FR3127701A1 - PROCESS FOR SEPARATION OF ALL OR PART OF THE COMPOUNDS OF A BIOGAS IN THE LIQUID STATE OR IN THE TWO-PHASE STATE - Google Patents
PROCESS FOR SEPARATION OF ALL OR PART OF THE COMPOUNDS OF A BIOGAS IN THE LIQUID STATE OR IN THE TWO-PHASE STATE Download PDFInfo
- Publication number
- FR3127701A1 FR3127701A1 FR2111835A FR2111835A FR3127701A1 FR 3127701 A1 FR3127701 A1 FR 3127701A1 FR 2111835 A FR2111835 A FR 2111835A FR 2111835 A FR2111835 A FR 2111835A FR 3127701 A1 FR3127701 A1 FR 3127701A1
- Authority
- FR
- France
- Prior art keywords
- separation
- biogas
- mixture
- distillation column
- process according
- 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.)
- Pending
Links
- 238000000926 separation method Methods 0.000 title claims abstract description 51
- 239000007788 liquid Substances 0.000 title claims abstract description 36
- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000004821 distillation Methods 0.000 claims abstract description 36
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 36
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 16
- 230000001174 ascending effect Effects 0.000 claims abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 66
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 30
- 239000001569 carbon dioxide Substances 0.000 claims description 30
- 238000009434 installation Methods 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 description 5
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QUWBSOKSBWAQER-UHFFFAOYSA-N [C].O=C=O Chemical compound [C].O=C=O QUWBSOKSBWAQER-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 235000021183 entrée Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
-
- 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
- F25J3/0209—Natural gas or substitute natural gas
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0204—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
- F25J3/0209—Natural gas or substitute natural gas
- F25J3/0214—Liquefied natural gas
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0233—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 1 carbon atom or more
-
- 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
-
- 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
- F25J3/0247—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 4 carbon atoms or more
-
- 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
- F25J3/0266—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon dioxide
-
- 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
- F25J2200/04—Processes or apparatus using separation by rectification in a dual pressure main column system
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/04—Mixing or blending of fluids with the feed stream
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/62—Liquefied natural gas [LNG]; Natural gas liquids [NGL]; Liquefied petroleum gas [LPG]
Abstract
L’invention porte sur un procédé de séparation de tout ou partie de composés d’un biogaz à l’état liquide ou à l’état diphasique liquide/vapeur, contenant du méthane, du CO2 et éventuellement un hydrocarbure ou un mélange d’hydrocarbures de la famille C3 à C7, dans lequel le méthane est séparé des autres composés par distillation cryogénique en injectant dans une colonne de distillation le biogaz liquéfié à une température d’équilibre permettant l’obtention d’un mélange diphasique assurant la séparation des différents composés et un agent de liquéfaction à l’état liquide composé d’un hydrocarbure ou d’un mélange d’hydrocarbure(s) de la famille C3 à C7, l’agent de liquéfaction étant injecté en tête de colonne, au-dessus du niveau d’entrée du biogaz, à une température inférieure ou égale à la température de désublimation du CO2 à une pression donnée de la colonne et en quantité proportionnelle au débit de vapeur du CO2ascendant en tête de colonne. Figure à publier avec l’abrégé : Fig. 2The invention relates to a method for separating all or part of compounds from a biogas in the liquid state or in the two-phase liquid/vapor state, containing methane, CO2 and optionally a hydrocarbon or a mixture of hydrocarbons. of the C3 to C7 family, in which the methane is separated from the other compounds by cryogenic distillation by injecting the liquefied biogas into a distillation column at an equilibrium temperature making it possible to obtain a two-phase mixture ensuring the separation of the various compounds and a liquefaction agent in the liquid state composed of a hydrocarbon or a mixture of hydrocarbon(s) of the C3 to C7 family, the liquefaction agent being injected at the top of the column, above the level biogas inlet, at a temperature less than or equal to the CO2 desublimation temperature at a given column pressure and in a quantity proportional to the flow of CO2 vapor ascending to the top of the column. Figure to be published with abstract: Fig. 2
Description
DOMAINE TECHNIQUE DE L’INVENTIONTECHNICAL FIELD OF THE INVENTION
La présente invention concerne le domaine de la valorisation des biogaz, et se rapporte plus particulièrement à un procédé de séparation de tout ou partie des composés d’un biogaz à l’état liquide ou à l’état diphasique liquide/vapeur, le biogaz contenant du méthane, du dioxyde de carbone et éventuellement des hydrocarbures de la famille C3à C7permettant sa liquéfaction.The present invention relates to the field of biogas upgrading, and relates more particularly to a process for separating all or part of the compounds of a biogas in the liquid state or in the two-phase liquid/vapor state, the biogas containing methane, carbon dioxide and possibly hydrocarbons of the C 3 to C 7 family allowing its liquefaction.
