U.S. patent application number 16/186267 was filed with the patent office on 2020-05-14 for low pressure refrigeration system with membrane purge.
The applicant listed for this patent is Carrier Corporation. Invention is credited to Haralambos Cordatos, Zissis A. Dardas, Yinshan Feng, Rajiv Ranjan, Parmesh Verma.
Application Number | 20200149791 16/186267 |
Document ID | / |
Family ID | 70551188 |
Filed Date | 2020-05-14 |
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United States Patent
Application |
20200149791 |
Kind Code |
A1 |
Ranjan; Rajiv ; et
al. |
May 14, 2020 |
LOW PRESSURE REFRIGERATION SYSTEM WITH MEMBRANE PURGE
Abstract
Disclosed is a refrigeration system including a heat transfer
fluid circulation loop configured to allow a refrigerant to
circulate through the circulation loop. A purge gas outlet is in
operable communication with the heat transfer fluid circulation
loop. The system also includes at least one gas permeable membrane
having a first side in operable communication with the purge gas
outlet and a second side. The membrane includes a separation layer
including a porous inorganic material with pores of a size to allow
passage of contaminants through the membrane and restrict passage
of the through the membrane, and a polymer coating over the
separation layer. A permeate outlet is in operable communication
with the second side of the membrane.
Inventors: |
Ranjan; Rajiv; (South
Windsor, CT) ; Feng; Yinshan; (Manchester, CT)
; Cordatos; Haralambos; (Colchester, CT) ; Verma;
Parmesh; (South Windsor, CT) ; Dardas; Zissis A.;
(Worcester, MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Carrier Corporation |
Palm Beach Gardens |
FL |
US |
|
|
Family ID: |
70551188 |
Appl. No.: |
16/186267 |
Filed: |
November 9, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
F25B 43/043 20130101;
F25B 41/06 20130101; F25B 13/00 20130101; F25B 41/04 20130101 |
International
Class: |
F25B 41/04 20060101
F25B041/04; F25B 13/00 20060101 F25B013/00; F25B 41/06 20060101
F25B041/06 |
Claims
1. A refrigeration system comprising a heat transfer fluid
circulation loop configured to allow a refrigerant to circulate
therethrough; a purge gas outlet in operable communication with the
heat transfer fluid circulation loop; at least one gas permeable
membrane having a first side in operable communication with the
purge gas outlet and a second side, said membrane comprising a
separation layer comprising a porous inorganic material with pores
of a size to allow passage of contaminants through the membrane and
restrict passage of the refrigerant through the membrane, and a
polymer coating over said separation layer; and a permeate outlet
in operable communication with the second side of the membrane.
2. The refrigeration system of claim 1, further comprising a prime
mover operably coupled to the permeate outlet, the prime mover
configured to move gas from the second side of the membrane to an
exhaust port leading outside the fluid circulation loop.
3. The refrigeration system of claim 1, wherein the heat transfer
fluid circulation loop comprises a compressor, a heat rejection
heat exchanger, an expansion device, and a heat absorption heat
exchanger, connected together in order by conduit; wherein the
purge gas outlet is in operable communication with at least one of
the heat rejection heat exchanger, the heat absorption heat
exchanger, or the membrane.
4. The refrigeration system of claim 2 wherein the prime mover
comprises a vacuum pump in operable communication with the second
side of the membrane.
5. The refrigeration system of claim 1, further comprising a filter
in operable communication with the purge outlet and the first side
of the membrane.
6. The refrigeration system of claim 1, wherein the separation
layer comprises a ceramic material.
7. The refrigeration system of claim 6, wherein the membrane
comprises zeolite.
8. The refrigeration system of claim 1, wherein the at least one
gas permeable membrane comprises a plurality of gas permeable
membranes; wherein the plurality of gas permeable membranes are
arranged in serial or parallel communication.
9. The refrigeration system of claim 1, wherein the polymer layer
comprises a polymer selected from a silicone rubber, fluorosilicone
or polyimide.
10. The refrigeration system of claim 1, wherein the polymer layer
has a thickness of 0.05 .mu.m to 50 .mu.m.
11. The refrigeration system of claim 1, further comprising a
controller configured to operate the fluid circulation loop in
response to a cooling demand signal and to operate the prime mover
in response to a determination of contaminants in the fluid
circulation loop.
