Title of Invention

AN IMPROVED PROCESS FOR THE SEPARATION OF A GAS STREAM

Abstract An improved process for the separation of a gas stream containing methane, C2 components, C3 components and 2 3 heavier hydrocarbon components into a volatile residue gas fraction containing a major portion of said methane and a relatively less volatile fraction containing a major portion of said C2 components, C3 components and heavier hydrocarbon components, in which process (a) said gas stream is treated in one or more heat exchange steps and at least one division step to produce at least a first feed stream that has been cooled under pressure to condense substantially all of it, and at least a second feed stream that has been cooled under pressure;(b) said substantially condensed first feed stream is expanded to a lower pressure whereby it is further cooled* and thereafter supplied to a fractionation tower at a top feed point; (c) said cooled second feed stream is expanded to said lower pressure, and thereafter supplied to said fractionation tower at a mid-column feed point; and (d) said cooled expanded first feed stream and said expanded second feed stream are fractionated at said lower pressure whereby the components of said relatively less volatile fraction are recovered; the improvement comprising: (1) a liquid distillation stream is withdrawn from said fractionation tower and heated; (2) said heated distillation stream is returned to a lower point on said fractionation tower that is separated from said withdrawal point by at least one theoretical stage; and (3) the quantities and temperatures of said feed streams to said fractionation tower are effective to maintain the overhead temperature of said fractionation tower at a temperature whereby the major portions of the components in said relatively less volatile fraction are recovered.
Full Text HYDROCARBON GAS PROCESSING
SPECIFICATION
BACKGROUND OF THE INVENTION
This invention relates to a process for the separation of a gas
containing hydrocarbons.
Ethylene, ethane, propylene, propane and/or heavier hydrocarbons can
be recovered from a variety of gases, such as natural gas, refinery-gas, and synthetic
gas streams obtained from other hydrocarbon materials such as coal, crude oil,
naphtha, oil shale, tar sands, and lignite. Natural gas usually has a major proportion of
methane and ethane, i.e., methane and ethane together comprise at least 50 mole
percent of the gas. The gas also contains relatively lesser amounts of heavier
hydrocarbons such as propane, butanes, pentanes and the like, as well as hydrogen,
nitrogen, carbon dioxide and other gases.
The present invention is generally concerned with the recovery of
ethylene, ethane, propylene, propane and heavier hydrocarbons from such gas streams.
A typical analysis of a gas stream to be processed in accordance with this invention
would be, in approximate mole percent, 92.12% methane, 3.96% ethane and other C2
components, 1.05% propane and other C3 components, 0.15% iso-butane, 0.21%
normal butane, 0.11% pentanes plus, with the balance made up of nitrogen and carbon
dioxide. Sulfur containing gases are also sometimes present.
The historically cyclic fluctuations in the prices of both natural gas and
its natural gas liquid (NGL) constituents have at times reduced the incremental value
of ethane, ethylene, propane, propylene. and heavier components as liquid products.
Competition for processing rights has forced plant operators to maximize the
processing capacity and recovery efficiency of their existing gas processing plants.
Available processes for separating these materials include those based upon cooling
and refrigeration of gas, oil absorption, and refrigerated oil absorption. Additionally,
cryogenic processes have become popular because of the availability of economical
equipment that produces power while simultaneously expanding and extracting heat
from the gas being processed. Depending upon the pressure of the gas source, the
richness (ethane, ethylene, and heavier hydrocarbons content) of the gas, and the
desired end products, each of these processes or a combination thereof may be
employed.
The cryogenic expansion process is now generally preferred for natural
gas liquids recovery because it provides maximum simplicity with ease of start up,
operating flexibility, good efficiency, safety, and good reliability. U.S. Pat. Nos.
4,157,904; 4,171,964; 4,185,978; 4.251,249; 4,278,457; 4,519,824; 4,617,039;
4,687,499; 4,689,063; 4,690,702; 4,854,955; 4,869,740; 4,889,545; 5,275,005;
5,555,748; 5,568,737; 5,771,712; 5,799,507; 5,881,569; 5,890,378; reissue U.S. Pat.
No. 33,408; and co-pending application no. 09/054,802 describe relevant processes
(although the description of the present invention in some cases is based on different
processing conditions than those described in the cited U.S. patents and patent
applications).
In a typical cryogenic expansion recovery process, a feed gas stream
under pressure is cooled by heat exchange with other streams of the process and/or
external sources of refrigeration such as a propane compression-refrigeration system.
As the gas is cooled, liquids may be condensed and collected in one or more
separators as high-pressure liquids containing some of the desired C2+ components.
Depending on the richness of the gas and the amount of liquids formed, the
high-pressure liquids may be expanded to a lower pressure and fractionated. The
vaporization occurring during expansion of the liquids results in further cooling of the
stream. Under some conditions, pre-cooling the high pressure liquids prior to the
expansion may be desirable in order to further lower the temperature resulting from
the expansion. The expanded stream, comprising a mixture of liquid and vapor, is
fractionated in a distillation (demethanizer) column. In the column, the expansion
cooled stream(s) is (are) distilled to separate residual methane, nitrogen, and other
volatile gases as overhead vapor from the desired C2 components. C3 components, and
heavier hydrocarbon components as bottom liquid product.
If the feed gas is not totally condensed (typically it is not), at least a
portion of the vapor remaining from the partial condensation can be passed through a
work expansion machine or engine, or an expansion valve, to a lower pressure at
which additional liquids are condensed as a result of further cooling of the stream.
The pressure after expansion is essentially the same as the pressure at which the
distillation column is operated. The combined vapor-liquid phases resulting from the
expansion are supplied as a feed to the column. In recent years, the preferred
processes for hydrocarbon separation involve feeding this expanded vapor-liquid
stream at a mid-column feed point, with an upper absorber section providing
additional rectification of the vapor phase.
The source of the reflux stream for the upper rectification section is
typically a portion of the above mentioned vapor remaining after partial condensation
of the feed gas, but withdrawn prior to work expansion. An alternate source for the
upper reflux stream may be provided by a recycled stream of residue gas supplied
under pressure. Regardless of its source, this vapor stream is usually cooled to
substantial condensation by heat exchange with other process streams, e.g., the cold
fractionation tower overhead. Some or all of the high-pressure liquid resulting from
partial condensation of the feed gas may be combined with this vapor stream prior to
cooling. The resulting substantially condensed stream is then expanded through an
appropriate expansion device, such as an expansion valve, to the pressure at which the
demethanizer is operated. During expansion, a portion of the liquid will usually
vaporize, resulting in cooling of the total stream. The flash expanded stream is then
supplied as top feed to the demethanizer. Typically, the vapor portion of the expanded
stream and the demethanizer overhead vapor combine in an upper separator section in
