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US20160187057A1 - Liquefied natural gas from rich natural gas - Google Patents

Liquefied natural gas from rich natural gas Download PDF

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Publication number
US20160187057A1
US20160187057A1 US14/977,180 US201514977180A US2016187057A1 US 20160187057 A1 US20160187057 A1 US 20160187057A1 US 201514977180 A US201514977180 A US 201514977180A US 2016187057 A1 US2016187057 A1 US 2016187057A1
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natural gas
gas
liquid
separator
rich
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US14/977,180
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James M. Meyer
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ASPEN ENGINEERING SERVICES LLC
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ASPEN ENGINEERING SERVICES LLC
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Publication of US20160187057A1 publication Critical patent/US20160187057A1/en
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0209Natural gas or substitute natural gas
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L3/00Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10Working-up natural gas or synthetic natural gas
    • C10L3/101Removal of contaminants
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L3/00Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10Working-up natural gas or synthetic natural gas
    • C10L3/101Removal of contaminants
    • C10L3/106Removal of contaminants of water
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0022Hydrocarbons, e.g. natural gas
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003Processes 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
    • F25J1/0047Processes 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 an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/0052Processes 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 an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02Processes 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
    • F25J1/0228Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0229Integration with a unit for using hydrocarbons, e.g. consuming hydrocarbons as feed stock
    • F25J1/023Integration with a unit for using hydrocarbons, e.g. consuming hydrocarbons as feed stock for the combustion as fuels, i.e. integration with the fuel gas system
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02Processes 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
    • F25J1/0228Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0235Heat exchange integration
    • F25J1/0237Heat exchange integration integrating refrigeration provided for liquefaction and purification/treatment of the gas to be liquefied, e.g. heavy hydrocarbon removal from natural gas
    • F25J1/0238Purification or treatment step is integrated within one refrigeration cycle only, i.e. the same or single refrigeration cycle provides feed gas cooling (if present) and overhead gas cooling
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/06Heat exchange, direct or indirect
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/08Drying or removing water
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/48Expanders, e.g. throttles or flash tanks
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/541Absorption of impurities during preparation or upgrading of a fuel
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/542Adsorption of impurities during preparation or upgrading of a fuel
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/543Distillation, fractionation or rectification for separating fractions, components or impurities during preparation or upgrading of a fuel
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00Processes or apparatus involving steps for the removal of impurities
    • F25J2220/60Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
    • F25J2220/62Separating low boiling components, e.g. He, H2, N2, Air
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00Processes or apparatus involving steps for the removal of impurities
    • F25J2220/60Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
    • F25J2220/64Separating heavy hydrocarbons, e.g. NGL, LPG, C4+ hydrocarbons or heavy condensates in general

Definitions

  • This invention relates generally to liquefied natural gas production from rich natural gas.
  • the combination of horizontal drilling and fracking has caused an oil boom across the United States.
  • the horizontal drilling and fracking process co-produces natural gas.
  • the co-produced gas is traditionally compressed and delivered via a pipeline.
  • the pipeline infrastructure has failed to keep pace with shale oil drilling operations. Consequently, large quantities of co-produced gas are flared.
  • lean natural gas gas that has a small amount of propane and heavier hydrocarbons—can be used as a fuel for an internal combustion engine that, in turn, drives an electrical generator. The generated electricity can be used for local power or sold to the electrical grid.
  • natural gas can be compressed and sold as Compressed Natural Gas (CNG).
  • CNG Compressed Natural Gas
  • natural gas can be liquefied into Liquefied Natural Gas (LNG).
  • natural gas can be converted to liquid fuel including methanol.
  • the associated gas produced from horizontal drilling and shale basins is rich gas, because the gas contains substantial amounts of heavier hydrocarbons including propane, butane, hexane, heptane and octane.
  • NGL Natural Gas Liquid
  • Rich gas is unsuitable for known flaring alternatives.
  • the heavier hydrocarbons cause the gas energy content to be too high for internal combustion.
  • the high energy content causes internal combustion engines to knock. Consequently, rich natural gas is unsuitable for LNG production.
  • the LNG-Pure process removes valuable NGL hydrocarbons for sale and distribution while concurrently producing a purified natural gas suitable for LNG, and is an economical alternative to a turboexpander plant.
  • Natural gas is compressed, and then cooled repeatedly until the desired pressure is achieved.
  • Each cycle of compression and cooling is called a compression stage, and all of the compressor stages as a whole are known as a compressor train.
