EP3177385A1 - Recovery of gases, especially permanent gases, from streams of matter, especially from offgas streams from polymerizations - Google Patents

Recovery of gases, especially permanent gases, from streams of matter, especially from offgas streams from polymerizations

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Publication number
EP3177385A1
EP3177385A1 EP15759631.3A EP15759631A EP3177385A1 EP 3177385 A1 EP3177385 A1 EP 3177385A1 EP 15759631 A EP15759631 A EP 15759631A EP 3177385 A1 EP3177385 A1 EP 3177385A1
Authority
EP
European Patent Office
Prior art keywords
stream
substance
retentate
permeate
fraction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15759631.3A
Other languages
German (de)
French (fr)
Inventor
Volker Witzleb
Werner Leitmayr
Christian Voss
Akos Tota
Martin Bauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linde GmbH
Original Assignee
Linde GmbH
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
Priority claimed from DE102014011750.2A external-priority patent/DE102014011750A1/en
Application filed by Linde GmbH filed Critical Linde GmbH
Publication of EP3177385A1 publication Critical patent/EP3177385A1/en
Withdrawn legal-status Critical Current

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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
    • B01D53/22—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
    • B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
    • 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
    • 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
    • B01D53/04—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 with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/144—Purification; Separation; Use of additives using membranes, e.g. selective permeation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/102—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/108—Hydrogen

Definitions

  • the invention relates to a method for purifying a stream, wherein the stream has a C 2+ fraction and at least one first gaseous substance and a second gaseous substance different therefrom, wherein the stream is subjected to a pressure swing adsorption to remove the C 2+ fraction.
  • EP 1 491 559 describes a process in which an inert gas from an exhaust gas stream of a polymer production plant can be purified by means of an adsorption process and subsequently reused.
  • Polymerization solvent and the monomer are separated adsorptively from the exhaust stream, so that the purified, inert gas is present at high pressure.
  • US Pat. No. 6,706,857 describes a process for the recovery of olefinic monomers from a polymerization process. This is a gas stream
  • Monomer and nitrogen purified by pressure swing adsorption In the recovery of C 2+ hydrocarbons (ie hydrocarbons having two or more carbon atoms) from streams by pressure swing adsorption is usually a mixture of at least two permanent gas components as a high pressure product, which is often thermally recovered only by burning.
  • the invention is based on the object of improving a method of the type mentioned at the outset in such a way that the range of uses of the high-gas product is widened.
  • the stream after removal of the C 2+ fraction, is separated by means of a membrane into a retentate and a permeate, wherein the retentate is rich in the first material, and wherein the permeate is rich in the second material ,
  • the first substance is thus preferably a substance which permeates worse through the membrane than the second substance, so that it is enriched in the retentate, whereas the second substance is depleted in the retentate.
  • the second material is better permeated through the membrane than the first material, so that the second substance is enriched in the permeate and the first substance is depleted in the permeate.
  • H 2 can be depleted to less than 1% by volume in the retentate.
  • Wassertsoffkonzentrationen can be achieved above 40 vol .-%.
  • the retentate is present at the same pressure level as the stream purified by the C 2+ fraction and can then be used accordingly, for example in a previous process - in particular without expensive compaction , Any pressure loss across the diaphragm, fittings and / or piping can be compensated by a blower. However, this is much less expensive compared to the situation in which the desired product is present on the permeate side.
  • the first and second substances are preferably gases, which for historical reasons are also referred to as permanent gases. These are hydrogen, nitrogen, methane, carbon monoxide and carbon dioxide.
  • the first substance is nitrogen and the second substance is hydrogen.
  • the C 2+ fraction preferably comprises ethylene or propylene.
  • Pressure swing adsorption of the C 2+ fraction purified stream used is at least one of the following: polysulfone (PSU), polyethersulfone (PES), polyimide (PI), polyamide (PA).
