US3057706A - Adjusting the heating value and specific gravity of natural gas - Google Patents

Adjusting the heating value and specific gravity of natural gas Download PDF

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US3057706A
US3057706A US744595A US74459558A US3057706A US 3057706 A US3057706 A US 3057706A US 744595 A US744595 A US 744595A US 74459558 A US74459558 A US 74459558A US 3057706 A US3057706 A US 3057706A
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gas
line
natural gas
heavier hydrocarbons
methane
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Jr Walton H Marshall
Wilfred C Gains
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Conch International Methane Ltd
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Conch International Methane Ltd
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Priority to NL240564D priority Critical patent/NL240564A/xx
Priority to BE579952D priority patent/BE579952A/xx
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Priority to US744595A priority patent/US3057706A/en
Priority to DEC19256A priority patent/DE1089918B/de
Priority to ES0250320A priority patent/ES250320A1/es
Priority to FR798453A priority patent/FR1230750A/fr
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    • 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
    • F25J3/0214—Liquefied natural gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • C10G9/38—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours produced by partial combustion of the material to be cracked or by combustion of another hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/06—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by mixing with gases
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C9/00—Methods or apparatus for discharging liquefied or solidified gases from vessels not under pressure
    • F17C9/02—Methods or apparatus for discharging liquefied or solidified gases from vessels not under pressure with change of state, e.g. vaporisation
    • F17C9/04—Recovery of thermal energy
    • 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
    • F25J3/0238—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 2 carbon atoms 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
    • 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
    • F25J2200/74—Refluxing the column with at least a part of the partially condensed overhead 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/82—Processes or apparatus using other separation and/or other processing means using a reactor with combustion or catalytic reaction
    • 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
    • F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
    • F25J2260/60—Integration in an installation using hydrocarbons, e.g. for fuel purposes
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • This invention relates generally to improvements in the art of reforming natural gas, and more particularly, but not by way of limitation, to an improved method of adjusting the heating value and specific gravity of a natural gas containing a wide range of hydrocarbons.
  • the liquefied natural gas is revaporized and used as a fuel.
  • the natural gas can be revaporized and used directly as a fuel.
  • the gas specifications for existing equipment therein are different from the specifications of the revaporized natural gas, thereby requiring that the revaporized natural gas be reformed to a lower heating value and new specific gravity before use.
  • natural gas usually contains a rather wide range of hydrocarbons when produced.
  • methane comprises the major proportion of the natural gas, with the heavier hydrocarbons, such as ethane, propane, butane and the like being present in the gas in minor proportions.
  • the heating value and specific gravity of methane are nearer to the usual specifications for a gaseous fuel in the remote locality (compared with the heating value and specific gravity of the heavier hydrocarbons) it is ordinarily considered most desirable to remove the heavier hydrocarbons before liquefying and shipping the natural gas.
  • the separation of the heavier hydrocarbons prior to liquefaction complicates the liquefaction operations.
  • we have found that the heavier hydrocarbons may be easily and economically separated when the liquefied natural gas is revaporized, and that the heavier hydrocarbons may be most economically utilized in the remote locality having a natural gas shortage.
  • the present invention contemplates a novel method of adjusting the heating value and specific gravity of a natural gas containing a wide range of hydrocarbons, wherein the heavier hydrocarbons are used in the formation of a carrier gas for subsequent blending with the methane component to produce a gaseous fuel having the required heating value and specific gravity.
  • the heavier hydrocarbons used for forming the carrier gas are first oxidized by partial combustion with air. The products of combustion are subsequently reacted with water to form a carrier gas having a low 3,057,706 Patented Oct. 9, 1962 heating value and containing an appreciable proportion of carbon dioxide. The reactions are carried out in such a manner that the heat generated by the reactions is effectively used to preheat the reactants and provide an economical process.
  • the carbon dioxide may be subsequently removed from the carrier gas prior to blending of the gas with the methane when it is desired to reduce the specific gravity of the resulting fuel.
  • This invention further contemplates the formation of a carrier gas in combination with the separation of the heavier hydrocarbons from the methane in a liquefied natural gas feed stream, such that heat made available in the formation of the carrier gas may be effectively utilized in the separation of the heavier hydrocarbons and methane, and wherein work may be recovered from the revaporized methane.
