US0096.

88591B2

(12) United States Patent (10) Patent No.: US 9,688,591 B2

Sawyer et al. (45) Date of Patent: Jun. 27, 2017
(54) ETHYLENE SEPARATION PROCESS (56) References Cited
U.S. PATENT DOCUMENTS
(71) Applicants: Gary A. Sawyer, Media, PA (US);
Robert S. Bridges, Friendswood, TX 3,349,147 A * 10/1967 Clay et al. .................... 585,628
(US); Steven T. Coleman, Humble, TX 6,884,917 B1 * 4/2005 Coleman ......... ... 585,643
(US); Allen David Hood, Jr., Houston, 7,214,841 B2 * 5/2007 Gartside et al. .............. 585,324
TX (US) 7,525,007 B2 4/2009 Sumner
7,586,018 B2* 9/2009 BoZZano et al. .............. 585/.317
7,964,762 B2 6, 2011 Bouvart et al.
(72) Inventors: Gary A. Sawyer, Media, PA (US); 8,586,813 B2 11/2013 Ramachandran et al.
Robert S. Bridges, Friendswood, TX 2004/0254414 A1 12, 2004 Hildreth et al.
(US); Steven T. Coleman, Humble, TX 2006,0004242 A1* 1 2006 Verma et al. ................. 585,809
(US); Allen David Hood, Jr., Houston, 2006, O161033 A1 7/2006 Chodorge et al.
2008. O154077 A1* 6/2008 Bozzano et al. .............. 585,314
TX (US)
(Continued)
(73) Assignees: Equistar Chemicals, LP, Houston, TX
(US); Lyondell Chemical Technology, FOREIGN PATENT DOCUMENTS
L.P., Houston, TX (US) EA O14835 B1 2, 2011
RU 2006116190 A 12/2007
(*) Notice: Subject to any disclaimer, the term of this WO WO-2011113836 A1 9, 2011
patent is extended or adjusted under 35
U.S.C. 154(b) by 51 days. OTHER PUBLICATIONS
(21) Appl. No.: 13/738,685 James R. Fair, “Distillation.” Aug. 17, 2001, Wiley, Kirk-Othmer
Encyclopedia of Chemical Technology, p. 756.*
(22) Filed: Jan. 10, 2013 (Continued)
(65) Prior Publication Data
Primary Examiner — Tam M. Nguyen
US 2014/O194664 A1 Jul. 10, 2014
(57) ABSTRACT
(51) Int. C.
Ethylene separation processes are described herein. The
CD7C 4/6 (2006.01) ethylene separation processes generally include introducing
C07C 7/04 (2006.01) a feed stream including ethylene and butene into a de
CD7C 6/04 (2006.01) ethenizer, and separating the ethylene from the butene via
(52) U.S. C. fractional distillation within the de-ethenizer to form an
CPC ......... - - - - - - - - - C07C 704 (2013.01); C07C 4/06 overhead stream including separated ethylene and a bottoms
(2013.01); C07C 6/04 (2013.01) stream including separated butene, wherein the de-ethenizer
(58) Field of Classification Search operates at a pressure of less than 350 psig.
USPC ...... - - - - - - - - - - - - - - 585/643, 644; 62/620, 632, 634

See application file for complete search history. 6 Claims, 1 Drawing Sheet
 US 9,688,591 B2
Page 2

(56) References Cited

U.S. PATENT DOCUMENTS
2010, 0145120 A1* 6, 2010 Bouvart .................... CO7C 4/O2
585,324
2012fOO95275 A1 4/2012 Coleman et al.
2013,0245.348 A1 9, 2013 Vermeiren et al.
2014/0081061 A1* 3/2014 Stanley ................. CO7C 5/2512
585,314

OTHER PUBLICATIONS
S. H. Lee et al., "Optimize design for distillation feed,” Jun. 2011,
Hydrocarbon Processing, p. 2.*
Singapore Search Report and Written Opinion for SG Application
No. 1120 1504150R mailed May 3, 2016.
* cited by examiner
U.S. Patent Jun. 27, 2017 US 9,688,591 B2

Ea

F.G. f.

