US20110094264A1 - Producing purified hydrocarbon gas from a gas stream comprising hydrocarbons and acidic contaminants - Google Patents

Producing purified hydrocarbon gas from a gas stream comprising hydrocarbons and acidic contaminants Download PDF

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US20110094264A1
US20110094264A1 US12/995,411 US99541109A US2011094264A1 US 20110094264 A1 US20110094264 A1 US 20110094264A1 US 99541109 A US99541109 A US 99541109A US 2011094264 A1 US2011094264 A1 US 2011094264A1
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stream
gas
reheated
vessel
acidic contaminants
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Henricus Abraham GEERS
William David Prince
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Shell USA Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25J3/02—Processes 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
    • F25J3/0204—Processes 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
    • F25J3/0209—Natural gas or substitute natural gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25J3/02—Processes 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
    • F25J3/0228—Processes 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 separated product stream
    • F25J3/0233—Processes 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 separated product stream separation of CnHm with 1 carbon atom or more
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25J3/02—Processes 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
    • F25J3/0228—Processes 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 separated product stream
    • F25J3/0266—Processes 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 separated product stream separation of carbon dioxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25J3/0605—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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25J3/0635—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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25J3/067—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 carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/02—Processes or apparatus using separation by rectification in a single pressure main column system
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/20—Processes or apparatus using other separation and/or other processing means using solidification of components
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
    • F25J2220/64—Separating heavy hydrocarbons, e.g. NGL, LPG, C4+ hydrocarbons or heavy condensates in general
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
    • F25J2220/66—Separating acid gases, e.g. CO2, SO2, H2S or RSH
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
    • F25J2220/68—Separating water or hydrates
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25J2240/00—Processes or apparatus involving steps for expanding of process streams
    • F25J2240/02—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to a process for the removal of acidic contaminants from a gas stream comprising hydrocarbons and acidic contaminants.
  • the invention especially relates to a process in which carbon dioxide and hydrogen sulphide are removed from natural gas that contains hydrocarbons and acidic contaminants.
  • Such a process is known from WO-A 2004/070297.
  • This document discloses a process in which a natural gas stream comprising hydrocarbons and acidic contaminants is first cooled in a first vessel to remove water from the natural gas, and subsequently the natural gas is further cooled in a second vessel to solidify acidic contaminants or dissolve such contaminants in a liquid, which contaminants are removed so that a purified natural gas is recovered.
  • solid acidic contaminants may block the outlet of the second vessel.
  • a warm liquid comprising natural gas condensates may be introduced into the lower part of the vessel so that at least part of the solid acidic contaminants melts.
  • WO-A 2007/030888 a similar process for the removal of acidic contaminants from natural gas is described.
  • the formed solid acidic contaminants are heated to a temperature above the melting point temperature of the contaminants by means of a heat exchanger in the form of a bundle coil.
  • the fluid that is passed through the bundle coil can be the natural gas or any other process stream.
  • a liquid process stream derived from another part of the process can be mixed with the solid acidic contaminants to melt these contaminants.
  • the addition of a relatively warm stream to the solid acidic contaminants has the advantage that it provides a more efficient and direct heat transfer than the indirect heat exchange via a bundle coil.
  • the invention provides a process for producing purified hydrocarbon gas from a gas stream comprising hydrocarbons and acidic contaminants, which process comprises the steps:
  • the reheated recycle stream is recycled to the vessel, to provide heat to the solid and optionally liquid contaminants to melt at least part of the solid acidic contaminants.
  • the process can be carried out also when no condensates are available.
  • the present process avoids the need to provide for a complex heat exchanger in the lower part of he vessel.
  • the gas stream can be any stream of gas that comprises acidic contaminants and hydrocarbons.
  • a natural gas stream i.e., a gas stream that contains significant amounts of methane and that has been produced from a subsurface reservoir. It includes a methane natural gas stream, an associated gas stream or a coal bed methane stream.
