EP1199533A1 - System and process for rejecting into air residual gases from air destillation or air liquefaction plants - Google Patents

System and process for rejecting into air residual gases from air destillation or air liquefaction plants Download PDF

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Publication number
EP1199533A1
EP1199533A1 EP01402540A EP01402540A EP1199533A1 EP 1199533 A1 EP1199533 A1 EP 1199533A1 EP 01402540 A EP01402540 A EP 01402540A EP 01402540 A EP01402540 A EP 01402540A EP 1199533 A1 EP1199533 A1 EP 1199533A1
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EP
European Patent Office
Prior art keywords
chimney
oxygen
nitrogen
air
enclosure
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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Application number
EP01402540A
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German (de)
French (fr)
Inventor
Daniel Gourdain
Jean-Marc Peyron
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA a Directoire et Conseil de Surveillance pour lEtude et lExploitation des Procedes Georges Claude
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Publication of EP1199533A1 publication Critical patent/EP1199533A1/en
Withdrawn legal-status Critical Current

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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
    • F25J3/04—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 for air
    • F25J3/04763—Start-up or control of the process; Details of the apparatus used
    • F25J3/04769—Operation, control and regulation of the process; Instrumentation within the process
    • F25J3/04812—Different modes, i.e. "runs" of operation
    • F25J3/04824—Stopping of the process, e.g. defrosting or deriming; Back-up procedures
    • 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
    • F25J3/04—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 for air
    • F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
    • F25J3/04157—Afterstage cooling and so-called "pre-cooling" of the feed air upstream the air purification unit and main heat exchange line
    • 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
    • F25J3/04—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 for air
    • F25J3/04763—Start-up or control of the process; Details of the apparatus used
    • F25J3/04769—Operation, control and regulation of the process; Instrumentation within the process
    • F25J3/04854—Safety aspects of operation
    • 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
    • F25J3/04—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 for air
    • F25J3/04763—Start-up or control of the process; Details of the apparatus used
    • F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
    • 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
    • F25J2205/34—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes as evaporative cooling tower to produce chilled water, e.g. evaporative water chiller [EWC]
    • 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
    • F25J2240/60—Expansion by ejector or injector, e.g. "Gasstrahlpumpe", "venturi mixing", "jet pumps"
    • 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
    • F25J2270/02—Internal refrigeration with liquid vaporising 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/0318—Processes
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/2931—Diverse fluid containing pressure systems

