ASYMMETRIC MODIFIED CARBON MOLECULAR SIEVE FIBER MEMBRANES WITH IMPROVED PERMEABILITY

专利摘要:
Modified Carbon Molecular Sieve Modified Asymmetric Hollow Fiber Membranes Having Improved Permeability The present invention provides a modified cms asymmetric hollow fiber membrane having improved gas separation performance properties and a process for preparing a cms asymmetric hollow fiber membrane having improved gas separation performance properties. The process comprises treating a polymeric fiber precursor with a solution containing a modifying agent prior to pyrolysis. The concentration of the modifying agent in the solution may be selected to obtain a modified cms asymmetric hollow fiber membrane having a desired combination of gas permeability and selectivity properties. The precursor fiber is then pyrolysed to form a modified CMS asymmetric hollow fiber membrane having improved gas permeability.
公开号:BR112016007089A2
申请号:R112016007089
申请日:2014-09-30
公开日:2020-05-12
发明作者:Bhuwania Nitesh；Jason Williams Paul；John Koros William
申请人:Georgia Tech Res Inst；Shell Int Research；
IPC主号:

专利说明:

MEMBRANES OF HOLY FIBER FROM MOLECULAR CARBON SCREEN
ASYMMETRIC MODIFIED HAVING IMPROVED PERMEABILITY
[001] This application claims priority under 35 U.S.C. § 119 (e) for U.S. Provisional Application No. 61 / 884,548, filed September 30, 2013.
BACKGROUND OF THE INVENTION
1. Field of invention
[002] The present invention relates generally to modified carbon molecular sieve membranes (modified CMS) _f and more particularly to asymmetric modified CMS hollow fiber membranes.
2. Description of the Related Art
[003] Molecular carbon sieve membranes (CMS) have demonstrated a great potential for the separation of gases, such as for the removal of carbon dioxide (CO ₂ ) and other acid gases from natural gas streams. Symmetrical CMS hollow fiber membranes are preferred for large scale, high pressure applications.
[004] Asymmetric hollow fiber membranes have the potential to provide high flows required for productive separation, due to the reduction of the separation layer to a thin integral coating on the outer surface of the membrane. The asymmetric hollow morphology, that is, a thin integral coating supported by a porous or substructure base layer, provides the fibers with strength and flexibility, making them capable of resisting large differences in pressure of force that lead to the transmembrane. In addition, asymmetric hollow fiber membranes provide a high surface area for the volume ratio.
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[005] The asymmetric CMS hollow fiber membranes comp r e e n dem a thin and dense coating layer supported p < > r a porous substructure. Hollow fibers polymeric asymmetrical fibers, or precursor fibers, are
conventionally formed by an abruptly wet / dry jet spinning process, also known as a wet / dry
process of wet / dry wiring. The precursor fibers are, then, pyrolysed at a temperature above temperature glass transition of the polymer to prepare the membranes asymmetric CMS hollow fiber.
[006] The polymer solution used for spinning an asymmetric hollow fiber is referred to as a drug. During spinning, the drug surrounds an inner fluid, which is known as the transmissible fluid. The drugs and transmissible fluid are co-extruded through a die in an air gap during the dry jet stage. The fiber
cut is, then immersed in a cooled bath abruptly watery in the cold cooling step wet, that causes a phase separation process
damp to occur. After phase separation occurs,
fibers are collected by a winding drum and subjected to a solvent exchange process. [0 0 7] 0; solvent exchange process is a step and xt remake n t e important in the manufacturing process of membrane. If the porous precursor fibers contain water in the moment in that they are subjected to high
temperatures, for example, during drying or pyrolysis, the removal of water causes significant changes in
structure and fiber and CMS membrane properties
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Resulting 3/80. The high capillary forces associated with the removal of water within the small radius of the pores close to the coating cause densitization of the structure in this region, which results in a less permeable membrane. To avoid this, the solvent exchange process replaces the water that is present in the porous substructure of the precursor fiber having a lower surface tension.
[008] A conventional solvent exchange process involves two or more steps, with each step using a different solvent. The first step or series of steps involves contacting the precursor fiber with one or more solvents that are effective in removing water from the membrane. This generally involves the use of one or more water-miscible alcohols that are sufficiently inert for the polymer. Aliphatic alcohols having 1-3 carbon atoms, that is, methanol, ethanol, propanol, isopropanol, and combinations of the above, first solvent. They are particularly effective as a second step or series of steps involve contacting the fiber with one or more solvents which are effective to replace the first solvent with one or more volatile organic compounds having a low surface tension. Among the organic compounds that are useful as a second solvent are straight or branched chain aliphatic alkanes, C5 or greater.
[009] The process of solvent exchange typically
involves immersion of the precursor fibers in a first
solvent for a first * effective time, which may vary up to a number of days, and then immersion of crecursor fibers in a second solvent for a second
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4/80 effective time, which can also vary up to a number of days. When precursor fibers are produced continuously, as in a commercial capacity, a long precursor fiber can be continuously drawn through a series of contact vessels, where it is placed in contact with each of the solvents. The solvent exchange process is usually carried out at room temperature.
[010] The precursor fibers are then dried by heating to temperatures above the boiling point of the final solvent, used in the solvent exchange process and subjected to pyrolysis in order to form asymmetric CMS hollow fiber membranes.
[Oil] The choice of precursor polymer, the formation and
treatment gives fiber precu rsora before pyrolysis, and at conditions in pyrolysis all influences you the properties in performance in a memk irana hollow fiber Asymmetric CMS.
[012] The important properties of asymmetric CMS hollow fiber membranes include permeability and selectivity. Permeability measures the normalized pressure flow of a given compound, while selectivity measures the ability of a gas to permeate through the membrane versus a different gas. These properties, and the methods by which asymmetric CMS hollow fiber membranes can be tested to determine these properties, are described in more detail in, for example, U.S. Patents of Nos. 6,565,631 and 8,486,179, the contents of both of which are incorporated herein by reference.
[013] Although asymmetric CMS hollow fiber membranes have encouraging selectivities, they have lower permeability after pyrolysis than
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5/80 would be expected based on the increase in permeability in the corresponding dense films before and after pyrolysis of the same precursor polymer. The lower-than-expected permeability is thought to be caused, at least in part, by a phenomenon known as the collapse of the substructure morphology.
[014] As described in U.S. Patent Application No.
3 / 666,370, whose contents are incorporated by reference, collapse of the substructure morphology occurs when the intensive heat treatment during pyrolysis relaxes the polymer chains, causing their segments to move close to each other and the collapse of the pores in the substructure.
This collapse of the substructure's morphology results. in an increase in thickness
O. The separation of the membrane and thus a drop in permeability.
Due to the drop in weight and stability, the advantage of having a high transport flow in one. asymmetric fiber is less significant.
[015] In U.S. Patent Application No. 13 / 666,370,
Bhuwania et al. describes a method for treating precursor fibers in order to limit the collapse of the substructure that occurs during pyrolysis. Bhuwania et al. showed that immersion of the precursor fibers in a chemical modifying agent, such as vinyl trimethoxy silane (VTMS), before pyrolysis, asymmetric CMS hollow fibers having an increased permeability can be formed. Without being bound by any theory, Bhuwania et al. describes that the chemical modifying agent thermally and / or physically stabilizes the precursor fiber prior to pyrolysis.
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[016j It has now surprisingly been found that by contacting a precursor fiber with a solution containing the modifying agent at a concentration less than 100%, the permeability of the resulting asymmetric modified CMS hollow fiber membrane can be increased to a degree well beyond what is achieved by immersing the precursor fiber in the chemical modifying agent alone, as described in US Patent Application No. 13 / 666,370, without having an adverse effect on the selectivity of the modified CMS hollow fiber membrane. SUMMARY OF THE INVENTION
[017] It is an object of at least one embodiment of the present invention to provide a process for the preparation of an asymmetric modified CMS hollow fiber membrane having improved gas separation performance properties by treating a polymeric precursor fiber with a solution containing a modifying agent before pyrolysis. The concentration of the modifying agent in the solution can be selected in order to obtain an asymmetric modified CMS hollow fiber membrane having a desired combination of gas permeability and selectivity properties. The precursor fiber is then preferably placed in contact with an atmosphere containing moisture. The treated precursor fiber is pyrolyzed to form a CMS hollow fiber membrane
modified asymmetric : having pe rmeability in gas aperf eiçoadi The. [018] Po example, the with centering of agent in modification in the solution Can be selected for i get an membrane hollow fiber Modified CMS each asymmetric i having an
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7/80 gas permeability property which is at least a 400% increase over an equivalent asymmetric CMS hollow fiber membrane that has not been treated with the modifying agent. The concentration of the modifying agent in the solution can also be selected to obtain an asymmetric modified CMS hollow fiber membrane which is useful for the separation of particular components within a gas stream. For example, the concentration of the modifying agent can be selected to obtain an asymmetric modified CMS hollow fiber membrane that is useful for separating acid gases, such as CO2 and H2S, from a hydrocarbon-containing gas stream, such as natural gas. The concentration of the modifying agent can also be selected to obtain a hollow fiber membrane. Asymmetric modified CMS that is configured for the separation of particular gases, including, but not limited to, CO2 and CH ₄ , H2S and CH ₄ , CO2 / H2S and CH ₄ , CO ₂ and ΙΊ2, C'2 and N2, U2 and CH ₄ , He and CH ₄ , H2 and CH ₄ , Ho and COH 4, ethylene and ethanol, propylene and propane, and ethylene / propylene and ethane / propane, each of which can be carried out within a gas comprising additional components.
[019 j It is also an object of at least one embodiment of the present invention to provide a process for the preparation of an asymmetric modified CMS hollow fiber membrane having an improved gas permeability property by treating a precursor fiber with a solution containing a modifying agent, where the modifying agent is present in the solution at a concentration between about 1 and about
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8/80 weight percent, and then subjected to pyrolysis of the treated fibers to form an asymmetric modified CMS hollow fiber membrane.
[020] In another aspect, it is an objective of at least one embodiment of the present invention to provide a process for forming an asymmetric modified CMS hollow fiber membrane, wherein at least one of the solvent exchange materials with which the fiber precursor is brought into contact before pyrolysis contains a modifying agent in an amount that is effective in improving the gas permeability of the asymmetric modified CMS hollow fiber membrane. In preparing an asymmetric CMS hollow fiber membrane, the polymeric hollow fiber is cut and then immersed in an aqueous bath - a process known as the abruptly wet, dry jet cooled method. Then, in a solvent exchange step, the fiber is brought into contact with an organic compound having a low surface tension, such as n-hexane, which enters the pores of the fiber. By replacing the organic compound from the conventional solvent exchange process with a solution comprising the organic compound and a modifying agent, it has now been discovered that the pyrolysis of the treated precursor fibers produces asymmetric modified CMS hollow fiber membranes having permeability properties of improved gas.
[021] In this way, at least one embodiment of the present invention is directed to a process for forming an asymmetric modified CMS hollow fiber membrane that includes the formation of an asymmetric hollow polymer fiber, which puts in contact the hollow polymer fiber common
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9/80 hun perme, form me, invent me fiber ecu contact that comprises an agent of an ethical amount to improve the membrane of
CMS to hollow fiber hollow membrane
Rec ibra skin with modifi
[022j It is a mode of your pores.
polymer for another embodiment is a permeability agent of the present with one of mc which prevents the perfection of the membrane formed by the membrane inside a fiber which removes the moisture agent contained within the polymeric precursor fit. During a morphology stabilizer it acts
In at least one preferred form the morphology comprises one as one containing p <
ίο. In morphological modality within the membrane of
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10/80 can generally be measured by elementary analysis. Preferably, the asymmetric modified CMS hollow fiber membrane contains between about 0.1 and about 10 mol% of an indicator element, such as silicon.
BRIEF DESCRIPTION OF THE DRAWINGS
[023] A clear conception of the advantages and characteristics of one or more modalities will become more easily evident by reference to the exemplary and, therefore, non-limiting modalities, illustrated in the drawings:
[024] FIG. 1 is an illustration of an exemplary precursor fiber treatment process according to various embodiments of the present invention.
[025] FIG. 2 is an illustration of a reaction of the type believed to occur when a precursor fiber is brought into contact with a modifying agent according to various embodiments of the present invention.
[026] FIG. 3 is an illustration of a film of the type believed to form on the outer coating layer of an asymmetric hollow precursor fiber, when the precursor fiber is brought into contact with a modifying agent in high concentrations.
[027] FIG. 4 shows the results of the test of a dynamic mechanical analysis, demonstrating the loss of storage module observed in the heating of Matrimid® 5218 precursor fibers to its glass transition temperature (T _a ) and the restriction of such losses observed with treated precursor fibers Matrimid® 5218 according to various embodiments of the present invention.
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[028 already FIG. 5A shows the results of the “ ³ Si solid state nuclear magnetic resonance (NMR) test, demonstrating the presence of siloxane bridges in a precursor fiber treated according to the modalities of the present invention.
[029] FIG. 5B shows the results of the “ ³ Si solid state nuclear magnetic resonance (NMR) test, demonstrating the presence of siloxane bridges in a hollow asymmetric carbon molecular sieve fiber treated according to the modalities of the present invention.
