EP0361557A1 - Process for treating natural gas containing hydrocarbons and hydrogen sulfide - Google Patents

Process for treating natural gas containing hydrocarbons and hydrogen sulfide Download PDF

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Publication number
EP0361557A1
EP0361557A1 EP89202108A EP89202108A EP0361557A1 EP 0361557 A1 EP0361557 A1 EP 0361557A1 EP 89202108 A EP89202108 A EP 89202108A EP 89202108 A EP89202108 A EP 89202108A EP 0361557 A1 EP0361557 A1 EP 0361557A1
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Prior art keywords
natural gas
zone
heat exchange
washing
hydrocarbons
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EP89202108A
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German (de)
French (fr)
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EP0361557B1 (en
Inventor
Joachim Dr. Wilhelm
Ulf Jauernik
Manfred Dr. Kriebel
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GEA Group AG
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Metallgesellschaft AG
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Priority to AT89202108T priority Critical patent/ATE67298T1/en
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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
    • F25J3/0228—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
    • F25J3/0242—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 3 carbon atoms or more
    • 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
    • C10G5/00—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas
    • C10G5/06—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas by cooling or compressing
    • 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
    • F25J3/0238—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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • 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
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
    • 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
    • F25J2205/50—Processes or apparatus using other separation and/or other processing means using absorption, i.e. with selective solvents or lean oil, heavier CnHm and including generally a regeneration step for the solvent or lean oil
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S62/00—Refrigeration
    • Y10S62/921—Chlorine
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S62/00—Refrigeration
    • Y10S62/922—Sulfur
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S62/00—Refrigeration
    • Y10S62/931—Recovery of hydrogen
    • Y10S62/932—From natural gas

