WO1992011918A1 - Membrane process and apparatus for removing a component from a fluid stream - Google Patents

Membrane process and apparatus for removing a component from a fluid stream Download PDF

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Publication number
WO1992011918A1
WO1992011918A1 PCT/US1991/009301 US9109301W WO9211918A1 WO 1992011918 A1 WO1992011918 A1 WO 1992011918A1 US 9109301 W US9109301 W US 9109301W WO 9211918 A1 WO9211918 A1 WO 9211918A1
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WO
WIPO (PCT)
Prior art keywords
stream
vapor
unit
membrane
pressure
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.)
Ceased
Application number
PCT/US1991/009301
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English (en)
French (fr)
Inventor
Johannes G. Wijmans
Jürgen Kaschemekat
Richard W. Baker
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.)
Membrane Technology and Research Inc
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Membrane Technology and Research Inc
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 Membrane Technology and Research Inc filed Critical Membrane Technology and Research Inc
Priority to JP50333692A priority Critical patent/JP2002517161A/ja
Publication of WO1992011918A1 publication Critical patent/WO1992011918A1/en
Anticipated expiration legal-status Critical
Ceased 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
    • B01D53/225—Multiple stage 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
    • B01D53/22—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)

Definitions

  • ammonia or organic vapors arise from numerous industrial and commercial processes.
  • One method of removing the vapor from the gas stream is by means of a membrane
  • a typical membrane vapor separation system includes a membrane unit, a pump
  • step depends on the vapor/liquid equilibrium at the operating conditions under which the condensation is performed. It is frequently the case that the condenser vent gas contains
  • vent gas is often
  • the feed gas contains 2%
  • the vapor-enriched stream from the membrane separation step contains 20% vapor
  • This stage can be designed to produce a discharge stream with a
  • decanter or other recovery unit may be passed to the feed side of the pervaporation unit
  • feed solution can give rise to problems similar to those discussed above for gas or vapor
  • the invention is a vapor recovery system and process that permits condenser vent
  • a small auxiliary membrane module or set of modules is installed
  • This module takes as its feed the vent gas from the condenser, and returns a vapor-enriched
  • the module can be sized to
  • This discharge stream may then be mixed with the feed without
  • the invention is a system and process that combines membrane
  • recovery process could be an extraction process, a physical or chemical absorption process
  • waste gas from the recovery process is waste gas from the recovery process
  • the invention is a system and process that combines pervaporation with any-
  • auxiliary membrane module or set of modules, before returning to the main pervaporation unit or elsewhere.
  • auxiliary module(s) may be different from those in the gas separation embodiments.
  • auxiliary module(s) may be provided by the main condenser.
  • the auxiliary module(s) may be provided by the main condenser.
  • the auxiliary module(s) may be provided by the main condenser.
  • module(s) may be installed across the recovery unit only and provided with their own
  • Figure 1 is a schematic drawing showing a membrane separation process carried out with
  • a system including a main membrane unit, a pump, a condenser and an auxiliary
  • Figure 2 is a schematic drawing showing a membrane separation process carried out with
  • a system including a main membrane unit, a pump, a compressor, a condenser and an
  • FIG 3 is a schematic drawing showing a membrane separation process carried out with a system including a compressor, a main membrane unit, a condenser and an auxiliary
  • Figure 4 is a graph showing membrane area and pump capacity required to reduce the
  • Figure 5 is a schematic drawing showing a pervaporation/purification process carried out
  • a system including a main pervaporation unit, a condenser, a recovery or further
  • Figure 6 is a schematic drawing showing a pervaporation/purification process carried out
  • a system including a main pervaporation unit, a condenser, a recovery or further
  • vapor refers to a liquefiable component of a gas stream.