  • An important object of this invention is to economize the liquefaction and subsequent conversion of natural gas to a gaseous fuel having a modified heating value and specific gravity.
  • Another object of this invention is to eificiently and economically adjust the heating value and specific gravity of natural gas.
  • a further object of this invention is to utilize at least a portion of the heavier hydrocarbons in a natural gas containing a wide range of hydrocarbons to form a carrier gas, which in turn may be used for adjusting the heating value and specific gravity of the methane component of the natural gas.
  • Another object of this invention is to provide an economical and efficient method of forming a carrier gas having a low heating value and an easily adjustable specific gravity.
  • Another object of this invention is to utilize the heat generated in the formation of a carrier gas for facilitating the separation of the heavier hydrocarbons from the methane of a liquefied natural gas feed stream, and for the revaporization of the methane component.
  • a still further object of this invention is to recover work in the revaporization and reforming of a liquefied natural gas to a lower heating value.
  • FIGURE 1 is a part of a flow diagram illustrating a' FIG. 1, reference character 4 designates a line leading from a suitable insulated storage tank (not shown) for transferring liquefied natural gas to a pump 6.
  • the liquefied natural gas will normally be stored at about atmospheric pressure, or slightly above, and have a temperature of from 240 to 258 F., depending upon the composition of the gas. .For the purpose of the present description, it will be assumed that the liquefied natural gas being fed to the pump 6 has a temperature of -246 F. and the following analysis, although it will be understood that the cornposition' will vary, depending upon where the natural gas was produced,, and the following analysis is included herein only as an example.
  • the pump 6 forces the liquefied natural gas through a line 8 at increased pressure to the medial portion of a fractionating tower 10.
  • the tower 10 may be of any desired construction which provides a vertically extending fractionating zone for separating the heavier hydrocarbons from the methane of the liquefied gas fed to the tower, and which will provide a revaporization of the methane, as will be more fully hereinafter set forth.
  • the pump 6 substantially increases the pressure of the liquefied natural gas being fed to the tower 10, and preferably increases this pressure to about 585 p.s.i.g.
  • a pair of heat exchangers 12 and 14 are interposed in the line 8 between the pump 6 and the tower 10 for heating the liquefied natural gas being fed to the fractionating tower.
  • the heat exchangers 12 and 14 receive suitable heating mediums, as will be hereinafter described, having sufficient heat to warm the liquefied natural gas to approximately its bubble point temperature prior to injection of the liquefied natural gas into the tower 10.
  • the liquefied natural gas is preferably slightly reduced in pressure as it enters the medial portion of the fractionating tower 10, as from 585 p.s.i.g. to 535 p.s.i.g., to facilitate the revaporization of the methane component and provide an upward fiow of the methane vapors into the upper end of the tower 10, with a simultaneous downward fiow of the heavier hydrocarbons into the lower portion of the tower 10.
  • the contents of the lower end portion of the tower 10 are circulated through a reboiler 16, heated as will be hereinafter set forth, a maintain the contents of the lower portion of the tower 10 at a temperature which will induce the revaporization of any methane in the lower portion of the tower, with a consequent upward flow of the methane vapors into the upper portion of the fractionating tower.
  • the reboiler 16 is heated to such an extent that the contents in the lower end portion of the tower 10 will be maintained at a temperature of about 135 F.
  • the vapors collecting in the upper end portion of the tower are directed through a line 18 to the heat exchanger 12 interposed in the liquefied natural gas feed line 8.
  • the temperature of the overhead vapors discharging from the tower 10 will be about 118 F. to provide a warming of the liquefied natural gas being passed through the heat exchanger 12.
  • the methane enriched vapors being passed through the line 18 will be cooled by passage through the heat exchanger 12, with the temperature of these vapors being reduced to about 120 F.
  • the overhead vapors passed through the line 18 will be substantially all methane and contain only a minor proportion of the heavier hydrocarbons.
