WO1996027430A1 - Membrane en composite de silicone, modifiee chimiquement par des rayonnements, pour l'ultrafiltration - Google Patents

Membrane en composite de silicone, modifiee chimiquement par des rayonnements, pour l'ultrafiltration Download PDF

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Publication number
WO1996027430A1
WO1996027430A1 PCT/DE1996/000336 DE9600336W WO9627430A1 WO 1996027430 A1 WO1996027430 A1 WO 1996027430A1 DE 9600336 W DE9600336 W DE 9600336W WO 9627430 A1 WO9627430 A1 WO 9627430A1
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WO
WIPO (PCT)
Prior art keywords
membranes
silicone
membrane
radiation
irradiating
Prior art date
Application number
PCT/DE1996/000336
Other languages
German (de)
English (en)
Inventor
Matthias Schmidt
Klaus-Viktor Peinemann
Nico Scharnagl
Klaus Friese
Rolf Schubert
Original Assignee
Gkss-Forschungszentrum Geesthacht 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
Application filed by Gkss-Forschungszentrum Geesthacht Gmbh filed Critical Gkss-Forschungszentrum Geesthacht Gmbh
Publication of WO1996027430A1 publication Critical patent/WO1996027430A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • B01D71/701—Polydimethylsiloxane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/081—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing particle radiation or gamma-radiation
    • B01J19/085—Electron beams only

Definitions

  • the invention relates to a silicone membrane, in particular a silicone composite membrane, for separating low molecular weight compounds from organic solvents.
  • the separation of low molecular weight compounds from organic solvents is usually carried out on an industrial scale by means of thermal processes, for example rectification / distillation, evaporation and extraction.
  • thermal processes for example rectification / distillation, evaporation and extraction.
  • these thermal separation processes require a large amount of energy.
  • Membrane separation processes are of interest in this regard.
  • such processes have the disadvantage that the membranes known hitherto can only be used to an extremely limited extent in organic solvents.
  • the chemical stability of the membranes used in organic solvents, such as toluene, n-hexane and isooctane, is generally not given.
  • the object of the present invention is therefore to provide a membrane which has low molecular weight compounds with average molar masses, in particular between 300 and 2000 g / mol, of organic Solvents, for example n-hexane, toluene, isooctane, methanol and ethanol, can be separated.
  • organic Solvents for example n-hexane, toluene, isooctane, methanol and ethanol
  • silicone membranes are used for the first time to separate low molecular weight compounds from organic solvents. These are in particular silicone composite membranes. The invention is therefore explained in more detail below with reference to these composite membranes.
  • silicone composite membranes known per se can be used. These can be modified silicones on microporous carrier membranes (polyvinylidefluoride (PVDF), polyacrylonitrile (PAN), polypropylene (PP), polyethylene (PE), polyetheretherketone (PEEK), polyether sulfone (PES) and other solutions i ttel stabi 1 e polymers).
  • PVDF polyvinylidefluoride
  • PAN polyacrylonitrile
  • PP polypropylene
  • PE polyethylene
  • PEEK polyetheretherketone
  • PES polyether sulfone
  • the membranes of the invention are irradiated with rays of low energy, in particular electron beams. In this way, high productivity is achieved with short irradiation times.
  • a low-energy accelerator in particular of the LEA 1 type (Low Energy Accelerator), is preferably used.
  • the electron accelerator technology used allows easy integration into the overall technology due to the low radiation protection expenditure. Membrane irradiation is thus possible immediately after the actual membrane production. However, it is also possible to separate the manufacture of the membrane known per se from the radiation in terms of time and space.
  • irradiate the membranes according to the invention with a low radiation dose of 10 kGy to 150 kGy. Even with irradiation with a dose from 10 kGy, significant increases in the retention of the irradiated membranes are possible. At the same time, there are only insignificantly reduced material flows.
  • the separation and permeation properties of the membranes according to the invention can be influenced in a targeted manner by varying the thickness of the separation layer and the radiation dose.
  • a low-energy accelerator it is possible, by choosing the irradiation parameters, to adapt the diffusion distribution within certain limits to the layer thickness of the layer to be modified or the actual separating layer. This makes it possible to limit impairments of the support layer by radiation-chemical degradation.
  • Such a low-energy accelerator can be integrated in a production line without complex biological screening.
  • a silicone membrane or silicone composite membrane which has been modified by radiation chemistry and can be used for ultrafiltration.
  • the radiation-chemical postcrosslinking can take place in a single and simple, highly productive process step without chemical additives or waste products, as well as at room temperature and without oxygen exclusion.
  • the radiation-chemical post-crosslinking gives the membranes a solvent stability which cannot be achieved by conventional chemical-thermal crosslinking processes.
  • This membrane was then irradiated with 69 kGy both under nitrogen atmosphere and from the air atmosphere.
  • the irradiated membranes achieved a retention of approx. 90% with a material flow of around 3 l / m 'h bar. This shows, among other things, that the influence of atmospheric oxygen during irradiation from the air atmosphere plays only an insignificant role in the doses used.
  • Unmodified PVDF / PDMS (8 ⁇ m) membranes were used to separate 1 g / 1 polyethyl englykol 1500 from toluene. This caused an irreversible destruction of these unmodified membranes.
  • PVDF / PDMS (12 ym) membranes were irradiated with 100 kGy from the air atmosphere. These irradiated membranes had a cut-off of approx. 800 g / mol when separating low molecular weight compounds from toluene. The material flow in this case was about 2.70 l / m * h bar. This shows that even in this case, expensive nitrogen inerting is not necessary.
  • PVDF / PDMS (1.5 ⁇ m) membranes were irradiated with 69 kGy. When these irradiated membranes were used to separate 1 g / 1 of polyethyl englykol 1500 from ethanol, retention of 96% was achieved with a material flow of 1.2 l / m 1 h bar. Similar values were achieved when the irradiated membranes were used in methanol.
  • Membranes from PVDF / PDMS (8 ⁇ m) composite systems were used, which were irradiated with 69 kGy from the air atmosphere.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne des membranes en silicone, en particulier en composite de silicone, qui ont été modifiées chimiquement par des rayonnements. Dans les solvants organiques testés, ces membranes soumises à des rayonnements se sont révélées stables et peuvent donc être employées, dans les procédés de séparation par membranes, pour séparer des composés de faible poids moléculaire contenus dans des solvants organiques.
PCT/DE1996/000336 1995-03-04 1996-02-29 Membrane en composite de silicone, modifiee chimiquement par des rayonnements, pour l'ultrafiltration WO1996027430A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19507584A DE19507584C2 (de) 1995-03-04 1995-03-04 Strahlenchemisch modifizierte Silikonkompositmembran für die Ultrafiltration
DE19507584.6 1995-03-04