[030] FIG. 6 shows the results of the ¹³ C solution nuclear magnetic resonance (NMR) test,
demonstrating what the modifies agent . no action : reacts with precursor fiber polymer. [031] FIG »7 shows the images of SEM of fibers hollow CMS mo d i f i s asymmetric as for put on in contact an precursor fiber Matr imi d® 5 [ 118 with an solution that composed : sells 75 percent in weight (7 5% in p eso)
of VTMS and pyrolyzed at 550 ° C.
[032] FIG. 8 shows SEM images of asymmetric modified CMS hollow fibers prepared by contacting a Matrimid® 5218 precursor fiber with a solution comprising 50 percent by weight (50% by weight) of VTMS and pyrolyzed at 550 ° C.
[033] FIG. 9 shows SEM images of asymmetric modified CMS hollow fibers prepared by contacting a Matrimid precursor fiber with a solution comprising 25 weight percent (25 weight%) of VTMS and pyrolyzed at 550 ° C.
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[034] FIG. 10 shows SEM images of asymmetric modified CMS hollow fibers prepared by contacting a Matrimid® 5218 precursor fiber with a solution comprising 10 percent by weight (10% by weight) of VTMS and pyrolyzed at 550 ° C.
[035] FIG. 11 shows SEM images of asymmetric modified CMS hollow fibers prepared by contacting a Matrimid® 5218 precursor fiber with a solution comprising 5 percent by weight (5% by weight) of VTMS and pyrolyzed at 550 ° C.
[036j FIG. 12 shows the SEM pictures in hollow fibers Modified CMS asymmetric s prepared per put on contact a fiber precursor Matrimid® 5218 with a solution comprising 1 percent and τη weight (1% in Weight ) of VTMS and
pyrolyzed at 550 °
[037] FIG. 13 it's a representation the graphics From 1 Γ s u Itados of you ste that demonstrate properties in sepa gas ration improved specimens for fibers> hollow CMS modified The prepared symmetric according with
embodiments of the present invention.
[038] FIG. 14 is an illustration of an exemplary pyrolysis process that can be used with various embodiments of the present invention.
[039] Figure 15A shows the CO ₂ permeability of exemplary asymmetric modified CMS hollow fiber membranes (prepared by treating Matrimid 2158® precursor fibers with a solution containing 10% by weight of VTMS and pyrolysis at two different temperatures) in a gas mixed containing 50 mol% CO ₂ and 50 mol% CH ₄ and
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13/80 at pressures up to 800 pounds per square inch (psi) (5.52 x 10 ⁶ Pa).
[040] Fig 15B shows the selectivity of CO ₂ / CH ₄ of exemplary asymmetric modified CMS hollow fiber membranes (prepared by treating Matrimid 2158® precursor fibers with a solution containing 10% by weight of VTMS and pyrolysis at two different temperatures ) in a mixed gas containing 50 mol% CO ₂ and 50 mol% CH ₄ and at pressures up to 800 pounds per square inch (psi) (5.52 x 10 ⁶ Pa).
DETAILED DESCRIPTION OF THE INVENTION
Asymmetric and Modified CMS Hollow Fiber Membranes
Morphology Stabilizers
[041] An asymmetric modified CMS hollow fiber membrane is an asymmetric CMS hollow fiber membrane that
was treated with an agent of modification autS S pyrolysis, in such a way what the collapse of substructure CÃ Qâ fiber during pyrolysis is 1 limit, taunting one increase of
p e rme rity of the asymmetric CMS hollow fiber membrane gas over one that was prepared in the same way, but without being treated with the modifying agent.
[042] Treatment of the precursor fiber with a modifying agent also alters the elemental composition of the asymmetric CMS hollow fiber membrane. For example, the modifying agent may contain elements, such as silicon, metals or combinations thereof, the presence of which decreases the weight percentage of carbon in a modified CMS hollow fiber membrane. A modified CMS hollow fiber membrane can comprise, for example, between about 60% and about 80% by weight of carbon, compared to
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14/80 is a conventional CMS hollow fiber membrane, which typically comprises at least 80% by weight of carbon. A modified CMS hollow fiber membrane is not defined by the amount or percentage of carbon in its elemental composition and does not require a particular minimum amount or percentage of
carbon being present.
[043] It has now been found that the modifying agent does not need to react with the polymer precursor fiber itself, but rather the modifying agent can react with the moisture that is present in the pores of a precursor fiber or is molecularly sorbed between the segments of the chain polymer. The modifying agent is believed to react with the moisture that is present in the pores of the precursor fiber
for one sol-gel reaction process to form a
solid morphology stabilizer structure. Fig. 1
illustrates the two stages of the sol-gel reaction contemplated, on what vinyltrimethoxysilane (VTMS), a change preferred, is converted to a stabilizer of
morphology within the pores of an asymmetric hollow fiber.
In a first stage, the modification agent suffers reactions hydrolysis and polycondensation to form a network of chain type. The first stage is illustrated, for example, in Fig. 2, which shows the hydrolysis reactions and
condensation of vinyltrimethoxysilane (VTMS) to form a chain-type network. It is believed that
first step, that is, the reaction of the modifying agent
to form a chain-like network, it is caused by contacting a precursor fiber with the modifying agent, such as by immersing the precursor fiber in a solution containing the modifying agent, and then
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put on CO fiber contact precursor with moisture, such like put the fi br a under a atmosphere wet. In a se gunda step, the re of like jail is converted to an structure ; only going. How illu strado in Fig. 1, we believe is that the seconditapa occurs during and the pyrolysis of fiber precursor
[044] The result of the reaction is the formation of a morphology stabilizer. The term morphology stabilizer, as used herein, refers to the residue
of an agent : from moc lification what acts to restrict the collapse of pores during The pyrolysis and that resides in substructure porous fiber the CA Asymmetric modified CMS.
The morphology stabilizer is a glassy structure that acts as a kind of scaffolding within a pore, thus preventing the collapse of the pore. In some embodiments, the morphology stabilizer can be porous. When the morphology stabilizer is porous, such as a morphology stabilizer comprising mesopores, its interference with the gas stream through the modified CMS hollow fiber membrane is reduced.
[045j The formation of a morphology stabilizer through a sol-gel reaction process, as well as the relationship between the morphology stabilizer and the modified CMS hollow fiber membrane, has been discovered and confirmed through a number of studies.
Example 1
[046] The Matrimid® 5218 precursor fibers were immersed in pure VTMS at room temperature for about twelve hours. The fibers were then removed and placed in a glove bag saturated with moisture air
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16/80 relative to about 100%. After about 48 hours, the fibers were removed from the glove bag and dried under vacuum at 150 ° C for about 12 hours. A portion of the Matrimid® 5218 treated precursor fibers was reserved for the test. The remainder of the treated Matrimid® 5218 precursor fibers was pyrolyzed under an atmosphere of ultra-high purity argon (-99.9%) at a maximum pyrolysis temperature of about 650 ° C. The fibers were kept at the maximum pyrolysis temperature for about two hours.
[047] Both Matrimid® 5218 treated precursor fibers, that is, the pre-pyrolysis fibers, and the modified CMS hollow fibers, that is, the post-pyrolysis fibers, were tested by solid state nuclear magnetic resonance “ ⁹ Si (NMR). After treatment with VTMS, Matrimid® 5218 precursor fibers exhibited peaks that were indicative of siloxane bonds, also sometimes referred to as siloxane bridges. These siloxane bridges are indicative of the hydrolysis and condensation of VTMS through a sol-gel reaction. After being subjected to pyrolysis,
the fibers the CA CMS also exhibited spikes that have been i n d i c a t i v o s in bridges siloxane. NMR solid state ²⁹ Si demons t ra what the hollow fibers Mo d i f i ced CMS
asymmetric particles comprise a residue from the sol-gel reaction.
The results of this study are shown in the Figures 5A and 5B. Example 2 [048] Matrimid® precursor fibers 5218 were ime rs in pure VTMS at room temperature during fence in twelve hours. The fibers were then I removed from and
placed in a glove bag saturated with moisture air
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17/80 relative to about 100%. After about 48 hours, the fibers were removed from the glove bag and dried under vacuum at 150 ° C for about 12 hours.
[049] Matrimid® 5218 treated precursor fibers were tested by solution 13 nuclear magnetic resonance
C (NMR) and the results compared to the ^lj C solution nuclear magnetic resonance spectrum for untreated Matrimid® 5218 precursor fibers. The results are shown in Figure 6. In particular, the solution C C NMR spectrum of the precursor fibers treated Matrimid® 5218 has no substantial difference from the NMR spectrum of ¹³ C solution of Matrimid® 5218 precursor fibers that have not been contacted with the VTMS modifying agent. These results indicate that the modifying agent does not react with the Matrimid® 5218 precursor fiber, that is, that the sol-gel reaction did not occur between the modifying agent and the precursor polymer. Instead, it was determined that the sol-gel reaction occurred between the modifying agent and moisture that is present within the pores of Matrimid® 5218 precursor fibers.
Precursor Fibers
[050 j The asymmetric polymer precursor fiber can comprise any polymeric material that, after being subjected to pyrolysis, produces a CMS membrane that allows the passage of the desired gases to be separated, for example, carbon dioxide and natural gas, and in than at least one of the desired gas permeates through the CMS fiber at a different diffusion rate than that of the other components. Polyimides are preferred polymer precursor materials. Suitable polyimides include, for example,
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18/80 example, Ultem® 1000, Matrimid® 5218, 6FDA / BPDA-DAM, 6FDA6FpDA, and 6FDA-IPDA.
[051] The polyimide commercially sold as Matrimid® 5218 is a specialty diamine-based thermoplastic polyimide, 5 (6) -amino-1- (4'-aminophenyl) -1,3, trimethylindane. Its structure is:
[052] The Matrimid® 5218 polymers used in the Examples were obtained from Huntsman International LLC. 6FDA / BPDA-DAM is a polymer composed of 2,4,6 trimethyl-1,3-phenylene diamine (DAM), 3,3,4,4biphenyl tetracarboxylic dianhydride (BPDA), and 5.5- [2,2,2 -trifluor-1 (trifluoromethyl) ethylidene] bis-1,3-isobenzofurandione (6FDA), and having the structure:
[053] To obtain the aforementioned polymers, one can use available sources or synthesize them. For example, such a polymer is described in U.S. Patent No. 5,234,471, the content of which is incorporated herein by reference.
[054] Examples of other suitable precursor polymers include polysulfones; poly (styrenes), including styrene-containing copolymers, such as styrene acrylonitrile copolymers, styrene-butadiene copolymers and
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19/80 styrene-vinylbenzyl halide copolymers: polycarbonates; cellulosic polymers, such as cellulose acetatobutyrate, cellulose propionate, ethyl cellulose, methyl cellulose, nitrocellulose, etc .; polyamides and polyimides, including aryl polyamides and aryl polyimides; polyethers; polyetherimides; polyethylketones; poly (arylene oxides), such as poly (phenylene oxide) and poly (xylene oxide); poly (stearide-diisocyanate); polyurethanes; polyesters (including polyarylates), such as poly (ethylene terephthalate), poly (alkyl methacrylates), poly (acrylates), poly (phenylene terephthalate), etc .; polypyrrolones; polysulfides; polymers from monomers having alpha-olefinic unsaturation other than that mentioned above, such as poly (ethylene), poly (propylene), poly (butene-1), poly (4-methyl pentene-1), polyvinyls, for example, poly (vinyl chloride), poly (vinyl fluoride), poly (vinylidene chloride), poly (vinylidene fluoride), poly (vinyl alcohol), poly (vinyl esters), such as poly (vinyl acetate) and poly ( vinyl propionate), poly (vinyl pyridines), poly (vinyl pyrrolidones), poly (vinyl ethers), poly (vinyl ketones), poly (vinyl aldehydes), such as poly (formal vinyl) and poly (vinyl butyral), poly (vinyl amides), poly (vinyl amines), poly (vinyl urethanes), poly (vinyl ureas), poly (vinyl phosphates), and poly (vinyl sulfates); polyalyls; poly (benzobenzimidazole);
polyhydrazides;
polyoxadiazoles;
politriazoles; poly (benzimidazole); polycarbodiimides; polyphosphazines; etc., and interpolymers, including block interpolymers containing repeating units from the above, such as sodium salt terpolymers of
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20/80 acrylonitrile-vinyl bromide from parasulf of enilmet alii ethers; and grafts and mixtures containing any of the above. Typical substituents that provide substituted polymers include halogens, such as fluorine, chlorine and bromine; hydroxyl groups; lower alkyl groups; lower alkoxy groups; monocyclic aryl; lower and similar acyl groups.
[05.5j Preferably, the polymer is a rigid, glassy polymer at room temperature, as opposed to a rubber polymer or a flexible glassy polymer. Glassy polymers are differentiated from rubber polymers by the rate of segmental movement of polymer chains. Polymers in the glassy state do not have the rapid molecular movements that allow rubber polymers of their liquid type nature and their ability to adjust segmental configurations quickly over large distances (> 0.5 nm). There are glassy polymers in an unbalanced state with molecular chains entangled with immobile molecular structures in frozen conformations.
