EP0387128A1 - Process and apparatus for the recovery of the heaviest hydrocarbons from a gaseous mixture - Google Patents
Process and apparatus for the recovery of the heaviest hydrocarbons from a gaseous mixture Download PDFInfo
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- EP0387128A1 EP0387128A1 EP90400549A EP90400549A EP0387128A1 EP 0387128 A1 EP0387128 A1 EP 0387128A1 EP 90400549 A EP90400549 A EP 90400549A EP 90400549 A EP90400549 A EP 90400549A EP 0387128 A1 EP0387128 A1 EP 0387128A1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
- F25J3/0219—Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G5/00—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas
- C10G5/06—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas by cooling or compressing
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0242—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 3 carbon atoms or more
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0252—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
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- 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
- F25J2200/74—Refluxing the column with at least a part of the partially condensed overhead gas
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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
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
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- 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
- F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
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- 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
- F25J2205/80—Processes or apparatus using other separation and/or other processing means using membrane, i.e. including a permeation step
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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
- F25J2270/00—Refrigeration techniques used
- F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
Definitions
- the present invention relates to the technique for recovering the heaviest hydrocarbons from a gas mixture. It relates more particularly to a process for recovering the heaviest hydrocarbons from a gaseous mixture further containing lighter constituents including hydrogen, in particular for the recovery of LPG (C3+) from a residual gas from an oil refinery.
- the object of the invention is to provide a clearly more economical method eliminating all these drawbacks.
- the method according to the invention is characterized in that: - part of the hydrogen is removed from the mixture; the remaining mixture is introduced at an intermediate level of a distillation column comprising a top condenser which provides reflux in the column, this condenser being cooled by a cooling device capable of providing a cold temperature TF of the order of -40 ° C or higher than this value; and the hydrogen content of said remaining mixture is determined so that the dew point, at column pressure, of the fraction of this remaining mixture constituted by said lighter constituents is greater than the temperature TF but close to it .
- the partial elimination of the hydrogen is carried out by permeation.
- this elimination partial hydrogen is carried out by PSA adsorption (Pressure Swing Adsorption), said remaining mixture being constituted by the residual gas from this adsorption and being compressed before being introduced into the column, the composition of said remaining mixture being optionally adjusted by permeation.
- PSA adsorption Pressure Swing Adsorption
- the invention also relates to an installation intended for the implementation of such a method.
- This installation is characterized in that it includes: - means for removing part of the hydrogen from the mixture, providing a remaining mixture; and a distillation column supplied with this remaining mixture and comprising a top condenser which provides reflux in the column, this condenser being cooled by a cooling device capable of providing a cold temperature TF of the order of -40 ° C or greater than this value; the means for partial elimination of hydrogen being adapted so that the fraction of said remaining mixture constituted by said lighter constituents has, at column pressure, a dew point above the temperature TF but close to it.
- an oil refinery waste gas of the following typical composition is treated: 74% H2, 12.2% C1, 9.5% C2, 2.7% C3, 1.6% C4 +, as well as traces of benzene compounds and water, in order to recover LPG (C3+).
- the gas to be treated is introduced at 31 bars, via a line 1, into the high-pressure space of a permeator 2.
- the permeate forming approximately two-thirds of the initial flow rate and consisting of hydrogen at a purity of 98 to 99% is removed from the permeator at low pressure under a few bars, via a line 3.
- the residue from the permeation containing almost all of the hydrocarbons, has the following composition: 21.3% H2, 36.7% C1, 28.9% C2, 8.2% C3, 4.9% C4+, as well as traces of benzene compounds and water.
- This residue is dried in a desiccator 4, then cooled in a heat exchanger. indirect heat 5, then introduced at about 30 bars at an intermediate level of a distillation column 6.
- the column 6 is equipped in the tank with a reboiler 7 operating at approximately 100 ° C, and at the head of a condenser 8 operating at approximately -40 ° C and refrigerated by a cooling device 9 consisting of a refrigeration unit, for example in "Freon", on one floor.
