This invention relates to a process for the separation of a hydrocarbon bearing gas stream containing significant quantities of components more volatile than methane (e.g., hydrogen, nitrogen, etc.) into two fractions: a first fraction containing predominantly methane and the more volatile components, and a second fraction containing the recovered desirable ethane/ethylene and heavier hydrocarbon components.
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. Hydrocarbon bearing gas typically contains components more volatile than methane (e.g., hydrogen, nitrogen, etc.) and often unsaturated hydrocarbons (e.g., ethylene, propylene, etc.) and aromatic hydrocarbons (e.g., benzene, toluene, etc.) in addition to methane, ethane, and hydrocarbons of higher molecular weight such as propane, butane, and pentane. Sulfur-containing gases and carbon dioxide are also sometimes present.
The present invention is generally concerned with the recovery of ethylene, ethane, and heavier (C2+) hydrocarbons from such gas streams. Recent changes in ethylene demand have created increased markets for ethylene and derivative products. In addition, fluctuations in the prices of both natural gas and its natural gas liquid (NGL) constituents have increased the value of ethane and heavier components as liquid products. These market conditions have resulted in the demand for processes which can provide high ethylene and ethane recovery and more efficient recovery of all these products. 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 startup, operating flexibility, good efficiency, safety, and good reliability. U.S. Pat. Nos. 3,292,380; 4,061,481; 4,140,504; 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; 5,566,554; 5,568,737; 5,771,712; 5,799,507; 5,881,569; 5,890,378; 5,983,664; 6,182,469; 6,578,379; 6,712,880; 6,915,662; 7,191,617; 7,219,513; reissue U.S. Pat. No. 33,408; and co-pending application Ser. Nos. 11/430,412; 11/839,693; 11/971,491; 12/206,230; 12/689,616; 12/717,394; 12/750,862; 12/772,472; 12/781,259; 12/868,993; 12/869,007; and 12/869,139 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 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 or deethanizer) column. In the column, the expansion cooled stream(s) is (are) distilled to separate residual methane, hydrogen, nitrogen, and other volatile gases as overhead vapor from the desired C2 components, C3 components, and heavier hydrocarbon components as bottom liquid product, or to separate residual methane, C2 components, hydrogen, nitrogen, and other volatile gases as overhead vapor from the desired C3 components and heavier hydrocarbon components as bottom liquid product.
If the feed gas is not totally condensed (typically it is not), 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 feed to the column.
In the ideal operation of such a separation process, the residue gas leaving the process will contain substantially all of the methane and more volatile components in the feed gas with essentially none of the heavier hydrocarbon components, and the bottoms fraction leaving the demethanizer will contain substantially all of the heavier hydrocarbon components with essentially no methane or more volatile components. In practice, however, this ideal situation is not obtained because the conventional demethanizer is operated largely as a stripping column. The methane product of the process, therefore, typically comprises vapors leaving the top fractionation stage of the column, together with vapors not subjected to any rectification step. Considerable losses of ethylene and ethane occur because the top liquid feed contains substantial quantities of C2+ components and heavier hydrocarbon components, resulting in corresponding equilibrium quantities of C2+ components in the vapors leaving the top fractionation stage of the demethanizer. This problem is exacerbated if the gas stream(s) being processed contain relatively large quantities of components more volatile than methane (e.g., hydrogen, nitrogen, etc.) because the volatile vapors rising up the column strip C2+ components from the liquids flowing downward. The loss of these desirable C2+ components could be significantly reduced if the rising vapors could be brought into contact with a significant quantity of liquid (reflux) capable of absorbing the C2+ components from the vapors.
