US3791157A - Process for purification of natural gas - Google Patents
Process for purification of natural gas Download PDFInfo
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- US3791157A US3791157A US00087853A US3791157DA US3791157A US 3791157 A US3791157 A US 3791157A US 00087853 A US00087853 A US 00087853A US 3791157D A US3791157D A US 3791157DA US 3791157 A US3791157 A US 3791157A
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- natural gas
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- 238000000034 method Methods 0.000 title claims abstract description 71
- 230000008569 process Effects 0.000 title claims abstract description 66
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 148
- 239000003345 natural gas Substances 0.000 title claims description 48
- 238000000746 purification Methods 0.000 title abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 133
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000000047 product Substances 0.000 claims abstract description 81
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 50
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 238000009833 condensation Methods 0.000 claims abstract description 8
- 230000005494 condensation Effects 0.000 claims abstract description 8
- 239000012263 liquid product Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 104
- 239000007791 liquid phase Substances 0.000 claims description 46
- 239000007792 gaseous phase Substances 0.000 claims description 21
- 230000002829 reductive effect Effects 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 8
- 230000036961 partial effect Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 abstract description 52
- 239000007789 gas Substances 0.000 abstract description 49
- 229930195733 hydrocarbon Natural products 0.000 abstract description 45
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 45
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 42
- 239000000356 contaminant Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005191 phase separation Methods 0.000 abstract description 6
- 239000000470 constituent Substances 0.000 abstract description 5
- 239000012808 vapor phase Substances 0.000 description 18
- 230000003750 conditioning effect Effects 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 230000001143 conditioned effect Effects 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JVFDADFMKQKAHW-UHFFFAOYSA-N C.[N] Chemical compound C.[N] JVFDADFMKQKAHW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- FNYLWPVRPXGIIP-UHFFFAOYSA-N Triamterene Chemical compound NC1=NC2=NC(N)=NC(N)=C2N=C1C1=CC=CC=C1 FNYLWPVRPXGIIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
- F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
- F25J3/066—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of nitrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
- F25J1/0022—Hydrocarbons, e.g. natural gas
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- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
- F25J1/004—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by flash gas recovery
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- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
- F25J1/0045—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by vaporising a liquid return stream
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- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
- F25J1/0201—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using only internal refrigeration means, i.e. without external refrigeration
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
- F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
- F25J1/0244—Operation; Control and regulation; Instrumentation
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- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
- F25J3/0605—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the feed stream
- F25J3/061—Natural gas or substitute natural gas
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- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
- F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
- F25J3/0635—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of CnHm with 1 carbon atom or more
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- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25J2205/00—Processes or apparatus using other separation and/or other processing means
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- F25J2220/00—Processes or apparatus involving steps for the removal of impurities
- F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25J2220/00—Processes or apparatus involving steps for the removal of impurities
- F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
- F25J2220/62—Separating low boiling components, e.g. He, H2, N2, Air
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- F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
- F25J2220/66—Separating acid gases, e.g. CO2, SO2, H2S or RSH
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- F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
- F25J2235/60—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being (a mixture of) hydrocarbons
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- F25J2240/00—Processes or apparatus involving steps for expanding of process streams
- F25J2240/60—Expansion by ejector or injector, e.g. "Gasstrahlpumpe", "venturi mixing", "jet pumps"
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- F25J2245/00—Processes or apparatus involving steps for recycling of process streams
- F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
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- F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
- F25J2290/42—Modularity, pre-fabrication of modules, assembling and erection, horizontal layout, i.e. plot plan, and vertical arrangement of parts of the cryogenic unit, e.g. of the cold box
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S62/00—Refrigeration
- Y10S62/927—Natural gas from nitrogen
Definitions
- the vapor from the second separation is 2,743,590 5/1956 Grunberg 62/26 cooled and returned to the first separation while the 2, 12, 1/1 7 T m y 62/28 vapor product from first separation along with the liq- 3,607,733 9/1971 Harper 62/28 uid product from the second separation are separately $512,368 5/1970 Harper 62/23 employed to effect condensation of the contaminated 3,293,869 12/1966 Karbosky.
- the process comprises cooling thehigh-pressure contaminated natural gas in two successive steps to condense at least a substantial part of the gas stream by passing it in indirect heat exchange relationship first with at least two separate fluid streams and second with a boiling liquid.
- the cooled feed mixture is then expanded to substantially atmospheric pressure in a first separation zone to produce a single hydrocarbon-rich liquid phase and a single contaminant-rich vapor phase.