- the overhead vapor of the column is partially condensed by the condenser 8 and then separated into a vapor phase and a liquid phase in a phase separator 10.
- the vapor phase contains almost all of the hydrogen, methane and ethane contained in the permeation residue, and is discharged via a pipe 11 as waste gas from the installation after having cooled the heat exchanger 5.
- the liquid phase is returned to reflux at the top of the column 6.
- the LPG are drawn off in the column tank by a line 12.
- the residue from the permeation contains a quantity of light hydrocarbons C1 and C2 imposed by the composition of the starting gas. Its hydrogen content is determined by an appropriate dimensioning of the permeator 2, so that the mixture of these light hydrocarbons and hydrogen (that is to say in practice the waste gas) has, at the pressure of the column 6, a dew point slightly higher than the coldest temperature which the condenser 8 can reach with a refrigeration unit 9 with a single stage, ie approximately -40 ° C.
- the upper part of column 6 performs an almost perfect elimination of hydrogen by washing, so that the only loss of LPG is that which occurs in the permeator 2.
- the minimum compatible with a refrigeration unit 9 with a single stage is kept the amount of hydrogen eliminated by permeation, and therefore the loss of LPG. In practice, it is found that this loss can be made negligible, so that the extraction efficiency of LPG is close to 100%.
- the benzene compounds in the starting gas have no drawbacks and are simply found in the LPG produced.
- the desiccator 4 can possibly be dispensed with.
- FIG. 2 differs from that of FIG. 1 only by the treatment of the gas upstream of the heat exchanger 5. It is particularly suitable when it is desired to produce very pure hydrogen, for example intended to electronic applications.
- the starting gas is firstly treated by PSA adsorption (Pressure Swing Adsorption) in a 2A adsorption device, which removes about the same amount of hydrogen as before.
- PSA adsorption Pressure Swing Adsorption
- the remaining mixture consisting of the waste gas from the device 2A, is available at a low pressure typically close to atmospheric pressure. It is recompressed to around 30 bars by a compressor 13, then cooled in the exchanger 5, then introduced into the column 6 as before.
- the invention can be applied to other cases of recovery of heavy hydrocarbons.
- it is possible to recover only the C4+s by choosing the pressure of the column and the hydrogen content of the mixture introduced into this column so that the dew point of the mixture H2 , C1, C2 and C3 constituting the waste gas of the column is greater than -40 ° C; we will choose a cooling device 9 adapted to this temperature, this device possibly being constituted by a simple circulation of water at room temperature.
Abstract
Une partie de l'hydrogène du gaz traité, qui est notamment un gaz résiduaire de raffinerie de pétrole, est tout d'abord éliminée (en 2). Le mélange restant est introduit à un niveau intermédiaire d'une colonne de distillation (6) qui comporte un condenseur de tête (8) fonctionnant à une température TF de l'ordre de -40°C ou plus. La teneur en hydrogène dudit mélange restant est choisie de manière que le point de rosée du gaz résiduaire évacué en tête de colonne soit légèrement supérieur à la température TF. Les hydrocarbures lourds sont recueillis en cuve de la colonne (6).Part of the hydrogen from the treated gas, which is in particular a waste gas from an oil refinery, is first eliminated (in 2). The remaining mixture is introduced at an intermediate level of a distillation column (6) which comprises an overhead condenser (8) operating at a temperature TF of the order of -40 ° C or more. The hydrogen content of said remaining mixture is chosen so that the dew point of the waste gas discharged at the head of the column is slightly higher than the temperature TF. The heavy hydrocarbons are collected in the bottom of column (6).