  • a feed gas stream containing a vapor is passed
  • the vapor may be of an organic compound or mixture of compounds, such as a hydrocarbon, a halogenated
  • hydrocarbon or the like or an inorganic compound, such as water, sulfur dioxide,
  • the other component or components of the feed gas stream may be other vapors
  • FIG. 1 A basic embodiment of the invention is shown in Figure 1. Referring to this
  • a vapor-containing feed gas stream, 1 passes to a membrane separation unit, 2,
  • the membrane separation step normally involves
  • the membrane may take the form of a homogeneous membrane, a membrane
  • the first is a composite membrane
  • the second is an asymmetric membrane in which the thin
  • Such membranes include U.S. Patents 2,243,701; 4,553,983; 4,230,463; and 4,840,646.
  • Spiral-wound modules are a preferred
  • the membranes may be configured as microporous hollow fibers
  • the driving force for membrane permeation is the pressure difference between the
  • the pressure drop across the membrane can be achieved by
  • a vacuum pump 5 is used to lower the pressure on the permeate side.
  • Stream, 6, from the vacuum pump is subjected to a condensation step.
  • Stream, 6, from the vacuum pump is subjected to a condensation step.
  • the condensation step may involve chilling, compression or a combination of these.
  • condenser may be water cooled, or may employ refrigerants that can take the gas down to lower temperatures, and produces a stream, 8, of liquified vapor.
  • condensation depends on the vapor concentration, the vapor/liquid equilibrium and the
  • the non-condensed gas fraction, 9, emerging from the condenser contains a higher
  • vapor concentration than the feed gas may contain a concentration as high as five
  • This condenser vent gas is passed
  • auxiliary membrane module or modules 10 which, like the main membrane
  • membrane area required for the auxiliary module is small compared with the main unit.
  • the auxiliary module, 10 is connected on its permeate side upstream of the vacuum
  • the residue stream, 11, from the auxiliary unit is recirculated to the feed side of the main membrane unit.
  • concentration of vapor in the stream 11 depends on the
  • the membrane area contained in the auxiliary module.
  • the membrane area is such
  • stream 11 should have a concentration about the same as stream 1.
  • a vapor-containing feed gas stream, 21, passes to a membrane separation
  • the driving force for membrane permeation is provided by a
  • step involves both compression and chilling.
  • the vapor-enriched stream, 26, passes to
  • the non-condensed gas fraction, 31, is passed through an auxiliary membrane
  • the driving force for auxiliary membrane -permeation is
  • the concentrated vapor stream, 34, from the auxiliary module joins with vapor-enriched stream, 24, from the main membrane unit and passes again through the vacuum pump, compressor and condenser.
  • the concentration of vapor in stream 33 may be tailored as discussed above. In this
  • feed gas stream, 41 passes to a compressor, 42.
  • membrane separation unit, 44 containing one or more membranes.
  • the permeate side of the membrane is at, or close to, atmospheric
  • pressurized stream, 48 It is then condensed in condenser, 49, and produces a stream, 50,
  • the non-condensed gas fraction, 51 is passed through an auxiliary membrane
  • the concentrated vapor stream, 54, from the auxiliary module joins with
  • the concentration of vapor in stream 53 may
  • Figures 1 , 2 and 3 all show a one-stage main membrane unit. However, it will be
  • multiple membrane stages or steps such as a two-step system, a two-stage system or other
  • Figures 1, 2 and 3 all show processes in which the residue stream from the
  • auxiliary module(s) is recirculated to the feed side of the main membrane unit.
  • auxiliary modu!e(s) can be tailored to achieve a residue
  • Figures 5 and 6 show embodiments of the invention as it relates to pervaporation.
  • the first is evaporation of the feed liquid to form a hypothetical saturated
  • permeate side vapor pressure can be reduced, for example, by drawing a vacuum on the
  • feed solution may also be heated to raise the vapor pressure on the feed side.
  • Figure 5 shows a pervaporation embodiment that corresponds to the gas separation
  • condenser provides a recovery step from which the purified condensate is removed and
  • a pervaporation unit, 102 containing one or more membranes.
  • solution 101 is warmed before entering the