A number of processes have been developed to use a cold liquid that is predominantly methane as the reflux stream to contact the rising vapors in a rectification section in the distillation column. Typical process schemes of this type are disclosed in U.S. Pat. Nos. 4,889,545; 5,568,737; and 5,881,569, and in Mowrey, E. Ross, “Efficient, High Recovery of Liquids from Natural Gas Utilizing a High Pressure Absorber”, Proceedings of the Eighty-First Annual Convention of the Gas Processors Association, Dallas, Tex., Mar. 11-13, 2002. Unfortunately, these processes require the use of a compressor to provide the motive force for recycling the reflux stream to the demethanizer, adding to both the capital cost and the operating cost of facilities using these processes. In addition, the cold methane reflux creates temperatures within the distillation column that are −112° F. [−80° C.] and colder. Many gas streams of this type contain significant quantities of nitrous oxides (NOX) at times, which can accumulate in cold sections of a processing plant as NOX gums (commonly referred to as “blue ice”) at temperatures lower than this. “Blue ice” can become explosive upon warming, and has been identified as the cause of a number of deflagrations and/or explosions in processing plants.
Other processes have been developed that use a heavy (C4-C10 typically) hydrocarbon absorbent stream to reflux the distillation column. Examples of processes of this type are U.S. Pat. Nos. 4,318,723; 5,546,764; 7,273,542; and 7,714,180. While such processes generally operate at temperatures warm enough to avoid concerns about “blue ice”, the absorbent stream is typically produced from the distillation column bottoms stream, with the result that any aromatic hydrocarbons present in the feed gas will concentrate in the distillation column. Aromatic hydrocarbons such as benzene can freeze solid at normal processing temperatures, causing frequent disruptions in the processing plant.
In accordance with the present invention, it has been found that ethane recovery in excess of 88% can be obtained without requiring any temperatures to be lower than −112° F. [−80° C.]. The present invention is particularly advantageous when processing feed gases containing more than 10 mole % of components more volatile than methane.
For a better understanding of the present invention, reference is made to the following examples and drawings. Referring to the drawings:
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 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.
For convenience, process parameters are reported in both the traditional British units and in the units of the Système International d'Unitès (SI). The molar flow rates given in the tables may be interpreted as either pound moles per hour or kilogram moles per hour. The energy consumptions reported as horsepower (HP) and/or thousand British Thermal Units per hour (MBTU/Hr) correspond to the stated molar flow rates in pound moles per hour. The energy consumptions reported as kilowatts (kW) correspond to the stated molar flow rates in kilogram moles per hour.
The inlet gas is compressed to higher pressure in three stages before processing (compressors 10 and 15 driven by an external power source and compressor 13 driven by work expansion machine 14). Discharge coolers 11 and 16 are used to cool the gas between stages, and separators 12 and 17 are used to remove any water or other liquids that condense from the gas stream as it is cooled. The cooled compressed gas stream 54 leaving separator 17 is dehydrated in dehydration unit 18 to prevent hydrate (ice) formation under cryogenic conditions. Solid desiccant has typically been used for this purpose.
The dehydrated gas stream 61 at 100° F. [38° C.] and 560 psia [3,859 kPa(a)] enters heat exchanger 20 and is cooled by heat exchange with cool residue gas (stream 68a), liquid product at 28° F. [−2° C.] (stream 71a), demethanizer reboiler liquids at 13° F. [−11° C.] (stream 70), and propane refrigerant. Note that in all cases exchanger 20 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 61a enters separator 21 at 40° F. [4° C.] and 550 psia [3,790 kPa(a)] where the vapor (stream 62) is separated from the condensed liquid (stream 63). The separator liquid (stream 63) is expanded to the operating pressure (approximately 175 psia [1,207 kPa(a)]) of fractionation tower 28 by expansion valve 22, cooling stream 63a to 16° F. [−9° C.] before it is supplied to fractionation tower 28 at a lower column feed point.
The vapor (stream 62) from separator 21 is further cooled in heat exchanger 23 by heat exchange with cold residue gas (stream 68), demethanizer side reboiler liquids at −10° F. [−23° C.] (stream 69), flashed liquids (stream 65a), and propane refrigerant. The cooled stream 62a enters separator 24 at −42° F. [−41° C.] and 535 psia [3,686 kPa(a)] where the vapor (stream 64) is separated from the condensed liquid (stream 65). The separator liquid (stream 65) is expanded to slightly above the tower operating pressure by expansion valve 25, cooling stream 65a to −63° F. [−53° C.] before it is heated to −40° F. [−40° C.] in heat exchanger 23. The heated stream 65b is then supplied to fractionation tower 28 at a lower mid-column feed point.