- the liquid and vapor phases are separated and the liquid is further enriched by partial vaporization in heat exchange with the natural gas in the second step of cooling referred to earlier.
- the partially vaporized stream from the first separation thus yields a second hydrocarbon-rich liquid phase and a second contaminant-rich vapor phase in a second separation zone. These are in turn separated, and the second vapor phase is cooled 8nd reintroduced into the first separation zone.
- the liquid from the second separation and the vapor from the first are then separately passed as the fluid streams which cool the feed mixture by indirect heat exchange in the first cooling step before being withdrawn from the process as first and second product streams, respectively.
- This increase in separation effectiveness is achieved by performing a second separation of the liquid phase withdrawn from the first separation in a second separation zone following heating and partial vaporization of the liquid by indirect heat exchange with the cool feed stream in a subcooler.
- the vapor phase from this second separation contains an appreciably higher hydrocarbon content than the vapor phase from the first because of the higher temperature of the liquid and vapor in the second separation zone.
- this hydrocarbon content is not lost but recovered by first cooling the vapor phase from the second separation in an intercooler and then returning it to the first separation zone.
- high pressure as applied to the contaminant gas to be purified is used herein with reference to the pressures at which natural gas is typically produced at a wellhead or at which it is maintained in contemporary transmission systems. These pressures, however, do not represent critical limitations on the process which may accept gaseous feed at higher or lower pressures down to at least several atmospheres. Although the process is applicable to various contaminants, it is described herein with reference to nitrogen as the contaminant, an incombustible found in many hydrocarbon reservoirs. It will also be understood that the term purification as used herein refers to removal of a sufficient amount of contaminant to render the hydrocarbon gas marketable under the prevailing local conditions.
- FIG. 1 is a block diagram of a process system showing one embodiment for the practice of the invention
- FIG. 2 is an isobaric curve showing methane-nitrogen phase separation at 50 p.s.i.a.
- FIG. 3 is a schematic flow sheet of a process system depicting another embodiment falling within the scope of the invention.
- high pressure gaseous natural gas mixture contaminated by a large proportion of nitrogen, as for example 60 percent by volume, produced at a wellhead 9 at a high pressure, which is typically in excess of 100 atmospheres, is passed first through a feed conditioning system 10 shown in the upper part of the Figure and then through the two-stage separation process shown in the lower part of the Figure, the process system encompassing both aspects.
- the conditioning system is comprised of a separator 11, to remove free liquids from the produced gas, and a pressure regulator 12 to reduce feed gas pressure, if necessary.
- the separator may also include a heater, so that the temperature of the feed gas following pressure reduction in regulator 12 will remain above the hydrate formation temperature of between about 45F and 65F.
- a chiller 13 may be provided to cool the feed gas in cases where the temperature following the pressure regulator 12 is appreciably higher than the hydrate formation temperature. In the chiller, the feed gas is cooled by one of the product streams, such as the nitrogen-rich stream as shown here entering chiller at 41 and discharging at 42. Suspended water and hydrocarbons condensed from the feed gas in the chiller are collected in a filter-separator 14.
- the feed gas is passed through a dryer system 15 to remove vaporized water and troublesome heavier hydrocarbons.
- the dryer system typically comprises beds of desiccant or molecular sieve as well as activated charcoal, which must be periodically regenerated using hot, dry gas heated by gas or electrical heaters included as part of the dryer system. Gas for this purpose may be drawn from the nitrogenrich stream through a line 39 and discharged from the dryer system through line 40.
- the conditioning system functions to stabilize the pressure and temperature of the feed mixture and to remove therefrom unwanted components which would freeze in the subsequent processing.
- the conditioned feed mixture leaves the conditioning system through line 16 and enters a heat exchanger 17 which may consist of one or more units arranged so as to take full advantage of the cooling capacity of the separate streams of hydrocarbon-rich product and nitrogen-rich product as they are warmed from the low temperatures at which they are separated in the process, as will be described later.
- the feed stream passes in parallel counterflow heat exchange relation to each of the product streams, which in turn flow through separate passages or else through separate heat exchange units, as is the case in a preferred embodiment to be described in connection with FIG. 3.
- the cooled feed mixture is passed through a line 18 to the subcooler 19 where it is further cooled by heat exchange with a stream of low temperature boiling liquid drawn from the first stage separation vessel.
- the subcooler is typically a tube-and-shell heat exchanger with the cooled feed passing through coiled tubes in counterflow relation to the boiling liquid in the shell.