Description
La présente invention est relative à la technique de récupération des hydrocarbures les plus lourds d'un mélange gazeux. Elle concerne plus particulièrement un procédé de récupération des hydrocarbures les plus lourds d'un mélange gazeux contenant en outre des constituants plus légers dont l'hydrogène, notamment pour la récupération des GPL (C₃⁺) d'un gaz résiduaire de raffinerie de pétrole.The present invention relates to the technique for recovering the heaviest hydrocarbons from a gas mixture. It relates more particularly to a process for recovering the heaviest hydrocarbons from a gaseous mixture further containing lighter constituents including hydrogen, in particular for the recovery of LPG (C₃⁺) from a residual gas from an oil refinery.
Dans les procédés habituels de récupération de GPL, on élimine à peu près totalement l'hydrogène par condensation partielle du mélange jusque vers -80°C.In the usual LPG recovery processes, the hydrogen is eliminated almost completely by partial condensation of the mixture down to -80 ° C.
Cette technique présente plusieurs inconvénients :
- l'obtention d'une température basse de -80°C conduit à l'utilisation d'un groupe frigorifique coûteux à deux étages ;
- le rendement de récupération des GPL est limité en fonction de la température basse choisie, par exemple à 97 ou 98 % pour -80°C ;
- la ligne d'échange thermique constitue un investissement coûteux ;
- les composés benzéniques et l'eau, mêmes présents à de très faibles teneurs, risquent de cristalliser dans la ligne d'échange thermique, conduisant à des bouchages ; il est donc nécessaire d'éliminer au préalable ces constituants.This technique has several drawbacks:
- obtaining a low temperature of -80 ° C leads to the use of an expensive two-stage refrigeration unit;
- the LPG recovery yield is limited depending on the low temperature chosen, for example 97 or 98% for -80 ° C;
- the heat exchange line is an expensive investment;
- the benzene compounds and water, even present at very low contents, risk crystallizing in the heat exchange line, leading to blockages; it is therefore necessary to remove these constituents beforehand.
L'invention a pour but de fournir un procédé nettement plus économique éliminant tous ces inconvénients.The object of the invention is to provide a clearly more economical method eliminating all these drawbacks.
A cet effet, le procédé suivant l'invention est caractérisé en ce que :
- on élimine une partie de l'hydrogène du mélange ;
- on introduit le mélange restant à un niveau intermédiaire d'une colonne de distillation comportant un condenseur de tête qui assure un reflux dans la colonne, ce condenseur étant refroidi par un appareil de refroidissement capable de fournir une température froide TF de l'ordre de -40°C ou supérieure à cette valeur ; et
- on détermine la teneur en hydrogène dudit mélange restant de façon que le point de rosée, à la pression de la colonne, de la fraction de ce mélange restant constituée par lesdits constituants plus légers soit supérieure à la température TF mais voisin de celle-ci.To this end, the method according to the invention is characterized in that:
- part of the hydrogen is removed from the mixture;
the remaining mixture is introduced at an intermediate level of a distillation column comprising a top condenser which provides reflux in the column, this condenser being cooled by a cooling device capable of providing a cold temperature TF of the order of -40 ° C or higher than this value; and
the hydrogen content of said remaining mixture is determined so that the dew point, at column pressure, of the fraction of this remaining mixture constituted by said lighter constituents is greater than the temperature TF but close to it .
Dans un premier mode de mise en oeuvre, l'élimination partielle de l'hydrogène est effectuée par perméation.In a first embodiment, the partial elimination of the hydrogen is carried out by permeation.
Dans une variante particulièrement adaptée aux cas où l'on souhaite produire simultanément de l'hydrogène pur, cette élimination partielle d'hydrogène est effectuée par adsorption PSA (Pressure Swing Adsorption), ledit mélange restant étant constitué par le gaz résiduaire de cette adsorption et étant comprimé avant d'être introduit dans la colonne, la composition dudit mélange restant étant éventuellement ajustée par perméation.In a variant particularly suitable for cases where it is desired to produce pure hydrogen simultaneously, this elimination partial hydrogen is carried out by PSA adsorption (Pressure Swing Adsorption), said remaining mixture being constituted by the residual gas from this adsorption and being compressed before being introduced into the column, the composition of said remaining mixture being optionally adjusted by permeation.