Definitions

  • the present invention relates to an installation and a method for venting of residual gases from distillation or liquefaction units air, and in particular is usable in those of these installation installations the air which include a chimney for example of concrete and a water-nitrogen tower.
  • the word 'oxygen' must be interpreted to understand fluids comprising at least 75% mol. oxygen and preferably minus 95% mol. of oxygen
  • the word 'nitrogen' must be interpreted to understand fluids comprising at least 90% mol. nitrogen, preferably minus 95% mol. of nitrogen
  • the word 'argon' must be interpreted to understand fluids comprising at least 60% mol. argon.
  • the water that is intended to cool the air entering upstream of the purification devices is itself cooled in a water-nitrogen tower, at the top of which it is injected, by heat exchange with dry nitrogen.
  • the resulting wet nitrogen is then vented permanently or at least almost permanently at the top of the tower.
  • products polluted or not from the distillation or liquefaction of air, including oxygen these are collected in a concrete chimney and evacuated by the top of the chimney.
  • FIG. 1 Such a venting installation is shown diagrammatically in FIG. 1, showing a section of this installation by a vertical plane.
  • an installation for venting the residual gases of an air distillation or liquefaction unit includes a water-nitrogen tower 1 and a chimney 2 joined by a common partition 3.
  • the water-nitrogen tower has, near its base, a pipe dry nitrogen inlet 11, and, in its upper part, a pipe inlet for hot water to be cooled 12, water which is itself intended to cool then air as mentioned above; thus, nitrogen follows in the turn 1 a generally vertical path upwards to an upper enclosure 13, comprising at its top a discharge port 14 of nitrogen humid in the atmosphere, while cold water 16, pumped to the party bottom of the tower, is directed towards the devices where it is brought into contact with the air to cool.
  • the chimney 2 has, near its base, residual gas inlet pipes to be discharged into the atmosphere, for example an air duct 21, a nitrogen duct 22 and an oxygen duct 23; the chimney 2 has at its top a gas discharge outlet 24 residual.
  • the invention set out below remedies this drawback and consists for this purpose in an installation for venting residual gases from a air distillation or liquefaction process, characterized in that it includes a residual gas discharge chimney opening into the atmosphere and suitable for evacuating at least oxygen in particular intermittently, and means to reduce the rate of concentration of oxygen from the gases discharged through the chimney, possibly consisting of means for mixing an inert gas, miscible with oxygen and further lower density than oxygen under the same temperature conditions and pressure, preferably of lower density than air in the same temperature and pressure conditions, to exhaust gases.
  • the installation comprises an evacuation enclosure almost permanent in the atmosphere of inert gas miscible with oxygen and lower density than air under the same temperature conditions and pressure, and means for connecting the respective interior spaces of the evacuation enclosure and the chimney to transmit in the chimney at least part of said inert gas so that at least the oxygen in the chimney is mixed with the inert gas, and thus the rate of oxygen concentration of the exhaust gases from the chimney is reduced.
  • the invention also consists of a method of venting by a vent outlet from a distillation or liquefaction unit air, residual gases comprising oxygen, characterized in that we mix at least with oxygen, wet or dry nitrogen, and we discharges the mixture of oxygen and nitrogen obtained at a speed at least equal to approximately 7 m / s at the outlet.
  • FIG. 2 is a schematic section of an installation according to the invention, according to a plan vertical.
  • the water-nitrogen tower 1 comprises, near its base, a dry nitrogen inlet pipe 11 and, in its upper part, a hot water supply line to be cooled 12, water which is itself intended then cooling the air circulating in the unit; thus, nitrogen follows in the first turn a generally vertical path to the upper enclosure 13; however, the top of the tower has no mouth evacuation of wet nitrogen; on the other hand, an outlet 15 of wet nitrogen is drilled in the partition 3 common to tower 1 and to the chimney 2, for example near the top of tower 1 and in any case naturally above the level of the hot water supply line 12 in enclosure 13; thus, this mouth 15 opens in the upper part from the stack 2 and the nitrogen follows in the enclosure 13 a path which ends approximately horizontally; cold water 16 is as before directed towards the devices where it is brought into contact with the air to be cooled.
  • the chimney 2 also as before, has, near from its base, residual gas inlet pipes to be evacuated into the atmosphere, namely here an air duct 21, a nitrogen duct 22 and a oxygen conduit 23; the chimney 2 has at its top, here approximately at the same level as that of tower 1, a mouth 24.
  • the chimney 2 is internally equipped, approximately at the discharge outlet 15 for wet nitrogen, a set of nozzles 25 whose apex is at a level below the top of the discharge mouth 15, so that, whatever the gas introduced at the base of the chimney 2, on the one hand it has passed through the nozzles of the set 25 before reaching the level of the top of the mouth evacuation 15 of wet nitrogen, and on the other hand it is at least partially and if possible completely mixed with wet nitrogen before reaching the exhaust outlet 24 from the chimney;
  • the nozzle assembly 25 is calculated and designed to allow on the one hand to evacuate preferably the total flow, and on the other hand to obtain an evacuation speed of at least 7 m / s approximately, preferably at least 10 m / s, advantageously at least 12 m / s, or, better, at least 20 m / s, in the case of an initial oxygen flow only, at the level of the exhaust outlet 24 of the chimney 2.
  • the nozzles thus defined naturally allow an alternative to pass a lower flow at the total flow, the
  • the invention is not limited to the embodiment described above and shown, and we can provide others without leaving of its scope, and in particular one can plan to use the invention in installations without water-nitrogen tower, but where there is a surplus of residual nitrogen (for example impure or more generally not recoverable as is) that we transfer to a venting chamber, or to mix oxygen with not nitrogen but another gas miscible with it and lower density than air, provided that this gas is inert at least in the operating conditions, that is to say in particular is neither toxic nor explosive, no fuel, no oxidizer, alone or mixed with oxygen. It is it is also possible, as a variant, to provide a water-nitrogen tower 1 of which the upper enclosure 13 would have at its top, as in FIG. 1, a discharge outlet 14, through which the gas or gases would be discharged chimney 2, but this technique would be a little less effective in terms of dilution.
  • residual nitrogen for example impure or more generally not recoverable as is

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  • Separation By Low-Temperature Treatments (AREA)

Abstract

The installation has a residual gas outlet chimney (2) for intermittent release of oxygen into the atmosphere, equipped with a system (13, 15) for mixing the oxygen with an inert gas to reduce the concentration of oxygen in the emitted gases. The inert gas, e.g. nitrogen, argon, air or a mixture of these, is mixed with the oxygen at a lower density than the oxygen and at the same temperature and pressure. The installation has a quasi-permanent evacuation chamber (13) for the inert gas, forming part of a nitrogen/water tower (1), and a connector (15) linking the chamber to the outlet chimney (2). Apart from the connector (15), the tower is separated from the chimney by a partition (3), and the chimney has a set of nozzles (25) through which gases injected at the bottom of the chimney have to pass, the top of the nozzles being below the level of the top of the connector (15). At the outlet from the chimney the mixture of oxygen and inert gases achieves a speed of 7 - 20 m/s.

Description

La présente invention concerne une installation et un procédé de mise à l'air des gaz résiduels des unités de distillation ou de liquéfaction d'air, et notamment est utilisable dans celles de ces installations de mise à l'air qui comprennent une cheminée par exemple en béton et une tour eau-azote.The present invention relates to an installation and a method for venting of residual gases from distillation or liquefaction units air, and in particular is usable in those of these installation installations the air which include a chimney for example of concrete and a water-nitrogen tower.

Dans ce texte le mot 'oxygène' doit être interprété pour comprendre les fluides comprenant au moins 75% mol. d'oxygène et de préférence au moins 95% mol. d'oxygène, le mot 'azote' doit être interprété pour comprendre les fluides comprenant au moins 90% mol. d'azote, de préférence au moins 95% mol. d'azote et le mot 'argon' doit être interprété pour comprendre les fluides comprenant au moins 60% mol. d'argon.In this text the word 'oxygen' must be interpreted to understand fluids comprising at least 75% mol. oxygen and preferably minus 95% mol. of oxygen, the word 'nitrogen' must be interpreted to understand fluids comprising at least 90% mol. nitrogen, preferably minus 95% mol. of nitrogen and the word 'argon' must be interpreted to understand fluids comprising at least 60% mol. argon.