  • PSU polysulfone
  • PES polyethersulfone
  • PI polyimide
  • PA polyamide
  • the material stream to be purified originates from an upstream of the Pressure swing adsorption performed process (eg, a process step or process in the form of a synthesis), wherein the stream is preferably an exhaust gas stream from such a process.
  • the exhaust gas flow may be, for example, a purge gas or a stripping gas.
  • the process or method is a polymerization. Under such a
  • Polymerization in the present case is understood to mean a polyreaction (also called a polymer formation reaction, named after IUPAC "Polymerization"), i. a synthesis reaction that converts similar or different monomers into polymers.
  • a polyreaction also called a polymer formation reaction, named after IUPAC "Polymerization”
  • IUPAC polymer formation reaction
  • polymerization may be a so-called chain polymerization or a so-called step growth reaction (e.g., polycondensation or polyaddition).
  • the material stream is preferably an exhaust gas stream, in particular a purge gas stream which is obtained during a polymerization.
  • Monomers used here such as, for example, ethylene or propylene (constituents of the C 2+ fraction), are then present in the stream of material or gas which further comprises, for example, nitrogen as the first substance (for example, if the polymer produced during the polymerization with nitrogen rinsed) and continue to use hydrogen as a second substance.
  • the permeate for example containing hydrogen
  • the permeate is preferably incinerated or, if appropriate, supplied as an export stream to another use.
  • Fig. 1 is a schematic representation of an embodiment of a
  • the method according to the invention makes it possible to separate a stream S, in particular in the form of an exhaust stream, consisting of at least two permanent gas components and at least one C 2+ hydrocarbon. This is in particular after an optional compression of the stream 5 in a first step, the C 2+ fraction separated by pressure swing adsorption (DWA) 10.
  • DWA pressure swing adsorption
  • the resulting C 2+ -free exhaust stream or stream S ' which is the high-pressure product of the DWA
  • the fraction S "adsorbed in the pressure swing adsorption is desorbed at a lower pressure and optionally fed to another use
  • the DWA is carried out at pressures of 5 bar to 30 bar and at a temperature of 10 ° C to 50 ° C.
  • Permanent gas components are separated into the retentate R and permeate P and also recycled or otherwise used.
  • the membrane separation is carried out at a pressure in the range of 5 bar to 30 bar and at a temperature in the range of 20 ° C to 80 ° C.
  • a stream S in the form of a purge gas stream comprising nitrogen, hydrogen and a monomer such as ethylene or propylene.
  • the high pressure product S ' only nitrogen and hydrogen.
  • this gas stream can be obtained by adding a downstream membrane separation 20, a nitrogen-rich retentate R at high pressure and a hydrogen-enriched permeate P at low pressure, the pressure loss substantially when passing through the Membrane 20 occurs.
  • the hydrogen-rich permeate stream P is furthermore preferably at least partially thermally utilized, it can be present at high pressure
  • Nitrogen / retentate R can be recycled to the polymerization process 30, whereby the need for fresh nitrogen in the polymerization process can be reduced.
  • N 2 is preferred for flushing the polymer outgassing container (PAB) or the
  • Reactor itself used Especially with the PAB N 2 is used continuously.
  • the recovery reduces the need for fresh N 2 , as well as reducing the amount of flaked fuel, which is an advantage under stringent environmental regulations.

Landscapes

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

Abstract

The invention relates to a method of cleaning a stream of matter (S), wherein the stream of matter (S) includes a C2+ fraction and at least one first gaseous substance and a different second gaseous substance, wherein the stream of matter (S) is subjected to a pressure swing adsorption (10) to remove the C2+ fraction. According to the invention, the stream of matter (S), after the removal of the C2+ fraction by means of a membrane (20), is separated into a retentate (R) and a permeate (P), wherein the first substance is enriched in the retentate (R) and the second substance is depleted in the retentate (R), and wherein the first substance is depleted in the permeate (P) and the second substance is enriched in the permeate (P).

