Note: Descriptions are shown in the official language in which they were submitted.
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PURIFICATION OF HYDROFORMYLATED AND HYDROGENATED FATTY
ALKYL ESTER COMPOSITIONS
This application claims the benefit of U.S. Provisional Application No.
60/958,473
filed July 6, 2007.
Subjecting a seed oil or vegetable oil to sequential operations of alkanolysis
(e.g.
methanolysis), hydroformylation and hydrogenation, yields a complex mixture of
saturated
and unsaturated compounds. These compounds have molecular weights that lead to
high
boiling points and low vapor pressui-es and often exhibit small differences in
their volatility
such that their separation via simple distillation becomes exceedingly
difficult, impractical
or economically unattractive. Boiling points in excess of 150 degrees
centigrade ( C) at-e
typical. A combination of low relative volatilities and high boiling points
poses a
significant engineering challenge when one seeks to separate ot- reduce levels
of one ot-
more compounds from the complex mixture and brings into play a myriad of
separation
operation possibilities. Selection of a combination of separation operations
that yields
I5 desirable component fractions, at least some of which, prefetably most of
which and more
preferably substantially all of which, have a composition suitable for further
processing or
reactions, while minimizing both yield loss and generation of undesirable
components (e.g.
"bad heavies" (discussed below)) and remaining commercially viable or
practical is far
from straightforward.
An aspect of an invention embodied in appended claims is a method of
separating at
least one component from a composition that comprises at least two seed oil
derivatives
(e.g. fatty acid alkyl esters, hydrogenated fatty acid alkyl esters,
hydroformylated fatty acid
alkyl esters oi- hydroformylated and hydrogenated fatty acid alkyl esters),
the method
comprising steps:
a. subjecting the composition to a first separation operation, the first
operation
comprising a short contact time or low residence time evaporation, a low
pressure (high
vacuum) operation, a stripping operation, or a polarity driven separation
operation, the first
separation selectively partitioning the composition into a first portion and a
first remainder;
b. subjecting the first remainder to at least one additional separation opet-
ation,
the additional operation comprising a short contact titne or low residence
time evaporation,
a low pressut-e operation, a stripping operation, or a polarity driven
separation operation,
each additional separation being the same as, or different frotn, each othet-
and the first
separation, the additional separation operation selectively partitioning the
first remaindei-
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into at least one additional portion and at least one additional remainder,
the additional
portion being the same as, or different from, the first portion; and
c. recycling at least a portion of the additional remainder to the first
separation
as a co-feed with the composition.
A preferred variation of the above method comprises a pre-treatment step that
precedes step a., the pre-treatment step comprising subjecting the composition
to conditions
sufficient to effectively de-gas the composition, thereby removing at least a
portion of
volatile compounds that have a normal boiling point (standard pressure and
tenlperature) of
less than 150 degrees centigrade ( C), using methyl capronate as a dividing
point for
removing volatile methyl esters.
Irrespective of whether one practices the above method or its preferred
variation, at
least one of the first separation operation and an additional separation
operation preferably
effects separation of saturated components of the composition from monol
(single hydroxyl
moiety) and diol (two hydroxyl moietes) fractions of the composition by way of
a simulated
moving bed (SMB).
In one illustrative embodiment of the above method or its preferred variation,
the
first portion comprises monols and diols and an additional separation effects
separation of
the first portion into a monol-rich fraction and a diol-rich fraction by way
of a simulated
moving bed.
Figure (Fig) 1 is a schematic block diagram that illustrates a first
separation
operation that separates a composition into a mixture of diols and heavies as
a first portion
and a mixture of saturates and monols as a first remainder. Fig 1 also shows
an additional
separation operation that separates the first remainder into a saturate
fraction and a monol
fraction.
Fig 2 is a schematic block diagram that illustrates a first separation
operation that
separates a composition into a first portion that primarily, preferably
substantially,
comprises saturated compounds present in the mixture and a first remainder
comprising
monols, diols and heavies. Fig 2 also shows an additional separation operation
that
separates the first remainde-- into a monol fraction and an additional
remainder comprising
diols and heavies.
Fig 3 is a graphic portrayal of vapor pressure of the components/fractions
identified
in Table 1 below.
Fig 4 is a schematic illustration of a series of cascaded SPE combinations in
conjunction with recycle as used in Example (Ex) 1 through Ex 4 below.
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Fig 5 is a schematic illustration of three connected SPEs in a cascaded mode
for
continuous operation as used in Ex 5 below.
Fig 6 is a schematic illustration of a variation of three connected SPEs in a
cascaded
mode for continuous operation as used in Ex 6 below.
Fig 7 is a schematic illustration of a combination of two packed distillation
columns
and one SPE as used in Ex 7 below.
Fig 8 is a schematic illustration of a combination of two packed distillation
columns
and one SPE as shown in Ex 11 below.
Fig 9 is schematic illustration of a SMB apparatus operation, showing
components
that have greater polar-ity classed as "slow moving" and those that have
lesser polarity as
"fast moving".
Fig 10 is a schematic illustration of separation scheme that uses two SMBs to
separate a seed oil derivative feed stream as shown in Ex 22 below.
Fig I I is a schematic illustration of a separation scheme based upon cascaded
SPEs
followed by an SMB as shown in Ex 23 - Ex 26 below.
Fig 12 is a schematic illustration of a SMB followed by parallel distillation
of
EXTRACT and RAFFINATE exiting the SMB as shown in Ex 27 - Ex 30 below.
Fig 13 is a schematic illustration of an ASPEN flow sheet for a method of
separating
that uses distillation for a first separation operation and SMB for an
additional separation as
shown in Ex 15 below.
Fig 14 is a schematic illustration of a SPE to provide a saturate-reduced
residue
stream (Heavies) with distillate being fed to multiple packed distillation
columns as shown
in Ex 31 below.
Fig 15 is a schematic illustration of a variation of Fig 14 using a WFE as a
specific
SPE as in Ex 32 below.
Unless stated to the contrary, implicit from the context, or customary in the
art, all
pat-ts and percents are based on weight. For purposes of United States patent
practice, the
contents of any patent, patent application, or publication referenced herein
are hereby
incorporated by reference in their entirety (or the equivalent US version
thereof is so
incorporated by reference) especially with respect to the disclosure of
synthetic techniques,
definitions (to the extent not inconsistent with any definitions provided
herein) and general
knowledge in the art.
The term "comprising" and derivatives thereof does not exclude the presence of
any
additional component, step or procedure, whether or not the same is disclosed
herein. In
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order to avoid any doubt, all compositions claimed herein through use of the
term
"comprising" may include any additional additive, adjuvant, or compound
whether
polymeric or otherwise, unless stated to the contrary. In contrast, the term,
"consisting
essentially of" excludes from the scope of any succeeding recitation any other
component,
step or procedure, excepting those that are not essential to operability. The
term "consisting
of" excludes any component, step or procedure not specifically delineated or
listed. The
term "or", unless stated otherwise, refers to the listed members individually
as well as in any
combination.
Expressions of temperature may be in terms either of degrees Fahrenheit ( F)
together with its equivalent in C or, more typically, simply in C.
The short contact time or low residence time evaporation operation occurs via
use of
an apparatus selected from a group consisting of a falling film evaporator
(FFE), a wiped
film evaporator (WFE), a rolled film evaporator (RFE), a horizontal evaporator
(HE), or a
short path evaporator (SPE). The short contact time or low residence time
evaporation
operation preferably works in combination with rectification. While a boiling
tube
evaporator (BTE) may be used as a short contact time or low residence time
evaporation
apparatus if desired, solvent removal represents a more typical use of a BTE.
The low pressure (high vacuum) operation occurs via use of an apparatus
selected
from a group consisting of various forms of a packed tower distillation
device. Such a
device is preferably a packed tower distillation device that contains an ultra-
low pressure
drop packed section. Where packing is present in a section, the packing is
preferably
structured packing. Structured packing typically comprises wire mesh or
corrugated metal
sheets that allow one to achieve higher mass transfer efficiency and a lower
pressure drop,
both relative to random-dumped packing. A packed section that contains
structured packing
also has a much lower pressure drop than a plurality of distillation trays due
at least in part
to a requirement to impose sufficient pressure to drive a gas flow through a
liquid layer
(also known as "liquid head") on each distillation tray.
The ultra-low pressure drop packed section has a pressure drop that is
preferably less
than or equal to about 20 millimeters of mercury (mm Hg) (2.7 kilopascals
(kPa)), more
preferably less than or equal to 15 mm Hg (2.0 kPa), still more preferably
less than or equal
to 10 mm Hg (1.3 kPa) and even more preferably less than or equal to 5 mm Hg
(0.6 kPa).
While certain pressure drop upper limits are noted above as pr-eferred upper
limits, all have
a lower limit of greater than 0 mm Hg (greater than 0 kPa) and, by way of
example, less
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than or equal to about 20 mm Hg necessarily includes all integers and real
numbers less
than or equal to 20 and greater than 0.
The stripping operation occurs via use of an apparatus selected from a group
consisting of a steam stripping device, an inert gas stripping device and a
condensable vapor
stripping device. Such a device may consist of a packed tower containing
structured
packing or random-dumped packing, a trayed tower containing distillation
trays, or a vessel
of any kind having provision for contacting steam, gas, or condensable vapor
with the liquid
phase.
The polarity driven separation operation occurs via use of a chromatographic
] 0 separation device, preferably a SMB separation device.
In practice of the above method or its preferred variation, the first
separation
operation preferably occurs via a packed distillation tower and the first
portion comprises
saturates.
The additional separation operation preferably occurs via an apparatus
comprising a
series of cascaded SPE and rectifier combinations and the additional
separation effects
removal of at least a portion of monols and diols contained in the first
remainder.
Other preferred options for respective first and additional separation
operation
combinations include: either a dividing wall column (DWC) or two low pressure
distillation
columns, one to remove saturates and monols from a seed oil derivative thereby
leaving a
fraction that comprises at least one diol and at least one heavy, and a second
to separate
saturates and monols to provide a monol rich portion, optionally with an
intermediate SPE
to remove heavies from the diols/heavies fraction; two low pressure
distillation columns,
one to remove saturates from a seed oil derivative thereby leaving a fraction
that comprises
at least one monol, at least one diol, and at least one heavy, and a second to
separate monols
from the fraction to provide a monol rich portion and a diols/heavies portion,
optionally
with a SPE following the second distillation column to remove heavies from the
diols/heavies fraction; a low pressure distillation column and a SMB, the
distillation column
to retnove saturates from a seed oil derivative thereby leaving a fraction
that comprises at
least one monol and at least one diol, and the SMB to separate monol(s) from
the fraction to
provide a monol-rich portion and a diol-rich portion, optionally in
combination with one or
more of a) a SPE to remove heavies from the seed oil derivative, thereby
providing a
purified seed oil derivative as a feed to the distillation column, b) a BTE
and a distillation
column to remove solvent from the monol-rich portion that exits the SMB, and
c) a BTE
and distillation column to remove solvent from the diol-rich portion that
exits the SMB; a
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series of cascaded combinations of a SPE and a rectifier and a SMB, the series
of cascaded
SPE/rectifier combinations to remove saturates from a seed oil derivative
thereby leaving a
monol/diol fraction that comprises at least one monol and at least one diol,
and the SMB to
separate monols from the monol/diol fraction to provide a monol-rich portion
and a diol-
rich portion, optionally in combination with one or more of d) a SPE to remove
heavies
from the seed oil derivative, thereby providing a purified seed oil derivative
as a feed to the
distillation column, e) a BTE and distillation column to remove solvent from
the monol-rich
portion that exits the SMB, and f) a BTE and distillation column to remove
solvent from the
diol-rich portion resulting from the SMB; a series of cascaded SPE and
rectifier
combinations for the first separation operation and a packed distillation
tower for the
additional separation operation; a series of cascaded SPEs operating in series
or with
recycle; two SMBs, the first to remove saturates and monols from a seed oil
derivative
thereby leaving a diol/heavy fraction that comprises at least one diol and at
least one heavy,
and a second to separate saturates and monols to provide a monol-rich portion,
optionally
in combination with one or more of g) an intermediate SPE to remove heavies
from the
diol/heavy fraction, h) a BTE and distillation column to remove solvent from
the monol-rich
portion that exits the SMB, and i) a BTE and distillation column to remove
solvent from the
diol-rich portion that exits the SMB; a SMB and a low pressure distillation
column or a
series of SPE/rectifier combinations, the SMB to separate saturates and monols
as a first
fraction from a seed oil derivative, thereby leaving a leaving a second or
diol-rich fraction
that comprises at least one diol, and the distillation column or series of
cascaded
SPE/rectifier combinations (also referred to as "evaporators with rectified
sections") to
separate saturates from the first fraction providing a monol-rich portion,
optionally with one
or more of j) a boiling tube evaporator and a distillation column to remove
solvent from the
diol-rich fraction, k) a BTE and distillation column to remove solvent from
the monol rich
portion, and 1) a BTE to remove heavies from the seed oil derivative, thereby
resulting in a
purified seed oil derivative feed to the SMB. Skilled artisans may use
guidance provided by
these preferred options to select other suitable apparatus choices for the
first and additional
separation operations from among the devices disclosed herein and their
variations.
