Patent Grant
11255603
The disclosure relates generally to the field of fluid separation. More specifically, the disclosure relates to the cryogenic separation of contaminants, such as acid gas, from a hydrocarbon.
This section is intended to introduce various aspects of the art, which may be associated with the present disclosure. This discussion is intended to provide a framework to facilitate a better understanding of particular aspects of the present disclosure. Accordingly, it should be understood that this section should be read in this light, and not necessarily as admissions of prior art.
The production of natural gas hydrocarbons, such as methane and ethane, from a reservoir oftentimes carries with it the incidental production of non-hydrocarbon gases. Such gases include contaminants, such as carbon dioxide (“CO2”), hydrogen sulfide (“H2S”), carbonyl sulfide, carbon disulfide, various mercaptans, and mixtures thereof. When a feed stream being produced from a reservoir includes these contaminants mixed with hydrocarbons, the stream is oftentimes referred to as “sour gas.” The contaminants themselves are oftentimes referred to as “acid gas.”
Many natural gas reservoirs have relatively low percentages of hydrocarbons and relatively high percentages of contaminants. Contaminants may act as a diluent and lower the heat content of hydrocarbons. Further, some contaminants, like sulfur-bearing compounds, can be noxious. Additionally, in the presence of water some contaminants can react to form corrosive compounds.
It is desirable to remove contaminants from a stream containing hydrocarbons to produce sweet and concentrated hydrocarbons. Specifications for pipeline quality natural gas typically call for a maximum of 2-4 mole % CO2 and ¼ grain H2S per 100 scf (4 ppmv) or 5 mg/Nm3 H2S. Specifications for lower temperature processes such as natural gas liquefaction plants or nitrogen rejection units typically require less than 50 ppm CO2.
The separation of contaminants from hydrocarbons is difficult and consequently significant work has been applied to the development of hydrocarbon/contaminant separation methods. These methods can be placed into three general classes: absorption by solvents (physical, chemical, and hybrids), adsorption by solids, and distillation.
Separation by distillation of some mixtures can be relatively simple and, as such, is widely used in the natural gas industry. However, distillation of mixtures of natural gas hydrocarbons, such as those containing primarily methane, and one of the most common contaminants in natural gas, carbon dioxide, can present significant difficulties. Conventional distillation principles and conventional distillation equipment are predicated on the presence of only vapor and liquid phases throughout the distillation tower. However, the separation of CO2 from methane by distillation involves temperature and pressure conditions that result in solidification of CO2 if pipeline or better quality hydrocarbon product is desired. The required temperatures are cold temperatures typically referred to as cryogenic temperatures.
Certain cryogenic distillations can overcome the above mentioned difficulties. These cryogenic distillations provide the appropriate mechanism to handle the formation and subsequent melting of solids during the separation of solid-forming contaminants from hydrocarbons. The formation of solid contaminants in equilibrium with vapor-liquid mixtures of hydrocarbons and contaminants at particular conditions of temperature and pressure takes place in a freezing section.
One challenge is the increasing need to process gas from reservoirs having a high acid gas content. For example, some reservoirs may have greater than 10 mole %, or 15 mole %, or 20 mole % acid gas and up to 30 mole %, or 40 mole %, or 50 mole %, or 60 mole %, or 70% mole %, or 80 mole % acid gas. Some reservoirs may even have greater than 50 mole % acid gas. Conventional technologies and even certain cryogenic distillations may have difficulty processing such a high proportion of acid gas. The challenge is greatly accentuated when the proportion or fraction of acid gas in the feed gas increases over time. Processing increased contaminants may also impact the volume of processed natural gas.
Another challenge is that a gas processing plant may be required to process feed gas from more than one reservoir, where each of the reservoirs supplies a feed gas with different acid gas fractions. Therefore, a need exists for a gas processing plant that can accommodate a wide range of acid gas fractions in a feed gas with a minimum of plant re-design. Additionally, a need exists for a gas processing plant that can substantially maintain its output regardless of the amount of contaminants in the feed gas input to the plant.
The present disclosure provides a method of treating, in a gas treatment plant, a feed gas stream comprising hydrocarbon gas and acid gas. The method includes: (a) measuring the acid gas concentration in the feed gas stream at a first time to determine a first acid gas fraction; (b) cooling and liquefying at least a portion of the feed gas stream in a first feed refrigeration unit; (c) separating the liquefied acid gas from the first portion of the feed gas stream to create a first vapor stream having a first composition; (d) separating from the first vapor stream, primarily by freezing, substantially all of the acid gas remaining in the first vapor stream to create a hydrocarbon gas stream; (e) melting the frozen acid gas; (f) removing the melted acid gas and the liquefied acid gas, which together form a bottoms stream; (g) removing the hydrocarbon gas stream; (h) measuring the acid gas concentration in the feed gas stream at a second time to determine a second acid gas fraction, and if the second acid gas fraction is substantially higher than the first acid gas fraction, treating the feed gas stream by (I) cooling and liquefying a first portion of the acid gas using the first feed refrigeration unit and cooling and liquefying at least a second portion of the acid gas stream in at least one additional feed refrigeration unit and (II) separating the liquefied acid gas from the second portion of the feed gas stream to create a second vapor stream having a second composition, wherein the second composition is substantially similar to the first composition; and (h) repeating steps (d)-(f).
Also described herein is a method of processing a feed gas stream comprising determining the concentration of carbon dioxide in the feed gas stream; directing the feed gas stream through a flow control valve, wherein the flow control valve is configured to separate the feed gas stream into one or more fractions depending on the concentration of carbon dioxide in the feed gas stream and the heat exchange capacity of the feed refrigeration units; directing each fraction of the feed gas stream through a separate feed refrigeration unit to produce cooled feed streams; and introducing the cooled feed streams into a cryogenic distillation column. In some embodiments, if the carbon dioxide concentration is less than a first threshold, the flow control valve is configured to direct the feed gas stream in a single fraction to a single feed refrigeration unit. In other embodiments, if the carbon dioxide concentration is greater than a first threshold but less than a second threshold, the flow control valve is configured to separate the feed gas stream into two fractions. In other embodiments, if the carbon dioxide concentration is greater than a first and a second threshold but less than a third threshold, the flow control valve is configured to separate the feed gas stream into three fractions. In other embodiments if the carbon dioxide concentration is greater than a first, second, and third threshold, the flow control valve may be configured to separate the feed gas stream into at least four fractions.
Also described herein are methods for treating a feed gas stream comprising hydrocarbons and carbon dioxide. In the method a system is provided that has a variable capacity feed refrigeration system, a cryogenic distillation system, a variable capacity bottoms pump capacity, and a variable capacity bottoms heat exchange capacity. As feed gas stream is introduced into the system the concentration of carbon dioxide in the feed gas stream is measured. The concentration of carbon dioxide is then used to determine the refrigeration capacity of the feed refrigeration system that is activated and used, where the refrigeration capacity needed is that which is needed to maintain the carbon dioxide concentration of the cooled vapor stream entering the cryogenic distillation system is maintained within a predetermine range, such as from 10-30 mole %, or from 15-25 mole %, or from 18-25 mole %, or from 20-25 mole %. For example, as the concentration of carbon dioxide in the feed gas stream is measured, the number of feed refrigeration units activated and used at any one time to cool the feed gas stream may vary, so long as the concentration of carbon dioxide in the vapor portion of the cooled feed gas stream that enters the cryogenic distillation system is maintained within the predetermined range. The bottoms pump capacity, i.e., the capacity of the pumps that pump the bottoms stream exiting from the cryogenic distillation tower, may also be varied depending on the concentration of carbon dioxide in the feed gas stream. Thus, as the concentration of carbon dioxide in the feed gas stream increases the capacity of the bottoms pumps will be varied to increase to pump the increased volume of the bottoms stream. Likewise, the capacity of the bottoms heat exchanger may be increased to handle increased heating duty of the reboiler streams being returned to the cryogenic distillation tower.
