WO2005079960A1 - Procede ameliore de separation de substances au moyen de membranes - Google Patents

Procede ameliore de separation de substances au moyen de membranes Download PDF

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Publication number
WO2005079960A1
WO2005079960A1 PCT/EP2005/001500 EP2005001500W WO2005079960A1 WO 2005079960 A1 WO2005079960 A1 WO 2005079960A1 EP 2005001500 W EP2005001500 W EP 2005001500W WO 2005079960 A1 WO2005079960 A1 WO 2005079960A1
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WO
WIPO (PCT)
Prior art keywords
membrane
stage
component
mixture
permeate
Prior art date
Application number
PCT/EP2005/001500
Other languages
German (de)
English (en)
Inventor
Stefan Bitterlich
Hartwig Voss
Original Assignee
Basf Aktiengesellschaft
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 Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO2005079960A1 publication Critical patent/WO2005079960A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/58—Multistep processes
    • 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
    • B01D53/22—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 diffusion
    • B01D53/225—Multiple stage diffusion
    • B01D53/226—Multiple stage diffusion in serial connexion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/362—Pervaporation

Definitions

  • the present invention relates to an improved process for the separation of a mixture by means of at least two membrane stages connected in series, the mixture being fed as a feed stream to the first membrane stage, a mixture essentially containing component A being drawn off there as permeate and the remaining mixture depleted with respect to component A as Withdrawing the retentate and feeding this retentate stream to the first membrane stage as a new feed stream to the second membrane stage, in which this mixture is changed by removing a permeate stream containing component A such that the concentration of the mixture withdrawn as a retentate stream from the second membrane stage with respect to component A is further reduced.
  • Membrane processes for the separation of mixtures are generally known to the person skilled in the art, e.g. microfiltration, ultra and nanofiltration, reverse osmosis, pervaporation and gas and vapor permeation.
  • a mixture (feed) to be separated is fed to at least one membrane apparatus, which mixture is separated in the apparatus into at least one stream (permeate) passing through the membrane and one stream (retentate) not passing through the membrane.
  • both the feed and permeate streams are essentially liquid (possibly with admixtures of solids).
  • Membrane separation processes are frequently used when it comes to removing this from a mixture which contains a component A as selectively as possible up to a predetermined residual concentration. This may be necessary, for example, because all the other components contained in the mixture are valuable substances and should be recovered as pure as possible, or because component A in turn should be obtained as pure as possible for further use.
  • the membranes used can be those which function according to the so-called solution diffusion mechanism, ie the components dissolve in the membrane, for example a polymer film, diffuse through and desorb on the other side.
  • meso- or microporous membranes in which, instead of the solution, adsorption takes place on the inside of the pores, followed by surface diffusion in the pores, or a porous membrane which separates by means of Knudsen diffusion, or a membrane that works after simple size exclusion (sieve effect).
  • the separation of the mixture supplied as a feed stream to the membrane generally takes place in that the permeability of the membrane to the components is different, that is, in other words, it has selectivity.
  • different measures are used for the selectivity of the membrane.
  • permselectivity In the case of pervaporation and vapor and gas permeation, the so-called permselectivity is often given as a measure of the selectivity.
  • the permselectivity is defined as the quotient of the permeances of two components, with the higher permeance usually being written into the counter, so that the permselectivity is> 1.
  • the permeance in turn, is defined as the local area-specific flow of a certain component, divided by the local transmembrane difference of the partial pressures of this component (on the feed or permeate side) or the fugacities of this component.
  • the permeance can be determined by using the equilibrium vapor pressure at the given temperature for the fugacity of the component.
  • separation factor ⁇ which is defined as follows, is more widespread as a measure of the selectivity:
  • Xj local mole or mass fraction of component i in the feed
  • Y ⁇ local mole or mass fraction of component i in the permeate.
  • retention R which is defined as follows:
  • C B , P and C B , R are the concentrations of component B in the permeate and retentate.
  • the membrane selectively separates component A from the mixture by means of the permeate stream.
  • the proportions in the permeate stream shift accordingly to component B.
  • the selectivity is influenced by the choice of membrane material, the type and composition of the components to be separated, as well as pressure and temperature.