En effet, lors de la mise en oeuvre des processus de distillation et de liquéfaction d'air dans les unités traitant de grandes quantités d'air (sensiblement égales ou supérieures à 1 000 tonnes par jour), l'eau qui est destinée à refroidir l'air entrant en amont des appareils d'épuration est elle-même refroidie dans une tour eau-azote, à la partie supérieure de laquelle elle est injectée, par échange thermique avec de l'azote sec. L'azote humide résultant est ensuite mis à l'air en permanence ou au moins en quasi-permanence au sommet de la tour. Par ailleurs, pour la mise à l'air des produits pollués ou non issus de la distillation ou de la liquéfaction de l'air, dont l'oxygène, ceux-ci sont collectés dans une cheminée en béton et évacués par le sommet de la cheminée.Indeed, during the implementation of the distillation and air liquefaction in units handling large quantities of air (substantially equal to or greater than 1,000 tonnes per day), the water that is intended to cool the air entering upstream of the purification devices is itself cooled in a water-nitrogen tower, at the top of which it is injected, by heat exchange with dry nitrogen. The resulting wet nitrogen is then vented permanently or at least almost permanently at the top of the tower. In addition, for the venting of products polluted or not from the distillation or liquefaction of air, including oxygen, these are collected in a concrete chimney and evacuated by the top of the chimney.

Pour rendre l'installation de mise à l'air plus compacte et faciliter sa construction, il est possible d'accoler la cheminée et la tour eau-azote.To make the venting system more compact and to facilitate its construction, it is possible to add the chimney and the water-nitrogen tower.

Une telle installation de mise à l'air est schématisée sur la figure 1, montrant une section de cette installation par un plan vertical.Such a venting installation is shown diagrammatically in FIG. 1, showing a section of this installation by a vertical plane.

Sur cette figure 1, une installation de mise à l'air des gaz résiduels d'une unité de distillation ou de liquéfaction d'air comprend une tour eau-azote 1 et une cheminée 2 accolées par une cloison commune 3.In this figure 1, an installation for venting the residual gases of an air distillation or liquefaction unit includes a water-nitrogen tower 1 and a chimney 2 joined by a common partition 3.

La tour eau-azote comporte, à proximité de sa base, une conduite d'arrivée d'azote sec 11, et, dans sa partie supérieure, une conduite d'arrivée d'eau chaude à refroidir 12, eau qui est elle-même destinée à refroidir ensuite de l'air comme mentionné plus haut ; ainsi, l'azote suit dans la tour 1 un trajet globalement vertical vers le haut jusqu'à une enceinte supérieure 13, comportant à son sommet une bouche d'évacuation 14 d'azote humide dans l'atmosphère, tandis que l'eau froide 16, pompée à la partie inférieure de la tour, est dirigée vers les appareils où elle est mise en contact avec l'air à refroidir. La cheminée 2 comporte, à proximité de sa base, des conduits d'arrivée de gaz résiduels à évacuer dans l'atmosphère, par exemple un conduit d'air 21, un conduit d'azote 22 et un conduit d'oxygène 23 ; la cheminée 2 comporte à son sommet une bouche d'évacuation 24 de gaz résiduels.The water-nitrogen tower has, near its base, a pipe dry nitrogen inlet 11, and, in its upper part, a pipe inlet for hot water to be cooled 12, water which is itself intended to cool then air as mentioned above; thus, nitrogen follows in the turn 1 a generally vertical path upwards to an upper enclosure 13, comprising at its top a discharge port 14 of nitrogen humid in the atmosphere, while cold water 16, pumped to the party bottom of the tower, is directed towards the devices where it is brought into contact with the air to cool. The chimney 2 has, near its base, residual gas inlet pipes to be discharged into the atmosphere, for example an air duct 21, a nitrogen duct 22 and an oxygen duct 23; the chimney 2 has at its top a gas discharge outlet 24 residual.

On peut noter que l'azote humide mis à l'air par la tour eau-azote 1 est rejeté en permanence. En revanche, à différentes étapes du processus, il est possible qu'un seul gaz résiduel soit mis à l'air par la cheminée 2. Le dimensionnement de la cheminée doit être naturellement choisi pour que celle-ci puisse mettre à l'air simultanément les trois gaz, circonstance qui peut survenir ; ainsi, la cheminée est dimensionnée pour mettre à l'air le débit total maximal des gaz à une vitesse de sortie typiquement d'environ 20 m/s. Cette conception n'est cependant pas dénuée d'inconvénient : si un seul gaz est mis à l'air, par suite du faible débit, la vitesse de mise à l'air est très inférieure à la valeur choisie, ici 20 m/s ; cela peut avoir des conséquences très fâcheuses dans le cas où le gaz mis à l'air seul est de l'oxygène : comme l'oxygène est plus lourd que l'air, peu après sa sortie de la cheminée, il a tendance à redescendre vers le sol, et dans certaines conditions climatiques (par exemple vent presque nul) son taux de concentration au sol peut devenir localement supérieur à 25%, ce qui est excessif car dangereux par suite notamment des propriétés comburantes de ce gaz.It can be noted that the wet nitrogen put into the air by the water-nitrogen tower 1 is permanently rejected. However, at different stages of the process, it is possible that only one residual gas is vented through the chimney 2. The dimensioning of the chimney must be naturally chosen so that this can simultaneously air the three gases, a circumstance which may occur; thus, the chimney is sized to vent the flow maximum total gas at typically 20 exit speed m / s. This design is not without drawbacks: if a only gas is vented, due to the low flow rate, the venting speed is much lower than the chosen value, here 20 m / s; this can have consequences very annoying if the gas vented alone is oxygen: as oxygen is heavier than air, shortly after it leaves the chimney, it tends to descend to the ground, and in some climatic conditions (for example almost zero wind) its concentration rate on the ground can locally become more than 25%, which is excessive as dangerous as a result in particular of the oxidising properties of this gas.