  • the amount of the hydrocarbon fraction in such a gas stream is suitably from 10 to 85 mol % of the gas stream, preferably from 25 to 80 mol %.
  • the hydrocarbon fraction of the natural gas stream comprises at least 75 mol % of methane, preferably 90 mol %.
  • the hydrocarbon fraction in the natural gas stream may suitably contain from 0 to 20 mol %, suitably from 0.1 to 10 mol %, of C 2 - C 6 compounds.
  • the gas stream may also comprise up to 20 mol %, suitably from 0.1 to 10 mol % of nitrogen, based on the total gas stream.
  • Gas streams such as natural gas streams, may become available at a temperature of from ⁇ 5 to 150° C. and a pressure of from 10 to 700 bar, suitably from 20 to 200 bar.
  • the gas stream comprises suitably hydrogen sulphide and/or carbon dioxide as acidic contaminants. It is observed that also minor amounts of other contaminants may be present, e.g. carbon oxysulphide, mercaptans, alkyl sulphides and aromatic sulphur-containing compounds. The major part of these components will also be removed in the process of the present invention.
  • the amount of hydrogen sulphide in the gas stream containing methane is suitably in the range of from 5 to 40 volume % of the gas stream, preferably from 20 to 35 volume % and/or the amount of carbon dioxide is in the range of from 10 to 90 vol %, preferably from 20 to 75 vol %, based on the total gas stream. It is observed that the present process is especially suitable for gas streams comprising large amounts of contaminants, e.g. 10 vol % or more, suitably between 15 and 90 vol %.
  • Gas stream containing the large amounts of contaminants as described above cannot be processed using conventional techniques as amine extraction techniques as they will become extremely expensive, especially due to the large amounts of heat needed for the regeneration of loaded amine solvent.
  • the gas stream, and in particular natural gas streams produced from a subsurface formation may typically contain water.
  • water In order to prevent the formation of gas hydrates in the present process, at least part of the water is suitably removed. Therefore, the natural gas stream that is used in the present process has preferably been dehydrated. This can be done by conventional processes.
  • a suitable process is the one described in WO-A 2004/070297.
  • Other processes for forming methane hydrates or for drying natural gas are also possible.
  • Other dehydration processes include treatment with molecular sieves or drying processes with glycol or methanol.
  • water is removed until the amount of water in the natural gas stream comprises at most 50 ppmw, preferably at most 20 ppmw, more preferably at most 1 ppmw of water, based on the total natural gas stream.
  • acidic contaminants that are usually present in natural gas streams include hydrogen sulphide and carbon dioxide. It is also possible that the natural gas stream contains other components, including ethane, propane and hydrocarbons with four or more carbon atoms, even after an optional earlier recovery of condensates. It will be appreciated that when a portion of acidic contaminants, e.g., carbon dioxide, solidifies in the cooling stage, other components, e.g., hydrogen sulphide and hydrocarbons other than methane, may liquefy. The liquid components are suitably removed together with the solid acidic contaminants from the vapour.
  • the gas stream is cooled.
  • the cooling may be effected by any known method, such as indirect heat exchange and expansion.
  • a direct heat exchange e.g., by spraying with a cold liquid, as shown in WO-A 2004/070297, is also possible.
  • expansion causes a lowering of temperature, so that cooling may be achieved by expansion and adapting pressure.
  • the expansion is done by isenthalpic expansion, preferably isenthalpic expansion over an orifice or a valve, especially a Joule-Thomson valve or a series of Joule-Thomson valves.
  • the expansion is done by nearly isentropic expansion, especially by means of an expander, preferably a turbo expander, or a laval nozzle.
  • the cooling may be conducted in several steps. It is preferred that the gas stream is subjected to heat exchange with one or more other cold process streams or external streams. Cold external streams may be suitably streams from an LNG (liquefied natural gas) plant, such a cold LNG stream or a refrigerant stream, or from an air separation unit.
