposition zone where
in the hydrates undergo continuous dissociation
and reconversion into gas. '
Transference'of the hydrates from the conver
chloride, bromoform, chloroform, ethylene di
chloride, methylene chloride, methyl iodide,
methylene iodide, and the tri-halogen compounds
For purposes of de
40 scription, carbon tetrachloride will be referred
sion zone to the decomposition zone may be facili
tated by the use of a hydrate carrier ñuid, which '
in the broad aspects of the invention may be>
any suitable ñuid medium capable of entraining
and aiding the transference of the hydrate
crystals. I may employ as the carrier ñuid, re
sidual liquid remaining after the hydration, or
capable of forming with a hydrate-forming'hy
drocarbon under proper temperature and pres
sure conditions, a mixed hydrocarbon-halo
genated hydrocarbon hydrate. Included among
such halogenated hydrocarbons are carbon tetra
of methane andV ethane.
to hereinafter as the additive, with the under
standing that it is to be regarded as typical of
suitable additives in general, and of the- class
consisting of the halogenated hydrocarbons.
The additive, e. g. carbon tetrachloride, may
be introduced, as later described, to the hydrate
forming zone in which it is converted. together
a non-aqueous liquid, such as kerosene or other
with the hydrocarbon, into a mixed hydrate. The
mineral oil fraction, to particular advantage be
exact nature and composition of the resulting
cause of its further utility as a dispersing medium 50 hydrate complex is not known at present, and
l for water particles to be consumed in the hydra-
tion, and also for the later described additive,
if used. After separation from the -hydrates or
consequently the expression “mixed hydrate” is
used as a term of designation, rather than of
definition, and is not intended _to be limitative
hydratable components. as in the decomposition
with respect to any particular form or composi
zone, the carrier liquid may be returned to the 55 tion
of the hydrate complex. That composition
2,410,583
4
may lbe in the nature of 'a depressed vapor vpres
sure mixture of the two hydrates, or of a double
hydrate of the hydrocarbons and carbon tetra-'
chloride, or it may involve a solution of some of
the hydrocarbon in the carbon tetrachloride hy
drate, or a solution of some of the carbon tetra
chloride in the hydrocarbon hydrate. Whatever
its exact composition may be, the mixed hydrate
has the important property oi.' low vapor pres
sure, of which advantage may be taken for the
purposes of the present process.
The invention contemplates various additional
particular features of operation, such as partial
hydration oi' the hydrocarbon components of the
gas alone, followed by hydration of unconverted
hydrocarbons together with the additive. Con
gated into hydrated hydrocarbon components
which, together with any higher boiling non
hydrate-forming hydrocarbon components, are
continuously withdrawn from the base of the
column through line I3, and gaseous inert con
stituents which are separately and continuously
withíi‘rawn from the top of the column through
line
.
The hydrate formed in column-I I, and which
preferably is a mixed hydrocarbon-carbon tetra
chloride hydrate, is continuously discharged in a
stream of the carrier liquid, e. g. kerosene,
through lines I3, I3a and heat exchanger I5 into
the hydrate decomposition zone I6. The pressure
on the hydrates may be reduced at the discharge
side of valve I'I should it be desired to facilitate
dissociation of the hydrates by virtue of the re
templated also are methods for the recovery of
duced pressure. Ordinarily, however, it may be
the additive from both the separated hydrocarbon
desired to decompose the hydrates at increased
and inert gas streams, and return of the re
20 pressure in order to permit absorption recovery
covered additive to the hydrate-forming zone.
of the carbon tetrachloride at pressures suñl
All the objects and features of the invention
ciently high for most eñicient operation. Ac
will be more fully explained, and understood to
cordingly, 'the hydrate-carrier stream may be
better advantage from the following descrip
forced by pump P into zone I6, wherein the
tion of a'typical system 'illustrated by the ac
hydrate dissociation may occur under any desired
companying drawings, in which:
Fig. 1 is a schematic layout, in flow sheet form,
While the hydrate decomposition zone I6 may
illustrating a typical system embodying the in
be of any suitable type and form, it is preferred
vention; and
pressure.
Fig. 2 is a View, largely diagrammatic, showing
-
Y
to use a vertically extended column to more effec
the hydrate-forming zone in vertical section, and 30 tively remove hydrate-forming hydrocarbons and
carrier liquid from the gas going to the outlet
including also a secondary hydrate decomposition
line I8. Heat may be supplied to the column I6
zone to be used if required.