Le procédé selon l’invention est destiné notamment, mais non exclusivement, à l’épuration du biogaz à l’état liquide ou à l’état diphasique liquide/vapeur aux fins de récupérer tout ou partie de ses composés, et en particulier le méthane pour être utilisé comme carburant pour les véhicules ou pour être injecté dans un réseau de gaz naturel ainsi que le dioxyde de carbone.The process according to the invention is intended in particular, but not exclusively, for the purification of biogas in the liquid state or in the two-phase liquid/vapor state for the purpose of recovering all or part of its compounds, and in particular methane to be used as fuel for vehicles or to be injected into a natural gas network as well as carbon dioxide.
ETAT DE LA TECHNIQUESTATE OF THE ART
Parmi les méthodes d’épuration du biogaz connues, les méthodes conventionnellement utilisées pour séparer le méthane du dioxyde de carbone sont la séparation membranaire, la PSA (Pressure Swing Adsorption – adsorption par variation de pression) et la distillation cryogénique.Among the known biogas purification methods, the methods conventionally used to separate methane from carbon dioxide are membrane separation, PSA (Pressure Swing Adsorption) and cryogenic distillation.
La séparation membranaire est basée sur l’utilisation de membranes réalisées dans des matériaux laissant passer le dioxyde de carbone et retenant le méthane. La PSA est basée sur l’adsorption du dioxyde de carbone dans les composants solides de la colonne d’adsorption à haute pression et une désorption à basse pression. La distillation cryogénique repose quant à elle sur des abaissements successifs de la température jusqu’à la production de dioxyde de carbone liquide et de biométhane liquéfié ou de désublimation du dioxyde de carbone qui produit du dioxyde de carbone liquide et du bio-méthane gazeux.Membrane separation is based on the use of membranes made of materials that allow carbon dioxide to pass through and retain methane. PSA is based on the adsorption of carbon dioxide in the solid components of the high pressure adsorption column and low pressure desorption. Cryogenic distillation is based on successive lowering of the temperature until the production of liquid carbon dioxide and liquefied biomethane or desublimation of carbon dioxide which produces liquid carbon dioxide and gaseous bio-methane.
Ces méthodes conventionnellement utilisées présentent cependant des inconvénients pour séparer un biogaz à l’état liquide ou à l’état diphasique. Soit elles ne permettent pas d’atteindre des taux de pureté du méthane récupéré satisfaisants, soit elles ne permettent pas de récupérer le dioxyde de carbone, soit elles s’avèrent inadaptées pour le traitement d’un biogaz liquéfié ou contenant des hydrocarbures, notamment le butane, utilisés pour liquéfier le biogaz. Ainsi la technique de la séparation membranaire n’est pas à privilégier lorsque le biogaz comporte des hydrocarbures, et en particulier du butane, ce dernier détériorant les membranes rapidement. La PSA ne permet pas d’atteindre quant à elle les taux de pureté souhaités. Par ailleurs, cette méthode nécessite l’apport d’une quantité importante de chaleur ce qui va à l’encontre de l’utilisation de froid préalablement dépensé pour liquéfier le biogaz. La technique de distillation cryogénique présente quant à elle l’inconvénient de produire des particules solides de dioxyde de carbone (cristaux de neige carbonique) qui peuvent créer des bouchons dans les échangeurs de chaleur et le garnissage dans la tête de colonne.However, these conventionally used methods have drawbacks for separating a biogas in the liquid state or in the two-phase state. Either they do not make it possible to achieve satisfactory levels of purity of the recovered methane, or they do not make it possible to recover the carbon dioxide, or they prove to be unsuitable for the treatment of a liquefied biogas or one containing hydrocarbons, in particular butane, used to liquefy biogas. Thus the technique of membrane separation is not to be preferred when the biogas contains hydrocarbons, and in particular butane, the latter deteriorating the membranes quickly. PSA does not achieve the desired purity levels. Moreover, this method requires the supply of a large quantity of heat which goes against the use of cold previously spent to liquefy the biogas. The cryogenic distillation technique has the disadvantage of producing solid particles of carbon dioxide (dry ice crystals) which can create plugs in the heat exchangers and the packing in the column head.
