CA2237748C - Process for recovering sf6 from a gas - Google Patents
Process for recovering sf6 from a gas Download PDFInfo
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- CA2237748C CA2237748C CA002237748A CA2237748A CA2237748C CA 2237748 C CA2237748 C CA 2237748C CA 002237748 A CA002237748 A CA 002237748A CA 2237748 A CA2237748 A CA 2237748A CA 2237748 C CA2237748 C CA 2237748C
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- 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
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- 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
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- 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
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- Separation Using Semi-Permeable Membranes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A process for recovering SF6 from a gas is provided.
The process includes the step of contacting a gas stream comprising SF6 and at least one of N2, O2, CO2, and H2O with a membrane in at least one membrane separation unit at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in at least one of N2, O2, CO2, ancL H2O.
A process for forming solidified Mg metal is also provided. The process includes recovering and/or recycling of SF6 and/or CO2.
The process includes the step of contacting a gas stream comprising SF6 and at least one of N2, O2, CO2, and H2O with a membrane in at least one membrane separation unit at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in at least one of N2, O2, CO2, ancL H2O.
A process for forming solidified Mg metal is also provided. The process includes recovering and/or recycling of SF6 and/or CO2.
Description
FIELD OF THE INVENTION
The present invention generally relates to a gas separation process. The invention particularly relates to a process for recovering SF6 and/or C02 from a gas stream using membrane separation techniques. The invention also particularly relates to a process for forming solidified magnesium metal, which process includes recovering and/or recycling of SF6 and/or C02.
BACKGROUND OF THE INVENTION
IO Nfagnesium is often formed into ingots, bars, sheets, or rocs, and sold as a commercial product. Typically, the magnesium is given a particular shape by a casting process which involves melting the magnesium and pouring it into a mold.
Magnesium in the molten state, however, requires some form of protection to inhibit oxidation and to prevent burning. When molten magnesium is exposed to ambient air, a thick layer of magnesium oxide forms on the surface of the melt. However, this layer of magnesium oxide is not adequate to provide the. necessary protection. In a matter of ju~:t seconds, many blooms form on the surface of the molten. magnesium which first glow red and then burst into white flames. As a result, the Mg0 (on the surface) is not smootr. or coherent with the molten surface. Moreover, Mg0 occupi~'s much less volume than the metal from which it is formed. Thus, the entire surface of the molten magnesium that is exposed to ambient air is not protected. In addition, the boiling point of magnesium is relatively low.
This results in a high vapor pressure which further puts critical demands on the Mg0 layer.
One solution to th.e oxidation problem has been to isolate the melt from the air with a non-reactive barrier consist=ing of a flux of salts (e. g., 50% MgCl2, 25o KCl, 18o BaCl2, 4o CaF2, 3% :~g0). The flux is liquid at the temperature of molten magnesium and has a surface tension that enables the flux to encase the melt with a relatively impermeable fluid film.
However, the use of a salt flux cover has a number of drawbacks. For example, it reduces the magnesium metal yield. The salt flux forms a sludge composed of oxides and inter-metallic particles. The sludge is generated by oxidation and agitation of the molten metal bath.
Oxidation of the salt flux also produces dross floating on the metal surface. Both the sludge and the dross have a considE:rable amount of metallic magnesium trapped in their structure which reduces yield.
The sludge and dross also create other problems. For example, the sludge settles to the bottom of the pot where it may insulate and cause hot spots on the pot.
Additionally, both present disposal problems. Flux can contaminate (e. g., corrosion effects) the finished castings by forming flux inclusions or oxides. Flux fumes and flux dust can also cause serious corrosion problems in the plant.
Another approach t-_o solving the problem associated with molten magnesium :is to use inhibitors in the air. The early practice was to burn coke or sulfur to produce the gaseous agent, C02 or 502. An atmosphere of C02 was found to be superior to the commonly used commercial atmospheres of N2, Ar, or He because of the absence of vaporization of the magnesium, the absence of excessive reaction products, and the necessity for t:he enclosure above the molten metal to be extremely air tight. Some of these gases are also very expensive to use. Additionally, small amounts of S02 (<1%) 'was found to be sufficient for protecting the molten magnesium from burning, even if air and moisture are present in the atmosphere above the melt.
However, the use c>f these inhibitors also has several drawba~~ks. For example, both C02 and S02 pose pollution problems such as breathing discomfort for plant personnel, residual sludge disposal, and a corrosive atmosphere which is detrimental to both plant and equipment. Furthermore, S02 is toxic and can cause explosions.
While BF3 has been mentioned as being a very effective inhibitor, it is not suitable for commercial processes because' it is extremely toxic and corrosive.
Sulfur hexafluoride (SF6) has also been mentioned as one of many fluorine-containing compounds that can be used in air as an oxidation inhibitor for molten magnesium.
However, it was overlooked for many years. When its important dielectric properties were applied to electric equipment, it was tried as an inhibitor in die casting operations. SF6 was discarded at that point, however, because of its severe attack on the ferrous equipment. In addition, the use of pure SF6 for protecting molten magnesium has been reported to have caused explosions.
Later, it was found that at low concentrations of SF6 in air (<1%) , a protective thin film of Mg0 (and MgF2) is formed on the magnesium melt surface. Advantageously, even at high temperatures in air, SF6 showed negligible or no reactions.
However, the combination of SF6 and air has some drawba~~ks. For example, since SF6 is adsorbed by the thin film, there must be a continuous supply of the gas to maintain the otherwise unstable film. Moreover, at higher temper<~tures, higher concentrations of SF6 are necessary.
At the higher concentrations, S02 and MgF2 are formed, and magnes=ium is wastefully further oxidized.
It. was then found that C02 could be used together with SF6 and air. A gas atmosphere of air, SF6, and C02 has severa_ advantages. First, it is non-toxic and non-corros~_ve. Second, it eliminates the use of salt fluxes and them need to dispose of the resulting sludge. Third, using :such a gas atmosphere results in a lower metal loss, elimination of corrosion effects, and clean castings.
The present invention generally relates to a gas separation process. The invention particularly relates to a process for recovering SF6 and/or C02 from a gas stream using membrane separation techniques. The invention also particularly relates to a process for forming solidified magnesium metal, which process includes recovering and/or recycling of SF6 and/or C02.
BACKGROUND OF THE INVENTION
IO Nfagnesium is often formed into ingots, bars, sheets, or rocs, and sold as a commercial product. Typically, the magnesium is given a particular shape by a casting process which involves melting the magnesium and pouring it into a mold.
Magnesium in the molten state, however, requires some form of protection to inhibit oxidation and to prevent burning. When molten magnesium is exposed to ambient air, a thick layer of magnesium oxide forms on the surface of the melt. However, this layer of magnesium oxide is not adequate to provide the. necessary protection. In a matter of ju~:t seconds, many blooms form on the surface of the molten. magnesium which first glow red and then burst into white flames. As a result, the Mg0 (on the surface) is not smootr. or coherent with the molten surface. Moreover, Mg0 occupi~'s much less volume than the metal from which it is formed. Thus, the entire surface of the molten magnesium that is exposed to ambient air is not protected. In addition, the boiling point of magnesium is relatively low.
This results in a high vapor pressure which further puts critical demands on the Mg0 layer.
One solution to th.e oxidation problem has been to isolate the melt from the air with a non-reactive barrier consist=ing of a flux of salts (e. g., 50% MgCl2, 25o KCl, 18o BaCl2, 4o CaF2, 3% :~g0). The flux is liquid at the temperature of molten magnesium and has a surface tension that enables the flux to encase the melt with a relatively impermeable fluid film.
However, the use of a salt flux cover has a number of drawbacks. For example, it reduces the magnesium metal yield. The salt flux forms a sludge composed of oxides and inter-metallic particles. The sludge is generated by oxidation and agitation of the molten metal bath.
Oxidation of the salt flux also produces dross floating on the metal surface. Both the sludge and the dross have a considE:rable amount of metallic magnesium trapped in their structure which reduces yield.
The sludge and dross also create other problems. For example, the sludge settles to the bottom of the pot where it may insulate and cause hot spots on the pot.