When using a SMB to effect separation in accord with the present invention,
one
may select from a variety of combinations of solvent and media, some more
effective than
others. Skilled artisans who work with SMB apparatus readily understand use of
both
solvent and media. For purposes of the present invention, select desirable
solvents or
mixtures of solvents characterized by a MOSCED polarity parameter, tau (i),
that lies
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within a range of from about 4 to about 12 Joules per milliliter (J/mL)0-5, a
MOSCED
acidity parameter, alpha (a), that lies within a range of from about 0(J/mL)0*
5to about 6
(J/mL) ,5 , and a basicity parameter, beta ((3), that lies within a range of
from about 1
(J/mL)0-5 to about 12 (J/mL) .5. The foregoing solvents or mixtures of
solvents provide very
effective results when used in conjunction with absorbent media selected from
silica gel or
alumina or ion-exchange beads. See M. L. Lazzaroni et al., "Revision of MOSCED
Parameters and Extension to Solid Solubility Calculations", Ind. Eng. Chem.
Res., vol
44(1 1), pages 4075-4083 (2005) for a more detailed explanation of i, a and P.
A combination of ethyl acetate as solvent and silica gel as media provides
very
satisfactory results when used in conjunction with a SMB in accord with the
present
invention. Other suitable combinations include acetonitrile as solvent and
silica gel as
media, methyl isobutyl ketone (MIBK) as solvent and silica gel as media,
tetrahydrofuran
(THF) as solvent and silica gel as media, methyl tert-butylether (MTBE) as
solvent and
silica gel as media, toluene as solvent and silica gel as media; and a mixture
of heptane and
ethanol as solvent and alumina as media. The foregoing combinations represent
preferred
combinations, but do not constitute an exhaustive list of all possible
combinations of solvent
and media that may be used with greater or lesser success in terms of
effectiveness per
dollar spent on the combination.
The seed oil derivative may be any of a variety of derivatives including fatty
acid
alkyl esters, hydrogenated fatty alkyl esters, hydroformylated fatty acid
alkyl esters or
hydroformylated and hydrogenated fatty acid alkyl esters. The seed oil
derivative is
preferably a hydroformylated and hydrogenated fatty acid alkyl ester or seed
oil alcohol
derivative. Methyl esters represent a preferred species of alkyl esters for
purposes of the
present invention.
The seed oil derivative may be prepared from any of a number of plant (e.g.
vegetable), seed, nut or animal oils including, but not limited to palm oil,
palm kernel oil,
castor oil, vernonia oil, lesquerella oil, soybean oil, olive oil, peanut oil,
rapeseed oil, corn
oil, sesame seed oil, cottonseed oil, canola oil, safflower oil, linseed oil,
sunflower oil; high
oleic oils such as high oleic sunflower oil, high oleic safflower oil, high
oleic corn oil, high
oleic rapeseed oil, high oleic soybean oil and high oleic cottonseed oil;
genetically-modified
variations of oils noted in this paragraph, and mixtures thereof. Preferred
oils include
soybean oil (both natural and genetically-modified), sunflower oil (including
high oleic) and
canola oil (including high oleic). Soybean oil (whether natural, genetically
modified or high
oleic) represents an especially preferred seed oil. As between a high oleic
oil and its natural
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oil counterpart (e.g. high oleic soybean oil versus soybean oil), the high
oleic oil tends to
have a simpler, albeit still complex, mixture of components that makes
separation of a
composition comprising the high oleic oil easier than separation of a
composition
comprising the natural oil counterpart of the high oleic oil.
Selecting separation technology and associated apparatus and apparatus
sequencing
and connectivity for use in effecting recovery or separation of a component or
a plurality of
different components from a composition that comprise at least two seed oil
derivatives,
more often several seed oil derivatives, constitutes a complex and many-
faceted challenge.
Facets include, but are not limited to, heat history, pressure drop, waste
production,
productivity, feedstock composition, feedstock flexibility, product stream
flexibility,
selectivity, presence or absence of packing in certain apparatus, apparatus or
combination of
apparatus choices, and economics. Several of the facets compete with each
other. For
example, recovering or separating a single component, such as a monol, from a
mixture of
several seed oil derivatives, while technically feasible provided one does not
care about
consequences such as low yield, generation of unwanted byproducts due to
excessive heat
history, or dealing with disposition or use of other components of the mixture
of seed oil
derivatives, may at the same time be, for example, environmentally
unacceptable,
economically unattractive or both.
C. Triantafyllou and R. Smith, in an article entitled "The Design and
Optimisation of
Fully Thermally coupled Distillation Columns", Trans IChemE, volumn70, Part A,
pages
118-132 (March 1992), teach that for most separations, fully thermally coupled
distillation
columns, also known as "dividing wall columns" or as "Petlyuk columns", are
thermodynamically more efficient than conventional arrangements of multiple
distillation
columns. They also teach, at page 118, that "capital savings result from use
of a single
reboiler and condenser compared with a conventional arrangement".
Major components of interest in compositions subjected to the foregoing
process
include the following where (I) represents a monol, (II) represents a diol and
(111) represents
a triol. Skilled artisans recognize that (I), (II) and (1II) each represent
one of at least two
positional isomers. The present invention includes all such positional
isomers. Potential
positional isomer locations occur in a molecule of a fatty acid methyl ester
derived from a
seed oil, which seed oil typically contains a measurable fraction of 16 carbon
atom (CiO, 18
carbon atom (C18) and 20 carbon atom (C-,()) chains, between carbon atoms 9
and 10
(C9/Ci()), 12 and 13 (Ci2/Ci3) and 15 and 16 (C15/Ci6). Seee.g.:
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OH HO OH 0 HO HO OH
O
OCH, OCH, OCH,,
Ca0H400_a
328.53 CaiHazOn ( I~ ) Ca,HnaOs
328.297745 358.56 388.58
358.308310 388.318874 ( )
as well as saturates such as the following or their isomers:
O
0
OCH3 OCH,
C'17H3402 C19H3802
270.45 298.50
270.255880 298.287180
Additional components of the above compositions include cyclic ethers such as
the
following or their isomers (including positional isomers):
O
0
OCH3
C21 H4003
340.54
340.297745
as well as lactols such as the following or their isomers (including
positional isomers:
O OH
O
~OCH3
C21 H3804
354.53
354.277009
Skilled artisans sometimes refer to high molecular weight species or molecules
as
"heavies". Alternately, "heavies" refers to oligomers or oligomeric esters
that have a higher
vapor pressure than, for example, vapor pressure of principal components of a
monol-rich
stream. The present invention divides heavies into two groups, nominally "good
heavies"
and "bad heavies", based respectively upon presence or absence of hydroxy (OH)
functionality suitable for creation of polyols via polymerization. Good heavy
production
involves a head-to-tail reaction between a hydroxy group-functionalized
monomer and an
ester group-functionalized second monomer. Bad heavies result from reactions
between
reactants, products or both present during one or more of hydroformylation,
hydrogenation
and monomer recovery.
Bad heavies, when present in a composition, tend to adversely affect physical
properties of the composition when used in downstream applications of the
composition,
especially when such downstream applications involve conditions such as a
temperature
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sufficient to effect a reaction between a bad heavy and another component of
the
composition. Good heavies, on the other hand, do not have a significant
adverse impact
upon physical properties of the composition when used in many downstream
applications
even if they react with other components of the composition.
In order to limit adverse effects that result from presence of "bad" heavies,
one may
do either or both of minimizing heavy production and removing at least a
portion of heavies
present in a product or intermediate product. Skilled artisans recognize that
removal or
separation of heavies necessarily applies to both "good" and "bad" heavies. An
optional,
sometimes preferred, variation of the above-noted aspect of the invention
involves
removing at least a portion of heavies present in the additional remainder
before recycling at
least a portion of said additional remainder to the first separation as a co-
feed with the
composition.
Skilled artisans recognize that several techniques exist to effect separation
of heavies
from the additional remainder. While two of such techniques find particular
favor when
applied to the present invention, other techniques may be used in place of or
in combination
with either of both of the said two techniques. One of the two techniques,
especially useful
when dealing with hydrogenation effluent that contains "good heavies" relies
upon relative
volatility differences between the good heavies, which tend to have a high
boiling point
relative to hydroxy-functional components present in a composition that have a
comparable
hydroxy-functionality, yet do not have a molecular weight sufficient to
classify them as
"heavies". The other of the two techniques employs a polarity di=iven device
to concentrate
species that have similar functional make-ups based upon differences in
polarity rather than
differences in volatility and preferentially remove "bad heavies". Skilled
artisans also
recognize that, subsequent to separation, heavies in general and good heavies
in particular
may be converted to monomer form via methods such as methanolysis, polymerized
to
generate a useful downstream product or recycled for further processing as
noted above.
While either technique may be used alone, the two techniques may be used in
combination
with each other, with another existing technique or both.
Peters and Timmerhaus, in Plant Design and Economics for Chemical En ineers
McGraw Hill (1968), provide teachings relative to merits of a plate
distillation tower versus
a packed distillation tower and suggest that an optimum tower choice involves
consideration
of a detailed cost analysis as well as selection of optimum operating
conditions. They allow
substitution of a qualitative analysis of column internal options to replace
the cost analysis.
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They emphasize desirability of packed tower use where low liquid hold-up (low
residence
time) and reduced pressure drop (low or reduced boiling point) are prime
considerations.
From the teachings of Peters and Timmerhaus, a logical conclusion is that
distillation of high boiling monomers that have a potential to thermally
degrade imposes a
design constraint that mandates use of low pressure and minimal residence
time. Skilled
artisans recognize that each organic component has a degradation temperature
(e.g. a
temperature above which the component tends to degrade at an unacceptable rate
and/or an
unacceptable extent). "Low pressure" allows for distillation to take place at
a temperature
below the temperature of decomposition and "minimal residence time" means a
time shorter
than that time at which the extent of degradation becomes unacceptable. When
the method
of separation noted in the above aspect of the invention involves use of a
distillation tower
to effect a separation or partitioning of seed oil derivatives, the
distillation tower is
preferably a packed distillation tower. The packed distillation tower may be,
for example,
either a simple distillation tower or a DWC.