Description

Beschreibung  description
Rückgewinnung von Gasen, insbesondere Permanentqasen, aus Stoffströmen, insbesondere aus Abgasströmen von Polymerisationen Recovery of gases, in particular permanent gases, from material streams, in particular from waste gas streams of polymerizations
Die Erfindung betrifft ein Verfahren zum Reinigen eines Stoffstromes, wobei der Stoffstrom eine C2+-Fraktion sowie zumindest einen ersten gasförmigen Stoff und einen davon verschiedenen zweiten gasförmigen Stoff aufweist, wobei der Stoffstrom zum Entfernen der C2+-Fraktion einer Druckwechseladsorption unterzogen wird. The invention relates to a method for purifying a stream, wherein the stream has a C 2+ fraction and at least one first gaseous substance and a second gaseous substance different therefrom, wherein the stream is subjected to a pressure swing adsorption to remove the C 2+ fraction.
Derartige Reinigungsverfahren sind aus dem Stand der Technik bekannt. So beschreibt z.B. die EP 1 491 559 ein Verfahren, bei dem ein inertes Gas aus einem Abgasstrom einer Polymerherstellungsanlage mittels eines Adsorptionsverfahrens aufgereinigt und anschließend wiederverwendet werden kann. Das Such cleaning methods are known from the prior art. Thus, e.g. EP 1 491 559 describes a process in which an inert gas from an exhaust gas stream of a polymer production plant can be purified by means of an adsorption process and subsequently reused. The
Polymerisationslösemittel sowie das Monomer werden dabei adsorptiv aus dem Abgasstrom abgetrennt, so dass das gereinigte, inerte Gas bei hohem Druck vorliegt. Polymerization solvent and the monomer are separated adsorptively from the exhaust stream, so that the purified, inert gas is present at high pressure.
Weiterhin beschreibt die US 6 706 857 ein Verfahren zur Rückgewinnung olefinischer Monomere aus einem Polymerisationsprozess. Hierbei wird ein Gasstrom aus Furthermore, US Pat. No. 6,706,857 describes a process for the recovery of olefinic monomers from a polymerization process. This is a gas stream
Monomer und Stickstoff mittels Druckwechseladsorption gereinigt. Bei der Rückgewinnung von C2+-Kohlenwasserstoffen (d.h. Kohlenwasserstoffe mit zwei oder mehr Kohlenstoffatomen) aus Stoffströmen mittels Druckwechseladsorption fällt regelmäßig ein Gemisch aus mindestens zwei Permanentgaskomponenten als Hochdruckprodukt an, das häufig lediglich durch Verbrennen thermisch verwertet wird. Der Erfindung liegt hiervon ausgehend die Aufgabe zugrunde, ein Verfahren der eingangs genannten Art dahingehend zu verbessern, dass das Verwendungsspektrum des Hochgasproduktes erweitert wird. Monomer and nitrogen purified by pressure swing adsorption. In the recovery of C 2+ hydrocarbons (ie hydrocarbons having two or more carbon atoms) from streams by pressure swing adsorption is usually a mixture of at least two permanent gas components as a high pressure product, which is often thermally recovered only by burning. On this basis, the invention is based on the object of improving a method of the type mentioned at the outset in such a way that the range of uses of the high-gas product is widened.
