Note: Descriptions are shown in the official language in which they were submitted.
POROUS MATERIALS FOR NATURAL GAS LIQUIDS SEPARATIONS
BACKGROUND
Field
[0001] Embodiments of the disclosure relate to separations for components of a
natural gas
stream. In particular, embodiments of the disclosure relate to producing
substantially pure
methane from natural gas using porous materials to capture heavier carbon
components such as
natural gas liquids (NGLs). The disclosure also relates to recovery of heavier
hydrocarbons, such
as ethane, propane and butane from a natural gas stream, and separations of
hydrocarbon gas
streams comprised mostly of hydrocarbons heavier than methane.
Description of the Related Art
[0002] Raw natural gas contains concentrations of natural gas liquids (NGLs)
and other non-
methane contaminants that need to be removed by gas processing in order to
meet specifications
required by a pipeline or end use. As well, NGL components such as ethane,
propane and butane
can have higher sales values than pipeline gas, which is largely comprised of
methane. Ethane is a
valuable chemical feedstock, and propane and butane can be blended to form
liquefied petroleum
gas (LPG) which is a valuable residential fuel. Therefore, NGLS are often
times extracted and
fractionated in gas processing plants in accordance with the specific
requirements of the regional
markets and customers. Generally, commercial NGL specifications require less
than abut 0.5%
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by liquid volume of methane and less than 500 ppm of CO2 by volume in liquid.
[0003] As a commercial fuel source, natural gas distributors and consumers
need to know the
expected range of quality of the fuel being delivered, and ideally need to
have some control over
the variability of that fuel to assure compliance with regulations, to protect
equipment, and most
importantly, to ensure safety for all involved in natural gas processing,
transport, and use.
Therefore, specifications help limit the range of variability inherent in
natural gas transported
around the world. Generally, pipeline specifications indicate that there
should be less than about
4.0 mol.% of other non-hydrocarbon gases (for example N2 + CO2) in the natural
gas, less than
about 10 mol.% ethane in the natural gas, and the specific energy content of
the natural gas should
not exceed about 1,100 British thermal unit per standard cubic foot of natural
gas (btu/scf).
[0004] Variables that affect choice of the most cost-effective process for
maximizing NGL
separation and recovery include: inlet conditions such as for example gas
pressure, richness and
contaminants; downstream conditions such as for example residue gas pressure,
liquid products
desired, and liquid fractionation infrastructure; and overall conditions such
as for example utility
costs and fuel value, location, existing location infrastructure and market
stability. Because of this
variability, there are a number of ways to recover NGLs from natural gas
streams, and market
demand and perceived return on investment drive the technology choice.
[0005] Mechanical refrigeration is a conventional option for NGL recovery,
where natural gas is
chilled until heavy components such as hexanes and heavier hydrocarbons (C>6
hydrocarbons)
condense out of the feed gas. Some of the intermediate components, such as
butane and pentane
can also be recovered, but there is limited recovery of ethane and propane. In
order to achieve
better recovery of ethane and propane from feed gases, cryogenic or
turboexpander processes are
typically used. These 'cryo' processes use the expansion of the natural gas
stream to reduce the
temperature to about -120 F to about -140 F, so that most of the natural gas
becomes liquefied
and can be separated using distillation columns. This technology offers
improved NGL recovery
potential, but at much higher capital and operating expenditures. Cryo
processes also require
longer lead times to build and fabricate the specialty equipment necessary for
their operation, such
as the turboexpanders and aluminum heat exchangers.
[0006] Expander-based cryogenic processes require high inlet pressures to
produce desired
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distillation column top temperatures for achieving optimal ethane and propane
recovery. In most
instances, an inlet pressure of greater than about 800 psia is desired for
expander processes,
meaning that low pressure gases must require significant inlet compression for
separation to be
efficient. Economies of scale then dictate that large cryogenic trains are
necessary to share the
"per unit cost" of compression, both at the inlet and to bring sales gas back
to suitable pipeline
pressures. These large trains are less tolerant of turndown because with
reduced flow, either the
turboexpander will not be able to achieve the low temperatures needed to
operate the
distillation/demethanizer column or the flowrates in the demethanizer will be
insufficient to
maintain the proper flow patterns.
[0007] Carbon dioxide in a feed gas will normally be split between the heavier
hydrocarbons and
methane, potentially affecting the product specifications, both for heavy and
light products.
Carbon dioxide can also freeze in a cryogenic or refrigeration process. Any
'cold' process for
recovery of heavier hydrocarbons when carbon dioxide is present in the inlet
gas must either
operate in a region that will avoid freezing or provide carbon dioxide removal
from one or more
streams. Separation with greater than about 2 mol.% carbon dioxide in the
inlet gas is not possible
with cryogenic processes because freezing will result at either the top of the
demethanizer column
or at the side of the reboiler. This means that a cryogenic ethane recovery
facility will require
treating of carbon dioxide at more than one location of the process.
[0008] As richness of an inlet gas increases, heat exchanger pinch points will
begin to appear in a
cryogenic process. An external refrigeration system will be required to
complement the cryogenic
process to avoid these pinch points and to provide the energy to compensate
for the relatively large
amounts of energy leaving the system as liquid NGL product. Specifically, this
occurs when the
process is targeted to enhance recovery of ethane from a raw natural gas
stream. As ethane
recovery percentage increases, energy intensity also increases significantly.
A typical ethane
recovery range can be between about 60-85% for a cryogenic process, and any
greater percentage
of ethane recovery becomes more difficult and energy intensive because of the
significant
recompression horsepower required to enhance ethane recovery processes. Ethane
recovery using
mechanical refrigeration is not practical for industrial application.
[0009] The presence of large amounts of light inert gases also impacts ethane
recovery in a
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cryogenic plant because the light components interfere with the efficiency and
the ability to
condense the reflux stream within the cryogenic process.
[0010] Undesirably, in existing processes, unrecovered propane and butane in a
sales gas stream,
which are more valuable as liquid products, will be sold at a discount in the
sales gas (methane).
In addition, unrecovered propane and butane will result in an increase in
heating value and
dewpoint of the sales gas, potentially exceeding pipeline specifications and
resulting in financial
penalties.
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SUMMARY OF THE INVENTION
[0011] Embodiments of the disclosure solve problems associated with
conventional `cryo'
facilities and recovery limitations of refrigeration facilities, by using
physical adsorption to achieve
separation of NGL products from methane with high efficiency. In some
embodiments,
substantially 100%, for example greater than about 90%, greater than about
95%, or greater than
about 98%, of the propane, butane, pentane, and heavier C>6 hydrocarbons can
be separated and
recovered from methane. In some embodiments, up to about 98% or about 99% of
an ethane
product can be effectively separated from methane as well. This can all be
achieved without, or
in the absence of, the use of turboexpanders, other specialty equipment, high
pressures, or low
cryo temperatures. For example, in embodiments of the present disclosure
substantially pure
methane suitable for transport in a natural gas pipeline, optionally to
consumers for consumer use,
at about 90%, about 95%, about 98%, or about 99% by mol.% can be obtained from
a single,
continuous pressure swing adsorption process carried out at about ambient
temperature and below
about 500 psia pressure.
[0012] Unlike turboexpander/cryo designs, the ability to operate at reduced
flowrates or capacity
("turndown") for prolonged periods of time without the loss of heavy
hydrocarbon recovery
efficiency is also possible. Efficiency during turndown is necessary to
operate a process at
flowrates that are less than what was originally designed or intended due to
external conditions,
such as for example changes to the feed supply upstream of the process, or
maintenance of certain
equipment in which the process is integrated with, or at later stages of a
plant lifecycle.
[0013] Additionally, in pressure swing adsorption (PSA) systems and methods of
the present
disclosure, carbon dioxide freezing and its inherent complications to
operations and processing is
not an issue when using adsorption to achieve separation. In example
embodiments of the present
disclosure, during a single, continuous process to obtain substantially pure
methane gas, adsorbents
and adsorbent beds need not be moved, transferred, externally stripped outside
of a continuous
pressure swing process, or regenerated outside of a continuous pressure swing
process. Desorption
as part of the continuous PSA process regenerates the adsorbents of the
present disclosure.
Adsorbent in an adsorbent bed can be stationary, and any adsorbed materials
removed via cyclical
pressure swing. For example, adsorbents and adsorbent beds of the present
disclosure are used in
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cyclical pressure swing processes, optionally at about ambient temperature and
less than about 500
psia pressure, to separate methane from heavier components without or in the
absence of heating
or temperature swing, for example without application of microwaves to an
adsorbent or adsorbent
bed.
[0014] In contrast to a cryogenic process, achieving greater than 85% ethane
recovery from a raw
natural gas stream using a PSA process is disclosed here with no additional
specialty equipment.
Embodiments of high recovery PSA processes do not increase process complexity,
nor do the
embodiments here consume increasingly significant amounts of horsepower to
achieve enhanced
separations and recoveries. Embodiments of systems and methods disclosed here
require no
second or subsequent separation for methane, which is obtained in a
substantially pure condition
meeting product specifications for market in one single pass through one train
of PSA beds.
Additional separation steps subsequent to one PSA train can be applied for
further separation of
target components heavier than methane, for example ethane and propane.
[0015] When ethane recovery economics are based on varying value margin
between ethane's fuel
value and its value as chemical feedstock, the ability to reject (with
methane) or recover ethane
separately from methane can become important to the profitability of a gas
processing facility.
The design and operation of various embodiments of the disclosure here allow
systems and
processes to have the flexibility to recover ethane in or reject ethane from
the heavy product with
minimal impact to recovery of the other heavier hydrocarbons (heavier than
ethane) present in the
natural gas stream based on market demand. Difficulty exists in natural gas
separations because
of multiple components heavier than methane existing in one stream, for
example versus other
gases such as biogas. Biogas in many instances has very few heavy hydrocarbons
for removal, so
separating the components of biogas, for example primarily methane and CO2,
does not suffer the
same challenges as natural gas separations via pressure swing adsorption and
vacuum swing
adsorption.
[0016] This flexibility of operation to meet market demand without over
designing or over
commitment to capital equipment is valuable to owners and operators of NGL
facilities. Efficiency
is gained by using a flexible PSA processing solution that enables a natural
gas separations facility
to operate in high ethane recovery, or full ethane rejection mode without
sacrificing the recovery
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of propane and butane as NGLs separate from the sales gas (methane). In some
embodiments of
the present invention, temperature swings, heating, and/or cooling are not
used during a continuous
PSA/vacuum swing adsorption cycle, and the process is carried out at about
ambient temperature
and at pressures generally less than about 500 psia.