When the method of the present invention yields a mixture that has a low
saturate
content and a high monol content as one of the first portion, an additional
portion or an
additional remainder, such a mixture finds utility in producing flexible
polyurethane
products. If the mixture is low in saturates and monols and high in diols, it
has utility in
producing molded (rigid) parts.
Modeling Hydroformylated - Hydrogenated Seed Oil Derivative Separation Options
Use a combination of process flowsheet development approaches based upon
commercially available and industrially recognized process engineering
simulation tools
and software developed by AspenTech including, but not limited to, Aspen Plus
TM 2004.1
and Aspen DynamicsTM 2004.1. For a given process or process step, process
input
parameters that support a mathematical representation of a specific unit
operation include
physical connections, hydraulics, performance specifications (e.g. purity and
pressure drop
limitations) and thermodynamic properties (e.g. heat capacity, heat of
vaporization and
vapor pressure) of chemicals being processed using equipment associated with
the specific
unit operation. This approach works well for unit operations such as
evaporation, mixing,
distillation, heat exchange and pumping.
The AspenTech simulation tools and software include chemical and physical
properties for a number of materials. The collection of included materials,
while extensive,
must be supplemented for purposes of the present invention, either by actual
measurements
or properties for certain materials or by estimates of such measurements or
properties.
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Illustrative estimates include gas chromatograph (GC) retention times as well
as
extrapolation of curves from experimental data and use of physical property
estimation
techniques such as group contribution models. For guidance on estimates and
previously
developed physical property information, see, respectively, Danner et al,
Manual for
Predicting Chemical Process Desi ng Data, DIPPR (AIChE), New York, (1983) and
Reid et
al., The Properties of Gases and Liquids, 4`h Ed, McGraw-Hill, New York
(1987).
Accomplish simulation of wiped film evaporation (WFE) and short-path
evaporation
(SPE), neither of which is included among AspenTech simulation tools and
software, by
combining existing vapor liquid equilibrium (VLE) models into a functional
single unit
operation that accounts for the behavior of either a WFE or a SPE.
Model simulation of a WFE by first combining a series of Aspen Plus flash
blocks
specifying pressure and vapor fraction to provide a set of modeled results and
then
comparing the set of modeled results with experimental results achieved by an
operating
WFE. Each flash block has a liquid stream that is fed to the next flash block
in the series.
Each flash block, has a vapor stream and all flash block vapor streams, when
taken together,
form a combined vapor stream for purposes of modeling evaporator behavior.
For SPE simulation, use the approach detailed above for WFE simulation, but
recognize that differences in performance and operation of a SPE relative to a
WFE (e.g.
combine and condense the combined vapor stream at an internal heat exchange
temperature
associated with the SPE in operating the SPE versus an external heat exchanger
in an
operating WFE) necessarily lead to differences in modeling results. This
approach to
simulation allows one to model several SPE or WFE unit operations in series or
in parallel.
Examples contained herein (e.g. Ex 31 below) model the performance of a SPE by
using a series of four cascaded Aspen Plus flash blocks with a residue stream
from one flash
block feeding the next flash block in the cascade for residue streams from the
first three
flash blocks and vapor streams from the four blocks being combined and
condensed. The
examples also model a WFE is modeled as a single flash block or evaporator.
Skilled
artisans understand that, when compared to modeling data, operation of various
vendor-
supplied apparatus, such as WFE or SPE, may differ from modeling projections
with some
operations being more efficient and others being less efficient. Skilled
artisans also
understand that some vendor-supplied apparatus may differ in terms of having a
unit
operation identical to, for example, four cascaded flash blocks, in that a
vendor may choose
a unit operation more accurately modeled by a greater or lesser number of
flash blocks.
12
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Nonetheless, the modeling data provides a very useful guide in selecting
apparatus and
using the same in accord with the present invention.
Modeling of SMB operations, also excluded from AspenTech simulation tools and
software, employs a different approach that begins with collecting
experimental data from
an SMB separation and converting that experimental data into empirical
relationships. The
empirical relationships allow one to include SMB as part of a simulated
separation
operation without directly using thermodynamic or absorption properties as
input for
AspenTech simulation tools and software to simulate a SMB separation. As an
added
benefit, use of the empirical relationships allows one to model a complete
separation that
includes feedstream to the SMB and a product stream from the SMB.
Selection of the appropriate simulation modeling approach allows one to begin
with
a multi-component composition, such as one that includes at least two seed oil
derivatives,
and model production of a desired produced product stream or range of desired
produced
product streams.
Examples
Use one of four feed (seed oil alcohol derivative) compositions detailed in
Table 1
below for all succeeding examples other than Ex 19 through Ex 22. Table 1
identifies
composition components or fractions either specifically, as in methyl
palmitate, or
generically, as in monols, and provides an identifier or "Aspen Alias" along
with weight
fractions of each composition component or fraction. In this Example section,
use a
component name or a fraction name interchangeably with its Aspen Alias. In
other words,
use the component or fraction name with or without its Aspen Alias as in using
the Aspen
Alias alone without changing the spirit or scope of this invention or the
examples that
illustrate this invention. The four seed oils are soybean oil (commercially
available from
AG Environmental Products, under the trade designation SOYCLEAR"'M 1500),
hydroformylated soybean oil, canola oil (commercially available from AG
Environmental
Products, under the trade designation CANOLAGOLDTM CE-110) and sunflower oil
(commercially available from ACH Food Companies, under the trade designation
TRISUN
EXTRA'"' RBWD).
13
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Table 1
Name Aspen Alias Feed Stream Feed Stream B Feed Stream C Feed Stream D
A - Soy Oil - HF Soy Oil - Canola Oil - Sunflower
Derivative Derivative Derivative Oil Derivative
(Soy Oil (HF Soy Oil (Canola Oil (Sunflower Oil
Alcohol Alcohol Alcohol Alcohol
Monomer) Monomer) Monomer) Monomer)
Methyl C16SA-ME 0.11 0.05 0.06 0.035
Pal mi tate
Methyl C 18SA-ME 0.18 0.10 0.15 0.045
Stearate
Monols 18MHM-ME 0.39 0.33 0.57 0.85
Diols 18DHM-ME 0.28 0.46 0.15 0.05
Triols 18THM-ME 0.015 0.05 0.05 0.01
Heavies Heavies 0.025 0.01 0.02 0.01
Total 1.00 1.00 1.00 1.00
In rnodeling distillation equipment for use in modeling a separation process,
vapor
pressure constitutes a primary, if not the principle, driving force. See Fig 3
below for a
graphic portrayal of vapor pressure of the components/fractions identified in
Table 1 above.
(Ex) 1- Simulation of Cascaded SPE Combinations in Conjunction with Recycle -
Feed
Stream A
Connect six short path evaporators (SPEs), numbered SPE-1 through SPE-6 in a
cascaded and recycle mode to simulate continuous operation to effect
separation of Feed
Stream A (see Table 1 above). Table 2 below summarizes effluent composition
from each
of SPE-1 through SPE-6. See Fig 4 below for a schematic illustration of the
connected
SPEs where distillate (Dist) or a remaining fraction (F) or extract (E) that
cascades from one
SPE, e.g. SPE-l, to a sequential SPE, in this case SPE-2 and SPE-4, bears a
label linking it
to the SPE that generates the distillate, in this case Dist-lA feeds to SPE-4
and R-l F.
"WFE-Feed" represents a feedstream from a WFE. Introduce the feedstream and,
once it
becomes available through operation of the connected SPEs, R-4E to SPE- 1.
Operate SPE-
1 with a driving force sufficient to result in a mass distillate:feed (D:F)
ratio of 0.875.
Operating SPE-I effects separation of its feedstream into Dist- IA and R-IF.
Feed Dist-lA
to SPE-4 and R-1F to SPE-2 together with, once it becomes available through
operation of
the connected SPEs, R-3F as a feedstream for SPE-2. Similarly, Dist-2A feeds
to SPE-3
and R-2F feeds to SPE-5. Operate SPE-2 through SPE-6 with driving forces
sufficient to
result in respective D:F ratios as follows: SPE-2 = 0.928, SPE-5 = 0.803, SPE-
6 = 0.632,
SPE-4 = 0.062 and SPE-3 = 0.05 1. In operation of, for example, SPE-2, Dist-2A
constitutes
a feedstream for SPE-3 and R-2F constitutes a feedstream for SPE-5. SPE-5
yields a purge
stream (Dist-5A) with a monol:diol weight ratio of 65:32 and a feedstream for
SPE-6 (R-
5E). SPE-6 yields a diol-rich stream (Dist-6A) and a stream (R-6D) that passes
through a
14
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
heat exchanger (HEX-1) to yield a heavy-rich stream. SPE-4 yields a saturate-
rich stream
(Dist-4A) and SPE-3 yields a monol-rich stream (Dist 3A).
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
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16
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Ex 2 through 4
Replicate Ex I with changes to D:F ratios and, respectively Feed Stream B for
Ex 2,
Feed Stream C for Ex 3 and Feed Stream D for Ex 4. See Table 1 above for
composition of
each Feed Stream. Tables 3 through 5 below summarize effluent data for each of
SPE-1
through SPE-6 for, respectively, Ex 2 through Ex 4 using the same format as in
Table 1
above.
In Ex 2, operate SPE-1 with sufficient driving force to yield a D:F ratio of
0.777,
operate SPE-2 to yield a D:F ratio of 0.466, operate SPE-5 to yield a D:F
ratio of 0.812,
operate SPE-6 to yield a D:F ratio of 0.742, operate SPE-4 to yield a D:L
ratio of 0.061, and
operate SPE-3 to yield a D:F ratio of 0.216.
In Ex 3, operate SPE-1 with sufficient driving force to yield a D:F ratio of
0.857,
operate SPE-2 to yield a D:F ratio of 0.900, operate SPE-5 to yield a D:F
ratio of 0.798,
operate SPE-6 to yield a D:L ratio of 0.716, operate SPE-4 to yield a D:F
ratio of 0.051, and
operate SPE-3 to yield a D:L ratio of 0.262.
In Ex 4, operate SPE-1 with sufficient driving force to yield a D:F ratio of
0.864,
operate SPE-2 to yield a D:F ratio of 0.905, operate SPE-5 to yield a D:F
ratio of 0.800,
operate SPE-6 to yield a D:F ratio of 0.711, operate SPE-4 to yield a D:F
ratio of 0.053 1,
and operate SPE-3 to yield a D:F ratio of 0.264.
Ex 1-4 and the data presented in Tables 2 through 5 demonstrate effective
separation
of feed streams that represent four different seed oil derivatives (seed oil
alcohol monomers)
using a series of cascaded SPE combinations with recycle.
17
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
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CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
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19
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
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CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Ex 5 - SPE Simulation Using Feedstream D (Variation A)
As schematically illustrated in Fig 5 below, connect three SPEs, numbered SPE-
1,
SPE-2 and SPE-4, in a cascaded mode for continuous operation. Table 6 below
summarizes
Feed Stream composition and effluent Stream results from the SPEs and Fig 5
depicts
connectivity between SPEs as described below. In Table 6, label distillate
from each SPE-#
as DIST-# or D-# and each SPE's residue streatn or effluent stream as R-#,
where "#"
corresponds in each instance to number of the SPE generated by the SPE as in
DIST- 1, D-1
and R-1 for SPE- 1.