the fractionation tower as residual methane product gas. Alternatively, the cooled and
expanded stream may be supplied to a separator to provide vapor and liquid streams,
so that thereafter the vapor is combined with the tower overhead and the liquid is
supplied to the column as a top column feed.
The purpose of this process is to perform a separation that produces a
residue gas leaving the process which contains substantially all of the methane in the
feed gas with essentially none of the C2 components and heavier hydrocarbon
components, and a bottoms fraction leaving the demethanizer which contains
substantially all of the C2 components and heavier hydrocarbon components with
essentially no methane or more volatile components while meeting plant
specifications for maximum permissible carbon dioxide content. The present
invention provides a means for providing a new plant or modifying an existing
processing plant to achieve this separation at significantly lower capital cost by
reducing the size of or eliminating the need for a product treating system for removal
of carbon dioxide. Alternatively, the present invention, whether applied in a new
facility or as a modification to an existing processing plant, can be used to recover
more C2 components and heavier hydrocarbon components in the bottom liquid
product for a given carbon dioxide concentration in the feed gas than other processing
schemes.
In accordance with the present invention, it has been found that C2
recoveries in excess of 84 percent can be maintained while maintaining the carbon
dioxide content of the bottom liquid product within specifications and providing
essentially complete rejection of methane to the residue gas stream. The present
invention, although applicable at lower pressures and warmer temperatures, is
particularly advantageous when processing feed gases at pressures in the range of 600
to 1000 psia or higher under conditions requiring column overhead temperatures of
-120°F or colder.
The present invention uses a modified reboiler scheme which can be
applied to any type of NGL recovery system. In a typical reboiler or side reboiler
application in a distillation column, the entire column down-flowing liquid stream is
withdrawn from the tower and passed through a heat exchanger, then returned to the
column at essentially the same point in the column. In this modified reboiler system,
a portion of the column down-flowing liquid is withdrawn from a point higher in the
column, i.e., separated from the return point by at least one theoretical stage. Even
though the flow rate of the liquid may be lower, it is usually much colder and can have
advantages in improving recovery or reducing exchanger size.
It has been found that when the present invention is applied to prior art
processes for NGL recovery, the recovery of C2 components and heavier components
is improved by one to two percent. The improvement in recovery is much greater,
however, when it is desirable to reduce the carbon dioxide content in the recovered
NGL product. Recovery of ethane in a typical NGL recovery plant also results in
recovery of at least some of the carbon dioxide contained in the feed gas because
carbon dioxide falls in between methane and ethane in relative volatility. Therefore,
as ethane recovery increases, so does the recovery of carbon dioxide in the NGL
product. By applying the modified reboiler scheme of the present invention, the
applicants have found that it is possible to significantly improve recovery of ethane in
the NGL product compared to use of the conventional reboiler or side reboiler systems
when the column is reboiled to meet the desired carbon dioxide content in the NGL
product.
For a better understanding of the present invention, reference is made
to the following examples and drawings. Referring to the drawings:
FIG. 1 is a flow diagram of a prior art cryogenic natural gas processing
plant;
FIG. 2 is a flow diagram of an alternative adaptation of the prior art
cryogenic natural gas processing plant;
FIG. 3 is a flow diagram illustrating how the processing plants of
FIGS. 1 and 2 can be adapted to be a natural gas processing plant in accordance with
the present invention;
. FIG. 4 is a flow diagram illustrating an alternative adaptation of FIGS.
1 and 2 to be a natural gas processing plant in accordance with the present invention;
FIG. 5 is a flow diagram illustrating how an alternative prior art
process can be adapted to be a natural gas processing plant in accordance with the
present invention;
FIG. 6 is a diagram illustrating the modified reboiler scheme of the
present invention for a processing plant wherein the scheme includes a thermosiphon
system;
FIG. 7 is a diagram illustrating the modified reboiler scheme of the
present invention for a processing plant wherein the scheme includes a pumped
system;
FIG. 8 is a diagram illustrating the modified reboiler scheme of the
present invention for a processing plant wherein the scheme includes a pumped
system; and
FIG. 9 is a diagram illustrating the modified reboiler scheme of the
present invention for a processing plant wherein the scheme includes a split column
system.
In the following explanation of the above figures, tables are provided
summarizing flow rates calculated for representative process conditions. In the tables
appearing herein, the values for flow rates (in pound moles per hour) have been
rounded to the nearest whole number for convenience. The total stream rates shown
in the tables include all non-hydrocarbon components and hence are generally larger
than the sum of the stream flow rates for the hydrocarbon components. Temperatures
indicated are approximate values rounded to the nearest degree. It should also be
noted that the process design calculations performed for the purpose of comparing the
processes depicted in the figures are based on the assumption of no heat leak from (or
to) the surroundings to (or from) the process. The quality of commercially available
insulating materials makes this a very reasonable assumption and one that is typically
made by those skilled in the art.
DESCRIPTION OF THE PRIOR ART
FIG. 1 is a process flow diagram showing the design of a processing
plant to recover C2+ components from natural gas using prior art according to U.S.
Pat. No. 4,157,904. Because this is a large plant designed for 1.0 billion cubic feet of
feed gas per day, the demethanizer (fractionation tower) is to be constructed in two
sections, absorber column 17 and stripper column 19. In this simulation of the
process, inlet gas enters the plant at 86°F and 613 psia as stream 31. If the inlet gas
contains a concentration of sulfur compounds which would prevent the product
streams from meeting specifications, the sulfur compounds are removed by
appropriate pretreatment of the feed gas (not illustrated). In addition, the feed stream
is usually dehydrated to prevent hydrate (ice) formation under cryogenic conditions.
Solid desiccant has typically been used for this purpose.
The feed stream 31 is cooled in exchanger 10 by heat exchange with
cool residue gas at -99°F (stream 37a), demethanizer reboiler liquids at 31 °F (stream
42), demethanizer lower side reboiler liquids at -5°F (stream 41) and demethanizer
upper side reboiler liquids at -99°F (stream 40). Note that in all cases exchanger 10 is
representative of either a multitude of individual heat exchangers or a single
multi-pass heat exchanger, or any combination thereof. (The decision as to whether to
use more than one heat exchanger for the indicated cooling services will depend on a
number of factors including, but not limited to, inlet gas flow rate, heat exchanger
size, stream temperatures, etc.) The cooled stream 31a enters separator 11 at -82°F
and 603 psia where the vapor (stream 32) is separated from the condensed liquid
(stream 35).
The vapor (stream 32) from separator 11 is divided into two streams,
33 and 34: Stream 33, containing about 18 percent of the total vapor, is combined
with the condensed liquid from separator 11. The combined stream 36 passes through