The present disclosure also provides a method of designing and constructing a hydrocarbon gas treatment plant. A target hydrocarbon production range is established for a hydrocarbon gas meeting a required product specification. A cryogenic distillation column is designed and constructed with a vapor capacity to meet the target hydrocarbon production range. An overhead refrigeration and separation system is designed and constructed with a vapor capacity to meet the target hydrocarbon production range. A variable feed refrigeration system is incorporated to cool an inlet feed of the hydrocarbon gas. The variable feed refrigeration system is designed to handle the target hydrocarbon production range and a wide range of contaminant concentrations in the inlet feed. A variable bottoms heating system is incorporated, which is capable of handling heating duties associated with the wide range of contaminant concentrations in the inlet feed. A variable bottoms pumping system is incorporated, which is capable of handling liquid flows associated with the wide range of contaminant concentrations in the inlet feed.
The present disclosure further provides a gas treatment system for treating feed gas including hydrocarbon gas and acid gas. The system includes a first refrigeration unit that, when activated, cools and liquefies part of the acid gas in a feed gas stream, wherein the feed gas stream has a first acid gas fraction. At least one additional feed refrigeration unit is incorporated into the system and activated with the first feed refrigeration unit only when the feed gas stream has a second acid gas fraction substantially higher than the first acid gas fraction. The at least one additional feed refrigeration unit cools and liquefies part of the acid gas in the feed gas stream only when the feed gas stream has a second acid gas fraction substantially higher than the first acid gas fraction. A separator separates the liquefied acid gas from the feed gas stream to create a vapor stream having a composition that is substantially constant regardless of how many of the first feed refrigeration unit and the at least one additional feed refrigeration units are activated. A cryogenic distillation column freezes substantially all of the acid gas remaining in the vapor stream to create a hydrocarbon gas stream and an amount of frozen acid gas. A bottoms stream heat exchanger heats a bottoms stream that includes the liquefied acid gas and the amount of frozen acid gas after it has been melted. At least one bottoms stream pump removes the melted acid gas and the liquefied acid gas, which together form a bottoms stream. The number of the at least one bottoms stream pumps is selected as a function of the first acid gas fraction or the second acid gas fraction.
The foregoing has broadly outlined the features of the present disclosure so that the detailed description that follows may be better understood. Additional features will also be described herein.
These and other features, aspects and advantages of the disclosure will become apparent from the following description, appending claims and the accompanying drawings, which are briefly described below.
It should be noted that the figures are merely examples and no limitations on the scope of the present disclosure are intended thereby. Further, the figures are generally not drawn to scale, but are drafted for purposes of convenience and clarity in illustrating various aspects of the disclosure.
For the purpose of promoting an understanding of the principles of the disclosure, reference will now be made to the features illustrated in the drawings and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the disclosure is thereby intended. Any alterations and further modifications, and any further applications of the principles of the disclosure as described herein are contemplated as would normally occur to one skilled in the art to which the disclosure relates. It will be apparent to those skilled in the relevant art that some features that are not relevant to the present disclosure may not be shown in the drawings for the sake of clarity.
At the outset, for ease of reference, certain terms used in this application and their meanings as used in this context are set forth. To the extent a term used herein is not defined below, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Further, the present techniques are not limited by the usage of the terms shown below, as all equivalents, synonyms, new developments, and terms or techniques that serve the same or a similar purpose are considered to be within the scope of the present claims.
As one of ordinary skill would appreciate, different persons may refer to the same feature or component by different names. This document does not intend to distinguish between components or features that differ in name only. The figures are not necessarily to scale. Certain features and components herein may be shown exaggerated in scale or in schematic form and some details of conventional elements may not be shown in the interest of clarity and conciseness. When referring to the figures described herein, the same reference numerals may be referenced in multiple figures for the sake of simplicity. In the following description and in the claims, the terms “including” and “comprising” are used in an open-ended fashion, and thus, should be interpreted to mean “including, but not limited to.”
The term “acid gas” and “sour gas” refers to any gas that dissolves in water to produce an acidic solution. Non-limiting examples of acid gases include hydrogen sulfide (H2S), carbon dioxide (CO2), sulfur dioxide (SO2), and mixtures thereof. The term “trace sulfur compounds” includes carbon disulfide (CS2), carbonyl sulfide (COS), mercaptans, and mixtures thereof. The term “acid gas injection” (AGI) refers to the disposal of an acid gas stream by increasing its pressure and introducing the pressurized stream into a subterranean reservoir.
The term “cryogenic” in the natural gas industry is used to refer to low temperature conditions, such as −40° Fahrenheit (−40° Celsius) or colder. The low temperature conditions are often those involved with propane refrigeration at atmospheric pressure or colder refrigerants. Cryogenic used in reference to a fluid means that the fluid is at a cryogenic temperature. Cryogenic used in reference to an item or material means that the item or material is suitable for operating at a cryogenic temperature and/or suitable for containing a cryogenic fluid. For example, a cryogenic vessel is a vessel that is suitable for containing a cryogenic fluid.
The term “cryogenic distillation” refers to a distillation process that is carried out at conditions involving cryogenic temperatures.
The term “Controlled Freeze Zone™ (CFZ™) process” refers to a process that takes advantage of the freezing potential of carbon dioxide (CO2) in cryogenic distillation, rather than avoiding solidification of carbon dioxide. In the CFZ™ process, acid gas components are separated by cryogenic distillation through the controlled freezing and melting of carbon dioxide in a distillation column without the use of freeze-suppression additives. The CFZ™ process uses a cryogenic distillation column with an internal freezing section, a CFZ™ section, to handle the solidification and subsequent melting of CO2 in a rather controlled fashion. The freezing section does not contain packing or typical trays like in conventional distillation columns. Instead, the freezing section contains one or more spray nozzles and a melt tray. In operation, solid CO2 forms in the vapor space in the freezing section and falls into a liquid on the melt tray. Substantially all of the solids that form are confined to the freezing section. The portions of the distillation column above and below the freezing section of the column may be similar to conventional cryogenic demethanizer columns. For example, in the rectification section above the freezing section, methane (CH4) is enriched to produce an overhead methane-rich stream, while the stripping section below the freezing section generates a liquid bottoms stream containing contaminants such as CO2 and hydrogen sulfide (H2S) with very little residual methane. The overhead methane-rich stream may be sold or further processed and the acid gas rich bottoms stream may be disposed as waste or further processed.
The term “heat exchanger” refers to a device designed to efficiently transfer or “exchange” heat from one matter to another. Exemplary heat exchanger types include a co-current or counter-current heat exchanger, an indirect heat exchanger (e.g., spiral wound heat exchanger, plate-fin heat exchanger such as a brazed aluminum plate fin type, shell-and-tube heat exchanger, etc.), direct contact heat exchanger, or some combination of these, and so on.
As referenced in this application, the terms “stream,” “gas stream,” “vapor stream,” and “liquid stream” refer to different stages of a feed stream as the feed stream is processed in a distillation tower that separates methane, the primary hydrocarbon in natural gas, from contaminants. Although the phrases “gas stream,” “vapor stream,” and “liquid stream,” refer to situations where a gas, vapor, and liquid is mainly present in the stream, respectively, there may be other phases also present within the stream. For example, a gas may also be present in a “liquid stream.” In some instances, the terms “gas stream” and “vapor stream” may be used interchangeably.
A gas processing plant using the CFZ™ process was tested with feed gases having a CO2 content ranging from 8 mole % to 71 mole %, and a H2S content ranging from 0 to 36 mole %. While reviewing the operational results of the CFZ plant, it was remarkable to observe the consistency of the CO2 profiles in the vapor streams entering the CFZ section, progressing thru this section into the upper rectifying section of the tower, and exiting the tower overheads as a product.