Definitions

  • the invention relates to a process for the treatment of natural gas, which in addition to methane contains hydrocarbons having 2 to 4 carbon atoms per molecule and H2S, for the partial removal of the hydrocarbons and the H2S.
  • the hydrocarbons with 5 and more carbon atoms per molecule can be removed relatively easily by adsorption.
  • the object of the present process is to remove the more difficult to separate C2 to C4 hydrocarbons and at the same time also the H2S, which also damages the reforming catalyst, to a sufficient extent.
  • this is achieved in that the natural gas, which has a pressure of at least 5 bar, is indirectly cooled in a heat exchange zone to temperatures from -30 to -100 ° C and condensate is separated, that the condensate is expanded and passed through the heat exchange zone as a coolant that one cools a washing liquid coming from a regeneration zone in the heat exchange zone to temperatures of -30 to -80 ° C and passes into a washing zone, to which the natural gas freed of condensate is also fed, that washing liquid loaded with H2S and hydrocarbons is fed from the washing zone through the heat exchange zone and into the regeneration zone, and that the natural gas cleaned in the scrubbing zone is expanded and passed through the heat exchange zone.
  • the cold necessary for the process is achieved by relaxing the condensate and also by relaxing the natural gas coming from the washing zone.
  • a refrigeration system can advantageously be dispensed with. Since the cooling requirement in the washing zone is not high because the necessary amount of washing liquid is kept low, the cold generated by condensation is also sufficient to cool the washing liquid in front of the washing zone sufficiently.
  • the condensate separated from the cooled natural gas is expediently expanded in two stages and the expansion gas formed in the process is passed through the heat exchange zone.
  • the washing liquid used is methanol, acetone or other C1 to C3 oxo hydrocarbons.
  • Natural gas containing hydrocarbons and H2S is introduced in line (1).
  • the solids and also the hydrocarbons having 5 and more carbon atoms per molecule have preferably been separated from this natural gas beforehand.
  • the natural gas in line (1) thus contains in addition to H2S especially C2, C3 and C- hydrocarbons.
  • This natural gas is in a heat exchange zone (2), e.g. a plate heat exchanger, indirectly cooled to temperatures from -30 to -100 ° C and preferably -40 to -90 ° C. This cooling creates condensate, which contains the main part of the hydrocarbons and also a considerable part of the H2S.
  • this mixture is led to a separator (5), from which the condensate is drawn off through line (6).
  • the gas mixture is added to a washing column (8) in line (7).
  • the condensate is partially expanded via the expansion valve (10) and fed to a separation tank (11).
  • the expansion gas is drawn off in line (12) and the condensate is expanded again via the expansion valve (13).
  • the expansion of the condensate in the valves (10) and (13) leads to a considerable drop in temperature.
  • the condensate which is led through the heat exchange zone (2) in the line (14) can effectively serve as a coolant.
  • the exhaust gas resulting from the heating in the heat exchange zone (2) is available in line (15) and, since it is high in calorific value, it can be used as fuel gas.
  • the washing column (8) is fed through the line (20) with a washing liquid at temperatures of -30 to -80 ° C and preferably -60 to -70 ° C. Below is of it assumed that this is methanol, but other washing liquids are also possible per se.
  • the column (8) usually contains trays or packing. In it, the H2S is sufficiently washed out of the natural gas introduced in line (7), and the methanol also absorbs hydrocarbons. Purified natural gas is drawn off in the line (21), it is at least partially expanded in the expansion valve (22) and the temperature is thereby reduced. The natural gas is then passed together with the gas of line (12) through the heat exchange zone (2), where it serves as a coolant, and is available in line (24) as a product for further use.
  • the washing liquid loaded with H2S and hydrocarbons is withdrawn from the column (8) in the line (26), expediently expanded in the expansion valve (27) and the mixture is placed in a separation container (28).
  • An H2S-containing exhaust gas is passed through line (29) to the condensate of line (14) and the washing liquid is passed through line (30) after passing through the heat exchange zone (2) to a regeneration system (31).
  • the load is largely removed from the washing liquid in a manner known per se by stripping or heating and also by a combination of these measures.
  • An exhaust gas is drawn off in line (32) and leads to a further treatment, not shown.
  • Regenerated washing liquid is drawn off in line (20) and returned to the washing column (8) via a pump (not shown).
  • a partial flow of the product gas of the line (24) can be used, which can be obtained via the Line (34) shown in broken lines leads and used as stripping gas.
  • the product gas of line (24) consists mainly of methane and may also contain 2 to 20 vol .-% of C2 hydrocarbons.
  • the content of C3-hydrocarbons is usually below 0.1 vol .-% and the H2S content is at most about 1/10 of the H2S content in the gas line (1). In this purity, it is well suited as a feed gas for catalytic steam reforming to generate a gas mixture containing CO and H2.
  • the composition of the natural gas of line (1) is as follows: CH4 75 vol .-% C2H6 20 vol.% C3H8 1 vol .-% N2 3 vol.% CO2 1 vol .-%.
  • the natural gas which also contains 400 vol. Ppm H2S, has a pressure of 28 bar and a temperature of 30 ° C. It is cooled to -73 ° C in a plate heat exchanger (2) and thus reaches the separator (5).
  • the separated condensate is expanded to 10 bar in the expansion valve (10) and further expansion to 2 bar in the valve (13).
  • the gas in line (7) which is fed to the washing column (8), still contains about half of the C2-hydrocarbons and H2S, as well as N2 and CO2 and traces of C3-hydrocarbons.
  • the column (8) is given methanol of -70 ° C. in a quantity of 10 m3 / h as washing liquid, a pressure of 28 bar prevailing in the washing column.
  • the washed gas which is practically free of H2S and C3 hydrocarbons and contains only a small amount of C2 hydrocarbons, is passed through the expansion valve (22), the pressure being reduced to 10 bar.
  • the loaded washing liquid drawn off from the washing column in line (26) is let down to 2 bar; the expansion gas released during the expansion is mixed with the gas in line (14).
  • 7,000 Nm 3 / h of exhaust gas are obtained in line (15) with a pressure of 2 bar and a temperature of + 10 ° C.
  • the methanol reaches the regeneration (31) in the line (30), where it is largely freed of the load at temperatures of + 10 ° C. by stripping with natural gas from the line (34).
  • the methanol is then fed back to the washing column (8) via a pump (not shown).

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  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Industrial Gases (AREA)

Abstract

Aus Erdgas, das neben Methanol auch Kohlenwasserstoffe mit 2 bis 4 C-Atomen pro Molekül und H₂S enthält, werden das H₂S und die Kohlenwasserstoffe teilweise entfernt. Das Erdgas mit einem Druck von mindestens 5 bar wird in einer Wärmeaustauschzone indirekt auf Temperaturen von -30 bis -100°C gekühlt. Aus dem gekühlten Erdgas trennt man Kondensat ab, entspannt das Kondensat und leitet es als Kühlmittel durch die Wärmeaustauschzone (2). Waschflüssigkeit wird in der Wärmeaustauschzone (2) auf Temperaturen von -30 bis -80°C gekühlt und in einer Waschzone (8) mit dem von Kondensat befreiten Erdgas zusammengeführt. Die aus der Waschzone (8) abgezogene, beladene Waschflüssigkeit leitet man durch die Wärmeaustauschzone (2). Das in der Waschzone gereinigte Erdgas wird entspannt und ebenfalls durch die Wärmeaustauschzone (2) geleitet.

