WO2018172698A1 - Method and appliance for the distillation of a mixture of carbon dioxide and a less volatile component - Google Patents

Method and appliance for the distillation of a mixture of carbon dioxide and a less volatile component Download PDF

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Publication number
WO2018172698A1
WO2018172698A1 PCT/FR2018/050684 FR2018050684W WO2018172698A1 WO 2018172698 A1 WO2018172698 A1 WO 2018172698A1 FR 2018050684 W FR2018050684 W FR 2018050684W WO 2018172698 A1 WO2018172698 A1 WO 2018172698A1
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WIPO (PCT)
Prior art keywords
gas
liquid
carbon dioxide
enriched
capacity
Prior art date
Application number
PCT/FR2018/050684
Other languages
French (fr)
Inventor
Axelle GAERTNER
Ludovic Granados
Bhadri PRASAD
Jorge Ernesto TOVAR RAMOS
Jean-Pierre Tranier
Original Assignee
L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
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Application filed by L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude filed Critical L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
Publication of WO2018172698A1 publication Critical patent/WO2018172698A1/en

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0219—Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—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
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/08—Separating gaseous impurities from gases or gaseous mixtures or from liquefied gases or liquefied gaseous mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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
    • F25J2200/02—Processes or apparatus using separation by rectification in a single 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
    • F25J2200/72—Refluxing the column with at least a part of the totally 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
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • 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
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
    • 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
    • F25J2210/12—Refinery or petrochemical off-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
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/80—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
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/80—Separating impurities from carbon dioxide, e.g. H2O or water-soluble contaminants
    • F25J2220/84—Separating high boiling, i.e. less volatile components, e.g. NOx, SOx, H2S
    • 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
    • F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/80—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being 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
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/02—Recycle of a stream in general, e.g. a by-pass 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
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/62—Details of storing a fluid in a tank
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention relates to a process and apparatus for the distillation of a mixture of carbon dioxide and a less volatile component.
  • a mixture comprising as main components of carbon dioxide and at least one component less volatile than carbon dioxide, for example a solvent can be produced by a chemical process. In this case, it is interesting to separate the less volatile component and the carbon dioxide.
  • a solvent is a substance, liquid or supercritical at its temperature of use, which has the property of dissolving, diluting or extracting other substances without modifying them chemically and without itself modifying itself.
  • the solvent may be for example acetone, water, dimethylacetamide (DMAc), dimethylsulfoxide (DMSO).
  • composition of the mixture may vary in less volatile component from about 1% to 30% mol. less volatile component or less volatile components, for example acetone, the remainder of the gaseous mixture being substantially CO2.
  • CO2 can be used as a solvent for acetone (and other equivalent molecules). There is an economic interest in recovering this CO2 to minimize the amount of "fresh" CO2 to consume.
  • the present invention proposes to operate the distillation column at between 20 and 25 bar abs, in order to save a machine for pressurizing the carbon dioxide.
  • CO2 recovery from CO2 / COIT1 is less volatile and allows recycling for reuse by reducing the use of fresh CO2.
  • a modification of the process makes it possible to increase the CO2 efficiency and to envisage the recycling of the solvent.
  • a way of maximizing the CO2 recovery efficiency is to start from a supercritical CO2 mixture.
  • less volatile component pressure greater than 73 bara
  • a cooler is used before supercritical CO2 is released. The temperature is chosen as cold as possible.
  • the system used consists of:
  • a separator pot for recovering the "pure” gaseous CO2 and a CO2 / solvent mixture in the liquid state.
  • the expanded flow rate is sent into a capacity, which is optionally a phase separator, to form a first liquid possibly enriched with a less volatile component and possibly a first gas enriched with carbon dioxide.
  • At least a portion of the optionally enriched liquid of less volatile component is sent to a distillation column.
  • a second carbon dioxide-enriched gas is withdrawn from the top of the column and a second liquid enriched with the less volatile component of the column vessel.
  • At least a portion of the condensed gas and / or at least a portion of the carbon dioxide enriched liquid is sent to a point upstream of the capacity or capacity.
  • At least a portion of the condensed gas and / or at least a portion of the liquid is recycled to a reactor from which the gas mixture originates. At least a portion of the second enriched liquid is recycled to a less volatile component to a reactor from which the gas mixture originates.
  • the second enriched liquid is separated into a less volatile component to form a less volatile component depleted gas and a less volatile component rich liquid product, the depleted gas is condensed and the condensed depleted gas is returned to the capacity.
  • At least a portion of the condensed gas and / or at least a portion of the liquid is returned upstream of the capacity, or even the reactor.
  • the liquid or condensed gas is pressurized in a pump upstream of the capacity.
  • At least a portion of the second liquid is heated to partially vaporize it, separated in a phase separator, the liquid is withdrawn as a product, the phase separator gas is condensed against the second liquid and the condensed gas is sent to the capacity.
  • the mixture contains at least 70 mol%. of carbon dioxide, or even at least 90 mol%. of carbon dioxide.
  • an apparatus for separating a gaseous mixture of carbon dioxide and a less volatile component less volatile than carbon dioxide comprising means for cooling the gaseous mixture to be separated, a valve for expanding the cooled gas mixture to form a relaxed flow, possibly two-phase, a capacity, which is optionally a phase separator, means for sending the expanded flow rate to the capacity, a first pipe for withdrawing the capacity of a first liquid optionally enriched with a less volatile component, optionally a line for withdrawing a first carbon dioxide-enriched gas from the capacity, a distillation column connected to the first line, a line for withdrawing a second gas enriched with carbon dioxide from the head of the the column, a line for withdrawing a second liquid enriched with a less volatile component of the column vessel, optionally a condenser for condensing at least a portion of the first gas and / or second gas enriched with carbon dioxide and / or means for withdrawing a carbon dioxide-enriched liquid from the top of the column and means
  • the gaseous mixture is produced in a reactor fed with carbon dioxide.
  • the means for sending at least a portion of the condensed gas into the condenser and / or at least a portion of the carbon dioxide enriched liquid at a point upstream of the capacity can be connected to the reactor.
  • Figure 1 illustrates a process for producing a gaseous mixture of carbon dioxide and solvent followed by a method of separating the mixture.