It will be understood that the gas fed to the ' in any suitable manner, as by a bottom coil
heater I9, to eiîect complete dissociation of the
system under pressure through line Ill, may con
sist of any of various mixtures of one or more 35 hydrate. The residual carrier liquid is dis
charged through line 20 and exchanger I5 for
hydrate-forming components, with one or more
recirculation to the hydrate-forming zone I‘I,
inert constituents which either are incapable of
after again mixing the carrier with water and
forming hydrates under any conditions, or under
the particular conditions existing in the hydrate
carbon tetrachloride. Any suitable methods and
forming zone. As illustrative, assume that the 40 apparatus Imay be employed at 2| for mixing
system is to be operated for extracting from a _ and proportioning4 the carrier liquid, water and
natural gas containing hydrate-forming hydro
carbon tetrachloride to be recirculated, and for
supplying any necessary make-up carrier, water
carbons included in the C1, C2, and Ca range, an
and carbon tetrachloride. _It is contemplated
inert fraction containing a high percentage of
nitrogen, the nitrogen content for example run 45 that the resulting mixture may be in the form
of an emulsion formed by suitably mixing and
ning as high as from 10 to 15% >by volume of
agitating the carrier liquid, water and carbon
the natural gas. In order to reduce the heat load
tetrachloride together _with an emulsifying agent,
(resulting from the heat of hydrate formation)
for example dioctyl sodium sulfo succinate, known
on the hydrate-forming column II, the gas first
may be passed through one or more coolers I2 ' commercially as "Aerosol OT.” The mixture, or
emulsion, is discharged by pump 22 through line
within which the gas temperature may be lowered
as desired. ‘Within column II, the gas is con
4 23 and cooler 24 to the top of the hydrate
tacted with Water, and preferably also with a
non-aqueous carrier liquid and a hydrate
forming column II. Where operation of the co1
forming additive, under temperature and pressure '
location of a carrier liquid-water mixture, all
as later explained, such mixture, containing no
carbon tetrachloride, may be supplied from the
conditions causing conversion to their solid hy
drates of substantially all, or at least a greater
portion of the hydrate-forming components of
the gas. 'I‘he more particular details and aspects
umn requires the introduction at an intermediate
mixing and proportioning plant 2I by pump 26
through line 21.
of the hydrate formation within the column II,
The _ hydrocarbon gas leaving column I6
will be described later with reference to Fig. 2.
through line I8, and containing water and carbon
.At this point itvwill suñ‘lce to observe that the
tetrachloride vapors, may be passed directly
gas and water may be contacted within the
through line 28 to the extractor 29, or the gas
column II under any suitable temperature and
may be subjected to partial condensation in con
pressure conditions at which the desired degree 65 denser 30 to provide a suitable amount of con
of hydrate formation will occur, for example at
densate to be returned from accumulator 3I
a temperature between 35 and 45". F. and under
through line 32 and pump 33 to the column I6 as
pressure between 400 and 650 pounds per square
reñux, the uncondensed gas passing through line
inch. The presence of the additive, if used, may
34 connecting with the extractor feed line 28.
lower very considerably the required pressure 70 'I'he carbon Atetrachloride content of the hydro
for the hydrate formation at a given temper
carbon gas stream is extracted in column 29 by
ature, or conversely, permit the Vuse of consider
intimately vcontacting the rising gas stream
ably high temperatures to effect the hydrate
therein with a downwardly flowing absorption
formation under a given pressure. As a result
liquid, such as a fairly high boiling mineral oil
of its treatment in column II, the gas is segre
fraction, in which the carbon tetrachloride is re
2,410,583
5.
covered by absorption. The extractor column
to be sent to the mixing and proportloning plant
may be operated at any suitable pressure and
2 I.
oil rate to eiîect solution from the gas phase of
The non-hydrated gas rising from the bottom
the carbon tetrachloride vapor. The purified hy
section of the column 60 flows through the baiiled
drocarbon gas is taken from the column through el vapor neck 1I extending above plate 12, into the
line 35 for such disposal as may be desired.
upper section of the column wherein the gas is
Water condensate accumulating within the bot
contacted with a down-flowing stream of mixed
tom of the extractor, may be intermittently or
or emulsifìed non-aqueous carrier liquid, water
continually drawn olf through ‘line 36.
and additive such as halogenated hydrocarbon,
The inert gas, containing some carbon tetra 10 e. g. carbon tetrachloride. The latter mixture or
' chloride and withdrawn from the hydrate-form
emulsion entering the column through line 25
ing zone through line I4, may be similarly given
and cooler 13 may contain the carrier, Water and
an absorption oil treatment for extraction of the . carbon tetrachlorite in any desired proportions,
carbon tetrachloride. Accordingly, the inert gas
so long as the water present in the column is
stream may be introduced from line I4 into a,
sufficient for formation of the mixed hydrate, and
second extractor column 31 wherein the gas is.
