Information
-
Patent Grant
-
6230519
-
Patent Number
6,230,519
-
Date Filed
Wednesday, November 3, 199924 years ago
-
Date Issued
Tuesday, May 15, 200123 years ago
-
Inventors
-
Original Assignees
-
Examiners
Agents
-
CPC
-
US Classifications
Field of Search
US
- 062 643
- 062 644
- 062 912
-
International Classifications
-
Abstract
A cryogenic air separation process having improved flexibility and operating efficiency wherein refrigeration generation for the process is decoupled from the flow of process streams and is produced by one or more closed loop circuits.
Description
TECHNICAL FIELD
This invention relates generally to the separation of feed air by cryogenic rectification to produce, inter alia, gaseous nitrogen and gaseous oxygen.
BACKGROUND ART
The production of gaseous nitrogen and gaseous oxygen by the cryogenic rectification of feed air requires the provision of a significant amount of refrigeration to drive the separation. Generally such refrigeration is provided by the turboexpansion of a process stream, such as a portion of the feed air. While this conventional practice is effective, it is limiting because an increase in the amount of refrigeration inherently affects the operation of the overall process. It is therefor desirable to have a cryogenic air separation process wherein the provision of the requisite refrigeration is independent of the flow of process streams for the system.
One method for providing refrigeration for a cryogenic air separation system which is independent of the flow of internal system process streams is to provide the requisite refrigeration in the form of exogenous cryogenic liquid brought into the system. Unfortunately such a procedure is very costly.
Accordingly it is an object of this invention to provide an improved cryogenic air separation process wherein the provision of the requisite refrigeration for the separation is independent of the flow of process streams.
It is another object of this invention to provide a cryogenic air separation process wherein the provision of the requisite refrigeration for the separation is independently and efficiently provided to the system.
SUMMARY OF THE INVENTION
The above and other objects which will become apparent to those skilled in the art upon a reading of this disclosure, are attained by the present invention, one aspect of which is:
A process for the production of gaseous nitrogen and gaseous oxygen by the cryogenic rectification of feed air comprising:
(A) compressing a multicomponent refrigerant fluid, cooling the compressed multicomponent refrigerant fluid, expanding the cooled, compressed multicomponent refrigerant fluid, and warming the expanded multicomponent refrigerant fluid by indirect heat exchange with said cooling compressed multicomponent refrigerant fluid and also with feed air to produce cooled feed air;
(B) passing the cooled feed air into a higher pressure cryogenic rectification column and separating the feed air by cryogenic rectification within the higher pressure cryogenic rectification column into nitrogen-enriched fluid and oxygen-enriched fluid;
(C) passing nitrogen-enriched fluid and oxygen-enriched fluid into a lower pressure cryogenic rectification column, and separating the fluids passed into the lower pressure column by cryogenic rectification to produce nitrogen-rich fluid and oxygen-rich fluid;
(D) withdrawing nitrogen-rich fluid from the upper portion of the lower pressure column and recovering the withdrawn nitrogen-rich fluid as product gaseous nitrogen; and
(E) withdrawing oxygen-rich fluid from the lower portion of the lower pressure column and recovering the withdrawn oxygen-rich fluid as product gaseous oxygen.
Another aspect of the invention is:
A process for the production of gaseous nitrogen and gaseous oxygen by the cryogenic rectification of feed air comprising:
(A) compressing a high temperature multicomponent refrigerant fluid, cooling the compressed high temperature multicomponent refrigerant fluid, expanding the cooled, compressed high temperature multicomponent refrigerant fluid, and warming the expanded high temperature multicomponent refrigerant fluid by indirect heat exchange with said cooling compressed high temperature multicomponent refrigerant fluid and with low temperature multicomponent refrigerant fluid and also with feed air;
(B) compressing low temperature multicomponent refrigerant fluid, cooling the compressed low temperature multicomponent refrigerant fluid, expanding the cooled, compressed low temperature multicomponent refrigerant fluid, and warming the expanded low temperature multicomponent refrigerant fluid by indirect heat exchanger with said cooling compressed low temperature multicomponent refrigerant fluid and also with feed air to produce cooled feed air;
(C) passing the cooled feed air into a higher pressure cryogenic rectification column and separating the feed air by cryogenic rectification within the higher pressure cryogenic rectification column into nitrogen-enriched fluid and oxygen-enriched fluid;
(D) passing nitrogen-enriched fluid and oxygen-enriched fluid into a lower pressure cryogenic rectification column, and separating the fluids passed into the lower pressure column by cryogenic rectification to produce nitrogen-rich fluid and oxygen-rich fluid;
(E) withdrawing nitrogen-rich fluid from the upper portion of the lower pressure column and recovering the withdrawn nitrogen-rich fluid as product gaseous nitrogen; and
(F) withdrawing oxygen-rich fluid from the lower portion of the lower pressure column and recovering the withdrawn oxygen-rich fluid as product gaseous oxygen.