  • a solvent such as acetone, dimethylacetamide (DMAc) or dimethylsulfoxide (DMSO)
  • a way of maximizing the CO 2 recovery efficiency is to start from a supercritical CO 2 / less volatile component mixture, for example solvent (pressure> 73 bara) and to relax it at pressures lower than 30 bara and greater than 6 bara .
  • the invention is based on the use of a cooler before the supercritical CO2 is released (the temperature is chosen as cold as possible) and then a distillation, with recovery of the pure CO2 at the top of the column. .
  • the invention proposes a system consisting of:
  • a cooler 5 (with water for example) supply to bring the mixture 3 to the optimum temperature, below 0 ° C,
  • a separator pot 9 making it possible to recover the "pure" CO2 gas 13 and a less volatile CO 2 / component mixture, for example a solvent in the liquid state 1 1, a distillation column 15 incorporating a condenser 31 and a reboiler 19.
  • the production process the gaseous mixture is carried out in a reactor R supplied with liquid carbon dioxide 1 at a supercritical pressure as well as with other fluids such as the solvent.
  • This reactor R produces a mixture of solvent and gaseous carbon dioxide 3.
  • the composition of the mixture can vary between 30 mol%. of less volatile component (s) and 70 mol%. of carbon dioxide to 99.9 mol% of carbon dioxide dioxide and 0.1% of less volatile component (s), the reactor process being cyclic.
  • the mixture is cooled by heat exchange in the cooler 5, expanded in the valve 7 to produce a two-phase flow and separated in a phase separator 9.
  • the temperature of the phase separator varies according to the composition of the gaseous mixture 3.
  • the invention proposes to treat the flow 3 resulting from a batch process carried out in the reactor R. It is a question of separating the liquid and vapor phases of a mixture 3 (two or more compounds) by rapid expansion in the valve 7 and accumulate the liquid produced in the separator pot 9 to supply the column 15 downstream, continuously and stably to ensure continuous operation.
  • the method according to the invention consists in sizing a retention, constituted by the capacitance 9, sufficiently large to smooth the variations of the discontinuous process.
  • the recovery and accumulation of the liquid phase resulting from the expansion of the mixture makes it possible to feed the column installed downstream of the process, in a homogeneous and continuous manner.
  • This very flexible system makes it possible to tolerate a diet with large variations in flow rate and / or composition.
  • the methodology is based on a real case but can be applied to other flows and different composition ratios. The number of phases and the duration of each is not limiting.
  • the reactor process operates per phase with four phases per day.
  • the flow rate, the composition and therefore the liquid fraction vary depending on the phase.
  • the invention proposes to assign two roles to pot 9: phase separator and liquid retention.
  • the diameter of the pot 9 is defined according to the standard sizing criteria for a separator pot.
  • the height of the separator 9 is imposed by the "retention" liquid function.
  • the present invention substantially reduces (by approximately 50%) the diameter of the column 15 because the flow rate to be treated in the column is much lower than the flow rate that would be dimensioning without this invention. (with maximum liquid fraction).
  • the liquid 1 1 of the phase separator is sent to an intermediate point of the distillation column 15 which operates at about 22 bar abs.
  • the bottom liquid 17 of the column 15, enriched with less volatile solvent than the carbon dioxide, is withdrawn from the column and sent to a reboiler 19 heated by steam 21.
  • the steam produced is returned to the column and the even richer solvent liquid 23 is recovered as product.
  • the overhead gas 27 of the column is divided in two, a portion 29 being condensed in the condenser 31 and returned to the column as reflux 33.
  • the other portion 35 is mixed with the gas 13 of the phase separator to form a flow gas 37 enriched with carbon dioxide.
  • the head of the column is at -20 ° C and the tank is at 180 ° C, so only the head of the column needs to be isolated.
  • the flow 37 is condensed by a refrigerant group 41 which can also serve to cool the condenser 31.
  • the liquid formed by condensing the flow 37 is returned to the reactor R to reduce the amount of carbon dioxide 1 required.
  • the product at the top of the column is very high purity CO2, it can be mixed with CO2 from the expansion to obtain an overall purity higher than 99.8 mol%. in CO 2 .
  • the flow 25 connects the reboiler 19 with the reactor R inlet.
  • the overhead condenser unlike that of FIG. 1, receives all the overhead gas from the column 15, condenses it and returns a portion 33 as reflux.
  • the remainder of the condensed gas 32 is pumped by a pump 34 and divided, a portion 44 being returned to the capacity 9 through the valve 46 and the remainder 43 being recycled to the reactor R.
  • the objective of returning a liquid rich in CO2 Capacity 9 is to stabilize the feed composition of the column during transient phases where the production of the reactor R shows large fluctuations.
  • the diagram in Figure 3 consumes more energy but allows to have two temperature levels and decreases the temperature gradient of the column.
  • it comprises a heat exchanger, a heater 46, a phase separator 47 and a pump 53.
  • the tank liquid 23 of the reboiler 19 is heated in an exchanger, heated again in a heater 46 at the desired degree of vaporization and the two-phase flow formed is separated in the separator 47.
  • the less volatile component-rich liquid 49 serves as a product.
  • the gas 51 serves to heat the liquid 23 in the exchanger and is thus condensed.
  • a pump 53 pressurizes it and returns it to the capacity.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Gas Separation By Absorption (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

The invention relates to an appliance for separating a gas mixture of carbon dioxide and a less volatile component which is less volatile than carbon dioxide, said appliance comprising means (5) for cooling the gas mixture to be separated (3), a valve (7) for expanding the cooled gas mixture in order to form an expanded flow, a capacity (9), means for sending the expanded flow to the capacity, a first conduit for drawing off a first liquid (11) from the capacity, a distillation column (15) connected to the first conduit, a conduit for drawing off a second gas (27) enriched with carbon dioxide from the head of the column, a conduit for drawing off a second liquid (17) enriched with a less volatile component from the tank of the column, a condenser (31, 41) for condensing at least part of the first gas and/or the second gas enriched with carbon dioxide, and means for sending at least part (43, 45) of the condensed gas to the condenser at a point upstream of the capacity.