the quantity of carrier liquid is adequate for en
contacted with down-flowing absorption oil.
trainment and transference of the formed hy
Carbon tetrachloride-free gas is taken from the
drates. The carbon tetrachloride content of the
top ofthe column through line 38. Water ac
mixture or emulsion is not critical and may run
cumulating in the bottom of the column is with 20 in the neighborhood of 10% to 90%, depending
drawn through line 39.
upon various considerations including the quan
The absorption oil streams with their absorbed
tity and composition of the hydrate-forming hy
carbon tetrachloride, are withdrawn from the ex
drocarbons in the gas being treated. Intimate
tractors 29 and 31 through lines 39a and 40 to be
association of the gas and liquid mixture intro
taken through line 4 I, heat exchanger 42 and line
duced through line 25, results in the formation
43 to a still 44 supplied with heat as by the bottom
within the upper section of the column of what
coil 45, and also, if desired. by live steam through
has been termed the mixed hydrocarbon-carbon
line 45|. In still 44 the absorption oil is heated
tetrachloride hydrate. The latter forms at stages
suiliciently to vaporize the carbon tetrachloride,
or on the bubble trays progressing upwardly
the latter passing through li'ne 46 to condenser
within the column, and the formed hydrate is
41 and the condensate accumulator 48.
A por
continuously flushed downward through the
tion of the condensate may be returned through
trays in the carrier liquid into vchamber 14 from
line 49 and pump 50 to the top of the still as
which the hydrates are transferred through line
I3 to the decomposition zone I6.
reflux. From accumulator 48 the carbon tetra
chloride is discharged by Dump 5I «through line i
In the upper section of the column, the gas is
52 to the mixing and proportioning plant 2 I. The
effectively depleted of its hydratable hydrocar
stripped absorption oil leaving the bottom of the
bon content by reason of the hydrate-forming
still through line 53 is forced by pump '54 through
load on this section of the column having beeny
exchanger 42, line 55, cooler 56 and the branch
reduced by and to the extent of the hydrates
lines 51 and 58 into the extractor columns 29 and
forming in the bottom section of the column.
31.
Complete final hydration of the hydrocarbons is
Further consideration now may be given the
further and effectively assured by reason of the
operation of the hydrate-forming column II and
relative ease of formation of the mixed hydro
the methods contemplated for securing high per
carbon and carbon tetrachloride hydrate, and its
vccrmparatively low vapor pressure and resultant
centage removal, in the form of their hydrates, of
stability.
the hydrate-forming componentsl of the gas
Reference previously has been made to. pre
treated. Referring to Fig. 2, the hydrate-forming
zone I I may consist essentially of a fractionating
column 60 containing a vertical series of bubble
trays conventionally illustrated at ISI~ According
to the method of operation specifically illustrated,
the precooled gas introduced to the bottom of
the column through line III rises through the
lower series of bubble trays 6I in intimate contact
with a mixture or emulsion of the non-aqueous
carrier liquid and water Dre-cooled in cooler 62
and introduced to an intermediate location in the
cooling of the gas, as well as the water and car
rier liquids, to compensate for heat of hydrate
formation.f Such heat may further be compen
sated by the withdrawal of heat of hydrate for
mation from within the column itself. Typically,
the several bubble trays 6I may carry cooling
coils 15 to which a ‘suitable refrigerant or cooling
fluid is supplied from line 16 through manifold
11 and the valved branches 18, the valves 19 being individually adjustable to permit selective
with this carrier and water stream produces par
temperature ,control on any of the trays. After
passage through the coils 15, the cooling fluid
tial hydration of the hydrate-forming hydrocar
enters the outlet manifold to be discharged
column through line 63, Co-mingling of the gas
through line 8|.
bon components of the gas, the resulting hy
According to the method just described, hydro
drates being entrained in the carrier liquid and
carbon hydrates are formed in the lower section
carried downwardly through the usual overflow
of the column, and the mixed lhydrocarbon-car
pipes 64 to the bottom of the column. The hy
bon
tetrachloride hydrate is formed in the upper
drates thus are transferred in the carrier liquid
section of the column, by selective introduction Y
through line 65 (and by pump P’ if desired), and
of the two aqueous liquids through lines 63 and
the heat exchanger 66 into a hydrate decomposi
25 and separate withdrawal of the hydrates
tion zone 61 supplied with heat by the bottom
through lines 65 and- I3. If desired, the entire
coil 68. In column 61 the hydrates are dissoci
column may be used for the formation of the
ated to release the hydrocarbon gas for removal
.mixed hydrate, in which vevent plate 12 may be
and such use as may be desired, through line 69.
