WO2000013768A1 - Membrane de verre supportée pour une séparation des gaz - Google Patents

Membrane de verre supportée pour une séparation des gaz Download PDF

Info

Publication number
WO2000013768A1
WO2000013768A1 PCT/US1999/020913 US9920913W WO0013768A1 WO 2000013768 A1 WO2000013768 A1 WO 2000013768A1 US 9920913 W US9920913 W US 9920913W WO 0013768 A1 WO0013768 A1 WO 0013768A1
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WO
WIPO (PCT)
Prior art keywords
glass
porous
support
suspension
coating
Prior art date
Application number
PCT/US1999/020913
Other languages
English (en)
Inventor
George Gavalas
Huanting Wang
Original Assignee
California Institute Of Technology
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 California Institute Of Technology filed Critical California Institute Of Technology
Publication of WO2000013768A1 publication Critical patent/WO2000013768A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
    • C03C11/005—Multi-cellular glass ; Porous or hollow glass or glass particles obtained by leaching after a phase separation step
    • 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
    • B01D53/228—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 characterised by specific membranes
    • 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
    • B01D71/02—Inorganic material
    • B01D71/04—Glass
    • 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
    • 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

  • Membranes can be used to separate gases. Membranes have certain advantages when used for gas separation, because of their low energy consumption and their suitability for small volume as well as large volume applications. At present, the commercially-used gas separation membranes are polymeric in hollow fiber or spiral wound geometries.
  • Inorganic gas separation membranes have certain additional advantages including the ability to operate at elevated temperatures. This ability is essential in certain integrated membrane reactor assemblies. These membranes are also capable of higher separation selectivity than polymeric membranes for certain gas mixtures.
  • Inorganic membranes are made in unsupported form or supported form.
  • Unsupported membranes are tubes, hollow fibers, or plates wherein the entire thickness of the membrane possesses the separation property.
  • Supported membranes consist of a thin layer of the material that provides the separation property deposited on a porous ceramic support.
  • the support can be, for example, a tube or plate that provides the mechanical strength.
  • the ceramic support is often porous alumina, although other materials have been used.
  • the supported form provides high productivity and mechanical strength. The cost of the ceramic support and the steps of depositing the layer often increase the cost of supported inorganic membranes as compared with the polymeric membranes .
  • Membrane productivity is quantified by the permeance Q, which for a gas i is defined as
  • Membrane selectivity refers to the relative permeation rate of two or more gases.
  • the ratio of the permeances of two gases, Qi/Qj , measured one gas at a time, is often called the ideal selectivity or ideal separation factor. More important is the permeance ratio measured for two gases in a mixture, for which we will use the term mixture selectivity, or simply, selectivity, to distinguish it from the ideal selectivity.
  • the mixture selectivity is the relevant property in regard to actual applications.
  • the function of a membrane is to separate the feed gas into two streams. One stream, usually called the permeate gas, consists of the gas that permeated through the membrane and is enriched in the components that have higher selectivity.
  • the other stream is enriched in the components that have lower selectivity.
  • Membrane properties generally depend on temperature, total pressure and mixture composition. Under conditions of sufficiently low pressure and/or sufficiently high temperature, the permeance and selectivity become independent of total pressure and composition. Permeation is then said to take place in the Henry's Law regime.
  • Inorganic membranes can be classified as dense or microporous .
  • Dense membranes made of palladium and other metals are very selective to hydrogen permeation.
  • Other dense membranes are made of ion conducting perovskite or other complex oxides and can be selective to oxygen permeation.
  • Dense silica membranes selective to hydrogen permeation have also been fabricated.
  • Microporous silica, carbon and zeolite membranes have been developed that are suitable for a variety of separations, important examples of which are carbon dioxide - methane, olefin-para fin and branched alkanes-straight chain alkanes. Carbon membranes are also suitable for oxygen-nitrogen separation.
  • Microporous silica membranes have been studied extensively because of their wide applicability.