L'invention a également pour objet une installation destinée à la mise en oeuvre d'un tel procédé. Cette installation est caractérisée en ce qu'elle comprend :
- des moyens d'élimination d'une partie de l'hydrogène du mélange, fournissant un mélange restant ; et
- une colonne de distillation alimentée par ce mélange restant et comportant un condenseur de tête qui assure un reflux dans la colonne, ce condenseur étant refroidi par un appareil de refroidissement capable de fournir une température froide TF de l'ordre de -40°C ou supérieure à cette valeur ;
- les moyens d'élimination partielle d'hydrogène étant adaptés pour que la fraction dudit mélange restant constituée par lesdits constituants plus légers ait, à la pression de la colonne, un point de rosée supérieur à la température TF mais voisin de celle-ci.The invention also relates to an installation intended for the implementation of such a method. This installation is characterized in that it includes:
- means for removing part of the hydrogen from the mixture, providing a remaining mixture; and
a distillation column supplied with this remaining mixture and comprising a top condenser which provides reflux in the column, this condenser being cooled by a cooling device capable of providing a cold temperature TF of the order of -40 ° C or greater than this value;
the means for partial elimination of hydrogen being adapted so that the fraction of said remaining mixture constituted by said lighter constituents has, at column pressure, a dew point above the temperature TF but close to it.
Des exemples de mise en oeuvre de l'invention vont maintenant être décrits en regard des dessins annexés, sur lesquels les figures 1 et 2 représentent schématiquement deux installations conformes à l'invention.Examples of implementation of the invention will now be described with reference to the accompanying drawings, in which Figures 1 and 2 schematically represent two installations according to the invention.
Dans les exemples représentés, on traite un gaz résiduaire de raffinerie de pétrole de composition typique suivante : 74 % H₂, 12,2 % C₁, 9,5 % C₂, 2,7 % C₃, 1,6 % C₄ ⁺, ainsi que des traces de composés benzéniques et d'eau, en vue d'en récupérer des GPL (C₃⁺).In the examples shown, an oil refinery waste gas of the following typical composition is treated: 74% H₂, 12.2% C₁, 9.5% C₂, 2.7% C₃, 1.6% C₄ ⁺, as well as traces of benzene compounds and water, in order to recover LPG (C₃⁺).
Le gaz à traiter est introduit sous 31 bars, via une conduite 1, dans l'espace haute-pression d'un perméateur 2. Le perméat, formant à peu près les deux-tiers du débit initial et constitué par de l'hydrogène à une pureté de 98 à 99 %, est évacué du perméateur en basse-pression sous quelques bars, par une conduite 3. Le résidu de la perméation, contenant la quasi-totalité des hydrocarbures, présente la composition suivante : 21,3 % H₂, 36,7 % C₁, 28,9 % C₂, 8,2 % C₃, 4,9% C₄⁺, ainsi que des traces de composés benzéniques et d'eau. Ce résidu est desséché dans un appareil de dessication 4, puis refroidi dans un échangeur de chaleur indirect 5, puis introduit sous environ 30 bars à un niveau intermédiaire d'un colonne de distillation 6.The gas to be treated is introduced at 31 bars, via a line 1, into the high-pressure space of a permeator 2. The permeate, forming approximately two-thirds of the initial flow rate and consisting of hydrogen at a purity of 98 to 99% is removed from the permeator at low pressure under a few bars, via a