L’invention vise à remédier à ces problèmes en proposant un procédé de séparation permettant de séparer les composés d’un biogaz à l’état liquide ou à l’état diphasique liquide/vapeur de manière à récupérer le méthane à un taux de pureté élevé ainsi que de récupérer le dioxyde de carbone en évitant les problème de colmatage et formation de neige carbonique.The invention aims to remedy these problems by proposing a separation process making it possible to separate the compounds of a biogas in the liquid state or in the two-phase liquid/vapor state so as to recover the methane at a high level of purity. as well as to recover the carbon dioxide by avoiding the problem of clogging and formation of dry ice.
OBJET DE L’INVENTIONOBJECT OF THE INVENTION
A cet effet, et selon un premier aspect, l’invention propose un procédé de séparation de tout ou partie de composés d’un biogaz à l’état liquide ou à l’état diphasique liquide/vapeur, contenant du méthane, du dioxyde de carbone et éventuellement d’un hydrocarbure ou d’un mélange d’hydrocarbures de la famille C3à C7, le procédé étant remarquable en ce qu’une première séparation pour séparer le méthane des autres composés est réalisée par distillation cryogénique dans une première colonne de distillation comportant une tête de colonne portée à la température de condensation du méthane à une pression donnée, la première séparation étant réalisée en injectant dans la première colonne de distillation :
- en alimentation principale, le biogaz liquéfié à une température d’équilibre permettant l’obtention d’un mélange diphasique assurant la séparation des différents composés,
- en alimentation secondaire, un agent de liquéfaction à l’état liquide composé d’un ou d’un mélange d’hydrocarbure(s) de la famille C3à C7, l’agent de liquéfaction étant injecté en tête de la première colonne de distillation, au-dessus du niveau d’entrée du biogaz, à une température T1 inférieure ou égale à la température de désublimation du dioxyde de carbone à une pression donnée de la colonne de distillation et en quantité proportionnelle au débit de vapeur du dioxyde de carbone ascendant en tête de colonne.
- as the main supply, the liquefied biogas at an equilibrium temperature allowing the production of a two-phase mixture ensuring the separation of the various compounds,
- in secondary feed, a liquefaction agent in the liquid state composed of one or a mixture of hydrocarbon(s) of the C 3 to C 7 family, the liquefaction agent being injected at the top of the first column distillation, above the entry level of the biogas, at a temperature T1 less than or equal to the desublimation temperature of carbon dioxide at a given pressure of the distillation column and in a quantity proportional to the vapor flow rate of carbon dioxide carbon ascending at the top of the column.
L’injection d’un agent de liquéfaction en tête de colonne au-dessus de l’entrée du biogaz à une température et quantité déterminées, à savoir à une température inférieure ou égale à la température à laquelle le dioxyde de carbone dé-sublimerait dans la colonne de distillation maintenue à une pression donnée d’une part et en quantité proportionnelle au débit de vapeur du dioxyde de carbone ascendant en tête de colonne d’autre part, permet ainsi de dissoudre les cristaux de neige carbonique qui se forment en tête de la colonne de distillation utilisée pour séparer le méthane des autres composés en assurant une séparation satisfaisante du méthane gazeux du mélange liquide composé du dioxyde de carbone et de l’agent de liquéfaction.The injection of a liquefaction agent at the top of the column above the biogas inlet at a determined temperature and quantity, namely at a temperature lower than or equal to the temperature at which the carbon dioxide would de-sublimate in the distillation column maintained at a given pressure on the one hand and in a quantity proportional to the flow rate of carbon dioxide vapor rising at the top of the column on the other hand, thus makes it possible to dissolve the crystals of dry ice which form at the top of the column the distillation column used to separate the methane from the other compounds by ensuring satisfactory separation of the gaseous methane from the liquid mixture composed of carbon dioxide and the liquefaction agent.