heat exchanger 12 in heat exchange relation with the demethanizer overhead vapor
stream 37 resulting in cooling and substantial condensation of the stream. The
substantially condensed stream 36a at -139°F is then flash expanded through an
appropriate expansion device, such as expansion valve 13, to the operating pressure
(approximately 333 psia) of absorber column 17 of the fractionation tower. During
expansion a portion of the stream is vaporized, resulting in cooling of the total stream.
In the process illustrated in FIG. 1. the expanded stream 36b leaving expansion valve
13 reaches a temperature of-151°F and is supplied to separator section 17a in the
upper region of absorber tower 17. The liquids separated therein become the top feed
to theoretical stage 1 in rectifying section 17b. (An alternative routing for the
separator liquid (stream 35) in accordance with U.S. Pat. No.4,278,457 is indicated by
a dashed line whereby at least a portion of the liquid is expanded to approximately
333 psia by expansion valve 16, cooling stream 35 to produce stream 35a that is then
supplied to the rectifying section in absorber tower 17 at a bottom feed point or to
stripper tower 19 at an upper feed point.)
The remaining 82 percent of the vapor from separator 11 (stream 34)
enters a work expansion machine 14 in which mechanical energy is extracted from
this portion of the high pressure feed. The machine 14 expands the vapor
substantially isentropically from a pressure of about 603 psia to a pressure of about
333 psia, with the work expansion cooling the expanded stream 34a to a temperature
of approximately -125°F. The typical commercially available expanders are capable
of recovering on the order of 80-85% of the work theoretically available in an ideal
isentropic expansion. The work recovered is often used to drive a centrifugal
compressor (such as item 15). that can be used to re-compress the residue gas (stream
37c), for example. The expanded and partially condensed stream 34a is supplied as
feed to the distillation column at a lower feed point (below theoretical stage 7 in this
case).
The liquids (stream 38) from the bottom of absorber column 17 at
-127°F are supplied by pump 18 to stripper column 19 at a top feed point (stream
38a). The operating pressure of stripper column 19 (343 psia) is slightly higher than
the operating pressure of absorber column 17 so that the pressure difference between
the two towers provides the motive force for the overhead vapors (stream 39) at
-125°F from the top of stripper column 19 to flow to the bottom feed point on
absorber column 17.
The demethanizer in absorber tower 17 and stripper tower 19 is a
conventional distillation column containing a plurality of vertically spaced trays, one
or more packed beds, or some combination of trays and packing. As is often the case
in natural gas processing plants, the absorber tower may consist of two sections. The
upper section 17a is a separator wherein the partially vaporized top feed is divided
into its respective vapor and liquid portions, and wherein the vapor rising from the
lower distillation or rectifying section 17b is combined with the vapor portion (if any)
of the top feed to form the cold residue gas distillation stream 37 which exits the top
of the tower. The lower, rectifying section 17b and the stripper column 19 contain the
trays and/or packing and provide the necessary contact between the liquids falling
downward and the vapors rising upward. The stripper column 19 also includes
reboilers which heat and vaporize portions of the liquids flowing down the column to
provide the stripping vapors which flow up the column.
The liquid product (stream 43) exits the bottom of the tower at 43°F,
based on a typical specification of a methane to ethane ratio of 0.0237:1 on a molar
basis in the bottom product and is pumped to approximately 550 psia (stream 43a) in
pump 20. (The discharge pressure of the pump is usually set by the ultimate
destination of the liquid product. Generally the liquid product flows to storage and the
pump discharge pressure is set so as to prevent any vaporization of stream 43a as it
warms to ambient temperature.)
The residue gas (stream 37) passes countercurrently to the incoming
feed gas in: (a) heat exchanger 12 where it is heated to -99°F (stream 37a), (b) heat
exchanger 10 where it is heated to 79°F (stream 37b), and (c) heat exchanger 21
where it is heated to 110°F (stream 37c). The residue gas is then re-compressed in
two stages. The first stage is compressor 15 driven by expansion machine 14, and the
second stage is compressor 22 driven by a supplemental power source. After stream
37e is cooled to 115°F (stream 37f) by cooler 23 and to 86°F by heat exchanger 21,
the residue gas product (stream 37g) flows to the sales pipeline at 631 psia, sufficient
to meet line requirements (usually on the order of the inlet pressure).
A summary of stream flow rates and energy consumption for the
process illustrated in FIG. 1 is set forth in the following table:
As shown in Table I, the prior art illustrated in FIG. 1 achieves 84.89%
ethane recovery using the available residue compression horsepower (45,000 HP
maximum). However, the carbon dioxide concentration in the ethane product (the
methane, ethane, and carbon dioxide stream that results when the bottoms liquid
product is subsequently fractionated to separate the C2 components and lighter
components from the C3 components and heavier hydrocarbon components) is 7.59
mole percent, which exceeds the plant owner's specification of 6.0 mole percent
maximum. Thus, this plant design would require the addition of a treating system to
remove carbon dioxide from the hydrocarbons in order to produce a marketable liquid
product. There are many options for removing the carbon dioxide (treating the
incoming feed gas, treating the total liquid product, treating the ethane product after
fractionation, etc.), but all of these options will add not only to the capital cost of the
plant (due to the cost of installing the treating system) but also to the operating
expense of the plant (due to energy and chemical consumption in the treating system).
One way to keep the ethane product within the carbon dioxide
specification is to operate the demethanizer in a manner to strip the carbon dioxide
from the bottom liquid product, by adding more reboil heat to the column using the
side reboilers and/or the bottom reboiler. FIG. 2 represents such an alternative
operating scheme for the process depicted in FIG. 1. The process of FIG. 2 has been
applied to the same feed gas composition and conditions as described above for FIG. 1.
However, in the simulation of the process of FIG. 2 the process operating conditions
have been adjusted to control the bottom temperature of stripper column 19 such that
the carbon dioxide content of the ethane product is within specification.
In the simulation of this process, as in the simulation for the process of
FIG. 1, operating conditions were selected to keep the ethane recovery level as high as
possible without exceeding the available residue gas compression horsepower. The
feed stream 31 is cooled in exchanger tO by heat exchange with cool residue gas at
-96°F (stream 37«), demethanizer reboiler liquids at 50°F (stream 42), demethanizer
lower side reboiler liquids at 38°F (stream 41) and demethanizer upper side reboiler
liquids at -32°F (stream 40). The cooled stream 31a enters separator 11 at -72°F and
600 psia where the vapor (stream 32) is separated from the condensed liquid (stream
35).
The vapor (stream 32) from separator 11 is divided into two streams, 33
and 34. Stream 33, containing about 17 percent of the total vapor, is combined with
the condensed liquid from separator 11. The combined stream 36 passes through heat
exchanger 12 in heat exchange relation with the demethanizer overhead vapor stream
37 resulting in cooling and substantial condensation of the stream. The substantially
condensed stream 36a at -132°F is then flash expanded through expansion valve 13.