12. The refrigeration system of claim 11, wherein the controller is
configured to activate a purge back-flush mode in which gas is
transported from the second side of the membrane to the first side
of the membrane.
13. The refrigeration system of claim 11, wherein the controller is
configured to activate a heat source to heat the membrane to a
temperature to remove contaminants.
14. A method of operating a refrigeration system, comprising
circulating a refrigerant through a heat transfer fluid circulation
loop in response to a cooling demand signal; collecting purge gas
comprising contaminants from a purge outlet in the fluid
circulation loop; transferring the contaminants across a permeable
molecular sieve membrane with a prime mover, said membrane
comprising a porous inorganic or metal organic framework with pores
of a size to allow passage of the contaminants through the membrane
and restrict passage of the refrigerant through the membrane; and
periodically back-flushing the membrane by transporting gas from
the second side of the membrane to the first side of the membrane,
or periodically heating the membrane to a temperature to remove
contaminants, or both periodically transporting gas from the second
side of the membrane to the first side of the membrane and
periodically heating the membrane to a temperature to remove
contaminants.
15. The method of claim 14, comprising periodically back-flushing
the membrane by transporting gas from the second side of the
membrane to the first side of the membrane.
16. The method of claim 14 comprising periodically heating the
membrane to a temperature to remove contaminants.
17. The method of claim 14, further comprising passing the purge
gas through a filter before reaching the membrane.
18. The method of claim 14, further comprising transporting the
contaminants through a polymer coating on the inorganic or metal
organic framework membrane.
19. The method of claim 14, further comprising collecting the purge
gas in a purge gas collector between the purge outlet and the
membrane.
20. The method of claim 14, further comprising returning
refrigerant from the first side of the membrane to the fluid
circulation loop.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of Provisional
Application 62/584,073 filed Nov. 9, 2017, which is incorporated
herein by reference in its entirety.
BACKGROUND
[0002] This disclosure relates generally to chiller systems used in
air conditioning systems, and more particularly to a purge system
for removing contaminants from a refrigeration system.
[0003] Chiller systems such as those utilizing centrifugal
compressors may include sections that operate below atmospheric
pressure. As a result, leaks in the chiller system may draw air
into the system, contaminating the refrigerant. This contamination
degrades the performance of the chiller system. To address this
problem, existing low pressure chillers include a purge unit to
remove contamination. Existing purge units use a vapor compression
cycle to separate non-condensable gas from the refrigerant.
Existing purge units are complicated and lose refrigerant in the
process of removing contamination.
BRIEF DESCRIPTION
[0004] Disclosed is a refrigeration system including a heat
transfer fluid circulation loop configured to allow a refrigerant
to circulate therethrough. A purge gas outlet is in operable
communication with the heat transfer fluid circulation loop. The
system also includes at least one gas permeable membrane having a
first side in operable communication with the purge gas outlet and
a second side. The membrane includes a separation layer including a
porous inorganic material with pores of a size to allow passage of
contaminants through the membrane and restrict passage of the
refrigerant through the membrane, and a polymer coating over the
separation layer. A permeate outlet is in operable communication
with the second side of the membrane.
[0005] In some embodiments, the system further includes a prime
mover operably coupled to the permeate outlet, and the prime mover
is configured to move gas from the second side of the membrane to
an exhaust port leading outside the fluid circulation loop.
[0006] In any one or combination of the foregoing embodiments, the
heat transfer fluid circulation loop includes a compressor, a heat
rejection heat exchanger, an expansion device, and a heat
absorption heat exchanger, connected together in order by conduit,
and the purge gas outlet is in operable communication with at least
one of the heat rejection heat exchanger, the heat absorption heat
exchanger, or the membrane.
[0007] In any one or combination of the foregoing embodiments, the
system further includes a retentate return conduit operably
coupling the first side of the membrane to the fluid circulation
loop. In some embodiments, the prime mover is a vacuum pump.
[0008] In any one or combination of the foregoing embodiments, the
system further includes a purge gas collector operably coupled to
the purge outlet and the membrane.
[0009] In some embodiments, the system further includes a prime
mover operably coupled to the permeate outlet, the prime mover
configured to move gas from the second side of the membrane to an
exhaust port leading outside the fluid circulation loop. In some
embodiments, the prime mover includes a vacuum pump in operable
communication with the second side of the membrane.
[0010] In any one or combination of the foregoing embodiments, the
system further includes a filter in operable communication with the
purge outlet and the first side of the membrane.