  • LNG liquefied natural gas
  • One suitable stream comprises the purified hydrocarbon gas.
  • the cooling stage of the natural gas stream comprises one or more expansion steps.
  • turbo-expanders so-called Joule-Thomson valves and venturi tubes. It is preferred to at least partly cool the gas stream over a turbo-expander, releasing energy.
  • One advantageous effect of using the turbo-expander is that the energy that is released in the turbo-expander can suitably be used for compressing at least part of the purified hydrocarbon gas. Since the stream of the purified hydrocarbon gas is smaller than the gas stream now that acidic contaminants have been removed, the energy is suitably such that the purified hydrocarbon gas may be compressed to an elevated pressure that makes it suitable for transport in a pipeline.
  • the cooling steps eventually lead to the desired temperature at which acidic contaminants solidify.
  • the natural gas stream also may comprise hydrocarbons other than methane it is preferred to cool the natural gas stream, suitably by expansion, to a temperature below the dew point of propane. In this way the vaporous natural gas stream will develop liquid hydrocarbons, including propane, which can subsequently be recovered easily from the vapour.
  • the cooling in several steps, e.g., by indirect heat exchange and/or expansion. It is also possible to solidify by spraying with a cold liquid, as shown in WO-A 2004/070297.
  • solid acidic contaminants are obtained in a final expansion step.
  • the final expansion step is preferably achieved over a Joule-Thomson valve. Therefore, preferably, in a first step, which may be achieved by various intermediate steps and various methods, the gas stream is cooled to a temperature ranging from 1 to 40° C. above the freeze out temperature of the first acidic contaminant to freeze out, the freeze out temperature being the temperature at which solid contaminants are formed.
  • the cooling is effected till from 2 to 10° C. above the freeze out temperature.
  • the gas stream is preferably cooled to the temperature at which a mixture of solid and/or liquid acidic contaminants and a vapour comprising gaseous hydrocarbons are formed by expansion over a valve.
  • the gas stream is partly or completely liquid before being expanded over the valve, and solid contaminants are formed upon expansion. This ensures better separation performance in the vessel.
  • the gas stream is expanded from a pressure ranging from 40 to 200 bar to a pressure of 10 to 40 bar. Expansion over this pressure range suitably causes that solid acidic contaminants are formed. It will be appreciated by the person skilled in the art that at the formation of solid acidic contaminants also liquid acidic contaminants may be formed and/or hydrocarbons may condense. These liquid components are suitably separated together with the solid acidic contaminants.
  • the solidification of acidic contaminants may take place very rapidly, especially upon expansion over a valve, thereby forming the mixture comprising solid and optionally liquid acidic contaminants and a vapour comprising gaseous hydrocarbons.
  • the mixture is passed into a vessel wherein the separation between solid acidic contaminants and vapour takes place. By gravity the solid acidic contaminants, and any liquid that is formed, drop to the bottom of the vessel. After such separation the solid acidic contaminants can be removed from the process.
  • the purified hydrocarbon gas that is being recovered after the separation step can be used as product.
  • the recovered purified hydrocarbon gas may also be subjected to further treatment and/or purification.
  • the purified hydrocarbon gas may be subjected to fractionation.
  • the purified hydrocarbon gas is natural gas intended for pipeline transportation or for producing liquefied natural gas (LNG)
  • LNG liquefied natural gas
  • the purified natural gas may further purified. Further purification can for example be done in an additional cryogenic distillation column, suitably with a bottom temperature between ⁇ 30 and 10° C., preferably between ⁇ 10 and 5° C.
  • a reboiler may be present to supply heat to the column.
  • the top temperature column is between ⁇ 110 and ⁇ 80° C., preferably between ⁇ 100 and ⁇ 90° C.
  • a condenser may be present, to provide reflux and a liquefied (LNG) product.