La colonne 6 est équipée en cuve d'un rebouilleur 7 fonctionnant à environ 100°C, et en tête d'un condenseur 8 fonctionnant à environ -40°C et réfrigéré par un appareil de refroidissement 9 constitué par un groupe frigorifique, par exemple à "Fréon", à un seul étage. La vapeur de tête de la colonne est partiellement condensée par le condenseur 8 puis séparée en une phase vapeur et une phase liquide dans un séparateur de phases 10. La phase vapeur contient la quasi-totalité de l'hydrogène, du méthane et de l'éthane contenus dans le résidu de la perméation, et est évacuée par une conduite 11 en tant que gaz résiduaire de l'installation après avoir refroidi l'échangeur de chaleur 5. La phase liquide est renvoyée en reflux en tête de la colonne 6. Les GPL sont soutirés en cuve de colonne par une conduite 12.The
Le résidu de la perméation contient une quantité d'hydrocarbures légers C₁ et C₂ imposée par la composition du gaz de départ. On détermine sa teneur en hydrogène, par un dimensionnement approprié du perméateur 2, de façon que le mélange de ces hydrocarbures légers et de l'hydrogène (c'est-à-dire en pratique le gaz résiduaire) ait, à la pression de la colonne 6, un point de rosée légèrement supérieur à la température la plus froide que peut atteindre le condenseur 8 avec un groupe frigorifique 9 à un seul étage, soit environ -40°C.The residue from the permeation contains a quantity of light hydrocarbons C₁ and C₂ imposed by the composition of the starting gas. Its hydrogen content is determined by an appropriate dimensioning of the permeator 2, so that the mixture of these light hydrocarbons and hydrogen (that is to say in practice the waste gas) has, at the pressure of the
Ainsi, la partie supérieure de la colonne 6 effectue une élimination à peu près parfaite de l'hydrogène par lavage, de sorte que la seule perte en GPL est celle qui se produit dans le perméateur 2. En choisissant le point de rosée du gaz résiduaire très voisin de -40°C, on maintient au minimum compatible avec un groupe frigorifique 9 à un seul étage la quantité d'hydrogène éliminée par perméation, et donc la perte de GPL. En pratique, on constate que cette perte peut être rendue négligeable, de sorte que le rendement d'extraction des GPL est proche de 100 %.Thus, the upper part of
Par ailleurs, grâce à l'absence de toute ligne d'échange de chaleur cryogénique, les composés benzéniques du gaz de départ ne présentent aucun inconvénient et se retrouvent simplement dans les GPL produits. De même, si la teneur en eau du gaz de départ est suffisamment faible, on peut éventuellement se passer de l'appareil de dessication 4.Furthermore, thanks to the absence of any cryogenic heat exchange line, the benzene compounds in the starting gas have no drawbacks and are simply found in the LPG produced. Likewise, if the water content of the starting gas is sufficiently low, the desiccator 4 can possibly be dispensed with.
En variante, comme indiqué en trait mixte en 13, on peut avec la même installation produire en plus une coupe C₁/C₂ en soutirant du liquide en tête de la colonne 6. Cependant, on abaisse alors le point de rosée de la vapeur de tête et du gaz résiduaire, ce qui nécessite en compensation une plus forte élimination d'hydrogène par perméation et, par suite, conduit à une dégradation du rendement d'extraction des GPL.As a variant, as indicated in phantom in 13, it is possible with the same installation to produce in addition a C₁ / C₂ cut by withdrawing liquid at the head of
L'installation de la figure 2 ne diffère de celle de la figure 1 que par le traitement du gaz en amont de l'échangeur de chaleur 5. Elle convient notamment lorsque l'on désire produire de l'hydrogène très pur, par exemple destiné à des applications électroniques.The installation of FIG. 2 differs from that of FIG. 1 only by the treatment of the gas upstream of the
En effet, le gaz de départ est tout d'abord traité par adsorption PSA (Pressure Swing Adsorption) dans un appareil d'adsorption 2A, qui en élimine à peu près la même quantité d'hydrogène que précédemment. Le mélange restant, constitué par le gaz résiduaire de l'appareil 2A, est disponible à une basse pression typiquement voisine de la pression atmosphérique. Il est recomprimé à environ 30 bars par un compresseur 13, puis refroidi dans l'échangeur 5, puis introduit dans la colonne 6 comme précédemment.In fact, the starting gas is firstly treated by PSA adsorption (Pressure Swing Adsorption) in a 2A adsorption device, which removes about the same amount of hydrogen as before. The remaining mixture, consisting of the waste gas from the
