Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
- ~;27~3
"SEPARATION OF 1,3-BUTADIENE "
BACKGROUND OF THE INVENTION
The field of art to which the claimed invention pertains
is hydrocarbon separation. More specifically, the invention relates
to a process for separating l,3-butadiene from a feed mixture com-
prising 1,3-butadiene and at least one other C4 hydrocarbon, which
process employs a particular adsorbent and desorbent material.
BACKGROUND INFORMATION
It is well known in the separation art that certain crys-
talline aluminosilicates can be used to separate one hydrocarbon
type ~rom another hydrocarbon type. The separation of normal par-
affins from branched chain paraffins, for example, can be accom-
plished by using a type A zeolite ~hich has pore openings from 3 to
about 5 Angstroms. Such a separation process is disclosed in U.S.
Patents 2,985,589 to Broughton et al. and 3,201,491 to Stine. These
adsorbents allow a separation based on the physical size differences
in the molecules by allowing the smaller or normal hydrocarbons to
be passed into the cavities within the zeolitic adsorbent, while ex-
cluding the larger or branched chain molecules.
In addition to being used in processes for separating hy-
drocarbon types, adsorbents comprising type X or Y zeolites have also
been employed in processes to separate individual hydrocarbon isomers.
In the processes described, for example, in U.S. Patents 3,626,020 to
Neuzil, 3,663,638 to Neuzil, 3,665,046 to de Rosset, 3,668,266 to Chen
et al., 3,686,:343 to Bearden Jr. et al., 3,700,744 to Berger et al.,
3,734,974 to Neuzil, 3,894,109 to Rosback, 3,997,620 to Neuzil and
; .. -
263
B426,274 to Hedge, particular zeolitic adsorbents are used to sepa-
rate the para isomer of bi-alkyl substituted monocyclic aromatics
from the other isomers, particularly para-xylene from other xylene
isomers.
There is also separation art that deals specifically with
the separation of 1,3-butadiene from other C4 hydrocarbons, par-
ticularly monoolefins. U.S. Patents 3,311,671 to Baker and
3,992,471 to Priegnit~ teach the use of alkali metal-aluminum sili-
cates on zeolites in effecting that separation. U.S. Patent
3,596,436 ~o Dassesse discloses the use of activated charcoal to
separate diolefins from monoolefins, but requires that the entire
process be carried out in the vapor phase and provides for the
regeneration of the solid adsorbent (removal of diolefins) with
superheated steam.
In contradistinction to the above references, the present
invention achieves separation of butadiene from other C4 hydrocarbons
with activated or molecular sieve carbon in liquid phase and with a
hydrocarbon desorbent.
SUMMARY OF THE INVENTION
In brief summary the present invention is~ in one embodiment~
a process for separating l,~butadiene from a feed mixture comprising
1,3-butadiene and at least one other C4 hydrocarbon. The proces
romprjses contacting, in liquid phase at adsorption conditions, the
feed mixture with an adsorbent comprising acti~1ated or molecular sieve carbon
which selectively adsorbs the 1 ,3-butadiene. The unadsorbed portion of the feedis then removed from the adsorbent, and the 1,3-butadiene recovered by
desorption at
~2~ 63
desorption conditions with a liquid desorbent material
comprising a hydrocarbon. The feed mixture and the desorbent
material have boiling points of at least 5C difference.
Other embodiments of the present invention encompass
details about feed mixtures, flow schemes and operating condi-
tions, all of which are hereinafter disclosed in the following
discussion of each of the facets of the present invention.
B~IEF DFSCRIPTIO~ OF T~ FIGUR~S
Figures 1, 2 and 3 are schematic representations
of the liquid effluent composition versu~ volume eluted from
an adsorbent-packed column during the pulse tests more fully
described in Example I, hereinafter.
D~SCRIPTION OF T~E IN~ENTION
At the outset the definitions of various terms used
throughout this specification will be useful in making clear
the operation, objects and advantages of the present invention.