The glass transition temperature (Tg) is the point of division between the glassy or rubbery state. Above Tg, the polymer exists in the rubber coating; below Tg, the polymer exists in the glassy state. Generally, polymers
vrt .reos provide a selective environment for broadcasting gas ; and are favored for gas separation applications. The rigid, glassy polymers describe polymers with is . rigid polymer chain breaks that have mobility rot limited intramolecular action and are often
characterized by high transition temperatures
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21/80 glassy. Preferred polymer precursors have a glass transition temperature of at least 200 ° C.
[056] In rigid, glassy polymers, the diffusion coefficient tends to control selectivity, and glassy membranes tend to be selective in favor of small molecules, with a low boiling point. For example, preferred membranes can be made from rigid, glassy polymer materials that will pass carbon dioxide, hydrogen sulfide and nitrogen, preferably over methane and other light hydrocarbons.
Such polymers are well known in the art and include polyimides, polysulfones and cellulosic polymers.
[057] The asymmetric polymer precursor fiber can be a composite structure comprising a first polymer material supported on a second porous polymer material. Composite structures can be formed using more than one polymer material as the drug during the asymmetric hollow fiber spinning process.
[058] In some embodiments, the polymer precursor fiber may contain functional reactive groups that react with the modifying agent. As demonstrated in Example 2, the reaction of the modifying agent and the polymer precursor fiber are not necessary for the formation of either a morphology stabilizer or a modified CMS hollow fiber membrane. However, it is considered that some precursor polymer materials can react with the modifying agent. For example, precursors prepared using polymer materials that contain hydroxyl groups (—OH) or acid functional groups (such as —COOH) can react with the modifying agent. It is considered that
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22/80 this reaction can occur in addition to the sol-gel reaction between the modifying agent and moisture within the pores, and that pyrolysis still continues to result in a morphology stabilizer and an asymmetric modified CMS hollow fiber membrane.
Modification Agents
[0 59] The term modifying agent, as used herein, refers to a compound that is capable of undergoing a reaction within the pores of a polymer precursor fiber to form a morphology stabilizer without otherwise adversely affecting the mechanical properties of flora.
[060] Preferred modifying agents are those that undergo a polycondensation reaction to form siloxane bridges. For example, the modifying agent can be a silane having the general formula R ¹ R ^z R 'R ⁴ Si, where each of R ¹ , R ² , R °, and PÓ is, independently, Ci-Cg alkyl. yl or alkenyl, alkoxy, or halogen, with the proviso that the silane contains at least one C1-6 alkyl or alkenyl substituent, and at least one alkoxy or halogen substituent. The at least alkoxy or halogen substituent provides the silane with the ability to form a chain-like network of siloxane bonds. The at least C 1 -C 6 alkyl or alkenyl substituent provides that treatment of a fiber with the modifying agent does not make the fiber brittle. Subject to this condition, each of the substituents can be varied in order to provide the silane with the desired properties. For example, by selecting the substituent groups, one may be able to
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23/80 change the porosity of the resulting morphology stabilizer.
[061] In some preferred embodiments, vinyl trimethoxy silane (VTMS) is used as the modifying agent for the precursor treatment, but other silanes can also be used as a modifying agent. The modifying agent, for example, can be mois sion or an oil s iloxane, such as a disiloxane or a trisiloxane. For example, in various embodiments, the modifying agent can be selected from the group consisting of trimethoxysilane vinyl, triethoxysilane vinyl, dimethoxychlorosilane vinyl, vinyl detoxichlorosilane, vinyl methoxydichlorosilane, vinyl ethoxydichloro silane, vinyl trichloro silane, vinyl pentamethoxysiloxane, divinyl tetramethoxy, divinyl tetramethoxy and combinations thereof. In several particularly preferred embodiments, the at least one alkoxy or halogen substituent comprises methoxy or ethoxy. In several particularly preferred embodiments, the at least alkyl or alkenyl C1-Cg substituent comprises vinyl. Particularly preferred modifying agents include vinyl trimethoxy silane, vinyl triethoxy silane, ethanol trimethoxy silane, and methyl trimethoxy silane.
[062] Other modifying agents include those that undergo a polycondensation reaction to form metal oxide and / or metal oxo bonds.
For example, the modifying agent can be a metal alkoxide having the general formula rWr'Si, of R ¹ , R ² , R ³ , and R is, where M is a metal and where each independently, Ci-Cg alkyl or alkenyl, alkoxy, or halogen, with the proviso that the
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24/80 metal alkoxide contains at least one C 1-6 alkyl or alkenyl substituent and at least one alkoxy or halogen substituent. The at least alkoxy or halogen substituent provides the metal alkoxide with the ability to form a chain-type network of metal oxycarbonate bonds
and / or. goal l-oxo . 0, ρ ·; slo minus, substituent C 1 -C 6 alkyl or alkenyl predict what The treatment of a fiber with the alkoxide of metal no torr was going the brittle fiber. s lu way to this
condition, each of the substituents can be varied to provide the metal alkoxide with the desired properties. For example, by selecting the substituent groups, one may be able to alter the porosity of the resulting morphology stabilizer. In preferred embodiments, metal M is selected from the group consisting of Ge, B, Al, Ti, V, Fe, and combinations thereof.
Pyrolysis Treatment and Conditions
[063j When modifying a polyme.ro precursor fiber to prepare, an asymmetric modified CMS hollow fiber membrane has substantially not collapsed, the process comprises the steps of providing the precursor polymer, providing a contact solution comprising an agent modification (which is present in the solution at a concentration less than 100% by weight), and allowing at least a portion of the precursor polymer to contact at least a portion of the contact solution comprising the modifying agent to create a modified precursor polymer which, when pyrolyzed, produces an asymmetric modified CMS hollow fiber membrane, has substantially not collapsed. Preferably, the precursor polymer is immersed in
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25/80 a solution comprising the modifying agent at a desired concentration for a period of time sufficient to allow the modifying agent to enter the pores of the precursor fiber substructure. Preferably, the time period is from about 30 minutes to about 24 hours.
[064] The solution containing the modifying agent does not need to contact one end of the hollow precursor fiber in order to enter the pores of the substructure of the precursor fiber. Instead, it has been found that the modifying agent can penetrate the outer coating of the precursor fiber in a radial direction, and enter the pores of the fiber substructure in this manner.
[0 65j The contact of a precursor fiber with a modifying agent occurs, preferably, at room temperature. However, in some additional embodiments, the contact temperature can be carried out within a selected range of approximately 20 ° C of the glass transition temperature of the precursor polymer; from approximately 100 ° C of the glass transition temperature of the precursor polymer; and from about 100 ° C to approximately 250 ^° C.
[066] In several embodiments, the reaction of the modifying agent to form a morphology stabilizer may require the addition of a catalyst. For example, when vinyl triethoxy silane is used as the modifying agent, it may be desirable to add a catalyst to promote
reaction of sun-gel. I this is due to the slow reaction of groups ethoxy in comparison with groups methoxy from, for example, VTMS. S reaction ol-gel can and > to be promoted through
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adding an acid, such as a mineral acid, as is known in the art that a sol-gel reaction is frequent em um n t a going significantly under conditions
acidic. Preferred acid catalysts include any readily available mineral acid, such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, hydrofluoric acid, hydrobromic acid, perchloric acid, and combinations thereof.
[067] Once the precursor fiber has been brought into contact with the modifying agent, for example, by immersion in a solution containing the modifying agent a
a selected concentration the treated precursor fiber is
placed in contact with moisture, such as placing the
fiber under an atmospheric : it was containing moisture. The atmosphere containing moisture can be one that has one. relative humidity between about 50% and 100%. Precursor fibers are preferably kept under the atmosphere containing moisture
for a period of time between about 1 hour and 60 hours.
[068] The treated precursor fibers are then dried and pyrolyzed. Pyrolysis is advantageous, conducted under
an inert atmosphere. The pyrolysis temperature may be between about 500 ° C and about 800 ° C; alternatively,
the pyrolysis temperature can be between about 500 ° C
and about 700 ° C; alternatively, the temperature of pyrolysis may be between about 500 ° C and 650 ° C;
alternatively, the pyrolysis temperature can be between about 500 ° C and 600 ° C; alternatively, the pyrolysis temperature can be between about 500 ° C and 550 ° C; alternatively, the pyrolysis temperature can
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27/80 be between about 550 ° C and about 700 ° C;
alternatively, the pyrolysis temperature can be between about 50 ° C and about 650 ° C, alternatively, the pyrolysis temperature can be between about 600 ° C and about 700 ° C; alternatively, the pyrolysis temperature can be between about 600 ° C and about 650 ° C. The pyrolysis temperature is typically reached through a process in which the temperature is slowly increased. For example, when using a 650 ° C pyrolysis temperature, the pyrolysis temperature can be achieved by increasing the temperature from 50 ° C to 250 ° C at a ramp speed of 13.3 ° C / min,
increasing The temperatuie 2 50 ° C at 635 ° C to a velocity in ramp c ie 3 , 85 ° C / min, and there moistening the temperature in 635 ° C a 650 ^c 'C at speed of ramp 0.25 ° C / min • Once what the temperature of pyrolysis is reached, the fibers are heat temperature pyrolysis
for an immersion time, which can be a number of hours.
[069j The polymer precursor fibers can also be packaged and pyrolyzed as a bundle, in order to produce a large number of hollow fiber CMS membranes modified in a single pyrolysis operation. Although pyrolysis will generally be referred to in terms of pyrolysis of a fiber precursor, it should be understood that any description of pyrolysis used here is intended to include pyrolysis of precursor fibers that are packaged, as well as those that are not packaged.
[070j Typically, the heating of polymer precursor fibers packaged above the transition temperature
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28/80 glass of the polymer material, as it occurs during pyrolysis, causes the fibers to stick together. This adherence to the bundled fibers reduces their convenience for use as a CMS hollow fiber membrane. By treating polymer precursor fibers with a modifying agent, as described herein, adhesion between the fibers in a bundle can be reduced or eliminated. During treatment, the modifying agent reacts to form a thin film on the outer coating surfaces of the precursor fibers. For example, when a precursor fiber is treated with VTMS, the treated precursor fiber will comprise a thin film of material containing silicon on the surface of the outer coating, and after pyrolysis, the hollow modified CMS fiber will comprise a thin film of silica. on the surface of the outer covering. This thin film acts as a mechanical barrier, preventing fibers from sticking together during pyrolysis. As a result, the gas separation properties of asymmetric modified CMS hollow fiber membranes that are subjected to pyrolysis in a beam are similar to the asymmetric modified CMS hollow fiber membranes that are not aggregated during pyrolysis.
[071 j Thus, as will be described in more detail below, it is the concentration of the modifying agent during treatment and the pyrolysis temperature that most affect the gas separation properties of a modified CMS hollow fiber membrane produced from a selected precursor fiber.
Select the Modification Agent Concentration
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[072 j It has now surprisingly been found that dilution of the modifying agent prior to treatment of a polymer precursor fiber results in a modified CMS hollow fiber membrane having increased permeability through a modified CMS hollow fiber membrane
produced by treat I'm sorry a precurable polymer sor with a agent of modifier pure ion. The diluent can be > r any liquid q · eu no interfere with the reaction of οίΟ’ΘΙΤΓ.Θ ό-Θ
modification to form a morphology stabilizer. Suitable diluents include straight or branched chain aliphatic hydrocarbons, Cg or greater. Preferred diluents, for example, include n-hexane, toluene, and nheptane.
Comparative Example .1
[073] Matrimid® 5218 untreated precursor fibers were placed on a stainless steel wire mesh and held in place by wrapping a length of wire around the mesh and fibers. The mesh support containing the fibers was then loaded into a
pyroly if, like the type that is illustrated in Figui : a j. 4. At pyroly These sessions were carried out under an atmosphere of argon in purity ultra-high (99.9% pure) as follows: 1. 50 ° C to 2 50 ° C at a ramp speed of 1. 3 / ° C / min r 2 . 250 ° C to 635 ° C at ramp speed of 3 85
° C / min,
3,635 ° C at 650 ° C a ramp speed of 0.2 5 ° C / min, 4. Immersed color 2 hours at 650 ° C.
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[074j The resulting CMS fibers were tested on a single fiber module, as described by Koros et al. in US Patent No. 6,565,631, the contents of which are incorporated herein by reference. The CMS fiber module was tested using a constant pressure variable pressure permeability system for both mixed and pure gas feeds similar to that described by Koros et al. in US Patent No. 6,565,631. The CMS fibers were tested using a mixed gas feed containing 50 mol% CO2 and 50 mol% CH ₄ at a pressure of 150 psi (pounds per square inch) (1.03χ10 ^Ό Pa).
The temperature was maintained at 35 ⁰
[0 / b] CO2 permeability through CMS fibers was measured to be about 8 to 10 GPU. The selectivity of CO2 / CH4 was determined to be about 9 to 10 0.