As used herein the term “column” means a distillation or fractionation column or zone, i.e. a contacting column or zone, wherein liquid and vapor phases are countercurrently contacted to effect separation of a fluid mixture, as for example, by contacting of the vapor and liquid phases on a series of vertically spaced trays or plates mounted within the column and/or on packing elements such as structured or random packing. For a further discussion of distillation columns, see the Chemical Engineer's Handbook, fifth edition, edited by R. H. Perry and C. H. Chilton, McGraw-Hill Book Company, New York, Section 13,
The Continuous Distillation Process.
The term “double column” is used to mean a higher pressure column having its upper portion in heat exchange relation with the lower portion of a lower pressure column. A further discussion of double columns appears in Ruheman “The Separation of Gases”, Oxford University Press, 1949, Chapter VII, Commercial Air Separation.
Vapor and liquid contacting separation processes depend on the difference in vapor pressures for the components. The high vapor pressure (or more volatile or low boiling) component will tend to concentrate in the vapor phase whereas the low vapor pressure (or less volatile or high boiling) component will tend to concentrate in the liquid phase. Distillation is the separation process whereby heating of a liquid mixture can be used to concentrate the more volatile component(s) in the vapor phase and thereby the less volatile component(s) in the liquid phase. Partial condensation is the separation process whereby cooling of a vapor mixture can be used to concentrate the volatile component(s) in the vapor phase and thereby the less volatile component(s) in the liquid phase. Rectification, or continuous distillation, is the separation process that combines successive partial vaporizations and condensations as obtained by a countercurrent treatment of the vapor and liquid phases. The countercurrent contacting of the vapor and liquid phases can be adiabatic or nonadiabatic and can include integral (stagewise) or differential (continuous) contact between the phases. Separation process arrangements that utilize the principles of rectification to separate mixtures are often interchangeably termed rectification columns, distillation columns, or fractionation columns. Cryogenic rectification is a rectification process carried out at least in part at temperatures at or below 150 degrees Kelvin (K).
As used herein the term “indirect heat exchange” means the bringing of two fluid streams into heat exchange relation without any physical contact or intermixing of the fluids with each other.
As used herein the term “expansion” means to effect a reduction in pressure.
As used herein the term “product gaseous nitrogen” means a gas having a nitrogen concentration of at least 99 mole percent.
As used herein the term “product gaseous oxygen” means a gas having an oxygen concentration of at least 90 mole percent.
As used herein the term “feed air” means a mixture comprising primarily oxygen, nitrogen and argon, such as ambient air.
As used herein the terms “upper portion” and “lower portion” mean those sections of a column respectively above and below the mid point of the column.
As used herein the term “variable load refrigerant” means a multicomponent fluid, i.e. a mixture of two or more components in proportions such that the liquid phase of those components undergoes a continuous and increasing temperature change between the bubble point and the dew point of the mixture. The bubble point of the mixture is the temperature, at a given pressure, wherein the mixture is all in the liquid phase but addition of heat will initiate formation of a vapor phase in equilibrium with the liquid phase. The dew point of the mixture is the temperature, at a given pressure, wherein the mixture is all in the vapor phase but extraction of heat will initiate formation of a liquid phase in equilibrium with the vapor phase. Hence, the temperature region between the bubble point and the dew point of the mixture is the region wherein both liquid and vapor phases coexist in equilibrium. In the practice of this invention the temperature differences between the bubble point and the dew point for the multicomponent refrigerant fluid is at least 10° K, preferably at least 20° K and most preferably at least 50° K.
