DE102007062213A1 - Production of hydrogen- and carbon monoxide-containing gas, i.e. oxo gas, from a mixture of these gases and methane, involves separation in a cryogenic stripper and scrubbing with liquid carbon monoxide - Google Patents
Production of hydrogen- and carbon monoxide-containing gas, i.e. oxo gas, from a mixture of these gases and methane, involves separation in a cryogenic stripper and scrubbing with liquid carbon monoxide Download PDFInfo
- Publication number
- DE102007062213A1 DE102007062213A1 DE102007062213A DE102007062213A DE102007062213A1 DE 102007062213 A1 DE102007062213 A1 DE 102007062213A1 DE 102007062213 A DE102007062213 A DE 102007062213A DE 102007062213 A DE102007062213 A DE 102007062213A DE 102007062213 A1 DE102007062213 A1 DE 102007062213A1
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- Germany
- Prior art keywords
- gas
- carbon monoxide
- hydrogen
- methane
- washing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 143
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000007788 liquid Substances 0.000 title claims abstract description 27
- 238000000926 separation method Methods 0.000 title claims abstract description 16
- 238000005201 scrubbing Methods 0.000 title claims abstract description 12
- 239000007789 gas Substances 0.000 title claims description 102
- 239000000203 mixture Substances 0.000 title abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000005406 washing Methods 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 37
- 239000012071 phase Substances 0.000 claims description 35
- 238000003860 storage Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 description 24
- 238000010992 reflux Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012432 intermediate storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- BUHVIAUBTBOHAG-FOYDDCNASA-N (2r,3r,4s,5r)-2-[6-[[2-(3,5-dimethoxyphenyl)-2-(2-methylphenyl)ethyl]amino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound COC1=CC(OC)=CC(C(CNC=2C=3N=CN(C=3N=CN=2)[C@H]2[C@@H]([C@H](O)[C@@H](CO)O2)O)C=2C(=CC=CC=2)C)=C1 BUHVIAUBTBOHAG-FOYDDCNASA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013526 supercooled liquid Substances 0.000 description 1
Classifications
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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
- F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
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- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
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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
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
- F25J1/0027—Oxides of carbon, e.g. CO2
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- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
- F25J1/0221—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using the cold stored in an external cryogenic component in an open refrigeration loop
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- 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
- F25J3/0252—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 hydrogen
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- 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
- F25J3/0261—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon monoxide
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- 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
- F25J3/0271—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 H2/CO mixtures, i.e. of synthesis gas
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/046—Purification by cryogenic separation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
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- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/40—Features relating to the provision of boil-up in the bottom of a column
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- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/76—Refluxing the column with condensed overhead gas being cycled in a quasi-closed loop refrigeration cycle
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- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
- 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
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
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- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
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- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
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- F25J2210/42—Nitrogen
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2215/00—Processes characterised by the type or other details of the product stream
- F25J2215/02—Mixing or blending of fluids to yield a certain product
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- F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
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- F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
- F25J2290/62—Details of storing a fluid in a tank
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation By Low-Temperature Treatments (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Gewinnung eines Wasserstoff (H2) und Kohlenmonoxid (CO) enthaltenden Gasproduktes (Oxogas) durch kryogene Zerlegung eines Wasserstoff, Kohlenmonoxid und Methan (CH4) enthaltenden Einsatzes in einer, eine Methanwäsche umfassenden kryogenen Zerlegungseinrichtung (Gaszerleger), wobei innerhalb des Gaszerlegers aus dem Einsatz ein erster, mit Wasserstoff angereicherter Gasstrom erzeugt wird, der angewärmt, aus dem Gaszerleger herausgeführt und zumindest mit einem Teil eines ebenfalls im Gaszerleger aus dem Einsatz gewonnen zweiten, mit Kohlenmonoxid angereicherten Gasstroms zum Oxogas gemischt wird.The invention relates to a process for obtaining a gas product (oxo gas) containing hydrogen (H 2 ) and carbon monoxide (CO) by cryogenic decomposition of an insert containing hydrogen, carbon monoxide and methane (CH 4 ) in a cryogenic separation device (gas decomposer) comprising a methane wash. wherein within the Gaszerlegers from the use of a first, hydrogen-enriched gas stream is generated, which is warmed out of the gas separator and at least mixed with a part of a likewise obtained in the gas separator from the second application, enriched with carbon monoxide gas stream to the oxo gas.