  • Water and NGL can be removed from each stage of compression in a separator or removed at the final stage of compression in a single separator.
  • the remaining residue gas contains too much ethane and other hydrocarbons for motor-fuel grade LNG. Ethane is particularly difficult to remove.
  • a turboexpander plant is typically used to remove ethane. The process and system described herein purifies the residue gas into suitable LNG feedstock without the need for a costly turboexpander plant.
  • the residue gas is purified in two steps. First, the residue gas is passed through a molecular sieve bed to remove the remaining water to prevent ice and solid hydrate formation in the LNG processing equipment. Second, the dehydrated gas is delivered to a refluxed absorber where NGL is removed.
  • the pressure of the absorber is approximately 500 to 600 psi, but can be below the critical pressure of methane. Condenser refrigeration may be integrated within the LNG coldbox, resulting in minimal additional refrigeration cost for the combined LNG-Pure and LNG liquefaction processes. Consequently, motor-fuel grade LNG can be produced from rich natural gas with only a small additional capital cost relative to the LNG liquefaction process. Concurrently, valuable NGL is recovered for a second revenue stream. Alternatively, cooling may be provided by an independent refrigeration system.
  • FIG. 1 is a process flow diagram for the LNG-Pure process for purifying natural gas suitable for fuel-grade LNG.
  • references in the specification to “one embodiment”, “an embodiment”, “another embodiment, “a preferred embodiment”, “an alternative embodiment”, “one variation”, “a variation” and similar phrases mean that a particular feature, structure, or characteristic described in connection with the embodiment or variation, is included in at least an embodiment or variation of the invention.
  • the phrase “in one embodiment”, “in one variation” or similar phrases, as used in various places in the specification, are not necessarily meant to refer to the same embodiment or the same variation.
  • Couple or “coupled” as used in this specification and appended claims refers to an indirect or direct physical connection between the identified elements, components, or objects. Often the manner of the coupling will be related specifically to the manner in which the two coupled elements interact.
  • separatator means a vessel capable of separating a gas phase from a liquid phase into dedicated outlets or a vessel capable of separating a gas phase, hydrocarbon phase and aqueous phase into dedicated outlets.
  • NTL means liquid composed predominantly of paraffinic hydrocarbon containing two to eight carbon atoms.
  • LNG liquid composed predominantly of methane
  • coldbox means a cryogenic heat exchanger or refrigerated condenser.
  • a refrigerated unit can have a single coolant loop and a single cooled fluid loop, in some cases, the coldbox can include one or more of each fluid loop.
  • the coldbox can include two cooled fluid loops (e.g. item 6 in FIG. 1 ).
  • vent gas means gas produced downstream of a Joule-Thompson or other pressure reducing cooling valve.
  • fuel gas means gas removed from the top of the stabilizer.
  • the fuel gas can include methane and ethane.
  • FIG. 1 depicts a LNG system in which rich natural gas 1 flows into molecular sieve bed 2 to remove water from the natural gas.
  • the rich natural gas 1 can be obtained through a conventional compressor train or other suitable process.
  • the rich natural gas 1 can be obtained by condensation in one or more coolers as more fully described in U.S. Application Publication No. 2015-0344788-A1 which is incorporated herein by reference.
  • the rich natural gas 1 can be provided at conditions of about 500 to about 650 psi and 60 to 100° F., such as 600 psi and 70° F. Such conditions are typically maintained in the dry natural gas 3 and in the refluxed absorber 4 .
  • the rich natural gas can have as much as 2 vol % water, and most often from 0.5 to 1.5 vol % water.
  • dry natural gas can generally have less than 0.05 vol % water, and in most cases less than about 0.1 vol % water.
  • the dry natural gas 3 from molecular sieve bed 2 flows into the refluxed absorber 4 .
  • Natural gas and NGL flow, counter-currently through the refluxed absorber 4 .
  • the refluxed absorber can often be multistage separation column containing random packing, structure packing or trays.
  • the packed bed absorber can have from 5 to 10 theoretical stages.
  • the refluxed absorber 4 also does not include a reboiler.
  • Purified natural gas 5 flows from the top of refluxed absorber 4 into a section of LNG coldbox 6 .
  • the purified natural gas 5 can typically have a composition which is rich in methane, and can often have 3 to 10% ethane and 1 to 6% nitrogen.
  • the LNG coldbox 6 can typically operate sufficient to partially liquefied stream 5 . Typically this entails a temperature reduction to about ⁇ 100 to ⁇ 130° F. Typically a suitable refrigerant can be used to withdraw heat from the coldbox 6 .