Par température de désublimation, on désigne la température à laquelle la désublimation (passage de l’état gazeux à l’état solide) du dioxyde de carbone est provoquée. La température de désublimation peut être également désignée indifféremment de température de condensation solide, de cristallisation ou encore de sublimation inverse.By desublimation temperature, we mean the temperature at which the desublimation (transition from the gaseous state to the solid state) of carbon dioxide is caused. The desublimation temperature can also be referred to as the solid condensation, crystallization or reverse sublimation temperature without distinction.
Avantageusement, l’agent de liquéfaction est injecté au niveau du reflux de méthane.Advantageously, the liquefaction agent is injected at the level of the methane reflux.
Avantageusement, l’agent de liquéfaction est injecté dans la première colonne de distillation à une température T1 de l’ordre de -100°C.Advantageously, the liquefaction agent is injected into the first distillation column at a temperature T1 of the order of -100°C.
Avantageusement, l’agent de liquéfaction est soumis à un refroidissement en deux étages sous pression avant son injection dans la tête de la première colonne de distillation pour atteindre la température T1.Advantageously, the liquefaction agent is subjected to cooling in two stages under pressure before its injection into the top of the first distillation column to reach the temperature T1.
Avantageusement, la tête de la première colonne de distillation est mise en froid en tout ou partie par l’agent de liquéfaction.Advantageously, the head of the first distillation column is cooled in whole or in part by the liquefaction agent.
Avantageusement, le procédé comporte une étape de récupération du méthane à l’état gazeux à l’issue de la première séparation.Advantageously, the process includes a step for recovering the methane in the gaseous state after the first separation.
Selon un mode de réalisation avantageux, il est procédé à une deuxième séparation des composés du mélange liquide récupéré à l’issue de la première séparation et composé du dioxyde de carbone, de l’agent de liquéfaction et des éventuels hydrocarbures. Cette deuxième séparation est réalisée par distillation cryogénique dans une deuxième colonne de distillation après détente du mélange liquide pour atteindre une température et une pression d’équilibre permettant la séparation du dioxyde de carbone sous forme de condensat en tête de colonne et l’agent de liquéfaction additionné des éventuels hydrocarbures en résidus sous forme liquide en bas de colonne.According to an advantageous embodiment, a second separation of the compounds of the liquid mixture recovered at the end of the first separation and composed of carbon dioxide, the liquefaction agent and any hydrocarbons is carried out. This second separation is carried out by cryogenic distillation in a second distillation column after expansion of the liquid mixture to reach a temperature and an equilibrium pressure allowing the separation of the carbon dioxide in the form of condensate at the top of the column and the liquefaction agent added any hydrocarbons in residues in liquid form at the bottom of the column.
Avantageusement, la deuxième séparation est réalisée par mise en froid de la tête de la deuxième colonne à la température de condensation du dioxyde de carbone comprise entre -50 ° Celsius et -60° Celsius en fonction de la pression atteinte après la détente.Advantageously, the second separation is carried out by cooling the head of the second column to the carbon dioxide condensation temperature of between −50° Celsius and −60° Celsius depending on the pressure reached after expansion.
Avantageusement, le procédé de séparation comporte une étape de récupération du dioxyde de carbone à l’état gazeux (condensat) à l’issue de la deuxième séparation.Advantageously, the separation process comprises a step for recovering the carbon dioxide in the gaseous state (condensate) at the end of the second separation.
Avantageusement, le procédé comporte une étape de récupération de l’agent de liquéfaction additionné des éventuels hydrocarbures à l’issue de la deuxième séparation pour son réacheminement en tout ou partie vers la première colonne de distillation.Advantageously, the process comprises a step for recovering the liquefaction agent to which any hydrocarbons have been added at the end of the second separation for its rerouting in whole or in part to the first distillation column.