Figure imgaf001
H₂S and the hydrocarbons are partially removed from natural gas, which in addition to methanol also contains hydrocarbons with 2 to 4 carbon atoms per molecule and H₂S. The natural gas with a pressure of at least 5 bar is indirectly cooled in a heat exchange zone to temperatures from -30 to -100 ° C. Condensate is separated from the cooled natural gas, the condensate is expanded and passed as a coolant through the heat exchange zone (2). Washing liquid is cooled in the heat exchange zone (2) to temperatures from -30 to -80 ° C and combined in a washing zone (8) with the natural gas freed from condensate. The loaded washing liquid drawn off from the washing zone (8) is passed through the heat exchange zone (2). The natural gas cleaned in the washing zone is expanded and also passed through the heat exchange zone (2).
Figure imgaf001

Description

Die Erfindung betrifft ein Verfahren zur Behandlung von Erdgas, das neben Methan Kohlenwasserstoffe mit 2 bis 4 C-Atomen pro Molekül und H₂S enthält, zum teilweisen Entfernen der Kohlenwasserstoffe und des H₂S.The invention relates to a process for the treatment of natural gas, which in addition to methane contains hydrocarbons having 2 to 4 carbon atoms per molecule and H₂S, for the partial removal of the hydrocarbons and the H₂S.

Aus dem rohen Erdgas, das z.B. als Einsatzmaterial für die katalytische Dampfreformierung vorgesehen ist, kann man die Kohlenwasserstoffe mit 5 und mehr Kohlenstoffatomen pro Molekül durch Adsorption relativ leicht entfernen. Die Kohlenwasserstoffe, insbesondere die höheren Kohlenwasserstoffe, bilden bei der katalytischen Reformierung Koksablagerungen auf dem Katalysator und vermindern dessen Aktivität.From the raw natural gas, e.g. is intended as a feedstock for catalytic steam reforming, the hydrocarbons with 5 and more carbon atoms per molecule can be removed relatively easily by adsorption. The hydrocarbons, especially the higher hydrocarbons, form coke deposits on the catalyst during catalytic reforming and reduce its activity.

Aufgabe des vorliegenden Verfahrens ist es, auf wirtschaftliche Weise die schwieriger abzutrennenden C₂- bis C₄-Kohlenwasserstoffe und gleichzeitig auch das H₂S, das den Reformierkatalysator ebenfalls schädigt, gemeinsam im ausreichenden Maß zu entfernen. Erfindungsgemäß gelingt dies dadurch, daß man das Erdgas, das einen Druck von mindestens 5 bar aufweist, in einer Wärmeaustauschzone indirekt auf Temperaturen von -30 bis -100°C kuhlt und Kondensat abtrennt, daß man das Kondensat entspannt und als Kühlmittel durch die Wärmeaustauschzone leitet, daß man eine aus einer Regenerationszone kommende Waschflüssigkeit in der Wärmeaustauschzone auf Temperaturen von -30 bis -80°C kuhlt und in eine Waschzone leitet, welcher man auch das vom Kondensat befreite Erdgas zuführt, daß man aus der Waschzone mit H₂S und Kohlenwasserstoffen beladene Waschflüssigkeit durch die Wärmeaustauschzone und in die Regenerationszone leitet, und daß man das in der Waschzone gereinigte Erdgas entspannt und durch die Wärmeaustauschzone leitet.The object of the present process is to remove the more difficult to separate C₂ to C₄ hydrocarbons and at the same time also the H₂S, which also damages the reforming catalyst, to a sufficient extent. According to the invention this is achieved in that the natural gas, which has a pressure of at least 5 bar, is indirectly cooled in a heat exchange zone to temperatures from -30 to -100 ° C and condensate is separated, that the condensate is expanded and passed through the heat exchange zone as a coolant that one cools a washing liquid coming from a regeneration zone in the heat exchange zone to temperatures of -30 to -80 ° C and passes into a washing zone, to which the natural gas freed of condensate is also fed, that washing liquid loaded with H₂S and hydrocarbons is fed from the washing zone through the heat exchange zone and into the regeneration zone, and that the natural gas cleaned in the scrubbing zone is expanded and passed through the heat exchange zone.