Additionally, both present disposal problems. Flux can contaminate (e. g., corrosion effects) the finished castings by forming flux inclusions or oxides. Flux fumes and flux dust can also cause serious corrosion problems in the plant.
Another approach t-_o solving the problem associated with molten magnesium :is to use inhibitors in the air. The early practice was to burn coke or sulfur to produce the gaseous agent, C02 or 502. An atmosphere of C02 was found to be superior to the commonly used commercial atmospheres of N2, Ar, or He because of the absence of vaporization of the magnesium, the absence of excessive reaction products, and the necessity for t:he enclosure above the molten metal to be extremely air tight. Some of these gases are also very expensive to use. Additionally, small amounts of S02 (<1%) 'was found to be sufficient for protecting the molten magnesium from burning, even if air and moisture are present in the atmosphere above the melt.
However, the use c>f these inhibitors also has several drawba~~ks. For example, both C02 and S02 pose pollution problems such as breathing discomfort for plant personnel, residual sludge disposal, and a corrosive atmosphere which is detrimental to both plant and equipment. Furthermore, S02 is toxic and can cause explosions.
While BF3 has been mentioned as being a very effective inhibitor, it is not suitable for commercial processes because' it is extremely toxic and corrosive.
Sulfur hexafluoride (SF6) has also been mentioned as one of many fluorine-containing compounds that can be used in air as an oxidation inhibitor for molten magnesium.
However, it was overlooked for many years. When its important dielectric properties were applied to electric equipment, it was tried as an inhibitor in die casting operations. SF6 was discarded at that point, however, because of its severe attack on the ferrous equipment. In addition, the use of pure SF6 for protecting molten magnesium has been reported to have caused explosions.
Later, it was found that at low concentrations of SF6 in air (<1%) , a protective thin film of Mg0 (and MgF2) is formed on the magnesium melt surface. Advantageously, even at high temperatures in air, SF6 showed negligible or no reactions.
However, the combination of SF6 and air has some drawba~~ks. For example, since SF6 is adsorbed by the thin film, there must be a continuous supply of the gas to maintain the otherwise unstable film. Moreover, at higher temper<~tures, higher concentrations of SF6 are necessary.
At the higher concentrations, S02 and MgF2 are formed, and magnes=ium is wastefully further oxidized.
It. was then found that C02 could be used together with SF6 and air. A gas atmosphere of air, SF6, and C02 has severa_ advantages. First, it is non-toxic and non-corros~_ve. Second, it eliminates the use of salt fluxes and them need to dispose of the resulting sludge. Third, using :such a gas atmosphere results in a lower metal loss, elimination of corrosion effects, and clean castings.
Fourth, such a casting process provides a clean operation and improves the working conditions. In short, the addition of C02 provides much improved protection compared to the melt protection obtained with air/SF6 mixtures.
However, using a gas atmosphere of SF6 and COZ also has some disadvantages. Namely, both SF6 and C02 have been mentioned as being greenhouse gases, i.e., they have a high global warming potential. In addition, SF6 is a relatively expensive gas. Thus, there is a need in the art to reduce the total amount of SFE- and C02 that is used and released into t:he atmosphere.
A~~cordingly, it i=~ an object of the present invention to address this need in the magnesium industry. In particular, it is an object of the present invention to provide an efficient and economical process for recovering SF6 and/or C02 from the vent gas of a magnesium foundry and option<~lly recycling the recovered gas. These and other object: of the invention will become apparent in light of the following specification, and the appended drawings and claims.
SUMMARY OF THE INVENTION
In one aspect, the present invention relates to a process for recovering SF6 from a gas. The process includes the step of contacting a gas stream comprising SF6 and at least one of N2, 02, C02, and H20 with a membrane in at leant~ one membrane separation unit at conditions _ 5 _ effective to obtain a retentate stream rich in SF6 and a permeate stream rich in at least one of N2, 02, C02, and H20.
I:n one embodiment, the process according to the present invention involves separating SF6 from C02. The process includes the step of contacting a gas stream comprising SF6 and C02 with a membrane in two or more membra:ze separation units at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in C02.
Preferably, the ga.s stream is contacted with a membrane in three membrane separation units. The gas stream is contacted with a first membrane in a first membrane separation unit at conditions effective to obtain a firsts retentate stream rich in SF6 and a first permeate stream rich in C02. The first permeate stream is then contact=ed with a second membrane in a second membrane separation unit at conditions effective to obtain a second retentate stream depleted in C02 and a second permeate stream rich in C02. The first retentate stream is contacted with a third membrane in a third membrane separation unit at conditions effective to obtain a third retentate stream rich i:n SF6 and a third permeate stream depleted in SF6.
I:z another aspect, the present invention relates to a process for forming solidified Mg metal. The process includes the steps of:
(a) casting molten Mg metal in a gaseous atmosphere comprising SF6;
(b) cooling the molten Mg metal to form a solidified Mg metal;
~) obtaining a vent gas comprising SF6 and at least one of N2, 02, C02, and H20 from the casting step; and (d) contacting the vent gas with a membrane in at least one membrane separation unit at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in at least one of N2, 02, C02, and H20.
Prefer<~bly, at least a portion of the retentate stream is recycled to the casting' step to provide the gaseous atmosphere.
In one embodiment, the process for forming solidified Mg metal according to the present invention includes the steps of (a) casting molten Mg metal in a gaseous atmosphere comprising SF6 and C02;
(b) cooling the molten Mg metal to form a solidified Mg met<~1;
(c) obtaining a vent gas comprising SF6 and C02 from the casting step; and (d) contacting the vent gas with a membrane in two or more membrane separation units at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in C02. Preferably, at least a portion of the retentate stream and at least a portion of the permeate stream are recycled to the casting step to provide the gaseous atmosphere.
In a particularly preferred embodiment, prior to being recycled, the permeate stream and the retentate stream are contacted with a second and third membrane, respectively, to improve the purity of those streams.
T:he present invention will be described in greater detail with reference to the accompanying drawings in which like elements bear like reference numerals, and wherein:
Figure 1 illustrates an engineering design of a membrane system that can be employed in the present invention;
Figure 2 is a flow diagram of a preferred process for recovering SF6 and C02 according to the present invention;
Figure 3 is a flow diagram of a preferred process for forming solidified Mg metal according to the present invention;
Figure 3A is a flow diagram of another preferred process for forming solidified Mg metal according to the present invention;
Figure 4 is a flow diagram of a preferred process for forming solidified Mg metal according to the present _ g _ invention which incorporates the process for recovering SF6 and C02 depicted in Figure 2; and Figure 5 is a graph showing the permeability of N2 and SF6 through a particular membrane at different partial pressures of SF6.
I>ETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In a first aspect, the present invention relates to a process for recovering SF6 from a gas. The process includes the step of contacting a gas stream comprising SF6 and at least one of N2, 02, C02, and H20 with a membrane in at least one membrane separation unit at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in at least one of N2, 02, C02, and H20.
As used in this specification and the claims, the term "rich" means that the concentration of a particular component in that stream is greater than the concentration of the same component in the feed stream to the particular proces:~ step. Likewise, the term "depleted" means that the concent=ration of a particular component in that stream is less than the concentration of the same component in the feed st=ream to the particular process step.
Preferably, the gas stream to be separated contains from about 0.0001 to about 20o by volume of SF6, and the retentate stream contains from about 0.01 to about 1000 by volume of SF6.
_ g _ In a preferred embodiment, the purity of the permeate and retentate streams is improved by contacting the streams with additional membrane separation units arranged in series. Such a process may be carried out according to the multi-step membrane separation system shown in Figure 1.
As shown in Figure 1, each of the permeate and retentate streams may be passed to another membrane contacting unit to increase the purity of the stream. The number of contacting steps "m" and "n" may vary depending on the purity desired. By using such a process, it is possible to obtain 1000 recovery of SF6 with a purity approaching 100%
by volume.
Any membrane can be used in the process of the present invention so long as the membrane can selectively retain SF6 while passing the other components in the gas stream through. The membrane should also be substantially non-reactive with the gaseous components to be separated.
