US3101262A - Method and apparatus for avoiding nitric oxide-containing deposits in gas decomposing plants - Google Patents

Method and apparatus for avoiding nitric oxide-containing deposits in gas decomposing plants Download PDF

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Publication number
US3101262A
US3101262A US73291A US7329160A US3101262A US 3101262 A US3101262 A US 3101262A US 73291 A US73291 A US 73291A US 7329160 A US7329160 A US 7329160A US 3101262 A US3101262 A US 3101262A
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Prior art keywords
heat
gas
exchangers
nitric oxide
avoiding
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Expired - Lifetime
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US73291A
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English (en)
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Rottmayr Friedrich
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Linde GmbH
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Gesellschaft fuer Lindes Eismaschinen AG
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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
    • F25J3/08—Separating gaseous impurities from gases or gaseous mixtures or from liquefied gases or liquefied gaseous mixtures
    • 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
    • Y10S62/92—Carbon monoxide
    • 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
    • Y10S62/934—From nitrogen

Definitions

  • This invention concerns a method of and an apparatus useful for avoiding nitric oxide-containing depositspa rticularly, NO-resins such as nitrosites and nitrosates-m gas decomposing plants, particularly coke oven gas decomposing plants.
  • the hot leg in it are separated preferably the hydrocarbons which contain three or more carbon atoms per molecule.
  • the following heat-exchanger which cools down to about 145 C., is called the cold leg: in it are separated mainly the compounds with one and two carbon atoms per molecule, like methane, ethane, ethylene.
  • the so-called methane vapor-counter-flow heat-exchanger which cools down to about 180 C., the bulk of the methane and carbon monoxide are condensed.
  • the remaining hydrogen and hydrogen-nitrogen mixture, respectively, is subsequently freed, in a wash column, from the last traces of carbon monoxide, methane and oxygen.
  • the coke oven gas also is known to contain traces of nitric oxide (NO) which, though it is present only in very small amounts, e.g., several tenths of one part per million (p.p.m.), has a very disturbing effect in the decomposing apparatus because it is oxidized by the oxygen contained in the gas to N and N 0 and these compounds react with the higher olefins, particularly with the diole fins, forming nitrosites and nitrosates which are deposited in certain parts of the apparatus and constitute an explosion hazard. Explosions of such compounds lead frequently to the destruction of the evaporator for the hydrocarbons separated in liquid form.
  • NO nitric oxide
  • An object of the present invention is, therefore, to improve the general process in such manner as to avoid as far as possible the formation of these resins and thus explosion hazards engendered by the same.
  • This object is realized, according to the invention, by a method for avoiding nitric oxide-containing deposits in gas decomposing plants, particularly coke oven gas decomposing plants, where from pre-purified gases which contain only 1ow-boiling substances these constituents are separated by condensation in at least two series-connected heat-exchanges arranged at different temperature levels, which method is characterized in that the liquids separated from each heat-exchanger are collected separately and treated separately, preferably evaporated.
  • the liquid fractions withdrawn from the various heatexchangers are collected separately and are evaporated in separate evaporators, and the resulting gases are conducted to another processing plant, e.g., to an ethylene producthese liquids are conducted in known manner from the bottom to the top through the evaporators, it is possible that difiicultly vaporizable portions of the liquid, which contains in any case a great portion of N0 and of the resins, will accumulate on the bottom or in the lower parts of the evaporator and will lead to explosions there, though the probability of these accumulations is very low with separate evaporation.
  • the fractions accumulated in thetseparators are no longer conducted from the'bottom to the top through the respec tive evaporator but rather are conducted from the top to the bottom.
  • the droplets which have not completely evaporated and which contain relatively large amounts of N0 and resins, are removed from the evaporator with the downstream and are evaporated, if not sooner, during the subsequent heating of the gas outside of the decomposing apparatus.
  • the invention can be supplemented in an advantageous manner in this way that an additional separator is provided in the connecting lines between two heat-exchangers used for the separation, particularly in the connecting line between the cold leg and the methane evaporation counterfiow heat-exchanger, in which liquid droplets that have been carried along are deposited. This prevents these droplets, which contain particularly large amounts of NO, from getting into the following colder heat-exchangers -Where they could and would cause the separation of resins.
  • the liquid accumulating in these separators is fed to the evaporators corresponding to its composition.
  • the coke oven gas freed from benzol, ammonia, hydrogen sulfide and carbon dioxide, and cooled to a temperature of about 40 C., is fed through conduit 11 to a heat-exchanger 1, the so-called hot leg.
  • the gas is cooled by indirect heat-exchange with counterflowing methane (conduit 12) and hydrogen (conduit 13), to about --l10 C.
  • the hydrocarbons having three and more carbon atoms per molecule are mainly separated and are fed to a separator 6 through conduit 14.
  • the coke oven gas flows, then, through conduit 15 to a heatexchanger 2, which is generally called the cold leg.
  • the gas is cooled to about C.
  • the liquids collected in separators 6 and 8 are evaporated in evaporators 7 and 9 by indirect heat-exchange with high pressure nitrogen which is supplied, at 23, at a temperature of about 45 C. and a pressure of about 100 to 200 atm. abs.
  • the evaporation products leave the decomposing apparatus through conduits 24 and 25 and can be combined, after additional heating in counterflow precoolers (not represented), and conducted to an additional processing plant, preferably an ethylene production plant.
  • the nitrogen cooled in heat-exchangers 7 and 9 flows through conduit 26 and pipe coils 27, arranged in the so-called nitrogen evaporator, and is expanded through a valve 28 into a wash column 5.
  • the hydrogen-nitrogen-ca-rbon monoxide mixture issuing from the head of nitrogen evaporator 10 is conducted through conduit 30 to column 5.
  • the hydrogen flows through a conduit 13 from the head of the column, while the liquid nitrogen-carbon monoxide mixture accumulates in the base of the column.
  • This lattermixture is expanded through conduit 31, containing expansion valve 32, into part 29 of a nitrogen evaporator 10 and is evaporated there; it is withdrawn in gaseous form, through conduit 16, and heated again in the heat-exchangers 4 and 2.
  • the liquid accumulating in separator 3 is also conducted through conduit 21 to evaporator 9,
  • Apparatus for avoiding nitric oxide-containing deposits in gas decomposing plants for the production of hydrogen gas said apparatus including at least two seriesconnected heat-exchangers arranged at different temperature levels, each or said heat-exchangers being equipped at its bottom with a separator for condensed liquid, characterized in that each separator is connected by a separate line with the upper end of one evaporator which is separate from said heat exchangers.
  • Apparatus according to claim 3 further characterized in that a separator is provided in at least one connecting conduit between two heat-exchangers, said separator being connected with the upper end of the separate evaporator for the condensed liquid coming from the preceding of said two heat-exchangers.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Separation By Low-Temperature Treatments (AREA)
US73291A 1959-12-05 1960-12-02 Method and apparatus for avoiding nitric oxide-containing deposits in gas decomposing plants Expired - Lifetime US3101262A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEG28514A DE1106785B (de) 1959-12-05 1959-12-05 Verfahren und Einrichtung zur Vermeidung von stickoxydhaltigen Ablagerungen in Gaszerlegungsanlagen