  • Suitable absorbing liquids may comprise chemical solvents or physical solvents or mixtures thereof.
  • a preferred absorbing liquid comprises a chemical solvent and/or a physical solvent, suitably as an aqueous solution.
  • Suitable chemical solvents are primary, secondary and/or tertiary amines, including sterically hindered amines.
  • a preferred chemical solvent comprises a secondary or tertiary amine, preferably an amine compound derived from ethanolamine, more especially DIPA, DEA, MMEA (monomethyl-ethanolamine), MDEA (methyldiethanolamine) TEA (triethanolamine), or DEMEA (diethyl-monoethanolamine), preferably DIPA or MDEA. It is believed that these chemical solvents react with acidic compounds such as CO 2 and H 2 S.
  • Suitable physical solvents include tetramethylene sulphone (sulpholane) and derivatives, amides of aliphatic carboxylic acids, N-alkyl pyrrolidone, in particular N-methyl pyrrolidine, N-alkyl piperidones, in particular N-methyl piperidone, methanol, ethanol, ethylene glycol, polyethylene glycols, mono- or di(C 1 -C 4 )alkyl ethers of ethylene glycol or polyethylene glycols, suitably having a molecular weight from 50 to 800, and mixtures thereof.
  • the preferred physical solvent is sulfolane. It is believed that CO 2 and/or H 2 S are taken up in the physical solvent and thereby removed.
  • Other treatments may include a further compression, when the purified hydrocarbon gas is wanted at a higher pressure. If the amounts of acidic contaminants in the purified hydrocarbon gas are undesirably high, the purified hydrocarbon gas may be subjected to one or more repetitions of the present process.
  • the purified natural gas can be processed further in known manners, for example by catalytic or non-catalytic combustion to produce synthesis gas, to generate electricity, heat or power, or for the production of liquefied natural gas (LNG), or for residential use.
  • LNG liquefied natural gas
  • It is an advantage of the present process enables purification of natural gas comprising substantial amounts of acidic contaminants, resulting in purified natural gas comprising low levels of contaminants, especially of sulphur contaminants.
  • the production of LNG from such natural gas which would be very difficult if not impossible by conventional processes, is made possible.
  • the invention also provides LNG obtained from liquefying purified natural gas obtained by the process.
  • the LNG thus-obtained typically has very low concentrations of contaminants other than natural gas.
  • At least a part of the heated contaminant-rich stream is reheated to yield a reheated recycle stream.
  • the recycle of part of the reheated recycle stream is meant to melt at least part of the solid acidic contaminants in the vessel so that blocking is prevented and removal of the acidic contaminants is facilitated.
  • the heat that is being provided by the recycled reheated recycle stream is such that it causes the melting of all solid acidic contaminants. The skilled person may achieve this by selecting the desired temperature of the reheated recycle stream and/or the amount of reheated recycle stream.
  • the part of the contaminant-rich stream that is reheated to form the reheated recycle stream is preferably heated to form a liquid stream, more preferably without any solid acidic contaminant.
  • the heating up is done to a temperature well above the melting point of the solid acidic contaminants, such as at least 5° C. above the highest melting point.
  • the heat of the relatively warm liquid will melt at least part of the solid acidic contaminants in the vessel. It is even more preferred that the part of the heated contaminant-rich stream that is reheated to form the reheated recycle stream is heated to such a temperature that the stream becomes at least partly vaporous.
  • the vessel is preferably provided with internals. These internals will increase the contacting surface between cold solids and warm fluid as well as provide residence time to the components in the vessel so that acidic contaminants may condense and/or solidify and liquid hydrocarbons may be evaporated.
  • the skilled person may select the internals from a variety of possibilities. Very suitable are sieve plates, perforated plates or bubble trays. Their construction is relatively easy in the cryogenic environment of the vessel, whereas the contacting performance is very good.