- the subcooled feed mixture leaves the subcooler through line 20 still at a substantial fraction of its original pressure as controlled by the regulator 12.
- the small loss of pressure arises from the nominal pressure drop in each of the units of the preconditioning system and in passage through the tubes of the heat exchanger and subcooler.
- the feed stream is normally cooled at a pressure above its critical pressure, in which case the stream is liquidized during condensation without passing through a two-phase region.
- the subcooled feed from the subcooler could be either a liquid or a two-phase mixture, depending on the pressure and other conditions of operation.
- the subcooled feed is expanded through expander 21 to a pressure as near atmospheric as is feasible and consistent with design requirements of the various parts of the system.
- the pressure, after the final expansion is about 35 p.s.i.g.
- the choice of a separation pressure is a compromise between improved efficiency of separation favored by pressures near, or even below, atmospheric and the reduced size of pipes, valves, vessels and heat exchangers needed to handle the reduced volume of the gasous streams of the process at a pressure of several atmospheres.
- a further advantage of relatively higher separation pressure is that the increased pressure, at which the nitrogen-rich product is available after passage through the heat exchanger 17, provides a usable source of dry gas for regeneration of the dryers.
- the present twostage process exhibits a markedly reduced dependence of separation efficiency on the pressure at which the separations are performed, within a range of pressures of up to several atmospheres, absolute.
- the expander 21 is typically a throttle valve which produces a Joule-Thompson, or constant enthalpy expansion.
- an expansion engine or turbine could be used to achieve a nearly isentropic expansion affording greater cooling, still within the scope of the invention.
- Such an isentropic expander achieves improved cooling of the subcooled natural gas mixture by extraction of energy from the stream for performance of external work.
- the expanded feed from the expander passes in line 22 to an intercooler 23 where a portion of its low temperature is used to cool a stream of gas returning from the second stage separation vessel to the first stage.
- the intercooler provides passages for efficient transfer of heat from the interstage stream to the expanded feed stream.
- the expanded feed stream and the interstage gas stream approach thermal equilibrium at the discharge of the intercooler and are passed through lines 30 and 20, respectively, into a first stage separation vessel 24.
- the streams may be mixed before entering the vessel or, in a preferred embodiment as shown in FIG. 3, the streams are mixed in the intercooler to achieve the desired thermal equilibrium by direct heat exchange.
- the two streams enter the vessel and are separated into a single liquid phase and a single vapor phase which approach thermal equilibrium at the reduced separation pressure.
- the fraction of nitrogen in the liquid phase and in the vapor phase at equilibrium depends solely upon the pressure and temperature of the two phases; thus, for a given constant pressure in the first stage separation vessel, the composition of the two phases is governed by the temperature alone.
- the second product stream containing principally nitrogen is derived from the vapor phase in the first stage separation vessel, the hydrocarbon discharged along with the nitrogen-rich second product stream, and also therefore the overall process efficiency, is directly controlled by the degree of cooling of the two streams introduced into the first stage of separation.
- the nitrogen-rich gaseous phase separated in the first stage is withdrawn through line 35 and passed through separate passages of the heat exchanger 17 where it is warmed to near the temperature of the conditioned feed and then discharged through lines 36 and 41 to chiller l3 and back-pressure regulator 37.
- the backpressure regulator maintains a controlled, nearly constant pressure in the first stage separation vessel and affords a positive pressure at which the nitrogen-rich gas may be withdrawn through line 39 for dryer regeneration.
- the hydrocarbon-rich liquid phase separated in the first stage comprises a first interstage stream which is withdrawn through line 25, partially vaporized by passage in heat exchange relation to the relatively warmer feed stream entering the subcooler 19, and then introduced as a two-phase mixture into the second stage separation vessel 27'and' through line 26.
- the two-phase mixture is separated into a second single hydrocarbon-rich liquid phase and a second single nitrogen-rich gaseous phase in approximate thermal equilibrium, the liquid phase being richer in hydrocarbon than the first interstage stream from which itwas derived.
- the nitrogen contentof the liquid and vapor phases depends only upon the separation temperature, for a given controlled pressure. Consequently, and as hereinafter explained in relation to the phase diagram of FIG. 2, the purity of the hydrocarbon-rich first product stream derived from the liquid phase in the second separation vessel is governed by the amount of warming of the first interstage stream in passing through the subcooler prior tointroduction into the second separation vessel.
- the gaseous phase separated in the second separation vessel comprises a second interstage stream and passes through line 28 to the intercooler 23, and thence back to the first stage separator 24, as previously described.