Publications (1)

Publication Number Publication Date
WO1996027430A1 true WO1996027430A1 (fr) 1996-09-12

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1996/000336 WO1996027430A1 (fr) 1995-03-04 1996-02-29 Membrane en composite de silicone, modifiee chimiquement par des rayonnements, pour l'ultrafiltration

Country Status (2)

Country Link
DE (1) DE19507584C2 (fr)
WO (1) WO1996027430A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP2007014949A (ja) * 2005-07-05 2007-01-25 Gkss Forschungszentrum Geesthacht Gmbh 複合膜
WO2007050449A2 (fr) 2005-10-24 2007-05-03 Shell Internationale Research Maatschappij B.V. Procedes de production d'hydrocarbures alkyles a partir d'un liquide de procede de traitement thermique in situ
US7351873B2 (en) 2001-10-18 2008-04-01 Shell Oil Company Continuous process to separate colour bodies and/or asphalthenic contaminants from a hydrocarbon mixture
US8123946B2 (en) 2006-03-16 2012-02-28 Shell Oil Company Method and apparatus for removing metal sulphide particles from a liquid stream
EP2433702A1 (fr) 2010-09-27 2012-03-28 Shell Internationale Research Maatschappij B.V. Procédé pour la séparation d'inhibiteurs cinétiques à base de polymères d'hydrates
WO2012076532A1 (fr) 2010-12-08 2012-06-14 Shell Internationale Research Maatschappij B.V. Procédé pour purifier des carbonates contenant un groupe aryle
WO2012076519A1 (fr) 2010-12-08 2012-06-14 Shell Internationale Research Maatschappij B.V. Procédé pour purifier un carbonate de dialkyle
US8304564B2 (en) 2006-12-20 2012-11-06 Shell Oil Company Process for the removing poly(propylene oxide) from propylene oxide by membrane separation
US9034175B2 (en) 2007-03-27 2015-05-19 Shell Oil Company Method for reducing the mercury content of natural gas condensate and natural gas processing plant
WO2020069959A1 (fr) 2018-10-01 2020-04-09 Shell Internationale Research Maatschappij B.V. Processus d'élimination de fines de catalyseur par nanofiltration
WO2021058537A1 (fr) 2019-09-25 2021-04-01 Shell Internationale Research Maatschappij B.V. Procédé de réduction de dépôts d'injecteurs
WO2021099255A1 (fr) 2019-11-20 2021-05-27 Shell Internationale Research Maatschappij B.V. Procédé d'élimination de poly(oxyde de propylène) à partir d'oxyde de propylène par séparation membranaire