Darüber hinaus betrifft die Erfindung eine Vorrichtung zur Durchführung des Verfahrens.About that In addition, the invention relates to a device for implementation of the procedure.
Unter Oxogas sei im Folgenden ein Gasgemisch zu verstehen, das im Wesentlichen aus Wasserstoff und Kohlenmonoxid besteht, darüber hinaus in geringem Umfang jedoch auch andere Substanzen, wie z. B. Methan, enthält. Der Wasserstoffgehalt eines Oxogas liegt zwischen 10 und 90 mol% – vorzugsweise wird jedoch ein H2/CO-Verhältnis von 1 angestrebt.Under oxo gas is to be understood in the following, a gas mixture consisting essentially of hydrogen and carbon monoxide, in addition, however, to a small extent, other substances such. As methane contains. The hydrogen content of an oxo gas is between 10 and 90 mol% - but preferably a H 2 / CO ratio of 1 is desired.
Ein
gattungsgemäßes Verfahren sowie eine Vorrichtung
zur Durchführung dieses Verfahrens werden in der Patentanmeldung
Bedingt durch die Gewinnungsmethode, enthält der erste Gasstrom neben Wasserstoff und Kohlenmonoxid auch Methan, das bei Nachfolgeprozessen zu unerwünschten Nebenreaktionen bzw. zu einer Erhöhung der Ausschleusemenge und damit der Verluste führen kann.conditioned by the extraction method, contains the first gas stream In addition to hydrogen and carbon monoxide and methane, in subsequent processes to undesirable side reactions or to an increase the discharge amount and thus the losses can lead.
Aufgabe der Erfindung ist es daher, ein Verfahren der eingangs beschriebenen Art sowie eine Vorrichtung zur Durchführung des Verfahrens anzugeben, die es erlauben, ein Oxogas mit einem geringeren Methangehalt zu gewinnen, als es nach dem Stand der Technik möglich ist.task The invention is therefore a method of the type described above Art and a device for carrying out the method which allow an oxo gas with a lower methane content to win, as it is possible according to the state of the art is.
Die gestellte Aufgabe wird verfahrensseitig erfindungsgemäß dadurch gelöst, dass der erste, mit Wasserstoff angereicherte Gasstrom durch Wäsche (CO-Wäsche) mit einer kohlenmonoxidreichen Flüssigkeit aus dem gegen anzuwärmende Verfahrensströme abgekühlten Einsatz abgetrennt wird.The asked task is the method according to the invention thereby solved that the first, hydrogen-enriched gas stream by washing (CO-washing) with a carbon monoxide-rich Liquid from the process streams to be heated cooled use is separated.
Durch die erfindungsgemäße Wäsche des abgekühlten Einsatzes mit einer kohlenmonoxidreichen Flüssigkeit, kann ein deutlich geringere Methangehalt erreicht werden, als dies durch den Stand der Technik möglich ist.By the laundry according to the invention of the cooled Use with a carbon monoxide-rich liquid, can a significantly lower methane content can be achieved than through the state of the art is possible.