Thus, as described herein, a single cryogenic distillation plant can be designed which is capable of processing and purifying hydrocarbon gas streams containing a wide range of contaminants including CO2 and H2S. Such a plant allows management of the uncertainty or variability in feed composition over the life of the plant, regardless of the source of uncertainty or variability, while maintaining a known hydrocarbon sales product rate. Thus, this disclosure relates to a system and method for the design and construction of a hydrocarbon gas treatment plant that is capable of processing feed streams containing a wide range of contaminant concentrations.
The system and method may separate a raw gas feed stream comprising methane and various contaminants, such as carbon dioxide and hydrogen sulfide. The system may comprise a distillation tower 104, 204 (
The distillation tower 104, 204 may be separated into three functional sections: a lower section 106, a middle freezing section 108, which may be a CFZ™ section, and an upper section 110. The distillation tower 104, 204 may incorporate three functional sections when the upper section 110 is needed and/or desired.
The distillation tower 104, 204 may incorporate only two functional sections when the upper section 110 is not needed and/or desired. When the distillation tower does not include an upper section 110, a portion of vapor leaving the middle freezing section 108 may be condensed in a condenser 122 and returned as a liquid stream via a spray assembly 129. Moreover, lines 18 and 20 may be eliminated, elements 124 and 126 may be one and the same, and elements 150 and 128 may be one and the same. The stream in line 14, now taking the vapors leaving the middle controlled freeze section 108, directs these vapors to the condenser 122.
The lower section 106 may also be referred to as a stripper section. The middle freezing section 108 may also be referred to as a freezing section. The upper section 110 may also be referred to as a rectifier section.
The sections of the distillation tower 104 may be housed within a single vessel (
The sections of the distillation tower 204 may be housed within a plurality of vessels to form a split-tower configuration (
The split-tower configuration may be beneficial in situations where the height of the distillation tower, motion considerations, and/or transportation issues, such as for remote locations, need to be considered. This split-tower configuration allows for the independent operation of one or more sections. For example, when the upper section is housed within a single vessel and the lower and middle freezing sections are housed within a single vessel, independent generation of reflux liquids using a substantially contaminant-free, largely hydrocarbon stream from a packed gas pipeline or an adjacent hydrocarbon line, may occur in the upper section. And the reflux may be used to cool the upper section, establish an appropriate temperature profile in the upper section, and/or build up liquid inventory at the bottom of the upper section to serve as an initial source of spray liquids for the middle freezing section. Moreover, the middle freezing and lower sections may be independently prepared by chilling the feed stream, feeding it to the optimal location be that in the lower section or in the middle freezing section, generating liquids for the lower and the middle freezing sections, and disposing the vapors off the middle freezing section while they are off specification with too high a contaminant content. Also, liquid from the upper section may be intermittently or continuously sprayed, building up liquid level in the bottom of the middle freezing section and bringing the contaminant content in the middle freezing section down and near steady state level so that the two vessels may be connected to send the vapor stream from the middle freezing section to the upper section, continuously spraying liquid from the bottom of the upper section into the middle freezing section and stabilizing operations into steady state conditions. The split tower configuration may utilize a sump of the upper section as a liquid receiver for the pump 128, therefore obviating the need for a liquid receiver 126 in
The system may also include a pre-processing section 91 that processes the feed stream 10 to a suitable temperature, pressure, composition, and/or phase before entering the distillation tower 104, 204. The pre-processing section 91 may include a heat exchanger 100 (
The pre-processing section 91 may include an expander device 102 (
The pre-processing section 91 may include a feed separator 103 (
The pre-processing section 91 may include a dehydration unit 261 (
The pre-processing section 91 may include a filtering unit (not shown). The feed stream 10 may enter the filtering unit before entering the distillation tower 104, 204. The filtering unit may remove undesirable contaminants from the feed stream before the feed stream enters the distillation tower 104, 204. Depending on what contaminants are to be removed, the filtering unit may be before or after the dehydration unit 261 and/or before or after the heat exchanger 100.
The pre-processing section 91 may include a line 12 (
If the pre-processing section 91 includes the feed separator 103 (
The lower section 106 is constructed and arranged to separate the feed stream 10 into an enriched contaminant bottom liquid stream (i.e., liquid stream) and a freezing zone vapor stream (i.e., vapor stream). The lower section 106 separates the feed stream at a temperature and pressure at which no solids form. The liquid stream may comprise a greater quantity of contaminants than of methane. The vapor stream may comprise a greater quantity of methane than of contaminants. In any case, the vapor stream is lighter than the liquid stream. As a result, the vapor stream rises from the lower section 106 and the liquid stream falls to the bottom of the lower section 106.
The lower section 106 may include and/or connect to equipment that separates the feed stream. The equipment may comprise any suitable equipment for separating methane from contaminants, such as one or more packed sections 181, or one or more distillation trays with perforations, downcomers, and weirs (
The equipment may include components that apply heat to the stream to form the vapor stream and the liquid stream. For example, the equipment may comprise a first reboiler 112 that applies heat to the stream. The first reboiler 112 may be located outside of the distillation tower 104, 204. The equipment may also comprise a second reboiler 172 that applies heat to the stream. The second reboiler 172 may be located outside of the distillation tower 104, 204. Line 117 may lead from the distillation tower to the second reboiler 172. Line 17 may lead from the second reboiler 172 to the distillation tower. Additional reboilers, set up similarly to the second reboiler described above, may also be used.
The first reboiler 112 may apply heat to the liquid stream that exits the lower section 106 through a liquid outlet 160 of the lower section 106. The liquid stream may travel from the liquid outlet 160 through line 28 to reach the first reboiler 112 (
The first reboiler 112 may also apply heat to the stream within the distillation tower 104, 204. Specifically, the heat applied by the first reboiler 112 warms up the lower section 106. This heat travels up the lower section 106 and supplies heat to warm solids entering a melt tray assembly 139 (
The second reboiler 172 applies heat to the stream within the lower section 106. This heat is applied closer to the middle freezing section 108 than the heat applied by the first reboiler 112. As a result, the heat applied by the second reboiler 172 reaches the middle freezing section 108 faster than the heat applied by the first reboiler 112. The second reboiler 172 also helps with energy integration.
The equipment may include one or more chimney assemblies 135 (
Each chimney assembly 135 includes a chimney tray 131 that collects the liquid stream within the lower section 106. The liquid stream that collects on the chimney tray 131 may be fed to the second reboiler 172. After the liquid stream is heated in the second reboiler 172, the stream may return to the middle of lower section 106 to supply heat to the middle of lower section 106 and/or the melt tray assembly 139. Unvaporized stream exiting the second reboiler 172 may be fed back to the distillation tower 104, 204 below the chimney tray 131. Vapor stream exiting the second reboiler 172 may be routed under or above the chimney tray 131 when the vapor stream enters the distillation tower 104, 204.
The chimney tray 131 may include one or more chimneys 137. The chimney 137 serves as a channel that the vapor stream in the lower section 106 traverses. The vapor stream travels through an opening in the chimney tray 131 at the bottom of the chimney 137 to the top of the chimney 137. The opening is closer to the bottom of the lower section 106 than it is to the bottom of the middle freezing section 108. The top is closer to the bottom of the middle freezing section 108 than it is to the bottom of the lower section 106.
Each chimney 137 has attached to it a chimney cap 133. The chimney cap 133 covers a chimney top opening 138 of the chimney 137. The chimney cap 133 prevents the liquid stream from entering the chimney 137. The vapor stream exits the chimney assembly 135 via the chimney top opening 138.
After flowing to the bottom of the lower section 106, the liquid stream exits the distillation tower 104, 204 through the liquid outlet 160. The liquid outlet 160 is within the lower section 106 (
After exiting through the liquid outlet 160, the feed stream may travel via line 28 to the first reboiler 112, which may be considered part of the liquids processing section 190. The feed stream may be heated by the first reboiler 112 and vapor may then re-enter the lower section 106 through line 30. Unvaporized liquid may continue out of the distillation process via line 24.