[0017] In some embodiments of the present disclosure, systems and methods of
operating PSA
can be applied for dewpoint control, which is to prevent liquids from
developing in a pipeline as
gas, for example natural gas, is being transported. Dewpoint control can be
applied to remove
small amounts of liquids (less than about 3 mol.%) in the natural gas. In
other embodiments of
systems and methods of operating PSA of the present disclosure, substantially
all hydrocarbons
with a greater molecular weight than methane are recovered as NGL, and will
not be limited to
less than about 3 mol.% of a natural gas stream. In examples provided here,
NGLs, in addition to
or alternative to other gases with molecular weights greater than methane, for
example inert gases
such as CO2 and N2, are present at up to about 20 mol.% or about 30 mol.% in
an inlet natural gas
stream suitable for processing. Dewpoint control may be a possible application
for use, but
maximal recovery of hydrocarbons and the ability to then separate ethane from
the rest of the
NGLs in a potential PSA separation after already removing/recovering the
methane is disclosed
here.
[0018] Some embodiments of the present invention advantageously use activated
carbon or
adsorbents comprising activated carbon rather than, or without, zeolite
imidazole frameworks
(ZIFs) and metal organic frameworks (M0Fs). Instead, embodiments of systems
and methods
here apply carbon with a high surface area and a predominantly heterogeneous
microporous
structure. A broad range of pore sizes in the heterogeneous microporous
structure can be used
suitably as an adsorbent in adsorbent beds applied here, rather than a
uniformly angstrom-based
pore size found in ZIFS and MOFs. Suitably high adsorption of and selectivity
for hydrocarbons
with molecular weights greater than methane can be achieved when heterogeneous
porous carbon
structures exhibit pore sizes in a range of greater than about 1 nm (about 10
angstroms) and less
than about 50 nm (500 angstroms).
[0019] Suitable and advantageous adsorbents include high surface area
mesoporous and
microporous carbons optionally with heteroatoms, such as for example sulfur,
nitrogen, and/or
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oxygen, in the pores and/or incorporated into the porous material's chemical
structure to enhance
selectivity for NGL adsorption versus methane. In some embodiments, hydrated
pores in porous
carbons exhibit enhanced selectivity to NGLs to separate NGLs from natural gas
streams. Other
mesoporous and microporous materials, optionally including heteroatoms, are
also suitable
adsorbents for use in NGL separation processes.
[0020] Porous materials, which may be carbon-based for example, can be
modified by doping
precursor materials with heteroatoms such as sulfur, nitrogen, and/or oxygen,
and upon activating
the porous material, for example by physical and/or chemical activation,
optionally including
increased temperature, the elements are incorporated into the porous material,
physically,
chemically, or both.
[0021] Porous adsorbents of the present disclosure are operable at atmospheric
pressure, pressures
less than atmospheric, and pressure greater than atmospheric pressure. A wide
range of pore
volumes in porous adsorbents, such as porous carbon-based adsorbents, is
available. Micropores
for example between about 0.5 nm and about 10 nm, and between about 1 nm and
about 2 nm,
offer surprisingly and unexpectedly efficient hydrocarbon separations, for
example methane
separation from heavier NGLs, along with CO2 separation. Small pore sizes in
the Angstrom scale
(<1 nm) are not required. Enhanced selectivity of exemplified adsorbents to
NGLs versus methane
has been shown to occur in the presence of oxygen heteroatoms, and similar
enhanced selectivity
has been exemplified for higher molecular weight hydrocarbons versus ethane
with nitrogen
heteroatoms present in porous carbon adsorbents.
[0022] Additionally, activated carbon-based adsorbents are significantly less
expensive than ZIFs
and metal organic frameworks. However, in other embodiments of systems and
methods of the
present disclosure to obtain a substantially pure target hydrocarbon stream
from a mixed
hydrocarbon stream, other adsorbents and adsorbent support materials can be
used with or
alternative to carbon-based adsorbents, for example any one of or any
combination of ZIFs, MOFs,
molecular sieves, and other zeolites. Importantly, PSA systems and methods of
the present
disclosure allow for a substantially pure target hydrocarbon stream to be
obtained from one pass
of a mixed hydrocarbon gas through a PSA train system with adsorbent beds
without recycle or
additional PSA separation of the obtained substantially pure target
hydrocarbon stream.
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,
[0023] Embodiments of the present invention are well suited for any
hydrocarbon gas separation
application, for example with flow rates between about I million standard
cubic feet per day
(MMscfd) to about 250 MMscfd. At lower flow rates, example systems and methods
disclosed
here can be used to separate raw natural gases closer to a source, for example
production wells,
typically referred to as upstream operations. Due to the high recovery of NGLs
with embodiments
of the present invention over conventional technologies for dewpoint control,
higher value
hydrocarbons will provide greater revenue to the operator sooner and also
minimize the need for
flaring at the natural gas source, because the separated methane is better
suited to meet pipeline
transport specifications. In other embodiments, flow rates greater than about
40 MMscfd can allow
for application in gas processing midstream operations, where gas is gathered
to a centralized
processing facility, typically a further distance from a source of production.
Systems and methods
of the present disclosure may be stationary or mobile, depending on required
locations for
separation and required flow rates.
[0024] Therefore, disclosed herein is a method for continuous pressure swing
adsorption
separation of a pressurized feed gas stream, the method comprising the step of
separating
hydrocarbons heavier than methane from the pressurized feed gas stream to
produce at least two
product streams, a first product stream being substantially pure methane
suitable for transport by
natural gas pipeline, and a second product stream being substantially
comprised of components
with a greater molecular weight than methane. In some embodiments, the step of
separating
includes a feed step carried out at a pressure between about 50 psia and about
500 psia to produce
the stream being substantially pure methane. In other embodiments, the step of
separating
hydrocarbons can include recovering ethane in the first product stream being
substantially pure
methane or can include recovering ethane in the second product stream being
substantially
comprised of components with a greater molecular weight than methane. Still
other embodiments
include the step of recovering ethane in the second product stream being
substantially comprised
of components with a greater molecular weight than methane, and further
include the step of
separating the ethane from propane and butane via pressure swing adsorption.
[0025] In some embodiments, the method uses at least two fluidly coupled
trains of PSA units,
and further comprises the step of separating components of the second product
stream being
substantially comprised of components with a greater molecular weight than
methane, including
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propane and butane. In some other embodiments, each of the pressure swing
adsorption trains of
PSA units includes more than one individual adsorption bed. Still in other
embodiments, the step
of separating hydrocarbons comprises lengthening an amount of time of a
product purge step in a
PSA cycle to better separate two or more components which have similar
desorption fronts within
an adsorption bed.
[0026] In certain embodiments, the step of separating includes adjusting
separation parameters
such that CO2 in the pressurized feed gas stream can be separated to be in
either the first product
stream being substantially pure methane, or the second product stream being
substantially
comprised of components with a greater molecular weight than methane. In some
embodiments,
the step of separating can be carried out in a turndown mode, where the
turndown mode is reduced
by at least 50% relative to designed separation capacity, and still produce
the first product stream
being substantially pure methane, and the second product stream being
substantially comprised of
components with a greater molecular weight than methane.
[0027] In certain embodiments, the lowest pressure during separating may be
between about 1
psia and about 1.5 psia. In some embodiments, the method further comprises a
bed-to-tank-to-bed
equalization step, the bed-to-tank-to-bed equalization step reducing an amount
of adsorbent beds
required in the method, where a tank is a pressurizable vessel that does not
contain any adsorbent
and serves as an intermediate transit vessel for the gas moving from one bed
to another bed. Still
in other embodiments, the step of separating includes steps selected from the
group consisting of:
a feed step; an equalization down step; cocurrent depressurization occurring
before, in between or
after the equalization down step; countercurrent depressurization; light
reflux; an equalization up
step; and light product pressurization.
[0028] In certain embodiments, the first product stream being substantially
pure methane is
obtained in pass-through of the pressurized feed gas stream passing through a
PSA train with
adsorbent beds without recycle or additional PSA separation of the first
product stream being
substantially pure methane. In some embodiments, the step of separating is
carried out at about
ambient temperature without units for heating or cooling or vacuum. Still in
other embodiments,
the substantially pure methane suitable for transport by natural gas pipeline
is suitable for transport
to and use by consumers.
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[0029] In certain embodiments of the method, the step of separating includes
adjusting separation
parameters such that CO2 in the pressurized feed gas stream is separated into
the first product
stream, such that the second product stream comprises less than about 500 ppm
of CO2 by volume
in liquid, less than about 0.5 mol.% methane, and such that the second product
stream comprises
substantially hydrocarbon components with a greater molecular weight than
methane. Still yet in
some other embodiments, the step of separating includes the steps of: a feed
step; a plurality of
equalization down steps; a plurality of equalization up steps; cocurrent
depressurization occurring
before, in between, or after the equalization steps; countercurrent
depressurization; light reflux;
heavy reflux; and light product pressurization.
[0030] Additionally disclosed here is a pressure swing adsorption system, the
system comprising
a plurality of adsorbent beds, the adsorbent beds comprising adsorbents
comprising carbon,
wherein the pressure swing adsorption system is operable to continuously and
simultaneously
separate components of a raw natural gas stream into a substantially pure
methane stream and a
product stream being substantially comprised of components with a greater
molecular weight than
methane. In some embodiments, the system further comprises a second plurality
of adsorbent
beds, the adsorbent beds comprising adsorbents comprising carbon, and the
second plurality of
adsorbent beds operable to separate the components of the product stream being
substantially
comprised of components with a greater molecular weight than methane. Still in
other
embodiments, the substantially pure methane stream is obtained by passing the
raw natural gas
stream passing through the pressure swing adsorption system without recycle or
additional PSA
separation of the substantially pure methane stream. In some embodiments of
both methods and
systems, the substantially pure methane stream is at least about 98 mol.% pure
methane. In certain
embodiments, the system operates at about ambient temperature without units
for heating or
cooling or vacuum.
[0031] Still in other embodiments, the system further comprises a tank
operable for a bed-to-tank-
to-bed equalization step, where a tank is a pressurizable vessel that does not
contain any adsorbent
and serves as an intermediate transit vessel for the gas moving from one bed
to another bed. In
certain other embodiments of methods and systems, the substantially pure
methane stream has a
British thermal unit (btu) per standard cubic foot (set) value less than about
1,100 btu/scf. Still in
other embodiments of methods and systems, the substantially pure methane
stream is at least about
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90 mol.% pure methane. In certain embodiments of systems and methods, the
substantially pure
methane stream is at least about 95 mol.% pure methane. In certain embodiments
of systems and
methods, the substantially pure methane stream is at least about 98 mol.% pure
methane.