Der Einsatz wird vorzugsweise gegen anzuwärmende Verfahrensströme soweit abgekühlt, dass hierbei ein zweiphasiges Stoffgemisch gebildet wird, das aus einer wasserstoffreichen, CO und Methan enthaltenden Gas- und einer kohlenmonoxidreichen, H2 und Methan enthaltenden Flüssigphase besteht. Eine bevorzugte Variante des erfindungsgemäßen Verfahrens sieht vor, dass das aus dem Einsatz gebildete zweiphasige Stoffgemisch durch Phasentrennung in eine wasserstoffreiche Gas- und eine kohlenmonoxidreiche Flüssigphase getrennt und ein Teil der Gasphase der erfindungsgemäßen CO-Wäsche unterzogen wird. Eine andere Variante sieht hingegen vor, dass die Gesamtmenge des zweiphasigen Stoffgemisches in die für die Durchführung der CO-Wäsche vorgesehen Einrichtung (CO-Waschkolonne) eingeleitet und dort in die beiden Phasen getrennt. Zumindest ein Teil der Gasphase wird anschließen mit flüssigem CO gewaschen, während der restliche Teil der Gas- und die gesamte Flüssigphase der aus der CO-Waschkolonne abgezogen und der Methanwäsche zugeführt werden.The insert is preferably cooled sufficiently against process streams to be heated so that in this case a two-phase mixture is formed, which consists of a hydrogen-rich, CO and methane-containing gas and a carbon monoxide-rich, H 2 and methane-containing liquid phase. A preferred variant of the method according to the invention provides that the two-phase mixture formed from the insert is separated by phase separation into a hydrogen-rich gas phase and a carbon monoxide-rich liquid phase and a part of the gas phase of the CO wash according to the invention is subjected. On the other hand, another variant provides that the total amount of the two-phase substance mixture is introduced into the device (CO scrubbing column) provided for carrying out the CO scrubbing and separated there into the two phases. At least a portion of the gas phase is subsequently washed with liquid CO, while the remainder of the gas and the entire liquid phase is withdrawn from the CO wash column and fed to the methane wash.
Eine bevorzugte Ausgestaltung des erfindungsgemäßen Verfahrens sieht vor, dass neben Oxogas wenigstens ein weiters Kohlenmonoxid enthaltendes Produkt erzeugt wird, während eine andere Ausgestaltung des erfindungsgemäßen Verfahrens vorsieht, dass Oxogas als einziges Kohlenmonoxid enthaltendes Produkt erzeugt wird.A preferred embodiment of the invention Method provides that in addition to oxogas at least one more carbon monoxide containing product is generated while another Embodiment of the method according to the invention provides that oxo gas is the only product containing carbon monoxide is produced.
Das erfindungsgemäße Verfahren weiterbildend, wird vorgeschlagen, dass der zweite, kohlenmonoxidreiche Gasstrom eine CO-Reinheit aufweist, wie sie für einen Gasstrom erforderlich ist, der an der Anlagengrenze als CO-Produkt abgegeben werden soll. Zweckmäßiger Weise wird der zweite, kohlenmonoxidreiche Gasstrom innerhalb des Gaszerlegers gemeinsam mit einem CO-Produktstrom aus dem Einsatz abgetrennt. Ein durch Methanwäsche erzeugtes CO-Produkt weist i. Allg. einen sehr geringen Methangehalt auf, so dass der Methangehalt des erfindungsgemäß erzeugten Oxogases im Wesentlichen vom Methangehalt des ersten, wasserstoffreichen Gasstroms bestimmt wird.The further developing the method according to the invention proposed that the second, carbon monoxide-rich gas stream a Has CO purity as required for a gas stream is to be delivered as a CO product at the plant boundary. Appropriately, the second, carbon monoxide rich Gas flow within the gas separator together with a CO product stream separated from the insert. A produced by methane wash CO product has i. Gen. a very low methane content, so that the methane content of the invention produced Oxogases essentially from the methane content of the first, hydrogen-rich Gas flow is determined.
Eine weitere bevorzugte Ausgestaltung des erfindungsgemäßen Verfahrens sieht vor, dass der Kätebedarf für die kryogene Gaszerlegung zumindest zum Teil über einen Kältekreislauf gedeckt wird, in dem ein CO-Produktreinheit aufweisender Stoffstrom als Kreislaufmedium zirkuliert und dabei verflüssigt wird. Zweckmäßiger Weise wird ein Teil des verflüssigten Kohlenmonoxids entnommen und als Waschmittel für die erfindungsgemäße CO-Wäsche des abgekühlten Einsatzes verwendet.Another preferred embodiment of The inventive method provides that the Kätebedarf for the cryogenic gas separation is at least partially covered by a refrigeration cycle in which a CO product purity exhibiting material flow is circulated as a circulating medium and thereby liquefied. Appropriately, a portion of the liquefied carbon monoxide is removed and used as a detergent for the inventive CO wash of the cooled insert.