The liquids processing section 190 may include an expander device 114 (
The liquids processing section 190 may include a heat exchanger 116 (
The vapor stream in the lower section 106 rises from the lower section 106 to the middle freezing section 108. The middle freezing section 108 is maintained to receive a freezing zone liquid stream to form the solid and the vapor stream (i.e., hydrocarbon-enriched vapor stream) in the middle freezing section 108. The middle freezing section 108 is constructed and arranged to separate the feed stream 10 introduced into the middle freezing section into a solid and a vapor stream. The solid and the vapor stream are formed in the middle freezing section 108 when the freezing zone liquid stream is injected into the middle freezing section 108 at a temperature and pressure at which the solid and vapor stream form. The solid may be comprised more of contaminants than of methane. The vapor stream may comprise more methane than contaminants.
The middle freezing section 108 includes a lower section 40 and an upper section 39. The lower section 40 is below the upper section 39. The lower section 40 directly abuts the upper section 39. The lower section 40 is primarily but may not exclusively be a heating section of the middle freezing section 108. The upper section 39 is primarily but may not exclusively be a cooling section of the middle freezing section 108. The temperature and pressure of the upper section 39 are chosen so that the solid can form in the middle freezing section 108.
The middle freezing section 108 may comprise a melt tray assembly 139 that is maintained in the middle freezing section 108 (
The melt tray assembly 139 is constructed and arranged to melt a solid formed in the middle freezing section 108. When the warm vapor stream rises from the lower section 106 to the middle freezing section 108, the vapor stream immediately encounters the melt tray assembly 139 and supplies heat to melt the solid. The melt tray assembly 139 may comprise at least one of a melt tray 118, a bubble cap 132, a liquid 130 and heat mechanism(s) 134.
The melt tray 118 may collect a liquid and/or slurry mix. The melt tray 118 divides at least a portion of the middle freezing section 108 from the lower section 106. The melt tray 118 is at the bottom 45 of the middle freezing section 108.
One or more bubble caps 132 may act as a channel for the vapor stream rising from the lower section 106 to the middle freezing section 108. The bubble cap 132 may provide a path for the vapor stream that forces the vapor stream up the riser 140 and then down and around the riser 140 to the melt tray 118. The riser 140 is covered by a cap 141. The cap 140 prevents the liquid 130 from travelling into the riser 140. The cap 141 helps prevent solids from travelling into the riser 140. The vapor stream's traversal through the bubble cap 132 allows the vapor stream to transfer heat to the liquid 130 within the melt tray assembly 139.
One or more heat mechanisms 134 may further heat up the liquid 130 to facilitate melting of the solids into a liquid and/or slurry mix. The heat mechanism(s) 134 may be located anywhere within the melt tray assembly 139. For example, as shown in
The liquid 130 in the melt tray assembly is heated by the vapor stream. The liquid 130 may also be heated by the one or more heat mechanisms 134. The liquid 130 helps melt the solids formed in the middle freezing section 108 into a liquid and/or slurry mix. Specifically, the heat transferred by the vapor stream heats up the liquid, thereby providing the heat to melt the solids. The liquid 130 is at a level sufficient to melt the solids.
The middle freezing section 108 may also comprise a spray assembly 129. The spray assembly 129 cools the vapor stream that rises from the lower section 40. The spray assembly 129 sprays liquid, which is cooler than the vapor stream, on the vapor stream to cool the vapor stream. The spray assembly 129 is within the upper section 39. The spray assembly 129 is not within the lower section 40. The spray assembly 129 is above the melt tray assembly 139. In other words, the melt tray assembly 139 is below the spray assembly 129.
The temperature in the middle freezing section 108 cools down as the vapor stream travels from the bottom of the middle freezing section 108 to the top of the middle freezing section 108. The methane in the vapor stream rises from the middle freezing section 108 to the upper section 110. Some contaminants may remain in the methane and also rise. The contaminants in the vapor stream tend to condense or solidify with the colder temperatures and fall to the bottom of the middle freezing section 108.
The solids form the liquid and/or slurry mix when in the liquid 130. The liquid and/or slurry mix flows from the middle freezing section 108 to the lower distillation section 106. The liquid and/or slurry mix flows from the bottom of the middle freezing section 108 to the top of the lower section 106 via a line 22 (
The vapor stream that rises in the middle freezing section 108 and does not form solids or otherwise fall to the bottom of the middle freezing section 108, rises to the upper section 110. The upper section 110 operates at a temperature and pressure and contaminant concentration at which no solid forms. The upper section 110 is constructed and arranged to cool the vapor stream to separate the methane from the contaminants. Reflux in the upper section 110 cools the vapor stream. The reflux is introduced into the upper section 110 via line 18. Line 18 may extend to the upper section 110. Line 18 may extend from an outer surface of the distillation tower 104, 204.
After contacting the reflux in the upper section 110, the feed stream forms a vapor stream and a liquid stream. The vapor stream mainly comprises methane. The liquid stream comprises relatively more contaminants. The vapor stream rises in the upper section 110 and the liquid falls to a bottom of the upper section 110.
To facilitate separation of the methane from the contaminants when the stream contacts the reflux, the upper section 110 may include one or more mass transfer devices 176. Each mass transfer device 176 helps separate the methane from the contaminants. Each mass transfer device 176 may comprise any suitable separation device, such as a tray with perforations, or a section of random or structured packing 176 to facilitate contact of the vapor and liquid phases.
After rising, the vapor stream may exit the distillation tower 104, 204 through line 14. The line 14 may emanate from an upper part of the upper section 110. The line 14 may extend from an outer surface of the upper section 110.
From line 14, the vapor stream may enter a condenser 122. The condenser 122 cools the vapor stream to form a cooled stream. The condenser 122 at least partially condenses the stream.
After exiting the condenser 122, the cooled stream may enter a separator 124. The separator 124 separates the vapor stream into liquid and vapor streams. The separator may be any suitable separator that can separate a stream into liquid and vapor streams, such as a reflux drum.
Once separated, the vapor stream may exit the separator 124 as sales product. The sales product may travel through line 16 for subsequent sale to a pipeline and/or condensation to be liquefied natural gas.
Once separated, the liquid stream may return to the upper section 110 through line 18 as the reflux. The reflux may travel to the upper section 110 via any suitable mechanism, such as a reflux pump 150 (
The liquid stream (i.e., freezing zone liquid stream) that falls to the bottom of the upper section 110 collects at the bottom of the upper section 110. The liquid may collect on tray 183 (
The line 20 and/or outlet 260 connect to a line 41. The line 41 leads to the spray assembly 129 in the middle freezing section 108. The line 41 emanates from the holding vessel 126. The line 41 may extend to an outer surface of the middle freezing section 110.
The line 20 and/or outlet 260 may directly or indirectly (
In general a refrigeration unit is a mechanical system that provides cooling by changing the phases of its refrigerant fluid in a vapor compression cycle. Thus, typical refrigeration units comprise a refrigerant fluid that provides desired cooling by evaporating at a cold temperature and relatively low pressure. The resulting low pressure refrigerant vapor is then compressed to a higher pressure at which it can be condensed to a warmer temperature. The condensed, high pressure, refrigerant is then cooled by a drop in pressure via an expansion device, such as a Joule-Thomson valve. The cold, low pressure liquid refrigerant is then ready to start the cycle again by providing refrigeration, cooling the desired process fluid in a chiller/heat exchanger, while evaporating again.
Thus, each feed refrigeration unit in the present application accomplishes the activity of a refrigeration unit in that it provides means for cooling and compressing. For example, in some embodiments a feed refrigeration unit may comprise a heat exchanger and a single compressor. However, in other embodiments, a feed refrigeration unit may comprise a heat exchanger and multiple compressors. Alternatively, a feed refrigeration unit may be sized by altering the temperature of the refrigerant fluid to provide for more heat transfer or by increasing the flow of the refrigerant fluid to the refrigeration unit. As such, the number and size of the feed refrigeration units can provide for variable capacity and flexibility in heat capacity sizing, and thus be able to be used to cool and liquefy feed streams containing a wide range of contaminant concentrations.