F.G. 2
 US 9,688,591 B2
1. 2
ETHYLENE SEPARATION PROCESS One or more embodiments include the process of any
preceding paragraph, wherein the first pressure ranges from
CROSS-REFERENCE TO RELATED 250 psig to 325 psig and the second pressure ranges from
APPLICATIONS 300 psig to 400 psig.
One or more embodiments include the process of any
Not applicable. preceding paragraph, wherein a difference between the sec
ond pressure and the first pressure is from 50 psig to 100
STATEMENT REGARDING FEDERALLY psig.
SPONSORED RESEARCH OR DEVELOPMENT One or more embodiments include the process of any
10
preceding paragraph further including condensing a portion
Not applicable. of the overhead stream to form a recycle ethylene stream and
introducing the recycle ethylene stream to the de-ethenizer,
BACKGROUND wherein the overhead stream is compressed prior to con
15
densing.
Field of the Invention One or more embodiments include the process of any
The present invention generally relates to ethylene sepa preceding paragraph, further including introducing fresh
ration processes. More particularly, the present invention ethylene to the de-ethenizer as reflux supplement.
generally relates to ethylene separation within a propylene One or more embodiments include the process of any
production process. preceding paragraph, wherein the de-ethenizer operates at a
Related Art pressure of less than 350 psig.
This section introduces information from the art that may One or more embodiments include the process of any
be related to or provide context for some aspects of the preceding paragraph, wherein the feed stream further includ
techniques described herein and/or claimed below. This ing propylene.
information is background facilitating a better understand 25 One or more embodiments include the process of any
ing of that which is disclosed herein. This is a discussion of preceding paragraph further including condensing a portion
“related art. That such art is related in no way implies that of the overhead stream to form a recycle ethylene stream and
it is also “prior art. The related art may or may not be prior introducing the recycle ethylene stream to the de-ethenizer.
art. The discussion is to be read in this light, and not as One or more embodiments include the process of any
admissions of prior art. 30
preceding paragraph, wherein the fresh ethylene is intro
Ethylene separation processes within propylene produc duced to the de-ethenizer at a temperature of from -20° F.
tion processes often exchange fresh ethylene with the feed to to 10° F.
the ethylene separation process prior to introduction of the One or more embodiments include the process of any
fresh ethylene to a metathesis reaction. However, efforts are 35 preceding paragraph, wherein the metathesis product stream
continuously underway to improve ethylene separation pro is introduced to the de-ethenizer at a temperature of from 50°
cesses, including reducing energy requirements and other F. to 90°F.
costs in propylene production processes. One or more embodiments include the process of any
The present invention is directed to resolving, or at least preceding paragraph, wherein the metathesis product stream
reducing, one or all of the problems mentioned above. 40 is introduced to the de-ethenizer at a pressure of from 250
SUMMARY
psig to 350 psi.g.
The above paragraphs present a simplified Summary of
the presently disclosed subject matter in order to provide a
Various embodiments of the present invention include basic understanding of Some aspects thereof. The Summary
ethylene ene separation processes. The ethylene separation 45 is not an exhaustive overview, nor is it intended to identify
processes generally include introducing a feed stream key or critical elements to delineate the scope of the subject
including ethylene and butene into a de-ethenizer, and matter claimed below. Its sole purpose is to present some
separating the ethylene from the butene via fractional dis concepts in a simplified form as a prelude to the more
tillation within the de-ethenizer to form an overhead stream detailed description set forth below.
including separated ethylene and a bottoms stream including 50
separated butene, wherein the de-ethenizer operates at a BRIEF DESCRIPTION OF DRAWINGS
pressure of less than 350 psig,
Various embodiments of the present invention further The claimed subject matter may be understood by refer
include processes for producing propylene. The processes ence to the following description taken in conjunction with
generally include reacting a metathesis feed stream includ 55 the accompanying drawings, in which like reference numer
ing butene with ethylene in the presence of a metathesis als identify like elements, and in which:
catalyst via a metathesis reaction to form a metathesis FIG. 1 illustrates an embodiment of a propylene produc
product stream including propylene, ethylene and butene; tion process.
separating the ethylene from the propylene via fractional FIG. 2 illustrates an alternate embodiment of a propylene
distillation within a de-ethenizer to forman overhead stream 60 production process.