Membranes suitable for use in the present invention include glassy membranes such as polymer membranes made preferably from polyimides; polyamides; polyamide-imides;
polyesters polycarbonates; polysulfones; polyethersulfone;
polyetherketone; alkyl substituted aromatic polyesters;
blends of polyethersulfone, aromatic polyimides, aromatic polyamides, polyamides-imides, fluorinated aromatic polyimide, polyamide, and polyamide-imides; glassy polymeric membranes such as those disclosed in United States Patent 5,599,380;
cellulose acetates; and blends thereof, copolymers thereof, substituted polymers (e. g. alkyl, aryl) thereof and the like.
Other membranes suitable for use in the present invention include asymmetric membranes. Asymmetric membranes are prepared by the precipitation of polymer solutions in solvent-miscible nonsolvents. Such membranes are typified by a dense separating layer supported on an anisotropic substrate of a graded porosity and are generally prepared in one step. Examples of such membranes and their methods of manufacture are disclosed in U.S.
Patent Nos. 4,113,628; 4,378,324; 4,460,526; 4,474,662;
4,485,056; 4,512,893; 5,085,676; and 4,717,394, The '394 and '676 patents disclose preparation of asymmetric separation membranes from selected polyimides. Particularly preferred membranes are polyimide asymmetric gas separation membranes as disclosed in the '676 patent.
Yet other membranes suitable for use in the present invention include composite gas separation membranes.
These membranes typically have a dense separating layer on a preformed microporous substrate. The separating layer and the substrate are usually different in composition.
Composite gas separation membranes have evolved to a structure of an ultrathin, dense separating layer supported on an anisotropic, microporous substrate. These composite membrane structures can be prepared by laminating a preformed ultrathin dense separating layer on top of a preformed anisotropic support membrane. Examples of such membranes and their methods of manufacture are disclosed in U.S. Patent Nos. 4,664,669; 4,689,267; 4,741,829;
2,947,687; 2,953,502; 3,616,607; 4,714,481; 4,602,922;
2,970,106; 2,960,462; 4,713,292; 4,086,310; 4,132,824;
4,192,824; 4,155,793; and 4,156,597.
Alternatively, composite gas separation membranes may be prepared by multistep fabrication processes, wherein first an anisotropic, porous substrate is formed, followed by contacting the substrate with a membrane-forming solution. Examples of such methods are described in U.S.
Patent Nvs. 4,826,599; 3,648,845; and 3,508,994.
U.S. Patent No. 4,756,932 describes how composite hollow-fiber membranes may also be prepared by co-extrusion of multiple polymer solution layers, followed by precipitation in a solvent-miscible nonsolvent.
In the case of hollow-fiber membranes, the term "membrane" as used in the present invention is intended to include both the individual hollow fibers as well as multiple hollow fibers.
The membrane used in the present invention can be post-treated with, or coated by, or co-extruded with, a fluorinated or perfluorinated polymer layer in order to increase its ability to withstand harmful constituents in the gas stream from which SF6 is to be separated, at low levels or temporary contact with such components.
The temperature of the gas stream and/or the membrane during the contacting step in each membrane separation unit can vary from about -10°C to about 100°C. Preferably, the temperature is between about 10°C and 80°C. More preferably, the temperature ranges from ambient, i.e., from about 20°C to 25°C, to about 60°C.
It is preferred, according to the present invention, to have a pressure drop across the membrane in each membrane separation unit of less than about 2,000 psig.
More preferably, the pressure drop ranges from about 3 to about 200 psig. Even more preferably, the pressure drop is about 20 to about 60 psig.
The requisite pressure drop across the membrane can be provided in one of two ways. First, the feed gas stream can be compressed. Preferred compressors are sealed and oil-free, such as the compressors sold under the tradename POWEREX, available from the Powerex Harrison Company of Ohio. Second,and more preferably, the pressure drop across the membrane can be established by lowering the pressure on the permeate side of the membrane. To create the lower pressure on the permeate side, a vacuum pump or any other suction device can be used.
The flowrate of the gas stream across the membrane in each membrane separation unit can vary from about 0 to about 105 Nm3/h per square meter of membrane available for separation. Preferabl;r, the flowrate ranges from about 10-to about 10 Nm3/h-m2. More preferably, the flowrate ranges from about 0.1 t:o about 0.5 Nm3/h-m2.
Of course, the particular contacting conditions in each membrane separation unit may be the same or different, depending on various factors including the type of membrane employed as well as the' degree of separation or purity desired. The selection of such parameters is within the level of skill of the ordinary worker in this art.
In another preferred embodiment, the process according to the present invention is used to separate SF6 from C02 and that two or more membrane separation units are employed. Preferably, the gas stream to be separated comprises from about 0.0001 to about 20% by volume of SF6 and from about 0.01 to about 50o by volume of C02. Also preferably, the gas stream to be separated further comprises at least one of N2, 02, and H20. More preferably, the gas stream comprises both N2 and 02. An example of such an embodiment of the present invention is shown .in Figure 2.
Referring to Figure 2, a gas stream 10 comprising SF6, C02, N" and 02 is contacted with a first membrane separai~ion unit 100 at conditions effective to obtain a first :retentate stream 11 rich in SF6 and a first permeate stream 13 rich in C02. The first retentate stream preferably comprises from about 0.01 to about 1000 by volume of SF6, and the first permeate stream preferably comprises from about 0.1 to about 90% by volume of C02.
The first permeate stream 13 is then contacted with a second membrane separation unit 110 at conditions effective to obtain a second retentate stream 14 depleted in C02 and a second permeate stream 15 rich in C02. The first retentate stream 11 is contacted with a third membrane separation unit 120 at conditions effective to obtain a third retentate stream 12 rich in SF6 and a third permeate stream 16 depleted in SF6. In addition to being depleted in SF6 and C02, the second retentate stream 14 and the third :permeate stream 16 are rich in at least one of N2 and ~2' The particular membrane used in each membrane separation unit 100, 11.0, and 120 may be the same or differ~'nt. The membranes are selected depending various considerations known to those skilled in the art such as the degree of separation desired.
I:z a second aspect, the present invention relates to a process for forming solidified Mg metal. The process includes the steps of:
(a) casting molten Mg metal in a gaseous atmosphere comprising SF6 ;
(b) cooling the molten Mg metal to form a solidified Mg met<~l;
(c~) obtaining a vent gas comprising SF6 and at least one of N2, 02, C02, and H20 from the casting step; and (d) contacting the vent gas with a membrane in at least one membrane separation unit at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in at least one of N2, 02, C02, and H20.
Preferably, at least a portion of the retentate stream is recycled to the casting step to provide at least part of the gaseous atmosphere. Prior to being recycled, the retent~ate stream can be mixed with at least one of N2, 02, make-up SF6 and CO2.
A preferred exemplary embodiment of this process is shown :in Figure 3. Referring to Figure 3, a stream 20 of molten Mg metal is fed into a casting chamber 130 having a gaseous atmosphere comprising SF6. The molten Mg metal is then cooled to yield a solidified Mg metal which is withdrawn in line 21. The operating conditions and equipment necessary to carry out this step are well known to those skilled in the art.
The gaseous atmosphere in the casting chamber 130 preferably comprises from about 0.01 to about 20a by volume of SF6, and more preferably from about 0.1 to about 10% by volume of SF6. The balance of the gaseous atmosphere can be a mixture of N2 and 02 such as air, as well as other gaseou:~ components including C02 and H20.
A vent gas 22 is withdrawn from the casting chamber 130. The vent gas 22 comprises SF6, N2, 02, and H20, and optionG.lly HCl, C12, and particulates. The vent gas 22 typically contains from about 0.0001 to about 0.2o by volume of SF6. If HC1, C12, and particulates are present, then the vent gas 22 can be passed to a pretreatment unit 140 to remove these components.
Preferably, as shown in Figure 3A, the pretreatment unit 140 comprises filters 141 and 144, and a dry scrubber 142 and a wet scrubber 143. The vent gas 22 is passed into filter 141 to remove the particulates. The gas stream 22a exiting the filter 141 is introduced into the dry scrubber 142 to remove some of the halide components. The gas stream 22b exiting the dry scrubber 142 is then transferred to the wet scrubber 143 wherein the remaining halides are removed. The wet scrubber 143 produces a gas stream 22c which is essentially free of the halides. The gas stream 22c is then passed to an additional filter 144 to remove any remaining particulates in the gas stream 22c.