Introduce Feedstream D to SPE-1 and generate residue stream R-1 and distillate
stream D-1. Operate SPE-1 with a driving force sufficient to result in a mass
D:F ratio of
0.334. Separate material streams so as to feed R-1 to SPE-2, where it combines
with R-4,
and D-1 to SPE-4. Operate SPE-2 with a driving force sufficient to attain a
D:F ratio of
0.864. Recover D-2 to generate a refined monol stream. Operate SPE-4 with a
driving
force sufficient to result in a D:F ratio of 0.409 and yield D-4, a saturates
and monol rich
stream.
If desired, combine R-2 and D-4 to yield a combined stream ("COMB-STR") for
downstream uses such as generation of a polyol. See Table 6 below for
composition of the
feedstream ("WFE-FEED"); and each of D-1, D-2, D-4, R-1, R-2, R-4 and COMB-
STR.
Table 6
WFE- DIST- DIST- DIST R-1 F R-2F R-4E COMB-
FEED 1A 2A -4A STR
Mass Fraction
Aspen Alias
C16SA-ME 0.035 0.104 0.001 0.250 0.001 0.000 0.002 0.134
C18SA-ME 0.045 0.119 0.015 0.250 0.008 0.000 0.028 0.134
18MHM-ME 0.850 0.765 0.950 0.498 0.892 0.626 0.950 0.557
18DHM-ME 0.050 0.011 0.031 0.002 0.069 0.226 0.018 0.105
18THM-ME 0.010 0.001 0.003 0.000 0.015 0.064 0.002 0.030
HEAVY 0.010 0.000 0.000 0.000 0.015 0.084 0.000 0.039
Total Flow kg/hr 1000.0 333.8 745.7 136.6 666.2 117.8 197.3 254.3
Temperature C 100.0 50.0 50.0 50.0 152.4 157.4 149.1 101.1
Pressure mmHg 0.1 0.1 0.1 760.0 0.1 0.1 0.1 0.1
Ex 6 - SPE Simulation Using Feedstream D (Variation B)
Replicate Ex 5 using the same feedstream, but change the D:F ratio for SPE-4
from
0.409 to 0.461 and modify interconnectivity as schematically illustrated in
Fig 6 below.
Summarize Feed Stream composition and effluent Stream results from the SPEs as
in Ex 5
21
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
above in Table 7 below. As an option, combine D-2 and R-4 to form a modified,
refined
monol stream ("Monol-CB").
Table 7
WFE- DIST DIST DIST R-1 F R-2F R-4E COMB- MONO
FEED -1A -2A -4A STR L-CB
Mass Fraction
Aspen Alias
C16SA-ME 0.035 0.104 0.001 0.223 0.001 0.000 0.001 0.140 0.001
C18SA-ME 0.045 0.119 0.009 0.233 0.008 0.000 0.021 0.146 0.012
18MHM-ME 0.850 0.765 0.947 0.541 0.892 0.553 0.957 0.546 0.949
18DHM-ME 0.050 0.011 0.039 0.002 0.069 0.260 0.019 0.099 0.034
18THM-ME 0.010 0.001 0.004 0.000 0.015 0.078 0.002 0.029 0.004
HEAVY 0.010 0.000 0.000 0.000 0.015 0.108 0.000 0.040 0.000
Total Flow kg/hr 1000.0 333.8 574.3 153.9 666.2 91.9 179.9 245.8 754.2
Temperature C 100.0 50.0 50.0 50.0 152.4 158.8 150.1 91.9 75.4
Pressure mmHg 0.1 0.1 0.1 760.0 0.1 0.1 0.1 0.1 0.1
Ex 7- Sitnulation of Two Packed Distillation Columns and One SPE
Use a packed distillation column to reduce saturate content of a feed streatn,
thereby
yielding a"saturate-depleted feed stream". The packing is a BX packing, such
as that
supplied by Sulzer Chemtech with an assumed Height Equivalent to a Theoretical
Plate
(HETP) of 10 inches (25.4 centimeters (cm)). Use a SPE, either with or without
recycle, to
effect separation of the saturate-depleted feedstream into a monol-rich
stream, a diol-stream
and heavies-rich stream.
As a variation, one can also use a SPE to provide a saturate-depleted feed
stream and
a packed distillation column to separate remaining components of the feed
stream into, for
exatnple, a monol-rich stream, a diol-rich stream and a heavies-rich stream.
See Fig 7 below for a schematic illustration of a combination of two packed
(Sulzer
BX packing with an assumed HETP of 10 inches (25.4 cm)) distillation columns,
nominally
"SAT-1" and "SAT-OUT", and one SPE. In accord with Fig 7, preheat Feed Stream
A
using a heat exchanger (HEX-1), then pass the preheated feed stream to SAT-1,
modeled
using eight (8) equilibrium stages, which has an overhead (SAT1-D) with a
reduced diol
content and a bottoms stream (SAT 1-B) that has a reduced saturate content and
a reduced
monol content, each reduction being relative to the preheated feed stream. SAT-
1 has the
following design specifications (with corresponding Aspen aliases): 0.005 mass
fraction
monol (18MHM-ME) in SAT1-B and 0.005 mass fraction diol (18DHM-ME) in SAT1-D.
Control monol level in SATI-B by varying D:F ratio (Table 8) to meet SAT1-B
design
specifications and diol level in SAT 1-D by varying reflux ratio of SAT-1 to
meet the SAT 1-
22
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
D design specification. In this case, a reflux ratio, 2.78 meets the SATI-D
design
specification. SAT-1 has an overhead pressure specification of 0. 1 mm Hg.
Estimate
pressure drop across SAT-1 using hydraulic calculation software based upon the
Sulzer BX
packing. Skilled artisans recognize that other packing may be used if desired
and that a
change in packing or characteristics of such packing may vary results
presented herein
without departing from the spirit or scope of the present invention.
Feed SAT1-D to SAT-OUT, which has the following design specifications (with
corresponding Aspen aliases): 0.002 mass fraction based upon a combination of
methyl
palmitate (C16SA-ME) and methyl stearate (C18SA-ME) in bottoms stream SATOUT-B
and 0.005 mass fraction monol (18MHM-ME) in distillate stream SAT-OUT-D.
Control
saturate level in SATOUT-B by varying D:F ratio (Table 8) and monol level in
SAT-OUT-
D by varying reflux ratio of SATOUT. In this case, a reflux ratio of 1.82
meets the SAT-
OUT-D design specification. SATOUT has the same overhead pressure
specification as
S AT-1.
Feed SAT1-B to the SPE (nominally SPE-3) and operate the SPE with sufficient
thermal driving force and a mass D:F ratio of 0.768 to effect separation of a
diol-rich stream
from SAT1-B. Table 8 below contains composition information for the feed
stream and
each of the streams or components that enter or leave one of SAT-1, SAT-OUT
and the
SPE.
23
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
W O~ O~~ N N O O
C O C~ O M 0 M O O
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cr, O OLr; O~ [~ O~ N O C
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~ Q ^ x M N o o cr, c
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24
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Ex 8
Replicate Ex 7, but change the feed stream to Feed Stream B In addition,
change the
design specifications to 0.0055 mass fraction monol (18MHM-ME) in SAT 1-B and
0.0055
mass fraction diol (18DHM-ME) in SATI-D. Also, vary the SAT-1 column reflux
ratio,
5.99. For SATOUT, change the design specifications to 0.002 mass fraction for
a
combination of methyl palmitate and methyl stearate in SATOUT-B and 0.005 mass
fraction monol (18MHM-ME) in SAT-OUT-D. Control level of saturates in SAT-OUT-
B
as in Ex 7 and level of monol in SAT-OUT-D as in Ex 7. In this case, a reflux
ratio
(sometimes called a "column reflux ratio") of 1.57 meets the SAT-OUT-D design
specification. Operate the SPE with sufficient thermal driving force to
provide a D:F ratio
of 0.881. Table 9 below summarizes composition information as in Ex 7.
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
c o 0 oc o N c o 0
W ~ C O~ N`r N C
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U
.C^.. O 'CS o CC O
Z O C~ C O C~
N v; O
C~ C C C C O C c+',
m N n O O O- N C
r; O _ O o O
c o o c
c¾i.~ Q
~ F E ^ o Crs C^~~ ~ oc
oc
~ U V~q o 0 0 o M,
cr, N~n C o 0
cr, ~c o c o^ v, ~n o
v O(~ o o c o C o
x N.c ^ o~ C o
o00 C c o a - o
Q~ o 0 0 o C o v
v;O
C C 1'i ~~O O~ N v; N
C o r o~ -
C O C o0 O O N N
¾ C O C O C C v; N
v; CO
rt oc cJ IO O o x C C_
= oc.^C~ C O r O
¾ C ^ C C C C V
C C C C C C O C
O- r', ~t C C C v, C
¾ Q C C O C -
V; L3.
C C C O C C O C
O C M, rY V'...-,' .^. C ~
W C O
W O C C C O C O -
u
c~ W W W W W
d d ~ j c ro '~
W ~ c y ~
- oc oo oc
U U ~ x E~xNUa 8
26
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Ex 9
Replicate Ex 7, but change the feed stream to Feed Stream C and use the SAT-
1B,
SAT1-D, SAT-OUT-B and SAT-OUT-D design specifications from Ex 8. In addition,
change the design specifications to 0.0055 mass fraction monol (18MHM-ME) in
SAT1-B
and 0.0055 mass fraction diol (18DHM-ME) in SATI-D. A SAT-] column reflux
ratio of
1.48 meets the SATI-B design specifications and a SAT-OUT column reflux ratio
of 3.15
meets the SATOUT-D design specification. Operate the SPE with sufficient
thermal
driving force to provide a D:F ratio of 0.866. See Table 10 below for
composition
information as in Ex 7. As in Ex 7 and 8, model both distillation columns SAT-
1 and SAT-
OUT as packed distillation columns with BX packing, a HETP of 10 inches and an
overhead pressure of 0.1 mm Hg. Table 10 below summarizes composition
information as
in Ex 7.
27
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
c c o c c o 0
, c c ^ x - - oc :~
O O ~ M N N O O
W O C O O O O~
C~ " O^^ O Ooc
O O O oo - r _
C C C
~~-= O O.~^~ ~ r~ C O O
`~ C C C oo - O N C C
[] C C C C C C ^ r
~, ^^~G N C N~ C C
v Q c o o r r-, ~ c o~
o c N
0 o N - -,
U~ o 0 0 0 r
o N c oc C o hl
Z c o c c
c o c C o o~n r
^ N c
Do~
Q o c~ r
cr
C N^ oc o C cv ~ o
p Q~ o o? c r, -- o0
r c -
~ cr ,. o 0 0 0 0 0~n N
~" E~ x o^ o 0 o a c c
N l- O C C o~ O
v: c o o c o N
F~ ~~ N^ o o~ v_ cc
x ^
v: o o c o o c r ~~
C~o N c N o~ r: ~
F" W o o~ o ~1
Q' -^ N
U, c c O C O C N N~'
r N~G G o O^ C C
C'l
C~ O~ r~ O O M' C
c o 0 o C C r ~ c
C C C c c C . C C
CA o o c -
p ^^ C C C^ = ~ C
W ^~ vr "- o c o 0 0
~. o o C c: c c -
U
o r W W~ W W
vi cn x x~T ~ Ci ou
yIc x_ ~' Q`-= W c
~ Q U U cc oc x FC- e
28
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Ex 10
Replicate Ex 9, but change the feed or feed stream to Feed Stream D. In
addition,
change the SPE D:F ratio to 0.562. Column reflux ratios of 1.84 for SAT-1 and
2.4 for
SAT-OUT meet their respective or associated design specifications. Table 11
below
summarizes composition information as in Ex 7.