As the stream is expanded to the operating pressure of absorber column 17 (326 psia),
it is cooled to a temperature of approximately -152°F (stream 36b). The expanded
stream 36b is supplied to the tower as the top feed.
The remaining 83 percent of the vapor from separator 11 (stream 34)
enters work expansion machine 14 in which mechanical energy is extracted from this
portion of the high pressure feed. The machine 14 expands the vapor substantially
isentropically from a pressure of about 600 psia to the operating pressure of absorber
tower 17 (326 psia), with the work expansion cooling the expanded stream 34a to a
temperature of approximately -118°F. The expanded and partially condensed stream
34a is supplied as a feed to the distillation column at a lower feed point.
The liquids (stream 38) from the bottom of absorber column 17 at
-120°F are supplied by pump 18 to stripper column 19 at a top feed point (stream 38a).
The operating pressure of stripper column 19 (336 psia) is slightly higher than the
operating pressure of absorber column 17 so that the pressure difference between the
two towers provides the motive force for the overhead vapors (stream 39) at -118°F
from the top of stripper column 19 to flow to the bottom feed point on absorber
column 17.
The liquid product (stream 43) exits the bottom of tower 19 at 56°F.
This stream is pumped to approximately 5S0 psia (stream 43a) in pump 20. The
residue gas (stream 37) passes countercurrently to the incoming feed gas in: (a) heat
exchanger 12 where it is heated to -96°F (stream 37a), (b) heat exchanger 10 where it
is heated to 70°F (stream 37b). and (c) heat exchanger 21 where it is heated to 101°F
(stream 37c). The residue gas is then re-compressed in two stages, compressor 15
driven by expansion machine 14 and compressor 22 driven by a supplemental power
source. After stream 37c is cooled to 115°F (stream 37f) by cooler 23 and to 86°F by
heat exchanger 21, the residue gas product (stream 37g) flows to the sales pipeline at
631 psia.
A summary of stream flow rates and energy consumption for the
process illustrated in FIG. 2 is set forth in the following table:
The carbon dioxide concentration in the ethane product for the FIG. 2
process is 5.95 mole percent, complying with the plant owner's specification of 6.0
mole percent maximum. Note, however, that the methane to ethane ratio in the
bottom product is 0.0008:1 on a molar basis, versus the allowable ratio of 0.0237:1,
indicating the degree of over-stripping required to control the carbon dioxide content
of the liquid product at the required level. Comparison of the recover)' levels
displayed in Tables I and II shows that operating the FIG. 2 process in this manner to
reduce the carbon dioxide content in the ethane product causes a substantial reduction
in liquids recovery. The FIG. 2 process reduces ethane recovery from 84.89% to
68.94%, propane recovery from 96.90% to 96.61%, and butanes+ recovery from
99.33% to 99.25%.
There are two factors at work in the FIG. 2 process that result in less
liquids recovery from the bottom of stripper tower 19 compared to the FIG. 1 process.
First, when the temperature at the bottom of stripper column 19 is raised from 43°F in
the FIG. 1 process to 56°F in the FIG. 2 process, the temperatures at each point in the
column increase relative to their corresponding values in the FIG. 1 process. This
reduces the amount of cooling that the tower liquid streams (streams 40,41, and 42)
can supply to the feed gas in heat exchanger 10. As a result, the cooled feed stream
(stream 31a) entering separator 11 is warmer (-72°F for the FIG. 2 process versus
-82°F for the FIG. 1 process), which in turn results in the lower ethane retention in
absorber column 17 reflected by the ethane content of stream 38 (3841 Lb. Moles/Hr
for the FIG. 2 process versus 4734 Lb. Moles/Hr for the FIG. 1 process). Second, the
higher temperatures in stripper column 19 cause the temperatures in absorber column
17 to be higher, resulting in less methane liquid entering stripper column 19 (6842 Lb.
Moles/Hr in stream 38 for the FIG. 2 process versus 11021 Lb. Moles/Hr for the
FIG. 1 process). When this liquid methane is subsequently vaporized by the side
reboilers and main reboiler attached to stripper column 19, the methane vapor helps to
strip the carbon dioxide from the liquids flowing down the column. With less
methane available in the FIG. 2 process to strip the carbon dioxide, more of the ethane
in the liquids must be vaporized to serve as stripping gas. Since the relative
volatilities for carbon dioxide and ethane are very similar, the ethane vapor is a much
less effective stripping agent than the methane vapor, which reduces the stripping
efficiency in the column.
DESCRIPTION OF THE INVENTION
Example 1
FIG. 3 illustrates a flow diagram of a process in accordance with the
present invention. The feed gas composition and conditions considered in the process
presented in FIG. 3 are the same as those in FIG. 1. Accordingly, the FIG. 3 process
can be compared with that of the FIG. 1 process to illustrate the advantages of the
present invention.
In the simulation of the FIG. 3 process, inlet gas enters at 86°F and a
pressure of 613 psia as stream 31. The feed stream 31 is cooled in exchanger 10 by
heat exchange with cool residue gas at -99°F (stream 37a), demethanizer reboiler
liquids at 30°F (stream 42), demethanizer side reboiler liquids at -4°F (stream 41) and
a portion of the liquids from the bottom of the absorber column at -128°F (stream 45).
The cooled stream 31a enters separator 11 at -84°F and 603 psia where the vapor
(stream 32) is separated from the condensed liquid (stream 35).
The vapor (stream 32) from separator 11 is divided into gaseous first
and second streams, 33 and 34. Stream 33, containing about 19 percent of the total
vapor, is combined with the condensed liquid (stream 35) to form stream 36.
Combined stream 36 passes through heat exchanger 12 in heat exchange relation with
the cold residue gas (stream 37) where it is cooled to -138°F. The resulting
substantially condensed stream 36a is then flash expanded through an appropriate
expansion device, such as expansion valve 13, to the operating pressure
(approximately 332 psia) of absorber tower 17. During expansion a portion of the
stream is vaporized, resulting in cooling of the total stream. In the process illustrated
in FIG. 3, the expanded stream 36b leaving expansion valve 13 reaches a temperature
of -151°F and is supplied to absorber column 17 as the top column feed. The vapor
portion (if any) of stream 36b combines with the vapors rising from the top
fractionation stage of the column to form distillation stream 37, which is withdrawn
from an upper region of the tower.
Returning to the gaseous second stream 34, the remaining 81 percent
of the vapor from separator 11 enters a work expansion machine 14 in which
mechanical energy is extracted from this portion of the high pressure feed. The
machine 14 expands the vapor substantially isentropically from a pressure of about
603 psia to a pressure of about 332 psia, with the work expansion cooling the
expanded stream 34a to a temperature of approximately -127°F. The expanded and
partially condensed stream 34a is thereafter supplied as feed to absorber column 17 at
a lower column feed point.
Alternatively as shown by the dashed line, the condensed liquid
(stream 35) from separator 11 could be flash expanded through an appropriate
expansion device, such as expansion valve 16, to the operating pressure of absorber
tower 17, cooling stream 35 to produce stream 35a. The expanded stream 35a
leaving expansion valve 16 could then be supplied to absorber tower 17 at a lower
column feed point or to stripper tower 19 at an upper column feed point.
The liquids (stream 38) from the bottom of absorber column 17 enter
pump 18 at -128°F and are pumped to higher pressure (stream 38a) and divided into
two portions. One portion (stream 44), containing about 55% of the total liquid, is