Of course, the particular type of filters and scrubbers employed can be readily determined by those skilled in the art. Also, the number and the relative positions of the filters and scrubbers may vary depending on the desired purity of the resulting gas stream.
By way of example, dry scrubbers are usually resin-type scrubbers or soda-lime. Exemplary wet scrubbers that can be used in the present invention are described in the brochure entitled, "Selecting a CDOTM for Your Particular Application" from DELATECH Corporation..
_ When various harmful constituents, e.g., halides, have to be rsmoved, it is prefer=red to use a dry scrubber or scrubbers in series with a wet scrubber or scrubbers.
Preferably, upstream of the scrubber or scrubbers, one or more filters are employed to remove the particulates from the vent gas. It is preferred to use a filter having a pore size diameter of less than 20 micrometers, and more preferably, less than 10 micrometers.
If there are remaining particulates in the purified vent gas before it is passed to the membrane separation unit, ~_t is contemplated by the present invention to employ an additional filter or filters to remove such particulates.
Referring again to Figure 3, a gas stream 23 comprising SF6, N2, 02, and H20 is withdrawn from the 1S pretreatment unit 140. The gas stream 23 is then passed to a membrane separation unit 150 to produce a retentate stream 25 rich in SF6 and a permeate stream 24 depleted in SF6. The permeate stream 24, which primarily contains N2, 02, anc' H20, can be vented to the atmosphere.
The concentration of SF6 in the retentate stream 25 can be set at a desired level by changing the parameters of the membrane separation unit 150 (e. g., pressure drop across the membrane, temperature, and feed to membrane area ratio). Preferably, the retentate stream 25 comprises from about 30 to about 100% :by volume of SF6.
Tr:e SF6 concentration of the retentate stream 25 can also be: adjusted in a mixing unit 160 wherein the recovered SF6 is mixed with a mixture of N2 and 02 26, and/or makeup SF6 2'7 to yield a recycle stream 28. It should be noted that t=he ratio of N2/02 added to the recycle stream 28 can be adjusted so that the recycle stream 28 can have the desired ratio of the gas constituents. The recycle stream 28 is then passed to the casting chamber 130 to provide at least part of the SF6 gaseous atmosphere.
7.n another preferred embodiment, the process for forming solidified Mg metal according to the present invention includes the steps of:
(a) casting molten Mg metal in a gaseous atmosphere comprising SF6 and C02;
(b) cooling the molten Mg metal to form a solidified Mg metal;
(c) obtaining a vent gas comprising SF6 and COZ from the casting step; and (d) contacting the vent gas with a membrane in two or more membrane separation units at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in C02. Preferably, at least a portion of the retent.ate stream and at least a portion of the permeate stream are recycled to the casting step to provide the gaseous atmosphere. More preferably, prior to being recycled, the permeate stream and the retentate stream are contacted with a second and third membrane, respectively, to improve the purity of those streams.
A particularly preferred exemplary embodiment of this process is shown in Figure 4. Referring to Figure 4, a stream 20 of molten Mg metal is fed into a casting chamber 130 having a gaseous atmosphere comprising SF6 and C02.
The molten Mg metal is then cooled to yield a solidified Mg metal which is withdrawn in line 21.
The gaseous atmosphere in the casting chamber 130 preferably comprises from about 0.01 to about 20o by volume of SF6 and from about 30 to about 70o by volume of C02.
More preferably, the gaseous atmosphere comprises from about 0.1 to about loo by volume of SF6 and from about 40 to about 60o by volume of C02. The balance of the gaseous atmosphere can be a mixture of N2 and OZ such as air, as well as other gaseous components including H20.
A vent gas 22 is withdrawn from the casting chamber 130. 'The vent gas 22 comprises SF6, C02, N2, and 02, and optionally HCl, C12, and particulates. The vent gas 22 typically contains about 0.0001 to about 0.2o by volume of SF6 and from about 2 to about 30o by volume of C02. If HC1, C12, and particulates are present, then the vent gas 22 can be passed to a pretreatment unit 140 to remove those components.
A gas stream 23 ccmprising SF6, C02, N2, and 02 is then withdrawn from the pretreatment unit 140. The gas stream 23 is passed to a membrane separation system 150 that resembles the configuration depicted in Figure 2.
Ac3ain referring to Figure 4, the gas stream 23 is contacted with a first membrane separation unit 151 at conditions effective to obtain a first retentate stream 23a rich in SF6 and a first permeate stream 23b rich in C02.
The first retentate stream 23a preferably comprises from about 0.01 to about 100% by volume of SF6, and the first permeate stream 23b preferably comprises from about 0.1 to about 90% by volume of C02.
The first permeate stream 23b is then contacted with a second membrane separation unit 152 at conditions effective to obtain a second retentate stream 23c depleted in C02 and a second permeate stream 25a rich in C02. The first retentate stream 23a is contacted with a third membrane separation unit 153 at conditions effective to obtain a third :retentate stream 25 rich in SF6 and a third permeate stream 23d depleted in SF6.
In addition to being depleted in SF6 and C02, the second retentate stream 23c and the third permeate stream 23d are rich in at least one of N2 and 02. These streams can been combined to form a purified vent stream 24.
The second permeate stream 25a and the third retentate stream 25 can been mixed together in a conditioner unit 170 along with a mixture of N2 and 02 26, and make-up C02 26a and matte-up SF6 27 to form a recycle stream 28. Again, the ratio of N2/02 can be adjusted to obtain any desired concentration in the recycle stream 28. The recycle stream 28 is passed to the casting chamber 130 to provide at least part of the N2/02/SF6/C02 gaseous atmosphere.
EXAMPLES
The following examples are provided to illustrate the present invention and are not to be construed as a limitation thereof.
Example 1 A gas stream comprising SF6 and N2 was contacted with an asymmetric composite hollow fiber membrane with a surface area of 0.13 m' at various partial pressures of SF6 to determine its permeability relative to N2. The gas stream was contacted with the membrane at a temperature of 20°C and at a flowrate rate of 200 sccm. The pressure of the feed gas was kept at 3 bar. The permeability of each of these components is graphically shown in Figure 5. As seen from Figure 5, the selectivity of SF6/N2 is on the order of 500.
Based on the above selectivity, a computer simulation of a single stage membrane separation unit was conducted.
The concentration and the pressure of the feed, permeate, and retentate as well as the percentage recovery of SF6 are shown in Table 1 below.
Feed Permeate Retentate SF6 Recovery Flowrate 0.19 0.15 0.04 (Nm3 / h-m2 ) [SF ] 0.01 9.2 x 10-5 1 (vo~ %) [N2] 99.99 99.99991 0 (vol % ) Pressure 9 1 8.7 (bar) 99.70 Example 2 In an actual experiment, a gas stream comprising O.lo by vol,ime of SF6 and the balance air was contacted with an asymmetric composite hollow fiber membrane with a surface area o:f 690 m2 at a temperature of 20°C in a cascade design process as shown in Figure 1 wherein n = 1 and m = 0. The flowrate, concentration, and pressure of the feed, permeate, and retentate streams are reported below in Table 2. Tha_ percentage recovery of SF6 is also reported in Table :2 .
Feed Permeate Retentate SF6 Recovery Flowrate 447.7 443.62 4.08 (scfh) (SF ] 0.100 0.0075 10.0670 (vo~ %) Pressure 5.6 1 5.5 (bar) 92.3e Example 3 In a computer simulation, a gas stream comprising SF6, C02, and air is passed to a three-stage membrane separation system as shown in Figure 2 to recovery both SF6 and C02.
The membrane in each stage is the same asymmetric composite hollow fiber membrane and the contacting temperature in each stage is 20°C. The flowrate, concentration, and pressure of the feed, permeate, and retentate streams of each stage are reported below in Table 3. The percentage recovery of SF6 and C02 is also reported in Table 3.