29
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
v;
w r c ~
o 0 0~c o, ~'r c o
c o o~- M. oc c o
W o 0 0 0 0 0~ `
x
Q c o_ o c~~ r N ~
r~ o 0 0~ o o c~v o
C^ C_ ~ s oc ~ C O
[] O C
U q o o^oc v Mn c~ O C
W C o o~c --~n v;
~F" o 0 0 0 0 0 r
z CNN~CC-
,~ o 0 0 00
v o v o o c c
E~-Q v o 0 0 ~
Q c c c r
v:
~ Q~~ o c o 0 0 0`O
~ v~ C c o 0 o C o o"o
~' n o~n o 0 0~ o 0
¾~ q v O O O^ x O '-
~ C o C o 0 0 0~
E~ q r- oc o c ox c
Q F" .. c o~ c C M, " o
cn
o o~G 00 M, M, OG oc
W c c o oc t`' v' `c r-
.^ O O C O C~ N
`~ q C O~ O O C~ ^ O
U, C o C C C C O~ C
v'~ ~ O O C O~ O O
Q Q O O x O O C O ~
U C C C C C C -
q v'; v'~ C O^ O'~' O O
W M, ~~n n-- O C
W O O oc O C O O C O
[I, C C C O o o,_, -
c~ W W~ W W ~
f-L+ ~ ~/] q
f -
U 20 oc oo
d U -~
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Skilled artisans understand that one may make any of a number of modifications
of the
separations provided in Ex 7-10 depending upon desired composition of one or
more
streams. For example, one may use the first packed column, SAT-l, to effect
removal of at
least a substantial portion of saturated contained in the feed stream and
operate SAT-1 such
that SAT1-B contains a higher fraction of monol relative to total SAT1-B
composition than
the fraction of mono] relative to the feed stream. Feeding SATI-B to SAT-OUT
allows
monol recovery as SAT-OUT-D and use of the SPE to separate diol as overhead
(SAT-
OUT-D or R-3D). In addition, one may also add precursor operations and/or
downstream
operations depending upon desired handling of, respectively, feedstreams prior
to the
separation detailed in any of Ex 7-10 or downstream handling of streams
exiting one or
more of the separation apparatus. Further, one may substitute a third
distillation column,
preferably a packed distillation column, for the SPE.
Ex 11
Using Feed Stream A, but a combination of two packed distillation columns,
nominally "SAT-1" and "SAT-OUT", and one SPE as shown in Fig 8 below rather
than that
shown in Fig. 7 below, replicate Ex 7 with a number of changes. First, change
SAT-1 to the
following design specifications (with associated Aspen aliases): 0.0065 mass
fraction
methyl palmitate (C 16SA-ME) and methyl stearate (C 18SA-ME) in SAT 1-B and
0.0065
mass fraction diol (18MHM-ME) in SAT1-D. Second, a SAT-1 reflux ratio of 0.66
meets
associated design specifications. Third, change SAT-OUT design specifications
to: 0.007
mass fraction based upon monol (18MHM-ME) in bottoms stream SATOUT-B and
0.0055
mass fraction diol (18DHM-ME) in distillate stream SAT-OUT-D. Fourth, a SAT-
OUT
column reflux ratio of 6.13 meets associated design specifications. Fifth,
feed SAT-OUT-
B, rather than SAT1-B, to the SPE (nominally SPE-3) and operate the SPE with
the same
thermal driving force and mass D:F ratio as in Ex 7 and a mass D:F ratio of
0.768 to effect
separation of a diol-rich stream from SAT-OUT-B. Table 12 below contains
composition
information for the feed stream and each of the streams or components that
enter or leave
one of SAT-1, SAT-OUT and the SPE. See Table 12 below for composition
information as
in Ex 7.
31
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
C o c~ rr, M, O
> ^ C C~ oc N- O
O C.~ ~ o M d' C C
W C O O O c C~ ~~
Q O_ O O Ol oc N'-' O
c v'~ cr", ~ N
Y o O o ~
O O O J~ O C~ C~
CD O C o C C C N
c t~ x t~ oo - ,-. .=~
O
v c c^ oc .~ o
~ p ^ o 0 o r
^ N cr, c o o~ o
O- oQ o C C N N o
o:~ ~ o o C~ ^ o
~-a ~ o 0 0 0 0~,
r, - o c~ _ o
oc c c o~ o~ o
~ Q ~ o O N
oc -
o o
o0 0
v C~ o 0 0 0 0 0~ N~
x~ ~'~
6 _
¾~ o 0 o c c o a c
v; C p o c o 0 0 o r,
~ o.c ~n r - n co C o
O O F O~ N r; N O O
O C v'; c+;
C C o 0 0 o t~ ~`n
v'~ 00
~, C C V C~ N r', N ,_,
O v'~ c+'C C- C
cr~ O C C O C C I~ - C
c*', - l~ O^ C N C O
oo
c'~, ~O C C C O~ O'"
U p O o O C N
C C C o ~'; v'~ C o 0
~, - oo :S oo -- N C O
-r; N O O O ,rI C~
Q O C C C C C C
p C~ O o~n N o O C_
[]~ - ~~', N C C O C C
W C o o C C
= r~ W U
CJ.
u-
~¾ U U x oo ~o x FC x F~ Gi ~
. . . . . . El
32
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Ex 12
Replicate Ex 11, but use Feed Stream B and make a number of changes. First,
change the SAT 1-B design specifications to: 0.0035 mass fraction methyl
palmitate
(C 16SA-ME) and methyl stearate (C 18SA-ME). Second, change the SAT 1-D design
specification to 0.0055 mass fraction diol (18MHM-ME). Third, a SAT-1 column
reflux
ratio of 1. 11 meets associated design specifications. Fourth, a SAT-OUT-D
column reflux
ratio of 9.35 meets associated design specifications. Fifth, change the SPE
D:F ratio to
0.780. See Table below for composition information as in Ex above. See Table
13 below
for composition information as in Ex 7 above.
33
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
W ooo~rN~t~ o o
> o 0 o c~ o~ co ~
ooo~ o_, o0
w oooooo^ "-"~
Q ooo~rc~~t~ 000
M o 0 o N C~ 00 ~
0 0 0 l~ -- O O
o O O o c O^
O O O N ~ o~ Q~
_ o 0 o O~ o o ~ O~
(Q O O O O O O~
cr, O O t- co ~O 6l oo O O
0 0 o t~ O^
Q O O O o0 O O N O O
~ O O O O O O v~
O O~ n~O O O M N o
O O O 00 O O O~ O~
O o 0 0 0 o M
W ~~ O O O O~ O
~, F'' M~O O O O O~ O
Q Q O o 0 0 0 0^
~
E--~ F" o 0 0~ C O~ co cr N
m Q~~ O O O o0 0 o N ~`!
.~ ~/] ~ O O O o O O v N N
~ E Q O O00 O O O M O O
~ O o O~ o 0 0~ o-
V~ O O o o O o o M v~
E O O 00 -t~ N N o ~
¾ O o M v o o~ o O
v~ O O o o O o 00
o M~D o O~ N N o~
O o 00 ~ ~
~~ O O M v; O O~ ~~O.'
O O O O O O 00
00 IO 1.0 O O O 00 O O
~, M v~ o 0 0 0~
L M O o 0 0 0~ O
~ O O O O O O~-
O
Q~ O^ M~t O O OO O
~ o 0 0 0 o O,_
Q O O~ o~ O o_ O OO o0
w O^ M~ O O O o 0
fy ::D O O O O O~
oo
w ~~_~QFx"¾u. ' ~x
0o
~ 00 00 E
~QUU xE-~.xFU-~G~
34
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Ex 13
Replicate Ex 1 1 with changes. First, use Feed Stream C rather than Feed
Stream A.
Second, change the SAT1-B design specifications to 0.005 mass fraction methyl
palmitate
(C16SA-ME) and methyl stearate (C18SA-ME) and the SATI-D design specification
to
0.005 mass fraction diol (18MHM-ME). Third, a SAT-1 column retlux ratio of
2.07 meets
associated design specifications. Fourth, change the SAT-OUT, design
specifications to
0.0055 mass fraction based upon monol (18MHM-ME) in bottoms stream SATOUT-B
and
0.0055 mass fraction diol (18DHM-ME) in distillate stream SAT-OUT-D. Fifth, a
SAT-
OUT column retlux ratio of 5.03 meets associated design specifications. Sixth,
change the
SPE D:F ratio to 0.765. See Table 14 below for composition information.
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
W ^^ o N N~c o 0
o o c - N ~c
d C O C M c~'; M~ c~
W ^^ C O O O
Q ^_ 0 C N N~~: ~ O
C C C c C C~ x C
[~ Q-1
n x
^ ^ c O C C
`-' O O C[~ N
(~ O O O O O Ln
U~] C~ C l~ N~~ O O
j. G C c N r ~
c t~ x~ c C O~ N O
Z~ C C~ O~ O~ C G
Nt-^ C C^ ^ r~-, O~
d d C C O N
~C M O~ N C O~
~ C O O N N N
C.~
O G
x O O C~
C-
U C O c c c C C v', O
O v'~ x
F-' c C- x~G N N O C
¾ C C ^ C O~
C C G G C t~ r
x
E--o o[~ x c o N
d o 0 o C c o ~ N'-'
rr
Q o v n o 0 0- o 0
H o C C_ o C_
cy ~ o 0 0 -
cr,
Q c c C C C C G.
~~n t~ n v N o 0 0
~ - -~ o 00 k.
d c o C o C o_
~
Q c
c^^ o o c o 0
W ~c nr- nkn CIA o 0 0
u o C c C o
~ W W W
cz
V)c oVDo
-' ^ x x x W ~ ~ y ~'c
x
36
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Ex 14
Replicate Ex 11 with changes. First, use the same feed stream (HF sunflower
oil
alcohol monomer) as in Ex 10. Second, change the SATI-D design specifications
to 0.0055
mass fraction methyl palmitate (C16SA-ME) and methyl stearate (C18SA-ME) in
SAT1-B
and 0.0055 mass fraction diol (18MHM-ME). Third, a SAT-1 column reflux ratio
of 4.90
meets associated design specifications. Fourth, use the same SAT-OUT design
specifications as in Ex 13. Fifth, a column reflux ratio of 5.54 meets
associated design
specifications. Sixth, change the SPE D:F ratio to 0.755. See Table 15 below
for
composition information.
37
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
W o 0 0 0~ o^ N o 0
, c c ~r oc ~
0 o c cy ^~n ~c o 0
W o o^ o 0 0'- `r `~
x
Q c o o kr) No o
c c o 0 0 0'-'
C O C M
C O O oC ^ O~ O~
Q C C C C O C
N N
C O O O~ ~n v'; ~ C O
C O C O O C~
p G O C N O
z,~ O C oc
~~ C O~ C C C~ ^ C
W C~C O O C M. C O
~ C M, C C C C O
~ v; O O O C~ O C
Q Q C O O C C C~ ~^
~ O~O O N N~ M,
H F-' C C~ v; v~
d~ W c ~^ n v~ o0
Lr,
~C o o ~c N M,
~ C c~ c C C C o 0
Q~ Ll c o a^ o o o'
v~ o 0 o c c c oo
rli ;
v~ c o o c c o a ^ r
Q cQ o o a~ c c o N
o 0 0 0 0 0 0~ -
h c c C C^
~G M, C C C C M:
F" Q v c o~ cLn
o o c o 0 0~ ~
v; Ln o C C o~ .. c
Q o o x o o c o
o o C C C.