replaced by a bubble cap tray 6I, the water-car
If desired, the latter may connect into line 35 of
rier inlet line 63 dispensed with, and the com
Fig. 1. The residual carrier liquid and water may
be withdrawn through line 10 and exchanger. 66 75 position of the stream introduced to the top of
the column through line 25, adjusted to contain
asiduos
suiiicient carbon tetrachloridev and water for
' conversion of all the hydrate-forming hydrocar
temperature, separating said gaseous. inert con
stituent from the mixed hydrate, transferring
bons of the gas to a mixed hydrocarbon-carbon
tetrachloride hydrate. When- the column is op
erated‘in this manner, the mixed hydrate with
drawn through line 65, instead of through line
I3, may he taken through the valved line 83 into
line I3 for delivery to the decomposition zone I6,
all as illustrated in Fig. 1.
I claim:
said mixed hydrate from said conversion zone to
a decomposition zone, therein heating and dis
"sociating the hydrate, recovering said additive
from the products of the hydrate dissociation,
and returning the additive to the conversion zone.
5. The method of treating a gas comprising a
-
_
8
carbon components alone and at corresponding
l0 mixture of hydrate-forming hydrocarbon com
» 1. The method of treating a gas comprising a
ponents and an inert non-hydrate-forming con
mixture of hydrate-forming hydrocarbon com
ponents and an inert non-hydrate-forming con-_
stituent to separate said inert constituent, that
includes contacting said gas with Water and a
stituent to separate said inert constituent, that
hydrate-forming halogenated aliphatic hydro
includes contacting said gas with water and a
halogenated aliphatic hydrocarbon in a conver
sion zone under temperature and pressure con
ditions causing formation of a mixed hydrate ci'
carbon additive in a conversion zone under tem
said hydrocarbon components and halogenated
hydrocarbon, said mixed hydrate having sub
perature and pressure conditions causing forma
stantially lower vapor pressure than the hydrate
'_ tion of a mixed hydrate of said ìhydrocarbon
of said hydrocarbon components alone and at
components and additive, said mixed hydrate
corresponding temperature, separating said gas
having substantially lower vapor pressure than
eous inert constituent from the mixed hydrate,
the hydrate of said hydrocarbon components
transferring said mixed hydrate from said con
alone and at corresponding temperature, sepa
version zone to a second zone and therein dis
rating said inert constituent from the mixed hy
drate, continuously removing the hydrates from 2.5 sociating the hydrate to vaporize the halogenated
hydrocarbon and said hydrocarbon components,
said zone and dissociating the removed hydrates,
and recovering the halogenated ¿hydrocarbon
recovering said additive, and returning the addi
from the resulting vapors.
_ tive to the conversion zone.
' 6. The method of treating a gas comprising a
2. The method of treating a gas comprising a
vmixture of hydrate-forming hydrocarbon compo 30 mixture of hydrate-forming hydrocarbon com
ponents and an inert non-hydrate-forming con
nents and an inert non-hydrate-forming con
stituent to separate said inert constituent, that
stituent to separate said inert constituent, that,
includes contacting said gas with water intimate
ly mixed with a non-aqueous liquid and a hy
includes contacting said gas with water and a
halogenated aliphatic hydrocarbon in a conver
sion zone under temperature and pressure con
ditions causing formation of a mixed hydrate
of said hydrocarbon components and halogen
drate-forming halogenated aliphatic hydrocar
bon additive in a conversion zone and under tem
perature and pressure conditions causing forma
tion of a mixed hydrate of said hydrocarbon com
ated hydrocarbon, said mixed hydrate having
ponents and additive, said mixed hydrate having
substantially Alower vapor pressure than the hy
drate of said hydrocarbon components alone at
corresponding temperature, and separating said
inert constituent from the mixed hydrate, con
tinuously removing the hydrates from said zone
substantially lower vapor pressure than the hy
40 drate' of said hydrocarbon components alone and
and dissociating the removed hydrates, recover
45
ing said additive, and _returning the additive to
at corresponding temperature, separating said
gaseous inert constituent from the mixed hy
drate, transferring said mixed ‘hydrate from said
conversion zone to a second zone and therein dis
sociating the hydrate to vaporize the halogenated
hydrocarbon and said hydrocarbon components,
extracting the halogenated hydrocarbon from the
resulting vapors in absorption oil, heatingthe
absorption oil to vaporize the halogenated hydro
carbon therefrom, and condensing the halogen
the conversion zone.