including separated ethylene and a bottoms stream including While the invention is susceptible to various modifica
separated butene and propylene; and recycling the overhead tions and alternative forms, the drawings illustrate specific
stream from the de-ethenizer to the metathesis reaction in embodiments herein described in detail by way of example.
the form of vapor. It should be understood, however, that the description herein
One or more embodiments include the process of any 65 of specific embodiments is not intended to limit the inven
preceding paragraph further including compressing the over tion to the particular forms disclosed, but on the contrary, the
head stream from a first pressure to a second pressure. intention is to cover all modifications, equivalents, and
 US 9,688,591 B2
3 4
alternatives falling within the spirit and scope of the inven tion, for example. The metathesis catalyst may include from
tion as defined by the appended claims. 1 wt.% to 30 wt.% or from 5 wt.% to 20 wt.% transition
metal oxide, for example.
DETAILED DESCRIPTION The metathesis reaction may further include contacting
the butene with ethylene in the presence of an isomerization
Illustrative embodiments of the subject matter claimed catalyst (either sequentially or simultaneously with the
below will now be disclosed. In the interest of clarity, not all metathesis catalyst). The isomerization catalyst is generally
features of an actual implementation are described in this adapted to convert 1-butene present in the metathesis feed
specification. It will be appreciated that in the development stream to 2-butene for Subsequent reaction to propylene.
of any such actual embodiment, numerous implementation 10 Isomerization catalysts may include Zeolites, metal oxides
specific decisions must be made to achieve the developers (e.g., magnesium oxide, tungsten oxide, calcium oxide,
specific goals, such as compliance with system-related and barium oxide, lithium oxide and combinations thereof),
business-related constraints, which will vary from one mixed metal oxides (e.g., silica-alumina, Zirconia-Silica),
implementation to another. Moreover, it will be appreciated acidic clays (see, e.g., U.S. Pat. No. 5,153,165; U.S. Pat. No.
that such a development effort, even if complex and time
15 4,992,613: U.S. Patent Publication 2004/0249229 and U.S.
consuming, would be a routine undertaking for those of Patent Publication 2006/0084831) and combinations
thereof, for example. In one or more specific embodiments,
ordinary skill in the art having the benefit of this disclosure. the catalyst is magnesium oxide. The magnesium oxide may
In the description below, unless otherwise specified, all have a surface area of at least 1 m/g or at least 5 m/g, for
compounds described herein may be substituted or unsub example.
stituted and the listing of compounds includes derivatives The isomerization catalyst may be Supported on a Support
thereof. Further, various ranges and/or numerical limitations material. Suitable Support materials include silica, alumina,
may be expressly stated below. It should be recognized that titania, silica-alumina and combinations thereof, for
unless stated otherwise, it is intended that endpoints are to example.
be interchangeable. Further, any ranges include iterative 25 The metathesis reaction may occur at a pressure of from
ranges of like magnitude falling within the expressly stated 150 psig to 600 psig, or from 200 psig to 500 psig, or from
ranges or limitations. 240 psig to 450 psig, for example. The metathesis reactions
Embodiments described herein include ethylene separa may occur at a temperature of from 100° C. to 500° C., or
tion processes. The ethylene separation processes are dis from 200° C. to 400° C., or from 300° C. to 350° C., for
cussed primarily herein with reference to separating a 30 example. The methathesis reaction may occur at a weight
metathesis product stream within a propylene production hourly space velocity (WHSV) of from 3 hr' to 200 hr',
process. However, it is contemplated that the ethylene or from 20 hr' to 40 hr', for example.
separation processes described herein may be utilized within The contact time needed to obtain a desirable yield of
any process requiring separation of ethylene from butene. metathesis reaction products depends upon several factors,
Propylene production processes generally includes react 35 Such as the activity of the catalyst, temperature and pressure,
ing a metathesis feed stream including n-butene with ethyl for example. However, in one or more embodiments, the
ene in the presence of a metathesis catalyst to form a length of time during which the metathesis feed stream and
metathesis product stream including propylene, ethylene, the ethylene are contacted with the catalyst can vary from
butene and Cs olefins. As used herein, the term “metath 0.1 s to 4 hours or from 0.5 s to 0.5 hours, for example. The
esis' refers to an equilibrium reaction between two olefins 40 metathesis reaction may be conducted batch-wise or con
where the double bond of each olefin is broken to form tinuously with fixed catalyst beds, slurried catalyst, fluidized
intermediate reactants. These intermediates recombine to beds, or by using any other conventional contacting tech
form new olefin products. In one or more specific embodi niques, for example.