[0011] In any one or combination of the foregoing embodiments, the
separation layer includes a ceramic material.
[0012] In any one or combination of the foregoing embodiments,
wherein the membrane includes zeolite.
[0013] In any one or combination of the foregoing embodiments, the
at least one gas permeable membrane includes a plurality of gas
permeable membranes; wherein the plurality of gas permeable
membranes are arranged in serial or parallel communication.
[0014] In any one or combination of the foregoing embodiments, the
polymer layer includes a polymer selected from a silicone rubber,
fluorosilicone or polyimide.
[0015] In any one or combination of the foregoing embodiments, the
polymer layer has a thickness of 0.05 .mu.m to 50 .mu.m.
[0016] In any one or combination of the foregoing embodiments, the
system further includes a controller configured to operate the
fluid circulation loop in response to a cooling demand signal and
to operate the prime mover in response to a determination of
contaminants in the fluid circulation loop.
[0017] In any one or combination of the foregoing embodiments, the
controller is configured to activate a purge back-flush mode in
which gas is transported from the second side of the membrane to
the first side of the membrane.
[0018] In any one or combination of the foregoing embodiments, the
controller is configured to activate a heat source to heat the
membrane to a temperature to remove contaminants.
[0019] Also disclosed is a method of operating a refrigeration
system, comprising circulating a refrigerant through a heat
transfer fluid circulation loop in response to a cooling demand
signal. Purge gas comprising contaminants is collected from a purge
outlet in the fluid circulation loop. The contaminants are
transferred across a permeable molecular sieve membrane with a
prime mover, said membrane comprising a porous inorganic or metal
organic framework with pores of a size to allow passage of the
contaminants through the membrane and restrict passage of the
refrigerant through the membrane. The method also includes
periodically back-flushing flushing the membrane by transporting
gas from the second side of the membrane to the first side of the
membrane, or periodically heating the membrane to a temperature to
remove contaminants, or both periodically transporting gas from the
second side of the membrane to the first side of the membrane and
periodically heating the membrane to a temperature to remove
contaminants.
[0020] In any one or combination of the foregoing embodiments, the
method includes periodically back-flushing the membrane by
transporting gas from the second side of the membrane to the first
side of the membrane.
[0021] In any one or combination of the foregoing embodiments, the
method also includes periodically heating the membrane to a
temperature to remove contaminants.
[0022] In any one or combination of the foregoing embodiments, the
method also includes passing the purge gas through a filter before
reaching the membrane.
[0023] In any one or combination of the foregoing embodiments, the
method also includes transporting the contaminants through a
polymer coating on the inorganic or metal organic framework
membrane.
[0024] In any one or combination of the foregoing embodiments, the
method also includes collecting the purge gas in a purge gas
collector between the purge outlet and the membrane.
[0025] In any one or combination of the foregoing embodiments, the
method also includes returning refrigerant from the first side of
the membrane to the fluid circulation loop.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] The following descriptions should not be considered limiting
in any way. With reference to the accompanying drawings, like
elements are numbered alike:
[0027] FIG. 1 is a schematic depiction of a refrigeration system
including a vapor compression heat transfer refrigerant fluid
circulation loop;
[0028] FIG. 2 is a schematic depiction of an example embodiment of
a membrane purge system for a refrigeration system;
[0029] FIG. 3 is a schematic depiction of a separation
membrane;
[0030] FIG. 4 is a schematic depiction of an example embodiment of
a membrane purge system with purge collector and relevant
components of a vapor compression heat transfer refrigerant fluid
circulation loop; and
[0031] FIG. 5 is a schematic depiction of another example
embodiment of a membrane purge system with purge collector and
relevant components of a vapor compression heat transfer
refrigerant fluid circulation loop.
DETAILED DESCRIPTION
[0032] A detailed description of one or more embodiments of the
disclosed apparatus and method are presented herein by way of
exemplification and not limitation with reference to the
Figures.
[0033] With reference to FIG. 1, a heat transfer fluid circulation
loop such as can be used in a chiller is shown in block diagram
form in FIG. 1. As shown in FIG. 1, a compressor 10 pressurizes
heat transfer fluid in its gaseous state, which both heats the
fluid and provides pressure to circulate it throughout the system.