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DE102007033258A1 (de) 2007-07-17 2009-01-22 Schott Ag Verfahren zum Regenerieren verbrauchter Trennmedien zur erneuten Verwendung
DE102007048879A1 (de) 2007-10-11 2009-04-16 Schott Ag Wiederaufbereitung von fluiden Sägeslurries sowie deren Verwendung zur Herstellung von Wafern mit verbesserten Oberflächen
DE102009001230A1 (de) 2009-02-27 2010-09-02 Evonik Oxeno Gmbh Verfahren zur Abtrennung und teilweiser Rückführung von Übergangsmetallen bzw. deren katalytisch wirksamen Komplexverbindungen aus Prozessströmen
DE102009047351A1 (de) 2009-12-01 2011-06-09 Evonik Goldschmidt Gmbh Komposit-Siliconmembranen mit hoher Trennwirkung
DE102010025606A1 (de) 2010-06-30 2012-01-05 Schott Solar Ag Verfahren zur Wiederaufbereitung von verbrauchten Sägeflüssigkeiten aus der Herstellung von Siliziumwafern
DE102013200120A1 (de) 2013-01-08 2014-07-10 PolyAn Gesellschaft zur Herstellung von Polymeren für spezielle Anwendungen und Analytik mbH Verfahren zur Herstellung eines Kunststoffartikels mit hydrophober Pfropfbeschichtungsowie Kunststoffartikel
DE102014209421A1 (de) 2014-05-19 2015-11-19 Evonik Degussa Gmbh Membrangestützte Katalysatorabtrennung bei der Epoxidierung von cyclischen, ungesättigten C12-Verbindungen zum Beispiel Cyclododecen (CDEN)
DE102014209413A1 (de) 2014-05-19 2015-11-19 Evonik Degussa Gmbh Membrangestützte Katalysatorabtrennung bei der Epoxidierung von Fettsäurealkylestern
JP6824269B2 (ja) 2015-11-25 2021-02-03 エボニック オペレーションズ ゲーエムベーハー プロペンおよび過酸化水素から１，２−プロパンジオールを製造するための方法
TWI707847B (zh) 2015-11-26 2020-10-21 德商贏創運營有限公司 丙烯之環氧化方法
CN108430983B (zh) 2015-11-26 2022-02-22 赢创运营有限公司 用于丙烯的环氧化的方法和反应器
EA033968B1 (ru) 2015-11-26 2019-12-16 Эвоник Дегусса Гмбх Способ эпоксидирования олефина
HUE050560T2 (hu) 2016-01-19 2020-12-28 Evonik Operations Gmbh Eljárás olefin epoxidálására
EA035906B1 (ru) 2016-03-21 2020-08-28 Эвоник Оперейшнс Гмбх Способ эпоксидирования пропилена
EP3246323A1 (fr) 2016-05-17 2017-11-22 Evonik Degussa GmbH Procédé intégré pour la préparation d´oxyde de propéne sur la base de propane
EP3406603A1 (fr) 2017-05-22 2018-11-28 Evonik Degussa GmbH Procédé d'epoxydation de propène
US10890570B2 (en) * 2017-11-29 2021-01-12 Michigan Technological University Gas measurement device
EP3988524B1 (fr) 2020-10-21 2022-11-30 Evonik Operations GmbH Procédé de préparation de 1,2-propanediol
WO2023152083A1 (fr) 2022-02-11 2023-08-17 Evonik Operations Gmbh Procédé amélioré de production de 1,2-alcanediol à partir de l'alcène correspondant et de peroxyde d'hydrogène

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2763609A (en) * 1952-06-03 1956-09-18 Gen Electric Vulcanization of silicone rubber with high energy electrons
US3819772A (en) * 1973-02-23 1974-06-25 Us Health Education & Welfare Method of making thin defect-free silicone rubber films and membranes
EP0143552A2 (fr) * 1983-10-27 1985-06-05 Nitto Denko Corporation Membrane composite et son procédé de fabrication
JPS61107908A (ja) * 1984-10-30 1986-05-26 Nitto Electric Ind Co Ltd 複合半透膜の製造方法
EP0532199A1 (fr) * 1991-08-30 1993-03-17 Membrane Products Kiryat Weizmann Ltd. Membranes en silicone stables aux solvants