Avantageusement, l’agent de liquéfaction est un hydrocarbure linéaire ou non linéaire du type alcène de la famille C3à C7ou un mélange d’hydrocarbures de la famille C3à C7.Advantageously, the liquefaction agent is a linear or non-linear hydrocarbon of the alkene type of the C 3 to C 7 family or a mixture of hydrocarbons of the C 3 to C 7 family.
Avantageusement, l’agent de liquéfaction est un hydrocarbure ou un mélange d’hydrocarbures identique(s) ou de propriétés physico-chimiques équivalentes à l’éventuel hydrocarbure ou mélange d’hydrocarbures présent dans le biogaz.Advantageously, the liquefaction agent is a hydrocarbon or a mixture of identical hydrocarbons or of physico-chemical properties equivalent to the possible hydrocarbon or mixture of hydrocarbons present in the biogas.
L’invention concerne également une installation permettant la séparation de tout ou partie d’un biogaz à l’état liquide ou à l’état diphasique liquide/vapeur, contenant du méthane, du dioxyde de carbone et éventuellement un hydrocarbure ou un mélange d’hydrocarbures, mettant en œuvre le procédé de séparation tel que décrit précédemment.The invention also relates to an installation allowing the separation of all or part of a biogas in the liquid state or in the two-phase liquid/vapor state, containing methane, carbon dioxide and optionally a hydrocarbon or a mixture of hydrocarbons, implementing the separation process as described previously.
L’avantage du procédé de séparation selon l’invention et de l’installation associée est de permettre d’obtenir des taux de pureté élevés des composés séparés du biogaz, soit de l’ordre de 99,9 % pour chacun des composés (méthane et dioxyde de carbone) et du même ordre pour l’agent de liquéfaction récupéré en sortie de la deuxième séparation.The advantage of the separation process according to the invention and of the associated installation is to make it possible to obtain high levels of purity of the compounds separated from the biogas, i.e. of the order of 99.9% for each of the compounds (methane and carbon dioxide) and of the same order for the liquefaction agent recovered at the outlet of the second separation.
L’avantage du procédé de séparation selon l’invention et l’installation, dans le cas d’un biogaz non liquide ou bien à l’état diphasique, est d’empêcher la formation de neige carbonique en tête de colonne lors de la séparation du méthane des autres composés du biogaz.The advantage of the separation process according to the invention and the installation, in the case of a non-liquid biogas or else in the two-phase state, is to prevent the formation of dry ice at the top of the column during the separation. methane from other biogas compounds.
BREVE DESCRIPTION DES FIGURESBRIEF DESCRIPTION OF FIGURES
D’autres caractéristiques et avantages de l’invention ressortiront de la description détaillée de l’invention qui va suivre en référence aux figures annexées et dans lesquelles :
Claims (13)
- en alimentation principale, le biogaz liquéfié à une température d’équilibre permettant l’obtention d’un mélange diphasique assurant la séparation des différents composés,
- en alimentation secondaire, un agent de liquéfaction à l’état liquide composé d’un mélange d’hydrocarbure(s) de la famille C3à C7,
- l’agent de liquéfaction étant injecté en tête de la première colonne de distillation (10), au-dessus du niveau d’entrée du biogaz, à une température T1 inférieure ou égale à la température de désublimation du dioxyde de carbone à une pression donnée de la colonne de distillation et en quantité proportionnelle au débit de vapeur du dioxyde de carbone ascendant en tête de colonne.
- as the main supply, the liquefied biogas at an equilibrium temperature allowing the production of a two-phase mixture ensuring the separation of the various compounds,
- in secondary feed, a liquefaction agent in the liquid state composed of a mixture of hydrocarbon(s) of the C 3 to C 7 family,
- the liquefaction agent being injected at the top of the first distillation column (10), above the entry level of the biogas, at a temperature T1 lower than or equal to the desublimation temperature of the carbon dioxide at a given pressure of the distillation column and in an amount proportional to the flow rate of carbon dioxide vapor ascending to the top of the column.