Q v, tn o o c o . c o
o 0 0 o c 7=, c
^ o 0 0 o c
"c x_ ~ Q E Q c~ -~~ x
Q U U x oc oo ~ 5 ~ Ey Ci E
38
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Ex 15 - Simulation of distillation followed by SMB -Feed Stream A
See Fig 13 below for a schematic illustration of an ASPEN flow sheet for a
method
of separating that uses distillation for a first separation operation and SMB
for an additional
separation. As shown in Fig 13, Feedstream A initially passes through a
boiling tube
evaporator (BTE-1) that vaporizes about 94% of a feedstream's mass under a
reduced
pressure or vacuum of one mm Hg to yield a vapor stream designated as BTEI-V.
While a
reduced pressure of 1 mm Hg is used in this Ex 15, skilled artisans understand
that such a
high vacuum may be excessive for some purposes and desire to use a lower
vacuum such as
5 mm Hg or 10 mm Hg or even lower. Choice of such a lower vacuum does not,
however,
depart from the spirit or scope of this invention. The balance of the
feedstream
(approximately 5 percent by weight, based upon total feedstream weight when
fed to BTE-
1) bears a designation of BTEI-L and remains as a liquid (not vaporized). BTE1-
L has an
enriched heavies content relative to the feedstream entering BTE-1.
BTE 1-V passes through a heat exchanger (HEX-1) and enters a packed
distillation
tower (SAT-1) to effect separation of BTE1-V into an overhead stream that is
rich in at least
one saturate (SAT1-D) and a bottoms stream that has a reduced saturate content
(SATI-B),
in each case relative to saturate content of the feedstream entering the
packed distillation
tower. Use eight equilibrium stages with a design specification of 0.0015 mass
fraction
methyl stearate (C18SA-ME) in bottoms stream SATI-B and a design specification
of 0.01
mass fraction monol (18MHM-ME) in column distillate SAT1-D. Control methyl
stearate
content in bottoms stream SAT1-B by varying distillate to feed ratio (D:F) and
control
monol content in SAT1-D by varying distillation column reflux ratio. Co-feed
SAT1-B
after it is diluted with an equal mass of solvent (EA-FD) to give the stream
SMB-FEED and
a solvent stream (ELUENT) that comprises ethyl acetate or another suitable
solvent to a
simulated moving bed (SMB) that splits SAT1-B into two streams, a raffinate
stream that
has an enriched monol content and an extract stream that has an enriched diol
content, in
each case relative to SAT1-B.
Feed the extract stream to a boiling tube evaporator (BTE-EX) to vaporize
approximately 95 percent by weight of the extract stream at 350 mmHg, thereby
effectively
separating a substantial fraction of the solvent from the extract stream as
recovered solvent
(BTE-EXV 1) and leaving an oil product that has the enriched diol content (BTE-
EXL1).
Feed BTE-EXLI to a second distillation column (DIST-EX1) to effect further
removal of
solvent. Simulate operation of DIST-EX1 using five equilibrium stages, a
reflux ratio of 5
and a design specification of 0.001 mass fraction of solvent in a bottoms
stream exiting
39
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
DIST-EX 1. Tune DIST-EXI operation to meet the design specification by varying
distillate
to feed (D:F) ratio. Distillate exiting DIST-EX1 (designated as DIST-EXID)
constitutes
recovered process solvent. The bottoms stream exiting DIST-EX1 (designated as
DIST-
EX1B) constitutes an oil product with an enriched diol content, based upon
weight percent
of diol in the product relative to weight percent of diol in the soy oil
feedstream.
Feed the raffinate stream to a boiling tube evaporator (BTE-RAF) to vaporize
approximately 93 percent by weight of the stream at 350 mmHg, thereby
effectively
separating a substantial fraction of the solvent from the raffinate streatn as
recovered solvent
(BTE-RFV 1) and leaving an oil product enriched in monol content (BTE-RFLI ).
Feed
BTE-RFL1 to a third distillation column (DIST-RF1) to effect further removal
of solvent.
Simulate operation of DIST-RFI using five equilibrium stages, a reflux ratio
of 5 and a
design specification of 0.001 mass fraction of solvent in a bottoms stream
exiting DIST-
RF1. Tune DIST-RFI operation to meet the design specification by varying
distillate to
feed (D:F) ratio. Distillate exiting DIST-RFI (designated as DIST-RF1D)
constitutes
recovered process solvent. The bottoms stream exiting DIST-RF 1(designated as
DIST-
RF 1 B) constitutes an oil product with an enriched monol content, based upon
weight
percent of monol in the product relative to weight percent of monol in the soy
oil
feedstream. Table 16 below summarizes composition information for each stream
in this
Ex 15.
Ex 16 through 18
Replicate Ex 15 three times for Ex 16 (Feed Stream B ), Ex 17 (Feed Stream C)
and
Ex 18 (Feed Stream D) and summarize composition information as for Ex 15 in
Tables 17
through 198 below.
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
C o0 01 ~~ o C
c C^ C o c o C N N
W
- o c o 0 0 0 o, N r, C C
0 o C C^ C oo N~~ o 0
~ o o c o 0 0 0~ ~~rl õ) õ)
~ o 0 0 0 0 00 -
E- d
0. W
C c c c c C C n N v c
_ o o C C C C o ,, a.; o 0
o c o c o~
[~] O C O O O O O C oc~~
F- d
m W
oLn r, ~ c o~ C~n C
O-- ~~ N C O~ N~ C C
C C O C C a~ N
W
v" O N~O lO v'~l
a O O-~ t O r, ~ C~~ C
~ C C C C C C C C N
7~
N CL~
~
\O ^ C C C C C C 0~ N c'~; C:S~ C
--~ O O O O O O o0 N c%, O N O
~ C C C C C O C~S _
C C C C C C C C N x O - M
-
W N
N C N-- ~G ~- t~ c, O~ O
x Oc~ C O ~,~, ~, N O
C C C C C C C C ~T' v'~ - c'r
W
E-~
Cq
C C C C C C C C ~n N C^ C
j -- C C o C C C~ a o W o
y~ C o 0 o C o C o~
W o 0 0 0 0 o c o ~ xr-~
x
W N
o o C o C o o c~ N x ~ ~ ,~
y~ o o c C o C C r, r,
E~
Pa
C W cu -a U
W W x ~
cw`a V~ vi >
xxx u ~ww ~ ~ ~
oc
U'~¾x~~- -xWHx~HHa~
41
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
E o 0 0^ n N o N o, 'c oo
o 0 0 0 0 0 0 0 `~ ~~`' o
F-~ -
- o c c o o c~ ^ o r, -- o
F~ ^ o c o 0 0 o co
Z c c c o o~ Nc v~ c'l ~
W o 0 0 0 0 o c N oo cr=
w w
o c c c o C~ c~ o
N
r,J.a o o C o 0 0 0 o N oo ~
^ c o 0 0 0 o a~ ~~ oo o
o o o c c ~ o~ 4 r- cr
p o o c o c o ~~` ^
0 0 o c c o a ~~~ o
oc r-~ 0~ c-i Lr;
0 0 0 o c .^.= o ~ i 1 ` 1 ~
p r C C^.. C C C r-. ~r ^~~ o
^ c c c c c c oC C~O O~ cn O
c o 0 0 0 0 0 0
F~
o=' o c i n , "'= =
~~ r
c4 0 0 0 0 0 0 o c Ln ^
H
Ca
Q N ^ o o c c o ~ ~ Lr'=
o c o o c o o~ - O o
~ r, v ^ Ln
W o c o 0 0 0 0 0
Ev:
^ C C^ oc a c r~ o~t C
p~ O O O^~~, O O O~O N^ Lr)
X C C C C C C C C (V N^
h
G w w bj~ L
w X
~ p L
2 :-5: >'
~~ rTi ,'7" x ~"' LL ,L LL CI. y'^
CL
~ +~i.= cC N Ic oc
,,~p Q ,j0
42
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
H o o c N oo -- cr, ~c cc oo cy "q o
Q ~ O O~ O O O oo M, ~~G O~ Kl
Z O O O O O O O O N N~ N O
w
~ o 0 0 0 0 0~, ^~ oo C
^ o 0 0 0 0 0 o0 0 0 0~ c,-; o
0 0 o c o 0 o a ~_ ~
¾ o C o 0 0 0 0 0 ~
W
~ C C C C C C~C t C ~G K, C
N O O O O C O l~ oc~
C O O O O O O a M~^ ~
Q C C C CC C C O l~
~
^ C C C C C C:S N M, l~ - C
O O C^^ O o0 N r", ~C O O
CQ O C C C O C C x N l
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CA 02692591 2010-01-05
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CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
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CA 02692591 2010-01-05
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CA 02692591 2010-01-05
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CA 02692591 2010-01-05
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CA 02692591 2010-01-05
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CA 02692591 2010-01-05
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CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
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CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
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56
CA 02692591 2010-01-05
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Ex 19-21 - Experimental SMB Separations
Using a pilot-scale or laboratory scale CSEPO model C912 (Knauer GmbH)
carousel-style, multi-column (12 stainless steel tubing columns having an
inner diameter
(I.D.) of 0.43 inch (1.1 centimeter (cm)) and a length of 36 inches (91.4 cm))
SMB
apparatus, ethyl acetate as a solvent and a 70-230 mesh (63-2 10 um) silica
gel as media,
effect separations between monol and diol components contained in each of the
feedstreams
for, respectively, Ex 19 and Ex 20 and effect the separations between
saturates and monol
for Ex 21. Tables 20, 22 and 24 list SMB operating parameters for,
respectively, Ex 19, Ex
20 and Ex 21. Tables 21, 23 and 25 show feed stream composition, raffinate
composition
and extract composition, each in wt% relative to total weight of, for example,
feed stream
when providing wt% of feed stream components, respectively for Ex 19, Ex 20
and Ex 21.
In Tables 21, 23 and 25, components designated as, for example "FameC 14"
refer to a fatty
acid methyl ester that contains 14 carbon atoms. Listing other components
generically, such
as diols, lactones, lactols and heavies provides sufficient information to
illustrate effective
separation via SMB operation. The feedstream for Ex 19 is an experimental seed
oil
derivative prepared by methanolysis, hydroformylation and hydrogenation of
soybean oil.
The feedstream for Ex 20 is an experimental mixture of methanolyzed,
hydroformylated and
hydrogenated soy bean oil derivatives that has a reduced saturate content. The
feedstream
for Ex 21 is the raffinate from Ex 19 after modification via rotary
evaporation to reduce
feedstream ethyl acetate content to 50 wt%, based upon feedstream weight. Fig
9 below
schematically illustrates SMB apparatus operation, showing components that
have greater
polarity classed as "slow moving" and those that have lesser polarity as "fast
moving". For
ease of illustration, Fig 9 also shows a configuration known as a "3-3-3-3"
configuration,
rather than a"2-5-4-1 configuration" as used in these Ex 19-21. Other
configurations may
also be used if desired.