  • the overhead vapors discharging through the line 18 will be approximately comprised of 98.45 mol percent of CH; and 1.55 mol percent C H
  • the condensate refluxed through the line 24 to the upper end of the tower 10 will have a slightly higher percentage of the heavier hydrocarbons, with a typical analysis being 97.81 mol percent CH6 and 2.19 mol percent C H
  • the condensate in the lower end portion of the tower 10 will be substantially all heavier hydrocarbons, with a typical analysis being:
  • composition Mol. percent CH 1.0 C H 45.7 C H 32.1 iC H 7.7 1'1C H1o iC H 2.4 I1C5H12 c rt 1.2 C7H16 0.8
  • the heavier hydrocarbons in the lower end portion of the tower 10 are discharged from the tower through a line 26 for the formation of a carrier gas, as will be hereinafter described.
  • the overhead methane enriched vapors from the tower 10 will be cooled to about -l20 F. by passage thereof in heat exchange relation with the liquefied natural gas being fed to the tower 10.
  • the vapor is directed through a line 28 to a suitable expander 30 for recovering work from the revaporized methane.
  • the expander 30 may take any desired form, such as a turbine, which will provide a workproducing zone through which the revaporized methane may be expanded to recover energy therefrom.
  • the methane being fed to the expander 30 is passed through four heat exchangers 32 through 35 to raise the temperature of the methane vapors and increase the energy recovered by expansion of the vapors through the expander 30.
  • Suitable heating mediums made available by the formation of the carrier gas, as will be hereinafter described, are passed through the heat exchangers 32, 34 and 35; whereas the expanded methane vapors discharging from the expander 30 may be directed through a line 36 back through the heat exchanger 33.
  • the heat exchangers 32 through 35 are operated at such temperatures as to raise the temperature of the methane vapors to about 700 F., with the pressure of the methane vapors being about 525 p.s.i.g. prior to expansion thereof.
  • the pressure of the methane vapors is decreased to about p.s.i.g. by passage through the expander 30, with the temperature being decreased proportionately.
  • the temperature of the expanded vapors discharging from the expander 30 through the line 36 will be at a higher temperature than the methane vapors as they are passed from line 28 through the heat exchanger 33, such that the expanded vapors may be used as a heating medium for the methane vapors prior to expansion.
  • the expanded methane vapors discharging through the line 36 from the heat exchanger 33 are at a temperature of about 100 F. and a pressure of about 100 p.s.i.g. for subsequent use thereof as a fuel.
  • the liquefied heavier hydrocarbons discharging from the lower end of the fractionating tower 10 are expanded through a suitable expansion valve 38 to at least partially revaporize the heavier hydrocarbons.
  • the combined vapors and liquid are then directed through a line 40 to a heat exchanger 42 as illustrated in FIG. 2.
  • the expansion valve 38 reduces the pressure of the heavier hydrocarbons to about 185 p.s.i.g.
  • the heavier hydrocarbons passing through the heat exchanger 42 are further heated, preferably to a temperature of about 147 F., and will have a pressure of about p.s.i.g.
  • the revaporized heavier hydrocarbons may then all be used to form the carrier gas, or a portion thereof may be blended back with the revaporized methane in the line 36 through a by-pass line 44.
  • the amount of the heavier hydrocarbons needed for forming the carrier gas will depend upon the ultimate desired characteristics of the fuel gas. Therefore, a variable proportion, from Zero to the major portion of the heavier hydrocarbons, may be by-passed through the line 44 for mixing with the methane in the line 36, depending upon the initial composition of the liquefied natural gas, as Well as the desired final characteristics of the fuel gas. In the example being described, slightly more than one-half of the heavier hydrocarbons are by-passed through the line 44 back to the line 36. With 255,398 pounds per hr.
  • the revaporized heavier hydrocarbons to be used in formation of the carrier gas are passed from the line 40 through a preheater 46 for raising the temperature of these vapors and facilitating subsequent oxidation of the vapors with air in suitable partial oxidation furnaces 48.
  • the revaporized heavier hydrocarbons discharging through the line 50 from the preheater 46 to the furnaces 48 is at a temperature of about 1000 F.
  • the preheater 46 may conveniently be in the form of a gas heater to utilize a portion of the natural gas being handled.