[0032] Also disclosed here is a method for continuous pressure swing
adsorption separation of a
pressurized feed gas stream, the method comprising the step of separating
hydrocarbons heavier
than a target hydrocarbon from the pressurized feed gas stream to produce at
least two product
streams, a first product stream being substantially pure target hydrocarbon,
and a second product
stream being substantially comprised of components with a greater molecular
weight than the
target hydrocarbon. In some embodiments, inlet pressure for the pressurized
feed gas stream can
range from about 30 psia to about 250 psia. In some embodiments, inlet
temperature is between
about 278 K to about 348 K. In other embodiments, inlet temperature is between
about 278 K to
about 323 K. In yet other embodiments, the lowest pressure applied during the
method is between
about 1.0 psia and about 7.0 psia. Still in other embodiments, the second
product stream comprises
at least about 90 mol.% hydrocarbons heavier than ethane, substantially no
CO2, and no more than
about 0.5 mol.% of methane and about 0.5 mol.% of ethane. In other
embodiments, the step of
separating includes the following PSA steps: a feed step; a heavy reflux step;
at least one
equalization down step; a countercurrent depressurization step; a light reflux
step; at least one
equalization up step; and a light product pressurization step.
[0033] In addition, disclosed here is a pressure swing adsorption system, the
system comprising a
plurality of adsorbent beds, wherein the pressure swing adsorption system is
operable to
continuously and simultaneously separate components of a pressurized feed gas
stream into a
substantially pure target hydrocarbon stream and a product stream being
substantially comprised
of components with a greater molecular weight than the target hydrocarbon
stream. In some
embodiments, the adsorbent beds comprise at least one material selected from
the group consisting
of: carbon-based adsorbents; silica gels; activated aluminas; zeolite
imidazole frameworks (ZIFs);
metal organic frameworks (M0Fs); molecular sieves; other zeolites; and
combinations thereof.
Still in other embodiments, system inlet pressure is between about 30 psia to
about 250 psia. In
other embodiments, the lowest pressure in the system while operating is
between about 1.0 psia
and about 7.0 psia. In other embodiments, inlet temperature is between about
278 K to about 348
K. In some embodiments, inlet temperature is between about 278 K to about 323
K.
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CA 3078066 2020-04-28
[00341 In some embodiments, the system includes one or more equalization tanks
and operates
with at least one step selected from the group consisting of: a feed step; a
heavy refhix step; one or
more equalization steps; a countercurrent depressurization step; a light
reflux step; and a light
product pressurization step. In other embodiments, the system includes 6
adsorption beds
operating with 9 cycle steps and includes: a feed step; a heavy reflux step;
two equalization down
steps; a countercurrent depressurization step; alight reflux step; two
equalization up steps; and a ,
light product pressurization step.
[0034A] In a broad aspect, the present invention embodies a method for
continuous pressure
swing adsorption separation of a pressurized feed gas stream. The method
comprises the step of
separating hydrocarbons heavier than methane from the pressurized feed gas
stream by applying an
adsorbent porous material to produce at least two product streams. A first
product stream is
substantially pure methane suitable for transport by natural gas pipeline, and
a second product
stream is substantially comprised of components with a greater molecular
weight than methane.
The porous material exhibits pore diameters between about I nm and about 2
urn, creating at least
0.3 cm3/g of pore volume.
[0034B] In a further aspect, the present invention provides a selective an
system. The
system comprises at least one adsorbent bed comprising adsorbent, including
porous material
comprising carbon_ The selective adsorption system is operable to continuously
and
simultaneously separate components of a mixed gas stream comprising carbon
dioxide into a
substantially pure carbon dioxide stream, by selective adsorption of carbon
dioxide at pressures
greater than about 1 bar versus other gases in the mixed gas stream. A by
product stream is.
substantially comprised of remaining components from the mixed gas stream, and
the porous
material exhibits pore diameters between about 1 nm and about 2 urn, creating
at least
, 03 cm3/g of pore volume.
13
Date Regue/Date Received 2023-02-01
[0034C] In a still further aspect, the present invention provides an
adsorption system comprising at
least one adsorbent bed comprising an adsorbent porous material. The at least
one adsorbent bed is
operable at pressures at about 1 bar or greater, and the adsorption system is
operable to separate
components of a feed gas stream into a substantially pure target hydrocarbon
stream and a product
stream being substantially comprises of components with a greater molecular
weight than the
target hydrocarbon stream. The at least one adsorbent bed comprises at least
cme material selected
from the group consisting of carbon-based adsorbents, silica gels, activated
aluminas, zeolite
imidazole frameworks (BF's), metal organic frameworks (M0Fs), molecular
sieves, other zeOliteSv
and combinations thereof. The material exhibits pore diameters between about 1
nm and about 2
nm mating at least ;033/g of pore volume.
13a
Date Regue/Date Received 2023-02-01
BRIEF DES 110 HE DRAWLNG,
[0035] These and other features, aspects, and advantages of the present
disclosure will become
better understood with regard to the following descriptions, and accompanying
drawings.
It is to be noted, however, that the drawings illustrate only several
embodiments of the disclosure
and are therefore not to be considered limiting of the disclosure's scope as
it can admit to other
equally effective embodiments.
[0036] FIG. lA shows a schematic of an example PSA cycle step schedule using 6
beds to achieve
production of a substantially pure methane product, for example suitable for
transport in a pipeline
and consumer use, or to achieve production of a substantially pure target
molecular weight
hydrocarbon separated from other higher molecular weight hydrocarbons.
[0037] FIG. 1B shows a graphic representation of the steps occurring in
separate beds during a
PSA cycle for certain unit steps shown in FIG. 1A.
[0038] FIG. 2A shows a sthematie'rof an exartinle PS.Kcycle step schedule
using 7 beds to achieve
production of a substantially pure methane product, for example suitable for
transport in a pipeline
and consumer use, or to achieve production of a substantially pure target
molecular weight
hydrocarbon separated from other higher molecular weight hydrocarbons.
[0039] FIG. 2B shows a graphic representation of the.. steps occurring in
separate beds during a
PSA cycle for certain unit steps shown in FIG. 2A.
[0040] FIG. 3A shows a schematic of an example PSA cycle step schedule using 6
beds to achieve
production of a substantially pure methane product, for example suitable for
transport in a pipeline
and consumer us; or to achieve production of a substantially pure target
molecular weight
hydrocarbon separated from Other higher molecular weight hydrocarbons.
[0041] FIG. 3B shows a gtaphic representation of the steps occurring in
separate beds during a
PSA cycle for certain unit steps shown in FIG. 1.A.
[0042] FIG. 4A shows a schematic of an example' PSA cycle step schedule using
7 beds to achieve
production of a substantially pure methane product, for example suitable for
tra sport in a pipeline
and consumer use, or to achieve production of a substantially pure target
molecular weight
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Date Recue/Date Received 2023-02-01
hydrocarbon separated from other higher molecular weight hydrocarbons.
[0043] FIG. 4B shows a graphic representation of the steps occurring in
separate beds during a
PSA cycle for certain unit steps shown in FIG. 4A.
[0044] FIG. 5A shows a schematic of an example PSA cycle step schedule using 6
beds to achieve
production of a substantially pure methane product, for example suitable for
transport in a pipeline
and consumer use, or to achieve production of a substantially pure target
molecular weight
hydrocarbon separated from other higher molecular weight hydrocarbons.
[0045] FIG. 5B shows a graphic representation of the steps occurring in
separate beds during a
PSA cycle for certain unit steps shown in FIG. 5A.
[0046] FIG. 6A shows a schematic of an example PSA cycle step schedule using 7
beds to achieve
production of a substantially pure methane product, for example suitable for
transport in a pipeline
and consumer use, or to achieve production of a substantially pure target
molecular weight
hydrocarbon separated from other higher molecular weight hydrocarbons.
[0047] FIG. 6B shows a graphic representation of the steps occurring in
separate beds during a
PSA cycle for certain unit steps shown in FIG. 6A.
[0048] FIG. 7A shows a schematic of an example PSA cycle step schedule using 5
beds to achieve
production of a substantially pure methane product, for example suitable for
transport in a pipeline
and consumer use, or to achieve production of a substantially pure target
molecular weight
hydrocarbon separated from other higher molecular weight hydrocarbons.
[0049] FIG. 7B shows a graphic representation of the steps occurring in
separate beds during a
PSA cycle for certain unit steps shown in FIG. 7A.
[0050] FIG. 8 shows a schematic of an example PSA cycle step schedule using 6
beds to achieve
production of a substantially pure methane product, for example suitable for
transport in a pipeline
and consumer use, or to achieve production of a substantially pure target
molecular weight
hydrocarbon separated from other higher molecular weight hydrocarbons.
[0051] FIG. 9 shows a schematic of an example PSA cycle step schedule using 6
beds to achieve
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CA 3078066 2020-04-28
production of a substantially pure methane product, for example suitable for
transport in a pipeline
and consumer use, or to achieve production of a substantially pure target
molecular weight
hydrocarbon separated from other higher molecular weight hydrocarbons.
[0052] FIG. 10 shows a schematic of an example PSA cycle step schedule using 6
beds to achieve
production of a substantially pure methane product, for example suitable for
transport in a pipeline
and consumer use, or to achieve production of a substantially pure target
molecular weight
hydrocarbon separated from other higher molecular weight hydrocarbons.
[0053] FIG. 11 is a graph showing increased propane uptake at 9 bar pressure
for a variety of
microporous materials at increasing pore volumes.
[0054] FIG. 12 is a graph showing increased ethane uptake at 9 bar pressure
for a variety of
microporous materials at increasing pore volumes.
[0055] FIG. 13 is a graph showing relatively stable methane uptake at 9 bar
pressure for a variety
of microporous materials at increasing pore volumes.
[0056] FIG. 14 is a graph showing increased CO2 uptake at 9 bar pressure for a
variety of
microporous materials at increasing pore volumes.
[0057] FIG. 15 is a graph showing propane uptake at 9 bar pressure for a
variety of nanoporous
materials at increasing pore volumes.
[0058] FIG. 16 is a graph showing ethane uptake at 9 bar pressure for a
variety of nanoporous
materials at increasing pore volumes.
[0059] FIG. 17 is a graph showing methane uptake at 9 bar pressure for a
variety of nanoporous
materials at increasing pore volumes.
[0060] FIG. 18 is a graph showing CO2 uptake at 9 bar pressure for a variety
of nanoporous
materials at increasing pore volumes.
[0061] FIG. 19 is a graph showing increased propane uptake at 9 bar pressure
for a variety of
microporous materials at increasing pore volumes.
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[0062] FIG. 20 is a graph showing increased ethane uptake at 9 bar pressure
for a variety of
microporous materials at increasing pore volumes.
[0063] FIG. 21 is a graph showing relatively stable methane uptake at 9 bar
pressure for a variety
of microporous materials at increasing pore volumes.
[0064] FIG. 22 is a graph showing increased CO2 uptake at 9, bar pressure for
a variety of
microporous materials at increasing pore volumes.
[0065] FIG. 23 is a graph showing increased propane uptake at 5 bar pressure
for a variety of
microporous materials at increasing pore volumes.
[0066] FIG. 24 is a graph showing increased ethane uptake at 5 bar pressure
for a variety of
microporous materials at increasing pore volumes.
[0067] FIG. 25 is a graph showing relatively stable methane uptake at 5 bar
pressure for a variety
of microporous materials at increasing pore volumes.