100
a, 100b, 100n. A flow control valve 293 is configured to direct the flow of the feed stream to the at least one feed refrigeration unit 100a-n. The feed stream 10 may be cooled within the at least one feed refrigeration unit 100a-n. Each of the feed refrigeration units 100a-n helps drop the temperature of the feed stream 10 to a level suitable for introduction into the distillation tower 104, 204. In an aspect, any number of feed refrigeration units may be employed with the system, and this is expressed by the use of the suffix ‘n’ when referring to feed refrigeration unit 100n. In another aspect, the feed refrigeration units may have standardized or substantially similar performance characteristics, such as cooling capacity or a power rating of the source of refrigeration.
The number of feed refrigeration units 100a-n used depends on the amount of acid gas (e.g., carbon dioxide, hydrogen sulfide) in the feed stream 10. As a non-limiting example, if four feed refrigeration units with substantially similar performance characteristics are used, the following feed refrigeration unit deployment strategy may be implemented:
This feed refrigeration unit deployment strategy may also be implemented in reverse. That is, the cryogenic distillation system may be constructed with multiple feed refrigeration units, but only some may be in use at any given time. For example, if four feed refrigeration units are running but the acid gas fraction in the feed stream drops below the threshold set for use of four feed refrigeration units, one or more of the four feed refrigeration units may be taken out of service. Of course, the number and performance characteristics of the feed refrigeration units 100a-n may be varied as desired. Additionally, the acid gas fraction thresholds at which feed refrigeration units 100a-n are activated or taken out of commission may vary as desired.
The amount of the feed stream 10 sent by the flow control valve 293 to each feed refrigeration units 100a-n in use may be equalized or varied between the feed refrigeration units 100a-n in use. For example, the amount of the feed stream 10 sent by the flow control valve 293 to the feed refrigeration units 100a-n in use may equalized for all but the last of the feed refrigeration units 100a-n in use, where the remaining feed refrigeration unit 100n in use may then be configured to process any excess volumes of feed gas. As another example, the amount of the feed stream 10 sent by the control valve 293 to the feed refrigeration units 100a-n may be varied to optimize each feed refrigeration unit's capacity so that all but the last feed refrigeration unit is operating at its rated cooling capacity with the last feed refrigeration unit 100n being used to process any excess volume of the feed gas.
Returning to
With increased sour liquid in the bottoms stream, there may be a need for additional capability to heat the bottoms stream to extract any remaining hydrocarbons therein. The liquids processing section 391 (
For example, the bottoms stream heat exchangers 112a-n may also be designed to be activated based on the methane content in the bottoms stream. Thus, if the methane content is greater than 1 mole %, or greater than 1.5 mole %, this may indicate that increased heating duty in the reboiler system is needed.
A feature of the disclosure is that varied or increased feed stream volumes can be processed by the system because a substantial portion of the sour gas contained therein is liquefied in the heat exchangers 100a-n prior to entering the distillation tower 104, 204. In an aspect, this liquefied acid gas is fed into the lower section 106 and exits the lower section 106 through the liquid outlet 160 to be heated by the bottoms stream heat exchangers 112a-n and pumped out of the system by the bottoms stream pump(s) 191a-n. The feed refrigeration units 100a-n, the bottoms stream heat exchangers 112a-n, and bottoms stream pumps 191a-n may be maintained so that the middle freezing section 108 is processing a vapor/liquid having a substantially constant acid gas fraction, such as between about 10 mole % and about 30 mole % acid gas, or between about 15 mole % and about 25 mole % acid gas, or between about 18 mole % and about 23 mole % acid gas, or about 21 mole % acid gas. In this manner, a standardized distillation tower 104, 204 design may be used for any gas processing facility, regardless of possible acid gas concentrations in the feed stream.
The method may include maintaining an upper section 110. The upper section 110 operates as previously discussed. The method may also include separating the feed stream in the upper section 110 as previously discussed.
A method of treating, in a gas treatment plant, feed gas including hydrocarbon gas and acid gas is described herein. The method may comprise cooling and liquefying at least part of the acid gas in a first feed gas stream using a first feed refrigeration unit. The first feed gas stream has a first acid gas fraction. The liquefied acid gas is separated from the first feed gas stream to create a first vapor stream having a first composition. Substantially all of the acid gas remaining in the first vapor stream is separated from the first vapor stream, primarily by freezing, to create a hydrocarbon gas stream. The frozen acid gas is melted. The melted acid gas and the liquefied acid gas are removed to form a bottoms stream. The hydrocarbon gas stream is then removed. When a second feed gas stream, having a second acid gas fraction substantially higher than the first acid gas fraction, is to be treated, part of the acid gas in the second feed gas stream is liquefied using the first feed refrigeration unit and at least one additional feed refrigeration unit, and the liquefied acid gas is separated from the second feed gas stream to create a second vapor stream having a second composition. The second composition is substantially similar to the first composition. The frozen acid gas from the second feed gas stream is then melted and removed to the bottoms stream.
An additional method of processing a feed gas stream may be as follows. Introducing a feed gas stream to a pre-processing system, wherein the pre-processing system comprises a dehydration unit, a contaminant detection unit, a flow control valve, and two or more feed refrigeration units. The feed stream may be dehydrated in the dehydration unit. The contaminant detection unit is used to determine the concentration of acid gas contaminants, such as carbon dioxide, in the feed stream. The acid gas concentration is then used to determine the flow of the feed gas through the flow control valve into the two or more feed refrigeration units. For example, if the acid gas concentration in the feed stream is less than a first threshold, such as less than 30 mole %, or less than 32 mole %, or less than 35 mole %, or less than 40 mole %, the flow control valve directs the entire feed stream into the first feed refrigeration unit. However, if the acid gas concentration in the feed stream is greater than the first threshold and less than a second threshold, such as less than 50 mole %, or less than 52 mole %, or less than 55 mole %, or less than 58 mole %, then the flow control valve directs a first portion of the feed stream to the first feed refrigeration unit and the remaining portion of the feed stream to the second feed refrigeration unit. Further, if the acid gas concentration in the feed stream is greater than the second threshold and is less than a third threshold, such as 60 mole %, or less than 63 mole %, or less than 65 mole %, or less than 67 mole %, then the flow control valve directs a first portion of the feed stream to the first feed refrigeration unit, a second portion of the feed stream to the second feed refrigeration unit, and the remaining portion of the feed stream to a third feed refrigeration unit. Likewise, if the acid gas concentration in the feed stream is greater than the third threshold and is less than fourth threshold, such as less than 70 mole %, or less than 71 mole %, or less than 72 mole %, or less than 76 mole %, or less than 78 mole %, then the flow control valve directs a first portion of the feed stream to the first feed refrigeration unit, a second portion of the feed stream to the second feed refrigeration unit, a third portion of the feed stream to a third feed refrigeration unit, and a fourth portion of the feed stream to a fourth feed refrigeration unit. Each of the streams coming from the two or more feed refrigeration units are then introduced to the cryogenic distillation column, wherein the acid gases are separated from the methane in the feed stream.
A method of designing and constructing a hydrocarbon gas treatment plant may be as follows. A target hydrocarbon production range for a hydrocarbon gas meeting a required product specification is established. A cryogenic distillation column is designed and constructed with a vapor capacity to meet the target hydrocarbon production range. An overhead refrigeration and separation system is designed and constructed with a vapor capacity to meet the target hydrocarbon production range. A variable feed refrigeration system is incorporated to cool an inlet feed of the hydrocarbon gas. The variable feed refrigeration system is designed to handle the target hydrocarbon production range and a wide range of contaminant concentrations in the inlet feed. A variable bottoms heating system is incorporated which is capable of handling heating duties associated with the wide range of contaminant concentrations in the inlet feed. A variable bottoms pumping system is incorporated which is capable of handling liquid flows associated with the wide range of contaminant concentrations in the inlet feed.