  • the pervaporation step normally involves running the
  • That component is concentrated in the vapor stream, 104, permeating the
  • the membrane may take any of the membrane
  • nitrile rubber neoprene, polydimethylsiloxane (silicone rubber), chlorosulfonated
  • polyethylene polysilicone-carbonate copolymers, fluororelastomers, plasticized pol vinylchloride, polyurethane, cis-polybutadiene, cis-polyisoprene, poly(butene-l),
  • polystyrene-butadiene copolymers styrene/butadiene/styrene block copolymers
  • membrane materials among others, might be used: polyvinylalcohol, cellulose and
  • ethylcellulose ethylcellulose, chitosan, crosslinked alginic acid, and ion-exchange membranes, such as
  • membrane materials among others, might be used: polyamides, cellulose and derivatives,
  • cellulose diacetate such as cellulose diacetate, cellulose triacetate, cellulose nitrate and ethylcellulose.
  • the form of the module containing the membrane may be any material.
  • the form of the module containing the membrane may be any material.
  • Liquid stream, 106, from the condenser passes to the
  • recovery, second separation or further purification unit, 107 A variety of techniques can be used to further purify the condensed permeate. If the content of the permeate and the
  • the permeate may form two phases,
  • stream 108 represents the stream rich in the desired component
  • stream 108 would be the organic-rich stream and stream 109 would be the residual
  • stream 109 may be very different from that of incoming feed stream 101.
  • Stream 109
  • organic may be saturated with organic, for example.
  • the non-product stream, 109 is passed through an auxiliary pervaporation module
  • stream 109 is heated to increase
  • module, 110 is connected on its permeate side upstream of the condenser, 105.
  • composition of stream 111 depends on the membrane area contained in the auxiliary module.
  • the membrane area is such that there is not a big difference
  • stream 111 should
  • the system may also include a
  • purification unit handles the condensates from both condensers. Other optional
  • recovery unit may serve both condensers. Less desirably, separate pumps may be provided
  • a pervaporation unit, 202 containing one or more membranes.
  • pervaporation step normally involves running the feed solution across a membrane that is
  • permeating, stream, 203 is correspondingly depleted in the component.
  • the solution may be heated before entering the pervaporation
  • the membranes and modules may be chosen and configured according to the same
  • condenser, 205 which liquefies the permeating vapor and
  • the condenser passes to the recovery or further purification unit, 207, which, as in Figure
  • Stream 208 represents the stream rich in
  • stream 209 represents the non-product stream.
  • Stream 209 is
  • stream 209 is heated to increase the feed side vapor pressure.
  • auxiliary module, 210 is connected on its permeate
  • module passes through condenser, 213, emerging as liquid stream, 214, which in turn
  • liquid contains three components of differing physical properties, such as a hydrophobic
  • main pervaporation unit includes
  • multiple membrane stages or steps such as a two-step system, a two-stage system or other
  • FIGS 5 and 6 show processes in which the residue stream from the auxiliary
  • auxiliary module(s) can be tailored to achive a residue stream concentration
  • FIGs 5 and 6 show systems and processes in which a driving means for
  • a vacuum pump combined with a condenser, an eductor or any other means
  • the membranes used in the main pervaporation unit and
  • auxiliary modules are of the same type, selective to the component that is to be separated.
  • useful embodiments are also possible using membranes of unlike
  • VOCs volatile organic compounds
  • halogenated hydrocarbons particularly halogenated hydrocarbons or aromatic
  • Examples 1-3 compare the removal of a condensable vapor from a feed stream
  • auxiliary module or modules are computer calculations, performed using
  • the feed stream has a
  • chlorinated or fluorinated organic solvents from air or nitrogen, sulfur
  • the examples are in three groups.
  • the Group I examples assume a feed
  • the Group 2 examples also achieve 75% removal, from 4% vapor in the feed to 1% in the residue.
  • the Group 3 examples achieve
  • the pressure on the permeate side of the main membrane unit was set to 2 cmHg
  • Example 1A The calculations described in Example 1A were repeated using a system design as