L'invention exposée dans la suite remédie à cet inconvénient et consiste à cette fin en une installation de mise à l'air de gaz résiduels d'un processus de distillation ou de liquéfaction d'air, caractérisée en ce qu'elle comprend une cheminée d'évacuation de gaz résiduels débouchant dans l'atmosphère et adaptée pour évacuer notamment de l'oxygène au moins par intermittence, et des moyens pour réduire le taux de concentration en oxygène des gaz évacués par la cheminée, éventuellement constitués par des moyens de mélanger un gaz inerte, miscible avec l'oxygène et de plus faible densité que l'oxygène dans les mêmes conditions de température et de pression, de préférence de plus faible densité que l'air dans les mêmes conditions de température et de pression, aux gaz évacués.The invention set out below remedies this drawback and consists for this purpose in an installation for venting residual gases from a air distillation or liquefaction process, characterized in that it includes a residual gas discharge chimney opening into the atmosphere and suitable for evacuating at least oxygen in particular intermittently, and means to reduce the rate of concentration of oxygen from the gases discharged through the chimney, possibly consisting of means for mixing an inert gas, miscible with oxygen and further lower density than oxygen under the same temperature conditions and pressure, preferably of lower density than air in the same temperature and pressure conditions, to exhaust gases.

De préférence, l'installation comprend une enceinte d'évacuation quasi-permanente dans l'atmosphère du gaz inerte miscible avec l'oxygène et de plus faible densité que l'air dans les mêmes conditions de température et de pression, et des moyens de liaison des espaces intérieurs respectifs de l'enceinte d'évacuation et de la cheminée pour transmettre dans la cheminée au moins une partie dudit gaz inerte de manière qu'au moins à l'oxygène de la cheminée soit mélangé du gaz inerte, et ainsi le taux de concentration en oxygène des gaz évacués par la cheminée soit réduit.Preferably, the installation comprises an evacuation enclosure almost permanent in the atmosphere of inert gas miscible with oxygen and lower density than air under the same temperature conditions and pressure, and means for connecting the respective interior spaces of the evacuation enclosure and the chimney to transmit in the chimney at least part of said inert gas so that at least the oxygen in the chimney is mixed with the inert gas, and thus the rate of oxygen concentration of the exhaust gases from the chimney is reduced.

Grâce à cet agencement, il est possible de réduire notablement le taux de concentration en oxygène du gaz émis en sortie de cheminée, même si uniquement de l'oxygène est introduit à proximité de la base de la cheminée.Thanks to this arrangement, it is possible to significantly reduce the oxygen concentration rate of the gas emitted from the chimney, even if only oxygen is introduced near the base of the fireplace.

L'installation peut en outre présenter une ou plusieurs des caractéristiques suivantes :

  • l'enceinte d'évacuation est une enceinte appartenant à une tour eau-azote ;
  • le gaz inerte est l'azote ou l'argon ou de l'air ou un mélange de ces gaz ;
  • l'enceinte d'évacuation appartient à une tour eau-azote accolée à la cheminée, et les espaces intérieurs de l'enceinte et de la cheminée sont séparés par une cloison comportant, en tant que moyens de liaison des espaces intérieurs, une bouche d'évacuation dans la cheminée, d'azote humide contenu dans l'enceinte ;
  • la cheminée est équipée intérieurement d'un ensemble de buses par où transite une partie ou la totalité du gaz introduit à la base de la cheminée ;
  • les moyens de liaison comportent une bouche d'évacuation ménagée dans une cloison séparant les espaces internes de l'enceinte et de la cheminée, et la cheminée est équipée intérieurement d'un ensemble de buses disposé de telle sorte que son sommet soit à un niveau inférieur au sommet de la bouche d'évacuation ;
  • l'enceinte d'évacuation appartient à une tour eau-azote comportant, à proximité de sa base, une conduite d'arrivée d'azote sec, et, dans sa partie supérieure, une conduite d'arrivée d'eau chaude à refroidir, au-dessus du niveau de laquelle est ménagée une bouche d'évacuation d'azote humide, s'ouvrant dans la cheminée ; et
  • la cheminée comporte, à proximité de sa base, des conduits d'arrivée d'air, et/ou d'arrivée d'azote, et/ou d'arrivée d'oxygène et/ou d'arrivée d'un autre gaz issu de la distillation.
The installation can also have one or more of the following characteristics:
  • the evacuation enclosure is an enclosure belonging to a water-nitrogen tower;
  • the inert gas is nitrogen or argon or air or a mixture of these gases;
  • the evacuation enclosure belongs to a water-nitrogen tower attached to the chimney, and the interior spaces of the enclosure and the chimney are separated by a partition comprising, as means of connecting the interior spaces, a mouth of 'evacuation in the chimney, of wet nitrogen contained in the enclosure;
  • the chimney is internally equipped with a set of nozzles through which passes part or all of the gas introduced at the base of the chimney;
  • the connection means comprise a discharge mouth formed in a partition separating the internal spaces of the enclosure and the chimney, and the chimney is internally equipped with a set of nozzles arranged so that its top is at a level lower than the top of the discharge mouth;
  • the evacuation enclosure belongs to a water-nitrogen tower comprising, near its base, a dry nitrogen inlet pipe, and, in its upper part, a hot water inlet pipe to be cooled, above the level of which is provided a mouth for discharging wet nitrogen, opening into the chimney; and
  • the chimney comprises, near its base, air inlet and / or nitrogen inlet and / or oxygen inlet and / or inlet of another gas from distillation.