Das Verhältnis von Wasserstoff zu Kohlenmonoxid (H/C-Verhältnis) im Oxogas ist abhängig von den Zusammensetzungen und den Mengen der beiden Gasströme, aus denen erfindungsgemäß das Oxogas gemischt wird. Vorzugsweise wird Oxogas mit einem molaren H2/CO-Verhältnis erzeugt, das zwischen 1,5 und 0,66 und bevorzugt bei 1 liegtThe ratio of hydrogen to carbon monoxide (H / C ratio) in the oxogas is dependent on the compositions and the amounts of the two gas streams from which the oxo gas is mixed according to the invention. Preferably, oxo gas is produced with a molar H 2 / CO ratio of between 1.5 and 0.66 and preferably 1
Aufgrund von Störungen oder während der An- und Abfahrprozedur, stimmen häufig in der Praxis die von einem Verbraucher geforderte und die im Gaszerleger erzeugte Menge an CO-Produkt nicht überein. Muss der Verbraucher beispielsweise wegen einer Störung mit verminderter Leistung arbeiten, kann für die Dauer der Störung oder bis zu einer entsprechenden Leistungsanpassung die im Gaszerleger erzeugte CO-Produktmenge nicht vollständig an den Verbraucher abgegeben werden. In einem solchen Fall wird nach dem Stand der Technik zu viel produziertes CO auf die Fackel gegeben. Andererseits kann die im Gaszerleger produzierte CO-Produktmenge aber auch geringer sein, als sie vom Verbraucher benötigt wird. Um kurzzeitig auftretende Unterschiede zwischen der im Gaszerleger produzierten und der vom Verbraucher geforderten Menge an CO-Produkt rasch ausgleichen zu können, sieht eine Weiterbildung des erfindungsgemäßen Verfahrens vor, dass überschüssig im Gaszerleger erzeugtes, CO-Produktreinheit aufweisendes Gas vorzugsweise gegen flüssigen Stickstoff abgekühlt und verflüssigt und zur Zwischenspeicherung in einen wärmeisolierten CO-Speicherbehälter eingeleitet wird. In Betriebsphasen, in denen die im Gaszerleger eine geringere, als die vom Verbraucher geforderte CO-Produktmenge erzeugt wird, wird flüssiges CO aus dem Speicherbehälter entnommen, verdampft und mit passendem Druck und in geeigneter Menge dem CO-Produkt zugemischt und zum Verbraucher geführt.by virtue of disturbances or during the start-up and shut-down procedure, In practice, they are often the same as those of a consumer required and the amount of CO product generated in the gas separator do not match. For example, the consumer needs to be disturbed can work with reduced power, for the duration the fault or until a corresponding power adjustment the amount of CO produced in the gas separator does not fully dissipate the consumer. In such a case is after the prior art too much CO produced on the torch. On the other hand, the amount of CO produced in the gas separator can but also lower than the consumer needs becomes. To short-term differences between the gas separator produced and demanded by the consumer amount of CO product To be able to compensate quickly, sees a further development of the inventive method that excess Gas produced in the gas separator, having CO product purity preferably gas cooled against liquid nitrogen and liquefied and for temporary storage in a thermally insulated CO storage tank is initiated. In operating phases in which the gas separator a lower than the amount of CO required by the consumer is generated, liquid CO from the storage tank removed, evaporated and with appropriate pressure and in an appropriate amount of the CO product mixed and led to the consumer.