- the liquid withdrawn from the second stage separation vessel through line 31 comprises the hydrocarbonrich first product stream.
- delivery of this product is to be at a pressure above the separation pressure, it can be advantageously pumped to its final delivery pressure while still in a liquid state by means of a product pump 32. Power required to pressurize the first product stream as a liquid is many times lessthan that required to compress the product in the gaseous state.
- the pressurized first product liquid is passed through line 33 into separate passages of heat exchanger 17 where it is vaporized and warmed to near the temperature of the entering conditioned feed gas mixture.
- the gaseous hydrocarbon-rich first product stream is then discharged through discharge line 34 at final delivery pressure as provided by pump 32, but slightly reduced by nominal pressure drop in the heat exchanger and related discharge piping.
- the process yields a hydrocarbon-rich product containing, for example, less than 7 percent of nitrogen at a rate of about 4,300,000 standard cubic feet per day.
- Table I shows the approximate pressure, temperature, nitrogen content, and weight flow rate at various locations in the process system op erating under one typical set of controlled conditions.
- the different temperatures of the first and second separations illustrate a 30 difference in temperature between these separations. It is this difference between the temperature at which the two separations are performed that results in the improved efficiency of sepa ration.
- the example presented does not represent a limiting, but rather a typical case.
- the nitrogen content of the hydrocarbon-rich product (lines 31, 33 and 34) can be higher or lower as required by the gas user. Such variation is accomplished by lower or higher tempera ture in the second stage separation vessel 27, respectively.
- the residual methane content of the nitrogen-rich product stream can be varied; for example, increasing subcooler heat transfer capacity lowers the temperature of the subcooled feed in line 20, resulting in a lower temperature in the first stage separation vessel 24 and a corresponding reduction of methane in the vapor leaving the first stage through line 35 and the process system through line 36.
- the methane-rich product composition is assumed to be specified, thus fixing the point 53 on the liquid composition curve. Accordingly, the temperature T of the second stage of separation is determined and, therefore, the composition of the vapor from the second stage at 54. Similarly, it can be seen that decreasing the methane content of the first stage vapor, shown by the point 56, requires a reduction of the first stage separation temperature T and an accompanying increase in nitrogen content of the first stage liquid, shown by the point 55.
- a material and species balance clearly shows that when the composition of the first stage liquid, point 55, and second stage vapor, point 54, are identical, all of the interstage liquid flowing from the first stage must be vaporized in the second stage and none is available as a methanerich liquid product from the system.
- the nitrogen content of the liquid from the first stage of separation would be increased from 30 percent to 55 percent (assuming the purity of the hydrocarbon-rich product to be left unchanged).
- This limiting case would require additional cooling of the feed gas mixture such that the temperature of the combined streams from lines 29 and 30 entering the first separation zone would be about -289F, some 10F colder than the temperature under the conditions shown, and the methane content of the nitrogen-rich vapor product from the first stage of separation would be about 4 percent.
- both separation vessels as shown are at a pressure of about 50 p.s.i.a., with the second stage vessel at slightly higher pressure. This may be accomplished by employing a static head of liquid flowing down through line 25, subcooler shell 19 and line 26 to maintain a slight positive pressure in the lower vessel 27.
- a liquid pump in line may be used for the same purpose, or else a gas pump can be used to force gas through line 28, intercooler 23, and line 29 to the first stage vessel 24. In this latter case, the second stage vessel is at a lower pressure than the first stage vessel. Variations such as the foregoing may be employed in various embodiments without departing from the invention.
- first stage separation vessel 24, the intercooler 23, the second stage separation vessel 27, and the subcooler 19 are each shown as separate components, whereas the heat exchanger 17 is shown as a single unit.
- the subcooler and second stage vessel may be advantageously combined in a single unit; the intercooler and the first stage vessel likewise may be integrated into a single unit; whereas the heat exchanger may be comprised of separate primary and secondary heat exchangers in which two streams of feed gas mixture are separately cooled by the hydrocarbon-rich first product stream and nitrogen-rich second product stream, respectively.
- FIG. 3 a preferred embodiment of the invention is depicted showing some detail of construction of the various elements as well as additional valves and lines for effecting control of the process.
- the system of FIG. 3 shows a feed conditioning system similar to that of FIG. 1.
- feed gas mixture produced at the wellhead 59 is passed successively through separator 61, regulator 62, chiller 63, filter-separator 64, and dryer system 65 comprising feed conditioning system 60. Thereafter, conditioned feed gas mixture is introduced into the low temperature portions of the process system.