As used herein the term “fluorocarbon” means one of the following: tetrafluoromethane (CF
4
), perfluoroethane (C
2
F
6
), perfluoropropane (C
3
F
8
), perfluorobutane (C
4
F
1
l), perfluoropentane (C
5
F
12
)I perfluoroethene (C
2
F
4
), perfluoropropene (C
3
F
6
), perfluorobutene (C
4
F
8
), perfluoropentene (C
5
F
10
), hexafluorocyclopropane (cyclo-C
3
F
6
) and octafluorocyclobutane (cyclo-C
4
F
8
) As used herein the term “hydrofluorocarbon” means one of the following: fluoroform (CHF
3
), pentafluoroethane (C
2
HF
5
), tetrafluoroethane (C
2
H
2
F
4
), heptafluoropropane (C
3
HF
7
), hexafluoropropane (C
3
H
2
F
6
), pentafluoropropane (C
3
H
3
F
5
), tetrafluoropropane (C
3
H
4
F
4
), nonafluorobutane (C
4
HF
9
), octafluorobutane (C
4
H
2
F
8
), undecafluoropentane (C
5
HF
11
), methyl fluoride (CH
3
F), difluoromethane (CH
2
F
2
), ethyl fluoride (C
2
H
5
F), difluoroethane (C
2
H
4
F
2
), trifluoroethane (C
2
H
3
F
3
), difluoroethene (C
2
H
2
F
2
), trifluoroethene (C
2
HF
3
), fluoroethene (C
2
H
3
F), pentafluoropropene (C
3
HF
5
), tetrafluoropropene (C
3
H
2
F
4
), trifluoropropene (C
3
H
3
F
3
), difluoropropene (C
3
H
4
F
2
), heptafluorobutene (C
4
HF
7
), hexafluorobutene (C
4
H
2
F
6
) and nonafluoropentene (C
5
HF
9
)
As used herein the term “fluoroether” means one of the following: trifluoromethyoxy-perfluoromethane (CF
3
—O—CF
3
), difluoromethoxy-perfluoromethane (CHF
2
—O—CF
3
), fluoromethoxy-perfluoromethane (CH
2
F—O—CF
3
), difluoromethoxy-difluoromethane (CHF
2
—O—CHF
2
), difluoromethoxy-perfluoroethane (CHF
2
—O—C
2
F
5
), difluoromethoxy-1,2,2,2-tetrafluoroethane (CHF
2
—O—C
2
HF
4
), difluoromethoxy-1,1,2,2-tetrafluoroethane (CHF
2
—O—C
2
HF
4
), perfluoroethoxy-fluoromethane (C
2
F
5
—O—CH
2
F), perfluoromethoxy-1,1,2-trifluoroethane (CF
3
—O—C
2
H
2
F
3
), perfluoromethoxy-1,2,2-trifluoroethane (CF
3
O—C
2
H
2
F
3
), cyclo-1,1,2,2-tetrafluoropropylether (cyclo-C
3
H
2
F
4
—O—) cyclo-1,1,3,3-tetrafluoropropylether (cyclo-C
3
H
2
F
4
—O—), perfluoromethoxy-1,1,2,2-tetrafluoroethane (CF
3
—O—C
2
HF
4
), cyclo-1,1,2,3,3-pentafluoropropylether (cyclo-C
3
H
5
—O—), perfluoromethoxy-perfluoroacetone (CF
3
—O—CF
2
—O—CF
3
), perfluoromethoxy-perfluoroethane (CF
3
—O—C
2
F
5
), perfluoromethoxy-1,2,2,2-tetrafluoroethane (CF
3
—O—C
2
HF
4
), perfluoromethoxy-2,2,2-trifluoroethane (CF
3
-O—C
2
H
2
F
3
), cyclo-perfluoromethoxy-perfluoroacetone (cyclo-CF
2
—O—CF
2
—O—CF
2
—) and cyclo-perfluoropropylether (cyclo-C
3
F
6
—O).
As used herein the term “atmospheric gas” means one of the following: nitrogen (N
2
), argon (Ar), krypton (Kr), xenon (Xe), neon (Ne), carbon dioxide (CO
2
), oxygen (O
2
) and helium (He).
As used herein the term “non-toxic” means not posing an acute or chronic hazard when handled in accordance with acceptable exposure limits.
As used herein the term “non-flammable” means either having no flash point or a very high flash point of at least 600° K.
As used herein the term “low-ozone-depleting” means having an ozone depleting potential less than 0.15 as defined by the Montreal Protocol convention wherein dichlorofluoromethane (CCl
2
F
2
) has an ozone depleting potential of 1.0.
As used herein the term “non-ozone-depleting” means having no component which contains a chlorine, bromine or iodine atom.
As used herein the term “normal boiling point” means the boiling temperature at 1 standard atmosphere pressure, i.e. 14.696 pounds per square inch absolute.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1
is a schematic representation of one preferred embodiment of the invention wherein a single multicomponent refrigerant circuit is used to produce the refrigeration for the separation.
FIG. 2
is a schematic representation of another preferred embodiment of the invention wherein two multicomponent refrigerant circuits, a high temperature circuit and a low temperature circuit, are used to produce the refrigeration for the system.
FIG. 3
is a schematic representation of another preferred embodiment of the invention wherein the multicomponent refrigerant fluid circuit employs internal recycle.
DETAILED DESCRIPTION
In general, the invention comprises the decoupling of the refrigeration generation for a cryogenic air separation process from the flow of process streams for the process. This enables one to change the amount of refrigeration put into the process without requiring a change in flow of process streams. For example, one may now operate the process to produce large amounts of liquid product in addition to the gaseous products without burdening the system with excessive turboexpansion of process streams to generate the refrigeration necessary to produce such liquid product.
The invention will be described in greater detail with reference to the Drawings. In
FIG. 1
there is illustrated a cryogenic air separation plant having three columns, a double column having higher and lower pressure columns, and an argon sidearm column.