Description

Procédé et appareil de distillation d'un mélange de dioxyde de carbone et d'un composant moins volatil La présente invention est relative à un procédé et à un appareil de distillation d'un mélange de dioxyde de carbone et d'un composant moins volatil.  The present invention relates to a process and apparatus for the distillation of a mixture of carbon dioxide and a less volatile component.
Un mélange comprenant comme composants principaux du dioxyde de carbone et au moins un composant moins volatil que le dioxyde de carbone, par exemple un solvant peut être produit par un procédé chimique. Dans ce cas, il est intéressant de séparer le composant moins volatil et le dioxyde de carbone.  A mixture comprising as main components of carbon dioxide and at least one component less volatile than carbon dioxide, for example a solvent can be produced by a chemical process. In this case, it is interesting to separate the less volatile component and the carbon dioxide.
Un solvant est une substance, liquide ou supercritique à sa température d'utilisation, qui a la propriété de dissoudre, de diluer ou d'extraire d'autres substances sans les modifier chimiquement et sans lui-même se modifier. Dans le cadre de la présente invention, le solvant considéré peut être par exemple l'acétone, de l'eau, le dimethylacetamide (DMAc), le dimethylsulfoxide (DMSO).  A solvent is a substance, liquid or supercritical at its temperature of use, which has the property of dissolving, diluting or extracting other substances without modifying them chemically and without itself modifying itself. In the context of the present invention, the solvent may be for example acetone, water, dimethylacetamide (DMAc), dimethylsulfoxide (DMSO).
La composition du mélange peut varier en composant moins volatil d'environ 1 % à 30% mol. du composant moins volatil ou des composants moins volatils, par exemple l'acétone, le reste du mélange gazeux étant substantiellement du CO2.  The composition of the mixture may vary in less volatile component from about 1% to 30% mol. less volatile component or less volatile components, for example acetone, the remainder of the gaseous mixture being substantially CO2.
Dans certains procédés chimiques, le CO2 peut être utilisé comme solvant de l'acétone (et autre molécule équivalente). Il y a un intérêt économique à récupérer ce CO2 pour minimiser les quantités de CO2 « frais » à consommer.  In some chemical processes, CO2 can be used as a solvent for acetone (and other equivalent molecules). There is an economic interest in recovering this CO2 to minimize the amount of "fresh" CO2 to consume.
La séparation du solvant et du dioxyde de carbone devient moins facile si la pression augmente. Toutefois la présente invention propose d'opérer la colonne de distillation à entre 20 et 25 bars abs, afin d'économiser une machine pour pressuriser le dioxyde de carbone.  The separation of the solvent and the carbon dioxide becomes less easy if the pressure increases. However, the present invention proposes to operate the distillation column at between 20 and 25 bar abs, in order to save a machine for pressurizing the carbon dioxide.
La récupération du CO2 du mélange CO2/COIT1 posant moins volatil permet son recyclage pour réutilisation en diminuant le recours à du CO2 frais. Une modification du procédé permet d'augmenter le rendement CO2 et d'envisager le recyclage du solvant.  CO2 recovery from CO2 / COIT1 is less volatile and allows recycling for reuse by reducing the use of fresh CO2. A modification of the process makes it possible to increase the CO2 efficiency and to envisage the recycling of the solvent.
Dans le cadre d'une séparation CO2/composant moins volatil, dans le cas où la pureté du CO2 attendue n'excède pas 97% mol., un moyen de maximiser le rendement de récupération du CO2 est de partir d'un mélange supercritique CO2/composant moins volatil (pression supérieure à 73 bara) et de le détendre à des pressions inférieures à 30 bara et supérieure à 6 bara. Pour maximiser la récupération de CO2, un refroidisseur est utilisé avant la détente du CO2 supercritique. La température est choisie la plus froide possible. In the context of a less volatile CO2 / component separation, in the case where the purity of the expected CO2 does not exceed 97 mol%, a way of maximizing the CO2 recovery efficiency is to start from a supercritical CO2 mixture. less volatile component (pressure greater than 73 bara) and to relax it at pressures below 30 bara and above 6 bara. To maximize CO2 recovery, a cooler is used before supercritical CO2 is released. The temperature is chosen as cold as possible.
Le système utilisé est constitué de :  The system used consists of:
un refroidisseur (à eau par exemple) d'alimentation pour amener le mélange à la température optimale,  a cooler (water for example) supply to bring the mixture to the optimum temperature,
une vanne de détente,  a valve of relaxation,
un pot séparateur permettant de récupérer le CO2 gazeux « pur » et un mélange CO2/solvant à l'état liquide.  a separator pot for recovering the "pure" gaseous CO2 and a CO2 / solvent mixture in the liquid state.
Cette installation, qui minimise le CAPEX, produit du CO2 gazeux à une pureté >97% mol. avec un rendement compris entre 60% et 90%. Le CO2 complémentaire ainsi que le solvant sont envoyés aux effluents.  This installation, which minimizes CAPEX, produces CO2 gas with a purity> 97% mol. with a yield of between 60% and 90%. The additional CO2 and the solvent are sent to the effluents.
Selon un objet de l'invention, il est prévu un procédé de séparation d'un mélange gazeux de dioxyde de carbone et d'un composant moins volatil que le dioxyde de carbone dans lequel :  According to one object of the invention, there is provided a method of separating a gaseous mixture of carbon dioxide and a less volatile component than carbon dioxide in which:
i) On refroidit le mélange gazeux à séparer et on le détend pour former un débit détendu, éventuellement diphasique.  i) The gaseous mixture to be separated is cooled and expanded to form a relaxed flow, possibly two-phase.
ii) On envoie le débit détendu dans une capacité, qui est éventuellement un séparateur de phase, pour former un premier liquide éventuellement enrichi en composant moins volatil et éventuellement un premier gaz enrichi en dioxyde de carbone.  ii) The expanded flow rate is sent into a capacity, which is optionally a phase separator, to form a first liquid possibly enriched with a less volatile component and possibly a first gas enriched with carbon dioxide.
iii) On envoie au moins une partie du liquide éventuellement enrichi en composant moins volatil à une colonne de distillation.  iii) At least a portion of the optionally enriched liquid of less volatile component is sent to a distillation column.