Vorteilhafterweise wird beim Auskondensieren der Kohlenwasserstoffe auch ein beträchtlicher Teil des H₂S mit auskondensiert. Dadurch wird die nachfolgende Waschzone entlastet. Diese Waschzone ist so ausgelegt, daß man hier die notwendige Entfernung des H₂S aus dem Erdgas erreicht. In der Waschzone werden üblicherweise auch C₃- und C₄-Kohlenwasserstoffe aus dem Erdgas entfernt, wodurch die vorausgehende Kondensation weniger zu leisten hat.Advantageously, when the hydrocarbons are condensed out, a considerable part of the H₂S is also condensed out. This relieves the load on the subsequent washing zone. This washing zone is designed so that you can reach the necessary removal of the H₂S from the natural gas. In the washing zone, C₃ and C₄ hydrocarbons are usually removed from the natural gas, so that the previous condensation has to do less.

Die für das Verfahren notwendige Kälte wird durch Entspannen des Kondensats sowie auch durch die Entspannung des aus der Waschzone kommenden Erdgases erreicht. Vorteilhafterweise kann auf eine Kälteanlage verzichtet werden. Da der Kältebedarf in der Waschzone nicht hoch ist, weil die notwendige Menge an Waschflüssigkeit niedrig gehalten wird, reicht die durch Kondensation erzeugte Kälte auch aus, um die Waschflüssigkeit vor der Waschzone genügend zu kühlen.The cold necessary for the process is achieved by relaxing the condensate and also by relaxing the natural gas coming from the washing zone. A refrigeration system can advantageously be dispensed with. Since the cooling requirement in the washing zone is not high because the necessary amount of washing liquid is kept low, the cold generated by condensation is also sufficient to cool the washing liquid in front of the washing zone sufficiently.

Zweckmäßigerweise wird das aus dem gekühlten Erdgas abgetrennte Kondensat zweistufig entspannt und das dabei gebildete Entspannungsgas durch die Wärmeaustauschzone geleitet.The condensate separated from the cooled natural gas is expediently expanded in two stages and the expansion gas formed in the process is passed through the heat exchange zone.

Als Waschflüssigkeit verwendet man Methanol, Aceton oder andere C₁- bis C₃-Oxo-Kohlenwasserstoffe.The washing liquid used is methanol, acetone or other C₁ to C₃ oxo hydrocarbons.

Einzelheiten und Ausgestaltungsmöglichkeiten des Verfahrens werden mit Hilfe der Zeichnung erläutert.Details and design options of the method are explained with the aid of the drawing.

Erdgas, das Kohlenwasserstoffe und H₂S enthält, wird in der Leitung (1) herangeführt. Vorzugsweise hat man aus diesem Erdgas die Feststoffe und auch die Kohlenwasserstoffe mit 5 und mehr C-Atomen pro Molekül bereits zuvor abgetrennt. Das Erdgas in der Leitung (1) enthält somit neben H₂S vor allem noch C₂-, C₃- und C₄-Kohlenwasserstoffe. Dieses Erdgas wird in einer Wärmeaustauschzone (2), z.B. einem Plattenwärmetauscher, auf Temperaturen von -30 bis -100°C und vorzugsweise -40 bis -90°C indirekt gekühlt. Bei dieser Kühlung entsteht Kondensat, welches den Hauptteil der Kohlenwasserstoffe und auch einen beträchtlichen Teil des H₂S enthält. In der Leitung (4) führt man dieses Gemisch zu einem Abscheider (5), aus dem man das Kondensat durch die Leitung (6) abzieht. Das Gasgemisch gibt man in der Leitung (7) einer Waschkolonne (8) auf.Natural gas containing hydrocarbons and H₂S is introduced in line (1). The solids and also the hydrocarbons having 5 and more carbon atoms per molecule have preferably been separated from this natural gas beforehand. The natural gas in line (1) thus contains in addition to H₂S especially C₂, C₃ and C- hydrocarbons. This natural gas is in a heat exchange zone (2), e.g. a plate heat exchanger, indirectly cooled to temperatures from -30 to -100 ° C and preferably -40 to -90 ° C. This cooling creates condensate, which contains the main part of the hydrocarbons and also a considerable part of the H₂S. In line (4) this mixture is led to a separator (5), from which the condensate is drawn off through line (6). The gas mixture is added to a washing column (8) in line (7).