- the feed conditioning steps are not a part of the invention, the design, arrangement, and practical operation of the process depends upon the manner and success with which the conditioning is performed.
- liquids accumulated in separator 61 are removed through drain valve 93; provision is made for cleaning filter-separator 64 by closing valves 95 and 96 while bypassing feed through valve 97. Liquids such as water and light oil accumulated in filter-separator 64 may be drained periodically through valve 98.
- the dryer system 65 consists typically of a set of two or more desiccant or molecular sieve-type dryer vessels shown at 103 and 104, associated valves 99, 100, 101, 102, 105, 106, 107 and 108, and a heater 109.
- the valves are operated such that while one dryer dehydrates the feed gas flowing through the system, the other dryer is regenerated by a reverse flow of hot, dry nitrogen-rich gas from the process. Powdered material entrained in the gas stream as it fiows through the dryer bed is removed from the conditioned feed gas by means of a particle filter 110 which can be cleaned periodically by closing valves 111 and 112 and bypassing the feed gas through valve 113.
- Conditioned feed gas enters the process system proper through line 66 and shutoff valve 114.
- the feed gas stream is cooled in a pair of heat exchangers 67, consisting of primary heat exchanger 115 and secondary heat exchanger 116.
- the division of feed gas mixture between primary and secondary heat exchanger is controlled by balancing valves 117 and 118 in the feed mixture lines at the inlet of each heat exchanger.
- the heat exchangers are typically coiled tube-and-shell type construction, commonly referred to as Giauque- I-Iampson type. The process is amenable also to other forms of heat exchangers.
- the cold feed mixture is further cooled in subcooler 69, installed within the second stage separation vessel 77.
- the subcooler comprises high pressure passages, which are typically coils of tubing indicated at 150, arranged for counterflow heat exchange with upflowing boiling liquid in a low pressure shroud 151.
- the shroud has an inlet pipe 152 for liquid from the first stage and is open at the top to permit escape of warmed liquid 76 and vapor boil-off into the second stage separation vessel 77.
- a spray baffle 149 minimizes entrainment of liquid in the vapor phase.
- Bypass valve 120 in conjunction with valve 121 permits controlled bypassing of the cooled feed mixture around the subcooler for particular purposes such as starting or control of the subcooled feed temperature.
- the subcooled feed passes through line 70 to expander 71, in this case a Joule-Thompson expansion valve.
- the expanded feed then passes through line 72 to intercooler 73 and thence through pipe 126 to first stage separation vessel 74.
- intercooler 73 consists of a mixing tube.
- the high velocity of the expanded feed mixture in line 72 is employed by means of a nozzle 122 directed concentrically toward the throat of a venturi 124.
- the second interstage stream consisting of gas withdrawn from the second stage separation vessel through line 78, is entrained from a chamber 123 by the high velocity feed stream issuing from the nozzle and, as the two streams mix in the venturi, the entrained second interstage stream gains momentum.
- This momentum is converted into additional pressure of the combined stream in a diffuser 125.
- This device is referred to as an eductor pump and has the effect, as explained above, of pressurizing the second interstage stream before passing into the first separation vessel. Consequently, the second separation vessel is maintained at a lower pressure than the first. It should be noted that the slightly lower pressure of the second separation vessel is opposite to the system of FIG. 1 in which a. liquid head maintains the second separation vessel at slightly higher pressure than the first separation vessel.
- the heat exchange between the second interstage stream and the expanded feed mixture takes place by direct mixing in the diffuser of the eductor pump and in the downstream mixing tube (intercooler) 126.
- the mixed two-phase stream is introduced into the first stage separation vessel 74 by a distributor 128.
- the mixture separates into a single hydrocarbon-rich liquid phase 129 and a single nitrogen-rich gaseous phase occupying the space above the liquid 127.
- the composition of these two phases is governed by the temperature of the separation and, accordingly, by the cooling of the feed stream in the heat exchangers and subcooler.
- FIG. 3 depicts a particular arrangement of the distributor 128 designed to facilitate the separation of gaseous and liquid phases entering the vessel.
- the mixed two-phase stream from the mixing I tube 126 enters the annular space between the distributor shroud 154 and the vapor tube 155 below the inlet 156 of the vapor tube.
- the vapor phase rises to enter the vapor tube while the liquid falls to the bottom of the annular space. Separation may be improved by introducing the mixture eccentrically with respect to the distributor shroud in order to cause swirling flow.