A "feed mixture" is a mixture containing one or more
extract components and one or more raffinate components to
be fed to an adsorbent of the process. mhe term "feed stream"
indicates a stream of feed mixture which passes to an adsorbent
used in the process.
An "extract component" is a type of compound or a
compound that is more selectively adsorbed by the adsorbent
while a "raffinate component" is a compound or type of com-
pound that is less selectively adsorbed. In this process,
1,3-butadiene is the extract component and one or more
other C4 hydrocarbons is a raffinate component. The term
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~ m /
~l2~ 63
"raffinate stream" or "raffinate output stream" means a
stream through which a raffinate component is removed from
an adsorbent. The composition of the raffinate stream can
vary from es3entially 100~ desorbent material ~hereinafter
defined~ to essentially 100%
J~ - 3a -
r~:~
rm/ l
~ 3Z ~3
raffinate components. The term "extract stream" or "extract output
stream" shall mean a stream through which an extract material which
has been desorbed by a desorbent material is removed from the adsor-
bent. The composition of the extract stream, likewise, can vary from
essentially 100~ desorbent material to essentially 100% extract com-
ponents. Although it is possible by the process of this invention
to produce high-purity extract product (hereinafter defined) or a
raffinate product (hereinafter defined) at high recoveries, it will
be appreciated that an extract component is never completely adsorbed
by the adsorbent, nor is a raffinate component completely non-adsorbed
by the adsorbent. Therefore, small amounts of a raffinate component
can appear in the extract stream and likewise, small amounts of an
extract component can appear in the raffinate stream. The extract
and raffinate streams then are further distinguished from each other
and from the feed mixture by the ratio of the concentrations of an
extract component and a specific raffinate component, both appearing
in the particular stream. For example, the ratio of concentration of
the more selectively adsorbed 1,3-butadiene to the concentration of
less selectively adsorbed other C4 hydrocarbons will be highest in
the extract stream, next highest in the feed mixture, and lowest in
the raffinate stream. Likewise~ the ratio of the less selectively
adsorbed other C4 hydrocarbons to the more selectively adsorbed
1,3-butadiene will be highest in the raffinate stream, next highest
in the feed mixture, and the lowest in the extract stream. The term
"desorbent material" shall mean generally a material capable of de-
sorbing an extract component. The term "desorbent stream" or "desor-
bent input stream" indicates the stream throug~f which desorbent mate-
rial passes to the adsorbent. When the extract stream and the raffinate
~27~3Ztii3
stream contain desorbent materials, at least a portion of the ex-
tract stream and preferably at least a portion of the raffinate
stream from the adsorbent will be passed to separation means, typ-
ically fractionators, where at least a portion of desorbent material
will be separated at separation conditions to produce an extract
product and a raffinate product. The terms "extract product" and
"raffinate product" mean products produced by the process contain-
ing, respectively, an extract component and a raffinate component
in higher concentrations than those found in the respective extract
stream and the raffinate stream. The term "selective pore volume"
of the adsorbent is defined as the volume of the adsorbent which
selectively adsorbs extract components from a feed mixture. The
term "non-selective void volume" of an adsorbent is the volume of an
adsorbent which does not selectively retain an extract component from
a feed mixture. This volume includes the cavities of the adsorbent
which contain no adsorptive sites and the interstitial void spaces
between adsorbent particles. The selective pore volume and the non-
selective void volume are generally expressed in volumetric quantities
and are of importance in determining the proper flow rates of fluid
required to be passed into the process for efficient operations to
take place for a given quantity of adsorbent.
1,3-Butadiene, industrially the most important diolefin~ is
used to produce polymer components used, for example, in synthetic
rubber and is also used as a chemical intermediate for a great va-
riety of compounds.
Butadiene is synthesized commercially by four main methods:
(1) by catalytic dehydrogenation of concentrated n-butylenes; ~2~ by
catalytic dehydrogenation o~ n-butane; (3) as a by-product, in rather
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low yield, from severe high-temperature cracking of liquid hydro-
carbons for production of unsaturates; and (4) from ethyl alcohol
by a combination of catalytic dehydrogenation and dehydration.