Das Kondensat wird über das Entspannungsventil (10) teilweise entspannt und einem Trennbehälter (11) zugeführt. Das Entspannungsgas zieht man in der Leitung (12) ab und entspannt das Kondensat über das Entspannungsventil (13) nochmals. Die Entspannung des Kondensats in den Ventilen (10) und (13) führt zu einer erheblichen Temperaturabsenkung. Dadurch kann das Kondensat, das man in der Leitung (14) durch die Wärmeaustauschzone (2) führt, in wirksamer Weise als Kühlmittel dienen. Das durch die Erwärmung in der Wärmeaustauschzone (2) entstehende Abgas steht in der Leitung (15) zur Verfügung, es kann, da es heizwertreich ist, als Brenngas verwendet werden.The condensate is partially expanded via the expansion valve (10) and fed to a separation tank (11). The expansion gas is drawn off in line (12) and the condensate is expanded again via the expansion valve (13). The expansion of the condensate in the valves (10) and (13) leads to a considerable drop in temperature. As a result, the condensate which is led through the heat exchange zone (2) in the line (14) can effectively serve as a coolant. The exhaust gas resulting from the heating in the heat exchange zone (2) is available in line (15) and, since it is high in calorific value, it can be used as fuel gas.

Der Waschkolonne (8) führt man durch die Leitung (20) eine Waschflüssigkeit mit Temperaturen von -30 bis -80°C und vorzugsweise -60 bis -70°C zu. Nachfolgend wird davon ausgegangen, daß es sich hierbei um Methanol handelt, doch sind an sich auch andere Waschflüssigkeiten möglich. Die Kolonne (8) enthält üblicherweise Böden oder Füllkörper. In ihr wird das H₂S aus dem in der Leitung (7) herangeführten Erdgas in ausreichendem Maß ausgewaschen, dabei nimmt das Methanol auch Kohlenwasserstoffe auf. Gereinigtes Erdgas zieht man in der Leitung (21) ab, entspannt es mindestens teilweise im Entspannungsventil (22) und senkt dadurch die Temperatur. Das Erdgas wird dann zusammen mit dem Gas der Leitung (12) durch die Wärmeaustauschzone (2) geführt, wo es als Kühlmittel dient und steht in der Leitung (24) als Produkt zur weiteren Verwendung zur Verfügung.The washing column (8) is fed through the line (20) with a washing liquid at temperatures of -30 to -80 ° C and preferably -60 to -70 ° C. Below is of it assumed that this is methanol, but other washing liquids are also possible per se. The column (8) usually contains trays or packing. In it, the H₂S is sufficiently washed out of the natural gas introduced in line (7), and the methanol also absorbs hydrocarbons. Purified natural gas is drawn off in the line (21), it is at least partially expanded in the expansion valve (22) and the temperature is thereby reduced. The natural gas is then passed together with the gas of line (12) through the heat exchange zone (2), where it serves as a coolant, and is available in line (24) as a product for further use.

Die mit H₂S und Kohlenwasserstoffen beladene Waschflüssigkeit zieht man aus der Kolonne (8) in der Leitung (26) ab, entspannt es zweckmäßigerweise im Entspannungsventil (27) und gibt das Gemisch einem Trennbehälter (28) auf. Ein H₂S-haltiges Abgas führt man über die Leitung (29) zum Kondensat der Leitung (14) und die Waschflüssigkeit gibt man über die Leitung (30) nach Hindurchleiten durch die Wärmeaustauschzone (2) zu einer Regenerationsanlage (31). In der Anlage (31) wird in an sich bekannter Weise durch Strippen oder Erhitzen sowie auch durch eine Kombination dieser Maßnahmen die Beladung aus der Waschflüssigkeit weitgehend entfernt. Ein Abgas zieht man in der Leitung (32) ab und führt es zu einer nicht dargestellten Weiterbehandlung.The washing liquid loaded with H₂S and hydrocarbons is withdrawn from the column (8) in the line (26), expediently expanded in the expansion valve (27) and the mixture is placed in a separation container (28). An H₂S-containing exhaust gas is passed through line (29) to the condensate of line (14) and the washing liquid is passed through line (30) after passing through the heat exchange zone (2) to a regeneration system (31). In the system (31), the load is largely removed from the washing liquid in a manner known per se by stripping or heating and also by a combination of these measures. An exhaust gas is drawn off in line (32) and leads to a further treatment, not shown.

Regenerierte Waschflüssigkeit wird in der Leitung (20) abgezogen und über eine nicht dargestellte Pumpe der Waschkolonne (8) wieder zugeführt. Zum Regenerieren in der Anlage (31) kann man z.B. einen Teilstrom des Produktgases der Leitung (24) verwenden, welchen man über die gestrichelt eingezeichnete Leitung (34) heranführt und als Strippgas benutzt.Regenerated washing liquid is drawn off in line (20) and returned to the washing column (8) via a pump (not shown). For regeneration in the system (31), for example, a partial flow of the product gas of the line (24) can be used, which can be obtained via the Line (34) shown in broken lines leads and used as stripping gas.