Si la teneur en hydrogène du gaz résiduaire de l'appareil 2A conduit à un point de rosée du gaz résiduaire de la colonne voisin de -40°C ou supérieur à cette valeur, on choisit simplement un groupe frigorifique 9 fonctionnant à ce point de rosée. Le rendement d'extraction des GPL sera alors toujours pratiquement de 100 %, puisqu'aucune perte en GPL ne se produit dans l'appareil 2A.If the hydrogen content of the waste gas from the
Par contre, si cette teneur en hydrogène est trop élévée (d'où un point de rosée en tête de colonne inférieur à -40°C), on l'abaisse à une valeur fournissant un point de rosée légèrement supérieur à -40°C, au moyen d'un perméateur 14 monté entre la sortie du compresseur 13 et de l'échangeur 5, comme schématisé en trait interrompu à la figure 2.On the other hand, if this hydrogen content is too high (hence a dew point at the top of the column below -40 ° C), it is lowered to a value providing a dew point slightly above -40 ° C , by means of a
On comprend que l'invention peut s'appliquer à d'autres cas de récupération d'hydrocarbures lourds. Par exemple, avec le même gaz de départ que ci-dessus, on peut récupérer uniquement les C₄⁺, en choisissant la pression de la colonne et la teneur en hydrogène du mélange introduit dans cette colonne de façon que le point de rosée du mélange H₂, C₁, C₂ et C₃ constituant le gaz résiduaire de la colonne soit supérieur à -40°C ; on choisira un appareil de refroidissement 9 adapté à cette température, cet appareil pouvant éventuellement être constitué par une simple circulation d'eau à la température ambiante.It is understood that the invention can be applied to other cases of recovery of heavy hydrocarbons. For example, with the same starting gas as above, it is possible to recover only the C₄⁺s, by choosing the pressure of the column and the hydrogen content of the mixture introduced into this column so that the dew point of the mixture H₂ , C₁, C₂ and C₃ constituting the waste gas of the column is greater than -40 ° C; we will choose a
Claims (10)
- on élimine une partie de l'hydrogène du mélange ;
- on introduit le mélange restant à un niveau intermédiaire d'une colonne de distillation (6) comportant un condenseur de tête (8) qui assure un reflux dans la colonne, ce condenseur étant refroidi par un appareil de refroidissement (9) capable de fournir une température froide TF de l'ordre de -40°C ou supérieure à cette valeur ; et
- on détermine la teneur en hydrogène dudit mélange restant de façon que le point de rosée, à la pression de la colonne, de la fraction de ce mélange restant constituée par lesdits constituants plus légers soit supérieure à la température TF mais voisin de celle-ci.1. Method for recovering the heaviest hydrocarbons from a gaseous mixture further containing lighter constituents including hydrogen, in particular for recovering LPG (C₃⁺) from a residual gas from an oil refinery, characterized in that than :
- part of the hydrogen is removed from the mixture;
- The remaining mixture is introduced at an intermediate level of a distillation column (6) comprising a top condenser (8) which provides reflux in the column, this condenser being cooled by a cooling device (9) capable of supplying a cold temperature TF of the order of -40 ° C or higher than this value; and
the hydrogen content of said remaining mixture is determined so that the dew point, at column pressure, of the fraction of this remaining mixture constituted by said lighter constituents is greater than the temperature TF but close to it .