The first two methods are the most frequently used methods.
All of the conversion processes yield products in which
1,3-butadiene is mixed with other closely bolling hydrocarbons.
For example, when concentrated 2-butene and l-butene are catalyt-
ically dehydrogenated to produce 1,3-butadiene the stabilized
effluent from this operation contains, in addition to 1,3-butadiene,
unreacted isomeric n-butenes, some n-butane, isobutane, isobutylene,
appreciable concentration of C3 components, and small concentrations
of components heavier than C4 hydrocarbons.
Table 1 below lists the hydrocarbons frequently found in
crude butadiene fractions from such sources and is indicative of the
composition of the feed mixture that might be expected for use in the
process of the present invention. The relative amounts of these hy-
drocarbons present in crude butadiene vary considerably, depending
upon the type of hydrocarbon conversion process employed. Other C4
unsaturates, primarily monoolefins, are always present in major
amounts. Non-conjugated diolefins and acetylenes are minor consti-
tuents, but they generally increase with increasing temperature dur-
ing hydrocarbon conversion. For the most part, however, they are
highly objectionable contaminants in purified butadiene and hence
their concentrations in the latter must be carefully controlled.
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TABLE 1
COMPOSITION OF CRUDE BUTADIENE FRACTIONS
C Vol. %
C3 Hydrocarbons 0.9
Isobutylene -6.9 27.7
l-Butene -6.3 17.2
1,3-Butadiene -4.4 39.1
n-Butane -0.5 4.1
t-2-Butene +0.9 6.0
c-2-Butene +3.7 ~.5
C4 Acetylenes +5.1 0.2
1,2-Butadiene ~10.9 CO.l
C5 Hydrocarbons o.l
To separate the 193-butadiene from a feed mixture in
accordance with the presPnt invention, the mixture is contacted
with the adsorbent and the 1,3-butadiene is more selectively
adsorbed and retained by the adsorbent while the other components
of the feed mixture are relatively unadsorbed and are removed
from the interstitial void spaces between the particles of adsor-
bent and the surface of the adsorbent. The adsorbent containing
the more selectively adsorbed 1,3-butadiene is referred to as a
"rich" adsorbent. The 1,3-butadiene is then recovered from the
~0 rich adsorbent by contact;ng the rich adsorbent with a desorbent
material.
The term i'desorbent material" as used herein shall mean
any fluid substance capable of removing a selectively adsorbed feed
~2}7~ 63
component from the adsorbent. Generally, in a swin~-bed system in
which the selectively adsorbed feed component is removed from the
adsorbent by a purge stream, desorbent material selection is not too
critical and desorbent materials comprising gaseous hydrocarbons such
as methane, ethane, etc., or other types of gases such as nitrogen
or hydrogen may be used at elevated temperatures or reduced pres-
sures or both to effectively purge the adsorbed feed component from
the adsorbent. However, in adsorptive separation processes which
are generally operated continuously at substantially constant pres-
sures and temperatures to ensure liquid phase, the desorbent material
relied upon must be judiciously selected to satisfy several criteria.
First, the desorbent material must displace the extract components
from the adsorbent with reasonable mass flow rates without itself
being so strongly adsorbed as to unduly prevent the extract compo-
nent from displacing the desorbent material in a following adsorption
cycle. Expressed in terms of the selectivity (hereinafter discussed
in more detail), it is preferred that the adsorbent be more selective
for the extract component with respect to a raffinate component than
it is for the desorbent material with respect to a raffinate compo-
nent. Secondly, desorbent materials must be compatible with the par-
ticular adsorbent and the particular feed mixture. More specifically,
they must not reduce or destroy the critical selectivity of the ad-
sorbent for the extract components with respect to the raffinate
component. Desorbent materials to be used in the process of this
invention should additionally be substances which are easily sepa-
rable from the feed mixture that is passed into the process. After
desorbing the extract components of the feed, both desorbent material
and the extract components are typically removed in admixture from
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the adsorbent. Likewise, one or more raffinate components is typ-
ically withdrawn from the adsorbent in admixture with desorbent
material and without a method of separating at least a portion of
desorbent material, such as distillation, neither the purity of the
extract product nor the purity of the raffinate product would be
very high. It is therefore contemplated that any desorbent material
used in this process will have a substantially different average
boiling point than that of the feed mixture to allow separation of
desorbent material from feed components in the extract and raffinate
streams by simple fractionation thereby permitting reuse of desor-
bent material in the process. The term "substantially different"
as used herein shall mean that the difference between the average
boiling points between the desorbent material and the feed mixture
shall be at least about ~C. The boiling range of the desorbent
material may be higher or lower than that of the feed mixture.