Feed Permeate Retentate Recovery First Stage Flowrate (Nm3/h-m2) 0.25 0.21 0.04 [SF6] (vol %) 0.02 0.00 0.12 100%
S [C02] (vo1 %) 5.00 6.00 0.00 100%
[N2] (vol %) 75.98 71.19 99.86 [02] (vol %) 19.00 22.81 0.02 Pressure (bar) 9 0.5 8.7 Second Stage Flowrate (Nm3/h-m2) 0.63 0.23 0.40 [SF ] (vol o ) 0 . 00 0 . 00 0 . 00 [CO ] (vol %) 6.00 16.68 0.07 99.30 [N ] (vol o ) 71 . 46 . 11 85 . 11 [O ] (vol %) 22.81 37.21 14.82 Pressure (bar) 8 0.9 7.7 Third Stage Flowrate (Nm3/h-m2) 0.1270 0.1266 0.0004 [SF ] (vol %) 0.12 0.00 34.96 99%
[CO ] (vol %) 0.00 0.00 0.00 [N ] (vol %) 99.86 99.98 65.04 [O ] (vol %) 0.02 0.02 0.00 Pressure (bar) 6.98 0.2 6.68 While the invention has been described with preferred embodiments, it is to be understood that variations and modifi~~ations may be resorted to as will be apparent to those skilled in the art. Such variations and modifications are to be considered within the purview and the scope of the claims appended hereto.
However, using a gas atmosphere of SF6 and COZ also has some disadvantages. Namely, both SF6 and C02 have been mentioned as being greenhouse gases, i.e., they have a high global warming potential. In addition, SF6 is a relatively expensive gas. Thus, there is a need in the art to reduce the total amount of SFE- and C02 that is used and released into t:he atmosphere.
A~~cordingly, it i=~ an object of the present invention to address this need in the magnesium industry. In particular, it is an object of the present invention to provide an efficient and economical process for recovering SF6 and/or C02 from the vent gas of a magnesium foundry and option<~lly recycling the recovered gas. These and other object: of the invention will become apparent in light of the following specification, and the appended drawings and claims.
SUMMARY OF THE INVENTION
In one aspect, the present invention relates to a process for recovering SF6 from a gas. The process includes the step of contacting a gas stream comprising SF6 and at least one of N2, 02, C02, and H20 with a membrane in at leant~ one membrane separation unit at conditions _ 5 _ effective to obtain a retentate stream rich in SF6 and a permeate stream rich in at least one of N2, 02, C02, and H20.
I:n one embodiment, the process according to the present invention involves separating SF6 from C02. The process includes the step of contacting a gas stream comprising SF6 and C02 with a membrane in two or more membra:ze separation units at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in C02.
Preferably, the ga.s stream is contacted with a membrane in three membrane separation units. The gas stream is contacted with a first membrane in a first membrane separation unit at conditions effective to obtain a firsts retentate stream rich in SF6 and a first permeate stream rich in C02. The first permeate stream is then contact=ed with a second membrane in a second membrane separation unit at conditions effective to obtain a second retentate stream depleted in C02 and a second permeate stream rich in C02. The first retentate stream is contacted with a third membrane in a third membrane separation unit at conditions effective to obtain a third retentate stream rich i:n SF6 and a third permeate stream depleted in SF6.
I:z another aspect, the present invention relates to a process for forming solidified Mg metal. The process includes the steps of:
(a) casting molten Mg metal in a gaseous atmosphere comprising SF6;
(b) cooling the molten Mg metal to form a solidified Mg metal;
~) obtaining a vent gas comprising SF6 and at least one of N2, 02, C02, and H20 from the casting step; and (d) contacting the vent gas with a membrane in at least one membrane separation unit at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in at least one of N2, 02, C02, and H20.
Prefer<~bly, at least a portion of the retentate stream is recycled to the casting' step to provide the gaseous atmosphere.
In one embodiment, the process for forming solidified Mg metal according to the present invention includes the steps of (a) casting molten Mg metal in a gaseous atmosphere comprising SF6 and C02;
(b) cooling the molten Mg metal to form a solidified Mg met<~1;
(c) obtaining a vent gas comprising SF6 and C02 from the casting step; and (d) contacting the vent gas with a membrane in two or more membrane separation units at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in C02. Preferably, at least a portion of the retentate stream and at least a portion of the permeate stream are recycled to the casting step to provide the gaseous atmosphere.
In a particularly preferred embodiment, prior to being recycled, the permeate stream and the retentate stream are contacted with a second and third membrane, respectively, to improve the purity of those streams.
T:he present invention will be described in greater detail with reference to the accompanying drawings in which like elements bear like reference numerals, and wherein:
Figure 1 illustrates an engineering design of a membrane system that can be employed in the present invention;
Figure 2 is a flow diagram of a preferred process for recovering SF6 and C02 according to the present invention;
Figure 3 is a flow diagram of a preferred process for forming solidified Mg metal according to the present invention;
Figure 3A is a flow diagram of another preferred process for forming solidified Mg metal according to the present invention;
Figure 4 is a flow diagram of a preferred process for forming solidified Mg metal according to the present _ g _ invention which incorporates the process for recovering SF6 and C02 depicted in Figure 2; and Figure 5 is a graph showing the permeability of N2 and SF6 through a particular membrane at different partial pressures of SF6.
I>ETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In a first aspect, the present invention relates to a process for recovering SF6 from a gas. The process includes the step of contacting a gas stream comprising SF6 and at least one of N2, 02, C02, and H20 with a membrane in at least one membrane separation unit at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in at least one of N2, 02, C02, and H20.
As used in this specification and the claims, the term "rich" means that the concentration of a particular component in that stream is greater than the concentration of the same component in the feed stream to the particular proces:~ step. Likewise, the term "depleted" means that the concent=ration of a particular component in that stream is less than the concentration of the same component in the feed st=ream to the particular process step.
Preferably, the gas stream to be separated contains from about 0.0001 to about 20o by volume of SF6, and the retentate stream contains from about 0.01 to about 1000 by volume of SF6.
_ g _ In a preferred embodiment, the purity of the permeate and retentate streams is improved by contacting the streams with additional membrane separation units arranged in series. Such a process may be carried out according to the multi-step membrane separation system shown in Figure 1.
As shown in Figure 1, each of the permeate and retentate streams may be passed to another membrane contacting unit to increase the purity of the stream. The number of contacting steps "m" and "n" may vary depending on the purity desired. By using such a process, it is possible to obtain 1000 recovery of SF6 with a purity approaching 100%
by volume.
Any membrane can be used in the process of the present invention so long as the membrane can selectively retain SF6 while passing the other components in the gas stream through. The membrane should also be substantially non-reactive with the gaseous components to be separated.
Membranes suitable for use in the present invention include glassy membranes such as polymer membranes made preferably from polyimides; polyamides; polyamide-imides;
polyesters polycarbonates; polysulfones; polyethersulfone;
polyetherketone; alkyl substituted aromatic polyesters;
blends of polyethersulfone, aromatic polyimides, aromatic polyamides, polyamides-imides, fluorinated aromatic polyimide, polyamide, and polyamide-imides; glassy polymeric membranes such as those disclosed in United States Patent 5,599,380;
cellulose acetates; and blends thereof, copolymers thereof, substituted polymers (e. g. alkyl, aryl) thereof and the like.
Other membranes suitable for use in the present invention include asymmetric membranes. Asymmetric membranes are prepared by the precipitation of polymer solutions in solvent-miscible nonsolvents. Such membranes are typified by a dense separating layer supported on an anisotropic substrate of a graded porosity and are generally prepared in one step. Examples of such membranes and their methods of manufacture are disclosed in U.S.
Patent Nos. 4,113,628; 4,378,324; 4,460,526; 4,474,662;
4,485,056; 4,512,893; 5,085,676; and 4,717,394, The '394 and '676 patents disclose preparation of asymmetric separation membranes from selected polyimides. Particularly preferred membranes are polyimide asymmetric gas separation membranes as disclosed in the '676 patent.
Yet other membranes suitable for use in the present invention include composite gas separation membranes.
These membranes typically have a dense separating layer on a preformed microporous substrate. The separating layer and the substrate are usually different in composition.