ments discussed herein, the two olefins include ethylene and The metathesis product stream generally includes ethyl
butene and the new olefin product is propylene. 45 ene, propylene, Ca olefins, and Cs olefins (including pen
As discussed previously herein, n-butene is fed to the tene and hexene, for example). Therefore, the propylene
metathesis reaction via the metathesis feed stream. The production process often includes separating the compo
ethylene may be fed to the reaction by any suitable method nents of the metathesis product stream. An example of a
known to one skilled in the art. For example, the ethylene method of separation is shown in U.S. Pat. No. 7,214,841,
may be fed to the metathesis reaction via an inlet separate 50 which is hereby incorporated by reference, and such method
from an inlet utilized to feed the metathesis feed stream. generally includes separation within a fractionation system.
Alternatively, the ethylene may be combined with the As used herein, the term “fractionation” refers to processes
metathesis feed stream prior to the metathesis feed stream for the separation of components based on the relative
passing through Such inlet. volatility and/or boiling point of the components. The frac
Metathesis catalysts are well known in the art (see, e.g., 55 tionation processes may include those known in the art and
U.S. Pat. No. 4,513,099 and U.S. Pat. No. 5,120,894). the term “fractionation' can be used interchangeably with
Generally, the metathesis catalyst includes a transition metal the terms “distillation' and “fractional distillation' herein.
oxide. Such as transition metal oxides of cobalt, molybde The fractionation system generally includes a de-ethen
num, rhenium, tungsten and combinations thereof, for izer. The de-ethenizer receives and separates the metathesis
example. In one or more specific embodiments, the metath 60 product stream to form an overhead stream and a bottoms
esis catalyst includes tungsten oxide. The metathesis catalyst stream. The overhead stream is composed primarily of the
may be supported on a carrier, Such as silica, alumina, recovered ethylene and at least a portion of the overhead
titania, Zirconia, Zeolites, clays and mixtures thereof, for stream may be recycled back to the metathesis reaction
example. In one or more embodiments, the carrier is selected (discussed in further detail below). The bottoms stream
from silica, alumina and combinations thereof. The catalyst 65 generally includes the propylene, butene and Cs olefins.
may be Supported on a carrier by methods known in the art, Reflux is a distillation technique involving the condensa
Such as adsorption, ion-exchange, impregnation or Sublima tion of vapors and the return of this condensate to the system
 US 9,688,591 B2
5 6
from which it originated. Inside the distillation column, the stream. The de-butenizer overhead stream is composed
downflowing reflux liquid provides cooling and condensa primarily of the recovered butene and the de-butenizer
tion of the upflowing vapors, thereby increasing the effi bottoms stream generally includes the Cs olefins. Option
ciency of the distillation column. Typically, the reflux liquid ally, at least a portion of the de-butenizer overhead stream
is the portion of the overhead stream from a distillation may be recycled back to the metathesis reaction.
column that is returned to the upper part of the column. The processes described herein advantageously can
Often, the entire de-ethenizer overhead stream is condensed reduce heating requirements in the metathesis reactor and/or
to form a condensed stream, which may then be split into a the de-ethenizer, possibly by half of heating requirements
reflux liquid stream and a recycle ethylene stream. In Such for similar systems absent the embodiments of the invention.
processes, the recycle ethylene stream is returned to the 10
For example, embodiments described herein provide for a
metathesis reaction in liquid form. metathesis product stream entering the de-ethenizer having
One or more embodiments include partially condensing a temperature of from 50°F. to 90°F. and a pressure of from
the overhead stream to form a reflux liquid stream and a 250 psig to 350 psig, which may eliminate the need for heat
recycle ethylene stream, which may then be returned to the
metathesis reaction in vapor form. Alternatively, when no 15 exchange of the metathesis product stream.
portion of the overhead product will be utilized as reflux It is noted, however, that while the addition of a com
liquid, it is contemplated that the overhead stream may be pressor for the ethylene recycle stream may add capital cost
recycled (i.e., returned to the metathesis reaction) without to the process, lower system pressures in the metathesis
passing through a condenser. reaction and the de-ethenizer can offset the compressor
When recycling ethylene as vapor to the metathesis capital cost.