  • An even more preferred embodiment comprises a vessel that has been provided with at least one deflecting means that has been arranged in the interior of the vessel. Downwards-falling solid and liquid acidic contaminants are distributed more homogeneously over the cross-section of the vessel, thereby improving the separation between solid and acidic contaminants on the one hand and the gaseous hydrocarbons on the other.
  • the shape of the deflecting means can be selected from a variety of shapes; the deflecting means may, e.g., be square, circular or of a ring-shape.
  • the deflecting means has downwards-directed slopes to avoid build up of solid material on the deflecting means.
  • a very suitable shape is a cone or a combination of a cone and an inverted cone. Whereas the cone ensures a smooth distribution of solid and liquid material, the inverted cone provides for a suitable passage for upwards-flowing gases.
  • the deflecting means suitably covers from 5 to 75% of the cross-section of the vessel.
  • the reheating of part of the heated contaminant-rich stream requires energy.
  • a part of the heated contaminant-rich stream is separated and this part of the heated contaminant-rich stream is reheated to form the reheated recycle stream.
  • the size of the part of the heated contaminant-rich stream that is separated can be selected by the skilled person depending on conditions such as the temperature of the reheated recycle stream and the amount and nature of the solid acidic contaminants.
  • the part of the heated contaminant-rich stream that is separated is selected such that the reflux ratio ranges from 0.5 to 10. This embodiment is especially advantageous when the part of the heated contaminant-rich stream is heated up to form a vaporous recycle stream.
  • substantially the entire heated contaminant-rich stream that is withdrawn from the vessel is reheated to form the reheated recycle stream, and a part of the thus obtained reheated recycle stream is recycled to the mixture.
  • This embodiment is especially useful when the heated contaminant-rich stream is heated up to a liquid.
  • a part of the reheated recycle stream is recycled, whereas the other part is withdrawn, optionally after recovery of entrained hydrocarbons.
  • the size of the part that is being recycled can be determined by the skilled person, based on the conditions, also indicated above.
  • the part of the reheated recycle stream that is recycled to the mixture is selected such that the reflux ratio ranges from 0.5 to 10.
  • the way in which the contaminant-rich stream is reheated can be done in any feasible way. External, e.g., electrical, heaters are possible. However, preferably, the reheating of at least part of the contaminant-rich stream is conducted via heat exchange. Any process stream with a sufficiently higher temperature can be used for this. This includes any condensate stream or hydrate-stream. Preferably, the heat exchange is conducted with at least part of the gas stream. Alternatively, a warm fluid may be added to the contaminant-rich stream. Suitable warm fluids include a natural gas condensate.
  • the contaminant-rich stream mainly comprises carbon dioxide and is therefore a CO 2 -rich stream
  • CO 2 -rich stream is further pressurised and injected into a subterranean formation, preferably for use in enhanced oil recovery or for storage into an aquifer reservoir or for storage into an empty oil reservoir. It is an advantage that a liquid CO 2 -rich stream is obtained, as this liquid stream requires less compression equipment to be injected into a subterranean formation.
  • FIG. 1 shows a schematic embodiment of a vessel wherein a recycle stream is being applied.
  • FIG. 2 shows another embodiment of such a vessel.
  • FIG. 3 shows a schematic flow scheme of a natural gas purification unit using the process of the present invention.
  • FIG. 1 shows a vessel wherein a dehydrated natural gas stream is cooled by expansion in a Joule-Thomson valve 2 .
  • a Joule-Thomson valve 2 instead of a Joule-Thomson valve a venturi tube or a turbo-expander may be used.
  • the thus cooled mixture of solids and vapour is passed through a line 3 to a vessel 4 .
  • Line 3 that connects the valve 2 with the vessel 4 is short so that the solids will not block the entry of the mixture to the vessel 4 . It is also possible to do away with the line 3 altogether and connect the Joule Thomson valve directly to the wall of vessel 4 .
  • the cooled mixture is separated in vessel 4 to a purified hydrocarbon gas that exits the vessel 4 via an outlet 5 .