Referring now to
FIG. 1
, feed air
60
is compressed by passage through base load compressor
30
to a pressure generally within the range of from 40 to 200 pounds per square inch absolute (psia). Resulting compressed feed air
61
is cooled of the heat of compression in aftercooler
31
and resulting feed air stream
62
is then cleaned of high boiling impurities such as water vapor, carbon dioxide and hydrocarbons by passage through purifier
132
. Purified feed air stream
63
is cooled by passage through main heat exchanger
1
by indirect heat exchange with return streams and by refrigeration generated by the multicomponent refrigerant fluid circuit as will be more fully described below, and then passed as stream
65
into higher pressure column
10
which is operating at a pressure generally within the range of from 40 to 200 psia. Within higher pressure column
10
the feed air is separated by cryogenic rectification into nitrogen-enriched vapor and oxygen-enriched liquid. Nitrogen-enriched vapor is withdrawn from the upper portion of higher pressure column
10
in stream
71
and condensed in main condenser
9
by indirect heat exchange with boiling lower pressure column bottom liquid. Resulting nitrogen-enriched liquid
72
is returned to column
10
as reflux as shown by stream
73
. A portion
74
of the nitrogen-enriched liquid
72
is passed from column
10
to subcooler
3
wherein it is subcooled to form subcooled stream
77
which is passed into the upper portion of column
11
as reflux. If desired, a portion
75
of stream
73
may be recovered as product liquid nitrogen. Also, if desired, a portion (not shown) of nitrogen-enriched vapor stream
71
may be recovered as product high pressure nitrogen gas.
Oxygen-enriched liquid is withdrawn from the lower portion of higher pressure column
10
in stream
69
and passed to subcooler
2
wherein it is subcooled. Resulting subcooled oxygen-enriched liquid
70
is then divided into portion
93
and portion
94
. Portion
93
is passed into lower pressure column
11
and portion
94
is passed into argon column condenser
5
wherein it is at least partially vaporized. The resulting vapor is withdrawn from condenser
5
in stream
95
and passed into lower pressure column
11
. Any remaining oxygen-enriched liquid is withdrawn from condenser
5
and then passed into lower pressure column
11
.
Lower pressure column
11
is operating at a pressure less than that of higher pressure column
10
and generally within the range of from 15 to 180 psia. Within lower pressure column
11
the various feeds into that column are separated by cryogenic rectification into nitrogen-rich vapor and oxygen-rich liquid. Nitrogen-rich vapor is withdrawn from the upper portion of column
11
in stream
83
, warmed by passage through heat exchangers
3
,
2
and
1
, and recovered as product gaseous nitrogen in stream
86
having a nitrogen concentration of at least
99
mole percent, preferably at least 99.9 mole percent, and most preferably at least 99.999 mole percent. For product purity control purposes a waste stream
87
is withdrawn from column
11
from a level below the withdrawal point of stream
83
, warmed by passage through heat exchangers
3
,
2
and
1
, and removed from the system in stream
90
. Oxygen-rich liquid is partially vaporized in the lower portion of column
11
by indirect heat exchange with condensing nitrogen-enriched vapor in main condenser
4
as was previously described. Resulting oxygen-rich vapor is withdrawn from the lower portion of column
11
in stream
81
having an oxygen concentration generally within the range of from 90 to 99.9 mole percent. Oxygen-rich vapor in stream
81
is warmed by passage through main heat exchanger
1
and recovered as product gaseous oxygen in stream
82
.
Fluid comprising oxygen and argon is passed in stream
91
from lower pressure column
11
into argon column
12
wherein it is separated by cryogenic rectification into argon-richer fluid and oxygen-rich fluid. Oxygen-richer fluid is passed from the lower portion of column
12
in stream
92
into lower pressure column
11
. Argon-richer fluid is passed from the upper portion of column
12
as vapor into argon column condenser
5
wherein it is condensed by indirect heat exchange with the aforesaid subcooled oxygen-enriched liquid. Resulting argon-richer liquid is withdrawn from condenser
5
. A portion of the argon-richer liquid is passed into argon column
12
as reflux and another portion is recovered as product argon having an argon concentration generally within the range of from 95 to 99.9 mole percent as shown by stream
96
.
There will now be described in greater detail the operation of the multicomponent refrigerant fluid. circuit which serves to generate preferably all the refrigeration passed into the cryogenic rectification plant thereby eliminating the need for any turboexpansion of a process stream to produce refrigeration for the separation, thus decoupling the generation of refrigeration for the cryogenic air separation process from the flow of process streams, such as feed air, associated with the cryogenic air separation process.