iv) On soutire un deuxième gaz enrichi en dioxyde de carbone de la tête de la colonne et un deuxième liquide enrichi en composant moins volatil de la cuve de la colonne.  iv) A second carbon dioxide-enriched gas is withdrawn from the top of the column and a second liquid enriched with the less volatile component of the column vessel.
v) On condense au moins une partie du premier gaz et/ou du deuxième gaz enrichi en dioxyde de carbone et/ou on soutire un liquide enrichi en dioxyde de carbone de la tête de la colonne, et  v) Condensing at least a portion of the first gas and / or second carbon dioxide enriched gas and / or withdrawing a carbon dioxide-enriched liquid from the top of the column, and
vi) On envoie au moins une partie du gaz condensé et/ou au moins une partie du liquide enrichi en dioxyde de carbone à un point en amont de la capacité ou à la capacité.  vi) At least a portion of the condensed gas and / or at least a portion of the carbon dioxide enriched liquid is sent to a point upstream of the capacity or capacity.
Selon d'autres aspects facultatifs de l'invention :  According to other optional aspects of the invention:
On recycle au moins une partie du gaz condensé et/ou au moins une partie du liquide à un réacteur d'où provient le mélange gazeux. On recycle au moins une partie du deuxième liquide enrichi en composant moins volatil vers un réacteur d'où provient le mélange gazeux. At least a portion of the condensed gas and / or at least a portion of the liquid is recycled to a reactor from which the gas mixture originates. At least a portion of the second enriched liquid is recycled to a less volatile component to a reactor from which the gas mixture originates.
On sépare le deuxième liquide enrichi en composant moins volatil pour former un gaz appauvri en composant moins volatil et un produit liquide riche en composant moins volatil, on condense le gaz appauvri et on renvoie le gaz appauvri condensé vers la capacité.  The second enriched liquid is separated into a less volatile component to form a less volatile component depleted gas and a less volatile component rich liquid product, the depleted gas is condensed and the condensed depleted gas is returned to the capacity.
Aucun gaz n'est soutiré de la capacité.  No gas is withdrawn from the capacity.
On renvoie au moins une partie du gaz condensé et/ou au moins une partie du liquide en amont de la capacité, voire du réacteur.  At least a portion of the condensed gas and / or at least a portion of the liquid is returned upstream of the capacity, or even the reactor.
- On pressurise le liquide ou le gaz condensé dans une pompe en amont de la capacité.  - The liquid or condensed gas is pressurized in a pump upstream of the capacity.
On réchauffe au moins une partie du deuxième liquide pour le vaporiser partiellement, on le séparer dans un séparateur de phases, on soutire le liquide comme produit, on condense le gaz du séparateur de phases contre le deuxième liquide et on envoie le gaz condensé à la capacité.  At least a portion of the second liquid is heated to partially vaporize it, separated in a phase separator, the liquid is withdrawn as a product, the phase separator gas is condensed against the second liquid and the condensed gas is sent to the capacity.
Le mélange contient au moins 70% mol. de dioxyde de carbone, voire au moins 90% mol. de dioxyde de carbone.  The mixture contains at least 70 mol%. of carbon dioxide, or even at least 90 mol%. of carbon dioxide.
Selon un autre objet de l'invention, il est prévu un appareil de séparation d'un mélange gazeux de dioxyde de carbone et d'un composant moins volatil moins volatil que le dioxyde de carbone comprenant des moyens pour refroidir le mélange gazeux à séparer, une vanne pour détendre le mélange gazeux refroidi pour former un débit détendu, éventuellement diphasique, une capacité, qui est éventuellement un séparateur de phase, des moyens pour envoyer le débit détendu à la capacité, une première conduite pour soutirer de la capacité un premier liquide éventuellement enrichi en composant moins volatil, éventuellement une conduite pour soutirer un premier gaz enrichi en dioxyde de carbone de la capacité, une colonne de distillation reliée à la première conduite, une conduite pour soutirer un deuxième gaz enrichi en dioxyde de carbone de la tête de la colonne, une conduite pour soutirer un deuxième liquide enrichi en composant moins volatil de la cuve de la colonne, éventuellement un condenseur pour condenser au moins une partie du premier gaz et/ou du deuxième gaz enrichi en dioxyde de carbone et/ou des moyens pour soutirer un liquide enrichi en dioxyde de carbone de la tête de la colonne et des moyens pour envoyer au moins une partie du gaz condensé dans le condenseur et/ou au moins une partie du liquide enrichi en dioxyde de carbone à un point en amont de la capacité ou à la capacité. According to another object of the invention, there is provided an apparatus for separating a gaseous mixture of carbon dioxide and a less volatile component less volatile than carbon dioxide comprising means for cooling the gaseous mixture to be separated, a valve for expanding the cooled gas mixture to form a relaxed flow, possibly two-phase, a capacity, which is optionally a phase separator, means for sending the expanded flow rate to the capacity, a first pipe for withdrawing the capacity of a first liquid optionally enriched with a less volatile component, optionally a line for withdrawing a first carbon dioxide-enriched gas from the capacity, a distillation column connected to the first line, a line for withdrawing a second gas enriched with carbon dioxide from the head of the the column, a line for withdrawing a second liquid enriched with a less volatile component of the column vessel, optionally a condenser for condensing at least a portion of the first gas and / or second gas enriched with carbon dioxide and / or means for withdrawing a carbon dioxide-enriched liquid from the top of the column and means for sending at least a part of the condensed gas in the condenser and / or at least part of the carbon dioxide-enriched liquid at a point upstream of the capacity or capacity.
Eventuellement, le mélange gazeux est produit dans un réacteur alimenté par du dioxyde de carbone.  Optionally, the gaseous mixture is produced in a reactor fed with carbon dioxide.
Les moyens pour envoyer au moins une partie du gaz condensé dans le condenseur et/ou au moins une partie du liquide enrichi en dioxyde de carbone à un point en amont de la capacité peuvent être reliés au réacteur.  The means for sending at least a portion of the condensed gas into the condenser and / or at least a portion of the carbon dioxide enriched liquid at a point upstream of the capacity can be connected to the reactor.