  • the air being used for combustion in the furnaces 48 is provided by a suitable compressor 52 having a suitable filter 54 on the intake thereof as illustrated in FIG. 1.
  • the air discharging through the line 56 from the compressor 52 is preferably at a pressure only slightly above atmospheric, such as 2 p.s.i.g., with a temperature of about 100 F., depending somewhat upon atmospheric conditions.
  • the air is directed by the line 56 into the lower section of a glycol contactor 58.
  • the contactor 58 may be of any desired construction which will provide an intimate contact of the air flowing upwardly through the tower with cold glycol flowing downwardly through the tower to provide a substantial drying and cooling of the air passed through the contactor.
  • the air discharging from the upper end of the contactor 58 is directed through another line 60 to the lower end of a second glycol contactor 62.
  • An intermediate stage compressor 64 is interposed in the line 60 to increase the pressure of the air entering the second contactor 62. Glycol is circulated through the contactors 58 and 62 as will be described below.
  • the second contactor 62 completes the further removal of Water from the air and discharges the essentially moisture-free air through a line 66 for further compression by a compressor 68 before being fed to the partial oxidation furnaces 48.
  • the air is first, however, preferably preheated to the same temperature as the heavier hydrocarbons fed to the furnaces 48. Therefore, the air in the line 66 is forced by the compressor 68 partially through a line 70 to a heat exchanger 72 heated by the products of combustion, as Will be described. However, the major portion of the air may be by-passed through a line 74 around the heat exchanger 72 to combine with the partially preheated air at the inlet of a preheater 76.
  • the preheater 76 may be of any desired type, such as a gas fired heater, to heat the air to a temperature corresponding to the temperature of the heavier hydrocarbon vapors in the line 50, with the heated air being discharged through a line 78 to combine with the revaporized heavier hydrocarbons in the line 50 upstream of the furnaces 48.
  • the temperature Composition Mol. percent CH 0.07 H 24.10 CO 20.06 H O 4.51 N 50.17 CO 1.09
  • the intermediate gas (the products of combustion) discharging from the furnaces 48 will have a temperature of about 2500 F. and is directed through a line 80 to the heat exchanger '72 for preheating a portion of the air as previously described.
  • the intermediate gas in the line 80 is quenched with water directed through a line 82 into the line 80.
  • This water may be obtained from any desired source, and is forced through the line 82 by a pump 84 at a pressure of about 200 p.s.i.g. Also, it is preferred that the water pumped through the line 82 have a temperature of about 235 F.
  • the intermediate gas After passage through the heat exchanger 72, the intermediate gas is further quenched with water from a line 86 leading from the line 82, before the intermediate gas is fed into the lower section of a gas scrubber 88. An excess of water is mixed with the intermediate gas in the line 80 to substantially cool the intermediate gas being fed to the scrubber 88.
  • Water is recirculated through the gas scrubber 88 by means of a line 90 and pump 92 to further cool the intermediate gas and remove a portion of the water which was used to quench the intermediate gas.
  • the excess water obtained by operation of the scrubber 88 may be drained through a line 94 to a suitable disposal point (not shown).
  • the intermediate gas discharging through a line 96 from the top of the gas scrubber 88 is at about 135 p.s.i.g. and 300 F., and has the following analysis.
  • the intermediate gas in the line 96 is fed to a series of shift converters 98, as illustrated in FIG. 1, to produce the carrier gas.
  • the major portion of the intermediate gas in the line 96 is directed *by a by-pass line 100 through a heat exchanger 101 for heating this portion of the intermediate gas before the gas is fed to the shift converters 98.
  • the heat exchanger 101 is heated by the products discharging from the shift converters 98, such that a substantial proportion of the intermediate gas is prelgesated prior to reaction thereof in the shift converters
  • a catalytic reaction takes place, principally between carbon monoxide and water, to produce carbon dioxide and hydrogen in accordance with the reaction: CO+H O CO +H
  • the reaction is an exothermic reaction which raises the temperature of the gases in the converters to about 840 F., and it is promoted by the use of such catalysts as brown iron oxide.
