US2293601A - Process of production of mixtures of gases hard to liquefy - Google Patents

Process of production of mixtures of gases hard to liquefy Download PDF

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US2293601A
US2293601A US340167A US34016740A US2293601A US 2293601 A US2293601 A US 2293601A US 340167 A US340167 A US 340167A US 34016740 A US34016740 A US 34016740A US 2293601 A US2293601 A US 2293601A
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nitrogen
liquid
mixture
hydrogen
gas
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Etlenne Alfred
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Air Liquide SA
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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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
    • 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
    • F25J3/0219—Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
    • 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
    • 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
    • F25J3/0271—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
    • 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
    • F25J3/0276—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/N2 mixtures, i.e. of ammonia synthesis 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
    • F25J5/00—Arrangements of cold exchangers or cold accumulators in separation or liquefaction plants
    • F25J5/002—Arrangements of cold exchangers or cold accumulators in separation or liquefaction plants for continuously recuperating cold, i.e. in a so-called recuperative heat exchanger
    • F25J5/007—Arrangements of cold exchangers or cold accumulators in separation or liquefaction plants for continuously recuperating cold, i.e. in a so-called recuperative heat exchanger combined with mass exchange, i.e. in a so-called dephlegmator
    • 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
    • F25J2200/50—Processes or apparatus using separation by rectification using multiple (re-)boiler-condensers at different heights of the column
    • 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
    • F25J2200/80—Processes or apparatus using separation by rectification using integrated mass and heat exchange, i.e. non-adiabatic rectification in a reflux exchanger or dephlegmator
    • 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
    • F25J2200/90—Details relating to column internals, e.g. structured packing, gas or liquid distribution
    • 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
    • F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
    • 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
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/14—Coke-ovens 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
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/42—Nitrogen
    • 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
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/20—Ammonia synthesis gas, e.g. H2/N2 mixture
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2240/00—Processes or apparatus involving steps for expanding of process streams
    • F25J2240/02—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/04—Internal refrigeration with work-producing gas expansion loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/42—Quasi-closed internal or closed external nitrogen refrigeration cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/904—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by liquid or gaseous cryogen in an open loop
    • 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
    • Y10S62/902—Apparatus
    • Y10S62/905—Column