Table 20. Ex 19 Operating Parameters
Stream Flow Rate
Eluent Flow 6.72 mL/min
Feed Flow 1.71 mL/min
Extract Flow 5.41 mL/min
Raffinate Flow 3.03 mL/min
Step time 585 seconds
57
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Table 21. Ex 19 Composition Information
Component Feed (wt %) Raffinate (wt %) Extract (wt %)
FameC14 0.0329 0.0188 0
FameC15 0.0103 0.005842 0
Palmitate 4.6996 2.6138 0.0175
FameC17 0.0513 0.0292 0
FameCl8s 0.0185 0.0116 0
Stearate 7.7677 4.3953 0.001475
Monol Palmitate 0.0531 0.0307 0
FameC20 0.188 0.1112 0.002229
Monoaldehyde 0.0607 0.0413 0.004129
MonolStearate 17.6414 9.8308 0.006566
Cyclic Ether 0.2949 0.3186 0
Monol020 0.101 0.0692 0.003611
Lactols 0.1149 0.0613 0
Diol 13.8295 0.455 4.0688
Lactones 0.2122 0.0864 0.01
Triols 0.8488 0.0943 0.2112
Heavies 1.4441 0.9087 0
Total 47.37 19.08 4.33
Table 22. Ex 20 Operating Parameters
Stream Flow Rate
Eluent Flow 3.85 mL/min
Feed Flow 0.94 mL/min
Extract Flow 3.09 mL/min
Raffinate Flow 1.7 mL/min
Step time 834 seconds
58
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Table 23. Ex 20 Composition Information
Mass
Component Feed (wt %) Raffinate (wt %) Extract (wt %) Balance
Palmitate 0.0268 0.006419 0.004221 0.9374
Stearate 0.1277 0.0664 0 0.9270
Monol Palmitate 0.0228 0.0121 0 0.9461
FameC20 0.118 0.067 0 1.0123
Monoaldehyde 0.1706 0.0663 0.004905 0.7860
Monol_Stearate 28.2556 15.7469 0.0649 1.0010
Cyclic Ether 1.0396 0.4674 0.002734 0.8101
Monol020 0.4649 0.1492 0.0228 0.7311
Lactols 0.8546 0.2933 0.1128 1.0396
Diol 18.675 0.8061 5.3951 1.0131
Lactones 0.371 0.1395 0.0364 0.9883
Total 50.13 17.82 5.64 0.9987
Table 24. Ex 21 Operating Parameters
Stream Flow Rate
Eluent Flow 5.92 mL/min
Feed Flow 0.57 mL/min
Extract Flow 4.31 mL/min
Raffinate Flow 2.14 mL/min
Step time 480 seconds
Table 25. Ex 21 Composition Information
Extract (wt Mass
Component Feed (wt %) Raffinate (wt %) %) Balance
Fame C14 0.0489 0.0123 0 0.9444
Fame 015 0.021 0.0161 0.00925 6.2090
Palmitate 6.8451 1.7828 0.004107 0.9824
Fame C 17 0.077 0.0193 0 0.9410
Fame C 18s 0.0168 0.001259 0 0.2814
Stearate 11.51 2.9932 0.009779 0.9828
MonolPalmitate 0.0794 0.00268 0.0101 1.0886
FameC20 0.2853 0.0629 0.005759 0.9804
Monoaldehyde 0.0773 0.0248 0 1.2045
MonolStearate 25.9643 0.7578 3.1228 1.0190
Cyclic Ether 0.7822 0.0727 0.003585 0.3836
Monol_C20 0.1821 0.0139 0.0132 0.8347
Lactols 0.2205 0 0.177 6.0697
Diol 1.2183 0.0114 0.1362 0.8805
Lactones 0.2466 0.0349 0.0101 0.8410
Triols 0.2504 0.0076 0.0105 0.4310
Heavies 2.2398 0.5752 0 0.9642
Total 50.07 6.39 3.51 1.0096
Example 22: Simulation of Dual SMB Units -Feedstream A
See Fig 10 below for a schematic illustration of a separation scheme that uses
two
SMBs to separate a seed oil derivative feed stream. As shown in Fig 10, mix an
59
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
experimental seed oil derivative prepared by methanolysis, hydroformylation
and
hydrogenation of a soybean oil as in Ex 19 (SMB Soy Feed) and an ethyl acetate
eluent
stream (SMB-EA-FEED) to form a stream (SMB-FEED- 1) with a composition such as
that
shown as Mass Fraction (Mass Frac or Mass Frac Aspen Alias) amounts in Table
22 below
in a column labeled "SMB-FEED" as it passes through a first SMB unit (SMB-1)
along
with an eluent. SMB-1 yields two output streams, a raffinate stream
(Raffinate) that has an
enriched monol content and an extract (Extract) stream that has an enriched
diol content,
enriched in each case being relative to SMB-FEED-1. The separation as modeled
by SMB-
1 is based on experimental results as described in Ex 19 above.
Continuing with Fig 10, feed the SMB-1 extract stream to a boiling tube
evaporator
(BTE-EX- 1) to vaporize approximately 95 percent by weight (wt%) of the
extract stream at
350 mm Hg, thereby effectively separating a substantial fraction of the
solvent from the
extract stream as recovered solvent (BTE-EXV 1) and leaving an oil product
that has the
enriched, relative to the SMB-1 extract stream fed to BTE-EX1), diol content
(BTE-EXL1).
Feed BTE-EXL1 to a distillation column (DIST-EX1) to effect further removal of
solvent.
Simulate operation of DIST-EX 1 using five equilibrium stages, a reflux ratio
of 10 and a
design specification of 0.001 mass fraction of solvent in a bottoms stream
exiting DIST-
EXI. Tune DIST-EX1 operation to meet the design specification by varying
distillate to
feed (D:F) ratio. Distillate exiting DIST-EX1 (designated as DIST-EXID)
constitutes
recovered process solvent (ethyl acetate). The bottoms stream exiting DIST-EX
1
(designated as DIST-EX1B) constitutes an oil product with an enriched diol
content, based
upon weight percent of diol in the product, relative to weight percent of diol
in both the soy
oil feed stream and BTE-EXLI.
Feed the raffinate stream from SMB-1 to a boiling tube evaporator (BTE-RAF-1)
to
vaporize approximately 66 wt% of the raffinate stream at 350 mmHg, thereby
effectively
separating a substantial fraction of the solvent from the raffinate stream as
recovered solvent
(BTE-RAF1-V) and leaving an oil product that has the enriched monol content
(BTE-RAF-
1-L). Control the vaporization in BTE-RAF-1 such that the BTE-RAF-1-L contains
approximately 50 wt% solvent (ethyl acetate). Skilled artisans recognize that
solvent
content in BTE-RAF-1-L may be readily varied to greater or lesser amounts than
50 wt%
without departing from the spirit or scope of the present invention.
Cool BTE-RAF-1-L to 25 C to form SMB-FEED-2. Pass SMB-FEED-2 through a
second SMB separation unit (SMB-2). SMB-FEED-2 has a composition such as that
shown
as Mass Fraction (Mass Frac) amounts in Table 26 below in a column labeled
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
"SMBFEED2". SMB-2 splits SMB-FEED-2 into two streams, a raffinate stream
(RAFFINATE-2) that has an enriched saturate content and an extract (EXTRACT-2)
stream
that has an enriched monol content, enriched in each case relative to SMB-FEED-
2. The
separation as modeled by SMB-2 is based on experiment results as described in
Ex 20
above.
Feed EXTRACT-2 to a boiling tube evaporator (BTE-EX-2) to vaporize
approximately 95 wt% of EXTRACT-2 at 250 mm Hg, thereby effectively separating
a
substantial fraction of the solvent from the extract stream as recovered
solvent (BTE-EX-2-
V) and leaving an oil product that has the enriched, relative to EXTRACT-2,
monol content
(BTE-EX-2-L). Feed BTE-EX-2-L to a second distillation column (DIST-EX2) to
effect
further removal of solvent. Simulate operation of DIST-EX2 using five
equilibrium stages,
a reflux ratio of 10 and a design specification of 0.001 mass fraction of
solvent in a bottoms
stream exiting DIST-EX2. Tune DIST-EX2 operation to meet the design
specification by
varying distillate to feed (D:F) ratio. Distillate exiting DIST-EX2
(designated as DIST-
EX2D) constitutes recovered process solvent. The bottoms stream exiting DIST-
EX2
(designated as DIST-EX2B) constitutes an oil product with an enriched monol
content,
based upon weight percent of monol in the product relative to weight percent
of monol in
the SMB-2 feed stream.
Feed the raffinate stream from SMB-2 to a boiling tube evaporator (BTE-RAF-2)
to
vaporize approximately 95 wt% of the extract stream at 350 mm Hg, thereby
effectively
separating a substantial fraction of the solvent from the extract stream as
recovered solvent
(BTE-RAF-2-V) and leaving an oil product that has the enriched saturate
content (BTE-
RAF-2-L). Feed BTE-RAF-2-L to a third distillation column (DIST-RAF-2) to
effect
further removal of solvent. Simulate operation of DIST-RAF-2 using five
equilibrium
stages, a reflux ratio of 10 and a design specification of 0.001 mass fraction
of solvent in a
bottoms stream exiting DIST-RAF-2. Tune DIST-RAF-2 operation to meet the
design
specification by varying distillate to feed (D:F) ratio. Distillate exiting
DIST-RAF-2
(designated as DIST-RAF-2D) constitutes recovered process solvent. The bottoms
stream
exiting DIST-RAF-2 (designated as DIST-RAF2-B) constitutes an oil product with
an
enriched saturates content, based upon wt% of saturates in the product
relative to weight
percent of saturates in the SMB-2 feed stream.
Table 26 below summarizes simulation results from this Ex. 22.
61
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
C O cn r=, O O- N O
C O~ O O O v~ O ~ 0
w~ O O O O O O O O v ~
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62
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
o C o C o 0 o M v o
d W
cy C C c~ C C ~n C C a C
rs., ~~n - o 0 0 0~n ~~
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N c c~ c c o
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rr
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63
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Similar results are expected with different feed streams, especially with feed
streams
used in Ex 12 (Feedstream B), Ex 13 (Feedstream C) and Ex 14 (Feedstream D),
the
compositions of which are shown in Table 1 above. Skilled artisans readily
understand that
results will vary depending upon selection of oil for the feed stream, as
shown in Ex 11
through Ex 14 above. Those results will also vary with other seed oils,
whether
hydroformylated or hydroformylated and hydrogenated as discussed hereinabove,
that are
chosen for use as a feed stream.
Example 23-26 Simulation of SPE and SMB
Fig 11 below provides a schematic illustration of a separation scheme based
upon
cascaded SPEs followed by an SMB. The separation scheme so illustrated
suitably effects
separation of feed streams such as, but not limited to, those shown in Table 1
above. For Ex
23, pass a Feedstream A through a series of flash separation blocks that
represent a
cascaded group of SPE units and recycle streams. Use the cascaded group of SPE
units
(Stage-1 A through Stage- I F) to remove saturates from the feed stream
generating a fraction
(R-1F) enriched in monols, diols, triols, and heavies relative to their
component levels in
Feedstream A. Solvent stream (EA) may, but need not, be combined with R-1F
("combined
feed stream").
Co-feed R-1F or, if desired, the combined feed stream with an eluent stream
(ELUENT) to an SMB unit (labeled as "SMB" in Fig 11) that splits co-feed
materials into
two streams, a raffinate stream that has enriched monol content ("RAFFINATE"
in Fig 11)
and an extract stream that has an enriched diol content ("EXTRACT" in Fig 11),
in each
case relative to the co-feed. Similar to the way SMB experimental results were
used in Ex
22 above, SMB separation modeling has a basis in experiment results as
described in Table
23 above.
Use boiling tube evaporator BTE-EX to vaporize and recover SMB process solvent
from the extract stream and BTE-RAF to do the same for the raffinate stream.
Recover
additional process solvent stream from bottoms stream (BTE-EXLI) via packed
distillation
column DIST-EXI and from bottoms stream (BTE-RFL1) via packed distillation
column
DIST-RF1. DIST-EXI generates two streams, a distillate stream containing
recovered
process solvent (DISTEX 1 D) and a bottoms stream (DISTEXIB) containing
enriched diol
concentrations relative to the SMB feed stream. DIST-RFI generates two
streams, a
distillate stream containing recovered process solvent (DISTRFID) and a
bottoms stream
(DISTRFI B) containing enriched monol concentrations relative to the SMB feed
stream. If
64
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
desired, an additional SPE may be used to further remove heavies from the
DISTRFIB
stream.