  • the following is a typical analysis of the composition of the gas leaving the shift converters 98 through the line 102.
  • Composition Mol. percent CH 0.04 H 22.07 CO 1.05
  • the carrier gas is directed through a line 108 to the heat exchanger 34, which is also used to heat the methane vapors flowing to the expander 30.
  • the carrier gas directed through the heat exchanger 34 will be at a temperature level between the carrier gas directed through the heat exchanger 35 and the expanded methane vapors being directed through the heat exchanger 33 to provide a progressive heating of the methane vapors being fed to the expander 30.
  • the temperature of the carrier gas being directed through the heat exchanger 34 will be at about 405 F.
  • the carrier gas discharging from the heat exchanger 34 is directed (see FIG. 2) into the lower section of a secondary gas scrubber 110.
  • the scrubber 110 may be any desired construction which will provide a removal of water and a reduction in temperature of the carrier gas flowing upwardly through the scrubber by water flowing downwardly through the scrubber.
  • the water used in the scrubber 110 may be fed to the upper section of the scrubber by a line 112 leading from the water line 82 previously described.
  • the water collecting in the lower end of the scrubber 119 is discharged through a line 114 to a steam drum 116. This water will be at a temperature of about 275 F. and a pressure of about 110 p.s.i.g. upon being flashed into the steam drum 116.
  • the steam drum 116 is preferably operated at a pressure of about 8 p.s.i.g. to provide the conversion of a portion of the water to steam in the steam drum.
  • the condensate in the drum 116 remaining after flashing is directed through a. line 118 to the inlet of the pump 84 which supplies water to the water line 82.
  • the pump 84 increases the pressure of the water fed through the line 118 to about 200 p.s.i.g. for recirculation through the scrubber 110, as well as for quenching the intermediate gas in the line 80 as previously described.
  • the major portion of the water flowing through the line 82 is obtained from the line 118, such that the temperature of the water in the line 82 may be easily retained at about 235 F.
  • Such make-up water as is necessary is fed to the pump 84 through another line 120 from a suitable source of supply (not shown).
  • the carrier gas discharging from the upper end of the scrubber 110 through a line 122 has a low heating value by comparison with the methane gas and may (after removing the remaining water therefrom) be used for blending with the methane and heavier hydrocarbon vapors in the line 36 to form a fuel gas having a heating value lower than the heating value of the original natural gas.
  • the carrier gas in the line 122 contains a substantial amount of carbon dioxide, which provides the carrier gas with a specific gravity normally higher than the specific gravity of the original natural gas and which, in some cases, would provide the resulting fuel gas with a specific gravity higher than the specifications for the equipment in the locality where the fuel gas is to be burned.
  • the carrier gas when a lower specific gravity is required, we prefer to direct the carrier gas from the line 122 into the lower section of a hot carbonate absorption tower 124 for the removal of carbon dioxide by a hot carbonate system, as will be hereinafter described. It will be understood, how ever, that the CO may be removed by use of an amine system, water scrubbing, or the like.
  • the carrier gas discharging from the upper end of the absorption tower 124 has a temperature of about 235 F. and is directed through a line 126 back to the reboiler 16 of the fractionating tower 10, as illustrated in FIG. 1. As previously described, this hot gas forms the heating medium for the reboiler 16 to maintain the desired temperature for the contents in the lower end of the fractionating tower 10.
  • the carrier gas is directed from the reboiler 16 back through a line 128 to the heat exchanger 42 (FIG. 2) utilized for revaporizing the heavier hydrocarbons prior to utilization of the heavier hydrocarbons in the formation of the carrier gas.
  • the collected water is discharged from the lower end of the separator 130 through a line 132 to a suitable disposal point (not shown).
  • the remaining vapor passing through the separator 130 is discharged through a line 134 to a second separator 136 for a substantially complete removal of water from the gas.
  • the heat exchanger 138 may be cooled by water, since the carrier gas being fed to the second separator 136 is at a temperature of about 200 F.
  • the water separated in the separator 136 is discharged through a line 140 to a suitable disposal point (not shown).