- une alimentation principale pour l’injection du biogaz liquéfié à une température d’équilibre permettant l’obtention d’un mélange diphasique assurant la séparation des différents composés et
- une alimentation secondaire pour l’injection d’un agent de liquéfaction à l’état liquide composé d’un mélange d’hydrocarbure(s) de la famille C3 à C7, l’alimentation secondaire étant arrangée pour injecter l’agent de liquéfaction en tête de la première colonne de distillation (10), au-dessus du niveau d’entrée du biogaz.
- a main supply for the injection of liquefied biogas at an equilibrium temperature allowing the production of a two-phase mixture ensuring the separation of the various compounds and
- a secondary supply for the injection of a liquefaction agent in the liquid state composed of a mixture of hydrocarbon(s) of the C3 to C7 family, the secondary supply being arranged to inject the liquefaction agent in head of the first distillation column (10), above the entry level of the biogas.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2022/077360 WO2023052624A1 (en) | 2021-10-01 | 2022-09-30 | Method for separating all or some of the compounds from a biogas in the liquid state or in the two-phase state |
| CA3214414A CA3214414A1 (en) | 2021-10-01 | 2022-09-30 | Method for separating all or some of the compounds from a biogas in the liquid state or in the two-phase state |
| ARP220102661A AR127216A1 (en) | 2021-10-01 | 2022-09-30 | PROCEDURE FOR TOTAL OR PARTIAL SEPARATION OF THE COMPOUNDS OF A BIOGAS IN LIQUID STATE OR IN LIQUID/VAPOR BIPHASIC STATE |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2110431A FR3127702A1 (en) | 2021-10-01 | 2021-10-01 | PROCESS FOR SEPARATION OF ALL OR PART OF THE COMPOUNDS OF A BIOGAS IN THE LIQUID STATE OR IN THE TWO-PHASE STATE |
| FR2110431 | 2021-10-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| FR3127701A1 true FR3127701A1 (en) | 2023-04-07 |
Family
ID=80735992
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR2110431A Pending FR3127702A1 (en) | 2021-10-01 | 2021-10-01 | PROCESS FOR SEPARATION OF ALL OR PART OF THE COMPOUNDS OF A BIOGAS IN THE LIQUID STATE OR IN THE TWO-PHASE STATE |
| FR2111835A Pending FR3127701A1 (en) | 2021-10-01 | 2021-11-08 | PROCESS FOR SEPARATION OF ALL OR PART OF THE COMPOUNDS OF A BIOGAS IN THE LIQUID STATE OR IN THE TWO-PHASE STATE |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR2110431A Pending FR3127702A1 (en) | 2021-10-01 | 2021-10-01 | PROCESS FOR SEPARATION OF ALL OR PART OF THE COMPOUNDS OF A BIOGAS IN THE LIQUID STATE OR IN THE TWO-PHASE STATE |
Country Status (1)
| Country | Link |
|---|---|
| FR (2) | FR3127702A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2296607A1 (en) * | 1975-01-02 | 1976-07-30 | Lummus Co | NATURAL GAS TREATMENT |
| FR2312001A1 (en) * | 1975-05-20 | 1976-12-17 | Snam Progetti | Sepn. of carbon dioxide from natural gas - using double distillation with second column at lower pressure |
| US4318723A (en) * | 1979-11-14 | 1982-03-09 | Koch Process Systems, Inc. | Cryogenic distillative separation of acid gases from methane |
| US20030047492A1 (en) * | 2001-09-04 | 2003-03-13 | Hopewell Richard B. | High ethane recovery from a ryan/holmes additive recovery column |
-
2021
- 2021-10-01 FR FR2110431A patent/FR3127702A1/en active Pending
- 2021-11-08 FR FR2111835A patent/FR3127701A1/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2296607A1 (en) * | 1975-01-02 | 1976-07-30 | Lummus Co | NATURAL GAS TREATMENT |
| FR2312001A1 (en) * | 1975-05-20 | 1976-12-17 | Snam Progetti | Sepn. of carbon dioxide from natural gas - using double distillation with second column at lower pressure |
| US4318723A (en) * | 1979-11-14 | 1982-03-09 | Koch Process Systems, Inc. | Cryogenic distillative separation of acid gases from methane |
| US20030047492A1 (en) * | 2001-09-04 | 2003-03-13 | Hopewell Richard B. | High ethane recovery from a ryan/holmes additive recovery column |