L'invention sera décrite en plus de détails en se référant aux figures qui illustrent schématiquement des procédés selon l'invention.  The invention will be described in more detail with reference to the figures which schematically illustrate methods according to the invention.
La Figure 1 illustre un procédé de production d'un mélange gazeux de dioxyde de carbone et de solvant suivi par un procédé de séparation du mélange.  Figure 1 illustrates a process for producing a gaseous mixture of carbon dioxide and solvent followed by a method of separating the mixture.
Dans le cadre d'une séparation du mélange CO2/composant moins volatil, ici un solvant, tel que l'acétone le dimethylacetamide (DMAc) ou le dimethylsulfoxide (DMSO), dans le cas où la pureté du CO2 attendue est supérieure à 99%, un moyen de maximiser le rendement de récupération du CO2 est de partir d'un mélange supercritique CO2/composant moins volatil, par exemple solvant (pression >73 bara) et de le détendre à des pressions inférieures à 30 bara et supérieure à 6 bara.  In the context of a separation of the less volatile CO2 / component mixture, here a solvent, such as acetone, dimethylacetamide (DMAc) or dimethylsulfoxide (DMSO), in the case where the purity of the expected CO2 is greater than 99% a way of maximizing the CO 2 recovery efficiency is to start from a supercritical CO 2 / less volatile component mixture, for example solvent (pressure> 73 bara) and to relax it at pressures lower than 30 bara and greater than 6 bara .
Pour maximiser la récupération de CO2, l'invention repose sur l'utilisation d'un refroidisseur avant la détente du CO2 supercritique (la température est choisie la plus froide possible) puis d'une distillation, avec récupération du CO2 pur en tête de colonne.  To maximize CO2 recovery, the invention is based on the use of a cooler before the supercritical CO2 is released (the temperature is chosen as cold as possible) and then a distillation, with recovery of the pure CO2 at the top of the column. .
L'invention propose un système constitué de :  The invention proposes a system consisting of:
un refroidisseur 5 (à eau par exemple) d'alimentation pour amener le mélange 3 à la température optimale, inférieure à 0°C,  a cooler 5 (with water for example) supply to bring the mixture 3 to the optimum temperature, below 0 ° C,
une vanne de détente 7,  an expansion valve 7,
un pot séparateur 9 permettant de récupérer le CO2 gazeux « pur » 13 et un mélange CO2/ composant moins volatil, par exemple solvant à l'état liquide 1 1 , une colonne de distillation 15 intégrant condenseur 31 et rebouilleur 19. Le procédé de production du mélange gazeux s'effectue dans un réacteur R alimenté en dioxyde de carbone liquide 1 à une pression supercritique ainsi qu'en d'autres fluides tel que le solvant. Ce réacteur R produit un mélange de solvant et de dioxyde de carbone gazeux 3. La composition du mélange peut varier entre 30% mol. de composant(s) moins volatil(s) et 70% mol. de dioxyde de carbone à 99,9% mol. de dioxyde de dioxyde de carbone et 0,1 % de composant(s) moins volatil(s), le procédé du réacteur étant cyclique. a separator pot 9 making it possible to recover the "pure" CO2 gas 13 and a less volatile CO 2 / component mixture, for example a solvent in the liquid state 1 1, a distillation column 15 incorporating a condenser 31 and a reboiler 19. The production process the gaseous mixture is carried out in a reactor R supplied with liquid carbon dioxide 1 at a supercritical pressure as well as with other fluids such as the solvent. This reactor R produces a mixture of solvent and gaseous carbon dioxide 3. The composition of the mixture can vary between 30 mol%. of less volatile component (s) and 70 mol%. of carbon dioxide to 99.9 mol% of carbon dioxide dioxide and 0.1% of less volatile component (s), the reactor process being cyclic.
Le mélange est refroidi par échange thermique dans le refroidisseur 5, détendu dans la vanne 7 pour produire un débit diphasique et séparé dans un séparateur de phases 9. La température du séparateur de phases varie selon la composition du mélange gazeux 3.  The mixture is cooled by heat exchange in the cooler 5, expanded in the valve 7 to produce a two-phase flow and separated in a phase separator 9. The temperature of the phase separator varies according to the composition of the gaseous mixture 3.
Comme le rapport entre le solvant et le CO2 dans le débit 3 ainsi que la valeur du débit 3 varie avec le temps (procédé discontinu), pour certains procédés réalisés dans le réacteur R, il est nécessaire de stabiliser l'alimentation d'une colonne de distillation 15 dont l'alimentation est par essence très variable.  Since the ratio between the solvent and the CO2 in the flow rate 3 and the value of the flow rate 3 varies with time (batch process), for some processes carried out in the reactor R, it is necessary to stabilize the supply of a column distillation 15 whose feed is in essence very variable.
L'opération de la colonne de distillation 15 avec une grande variabilité de composition et de débit ne serait tout simplement pas possible sans stabiliser au préalable ces fluctuations dans une plage de fonctionnement plus réduite.  The operation of the distillation column 15 with great compositional and flow rate variability would simply not be possible without previously stabilizing these fluctuations in a smaller operating range.
Plus généralement, l'invention propose de traiter le débit 3 issu d'un procédé discontinu réalisé dans le réacteur R. Il s'agit de séparer les phases liquide et vapeur d'un mélange 3 (deux composés ou plus) par détente rapide dans la vanne 7 et d'accumuler le liquide produit dans le pot séparateur 9 afin d'alimenter la colonne 15 en aval, de façon continue et stable pour lui assurer un fonctionnement continu.  More generally, the invention proposes to treat the flow 3 resulting from a batch process carried out in the reactor R. It is a question of separating the liquid and vapor phases of a mixture 3 (two or more compounds) by rapid expansion in the valve 7 and accumulate the liquid produced in the separator pot 9 to supply the column 15 downstream, continuously and stably to ensure continuous operation.