  • Concentrations or purities in the streams leaving the process depend not only on the membrane properties, but also on the structure of the process and the process parameters set in it.
  • a membrane process contains at least one membrane stage.
  • the term membrane stage designates a membrane unit consisting of one or more membrane apparatuses, in which firstly only one membrane type is contained and secondly, feed and permeate sides each represent connected spaces that are not subdivided by pressure-increasing devices or by membranes.
  • a membrane stage can e.g. consist of a single membrane apparatus as known to the person skilled in the art, e.g. Apparatus containing membranes in the form of flat, tubular, capillary, pillow or spiral wrap modules. However, it can also contain several individual devices connected in parallel and / or in series.
  • the respective feed mixture can flow in parallel to the membrane apparatuses to be assigned to the membrane stage (or the retentate mixture emerging from a membrane apparatus or a plurality of membrane apparatuses connected in parallel as a feed into a membrane apparatus or a plurality of membrane apparatuses connected in parallel, which is in principle within a membrane stage as often as required, but in practice, due to the pressure loss that occurs, it can be economically repeated a maximum of approx. 10 times.
  • the mixture is fed as feed stream to the first membrane stage, there a mixture essentially containing component A is withdrawn as permeate and the remaining mixture which is depleted in relation to component A is withdrawn as retentate and
  • the second membrane stage has a lower selectivity with regard to component A than the first membrane stage.
  • component A in particular should be withdrawn from the mixture as completely as possible or removed as a permeate stream which is as pure as possible.
  • inventive design of the method in which the downstream membrane stage has (have) a lower selectivity with respect to component A compared to the previous membrane stage, naturally reduces the concentration of component A in the permeate of the downstream membrane stage compared to one of the prior art Arrangement corresponding to the technology, in which instead of the arrangement according to the invention there is either a single membrane stage or the downstream membrane stage contains the same membrane type as the first membrane stage, provided that either the retentate final concentration or the membrane surface are the same in both cases.
  • An advantage of the method according to the invention is that component A, provided that its permeance is at least as large as in the first membrane stage, is more depleted with the same membrane area, or that for a given concentration of A less membrane area is required in the second membrane stage than if you use a membrane with the same or higher selectivity for A in the second membrane stage. It is thus advantageously possible to obtain higher final purities in the mixture of component A or with a given degree of purity, the required membrane area can be reduced.
  • the values for permselectivity or separation factor of the membranes used in the process according to the invention are generally above 1 with regard to component A, since depletion of this component is desired.
  • the selectivity values are usually in a range from approximately 1.5 to 10000, preferably 2 to 5000, particularly preferably 2 to 1000.
  • the respective specific numerical values are influenced by the specified separation task (membrane used, components contained, process parameters).
  • the reduction in the selectivity of the downstream, second membrane stage according to the invention is achieved by selecting appropriate membranes. The selection is based on generally available selectivity data for available membranes. If necessary, the required selectivity data can also be determined by a person skilled in the art on the basis of measurements with the mixture of substances to be separated.
  • the selectivity of the membrane type contained in the second stage with respect to component A is reduced to a maximum of 80% based on the selectivity in the upstream membrane stage, preferably to about 50% of the selectivity which the membrane type used in the first membrane stage has with respect to component A.
  • the permeate obtained in the second membrane stage can be discarded if the economic, technical and legal framework allows, e.g. an exhaust gas or waste water stream are supplied; however, it can also be returned to the first membrane stage for the purpose of recovering valuable components. Arrangements with more than two membrane stages can also be particularly recommended.
  • the specific design of the method according to the invention is influenced by the respective separation task. If more than two membrane stages are used in the method according to the invention, the second, third or fourth stage can also relate to the first membrane stage, which contains a membrane with higher selectivity with regard to component A compared to the second, downstream membrane stage act on the entire separation process. It is essential that the ("second") membrane stage downstream of a considered ("first”) membrane stage is reduced in terms of selectivity.