In some embodiments, the heat transfer fluid, or refrigerant,
comprises an organic compound. In some embodiments, the refrigerant
comprises a hydrocarbon or substituted hydrocarbon. In some
embodiments, the refrigerant comprises a halogen-substituted
hydrocarbon. In some embodiments, the refrigerant comprises a
fluoro-substituted or chloro-fluoro-substituted hydrocarbon. The
hot pressurized gaseous heat transfer fluid exiting from the
compressor 10 flows through conduit 15 to heat exchanger condenser
20, which functions as a heat exchanger to transfer heat from the
heat transfer fluid to the surrounding environment, resulting in
condensation of the hot gaseous heat transfer fluid to a
pressurized moderate temperature liquid. The liquid heat transfer
fluid exiting from the condenser 20 flows through conduit 25 to
expansion valve 30, where the pressure is reduced. The reduced
pressure liquid heat transfer fluid exiting the expansion valve 30
flows through conduit 35 to heat exchanger evaporator 40, which
functions as a heat exchanger to absorb heat from the surrounding
environment and boil the heat transfer fluid. Gaseous heat transfer
fluid exiting the evaporator 40 flows through conduit 45 to the
compressor 10, thus completing the heat transfer fluid loop. The
heat transfer system has the effect of transferring heat from the
environment surrounding the evaporator 40 to the environment
surrounding the condenser 20. The thermodynamic properties of the
heat transfer fluid must allow it to reach a high enough
temperature when compressed so that it is greater than the
environment surrounding the condenser 20, allowing heat to be
transferred to the surrounding environment. The thermodynamic
properties of the heat transfer fluid must also have a boiling
point at its post-expansion pressure that allows the temperature
surrounding the evaporator 40 to provide heat to vaporize the
liquid heat transfer fluid.
[0034] With reference now to FIG. 2, there is shown an example
embodiment of a purge system that can be connected to a vapor
compression heat transfer fluid circulation loop such as FIG. 1. As
shown in FIG. 2, the purge system receives gas comprising
refrigerant gas and contaminants (e.g., nitrogen, oxygen, water
vapor) through a connection 52 to a membrane separator 54 on a
first side of a membrane 56. A prime mover such as a vacuum pump 58
connected to the membrane separator 54 through connection 60
provides a driving force to pass the contaminants through the
membrane 56 and exit the system from a second side of the membrane
56 through an outlet 62. In some embodiments, the prime mover can
be in the fluid loop, e.g., a refrigerant pump or compressor.
Refrigerant gas remains on the first side of the membrane 56 and
can return to the fluid circulation loop through connection 64.
[0035] The membrane 56 comprises a porous inorganic material.
Examples of porous inorganic materials can include ceramics such as
metal oxides or metal silicates, more specifically aluminosilicates
(e.g., Chabazite Framework (CHA) zeolite, Linde type A (LTA)
zeolite, porous carbon, porous glass, clays (e.g., Montmorillonite,
Halloysite). Porous inorganic materials can also include porous
metals such as platinum and nickel. Hybrid inorganic-organic
materials such as a metal organic framework (MOF) can also be used.
Other materials can be present in the membrane such as a carrier in
which a microporous material can be dispersed, which can be
included for structural or process considerations.
[0036] Metal organic framework materials comprise metal ions or
clusters of metal ions coordinated to organic ligands to form one-,
two- or three-dimensional structures. A metal-organic framework can
be characterized as a coordination network with organic ligands
containing voids. The coordination network can be characterized as
a coordination compound extending, through repeating coordination
entities, in one dimension, but with cross-links between two or
more individual chains, loops, or spiro-links, or a coordination
compound extending through repeating coordination entities in two
or three dimensions. Coordination compounds can include
coordination polymers with repeating coordination entities
extending in one, two, or three dimensions. Examples of organic
ligands include, but are not limited to, bidentate carboxylates
(e.g., oxalic acid, succinic acid, phthalic acid isomers, etc.),
tridentate carboxylates (e.g., citric acid, trimesic acid), azoles
(e.g., 1,2,3-triazole), as well as other known organic ligands. A
wide variety of metals can be included in a metal organic
framework. Examples of specific metal organic framework materials
include but are not limited to zeolitic imidazole framework (ZIF),
HKUST-1.