Dieses Problem wird durch ein Verfahren mit den Merkmalen des Anspruchs 1 gelöst. Vorteilhafte Ausgestaltungen der Erfindung sind u.a. in den Unteransprüchen angegeben und werden nachfolgend beschrieben. Erfindungsgemäß ist vorgesehen, dass der Stoffstrom, nach der Entfernung der C2+- Fraktion, mittels einer Membran in ein Retentat und ein Permeat aufgetrennt wird, wobei das Retentat reich am ersten Stoff ist, und wobei das Permeat demgegenüber reich an dem zweiten Stoff ist. Der erste Stoff ist also bevorzugt ein Stoff der gegenüber dem zweiten Stoff schlechter durch die Membran permeiert, so dass er im Retentat angereichert wird, wohingegen der zweite Stoff im Retentat abgereichert wird. Weiterhin ist der zweite Stoff im Vergleich zum ersten Stoff besser durch die Membran permeiert, so dass der zweite Stoff im Permeat angereichert wird und der erste Stoff im Permeat abgereichert wird. Aus einem 10/90 H2/N2-Gemisch im Feed kann z.B. H2 auf kleiner 1 vol.-% im Retentat abgereichert werden. Gleichzeitig können im Permeat Wassertsoffkonzentrationen oberhalb von 40 vol.-% erreicht werden. This problem is solved by a method having the features of claim 1. Advantageous embodiments of the invention are specified inter alia in the dependent claims and are described below. According to the invention, it is provided that the stream, after removal of the C 2+ fraction, is separated by means of a membrane into a retentate and a permeate, wherein the retentate is rich in the first material, and wherein the permeate is rich in the second material , The first substance is thus preferably a substance which permeates worse through the membrane than the second substance, so that it is enriched in the retentate, whereas the second substance is depleted in the retentate. Furthermore, the second material is better permeated through the membrane than the first material, so that the second substance is enriched in the permeate and the first substance is depleted in the permeate. From a 10/90 H 2 / N 2 mixture in the feed, for example, H 2 can be depleted to less than 1% by volume in the retentate. At the same time in the permeate Wassertsoffkonzentrationen can be achieved above 40 vol .-%.
Besonders vorteilhaft ist dabei bei dem erfindungsgemäßen Verfahren, dass das Retentat auf dem gleichen Druckniveau vorliegt, wie der von der C2+-Fraktion gereinigte Stoffstrom und sodann entsprechend genutzt werden kann, z.B. in einen vorangegangenen Prozess - insbesondere ohne aufwändige Verdichtung - zurückgeführt werden kann. Ein etwaiger Druckverlust über die Membran, Armaturen und/oder Rohrleitungen kann durch ein Gebläse ausgeglichen werden. Dies ist aber wesentlich weniger aufwändig im Vergleich zur Situation, bei der das gewünschte Produkt auf der Permeatseite vorliegt. It is particularly advantageous in the process according to the invention that the retentate is present at the same pressure level as the stream purified by the C 2+ fraction and can then be used accordingly, for example in a previous process - in particular without expensive compaction , Any pressure loss across the diaphragm, fittings and / or piping can be compensated by a blower. However, this is much less expensive compared to the situation in which the desired product is present on the permeate side.
Bei dem ersten und dem zweiten Stoff handelt es sich bevorzugt um Gase, die aus historischen Gründen auch als Permanentgase bezeichnet werden. Hierbei handelt es sich um Wasserstoff, Stickstoff, Methan, Kohlenmonoxid sowie Kohlendioxid. The first and second substances are preferably gases, which for historical reasons are also referred to as permanent gases. These are hydrogen, nitrogen, methane, carbon monoxide and carbon dioxide.
Bevorzugt ist der erste Stoff Stickstoff und der zweite Stoff Wasserstoff. Weiterhin umfasst die C2+-Fraktion bevorzugt Ethylen oder Propylen. Preferably, the first substance is nitrogen and the second substance is hydrogen. Furthermore, the C 2+ fraction preferably comprises ethylene or propylene.
Weiterhin weist bevorzugt die Membran, die zum Auftrennen des zuvor durch Furthermore, preferably, the membrane for separating the previously by
Druckwechseladsorption von der C2+-Fraktion gereinigten Stoffstromes verwendet wird, zumindest einen der folgenden Stoffe auf bzw. ist aus zumindest einem der folgenden Stoffe gebildet: Polysulfon (PSU), Polyethersulfon (PES), Polyimid (PI), Polyamid (PA). Mit derartigen Membranen ist z.B. die Trennung folgender Stoffpaare möglich: H2/N2, H2/CH4, und N2/C2+ (C2+ bezeichnet Kohlenwasserstoffe mit zwei oder mehr Pressure swing adsorption of the C 2+ fraction purified stream used is at least one of the following: polysulfone (PSU), polyethersulfone (PES), polyimide (PI), polyamide (PA). With such membranes, for example, the separation of the following pairs of substances is possible: H 2 / N 2 , H 2 / CH 4 , and N 2 / C 2+ (C 2+ refers to hydrocarbons having two or more
Kohlenstoffatomen). Carbon atoms).