[0068] FIG. 26 is a graph showing increased CO2 uptake at 5 bar pressure for a
variety of
microporous materials at increasing pore volumes.
[0069] FIG. 27 is a graph showing propane uptake at 5 bar pressure for a
variety of nanoporous
materials at increasing pore volumes.
[0070] FIG. 28 is a graph showing ethane uptake at 5 bar pressure for a
variety of nanoporous
materials at increasing pore volumes.
[0071] FIG. 29 is a graph showing relatively stable methane uptake at 5 bar
pressure for a variety
of nanoporous materials at increasing pore volumes.
[0072] FIG. 30 is a graph showing CO2 uptake at 5 bar pressure for a variety
of nanoporous
materials at increasing pore volumes.
[0073] FIG. 31 is a graph showing increased propane uptake at 5 bar pressure
for a variety of
microporous materials at increasing pore volumes.
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[0074] FIG. 32 is a graph showing increased ethane uptake at 5 bar pressure
for a variety of
microporous materials at increasing pore volumes.
[0075] FIG. 33 is a graph showing relatively stable methane uptake at 5 bar
pressure for a variety
of microporous materials at increasing pore volumes.
[0076] FIG. 34 is a graph showing increased CO2 uptake at 5 bar pressure for a
variety of
microporous materials at increasing pore volumes.
[0077] FIG. 35 is a graph showing increased propane uptake at 1 bar pressure
for a variety of
microporous materials at increasing pore volumes.
[0078] FIG. 36 is a graph showing increased ethane uptake at 1 bar pressure
for a variety of
microporous materials at increasing pore volumes.
[0079] FIG. 37 is a graph showing relatively stable methane uptake at 1 bar
pressure for a variety
of microporous materials at increasing pore volumes.
[0080] FIG. 38 is a graph showing CO2 uptake at 1 bar pressure for a variety
of microporous
materials at increasing pore volumes.
[0081] FIG. 39 is a graph showing gas uptake at 9 bar for CO2, methane (C1),
ethane (C2), and
propane (C3) on porous materials of varying BET (Brunauer-Emmett-Teller)
surface area (SA).
[0082] FIG. 40 is a graph showing gas uptake at 1 bar for CO2, methane (CI),
ethane (C2), and
propane (C3) on porous materials of varying BET SA.
[0083] FIG. 41 is a graph showing gas uptake at 9 bar for CO2, methane (C1),
ethane (C2), and
propane (C3) on porous materials of varying oxygen content in wt. %, with
oxygen as a heteroatom
on activated carbon.
[0084] FIG. 42 is a graph showing gas uptake at 1 bar for CO2, methane (CI),
ethane (C2), and
propane (C3) on porous materials of varying oxygen content in wt. %, with
oxygen as a heteroatom
on activated carbon.
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DETAILED DESCRIPTION OF THE INVENTION
[0085] So that the manner in which the features and advantages of the
embodiments of systems
and methods of natural gas liquids recovery from pressure swing adsorption and
vacuum swing
adsorption as well as others, which will become apparent, may be understood in
more detail, a
more particular description of the embodiments of the present disclosure
briefly summarized
previously may be had by reference to the embodiments thereof, which are
illustrated in the
appended drawings, which form a part of this specification. It is to be noted,
however, that the
drawings illustrate only various embodiments of the disclosure and are
therefore not to be
considered limiting of the present disclosure's scope, as it may include other
effective
embodiments as well.
[0086] Referring first to FIG. 1A, a schematic is provided of an example PSA
cycle step schedule
using 6 beds to achieve production of a substantially pure methane product,
for example suitable
for transport in a pipeline and consumer use, or to achieve production of a
substantially pure target
molecular weight hydrocarbon separated from other higher molecular weight
hydrocarbons. In
FIG. IA proceeding from left to right, the individually labeled blocks, such
as "Feed" for example,
represent cycle steps, where the time for a cycle step (some amount of unit
step(s) as shown in the
Figures) can range from about 5 seconds or about 15 seconds to many minutes in
duration. As
well, the duration of each cycle step can also vary depending on the
separation to be carried out.
In the present disclosure, the quantity of unit steps can vary and the time
period for each unit step
and cycle step can vary. Depending on the unit steps and cycle steps, idle
steps may or may not
be part of a PSA method or system.
[0087] Referring to Beds 1-6, which include at least one adsorbent material
that is selective for
hydrocarbons, for example an adsorption bed comprising a heterogeneous high
surface area
carbon-containing adsorbent, a first step labelled "Feed" is carried out at a
constant, high pressure,
optionally the highest-available pressure of the PSA cycle. A light product
stream containing
lighter species, such as for example methane and/or ethane, is produced also
at a high pressure,
optionally about the highest-available pressure of a PSA cycle. Heavier
hydrocarbon components
and other components with a molecular weight greater than methane are adsorbed
to the adsorbent
at high pressure. For example, the Feed step in the present disclosure can be
carried out at between
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about 689 kPa (50 psia) and about 3,447 kPa (500 psia). The temperature of a
gas composition at
the Feed step in embodiments of the present disclosure can be between about
278 K to about 318
K, about 278 K to about 348 K, or between about 278 K to about 323 K.
[0088] In certain embodiments, the adsorbent is selected from a group
including, but not limited
to, zeolites, activated carbon, silica gel, and alumina. In some embodiments,
activated, porous
carbon particles derived from low-cost carbon sources are used as an
adsorbent. Highly-
microporous carbon particles advantageously have a much higher surface area
than typical
activated carbon. In another embodiment, the adsorbent can be carbon-based
molecular sieves. In
other embodiments, the adsorbent can include, or not include, metal-oxide
based molecular sieves
or metal organic frameworks. In certain embodiments, the adsorbent can include
nanoparticles.
The adsorbent material can be presented in a variety of physical forms,
including but not limited
to powders, beads, pellets, granules, rods, and coatings on sheets or
encapsulated between metal
fibers. The adsorbent material should have a large working capacity observed
for hydrocarbons,
such as methane and ethane, especially in a system operating between about 100
kPa to about 3500
kPa (about 14.7 psia to about 500 psia). Separate beds may use the same
adsorbent materials or
different adsorbent materials. Separate trains of PSA beds may use the same
adsorbent materials
in one or more layers within each bed or different adsorbent materials in one
or more layers within
each bed.
[0089] In some embodiments, suitable pressures for disclosed systems and
methods applying the
microporous or mesoporous adsorbent materials include pressures at about I bar
or greater. Porous
materials, including porous carbon-containing materials with optional
heteroatoms, can include
those materials with a surface area of at least 1,200 m2/g, and a total pore
volume of at least 0.8
cm3/g. In some embodiments, a majority of pores of the porous material have
diameters of less
than about 2 nm as measured from N2 sorption isotherms using the BET (Brunauer-
Emmett-
Teller) method. Porous materials, including porous carbon-containing materials
with optional
heteroatoms, can include those materials with a surface area of between at
least about 1,200 m2/g
and about 3,500 m2/g, or between at least about 1,200 m2/g and about 3,000
m2/g, and a total pore
volume of between at least about 0.8 cm3/g and about 1.4 cm3/g, or between at
least about 0.8
cm3/g and about 1.2 cm3/g.
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CA 3078066 2020-04-28
[0090] In some embodiments, a majority of the pores of the porous material
have diameters
between about 0.5 nm to about 10 nm, or between about 1 nm to about 5 nm, or
between about 1
nm to about 2 nm. In certain embodiments, the porous material has an oxygen
content of more
than about 4 wt. %, or between about 5 wt. % and about 25 wt. %, or between
about 10 wt. % and
about 20 wt. %, or between about 10 wt. % and about 15 wt. % as measured by X-
ray photoelectron
spectroscopy (XPS). Suitable porous materials can have an oxygen content
between about 4% and
20% as measured by XPS.
[0091] In some embodiments, more than 50% of the pores of the porous material
have diameters
of less than about 2 nm. Porous adsorbent materials of the present disclosure
can separate gases
including natural gas in addition to or alternative to other mixtures of
gases, for example carbon
dioxide byproduct streams of combustion processes. In some embodiments, the
porous material
has a nitrogen content of at least 1% as measured by XPS, which enhances the
selectivity of the
porous material in capturing gases heavier than ethane, in addition to or
alternative to an oxygen
content of at least 1% as measured by XPS or a sulfur content of at least 1%
as measured by XPS.
[0092] In some embodiments, the porous material has a nitrogen content between
about 1% and
about 12% as measured by XPS, which enhances the selectivity of the porous
material in capturing
gases heavier than ethane. In some embodiments, the porous material comprises
a porous carbon
material with a carbon content of between about 75% and about 95%, or between
about 75% and
about 90%, as measured by XPS.
[0093] Enhanced selectivity of CO2 capture from methane using porous material,
such as porous
carbon material, occurs above about 1 bar. Nano-pores (pores < 1 nm pore
diameters) do not
provide necessary enhancement in selectivity at increased pressures for
adsorption in some
embodiments.
[0094] Still referring to Bed 1 in FIG. IA, after the Feed step, next two
consecutive light end
equalization down steps, denoted by "Eqdl" and "Eqd2," are carried out from
the light end of the
bed to reduce the pressure of the bed and enrich the bed with heavier species
as they desorb from
the adsorbent material. Next, a countercurrent depressurization step, denoted
by "Cnd," is carried
out, in which gas is withdrawn from the feed end of the bed to constitute a
heavy product while
the pressure of the bed reaches the lowest pressure, or close to the lowest
pressure, of the PSA
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cycle. The lowest pressure in the PSA process cycle in embodiments of the
disclosure here can be
about 1 psia or about 1.5 psia. Vacuum may or not be applied to increase heavy
product recovery.
Afterwards, a light reflux step, denoted by "LR," is carried out at a constant
low pressure,
optionally, not necessarily, the lowest-available pressure of the PSA cycle,
during which a small
fraction of the light product stream containing the lighter species is fed
into the light end of a bed
to produce additional heavy product enriched in the heavier species.
[0095] Next, two consecutive light end equalization up steps, denoted by
"Equ2," "Equl," are
carried out through the light end that individually take all the gas coming
from light end
equalizations down steps, (Eqdl, Eqd2), taking first the gas coming from the
last down
equalization step Eqd2 (for example at Bed 4) and taking last the gas coming
from the first down
equalization step Eqd1 (for example at Bed 3), resulting in each case with a
partial re-
pressurization of Bed 1. Afterward, a light product pressurization step,
denoted by "LPP," is
carried out, wherein a small fraction of the light product stream containing
the lighter species is
fed into the light end of the bed to finalize the re-pressurization of the bed
to the highest pressure
prior to starting the Feed step corresponding to the next cycle.