[0037] In some embodiments, pore sizes can be characterized by a
pore size distribution with an average pore size from 2.5 .ANG. to
10.0 .ANG., and a pore size distribution of at least 0.1 .ANG.. In
some embodiments, the average pore size for the porous material can
be in a range with a lower end of 2.5 .ANG. to 4.0 .ANG. and an
upper end of 2.6 .ANG. to 10.0 .ANG.. .ANG.. In some embodiments,
the average pore size can be in a range having a lower end of 2.5
.ANG., 3.0 .ANG., 3.5 .ANG., and an upper end of 3.5 .ANG., 5.0
.ANG., or 6.0 .ANG.. These range endpoints can be independently
combined to form a number of different ranges, and all ranges for
each possible combination of range endpoints are hereby disclosed.
Porosity of the material can be in a range having a lower end of
5%, 10%, or 15%, and an upper end of 85%, 90%, or 95% (percentages
by volume). These range endpoints can be independently combined to
form a number of different ranges, and all ranges for each possible
combination of range endpoints are hereby disclosed.
[0038] The above microporous materials can be can be synthesized by
hydrothermal or solvothermal techniques (e.g., sol-gel,) where
crystals are slowly grown from a solution. Templating for the
microstructure can be provided by a secondary building unit (SBU)
and the organic ligands. Alternate synthesis techniques are also
available, such as physical vapor deposition or chemical vapor
deposition, in which metal oxide precursor layers are deposited,
either as a primary microporous material, or as a precursor to an
MOF structure formed by exposure of the precursor layers to
sublimed ligand molecules to impart a phase transformation to an
MOF crystal lattice.
[0039] In some embodiments, the above-described inorganic or MOF
membrane materials can provide a technical effect of promoting
separation of contaminants (e.g., nitrogen, oxygen, or water
molecules) from refrigerant gas, and low refrigerant loss. Other
membrane materials, such as porous and non-porous polymers can be
subject to solvent interaction with the matrix material, which can
interfere with effective separation. In some embodiments, the
capabilities of the materials described herein can provide a
technical effect of promoting the implementation of various example
embodiments of refrigeration systems with purge, as described in
more detail with reference to the example embodiments below. For
example, non-porous polymers are typically used as membranes in air
separation, operating on a mechanism known as "solution-diffusion",
whereby molecules are separated by first dissolving into the
polymer matrix and then diffusing at different rates across the
membrane layer. In most instances, separation is accomplished based
on differences in the size of the molecules. However, while
refrigerant molecules are much larger than non-condensable air and
water vapor molecules, they have been found to have very high
solubility into such polymer films, which results in lower
separation factors than anticipated based on molecular size.
[0040] As mentioned above, the microporous molecular sieve material
can be disposed on a gas permeable inorganic porous support such as
alumina or zirconia, or other porous ceramic or metallic (e.g., Fe,
Ni) material. Thickness of the support can range from 10 .mu.m to
10 mm, more specifically from 100 nm to 750 nm, and even more
specifically from 250 nm to 500 nm. In the case of tubular
membranes 70 as described in FIG. 3, fiber diameters can range from
0.1 mm to 100 mm, and fiber lengths can range from 0.02 m to 2
m.
[0041] In some embodiments, the microporous material can be
deposited on the support as particles in a powder or dispersed in a
liquid carrier using various techniques such as spray coating, dip
coating, solution casting, etc. The dispersion can contain various
additives, such as dispersing aids, rheology modifiers, etc.
Polymeric additives can be used; however, a polymer binder is not
needed, although a polymer binder can be included and in some
embodiments is included. However, a polymer binder present in an
amount sufficient to form a contiguous polymer phase can provide
passageways in the membrane for larger molecules to bypass the
molecular sieve particles. Accordingly, in some embodiments a
polymer binder is excluded. In other embodiments, a polymer binder
can be present in an amount below that needed to form a contiguous
polymer phase, such as embodiments in which the membrane is in
series with other membranes that may be more restrictive. In some
embodiments, particles of the microporous material (e.g., particles
with effective diameter of 0.01 .mu.m to 10 mm, or in some
embodiments from 0.5 .mu.m to 10 .mu.m, can be applied as a powder
or dispersed in a liquid carrier (e.g., an organic solvent or
aqueous liquid carrier) and coated onto the support followed by
removal of the liquid. In some embodiments, the application of
solid particles of microporous material from a liquid composition
to the support surface can be assisted by application of a pressure
differential across the support. For example a vacuum can be
applied from the opposite side of the support as the liquid
composition comprising the solid microporous particles to assist in
application of the solid particles to the surface of the
support.