Disclosed aspects may be used in hydrocarbon management activities. As used herein, “hydrocarbon management” or “managing hydrocarbons”” includes hydrocarbon extraction, hydrocarbon production, hydrocarbon exploration, identifying potential hydrocarbon resources, identifying well locations, determining well injection and/or extraction rates, identifying reservoir connectivity, acquiring, disposing of and/or abandoning hydrocarbon resources, reviewing prior hydrocarbon management decisions, and any other hydrocarbon-related acts or activities. The term “hydrocarbon management” is also used for the injection or storage of hydrocarbons or CO2, for example the sequestration of CO2, such as reservoir evaluation, development planning, and reservoir management. The disclosed methodologies and techniques may be used in extracting hydrocarbons from a subsurface region and processing the hydrocarbons. Hydrocarbons and contaminants may be extracted from a reservoir and processed. The hydrocarbons and contaminants may be processed, for example, in the distillation tower previously described. After the hydrocarbons and contaminants are processed, the hydrocarbons may be extracted from the processor, such as the distillation tower, and produced. The contaminants may be discharged into the Earth, etc. For example, the method for producing hydrocarbons disclosed herein may include producing the hydrocarbon-enriched vapor stream extracted from the distillation tower. The method may also include removing the hydrocarbon-enriched vapor stream from the distillation tower before producing the hydrocarbon-enriched vapor stream. The initial hydrocarbon extraction from the reservoir may be accomplished by drilling a well using hydrocarbon drilling equipment. The equipment and techniques used to drill a well and/or extract these hydrocarbons are well known by those skilled in the relevant art. Other hydrocarbon extraction activities and, more generally, other hydrocarbon management activities, may be performed according to known principles.
As utilized herein, the terms “approximately,” “about,” “substantially,” and similar terms are intended to have a broad meaning in harmony with the common and accepted usage by those of ordinary skill in the art to which the subject matter of this disclosure pertains. It should be understood by those of skill in the art who review this disclosure that these terms are intended to allow a description of certain features described and claimed without restricting the scope of these features to the precise numeral ranges provided. Accordingly, these terms should be interpreted as indicating that insubstantial or inconsequential modifications or alterations of the subject matter described and are considered to be within the scope of the disclosure.
It should be understood that the numerous changes, modifications, and alternatives to the preceding disclosure can be made without departing from the scope of the disclosure. The preceding description, therefore, is not meant to limit the scope of the disclosure. Rather, the scope of the disclosure is to be determined only by the appended claims and their equivalents. It is also contemplated that structures and features in the present examples can be altered, rearranged, substituted, deleted, duplicated, combined, or added to each other.
The articles “the,” “a” and “an” are not necessarily limited to mean only one, but rather are inclusive and open ended so as to include, optionally, multiple such elements.
This application claims the benefit of U.S. Provisional Application Ser. No. 62/232,149 filed Sep. 24, 2015, the entirety of which is incorporated by reference herein.
| Number | Name | Date | Kind |
|---|---|---|---|
| 2621216 | White | Dec 1952 | A |
| 2843219 | Habgood | Jul 1958 | A |
| 2863527 | Herbert | Dec 1958 | A |
| 2960837 | Swenson et al. | Nov 1960 | A |
| 3050950 | Karwat et al. | Aug 1962 | A |
| 3109726 | Karwat | Nov 1963 | A |
| 3349571 | Nebgen | Oct 1967 | A |
| 3393527 | Swensen et al. | Jul 1968 | A |
| 3400512 | McKay | Sep 1968 | A |
| 3421984 | Jensen et al. | Jan 1969 | A |
| 3683634 | Streich | Aug 1972 | A |
| 3705625 | Whitten et al. | Dec 1972 | A |
| 3767766 | Tjoa et al. | Oct 1973 | A |
| 3824080 | Smith et al. | Jul 1974 | A |
| 3840437 | Awan | Oct 1974 | A |
| 3842615 | Reigel et al. | Oct 1974 | A |
| 3848427 | Loofbourow | Nov 1974 | A |
| 3895101 | Tsuruta | Jul 1975 | A |
| 3929635 | Buriks et al. | Dec 1975 | A |
| 3933001 | Muska | Jan 1976 | A |
| 4129626 | Mellbom | Dec 1978 | A |
| 4246015 | Styring | Jan 1981 | A |
| 4270937 | Adler | Jun 1981 | A |
| 4280559 | Best | Jul 1981 | A |
| 4281518 | Muller et al. | Aug 1981 | A |
| 4318723 | Holmes et al. | Mar 1982 | A |
| 4319964 | Katz et al. | Mar 1982 | A |
| 4336233 | Appl et al. | Jun 1982 | A |
| 4344485 | Butler | Aug 1982 | A |
| 4370156 | Goddin et al. | Jan 1983 | A |
| 4382912 | Madgavkar et al. | May 1983 | A |
| 4383841 | Ryan et al. | May 1983 | A |
| 4405585 | Sartori et al. | Sep 1983 | A |
| 4417449 | Hegarty et al. | Nov 1983 | A |
| 4417909 | Weltmer | Nov 1983 | A |
| 4421535 | Mehra | Dec 1983 | A |
| 4441900 | Swallow | Apr 1984 | A |
| 4444577 | Perez | Apr 1984 | A |
| 4459142 | Goddin | Jul 1984 | A |
| 4462814 | Holmes et al. | Jul 1984 | A |
| 4466946 | Goddin et al. | Aug 1984 | A |
| 4511382 | Valencia et al. | Apr 1985 | A |
| 4512782 | Bauer et al. | Apr 1985 | A |
| 4533372 | Valencia et al. | Aug 1985 | A |
| 4551158 | Wagner et al. | Nov 1985 | A |
| 4563202 | Yao et al. | Jan 1986 | A |
| 4592766 | Kumman et al. | Jun 1986 | A |
| 4602477 | Lucadamo | Jul 1986 | A |
| 4609388 | Adler et al. | Sep 1986 | A |
| 4636334 | Skinner et al. | Jan 1987 | A |
| 4695672 | Bunting | Sep 1987 | A |
| 4697642 | Vogel | Oct 1987 | A |
| 4710213 | Sapper et al. | Dec 1987 | A |
| 4717408 | Hopewell | Jan 1988 | A |
| 4720294 | Lucadamo et al. | Jan 1988 | A |
| 4747858 | Gottier | May 1988 | A |