[0096] FIG. 1B shows a graphic representation of the steps in a PSA cycle for
certain unit steps in
FIG. 1A. In a bed undergoing a Feed step at high pressure, feed stream 100
enters a bed, thereby
producing a light end stream 102 at the light end of the bed that is enriched
with the lighter species
and at essentially the pressure of the feed stream. A light product stream 104
is withdrawn and a
portion of light end stream 102 is withdrawn for light reflux stream 106, and
a portion of light end
stream 102 is withdrawn for light product pressurization stream 108. During a
first equalization
down in a bed (Eqdl) a first equalization up occurs in another bed (Equl)
shown by stream 110,
and during a second equalization down in a bed (Eqd2) a second equalization up
occurs in another
bed (Equ2) shown by stream 112.
[0097] During light reflux, light reflux stream 106 drives heavy product at
low pressure via stream
114, and this is combined with heavy product from countercurrent
depressurization in stream 116.
A heavy product stream at the heavy (feed) end of a bed that is enriched with
the heavier species
leaves a bed at pressures ranging between the feed pressure and the lowest
pressure of the cycle,
which may be less than atmospheric pressure with the aid of a vacuum pump.
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CA 3078066 2020-04-28
[0098] The process may utilize any arbitrary number of equalization down steps
with the same
number of corresponding equalization up steps. In some embodiments,
equalization tanks without
adsorbent material are used to reduce the required number of adsorbent beds,
and the number of
equalization tanks mediating an equalization step is either equal to the
number of down
equalization steps or equal to that number minus one. An increase in the
number of adsorbent beds
used and/or equalization tanks used can lead to an increase in the number of
equalization steps
used.
[0099] Referring now to FIG. 2A, a schematic is provided of an example PSA
cycle step schedule
using 7 beds to achieve production of a substantially pure methane product,
for example suitable
for pipeline transport and consumer use, or to achieve production of a
substantially pure target
molecular weight hydrocarbon separated from other higher molecular weight
hydrocarbons. FIG.
2A is similar to the configuration shown in FIG. 1A, with similarly labelled
cycle steps meaning
the same as that described for FIG. 1A, except that a 7th bed is shown, and an
additional
equalization up step "Equ3" and an additional equalization down step "Eqd3"
are shown as part
of the process. In other configurations, more or fewer than 6 or 7 beds can be
used with or without
any number of equalization tanks, where the equalization tanks do not contain
adsorbent material,
but help reduce the number of required adsorbent beds for a given separation.
In addition to
countercurrent depressurization, cocurrent depressurization steps also can be
utilized.
[00100] FIG. 2B shows a graphic representation of the steps in a PSA cycle
for certain unit
steps in FIG. 2A. FIG. 2B is similar to the configuration shown in FIG. 1B,
with similarly labelled
units being the same as that described for FIG. IA, except that with a 7th bed
as shown in FIG. 2A
an additional equalization up step "Equ3" and an additional equalization down
step "Eqd3" are
shown as part of the process, with stream 118 in FIG. 2B.
[00101] Referring now to FIG. 3A, a schematic is provided of an example
PSA cycle step
schedule using 6 beds to achieve production of a substantially pure methane
product, for example
suitable for transport in a pipeline and consumer use, or to achieve
production of a substantially
pure target molecular weight hydrocarbon separated from other higher molecular
weight
hydrocarbons. FIG. 3A is similar to the configuration shown in FIGS. IA and
2A, with similarly
labelled cycle steps meaning the same as that described for FIG. IA and 2A,
except that an
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CA 3078066 2020-04-28
additional heavy reflux step "HR" is shown as part of the process. In other
configurations, more
or fewer than 6 or 7 beds can be used with or without any number of
equalization tanks, where the
equalization tanks do not contain adsorbent material, but help reduce the
number of required
adsorbent beds for a given separation. In addition to countercurrent
depressurization, cocurrent
depressurization steps also can be utilized.
[00102] FIG. 3B shows a graphic representation of the steps in a PSA cycle
for certain unit
steps in FIG. 3A. FIG. 3B is similar to the configurations shown in FIGS. 1B
and 2B, with
similarly labelled units being the same as that described for FIG. IA, except
that with a heavy
reflux step as shown in FIG. 3A, an additional heavy reflux step "HR" is shown
as part of the
process, with stream 120 in FIG. 3B showing a portion of gas from the light
reflux step in one bed
proceeding for use in the HR step in another bed. After heavy reflux, product
stream 122 returns
light product to light end stream 102. In general, reflux steps such as light
reflux and heavy reflux
are used in pressure swing adsorption processes to help produce products at
greater recovery rates
and at greater purity. In FIG. 3B a compressor pump 124 is shown to indicate
that stream 120 is
pressurized to ultimately produce product stream 122 which comprises light
product at high
pressure. Also shown is optional vacuum pump 126 which can apply a vacuum to
stream 116 and
a bed in which countercurrent depressurization is taking place to produce
heavy product at low
pressure.
[00103] One of ordinary skill in the art will understand other compressor
and vacuum pumps
can be applied as necessary between beds to create desired pressure swings
within a pressure swing
system during operation. In certain embodiments of systems and methods of the
present
disclosure, vacuum pumps and applied vacuum is optional.
[00104] Referring now to FIG. 4A, a schematic is provided of an example
PSA cycle step
schedule using 7 beds to achieve production of a substantially pure methane
product, for example
suitable for pipeline transport and consumer use, or to achieve production of
a substantially pure
target molecular weight hydrocarbon separated from other higher molecular
weight hydrocarbons.
FIG. 4A is similar to the configuration shown in previous figures, for example
FIG. 3A, with
similarly labelled cycle steps meaning the same as that described for previous
figures, except that
an additional idle step "I" is shown as part of the process. In other
configurations, more or fewer
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CA 3078066 2020-04-28
than 6 or 7 beds can be used with or without any number of equalization tanks,
where the
equalization tanks do not contain adsorbent material, but help reduce the
number of required
adsorbent beds for a given separation. In addition to countercurrent
depressurization, cocurrent
depressurization steps also can be utilized.
[00105] FIG. 4B shows a graphic representation of the steps in a PSA cycle
for certain unit
steps in FIG. 4A. FIG. 4B is similar to the configuration shown in FIGS. 1B,
2B, and 3B, with
similarly labelled units being the same as that described for previous
figures. As noted, FIG. 4B
represents an idle step "I" also shown in FIG. 4A. In some embodiments, an
optional idle step is
used to allow other beds in a PSA system to match up for sequencing purposes.
An idle step is a
period of time in a PSA cycle where a bed is not producing gas, regenerating,
or adsorbing gas.
[00106] Referring now to FIG. 5A, a schematic is provided of an example
PSA cycle step
schedule using 6 beds to achieve production of a substantially pure methane
product, for example
suitable for pipeline transport and consumer use, or to achieve production of
a substantially pure
target molecular weight hydrocarbon separated from other higher molecular
weight hydrocarbons.
FIG. 5A is similar to the configurations shown in previous figures, with
similarly labelled cycle
steps meaning the same as that described for previous figures. In other
configurations, more or
fewer than 6 or 7 beds can be used with or without any number of equalization
tanks, where the
equalization tanks do not contain adsorbent material, but help reduce the
number of required
adsorbent beds for a given separation. In addition to countercurrent
depressurization, cocurrent
depressurization steps also can be utilized.
[00107] FIG. 5B shows a graphic representation of the steps in a PSA cycle
for certain unit
steps in FIG. 5A. FIG. 5B is similar to the configuration of previously
labeled figures, with
similarly labelled units being the same as that described for previous
figures.
[00108] Referring now to FIG. 6A, a schematic is provided of an example
PSA cycle step
schedule using 7 beds to achieve production of a substantially pure methane
product, for example
suitable for pipeline transport or consumer use, or to achieve production of a
substantially pure
target molecular weight hydrocarbon separated from other higher molecular
weight hydrocarbons.
FIG. 6A is similar to the configuration shown in previous figures, with
similarly labelled cycle
steps meaning the same as that described for previous figures. In other
configurations, more or
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CA 3078066 2020-04-28
fewer than 6 or 7 beds can be used with or without any number of equalization
tanks, where the
equalization tanks do not contain adsorbent material, but help reduce the
number of required
adsorbent beds for a given separation. In addition to countercurrent
depressurization, cocurrent
depressurization steps also can be utilized.
[00109] FIG. 6B shows a graphic representation of the steps in a PSA cycle
for certain unit
steps in FIG. 6A. FIG. 6B is similar to the configuration of previously
labeled figures, with
similarly labelled units being the same as that described for previous
figures. FIG. 6B includes
stream 113 which shows a transfer of gas from one bed to another during Eqd3
and Equ3.
[00110] Referring now to FIG. 7A, a schematic is provided of an example
PSA cycle step
schedule using 5 beds to achieve production of a substantially pure methane
product, for example
suitable for transport in a pipeline or consumer use, or to achieve production
of a substantially pure
target molecular weight hydrocarbon separated from other higher molecular
weight hydrocarbons.
FIG. 7A is similar to the configuration shown in previous figures, with
similarly labelled cycle
steps meaning the same as that described for previous figures. In other
configurations, more or
fewer than 5 beds can be used with or without any number of equalization
tanks, where the
equalization tanks do not contain adsorbent material, but help reduce the
number of required
adsorbent beds for a given separation. In addition to countercurrent
depressurization, cocurrent
depressurization steps also can be utilized.
[00111] FIG. 7B shows a graphic representation of the steps in a PSA cycle
for certain unit
steps in FIG. 7A. FIG. 7B is similar to the configuration of previously
labeled figures, with
similarly labelled units being the same as that described for previous
figures.
[00112] FIGS. 8-10 show schematics of example PSA cycle step schedules
using 6 beds to
achieve production of a substantially pure methane product, for example
suitable for transport in
a pipeline and consumer use, or to achieve production of a substantially pure
target molecular
weight hydrocarbon separated from other higher molecular weight hydrocarbons.
In FIG. 8, a
countercurrent depressurization step is followed by an idle step, and the idle
step precedes a light
reflux step. In FIG. 9, an idle step falls in between LR and Equ2. In FIG. 10,
an idle step precedes
a CnD step and follows Eqd2. FIGS. 8-10 show the flexibility in design for PSA
schedules in
embodiments of the present disclosure. While the time of unit steps
corresponding to individual
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CA 3078066 2020-04-28
cycle steps may be increased or decreased to impact cycle times, idle steps
may in some
embodiments be necessary to keep gas flows internally consistent between
adsorbent beds or tanks.
[00113] For example, comparing FIG. 8 to FIG. 1A, the countercurrent
depressurization
step of FIG. 8 has been decreased to 2 unit steps of time, rather than 3 as
shown in FIG. 1A. This
may be desired if less heavy product needs to be withdrawn at low pressure
during countercurrent
depressurization during a separation. Unit steps can be the same amount of
time or different
amounts of time within a PSA system and between PSA systems, optionally
resulting in idle steps,
to achieve a desired separation between hydrocarbon components of varying
molecular weight.