  • a liquid/vapor mixture 7 is withdrawn from the LNG coldbox 6 , and the vapor and liquid are separated in overhead separator 9 .
  • the resulting liquid stream 10 comprising primarily methane, is refluxed to refluxed absorber 4 .
  • the liquid stream can generally have at least 75 mol % methane, and often more than 85 mol % methane, at a temperature between typically ⁇ 100° F. and ⁇ 130° F. and a pressure typically between 500 to about 650 psi.
  • Purified natural gas 8 flows from the top of overhead separator 9 back into coldbox 6 .
  • the purified natural gas 8 can typically have from 70 to 95 vol % methane, and most often from 85 to 90 vol % methane.
  • the purified natural gas 8 can also have a temperature from ⁇ 110 to ⁇ 130° F. Additional cooling in coldbox 6 produces stream 11 to achieve a fully liquefied precursor to LNG. Stream 11 is cooled sufficiently to prevent large quantities of methane from evaporating when stream 11 is depressurized. Stream 11 can be cooled even further by Joule Thompson valve 22 . Although operating parameters can vary, stream 19 can have a temperature from ⁇ 250 to ⁇ 270° F. Stream 19 from Joule Thompson valve 22 can also consist of a two-phase mixture of LNG and gas. The two-phase mixture 19 is separated in separator 20 . Vent gas 21 is removed from the top of separator 20 . Motor-fuel grade LNG 23 flows from the bottom of separator 20 . Although actual product LNG compositions can vary based on feedstock and operating parameters, the motor-fuel grade LNG 23 can typically have 90 to 99 vol % methane, and often more than 93 vol % methane.
  • NGL 12 from refluxed absorber 4 is ethane rich, e.g. typically from 30 to 60 vol % ethane although other components such as propane and butane can also be present.
  • the NGL 12 is fed to stabilizer 13 in order to remove a majority of the ethane.
  • the stabilizer can generally be operated at 100 to 200 psi.
  • the stabilizer can be a vapor/liquid mass transfer column with 5 to 10 theoretical stages.
  • NGL 14 flows from the bottom of stabilizer 13 into reboiler 15 .
  • Reboiler 15 vaporizes part of the NGL 14 .
  • the reboiler 15 can be operated such that the ethane in the NGL is controlled to a desired composition, typically 2 to 8 mole %.
  • the gas 16 from reboiler 15 flows into stabilizer 13 .
  • the countercurrent flow of liquid and gas in stabilizer 13 purifies NGL 17 that flows from reboiler 14 to NGL storage tank 18 .
  • the purified NGL 17 can typically have a composition of mole percent ethane, 2 to 8 and most often 3 to 5 mole percent ethane.
  • Fuel gas 14 flows out of the top of stabilizer 13 . Although conditions can vary, fuel gas 14 can have 15 to 40 vol % and most often 20 to 30 vol % methane.
  • the molecular sieve bed 2 can be any suitable water scavenger unit.
  • suitable water scavenging units can include water retention membranes, emulsive beds and the like.
  • the Joule Thompson valve 22 can be any pressure reducing valve or mechanism which allows a reduction in pressure to form the two phase mixture.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

Rich natural gas is dried in a water scavenger unit, and then purified in a refluxed absorber. The refluxed stream for the absorber is a stream of predominantly methane condensed by cryogenic refrigeration. The refluxed absorber is operated below the critical point of methane, to allow condensation to occur. Liquefied natural gas is condensed in a cryogenic box, and then further cooled. Natural gas liquid from the refluxed absorber is stabilized for storage and transport.

Description

    RELATED APPLICATION
  • This application claims priority to and incorporates by reference U.S. Provisional Patent Application No. 62/096,319, filed Dec. 23, 2014 and having the same inventor as the present application.
  • FIELD OF INVENTION
  • This invention relates generally to liquefied natural gas production from rich natural gas.
  • BACKGROUND
  • The combination of horizontal drilling and fracking has caused an oil boom across the United States. The horizontal drilling and fracking process co-produces natural gas. The co-produced gas is traditionally compressed and delivered via a pipeline. However, the pipeline infrastructure has failed to keep pace with shale oil drilling operations. Consequently, large quantities of co-produced gas are flared.