The following description illustrates the multicomponent refrigerant fluid system for providing refrigeration throughout the primary heat exchanger
1
. Multicomponent refrigerant fluid in stream
105
is compressed by passage through recycle compressor
32
to a pressure generally within the range of from 60 to 1000 psia to produce compressed refrigerant fluid
106
. The compressed refrigerant fluid is cooled of the heat of compression by passage through aftercooler
33
and may be partially condensed. The resulting multicomponent refrigerant fluid in stream
101
is then passed through heat exchanger
1
wherein it is further cooled and generally is at least partially condensed and may be completely condensed. The resulting cooled, compressed multicomponent refrigerant fluid
102
is then expanded or throttled through valve
103
. The throttling preferably partially vaporizes the multicomponent refrigerant fluid, cooling the fluid and generating refrigeration. For some limited circumstances, dependent on heat exchanger conditions, the compressed fluid
102
may be subcooled liquid prior to expansion and may remain as liquid upon initial expansion. Subsequently, upon warming in the heat exchanger, the fluid will have two phases. The pressure expansion of the fluid through a valve would provide refrigeration by the Joule-Thomson effect, i.e. lowering of the fluid temperature due to pressure expansion at constant enthalpy. However, under some circumstances, the fluid expansion could occur by utilizing a two-phase or liquid expansion turbine, so that the fluid temperature would be lowered due to work expansion.
Refrigeration bearing multicomponent two phase refrigerant fluid stream
104
is then passed through heat exchanger
1
wherein it is warmed and completely vaporized thus serving by indirect heat exchange to cool stream
101
and also to transfer refrigeration into the process streams within the heat exchanger, including feed air stream
63
, thus passing refrigeration generated by the multicomponent refrigerant fluid refrigeration circuit into the cryogenic rectification plant to sustain the cryogenic air separation process. The resulting warmed multicomponent refrigerant fluid in vapor stream
105
is then recycled to compressor
32
and the refrigeration cycle starts anew. In the multicomponent refrigerant fluid refrigeration cycle while the high pressure mixture is condensing, the low pressure mixture is boiling against it, i.e. the heat of condensation boils the low-pressure liquid. At each temperature level, the net difference between the vaporization and the condensation provides the refrigeration. For a given refrigerant component combination, mixture composition, flowrate and pressure levels determine the available refrigeration at each temperature level.
The multicomponent refrigerant fluid contains two or more components in order to provide the required refrigeration at each temperature. The choice of refrigerant components will depend on the refrigeration load versus temperature for the specific process. Suitable components will be chosen depending upon their normal boiling points, latent heat, and flammability, toxicity, and ozone-depletion potential.
One preferable embodiment of the multicomponent refrigerant fluid useful in the practice of this invention comprises at least two components from the group consisting of fluorocarbons, hydrofluorocarbons and fluoroethers.
Another preferable embodiment of the multicomponent refrigerant fluid useful in the practice of this invention comprises at least one component from the group consisting of fluorocarbons, hydrofluorocarbons and fluoroethers, and at least one atmospheric gas.
Another preferable embodiment of the multicomponent refrigerant fluid useful in the practice of this invention comprises at least two components from the group consisting of fluorocarbons, hydrofluorocarbons and fluoroethers, and at least two atmospheric gases.
Another preferable embodiment of the multicomponent refrigerant fluid useful in the practice of this invention comprises at least one fluoroether and at least one component from the group consisting of fluorocarbons, hydrofluorocarbons, fluoroethers and atmospheric gases.
In one preferred embodiment the multicomponent refrigerant fluid consists solely of fluorocarbons. In another preferred embodiment the multicomponent refrigerant fluid consists solely of fluorocarbons and hydrofluorocarbons. In another preferred embodiment the multicomponent refrigerant fluid consists solely of fluorocarbons and atmospheric gases. In another preferred embodiment the multicomponent refrigerant fluid consists solely of fluorocarbons, hydrofluorocarbons and fluoroethers. In another preferred embodiment the multicomponent refrigerant fluid consists solely of fluorocarbons, fluoroethers and atmospheric gases.
The multicomponent refrigerant fluid useful in the practice of this invention may contain other components such as hydrochlorofluorocarbons and/or hydrocarbons. Preferably, the multicomponent refrigerant fluid contains no hydrochlorofluorocarbons. In another preferred embodiment of the invention the multicomponent refrigerant fluid contains no hydrocarbons. Most preferably the multicomponent refrigerant fluid contains neither hydrochlorofluorocarbons nor hydrocarbons. Most preferably the multicomponent refrigerant fluid is non-toxic, non-flammable and non-ozone-depleting and most preferably every component of the multicomponent refrigerant fluid is either a fluorocarbon, hydrofluorocarbon, fluoroether or atmospheric gas. The invention is particularly advantageous for use in efficiently reaching cryogenic temperatures from ambient temperatures. Tables 1-8 list preferred examples of multicomponent refrigerant fluid mixtures useful in the practice of this invention. The concentration ranges given in the Tables are in mole percent.