- a mist-extractor section employing a suitable packing material 136 is contained between screens 137 and 138 near the top of the first vessel such that a mixture removal of entrained liquid from the nitrogen-rich gas stream is effected.
- the nitrogen-rich second product is withdrawn from the first stage vessel through the dome 159 containing the distributor and through line 85, warmed in the secondary heat exchanger 116 and discharged through line 86, back pressure regulator 87 and line 88 to atmosphere or other use as a by-product.
- Nitrogen-rich gas is available for purging the dryers through valve 131, line 89, heater 109, and valves 107 or 108 with exhaust through valves 101 or 102. Also, nitrogen-rich gas at a temperature below that of the feed mixture is available for cooling feed mixture in the chiller 63 by flowing through valves 132 and 133 in lines 91 and 92, valve 90 being closed for this purpose.
- the hydrocarbon-rich liquid phase 129 in the first stage separation zone is withdrawn as the first interstage stream through line 75, at a rate controlled by valve 79, and into shroud 151 enclosing the subcooler coils 150.
- the liquid stream passing over the coils is partially boiled by heat exchange with the relatively warmer feed mixture in the coils and finally leaves the subcooler at 26 through an opening in the top of the shroud.
- Splash guard 149 prevents excessive entrainment of liquid in the gaseous phase separated from the warm liquid in the vessel and withdrawn as the second interstage stream through line 78, as described previously.
- the operation of the process can be controlled to vary the product purity within limited ranges by changing the temperature at which the second stage separation is effected at a given pressure, a relatively small increase in temperature serving to increase the purity of the liquid product as can be seen by studying the curves of FIG. 2.
- To increase product purity above the nominal level requires more heating of the liquid from the first stage as it passes through the subcooler.
- One practical method of providing more heat in the subcooler is to increase the temperature of the cooled feed mixture entering the subcooler, either by bypassing a portion of one or both of the product streams around the heat exchangers.
- One method of controlling the temperature of the cold feed mixture is to bypass a portion of the nitrogen-rich second product stream through valve 135 to the discharge line 86.
- the hydrocarbon-rich first product stream derived from the liquid phase 80 in the second stage separation vessel is withdrawn through line 81 to product pump 82.
- liquid may be drawn directly from the first stage vessel through line 75 and valve 139 into the .product pump. If desired to retain liquid in the second stage vessel, valve 140 may also be closed.
- an accumulator 141 is provided to dampen the pulsations.
- the stream of first product liquid, pressurized in excess of the required delivery pressure by the pump, is passed through line 83, warmed and vaporized in the primary heat exchanger 115, and discharged through product valve 143 to the delivery line at 84 or a back pressure regulator 142 through to flare stack 94 in the event of over-pressure or in the event that closure of discharge valve 43 becomes necessary.
- a portion of the product pump discharge may be bypassed through valve 145 and line 146 back into the second stage separation vessel to afford one method of controlling the net flow of liquid pumped from the process system.
- Another equivalent method is to controllably vary the pump speed.
- a small sample of the first product can be periodically or continuously withdrawn at 147 for analysis in composition analyzer 148.
- the latter may be a comparative infrared absorption device which continuously monitors the composition of the hydrocarbon-rich product and provides an output signal which can be used for control purposes.
- Alternate analysis methods such as flame pyrometer-based calorimeters may be used to directly monitor product heating valve.
- Another important feature of the process necessary to achieve the substantial condensation of the feed stream is the manner of using the fluid product streams as heat exchange media for the feed stream. To this end, it is important to take advantage of the greatest possible cooling capability of both product streams. This result is achieved in one embodiment of the invention by use of parallel countercurrent heat exchangers.
- the object of this and present conventional processes is to make available in usable form the latent fuel energy of the hydrocarbon.
- the measure of the effectiveness of such processes is the energy made available over and above that consumed in the operation of the process, i.e., the net energy production.
- the net energy production is substantially equal to that of much more complicated fractionation processes entailing much greater capital expenditures.
- subcooling and at least partially liquefying the cooled natural gas mixture by passing at least a portion of the cooled mixture in heat exchange relation to a first interstage stream in subcooler means
- step (b) g. partially vaporizing the first interstage stream by passing at least a portion of the stream in heat exchange relation to the cooled natural gas mixture in the subcooler means as recited in step (b),
- step (d) partially condensing the second interstage stream by passing at least a portion of the stream in heat exchange relation to the expanded mixture in intercooler means as recited in step (d), the partially condensed second interstage stream being introduced into the first stage separation zone as recited in step (e),
- step (f) separately passing at least a portion of the second product stream withdrawn from the first stage sep aration zone as recited in step (f) and at least a portion of the first product stream withdrawn from the second stage separation zone as recited in step (i) in heat exchange relation to the natural gas mixture in heat exchanger means as recited in step (a).