In the preferred isothermal, isobaric, liquid-phase opera-
tion of the process of this invention, it has been found that the
effective desorbent materials comprise hydrocarbons, particularly a
C3 or C5 through C1O n-olefin. The ability to operate in the liquid
phase, in contradistinction to the aforementioned U.S. Patent to
Dassesse, is a distinct advantage in view of the energy savings and
relative simplicity of operation.
The prior art has recognized that certain characteristics
of adsorbents are highly desirable, if not absolutely necessary, to
the successful 6peration of a selective adsorption process. Among
such characteristics are: adsorptive capacity for some volume of an
extract component per volume of adsorbent; the selective adsorption
of an extract component with respect to a raffinate component and
the desorbent material~ and~ sufficiently fast rates of adsorption
and desorption of the extract components to and from the adsorbent.
_g_
82~3
Capacity of the adsorbent for adsorbing a specific volume
of one or more extract components is, of course, a necessityi without
such capacity the adsorbent is useless for adsorptive separation.
Furthermore, the higher the adsorbent's capacity for an extract com-
ponent the better is the adsorbent. Increased capacity of a particu-
lar adsorbent makes it possible to reduce the amount of adsorbent
needed to separate the extract component contained in a particular
charge rate of feed mixture. A reduction in the amount of adsorbent
required for a specific adsorptive separation reduces the cost of the
separation process. It is important that the good initial capacity
of the adsorbent be maintained during actual use in the separation
process over some economically desirable life.
The second necessary adsorbent characteristic is the ability
of the adsorbent to separate components of the feed; or, in other
words, that the adsorbent possess adsorptive selectivity, (B) for one
component as compared to another component. Relative selectivity can
be expressed not only for one feed component as compared to another
but can also be expressed between any feed mixture component and the
desorbent material. The selectivity, ~B), as used throughout this
specification is defined as the ratio of the two components of the
adsorbed phase over the ratio of the same two components in the unad-
sorbed phase at equilibrium conditions.
Relative selectivity is shown as Equation 1 below:
Equation 1
Selectivity = (B~ = [vol. percent C/vol. percent D3A
[vol. percent C/vol. percent D U
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~ 7~3Z Çj3
where C and D are two components of the feed represented in volume
percent and the subscripts A and U represent the adsorbed and unad-
sorbed phases respectively. The equilibrium conditions are deter-
mined when the feed passing over a bed of adsorbent does not change
composition after contacting the bed o-f adsorbent. In other words,
there is no net transfer of material occurring between the unad-
sorbed and adsorbed phases.
Where selectivity of two components approaches 1.0 there
is no preferential adsorption of one component by the adsorbent with
respect to the other; they are both adsorbed (or non-adsorbedl to
about the same degree with respect to each other. As the (B) becomes
less than or greater than 1.0 there is a preferential adsorption by
the adsorbent for one component with respect to the other. When
comparing the selectivity by the adsorbent of one component C over
component D, a ~B) larger than 1.0 indicates preferential adsorption
of component C within the adsorbent. A (B) less than 1.0 would in-
dicate that component D is preferentially adsorbed leaving an unad-
sorbed phase richer in component C and an adsorbed phase richer in
component D. While separation of an extract component from a raf-
finate component is theoretically possible when the selectivity of
the adsorbent for the extract component with respect to the raffinate
component just exceeds a value of 1.0, it is preferred that such
selectivity have a value approaching or exceeding 2. Like relative
volatility, the higher the selectivity the easier the separation is
to perform. Higher selectivities permit a smaller amount of adsor-
bent to be used in the process. Ideally desorbent materials should
have a selectivity equal to about 1 or less than 1 with respect to
all extract components so that all of the extract components can be
_ 1 1
~7~3~263
extracted as a class and all raffinate components clearly rejected
into the raffinate stream.