  • the permeate or retentate streams may be subjected to other separation operations known per se, such as distillation, extraction, adsorption, absorption, crystallization or at least one further membrane separation step.
  • a type of membrane can be used, such as that used in the upstream, inventive Procedure is used.
  • a different type of membrane for example a type of membrane which differs in its selectivity from the upstream membranes designed according to the invention.
  • selectivity can also be understood to mean that the downstream membrane has a selectivity for at least one of the components present in the starting mixture apart from component A, the selectivity considered here likewise to be understood in the sense of the definition given above.
  • This interconnection can be designed, for example, in such a way that a stream which is removed from the process according to the invention as a permeate stream (preferably the permeate from the first membrane stage of the process according to the invention) and which essentially contains component A is fed to a membrane stage which has one or more membranes , whose permselectivity or separation factor with respect to component A is now less than 1 and for another component B contained is greater than 1, ie at this point component B is now preferably withdrawn as a new permeate stream and the rest of the mixture leaves as retentate this membrane stage in a higher concentration based on component A.
  • the permeate from the latter step is returned, for example, before the first or second membrane stage of the process according to the invention.
  • FIG. 1 A particularly advantageous embodiment of the method according to the invention is shown in FIG. 1. It has two membrane stages (I) and (II) according to the invention and the permeate from the second membrane stage (II) is conducted via line (4) to a further, third membrane stage (III).
  • This third membrane stage has the same membrane type as the first stage of the process according to the invention and thus has the same selectivity with regard to component A as the first membrane stage.
  • the retentate from the third membrane stage is carried out before the first membrane stage.
  • the membranes used in the membrane apparatus according to the invention can be made from a large number of suitable materials known to the person skilled in the art, such as polymers, carbon, metal or ceramic, or else from composites of the materials.
  • the process according to the invention can be used particularly advantageously in membrane processes which operate on the principle of pervaporation, vapor permeation or gas permeation, it being possible to set the process conditions which are customary in each case and described in a large number of publications.
  • Applications here are, for example, the dewatering of air or of organic components or mixtures (for example, the completion of organic solvents such as ethanol), the removal of organic components from gas or water.
  • streams such as or the separation of gas mixtures such as the separation of acid gases from natural or biogas, air separation or the separation of hydrogen from process gas streams.
  • the process according to the invention can thus be used advantageously, for example for the recovery of hydrogen, ethylene or propylene from purge gas streams which are obtained in chemical or petrochemical processes (for example production processes for ammonia, ethylene oxide or polyolefins).
  • the condition of the respective permeate must be conditioned in a suitable manner; i.e. in the case of pervaporation, the permeate must be condensed and brought to a pressure greater than or equal to the inlet pressure at the point to which it is returned by means of a pump.
  • the condensed permeate should be recycled upstream of the evaporator upstream of the membrane stage.
  • the permeate In the case of gas permeation, the permeate must be brought to a pressure greater than or equal to the inlet pressure at the point to which it is returned by means of a compressor.
  • the process according to the invention offers a process-technically simple and effective possibility of separating mixtures. Relatively high purities can be achieved with low membrane areas.
  • Permeate is separated from the starting mixture 1, which contains 20 mol% of the slightly permeable component A, in two successive membrane stages.
  • the plant is designed and operated in such a way that the permeate from the first stage contains 60 mol% and the retentate from the second stage contains 1 mol% A.
  • case 1 being the comparative example
  • case 2 being an example according to the invention.
  • Permeate is separated from the starting mixture 1, which contains 20 mol% of the slightly permeable component A, in two successive membrane stages, and the permeate from the second stage is returned to the first stage.
  • the plant is designed and operated in such a way that the permeate from the first stage contains 70 mol% and the retentate from the second stage contains 1 mol% A.
  • case 1 being the comparative example
  • case 2 being an example according to the invention
  • case 1 being the comparative example
  • case 2 being an example according to the invention