supplied to stripper column 19 at a top feed point. The operating pressure of stripper
column 19 (342 psia) is slightly higher than the operating pressure of absorber column
17 so that the pressure difference between the two towers provides the motive force
for the overhead vapors (stream 39) at -123°F from the top of stripper column 19 to
flow to the bottom feed point on absorber column 17.
The other portion (stream 45), containing the remaining 45% of the
pumped liquid stream 38a, is directed to heat exchanger 10 where it supplies part of
the feed gas cooling as it is heated to -20°F and partially vaporized. The heated
stream 45a is thereafter supplied to stripper column 19 at a mid-column feed point,
separated from the top feed point where stream 44 enters the column by at least one
theoretical stage. In this case, the partially vaporized stream flows to the same point
on the column that was used for the upper side reboiler return (theoretical stage 8 in
stripper tower 19) in the FIG. 1 process, which is the equivalent of seven theoretical
stages lower than the liquid stream withdrawal point in the fractionation system (the
top feed point where stream 44 enters stripper column 19).
The liquid product (stream 43) exits the bottom of tower 19 at 42°F.
This stream is pumped to approximately 550 psia (stream 43a) in pump 20. The
residue gas (stream 37) passes countercurrently to the incoming feed gas in: (a) heat
exchanger 12 where it is heated to -99°F (stream 37a), (b) heat exchanger 10 where it
is heated to 80°F (stream 37b). and (c) heat exchanger 21 where it is heated to 105°F
(stream 37c). The residue gas is then re-compressed in two stages, compressor 15
driven by expansion machine 14 and compressor 22 driven by a supplemental power
source. After stream 37e is cooled to 115°F (stream 371) by cooler 23 and to 86°F by
heat exchanger 21, the residue gas product (stream 37g) flows to the sales pipeline at
631 psia.
A summary of stream flow rates and energy consumption for the
process illustrated in FIG. 3 is set forth in the following table:
A comparison of Tables 1 and III shows that, compared to the prior art,
the present invention improves ethane recovery from 84.89% to 86.12%, propane
recovery from 96.90% to 97.10%, and butanes+ recovery from 99.33% to 99.41%.
Comparison of Tables I and III further shows that the improvement in yields was
achieved using equivalent horsepower (utility) requirements.
By using the modified reboiler approach, the column liquid flowing to
heat exchanger 10 (stream 45) is colder than the corresponding stream 40 of the FIG.
1 process. This increases the cooling available to the inlet gas, because not only can
considerably more duty be obtained from the liquids with this scheme, but the liquids
are available at a colder temperature level than would be possible with a conventional
reboiler scheme. The result is increased C2+ component and heavier hydrocarbon
component recoveries for the FIG. 3 process while using essentially the same amount
of residue gas compression horsepower as the prior art FIG; 1 process.
Example 2
In those cases where the carbon dioxide content of the liquid product is
an issue (due to more stringent product specifications imposed by the client as in the
FIG. 2 prior art process described previously, for instance), the present invention
offers very significant recovery and efficiency advantages over the prior art process
depicted in FIG. 2. The operating conditions of the FIG. 3 process can be altered to
reduce the carbon dioxide content in the liquid product of the present invention as
illustrated in FIG. 4. The feed gas composition and conditions considered in the
process presented in FIG. 4 are the same as those in FIGS. 1 and 2. Accordingly, the
FIG. 4 process can be compared with that of the FIGS. 1 and 2 processes to illustrate
the advantages of the present invention.
In the simulation of the FIG. 4 process, the inlet gas cooling and
separation scheme is essentially the same as that used in FIG. 3. The main difference
is that the plant controls have been adjusted to increase the proportion of the liquids
from the bottom of absorber tower 17 (stream 45) that are heated in heat exchanger 10
and supplied to stripper tower 19 at a mid-column feed point. The plant controls have
also been adjusted to raise the bottom temperature of stripper column 19 slightly
(from 42°F in the FIG. 3 process to 45°F in the FIG. 4 process) to maintain the
methane to ethane ratio in the bottom product at the specified 0.0237:1 molar ratio.
The increased quantity of heated stream 45a entering stripper tower 19 and the higher
bottoms temperature both increase the stripping inside the tower, which results in
wanner temperatures for the FIG. 4 process relative to the FIG. 3 process throughout
both absorber column 17 and smpper column 19, with the net effect of reducing the
carbon dioxide content of the liquid product, stream 43, leaving stripper column 19.
The warmer column temperatures also result in a slight reduction in the refrigeration
that is available from the process streams to be applied to the column feed streams. In
particular, this requires slightly reducing the proportion of the separator feed gas
(stream 32) that is directed ;o heat exchanger 12 via stream. 33, thereby reducing the
quantity of stream 36b entering at the top feed point of absorber tower 17.
A summary of stream flow rates and energy consumption for the
process illustrated in FIG. 4 is set forth in the following table:
The carbon dioxide concentration in the ethane product for the FIG. 4
process is 5.80 mole percent, well below the specification required by the client.
Comparison of the recovery levels displayed in Tables I and IV shows that the present
invention allows achieving the required carbon dioxide content while maintaining
almost the same liquids recovery efficiency as the FIG. 1 process. Although the
ethane recovery decreases slightly from 84.89% to 84.61%, the propane recovery and
the butanes+ recovery both increase slightly, from 96.90% to 96.96% and from
99.33% to 99.39%, respectively. Comparison of Tables I and IV further shows that
maintaining the product yields was achieved using essentially the same horsepower
(utility) requirements.
Comparison of the recovery levels displayed in Tables II and IV shows
that the present invention allows achieving much higher liquids recovery efficiency
than the FIG. 2 process when it is operated in a fashion to limit the carbon dioxide
content of its liquid product. Compared to the FIG. 2 process, the FIG. 4 process
raises the ethane recovery from 68.94% to 84.61%, almost 15.7 percentage points
higher. The propane recovery and the butanes+ recovery also increase somewhat,
from 96.61% to 96.96% and from 99.25% to 99.39%, respectively. Comparison of
Tables II and IV further shows that the higher the product yields were not simply the
result of increasing the horsepower (utility) requirements. To the contrary, when the
present invention is employed as in Example 2, not only do the ethane, propane, and
butanes+ recoveries increase over those of the prior art process, but liquid recovery
efficiency also increases by 23 percent (in terms of ethane recovered per unit of
horsepower expended).
As with the process of FIG. 3, a significant benefit achieved by the
embodiment of FIG. 4 is that the modified reboiler scheme provides colder column
liquids for use in refrigerating the incoming feed streams. This increases the cooling
available to the inlet gas, as not only can considerably more duty be obtained from the
liquid in this case, but at a colder temperature level. At the same time, more methane
is introduced lower in stripper column 19 than would otherwise be there when
reboiling the column to meet the carbon dioxide content. (Note that stream 45 in the
FIG. 4 process contains 5721 Lb. Moles/Hr of methane and is introduced at
theoretical stage 8 of stripper column 19. whereas stream 40 in the FIG. 2 process
contains only 1886 Lb. Molcs/Hr of methane and is introduced at the top of stripper