Une solution alternative dans cette situation serait de maintenir un débit d'alimentation minimal dans la colonne 15, ce qui nécessite :  An alternative solution in this situation would be to maintain a minimum feed rate in column 15, which requires:
l'installation de lignes supplémentaires (tuyaux, vannes et instrumentation), installation of additional lines (pipes, valves and instrumentation)
le dimensionnement de la colonne 15 pour la charge maximale. La stabilité de la composition n'est pas maintenue dans ce cas.  the dimensioning of the column 15 for the maximum load. The stability of the composition is not maintained in this case.
La méthode selon l'invention consiste à dimensionner une rétention, constituée par la capacité 9, suffisamment importante pour lisser les variations du procédé discontinu. En effet, la récupération et accumulation de la phase liquide issue de la détente du mélange permet d'alimenter la colonne installée en aval du procédé, de façon homogène et continue. Ce système très flexible permet de tolérer une alimentation avec des fortes variations dans le débit et/ou la composition. La méthodologie est basée sur un cas réel mais peut être appliquée à d'autres débits et des rapports de composition différents. Le nombre de phases ainsi que la durée de chacune n'est pas limitant. The method according to the invention consists in sizing a retention, constituted by the capacitance 9, sufficiently large to smooth the variations of the discontinuous process. In fact, the recovery and accumulation of the liquid phase resulting from the expansion of the mixture makes it possible to feed the column installed downstream of the process, in a homogeneous and continuous manner. This very flexible system makes it possible to tolerate a diet with large variations in flow rate and / or composition. The methodology is based on a real case but can be applied to other flows and different composition ratios. The number of phases and the duration of each is not limiting.
Dans un cas typique, le procédé du réacteur fonctionne par phase avec quatre phases par jour. Le débit, la composition et donc la fraction liquide varient selon la phase.  In a typical case, the reactor process operates per phase with four phases per day. The flow rate, the composition and therefore the liquid fraction vary depending on the phase.
Figure imgf000008_0001
En extrapolant les données du procédé simulées (simulation phase par phase + points complémentaires simulant les étapes transitoires - incrémentation par 15 min), il est possible de définir la phase liquide globale (volume et composition).
Figure imgf000008_0001
By extrapolating the simulated process data (phase-to-phase simulation + complementary points simulating the transient stages - incrementation by 15 min), it is possible to define the overall liquid phase (volume and composition).
L'invention propose d'attribuer deux rôles au pot 9 : séparateur de phases et rétention liquide. Le diamètre du pot 9 est défini selon les critères de dimensionnement classique pour un pot séparateur. La hauteur du séparateur 9 est imposée par la fonction « rétention » liquide. The invention proposes to assign two roles to pot 9: phase separator and liquid retention. The diameter of the pot 9 is defined according to the standard sizing criteria for a separator pot. The height of the separator 9 is imposed by the "retention" liquid function.
En plus d'assurer un fonctionnement continu, la présente invention permet de réduire notablement (d'approximativement 50%) le diamètre de la colonne 15 car le débit à traiter 1 1 dans la colonne est très inférieur au débit qui serait dimensionnant sans cette invention (avec fraction liquide maximale).  In addition to ensuring continuous operation, the present invention substantially reduces (by approximately 50%) the diameter of the column 15 because the flow rate to be treated in the column is much lower than the flow rate that would be dimensioning without this invention. (with maximum liquid fraction).
Le liquide 1 1 du séparateur de phases est envoyé à un point intermédiaire de la colonne de distillation 15 qui opère à environ 22 bars abs.  The liquid 1 1 of the phase separator is sent to an intermediate point of the distillation column 15 which operates at about 22 bar abs.
Le liquide de cuve 17 de la colonne 15, enrichi en solvant moins volatil que le dioxyde de carbone, est soutiré de la colonne et envoyé à un rebouilleur 19 chauffé par de la vapeur d'eau 21 . La vapeur produite est renvoyée à la colonne et le liquide encore plus riche en solvant 23 est récupéré comme produit.  The bottom liquid 17 of the column 15, enriched with less volatile solvent than the carbon dioxide, is withdrawn from the column and sent to a reboiler 19 heated by steam 21. The steam produced is returned to the column and the even richer solvent liquid 23 is recovered as product.
Le gaz de tête 27 de la colonne est divisé en deux, une partie 29 étant condensée dans le condenseur 31 et renvoyée à la colonne comme reflux 33. L'autre partie 35 est mélangée avec le gaz 13 du séparateur de phase pour former un débit gazeux 37 enrichi en dioxyde de carbone.  The overhead gas 27 of the column is divided in two, a portion 29 being condensed in the condenser 31 and returned to the column as reflux 33. The other portion 35 is mixed with the gas 13 of the phase separator to form a flow gas 37 enriched with carbon dioxide.
Il est également possible de prendre le gaz 35 directement dans la colonne. La tête de la colonne est à -20°C et la cuve est à 180°C, donc seule la tête de colonne a besoin d'être isolée.  It is also possible to take the gas directly into the column. The head of the column is at -20 ° C and the tank is at 180 ° C, so only the head of the column needs to be isolated.
Le débit 37 est condensé par un groupe frigorigène 41 qui peut également servir à refroidir le condenseur 31 . Le liquide formé en condensant le débit 37 est renvoyé au réacteur R pour réduire la quantité de dioxyde de carbone 1 requise.  The flow 37 is condensed by a refrigerant group 41 which can also serve to cool the condenser 31. The liquid formed by condensing the flow 37 is returned to the reactor R to reduce the amount of carbon dioxide 1 required.
Le produit en tête de la colonne est du CO2 très haute pureté, il peut être mélangé au CO2 issu de la détente pour obtenir une pureté globale supérieure à 99,8% mol . en CO2. The product at the top of the column is very high purity CO2, it can be mixed with CO2 from the expansion to obtain an overall purity higher than 99.8 mol%. in CO 2 .
En pied de colonne se retrouvent le composant moins volatil et du CO2 « perdu ». C'est le taux de récupération de CO2 souhaité qui définit le rebouillage (avec de la vapeur d'eau par exemple) nécessaire.  At the bottom of the column are the less volatile component and "lost" CO2. It is the desired CO2 recovery rate that defines the reboiling (with water vapor for example) required.