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5183887A (ja) * 1975-01-21 1976-07-22 Sumitomo Chemical Co Butsushitsubunryonohakumakuoseizosuruhoho
JPS58210805A (ja) * 1982-05-31 1983-12-08 Sumitomo Chem Co Ltd 半透膜の製造方法
SU1597207A1 (ru) * 1988-08-29 1990-10-07 Институт электроники им.У.А.Арифова Способ модификации полимерной мембраны из поливинилтриметилсилана

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2763609A (en) * 1952-06-03 1956-09-18 Gen Electric Vulcanization of silicone rubber with high energy electrons
US3819772A (en) * 1973-02-23 1974-06-25 Us Health Education & Welfare Method of making thin defect-free silicone rubber films and membranes
EP0143552A2 (fr) * 1983-10-27 1985-06-05 Nitto Denko Corporation Membrane composite et son procédé de fabrication
JPS61107908A (ja) * 1984-10-30 1986-05-26 Nitto Electric Ind Co Ltd 複合半透膜の製造方法
EP0532199A1 (fr) * 1991-08-30 1993-03-17 Membrane Products Kiryat Weizmann Ltd. Membranes en silicone stables aux solvants

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 106, no. 10, 9 March 1987, Columbus, Ohio, US; abstract no. 68416 *
DATABASE WPI Section Ch Week 8627, Derwent World Patents Index; Class A88, AN 86-173886 *
NORIHIKO MINOURA: "Permeability of Irradiated Silicone Rubber Membranes to Gases", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 22, no. 3, 1978, NEW-YORK, US, pages 833 - 836, XP002006499 *
PATENT ABSTRACTS OF JAPAN vol. 10, no. 292 (C - 376) 3 October 1986 (1986-10-03) *

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US7351873B2 (en) 2001-10-18 2008-04-01 Shell Oil Company Continuous process to separate colour bodies and/or asphalthenic contaminants from a hydrocarbon mixture
JP2007014949A (ja) * 2005-07-05 2007-01-25 Gkss Forschungszentrum Geesthacht Gmbh 複合膜
US7601263B2 (en) 2005-07-05 2009-10-13 Gkss-Forschungszentrum Geesthacht Gmbh Composite membrane and process
WO2007050449A2 (fr) 2005-10-24 2007-05-03 Shell Internationale Research Maatschappij B.V. Procedes de production d'hydrocarbures alkyles a partir d'un liquide de procede de traitement thermique in situ
WO2007050450A2 (fr) 2005-10-24 2007-05-03 Shell Internationale Research Maatschappij B.V. Procedes de craquage d'un produit brut pour obtenir des produits bruts additionnels
US8123946B2 (en) 2006-03-16 2012-02-28 Shell Oil Company Method and apparatus for removing metal sulphide particles from a liquid stream
US8304564B2 (en) 2006-12-20 2012-11-06 Shell Oil Company Process for the removing poly(propylene oxide) from propylene oxide by membrane separation
US9034175B2 (en) 2007-03-27 2015-05-19 Shell Oil Company Method for reducing the mercury content of natural gas condensate and natural gas processing plant
EP2433702A1 (fr) 2010-09-27 2012-03-28 Shell Internationale Research Maatschappij B.V. Procédé pour la séparation d'inhibiteurs cinétiques à base de polymères d'hydrates
WO2012076532A1 (fr) 2010-12-08 2012-06-14 Shell Internationale Research Maatschappij B.V. Procédé pour purifier des carbonates contenant un groupe aryle
WO2012076519A1 (fr) 2010-12-08 2012-06-14 Shell Internationale Research Maatschappij B.V. Procédé pour purifier un carbonate de dialkyle
WO2020069959A1 (fr) 2018-10-01 2020-04-09 Shell Internationale Research Maatschappij B.V. Processus d'élimination de fines de catalyseur par nanofiltration
WO2021058537A1 (fr) 2019-09-25 2021-04-01 Shell Internationale Research Maatschappij B.V. Procédé de réduction de dépôts d'injecteurs
WO2021099255A1 (fr) 2019-11-20 2021-05-27 Shell Internationale Research Maatschappij B.V. Procédé d'élimination de poly(oxyde de propylène) à partir d'oxyde de propylène par séparation membranaire

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Publication number Publication date
DE19507584C2 (de) 1997-06-12
DE19507584A1 (de) 1996-09-12

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