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WO2008147181A1 - Procédé d'enlèvement d'un gaz à partir d'un flux de gaz de traitement par l'intermédiaire de cristaux liquides - Google Patents

Procédé d'enlèvement d'un gaz à partir d'un flux de gaz de traitement par l'intermédiaire de cristaux liquides Download PDF

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Publication number
WO2008147181A1
WO2008147181A1 PCT/NL2008/050145 NL2008050145W WO2008147181A1 WO 2008147181 A1 WO2008147181 A1 WO 2008147181A1 NL 2008050145 W NL2008050145 W NL 2008050145W WO 2008147181 A1 WO2008147181 A1 WO 2008147181A1
Authority
WO
WIPO (PCT)
Prior art keywords
solvent
liquid crystals
isotropic
component
phase change
Prior art date
Application number
PCT/NL2008/050145
Other languages
English (en)
Inventor
Joachim Gross
Peter Johannes Jansens
Original Assignee
Technische Universiteit Delft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Technische Universiteit Delft filed Critical Technische Universiteit Delft
Publication of WO2008147181A1 publication Critical patent/WO2008147181A1/fr

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Classifications

    • 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
    • B01D53/14—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 absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • 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
    • B01D53/14—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 absorption
    • B01D53/1456—Removing acid components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • 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
    • B01D2257/80—Water
    • 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