Besonders bevorzugt stammt der zu reinigende Stoffstrom aus einem stromauf der Druckwechseladsorption durchgeführten Prozess (z.B. ein Verfahrensschritt oder Verfahren in Form einer Synthese), wobei der Stoffstrom bevorzugt ein Abgasstrom aus einem solchen Prozess ist. Hierbei kann der Abgasstrom z.B. ein Spülgas oder ein Strippgas sein. Particularly preferably, the material stream to be purified originates from an upstream of the Pressure swing adsorption performed process (eg, a process step or process in the form of a synthesis), wherein the stream is preferably an exhaust gas stream from such a process. In this case, the exhaust gas flow may be, for example, a purge gas or a stripping gas.
Gemäß einer Ausgestaltung des erfindungsgemäßen Verfahrens handelt es sich bei dem Prozess bzw. Verfahren um eine Polymerisation. Unter einer solchen According to one embodiment of the method according to the invention, the process or method is a polymerization. Under such a
Polymerisation wird vorliegend eine Polyreaktion (auch Polymerbildungsreaktion, nach IUPAC "Polymerization" genannt) verstanden, d.h. eine Synthesereaktion, die gleichartige oder unterschiedliche Monomere in Polymere überführt. Die Polymerization in the present case is understood to mean a polyreaction (also called a polymer formation reaction, named after IUPAC "Polymerization"), i. a synthesis reaction that converts similar or different monomers into polymers. The
Polymerisation kann insbesondere eine so genannte Kettenpolymerisation sein oder eine so genannte Stufenwachstumsreaktion (z.B. Polykondensation oder Polyaddition).  In particular, polymerization may be a so-called chain polymerization or a so-called step growth reaction (e.g., polycondensation or polyaddition).
So handelt es sich bei dem Stoffstrom bevorzugt um einen Abgasstrom, und zwar insbesondere um einen Spülgasstrom, der bei einer Polymerisation anfällt. Hierbei verwendeten Monomere, wie z.B. Ethylen oder Propylen (Bestandteile der C2+- Fraktion), befinden sich dann in dem Stoff- bzw. Abgasstrom, der des Weiteren z.B. Stickstoff als ersten Stoff aufweist (z.B. wenn das bei der Polymerisation erzeugte Polymer mit Stickstoff gespült wird) sowie weiterhin Wasserstoff als zweiten Stoff. Thus, the material stream is preferably an exhaust gas stream, in particular a purge gas stream which is obtained during a polymerization. Monomers used here, such as, for example, ethylene or propylene (constituents of the C 2+ fraction), are then present in the stream of material or gas which further comprises, for example, nitrogen as the first substance (for example, if the polymer produced during the polymerization with nitrogen rinsed) and continue to use hydrogen as a second substance.
Bevorzugt wird nach der Membrantrennung das Retentat in den stromauf der Preferably, after the membrane separation, the retentate in the upstream of
Druckwechseladsorption durchgeführten Prozess zurückgeführt und z.B. zum Spülen eines erzeugten Polymers oder zum Inertisieren einer Polymerisation verwendet. Das Permeat (z.B. Wasserstoff enthaltend) wird hingegen vorzugsweise verbrannt oder ggf. als Exportstrom einer sonstigen Verwendung zugeführt. Pressure swing adsorption carried out process and e.g. used to rinse a generated polymer or to inertize a polymerization. By contrast, the permeate (for example containing hydrogen) is preferably incinerated or, if appropriate, supplied as an export stream to another use.