  • Deflecting means 15 has the shape of a cone.
  • a warm recycle stream is recycled into the vessel 4 .
  • an additional electrical immersion heater or bundle coil 14 through which a warm fluid is passed, may be provided to provide additional energy. Due to the recycle of warm fluids solid acidic contaminants melt and the remaining liquid, i.e., the heated contaminant-rich stream, is withdrawn from the vessel 4 via a line 7 , optionally by pumping.
  • the entire heated contaminant-rich stream in line 7 is subjected to heat exchange in heat exchanger 10 , through which a warm fluid, e.g. the natural gas stream, is being passed to reheat the contaminant-rich stream.
  • a part of the thus reheated stream is withdrawn from the process via a line 11 .
  • Another part is recycled to the vessel via line 9 .
  • the part that is being recycled can be fed into the vessel 4 in any known way.
  • the lines 9 and 11 have been provided with valves 12 and 13 to control the flow of recycle stream to the vessel 4 and the liquid level inside vessel 4 .
  • the line-up of FIG. 1 is especially suitable for the situations in which the reheated recycle stream is maintained in the liquid phase.
  • FIG. 2 a situation is shown that is especially suitable for situations wherein recycle streams are reheated to become vaporous.
  • a natural gas stream is passed via a line 21 and a Joule-Thomson valve 22 and another short line 23 to a vessel 24 .
  • a venturi tube may be used instead of a Joule-Thomson valve.
  • Purified hydrocarbon gas is removed via an outlet 25 .
  • Solid acidic contaminants and optionally also some liquids fall down via a deflecting means 36 and are collected as layer 26 in the bottom part of vessel 24 .
  • the deflecting means 36 in this embodiment has been executed as a combination of a cone and an inverted cone.
  • the layer 26 comprising solid acidic contaminants can be heated to melt at least part of the solid acidic contaminants by the recycle of a reheated recycle stream via a nozzle 32 .
  • An additional heater 35 may optionally be provided. Due to the energy input of the recycle and/or heating solid acidic contaminants melt, and the remaining heated contaminants-rich stream is withdrawn from the vessel via line 27 , optionally via pumping.
  • the heated contaminant-rich stream is split into stream 29 , which is discarded or is sent to another part of the process, and stream 28 , which is subjected to heat exchange in a heat exchanger 30 .
  • the heat exchanger is similar to heat exchanger 10 in FIG. 1 .
  • a reheated recycle stream exits heat exchanger 30 via line 31 .
  • Line 31 debouches into the nozzle 32 through which the reheated recycle stream enters the vessel 24 .
  • Both lines 31 and 29 have been provided with valves 33 and 34 , respectively, to control the flow of recycle stream to the vessel 24 and the liquid level inside vessel 24 .
  • FIG. 3 shows a more extensive flow scheme of a unit wherein the present process can be carried out.
  • a natural gas stream is introduced via a line 101 into a dehydrating unit 118 .
  • water is being removed from the natural gas stream, e.g., by means of molecular sieves.
  • the water is eventually removed via a line 102 .
  • the dehydrated natural gas is passed via a line 103 to a turbo-expander 119 where it is cooled, and subsequently forwarded via a line 104 .
  • the natural gas in line 104 is cooled further via a heat exchanger 122 . Subsequently, the natural gas stream is passed via a line 105 for further heat exchange.
  • the natural gas stream may be passed to a heat exchanger 124 wherein it exchanges heat with purified hydrocarbon gas and heated contaminant-rich stream. If desired further heat exchange may optionally be established in heat exchanger 125 .
  • the further cooled natural gas stream is passed to a Joule-Thomson valve 126 where it is cooled to a temperature at which acidic contaminants solidify so that a mixture of solid acidic contaminants and vaporous hydrocarbons enter vessel 120 via a line 108 .