Definitions

  • This invention relates to the production of mixtures of dimcultly-liqueflable gases. one of which at least is obtained by liquefylng a gaseous mixture.
  • One feature of the invention is that it is applicable to the production of nitrogenhydrogen mixtures such as are to be utilized for ammonia synthesis and which must, as known,
  • nitrogen-hydrogen mixtures consist of one volume of nitrogen for three volumes of hydrogen.
  • nitrogen-hydrogen mixtures will be referred to, but it is to be understood that the invention is also applicable inter alla to the production of mixtures of other liqueflable gases, such as carbon monoxide-hydrogen mixtures which, for instance, are to be utilized for the synthesis of organic compounds, as methyl alcohol.
  • the nitrogen-hydrogen mixtures to be utilized for ammonia synthesis In order to prepare, by partial liquefaction from coke oven or other similar gases, the nitrogen-hydrogen mixtures to be utilized for ammonia synthesis, it has been proposed to carry out the partial liquefaction of the coke oven gas and its final washing with liquid nitrogen under such temperature and pressure conditions that the obtained mixture, which consists of nitrogen and hydrogen, has the composition N+H3, which is necessary for ammonia synthesis, but generally such temperature and pressure conditions cannot practically be made to prevail at the sam time in economic manner, and the final gaseous mixture generally contains less than one volume of nitrogen for three volumes of hydrogen. In order to obtain a gaseous mixture having the composition N-l-H3, the necessary makeup nitrogen is accordingly added to the final gaseous mixture. This addition of nitrogen is accompanied by no substantial thermal effect.
  • the liquid nitrogen is added in greater quantity and the non-vaporised portion of the liquid nitrogen is utilized for washing the expanded gas so as to free it from its carbon monoxide.
  • the obtained mixture of nitrogen and hydrogen contains less than one volume of nitrogen for three volumes of hydrogen, which will generally be the case, there must be subsequently added thereto th quantity of nitrogen in gaseous state which is necessary for obtaining a mixture of hydrogen and nitrogen suitable for ammonia synthesis.
  • the hydrogen (or more generally a first diificultlyliqueflable gas resulting from the separation of a gaseous mixture by liquefaction) is admixed with nitrogen (or a second gas hard to liquefy). namely under such conditions that a useful thermal efiect is brought about.
  • the process according to the present invention for producing mixtures of diflicultly-liquefiable gases consists in cooling a gaseous mixture, liquefying it so as to separate therefrom a first gas which is to become a constituent of the gaseous mixture to be produced, cooling a second gas which is also to become a constituent of the gaseous mixture to be produced, mixing the less volatile of these two constituents, in the liquid state, with the other constituent in the gaseous state, the constituent in the liquid state being at a temperature sufiiciently low and being of suiliciently great quantity, that at least a portion of said liquid constituent does not vaporise when the addition takes place, and maintaining the mixture of gas and liquid thus constituted in heat exchange relation to the gases to be cooled, for instance, the treated gaseous mixture, so that there is an exchange of heat from the gases to be cooled to the liquid and gaseous mixture, such exchange of heat taking place either at the end of the purification of the gaseous mixture during the course of its treatment.
  • the process consists in cooling the gaseous nitrogen, liquefying it and admixing it while in its liquid state with gaseous hydrogen, the liquid nitrogen being at so low a temperature and in so great a quantity that at least a portion of the liquid nitrogen does not vaporise at the time of the addition.
  • the mixture of gas and liquid thus iconstituted is then warmed up, its cold being mixture, of which it is a part, the temperature which corresponds to the partial pressure oi the nitrogen in the gaseous phase, which temperature constantly remains lower than the temperature which the nitrogen (or the less volatile gas) would have if it would vaporise alone under the pressure of the mixture.
  • the nitrogen-hydrogen mixture flows downward through the open-ended tubes E located inside the tubes C and is warmed by indirect contact with the gas rising in the tubes C. From the lower end of the tubes E, the nitrogen-hydrogen mixture is passed to an expansion engine F, in which it expands with production of external work, and with resultant lowering of its temperature. Liquid nitrogen under pressure is conveyed through the pipe G, expanded through the valve T to the pressure of the expanded hydrogen-nitrogen mixture and added thereto.
  • the liquid ,nitrogen introduced through the pipe G previously has been cooled to a low temperature by heat exchange with the products resulting from the separation of coke oven gas intotits constituents, and is in such quantity that the mixture resulting from its union with the expanded mixture of hydrogen and nitrogen has substantially the composition of N+H:. Under these conditions, the liquid nitrotoo small to accomplish a satisfactory washing of the coke-oven gases in the column A. In such cases supplementary liquid nitrogen will then be introduced into the column A through the pipe U at the top thereof.
  • the compressed coke oven gas which has previously been cooled under the same conditions as in the case of Fig. 1, and which still contains an important proportion of carbon monoxide, flows upwardly successively through a washing column P, a nest of tubes S and a second washing column A.
  • the compressed gas is washed with liquid nitrogen still containing some carbon monoxide and is stripped only incompletely of its carbon monoxide, in the nest of tubes 8 it is cooled as will be mentioned hereinafter.
  • Such cooling of the compressed gas in the tubes 8 brings about a partial condensation of the gas.
  • the uncondensed gas is washed with pure liquid nitrogen, conveyed to the column through the pipe K, which takes up in known manner the small.quantities of carbon monoxide which remain in the gaseous mixture.
  • the liquid nitrogen flows downwardly successively through the column A, the nest of tubes S and the column P, thereby growing richer in carbon monoxide.
  • nitrogen is compressed and brought to a low temperature in liquid state by being put in heat exchange with the products resulting from the separation of the coke oven gas into its constituents.
  • the cold liquid nitrogen thus obtained enters the pipe X and is divided into two parts.
  • One part passes through the exchanger M where it is cooled, and is expanded through the valve R and constitutes the aforementioned washing liquid nitrogen which is introduced to the upper end of column A through the pipe K.
  • the other part passes through the pipe G, is expanded through the valve T and is added to the substantially pure hydrogen-nitrogen mixture which results from the washing operation carried out in the column A, and which leaves through the pipe L.
  • This second portion of liquid nitrogen is in such quantity that the obtained mixture of gas and liquid has substantially the composition N-l-Ha.
  • the mixture of liquid and gas thus formed flows through the exchanger M, in which it cools the liquid nitrogen delivered at the top of the column A through the pipe K.
  • the nitrogen-hydrogen mixture When leaving the exchanger M, the nitrogen-hydrogen mixture, still containing some liquid and still under pressure, is passed through the pipe N around the nest of tubes S, where it cools the gaseous mixture rising through said tubes, and leaves through the pipe 0 after being wholly or partially vaporized.
  • the production of. cold is obtained, for instance, by means of a nitrogen cycle.
  • the liquid mixture of carbon monoxide and nitrogen resulting from the separation of the coke oven gas into its constituents is preferably utilized as the medium for the cooling of the compressed nitrogen which is to constitute the make-up liquid nitrogen in the two examples given above.