Das Produktgas der Leitung (24) besteht hauptsächlich aus Methan und kann daneben noch 2 bis 20 Vol.-% an C₂-Kohlenwasserstoffen enthalten. Der Gehalt an C₃-Kohlenwasserstoffen liegt zumeist unterhalb von 0,1 Vol.-% und der H₂S-Gehalt beträgt höchstens etwa 1/10 des H₂S-Gehalts im Gas der Leitung (1). Als Einsatzgas für die katalytische Dampfreformierung zum Erzeugen eines CO und H₂ enthaltenden Gasgemisches ist es in dieser Reinheit gut geeignet.The product gas of line (24) consists mainly of methane and may also contain 2 to 20 vol .-% of C₂ hydrocarbons. The content of C₃-hydrocarbons is usually below 0.1 vol .-% and the H₂S content is at most about 1/10 of the H₂S content in the gas line (1). In this purity, it is well suited as a feed gas for catalytic steam reforming to generate a gas mixture containing CO and H₂.

Beispielexample

In einer der Zeichnung entsprechenden Verfahrensführung werden pro Stunde 50 000 Nm³ Erdgas behandelt. Einzelheiten des Verfahrens wurden zum Teil berechnet. Aus dem Erdgas wurden in einer Vorstufe Kohlenwasserstoffe mit 5 und mehr C-Atomen sowie auch Verunreinigungen abgetrennt. Die Zusammensetzung des Erdgases der Leitung (1) ist folgende:
CH₄ 75 Vol.-%
C₂H₆ 20 Vol.-%
C₃H₈ 1 Vol.-%
N₂ 3 Vol.-%
CO₂ 1 Vol.-%.In a procedure corresponding to the drawing, 50,000 Nm³ of natural gas are treated per hour. Details of the procedure were partially calculated. In a preliminary stage, hydrocarbons with 5 and more carbon atoms as well as impurities were separated from the natural gas. The composition of the natural gas of line (1) is as follows:
CH₄ 75 vol .-%
C₂H₆ 20 vol.%
C₃H₈ 1 vol .-%
N₂ 3 vol.%
CO₂ 1 vol .-%.

Das Erdgas, das auch 400 Vol.-ppm H₂S enthält, weist einen Druck von 28 bar und eine Temperatur von 30°C auf. Es wird in einem Plattenwärmeaustauscher (2) auf -73°C gekühlt und gelangt so in den Abscheider (5). Das abgetrennte Kondensat wird im Entspannungsventil (10) auf 10 bar entspannt und eine weitere Entspannung erfolgt im Ventil (13) auf 2 bar.The natural gas, which also contains 400 vol. Ppm H₂S, has a pressure of 28 bar and a temperature of 30 ° C. It is cooled to -73 ° C in a plate heat exchanger (2) and thus reaches the separator (5). The separated condensate is expanded to 10 bar in the expansion valve (10) and further expansion to 2 bar in the valve (13).

Das Gas in der Leitung (7), das der Waschkolonne (8) zugeführt wird, enthält etwa noch die Hälfte der C₂-Kohlenwasserstoffe und des H₂S, dazu N₂ und CO₂ sowie Spuren von C₃-Kohlenwasserstoffen. Der Kolonne (8) gibt man als Waschflüssigkeit Methanol von -70°C in einer Menge von 10 m³/h auf, wobei in der Waschkolonne ein Druck von 28 bar herrscht. Das gewaschene Gas, das praktisch frei von H₂S und C₃-Kohlenwasserstoffen ist und nur noch einen geringen Rest an C₂-Kohlenwasserstoffen enthält, wird durch das Entspannungsventil (22) geleitet, wobei der Druck auf 10 bar reduziert wird. Gemischt mit dem Gas der Leitung (12) erhält man in der Leitung (24) pro Stunde 43 000 Nm³ behandeltes Erdgas mit einem Druck von 10 bar und einer Temperatur von 22°C, das neben CH₄ noch 10 Vol.-% C₂-Kohlenwasserstoffe, 0,1 Vol.-% C₃-Kohlenwasserstoffe, 3,4 Vol.-% N₂ und 0,7 Vol.-% CO₂ enthält. Der H₂S-Gehalt des Gases beträgt 5 Vol.-ppm.The gas in line (7), which is fed to the washing column (8), still contains about half of the C₂-hydrocarbons and H₂S, as well as N₂ and CO₂ and traces of C₃-hydrocarbons. The column (8) is given methanol of -70 ° C. in a quantity of 10 m³ / h as washing liquid, a pressure of 28 bar prevailing in the washing column. The washed gas, which is practically free of H₂S and C₃ hydrocarbons and contains only a small amount of C₂ hydrocarbons, is passed through the expansion valve (22), the pressure being reduced to 10 bar. Mixed with the gas from line (12), 43,000 Nm³ of treated natural gas are obtained in line (24) per hour with a pressure of 10 bar and a temperature of 22 ° C, which in addition to CH₄ contains 10% by volume of C₂ hydrocarbons , 0.1 vol .-% C₃ hydrocarbons, 3.4 vol .-% N₂ and 0.7 vol .-% CO₂ contains. The H₂S content of the gas is 5 ppm by volume.