Comparative Example 2
[0/6] The Matrimid® 5218 precursor fibers were
immersed in Pure VTMS ( -H sto yeah, 10 0 % by weight of VTMS) during a time dc 9 about 12 ho ras. At fibers were in; then removed starting gives only: solution and placed in a bag of
glove containing air at 100% relative humidity. After about 48 hours, the fibers were removed and dried by heating under vacuum at 150 ° C for about 12 hours. The treated precursor fibers were then placed on a stainless steel wire mesh and held in place by wrapping a length of wire around the mesh and fibers. The mesh support containing the fibers was then loaded into a pyrolysis facility, such as the type shown in Figure 14. The pyrolysis was
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31/80 performed under an argon atmosphere of ultra-high purity (99.9% pure) as follows:
1. 50 ° C at 2 5C ° C to a velocity in ramp 13, 3 ° C / min, 2. 250 ° C at 635 ° C a an velocity in ramp 3 , 8 5 ° C / min, 3,635 ° C at 650 ° C a an velocity in ramp 0 , 25 ° C / min, 4. Immersed by 2 1 loras to 65 ( ) ° C. [077] The fibers CMS modified resu Itantes fo ram
tested in a single fiber module such as that described by Koros et al. in US Patent No. 6,565,631, the contents of which are incorporated herein by reference. The CMS fiber module was tested in a constant pressure variable pressure permeability system for both mixed and pure gas feeds similar to that described by Koros et al. in US Patent No. 6,565,631. The modified CMS fibers were tested using a mixed gas feed containing 50 mol% CO2 and 50 mol% CH4 at a pressure of 150 psi (pounds per square inch) (1.0x10 ⁶ Pa). The temperature was maintained at 35 ° C.
[078] CO2 permeability through the modified CMS fibers was measured to be about 35 to 40 GPU. The selectivity of CO2 / CH4 was determined to be about 90 to 95.
Example 3
[079] A solution of hexane and VTMS was prepared. The VTMS consisted of 75 percent by weight (75 percent by weight) of the solution. The Matrimid® 5218 precursor fibers were immersed in the solution for a period of about twelve hours. At
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32/80 fibers were then removed from the solution and placed in a glove bag containing air with 100% relative humidity. After about 48 hours, the fibers were removed and dried by heating under vacuum at 150 ° C for about 12 hours. The treated precursor fibers were then placed on a stainless steel wire mesh and held in place by wrapping an uncle length around the mesh and fibers. The mesh support containing the fibers was then loaded into a pyrolysis plant, such as the type shown in Figure 14. The pyrolysis was carried out under an atmosphere of ultra-high purity argon (9 9.9% pure) as follows:
. 5 0 ^v C a
C / min,
2. 250 ° C at
C / min,
3,635 ° C a
50 ° C at a ramp speed of 13.3
635 ° C at a
650 ° C at a 3.85 ramp speed of 0.25 ramp
C / min,
4. Immersed for 2 hours at 650 °
[080j The resulting modified CMS fibers were tested on a single fiber module, such as that described by Koros et al. in U.S. Patent No. 6,565,631, the contents of which are incorporated herein by reference. The CMS fiber module was tested in a constant pressure variable pressure permeability system for both mixed and pure gas feeds similar to that described by Koros et al. in U.S. Patent No. 6,565,631. The modified CMS fibers were tested using a mixed gas feed containing 50 mol% CO2 and 50 mol%
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CH ₄ at a pressure of 150 psi (pounds per square inch) (1.0 x ^{10 6} Pa). The temperature was maintained at 35 ° C.
[081] CO ₂ permeability through the modified CMS fibers was measured to be about 40 to 42 GPU. The selectivity of CO2 / CH4 was determined to be about 95 to 100.
Example 4
[0 8 2 j One solution hexane and VTMS was ready. THE Composite TMS of 7 5 percent in Weight (75% by weight) of solution, with c hexane doing another : S 2 5 p ΌΓ C then in weight.
The Matrimid® 5218 precursor fibers were immersed in the solution for a period of about twelve hours. The fibers were then removed from the solution and placed in a glove bag containing air at 100% relative humidity. After about 48 hours, the fibers were removed and dried by heating under vacuum at 150 ° C for about 12 hours. The treated precursor fibers were then placed on a stainless steel wire mesh and held in place by wrapping a length of wire around the mesh and fibers. The mesh support containing fibers was then loaded into a pyrolysis facility, such as the type shown in Figure 14. The pyrolysis was performed under an atmosphere of
argon of purity last r high (99 , 9% pure) c how Follow: 1. 50 ° C at 2 5 0 ° C to a velocity in ramp in 1: 3 o ° C / min, 2. 250 ° C at 535 ° C to a velocity in ramp in 3; .85 ° C / min, 3,535 ° C a 550 ° C to a velocity in ramp in 0, .25
⁰ C / min,
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4. Immersed for 2 hours at 550 ° C.
[083] The resulting modified CMS fibers were analyzed by scanning electron microscopy (SEM). SEM analyzes showed restricted substructure collapse. A SEM image of the CMS fibers is shown in Figure 7.
Example 5
[084] A solution in hexane and VTMS was ready. THE TMS composed of 50 per percent in Weight (50% by weight) of solution. The fibers pr ecur Matr serums imi d® 5218 were immersed
in the solution for a period of about twelve hours. The fibers were then removed from the solution and placed in a glove bag containing air at 100% relative humidity. After about 48 hours, the fibers were removed and dried by heating under vacuum at 150 ° C for about 12 hours. The treated precursor fibers were then placed on a stainless steel wire mesh and held in place by wrapping a length of wire around the mesh and fibers. The mesh support containing fibers was then loaded into a pyrolysis facility, such as the type shown in Figure 14. The pyrolysis was performed under an atmosphere of
argon of ultra purity high (99 , 9% pure) c orno Follow: 1.50 ° C to 250 ° C to a velocity in ramp in i: 3 o ° C / min, 2,250 ° C to 635 ° C to a velocity in ramp in 3; .85 ° C / min, 3,635 ° C to 650 ° C to a velocity in ramp in 0, .25
° C / min,
4. Immersed for 2 hours st 650 ° C
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[085j The resulting modified CMS fibers were tested as described in Example 3. The permeability of
CO2 through the modified CMS fibers was measured to be about 45 5 was determined to be
Example 6
[086] A solution
VTMS composed of 50 solution, with hexane at 4 8 GPU. The selection of about 90 hexane and VTMS percent by weight making another 50>
. CO ₂ / CH ₄ to 95.
was prepared. A (50% by weight) of the weight percent.
The Matrimid® 5218 precursor fibers were immersed in the solution for a period of about twelve hours. The fibers were then removed from the solution and placed in a glove bag containing air at 100% relative humidity. After about 48 hours, the fibers were removed and dried by heating under vacuum at 150 ° C for about 12 hours. The treated precursor fibers were then placed on a stainless steel wire mesh and held in place by wrapping a length of wire around the mesh and fibers. The mesh support containing the fibers was then loaded into a pyrolysis facility, such as the type shown in Figure 14. The pyrolysis was performed under an atmosphere of ultra-high purity argon (99.9% pure ) as follows:
1.50 ° C to 250
C at a ramp speed of
13.3 ° C / min,
2,250 ° C to 535 ° C at a ramp speed of
3.85 ⁰ C / min,
3.53b ° C to 550 ° C at a ramp speed of
0.25 ⁰ C / min,
4. immersed for 2 hours at 550 ° C
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[087j The resulting modified CMS fibers were analyzed by scanning electron microscopy (SEM).
SEM analyzes mo straram co lapse in substructure restricted. An image in SEM of fi: br & s CMS is shown n Figure 8. Example 7 [088] A solution in hexane and VTMS was } ready. VTMS composed of 2 5 per percent in Weight (2 5% by weight) d
solution. The Matrimid® 5218 precursor fibers were immersed in the solution for a period of about twelve hours. The fibers were then removed from the solution and placed in a glove bag containing air at 100% relative humidity. After about 48 hours, the fibers were removed and dried by heating under vacuum at. 150 ° C for about 12 hours. The treated precursor fibers were then placed on a stainless steel wire mesh and held in place by wrapping a length of wire around the mesh and fibers. The mesh support containing fibers was then loaded into a pyrolysis facility, such as the type shown in Figure 14. The pyrolysis was performed under an atmosphere of
argon of purity ultra-high (99 , 9% pure) c orno Follow: 1. 50 ° C at 2 5 0 ° C at a velocity in ramp in 13, 3 ° C / min, 2. 250 ° C at 63 5 ° C at a velocity in ramp in 3.85 ° C / min, 3,635 ° C a 650 ° C at a velocity in ramp in 0.25
° C / min,
4. Immersed for 2 hours at 650 ° C
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[089j The resulting modified CMS fibers were tested as described in Example 3. The permeability of
CO ₂ through the modified CMS fibers was measured to be about 50 to 55 GPU. The selectivity of CO ₂ / CH ₄ was determined to be about 88 to 91.
Example 8
[090] One solution in hexane and VTMS was prepared. THE Composite TMS of 2 5 per percent in Weight (25% by weight) of solution, with c > hexane does endo ou ' trc : S 7 5 p or cent by weight.
The Matrimid® 5218 precursor fibers were immersed in the solution for a period of about twelve hours. The fibers were then removed from the solution and placed in a glove bag containing air at 100% relative humidity. After about 48 hours, the fibers were removed and dried by heating under vacuum at 150 ° C for about 12 hours. The treated precursor fibers were then placed on a stainless steel wire mesh and held in place by wrapping a length of wire around the mesh and fibers. The mesh support containing the fibers was then loaded into a pyrolysis facility, such as the type shown in Figure 14. The pyrolysis was performed under an atmosphere of ultra-high purity argon (99.9% pure ) as follows:
1.50 ° C to 250
C at a ramp speed of
13.3 ° C / min,
2,250 ° C to 535 ° C at a ramp speed: from
3.85 ⁰ C / min,
3.53b ° C to 550 ° C at a ramp speed: from
0.25 ⁰ C / min,
4. immersed for 2 hours at: 550 ° C
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[0 91 j The resulting modified CMS fibers were analyzed by scanning electron microscopy (SEM).
SEM analyzes mo straram CO lapse in substructure restricted. An image in SEM of fi: Hey hey S CMS is shown n Figure 9. Example 9 [092Ί A solution in hexane and VTMS was } ready. VTMS composed of 10 per percent in Weight (10% by weight) d
solution. The Matrimid® 5218 precursor fibers were immersed in the solution for a period of about twelve hours. The fibers were then removed from the solution and placed in a glove bag containing air at 100% relative humidity. After about 48 hours, the fibers were removed and dried by heating under vacuum at 150 ° C for about 12 hours. The treated precursor fibers were then placed on a stainless steel wire mesh and held in place by wrapping a length of wire around the mesh and fibers. The mesh support containing the fibers was then loaded into a pyrolysis facility, such as the type shown in Figure 14. The pyrolysis was performed under an atmosphere of
argon of purity ultra-high (99 , 9% pure) c orno Follow: 1. 50 ° C at 2 5 0 ° C at a velocity in ramp in 13, 3 ° C / min, 2. 250 ° C at 63 5 ° C at a velocity in ramp in 3.85 ° C / min, 3,635 ° C a 650 ° C at a velocity in ramp in 0.25
° C / min,
4. Immersed for 2 hours at 650 ° C
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[0 93j The resulting modified CMS fibers were tested as described in Example 3. The permeability of
CO2 through the modified CMS tibras was measured as
about 65 to 7 0 GPU. THE selectivity of CO2 / CH4 was determined as í being of fence of 8 b to 90.Example 10[094Ί A solution in hexane and VTMS was prepared ada. THE VTMS composed of 10 per percent in Weight (10% standing so) of
solution, with hexane making another 90 percent by weight.
The Matrimid® 5218 precursor fibers were immersed in the solution for a period of about twelve hours. The fibers were then removed from the solution and placed in a glove bag containing air at 100% relative humidity. After about 48 hours, the fibers were removed and dried by heating under vacuum at 150 ° C for about 12 hours. The treated precursor fibers were then placed on a stainless steel wire mesh and held in place by wrapping a length in line.
The mesh support containing fibers was then loaded into a pyrolysis facility, such as the type shown in
Figure 14. Pyrolysis was carried out under an argon atmosphere of ultra-high purity (99.9% pure) as follows:
1. 50 ° C a 2 5 0 ° C to a velocity in ramp in 1) 3 to 0 C / min, 2. 250 ° C : at 535 ° C to a velocity in ramp in 3, .85 C / min, 3.5 35 ° C : at 550 ° C to a velocity in ramp in 0, .25
⁰ C / min,
4. immersed for 2 hours at 550 ° C
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[095] The resulting modified CMS fibers were analyzed by scanning electron microscopy (SEM).
The analyses from SEM showed collapse in substructure restricted. An Image of SEM of fibers CMS is shown n Figure 8. Example 11 [096] One solution hexane and VTMS was ready. Composite VTMS out of 5 weight percent (5% by weight) d S01UÇdO o As Σ1 bras pr < Matrimid® ecursors 5218 were immersed
in the solution for a period of about twelve hours. The fibers were then removed from the solution and placed in a glove bag containing air at 100% relative humidity. After about 48 hours, the fibers were removed and dried by heating under vacuum at 150 ° C for about 12 hours. The treated precursor fibers were then placed on a stainless steel wire mesh and held in place by wrapping a length of wire around the mesh and fibers. The mesh support containing fibers was then loaded into a pyrolysis facility, such as the type shown in Figure 14. The pyrolysis was performed under an atmosphere of
argon of purity ultra-high (99 , 9% pure) c orno Follow: 1. 50 ° C at 2 5 0 ° C at a velocity in ramp in 13, 3 ° C / min, 2. 250 ° C at 63 5 ° C at a velocity in ramp in 3.85 ° C / min, 3,635 ° C a 650 ° C at a velocity in ramp in 0.25
° C / min,
4. Immersed for 2 hours at 650 ° C
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[097] The resulting modified CMS fibers were tested as described in Example 3. The permeability of
COg through the modified CMS fibers was measured to be about 18 to 20 GPU.