  • the gaseous mixture of hydrogen and nitrogen obtained as the other product of the separation of the coke oven gas into its constituents could also be so utilized.
  • the mixture of hydrogen and nitrogen will preferably be partly warmed before being utilized for cooling the nitrogen;
  • the preliminary cooling of the nitrogen it is obtained either by putting compressed nitrogen in 'heat exchange with the separation products and especially the liquid methane, or by directly expanding the compressed nitrogen, at the surrounding temperature, or after being partially cooled, to an intermediate pressure which permits its liquefaction by heat exchange with the cold separation products.
  • the origin of the make-up nitrogen utilized in the liquid state in the two above examples is immaterial.
  • the 'nitrogen can, for example, be obtained by rectifying the liquid mixture of nitrogen and carbon monoxide obtained by cooling and washing the coke oven gas, and warming up the gaseous nitrogen resulting from this rectification in order to compress it at the surrounding temperature.
  • the process according to the invention may be applied to the obtention of hydrogencarbon monoxide mixtures by partial liquefaction of hydrogen-containing gaseous mixtures. In that case the washing of the gas with liquid nitrogen will, of course, be dispensed with and there will be obtained a gaseous mixture consisting of hydrogen and a little carbon monoxide and nitrogen, to which carbon monoxide will be added in the liquid state. More generally, the process is applicable to the production of mixtures of diflicultly-liquefiable gases, one of which at least is obtained by the separation of a gaseous mixture by liquefaction.
  • a process for producing mixtures of difficultly-liquefliable gases containing a constituent of greater volatility and a constituent of less volatility which comprises cooling a gaseous mixture containing the constituent of greater volatility sufficiently to separate said constituent from other constituents of the gaseous mixture by liquefaction, mixing said separated constituent, in the gaseous state, with the constituent of less volatility, in the liquid state, the constituent of less volatility being in an amount sufficiently great and at a temperature sufficiently low that at least a portion thereof is not vaporized when added to the more volatile constituent in the gaseous state, and passing the resultant mixture of gas and liquid into heat exchange relation with the first-mentioned gaseous mixture to cool said first-mentioned gaseous mixture and to cause the liquid of the liquid-and-gas mixture to be vaporized.
  • process for producing mixtures of hydrogen and nitrogen having the composition N-i-Hz which comprises washing a gaseous mixture containing hydrogen with liquid nitrogen, mixing the resulting gaseous mixture containing hydrogen and nitrogen, in the gaseous state, with liquid nitrogen, the amount of admixed liquid nitrogen being sufficiently great and its temperature sumciently low that at least a portion thereof is not vaporized when added to the gaseous mixture containing hydrogen and nitrogen, andpassing the resulting mixture of gas and liquid into heat exchange relation with the gaseous mixture resulting from the washing of the first-mentioned gaseous mixture with liquid nitrogen to. cool it and to cause the liquid of said liquid-aAd-gas mixture to be vaporized.
  • a process for producing mixtures of hydrogen and nitrogen having the composition N-I-I-h which comprises washing a gaseous mixture containing hydrogen with liquid nitrogen, subjecting the resulting gaseous mixture containing hydrogen and nitrogen to cooling sufficient to liquefy at least part of the nitrogen thereof, mixing the remainder of the mixture, in the gaseous state, with liquid nitrogen, the amount of admixed liquid nitrogen being sufiiciently great and its temperature sufficiently low that at least a portion thereof is not vaporized when added to said remainder of the mixture, and passing the resulting mixture of gas and liquid into heat exchange relation with the gaseous mixture resulting from the washing of the first-mentioned gaseous mixture with liquid nitrogen to cool it and to cause the liquid of said liquid-and-gas mixture to be vaporized.
  • a process for producing mixtures of hydrogen and nitrogen having the composition N+Ha which comprises washing a gaseous mixture containing hydrogen with liquid nitrogen, mixing the resulting gaseous mixture containing hydrogen and nitrogen, in the gaseous state, with liquid nitrogen, the amount of admixed liquid nitrogen being sufliciently great and its temperature sufficiently low that at least a portion thereof is not vaporized when added to the gaseous mixture containing hydrogen and nitrogen, and passing the resulting mixture of gas and liquid into heat exchange relation with the first-mentioned gaseous mixture while it is being washed with the liquid nitrogen to cool said first-mentioned gaseous mixture and to cause the liquid of said liquid-and-gas mixture to be vaporized.
  • a process for producing a mixture of lowboiling gases which comprises partially liqueiying being in an amount sumciently great and at a a temperature suniciently low that at least a porthereoi is not vaporized when added to the gaseous efliuent 01! said partial liquefaction, and
  • a process for producing a mixture of hydrogen and nitrogen which comprises cooling a hydrogen-containing gaseous mixture sui'iiciently to partially liquei'y it, washing the non-liquid por tion of said gaseousmixture with liquid nitrogen, mixing the gases resulting from said washin operation with a further quantity of liquid nitrogen, saidiurther quantity of liquid nitrogen being in an amount sumciently great and at a temperature suiliciently low that at least a portion thereof is not vaporized when added to the gases from said washing operation, and passing the resultant mixture of gas and liquid into heat exchange relation with the gases to be partially liquefied.
  • a process for producing a mixture of hydrogen and nitrogen which comprises cooling a hydrogen-containing gaseous mixture sufllciently to partially liquefy it, washing the non-liquid portion of said gaseous mixture with liquid nitrogen, mixing the gases resulting from said washing operation with a further quantity of liquid nitrogen, said further quantity of liquid nitrogen being in an amount sufllciently great and at a temperature sufllciently low that at least a portion thereof is not vaporized when added to the gases from said washing operation, and passing the resultant mixture of gas and liquid into heat exchange relation to the non-liquid portion oi the gases resulting from. the partial liquefaction of the hydrogen-containing gaseous mixture while said non-liquid portion is being subjected to the washing with liquid nitrogen.
  • a process for producing a mixture 01' hydrogen and nitrogen which comprises cooling 9. hydrogen-containing gaseous mixture suiliciently to partially liquefy it, washing the non-liquid portion of said gaseous mixture with liquid nitrogen, turther'cooling the washed gases, expand ing said washed gases with external work, mixing the expanded gases with liquid nitrogen, said last-mentioned liquid nitrogen being in an amount sufllciently great and at a temperature suiiiciently low that at least a portion thereof is not vaporized when it is added to the expanded gases, and passing the resulting mixture of gas and liquid into heat exchange relation with the washed gases which are to be further cooled.
  • a process for producing a mixture of hydrogen and nitrogen which comprises cooling 9. hydrogen-containing gaseous mixture sufficiently to partially liqueiy it, washing the non-liquid portion of said gaseous mixture with liquid nitrogen, mixing the gases resulting from said washing operation with a further quantity of liquid nitrogen, said further quantity of liquid nitrogen being in an amount suiliciently great and at a temperature sufliciently low that at least a portion thereof is not vaporized when added to the gases from said washing operation, and passing the resultant mixture of gas and liquid into heat exchange relation first with said washing liquid nitrogen and then with the non-liquefied portion of the hydrogen-containing gaseous mixture while said non-liquid portion is being subjected to the washing with liquid nitrogen.