[0042] In some exemplary embodiments, the layer is applied with a
vacuum enhanced dip coating process where a surface of the support
is contacted with a liquid dispersion of the microporous material
dispersion while a vacuum is applied from the opposite side of the
support (or in the case of hollow tube membrane configuration of
FIG. 3, the tubular support 72 can be immersed in the liquid except
for the open ends). The vacuum will draw solvent from the
dispersion through the porous support, resulting in deposition of
the microporous particles onto the support. In the case of hollow
fiber membranes as shown in FIG. 3, this vacuum filtration
technique can be particularly effective, as the hollow core 76
provides an enclosed space from which to draw a vacuum without the
necessity of a vacuum frame or similar structure that would be
needed for a flat or planar membrane configuration.
[0043] After coating a layer of microporous particles onto the
support, the layer can be dried to remove residual solvent and
optionally heated to fuse the microporous particles together into a
contiguous layer. Exemplary heating conditions can be in a range
having at temperatures of at least 50.degree. C., 75.degree. C., or
100.degree. C., more specifically from 20.degree. C. to 75.degree.
C., and even more specifically from 20.degree. C. to 50.degree.
C.
[0044] Various membrane structure configurations can be utilized,
including but not limited to, flat or planar configurations,
tubular configurations, or spiral configurations. An example
embodiment of a tubular configuration is schematically depicted in
FIG. 3. As shown in FIG. 3, a tubular membrane 70 comprises a
porous support configured as tubular shell 72 surrounded by a
molecular sieve layer 74. Thickness of the molecular sieve layer
can range from 2 nm to 500 nm, more specifically from 2 nm to 100
nm, and even more specifically from 2 nm to 50 nm. The shell 72
defines a hollow core 76 that is open at both ends. In some
embodiments, multiple tubular membranes are disposed together in a
tube bank with a header (not shown) at each end in fluid
communication with the hollow cores 76. In use, purge gas
comprising refrigerant gas and contaminants is delivered to the
exterior of the membrane 70 at a greater pressure than that inside
the hollow cores 76 (e.g., by drawing a vacuum on the hollow cores
76 through the headers). This pressure differential provides a
driving force for non-condensable nitrogen, oxygen or water
molecules to pass through the molecular sieve layer while the
larger refrigerant molecules are restricted from passage through
the molecular sieve layer 74.
[0045] In some embodiments, the microporous material can be
configured as nanoplatelets such as zeolite nanosheets. Zeolite
nanosheet particles can have thicknesses ranging from 2 to 50 nm,
more specifically 2 to 20 nm, and even more specifically from 2 nm
to 10 nm. The mean diameter of the nanosheets can range from 50 nm
to 5000 nm, more specifically from 100 nm to 2500 nm, and even more
specifically from 100 nm to 1000 nm. Mean diameter of an
irregularly-shaped tabular particle can be determined by
calculating the diameter of a circular-shaped tabular particle
having the same surface area in the x-y direction (i.e., along the
tabular planar surface) as the irregularly-shaped particle. Zeolite
such as zeolite nanosheets can be formed from any of various
zeolite structures, including but not limited to, framework type
MFI, MWW, FER, LTA, FAU, and mixtures of the preceding with each
other or with other zeolite structures. In a more specific group of
exemplary embodiments, the zeolite such as zeolite nanosheets can
comprise zeolite structures selected from MFI, MWW, FER, LTA
framework type. Zeolite nanosheets can be prepared using known
techniques such as exfoliation of zeolite crystal structure
precursors. For example, MFI and MWW zeolite nanosheets can be
prepared by sonicating the layered precursors (multilamellar
silicalite-1 and ITQ-1, respectively) in solvent. Prior to
sonication, the zeolite layers can optionally be swollen, for
example with a combination of base and surfactant, and/or
melt-blending with polystyrene. The zeolite layered precursors are
typically prepared using conventional techniques for preparation of
microporous materials such as sol-gel methods.