Examples
[00114] In the examples that follow, one objective is to have a continuous
feed PSA cycle,
regardless of how that is achieved by dividing up the number of unit steps
within a unit block,
where the number of unit blocks is equal to the number of beds. In the first
example, with the aid
of FIGS. IA and 1B, there are 6 unit blocks because it is a 6-bed PSA cycle.
In the first example,
there are 2 unit steps in the fraction of the unit block corresponding to one
of the 6 beds. This
means there are 12 total unit steps in the first example, 2 for each bed. In
some PSA systems,
every other unit step should be about the same duration within the cycle, for
example odd
numbered unit steps being substantially the same length of time and even
numbered unit steps
being substantially the same length of time. Such a schedule can help keep the
flow of gases within
a multi-bed system internally consistent and balanced. To be a continuous feed
PSA cycle, the
feed step of each bed should occupy two unit steps, as shown in the first
example in FIG. 1A.
[00115] One of ordinary skill in the art would understand that the unit
blocks could very
well include 18 unit steps, i.e., 3 unit steps for each bed, and that the feed
step of each bed would
then occupy 3 unit steps. The durations of the other cycle steps could occupy
just 1 unit step or
several unit steps, as shown by the example in FIG. 1A, where, e.g., the feed
step occupies 2 unit
steps, an EqD step occupies 1 unit step and the CnD step occupies 3 unit
steps. The durations of
all the other cycle steps relative to the feed step could vary depending on
the number of unit steps
in a unit block, with the duration of the unit step time having no limitations
or restrictions and with
the number of unit steps in a unit block having no limitations or
restrictions, unless they are
imposed by the PSA process design. With these objectives in mind, non-limiting
examples are
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CA 3078066 2020-04-28
provided below.
[001161 Example 1 provides an example 6-bed, 8-cycle step (12 unit step)
adsorption bed
separation of the components of a raw natural gas stream with an initial feed
pressure of 100 psia
and 298 K. In other situations, more or fewer adsorption beds could be used,
at different
temperatures and pressures, and with optional equalization tanks. Example 1
follows the layout
shown in FIGS. IA and 1B. The feed gas composition is shown in Table 1. In
Example 1, the
unit step time of 60 seconds was used (with 2 unit steps per unit block as
described previously),
while the cycle step durations in this schedule ranged between 60 seconds and
180 seconds.
Table 1. Feed gas composition for Example 1.
Feed Gas Composition
Component Component Mol. fraction
CI Methane 80.0%
C2 Ethane 11.0%
C3 Propane 3.8%
C4 Butane 1.7%
C5+ Pentane and Heavier 0.8%
CO2 Carbon Dioxide 1.8%
N2 Nitrogen 0.9%
[00117] The example multi-bed PSA process produces a substantially pure
methane product
stream (sales gas) and also achieves high ethane, propane, and butane recovery
in the heavy
product stream, as shown in Table 2.
Table 2. Light and heavy product streams for Example I.
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,
Heavy Product Light Product
Component Recovery % Mol. fraction
Recovery % Mol. fraction
Cl 4.4% 15.8% 95.6%
98.4%
C2 98.3% 48.6% 1.5% 0.2%
C3 99.7% 17.1% 0.0% 0.0%
C4 100.0% 7.8% 0.0% 0.0%
C5+ 100.0% 3.5% 0.0% 0.0%
CO2 87.4% 7.1% 13.3% 0.3%
N2 1.9% 0.1% 97.0% 1.1%
[00118] There is flexibility in the PSA process to enable CO2 to be
separated in the light
product stream alternative to the heavy product stream. For example, Table 3
shows that the CO2
has been mostly separated into the light product, while still achieving high
ethane, propane, and
butane recovery in the heavy product stream.
Table 3. Light and heavy product streams for alternative embodiment of Example
1.
Heavy Product Light Product
Component Recovery % Mol. fraction
Recovery % Mol. fraction
Cl 2.2% 9.4% 97.8%
96.1%
C2 93.5% 55.6% 6.0% 0.8%
C3 98.9% 20.3% 0.0% 0.0%
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C4 100.0% 9.4% 0.0% 0.0%
C5+ 100.0% 4.2% 0.0% 0.0%
CO2 10.9% 1.1% 89.7% 2.0%
N2 2.0% 0.1% 97.9% 1.1%
[00119] Example 2 provides an example 7-bed, 10-cycle step (14 unit step)
adsorption bed
separation of the components of a raw natural gas stream with an initial feed
pressure of 500 psia
and 298 K. In other situations, more or fewer adsorption beds could be used,
at different
temperatures and pressures, and with optional equalization tanks. Example 2
follows the layout
shown in FIGS. 2A and 213. The feed gas composition is shown in Table 4. In
this example, the
unit step time of 60 seconds was used, while the cycle step durations in this
schedule ranged
between 60 seconds and 180 seconds.
Table 4. Feed gas composition for Example 2.
Feed Gas Composition
Component Component Mol. fraction
Cl Methane 80.0%
C2 Ethane 11.0%
C3 Propane 3.8%
C4 Butane 1.7%
C5+ Pentane and Heavier 0.8%
CO2 Carbon Dioxide 1.8%
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N2 Nitrogen 0.9%
[00120] The example multi-bed PSA process produces a substantially pure
methane product
stream (sales gas) and also achieves high ethane, propane, and butane recovery
in the heavy
product stream, as shown in Table 5.
Table 5. Light and heavy product streams for Example 2.
Heavy Product Light Product
Component Recovery % Mol fraction
Recovery % Mol fraction
Cl 2.2% 8.6% 97.0% 98.3%
C2 98.5% 52.9% 1.5% 0.2%
C3 99.3% 18.4% 0.7% 0.0%
C4 100.0% 8.5% 0.0% 0.0%
C5+ 100.0% 3.8% 0.0% 0.0%
CO2 88.5% 7.8% 13.3% 0.3%
N2 1.9% 0.1% 98.0% 1.1%
[00121] There is flexibility in the PSA process to enable CO2 to be
separated in the light
product stream alterative to the heavy product stream, as shown in Table 6.
Table 6. Light and heavy product streams for alternative embodiment of Example
2.
Heavy Product Light Product
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Component Recovery % Mol. fraction
Recovery % Mol. fraction
Cl 2.0% 8.8% 97.8% 95.9%
C2 94.3% 56.8% 6.0% 0.8%
C3 95.0% 19.8% 5.0% 0.2%
C4 100.0% 9.5% 0.0% 0.0%
C5+ 100.0% 4.2% 0.0% 0.0%
CO2 7.5% 0.7% 91.7% 2.0%
N2 2.0% 0.1% 97.9% 1.1%
[00122] Example 3 provides an example 7-bed, 10-cycle step (14 unit step)
adsorption bed
separation of the components of a raw natural gas stream with an initial feed
pressure of 500 psia
and temperatures of 278 K, 298 K, and 318 K. In other situations, more or
fewer adsorption beds
could be used, at different temperatures and pressures, and with optional
equalization tanks.
Example 3 follows the layout shown in FIGS. 2A and 213. The feed gas
composition is shown in
Table 7.
Table 7, Feed gas composition for Example 3.
Feed Gas Composition
Component Component Mol. fraction
Cl Methane 80.0%
C2 Ethane 11.0%
C3 Propane 3.8%
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C4 Butane 1.7%
C5+ Pentane and Heavier 0.8%
CO2 Carbon Dioxide 1.8%
N2 Nitrogen 0.9%
[00123] A multi-bed PSA process can achieve high ethane, propane, and
butane recovery
under a wide range of feed gas temperatures (from about 278 K to about 318 K),
as shown in Table
8.
Table 8. Heavy product streams for alternative embodiments of Example 3.
278K 298K 318K
Heavy Product Heavy Product Heavy Product
Component Recovery Mol. Recovery Mol. Recovery Mol.
% fraction % fraction %
fraction
Cl 2.0% 7.9% 2.2% 8.6% 2.3% 9.2%
C2 99.3% 54.6% 98.5% 52.9% 98.8% 53.1%
C3 96.5% 18.3% 99.3% 18.4% 99.8% 18.5%
C4 99.8% 8.7% 100.0% 8.5% 100.0%
8.5%
C5+ 100.0% 3.8% 100.0% 3.8% 100.0%
3.8%
CO2 73.6% 6.6% 88.5% 7.8% 77.6% 6.8%
N2 1.0% 0.0% 1.9% 0.1% 1.6% 0.1%
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[00124] In further separations of the "heavy" product carried out after
the separation of
methane from raw natural gas, "C2" (ethane) can be separated from C3, C4, C5+,
CO2, and N2.
Using multiple PSA units or trains fluidly coupled together, each having one
or more adsorbent
beds, each component of raw natural gas can be separated.
[00125] Example 4 provides an example 6-bed, 9-cycle step (12 unit step)
adsorption bed
separation of the components of a raw natural gas stream with an initial feed
pressure of no more
than 100 psia and no less than 60 psia, but preferably between about 70 psia
and about 80 psia
with the feed temperatures between about 278 K to 363 K. The lowest pressure
in the process is
between about 2.8 psia and about 7 psia. Example 4 follows the layout shown in
FIGS. 3A and
3B. The general gas composition range in which this example is applicable is
shown in Table 9.
Table 9. Feed gas composition range for Example 4.
Feed Gas Composition
Component Component Lower Limit of Upper
Limit of Mol.
MoL% Range % Range
Cl Methane 70.0% 88.0%
C2 Ethane 5.0% 14.0%
C3 Propane 3.0% 7.0%
C4 Butane 0.4% 3.0%
C5+ Pentane and Heavier 0.3% 3.0%
CO2 Carbon Dioxide 0.0% 3.0%
N2 Nitrogen 0.0% 2.0%
[00126] Example 4 provides a multi-bed PSA process where at least about
95% of the C3+
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is recovered in the heavy product, and all nitrogen is rejected into the light
product with the heavy
product gas having no more than 0.5 mol.% of methane. The light product,
containing mostly
methane, will meet specifications generally accepted to allow for pipeline
transportation and/or
consumer use.
[00127] Subsequently, if further separation of ethane from other non-
methane hydrocarbons
in the heavy product is desired, then an additional PSA unit comprising the
same 6-bed, 9 cycle
step process can be coupled to the first PSA unit to enact this additional
separation. In other words,
the 6 bed PSA system shown in FIGS. 3A and 3B can be repeated in series for
subsequent
separation of hydrocarbon species heavier than methane. The inlet pressure for
the subsequent
separation can range from about 30 psia to about 250 psia with the inlet
temperature between about
278 K to about 323 K, and the lowest pressure in the system being between
about 2.8 and about
7.0 psia. At least 90 mol.% of the C3+ is recovered with the product gas
having substantially no
CO2, no more than about 0.5 mol.% of methane, and having most of the ethane
removed. Table
provides a range of gas compositions in which the separation of ethane from
other non-methane
hydrocarbons is applicable.