The third important characteristic is th~ rate of exchange
of tne extract component of the feed mixture material, or in other
words, the relative rate of desorption of the extract component.
This characteristic relates d;rectly to the amount of desorbent mate-
rial that must be employed in ~he process to recover the extract com-
ponent ~rom the adsorbent; faster rates of exchange reduce the amount
of desorbent material needed to remove the extract component and
therefore permit a reduction in the operating cost of the process.
With faster rates of exchange, less desorbent material has to be
pumped through the process and separated from the extract stream for
reuse in the process.
A fourth important property o~ the adsorbent is the degree,
or lack thereof, it chemically reacts with or causes chemical change
to the feed and desorbent components. The above U.S. Patents to Baker
and Priegnitz, ~or example, teach the use of zeolitic materials as ad-
sorbents. Such materials, however, are known to react with hydrocar-
bons, particularly olefins. In contradistinction to such chemically
active adsorbents, the carbon adsorbents of the present invention
are chemically inert to the components of the process streams.
In order to test various adsorbents and desorbent material
with a particular feed mixture to measure the adsorbent characteris-
tics of adsorptive capacity and selectivity and exchange rate, a
dynamic testing apparatus is employed. The apparatus consists of an
adsorbent chamber of approximately 70 cc volume having inlet and out-
let portions at opposite ends of the chamber.~ The chamber is contained
within a temperature control means and? in additio~, pressure control
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equipment is used to operate the chamber at a constant predeter-
mined pressure. Chromatographic analysis equipment can be attached
to the outlet line of the chamber and used to analyze "on-stream"
the effluent stream leaving the adsorbent chamber.
A pulse test, performed using this apparatus and the fol--
lowing general procedure, is used to determine selectivities and
other data for various adsorbent systems. The adsorbent is filled to
equilibrium with a particular desorbent by passing the desorbent ma-
terial through the adsorbent chamber. At a convenient time, a pulse
of feed containing known concentrations of a non-adsorbed paraffinic tracer
~n-nonane for instance) and of the particular feed mixture of C4 hydrocarbons
diluted in desorbent is injected for a duration of several minutes
Desorbent flow is resumed, and the tracer and the constituents of the feed
mixture are eluted as in a liquid-solid chromatographic operation.
The effluent can be analyzed by on-stream chromatographic equip-
ment and traces of the envelopes of corresponding component peaks
developed. Alternately9 effluent samples can be collected period-
ically and later analyzed separately by gas chromatography.
From information derived from the chromatographic traces,
adsorbent performance can be rated in terms of capacity index for
an extract component9 selectivity for one C4 hydrocarbon with re-
spect to the other, and the rate of desorption of an extract com-
ponent by the desorbent. The capacity index may be characteri~ed
by the distance between the center of the peak envelope of the
selectively adsorbed Gomponent and the peak envelope of the tracer
component or some other known reference point. It is expressed in
terms of the volume in cubic centimeters of desorbent pumDed during
this time interval. Selectivity, (B), for an extract component with
13
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I_spect to a raLEinate component mcly be characterize(l by the riatio
of the clistance between the center of an extract component peak
envelol-e and the tracer peak ellveLope (or other reference polnt)
to thc corresponcling distance between the center of a raffinate
componellt peak envelope and the tracer peak envelope. The rate of
exchange of an extract component with the desorbent can generally
be characterized by the width of the peak envelopes at half
intens:ity. The narrower the peak width the faster the desorption
rate. The desorption rate can also be characterized by the distance
between the center of the tracer peak envelope and the disappearance
of an extract component which has just been desorbed. This distance
is again the volume of desorbent pumped during this time interval.