[0046] With reference again to FIG. 3, a polymer coating 78 is
disposed over the molecular sieve layer 74. The polymer can be
virtually any type of polymer that is resistant to erosion by the
refrigerant as a solvent and is capable of being coated onto the
molecular sieve layer, including but not limited to silicone
polymers (i.e., polysiloxanes), fluorosilicones, or polyimides. The
polymer coating can be applied by any technique including but not
limited to spray coating, dip coating, roll coating, or extrusion,
followed by curing of the polymer coating. In some embodiments, the
polymer coating 78 can be permeable to both refrigerant gas and the
contaminants, through either or both of porosity sieving or polymer
solvent effects. In some embodiments, the polymer coating 78 can
allow for passage of both types of gases via a solution-diffusion
mechanism. In some embodiments, the polymer coating can have a
thickness in a range with a lower end of 0.05 .mu.m, 0.1 .mu.m, 0.5
.mu.m, and an upper end of 4 .mu.m, 10 .mu.m, or 50 .mu.m. These
range endpoints can be independently combined to form a number of
different ranges, and all ranges for each possible combination of
range endpoints are hereby disclosed. In some embodiments, the
polymer coating can provide a technical effect of protecting the
molecular sieve layer 74 from exposure to contaminants such as
oils, or to physical damage. In some embodiments, the polymer
coating can provide a technical effect of reducing leakage of
refrigerant across the membrane through pinholes. Although the
polymer coating may not be impervious to refrigerant molecules, it
can fill in any pinholes and significantly reduce the rate of mass
transfer through any such pinholes. The inorganic layer 74 may also
contain grain boundaries, through which larger refrigerant
molecules can pass, which reduces the layer's selectivity. The
polymer coating can mask such grain boundaries, thereby reducing
refrigerant permeance through the membrane.
[0047] With reference now to FIG. 4, another purge system is shown
along with selected components of the refrigerant fluid circulation
loop of FIG. 1. As shown in FIG. 4, a purge collector 66 receives
gas vented from the condenser 20. In some embodiments, the
connection of the vent line to the condenser can be made at a high
point of the condenser structure. In some embodiments, the purge
collector can provide a technical effect of promoting higher
concentrations of contaminants at the membrane, which can promote
more effective mass transfer and separation. This effect can occur
through a stratification of gas in the purge collector in which
lighter contaminants concentrate toward the top of the purge
collector and heavier refrigerant gas concentrates toward the
bottom of the purge collector. In some embodiments, the purge
collector 66 can be any kind of vessel or chamber with a volume or
cross-sectional open space to provide for collection of purge gas
and for a low gas velocity during operation of the purge system
vacuum pump 58 to promote stratification. Stratification can also
occur at any time when the purge system is not operating (including
during operation of the refrigeration system fluid circulation
loop), as the purge collector 66 remains in fluid communication
with the condenser vent line with essentially stagnant gas in the
purge collector. Other embodiments can also be employed to promote
higher concentrations of contaminants at the membrane separator 54,
as discussed in more detail below.
[0048] In some embodiments, refrigerant from the first side of
membrane 56 can be returned to the refrigerant fluid circulation
loop. As shown in FIG. 4, a connection 67 returns retentate gas
from the first side of membrane 56 to the refrigerant fluid
circulation loop at the evaporator 40, through a control device
such as expansion valve 68 utilized to accommodate the pressure
differential between the first side of the membrane 56 (which is
close to the pressure at the condenser 20) and pressure at the
evaporator 40. It should be noted that the control device can
control either or both flow through or pressure drop across the
control device, and expansion valve 68 is shown as an integrated
control device unit that performs both functions for ease of
illustration, but could be separate components such as a control
valve and an expansion orifice. In some embodiments, utilization of
a bypass refrigerant return can provide a technical effect of
promoting greater concentrations of contaminants at the first side
of membrane 56 by removing gas at the membrane 56 that is
concentrated with refrigerant after removal of contaminant gas
molecules through the membrane 56, so that refrigerant-concentrated
gas can be displaced with gas from the purge collector 66 that has
a higher concentration of contaminants. The connection 67 can also
include a control or shut-off valve, which can be integrated with
an expansion device (i.e., an expansion valve), as described in
more detail in U.S. patent application Ser. No. 62/584,012, the
disclosure of which is incorporated herein by reference in its
entirety. In alternative embodiments (not shown), the bypass
conduit 67 can return refrigerant-laden gas to a colder side of the
condenser 20 or inlet of the compressor 10, in which case an
expansion device may not be needed due to lower pressure
differential compared to that of a bypass return to the evaporator
40. In such as case, the connection 67 can utilize a control device
such as a control or shut-off valve 68 that does not provide gas
expansion. Other system variations such as centrifugal separators
or chilling coils integrated with a purge chamber, pumped recycle
of permeate back to the retentate (upstream) side of the membrane,
cascaded multiple membranes, or alternative prime movers such as a
thermal prime mover or a pump or compressor in the fluid
circulation loop, are described in more detail in U.S. patent
application Ser. No. 15/808,837, entitled "Refrigeration Purge
System", filed on Nov. 9, 2017, the disclosure of which is
incorporated herein by reference in its entirety.