Weitere Merkmale und Vorteile der Erfindung sollen bei der nachfolgenden Further features and advantages of the invention are intended in the following
Figurenbeschreibung eines Ausführungsbeispiels anhand der Figur erläutert werden. Es zeigt: Figure description of an embodiment will be explained with reference to the figure. It shows:
Fig. 1 eine schematische Darstellung eines Ausführungsbeispiels eines Fig. 1 is a schematic representation of an embodiment of a
erfindungsgemäßen Verfahrens  inventive method
Das erfindungsgemäße Verfahren ermöglicht es, einen Stoffstrom S, insbesondere in Form eines Abgasstroms, bestehend aus wenigstens zwei Permanentgaskomponenten und wenigstens einem C2+-Kohlenwasserstoff, aufzutrennen. Hierzu wird insbesondere nach einer optionalen Verdichtung 5 des Stoffstromes in einem ersten Schritt die C2+- Fraktion mittels Druckwechseladsorption (DWA) 10 abgetrennt. Der resultierende C2+- freie Abgas- bzw. Stoffstrom S', der das Hochdruckprodukt der DWA) darstellt, setzt sich dabei aus nicht-adsorbierten Permanentgaskomponenten zusammen, wobei mindestens eine Komponente/Fraktion, z.B. ein erster Stoff, vergleichsweise schlecht permeiert (und sich entsprechend im Retentat R anreichert) und zumindest eine Komponente/Fraktion, z.B. ein zweiter Stoff, vergleichsweise gut durch die Membran 20 permeiert (und sich entsprechend in einem Permeat P anreichert). Die bei der Druckwechseladsorption adsorbierte Fraktion S" wird bei niedrigerem Druck desorbiert und ggf. einer weiteren Verwendung zugeführt. Gemäß einem Beispiel wird die DWA bei Drücken von 5 bar bis 30 bar sowie bei einer Temperatur von 10°C bis 50°C durchgeführt. The method according to the invention makes it possible to separate a stream S, in particular in the form of an exhaust stream, consisting of at least two permanent gas components and at least one C 2+ hydrocarbon. This is in particular after an optional compression of the stream 5 in a first step, the C 2+ fraction separated by pressure swing adsorption (DWA) 10. The resulting C 2+ -free exhaust stream or stream S ', which is the high-pressure product of the DWA), is composed of non-adsorbed permanent gas components, with at least one component / fraction, eg a first material, permeating comparatively poorly (and correspondingly accumulates in the retentate R) and at least one component / fraction, eg a second substance, permeates comparatively well through the membrane 20 (and correspondingly accumulates in a permeate P). The fraction S "adsorbed in the pressure swing adsorption is desorbed at a lower pressure and optionally fed to another use According to one example, the DWA is carried out at pressures of 5 bar to 30 bar and at a temperature of 10 ° C to 50 ° C.
Durch die erfindungsgemäße Hinzunahme einer der Druckwechseladsorption 10 nachgeschalteten Membrantrennung 20 können die nicht-adsorbierten By adding according to the invention one of the pressure swing adsorption 10 downstream membrane separation 20, the non-adsorbed
Permanentgaskomponenten in das Retentat R und Permeat P aufgetrennt und ebenfalls rückgeführt oder anderweitig genutzt werden. Gemäß einem Beispiel wird die Membrantrennung bei einem Druck im Bereich von 5 bar bis 30 bar sowie bei einer Temperatur im Bereich von 20°C bis 80°C durchgeführt.  Permanent gas components are separated into the retentate R and permeate P and also recycled or otherwise used. According to one example, the membrane separation is carried out at a pressure in the range of 5 bar to 30 bar and at a temperature in the range of 20 ° C to 80 ° C.
Das Besondere ist hierbei, dass die Retentatfraktion R trotz des zusätzlichen The special feature here is that the retentate fraction R despite the additional
Reinigungsschrittes auf dem Druckniveau des C2+-freien Abgasstroms S' bleibt und entsprechend genutzt werden kann. Gemäß einem Beispiel fällt bei einem Polymerisationsprozess 30 ein Stoffstrom S in Form eines Spülgasstroms aufweisend Stickstoff, Wasserstoff und einem Monomer wie z.B. Ethylen oder Propylen an. Cleaning step at the pressure level of C 2+ -free exhaust stream S 'remains and can be used accordingly. According to one example, in a polymerization process 30, a stream S in the form of a purge gas stream comprising nitrogen, hydrogen and a monomer such as ethylene or propylene.