Weiterhin betrifft die Erfindung eine Vorrichtung zur Gewinnung eines Wasserstoff (H2) und Kohlenmonoxid (CO) enthaltenden Gasproduktes (Oxogas) durch kryogene Zerlegung eines Wasserstoff, Kohlenmonoxid und Methan (CH4) enthaltenden Einsatzes, in einer, eine Methanwaschkolonne sowie Wärmetauscher zur Abkühlung und Anwärmung von Verfahrensströmen umfassenden kryogenen Zerlegungseinrichtung (Gaszerleger), in der aus dem Einsatz ein erster, mit Wasserstoff angereicherter Gasstrom erzeugbar und nach Anwärmung zumindest mit einem Teil eines ebenfalls im Gaszerleger aus dem Einsatz gewonnen zweiten, mit Kohlenmonoxid angereicherten Gasstroms zum Oxogas mischbar ist.Furthermore, the invention relates to a device for obtaining a hydrogen (H 2 ) and carbon monoxide (CO) containing gas product (oxo gas) by cryogenic decomposition of a hydrogen, carbon monoxide and methane (CH 4 ) containing insert, in one, a Methanwaschkolonne and heat exchangers for cooling and Warming of process streams comprehensive cryogenic separation device (gas separator) in the use of a first hydrogen-enriched gas stream generated and after heating at least with a part of a likewise recovered in the gas separator from the second application, enriched with carbon monoxide gas stream to the oxo gas miscible.
Die gestellte Aufgabe wird vorrichtungsseitig erfindungsgemäß dadurch gelöst, dass sie eine Wascheinrichtung aufweist, in der aus dem gegen anzuwärmende Verfahrensströme abgekühlten Einsatz durch Wäsche mit einer kohlenmonoxidreichen Flüssigkeit der erste, mit Wasserstoff angereicherte Gasstrom abtrennbar ist.The asked task is the device side according to the invention thereby solved that it has a washing device in the cooled from the process streams to be heated Use by washing with a carbon monoxide-rich liquid the first, hydrogen-enriched gas stream is separable.
Bevorzugte Varianten der erfindungsgemäßen Vorrichtung sehen vor, dass die Wascheinrichtung als Waschkolonne mit Packungen und/oder Stoffaustauschböden ausgeführt ist, wobei der gegen anzuwärmende Verfahrensströme abgekühlte Einsatz in den unteren Teil der Waschkolonne einleitbar und der erste, wasserstoffreiche Gasstrom vom Kopf der Waschkolonne abziehbar ist.preferred See variants of the device according to the invention that the washing device as a wash column with packing and / or mass transfer trays is carried out, wherein the process flows to be heated against cooled use in the lower part of the wash column Introduced and the first, hydrogen-rich gas stream from the head of Wash column is removable.
Liegt der gegen anzuwärmende Verfahrensströme abgekühlte Einsatz als zweiphasiges, aus einer wasserstoffreichen, CO und Methan enthaltenden Gas- und einer kohlenmonoxidreichen, H2 und Methan enthaltenden Flüssigphase bestehendes Stoffgemisch vor, so sehen zweckmäßige Weiterbildungen der Erfindung vor, dass vor der Wascheinrichtung ein Phasentrenner angeordnet ist, in dem das zweiphasige Stoffgemisch in seine Gas- und seine Flüssigphase zerlegbar ist oder das der untere Bereich der Wascheinrichtung als Phasentrenner ausgebildet ist, in dem die wasserstoffreiche, CO und Methan enthaltende Gasphase aus dem zweiphasigen Stoffgemisch abtrennbar ist. Zumindest ein Teil der abgetrennten Gasphase ist nachfolgend einer Wäsche mit einer kohlenmonoxidreichen Flüssigkeit zuführbar.If the use cooled against the process streams to be heated is present as a two-phase mixture comprising a hydrogen-rich, CO and methane-rich, H 2 and methane-containing liquid phase, expedient developments of the invention provide for a phase separator to be arranged upstream of the washing device in which the two-phase substance mixture can be separated into its gas phase and its liquid phase, or in which the lower region of the washing device is designed as a phase separator, in which the hydrogen-rich, CO and methane-containing gas phase can be separated from the two-phase substance mixture. At least part of the separated gas phase can subsequently be fed to a wash with a carbon monoxide-rich liquid.