[0049] Additional embodiments can also be employed to protect or
promote durability of the membrane. For example, in some
embodiments a controller (not shown) in operative communication
with various sensing and control components of the system can be
configured to periodically activate a purge backflush in which gas
is transported from the second (i.e., permeate) side of the
membrane to the first (i.e., retentate) side of the membrane. As
used herein, "periodically" means that activation can be based on
any sort of criteria including human operator activation, or
predetermined criteria including but not limited to the passage of
time, accumulated system operating time, accumulated system purge
cycle time, or measured system criteria such as measured pressure
differential across the membrane during purge cycle operation of
the prime mover. The backflush mode can be activated by isolating
the membrane separator 54 from the purge collector 66 and reversing
the direction of the driving force. For example, in the example
embodiments of FIGS. 4-5, this can be accomplished by switching a
3-way valve (not shown) in the conduit between the purge collector
66 and the membrane separator 54 to simultaneously connect a bypass
line (not shown) from the three-way valve connecting the suction
side of the vacuum pump 58 and the first side of the membrane 56
while isolating the first side of the membrane 56 from the purge
collector 66. A similar 3-way valve connection can be employed at
the suction side of the vacuum pump 58 to redirect the vacuum pump
connection between the second side of the membrane 56 or to the
bypass line to the first side of the membrane 56. In some
embodiments, the controller can be configured to periodically
expose the membrane 56 to heat to remove contaminants such as oil.
In some embodiments, the membrane can be heated to at least
200.degree. C., or to at least 300.degree. C., or to at least
400.degree. C. Heating can generally be kept under 200.degree. C.
in order to prevent degradation of the polymer layer 78, save
energy and simplify thermal management.
[0050] In some embodiments, durability and protection of the
membrane 56 can be promoted by a filter such as a coalescing
filter, moisture filter, or particulate filter between the purge
outlet and the membrane 56. In the example embodiment shown in FIG.
5, a coalescing filter 79 is disposed in the gas flow path between
the purge collector 66 and the membrane separator 54. One type of
coalescing filter can have a cylindrical inner rigid open mesh core
(e.g., stainless steel) around which a fiber coalescing medium
(e.g., borosilicate glass fiber) is disposed. In some embodiments,
the coalescing medium can have a gradient pore structure by using
layers of increasing pore size. The inlet gas first encounters the
smallest pores, which increase with penetration distance to allow
more space as the coalesced droplets grow. The coalescing medium
can be supported by an outer mesh structure to provide mechanical
strength which is then followed by a coarse outer wrap that serves
as a drainage zone. Gas flows into the hollow core of the cylinder
and then radially outward through the filter media. Tiny liquid
droplets are captured by the inner filter media and coalesce into
larger liquid droplets that are captured and removed in the
radially outward drainage zone.
[0051] The term "about", if used, is intended to include the degree
of error associated with measurement of the particular quantity
based upon the equipment available at the time of filing the
application. For example, "about" can include a range of .+-.8% or
5%, or 2% of a given value.
[0052] The terminology used herein is for the purpose of describing
particular embodiments only and is not intended to be limiting of
the present disclosure. As used herein, the singular forms "a",
"an" and "the" are intended to include the plural forms as well,
unless the context clearly indicates otherwise. It will be further
understood that the terms "comprises" and/or "comprising," when
used in this specification, specify the presence of stated
features, integers, steps, operations, elements, and/or components,
but do not preclude the presence or addition of one or more other
features, integers, steps, operations, element components, and/or
groups thereof.
[0053] While the present disclosure has been described with
reference to an exemplary embodiment or embodiments, it will be
understood by those skilled in the art that various changes may be
made and equivalents may be substituted for elements thereof
without departing from the scope of the present disclosure. In
addition, many modifications may be made to adapt a particular
situation or material to the teachings of the present disclosure
without departing from the essential scope thereof. Therefore, it
is intended that the present disclosure not be limited to the
particular embodiment disclosed as the best mode contemplated for
carrying out this present disclosure, but that the present
disclosure will include all embodiments falling within the scope of
the claims.
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