reaction, the ethylene vapor may be compressed via a Referring now to FIG. 1, a simplified process flow dia
compressor from a first pressure to a second pressure gram of a process 100 for producing propylene according to
sufficient to provide flow of the ethylene vapor to the embodiments disclosed herein is illustrated. FIG. 1 illus
metathesis reaction. In one or more embodiments, the first trates a process 100 including introducing a metathesis feed
pressure may range from 250 psig to 325 psig and the second 25 stream 102 to a metathesis reactor 104 having metathesis
pressure may range from 300 psig to 400 psig, for example. catalyst 105 (and optional isomerization catalyst—not
Alternatively, the difference in the first pressure and the shown) disposed therein to form metathesis product stream
second pressure may be from 50 psig to 100 psig, for 106 including propylene, ethylene, butene and Cs olefins.
example. One specific embodiment includes compressing FIG. 1 illustrates a specific embodiment wherein ethylene is
the overhead product to raise the condensing temperature 30
mixed with the metathesis feed stream 102 via line 108;
utilized in a Subsequent partial condenser. however, it is contemplated that the ethylene may contact the
One or more embodiments include introducing fresh metathesis feed stream via processes known in the art.
ethylene to the upper portion of the de-ethenizer, either in The metathesis product stream 106 is passed to a de
addition to, or as a replacement for the reflux liquid stream. ethenizer 110 to separate at least a portion of the ethylene
Accordingly, the fresh ethylene introduced to the de-ethen 35
izer is referred to as reflux supplement herein. As known in from the metathesis product stream 106 to form an overhead
the art, “fresh ethylene refers to ethylene that has not been stream 112 and a bottoms stream 114 including propylene
processed in the system being referred to, herein the pro and Ca olefins.
pylene production process. In one or more embodiments, the Fresh ethylene is introduced to the de-ethenizer 110 as
fresh ethylene is introduced to the de-ethenizer as reflux 40 reflux Supplement (in the same manner as the reflux liquid
supplement at a rate that is less than that of the reflux liquid ethylene is introduced to the de-ethenizer 110) via line 116.
Stream. In the specific embodiment illustrated in FIG. 1, the over
In one or more embodiments, the fresh ethylene/reflux head stream 112 is passed through a partial condenser 118 to
Supplement is introduced to the de-ethenizer at a tempera form a recycle ethylene stream 120 and a reflux liquid
ture of from -20°F. to 100°F., or from -10° F. to 50°F, or 45 stream 122. The recycle ethylene stream 120 is withdrawn
from -10° F. to 10° F. and a pressure of from 300 psig to from the partial condenser 118 as a vapor and is compressed
1000 psig, or from 400 psig to 900 psig, or from 600 psig to in compressor 128 and then recycled to the metathesis
800 psig, for example. reactor 104 via line 130. The reflux liquid stream 122 is
Generally, a de-ethenizer within a propylene production returned to the de-ethenizer 110.
process operates at a pressure of from 350 psig to 650 psig 50 Conversely, as shown in FIG. 2, the overhead stream 112
However, one or more embodiments of the present invention may be compressed within the compressor 128 prior to
include operating the de-ethenizer at a pressure lower than passing through the partial condenser 118, resulting in a
that referenced. For example, one or more embodiments higher condensing temperature than that shown in FIG. 1.
include operating the de-ethenizer at a pressure of less than As known in the art, the de-ethenizer bottoms stream 114
350 psig, or a pressure of less than 300 psig, or a pressure 55 may be passed through a re-boiler (not shown) and returned
of less than 250 psig. to the de-ethenizer 110 or further separated in additional
The fractionation system, in one or more embodiments, separation columns (not shown).