column 19). The additional methane provided by the present invention in the FIG. 4
process helps to strip the carbon dioxide from the liquids flowing downward in the
stripping column. The quantity of carbon dioxide in the NGL product can be adjusted
by appropriate control of the quantity of liquid withdrawn to feed the modified
reboiler system instead of feeding the top of the stripping column.
Other Embodiments
FIG. 5 is a flow diagram illustrating how the process and apparatus
described and depicted in U.S. Pat. No. 5,568,737 can be adapted to be a natural gas
processing plant in accordance with the present invention. FIGS. 6, 7, 8, and 9 are
diagrams showing some of the alternative methods for implementing the modified
reboiler scheme. FIG. 6 shows a typical thermosiphon type application wherein the
partial flow of liquid from fractionation tower 50 to reboiler 57 could be controlled
via valve 58 in liquid draw line 61. The liquid portion not withdrawn from the
column simply overflows chimney tray 51 onto distributor 52 for packing (or trays)
53 below. The heated stream in line 61a from reboiler 57 is returned to fractionation
tower 50 at a lower point which contains an appropriate feed distribution mechanism,
such as chimney tray 54 and distributor 55, to mix the heated stream with the
down-flowing tower liquids from packing 53 and supply the mixture to packing (or
trays) 56. FIGS. 7 and 8 show typical pumped adaptations wherein the total liquid
down-flow is withdrawn in liquid draw line 61 and pumped to higher pressure by
pump 60. The flow of the pumped liquid in line 61a is then divided via appropriate
control valves 58 and 59 to arrive at the desired quantity of liquid in line 62 flowing
to reboiler 57. The heated stream in line 62a from reboiler 57 is returned to
fractionation tower 50 at a lower point as described previously for the FIG. 6
embodiment. In the FIG. 7 embodiment, the liquid that does not flow to the reboiler
(in line 63) is returned to chimney tray 51 from which the liquid was initially
withdrawn, whereupon it can overflow chimney tray 51 onto distributor 52 for
packing (or trays) 53 below. In the FIG. 8 embodiment, the liquid that does not flow
to the reboiler (in line 63) is returned below chimney tray 51 from which the liquid
was initially withdrawn, directly to distributor 52 that supplies the liquid to packing
(or trays) 53 below. FIG. 9 shows how the pumped system described for FIG. 8 can
be implemented in a split column approach, such as upper column 65 and lower
column 50, which is the same as that used in FIGS. 3 and 4.
One skilled in the art will recognize that the present invention gams
some of its benefit by providing a colder stream to the side reboiler(s) and/or
reboiler(s), allowing additional cooling of the column feed or feeds. This additional
cooling reduces utility requirements for a given product recovery level, or improves
product recovery levels for a given utility consumption, or some combination thereof.
Further, one skilled in the art will recognize that the present invention also benefits by
introducing greater quantities of methane lower in the demethanizer to assist in
stripping carbon dioxide from the down-flowing liquids. With more methane
available for stripping the liquids, correspondingly less ethane is needed for stripping,
allowing more retention of ethane in the bottom liquid product. Therefore, the
present invention is generally applicable to any process, dependent on cooling any
number of feed streams and supplying the resulting feed stream(s) to the column for
distillation.
In accordance with this invention, the cooling of the demethanizer feed
streams may be accomplished in many ways. In the process of FIGS. 3 and 4, feed
stream 36 is cooled and substantially condensed by the demethanizer overhead vapor
stream 37, while the demethanizer liquids (streams 45,41, and 42) are used only for
gas stream cooling. In the process of FIG. 5, high pressure residue feed stream 48 is
also cooled and substantially condensed by portions of the distillation column
overhead vapor stream (streams 46 and 37), while the demethanizer liquids (streams
40 and 42) are used only for gas stream cooling. However, demethanizer liquids
could be used to supply some or all of the cooling and substantial condensation of
stream 36 in FIGS. 3 through 5 and/or stream 48 in FIG. 5 in addition to or instead of
gas stream cooling. Further, any stream at a temperature colder than the feed stream
being cooled may be utilized. For instance, a side draw of vapor from the
demethanizer could be withdrawn and used for cooling. Other potential sources of
cooling include, but are not limited to, flashed high pressure separator liquids and
mechanical refrigeration systems. The selection of a source of cooling will depend on
a number of factors including, but not limited to, inlet gas composition and
conditions, plant size, heat exchanger size, potential cooling source temperature, etc.
One skilled in the art will also recognize that any combination of the above cooling
sources or methods of cooling may be employed in combination to achieve the
desired feed stream temperature(s).
In accordance with this invention, the use of external refrigeration to
supplement the cooling available to the inlet gas from other process streams may be
employed, particularly in the case of an inlet gas richer than that used in Examples 1
and 2. The use and distribution of demethanizer liquids for process heat exchange,
and the particular arrangement of heat exchangers for inlet gas cooling must be
evaluated for each particular application, as well as the choice of process streams for
specific heat exchange services.
The high pressure liquid in FIGS. 3 through 5 (stream 35) need not all
be combined with the portion of the separator vapor (stream 33) flowing to heat
exchanger 12. Alternatively, this liquid stream (or a portion thereof) may be
expanded through an appropriate expansion device, such as expansion valve 16, and
fed to a lower mid-column feed point on the distillation column (absorber tower 17 or
stripper tower 19 in FIGS. 3 and 4. fractionation tower 17 in FIG. 5). The liquid
stream may also be used for inlet gas cooling or other heat exchange service before or
after the expansion step prior to flowing to the demethanizer.
It will also be recognized that the relative amount of feed found in each
branch of the column feed streams will depend on several factors, including gas
pressure, feed gas composition, the amount of heat which can economically be
extracted from the feed and the quantity of horsepower available. More feed to the
top of the column may increase recovery while decreasing power recovered from the
expansion machine thereby increasing the recompression horsepower requirements.
Increasing feed lower in the column reduces the horsepower consumption but may
also reduce product recover)'. The mid-column feed positions depicted in FIGS. 3
and 4 are the preferred feed locations for the process operating conditions described.
However, the relative locations of the mid-column feeds may vary depending on inlet
composition or other factors such as desired recovery levels and amount of liquid
formed during inlet gas cooling. Moreover, two or more of the feed streams, or
portions thereof, may be combined depending on the relative temperatures and
quantities of individual streams, and the combined stream then fed to a mid-column
feed position. FIGS. 3 and 4 are the preferred embodiment for the compositions and
pressure conditions shown. Although individual stream expansion is depicted in
particular expansion devices, alternative expansion means may be employed where
appropriate. For example, conditions may warrant work expansion of the
substantially condensed portion of the feed stream (36a in FIGS. 3 through S) or the
substantially condensed recycle stream (48b in FIG. 5).
FIGS. 3 and 4 depict a fractionation tower constructed in two sections