The vapor (stream 64) from separator 24 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 to the tower operating pressure, with the work expansion cooling the expanded stream 64a to a temperature of approximately −105° F. [−76° C.]. 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 13) that can be used to compress the inlet gas (stream 52), for example. The partially condensed expanded stream 64a is thereafter supplied as feed to fractionation tower 28 at an upper mid-column feed point.
The demethanizer in tower 28 is a conventional distillation column containing a plurality of vertically spaced trays, one or more packed beds, or some combination of trays and packing. The demethanizer tower consists of two sections: an upper absorbing (rectification) section that contains the trays and/or packing to provide the necessary contact between the vapor portion of the expanded stream 64a rising upward and cold liquid falling downward to condense and absorb the C2 components, C3 components, and heavier components from the vapors rising upward; and a lower, stripping (demethanizing) section that contains the trays and/or packing to provide the necessary contact between the liquids falling downward and the vapors rising upward. The demethanizing section also includes one or more reboilers (such as the reboiler and side reboiler described previously) which heat and vaporize a portion of the liquids flowing down the column to provide the stripping vapors which flow up the column to strip the liquid product, stream 71, of methane and lighter components. Stream 64a enters demethanizer 28 at an intermediate feed position located in the lower region of the absorbing section of demethanizer 28. The liquid portion of the expanded stream commingles with liquids falling downward from the absorbing section and the combined liquid continues downward into the stripping section of demethanizer 28. The vapor portion of the expanded stream rises upward through the absorbing section and is contacted with cold liquid falling downward to condense and absorb the C2 components, C3 components, and heavier components.
A portion of the distillation liquid (stream 72) is withdrawn from an intermediate region of the stripping section in fractionation column 28, below the feed position of expanded stream 64a in the lower region of the absorbing section but above the feed position of expanded liquid stream 63a in the stripping section. Withdrawing the distillation liquid at this location provides a liquid stream that is predominantly C2-C5 hydrocarbons containing very little of the volatile components (e.g., methane, hydrogen, nitrogen, etc.) and little of the aromatic hydrocarbons and heavier hydrocarbon components. This distillation vapor stream 72 is pumped to higher pressure by pump 30 (stream 72a) and then heated from −25° F. [−32° C.] to 77° F. [25° C.] and partially vaporized in heat exchanger 31 by heat exchange with the hot depropanizer bottom stream 78. The heated stream 72b then enters depropanizer 32 (operating at 265 psia [1,828 kPa(a)]) at a mid-column feed point.
The depropanizer in tower 32 is a conventional distillation column containing a plurality of vertically spaced trays, one or more packed beds, or some combination of trays and packing. The depropanizer tower consists of two sections: an upper absorbing (rectification) section that contains the trays and/or packing to provide the necessary contact between the vapor portion of the heated stream 72b rising upward and cold liquid falling downward to condense and absorb the C4 components and heavier components; and a lower, stripping (depropanizing) section that contains the trays and/or packing to provide the necessary contact between the liquids falling downward and the vapors rising upward. The depropanizing section also includes one or more reboilers (such as reboiler 33) which heat and vaporize a portion of the liquids flowing down the column to provide the stripping vapors which flow up the column to strip the bottom liquid product, stream 78, of C3 components and lighter components. Stream 72b enters depropanizer 32 at an intermediate feed position located between the absorbing section and the stripping section of depropanizer 32. The liquid portion of the heated stream commingles with liquids falling downward from the absorbing section and the combined liquid continues downward into the stripping section of depropanizer 32. The vapor portion of the heated stream rises upward through the absorbing section and is contacted with cold liquid falling downward to condense and absorb the C4 components and heavier components.