  • a venturi tube may be used instead of a Joule-Thomson valve. There separation takes place so that purified hydrocarbon gas is withdrawn at the top via a line 109 .
  • short line 108 connects the Joule Thomson valve 130 with the vessel 120 .
  • This line is typically short so that blocking of the line by solids is prevented. It is also possible to do away with the line altogether and connect the Joule Thomson valve directly to the wall of vessel 120 .
  • the solid and optionally liquid acidic contaminants and optionally liquid hydrocarbons are falling down, preferably along a deflecting means (not shown), towards the bottom of vessel 120 where they are collected and heated by means of a warm reheated recycle stream entering the vessel 120 via a line 117 , thereby melting solid acidic contaminants.
  • the thus obtained heated contaminant-rich stream is withdrawn from the vessel via a line 112 which is pumped further using pump 121 .
  • the heated contaminant-rich stream is divided into a part that is withdrawn via a line 113 and a part that is forwarded to the heat exchanger 122 via a line 115 .
  • heat exchanger 122 the part of the heated contaminant-rich stream is reheated by means of heat exchange with the natural gas stream provided via line 104 , to form a reheated recycle stream.
  • the reheated recycle stream is forwarded via line 116 to a valve 123 which controls the flow of the reheated recycle stream.
  • the line 117 which may be provided with a nozzle (not shown) the reheated recycle stream is introduced into vessel 120 .
  • the line 113 with the heated contaminant-rich stream leads the molten contaminants to the heat exchanger 124 , and subsequently, the contaminants are withdrawn via line 114 .
  • heat exchanger 124 the molten contaminants in line 113 and cold purified hydrocarbon gas in line 109 are subjected to heat exchange with the natural gas stream in line 105 .
  • the streams are shown in co-current fashion. It is evident to the skilled person that the streams may also be arranged in a counter-current way, e.g., the relatively warm natural gas stream is counter-current with the two other streams. It will be appreciated that it is also feasible to use only one of the other streams or use a stream from another process, such as a stream from an LNG plant and/or an air separation plant.
  • the purified hydrocarbon gas is passed via a line 110 to a compressor 127 .
  • the compression energy for compressor 127 is suitably provided by the expander 119 .
  • the compressed gas may be recovered as product in line 111 or used for further treatment.

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US12/995,411 2008-05-30 2009-05-28 Producing purified hydrocarbon gas from a gas stream comprising hydrocarbons and acidic contaminants Abandoned US20110094264A1 (en)

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US20120279235A1 (en) * 2011-02-02 2012-11-08 Oscomp Systems Inc. Apparatus and methods for decompressing and discharging natural gas utilizing a compressor or a temperature-actuated valve
US20190170440A1 (en) * 2017-12-05 2019-06-06 Larry Baxter Pressure-Regulated Melting of Solids
US20190170441A1 (en) * 2017-12-05 2019-06-06 Larry Baxter Pressure-Regulated Melting of Solids with Warm Fluids
US20190192998A1 (en) * 2017-12-22 2019-06-27 Larry Baxter Vessel and Method for Solid-Liquid Separation

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FR2959512B1 (fr) 2010-04-29 2012-06-29 Total Sa Procede de traitement d'un gaz naturel contenant du dioxyde de carbone
FR3030026B1 (fr) * 2014-12-11 2019-09-13 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede et appareil pour separer un gaz d'alimentation contenant au moins 20% mol. de co2 et au moins 20% mol de methane, par condensation partielle et/ou par distillation
GB2540425B (en) * 2015-07-17 2017-07-05 Sage & Time Llp A gas conditioning system
CN109224752B (zh) * 2018-08-27 2020-09-01 珠海格力电器股份有限公司 一种脱脂油回收装置和控制方法

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WO2009144275A1 (en) 2009-12-03
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RU2498175C2 (ru) 2013-11-10
AU2009253116A1 (en) 2009-12-03
RU2010153595A (ru) 2012-07-10

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