  • a common type of supported microporous silica membrane is made by coating a mesoporous support having pore diameter of about 50nm with a polymeric silica solution followed by drying and calcination.
  • a type of unsupported microporous silica membranes is made in the shape of hollow fibers that are typically about 50-100 ⁇ m outside diameter and 5-25 ⁇ m wall thickness. Membranes of this type are described in U.S. Patent Nos . 4,842,620 and 4,853,001. These microporous glass fibers are made by extrusion of a borosilicate glass melt containing Si0 2 , B 2 0 3 , and Na 2 0 with possibly smaller quantities of other oxides like A1 2 0 3 and Zr0 2 .
  • the membranes of the present invention provide very high selectivity for CH 4 , and low selectivity for C0 2 in the separation of CH 4 -C0 2 mixtures, in contrast with the membranes described in patents 4,842,620 and 4,853,001, and other membranes reported in the technical literature, that have high selectivity for carbon dioxide.
  • the membranes of the present invention is especially useful in separating methane from natural gas that contains large quantities of carbon dioxide where it is desired that methane is removed as the permeate gas and most of carbon dioxide remains in the retentate gas .
  • Figures 1A -IE show steps of forming the gas separation membrane;
  • Figures 2 and 3 show an elemental composition profile; and Figure 4 shows a graph of gas selectivity based on a function of sintering temperature.
  • Certain glass compositions form a single phase at sufficiently high temperatures, but upon cooling to some intermediate temperature and kept at that temperature for a certain length of time (annealing) separate into two intertwined phases.
  • the sizes of the domains of the phases depend on the glass composition and the temperature and duration of annealing.
  • One of the two phases is soluble in acid solutions, while the other phase is insoluble.
  • the phase-separated glass is leached in an acid solution to remove the acid-soluble phase. This leaves behind a porous glass that is only of the insoluble phase. Increasing the temperature and duration of annealing increases the size of the domains of the two phases, and therefore, increases the pore size of the glass obtained after leaching.
  • This technique is used in the Corning Vycor process typically to produce porous glass with pore diameters of 3-10nm. Diffusion in such pores follows approximately the Knudsen relation, where the permeation rate is inversely proportional to the square root of the molecular weight.
  • The, resulting selectivity is low and has not been of practical interest in gas separations like those of 0 2 -N 2 and CH 4 -C0 2 mixtures . To improve the selectivity, it is necessary to decrease the pore size.
  • the present application describes a new type of glass membrane which has small pore size and modified chemical composition.
  • the membrane has unique separation properties described in the Summary. Since these membranes are supported, they have good mechanical strength.
  • FIGs. 1A-1E show the steps of the process for forming the preferred system of the present application.
  • FIG. 1A shows the porous alumina tube 100 that is used as the membrane support.
  • a glass of a phase-separable composition is first ball-milled in a solvent to form a suspension of micron-sized particles.
  • a thin layer of these glass particles 102 is formed on one of the two cylindrical surfaces (inside or outside) of the tube 100 by dip coating.
  • FIG. IB shows the glass particle layer 102 deposited on the inside surface. The suspension viscosity and content of the glass, and speed of withdrawal can be used to adjust the thickness of the particle layer.
  • the coated tube is inserted for a few minutes into a furnace that is preheated to a temperature between 750 and 1200DC.
  • This heating treatment is used to sinter or melt the particle coating into a substantially continuous layer.
  • the particles melt or sinter, depending on temperature, into a smooth non-porous coating of glass.
  • the furnace temperature is preferably sufficiently high to cause sintering of the particles but not as high as to form a low viscosity melt that will penetrate into the pores by capillarity. Raising the sintering temperature also increases the extent of alumina dissolution into the melt.
  • Fig. 1C shows an optional step of heating/annealing the glass in order to enhance phase separation of the glass.
  • This heating/annealing step is carried out at 500-600DC for a specified length of time.
  • the coating is the phase-separated glass layer 110 shown in FIG. ID. It has been found that increasing the annealing temperature and time increases the pore size of the final membrane. A smaller pore size is obtained when there is no annealing step whatsoever.