- step (k) of claim 1 is repressurized to a relatively higher pressure in the liquid phase prior to passage through the heat exchanger means.
- step (j) of said claim 1 A process in accordance with claim 1 in which the partial condensation of the second interstage stream as recited in step (j) of said claim 1 is accomplished by direct mixing of at least a portion of said second interstage stream with the expanded subcooled natural gas mixture referred to in step (d) of said claim 1.
- step (a) thereof is carried out by passing separate portions of the natural gas mixture through parallel heat exchanger means in separate heat exchange relation with at least a portion of the first and second product streams passed separately through said parallel heat exchanger means.
- step (j) in claim 1 A process in accordance with claim 5 in which the partial condensation of the second interstage stream as recited in step (j) in claim 1 is accomplished by direct mixing of at least a portion of said second interstage stream with the expanded subcooled natural gas mixture referred to in step (d) of claim 1.
- step (e) of said claim I 9. A process in accordance with claim 1 in which the partially warmed natural gas mixture and the cooled second interstage stream referred to in step (e) of said claim I are subjected to a partial separation of liquid and gaseous phases thereof prior to discharge into said first stage separation zone.
- step (c) of said claim 1 is carried out so as to produce external work.
- step (c) of said claim 1 is carried out with the production of external work and a portion of the liquid phase in the second stage separation zone is removed as a liquid product and the balance of the liquid phase removed from the second stage separation zone is used in the heat exchange step referred to in step (k) of said claim 1.
- intercooler means and means for passing at least a portion of the expanded subcooled natural gas mixture in heat exchange relation to a second interstage stream in the intercooler means
- means for withdrawing from the first stage separation vessel means separate streams of the methan liquid phase as the first interstage stream and the nitrogen-rich gaseous phase as the second product stream and for introducing said first interstage stream into the subcooler means recited in (c) in heat exchange relation to the cooled natural gas mixture,
- means for continuously and separately withdrawing from the second stage separation vessel means separate streams of the methane-rich liquid phase as the first product stream and the nitrogen-rich gaseous phase as the second interstage stream,
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DE (1) | DE2155366C2 (de) |
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US4419114A (en) * | 1982-04-19 | 1983-12-06 | Sappsucker, Inc. | System and method for converting wellhead gas to liquefied petroleum gases (LPG) |
US4462813A (en) * | 1982-04-19 | 1984-07-31 | Sappsucker, Inc. | System and method for converting wellhead gas to liquefied petroleum gases (LPG) |
US4677235A (en) * | 1986-03-07 | 1987-06-30 | Uop Inc. | Production of aromatic hydrocarbons from natural gas |
US5289676A (en) * | 1991-10-23 | 1994-03-01 | Bechtel Group, Inc. | Efficient low temperature solvent removal of acid gases |
US5442924A (en) * | 1994-02-16 | 1995-08-22 | The Dow Chemical Company | Liquid removal from natural gas |
US6220091B1 (en) * | 1997-11-24 | 2001-04-24 | Applied Materials, Inc. | Liquid level pressure sensor and method |
US20080190025A1 (en) * | 2007-02-12 | 2008-08-14 | Donald Leo Stinson | Natural gas processing system |
CN102124290A (zh) * | 2007-12-21 | 2011-07-13 | 国际壳牌研究有限公司 | 生产气化烃物流的方法、液化气态烃物流的方法以及其中冷却和再加温氮基物流且其中液化和再气化烃物流的循环方法 |
US20160090542A1 (en) * | 2013-05-13 | 2016-03-31 | Refrigeration Engineering International Pty Limited | Apparatus and process to condition natural gas for transportation |
US20220049896A1 (en) * | 2020-08-16 | 2022-02-17 | Gtuit, Llc | System and method for treating associated gas |