may further include a de-propenizer and a de-butenizer as Therefore, the present invention is well adapted to attain
known in the art. The de-propenizer may receive and sepa the ends and advantages mentioned as well as those that are
rate the bottoms stream (from the de-ethenizer) to form a 60 inherent therein. The particular embodiments disclosed
de-propenizer overhead stream and a de-propenizer bottoms above are illustrative only, as the present invention may be
stream. The de-propenizer overhead stream is composed modified and practiced in different but equivalent manners
primarily of the propylene product. The de-propenizer bot apparent to those skilled in the art having the benefit of the
toms stream generally includes the butene and Cs olefins. teachings herein. Furthermore, no limitations are intended to
The de-butenizer may receive and separate at least a 65 the details of construction or design herein shown, other than
portion of the de-propenizer bottoms stream to form a as described in the claims below. It is therefore evident that
de-butenizer overhead stream and a de-butenizer bottoms the particular illustrative embodiments disclosed above may
 US 9,688,591 B2
7 8
be altered, combined, or modified and all such variations are 2. The process of claim 1, further comprising condensing
considered within the scope and spirit of the present inven a portion of the overhead stream to form a recycle ethylene
tion. stream and introducing the recycle ethylene stream to the
The invention illustratively disclosed herein suitably may de-ethenizer.
be practiced in the absence of any element that is not 5 3. A process for producing propylene comprising:
specifically disclosed herein and/or any optional element reacting a metathesis feed stream comprising butene with
disclosed herein. While compositions and methods are ethylene in the presence of a metathesis catalyst via a
described in terms of “comprising.” “containing,” or metathesis reaction to form a metathesis product stream
“including various components or steps, the compositions comprising propylene, ethylene and butene;
and methods can also “consist essentially of or “consist of 10
introducing the metathesis product stream at a tempera
the various components and steps. All numbers and ranges ture of 50-90° F. and a pressure of 250-350 psig and a
disclosed above may vary by some amount. Whenever a fresh ethylene stream at a temperature of -20 to 10° F.
numerical range with a lower limit and an upper limit is into a de-ethenizer,
disclosed, any number and any included range falling within separating the ethylene from the propylene and butene via
the range are specifically disclosed. In particular, every 15
range of values (of the form, “from about a to about b,” or, fractional distillation within a de-ethenizer using the
equivalently, “from approximately a to b,” or, equivalently, ethylene separation process of claim 1 to form an
“from approximately a-b') disclosed herein is to be under overhead stream composed primarily of separated eth
stood to set forth every number and range encompassed ylene and a bottoms stream comprising separated
within the broader range of values. butene and propylene; and
This concludes the detailed description. The particular recycling the overhead stream from the de-ethenizer to the
embodiments disclosed above are illustrative only, as the metathesis reaction in the form of vapor.
invention may be modified and practiced in different but 4. The ethylene separation process of claim 1, wherein
equivalent manners apparent to those skilled in the art fresh ethylene is introduced to the de-ethenizer at a pressure
having the benefit of the teachings herein. Furthermore, no 25 of from 400-900 psig,
limitations are intended to the details of construction or 5. The process of claim 3, wherein the de-ethenizer
design herein shown, other than as described in the claims operates at a pressure of less than 300 psig.
below. It is therefore evident that the particular embodiments 6. A process for producing propylene comprising:
disclosed above may be altered or modified and all such reacting a metathesis feed stream comprising butene with
variations are considered within the scope and spirit of the 30
ethylene in the presence of a metathesis catalyst via a
invention. Accordingly, the protection sought herein is as set metathesis reaction to form a metathesis product stream
forth in the claims below.
What is claimed is: comprising propylene, ethylene and butene;
1. A process for producing ethylene comprising: separating the ethylene from the propylene and butene via
introducing a feed stream comprising ethylene, propylene 35 fractional distillation within a de-ethenizer using the
and butene into a de-ethenizer at a temperature of from ethylene separation process of claim 1 to form an
50-90° F. and a fresh ethylene stream is introduced to overhead stream composed primarily of separated eth
the de-ethenizer at a temperature of -20 to 10° F. and ylene and a bottoms stream comprising separated
a pressure of 400-900 psig, butene and propylene;
separating the ethylene from the butene via fractional 40 recycling the overhead stream from the de-ethenizer to the
distillation within the de-ethenizer to form an overhead metathesis reaction in the form of vapor;
stream comprising separated ethylene and a bottoms introducing fresh ethylene at a temperature of -20 to 10°
stream comprising separated butene; F. into the de-ethenizer at a pressure of from 400-900
wherein the de-ethenizer operates at a pressure of less than psig.
350 psig.