  • There are several known alternatives to flaring. First, lean natural gas—gas that has a small amount of propane and heavier hydrocarbons—can be used as a fuel for an internal combustion engine that, in turn, drives an electrical generator. The generated electricity can be used for local power or sold to the electrical grid. Second, natural gas can be compressed and sold as Compressed Natural Gas (CNG). Third, natural gas can be liquefied into Liquefied Natural Gas (LNG). Fourth, natural gas can be converted to liquid fuel including methanol. However, the associated gas produced from horizontal drilling and shale basins is rich gas, because the gas contains substantial amounts of heavier hydrocarbons including propane, butane, hexane, heptane and octane. The aforementioned hydrocarbons are known as Natural Gas Liquid (NGL). Rich gas is unsuitable for known flaring alternatives. The heavier hydrocarbons cause the gas energy content to be too high for internal combustion. Specifically, the high energy content causes internal combustion engines to knock. Consequently, rich natural gas is unsuitable for LNG production. The LNG-Pure process removes valuable NGL hydrocarbons for sale and distribution while concurrently producing a purified natural gas suitable for LNG, and is an economical alternative to a turboexpander plant.
  • SUMMARY
  • Natural gas is compressed, and then cooled repeatedly until the desired pressure is achieved. Each cycle of compression and cooling is called a compression stage, and all of the compressor stages as a whole are known as a compressor train. Water and NGL can be removed from each stage of compression in a separator or removed at the final stage of compression in a single separator. The remaining residue gas contains too much ethane and other hydrocarbons for motor-fuel grade LNG. Ethane is particularly difficult to remove. A turboexpander plant is typically used to remove ethane. The process and system described herein purifies the residue gas into suitable LNG feedstock without the need for a costly turboexpander plant.
  • The residue gas is purified in two steps. First, the residue gas is passed through a molecular sieve bed to remove the remaining water to prevent ice and solid hydrate formation in the LNG processing equipment. Second, the dehydrated gas is delivered to a refluxed absorber where NGL is removed. The pressure of the absorber is approximately 500 to 600 psi, but can be below the critical pressure of methane. Condenser refrigeration may be integrated within the LNG coldbox, resulting in minimal additional refrigeration cost for the combined LNG-Pure and LNG liquefaction processes. Consequently, motor-fuel grade LNG can be produced from rich natural gas with only a small additional capital cost relative to the LNG liquefaction process. Concurrently, valuable NGL is recovered for a second revenue stream. Alternatively, cooling may be provided by an independent refrigeration system.
  • DRAWINGS
  • FIG. 1 is a process flow diagram for the LNG-Pure process for purifying natural gas suitable for fuel-grade LNG.
  • This drawing is provided to illustrate various aspects of the invention and is not intended to be limiting of the scope in terms of dimensions, materials, configurations, arrangements or proportions unless otherwise limited by the claims.
  • DETAILED DESCRIPTION
  • While these exemplary embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, it should be understood that other embodiments may be realized and that various changes to the invention may be made without departing from the spirit and scope of the present invention. Thus, the following more detailed description of the embodiments of the present invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the present invention, to set forth the best mode of operation of the invention, and to sufficiently enable one skilled in the art to practice the invention. Accordingly, the scope of the present invention is to be defined solely by the appended claims.
  • Terminology
  • The terms and phrases as indicated in quotation marks (“ ”) in this section are intended to have the meaning ascribed to them in this Terminology section applied to them throughout this document, including in the claims, unless clearly indicated otherwise in context. Further, as applicable, the stated definitions are to apply, regardless of the word or phrase's case, to the singular and plural variations of the defined word or phrase.
  • The term “or” as used in this specification and the appended claims is not meant to be exclusive; rather the term is inclusive, meaning either or both.
  • References in the specification to “one embodiment”, “an embodiment”, “another embodiment, “a preferred embodiment”, “an alternative embodiment”, “one variation”, “a variation” and similar phrases mean that a particular feature, structure, or characteristic described in connection with the embodiment or variation, is included in at least an embodiment or variation of the invention. The phrase “in one embodiment”, “in one variation” or similar phrases, as used in various places in the specification, are not necessarily meant to refer to the same embodiment or the same variation.
  • The term “couple” or “coupled” as used in this specification and appended claims refers to an indirect or direct physical connection between the identified elements, components, or objects. Often the manner of the coupling will be related specifically to the manner in which the two coupled elements interact.
  • The term “separator” means a vessel capable of separating a gas phase from a liquid phase into dedicated outlets or a vessel capable of separating a gas phase, hydrocarbon phase and aqueous phase into dedicated outlets.
  • The term “NGL” means liquid composed predominantly of paraffinic hydrocarbon containing two to eight carbon atoms.