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  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne un procédé pour séparer un mélange au moyen d'au moins deux étages membranaires en série. Selon ledit procédé, a) le mélange est acheminé en tant que flux d'alimentation au premier étage membranaire, où un mélange, contenant sensiblement le constituant A, est extrait en tant que perméat et le mélange résiduel, appauvri en constituant A, est extrait en tant que rétentat puis b) ce flux de rétentat est acheminé en tant que nouveau flux d'alimentation du premier étage membranaire au deuxième étage membranaire, où ce mélange est modifié par l'évacuation d'un flux de perméat contenant le constituant A, de sorte que la concentration du constituant A dans le mélange extrait du deuxième étage membranaire en tant que flux de rétentat est encore réduite, le deuxième étage membranaire présentant une sélectivité par rapport au constituant A inférieure à celle du premier étage membranaire.
PCT/EP2005/001500 2004-02-17 2005-02-15 Procede ameliore de separation de substances au moyen de membranes WO2005079960A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004007548.4 2004-02-17
DE102004007548A DE102004007548A1 (de) 2004-02-17 2004-02-17 Verbessertes Verfahren zur Stofftrennung mittels Membranen

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WO2005079960A1 true WO2005079960A1 (fr) 2005-09-01

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008110146A1 (fr) * 2007-03-13 2008-09-18 Forschungszentrum Jülich GmbH Dispositif et procédé pour séparer le co2 d'un gaz de procédé
US20150101985A1 (en) * 2012-03-21 2015-04-16 Korea Institute Of Energy Research Method for Separating Water/Ethanol Using NAA Zeolite Separator
US10774273B2 (en) 2017-07-31 2020-09-15 Uop Llc Process and apparatus for recovering hydrogen from residue hydroprocessing

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT507891B1 (de) 2009-06-10 2010-09-15 Axiom Angewandte Prozesstechni Vorrichtung und verfahren zur auftrennung eines gasgemisches
FR3010640B1 (fr) 2013-09-16 2015-09-04 Air Liquide Procede pour une epuration finale de biogaz pour produire du biomethane
US20150129413A1 (en) * 2013-11-08 2015-05-14 Membrane Technology And Research, Inc. Two-Step Membrane Gas Separation Process
DE102017210366A1 (de) 2017-06-21 2018-12-27 Robert Bosch Gmbh Verfahren zum Betreiben eines Bordnetzes
US11806669B2 (en) 2020-12-22 2023-11-07 Evonik Operations Gmbh Variable and self-regulating permeate recycling in organophilic nanofiltration

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5252219A (en) * 1992-12-18 1993-10-12 Permea, Inc. Compressed permeate sweep membrane separation process
US5538536A (en) * 1994-09-12 1996-07-23 L'air Liquide, Societe Anonyme Pour L'etude Et L'eploitation Des Procedes Georges Claude Process and apparatus for separation of a gaseous mixture by successive membranes of different selectivities
WO2004002609A2 (fr) * 2002-06-27 2004-01-08 Bp Corporation North America Inc. Procedes et appareil utilisant des membranes selectivement permeables aux solides et montees en plusieurs groupes pour la recuperation simultanee de produits specifies dans un melange de fluides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5252219A (en) * 1992-12-18 1993-10-12 Permea, Inc. Compressed permeate sweep membrane separation process
US5538536A (en) * 1994-09-12 1996-07-23 L'air Liquide, Societe Anonyme Pour L'etude Et L'eploitation Des Procedes Georges Claude Process and apparatus for separation of a gaseous mixture by successive membranes of different selectivities
WO2004002609A2 (fr) * 2002-06-27 2004-01-08 Bp Corporation North America Inc. Procedes et appareil utilisant des membranes selectivement permeables aux solides et montees en plusieurs groupes pour la recuperation simultanee de produits specifies dans un melange de fluides

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008110146A1 (fr) * 2007-03-13 2008-09-18 Forschungszentrum Jülich GmbH Dispositif et procédé pour séparer le co2 d'un gaz de procédé
US20150101985A1 (en) * 2012-03-21 2015-04-16 Korea Institute Of Energy Research Method for Separating Water/Ethanol Using NAA Zeolite Separator
US10774273B2 (en) 2017-07-31 2020-09-15 Uop Llc Process and apparatus for recovering hydrogen from residue hydroprocessing

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Publication number Publication date
DE102004007548A1 (de) 2005-09-01

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