L'invention consiste également en un procédé de mise à l'air par une bouche d'évacuation d'une cheminée d'une unité de distillation ou de liquéfaction d'air, de gaz résiduels comprenant de l'oxygène, caractérisé en ce que l'on mélange au moins à l'oxygène, de l'azote humide ou sec, et on évacue le mélange d'oxygène et d'azote obtenu à une vitesse au moins égale à approximativement 7 m/s au niveau de la bouche d'évacuation.The invention also consists of a method of venting by a vent outlet from a distillation or liquefaction unit air, residual gases comprising oxygen, characterized in that we mix at least with oxygen, wet or dry nitrogen, and we discharges the mixture of oxygen and nitrogen obtained at a speed at least equal to approximately 7 m / s at the outlet.

En variante :

  • on évacue le mélange d'oxygène et d'azote obtenu à une vitesse au moins égale à approximativement 10m/s au niveau de la bouche d'évacuation ;
  • on évacue le mélange d'oxygène et d'azote obtenu à une vitesse au moins égale à approximativement 12 m/s au niveau de la bouche d'évacuation ; ou
  • on évacue le mélange d'oxygène et d'azote obtenu à une vitesse au moins égale à approximativement 20 m/s au niveau de la bouche d'évacuation.
As a variant:
  • the mixture of oxygen and nitrogen obtained is evacuated at a speed at least equal to approximately 10 m / s at the level of the evacuation mouth;
  • the mixture of oxygen and nitrogen obtained is evacuated at a speed at least equal to approximately 12 m / s at the level of the evacuation mouth; or
  • the mixture of oxygen and nitrogen obtained is evacuated at a speed at least equal to approximately 20 m / s at the level of the evacuation mouth.

D'autres caractéristiques et avantages de l'invention ressortiront de la description qui va suivre, d'une forme de réalisation de cette invention donnée à titre d'exemple non limitatif, illustrée par la figure 2 jointe qui est une section schématique d'une installation selon l'invention, selon un plan vertical.Other characteristics and advantages of the invention will emerge from the following description of an embodiment of this invention given by way of nonlimiting example, illustrated by the attached FIG. 2 which is a schematic section of an installation according to the invention, according to a plan vertical.

Les éléments de la figure 2 qui correspondent à des éléments de la figure 1 déjà décrite portent les mêmes références numériques. The elements of Figure 2 which correspond to elements of the Figure 1 already described bear the same reference numerals.