TABLE 1
|
|
COMPONENT
CONCENTRATION RANGE
|
|
C
5
F
12
5-25
|
C
4
F
10
0-15
|
C
3
F
8
10-40
|
C
2
F
6
0-30
|
CF
4
10-50
|
Ar
0-40
|
N
2
10-80
|
|
TABLE 1
|
|
COMPONENT
CONCENTRATION RANGE
|
|
C
5
F
12
5-25
|
C
4
F
10
0-15
|
C
3
F
8
10-40
|
C
2
F
6
0-30
|
CF
4
10-50
|
Ar
0-40
|
N
2
10-80
|
|
TABLE 1
|
|
COMPONENT
CONCENTRATION RANGE
|
|
C
5
F
12
5-25
|
C
4
F
10
0-15
|
C
3
F
8
10-40
|
C
2
F
6
0-30
|
CF
4
10-50
|
Ar
0-40
|
N
2
10-80
|
|
TABLE 4
|
|
COMPONENT
CONCENTRATION RANGE
|
|
CHF
2
—O—C
2
HF
4
5-25
|
C
4
H
10
0-15
|
CF
3
—O—C
2
F
3
10-40
|
C
2
F
6
0-30
|
CF
4
10-50
|
Ar
0-40
|
N
2
10-80
|
|
TABLE 4
|
|
COMPONENT
CONCENTRATION RANGE
|
|
CHF
2
—O—C
2
HF
4
5-25
|
C
4
H
10
0-15
|
CF
3
—O—C
2
F
3
10-40
|
C
2
F
6
0-30
|
CF
4
10-50
|
Ar
0-40
|
N
2
10-80
|
|
TABLE 4
|
|
COMPONENT
CONCENTRATION RANGE
|
|
CHF
2
—O—C
2
HF
4
5-25
|
C
4
H
10
0-15
|
CF
3
—O—C
2
F
3
10-40
|
C
2
F
6
0-30
|
CF
4
10-50
|
Ar
0-40
|
N
2
10-80
|
|
TABLE 7
|
|
COMPONENT
CONCENTRATION RANGE
|
|
C
2
HCl
2
F
3
5-25
|
C
2
HClF
4
0-15
|
CF
3
—O—C
2
F
3
10-40
|
CHF
3
0-30
|
CF
4
0-25
|
Ar
0-40
|
N
2
10-80
|
|
TABLE 7
|
|
COMPONENT
CONCENTRATION RANGE
|
|
C
2
HCl
2
F
3
5-25
|
C
2
HClF
4
0-15
|
CF
3
—O—C
2
F
3
10-40
|
CHF
3
0-30
|
CF
4
0-25
|
Ar
0-40
|
N
2
10-80
|
|
In a preferred embodiment of the invention each of the two or more components of the refrigerant mixture has a normal boiling point which differs by at least 5 degrees Kelvin, more preferably by at least 10 degrees Kelvin, and most preferably by at least 20 degrees Kelvin, from the normal boiling point of every other component in the refrigerant mixture. This enhances the effectiveness of providing refrigeration over a wide temperature range which encompasses cryogenic temperatures. In a particularly preferred embodiment of the invention, the normal boiling point of the highest boiling component of the multicomponent refrigerant fluid is at least 50° K, preferably at least 100° K, most preferably at least 200° K, greater than the normal boiling point of the lowest boiling component of the multicomponent refrigerant fluid.
FIG. 2
illustrates another preferred embodiment of the invention wherein more than one multicomponent refrigerant fluid circuit is employed. In the specific embodiment illustrated in
FIG. 2
there are two multicomponent refrigerant fluid circuits employed, a high temperature circuit and a low temperature circuit. The multicomponent refrigerant fluid in the high temperature circuit will contain primarily higher boiling components and the multicomponent refrigerant fluid in the low temperature circuit will contain primarily lower boiling components. By the use of multiple multicomponent refrigerant fluid circuits such as the arrangement illustrated in
FIG. 2
, one can more effectively avoid any problems associated with the freezing of any component, thus improving the efficiency of the systems. The numerals of
FIG. 2
are the same as those of
FIG. 1
for the common elements and these common elements will not be described again in detail. The cryogenic air separation system illustrated in
FIG. 2
does not include an argon column so that subcooled oxygen-enriched liquid
70
is passed directly into lower pressure column
11
.
Referring now to
FIG. 2
, high temperature multicomponent refrigerant fluid in stream
110
is compressed by passage through recycle compressor
35
to a pressure generally within the range of from 60 to 500 psia to produce compressed high temperature refrigerant fluid
111
. The compressed refrigerant fluid is cooled of the heat of compression by passage through aftercooler
36
and may be partially condensed. The resulting high temperature multicomponent refrigerant fluid in stream
112
is then passed through heat exchanger
1
wherein it is further cooled and preferably is at least partially condensed and may be completely condensed. The cooled, compressed high temperature multicomponent refrigerant fluid
107
is then expanded or throttled through valve
108
. The throttling preferably partially vaporizes the high temperature multicomponent refrigerant fluid, cooling the fluid and generating refrigeration. Resulting high temperature multicomponent refrigerant fluid in stream
109
has a temperature generally within the range of from 120 to 270K, preferably from 120 to 250K. Stream
109
is then passed through heat exchanger
1
wherein it is warmed by indirect heat exchange with the cooling high temperature multicomponent refrigerant fluid in stream
112
, with feed air in stream
63
, and also with the multicomponent refrigerant fluid circulating in the other multicomponent refrigerant fluid circuit, termed the low temperature multicomponent refrigerant circuit, which is operating in a manner similar to that described in conjunction with the embodiment illustrated in FIG.