(17 and 19) because of the size of the plant. The decision whether to construct the
fractionation tower as a single vessel (such as 17 in FIG. S) or multiple vessels will
depend on a number of factors such as plant size, the distance to fabrication facilities,
etc.
While there have been described what are believed to be preferred
embodiments of the invention, those skilled in the art will recognize that other and
further modifications may be made thereto, e.g. to adapt the invention to various
conditions, types of feed, or other requirements, without departing from the spirit of
the present invention as defined by the following claims.
WE CLAIM:
1. An improved process for the separation of a gas stream
containing methane, C components, C components and heavier
2 3
hydrocarbon components into a volatile residue gas fraction
containing a major portion of said methane and a relatively less
volatile fraction containing a major portion of said C
2
components, C components and heavier hydrocarbon components, in
3
which process
(a) said gas stream is treated in one or more heat
exchange steps and at least one division step to produce at least
a first feed stream that has been cooled under pressure to
condense substantially all of it, and at least a second feed
stream that has been cooled under pressure;
(b) said substantially condensed first feed stream is
expanded to a lower pressure whereby it is further cooled, and
thereafter supplied to a fractionation tower at a top feed point|
(c) said cooled second feed stream is expanded to
said lower pressure* and thereafter supplied to said
fractionation tower at a mid-column feed point) and
(d) said cooled expanded first feed stream and said
expanded second feed stream are fractionated at said lower
pressure whereby the components of s«id rel«tively less volatile
fraction are recovered!
the improvement comprising
(1) a liquid distillation stream is withdrawn from
said fractionation tower and heated|
(2) said heated distillation stream is re-turned to a
lower point on said fractionation tower that is separated from
said withdrawal point by at least one theoretical stages and
(3) the quantities and temperatures of said feed
streams to said fractionation tower are effective to maintain the
overhead temperature of said fractionation tower at a temperature
whereby the major portions of the components in said relatively
less volatile fraction are recovered.
2. An improved process for the separation of a gas stream
containing methane, C components, C components and heavier
2 3
hydrocarbon components into a volatile residue gas fraction
containing a major portion of said methane and a relatively less
volatile fraction containing a major portion of said C
2
componentst C components and heavier hydrocarbon components, in
3
which process
(a) said volatile residue gas fraction is re-
compressed and a portion is withdrawn to form a compressed first
feed stream;
(b) said compressed first feed stream is cooled under
pressure to condone substantially all of it;
(c) said substantially condensed first feed stream is
expanded to a lower pressure whereby it is further cooled, and
thereafter supplied to a fractionation tow»r at a top feed point,
(d) said gas stream is treated in one or mere heat
exchange steps to produce at least a second feed stream that has
been cooled under pressure;
(e) said cooled second feed stream is expanded to said
lower pressure, and thereafter supplied to said fractionation
tower at a mid-column feed point, and
(f) said cooled expanded first feed stream and said
expanded second feed stream are fractionated at said lower
pressure whereby the components of said relatively less volatile
fraction are recovered;
the improvement wherein
(1) a liquid distillation stream is withdrawn from said
fractionation tower and heated;
(2) said heated distillation stream is returned to a
lower point on said fractionation tower that is separated from
said withdrawal point by at least one theoretical stage* and
(3) the quantities and temperatures of said feed streams
to said fractionation tower are effective to maintain the
overhead temperature of said fractionation tower at a temperature
whereby the major portions of the components in said relatively
less volatile fraction are recovered.
3. An improved process as claimed in claims 1 or 2 wherein
said liquid distillation stream is pumped after being withdrawn
from said fractination tower.
4. An improved process as claimed in claim 3 wherein
(*) said pumped liquid distillation stream is divided into
at least a first portion and a second portion}
(b) said first portion is heated, and
(c) said heated first portion is returned to a lower point
on said fractionation tower that is separated from said
withdrawal point by at least one theoretical stage.
5. An improved process as claimed in claims i or 2 wherein
said liquid distillation stream is directed in heat exchange
relation with at least a portion of said gas stream or said feed
streams, to supply said cooling thereto and thereby heat said
liquid distillation stream.
6. An improved process as claimed in claim 3 wherein said
pumped liquid distillation stream is directed in heat exchange
relation with at least a portion of said gas stream or said feed
streams, to supply said cooling thereto and thereby heat said
pumped liquid distillation stream.
7. An improved process as claimed in claim 4 wherein said
first portion is directed in heat exchange relation with at least
a portion of said gas stream or said feed streams, to supply said
cooling thereto and thereby heat said first portion.
8. An improved process as claimed in claims 1 or 2 wherein
the quantity and temperature of said heated distillation stream
and the heating supplied to said fractionation tower are
effective to maintain the bottom temperature of said
fractionation tower at a temperature to reduce the quantity of
carbon dioxide contained in said relatively less volatile
fraction.
9. An improved process as claimed in claim 3 wherein the
quantity and temperature of said heated distillation stream and
the heating supplied to said fractionation tower art effective to
maintain the bottom temperature of said fractionation tower at a
temperature to reduce the quantity of caroon dioxid, contained in
said relatively less volatile fraction.
10. An improved process as claimed in claim 4 wherein the
quantity and temperature of said heated first portion and the
heating supplied to said fractionation tower are effective to
maintain the bottom temperature of said fractionation tower at a
temperature to reduce the quantity of carbon dioxide contained in
said relatively less volatile fraction.
11. An improved process as claimed in claim 3 wherein the
quantity and temperature of said heated distillation stream and
the heating supplied to said fractionation tower are effective to
maintain the bottom temperature of said fractionation tower at a
temperature to reduce the quantity of carbon dioxide contained in
said relatively less volatile fraction.
12. An improved procss as claimed in claim 6 wherein the
quantity and temperature of said heated distillation stream and
the heating supplied to said fractionation tower are effective to
maintain the bottom temperature of said tractionation tower at a
temperature to reduct the quantity of carbon dioxide contained
in said relatively less volatile fraction.
13. An improved process as claimed in claim 7 wherein the
quantity and temperature of said heated first portion and the
heating supplied to said fractionation tower are effective to
maintain the bottom temperature of said fractionation tower at a
temperature to reduce the quantity of carbon dioxide contained in
said relatively less volatile fraction.
An improved process for the separation of a gas
stream containing methane, C2 components, C3 components and
2 3
heavier hydrocarbon components into a volatile residue gas
fraction containing a major portion of said methane and a
relatively less volatile fraction containing a major portion of
said C2 components, C3 components and heavier hydrocarbon