Plus le taux de récupération de CO2 est important, plus le produit (composant moins volatil par exemple solvant) en pied de colonne 15 est pur (dans l'hypothèse où il n'y a pas de tiers composé dans le mélange). Avec un rendement CO2 de l'ordre de 99%, la pureté du composant moins volatil par solvant soutiré est supérieure à 99% mol . Son recyclage en amont du procédé est possible, sans retraitement. Ainsi, le débit 25 relie le rebouilleur 19 avec l'entrée du réacteur R. The higher the CO2 recovery rate, the more pure the product (less volatile component for example solvent) at the bottom of the column (assuming there is no third compound in the mixture). With a CO2 efficiency of the order of 99%, the purity of the less volatile component per solvent withdrawn is greater than 99 mol%. Its recycling upstream of the process is possible without reprocessing. Thus, the flow 25 connects the reboiler 19 with the reactor R inlet.
Dans la Figure 2, seul le procédé de séparation de dioxyde de carbone et de composant moins volatil est représenté. Le mélange 3 de solvant et de dioxyde de carbone est détendu dans une vanne 7 pour former un liquide et envoyé à une capacité tampon 9. Le liquide est réchauffé dans un réchauffeur 10 pour le rendre diphasique et ensuite il est séparé dans une colonne de distillation 15 ayant un rebouilleur de cuve 19 et un condenseur de tête 31 .  In Figure 2, only the process of separating carbon dioxide and less volatile component is shown. The mixture of solvent and carbon dioxide is expanded in a valve 7 to form a liquid and sent to a buffer capacity 9. The liquid is heated in a heater 10 to make it two-phase and then it is separated in a distillation column 15 having a vessel reboiler 19 and a head condenser 31.
Le condenseur de tête, à la différence de celui de la Figure 1 reçoit tout le gaz de tête de la colonne 15, le condense et renvoie une partie 33 comme reflux. Le reste du gaz condensé 32 est pompé par une pompe 34 et divisé, une partie 44 étant renvoyé à la capacité 9 à travers la vanne 46 et le reste 43 étant recyclé dans le réacteur R. L'objectif de renvoyer un liquide riche en CO2 à la capacité 9 est de stabiliser la composition d'alimentation de la colonne pendant les phases transitoires où la production du réacteur R présente de grandes fluctuations.  The overhead condenser, unlike that of FIG. 1, receives all the overhead gas from the column 15, condenses it and returns a portion 33 as reflux. The remainder of the condensed gas 32 is pumped by a pump 34 and divided, a portion 44 being returned to the capacity 9 through the valve 46 and the remainder 43 being recycled to the reactor R. The objective of returning a liquid rich in CO2 Capacity 9 is to stabilize the feed composition of the column during transient phases where the production of the reactor R shows large fluctuations.
Le schéma de la Figure 3 consomme plus d'énergie mais permet d'avoir deux niveaux de température et diminue le gradient de température de la colonne. En plus des éléments de la Figure 2 il comprend un échangeur de chaleur, un réchauffeur 46, un séparateur de phases 47 et une pompe 53. Le liquide de cuve 23 du rebouilleur 19 est chauffé dans un échangeur, chauffé de nouveau dans un réchauffeur 46 au degré de vaporisation souhaitée et le débit diphasique formé est séparé dans le séparateur 47. Le liquide 49 riche en composant moins volatil sert de produit. Le gaz 51 sert à réchauffer le liquide 23 dans l'échangeur et est ainsi condensé. Une pompe 53 le pressurise et le renvoie à la capacité.  The diagram in Figure 3 consumes more energy but allows to have two temperature levels and decreases the temperature gradient of the column. In addition to the elements of FIG. 2, it comprises a heat exchanger, a heater 46, a phase separator 47 and a pump 53. The tank liquid 23 of the reboiler 19 is heated in an exchanger, heated again in a heater 46 at the desired degree of vaporization and the two-phase flow formed is separated in the separator 47. The less volatile component-rich liquid 49 serves as a product. The gas 51 serves to heat the liquid 23 in the exchanger and is thus condensed. A pump 53 pressurizes it and returns it to the capacity.

Claims

Revendications claims
1 . Procédé de séparation d'un mélange gazeux de dioxyde de carbone et d'un composant moins volatil que le dioxyde de carbone dans lequel : 1. A method of separating a gaseous mixture of carbon dioxide and a less volatile component than carbon dioxide in which:
i) On refroidit le mélange gazeux (3) à séparer et on le détend pour former un débit détendu, éventuellement diphasique.  i) The gaseous mixture (3) to be separated is cooled and expanded to form a relaxed, possibly two-phase flow.
ii) On envoie le débit détendu dans une capacité (9), qui est éventuellement un séparateur de phase, pour former un premier liquide (1 1 ) éventuellement enrichi en composant moins volatil et éventuellement un premier gaz (13) enrichi en dioxyde de carbone.  ii) The expanded flow is sent into a capacity (9), which is optionally a phase separator, to form a first liquid (1 1) optionally enriched with a less volatile component and optionally a first gas (13) enriched with carbon dioxide .
iii) On envoie au moins une partie du liquide éventuellement enrichi en composant moins volatil à une colonne de distillation (15).  iii) At least a portion of the optionally enriched liquid of less volatile component is sent to a distillation column (15).
iv) On soutire un deuxième gaz (27) enrichi en dioxyde de carbone de la tête de la colonne et un deuxième liquide (17) enrichi en composant moins volatil de la cuve de la colonne.  iv) A second carbon dioxide enriched gas (27) is withdrawn from the top of the column and a second liquid (17) enriched with the less volatile component of the column vessel.
v) On condense au moins une partie du premier gaz et/ou du deuxième gaz enrichi en dioxyde de carbone et/ou on soutire un liquide enrichi en dioxyde de carbone de la tête de la colonne, et  v) Condensing at least a portion of the first gas and / or second carbon dioxide enriched gas and / or withdrawing a carbon dioxide-enriched liquid from the top of the column, and
vi) On envoie au moins une partie du gaz condensé (43) et/ou au moins une partie du liquide enrichi en dioxyde de carbone à un point en amont de la capacité et/ou à la capacité.  vi) At least a portion of the condensed gas (43) and / or at least a portion of the carbon dioxide-enriched liquid is sent to a point upstream of the capacity and / or capacity.