  • the device is then leached with an acid solution shown in FIG. IE to remove some of the soluble components, principally boron oxide and sodium oxide. This removal makes the coating porous .
  • the extent of removal of boron oxide and sodium oxide during the leaching step can be reduced by one of the following methods, singly or in combination: eliminating the annealing step, reducing the severity of leaching, or introducing alumina into the melt.
  • the severity of leaching is determined by the temperature, duration and acid strength employed. Longer leaching, stronger acid, and higher temperature cause more extensive removal of boron oxide and sodium oxide and vice versa.
  • Alumina can be introduced by adding alumina powder in the original particle suspension. Alumina that is dissolved in the glass coating during the melting/sintering step has the same effect, namely to restrict the removal of sodium oxide and boron oxide solubilization during leaching.
  • the membranes were tested in a permeation cell.
  • One of the two sides, “the feed side”, of the membrane is exposed to the feed gas mixture, e.g. CH 4 -C0 2 .
  • the other side, “the permeate side” is exposed to a flow of helium gas.
  • the permeate gas is channeled to a gas chromatograph with a thermal conductivity detector.
  • PVB polyvinylbutyral
  • the particle loading of the suspension was 10%.
  • a porous ⁇ -Al 2 0 3 tube (ID 6mm, OD 9mm, mean pore diameter 0.2 ⁇ m)
  • EXAMPLE 2 A support tube was coated with the same suspension as in Example 1. After drying the tube was inserted for 15 minutes in a furnace preheated to 1100DC and then cooled in ambient air. The tube was subsequently annealed at 400DC for 2 hours and then leached for 3 hours at 90DC in 1 N HCl solution. The permeation results obtained with this membrane are also listed in Table 1.
  • a support tube was coated with the same suspension as in Example 1. After drying it was inserted in a furnace preheated to 1000DC for 30 minutes and then cooled in ambient air. The tube was then leached for 2 hours at 90DC in 1 N HCl solution. The permeation results obtained for this tube are included in Table 1.
  • a support tube was coated with the same suspension as in Example 1. After drying it was inserted in a furnace preheated to 1100DC for 30 minutes and then cooled in ambient air. The tube was then leached for 1.5 hours at 90DC in 1 N HCl solution. The permeation results obtained for this tube are included in
  • a support tube was coated with a suspension containing 5% glass particles but otherwise being identical to that of Example 1. After drying it was inserted in a furnace preheated to 1150DC for 15 minutes and then cooled in ambient air. The tube was then leached for 1 hour at 90DC in 1 N HCl solution and subsequently kept in water for 10 hours. The permeation results obtained for this tube are included in Table 1.
  • a support tube was coated with a suspension containing identical to that of example 4. After drying it was inserted in a furnace preheated at 800°C for 15 minutes and then cooled in ambient air. The tube was then leached for 15 minutes in I N HCl solution and subsequently kept in water for 10 hours.
  • the permeation results are included in Table 1. Effect of Sintering Tempera ture on Residual Sodium and Boron Content
  • the elemental composition of the cross sections of glass membranes prepared by sintering at 800°C or at 1100°C and leached at 90°C in 1 N HCl for 15 minutes or 1 hour was measured by electron microprobe analysis.
  • the elemental composition is plotted in Figures 2 and 3 in terms of the boron to silicon and sodium to silicon molar ratios versus distance from the outer surface of the membrane. The results show that the boron and sodium contents increase with distance and are higher at the higher sintering temperature. These results are explained by the effect of dissolved alumina which increases as the glass support interface is approached (increasing distance from the surface) and is also higher at the higher sintering temperature.
  • a series of membranes were prepared according to the procedure of Example 6 except that the leaching time and sintering temperature was varied. The results are shown in Figure 4. As shown in the figure at sintering temperatures below 900°C, a lower leaching time is needed to achieve high selectivity .
  • FIG. 5 shows the permeance and selectivity of the membrane of Example 4 versus composition of the feed gas at a total feed gas pressure of 1 atm.
  • the selectivity is very high at low CH 4 content and declines with increasing CH 4 content.
  • a membrane was prepared according to the procedure of example 6 except that instead of using an alumina tube, a porous Yttria-stabilized Zirconia disk was used.
  • a porous Yttria-stabilized Zirconia disk was used.
  • 150°C was 30 and 110 respectively.
  • alumina is not a necessary ingredient of the membranes and other materials can be used as membrane supports.