The adsorbent to be used in the process of this invention
comprises what is known as activated carbon or molecular sieve
carbon. Activated carbon is a common, commercially available mater-
ial, s-lch as Calgon Corporation's "Type PCB" granular carbon, or Union
Carbide Corporation's materlal having the trade-mark "PURASIV".
Type PCB as described in Calgon's brochure No. 23-108a, dated
August 1978, is an activated carbon having a large portion of micro-
pore volume in pores of 15 to 20 Angstrom units in diameter permeatedby a system of macropores larger than 1000 Angstroms in diameter.
PURASIV, as described in Union Carbide's brochure F-4866815M, is a
beaded activated carbon made from molten petroleum pitch shaped into
spherical particles and subsequently carbonized and activated.
The term "molecular sieve carbon" as used herein is not
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sl~:
` ` ~
il27~32 Eii3
intended to necessarily distinguish from those materials referred
to as "activated carbon" but to ensure that no material effective
for use in the present invention is excluded. There is consider-
able overlap between the two terms in question and probably in
most instances, for purposes of the present invention, the terms
are interchangeable. The particular molecular sieve carbons known
to be effective for use in the present invention are those having
an average pore size in excess of about 5 Angstrom units.
The adsorbent may be in the form of particles such as
extrudates, aggregates, tablets, macrospheres or granules having
a desired particle range, preferably from about 16 to about 60
mesh (Standard U,S, Mesh) which corresponds to a nominal aperture nf
1.1~ mm to 0.25 mm. Less water content in the adsor6ent is advantaqeous
from the standpoint of less water contamination of the product.
The adsorbent may be employed in the form of a dense
fixed bed which is alternatively contacted with a feed mixture
and a desorbent material in which case the process will be only
semi-continuous. In another embodiment, a set of two or more
static beds of adsorbent may be employed with appropriate valv;ng
so that a feed mixture can be passed through one or more adsor-
bent beds of a set while a desorbent material can be passed
through one or more of the other beds in a set. The flow of a
feed mixture and a desorbent material may be either up or down
through an adsorbent in such beds. Any of the conventional
apparatus employed in static bed fluid-solid contacting may be
used.
Moving bed or simulated moving bed Jflow systems, however,
have a much greater separation efficiency than fixed bed systems
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and are therefore preferred. In the moving bed or simulated moving
bed processes, the retention and displacement operations are con-
tinuously taking place which allows both continuous production of
an extract and a raffinate stream and the continual use of feed and
displacement fluid streams. One preferred embodiment of this pro-
cess utilizes what is known ;n the art as the simulated moving bed
countercurrent flow system. In such a system, it is the progressive
movement of multiple liquid access points down a molecular sieve
chamber that simulates the upward movement of molecular sieve con-
tained in the chamber. Reference can also be made to D.B. Broughton's
U.S. Patent 2,985,589, in which the operating principles and sequence
of such a flow system are described, and to a paper entitled, "Con-
tinuous Adsorptive Processing -- A New Separation Technique" by D.B.
Broughton presented at the 34th Annual Meeting of the Society of
Chemical Engineers at Tokyo, Japan on April 29 lg69,
for further explanation of the
simulated moving bed countercurrent process flow scheme.
Another embodiment of a simulated moving bed flow system
suitable for use in the process of the present invention is the
co-current high efficiency simulated moving bed process disclosed
in U.S. Patent 4,402,832 to Gerhold.