Composite gas separation membranes have evolved to a structure of an ultrathin, dense separating layer supported on an anisotropic, microporous substrate. These composite membrane structures can be prepared by laminating a preformed ultrathin dense separating layer on top of a preformed anisotropic support membrane. Examples of such membranes and their methods of manufacture are disclosed in U.S. Patent Nos. 4,664,669; 4,689,267; 4,741,829;
2,947,687; 2,953,502; 3,616,607; 4,714,481; 4,602,922;
2,970,106; 2,960,462; 4,713,292; 4,086,310; 4,132,824;
4,192,824; 4,155,793; and 4,156,597.
Alternatively, composite gas separation membranes may be prepared by multistep fabrication processes, wherein first an anisotropic, porous substrate is formed, followed by contacting the substrate with a membrane-forming solution. Examples of such methods are described in U.S.
Patent Nvs. 4,826,599; 3,648,845; and 3,508,994.
U.S. Patent No. 4,756,932 describes how composite hollow-fiber membranes may also be prepared by co-extrusion of multiple polymer solution layers, followed by precipitation in a solvent-miscible nonsolvent.
In the case of hollow-fiber membranes, the term "membrane" as used in the present invention is intended to include both the individual hollow fibers as well as multiple hollow fibers.
The membrane used in the present invention can be post-treated with, or coated by, or co-extruded with, a fluorinated or perfluorinated polymer layer in order to increase its ability to withstand harmful constituents in the gas stream from which SF6 is to be separated, at low levels or temporary contact with such components.
The temperature of the gas stream and/or the membrane during the contacting step in each membrane separation unit can vary from about -10°C to about 100°C. Preferably, the temperature is between about 10°C and 80°C. More preferably, the temperature ranges from ambient, i.e., from about 20°C to 25°C, to about 60°C.
It is preferred, according to the present invention, to have a pressure drop across the membrane in each membrane separation unit of less than about 2,000 psig.
More preferably, the pressure drop ranges from about 3 to about 200 psig. Even more preferably, the pressure drop is about 20 to about 60 psig.
The requisite pressure drop across the membrane can be provided in one of two ways. First, the feed gas stream can be compressed. Preferred compressors are sealed and oil-free, such as the compressors sold under the tradename POWEREX, available from the Powerex Harrison Company of Ohio. Second,and more preferably, the pressure drop across the membrane can be established by lowering the pressure on the permeate side of the membrane. To create the lower pressure on the permeate side, a vacuum pump or any other suction device can be used.
The flowrate of the gas stream across the membrane in each membrane separation unit can vary from about 0 to about 105 Nm3/h per square meter of membrane available for separation. Preferabl;r, the flowrate ranges from about 10-to about 10 Nm3/h-m2. More preferably, the flowrate ranges from about 0.1 t:o about 0.5 Nm3/h-m2.
Of course, the particular contacting conditions in each membrane separation unit may be the same or different, depending on various factors including the type of membrane employed as well as the' degree of separation or purity desired. The selection of such parameters is within the level of skill of the ordinary worker in this art.
In another preferred embodiment, the process according to the present invention is used to separate SF6 from C02 and that two or more membrane separation units are employed. Preferably, the gas stream to be separated comprises from about 0.0001 to about 20% by volume of SF6 and from about 0.01 to about 50o by volume of C02. Also preferably, the gas stream to be separated further comprises at least one of N2, 02, and H20. More preferably, the gas stream comprises both N2 and 02. An example of such an embodiment of the present invention is shown .in Figure 2.
Referring to Figure 2, a gas stream 10 comprising SF6, C02, N" and 02 is contacted with a first membrane separai~ion unit 100 at conditions effective to obtain a first :retentate stream 11 rich in SF6 and a first permeate stream 13 rich in C02. The first retentate stream preferably comprises from about 0.01 to about 1000 by volume of SF6, and the first permeate stream preferably comprises from about 0.1 to about 90% by volume of C02.
The first permeate stream 13 is then contacted with a second membrane separation unit 110 at conditions effective to obtain a second retentate stream 14 depleted in C02 and a second permeate stream 15 rich in C02. The first retentate stream 11 is contacted with a third membrane separation unit 120 at conditions effective to obtain a third retentate stream 12 rich in SF6 and a third permeate stream 16 depleted in SF6. In addition to being depleted in SF6 and C02, the second retentate stream 14 and the third :permeate stream 16 are rich in at least one of N2 and ~2' The particular membrane used in each membrane separation unit 100, 11.0, and 120 may be the same or differ~'nt. The membranes are selected depending various considerations known to those skilled in the art such as the degree of separation desired.
I:z a second aspect, the present invention relates to a process for forming solidified Mg metal. The process includes the steps of:
(a) casting molten Mg metal in a gaseous atmosphere comprising SF6 ;
(b) cooling the molten Mg metal to form a solidified Mg met<~l;
(c~) obtaining a vent gas comprising SF6 and at least one of N2, 02, C02, and H20 from the casting step; and (d) contacting the vent gas with a membrane in at least one membrane separation unit at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in at least one of N2, 02, C02, and H20.
Preferably, at least a portion of the retentate stream is recycled to the casting step to provide at least part of the gaseous atmosphere. Prior to being recycled, the retent~ate stream can be mixed with at least one of N2, 02, make-up SF6 and CO2.
A preferred exemplary embodiment of this process is shown :in Figure 3. Referring to Figure 3, a stream 20 of molten Mg metal is fed into a casting chamber 130 having a gaseous atmosphere comprising SF6. The molten Mg metal is then cooled to yield a solidified Mg metal which is withdrawn in line 21. The operating conditions and equipment necessary to carry out this step are well known to those skilled in the art.
The gaseous atmosphere in the casting chamber 130 preferably comprises from about 0.01 to about 20a by volume of SF6, and more preferably from about 0.1 to about 10% by volume of SF6. The balance of the gaseous atmosphere can be a mixture of N2 and 02 such as air, as well as other gaseou:~ components including C02 and H20.
A vent gas 22 is withdrawn from the casting chamber 130. The vent gas 22 comprises SF6, N2, 02, and H20, and optionG.lly HCl, C12, and particulates. The vent gas 22 typically contains from about 0.0001 to about 0.2o by volume of SF6. If HC1, C12, and particulates are present, then the vent gas 22 can be passed to a pretreatment unit 140 to remove these components.
Preferably, as shown in Figure 3A, the pretreatment unit 140 comprises filters 141 and 144, and a dry scrubber 142 and a wet scrubber 143. The vent gas 22 is passed into filter 141 to remove the particulates. The gas stream 22a exiting the filter 141 is introduced into the dry scrubber 142 to remove some of the halide components. The gas stream 22b exiting the dry scrubber 142 is then transferred to the wet scrubber 143 wherein the remaining halides are removed. The wet scrubber 143 produces a gas stream 22c which is essentially free of the halides. The gas stream 22c is then passed to an additional filter 144 to remove any remaining particulates in the gas stream 22c.
Of course, the particular type of filters and scrubbers employed can be readily determined by those skilled in the art. Also, the number and the relative positions of the filters and scrubbers may vary depending on the desired purity of the resulting gas stream.
By way of example, dry scrubbers are usually resin-type scrubbers or soda-lime. Exemplary wet scrubbers that can be used in the present invention are described in the brochure entitled, "Selecting a CDOTM for Your Particular Application" from DELATECH Corporation..
_ When various harmful constituents, e.g., halides, have to be rsmoved, it is prefer=red to use a dry scrubber or scrubbers in series with a wet scrubber or scrubbers.
Preferably, upstream of the scrubber or scrubbers, one or more filters are employed to remove the particulates from the vent gas. It is preferred to use a filter having a pore size diameter of less than 20 micrometers, and more preferably, less than 10 micrometers.
If there are remaining particulates in the purified vent gas before it is passed to the membrane separation unit, ~_t is contemplated by the present invention to employ an additional filter or filters to remove such particulates.