1
. In the multiple circuit embodiment illustrated in
FIG. 2
, the low temperature multicomponent refrigerant fluid in stream
104
has a temperature generally within the range of from 80 to 200K, preferably from 80 to 150K.
Table 9 presents illustrative examples of high temperature (column A) and low temperature (column B) multicomponent refrigerant fluids which may be used in the practice of the invention in accordance with the embodiment illustrated in FIG.
2
. The compositions are in mole percent.
TABLE 9
|
|
COMPOSITION
COMPOSITION
|
COMPONENT
(A)
(B)
|
|
C
2
HCl
2
F
3
5-30
0-25
|
C
2
HClF
4
0-30
0-15
|
C
2
H
2
F
4
10-30
0-15
|
C
2
HF
5
0-30
10-40
|
CHF
3
0-30
0-30
|
CF
4
0-30
10-50
|
Ar
0-15
0-40
|
N
2
0-15
10-80
|
|
The components and their concentrations which make up the multicomponent refrigerant fluids useful in the practice of this invention preferably are such as to form a variable load multicomponent refrigerant fluid and preferably maintain such a variable load characteristic throughout the whole temperature range of the method of the invention. This markedly enhances the efficiency with which the refrigeration can be generated and utilized over such a wide temperature range. The defined preferred group of components has an added benefit in that they can be used to form fluid mixtures which are non-toxic, non-flammable and low or non-ozone-depleting. This provides additional advantages over conventional refrigerants which typically are toxic, flammable and/or ozone-depleting.
One preferred variable load multicomponent refrigerant fluid useful in the practice of this invention which is non-toxic, non-flammable and non-ozone-depleting comprises two or more components from the group consisting of C
5
F
12
, CHF
2
—O—C
2
HF
41
C
4
HF
9
, C
3
H
3
F
5
, C
2
F
5
—O—CH
2
F, C
3
H
2
F
2
, CHF
2
—O—CHF
2
, C
4
F
10
, CF
3
—O—C
2
H
2
F
3
, C
3
HF
7
, CH
2
F—O—CF
3
, C
2
H
2
F
4
, CHF
2
—O—CF
3
, C
3
F
8
, C
2
HF
5
, CF
3
—O—CF
3
, C
2
F
6
, CHF
3
, CF
4
, O
2
, Ar, N
2
, Ne and He.
FIG. 3
illustrates another preferred embodiment of the invention wherein the multicomponent refrigerant fluid circuit employs internal recycle. This arrangement may provide higher process efficiency while alleviating freezing problems. The numerals of
FIG. 3
are the same as those of
FIGS. 1 and 2
for the common elements and these common elements will not be described again in detail.
Referring now to
FIG. 3
, heat exchanger
1
is represented as two segments identified as
1
A and
1
B. Stream
101
is partially condensed by partial traverse of segment
1
A and resulting two phase stream
112
is passed to phase separator
176
wherein it is separated into a vapor portion and a liquid portion. The vapor portion is passed out from phase separator
176
as stream
113
, completes the traverse of segment
1
A, passes as stream
114
through segment
1
B and then as stream
115
is passed through valve
116
. Stream
115
may be either totally liquid or a two phase stream. Resulting refrigeration bearing stream
117
is warmed by passage through segment
1
B, emerging therefrom as stream
118
. The liquid portion is withdrawn from phase separator
176
as stream
119
and is subcooled by completing the traverse of segment
1
A. Resulting subcooled stream
120
is throttled through valve
121
and as stream
122
combined with stream
118
to form stream
123
for passage through segment
1
A for completion of the circuit.
Although the invention has been described in detail with reference to certain preferred embodiments, those skilled in the art will recognize that there are other embodiments of the invention within the spirit and the scope of the claims.