US11460244B2 (en) * | 2016-06-30 | 2022-10-04 | Baker Hughes Oilfield Operations Llc | System and method for producing liquefied natural gas |
US11628451B2 (en) * | 2019-03-25 | 2023-04-18 | Sustainable Energy Solutions, Llc | Methods and systems for liquid separations |
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FR2443036A1 (fr) * | 1978-11-30 | 1980-06-27 | Orszagos Koolaj Gazipari | Procede de separation de constituants d'un melange de gaz/liquide |
FR2442650B1 (fr) * | 1978-11-30 | 1984-01-20 | Orszagos Koolaj Gazipari | Procede et dispositif de separation de liquide de gaz |
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Cited By (21)
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US4419114A (en) * | 1982-04-19 | 1983-12-06 | Sappsucker, Inc. | System and method for converting wellhead gas to liquefied petroleum gases (LPG) |
US4462813A (en) * | 1982-04-19 | 1984-07-31 | Sappsucker, Inc. | System and method for converting wellhead gas to liquefied petroleum gases (LPG) |
US4677235A (en) * | 1986-03-07 | 1987-06-30 | Uop Inc. | Production of aromatic hydrocarbons from natural gas |
US5289676A (en) * | 1991-10-23 | 1994-03-01 | Bechtel Group, Inc. | Efficient low temperature solvent removal of acid gases |
US5442924A (en) * | 1994-02-16 | 1995-08-22 | The Dow Chemical Company | Liquid removal from natural gas |
US6220091B1 (en) * | 1997-11-24 | 2001-04-24 | Applied Materials, Inc. | Liquid level pressure sensor and method |
US7883569B2 (en) * | 2007-02-12 | 2011-02-08 | Donald Leo Stinson | Natural gas processing system |
US8529666B2 (en) | 2007-02-12 | 2013-09-10 | Donald Leo Stinson | System for dehydrating and cooling a produced gas to remove natural gas liquids and waste liquids |
US20080305019A1 (en) * | 2007-02-12 | 2008-12-11 | Donald Leo Stinson | System for Separating a Waste Material and Hydrocarbon Gas from a Produced Gas and Injecting the Waste Material into a Well |
US20080308273A1 (en) * | 2007-02-12 | 2008-12-18 | Donald Leo Stinson | System for Separating a Waste Material from a Produced Gas and Injecting the Waste Material into a Well |
US20080190025A1 (en) * | 2007-02-12 | 2008-08-14 | Donald Leo Stinson | Natural gas processing system |
US8800671B2 (en) | 2007-02-12 | 2014-08-12 | Donald Leo Stinson | System for separating a waste material from a produced gas and injecting the waste material into a well |
US8388747B2 (en) | 2007-02-12 | 2013-03-05 | Donald Leo Stinson | System for separating a waste material and hydrocarbon gas from a produced gas and injecting the waste material into a well |
US20080302240A1 (en) * | 2007-02-12 | 2008-12-11 | Donald Leo Stinson | System for Dehydrating and Cooling a Produced Gas to Remove Natural Gas Liquids and Waste Liquids |
CN102124290A (zh) * | 2007-12-21 | 2011-07-13 | 国际壳牌研究有限公司 | 生产气化烃物流的方法、液化气态烃物流的方法以及其中冷却和再加温氮基物流且其中液化和再气化烃物流的循环方法 |
CN102124290B (zh) * | 2007-12-21 | 2014-09-24 | 国际壳牌研究有限公司 | 生产气化烃物流的方法、液化气态烃物流的方法以及其中冷却和再加温氮基物流且其中液化和再气化烃物流的循环方法 |
US20160090542A1 (en) * | 2013-05-13 | 2016-03-31 | Refrigeration Engineering International Pty Limited | Apparatus and process to condition natural gas for transportation |
US11460244B2 (en) * | 2016-06-30 | 2022-10-04 | Baker Hughes Oilfield Operations Llc | System and method for producing liquefied natural gas |
US11628451B2 (en) * | 2019-03-25 | 2023-04-18 | Sustainable Energy Solutions, Llc | Methods and systems for liquid separations |
US20220049896A1 (en) * | 2020-08-16 | 2022-02-17 | Gtuit, Llc | System and method for treating associated gas |
US12025373B2 (en) * | 2020-08-16 | 2024-07-02 | Gtuit, Llc | System and method for treating associated gas |
Also Published As
Publication number | Publication date |
---|---|
GB1353967A (en) | 1974-05-22 |
NL173884C (nl) | 1984-03-16 |
DE2155366C2 (de) | 1984-05-24 |
NL7115357A (de) | 1972-05-12 |
NL173884B (nl) | 1983-10-17 |
FR2112543A1 (de) | 1972-06-16 |
FR2112543B1 (de) | 1976-02-13 |
DE2155366A1 (de) | 1972-05-10 |
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