Also Published As
| Publication number | Publication date |
|---|---|
| FR3127702A1 (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2011246887B2 (en) | Process for treating a natural gas containing carbon dioxide | |
| EP0937679B1 (en) | Process and apparatus for the production of carbon monoxide and hydrogen | |
| FR2808223A1 (en) | Purification of effluent containing carbon dioxide and hydrocarbons comprises gas/liquid separation and combustion to recover carbon dioxide and water for recycling | |
| FR3066491B1 (en) | PROCESS FOR RECOVERING A C2 + HYDROCARBON CURRENT IN A REFINERY RESIDUAL GAS AND ASSOCIATED INSTALLATION | |
| FR2808460A1 (en) | Separation of carbon dioxide and hydrogen sulfide from mixture containing lighter gas, comprises use of vertical heat exchange zone for simultaneous rectification and refrigeration | |
| EP3465035B1 (en) | Process for cryogenic separation of a feed stream containing methane and air gases, facility for producing biomethane by purification of biogases derived from non-hazardous waste storage facilities (nhwsf) implementing the process | |
| FR2848121A1 (en) | PROCESS FOR TREATING AN ACID NATURAL GAS | |
| FR2680114A1 (en) | Air distillation process and plant and application to the supply of gas to a steelworks | |
| FR2764609A1 (en) | PROCESS FOR DEGAZOLINATING A GAS CONTAINING CONDENSABLE HYDROCARBONS | |
| FR2923000A1 (en) | Raw natural gas liquefaction method for producing liquid natural gas, involves recycling portion of fraction enriched in ethane by introducing portion of fraction in disengager, and liquefying gas phase to produce liquid natural gas | |
| FR2829401A1 (en) | Fractionating a gas produced by pyrolysis of hydrocarbons, including hydrogen and hydrocarbons, in particular 1-4C hydrocarbons, water and CO2 | |
| EP3628389A1 (en) | Method for producing biomethane from a flow of biogas comprising solidification of impurities | |
| WO2015140460A2 (en) | Method and device for cryogenically separating a synthesis gas containing carbon monoxide, methane and hydrogen | |
| FR2734495A1 (en) | PROCESS FOR THE RECOVERY OF CARBON MONOXIDE FROM PURGE GASES FROM THE SYNTHESIS OF ACETIC ACID WITH LOW CO, N2 AND H2 CONTENT | |
| FR3127701A1 (en) | PROCESS FOR SEPARATION OF ALL OR PART OF THE COMPOUNDS OF A BIOGAS IN THE LIQUID STATE OR IN THE TWO-PHASE STATE | |
| EP2140216B1 (en) | Method and device for separating a mixture containing at least hydrogen, nitrogen and carbon monoxide by cryogenic distillation | |
| FR2822839A1 (en) | Dehydrating and fractionating process, for wet natural gas, is integrated using methanol which is later recovered | |
| FR3034509B1 (en) | PROCESS FOR TREATING NATURAL GAS TO MINIMIZE LOSS OF ETHANE | |
| FR3094782A1 (en) | Purification and liquefaction of biogas by combining a crystallization system with a liquefaction exchanger | |
| FR2964390A1 (en) | PROCESS FOR TREATING NATURAL GAS CONTAINING CARBON DIOXIDE | |
| WO2023052624A1 (en) | Method for separating all or some of the compounds from a biogas in the liquid state or in the two-phase state | |
| EP2709745A1 (en) | Method for purification by means of adsorption with regeneration using a gas containing an undesired component in the purified gas | |
| EP3252408B1 (en) | Method for purifying natural gas and for liquefying carbon dioxide | |
| WO2017212136A1 (en) | Method and facility for combined production of a mixture of hydrogen and nitrogen as well as carbon monoxide by cryogenic distillation and scrubbing | |
| FR2847568A1 (en) | Process and installation for producing a krypton/xenon mixture from air by cryogenic distillation, producing a synthesis gas by partially oxidizing a hydrocarbon and separating the synthesis gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PLFP | Fee payment |
Year of fee payment: 2 |
|
| PLSC | Publication of the preliminary search report |
Effective date: 20230407 |
|
| PLFP | Fee payment |
Year of fee payment: 3 |