Die in der Leitung (26) aus der Waschkolonne abgezogene beladene Waschflüssigkeit wird auf 2 bar entspannt; das bei der Entspannung freigesetzte Entspannungsgas mischt man dem Gas der Leitung (14) zu. Man erhält auf diese Weise in der Leitung (15) 7 000 Nm³/h Abgas mit einem Druck von 2 bar und einer Temperatur von +10°C. Das Methanol gelangt in der Leitung (30) zur Regeneration (31), wo es bei Temperaturen von +10°C durch Strippen mit Erdgas aus der Leitung (34) von der Beladung weitgehend befreit wird. Über eine nicht dargestellte Pumpe wird das Methanol dann zurück zur Waschkolonne (8) geführt.The loaded washing liquid drawn off from the washing column in line (26) is let down to 2 bar; the expansion gas released during the expansion is mixed with the gas in line (14). In this way, 7,000 Nm 3 / h of exhaust gas are obtained in line (15) with a pressure of 2 bar and a temperature of + 10 ° C. The methanol reaches the regeneration (31) in the line (30), where it is largely freed of the load at temperatures of + 10 ° C. by stripping with natural gas from the line (34). The methanol is then fed back to the washing column (8) via a pump (not shown).

Claims (5)

1. Verfahren zur Behandlung von Erdgas, das neben Methan Kohlenwasserstoffe mit 2 bis 4 C-Atomen pro Molekül und H₂S enthält, zum teilweisen Entfernen der Kohlenwasserstoffe und des H₂S, dadurch gekennzeichnet, daß man das Erdgas, das einen Druck von mindestens 5 bar aufweist, in einer Wärmeaustauschzone indirekt auf Temperaturen von -30 bis -100°C kühlt und Kondensat abtrennt, daß man das Kondensat entspannt und als Kühlmittel durch die Wärmeaustauschzone leitet, daß man eine aus einer Regenerationszone kommende Waschflüssigkeit in der Wärmeaustauschzone auf Temperaturen von -30 bis -80°C kühlt und in eine Waschzone leitet, welcher man auch das vom Kondensat befreite Erdgas zuführt, daß man aus der Waschzone mit H₂S und Kohlenwasserstoffen beladene Waschflüssigkeit durch die Wärmeaustauschzone und in die Regenerationszone leitet, und daß man das in der Waschzone gereinigte Erdgas entspannt und durch die Wärmeaustauschzone leitet.1. A process for the treatment of natural gas which, in addition to methane, contains hydrocarbons having 2 to 4 carbon atoms per molecule and H₂S, for the partial removal of the hydrocarbons and the H₂S, characterized in that the natural gas, which has a pressure of at least 5 bar , indirectly in a heat exchange zone to temperatures from -30 to -100 ° C and condensate is separated, that the condensate is expanded and passed as a coolant through the heat exchange zone, that a washing liquid coming from a regeneration zone in the heat exchange zone to temperatures from -30 to Cools -80 ° C and passes into a washing zone, which also supplies the natural gas freed from the condensate, that one passes from the washing zone with H₂S and hydrocarbons-laden washing liquid through the heat exchange zone and into the regeneration zone, and that one cleans the natural gas cleaned in the washing zone relaxed and passes through the heat exchange zone. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Erdgas mit einem Druck von mindestens 10 bar zum indirekten Kühlen durch die Wärmeaustauschzone leitet.2. The method according to claim 1, characterized in that natural gas is passed at a pressure of at least 10 bar for indirect cooling through the heat exchange zone. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man das aus dem gekühlten Erdgas abgetrennte Kondensat zweistufig entspannt und das dabei gebildete Entspannungsgas durch die Wärmeaustauschzone leitet.3. The method according to claim 1 or 2, characterized in that the condensate separated from the cooled natural gas is expanded in two stages and the expansion gas thereby formed is passed through the heat exchange zone. 4. Verfahren nach Anspruch 1 oder einem der folgenden, dadurch gekennzeichnet, daß man die aus der Waschzone kommende, beladene Waschflüssigkeit teilweise entspannt und das dabei abgetrennte, H₂S-haltige Entspannungsgas durch die Wärmeaustauschzone leitet.4. The method according to claim 1 or one of the following, characterized in that the loaded washing liquid coming from the washing zone is partially relaxed and the separated, H₂S-containing expansion gas is passed through the heat exchange zone. 5. Verfahren nach Anspruch 1 oder einem der folgenden, dadurch gekennzeichnet, daß man als Waschflüssigkeit Methanol, Aceton oder andere C₁- bis C₃-Oxo-Kohlenwasserstoffe verwendet.5. The method according to claim 1 or one of the following, characterized in that methanol, acetone or other C₁ to C₃ oxo hydrocarbons are used as washing liquid.
EP89202108A 1988-09-02 1989-08-17 Process for treating natural gas containing hydrocarbons and hydrogen sulfide Expired - Lifetime EP0361557B1 (en)