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

Abstract

L'invention concerne un élément permettant de séparer des gaz. Un tube en alumine poreuse (100) est revêtu d'une couche de particules de verre mélangées (102), cette couche étant recuite afin de provoquer une séparation des phases. La couche de verre à phases séparées (110) est ensuite soumise à une lixivation acide afin d'éliminer l'une desdites phases, la phase restante étant poreuse et utilisée comme membrane de séparation des gaz supportée.
PCT/US1999/020913 1998-09-09 1999-09-09 Membrane de verre supportée pour une séparation des gaz WO2000013768A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US9961398P 1998-09-09 1998-09-09
US60/099,613 1998-09-09
US12308299P 1999-03-04 1999-03-04
US60/123,082 1999-03-04

Publications (1)

Publication Number Publication Date
WO2000013768A1 true WO2000013768A1 (fr) 2000-03-16

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008106038A1 (fr) * 2007-02-28 2008-09-04 Corning Incorporated Structures de verre extrudées, et leurs procédés de fabrication
WO2013073106A1 (fr) * 2011-11-18 2013-05-23 Canon Kabushiki Kaisha Procédé de fabrication d'un élément optique et procédé de fabrication d'un appareil de capture d'image
WO2013073150A3 (fr) * 2011-11-18 2013-06-27 Canon Kabushiki Kaisha Élément optique, appareil de capture d'image, et procédé de fabrication dudit élément optique
EP2891641A1 (fr) * 2014-01-02 2015-07-08 Denk Aqua GmbH Corps poreux ayant une surface spécifique agrandie et procédé de fabrication d'un tel corps poreux
US9212088B2 (en) 2011-12-15 2015-12-15 Canon Kabushiki Kaisha Method for manufacturing optical member
CN109020167A (zh) * 2017-06-09 2018-12-18 河北卓达建材研究院有限公司 一种提高棕色泡沫玻璃气孔率的方法
CN109020237A (zh) * 2017-06-09 2018-12-18 河北卓达建材研究院有限公司 一种原位提高白色泡沫玻璃气孔率的方法
CN109020193A (zh) * 2017-06-09 2018-12-18 河北卓达建材研究院有限公司 一种降低棕色泡沫玻璃密度的方法
CN109020242A (zh) * 2017-06-09 2018-12-18 河北卓达建材研究院有限公司 一种轻质棕色泡沫玻璃的制备方法
CN109020234A (zh) * 2017-06-09 2018-12-18 河北卓达建材研究院有限公司 一种彩色泡沫玻璃的制备方法
WO2019076740A1 (fr) 2017-10-19 2019-04-25 Sartorius Stedim Biotech Gmbh Procédé de fabrication d'une membrane polymère monocouche poreuse, membrane polymère monocouche poreuse et utilisation de cette membrane à des fins de filtration