- des moyens (2 ; 2A,14) d'élimination d'une partie de l'hydrogène du mélange, fournissant un mélange restant ; et
- une colonne de distillation (6) alimentée par ce mélange restant et comportant un condenseur de tête (8) qui assure un reflux dans la colonne, ce condenseur étant refroidi par un appareil de refroidissement (9) capable de fournir une température froide TF de l'ordre de -40°C ou supérieure à cette valeur ;
- les moyens d'élimination partielle d'hydrogène étant adaptés pour que la fraction dudit mélange restant constituée par lesdits constituants plus légers ait, à la pression de la colonne, un point de rosée supérieur à la température TF mais voisin de celle-ci.6. Installation for recovering the heaviest hydrocarbons from a gaseous mixture additionally containing lighter constituents including hydrogen, in particular for recovering LPG (C₃⁺) from a residual gas from an oil refinery, characterized in that that she understands:
- means (2; 2A, 14) for removing part of the hydrogen from the mixture, providing a remaining mixture; and
- a distillation column (6) fed by this remaining mixture and comprising a head condenser (8) which provides reflux in the column, this condenser being cooled by a cooling device (9) capable of providing a cold temperature TF of in the range of -40 ° C or higher than this value;
the means for partial elimination of hydrogen being adapted so that the fraction of said remaining mixture constituted by said lighter constituents has, at column pressure, a dew point above the temperature TF but close to it.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8903073 | 1989-03-09 | ||
FR8903073A FR2644160B1 (en) | 1989-03-09 | 1989-03-09 | PROCESS AND PLANT FOR RECOVERING THE HEAVIEST HYDROCARBONS FROM A GASEOUS MIXTURE |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0387128A1 true EP0387128A1 (en) | 1990-09-12 |
EP0387128B1 EP0387128B1 (en) | 1991-11-27 |
Family
ID=9379512
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90400549A Expired - Lifetime EP0387128B1 (en) | 1989-03-09 | 1990-02-28 | Process and apparatus for the recovery of the heaviest hydrocarbons from a gaseous mixture |
Country Status (7)
Country | Link |
---|---|
US (1) | US5053067A (en) |
EP (1) | EP0387128B1 (en) |
CA (1) | CA2011311A1 (en) |
DE (1) | DE69000004D1 (en) |
ES (1) | ES2026741T3 (en) |
FR (1) | FR2644160B1 (en) |
NO (1) | NO901038L (en) |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5504677A (en) * | 1992-10-15 | 1996-04-02 | Pollin; Robert E. | Automated payment system |
US5966698A (en) * | 1992-10-15 | 1999-10-12 | Pollin; Robert E. | Automated payment system and method |
US5647227A (en) * | 1996-02-29 | 1997-07-15 | Membrane Technology And Research, Inc. | Membrane-augmented cryogenic methane/nitrogen separation |
US5634354A (en) * | 1996-05-08 | 1997-06-03 | Air Products And Chemicals, Inc. | Olefin recovery from olefin-hydrogen mixtures |
US5785739A (en) * | 1997-01-24 | 1998-07-28 | Membrane Technology And Research, Inc. | Steam cracker gas separation process |
US5769927A (en) * | 1997-01-24 | 1998-06-23 | Membrane Technology And Research, Inc. | Monomer recovery process |
US5980609A (en) * | 1997-01-24 | 1999-11-09 | Membrane Technology And Research, Inc. | Hydrogen recovery process |
US6159272A (en) * | 1997-01-24 | 2000-12-12 | Membrane Technology And Research, Inc. | Hydrogen recovery process |
US6179996B1 (en) | 1998-05-22 | 2001-01-30 | Membrane Technology And Research, Inc. | Selective purge for hydrogenation reactor recycle loop |
US6264828B1 (en) | 1998-05-22 | 2001-07-24 | Membrane Tehnology And Research, Inc. | Process, including membrane separation, for separating hydrogen from hydrocarbons |