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DE3829878A DE3829878A1 (en) 1988-09-02 1988-09-02 METHOD FOR THE TREATMENT OF HYDROCARBONS AND H (ARROW ABBEERTS) 2 (ARROW DOWN) S INGREDIENT NATURAL GAS

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FR2641542B1 (en) * 1988-11-15 1994-06-24 Elf Aquitaine PROCESS FOR SIMULTANEOUS DECARBONATION AND DEGAZOLINATION OF A GASEOUS MIXTURE MAINLY CONSISTING OF METHANE AND HYDROCARBONS OF C2 AND MORE AND INCLUDING CO2
US5321952A (en) * 1992-12-03 1994-06-21 Uop Process for the purification of gases
US5325672A (en) * 1992-12-03 1994-07-05 Uop Process for the purification of gases
FR2722110B1 (en) * 1994-07-08 1996-08-30 Inst Francais Du Petrole PROCESS FOR DEACIDIFYING A GAS FOR THE PRODUCTION OF CONCENTRATED ACID GASES
US5659109A (en) * 1996-06-04 1997-08-19 The M. W. Kellogg Company Method for removing mercaptans from LNG
DE102004036708A1 (en) * 2004-07-29 2006-03-23 Linde Ag Process for liquefying a hydrocarbon-rich stream
US7645322B2 (en) * 2006-09-15 2010-01-12 Ingersoll Rand Energy Systems Corporation System and method for removing water and siloxanes from gas
GB0814556D0 (en) * 2008-08-11 2008-09-17 Edwards Ltd Purification of gas stream
US9528704B2 (en) 2014-02-21 2016-12-27 General Electric Company Combustor cap having non-round outlets for mixing tubes

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1794353A1 (en) * 1967-04-15 1973-02-15 Helmut Prof Dr Phys Knapp THE WASHING OF WATER VAPOR FROM A NATURAL GAS STREAM

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE935144C (en) * 1949-09-16 1955-11-10 Linde Eismasch Ag Process for the purification of gases, in particular those for synthesis and heating purposes
US3373574A (en) * 1965-04-30 1968-03-19 Union Carbide Corp Recovery of c hydrocarbons from gas mixtures containing hydrogen
ES358809A1 (en) * 1967-11-03 1970-06-01 Linde Ag Process and apparatus for the separation of a hydrogen-containing gaseous mixture
US4038332A (en) * 1975-10-09 1977-07-26 Phillips Petroleum Company Separation of ethyl fluoride
US4336045A (en) * 1981-06-29 1982-06-22 Union Carbide Corporation Acetylene removal in ethylene and hydrogen separation and recovery process
DE3247782A1 (en) * 1982-12-23 1984-06-28 Linde Ag, 6200 Wiesbaden METHOD FOR DISASSEMBLING A GAS MIXTURE TO BE USED IN A METHANOL SYNTHESIS GAS SYSTEM AT LOW TEMPERATURES
JPS60150456A (en) * 1984-01-19 1985-08-08 Diesel Kiki Co Ltd Fuel injector for internal-combustion engine
IT1190359B (en) * 1985-05-24 1988-02-16 Snam Progetti CRYOGENIC PROCEDURE FOR REMOVAL OF ACID GASES FROM GAS MIXTURES BY SOLVENT
US4654062A (en) * 1986-07-11 1987-03-31 Air Products And Chemicals, Inc. Hydrocarbon recovery from carbon dioxide-rich gases
DE3626561A1 (en) * 1986-08-06 1988-02-11 Linde Ag Process for removing C2+- or C3+-hydrocarbons from a gas mixture

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1794353A1 (en) * 1967-04-15 1973-02-15 Helmut Prof Dr Phys Knapp THE WASHING OF WATER VAPOR FROM A NATURAL GAS STREAM

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