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3600147A (en) * 1970-01-02 1971-08-17 Charles L Mckinnis Method of making a glass semipermeable membrane
US4220461A (en) * 1978-04-06 1980-09-02 Mrinmay Samanta Low temperature synthesis of vitreous bodies and their intermediates
US4395271A (en) * 1979-04-13 1983-07-26 Corning Glass Works Method for making porous magnetic glass and crystal-containing structures
US4853001A (en) * 1986-06-06 1989-08-01 Ppg Industries, Inc. Porous inorganic siliceous-containing gas enriching material and process of manufacture and use
US4966613A (en) * 1984-11-30 1990-10-30 Ppg Industries, Inc. Method of producing effective porous glass shapes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3600147A (en) * 1970-01-02 1971-08-17 Charles L Mckinnis Method of making a glass semipermeable membrane
US4220461A (en) * 1978-04-06 1980-09-02 Mrinmay Samanta Low temperature synthesis of vitreous bodies and their intermediates
US4395271A (en) * 1979-04-13 1983-07-26 Corning Glass Works Method for making porous magnetic glass and crystal-containing structures
US4966613A (en) * 1984-11-30 1990-10-30 Ppg Industries, Inc. Method of producing effective porous glass shapes
US4853001A (en) * 1986-06-06 1989-08-01 Ppg Industries, Inc. Porous inorganic siliceous-containing gas enriching material and process of manufacture and use

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008106038A1 (fr) * 2007-02-28 2008-09-04 Corning Incorporated Structures de verre extrudées, et leurs procédés de fabrication
US8302428B2 (en) 2007-02-28 2012-11-06 Corning Incorporated Extruded glass structures and methods for manufacturing the same
US9517969B2 (en) 2011-11-18 2016-12-13 Canon Kabushiki Kaisha Method for manufacturing a porous glass film
WO2013073150A3 (fr) * 2011-11-18 2013-06-27 Canon Kabushiki Kaisha Élément optique, appareil de capture d'image, et procédé de fabrication dudit élément optique
CN103946172A (zh) * 2011-11-18 2014-07-23 佳能株式会社 光学部件、摄像装置和光学部件的制造方法
US9487436B2 (en) 2011-11-18 2016-11-08 Canon Kabushiki Kaisha Optical member, image pickup apparatus, and method for manufacturing optical member
WO2013073106A1 (fr) * 2011-11-18 2013-05-23 Canon Kabushiki Kaisha Procédé de fabrication d'un élément optique et procédé de fabrication d'un appareil de capture d'image
US9212088B2 (en) 2011-12-15 2015-12-15 Canon Kabushiki Kaisha Method for manufacturing optical member
EP2891641A1 (fr) * 2014-01-02 2015-07-08 Denk Aqua GmbH Corps poreux ayant une surface spécifique agrandie et procédé de fabrication d'un tel corps poreux
CN109020167A (zh) * 2017-06-09 2018-12-18 河北卓达建材研究院有限公司 一种提高棕色泡沫玻璃气孔率的方法
CN109020237A (zh) * 2017-06-09 2018-12-18 河北卓达建材研究院有限公司 一种原位提高白色泡沫玻璃气孔率的方法
CN109020193A (zh) * 2017-06-09 2018-12-18 河北卓达建材研究院有限公司 一种降低棕色泡沫玻璃密度的方法
CN109020242A (zh) * 2017-06-09 2018-12-18 河北卓达建材研究院有限公司 一种轻质棕色泡沫玻璃的制备方法
CN109020234A (zh) * 2017-06-09 2018-12-18 河北卓达建材研究院有限公司 一种彩色泡沫玻璃的制备方法
WO2019076740A1 (fr) 2017-10-19 2019-04-25 Sartorius Stedim Biotech Gmbh Procédé de fabrication d'une membrane polymère monocouche poreuse, membrane polymère monocouche poreuse et utilisation de cette membrane à des fins de filtration
DE102017009784A1 (de) 2017-10-19 2019-04-25 Sartorius Stedim Biotech Gmbh Verfahren zur Herstellung einer porösen einlagigen Polymermembran, poröse einlagige Polymermembran und Verwendung derselben zur Filtration
US11529589B2 (en) 2017-10-19 2022-12-20 Sartorius Stedim Biotech Gmbh Method for producing a porous monolayer polymer membrane, porous monolayer polymer membrane, and use thereof for filtration

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