3. The method of treating a gas comprising a
mixture of hydrate-forming hydrocarbon com
ponents and an inert non-hydrate-forming con 50
ated hydrocarbon vapors.
«
stituent to separate said inert constituent, that
7. The method of treating a gas comprising a
includes contacting said gas with Water and car
mixture of hydrate-forming hydrocarbon com
bon tetrachloride in a conversion zone under
ponents and an inert non-hydrate-forming con
temperature and pressure conditions causing for
stituent to separate said inert constituent, that
mation of a mixed hydrate of said hydrocarbon
includes contacting said gas wtih Water and a
components and carbon tetrachloride, said mixed
hydrate having substantially lower vapor pres
sure than the hydrate of said hydrocarbon com
ponents alone at corresponding temperature, and
vaporizable halogenated aliphatic hydrocarbon
additive in a conversion zone under temperature
and pressure conditions causing formation of a
separating said gaseous inert constituent from 60 mixed hydrate of said hydrocarbon components
and additive, said mixed hydrate having substan
the mixed hydrate, continuously removing the
tially lower vapor pressure than the hydrate of
hydrates from said zone and dissociating the re
moved hydrates, recovering said additive, and i said hydrocarbon components alone and at cor
responding temperature, separating said Ygaseous
returning the additive to the conversion zone.
4. The method of treating a gas comprising a 65 inert constituent from the mixed hydrate, and
contacting the separated gas with absorption oil
mixture of hydrate-forming hydrocarbon com
to extract therefrom the additive carried by 'the
ponents and an inert non-hydrate-iorming con
gas from the conversion zone.
stituent to separate said inert constituent, that
8. The method of treating a gas comprising a
includes contacting said gas with water and
halogenated aliphatic hydrocarbon additive in a 70 mixture of hydrate-forming hydrocarbon compo
nents and an inert non-hydrate-forming con
conversion zone under temperature and pressure
stituent to separate said inert constituent, that
conditions causing formation vof a mixed hydrate
includes treating said gas to partially hydrate
of said hydrocarbon components and additive,
said hydrate-forming components, then contact
said mixed hydrate having substantially lower
ing the residual gas wtih water and a hydrate
vapor pressure than the hydrate of said hydro 75 forming halogenated aliphatic hydrocarbon ad
2,410,588
10
_ditive under temperature and pressure conditions
causing formation of a mixed hydrate of the hy
drocarbon components and additive, said mixed
hydrate, dlssociating the mixed hydrate, and re
covering said additive from the products of the
hydrate dissociation.
hydrate having substantially lower vapor pres
10. The method of treating a gas comprising a
mixture of hydrate-forming hydrocarbon com
ponents and an inert non-hydrate-forming con
stituent to separate said inert constituent, that
sure than the hydrate of said hydrocarbon com
ponents alonev and at corresponding temperature,
separating said inert constituent from the mixed
hydrate, dissociating the mixed hydrate, and re
includes treating saidegas to partially hydrate
said hydrate-forming components, then contact
covering saidadditive from the products of the
hydrate dissociation.
9. The method of treating a gas comprising a
mixture of hydrate-forming- hydrocarbon com
ponents and an inert non-hydrate-forming con
10.
ing the residual gas with water and carbon tetra
chloride under temperature and pressure condi
tions causing formation of a mixed hydrate of
the hydrocarbon components and carbon tetra
stituent to separate said inert constituent, that
chloride, said mixed hydrate having substantially
includes treating said gas to partially hydrate
lower vapor pressure than the hydrate of said
said hydrate-forming components, then contact 15 hydrocarbon components alone and at corre
ing the residual gas with water andI a halogen
sponding temperature, separating said inert con
ated aliphatic hydrocarbon under temperature
stituent from the mixed hydrate, heating and dis
and pressure conditions causing formation of a
sociating the hydrates producedrby said partial
mixed hydrate of the hydrocarbon components
hydration of said components, heating and dis
20
and halogenated hydrocarbon, said mixed hy
sociating the mixed hydrate, and separating car
drate having substantially lower vapor pressure
bon tetrachloride from the vapors resulting from
than the hydrate of said hydrocarbon compo
dissociation of the mixed hydrate.
nents alone and at corresponding temperature,
separating said inert constituent from the mixed
ARTHUR J. L. HUTCHINSON.
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