Nach der Abtrennung des Ethylens oder Propylens mittels DWA 10 enthält After separation of the ethylene or propylene by means of DWA 10 contains
das Hochdruckprodukt S' nur noch Stickstoff und Wasserstoff. Anstatt diesen Gasstrom wie bisher zu verwerfen oder rein thermisch zu verwerten, kann durch die Hinzunahme einer nachgeschalteten Membrantrennung 20 ein stickstoffreiches Retentat R bei hohem Druck und ein mit Wasserstoff angereichertes Permeat P bei niedrigem Druck gewonnen werden, wobei der Druckverlust im Wesentlichen beim Durchtritt durch die Membran 20 auftritt. Während der wasserstoffreiche Permeatstrom P weiterhin bevorzugt zumindest teilweise thermisch verwertet wird, kann der bei hohem Druck vorliegende the high pressure product S 'only nitrogen and hydrogen. Instead of rejecting this gas stream as before or to utilize it purely thermally, can be obtained by adding a downstream membrane separation 20, a nitrogen-rich retentate R at high pressure and a hydrogen-enriched permeate P at low pressure, the pressure loss substantially when passing through the Membrane 20 occurs. While the hydrogen-rich permeate stream P is furthermore preferably at least partially thermally utilized, it can be present at high pressure
Stickstoff/Retentat R in den Polymerisationsprozess 30 zurückgeführt werden, wodurch der Bedarf für frischen Stickstoff im Polymerisationsprozess verringert werden kann. Nitrogen / retentate R can be recycled to the polymerization process 30, whereby the need for fresh nitrogen in the polymerization process can be reduced.
N2 wird bevorzugt zur Spülung des Polymer-Ausgas-Behälters (PAB) oder des N 2 is preferred for flushing the polymer outgassing container (PAB) or the
Reaktors selbst verwendet. Vor allem beim PAB wird kontinuierlich N2 gebraucht. Durch die Rückgewinnung wird der Bedarf an frischen N2 verringert, sowie die gefackelte Menge reduziert, was bei strengen Umweltauflagen von Vorteil ist. Reactor itself used. Especially with the PAB N 2 is used continuously. The recovery reduces the need for fresh N 2 , as well as reducing the amount of flaked fuel, which is an advantage under stringent environmental regulations.
Bezugszeichenliste LIST OF REFERENCE NUMBERS
5 Verdichtung  5 compression
10 Druckwechseladsorption  10 pressure swing adsorption
20 Membrantrennung  20 membrane separation
30 Prozess, insbesondere Polymerisation 30 process, especially polymerization
S Stoff- bzw. Abgasstrom S substance or exhaust gas flow
S' C2+-gereinigter Stoffstrom  S 'C2 + purified material stream
S" Adsorbierte Komponenten (DWA) S "Adsorbed Components (DWA)
P Permeat P permeate
R Retentat  R retentate

Claims

Patentansprüche claims
Verfahren zum Reinigen eines Stoffstromes (S), wobei der Stoffstrom (S) eine C2+- Fraktion sowie zumindest einen ersten gasförmigen Stoff und einen davon verschiedenen zweiten gasförmigen Stoff aufweist, wobei der Stoffstrom (S) zum Entfernen der C2+-Fraktion einer Druckwechseladsorption (10) unterzogen wird, dadurch gekennzeichnet, dass der Stoffstrom (S1) nach der Entfernung der C2+-Fraktion mittels einer Membran (20) in ein Retentat (R) und ein Permeat (P) aufgetrennt wird, wobei der erste Stoff im Retentat (R) angereichert ist und der zweite Stoff im Retentat (R) abgereichert ist, und wobei der erste Stoff im Permeat (P) abgereichert ist und der zweite Stoff im Permeat (P) angereichert ist. A process for purifying a stream (S), wherein the stream (S) comprises a C 2+ fraction and at least one first gaseous substance and a second gaseous substance different therefrom, wherein the stream (S) for removing the C 2+ fraction a pressure swing adsorption (10), characterized in that the stream (S 1 ) after the removal of the C 2+ fraction by means of a membrane (20) into a retentate (R) and a permeate (P) is separated, wherein the first substance in the retentate (R) is enriched and the second substance in the retentate (R) is depleted, and wherein the first substance in the permeate (P) is depleted and the second material in the permeate (P) is enriched.
Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass der erste und der zweite Stoff aus der Gruppe umfassend Wasserstoff, Stickstoff, Methan, A method according to claim 2, characterized in that the first and the second substance from the group comprising hydrogen, nitrogen, methane,
Kohlenmonoxid und Kohlendioxid ausgewählt sind. Carbon monoxide and carbon dioxide are selected.
Verfahren nach einem der vorhergehenden Ansprüche, dadurch Method according to one of the preceding claims, characterized
gekennzeichnet, dass die Membran (20) zumindest einen der folgenden Stoffe aufweist oder aus zumindest einem der folgenden Stoffe gebildet ist: Polysulfon, Polyethersulfon, Polyimid, Polyamid. in that the membrane (20) comprises at least one of the following substances or is formed from at least one of the following substances: polysulfone, polyethersulfone, polyimide, polyamide.
Verfahren nach einem der vorhergehenden Ansprüche, dadurch Method according to one of the preceding claims, characterized
gekennzeichnet, dass der Stoffstrom (S) ein Abgasstrom ist. characterized in that the stream (S) is an exhaust gas stream.
Verfahren nach einem der vorhergehenden Ansprüche, dadurch Method according to one of the preceding claims, characterized
gekennzeichnet, dass der Stoffstrom (S) bei einem stromauf der characterized in that the stream (S) at an upstream of
Druckwechseladsorption (10) durchgeführten Prozess (30) anfällt. Pressure swing adsorption (10) carried out process (30) is obtained.
Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass das Retentat (R) in den Prozess (30) zurückgeführt wird. A method according to claim 5, characterized in that the retentate (R) is recycled to the process (30).
7. Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, dass der Prozess (30) eine Polymerisation umfasst, wobei der Stoffstrom als Abgasstrom (S) der Polymerisation (30) anfällt, wobei insbesondere ein durch Polymerisation hergestelltes Polymer mit einem Gasstrom gespült wird, wobei jener Stoffstrom als Abgasstrom (S) erzeugt wird. 7. The method according to claim 5 or 6, characterized in that the process (30) comprises a polymerization, wherein the material stream is obtained as exhaust gas stream (S) of the polymerization (30), wherein in particular a polymer produced by polymerization is purged with a gas stream, wherein that material flow is generated as exhaust gas flow (S).
8. Verfahren nach einem der vorhergehenden Ansprüche, dadurch 8. The method according to any one of the preceding claims, characterized
gekennzeichnet, dass die C2+-Fraktion Ethylen oder Propylen aufweist. 9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch in that the C 2+ fraction comprises ethylene or propylene. 9. The method according to any one of the preceding claims, characterized
gekennzeichnet, dass der erste Stoff Stickstoff ist.  characterized in that the first substance is nitrogen.
10. Verfahren nach einem der vorhergehenden Ansprüche, dadurch 10. The method according to any one of the preceding claims, characterized
gekennzeichnet, dass der zweite Stoff Wasserstoff ist.  characterized in that the second substance is hydrogen.
11. Verfahren nach einem der vorhergehenden Ansprüche, dadurch 11. The method according to any one of the preceding claims, characterized
gekennzeichnet, dass das Permeat (P) verbrannt wird oder anderweitig genutzt wird.  characterized in that the permeate (P) is burned or otherwise used.
EP15759631.3A 2014-08-07 2015-07-23 Recovery of gases, especially permanent gases, from streams of matter, especially from offgas streams from polymerizations Withdrawn EP3177385A1 (en)

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