Table 10. Inlet range of "heavy" gas composition for ethane separation.
Heavy Feed Gas Composition Following Initial Methane Separation
Component Component Lower Limit of Upper
Limit of Mol.
Mol.% Range % Range
Cl Methane 0.0% 3.0%
C2 Ethane 40.0% 70.0%
C3+ Propane 15.0% 60.0%
CO2 Carbon Dioxide 0.0% 10.0%
[00128] Table 11 shows the recovery percentage of C3+ after ethane
separation.
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Table 11. C3+ product range after ethane separation.
C3+ Product Composition
Component Component Lower Limit of Upper Limit of Mol.
Mol.% Range % Range
Cl Methane 0.0% 2.0%
C2 Ethane 0.0% 0.3%
C3+ Propane and heavier 90.0% 99.0%
CO2 Carbon Dioxide 0.0% 0.0%
[00129] In Example 4, where 2 series-linked 6-bed separations take place,
in both
adsorption bed separations, the first for methane separation and the second
for ethane separation,
the following PSA steps occur: a feed step; a heavy reflux (HR) step; two
equalization down steps
(Eqd 1, Eqd2); a countercurrent depressurization step (CnD); a light reflux
step (LR); two
equalization up steps (Equ2, Equl); and a light product pressurization step
(LPP). The LRR,
shown in FIG. 3B, is the light reflux ratio that represents the fraction of
the gas leaving the feed
step to be used as feed in the LR step.
[00130] Example 5 provides an example of a 7-bed, 10-cycle step (14 unit
step) adsorption
bed separation and follows the layout shown in FIGS. 4A and 413. One purpose
of this cycle is
similar to that of Example 4 (FIGS. 3A and 3B), except that the countercurrent
depressurization
step is made longer to ensure better regeneration. Similar to Example 4, the
purified methane
product will meet specifications generally accepted to allow for pipeline
transportation. The
sequence involves the following PSA steps: a feed step; a heavy reflux step
(HR); two equalization
down steps (Eqd I, Eqd2); a countercurrent depressurization step (CnD); an
idle step (I); a light
reflux step (LR); two equalization up steps (Equ2, EquI); and a light product
pressurization step
(LPP). The LRR is the light reflux ratio that represents the fraction of the
gas leaving the feed step
to be used as feed in the LR step.
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[00131] Example 6 provides an example of a second 6-bed, 9-step PSA cycle
and follows
the layout shown in FIGS. 5A and 5B. One purpose of this cycle is the same as
that of Example
4, for the removal of both methane and N2 and partial removal of both CO2 and
ethane from a raw
natural gas stream. The range of acceptable gas compositions for separation is
the same as
Example 4 (Table 9). One difference in inlet conditions, however, between
Examples 4 and 6 is
that the feed pressure is between about 80 psia and about 200 psia here for
Example 6 versus for
Example 4 with an initial feed pressure of no more than 100 psia and no less
than 60 psia, but
preferably between about 70 psia and about 80 psia.
[00132] The separation outcome of Example 6 is similar to Examples 4 and
5, and purified
methane product that meets pipeline specifications is produced. The sequence
involves the
following PSA steps: a feed step, a first equalization down step (Eqdl), a
heavy reflux step (HR),
a second equalization down step (Eqd2), a countercurrent depressurization step
(CnD), a light
reflux step (LR), two equalization up steps (Equ2, Equl), and a light product
pressurization step
(LPP). The LRR is the light reflux ratio that represents the fraction of the
gas leaving the feed step
to be used as feed in the LR step. The LRR and the light product
pressurization stream in a given
PSA system or method can vary from about substantially 0% to about
substantially 100%, for
example about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% of a
light product
stream produced at high pressure, depending on the desired separation
requirements and inlet
conditions of a natural gas stream. In certain embodiments exemplified here,
the LRR is between
about 4% and about 20% of a light product stream produced at high pressure and
LPP is about
between 4% and about 20% of the of a light product stream produced at high
pressure.
[00133] Example 7 is an example of a 7-bed, 11-step PSA cycle similar in
purpose to
Example 6, but is applicable when feed pressure is equal to or greater than
150 psia. Example 7
is represented via FIGS. 6A and 6B. The sequence involves the following PSA
steps: feed step;
two equalization down steps (Eqdl , Eqd2); a heavy reflux step (HR); a third
equalization down
step (Eqd3); a countercurrent depressurization step (CnD); a light reflux step
(LR); three
equalization up steps (Equ3, Equ2, Equl); and a light product pressurization
step (LPP). The LRR
is the light reflux ratio that represents the fraction of the gas leaving the
feed step to be used as
feed in the LR step.
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[00134] As discussed in Example 4, if the "heavy" products produced in
Examples 5, 6 and
7 require subsequent separation of ethane from the other non-methane
hydrocarbons purified, then
the cycle and sequence presented in Example 4 can be used for further
separation purposes. A 6-
bed 9-step cycle, from Example 4, will effectively separate ethane from all
other hydrocarbons
present, so a substantially pure ethane product is produced and a second NGL
product meeting
commercial specifications that is substantially free from ethane is also
produced. The need for
this additional separation step may be due to commercial or market
considerations or they can be
due to vapor pressure considerations. For example, ethane has a much higher
vapor pressure than
propane and other heavy hydrocarbons, so storage vessels and transportation
pipelines for NGLs
need to be maintained at much higher pressures if ethane is present in an NGL
product. Therefore,
there is a distinct advantage in being able to separate hydrocarbons by
example systems and
methods of the present disclosure, for example to isolate methane and to
isolate ethane.
[00135] Example 8 is a 5-bed, 7-step PSA cycle represented by FIGS. 7A and
7B. One
purpose of this cycle is the same as that of the 6-bed, 9-step PSA cycle shown
in Example 4 and
generally for the removal of ethane from a stream containing predominantly
hydrocarbons greater
than methane and is applicable when the feed pressure for the separation is no
more than about 30
psia. The sequence involves the following PSA steps: a feed step, a heavy
reflux step (HR), an
equalization down step (Eqdl), a counter depressurization step (CnD), a light
reflux step (LR), an
equalization up step (Equ 1 ), and a light product pressurization step (LPP).
The LRR is the light
reflux ratio that represents the fraction of the gas leaving the feed step to
be used as feed in the LR
step.
[00136] Table 12 shows data for elemental composition for certain porous
materials tested,
with certain experimental results being displayed in FIGS. 11-42. Data from
Tables 12-16 are
represented in FIGS. 11-42.
[00137] The porous materials may be prepared in various manners. For
instance, in some
embodiments, the porous materials are prepared by activating an organic
polymer precursor or
biological material ¨ these biological materials include, without limitation,
sawdust, coconut husk,
and combinations thereof ¨ in the presence of one or more hydroxide, such as
potassium
hydroxide. In some embodiments, the temperature of activation is between about
500 C and 800
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C. In some embodiments, the temperature of the activation is between about 700
C and 800
C. In some embodiments, the precursor materials used to make these porous
materials can contain
various chemical components, such as oxygen or nitrogen, so that the final
porous materials used
for adsorption will have elemental/chemical content physically and/or
chemically incorporated
within.
[00138] The following volumetric uptake measurements (sorption and
desorption) of all
gases by porous materials were performed in an automated Sievert instrument.
Samples were
initially pre-treated at 130 C for 1.5 hours under vacuum, and free volume
inside a sample cell
was determined under helium. Gas uptake experiments were carried out with high-
purity, research
grade gases at 24 C. Additional experimental results and characterizations of
porous materials
were obtained using XPS, Fourier-transform infrared spectroscopy (FTIR), Raman
spectroscopy,
and a BET surface area analyzer. All measured values for gas uptake have been
confirmed via
volumetric experiments, gravimetric experiments, multiple samples, and
multiple cycles of
experiments.
Table 12. Elemental composition of example porous materials tested for
uptake/adsorption of
CO2, methane, ethane, and propane.
Elemental Composition wt. %
Sample Material
Carbon Oxygen Sulfur Nitrogen
OPC 500 76.66 23.34 0 0
OPC 600 83.36 13.64 0 0
OPC 700 89.37 10.63 0 0
OPC 750 91.01 8.99 0 0
OPC 800 91.27 8.73 0 0
BPL 91.3 8.7 0 0
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Activated Charcoal Powder (ACP) 94.1 5.9 0 0
Asphalt n/a n/a n/a n/a
SPC-2-700 (Sulfur Containing) 78.89 13.73 7.37 0
NPC (Polyacrylonitrile (PAN)) 84.5 6,75 0 8.75
(Nitrogen Containing)
[00139] OPC 500, OPC 600, OPC 700, OPC 750, and OPC 800 represent tested
porous
carbons with oxygen content, where activation of the carbons occurred at 500
C, 600 C, 700 C,
750 C, and 800 C, respectively. BPL represents tested granulated, activated
carbon acquired
commercially from Calgon Carbon. Activated Charcoal Powder (ACP) represents
tested activated
charcoal that was commercially acquired from Mallinckrodt Chemicals. Asphalt
represents tested
asphalt derived from activated porous carbon at 700 C.
[00140] SPC-2-700 represents tested sulfur containing activated porous
carbon activated at
700 'C. NPC represents tested polyacrylonitrile derived porous carbon
activated at 600 C. Other
adsorbent materials can include polythiophene derived porous carbon activated
at about 800 "V,
polypyrrole derived porous carbon activated at about 500 C, and polypyrrole
derived porous
carbon activated at about 600 C.
[00141] Table 13 shows data for surface area and pore size distribution
for certain porous
materials tested, with certain results being displayed in FIGS. 11-42.
Table 13. Surface area and pore size distribution of example porous materials
tested for
uptake/adsorption of CO2, methane, ethane, and propane.
Pore Size Distribution
Surface
Sample Material Area Volume Volume Volume Volume Total
(ng/g)
(Micro) (Nano) (0- (Vi) (1-2 (Meso) Micro
(0-2 nm) 1 nm) nm) (2-50 nm) + Meso
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CA 3078066 2020-04-28
(cm3/g) (cm3/g) (cm3/g) (cm3/g) Pore
Volume
(cm3/g)
OPC 500 853 0.41 0.3 0.11 0.06 0.47
OPC 600 1980 0.94 0.38 0.56 0.16 1.10
OPC 700 2700 1.18 0.32 0.86 0.32 1.50
OPC 750 3310 1.24 0.12 1.12 0.58 1.82
OPC 800 3040 0.64 0.08 0.56 1.57 2.21
BPL 951 0.38 0.13 0.25 0.12 0.50
Activated Charcoal 845 0.32 0.11 0.21 0.11 0.43
Powder (ACP)
Asphalt 2910 1.01 0.13 0.88 0.39 1.40
SPC-2-700 (Sulfur 2180 0.76 0.16 0.6 0.35 1.11
Containing)
NPC 1410 0.68 0.2 0.48 0.6 1.28
(Polyacrylonitrile
(PAN)) (Nitrogen
Containing)
[00142] Table 14 shows data for CO2, methane, ethane, and propane uptake
at 1 bar for
certain porous materials tested, with certain results being displayed in FIGS.