  • The term “LNG” means liquid composed predominantly of methane.
  • The term “coldbox” means a cryogenic heat exchanger or refrigerated condenser. Although a refrigerated unit can have a single coolant loop and a single cooled fluid loop, in some cases, the coldbox can include one or more of each fluid loop. For example, in one case, the coldbox can include two cooled fluid loops (e.g. item 6 in FIG. 1).
  • The term “vent gas” means gas produced downstream of a Joule-Thompson or other pressure reducing cooling valve.
  • The term “fuel gas” means gas removed from the top of the stabilizer. Generally, the fuel gas can include methane and ethane.
  • LNG-Pure Process
  • FIG. 1 depicts a LNG system in which rich natural gas 1 flows into molecular sieve bed 2 to remove water from the natural gas. The rich natural gas 1 can be obtained through a conventional compressor train or other suitable process. In one example, the rich natural gas 1 can be obtained by condensation in one or more coolers as more fully described in U.S. Application Publication No. 2015-0344788-A1 which is incorporated herein by reference. Regardless, the rich natural gas 1 can be provided at conditions of about 500 to about 650 psi and 60 to 100° F., such as 600 psi and 70° F. Such conditions are typically maintained in the dry natural gas 3 and in the refluxed absorber 4. The rich natural gas can have as much as 2 vol % water, and most often from 0.5 to 1.5 vol % water.
  • Subsequent to dewatering, dry natural gas can generally have less than 0.05 vol % water, and in most cases less than about 0.1 vol % water. The dry natural gas 3 from molecular sieve bed 2 flows into the refluxed absorber 4. Natural gas and NGL flow, counter-currently through the refluxed absorber 4. Although other absorber configurations can be used, the refluxed absorber can often be multistage separation column containing random packing, structure packing or trays. In one example, the packed bed absorber can have from 5 to 10 theoretical stages. Advantageously, the refluxed absorber 4 also does not include a reboiler. Purified natural gas 5 flows from the top of refluxed absorber 4 into a section of LNG coldbox 6. The purified natural gas 5 can typically have a composition which is rich in methane, and can often have 3 to 10% ethane and 1 to 6% nitrogen. The LNG coldbox 6 can typically operate sufficient to partially liquefied stream 5. Typically this entails a temperature reduction to about −100 to −130° F. Typically a suitable refrigerant can be used to withdraw heat from the coldbox 6.
  • A liquid/vapor mixture 7 is withdrawn from the LNG coldbox 6, and the vapor and liquid are separated in overhead separator 9. The resulting liquid stream 10, comprising primarily methane, is refluxed to refluxed absorber 4. The liquid stream can generally have at least 75 mol % methane, and often more than 85 mol % methane, at a temperature between typically −100° F. and −130° F. and a pressure typically between 500 to about 650 psi. Purified natural gas 8 flows from the top of overhead separator 9 back into coldbox 6. The purified natural gas 8 can typically have from 70 to 95 vol % methane, and most often from 85 to 90 vol % methane. At this stage, the purified natural gas 8 can also have a temperature from −110 to −130° F. Additional cooling in coldbox 6 produces stream 11 to achieve a fully liquefied precursor to LNG. Stream 11 is cooled sufficiently to prevent large quantities of methane from evaporating when stream 11 is depressurized. Stream 11 can be cooled even further by Joule Thompson valve 22. Although operating parameters can vary, stream 19 can have a temperature from −250 to −270° F. Stream 19 from Joule Thompson valve 22 can also consist of a two-phase mixture of LNG and gas. The two-phase mixture 19 is separated in separator 20. Vent gas 21 is removed from the top of separator 20. Motor-fuel grade LNG 23 flows from the bottom of separator 20. Although actual product LNG compositions can vary based on feedstock and operating parameters, the motor-fuel grade LNG 23 can typically have 90 to 99 vol % methane, and often more than 93 vol % methane.