Referring again to Figure 3, a gas stream 23 comprising SF6, N2, 02, and H20 is withdrawn from the 1S pretreatment unit 140. The gas stream 23 is then passed to a membrane separation unit 150 to produce a retentate stream 25 rich in SF6 and a permeate stream 24 depleted in SF6. The permeate stream 24, which primarily contains N2, 02, anc' H20, can be vented to the atmosphere.
The concentration of SF6 in the retentate stream 25 can be set at a desired level by changing the parameters of the membrane separation unit 150 (e. g., pressure drop across the membrane, temperature, and feed to membrane area ratio). Preferably, the retentate stream 25 comprises from about 30 to about 100% :by volume of SF6.
Tr:e SF6 concentration of the retentate stream 25 can also be: adjusted in a mixing unit 160 wherein the recovered SF6 is mixed with a mixture of N2 and 02 26, and/or makeup SF6 2'7 to yield a recycle stream 28. It should be noted that t=he ratio of N2/02 added to the recycle stream 28 can be adjusted so that the recycle stream 28 can have the desired ratio of the gas constituents. The recycle stream 28 is then passed to the casting chamber 130 to provide at least part of the SF6 gaseous atmosphere.
7.n another preferred embodiment, the process for forming solidified Mg metal according to the present invention includes the steps of:
(a) casting molten Mg metal in a gaseous atmosphere comprising SF6 and C02;
(b) cooling the molten Mg metal to form a solidified Mg metal;
(c) obtaining a vent gas comprising SF6 and COZ from the casting step; and (d) contacting the vent gas with a membrane in two or more membrane separation units at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in C02. Preferably, at least a portion of the retent.ate stream and at least a portion of the permeate stream are recycled to the casting step to provide the gaseous atmosphere. More preferably, prior to being recycled, the permeate stream and the retentate stream are contacted with a second and third membrane, respectively, to improve the purity of those streams.
A particularly preferred exemplary embodiment of this process is shown in Figure 4. Referring to Figure 4, a stream 20 of molten Mg metal is fed into a casting chamber 130 having a gaseous atmosphere comprising SF6 and C02.
The molten Mg metal is then cooled to yield a solidified Mg metal which is withdrawn in line 21.
The gaseous atmosphere in the casting chamber 130 preferably comprises from about 0.01 to about 20o by volume of SF6 and from about 30 to about 70o by volume of C02.
More preferably, the gaseous atmosphere comprises from about 0.1 to about loo by volume of SF6 and from about 40 to about 60o by volume of C02. The balance of the gaseous atmosphere can be a mixture of N2 and OZ such as air, as well as other gaseous components including H20.
A vent gas 22 is withdrawn from the casting chamber 130. 'The vent gas 22 comprises SF6, C02, N2, and 02, and optionally HCl, C12, and particulates. The vent gas 22 typically contains about 0.0001 to about 0.2o by volume of SF6 and from about 2 to about 30o by volume of C02. If HC1, C12, and particulates are present, then the vent gas 22 can be passed to a pretreatment unit 140 to remove those components.
A gas stream 23 ccmprising SF6, C02, N2, and 02 is then withdrawn from the pretreatment unit 140. The gas stream 23 is passed to a membrane separation system 150 that resembles the configuration depicted in Figure 2.
Ac3ain referring to Figure 4, the gas stream 23 is contacted with a first membrane separation unit 151 at conditions effective to obtain a first retentate stream 23a rich in SF6 and a first permeate stream 23b rich in C02.
The first retentate stream 23a preferably comprises from about 0.01 to about 100% by volume of SF6, and the first permeate stream 23b preferably comprises from about 0.1 to about 90% by volume of C02.
The first permeate stream 23b is then contacted with a second membrane separation unit 152 at conditions effective to obtain a second retentate stream 23c depleted in C02 and a second permeate stream 25a rich in C02. The first retentate stream 23a is contacted with a third membrane separation unit 153 at conditions effective to obtain a third :retentate stream 25 rich in SF6 and a third permeate stream 23d depleted in SF6.
In addition to being depleted in SF6 and C02, the second retentate stream 23c and the third permeate stream 23d are rich in at least one of N2 and 02. These streams can been combined to form a purified vent stream 24.
The second permeate stream 25a and the third retentate stream 25 can been mixed together in a conditioner unit 170 along with a mixture of N2 and 02 26, and make-up C02 26a and matte-up SF6 27 to form a recycle stream 28. Again, the ratio of N2/02 can be adjusted to obtain any desired concentration in the recycle stream 28. The recycle stream 28 is passed to the casting chamber 130 to provide at least part of the N2/02/SF6/C02 gaseous atmosphere.
EXAMPLES
The following examples are provided to illustrate the present invention and are not to be construed as a limitation thereof.
Example 1 A gas stream comprising SF6 and N2 was contacted with an asymmetric composite hollow fiber membrane with a surface area of 0.13 m' at various partial pressures of SF6 to determine its permeability relative to N2. The gas stream was contacted with the membrane at a temperature of 20°C and at a flowrate rate of 200 sccm. The pressure of the feed gas was kept at 3 bar. The permeability of each of these components is graphically shown in Figure 5. As seen from Figure 5, the selectivity of SF6/N2 is on the order of 500.
Based on the above selectivity, a computer simulation of a single stage membrane separation unit was conducted.
The concentration and the pressure of the feed, permeate, and retentate as well as the percentage recovery of SF6 are shown in Table 1 below.
Feed Permeate Retentate SF6 Recovery Flowrate 0.19 0.15 0.04 (Nm3 / h-m2 ) [SF ] 0.01 9.2 x 10-5 1 (vo~ %) [N2] 99.99 99.99991 0 (vol % ) Pressure 9 1 8.7 (bar) 99.70 Example 2 In an actual experiment, a gas stream comprising O.lo by vol,ime of SF6 and the balance air was contacted with an asymmetric composite hollow fiber membrane with a surface area o:f 690 m2 at a temperature of 20°C in a cascade design process as shown in Figure 1 wherein n = 1 and m = 0. The flowrate, concentration, and pressure of the feed, permeate, and retentate streams are reported below in Table 2. Tha_ percentage recovery of SF6 is also reported in Table :2 .
Feed Permeate Retentate SF6 Recovery Flowrate 447.7 443.62 4.08 (scfh) (SF ] 0.100 0.0075 10.0670 (vo~ %) Pressure 5.6 1 5.5 (bar) 92.3e Example 3 In a computer simulation, a gas stream comprising SF6, C02, and air is passed to a three-stage membrane separation system as shown in Figure 2 to recovery both SF6 and C02.
The membrane in each stage is the same asymmetric composite hollow fiber membrane and the contacting temperature in each stage is 20°C. The flowrate, concentration, and pressure of the feed, permeate, and retentate streams of each stage are reported below in Table 3. The percentage recovery of SF6 and C02 is also reported in Table 3.
Feed Permeate Retentate Recovery First Stage Flowrate (Nm3/h-m2) 0.25 0.21 0.04 [SF6] (vol %) 0.02 0.00 0.12 100%
S [C02] (vo1 %) 5.00 6.00 0.00 100%
[N2] (vol %) 75.98 71.19 99.86 [02] (vol %) 19.00 22.81 0.02 Pressure (bar) 9 0.5 8.7 Second Stage Flowrate (Nm3/h-m2) 0.63 0.23 0.40 [SF ] (vol o ) 0 . 00 0 . 00 0 . 00 [CO ] (vol %) 6.00 16.68 0.07 99.30 [N ] (vol o ) 71 . 46 . 11 85 . 11 [O ] (vol %) 22.81 37.21 14.82 Pressure (bar) 8 0.9 7.7 Third Stage Flowrate (Nm3/h-m2) 0.1270 0.1266 0.0004 [SF ] (vol %) 0.12 0.00 34.96 99%
[CO ] (vol %) 0.00 0.00 0.00 [N ] (vol %) 99.86 99.98 65.04 [O ] (vol %) 0.02 0.02 0.00 Pressure (bar) 6.98 0.2 6.68 While the invention has been described with preferred embodiments, it is to be understood that variations and modifi~~ations may be resorted to as will be apparent to those skilled in the art. Such variations and modifications are to be considered within the purview and the scope of the claims appended hereto.