US6011192A (en) * | 1998-05-22 | 2000-01-04 | Membrane Technology And Research, Inc. | Membrane-based conditioning for adsorption system feed gases |
US6171472B1 (en) | 1998-05-22 | 2001-01-09 | Membrane Technology And Research, Inc. | Selective purge for reactor recycle loop |
US6190540B1 (en) | 1998-05-22 | 2001-02-20 | Membrane Technology And Research, Inc. | Selective purging for hydroprocessing reactor loop |
US6190536B1 (en) | 1998-05-22 | 2001-02-20 | Membrane Technology And Research, Inc. | Catalytic cracking process |
US6165350A (en) * | 1998-05-22 | 2000-12-26 | Membrane Technology And Research, Inc. | Selective purge for catalytic reformer recycle loop |
US6289693B1 (en) * | 1998-06-25 | 2001-09-18 | Chart Industries, Inc. | Cryogenic and membrane synthesis gas production |
US6592749B1 (en) | 1999-03-19 | 2003-07-15 | Membrane Technology And Research, Inc. | Hydrogen/hydrocarbon separation process, including PSA and membranes |
US6183628B1 (en) | 1999-03-19 | 2001-02-06 | Membrane Technology And Research, Inc. | Process, including PSA and membrane separation, for separating hydrogen from hydrocarbons |
US6389845B1 (en) * | 1999-10-05 | 2002-05-21 | American Air Liquide, Inc. | Method and apparatus for separation of SF6 from CF4 /air-containing gas stream |
US6589303B1 (en) | 1999-12-23 | 2003-07-08 | Membrane Technology And Research, Inc. | Hydrogen production by process including membrane gas separation |
US6568206B2 (en) * | 2001-07-18 | 2003-05-27 | Air Products And Chemicals, Inc. | Cryogenic hydrogen and carbon monoxide production with membrane permeate expander |
WO2005037421A2 (en) * | 2003-10-14 | 2005-04-28 | Advanced Technology Materials, Inc. | Hydrogen generation |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3250080A (en) * | 1962-11-07 | 1966-05-10 | Kerr Mc Gee Oil Ind Inc | Method of separating gaseous mixtures by diffusion and fractionation |
US4284423A (en) * | 1978-02-15 | 1981-08-18 | Exxon Research & Engineering Co. | Separation of carbon dioxide and other acid gas components from hydrocarbon feeds containing admixtures of methane and hydrogen |
US4374657A (en) * | 1981-06-03 | 1983-02-22 | Fluor Corporation | Process of separating acid gases from hydrocarbons |
US4411677A (en) * | 1982-05-10 | 1983-10-25 | Air Products And Chemicals, Inc. | Nitrogen rejection from natural gas |
US4681612A (en) * | 1984-05-31 | 1987-07-21 | Koch Process Systems, Inc. | Process for the separation of landfill gas |
US4732583B1 (en) * | 1984-12-03 | 1990-05-15 | Gas separation | |
US4595404A (en) * | 1985-01-14 | 1986-06-17 | Brian J. Ozero | CO2 methane separation by low temperature distillation |
US4602477A (en) * | 1985-06-05 | 1986-07-29 | Air Products And Chemicals, Inc. | Membrane-aided distillation for carbon dioxide and hydrocarbon separation |
-
1989
- 1989-03-09 FR FR8903073A patent/FR2644160B1/en not_active Expired - Fee Related
-
1990
- 1990-02-28 ES ES199090400549T patent/ES2026741T3/en not_active Expired - Lifetime
- 1990-02-28 EP EP90400549A patent/EP0387128B1/en not_active Expired - Lifetime
- 1990-02-28 DE DE9090400549T patent/DE69000004D1/en not_active Expired - Lifetime
- 1990-03-06 NO NO90901038A patent/NO901038L/en unknown
- 1990-03-07 CA CA002011311A patent/CA2011311A1/en not_active Abandoned
- 1990-03-09 US US07/489,944 patent/US5053067A/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
Eléments de la technique relevés: néant. * |
Also Published As
Publication number | Publication date |
---|---|
NO901038D0 (en) | 1990-03-06 |
EP0387128B1 (en) | 1991-11-27 |
FR2644160B1 (en) | 1991-05-10 |
NO901038L (en) | 1990-09-10 |
FR2644160A1 (en) | 1990-09-14 |
ES2026741T3 (en) | 1992-05-01 |
US5053067A (en) | 1991-10-01 |
CA2011311A1 (en) | 1990-09-09 |
DE69000004D1 (en) | 1992-01-09 |
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