Bei der Methanwascheinrichtung, handelt es sich vorzugsweise um eine Methanwascheinrichtung, wie sie dem Stand der Technik entspricht, die neben einer Methanwaschkolonne zur Abtrennung von Wasserstoff aus wasserstoffreichen, CO und Methan enthaltenden Gasphasen durch Wäsche mit flüssigem Methan auch eine H2-Strippkolonne zur Abtrennung von Wasserstoff aus kohlenmonoxidreichen Flüssigphasen und eine CO/CH4-Trennkolonne umfasst, in der Kohlenmonoxid aus Methan und CO enthaltende Flüssigphasen abtrennbar ist.The methane scrubber is preferably a methane scrubber as in the prior art which, in addition to a methane wash column for separating hydrogen from hydrogen-rich, CO and methane-containing gas phases by scrubbing with liquid methane, also has an H 2 -stripping column for separating off Includes hydrogen from carbon monoxide-rich liquid phases and a CO / CH 4 separation column, in which carbon monoxide from methane and CO-containing liquid phases is separable.
Eine Variante der erfindungsgemäßen Vorrichtung sieht eine Speichereinrichtung zur Zwischenspeicherung von Produktreinheit aufweisendem Kohlenmonoxid vor, die zwei Wärmetauscher sowie einen thermisch isolierten CO-Speicherbehälter umfasst. Die Speichereinrichtung erlaubt es, überschüssig erzeugtes, Produktreinheit aufweisendes Kohlenmonoxid im ersten Wärmetauscher vorzugsweise gegen flüssigen Stickstoff zu kondensieren und zur Zwischenspeicherung in den CO-Speicherbehälter einzuleiten. In Betriebszuständen, in denen mehr CO-Produkt gefordert wird, als im kryogenen Gaszerleger aktuell erzeugt wird, ermöglicht es die Speichereinrichtung weiterhin, flüssiges CO aus dem CO-Speicherbehälter zu entnehmen, im zweiten Wärmetauscher zu verdampfen und druck- und mengengeregelt dem CO-Produkt zuzumischen.A variant of the device according to the invention provides a storage device for intermediate storage of carbon monoxide having product purity, comprising two heat exchangers and a thermally insulated CO storage tank. The storage device allows excessively generated product purity having carbon monoxide in the first heat exchanger before preferably to condense against liquid nitrogen and initiate for intermediate storage in the CO storage tank. In operating states in which more CO product is required than is currently produced in the cryogenic gas separator, the storage device furthermore makes it possible to remove liquid CO from the CO storage container, to evaporate in the second heat exchanger and to control the pressure and quantity of the CO product admix.
Im Folgenden soll die Erfindung anhand eines in der Figur schematisch dargestellten Ausführungsbeispiels näher erläutert werden.in the The invention is based on a schematic in the figure illustrated embodiment illustrated become.
Im Ausführungsbeispiel werden aus einem aus Kohlenmonoxid (CO), Wasserstoff (H2) und Methan (CH4) bestehenden Synthesegas durch kryogene Gaszerlegung, neben Oxogas, ein Kohlenmonoxidprodukt sowie ein Rohwasserstoffstrom erzeugt.In the exemplary embodiment, a carbon monoxide product and a crude hydrogen stream are generated from a synthesis of carbon monoxide (CO), hydrogen (H 2 ) and methane (CH 4 ) synthesis gas by cryogenic gas separation, in addition to oxo.