The selectivity of CO ₂ / CH ₄ was determined to be about 99 to 100.
Example 12
[098] A solution of hexane and VTMS
VTMS comprised of b weight percent (5 weight percent) of the solution, with hexane making another 95 percent weight.
The Matrimid® 5218 precursor fibers were immersed in the solution for a period of about twelve hours. The fibers were then removed from the solution and placed in a glove bag containing air at 100% relative humidity. After about 48 hours, the fibers were removed and dried by heating under vacuum at 150 ° C for about 12 hours. The treated precursor fibers were then placed on a stainless steel wire mesh and held in place by wrapping a length of wire around the mesh and fibers. The mesh support containing the fibers was then loaded into a pyrolysis facility, such as the type shown in Figure 14. The pyrolysis was performed under an atmosphere of ultra-high purity argon (99.9% pure ) as follows:
1.50 ° C to 250
C at a ramp speed of
13.3 ⁰ C / min,
2,250 ° C to 535 ° C with a ramp speed of
3.85 ⁰ C / min,
3.53b ° C to 550 ° C at a ramp speed of
0.25 ⁰ C / min,
4. immersed for 2 hours at 550 ° C
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[099] Fibers The resulting modified CMS were analyzed by micros scanning electronic copy (SEM). SEM analyzes showed collapse of substructure partial. An image SEM of CMS fibers is shown in I figured 9.Example 13[100] A solution hexane and VTMS was prepared. THE VTMS composed of 1 percent by weight (1% by weight) of
solution. The Matrimid® 5218 precursor fibers were immersed in the solution for a period of about twelve hours. The fibers were then removed from the solution and placed in a glove bag containing air at 100% relative humidity. After about 48 hours, the fibers were removed and dried by heating under vacuum at 150 ° C for about 12 hours. The treated precursor fibers were then placed on a stainless steel wire mesh and held in place by wrapping a length of wire around the mesh and fibers. The mesh support containing the fibers was then loaded into a pyrolysis facility, such as the type shown in Figure 14. The pyrolysis was performed under an atmosphere of
argon of purity ultra-high (99 , 9% pure) c orno Follow: 1. 50 ° C at 2 5 0 ° C at a velocity in ramp in 13, 3 ° C / min, 2. 250 ° C at 63 5 ° C at a velocity in ramp in 3.85 ° C / min, 3,635 ° C a 650 ° C at a velocity in ramp in 0.25
° C / min,
4. Immersed for 2 hours at 650 ° C
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[101 j The resulting modified CMS fibers were tested as described in Example 3. The permeability of
CO ₂ through the modified CMS fibers was measured to be about 10 to 12 GPU.
The selectivity of CO ₂ / CH ₄ was determined to be about 99 to 100.
Example 14
[102Ί A solution of hexane and VTMS
VTMS composed of 1 weight percent by weight) gave solution, with hexane making another 99 weight percent.
The Matrimid® 5218 precursor fibers were immersed in the solution for a period of about twelve hours. The fibers were then removed from the solution and placed in a glove bag containing air at 100% relative humidity. After about 48 hours, the fibers were removed and dried by heating under vacuum at 150 ° C for about 12 hours. The treated precursor fibers were then placed on a stainless steel wire mesh and held in place by wrapping a length of wire around the mesh and fibers. The mesh support containing the fibers was then loaded into a pyrolysis facility, such as the type shown in Figure 14. The pyrolysis was performed under an atmosphere of ultra-high purity argon (99.9% pure ) as follows:
1.50 ° C to 250
C at a ramp speed of
13.3 ⁰ C / min,
2,250 ° C to 535 ° C at a ramp speed: from
3.85 ⁰ C / min,
3.53b ° C to 550 ° C at a ramp speed: from
0.25 ⁰ C / min,
4. immersed for 2 hours at: 550 ° C
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[103j The resulting modified CMS fibers were analyzed by scanning electron microscopy (SEM). SEM analyzes showed collapsed substructure morphology. A SEM image of the CMS fibers is shown in Figure 9.
[104] The test results from the Examples above are summarized in Table 1.
labera 1
P (CO ₂ ) [GPU] co ₂ / ch ₄ Matrimid® untreated CMS5218 (Temperature ofPyrolysis at 650 ° C> 8 ~ 10 99-100 Treated CMS (100% VTMS) Matrimid® 5218 (Pyrolysis Temperature at 650 ° C) 35-40 90-95 Treated CMS (75% VTMS)Matrimid® 5218 (Pyrolysis Temperature at 650 ° C) 4 0-42 95-100 Treated CMS (50% VTMS)Mat r imid® 5 218(Pyrolysis temperature at650 ° C) 4 5-4 8 90-95 Treated CMS (25% VTMS)Matrimid® 5218 (Pyrolysis Temperature at 650 ° C) 50-55 88-91 Treated CMS (10% VTMS)Matrimid® 5218 (Pyrolysis Temperature at 650 ° C) 65-7 0 8 5 - 9 0
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CMS treated (5% VTM S) 18-2 0 99-100 Matrimid® 52 18 (T empe ratu ra Pyrolysis 3. 650 ° C) CMS treated (1% VTM S) 10-12 99-100 Matrimid® 52 18 (Temperature Pyrolysis The 650 ° C)
[10bj As demonstrated by the Examples above, a precursor fiber of polyme.ro that is in contact with a solution that comprises a modifying agent that is present in an amount that is less than 100% of the solution, surprisingly, produces a membrane of modified CMS fiber having increased gas permeability when compared to a polymer precursor fiber which is brought into contact with 100% pure modifying agent. On the contrary, it was presently found until the concentration of the modifying agent reached a point where it appears not to be effective in significantly limiting the collapse of the substructure pores.
during p: Lrolysis, the gas permeability of the membrane of fiber CMS resulting modified actually increases by response to a decrease in the concentration of the modification in the treatment solution. For VTMS, the point in
that the solution does not appear to be effective in significantly restricting the collapse of the substructure it appears to occur at a concentration between about 1% and about 5% by weight.
Of the solutions tested, the solution that produced a modified CMS fiber membrane having the highest gas permeability contained in the modifying agent at a concentration of about 10% by weight.
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[106j Various embodiments of the present invention are directed to contacting a polymer precursor fiber with a solution comprising the modifying agent at a concentration between about 1% and about 95% by weight; alternatively, between about 1% and about 90%; alternatively, between about 1% and about
80%; alternati ^ 'the mind, in between fence : that of 1% and about i from : 75%; alternatively, in between fence in 1% and fence in 50%; alternatively nt e, in between fence in 1% and fence in 25%; alternatively nt e, in between fence in 1% and fence in 15%; alternatively nt e, in between fence in 1% and fence in 12%; alternatively nt e, between about EI ₍ o. and cer here 90% in Weight; alternatively nt e, in between fence in 5% and fence in 80%; a11 and rn at i vame nte, in between fence in 5% ç fence in 75%; a11 and rn at i vame nte, in between fence in 5% ç fence in 0 V / a11 and rn at i vame nte, in between fence in 5% ç fence in 25%; a11 and rn at i vame nte, in between fence in 5% ç fence in 15%; a11 and rn at i vame nte, in between fence in 5% ç fence in 12%; a11 and rn at i vame nte, in between fence in 5% ç fence in 10%; a11 and rnat i vame nte, between c about 8% and cer here of 9 0% in Weight;
alternat i ' vament Ϊ in between fence of 8% and fence in 80%; alternat i ' vament Ϊ in between fence of 8% and fence in 75%; alternat i ' vament Ϊ in between fence of 8% and fence in 7) U%, alternat i ' vament Ϊ in between fence of 8% and fence in 25%; alternat i ' vament Ϊ in between fence of 8% and fence in 15%; alternati ' vament and, in between fence of 8% and fence in 12%; alternati ' vament and, between c serca 10% and about 90 % in Weight; alt ernati vament and hey other c Orca, from 10% and about in 80%;
alternatively, between about 1C% and about
75%;
alternatively, between about 10% about
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alternat ivamerd ; .e, between about 10% and about 25%; a11 and rnat i vamen 1 re, between about 1C% and about 15%. At percentages a above represent the weight percentage of modi agent: the solution in contact.
[107] Treatment of a polymer precursor fiber with a modifying agent also results in the formation of
a film residual on the coating layer outside of modified CMS hollow fiber membrane
asymmetric. Specifically, it is believed that, in addition to
go through one sol-gel reaction process within the
pores of the precursor fiber, the modifying agent undergoes a similar reaction to form a film on the outer covering layer of the asymmetric modified CMS hollow fiber. Importantly, this film works to prevent the adhesion of precursor fibers together, when
they are heated above the transition temperature
glass of the polymer, such as during pyrolysis.
[108] This film also works, however, for
inhibit the gas flow through the pores that are
gifts on 9 the outer coating layer of the fiber,
decreasing the permeability (and effectiveness) of the membrane
hollow fiber CMS modified asymmetric. The formation of a
film through the sol-gel reaction of
vinyltrimethoxy: ssilane (VTMS), a modification agent
preferred method of the present invention, is illustrated in Fig.
In this way, by reducing the concentration of the agent modification, , the formation of the residual film is limited, leading to an increase in gas permeability of wire membrane resultant hollow CMS. Without being limited
by theory, it is believed that this effect to explain the
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48/80 surprising result that decreasing the concentration of the modifying agent in a contact solution results in a modified CMS hollow fiber membrane having an increased gas permeability property.
[109] Thus, it is an object of the present invention to treat a precursor fiber with a modifying agent, wherein the modifying agent is present at a concentration that is effective in limiting the formation of the residual film, substantially minimizing the thickness of the film. Preferably, the concentration of the modifying agent is selected in an amount that is effective, that is, high enough to significantly restrict the collapse of the substructure and effectiveness, that is, sufficiently low to limit the formation of a residual film on the coating layer. outer sheath of asymmetric modified CMS hollow fiber. In this way, an asymmetric modified CMS hollow fiber membrane having both an improved permeability property and beneficial anti-adherent properties can be prepared
[110] In various embodiments, the concentration of the modifying agent in the solution is selected to obtain an asymmetric modified CMS hollow fiber membrane having a gas permeability that is at least a 300% increase over a fiber membrane hollow equivalent asymmetric CMS that is not subjected to treatment with the modifying agent
In various embodiments, the concentration of the modifying agent in the solution is selected to obtain an asymmetric modified CMS hollow fiber membrane having a gas permeability that is at least an increase over an asymmetric CMS hollow fiber membrane
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49/80 equivalent that is not subjected to treatment with the modifying agent. In various embodiments, the concentration of the modifying agent in the solution is selected to obtain an asymmetric modified CMS hollow fiber membrane having a gas permeability that is at least a 500% increase over an asymmetric CMS hollow fiber membrane equivalent that is not subjected to treatment with the modifying agent. In various embodiments, the concentration of the modifying agent in the solution is selected to obtain an asymmetric modified CMS hollow fiber membrane having a gas permeability that is at least an increase of
600% compared to an equivalent asymmetric CMS hollow fiber membrane that is not subjected to treatment with the modifying agent.
[11.1 j As demonstrated by the Examples above, a substantial increase in permeability can also be caused without causing a substantial loss in selectivity. For example, in various embodiments, the concentration of the modifying agent in the solution is selected to obtain an asymmetric modified CMS hollow fiber membrane having a selectivity that is at least 80% of the selectivity of an equivalent asymmetric CMS hollow fiber membrane that it is not subjected to treatment with the modifying agent. In various embodiments, the concentration of the modifying agent in the solution is selected to obtain an equivalent asymmetric CMS hollow fiber membrane having a selectivity that is at least 85% of the selectivity of an equivalent asymmetric CMS hollow fiber membrane that is not subjected treatment with the modifying agent. In several modalities, the concentration of the modifying agent in the
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50/80 solution is selected to obtain an asymmetric modified CMS hollow fiber membrane having a selectivity that is at least 90% of the selectivity of an equivalent asymmetric CMS hollow fiber membrane that is not subjected to treatment with the modifying agent. In various embodiments, the concentration of the modifying agent in the solution is selected to obtain an asymmetric modified CMS hollow fiber membrane having a selectivity that is at least 95% of the selectivity of an equivalent asymmetric CMS hollow fiber membrane that is not subjected treatment with the modifying agent.
[112] In various embodiments, the concentration of the modifying agent in the solution is selected to obtain an asymmetric modified CMS hollow fiber membrane having a desired combination of gas permeability and selectivity properties. For example, the concentration of the modifying agent in the solution can be selected to obtain a hollow fiber membrane. Asymmetric modified CMS having properties that are useful for the separation of CO ₂ and CH ₄ within a gas stream comprising any number of additional components.