| 4761167 | Nicholas et al. | Aug 1988 | A |
| 4762543 | Pantermuehl et al. | Aug 1988 | A |
| 4769054 | Steigman | Sep 1988 | A |
| 4822393 | Markbreiter et al. | Apr 1989 | A |
| 4831206 | Zarchy | May 1989 | A |
| 4923493 | Valencia et al. | May 1990 | A |
| 4927498 | Rushmere | May 1990 | A |
| 4935043 | Blanc et al. | Jun 1990 | A |
| 4954220 | Rushmere | Sep 1990 | A |
| 4972676 | Sakai | Nov 1990 | A |
| 4976849 | Soldati | Dec 1990 | A |
| 5011521 | Gottier | Apr 1991 | A |
| 5062270 | Haut et al. | Nov 1991 | A |
| 5120338 | Potts et al. | Jun 1992 | A |
| 5137550 | Hegarty et al. | Aug 1992 | A |
| 5152927 | Rivers | Oct 1992 | A |
| 5233837 | Callahan | Aug 1993 | A |
| 5240472 | Sircar | Aug 1993 | A |
| 5247087 | Rivers | Sep 1993 | A |
| 5265428 | Valencia et al. | Nov 1993 | A |
| 5335504 | Durr et al. | Aug 1994 | A |
| 5345771 | Dinsmore | Sep 1994 | A |
| 5567396 | Perry et al. | Oct 1996 | A |
| 5620144 | Strock et al. | Apr 1997 | A |
| 5643460 | Marble et al. | Jul 1997 | A |
| 5700311 | Spencer | Dec 1997 | A |
| 5720929 | Minkkinen et al. | Feb 1998 | A |
| 5819555 | Engdahl | Oct 1998 | A |
| 5820837 | Marjanovich et al. | Oct 1998 | A |
| 5899274 | Frauenfeld et al. | May 1999 | A |
| 5956971 | Cole et al. | Sep 1999 | A |
| 5964985 | Wootten | Oct 1999 | A |
| 5983663 | Sterner | Nov 1999 | A |
| 6053007 | Victory et al. | Apr 2000 | A |
| 6053484 | Fan et al. | Apr 2000 | A |
| 6082133 | Barclay et al. | Jul 2000 | A |
| 6082373 | Sakurai et al. | Jul 2000 | A |
| 6162262 | Minkkinen et al. | Dec 2000 | A |
| 6223557 | Cole | May 2001 | B1 |
| 6240744 | Agrawal et al. | Jun 2001 | B1 |
| 6267358 | Gohara et al. | Jul 2001 | B1 |
| 6270557 | Millet et al. | Aug 2001 | B1 |
| 6274112 | Moffett et al. | Aug 2001 | B1 |
| 6336334 | Minkkinen et al. | Jan 2002 | B1 |
| 6374634 | Gallarda et al. | Apr 2002 | B2 |
| 6401486 | Lee et al. | Jun 2002 | B1 |
| 6416729 | DeBerry et al. | Jul 2002 | B1 |
| 6442969 | Rojey et al. | Sep 2002 | B1 |
| 6500982 | Hale et al. | Dec 2002 | B1 |
| 6505683 | Minkkinen et al. | Jan 2003 | B2 |
| 6516631 | Trebble | Feb 2003 | B1 |
| 6517801 | Watson et al. | Feb 2003 | B2 |
| 6539747 | Minta et al. | Apr 2003 | B2 |
| 6565629 | Hayashida et al. | May 2003 | B1 |
| 6605138 | Frondorf | Aug 2003 | B2 |
| 6631626 | Hahn | Oct 2003 | B1 |
| 6632266 | Thomas et al. | Oct 2003 | B2 |
| 6662872 | Gutek et al. | Dec 2003 | B2 |
| 6708759 | Leaute et al. | Mar 2004 | B2 |
| 6711914 | Lecomte | Mar 2004 | B2 |
| 6735979 | Lecomte et al. | May 2004 | B2 |
| 6755251 | Thomas et al. | Jun 2004 | B2 |
| 6755965 | Pironti et al. | Jun 2004 | B2 |
| 6818194 | DeBerry et al. | Nov 2004 | B2 |
| 6883327 | Iijima et al. | Apr 2005 | B2 |
| 6946017 | Leppin et al. | Sep 2005 | B2 |
| 6958111 | Rust et al. | Oct 2005 | B2 |
| 6962061 | Wilding et al. | Nov 2005 | B2 |
| 7001490 | Wostbrock et al. | Feb 2006 | B2 |
| 7004985 | Wallace et al. | Feb 2006 | B2 |
| 7066986 | Haben et al. | Jun 2006 | B2 |
| 7073348 | Clodic et al. | Jul 2006 | B2 |
| 7121115 | Lemaire et al. | Oct 2006 | B2 |
| 7128150 | Thomas et al. | Oct 2006 | B2 |
| 7128276 | Nilsen et al. | Oct 2006 | B2 |
| 7152431 | Amin et al. | Dec 2006 | B2 |
| 7211128 | Thomas et al. | May 2007 | B2 |
| 7211701 | Muller et al. | May 2007 | B2 |
| 7219512 | Wilding et al. | May 2007 | B1 |
| 7285225 | Copeland et al. | Oct 2007 | B2 |
| 7325415 | Amin et al. | Feb 2008 | B2 |
| 7424808 | Mak | Sep 2008 | B2 |
| 7437889 | Roberts et al. | Oct 2008 | B2 |
| 7442231 | Landrum | Oct 2008 | B2 |
| 7442233 | Mitariten | Oct 2008 | B2 |
| 7493779 | Amin | Feb 2009 | B2 |
| 7536873 | Nohlen | May 2009 | B2 |
| 7550064 | Bassler et al. | Jun 2009 | B2 |
| 7575624 | Cartwright et al. | Aug 2009 | B2 |
| 7597746 | Mak et al. | Oct 2009 | B2 |
| 7635408 | Mak et al. | Dec 2009 | B2 |
| 7637984 | Adamopoulos | Dec 2009 | B2 |
| 7637987 | Mak | Dec 2009 | B2 |
| 7641717 | Gal | Jan 2010 | B2 |
| 7662215 | Sparling et al. | Feb 2010 | B2 |
| 7691239 | Kister et al. | Apr 2010 | B2 |
| 7722289 | Leone et al. | May 2010 | B2 |
| 7729976 | Hill et al. | Jun 2010 | B2 |
| 7770872 | Delatour | Aug 2010 | B2 |
| 7795483 | Kulprathipanja et al. | Sep 2010 | B2 |
| 7806965 | Stinson | Oct 2010 | B2 |
| 7814975 | Hagen et al. | Oct 2010 | B2 |
| 7879135 | Ravikumar et al. | Feb 2011 | B2 |
| 7901583 | McColl et al. | Mar 2011 | B2 |
| 7955496 | Iqbal et al. | Jun 2011 | B2 |
| 8002498 | Leone et al. | Aug 2011 | B2 |
| 8020408 | Howard et al. | Sep 2011 | B2 |
| 8133764 | Dirks et al. | Mar 2012 | B2 |
| 8136799 | Griepsma | Mar 2012 | B2 |
| 8303685 | Schubert et al. | Nov 2012 | B2 |
| 8308849 | Gal | Nov 2012 | B2 |
| 8312738 | Singh et al. | Nov 2012 | B2 |
| 8372169 | Tsangaris et al. | Feb 2013 | B2 |
| 8381544 | Coyle | Feb 2013 | B2 |
| 8388832 | Moffett et al. | Mar 2013 | B2 |
| 8428835 | Habert et al. | Apr 2013 | B2 |
| 8475572 | Prast et al. | Jul 2013 | B2 |
| 8500105 | Nieuwoudt | Aug 2013 | B2 |
| 8529662 | Kelley et al. | Sep 2013 | B2 |
| 20020174687 | Cai | Nov 2002 | A1 |
| 20020189443 | McGuire | Dec 2002 | A1 |
| 20030181772 | Meyer et al. | Sep 2003 | A1 |
| 20060207946 | McColl et al. | Sep 2006 | A1 |
| 20060239879 | Lallemand et al. | Oct 2006 | A1 |
| 20070056317 | Amin et al. | Mar 2007 | A1 |
| 20070125537 | Lokhandwala | Jun 2007 | A1 |
| 20070144943 | Lemaire et al. | Jun 2007 | A1 |
| 20070193303 | Hawrysz | Aug 2007 | A1 |
| 20070277674 | Hirano et al. | Dec 2007 | A1 |
| 20080034789 | Fieler et al. | Feb 2008 | A1 |
| 20080091316 | Szczublewski | Apr 2008 | A1 |
| 20080092589 | Trainer et al. | Apr 2008 | A1 |
| 20080307827 | Hino et al. | Dec 2008 | A1 |
| 20090023605 | Lebl et al. | Jan 2009 | A1 |
| 20090220406 | Rahman | Sep 2009 | A1 |
| 20100011809 | Mak | Jan 2010 | A1 |
| 20100018248 | Fieler et al. | Jan 2010 | A1 |
| 20100024472 | Amin et al. | Feb 2010 | A1 |
| 20100031699 | Dam | Feb 2010 | A1 |
| 20100064725 | Chieng et al. | Mar 2010 | A1 |