  • the membrane area needed for the process and system of the invention is
  • the pump capacity is 71%.
  • the membrane area needed for the process and system of the invention is 76% of that needed
  • Example 2A The calculations described in Example 2A were repeated using a system design as
  • the membrane area needed for the process and system of the invention is
  • membrane area needed for the process and system of the invention is 90% of that needed
  • Feed concentration 5% vapor Feed pressure: 80 cmHg
  • Feed flow rate 100 scfm Membrane selectivity: 40 Residue concentration: 0.5% Condenser vent gas concentration: 20%
  • Example 3A The calculations described in Example 3A were repeated using a system design as
  • Feed concentration 5% vapor Feed pressure: 80 cmHg Feed flow rate: 100 scfm Membrane selectivity: 40 Residue concentration: 0.5% Condenser vent gas concentration: 20%
  • the membrane area needed for the process and system of the invention is 88%
  • the permeate pressure is 5 cmHg, the membrane area needed for the process and system
  • the membrane area of the invention is 91% of that needed for a conventional one-stage system, and the pump capacity is 91%.
  • the permeate pressure is 2 cmHg or 1 cmHg, the membrane area
  • needed for the process and system of the invention is about 95% of that needed for a
  • Example 4 compares the performance
  • Example 6 demonstrates the use of unlike membranes in the
  • main pervaporation unit and the auxiliary modules.
  • Example A Single-stage pervaporation unit not in accordance with the invention.
  • the condensed permeate stream is passed to the decanter for phase
  • the aqueous phase from the decanter is saturated with benzene at a
  • Example B Single-stage pervaporation unit with auxiliary modules
  • Example 4A The calculations described in Example 4A were repeated using a system
  • the separation is 10.1 m 2 .
  • main pervaporation unit is passed to the decanter for phase separation.
  • aqueous phase from the decanter is saturated with benzene at a concentration of
  • the auxiliary module is reduced to a concentration of 20 ppm and mixed with the
  • the system of the invention is improved compared with the performance of a
  • aqueous stream from the decanter is to increase the concentration of the feed to
  • Example A Single-stage pervaporation unit not in accordance with the invention.
  • the condensed permeate stream is passed to the decanter for each case.
  • the aqueous phase from the decanter is saturated with benzene
  • Example B Single-stage pervaporation unit with auxiliary modules
  • Example 5A The calculations described in Example 5A were repeated using a system
  • the separation is 10.1 m 2 .
  • main pervaporation unit is passed to the decanter for phase separation.
  • aqueous phase from the decanter is saturated with benzene at a concentration of
  • module is passed to an auxiliary condenser and thence to the decanter.
  • the main pervaporation unit, 102 was assumed to contain a water-
  • the water-enriched permeate, 104, from the pervaporation unit is passed to the
  • the decanter is passed to the auxiliary module, 110, which contains a butanol-
  • the residue. III, from this membrane can be discharged.
  • the permeate. 1 1 . is
  • compositions of the invention can be mixed with the incoming raw solution, 101, or could be passed to a second auxiliary module containing a water-selective membrane.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
PCT/US1991/009301 1990-12-28 1991-12-06 Membrane process and apparatus for removing a component from a fluid stream Ceased WO1992011918A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP50333692A JP2002517161A (ja) 1990-12-28 1991-12-06 流体流から成分を除去するための薄膜方法および装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/635,919 US5071451A (en) 1990-12-28 1990-12-28 Membrane process and apparatus for removing vapors from gas streams
US635,919 1990-12-28

Publications (1)

Publication Number Publication Date
WO1992011918A1 true WO1992011918A1 (en) 1992-07-23

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US (1) US5071451A (enExample)
EP (1) EP0564563A1 (enExample)
JP (2) JPH04277007A (enExample)
WO (1) WO1992011918A1 (enExample)

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US5071451A (en) 1991-12-10
JPH04277007A (ja) 1992-10-02
EP0564563A1 (en) 1993-10-13
JP2002517161A (ja) 2002-06-11
EP0564563A4 (enExample) 1994-01-05

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