  • the gas remaining after separation of the water is directed through a line 142 to the line 36 for blending with the revaporizcd methane (and heavier hydrocarbons previously mixed with the methane vapors) to form the final fuel gas.
  • the fuel gas in the line 36 downstream of the connection with the line 142 will have a heating value of about 540 B.t.u. per cu. ft. and a specific gravity of 0.6, which are the gas specifications for the majority of existing gas fired appliances in areas formerly served by manufactured gas.
  • the glycol contactors 58 and 62 are operated by a closed glycol cycle to provide an eflicient removal of moisture from the air being used to oxidize the heavier hydrocarbons in the formation of the carrier gas.
  • the glycol is stored in a surge drum 144 and is pumped into the upper sections of the containers 58 and 62 by suitable pumps 146 and 148.
  • the major portion of the glycol is pumped through a line 150 by the pump 146 into the upper section of the glycol contactor 58 at a pressure of about 30 p.s.i.g. to provide a low pressure operation for the contactor 58 and the removal of the major portion of the moisture from the air while the air is passing through the contactor 58.
  • a minor portion of the glycol is pumped through a line 152 by the pump 146 at a pressure of about 80 p.s.i.g. into the upper section of the higher pressure contactor 62.
  • the glycol being fed to both of the contactors 58 and 62 is at a temperature of about 25 R, such that the air passing through the contactors will heat the glycol to about 80 F., and the air will be cooled to reduce the horsepower required to compress the air in the compressors 64 and 68, as previously described.
  • the glycol leaving the lower end of the contactor 58 is forced by a pump 154 through a line 156 back to the heat exchanger 32 used in initially heating the methane vapors being fed through the line 28 to the expander 30.
  • the glycol leaving the lower end of the contactor 62 is fed through a line 158 into the line 156 to provide a passage of the major portion of the glycol through the heat exchanger 32.
  • the glycol at this point in the system will be at a temperature of about 80 F. to provide the initial warming of the methane vapors flowing to the expander 30.
  • the glycol is then directed on through the line 156 for passage through the heat exchanger 14 utilized in warming the liquefied natural gas being fed through the line 8 to the fractionating tower It).
  • the temperature of the glycol entering the heat exchanger 14 will be at about 62 F. to provide a substantial transfer of heat to the liquefied natural gas feed stream, such that the liquefied natural gas will be raised to approximately its bubble point temperature before being fed to the fractionating tower 10 as previously described.
  • the glycol leaving the heat exchanger 14 will be at a temperature of about 25 F. and is directed on through the line 156 back to the glycol surge drum 144 to complete the cycle.
  • the glycol will pick up a substantial amount of moisture by passage through the contactors 58 and 62. Therefore, a minor portion of the glycol being pumped through the line 156 is by-passed through a line 160 to a glycol still 162.
  • the glycol flowing through the line 169 is preheated in a heat exchanger 164 by the relatively pure glycol discharging from the still 162, as will be described.
  • the still 162 operates in the usual manner to provide an upward flow of water vapor to the upper section of the still and the downward flow of relatively pure glycol into the lower section of the still. Vapor is Withdrawn from the upper section of the still through a line 166 and passed through a water cooler 168. A portion of the cooled H O directed through the cooler 168 is refluxed back to the upper section of the still for maintaining the upper section of the still at the desired temperature, while the remaining cooled H O is directed to a suitable disposal point (not shown).
  • the contents in the lower end of the still 162 are circulated by a pump 170 partially through a line 172 into a reboiler 174, and partially through a line 176 back through the heat exchanger 164 to join with the glycol in the line 156.
  • the glycol being directed through the reboiler 174 is maintained at a temperature of about 285 F. and is recirculated to the lower section of the still to maintain the lower section of the still at the desired temperature. It will be apparent that the glycol forced by the pump 170 through lines 172 and 176 will be substantially pure, such that the glycol cycle will not become over-saturated with water.
  • carbon dioxide is removed from the carrier gas flowing through the absorption tower 124 (FIG. 2) by a hot carbonate cycle.
  • the carbonate leaving the lower end of the absorption tower 124 is directed through a line 178 to the upper section of a hot carbonate stripper 180 for removal of carbon dioxide from the hot carbonate.