Alternatively, concentration of the modifying agent in the solution can be selected to obtain an asymmetric modified CMS hollow fiber membrane that is useful for the separation of H ₂ S and
CH ₄ within a gas stream comprising any number of additional components.
Alternatively, the concentration of the modifying agent in the solution can be selected to obtain a hollow fiber membrane
Asymmetric modified CMS that is useful for separating a mixture of CO ₂ and H ₂ S (CO ₂ / H ₂ S) from CH ₄ within a
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51/80 gas stream comprising any number of additional components. Alternatively, the concentration of the modifying agent in the solution can be selected to obtain an asymmetric modified CMS hollow fiber membrane that is useful for the separation of CO and N ₂ within a gas stream comprising any number of additional components. Alternatively, the concentration of the modifying agent in the solution can be selected to obtain an asymmetric modified CMS hollow fiber membrane which is useful for separating O ₂ and N ₂ within a gas stream comprising any number of additional components. Alternatively, the concentration of the modifying agent in the solution can be selected to obtain an asymmetric modified CMS hollow fiber membrane that is useful for the separation of N ₂ and CH ₄ within a gas stream comprising any number of additional components. Alternatively, the concentration of the modifying agent in the solution can be selected to obtain an asymmetric modified CMS hollow fiber membrane that is useful for separating He and CH ₄ within a gas stream comprising any number of additional components. Alternatively, the concentration of the modifying agent in the solution can be selected to obtain an asymmetric modified CMS hollow fiber membrane that is useful for separating H ₂ and CH ₄ within a gas stream comprising any number of additional components. Alternatively, the concentration of the modifying agent in the solution can be selected to obtain an asymmetric modified CMS hollow fiber membrane that is useful for separating H ₂ and C ₂ H ₄ within a
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52/80 gas stream comprising any number of additional components. Alternatively, the concentration of the modifying agent in the solution can be selected to obtain an asymmetric modified CMS hollow fiber membrane that is useful for separating olefins from paraffins, such as separating ethylene and ethane or propylene and propane within a gas stream comprising any number of additional components. The concentration of the modifying agent in the solution can also be selected to obtain a fiber membrane
OCd
Asymmetric modified CMS which is useful for separating a mixture of olefins from a mixture of paraffins, such as ethylene and propylene (eti. 1 ene / prop i 1 and η o) from a mixture of ethane and propan (ethane / propane) within a gas stream comprising any number of additional components
[113j In one embodiment, the concentration of the modifying agent in the solution can be selected to obtain a hollow fiber membrane. Asymmetric modified CMS that is useful for separating acid gases, such as CO ₂ and H ₂ S, from a gas stream that contains or is rich in hydrocarbons, such as a natural gas stream.
[114 j In various embodiments, the concentration of the modifying agent in the solution is selected to obtain an asymmetric modified CMS hollow fiber membrane having desirable permeability and selectivity properties, as can be determined by testing the asymmetric modified CMS hollow fiber membrane in a single fiber module using a constant pressure variable pressure permeability system, such as the
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53/80 described by Koros et al. in US Patent No. 6,565,631. For example, where the concentration of the modifying agent in the solution is selected to obtain an asymmetric modified CMS hollow fiber membrane having properties that are desirable for the separation of CO2 and CH ₄ , the concentration of the modifying agent in the solution can be selected to to obtain an asymmetric modified CMS hollow fiber membrane having a CO permeability of at least 50 GPU and a selectivity of CO / CH ₄ of at least 60 when subjected to a mixed feed containing 50 mol% CO and 50 mol% CH ₄ at 150 psi (1.0 x 10 ^b Pa) and 35 ° C. Alternatively, the concentration of the modifying agent in the solution can be selected to obtain a hollow fiber membrane. Asymmetric CMS having one. CO2 permeability of at least 60 GPU and a selectivity of CO2 / CH4 of at least 80 when subjected to a mixed feed containing 50 mol% CO2 and 50 mol% CH ₄ at 150 psi ( 1.0 x ^{10 6} Pa) and 35 ° C.
[115 j Although the above examples show the way in which the concentration of the modifying agent in the solution can be selected to obtain a hollow fiber membrane
Asymmetric modified CMS having properties that are desirable for the separation of CO2 and CH ₄ , should be understood by a person skilled in the art who, when testing asymmetric CMS hollow fiber membranes prepared using varying concentrations of the modifying agent In separating a different gas stream, one can easily determine the concentration (or concentration range) of the modifying agent in the solution that produces an asymmetric modified CMS hollow fiber membrane
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54/80 which is particularly desirable for the separation of any gas stream.
Control of Modification Agent Concentration and Pyrolysis Temperature
[116] In various embodiments, the pyrolysis temperature is also selected to obtain an asymmetric modified CMS hollow fiber membrane having a desired combination of gas permeability and selectivity properties. The pyrolysis temperature at which a desired combination of properties is achieved will vary depending on the polymer precursor that is used. By carefully controlling both the concentration of the modifying agent used in the pre-pyrolysis treatment and the temperature of pyrolysis, an asymmetric modified CMS hollow fiber membrane having certain desired gas separation properties can be prepared.
[117] To demonstrate how the gas separation properties of a fiber membrane, hollow asymmetric modified CMS can be adjusted by controlling both the concentration of the modifying agent in the treatment step and the pyrolysis temperature, Matrimid® 5218 fibers were treated with a solution containing 10% by weight of VTMS as described in Examples 10 and 11. The precursor fibers were then subjected to pyrolysis at various temperatures in order to determine the most suitable pyrolysis temperature for a selected polymer precursor that was treated with a solution comprising a modifying agent at a concentration shown to produce improved gas permeability. For comparison, untreated Matrimid® 5218 fibers and fibers
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55/80 treated with Matrimid® 5218 with pure VTMS (i.e., 100%) were subjected to pyrolysis over a similar temperature range. The test is described in more detail below.
Example 15
[118] The precursor fibers treated Matrimid® 5218 with a 10% by weight solution of VTMS as in Examples 9 and 10 were subjected to pyrolysis under an atmosphere of ultra-high purity (99.9% pure) argon as follows :
1. 50 ° C at 250 ° C a a speed in ramp in 13, 3 ° C / min, 2. 250 the r * : a o 3 5 ° C a a speed in ramp in 3.85 ° C / min, 3,535 the r * : to 5 0 ° C a a speed in ramp in 0.2 5
° C / min,
. Immersed for 2 hc > ras and i 550 ° C. 119] The fibers CMS modified resulting were
tested as described in Example 3. The permeability of
CO2 through the modified CMS fibers was measured to be about 190 to 19b GPU. The selectivity of CO2 / CH4 was determined to be about 15 to 20.
Example 16
[120] The precursor fibers treated Matrimid® 5218 with a 10% by weight solution of VTMS as in Examples 9 and 10 were subjected to pyrolysis under an atmosphere of ultra-high purity (99.9% pure) argon as follows :
1. 50 ° C to 250 ° C at a ramp speed of 13.3 ° C / min,
2. 250 ° C to 585 ° C at a ramp speed of
3.85 ° C / min,
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3. 58 5 ° C to 60 0 ° C at a ramp speed of 0.25 ° C / min,
4. Immersed for 2 hours at 600 ° C.
[121] The resulting modified CMS fibers were tested as described in Example 3. The permeability of CO through the modified CMS fibers it was measured to be about 170 to 180 GPU. The selectivity of CO2 / CH4 was determined to be about 38 to 40.
Example 17
[122] The precursor fibers treated Matrimid® 5218 with a solution of 10% by weight of VTMS as in Examples 9 and 10 were subjected to pyrolysis, under an atmosphere of ultra-high purity argon (99.9% pure) as follows :
.1. 0 v ° C at 250 ° C a speed d * and ramp in 13.3 C / min s 2 . 250 o r · * at 610 ° C l a 'd speed and ramp in 3.85 C / min s 3. 610 The Q at 625 ° C l a 'd speed and ramp in 0.25 C / min s 4. immersed for 2 hours at 625 ° C.
[123] The resulting modified CMS fibers were tested as described in Example 3. CO2 permeability through the modified CMS fibers was measured to be about 70 to 75 GPU. The selectivity of CO2 / CH4 was determined to be about 75 to 80.
Comparative Example 3
[124] Matrimid® 5218 untreated precursor fibers were subjected to pyrolysis, under an atmosphere of ultra-high purity argon (99.9% pure) as follows:
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1. 50 ° C at 25 u ° C a a speed in 13.3 ramp "C / min, 2. 250 ° C at 535 ° C a speed in 3.85 ramp ° C / min, 3,535 ° C at 550 ° C a speed in 0.25 ramp ° C / min, 4. Immersed for 2 hours at 550 ° C. [12 b j As CMS fibers resulting were tested as described in E Example 3. A permeability in CO2 through CMS fibers fo i measured with < 2 being about in 2 0 to 3 0 GP (J. A selectivity CO2 / CH4 fo i determined c < how being about
30 d 4 0.
Comparative Example 4
[126] The precursor fibers treated Matrimid® 5218 with a pure VTMS solution (100% by weight) as in the Example
comparative 0 2 were subjected to pi roy .se, under an atmos < was in argon of ultra-high purity (99, 9% pure) like Follow: .1. 50 ¹ at 250 ° C : at a speed in ramp in 13.3 "C / min 2 . 250 0 a 53 5 ⁰ C at a speed in ramp in 3.85 "C / min 3. 5 3 5 The p at 550 ⁰ C at a speed in ramp in 0.25 "C / min 4. immersed for 2 hoi at 550 ° C. [127] » lS fibers Modified CMS r esm Ltantewere
tested as described in Example 3. CO ₂ permeability through the modified CMS fibers was measured to be about 100 to 120 GPU. The selectivity of CO2 / CH4 was determined to be about 20 to 25.
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Comparative Example 5
[128] The precursor fibers treated Matrimid® 5218 with
a solution c ie pure VTMS (100% in weight) il as in Example comparative THE 2 were submitted gone à pi rolysis, £ under an atmosphere in argon of purity last i oa-alta (99.9% pure) like Follow: 1. 50 ° C at 250 ° C at a velocity ramp in 13, 3 ° C / min, 2. 250 the r : at 58 5 ° C at a vel idleness ramp in 3.85 ° C / min, 3. 58 5 the r : at 60 0 ° C at a vel idleness ramp in 0.2 5
° C / min,
4. Immersed for 2 hours at 600 ° C.
[129] The resulting modified CMS fibers were tested as described in Example 3. The permeability of
CO2 through of fiber s ^; Modified CMS was measured as being from cei where is it 60 to 65 GPU. The selectivity * CO2 / CH4 was determined like .' being in about 30 to 35.
[130] The test results are summarized in Table 2. In addition, a comparison of the results at two different temperatures (550 ° C and 650 ° C) is shown in Figure 13. From these results, you can see since, the In order to obtain an asymmetric modified CMS hollow fiber membrane having superior performance from a Matrimid® 5218 precursor fiber treated with a VTMS modifying agent, the precursor fiber can be brought into contact with a treatment solution containing about 10 % by weight of VTMS and then pyrolyzed at a temperature between about 600 ° C and 650 ° C. Using the techniques described here, the appropriate ranges from: (a) to
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59/80 concentration of the modifying agent in the treatment solution, and (b) the pyrolysis temperature could similarly be determined by any precursor fiber. For many precursor fibers, including, for example, polyimide precursor fibers, desirable treatment concentrations and pyrolysis temperatures are expected to be similar to those demonstrated for the Matrimid® 5218 precursor fiber.
labera 2
P (CO ₂ ) [GPU] co ₂ / ch ₄ Matrimid® 5218 untreated CMS (Pyrolysis temperature at 550 ° C) 20-30 30-4 0 CM S no -1 -1 at d at M at r i m í d® 5218 (Temperature ofPyrolysis at 650 ° C) 8 - 10 99-100 Treated CMS (100% VTMS) Matrimid® 5218 (Pyrolysis Temperature at 550 ° C) 100-120 20-25 Treated CMS (100% VTMS) Matrimid® 5218 (Pyrolysis Temperature at 600 ° C) 6 0 ~ 6 5 30-35 Treated CMS (100% VTMS) Matrimid® 5218 (Pyrolysis Temperature at 650 ° C) 35-40 90-95 Treated CMS (10% VTMS) Matrimid® 5218 (Pyrolysis Temperature at 550 ° C) 190-195 15-20 Treated CMS (10% VTMS) Matrimid.® 5218 (Pyrolysis temperature at 600 ° C) 170-180 3 8 - 4 0 Treated CMS (10% VTMS)Matrimid® 5218(Pyrolysis temperature 70-75 7 5 - 8 0
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at 625 ° C) Treated CMS (10% VTMS) Matrimid® 5218 (Pyrolysis Temperature at 650 ° C) β 5 - '7 0 85-90
[131 j While the above examples show the way in which the modifying agent concentration and pyrolysis temperature can together be selected to obtain an asymmetric modified CMS hollow fiber membrane having properties that are desirable for the separation of CO ₂ and
CH ₄ , should be understood by someone skilled in the art who, when testing asymmetric modified CMS hollow fiber membranes
prepared using conct snt variable rations of the agent modification j and temperatures in pyrolysis for separation of any c < gas source, one can easily determine the
concentration (or range of concentrations) of the modifying agent and the pyrolysis temperature that produces an asymmetric modified CMS hollow fiber membrane that is particularly desirable for the separation of any gas stream.