Sur la figure 2, la tour eau-azote 1 comporte, à proximité de sa base, une conduite d'arrivée d'azote sec 11 et, dans sa partie supérieure, une conduite d'arrivée d'eau chaude à refroidir 12, eau qui est elle-même destinée à refroidir ensuite de l'air circulant dans l'unité ; ainsi, l'azote suit dans la tour tout d'abord un trajet globalement vertical jusqu'à l'enceinte supérieure 13; cependant, le sommet de la tour ne comporte pas de bouche d'évacuation d'azote humide; en revanche, une bouche d'évacuation 15 d'azote humide est percée dans la cloison 3 commune à la tour 1 et à la cheminée 2, par exemple à proximité du sommet de la tour 1 et en tout cas naturellement au-dessus du niveau de la conduite d'arrivée d'eau chaude 12 dans l'enceinte 13 ; ainsi, cette bouche 15 s'ouvre dans la partie supérieure de la cheminée 2 et l'azote suit dans l'enceinte 13 un trajet qui se termine approximativement horizontalement ; l'eau froide 16 est comme précédemment dirigée vers les appareils où elle est mise en contact avec l'air à refroidir. La cheminée 2, également comme précédemment, comporte, à proximité de sa base, des conduits d'arrivée de gaz résiduels à évacuer dans l'atmosphère, à savoir ici un conduit d'air 21, un conduit d'azote 22 et un conduit d'oxygène 23 ; la cheminée 2 comporte à son sommet, ici approximativement au même niveau que celui de la tour 1, une bouche d'évacuation 24. En outre, la cheminée 2 est équipée intérieurement, approximativement au niveau de la bouche d'évacuation 15 d'azote humide, d'un ensemble de buses 25 dont le sommet est à un niveau inférieur au sommet de la bouche d'évacuation 15, de telle manière que, quel que soit le gaz introduit à la base de la cheminée 2, d'une part il ait transité par les buses de l'ensemble 25 avant d'arriver au niveau du sommet de la bouche d'évacuation 15 d'azote humide, et d'autre part il soit au moins partiellement et si possible totalement mélangé à de l'azote humide avant de parvenir à la bouche d'évacuation 24 de la cheminée ; de plus, l'ensemble de buses 25 est calculé et conçu pour permettre d'une part d'évacuer de préférence le débit total, et d'autre part d'obtenir une vitesse d'évacuation d'au moins 7 m/s environ, de préférence au moins 10 m/s, avantageusement au moins 12 m/s, ou, mieux, au moins 20 m/s, dans le cas d'un débit initial d'oxygène seul, au niveau de la bouche d'évacuation 24 de la cheminée 2. Les buses ainsi définies permettent naturellement en alternative de passer un débit inférieur au débit total, le reste du débit ayant été alors évacué par des moyens d'évacuation intermédiaires.In FIG. 2, the water-nitrogen tower 1 comprises, near its base, a dry nitrogen inlet pipe 11 and, in its upper part, a hot water supply line to be cooled 12, water which is itself intended then cooling the air circulating in the unit; thus, nitrogen follows in the first turn a generally vertical path to the upper enclosure 13; however, the top of the tower has no mouth evacuation of wet nitrogen; on the other hand, an outlet 15 of wet nitrogen is drilled in the partition 3 common to tower 1 and to the chimney 2, for example near the top of tower 1 and in any case naturally above the level of the hot water supply line 12 in enclosure 13; thus, this mouth 15 opens in the upper part from the stack 2 and the nitrogen follows in the enclosure 13 a path which ends approximately horizontally; cold water 16 is as before directed towards the devices where it is brought into contact with the air to be cooled. The chimney 2, also as before, has, near from its base, residual gas inlet pipes to be evacuated into the atmosphere, namely here an air duct 21, a nitrogen duct 22 and a oxygen conduit 23; the chimney 2 has at its top, here approximately at the same level as that of tower 1, a mouth 24. In addition, the chimney 2 is internally equipped, approximately at the discharge outlet 15 for wet nitrogen, a set of nozzles 25 whose apex is at a level below the top of the discharge mouth 15, so that, whatever the gas introduced at the base of the chimney 2, on the one hand it has passed through the nozzles of the set 25 before reaching the level of the top of the mouth evacuation 15 of wet nitrogen, and on the other hand it is at least partially and if possible completely mixed with wet nitrogen before reaching the exhaust outlet 24 from the chimney; in addition, the nozzle assembly 25 is calculated and designed to allow on the one hand to evacuate preferably the total flow, and on the other hand to obtain an evacuation speed of at least 7 m / s approximately, preferably at least 10 m / s, advantageously at least 12 m / s, or, better, at least 20 m / s, in the case of an initial oxygen flow only, at the level of the exhaust outlet 24 of the chimney 2. The nozzles thus defined naturally allow an alternative to pass a lower flow at the total flow, the rest of the flow having then been evacuated by intermediate means of evacuation.

Ainsi, l'azote humide sortant de la tour 1 par la bouche d'évacuation 15, dont la densité est plus faible que celle de l'air, entraíne le flux de gaz provenant de la base de la cheminée, vers le haut, tout en se mélangeant à ce flux de gaz. De plus, le balayage permanent par l'azote ou le mélange d'azote, de la cheminée de mise à l'air, assure une protection contre toutes les impuretés émanant de l'extérieur. En outre, grâce au mélange de l'azote sortant en continu, avec l'oxygène initialement approximativement pur de l'installation, on s'affranchit de la sur-oxygénation de l'air et on réduit le risque que la concentration dans l'air au niveau du sol, de l'oxygène gazeux, s'élève au-delà d'environ 25%. Enfin, alors que dans les installations conventionnelles, les tours eau-azote nécessitent rarement une hauteur supérieure à une douzaine de mètres, tandis que les rejets des cheminées imposent à celles-ci couramment une hauteur de 16 mètres à 18 mètres environ, grâce à la sous-oxygénation du mélange évacué, il est possible de réduire la hauteur de la cheminée à la hauteur de la tour eau-azote, soit une douzaine de mètres.So the wet nitrogen coming out of tower 1 through the outlet 15, whose density is lower than that of air, causes the gas flow coming from the base of the chimney, upwards, while mixing with this gas flow. In addition, permanent nitrogen sweeping or mixing of nitrogen, from the vent chimney, provides protection against all impurities from the outside. In addition, thanks to the mixture of nitrogen continuously exiting, with initially approximately pure oxygen from the installation, it overcomes the over-oxygenation of the air and reduces the risk that the concentration in the air at ground level of oxygen gas, rises above about 25%. Finally, while in the facilities conventional, water-nitrogen towers rarely require a higher height a dozen meters, while the chimney releases require to these commonly a height of about 16 meters to 18 meters, thanks to the under-oxygenation of the evacuated mixture, it is possible to reduce the height of the chimney at the height of the water-nitrogen tower, i.e. dozen meters.