Claims (24)
1. A process for forming solidified Mg metal, said process comprising the steps of:
a) casting molten Mg metal in a gaseous atmosphere comprising SF6, and at least one of N2, O2, CO2 and H2O;
b) cooling said molten Mg metal to form a solidified Mg metal;
c) obtaining a vent gas comprising SF6 and at least one of N2, O2, CO2 and H2O from said casting step; and d) contacting said vent gas with a membrane in at least one membrane separation unit at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in at least one of N2, O2, CO2 and H2O.
a) casting molten Mg metal in a gaseous atmosphere comprising SF6, and at least one of N2, O2, CO2 and H2O;
b) cooling said molten Mg metal to form a solidified Mg metal;
c) obtaining a vent gas comprising SF6 and at least one of N2, O2, CO2 and H2O from said casting step; and d) contacting said vent gas with a membrane in at least one membrane separation unit at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in at least one of N2, O2, CO2 and H2O.
2. The process according to claim 1, wherein said gaseous atmosphere comprises from about 0.1 to about 10% by volume of SF6.
3. The process according to claim 1, wherein said vent gas comprises from about 0.0001 to about 0.2% by volume of SF6.
4. The process according to claim 1, wherein said retentate stream comprises from about 5 to about 100% by volume of SF6.
5. The process according to any one of claims 1 to 4, wherein said conditions comprise a temperature between about and about 80°C, a pressure drop between about 3 and about 200 psig, and a flowrate rate between about 10 -4 and about 10 Nm3/h-m2.
6. The process according to any one of claims 1 to 5, wherein said membrane is selected from the group consisting of polyimides, polyamides, polyamide-imides, polyesters, polycarbonates, polysulfones, polyethersulfone, polyetherketone, alkyl substituted aromatic polyesters, and blends of polyethersulfone, aromatic polyimides, aromatic polyamides, polyamides-imides, fluorinated aromatic polyimide, polyamide, and polyamide-imides.
7. The process according to any one of claims 1 to 6, wherein said vent gas is contacted with said membrane in two or more membrane separation units.
8. The process according to any one of claims 1 to 7, wherein said vent gas additionally comprises at least one of HC1 and C1 2, and wherein said vent gas is contacted with at least one caustic scrubber to remove said at least one of HC1 and C1 2 from said vent gas prior to contacting with said membrane.
9. The process according to any one of claims 1 to 8, wherein said vent gas additionally comprises particulates, and wherein said vent gas is contacted with at least one filter to remove said particulates from said vent gas prior to contacting with said membrane.
10. The process according to any one of claims 1 to 9, wherein at least a portion of said retentate stream is recycled to said casting step to provide said gaseous atmosphere.
11. The process according to claim 10, wherein said retentate stream is mixed with a mixture of N2 and O2 prior to being recycled to said casting step.
12. A process for forming solidified Mg metal, said process comprising the steps of:
a) casting molten Mg metal in a gaseous atmosphere comprising SF6 and CO2;
b) cooling said molten Mg metal to form a solidified Mg metal;
c) obtaining a vent gas comprising SF6 and CO2 from said casting step; and d) contacting said vent gas with a membrane in two or more membrane separation units at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in CO2.
a) casting molten Mg metal in a gaseous atmosphere comprising SF6 and CO2;
b) cooling said molten Mg metal to form a solidified Mg metal;
c) obtaining a vent gas comprising SF6 and CO2 from said casting step; and d) contacting said vent gas with a membrane in two or more membrane separation units at conditions effective to obtain a retentate stream rich in SF6 and a permeate stream rich in CO2.
13. The process according to claim 12, wherein said gaseous atmosphere comprises from about 0.1 to about 10% by volume of SF6, from about 40 to about 60% by volume of CO2, and the balance N2 and O2.
14. The process according to claim 12, wherein said vent gas comprises from about 0.0001 to about 0.2% by volume of SF6 and from about 2 to about 30% by volume of CO2.
15. The process according to claim 12, wherein said retentate stream comprises from about 0.01 to about 100% by volume of SF6, and said permeate stream comprises from about 0.1 to about 90% by volume of CO2.
16. The process according to any one of claims 12 to 15, wherein said conditions in each membrane separation unit comprise a temperature between about 10 and about 80°C, a pressure drop between about 3 and about 200 psig, and a flowrate rate between about 10 -4 and about 10 Nm3/h-m2.
17. The process according to any one of claims 12 to 16, wherein said membrane is selected from the group consisting of polyimides, polyamides, polyamide-imides, polyesters, polycarbonates, polysulfones, polyethersulfone, polyetherketone, alkyl substituted aromatic polyesters, and blends of polyethersulfone, aromatic polyimides, aromatic polyamides, polyamides-imides, fluorinated aromatic polyimide, polyamide, and polyamide-imides.
18. The process according to any one of claims 12 to 17, wherein said vent gas additionally comprises at least one of HC1 and C1 2, and wherein said vent gas is contacted with at least one caustic scrubber to remove said at least one of HC1 and C1 2 from said vent gas prior to contacting with said membrane.
19. The process according to any one of claims 12 to 18, wherein said vent gas additionally comprises particulates, and wherein said vent gas is contacted with at least one filter to remove said particulates from said vent gas prior to contacting with said membrane.
20. The process according to any one of claims 12 to 19, wherein at least a portion of said retentate stream and at least a portion of said permeate stream are recycled to said casting step to provide said gaseous atmosphere.
21. The process according to claim 20, wherein said retentate stream and said permeate stream are mixed with a mixture of N2 and O2 prior to being recycled to said casting step.
22. A process for forming solidified Mg metal, said process comprising the steps of:
a) casting molten Mg metal in a gaseous atmosphere comprising SF6 and CO2;
b) cooling said molten Mg metal to form a solidified Mg metal;
c) obtaining a vent gas comprising SF6 and CO2 from said casting step;
d) contacting said vent gas with a first membrane in a first membrane separation unit at conditions effective to obtain a first retentate stream rich in SF6 and a first permeate stream rich in CO2;
e) contacting said first permeate stream with a second membrane in a second membrane separation unit at conditions effective to obtain a second retentate stream depleted in CO2 and a second permeate stream rich in CO2; and f) contacting said first retentate stream with a third membrane in a third membrane separation unit at conditions effective to obtain a third retentate stream rich in SF6 and a third permeate stream depleted in SF6.
a) casting molten Mg metal in a gaseous atmosphere comprising SF6 and CO2;
b) cooling said molten Mg metal to form a solidified Mg metal;
c) obtaining a vent gas comprising SF6 and CO2 from said casting step;
d) contacting said vent gas with a first membrane in a first membrane separation unit at conditions effective to obtain a first retentate stream rich in SF6 and a first permeate stream rich in CO2;
e) contacting said first permeate stream with a second membrane in a second membrane separation unit at conditions effective to obtain a second retentate stream depleted in CO2 and a second permeate stream rich in CO2; and f) contacting said first retentate stream with a third membrane in a third membrane separation unit at conditions effective to obtain a third retentate stream rich in SF6 and a third permeate stream depleted in SF6.
23. The process according to claim 22, wherein at least a portion of said second permeate stream and at least a portion of said third retentate stream are recycled to said casting step to provide said gaseous atmosphere.
24. The process according to claim 22, wherein said second permeate stream and said third retentate stream are mixed with a mixture of N2 and O2 prior to being recycled to said casting step.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/856,756 US5855647A (en) | 1997-05-15 | 1997-05-15 | Process for recovering SF6 from a gas |
| US08/856,756 | 1997-05-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2237748A1 CA2237748A1 (en) | 1998-11-15 |
| CA2237748C true CA2237748C (en) | 2002-11-12 |
Family
ID=25324433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002237748A Expired - Lifetime CA2237748C (en) | 1997-05-15 | 1998-05-14 | Process for recovering sf6 from a gas |
Country Status (2)
| Country | Link |
|---|---|
| US (2) | US5855647A (en) |
| CA (1) | CA2237748C (en) |
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- 1998-10-30 US US09/182,771 patent/US6096114A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US6096114A (en) | 2000-08-01 |
| US5855647A (en) | 1999-01-05 |
| CA2237748A1 (en) | 1998-11-15 |
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