Definitions

  • the present invention relates to a method for the removal of a gas from a process gas stream by contacting the same with an absorption solvent for the removal of gas, followed by desorption of the gas to be removed.
  • Solvents for the removal of process stream substances are used on a large scale in various separation processes, such as extraction processes, absorption processes, extractive distillation, crystallisation processes, etc. This involves the dissolutions of the substances to be removed in the solvent, also referred to as "loading" the solvent.
  • the solvent containing the dissolved substances is subsequently treated, whereby the dissolved substances are removed from the solvent and the solvent generated herewith, which clearly contains fewer dissolved substances, can be reused.
  • a considerable drawback of such a process is that the cycle of loading the solvent and regenerating is associated with significant energy consumption, with the ensuing high operating expenses and capital expenditure .
  • the object of the present invention is to provide a method, in which the above-mentioned drawbacks are effectively eliminated, so as to render the cycles of loading and regenerating efficient and economical.
  • the present invention provides a method for the removal of a gas from a process gas stream by contacting the same with a solvent for the gas to be removed, followed by desorption of the gas to be removed, characterized in that as solvent liquid crystals are used.
  • isotropic liquid crystals are used, wherein after absorption of the gas to be removed under the influence of heat and/of pressure a phase- change from the isotropic to the nematic condition is realized, wherein the solubility of the gas to be removed is drastically reduced such that the gas to be removed desorbs for the most part, leaving a solvent that is sufficiently free of gas to be removed, and that can be reused.
  • conventional solvents are used.
  • absorption processes are conducted in such a way that for the removal of substances a solvent is contacted with a raw gas stream. The substances that are soluble in the solvent will dissolve. The solvent is then regenerated in a desorption step, also referred to as stripping.
  • Desorption involves the consumption of a significant amount of energy for the reduction of the partial pressure of the dissolved substances . This is often realized by using steam as stripping gas, with the temperature being raised and the partial pressure of the dissolved substances in the steam phase being lowered. This is necessary for the regeneration of the solvent.
  • the solvent used for the separation process i.e. the absorption and regeneration process
  • the solvent used for the separation process comprises of liquid crystals in the isotropic phase
  • the dissolved substances usually gases
  • loading that is to say absorption of the soluble substances, occurs in the solvent while this is in the above-mentioned isotropic phase.
  • these may be ordinary solvents, i.e. solvents that do not have a permanent molecular charge, or iogenic liquids (ionic liquid crystals) .
  • a phase contacting device e.g. a staged absorption column
  • the solvent phase is then at least partly isotropic.
  • the solvent phase undergoes a phase change to a liquid crystalline phase (e.g. a nematic phase ⁇ .
  • a phase change to a liquid crystalline phase (e.g. a nematic phase ⁇ .
  • liquid crystals as solvent for the solutes to be removed.
  • liquid crystals have increasingly been the subject of research activities, so far mainly directed at optical properties and related products such as, for example LCDs.
  • optical properties and related products such as, for example LCDs.
  • the general concept of liquid crystals is further clarified below.
  • Liquid crystals are substances with a molecular order between crystals and liquids. In a particular temperature range the molecules exhibit an imperfect long-range order of molecular orientation. However, if the temperature is raised to above a sharp phase change temperature, the molecular order is disrupted, bringing about an isotropic state. This phase change drastically alters the thermodynamic behaviour in relation to other components, comparable to a solubility switch. Despite intensive and wide interdisciplinary research directed at liquid crystals, their application as process solvents is a new field.
  • liquid crystals are suitable for use as absorbing (scrubbing) solvents in gas washing processes, in connection with the recovery of carbon dioxide from waste gasses .
  • liquid crystals are very well controllable low/non-volatile (green) solvents that may be rendered suitable for particular applications, has so far not been developed in the chemical engineering community, nor has it as yet been mentioned in scientific publications.
  • liquid crystals it may be stated that substance can exist in the solid, liquid of gaseous state.
  • FIG. 1 is an illustration of molecular order in a liquid phase, in various liquid crystalline phases and in a solid crystalline phase.
  • the two cubes in the top row from left to right represent liquid (isotropic) and crystal, respectively.
  • the four cubes in the bottom row from left to right represent: nematic (LC), smectic A (LC), smectic B (LC), and smectic C (LC) , respectively.
  • liquid crystals are very diverse; examples of this are liquid crystal thermometers, optical imaging, non-destructive mechanical tests of materials under stress, visualization of radio frequency waves in wave guides, medical applications where, for example, transient pressure transmitted by a walking foot on the ground is measured, erasable optical discs, full-colour electronic slides for computer- aided drawings (CAD) , light modulators for colour electronic imaging, stationary phase in chromatography, etc.
  • CAD computer- aided drawings
  • the present invention is based on a sharp phase change between the isotropic state of liquid crystals and the nematic state, at which phase change it was surprisingly shown that the solubility of the substances in the liquid crystals diminishes drastically, with the result that the dissolved substances desorb and disappear almost completely from the solvent.
  • liquid crystals may be used as an absorbing solvent in an absorption column at a temperature T ⁇ 55 , wherein the absorption capacity for carbon dioxide is X ⁇ 3 . If the liquid crystals are cooled by a few degrees Kelvin, the liquid crystalline phase undergoes a phase change to a nematic phase, and a phase separation is observed. Surprisingly, the solubility of carbon dioxide in a nematic liquid is shown to drop sharply to v des
  • the thus regenerated liquid crystals can be fed back to the absorption step with little effort.
  • the nematic-isotropic change thus serves as a switch in
  • the present approach may be said to be very advantageous and elegant because no phase change of the liquid takes place involving substantial energy-intensive temperature variations that range from approximately 30 to80 K.
  • the above-mentioned phase change from the isotropic to the nematic state is attained by lowering the temperature or raising the pressure.
  • An approximate temperature-variation of typically 20 K is desired.
  • the present invention is suitable for the efficient removal of CO 2 , H 2 S, etc. from process gas streams.
  • Solvents that is to say liquid crystals that are suitable for dissolving the solute, i.e. CO 2 , H 2 S, etc. are trans-4- (4-pentylcyclohexyl) -benzontrile or their derivatives. It is observed, that when CO 2 is removed from high-pressure gas streams, for example streams occurring with Syngas production (H 2 , CO, H 2 O, CO 2 ) or with fuel cell applications where reforming gas streams are treated, the pressure of the feed streams are typically in the range of 20-60 bars. When using a liquid crystalline solvent for the absorption of carbon dioxide in a traditional absorption column, wherein the solubility of the other gas components is considerably lower, the temperature of the absorption column is 50-150 0 C.
  • phase change between two mesomorphic phases such as nematic and smectic, but also between an isotropic phase and, for example, a smectic phase .
  • the invention will now be further explained by way of the Examples 1 - 3.
  • Example 1 Removal of CO 2 from a natural gas stream
  • a C0 2 -containing natural gas stream is contacted with a liquid crystal solvent in an absorption step.
  • the natural gas stream may comprise 10 mol % of CO 2 and has a temperature of approximately 40 0 C.
  • the solubility of CO 2 in isotropic PCH-5 is approximately 5% by mass.
  • a fourfold mass of liquid crystals is contacted with the natural gas stream for the absorption of CO 2 .
  • the product gas comprises residual amounts of CO 2 , depending on the purity of the regenerated liquid crystal solvent and the mass transport specifications of the apparatus.
  • the residual amount of CO 2 is estimated at approximately 1 molpercent .
  • the regeneration of the liquid crystal solvent occurs by lowering the temperature to approximately 25 0 C so as to achieve a nematic phase, and by using nitrogen as stripping gas. After absorption, the regenerated solvent is again recycled, so as to obtain an absorption/desorption cycle.
  • a process stream derived from a water stream "reforming" process after a water-gas gift is treated with liquid crystals to remove the carbon dioxide from the process stream (absorption) .
  • the process stream has a pressure of approximately 14 bars.
  • the process stream may contain 30 molpercent of CO 2 .
  • a counter stream is contacted with a liquid crystalline substance in a nematic phase. The carbon dioxide dissolves in the nematic liquid in an amount of approximately 5% by mass. The process continues as described in Example 1.
  • Example 1 a C ⁇ 2 ⁇ polluted natural gas field was de- scribed.
  • gas fields may be polluted with H 2 S with the process having a similar construction as that of Example 1.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