Publications (1)

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US3101262A true US3101262A (en) 1963-08-20

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US73291A Expired - Lifetime US3101262A (en) 1959-12-05 1960-12-02 Method and apparatus for avoiding nitric oxide-containing deposits in gas decomposing plants

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US (1) US3101262A (enrdf_load_stackoverflow)
DE (1) DE1106785B (enrdf_load_stackoverflow)
FR (1) FR1275724A (enrdf_load_stackoverflow)
NL (1) NL258639A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3181305A (en) * 1963-04-10 1965-05-04 Carl W Schoenfelder Method for isolating nitrogen trifluoride from nitrous oxide and tetrafluorohydrazine
US4959088A (en) * 1989-04-14 1990-09-25 Andrija Fuderer Method of producing nitric acid and refrigeration

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1830610A (en) * 1925-02-25 1931-11-03 Linde Richard Process of producing mixtures of hydrogen and nitrogen
US1865135A (en) * 1929-05-24 1932-06-28 Pollitzer Franz Apparatus for the separation of gas mixtures
US1913805A (en) * 1927-01-24 1933-06-13 Hausen Helmuth Process for separating gas mixtures more particularly coke oven gas
US2122238A (en) * 1934-03-23 1938-06-28 Union Carbide & Carbon Corp Process and apparatus for the separation of gas mixtures
US2591658A (en) * 1948-01-09 1952-04-01 Directie Staatsmijnen Nl Process and apparatus for the separation of coke-oven gas

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE883890C (de) * 1940-02-17 1953-07-23 Adolf Messer G M B H Verfahren zur Entfernung geringer Kohlensaeuregehalte aus Luft und Gasgemischen, welche zwecks Zerlegung auf Temperaturen unter dem Gefrierpunkt der Kohlensaeure abgekuehlt werden muessen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1830610A (en) * 1925-02-25 1931-11-03 Linde Richard Process of producing mixtures of hydrogen and nitrogen
US1913805A (en) * 1927-01-24 1933-06-13 Hausen Helmuth Process for separating gas mixtures more particularly coke oven gas
US1865135A (en) * 1929-05-24 1932-06-28 Pollitzer Franz Apparatus for the separation of gas mixtures
US2122238A (en) * 1934-03-23 1938-06-28 Union Carbide & Carbon Corp Process and apparatus for the separation of gas mixtures
US2591658A (en) * 1948-01-09 1952-04-01 Directie Staatsmijnen Nl Process and apparatus for the separation of coke-oven gas

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3181305A (en) * 1963-04-10 1965-05-04 Carl W Schoenfelder Method for isolating nitrogen trifluoride from nitrous oxide and tetrafluorohydrazine
US4959088A (en) * 1989-04-14 1990-09-25 Andrija Fuderer Method of producing nitric acid and refrigeration

Also Published As

Publication number Publication date
FR1275724A (fr) 1961-11-10
NL258639A (enrdf_load_stackoverflow)
DE1106785B (de) 1961-05-16

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