Das
Synthesegas
Aus
der in der Methan-Waschkolonne T1 aufsteigenden wasserstoffreichen,
CO enthaltenden Gasphase wird Kohlenmonoxid mittels des als Rücklauf
aufgegebenen flüssigen Methans
Bei
der Gaswäsche wird in der Methan-Waschkolonne T1 Lösungswärme
frei gesetzt. Um eine übermäßige Aufheizung
des Methanwaschmittels zu verhindern, die zu einer Verminderung
der Waschleistung führen würde, ist die Methan-Waschkolonne
T1 mit den drei Kühlkreisläufen
Die
kohlenmonoxidreiche Flüssigphase
Das
vorwiegend aus Methan und Kohlenmonoxid bestehende Stoffgemisch
Die
im Phasentrenner D abgetrennte Flüssigphase
Das
aus flüssigem Methan bestehende Sumpfprodukt
Das
CO-Produktreinheit aufweisende Kopfprodukt
Nach
Verdichtung in der Verdichtersektion C1 wird ein CO-Strom
Wird
vom CO-Verbraucher weniger CO-Produkt
Der
Kältehaushalt des kryogenen Gaszerlegungsprozesses wird über
flüssigen Stickstoff
ZITATE ENTHALTEN IN DER BESCHREIBUNGQUOTES INCLUDE IN THE DESCRIPTION
Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.
Zitierte PatentliteraturCited patent literature
- - EP 1479990 [0004] - EP 1479990 [0004]
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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DE102007062213A DE102007062213A1 (en) | 2007-12-21 | 2007-12-21 | Production of hydrogen- and carbon monoxide-containing gas, i.e. oxo gas, from a mixture of these gases and methane, involves separation in a cryogenic stripper and scrubbing with liquid carbon monoxide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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DE102007062213A DE102007062213A1 (en) | 2007-12-21 | 2007-12-21 | Production of hydrogen- and carbon monoxide-containing gas, i.e. oxo gas, from a mixture of these gases and methane, involves separation in a cryogenic stripper and scrubbing with liquid carbon monoxide |
Publications (1)
Publication Number | Publication Date |
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DE102007062213A1 true DE102007062213A1 (en) | 2009-06-25 |
Family
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DE102007062213A Withdrawn DE102007062213A1 (en) | 2007-12-21 | 2007-12-21 | Production of hydrogen- and carbon monoxide-containing gas, i.e. oxo gas, from a mixture of these gases and methane, involves separation in a cryogenic stripper and scrubbing with liquid carbon monoxide |
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DE (1) | DE102007062213A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015140460A2 (en) | 2014-03-17 | 2015-09-24 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method and device for cryogenically separating a synthesis gas containing carbon monoxide, methane and hydrogen |
CN110398133A (en) * | 2019-07-14 | 2019-11-01 | 杭州杭氧股份有限公司 | A kind of separating synthetic gas produces the cryogenic separation device of high-purity CO, compressed natural gas |
CN113862051A (en) * | 2021-09-27 | 2021-12-31 | 北京石油化工工程有限公司 | Double-refrigeration-cycle methane-washing synthesis gas cryogenic separation device and separation method |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1479990A1 (en) | 2003-05-19 | 2004-11-24 | L'Air Liquide Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et Exploitation des Procédés Georges Claude | Process and installation for providing a fluid mixture containing at least 10% carbon monoxide |
-
2007
- 2007-12-21 DE DE102007062213A patent/DE102007062213A1/en not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1479990A1 (en) | 2003-05-19 | 2004-11-24 | L'Air Liquide Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et Exploitation des Procédés Georges Claude | Process and installation for providing a fluid mixture containing at least 10% carbon monoxide |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015140460A2 (en) | 2014-03-17 | 2015-09-24 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method and device for cryogenically separating a synthesis gas containing carbon monoxide, methane and hydrogen |
CN110398133A (en) * | 2019-07-14 | 2019-11-01 | 杭州杭氧股份有限公司 | A kind of separating synthetic gas produces the cryogenic separation device of high-purity CO, compressed natural gas |
CN110398133B (en) * | 2019-07-14 | 2023-05-23 | 杭氧集团股份有限公司 | Cryogenic separation device for producing high-purity CO and compressed natural gas by separating synthesis gas |
CN113862051A (en) * | 2021-09-27 | 2021-12-31 | 北京石油化工工程有限公司 | Double-refrigeration-cycle methane-washing synthesis gas cryogenic separation device and separation method |
CN113862051B (en) * | 2021-09-27 | 2024-02-13 | 北京石油化工工程有限公司 | Double refrigeration cycle methane washing synthetic gas cryogenic separation device and separation method |
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