35-38.
Table 14. CO2, methane, ethane, and propane uptake at 1 bar for example porous
materials tested
for uptake/adsorption.
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Uptake at 1 bar pressure
Sample Material
CO2 (mmol/g) Methane Ethane Propane
(mmol/g) (mmol/g) (mmol/g)
OPC 500 1.91 0.6 3.22 2.91
OPC 600 2.02 0.68 6.05 6.58
OPC 700 1.48 0.7 5.97 8.46
OPC 750 2.65 0.66 6.81 9.57
OPC 800 1.2 0.76 4.56 5.2
BPL 1.5 0.45 2.77 2.85
Activated Charcoal Powder 2.03 0.83 3.24 3.77
(ACP)
Asphalt 1.74 0.72 n/a 7.78
SPC-2-700 (Sulfur Containing) 1.46 0.71 4.14 4.8
NPC (Polyacrylonitrile (PAN)) 2.32 0.84 2.62 3.78
(Nitrogen Containing)
[00143] Table 15 shows data for CO2, methane, ethane, and propane uptake
at 5 bar for
certain porous materials tested, with certain results being displayed in FIGS.
23-34.
Table 15. CO2, methane, ethane, and propane uptake at 5 bar for example porous
materials tested
for uptake/adsorption.
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Uptake at 5 bar pressure
Sample Material
CO2 (mmol/g) Methane Ethane Propane
(mmol/g) (mmol/g) (mmol/g)
OPC 500 5.59 1.96 4.18 3.89
OPC 600 7.64 3.06 8.95 8.63
OPC 700 6.92 2.903 11.27 12.95
OPC 750 8.93 2.98 12.013 15.098
OPC 800 5.63 3.088 9.32 7.84
BPL 4.52 1.96 4.33 4.45
Activated Charcoal Powder 4.84 3.15 4.59 5.53
(ACP)
Asphalt 7.56 3.05 n/a 11.98
SPC-2-700 (Sulfur Containing) 5.6 2.69 8.077 8.41
NPC (Polyacrylonitrile (PAN)) 6.1 2.83 3.94 6.75
(Nitrogen Containing)
[00144] Table 16 shows data for CO2, methane, ethane, and propane uptake
at 9 bar for
certain porous materials tested, with certain results being displayed in FIGS.
11-22.
Table 16. CO2, methane, ethane, and propane uptake at 9 bar for example porous
materials tested
for uptake/adsorption.
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Uptake at 9 bar pressure
Sample Material
CO2 (mmol/g) Methane Ethane Propane
(mmol/g) (mmol/g) (mmol/g)
OPC 500 6.65 2.4 4.6 5
OPC 600 10.91 4.4 9.62 10.55
OPC 700 11.72 4.34 13.41 15.41
OPC 750 13.01 4.56 14.85 17.24
OPC 800 9.01 4.43 10.8 9.14
BPL 5.8 3 5.04 5.5
Activated Charcoal Powder 6 4.09 5.06 7.25
(ACP)
Asphalt 11.7 4.492 n/a 14.25
SPC-2-700 (Sulfur Containing) 8.1 3.88 9.9 10.3
NPC (Polyacrylonitrile (PAN)) 7.83 3.91 4.12 9.1
(Nitrogen Containing)
[00145] Referring now to FIGS. 11-14, there is strong correlation between
microporosity
and gas uptake at 9 bar, especially for CO2 and propane, where increasing
microporosity leads to
better uptake/adsorption of these gases. For methane, there is some initial
uptake enhancement
with greater microporosity, but then there is no additional gains in uptake of
selectivity due to
microporosity, above about 0.5 cm3/g. FIG. 11 is a graph showing increased
propane uptake at 9
bar pressure for a variety of microporous materials at increasing pore
volumes. FIG. 12 is a graph
showing increased ethane uptake at 9 bar pressure for a variety of microporous
materials at
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increasing pore volumes. FIG. 13 is a graph showing increased methane uptake
at 9 bar pressure
for a variety of microporous materials at increasing pore volumes. FIG. 14 is
a graph showing
increased CO2 uptake at 9 bar pressure for a variety of microporous materials
at increasing pore
volumes.
[00146] Referring now to FIGS. 15-18, for nanoporous materials with
nanopores below
about 1 nm, there is little to no correlation between increased nanoporosity
volume and enhanced
uptake. FIG. 15 is a graph showing propane uptake at 9 bar pressure for a
variety of nanoporous
materials at increasing pore volumes. FIG. 16 is a graph showing ethane uptake
at 9 bar pressure
for a variety of nanoporous materials at increasing pore volumes. FIG. 17 is a
graph showing
methane uptake at 9 bar pressure for a variety of nanoporous materials at
increasing pore volumes.
FIG. 18 is a graph showing CO2 uptake at 9 bar pressure for a variety of
nanoporous materials at
increasing pore volumes.
[00147] Referring now to FIGS. 19-22, a correlation exists between about 1
nm and about
2 nm pores, where there is a correlation between increased pore volume with
gas uptake. FIG. 19
is a graph showing increased propane uptake at 9 bar pressure for a variety of
microporous
materials at increasing pore volumes. FIG. 20 is a graph showing increased
ethane uptake at 9 bar
pressure for a variety of microporous materials at increasing pore volumes.
FIG. 21 is a graph
showing relatively stable methane uptake at 9 bar pressure for a variety of
microporous materials
at increasing pore volumes. FIG. 22 is a graph showing increased CO2 uptake at
9 bar pressure
for a variety of microporous materials at increasing pore volumes.
[00148] Referring now to FIGS. 23-30, results are similar at 5 bar for
micropores and
nanopores as discussed at 9 bar. FIG. 23 is a graph showing increased propane
uptake at 5 bar
pressure for a variety of microporous materials at increasing pore volumes.
FIG. 24 is a graph
showing increased ethane uptake at 5 bar pressure for a variety of microporous
materials at
increasing pore volumes. FIG. 25 is a graph showing relatively stable methane
uptake at 5 bar
pressure for a variety of microporous materials at increasing pore volumes.
FIG. 26 is a graph
showing increased CO2 uptake at 5 bar pressure for a variety of microporous
materials at increasing
pore volumes. FIG. 27 is a graph showing propane uptake at 5 bar pressure for
a variety of
nanoporous materials at increasing pore volumes. FIG. 28 is a graph showing
ethane uptake at 5
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bar pressure for a variety of nanoporous materials at increasing pore volumes.
FIG. 29 is a graph
showing relatively stable methane uptake at 5 bar pressure for a variety of
nanoporous materials
at increasing pore volumes. FIG. 30 is a graph showing increased CO2 uptake at
5 bar pressure
for a variety of nanoporous materials at increasing pore volumes
[00149] Referring now to FIGS. 31-34, correlation for increased uptake in
increased pore
sizes for propane, ethane, and CO2 and enhancement of selectivity versus
methane occurs between
an about 1 nm to about 2 nm pore size range, and generally not less than 1 nm
or in the Angstrom
range. FIG. 31 is a graph showing increased propane uptake at 5 bar pressure
for a variety of
microporous materials at increasing pore volumes. FIG. 32 is a graph showing
increased ethane
uptake at 5 bar pressure for a variety of microporous materials at increasing
pore volumes. FIG.
33 is a graph showing relatively stable methane uptake at 5 bar pressure for a
variety of
microporous materials at increasing pore volumes. FIG. 34 is a graph showing
increased CO2
uptake at 5 bar pressure for a variety of microporous materials at increasing
pore volumes.
[00150] Referring now to FIGS. 35-38, selectivity enhancement observed by
increasing
microporosity does not apply to CO2 uptake at 1 bar pressure. This is
important in part because
CO2 capture is desired at the end of smokestacks and tailpipes, which operate
at atmospheric or
near atmospheric pressures. Enhanced CO2 selectivity for carbon capture using
porous materials
is not due to increasing surface area nor porosity (nano or otherwise). As
shown, modifications to
the physical characteristics of porous materials do not materially enhance
selective capture of CO2
at 1 bar, especially with Angstrom-sized pores. Observations of selectivity
may be due to size
exclusion or sieving only and not any enhancement of surface adsorption
phenomena. CO2 capture
above 1 bar, or more specifically enhanced CO2 capture in porous materials,
occurs at pressures
greater than atmospheric.
[00151] FIG. 35 is a graph showing increased propane uptake at 1 bar
pressure for a variety
of microporous materials at increasing pore volumes. FIG. 36 is a graph
showing increased ethane
uptake at 1 bar pressure for a variety of microporous materials at increasing
pore volumes. FIG.
37 is a graph showing relatively stable methane uptake at 1 bar pressure for a
variety of
microporous materials at increasing pore volumes. FIG. 38 is a graph showing
increased CO2
uptake at 1 bar pressure for a variety of microporous materials at increasing
pore volumes.
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[00152] Referring now to FIGS. 39-42, as surface area of the porous
material increased, gas
uptake does not increase for methane, but uptake increased for all other
gases. This indicates that
microporous materials, such as carbons, may be able to advantageously not
adsorb methane while
adsorbing other compositions such as carbon dioxide, ethane, and propane.
Porous materials are
better suited at selective capture of hydrocarbons with molecular weights
greater than methane.
Physical characteristics of the porous materials are enhanced for selectivity
of other gases other
than methane. One exception is CO2 uptake at 1 bar pressure, where there is
not observable
increase in CO2 uptake with increasing surface area, unless it is measured at
pressures greater than
atmospheric.
[00153] Looking at oxygen content in FIGS. 41-42, there is enhanced
selectivity for
hydrocarbons with increasing oxygen content to approximately 15%, but there is
noticeably no
impact to CO2 enhancement at 1 bar or atmospheric pressure. Enhancements to
CO2 adsorption
selectivity is not observed unless pressures are generally above atmospheric
pressure.
Additionally, looking to the uptake ratios between all the gases measured
shows that the lowest
uptake of ethane occurs in the presence of nitrogen content in the porous
material. This means
that selectivity of hydrocarbons of molecular weight greater than ethane can
be enhanced if the N
hetero atom is present in the porous material.
[00154] The singular forms "a," "an," and "the" include plural referents,
unless the context
clearly dictates otherwise.
[00155] In the drawings and specification, there have been disclosed
embodiments of
systems and methods for natural gas liquids recovery from pressure swing
adsorption and vacuum
swing adsorption of the present disclosure, and although specific terms are
employed, the terms
are used in a descriptive sense only and not for purposes of limitation. The
embodiments of the
present disclosure have been described in considerable detail with specific
reference to these
illustrated embodiments. It will be apparent, however, that various
modifications and changes can
be made within the spirit and scope of the disclosure as described in the
foregoing specification,
and such modifications and changes are to be considered equivalents and part
of this disclosure.
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