It is contemplated that at least a portion of the extract
output stream will pass into a separation means wherein at least a
portion of the desorbent material can be separated at separating
conditions to produce an extract product containing a reduced con-
centration of desorbent material. Preferably, ~ut not necessary to
the operation of the process, at least a portion of the raffinate
, ~
~,
-16-
~2q~3
output stream will also be passed to a separation means wherein at
least a portion of the desorbent material can be separated at sepa-
rat;ng conditions to produce a desorbent stream which can be reused
in the process and a raffinate product containing a reduced concen-
tration of desorbent material. Typically the concentration of
desorbent material in the extract procluct and the raffinate product
will be less than about 5 vol. % and more preferably less than about
1 vol. %. The separation means will typically be a fractionation
column, the design and operation of which is well known to the
separation art.
Although both liquid and vapor phase operations can be
used in many adsorptive separation processes, liquid-phase operation
is required for this process because of the lower temperature and
energy requirements and because of the higher yields of an extract
product that can be obtained with liquid-phase operation over those
obtained with vapor-phase operation. Adsorption conditions will
include a temperature range of from about 20C to about 250C, with
about 100C to about 200C being more preferred, and a pressure
sufficient to maintain liquid phase. Desorption conditions will
include the same range of temperatures and pressure as used for
adsorption conditions.
The size of the units which can utilize the process of
this invention can vary anywhere from those of pilot-plant scale
(see for example U.S. Patent 3,706,812) to those of commercial
scale and can range in flow rates from as little as a few cc an
hour up to many thousands of gallons per hour.
The following examples are presented for illustration
purposes and more specifically are presented to illustrate the
~782~ii3
selectivity relationships that make the process of the invention
possible. Reference to specific desorbent materials, ~eed mix-
tures and operating conditions is not intended to unduly restrict
the scope and spirit of the claims attached hereto.
EXAMPLE I
In this experiment, three pulse tests were performed to
evaluate the ability of the present invention to separate 1,3-
butadiene from other C4 hydrocarbons using three different carbon
adsorbents.
The testing apparatus was the above described pulse test
apparatus. For each pulse test, the column was maintained at a
temperature of 65C and a pressure sufficient to maintain liquid-
phase operations. Gas chromatographic analysis equipment was at-
tached to the column effluent stream in order to determine the
composition of the effluent material at given time intervals. The
feed mixture employed for each test contained about 5 vol. % each
of isobutane, normal butane, isobutylene, trans butene-2, cis-butene-2
and 1,3-butadiene and 70 vol. % desorbent material. The desorbent
material was hexene-l. The operations taking place for each test
were as follows. The desorbent material was run continuously at a
nominal liquid hourly space velocity (LHSV~ of 1.0 which amounted
to about l.l7 cc per minute feed rate of desorbent. At some con-
venient time interval the desorbent was stopped and the feed mix-
ture was run for a 10 minute interval at a rate of 1.0 cc per min-
ute. The desorbent stream was then resumed at l LHSY and continued
to pass into the adsorbent column until all of the feed components
had been eluted from the column as deter~ined by observing the
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2~3
chromatograph generated by the effluent material leaving the adsorp-
tion column. The sequence of operations usually takes about an
hour. The 10 minute pulse of feed and subsequent desorption may be
repeated in sequence as often as is desired. The chromatograph
tracings obtained are as shown in the attached Figures 1, 2 and 3.
Selectivities derived from the traces are given in Table 2, the
reference curve being isobutane which is presumed to be totally
non-adsorbed.
TABLE 2
Figure No. 1 2 3
Adsorbent Calgon ~olecular
PCB PurasivSieve Carbon
1,3-butadiene/n-butane 6.26 6.17 5.75
1,3-butadiene/isobutylene - 2.59 2.54 3.74
1,3-butadiene/trans-butene 2.05 2.12 2.13
1,3-butadiene/cis-butene2.06 2.18 2.17
-
The tracings of the figures for all three tests show a
clear and distinct separati~n of 1,3-butadiene from the other feed
components. The 1,3-butadiene is the last component to elute from
each pulse test which is indicative of being the most selectively
retained component with all three adsorbents. The high selectivities
given in Table 2 for 1,3~butadiene derived from the curves provides
a quantitative measure of the high degree of relative retention of
the 1,3 butadiene.
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