Similar results are expected with different feed streams, especially with feed
streams
used in Ex 12 (Feedstream B), Ex 13 (Feedstream C) and Ex 14 (Feedstream D),
the
compositions of which are shown in Table 1 above. Skilled artisans readily
understand that
results will vary depending upon selection of oil for the feed stream, as
shown in Ex 11
through Ex 14 above. Those results will also vary with other seed oils,
whether
hydroformylated or hydroformylated and hydrogenated as discussed hereinabove,
that are
chosen for use as a feed stream.
Example 27-30 (Simulation of SMB and Distillation)
Fig 12 below schematically illustrates separation via a SMB followed by
parallel
distillation of EXTRACT and RAFFINATE exiting the SMB. Mix Feedstream A and a
solvent stream (EA) to form a single stream (FEED) with a composition
represented by
mass fractions (MASS FRAC) in the column labeled "FEED" in Table 27 below.
Process
FEED through an SMB unit (SMB) along with an eluent (ELUENT) to yield two
streams, a
raffinate stream (RAFFINATE) that has an enriched monol content and an extract
(EXTRACT) stream that has an enriched diol content, in each case relative to
the original
component ratios in Feedstream A.
Feed EXTRACT stream to a boiling tube evaporator (BTE-EX) to vaporize
approximately 95 wt% of the extract stream at 350 mm Hg, thereby effectively
separating a
substantial fraction of the solvent from EXTRACT as recovered solvent (BTE-EXV
1) and
leaving an oil product that has the enriched diol content (BTE-EXL1). Feed BTE-
EXL1 to
a distillation column (DIST-EX1) to effect further removal of solvent.
Simulate operation
of DIST-EX1 using five equilibrium stages, a reflux ratio of 10 and a design
specification of
0.001 percent by weight solvent in a bottoms stream exiting DIST-EX1. Tune
DIST-EX I
operation to meet the design specification by varying distillate to feed (D:F)
ratio.
Distillate exiting DIST-EX 1(designated as DIST-EX I D) constitutes recovered
process
solvent. The bottoms stream exiting DIST-EX1 (designated as DIST-EXIB)
constitutes an
oil product with an enriched diol content, based upon weight percent of diol
in the product
relative to weight percent of diol in the Feedstream A.
Feed RAFFINATE to a boiling tube evaporator (BTE-RAF) to vaporize
approximately 90 wt% of the extract stream at 350 mm Hg, thereby effectively
separating a
substantial fraction of the solvent from the extract stream as recovered
solvent (BTE-RFV 1)
and leaving an oil product that has the enriched diol content (BTE-RFLI). Feed
BTE-RFLI
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
to a second distillation column (DIST-RF 1) to effect further removal of
solvent. Simulate
operation of DIST-RF1 using five equilibrium stages, a reflux ratio of 10 and
a design
specification of 0.001 percent by weight solvent in a bottoms stream exiting
DIST-RF1.
Tune DIST-RF I operation to meet the design specification by varying
distillate to feed
(D:F) ratio. Distillate exiting DIST-RFI (designated as DIST-RF1D) constitutes
recovered
process solvent. The bottoms stream exiting DIST-RF1 (designated as DIST-RF1B)
constitutes an oil product with an enriched monol content, based upon weight
percent of
inonol in the product relative to weight percent of monol in the Feedstreatn
A.
Similar results are expected with different feed streams, especially with feed
streams
used in Ex 12 (Feedstream B), Ex 13 (Feedstream C) and Ex 14 (Feedstream D),
the
compositions of which are shown in Table 1 above. Skilled artisans readily
understand that
results will vary depending upon selection of seed oil derivative for use as a
feed stream, as
shown in Ex 1 1 through Ex 14 above. Those results will also vary with other
seed oil
derivatives chosen as feedstreams, but such results do not depart from either
the spirit or
scope of the present invention.
66
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
o~ N v c o c
o 0 0 0 0 0 0 0~~ kr'
Fv:
Ca
Q cr, ^ c o 0 0 o r v^
N o o c ~
X, c c o o c o c~~`t
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Ca
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67
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
rm C~ c N V O O C~- ~
C C O:7~ O C O O~ V' ~C O O O O O O o~ N
Li.
C-- cr; c~', oo ^ N^~D kf', O
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d o c c O C o o O
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F o c o ^ r-, N o~ o, o - p o~c ~- N N o o c o -
U o c c ^ o o a~ v o ^ W ~ MDcv c o~~ v,
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c ^ o o c o o~ r cn ;~, o o c o 0 0 0 0 o r
F~
^ o 0 0 0 0 0 0 ~ - oo N c o C o 0 o n o ~
h -_ o o c C C c oo ~ r c ~ x c C o c o o c~ o c
Z o 0 0 0 0 0 0 ~t N ~ o q o 0 0 0 0 0 ~
W o 0 0 o c o o cC-4 r ~ C c o 0 0 0 0 0
- o 0 0 0 0 o a o o - p C m, cn C n N N-- cr. o
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- o c C o C o o, - r. C N o~ N M r.o - n r- o -
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68
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Ex 31
Use a SPE to provide a saturate-reduced residue stream (Heavies) with
distillate
being fed to multiple packed distillation columns (packed using the same BX
type of
packing as in Ex 7 above) as shown in Fig 14 below. As shown in Fig 14,
distillate from
the SPE passes sequentially through two distillate distillation columns,
nominally SPE,
"SAT-1" and "SAT-OUT", to effect separation of the distillate stream is
separated into, for
example, a saturate-rich stream, a monol-rich stream, and a diol-rich stream.
The heavies
produced by the SPE are reduced in saturates and may be used in applications
where monol,
diols, triol and heavies may be advantageously used in the absence of
saturates.
As shown in Fig 14, preheat Feedstream A (provided by a source not shown in
Fig
14) using heat exchanger (HEX-1) as in Ex 7 above, then pass the preheated
feed stream to
the SPE (nominally SPE-3), modeled using a series of four cascaded Aspen Plus
flash
blocks with a residue stream from one flash block feeding the next flash block
in the
cascade for residue streams from the first three flash blocks and vapor
streams from the four
blocks being combined and condensed as described hereinabove.
Operate SPE-3 with sufficient thermal driving force and a mass D:F ratio of
0.558 to
effect separation heated Feedstream A into a residue product (R-3D) that is
rich in heavies
relative to Feedstream A and a distillate product (SATI-FD) that is rich
saturates relative to
Feedstream A.
SAT-1, modeled using eight (8) equilibrium stages, has an overhead stream (SAT
1-
D) with a reduced monol content and a bottoms stream (SATI-B) that has a
reduced
saturate content, each reduction being relative to SATI-FD. SATI-B design
specifications
are: 0.007 mass fraction methyl palmitate (C16SA-ME) and methyl stearate
(C18SA-ME).
SAT1-D has a design specification of 0.007 mass fraction monol (18MHM-ME) in
SATl-
D. Control saturate level in SATI-B by varying D:F and monol level in SAT1-D
by
varying SAT-1 reflux ratio. In this case, a reflux ratio of 0.30 meets SATI-D
design
specifications. SAT-1 has an overhead pressure specification of 0.1 mm Hg.
Feed SAT1-B to SAT-OUT. Design specifications for SAT-OUT include: 0.007
mass fraction based upon monol (18MHM-ME) in bottoms stream SAT-OUT-B and
0.0055
mass fraction diol (18DHM-ME) in distillate stream SAT-OUT-D. Control saturate
level in
SAT-OUT-B by varying D:F ratio and monol in SAT-OUT-D by varying the SATOUT
column reflux ratio. In this case, a SATOUT column reflux ratio of 5.55 meets
SAT-OUT-
D design specifications. SAT-OUT has the same overhead pressure specification
as SAT-1.
Table 28 below summarizes simulation results from this Ex. 3 1.
69
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
o 0 0~c N%- c o
o 0 0~ c o 0 0 0
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c~~c ~c o C~ N o
p~ c oc o o N o c
~" C c c c C C N
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Q~~ C O O O
U' Ol O C~ O C O O O
^ T !'i G ^ ^ C O
,~ C~ O^~ O O= N_ C O
U C C C O O N
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oo ~ Ex Q x
W .s s
~ d U v oc oc cc ~ E~ ~ E~ Ci c
7n
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
Ex 32
Replicate Ex 3 1, but use a WFE (nominally WFE-3) as a specific case rather
than a
generic SPE as in Ex 31 to effect separation of heated Feedstream A. Fig 15
below
provides a schematic illustration of a combination resulting from that
substitution.
Model WFE-3 using two cascaded flash blocks. Operate WFE-3 with sufficient
thermal driving force and a mass D:F ratio of 0.670 to effect separation
heated Feedstream
A into a residue product (R-3D) that is rich in heavies relative to Feedstream
A and a
distillate product (SAT I-FD) that is rich saturates relative to Feedstream A.
Model SAT-1 as in Ex 31, but use the following design specifications: a) for
SAT1-B: 0.007 mass fraction methyl palmitate (C16SA-ME) and methyl stearate
(C18SA-
ME); and b) for SAT1-D : 0.007 mass fraction monol (18MHM-ME) in SATI-D. In
this
case, a SAT- I reflux ratio of 2.66 meets associated design specifications.
SAT-OUT has the following design specifications: 0.0075 mass fraction based
upon
monol (18MHM-ME) in bottoms stream SAT-OUT-B and 0.0075 mass fraction diol
(1 8DHM-ME) in distillate stream SAT-OUT-D. Control saturate level in SATOUT-B
by
varying D:F ratio and monol in SAT-OUT-D by varying the SAT-OUT column reflux
ratio.
In this case, a SAT-OUT column reflux ratio of 2.74 meets associated design
specifications.
Table 29 below summarizes simulation results from this Ex. 32.
71
CA 02692591 2010-01-05
WO 2009/009271 PCT/US2008/067585
~ C c oo v t~ - o o
C C o C c N o
~ o p a~~ ac\' o 0
p p o c o C C ~
z CO ~O OMO O O CO N ('V
a, c~~ N o 0
~`' o 0 0 0 0 o N r~
o^~ ~~ x
~ O C O O~ v O O M~
v% Q C C O O C C a N
^~ cr; t~ C C N C O
oc C ~ ~ ~ O C
un Q O C C C C O N
Q
E-~ o t~ N n~ o- ~ c
,'~ C c~n M c o~, C.J
r-. p O N O Coc Lr,
p C C C C C M, ^~
V:
Q Ra ^ O N O O M `n ^
O x ^
v, C C O C C O M, --
~t O~ l~ C O C C
oc
O p C o C C O
opc
N Q Q O C O O C C N
rA
C p C C C,7
~... ~G C p C C O~
MZ O O O O C
O O C p O C N~
E-' C~ ~~ M, M O O~ ~ O
Q w -- N rl- -- C C~ x
Uj C C O C C C~C
V;
J~ N V`, x v'> O~ O C
> C C C t~ cn t~ 0
O O M, C C~. C p
W C C C C C C M~~
C O O r
`'`'' O C c~; v'~ C C C
~ C C C O C O M, p
~ Q C oG U'C~ oC0 -~ N O .CJ O
N C OC ,n p
O O O C O O,__,
Q p~~ op0 ~ cV O C O
w -- M, N o 0 0 o c
O O o O C O p
w U
c oo' Q H¾ c~ a~ x
~ d U U~ o0 oc x E- Y F-~ wE
72