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  • Physics & Mathematics (AREA)
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  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Separation By Low-Temperature Treatments (AREA)
US340167A 1939-07-19 1940-06-12 Process of production of mixtures of gases hard to liquefy Expired - Lifetime US2293601A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2820769A (en) * 1955-04-07 1958-01-21 Stamicarbon Process for preparing hydrogen-nitrogen mixtures from coke oven gas
US2996458A (en) * 1957-04-02 1961-08-15 Texaco Inc Production of hydrogen-nitrogen mixtures
US3269130A (en) * 1957-01-04 1966-08-30 Air Prod & Chem Separation of gaseous mixtures containing hydrogen and nitrogen
US3872025A (en) * 1969-10-31 1975-03-18 Bethlehem Steel Corp Production and utilization of synthesis gas

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1279699B (de) * 1963-05-29 1968-10-10 Zd Y Vitezneho Unora Narodni P Verfahren und Vorrichtung zur Gewinnung eines Gasgemisches

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE524352C (de) * 1929-05-16 1931-05-06 Linde Eismasch Ag Verfahren zur Tiefkuehlung von zu zerlegenden Gasgemischen

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2820769A (en) * 1955-04-07 1958-01-21 Stamicarbon Process for preparing hydrogen-nitrogen mixtures from coke oven gas
US3269130A (en) * 1957-01-04 1966-08-30 Air Prod & Chem Separation of gaseous mixtures containing hydrogen and nitrogen
US2996458A (en) * 1957-04-02 1961-08-15 Texaco Inc Production of hydrogen-nitrogen mixtures
US3872025A (en) * 1969-10-31 1975-03-18 Bethlehem Steel Corp Production and utilization of synthesis gas

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DE925174C (de) 1955-03-14
NL74830C (enrdf_load_stackoverflow) 1944-03-15

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