  • NGL 12 from refluxed absorber 4 is ethane rich, e.g. typically from 30 to 60 vol % ethane although other components such as propane and butane can also be present. The NGL 12 is fed to stabilizer 13 in order to remove a majority of the ethane. The stabilizer can generally be operated at 100 to 200 psi. The stabilizer can be a vapor/liquid mass transfer column with 5 to 10 theoretical stages. NGL 14 flows from the bottom of stabilizer 13 into reboiler 15. Reboiler 15 vaporizes part of the NGL 14. Typically the reboiler 15 can be operated such that the ethane in the NGL is controlled to a desired composition, typically 2 to 8 mole %. The gas 16 from reboiler 15 flows into stabilizer 13. The countercurrent flow of liquid and gas in stabilizer 13 purifies NGL 17 that flows from reboiler 14 to NGL storage tank 18. The purified NGL 17 can typically have a composition of mole percent ethane, 2 to 8 and most often 3 to 5 mole percent ethane. Fuel gas 14 flows out of the top of stabilizer 13. Although conditions can vary, fuel gas 14 can have 15 to 40 vol % and most often 20 to 30 vol % methane.
  • ALTERNATIVE EMBODIMENTS AND VARIATIONS
  • The various embodiments and variations thereof, illustrated in the accompanying FIGURES and/or described above, are merely exemplary and are not meant to limit the scope of the invention. It is to be appreciated that numerous other variations of the invention have been contemplated, as would be obvious to one of ordinary skill in the art, given the benefit of this disclosure. All variations of the invention that read upon appended claims are intended and contemplated to be within the scope of the invention.
  • For instance, for some embodiments, an independent refrigeration system may be used instead of the LNG coldbox 8. Similarly, the molecular sieve bed 2 can be any suitable water scavenger unit. Non-limiting examples of suitable water scavenging units can include water retention membranes, emulsive beds and the like. In another optional aspect, the Joule Thompson valve 22 can be any pressure reducing valve or mechanism which allows a reduction in pressure to form the two phase mixture.

Claims (12)

Having described my invention, I claim:
1. A liquefied natural gas (LNG) system comprising:
a water scavenger unit fluidly connected to a rich natural gas source conduit and adapted to produce a dry natural gas;
a refluxed absorber disposed downstream of said water scavenger unit to receive the dry natural gas and form a purified natural gas and a natural gas liquid (NGL);
a refrigeration unit disposed downstream of said refluxed absorber configured to receive the purified natural gas from said refluxed absorber;
a first separator disposed downstream of said refrigeration unit configured to receive a first liquid/gas mixture from the refrigeration unit and separate liquid and gas phases into a first separator liquid outlet and a first separator gas outlet, wherein the first separator liquid outlet is fluidly connected to the refluxed absorber and the first separator gas outlet is fluidly connected to the refrigeration unit;
a pressure reduction valve disposed downstream of said refrigeration unit configured to receive liquid from said refrigeration unit;
a second separator disposed downstream of said pressure reduction valve configured to receive a second liquid/gas mixture from said pressure reduction valve and separate the liquid and gas phases into a second separator liquid outlet and a second separator gas outlet; and
an NGL upgrader disposed downstream of said refluxed absorber receiving the NGL, configured to remove a stabilizer gas from a top of said NGL upgrader and a hydrocarbon liquid from a bottom of said NGL upgrader.
2. The system of claim 1, wherein the water scavenger unit is a molecular sieve bed.
3. The system of claim 1, wherein the refrigeration unit is a coldbox.
4. The system of claim 3, wherein the first separator gas outlet is fluidly connected to the coldbox.
5. The system of claim 1, wherein the refrigeration unit is a cooler.
6. The system of claim 1, wherein the refluxed absorber does not have a reboiler.
7. The system of claim 1, wherein the pressure reduction valve is a Joule Thompson valve.
8. A process of producing liquefied natural gas from rich natural gas, comprising:
reducing water from a rich natural gas to form a dry natural gas;
passing the dry natural gas through a refluxed absorber to form a purified natural gas and a natural gas liquid;
cooling the purified natural gas to form a first liquid/gas mixture;
separating the first liquid/gas mixture into a methane rich liquid and a further purified natural gas;
refluxing the methane rich liquid to the refluxed absorber;
stabilizing the natural gas liquid to form a fuel gas and a purified natural gas liquid;
cooling the further purified natural gas and expanding the further purified natural gas to form a second liquid/gas mixture; and
separating the second liquid/gas mixture to form a vent gas and the liquefied natural gas.
9. The process of claim 8, wherein the refluxed absorber does not use a reboiler.
10. The process of claim 8, wherein the dry natural gas is formed using a molecular sieve bed.
11. The process of claim 8, wherein the stabilizing further includes a reboiler.
12. The process of claim 8, wherein the rich natural gas and dry natural gas are provided at conditions of 500 to 650 psi and 60 to 100° F.
US14/977,180 2014-12-23 2015-12-21 Liquefied natural gas from rich natural gas Abandoned US20160187057A1 (en)

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