  • Steam generated in the steam drum 116 is directed through a line 182 to the lower section of the stripper 180 for counter-flow with the hot carbonate fed to the upper section of the stripper.
  • the hot carbonate accumulating in the lower section of the stripper 180 is forced by a pump 184 through a line 186 back to the upper section of the absorption tower 124 to complete the hot carbonate cycle.
  • the steam and separated carbon dioxide accumulating in the upper end of the stripper 180 are directed through a line 138 to a suitable separator 190.
  • the carbon dioxide and steam being fed to the separator 190 are preferably cooled by a heat exchanger 192 to facilitate the condensation of the steam and the efficient separation of the CO and H in the separator 190.
  • the heat exchanger 192 may be cooled by water, since the temperature of the carbon dioxide and steam fed to the exchanger 192 is at a temperature of about 235 F.
  • Condensate collecting in the lower end of the separator is discharged through a line 194 to a suitable disposal point (not shown).
  • the carbon dioxide collecting in the upper end of the separator 190 is discharged through a line 196 to a suitable receiver (not shown) for use in any desired manner. Utilization of the separated carbon dioxide forms no part of the present invention and will therefore not be described herein.
  • the present invention provides a novel method of adjusting the heating value and specific gravity of a natural gas containing a range of hydrocarbons.
  • the heavier of the hydrocarbons are separated from the remaining gas and reformed to a carrier gas having a low heating value and substantially any desired specific gravity.
  • the reforming of the heavier hydrocarbons is accomplished by first partially oxidizing the heavier hydrocarbons to an intermediate gas, and then the intermediate gas is reacted with water to provide a carrier gas having a drastically reduced heating value.
  • the oxidation and reaction of the intermediate gas is accomplished by the utilization of the maximum amount of heat in the products for preheating the reactants in both steps of the reforming operation.
  • the present invention provides a novel method of separating the heavier hydrocarbons from methane in a liquefied natural gas as in a simple and economic manner, such that a portion of the heavier hydrocarbons may 'be efliciently utilized to form a carrier gas for blending with the remaining natural gas in the formation of a fuel gas having the desired heating value and specific gravity.
  • the separation of the heavier hydrocarbons from the methane in the liquefied natural gas is facilitated by utilizing the heat generated in the conversion of the heavier hydrocarbons to a carrier gas, and the revaporized methane may be used in the recovery of work in a system utilizing the present invention, with heat generated in the conversion of the heavier hydrocarbons being used to heat the revaporized methane and increasing the amount of work which may be recovered from the revaporized methane. It will be further apparent that economic utilization of the heavier hydrocarbons in a liquefied natural gas will simplify the liquefaction of the gas to provide the maximum in economy of liquefaction, transportation and reforming of natural gas for use in remote localities having a deficient natural gas supply.
  • the separation of the heavier hydrocarbons from the methane in a natural gas may be accomplished separately from the conversion of the heavier hydrocarbons to a carrier gas.
  • a liquefied natural gas may be revaporized and/ or separated into heavier and lighter hydrocarbons in one area, and then transported in gaseous form by pipeline or the like to a separate locality Where the reforming of the natural gas to a lower heating value is accomplished.
  • the liquefied natural gas may be revaporized and separated into heavier and lighter hydrocarbons in any desired manner, as by successively flashing the natural gas in such a manner that the components of the gas are progressively separated.
  • the natural gas contains an insufficient amount of heavier hydrocarbons for the formation of the carrier gas, a portion of the methane may be by-passed and used with the heavier hydrocarbons for this purpose.