components, in which process (a) said gas stream is treated in
one or more heat exchange steps and at least one division step to
produce at least a first feed stream that has been cooled under
pressure to condense substantially all of it, and at least a
second feed stream that has been cooled under pressure;(b) said
substantially condensed first feed stream is expanded to a
lower pressure whereby it is further cooled* and thereafter
supplied to a fractionation tower at a top feed point; (c) said
cooled second feed stream is expanded to said lower pressure, and
thereafter supplied to said fractionation tower at a mid-column
feed point; and (d) said cooled expanded first feed stream and
said expanded second feed stream are fractionated at said lower
pressure whereby the components of said relatively less volatile
fraction are recovered; the improvement comprising: (1) a liquid
distillation stream is withdrawn from said fractionation tower
and heated; (2) said heated distillation stream is returned to a
lower point on said fractionation tower that is separated from
said withdrawal point by at least one theoretical stage; and (3)
the quantities and temperatures of said feed streams to said
fractionation tower are effective to maintain the overhead
temperature of said fractionation tower at a temperature whereby
the major portions of the components in said relatively less
volatile fraction are recovered.

Documents:

IN-PCT-2001-550-KOL-FORM 27.pdf

IN-PCT-2001-550-KOL-FORM-27-1.pdf

IN-PCT-2001-550-KOL-FORM-27.pdf

in-pct-2001-550-kol-granted-abstract.pdf

in-pct-2001-550-kol-granted-assignment.pdf

in-pct-2001-550-kol-granted-claims.pdf

in-pct-2001-550-kol-granted-correspondence.pdf

in-pct-2001-550-kol-granted-description (complete).pdf

in-pct-2001-550-kol-granted-drawings.pdf

in-pct-2001-550-kol-granted-examination report.pdf

in-pct-2001-550-kol-granted-form 1.pdf

in-pct-2001-550-kol-granted-form 13.pdf

in-pct-2001-550-kol-granted-form 18.pdf

in-pct-2001-550-kol-granted-form 2.pdf

in-pct-2001-550-kol-granted-form 26.pdf

in-pct-2001-550-kol-granted-form 3.pdf

in-pct-2001-550-kol-granted-form 5.pdf

in-pct-2001-550-kol-granted-form 6.pdf

in-pct-2001-550-kol-granted-reply to examination report.pdf

in-pct-2001-550-kol-granted-specification.pdf

in-pct-2001-550-kol-granted-translated copy of priority document.pdf


Patent Number 224204
Indian Patent Application Number IN/PCT/2001/550/KOL
PG Journal Number 41/2008
Publication Date 10-Oct-2008
Grant Date 03-Oct-2008
Date of Filing 24-May-2001
Name of Patentee ELCOR CORPORATION
Applicant Address SUITE 1000, WELLINGTON CENTER, 14643 DALLAS PARKWAY, DALLAS, TX
Inventors:
# Inventor's Name Inventor's Address
1 WILKINSON, JOHN, D, 2800 W. DENGAR, MIDLAND, TX
2 CAMPBELL ROY E (DECEASED)
3 HUDSON HANK M, 2508 W.SINCLAIR, MIDLAND TX 79705
4 PIERCE MICHAEL, C 1640 DOE LANE, ODESSA, TX 79762
PCT International Classification Number F25J 3/02
PCT International Application Number PCT/US99/28023
PCT International Filing date 1999-11-24
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 09/439,508 1998-11-12 U.S.A.
2 60/110, 502 1998-12-01 U.S.A.