| 20100107687 | Andrian et al. | May 2010 | A1 |
| 20100132405 | Nilsen | Jun 2010 | A1 |
| 20100147022 | Hart et al. | Jun 2010 | A1 |
| 20100187181 | Sortwell | Jul 2010 | A1 |
| 20100310439 | Brok et al. | Dec 2010 | A1 |
| 20110132034 | Beaumont et al. | Jun 2011 | A1 |
| 20110154856 | Andrian et al. | Jun 2011 | A1 |
| 20110168019 | Northrop et al. | Jul 2011 | A1 |
| 20110192190 | Andrian et al. | Aug 2011 | A1 |
| 20110265512 | Bearden et al. | Nov 2011 | A1 |
| 20120006055 | Van Santen et al. | Jan 2012 | A1 |
| 20120031143 | Van Santem et al. | Feb 2012 | A1 |
| 20120031144 | Northrop et al. | Feb 2012 | A1 |
| 20120079852 | Northrop et al. | Apr 2012 | A1 |
| 20120125043 | Cullinane et al. | May 2012 | A1 |
| 20120204599 | Northrop et al. | Aug 2012 | A1 |
| 20120279728 | Northrop et al. | Nov 2012 | A1 |
| 20130032029 | Mak | Feb 2013 | A1 |
| 20130074541 | Kaminsky et al. | Mar 2013 | A1 |
| 20130098105 | Northrop | Apr 2013 | A1 |
| 20140137599 | Oelfke et al. | May 2014 | A1 |
| 20150158796 | Valencia et al. | Jun 2015 | A1 |
| 20150159939 | Valencia et al. | Jun 2015 | A1 |
| 20150159940 | Valencia et al. | Jun 2015 | A1 |
| 20150159941 | Valencia et al. | Jun 2015 | A1 |
| 20150159942 | Valencia et al. | Jun 2015 | A1 |
| 20150159943 | Valencia et al. | Jun 2015 | A1 |
| 20150159944 | Valencia et al. | Jun 2015 | A1 |
| 20150159945 | Valencia et al. | Jun 2015 | A1 |
| 20150159946 | Valencia et al. | Jun 2015 | A1 |
| 20150159947 | Valencia et al. | Jun 2015 | A1 |
| 20150300735 | Valencia | Oct 2015 | A1 |
| Number | Date | Country |
|---|---|---|
| 3 149 847 | Jul 1983 | DE |
| 0 133 208 | Feb 1985 | EP |
| 0 508 244 | Oct 1992 | EP |
| 1 338 557 | Mar 2005 | EP |
| 1010403 | Nov 1965 | GB |
| WO 2002032536 | Apr 2002 | WO |
| WO 2002039038 | May 2002 | WO |
| WO 2004047956 | Jun 2004 | WO |
| WO 2008034789 | Mar 2008 | WO |
| WO 2008095258 | Aug 2008 | WO |
| WO 2008152030 | Dec 2008 | WO |
| WO 2009023605 | Feb 2009 | WO |
| WO 2009029353 | Mar 2009 | WO |
| WO 2009087206 | Jul 2009 | WO |
| WO 2010023238 | Mar 2010 | WO |
| WO 2010052299 | May 2010 | WO |
| WO 2010136442 | Dec 2010 | WO |
| WO 2011026170 | Mar 2011 | WO |
| WO 2013095828 | Jun 2013 | WO |
| WO 2013142100 | Sep 2013 | WO |
| Entry |
|---|
| Aaron, D. et al. (2005) “Separation of CO2 from Flue Gas: A Review,” Separation Science and Technology, 40, pp. 321-348. |
| Amin, R. (2003) “Advanced Mini Natural Gas Liquefier,” LNG Journal, Mar.-Apr. 2003, pp. 20-23. |
| Black, S. (2006) “Chilled Ammonia Process for CO2 Capture,” Alstom Position Paper, Nov. 2006, 6 pgs. |
| Ciulla, Vincent (2007) “How the Engine Works,” About.com, Mar. 21, 2007, [retrieved from the internet on Aug. 17, 2012]. <URL: http://autorepair.about.com/cs/generalinfo/a/aa060500a.html>. |
| “Cryogenics” Science Clarified, May 2, 2006 [retrieved from the internet on Aug. 17, 2012]. <URL: http://www.scienceclarified.com/Co-Dl/Cryogenics.html>. |
| Denton, R. D. et al. (1985) “Integrated Low Temperature Processing of Sour Natural Gas,” Gas Processors Assoc., 64th th Ann. Conv., pp. 92-96. |
| Guccione, E. (1963) “New Approach to Recovery of Helium from Natural Gas,” Chem. Engr., Sep. 30, 1963, pp. 76-78. |
| Hassan, S. M. N. (2005) “Techno-Economic Study of CO2 Capture Process for Cement Plants,” University of Waterloo—Thesis. |
| Haut, R. C. et al. (1988) “Development and Application of the Controlled Freeze Zone Process,” SPE 17757, SPE Gas Tech. Symp.—Dallas, TX, pp. 435-443. |
| Haut, R. C. et al. (1988) “Development and Application of the Controlled Freeze Zone Process,” OSEA 88197, 7th Offshore So. East Asia Conf., Singapore, Feb. 1988, pp. 840-848. |
| Haut, R. C. et al. (1989) “Development and Application of the Controlled Freeze Zone Process,” SPE Production Engineering, Aug. 1989, pp. 265-271. |
| Im, U. K. et al. (1971) “Heterogeneous Phase Behavior of Carbon Dioxide in n-Hexane and n-Heptane at Low Temperatures,” Jrnl. of Chem. Engineering Data, v.16.4, pp. 412-415. |
| Mitariten, M. et al. (2007) “The Sorbead™ Quick-Cycle Process for Simultaneous Removal of Water, Heavy Hydrocarbons and Mercaptans from Natural Gas,” Laurance Reid Gas Conditioning Conf., Feb. 25-27, 2007. |
| Northrop, P. Scott et al. (2004) “Cryogenic Sour Gas Process Attractive for Acid Gas Injection Applications,” 83rd Ann. Gas Processors Assoc. Convention, New Orleans, LA., pp. 1-8 (XP007912217). |
| Pagcatipunan, C. et al. (2005) “Maximize the Performance of Spray Nozzle Systems,” CEP Magazine, Dec. 2005, pp. 38-44. |
| Reyes, S. C. et al. (1997) “Frequency Modulation Methods for Diffusion and Adsorption Measurements in Porous Solids,” J. Phys. Chem. B, v.101, pp. 614-622. |
| Rubin, E. S. et al. (2002) “A Technical, Economic and Environmental Assessment of Amine-based CO2 Capture Technology for Power Plant Greenhouse Gas Control,” U.S. Dept. of Energy, Oct. 2002, DOE/DE-FC26-00NT40935, 26 pages. |
| Spero, C. (2007) “Callide Oxyfuel Project,” CS Energy, cLET Seminar, Jul. 12, 2007, 9 pages. |
| Thomas, E. R. et al. (1987) “Conceptual Studies Using the Controlled Freeze Zone (CFZ) Process,” AlChE Summer Nat'l Mtg., Aug. 16-19, 1987. |
| Thomas, E. R. et al. (1988) “Conceptual Studies for CO2/Natural Gas Separation Using the Control Freeze Zone (CFZ) Process,” Gas Separation and Purification, v. 2, pp. 84-89. |
| Valencia, J. A. et al. (2008) “Controlled Freeze Zone™ Technology for Enabling Processing of High CO2 and H2S Gas Reserves,” SPE-IPTC 12708, Kuala Lumpur, IN, v.4.1, Jan. 2008, pp. 2358-2363. |
| Victory, D. J. et al. (1987) “The CFZ Process: Direct Methane-Carbon Dioxide Fractionation,” 66th Ann. GPA Convention, Mar. 16-18, Denver, CO. |
| Wilson, R.W. et al. (1968) “Helium: Its Extraction and Purification,” Journ. Petrol. Tech., v. 20, pp. 341-344. |
| Number | Date | Country | |
|---|---|---|---|
| 20170089638 A1 | Mar 2017 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62232149 | Sep 2015 | US |