Improved Solvent Exchange
[132] In several embodiments, the treatment of the polymer precursor fiber can be coupled with the solvent exchange process. After the precursor fibers are formed, such as by the wet, dry-jet method, the fibers are subjected to a process known as solvent exchange. In order to maintain the porosity of the fibers through drying, it is necessary to remove the water contained within the pores of the membrane. In this way, the solvent exchange process replaces the water that is present in the porous substructure of the fiber with an organic compound having a low surface tension. The precursor fiber is
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61/80 subjected to the solvent exchange process for a time that is effective in allowing the organic compound to replace the water that is present in the pores of the fiber.
[133] The solvent exchange preferably involves two or more steps, with each step using a different solvent exchange material. For example, a conventional solvent exchange process includes removing water from the membrane with a first solvent and then replacing the alcohol with a second solvent. The first step uses one or more solvent exchange materials that comprise a water miscible alcohol that is sufficiently inert to the polymer. Any compound that is effective for replacing water in the membrane is contemplated for use as a first solvent. Aliphatic alcohols having 1-3 carbon atoms, i.e., methanol, ethanol, propanol, isopropanol, and combinations of the above, are particularly effective as a first solvent exchange material.
[134] The second step is effective for replacing alcohol with one or more volatile organic compounds having a low surface tension. Any organic solvent that has sufficiently a low surface tension to prevent damage to the membrane pores during heating that is contemplated for use as a second solvent. Among the organic compounds, which are particularly useful as a second solvent exchange material, are straight or branched chain aliphatic alkanes, C ₅ or greater. Toluene has also been suggested for use as a second solvent. N-hexane was found to be an organic compound particularly suitable for use as the second
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62/80 solvent exchange material. Advantageously, the first and second solvent exchange materials must be sufficiently non-reactive with the membrane, in order to avoid any significant degradation of the membrane properties.
[135] Although the process described in this exemplary embodiment includes only two steps, the solvent exchange process can involve any number of steps and any number of solvents. A solvent exchange process can make use of any number of solvent exchange materials, with the solvent exchange material from each subsequent step being effective to replace the solvent exchange material from the previous step.
[136] It has now been found that using a solvent exchange material that includes an amount of a modifying agent, an asymmetric modified CMS hollow fiber membrane having improved gas permeability can be prepared. An. treatment
in a precursor fiber with an agent of modification, the end in restrict the collapse of substructure can be done zado in association with the proce exchange sso of solvent, an
modified CMS hollow fiber membrane having improved gas permeability can be prepared without the need for an additional process step beyond those that are typically carried out in the preparation of an asymmetric CMS hollow fiber membrane. The process of treating the precursor fiber with a modifying agent, as described herein, as part of the solvent exchange step can be referred to as a solvent exchange process
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[137 j In this way, in various embodiments, a modifying agent is added to the second solvent in the solvent exchange process. For example, the modifying agent is added to an organic solvent that has sufficiently low surface tension to maintain the membrane pores during drying. In an appropriate embodiment, the organic solvent is n-hexane. The concentration of the modifying agent in the organic solvent can be selected, as described in this specification.
[138] In an improved solvent exchange process, the precursor fiber is soaked in a solution that comprises an organic compound, such as n-hexane, and a modifying agent, such as VTMS, for a period of time that is effective to allow the modifying agent to react with a portion of the water in the pores of the fiber and the organic solvent to replace another portion of the water in the pores of the fiber. In this way, the precursor fibers acquire the benefits of treatment with the modifying agent without losing the benefits of the conventional solvent exchange process.
[139] The ability of the modifying agent to penetrate the outer coating of the asymmetric precursor fiber makes it particularly attractive for treating the fiber during the solvent exchange process. In a commercial process, a precursor fiber is often transmitted through the solvent exchange material in a continuous manner. In this way, the ends of the fiber rarely, if ever, come into contact with the solvent exchange material. Thus, for effective treatment during the commercial manufacture of a
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64/80 asymmetric CMS hollow fiber membrane, the modifying agent reaches the substructure of the precursor fiber through the outer coating of the fiber.
Asymmetric Modified CMS Hollow Fiber Membranes
[140] Various embodiments of the present invention are directed to an asymmetric CMS hollow fiber membrane having a morphology stabilizer within at least one of its pores. In a desirable embodiment, the pore is a substructure pore and the morphology stabilizer is porous.
Example 18
[141] Elementary analyzes were carried out on the following:
The. untreated precursor fibers Matrimid® 5218,
B. precursor fibers treated Matrimid® 5218 with pure VTMS (100%), according to Examples 1 and 2,
ç. asymmetric CMS hollow fibers prepared by pyrolysis of untreated Matrimid® 5218 precursor fibers at 550 ° C and 650 ^C C, and
d. asymmetric modified CMS hollow fibers prepared by pyrolysis of precursor fibers treated Matrimid® 5218 with pure VTMS (100%), according to Examples 1 and 2, at 550 ° C and 650 ° C.
and. asymmetric modified CMS hollow fibers prepared by pyrolysis of precursor fibers treated Matrimid® 5218 with a solution comprising 10% by weight of VTMS, as determined in Examples 9 and 10.
[142] Elementary analyzes were obtained from the ALS Environmental Lab in Tucson, Arizona. Elementary analyzes comprised a number of techniques for
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65/80 identify and measure the amount of carbon, hydrogen, nitrogen, oxygen, and silicon present in each fiber sample.
[143] The contents of carbon, hydrogen, and nitrogen were determined using a micro CHN Analysis method (ASTM D5373 / D5291). The instrument used in this method was a Perkin Elmer 2400 Series 11 CHN Analyzer. With this instrument, the samples were combustion at 935 ° C, followed by secondary combustion through the oven at 840 ° C during further oxidation and particle removal. The gas derived from combustion is transferred by a carrier gas, homogenized and purged through an IR detector. This detector measures carbon by CO ₂ and hydrogen gas from H ₂ O. Nitrogen is detected by the conductivity term, in which the NO ₂ gas from the resulting combustion is measured as nitrogen. The CHN results were then classified as a percentage by weight. The molar percentages of carbon, hydrogen and nitrogen were then calculated from the measured weight percentages. The samples were prepared as follows. A sample amount, derived from the sample matrix, was weighed in a microbalance having a capacity of 0.0001 mg. Each sample was then placed in a fuel tin capsule, pre-weighed and dripped in the instrument's oven for analysis. The instrument was calibrated for the specific matrix of the sample and the capsule used.
[144] The oxygen content was determined by an Oxygen Analysis method (ASTM D5373, modified). THE
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66/80 instrument used in this method was an LECO TruSpec Oxygen Analyzer. Each sample was placed in a capsule and weighed in a microbalance with a 0.001 mg capacity. The capsule was then dripped into the oven, which operates at 1300 ° C. In a reduction tube, divided O2 is combined with carbon black in the oven. All components of CO _X are flowed through copper oxide and are converted to CO ₂ . This resulting gas is analyzed for oxygen by IP detection. The instrument was calibrated for the specific sample matrix and the capsule used for combustion. The results were described as a percentage by weight of oxygen in the sample. The molar percentages of oxygen were then calculated from the measured weight percentages.
[14 5j The silicon content in modified CMS hollow fiber membranes was determined by a method using total dissolution. Specifically, the analyzes were performed using the ICP-OES technique. This technique involves digesting a sample with acids (such as, HCl, HNO3, HF) in a microwave oven, complexing with boric acid to neutralize HF, and bringing it to a final volume with nanopure water. The results were described as a percentage by weight of silicon in the sample. The molar percentages of silicon were then calculated from the measured weight percentages.
[146] The results of the elementary analyzes are shown in Tables 3, 4 and 5.
Table 3
Carbon(% by weight) Hydrogen (% by weight} Nitrogen (% by weight} Oxygen (% effi weight) Silicon (% by weight} Precur sora fibernon-treatmentMatrimid® 5218 / 5 _f 4.42 5, 32 14.50
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Fiber Precursor 73, 20 4.85 4.53 13, 19 4.23 VTMS (100%)treated Matrimid®5218
[147] Elemental analyzes demonstrate that Matrimid® 5218 precursor fibers that were treated by immersion in a liquid consisting of pure VTMS contained about 4% by weight of silicon. To ensure that the measured silicon is attributable to the chain-type network of siloxane bridges that are formed by the VTMS reaction and the moisture that resides within the pores of the asymmetric precursor hollow fiber, untreated precursor fibers Matrimid® 5218 were also subjected to analysis elementary. Matrimid® 5218 untreated precursor fibers were found to contain no measurable amount of silicon. In this way, the silicon found by elementary analysis of the treated precursor fibers Matrimid® 5218 can serve to indicate the amount of modifying agent bound to the condensed chain that resides in a precursor fiber after treatment.
Table 4
Carbon(% eiuWeight} Hydrogen (% by weight) Nitrogen (% by weight) Oxygen (% weight) Silicon(% inWeight} Not treated Untreated CMSMatrimid® 3218 (Temperature ofPyrolysis at 550 87.37 3.09 4, 8 4, 8Unbraided CMSMat rimid® 5 21 8 (Temperature ofPyrolysis at 650 91.19 2, 6ΊTreaty (100% VTMS) CMS treated(100% VTMS)Mat r imi d® 5218 (Temperature of 76, 06 3.24 3.96 D, 17
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Pyrolysis a 55 0Tra CMS t the da 76, 34 2.3 52.69 2.99 15, 6 3 (100% V TMS) Matrimid® 5218 (T emp erature in Pyrolysis a 65 0 ° C) Treated lllli VTMS) CMS treated (10% 85, 60 3.363 91 2.95 4.19 from V TMS) Matrimid® 5 218 (Temperat ·; ra in Pyrolysis a 55 0 "Ç; CMS treated (10% 87, 64 ' So, o.D 1.98 4.30 from V TMS) Rimid® mat 5218 (Tempe ratara in Pyrolysis a 600 ° C) CMS treated (10% 86.05 2.4 73.0 0 9 2.5 '/ 5.82 from V TMS) Matrimid® 5218 (Temperature in Pyrolysis a 65 0 ° C)
[14 8 j Elementary analyzes were also performed on asymmetric modified CMS hollow fibers that were prepared by treating Matrimid® 5218 precursor fibers with pure VTMS and then subjected to pyrolysis of the treated fibers. The results indicate that the modified CMS hollow fibers contain between about 11% by weight of silicon and about 16% by weight of silicon (between about 3 and about 6 mol% of silicon), depending on the pyrolysis temperature ( which ranged from 550 ° C to 650 ° C). To ensure that the measured silicon was attributable to the morphology stabilizer that is present after pyrolysis, CMS hollow fibers prepared by pyrolysis of untreated precursor fibers Matrimid® 5218 (using the same pyrolysis temperatures) were also subjected to analysis
Petition 870160023992, of 05/30/2016, p. 81/116
Elementary 69/80. CMS hollow fibers prepared from Matrimid® 5218 untreated precursor fibers were found to contain no measurable amount of silicon. In this way, the percentage by weight of silicon found by elementary analyzes of modified CMS hollow fibers can serve to indicate the amount of morphology stabilizer that resides in an asymmetric modified CMS hollow fiber membrane.
[149] Next, elementary analyzes were performed on the asymmetric modified CMS hollow fibers that were prepared by treating Matrimid® 5218 precursor fibers with a solution containing 10% by weight of VTMS, and then subjected to pyrolysis of the treated fibers. at different pyrolysis temperatures ranging from 550 ° C to 650 ° C. The modified CMS hollow fiber membranes have been found to contain between about 4 wt% silicon and about 6 wt% silicon (between about .1 and about 2 mole% silicon).