2. Procédé selon la revendication 1 dans lequel on recycle au moins une partie du gaz condensé (43) et/ou au moins une partie du liquide à un réacteur (R) d'où provient le mélange gazeux. 2. Method according to claim 1 wherein at least a portion of the condensed gas (43) and / or at least a portion of the liquid is recycled to a reactor (R) from which the gas mixture originates.
3. Procédé selon la revendication 1 ou 2 dans lequel on recycle au moins une partie (25) du deuxième liquide enrichi en composant moins volatil vers un réacteur (R) d'où provient le mélange gazeux. 3. The method of claim 1 or 2 wherein recycling at least a portion (25) of the second liquid enriched less volatile component to a reactor (R) from which the gas mixture.
4. Procédé selon l'une des revendications précédentes dans lequel on sépare le deuxième liquide (17) enrichi en composant moins volatil pour former un gaz (51 ) appauvri en composant moins volatil et un produit liquide (49) riche en composant moins volatil, on condense le gaz appauvri et on renvoie le gaz appauvri condensé vers la capacité (9). 4. Method according to one of the preceding claims wherein separates the second liquid (17) enriched less volatile component to form a gas (51) depleted less volatile component and a liquid product (49) rich in less volatile component, the depleted gas is condensed and the condensed depleted gas is returned to the capacity (9).
5. Procédé selon l'une des revendications précédentes dans lequel aucun gaz n'est soutiré de la capacité (9). 5. Method according to one of the preceding claims wherein no gas is withdrawn from the capacity (9).
6. Procédé selon l'une des revendications précédentes dans lequel on renvoie au moins une partie du gaz condensé (45) et/ou au moins une partie du liquide en amont de la capacité (9), voire du réacteur. 6. Method according to one of the preceding claims wherein is returned at least a portion of the condensed gas (45) and / or at least a portion of the liquid upstream of the capacity (9) or the reactor.
7. Procédé selon la revendication 6 dans lequel on pressurise le liquide ou le gaz condensé dans une pompe (34) en amont de la capacité (9). 7. The method of claim 6 wherein the liquid or the condensed gas is pressurized in a pump (34) upstream of the capacity (9).
8. Procédé selon une revendication précédente dans lequel on réchauffe au moins une partie du deuxième liquide pour le vaporiser partiellement, on le séparer dans un séparateur de phases (47), on soutire le liquide comme produit (49), on condense le gaz (51 ) du séparateur de phases contre le deuxième liquide et on envoie le gaz condensé à la capacité. 8. Method according to a preceding claim wherein the at least a portion of the second liquid is heated to partially vaporize it, it is separated in a phase separator (47), the liquid is withdrawn as product (49), the gas is condensed ( 51) of the phase separator against the second liquid and the condensed gas is sent to the capacity.
9. Appareil de séparation d'un mélange gazeux de dioxyde de carbone et d'un composant moins volatil moins volatil que le dioxyde de carbone comprenant des moyens (5) pour refroidir le mélange gazeux à séparer (3), une vanne (7) pour détendre le mélange gazeux refroidi pour former un débit détendu, éventuellement diphasique, une capacité (9), qui est éventuellement un séparateur de phase, des moyens pour envoyer le débit détendu à la capacité, une première conduite pour soutirer de la capacité un premier liquide (1 1 ) éventuellement enrichi en composant moins volatil, éventuellement une conduite pour soutirer un premier gaz (13) enrichi en dioxyde de carbone de la capacité, une colonne de distillation (15) reliée à la première conduite, une conduite pour soutirer un deuxième gaz (27) enrichi en dioxyde de carbone de la tête de la colonne, une conduite pour soutirer un deuxième liquide (17) enrichi en composant moins volatil de la cuve de la colonne, un condenseur (31 , 41 ) pour condenser au moins une partie du premier gaz et/ou du deuxième gaz enrichi en dioxyde de carbone et/ou des moyens pour soutirer un liquide enrichi en dioxyde de carbone de la tête de la colonne et des moyens pour envoyer au moins une partie (43, 45) du gaz condensé dans le condenseur et/ou au moins une partie du liquide enrichi en dioxyde de carbone à un point en amont de la capacité ou à la capacité. 9. Apparatus for separating a gaseous mixture of carbon dioxide and a less volatile component less volatile than carbon dioxide comprising means (5) for cooling the gaseous mixture to be separated (3), a valve (7) for expanding the cooled gaseous mixture to form a relaxed, possibly two-phase flow, a capacity (9), which is optionally a phase separator, means for sending the expanded flow rate to the capacity, a first line for drawing capacity first liquid (1 1) optionally enriched with less volatile component, optionally a pipe for withdrawing a first gas (13) enriched in carbon dioxide capacity, a distillation column (15) connected to the first pipe, a pipe for withdrawing a second gas (27) enriched with carbon dioxide from the top of the column, a pipe for withdrawing a second liquid (17) enriched with less volatile component of the tank of the column, a condenser (31, 41) for condensing at least a portion of the first gas and / or the second carbon dioxide-enriched gas and / or means for withdrawing a carbon dioxide-enriched liquid from the top of the column and means for sending at least a portion (43, 45) of the condensed gas into the condenser and / or at least a portion of the carbon dioxide-enriched liquid at a point upstream of the capacity or capacity.
10. Appareil selon la revendication 9 dans lequel le mélange gazeux (3) est produit dans un réacteur (R) alimenté par du dioxyde de carbone et dans lequel les moyens pour envoyer au moins une partie du gaz condensé dans le condenseur (31 , 41 ) et/ou au moins une partie du liquide enrichi en dioxyde de carbone à un point en amont de la capacité sont reliés au réacteur. An apparatus according to claim 9 wherein the gaseous mixture (3) is produced in a reactor (R) fed with carbon dioxide and wherein the means for sending at least a portion of the condensed gas into the condenser (31, 41). and / or at least a portion of the carbon dioxide enriched liquid at a point upstream of the capacity are connected to the reactor.
PCT/FR2018/050684 2017-03-24 2018-03-21 Method and appliance for the distillation of a mixture of carbon dioxide and a less volatile component WO2018172698A1 (en)

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CN108622898A (en) 2018-10-09

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