The overhead vapor (stream 73) from depropanizer 32 enters reflux condenser 34 and is cooled by propane refrigerant from 59° F. [15° C.] to −33° F. [−36° C.] to condense it before entering reflux separator 35 at 260 psia [1,793 kPa(a)]. If there is any uncondensed vapor (stream 74), it is expanded to the operating pressure of demethanizer 28 by expansion valve 38 and returned to demethanizer 28 at a lower column feed point. In the simulation of
The bottom liquid product from depropanizer 32 (stream 78) has been stripped of the C3 and lighter components, and is predominantly C4-C5 hydrocarbons. It leaves the bottom of depropanizer 32 at 230° F. [110° C.] and is cooled to −20° F. [−29° C.] in heat exchanger 31 as described earlier. Stream 78a is further cooled to −35° F. [−37° C.] with propane refrigerant in heat exchanger 39 (stream 78b) and then expanded to the operating pressure of demethanizer 28 in expansion valve 40. The expanded stream 78c is then supplied to demethanizer 28 as reflux, entering at the top feed location at −35° F. [−37° C.]. The C4-C5 hydrocarbons in stream 78c act as an absorbent to capture the C2+ components in the vapors flowing upward in the absorbing section of demethanizer 28.
In the stripping section of demethanizer 28, the feed streams are stripped of their methane and lighter components. The resulting liquid product (stream 71) exits the bottom of tower 28 at 24° F. [−4° C.] and is pumped to higher pressure in pump 29. The pumped stream 71a is then heated to 93° F. [34° C.] in heat exchanger 20 as described previously. The cold residue gas stream 68 leaves demethanizer 28 at −32° F. [−35° C.] and passes countercurrently to the incoming feed gas in heat exchanger 23 where it is heated to 32° F. [0° C.] (stream 68a) and in heat exchanger 20 where it is heated to 95° F. [35° C.] (stream 68b) as it provides cooling as previously described. The residue gas product then flows to the fuel gas distribution header at 165 psia [1,138 kPa(a)].
A summary of stream flow rates and energy consumption for the process illustrated in
In accordance with this invention, it is generally advantageous to design the absorbing (rectification) section of the demethanizer to contain multiple theoretical separation stages. However, the benefits of the present invention can be achieved with as few as two theoretical stages. For instance, all or a part of the reflux liquid (stream 78c) and all or a part of the expanded stream 64a can be combined (such as in the piping to the demethanizer) and if thoroughly intermingled, the vapors and liquids will mix together and separate in accordance with the relative volatilities of the various components of the total combined streams. Such commingling of the two streams, shall be considered for the purposes of this invention as constituting an absorbing section.
Feed gas conditions, plant size, available equipment, or other factors may indicate that elimination of work expansion machine 14, or replacement with an alternate expansion device (such as an expansion valve), is feasible. 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 reflux stream (stream 78b or stream 79a).
When the inlet gas is leaner, separator 21 in
The expanded liquid (stream 65a in
In accordance with the present 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 a rich inlet gas. The use and distribution of separator liquids and demethanizer side draw 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.
In accordance with the present invention, the splitting of the vapor feed for the
It will also be recognized that the relative amount of feed found in each branch of the split vapor feed of the
The present invention provides improved recovery of C2 components, C3 components, and heavier hydrocarbon components per amount of utility consumption required to operate the process. An improvement in utility consumption required for operating the demethanizer process may appear in the form of reduced power requirements for compression or re-compression, reduced power requirements for external refrigeration, reduced energy requirements for tower reboilers, or a combination thereof.
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.
The applicants claim the benefits under Title 35, U.S. Code, Section 119(e) of prior U.S. Provisional Application No. 61/295,119 which was filed on Jan. 14, 2010.
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“Dew Point Control Gas Conditioning Units,” SME Products Brochure, Gas Processors Assoc. Conference (Apr. 5, 2009)—2 pages. |
“Fuel Gas Conditioning Units for Compressor Engines,” SME Products Brochure, Gas Processors Assoc. Conference (Apr. 5, 2009)—2 pages. |
“P&ID Fuel Gas Conditioner,” Drawing No. SMEP-901, Date Drawn: Aug. 29, 2007, SME, available at http://www.sme-llc.com/sme.cfm?a=prd&catID=58&subID=44&prdID=155 (Apr. 24, 2009)—1 page. |
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Number | Date | Country | |
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20110167868 A1 | Jul 2011 | US |
Number | Date | Country | |
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61295119 | Jan 2010 | US |