Bien entendu, l'invention n'est pas limitée à la forme de réalisation ci-dessus décrite et représentée, et on pourra en prévoir d'autres sans sortir de son cadre, et notamment on pourra prévoir d'utiliser l'invention dans des installations sans tour eau-azote, mais où il existe un surplus d'azote résiduaire (par exemple impur ou plus généralement non valorisable tel quel) que l'on transfère dans une chambre de mise à l'air, ou encore de mélanger l'oxygène avec non pas de l'azote mais un autre gaz miscible avec lui et de plus faible densité que l'air, pourvu que ce gaz soit inerte au moins dans les conditions opératoires, c'est-à-dire en particulier ne soit ni toxique, ni explosif, ni carburant, ni comburant, seul ou en mélange avec l'oxygène. Il est également possible de prévoir, en variante, une tour eau-azote 1 dont l'enceinte supérieure 13 comporterait à son sommet, comme sur la figure 1, une bouche d'évacuation 14, par laquelle seraient évacués le ou les gaz de la cheminée 2, mais cette technique serait un peu moins efficace en terme de dilution.Of course, the invention is not limited to the embodiment described above and shown, and we can provide others without leaving of its scope, and in particular one can plan to use the invention in installations without water-nitrogen tower, but where there is a surplus of residual nitrogen (for example impure or more generally not recoverable as is) that we transfer to a venting chamber, or to mix oxygen with not nitrogen but another gas miscible with it and lower density than air, provided that this gas is inert at least in the operating conditions, that is to say in particular is neither toxic nor explosive, no fuel, no oxidizer, alone or mixed with oxygen. It is it is also possible, as a variant, to provide a water-nitrogen tower 1 of which the upper enclosure 13 would have at its top, as in FIG. 1, a discharge outlet 14, through which the gas or gases would be discharged chimney 2, but this technique would be a little less effective in terms of dilution.

Claims (13)