La présente invention concerne un procédé d'enlèvement d'un composant à partir d'un flux de gaz de traitement en utilisant des cristaux liquides en tant que solvant du gaz à enlever. La présente invention applique un changement de phase à partir de l'état isotropique jusqu'à l'état nématique, dans lequel la solubilité du gaz à enlever est réduite de manière drastique, de sorte que le composant à enlever se désorbe du solvant. Le changement de phase est réalisé en abaissant la température du solvant ou en élevant la pression. Conformément à la présente invention, des composants qui peuvent être enlevés incluent parmi d'autres : CO2, H2S, H2O, etc.
PCT/NL2008/050145 2007-05-18 2008-03-13 Procédé d'enlèvement d'un gaz à partir d'un flux de gaz de traitement par l'intermédiaire de cristaux liquides WO2008147181A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL2000654A NL2000654C2 (nl) 2007-05-18 2007-05-18 Werkwijze voor de verwijdering van een gas uit een procesgasstroom door vloeibare kristallen.
NL2000654 2007-05-18

Publications (1)

Publication Number Publication Date
WO2008147181A1 true WO2008147181A1 (fr) 2008-12-04

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2008/050145 WO2008147181A1 (fr) 2007-05-18 2008-03-13 Procédé d'enlèvement d'un gaz à partir d'un flux de gaz de traitement par l'intermédiaire de cristaux liquides

Country Status (2)

Country Link
NL (1) NL2000654C2 (fr)
WO (1) WO2008147181A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012091572A1 (fr) * 2010-12-30 2012-07-05 Feyecon B.V. Procédé de déshydratation qui utilise un sel de choline liquide ionique

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050244665A1 (en) * 2004-04-28 2005-11-03 Cryovac, Inc. Oxygen scavenging film with cyclic olefin copolymer
WO2007013119A1 (fr) * 2005-07-29 2007-02-01 Saes Getters S.P.A. Systemes getter comprenant une phase active introduite dans un materiau poreux reparti dans un organe a faible permeabilite

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050244665A1 (en) * 2004-04-28 2005-11-03 Cryovac, Inc. Oxygen scavenging film with cyclic olefin copolymer
WO2007013119A1 (fr) * 2005-07-29 2007-02-01 Saes Getters S.P.A. Systemes getter comprenant une phase active introduite dans un materiau poreux reparti dans un organe a faible permeabilite

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SUSANN M. BRANDER ET AL: "Reactive Foams for Air Purification", ENVIRON. SCI. TECHNOL., vol. 18, no. 4, 30 April 1984 (1984-04-30) - 30 April 1984 (1984-04-30), pages 224 - 230, XP002461420 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012091572A1 (fr) * 2010-12-30 2012-07-05 Feyecon B.V. Procédé de déshydratation qui utilise un sel de choline liquide ionique
CN103313771A (zh) * 2010-12-30 2013-09-18 费伊肯私人有限公司 采用离子液体脱水的方法
CN103313771B (zh) * 2010-12-30 2015-07-15 费伊肯私人有限公司 采用离子液体脱水的方法

Also Published As

Publication number Publication date
NL2000654C2 (nl) 2008-11-20

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