  • the method defined in claim 14 characterized further in drying the air by contact with glycol, heating the glycol to remove moisture therefrom, and passing the heated glycol in heat exchange relation with the overhead vapors from the fractionating tower prior to expansion thereof, and then passing the heated glycol in heat exchange relation with the compressed liquefied natural gas.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US744595A 1958-06-25 1958-06-25 Adjusting the heating value and specific gravity of natural gas Expired - Lifetime US3057706A (en)

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NL240564D NL240564A (enExample) 1958-06-25
BE579952D BE579952A (enExample) 1958-06-25
US744595A US3057706A (en) 1958-06-25 1958-06-25 Adjusting the heating value and specific gravity of natural gas
DEC19256A DE1089918B (de) 1958-06-25 1959-06-22 Verfahren zur Senkung des Heizwertes von Erdgas
ES0250320A ES250320A1 (es) 1958-06-25 1959-06-24 Procedimiento para reducir la potencia calorifica de un gas natural que contenga una variedad de hidrocarburos
FR798453A FR1230750A (fr) 1958-06-25 1959-06-24 Procédé pour ajuster le pouvoir calorifique et le poids spécifique du gaz naturel

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419369A (en) * 1965-03-19 1968-12-31 Phillips Petroleum Co Manufacturing town gas from liquefied natural gas
US3494751A (en) * 1966-02-05 1970-02-10 Messer Griesheim Gmbh Process for the fractionation of natural gas
US5937894A (en) * 1995-07-27 1999-08-17 Institut Francais Du Petrole System and method for transporting a fluid susceptible to hydrate formation
US20070012071A1 (en) * 2005-07-12 2007-01-18 Huang Shawn S LNG facility providing enhanced liquid recovery and product flexibility

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1918254A (en) * 1933-07-18 Befobming of natttbal gases
US1926170A (en) * 1928-05-24 1933-09-12 Phillips Petroleum Co Method of gas manufacture
US2177068A (en) * 1938-12-03 1939-10-24 Fluor Corp Process for treating gases
US2383715A (en) * 1943-04-17 1945-08-28 Jahn Fredrik W De Production of gas mixture for methanol
US2465235A (en) * 1949-03-22 Production of hydrogen
US2537708A (en) * 1945-08-11 1951-01-09 Standard Oil Dev Co Production of hydrogen-containing gas under pressure
US2568351A (en) * 1948-01-22 1951-09-18 Surface Combustion Corp Process for making fuel gas from natural gasoline and straight run gasoline
US2671718A (en) * 1948-12-23 1954-03-09 Surface Combustion Corp Continuous process for the manufacture of a supplement gas
US2795559A (en) * 1954-04-01 1957-06-11 Texas Co Production of hydrogen-nitrogen mixtures

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1918254A (en) * 1933-07-18 Befobming of natttbal gases
US2465235A (en) * 1949-03-22 Production of hydrogen
US1926170A (en) * 1928-05-24 1933-09-12 Phillips Petroleum Co Method of gas manufacture
US2177068A (en) * 1938-12-03 1939-10-24 Fluor Corp Process for treating gases
US2383715A (en) * 1943-04-17 1945-08-28 Jahn Fredrik W De Production of gas mixture for methanol
US2537708A (en) * 1945-08-11 1951-01-09 Standard Oil Dev Co Production of hydrogen-containing gas under pressure
US2568351A (en) * 1948-01-22 1951-09-18 Surface Combustion Corp Process for making fuel gas from natural gasoline and straight run gasoline
US2671718A (en) * 1948-12-23 1954-03-09 Surface Combustion Corp Continuous process for the manufacture of a supplement gas
US2795559A (en) * 1954-04-01 1957-06-11 Texas Co Production of hydrogen-nitrogen mixtures

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419369A (en) * 1965-03-19 1968-12-31 Phillips Petroleum Co Manufacturing town gas from liquefied natural gas
US3494751A (en) * 1966-02-05 1970-02-10 Messer Griesheim Gmbh Process for the fractionation of natural gas
US5937894A (en) * 1995-07-27 1999-08-17 Institut Francais Du Petrole System and method for transporting a fluid susceptible to hydrate formation
US20070012071A1 (en) * 2005-07-12 2007-01-18 Huang Shawn S LNG facility providing enhanced liquid recovery and product flexibility
US7404301B2 (en) * 2005-07-12 2008-07-29 Huang Shawn S LNG facility providing enhanced liquid recovery and product flexibility

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FR1230750A (fr) 1960-09-19
DE1089918B (de) 1960-09-29
ES250320A1 (es) 1960-01-16
BE579952A (enExample) 1900-01-01
NL240564A (enExample) 1900-01-01

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