Claims
- 1. A process for the production of gaseous nitrogen and gaseous oxygen by the cryogenic rectification of feed air comprising:(A) compressing a multicomponent refrigerant fluid, cooling the compressed multicomponent refrigerant fluid, expanding the cooled, compressed multicomponent refrigerant fluid to generate refrigeration, and warming the expanded multicomponent refrigerant fluid by indirect heat exchange with said cooling compressed multicomponent refrigerant fluid and also with feed air to produce cooled feed air; (B) passing the cooled feed air into a higher pressure cryogenic rectification column and separating the feed air by cryogenic rectification within the higher pressure cryogenic rectification column into nitrogen-enriched fluid and oxygen-enriched fluid; (C) passing nitrogen-enriched fluid and oxygen-enriched fluid into a lower pressure cryogenic rectification column, and separating the fluids passed into the lower pressure column by cryogenic rectification to produce nitrogen-rich fluid and oxygen-rich fluid; (D) withdrawing nitrogen-rich fluid from the upper portion of the lower pressure column and recovering the withdrawn nitrogen-rich fluid as product gaseous nitrogen; and (E) withdrawing oxygen-rich fluid from the lower portion of the lower pressure column and recovering the withdrawn oxygen-rich fluid as product gaseous oxygen.
- 2. The process of claim 1 wherein the expansion of the cooled, compressed multicomponent refrigerant fluid produces a two-phase multicomponent refrigerant fluid.
- 3. The process of claim 1 wherein the multicomponent refrigerant fluid comprises at least two components from the group consisting of fluorocarbons, hydrofluorocarbons and fluoroethers.
- 4. The process of claim 1 wherein the multicomponent refrigerant fluid comprises at least one component from the group consisting of fluorocarbons, hydrofluorocarbons and fluoroethers and at least one atmospheric gas.
- 5. The process of claim 1 wherein the multicomponent refrigerant fluid comprises at least two components from the group consisting of fluorocarbons, hydrofluorocarbons and fluoroethers and at least two atmospheric gases.
- 6. The process of claim 1 wherein the multicomponent refrigerant fluid comprises at least one fluoroether and at least one component from the group consisting of fluorocarbons, hydrofluorocarbons, fluoroethers and atmospheric gases.
- 7. The process of claim 1 wherein the normal boiling point of the highest boiling component of the multicomponent refrigerant fluid is at least 500K greater than the normal boiling point of the lowest boiling component of the multicomponent refrigerant fluid.
- 8. The process of claim 1 wherein the multicomponent refrigerant fluid comprises at least two components from the group consisting of C5F12, CHF2—O—C2HF4, C4HF9, C3H3F5, C2F5—O—CH2F, C3H2F6, CHF2—O—CHF2, C4F10, CF3—O—C2H2F3, C3HF7, CH2F—O—CF3, C2H2F4, CHF2—O—CF3, C3F8, C2HF5, CF3—O—CF3, C2F6, CHF3, CF4, O2, Ar, N2, Ne and He.
- 9. A process for the production of gaseous nitrogen and gaseous oxygen by the cryogenic rectification of feed air comprising:(A) compressing a high temperature multicomponent refrigerant fluid, cooling the compressed high temperature multicomponent refrigerant fluid, expanding the cooled, compressed high temperature multicomponent refrigerant fluid to generate refrigeration, and warming the expanded high temperature multicomponent refrigerant fluid by indirect heat exchange with said cooling compressed high temperature multicomponent refrigerant fluid and with low temperature multicomponent refrigerant fluid and also with feed air; (B) compressing low temperature multicomponent refrigerant fluid, cooling the compressed low temperature multicomponent refrigerant fluid, expanding the cooled, compressed low temperature multicomponent refrigerant fluid to generate refrigeration, and warming the expanded low temperature multicomponent refrigerant fluid by indirect heat exchange with said cooling compressed low temperature multicomponent refrigerant fluid and also with feed air to produce cooled feed air; (C) passing the cooled feed air into a higher pressure cryogenic rectification column and separating the feed air by cryogenic rectification within the higher pressure cryogenic rectification column into nitrogen-enriched fluid and oxygen-enriched fluid; (D) passing nitrogen-enriched fluid and oxygen-enriched fluid into a lower pressure cryogenic rectification column, and separating the fluids passed into the lower pressure column by cryogenic rectification to produce nitrogen-rich fluid and oxygen-rich fluid; (E) withdrawing nitrogen-rich fluid from the upper portion of the lower pressure column and recovering the withdrawn nitrogen-rich fluid as product gaseous nitrogen; and (F) withdrawing oxygen-rich fluid from the lower portion of the lower pressure column and recovering the withdrawn oxygen-rich fluid as product gaseous oxygen.
- 10. The process of claim 9 wherein the temperature of the expanded high temperature multicomponent refrigerant fluid is within the range of from 120 to 270K, and the temperature of the expanded low temperature multicomponent refrigerant fluid is within the range of from 80 to 200K.
- 11. The method of claim 1, wherein the multicomponent refrigerant fluid contains no hydrocarbons.
- 12. The method of claim 9, wherein the high temperature multicomponent refrigerant fluid contains no hydrocarbons and the low temperature multicomponent refrigerant fluid contains no hydrocarbons.
US Referenced Citations (14)
Foreign Referenced Citations (1)
| Number |
Date |
Country |
| 2631134 |
Jan 1978 |
DE |