Installation de mise à l'air de gaz résiduels d'un processus de distillation ou de liquéfaction d'air, caractérisée en ce qu'elle comprend une cheminée (2) d'évacuation de gaz résiduels débouchant dans l'atmosphère et adaptée pour évacuer notamment de l'oxygène au moins par intermittence et des moyens pour réduire le taux de concentration en oxygène des gaz évacués par la cheminée, éventuellement constitués par des moyens (13, 15) de mélanger un gaz inerte, miscible avec l'oxygène et de plus faible densité que l'oxygène dans les mêmes conditions de température et de pression, de préférence de plus faible densité que l'air dans les mêmes conditions de température et de pression, aux gaz évacués.Installation for venting residual gases from an air distillation or liquefaction process, characterized in that it comprises a chimney (2) for discharging residual gases opening into the atmosphere and suitable for discharging in particular oxygen at least intermittently and means for reducing the oxygen concentration rate of the gases evacuated by the chimney, possibly constituted by means (13, 15) of mixing an inert gas, miscible with oxygen and of lower density than oxygen under the same conditions of temperature and pressure, preferably lower density than air under the same conditions of temperature and pressure, to the exhaust gases. Installation selon la revendication 1 comprenant une enceinte (13) d'évacuation quasi-permanente dans l'atmosphère du gaz inerte miscible avec l'oxygène et de plus faible densité que l'air dans les mêmes conditions de température et de pression, et des moyens de liaison (15) des espaces intérieurs respectifs de l'enceinte (13) d'évacuation et de la cheminée (2) pour transmettre dans la cheminée (2) au moins une partie dudit gaz inerte de manière qu'au moins à l'oxygène de la cheminée soit mélangé du gaz inerte, et ainsi le taux de concentration en oxygène des gaz évacués par la cheminée soit réduit.Installation according to claim 1 comprising an enclosure (13) quasi-permanent evacuation of the miscible inert gas into the atmosphere with oxygen and lower density than air under the same conditions of temperature and pressure, and means for connecting (15) the spaces respective interiors of the discharge enclosure (13) and the chimney (2) for transmitting into the chimney (2) at least part of said gas inert so that at least the oxygen in the stack is mixed with the inert gas, and thus the oxygen concentration rate of the gases evacuated by the chimney is reduced. Installation selon la revendication 1 ou 2, caractérisée en ce que l'enceinte (13) d'évacuation est une enceinte appartenant à une tour eau-azote (1).Installation according to claim 1 or 2, characterized in that the discharge enclosure (13) is an enclosure belonging to a water-nitrogen tower (1). Installation selon l'une quelconque des revendications 1,2 et 3, caractérisée en ce que le gaz inerte est l'azote, de l'argon, de l'air ou un mélange de ces gaz.Installation according to any one of claims 1,2 and 3, characterized in that the inert gas is nitrogen, argon, air or a mixture of these gases. Installation selon la revendication 2,3 ou 4, caractérisée en ce que l'enceinte (13) d'évacuation appartient à une tour eau-azote (1) accolée à la cheminée (2), et les espaces intérieurs de l'enceinte (13) et de la cheminée (2) sont séparés par une cloison (3) comportant, en tant que moyens de liaison des espaces intérieurs, une bouche (15) d'évacuation dans la cheminée, d'azote humide contenu dans l'enceinte. Installation according to claim 2,3 or 4, characterized in that the discharge enclosure (13) belongs to a water-nitrogen tower (1) attached to the chimney (2), and the interior spaces of the enclosure ( 13) and the chimney (2) are separated by a partition (3) comprising, as means for connecting the interior spaces, a mouth (15) for evacuation in the chimney, of wet nitrogen contained in the enclosure . Installation selon l'une quelconque des revendications 1 et 5, caractérisée en ce que la cheminée (2) est équipée intérieurement d'un ensemble de buses (25) par où transite une partie ou la totalité du gaz introduit à la base de la cheminée.Installation according to any one of claims 1 and 5, characterized in that the chimney (2) is internally equipped with a set of nozzles (25) through which passes part or all of the gas introduced at the base of the chimney . Installation selon l'une quelconque des revendications 1 et 6, caractérisée en ce que les moyens de liaison (15) comportent une bouche d'évacuation ménagée dans une cloison (3) séparant les espaces internes de l'enceinte (13) et de la cheminée (2), et la cheminée est équipée intérieurement d'un ensemble de buses (25) disposé de telle sorte que son sommet soit à un niveau inférieur au sommet de la bouche d'évacuation (15).Installation according to any one of claims 1 and 6, characterized in that the connecting means (15) comprise a discharge mouth formed in a partition (3) separating the internal spaces of the enclosure (13) and the chimney (2), and the chimney is internally equipped with a set of nozzles (25) arranged so that its top is at a level below the top of the discharge mouth (15). Installation selon l'une quelconque des revendications 1 et 7, caractérisée en ce que l'enceinte d'évacuation (13) appartient à une tour eau-azote (1) comportant, à proximité de sa base, une conduite d'arrivée d'azote (11) sec, et, dans sa partie supérieure, une conduite d'arrivée d'eau chaude à refroidir (12), au-dessus du niveau de laquelle est ménagée une bouche d'évacuation d'azote humide (15), s'ouvrant dans la cheminée (2).Installation according to any one of claims 1 and 7, characterized in that the discharge enclosure (13) belongs to a water-nitrogen tower (1) comprising, near its base, an inlet pipe for dry nitrogen (11), and, in its upper part, a hot water supply pipe to be cooled (12), above the level of which a wet nitrogen discharge mouth (15) is formed, opening into the chimney (2). Installation selon l'une quelconque des revendications 1 et 8, caractérisée en ce que la cheminée (2) comporte, à proximité de sa base, des conduits d'arrivée d'air (21), et/ou d'arrivée d'azote (22), et/ou d'arrivée d'oxygène (23) et/ou d'arrivée d'un autre gaz issu de la distillation.Installation according to any one of claims 1 and 8, characterized in that the chimney (2) comprises, near its base, air inlet ducts (21), and / or nitrogen inlet ducts (22), and / or oxygen inlet (23) and / or arrival of another gas from the distillation. Procédé de mise à l'air par une bouche d'évacuation (24) d'une cheminée (2) d'une unité de distillation ou de liquéfaction d'air, de gaz résiduels comprenant de l'oxygène, caractérisé en ce que l'on mélange au moins à l'oxygène, de l'azote humide ou sec, et on évacue le mélange d'oxygène et d'azote obtenu à une vitesse au moins égale à approximativement 7 m/s au niveau de la bouche d'évacuation (24).Method of venting a chimney (2) of a unit for distilling or liquefying air, of residual gases comprising oxygen, through an outlet (24), characterized in that the 'at least wet or dry nitrogen is mixed with oxygen, and the mixture of oxygen and nitrogen obtained is evacuated at a speed at least equal to approximately 7 m / s at the mouth of evacuation (24). Procédé selon la revendication 9, caractérisé en ce que l'on évacue le mélange d'oxygène et d'azote obtenu à une vitesse au moins égale à approximativement 10 m/s au niveau de la bouche d'évacuation (24).Method according to claim 9, characterized in that the mixture of oxygen and nitrogen obtained is discharged at a speed at least equal to approximately 10 m / s at the discharge mouth (24). Procédé selon la revendication 10, caractérisé en ce que l'on évacue le mélange d'oxygène et d'azote obtenu à une vitesse au moins égale à approximativement 12 m/s au niveau de la bouche d'évacuation (24).A method according to claim 10, characterized in that the mixture of oxygen and nitrogen obtained is discharged at a speed at least equal to approximately 12 m / s at the discharge mouth (24). Procédé selon la revendication 11, caractérisé en ce que l'on évacue le mélange d'oxygène et d'azote obtenu à une vitesse au moins égale à approximativement 20 m/s au niveau de la bouche d'évacuation (24).A method according to claim 11, characterized in that the mixture of oxygen and nitrogen obtained is discharged at a speed at least equal to approximately 20 m / s at the discharge mouth (24).
EP01402540A 2000-10-19 2001-10-02 System and process for rejecting into air residual gases from air destillation or air liquefaction plants Withdrawn EP1199533A1 (en)

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FR0013382A FR2815549B1 (en) 2000-10-19 2000-10-19 INSTALLATION AND PROCEDURE FOR DISCHARGING RESIDUAL GASES FROM AIR DISTILLATION OR LIQUEFACTION UNITS

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