Table 5
Carbon(mol%) Hydrogen (mol%) Nitrogen (mol%) Oxygen (%in mol) Silence (% by mol) Not treated Untraceable CMSRimid® mat(Temperature ofPyrolysis a5 5 0 ° C)2 8.06 Matrimid® untreated CMS(T amp e r a t ii r a of;Pyrolysis a650 ° C) 81, 662.90 1, '/ 9Treaty (J.00% of VTMS} CMS treated(100% VTMS)Matrimid®(Temperature ofPyrolysis a35, 5 5 2.2 9 2.36 3.62
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70/80
550 ° C)Tra CMS each 65, 96 24.341.99 1.94 5, '7 7 (1.00% of V (MS) Matrimid® (T emp e r up to r a in Pyrolysis The 6.50 ° C)Treaty (1.0¾ inCMS treated (10% Ό 4.2 1 30.2 8Z, O .1 1.66 1, 3 4 from V TMS) Matrimid® (T emp e r at a. R a in Pyrolysis The 550 ° C) CMS treated (10% 69, 22 25, 882.2 / 1.1 / 1.4 s from V TMS) Matrimid® (Temperature) in Pyrolysis "The 6 0 0 ° C ' Airborne CMS. (10% 70, 08 z 4.17. 1 Ό 1, 5 7 2, 03 from V TMS) Matrimid® (Temperature in Pyrolysis ci 650 ”C)
[150] In one embodiment, the asymmetric modified CMS hollow fiber membrane comprises an amount of morphology stabilizer that can be determined by elementary analyzes, such that the asymmetric modified CMS hollow fiber membrane comprises a desired molar percentage of an element , whose only significant presence in the fiber is attributable to treatment with a modifying agent, that is, an indicator element. The indicator element comprises, for example, silicon and / or the metal element that forms the silane head and / or metal alkoxide modifying agents. For example, the asymmetric modified CMS hollow fiber membrane can comprise between about 0.1 mol% and about 10 mol% of the indicator element; alternatively, between about
Petition 870160023992, of 05/30/2016, p. 83/116
71/80
0.1 mol% and about 8 mol%; alternatively, between about 0.1 mol% and about 7 mol%; alternatively, between about 0.1 mol% and about 6 mol%; alternatively, between about 0.1 mol% and about 5 mol%; alternatively, between about 0.1 mol% and about 4 mol%; alternatively, between about 0.1 mol% and about 3 mol%; alternatively, between about 0.1 mol% and about 2 mol%; alternatively, between about 0.5 mol% and about 10 mol%; alternatively, between about 0.5 mol% and about 8 mol%; alternatively, between about 0.5 mol% and about 7 mol%; alternatively, between about 0.5 mol% and about 6 mol%; alternatively, between about 0.5 mol% and about 5 mol%; alternatively, between about 0.5 mol% and about 4 mol%; alternatively, between about 0.5 mol% and about 3 mol%; alternatively, between about 0.5 mol% and about 2 mol%; alternatively, between about 0.75 mol% and about 10 mol%; alternatively, between about 0.75 mol% and about 8 mol%; alternatively, between about 0.75 mol% and about 7 mol%; alternatively, between about 0.75 mol% and about 6 mol%; alternatively, between about 0.75 mol% and about 5 mol%; alternatively, between about 0.75 mol% and about 4 mol%; alternatively, between about 0.75 mol% and about 3 mol%; alternatively, between about 0.75 mol% and about 2 mol%; alternatively, between about 1 mol% and about 10 mol%; alternatively, between about 1 mol% and about 8 mol%; alternatively, between about 1% in
Petition 870160023992, of 05/30/2016, p. 84/116
72/80 mol and about 7 mol%; alternatively, between about
1% by mol and cerc the 6% in mol; alternatively and between about 1% by hand 1 and about 5% hey : n mol; alt ernati . again, between about 1 mol% and about 4% in mol; alternatively, between fence 1% in mol and fence 3% in
mol; alternatively, between about 1 mol% and about 2 mol%.
[151] Advantageously, the asymmetric modified CMS hollow fiber membrane can comprise an amount of morphology stabilizer, such that the asymmetric modified CMS hollow fiber membrane comprises a desired weight percentage of the indicator element. For example, in embodiments where the morphology stabilizer comprises a compound containing silicon, the asymmetric modified CMS hollow fiber membrane can comprise between about 0.1%
by weight and about 2 0 The. '0 in weigh 3 of s 1.1 rcio; alternatively between about in 0, 1 . % in weight and about 15% by weight; alternatively, en t re fence of 0.1 % by weight
and about 10-% by weight; alternatively, between about 0.1% by weight and about 8% by weight; alternatively, between about 0.1% by weight and about 6% by weight; alternatively, between about 0.1% by weight and about 5% by weight; alternatively, between about 0.5% by weight and about 20% by weight of silicon; alternatively between
about 0.5% in weight and about 15% by weight; alternatively, between fence 0.5% in weight í about 10% by weight; alte relatively, between fence of 0, 5% by weight
and about 8% by weight; alternatively, between about 0.5% by weight and about 6% by weight; alternatively, between about 0.5% by weight and about 5% by weight;
Petition 870160023992, of 05/30/2016, p. 85/116
73/80 alternatively, between about 1% by weight and about 20% by weight of silicon; alternatively, between about 1% by weight and about 15% by weight; alternatively between about
1% by weight and surround of 10 ^; no weight; alt < ernativament - Λ between about 1% by weight and about 8% in feet The; alternatively, in between fence 1% by weight and about 6%
by weight; alternatively, between about 1% by weight and about 5% by weight; alternatively, between about 2% by weight and about 20% by weight of silicon; alternatively, between about 2% by weight and about 15% by weight; alternatively, between about 2% by weight and about 10% by weight; alternatively, between about 2% by weight and about 8% by weight; alternatively, between about 2% by weight and about 6% by weight; alternatively, between about 2% by weight and about 5% by weight; alternatively, between about 3% by weight and about 20% by weight of silicon; alternatively, between about 3% by weight and about 15% by weight; alternatively, between about 3% by weight and about 10% by weight; alternatively, between about 3% by weight and about 8% by weight; alternatively, between about 3% by weight and about 6% by weight; alternatively, between about 3% by weight and about 5% by weight; alternatively, between about 4% in
weight and fence in 75 in Weight in silicon; a11 ernat ively, between fence in 4% in Weight and fence 15% by weight; alternatively, in between fence in 4% in pi 3so and about 10%
by weight; alternatively, between about 4% by weight and about 8% by weight; alternatively, between about 4% by weight and about 6% by weight.
Petition 870160023992, of 05/30/2016, p. 86/116
74/80
[152 j In various embodiments, a precursor fiber may comprise a layer of product from the modifying agent reaction on the outer coating of the fiber and an asymmetric modified CMS hollow fiber membrane may comprise a product layer from the residual modifying agent reaction. . For example, a precursor fiber that is treated with a modifying agent can comprise a layer of material containing silicon on the outer coating of the fiber. Likewise, the asymmetric modified CMS hollow fiber membrane may comprise a layer of a material containing residual silicon on the outer coating of the fiber. Alternatively, when a metal-containing modifying agent is used in the pre-pyrolysis treatment of the precursor fiber, the treated precursor fiber may comprise a layer of material containing metal on the outer coating of the fiber and the asymmetric modified CMS hollow fiber membrane may comprise a layer of material containing residual metal on the outer coating of the fiber.
[153] The product layer of the modifying agent reaction provides the precursor fibers treated with a nonstick property that is desirable for fiber pyrolysis in groups. Thus, modalities of the present invention are directed to a polymer precursor fiber that comprises a mechanical barrier layer that prevents the precursor fiber from adhering to other precursor fibers, when the fibers are heated to a temperature above the glass transition temperature. polymer material.
Petition 870160023992, of 05/30/2016, p. 87/116
75/80
[154] Modalities of the present invention are also directed to bundles of asymmetric modified CMS hollow fibers, wherein the modified CMS hollow fibers are substantially free from adherence to one another after pyrolysis. The modified CMS hollow fibers preferably comprise a layer of the residual modifying agent reaction product, such as a silica material, on the surface of the outer coating. As previously described, however, it is preferred that the product layer of the residual modifying agent reaction on a modified CMS hollow fiber membrane is thin so as to minimize interference with the gas flow through the outer coating of the membrane. asymmetric modified CMS hollow fiber.
Examples 19 to 70
[155] The procedure of Example 7 was performed using a number of different precursor polymers and modifying agents. As noted, additional polymers contemplated for use include:
Pl. 6FDA: BPDA-DAM
P2. 6FDA: BTDA-DAM
P 3. 6FDA: D SDA-DAM P 4. 6FDA: ODPA-DAM
[156] As noted, suitable modifying agents can include
Ml. vinyl triethoxy silane
M2. silane tripropoxy vinyl
M3, silane tributoxy vinyl
M4. divinyl dimethoxysilane
M5. divinyl dietoxysilane
Petition 870160023992, of 05/30/2016, p. 88/116
76/80
M6. titanium methoxy tetra
M7. titanium methoxypropoxide
M8. titanium tetrapropoxy
M9. titanium tetraethoxy
M10. vanadium methoxy tetra
Thousand. vanadium methoxypropoxide
M12. vanadium tetrapropoxy
M13. vanadium tetraethoxy
Example No. Precursor Polymer Modification Agent 19 PI Ml 20 PI M2 21 PI M3 22 PI M4 23 PI Μ5 24 PI M6 25 PI M7 2 β PI M8 27 PI M9 28 PI M10 29 PI MU 30 PI Ml 2 31 PI Ml 3 32 P2 Ml 33 P2 M2 34 P2 M3 35 P2 M4 3 6 P2 M5 3 i P2 M6 38 P2 M7 3 9 P2 M8 40 P2 M 3 41 P2 M10 42 P2 Thousand 43 P2 Ml 2 44 P2 Ml 3 45 P3 Ml 46 P3 M2 / [7 P3 M3 48 P3 M4 4 9 P3 M5 50 P3 M6 51 P3 M7 52 P3 M8 53 P3 M9 54 P3 M10 5 5 P3 MU 56 P3 Ml 2
Petition 870160023992, of 05/30/2016, p. 89/116
77/80
57 P3 Ml 3 58 P4 Ml 5 9 P4 M2 60 P4 M3 61 P4 M4 62 P4 M5 63 P4 M6 64 P4 M7 65 P4 M8 66 P4 M9 67 P4 M10 68 P4 Thousand 69 P4 Ml 2 7 0 P4 Ml 3
Treatment of Thermally Polymer Membranes
Rearranged
[157] The pores and channels within a polymer or fiber film typically have a wide range of sizes, which make polymer structures generally unsuitable for gas separation applications. In various embodiments, the pyrolysis of a polymer material forms a carbon molecular sieve material that has ordered pores. However, certain polymers can be treated to make the polymer itself suitable for gas separation applications. Thermally rearranged polymer membranes, also known as TR polymer membranes or TR polymer fibers, remedy the problem of variable pore sizes by thermally conducting spatial rearrangement of the segments of the rigid polymer chain in the glass phase to produce the pores with a more controlled size. These changes in the structure of the polymer are said to increase the permeability and selectivity properties, making the polymer suitable for gas separation.
[158] Preferred thermally rearranged polymer membranes comprise aromatic polymers
Petition 870160023992, of 05/30/2016, p. 90/116
78/80 which are interconnected with heterocyclic rings. Examples include, polybenzoxazole, polybenzothiazoles, and polybenzimidazoles. Preferred thermally rearranged polymer precursors comprise polyimides with ortho-positioned functional groups, such as, for example, HAB6FDA, a polyimide having the following structure.
[159] Phenylene-heterocyclic ring units in such materials have rigid chain elements and a high torsional energy barrier for rotation between the two rings, which prevents indiscriminate rotation. The thermal rearrangement of these polymers can thus be controlled to create pores having one. narrow size distribution, making them useful for gas separation applications.
[160] The temperature at which thermal rearrangement occurs is generally lower than the temperatures used for pyrolysis, as pyrolysis would convert the polymer fiber to a carbon fiber. Polyimides, for example, are typically heated to a temperature between about 250 ° C and about 500 ° C, more preferably, between about 300 ° C and about 450 ° C. The heating of the polymers generally takes place in an inert atmosphere over a period of several hours. Although the polymer is not subjected to the same pyrolysis stresses, heating the polymer to a temperature sufficient to cause
Petition 870160023992, of 05/30/2016, p. 91/116
79/80 thermal rearrangement also results in undesirable pore collapse.
[161] Des · this way, modal pres ages ente invention are dire CIO 1 ’ lated to the tra treatment of a material of polymer with a modification agent before of rearrangement thermal, in that treatment is effective for res' tring the collapse of unwanted pore of material in polymer termicarne > nte rearranged. 0 treatment of material of
polymer is carried out in the same manner as described above, with respect to the treatment of polymer precursor fibers which are then pyrolyzed to form the asymmetric CMS hollow fiber membranes. The difference being, of course, that the treated polymer material is subjected to thermal rearrangement, as is known in the art, as opposed to pyrolysis. Modalities of the present invention are also directed to a thermally rearranged polymer material having a restricted pore collapse, such as that which is treated with a modifying agent, as described herein.
[162 j You may notice that the described modalities provide original and new treatment processes, asymmetric modified CMS hollow fiber membranes, and thermally reorganized polymer membranes that have a number of advantages over those in the art. While it is shown and described here, certain specific structures that embody the invention, it will be manifest by those skilled in the art that various modifications and rearrangements of the parts can be made without departing from the spirit and scope of the underlying invention concept and that they are not limited to the particular shapes shown here and
Petition 870160023992, of 05/30/2016, p. 92/116
80/80 described, except to the extent, as indicated by the scope of the appended claims.

权利要求:
Claims (7)
[1]
1. Process for the preparation of an asymmetric modified CMS hollow fiber membrane having improved gas separation performance properties, characterized by the fact that it comprises:
The. provide a hollow fiber precursor of asymmetric polymer,
B. contacting the polymer precursor fiber with a solution comprising a modifying agent,
ç. contact the polymer precursor fiber of step b. with an atmosphere containing moisture to form a treated polymer fiber, and
d. pyrolysing the treated polymer fiber to form an asymmetric modified CMS hollow fiber membrane having improved gas permeability, wherein the concentration of the modifying agent in the solution is selected to obtain a modified CMS hollow fiber membrane with similar gas permeability .
[2]
2. Process, characterized by comprising between c and the solution.
[3]
3. Process,
C22 íiÜ ícl is * 12 IL jSú at least comprises between c and the solution.
[4]
4. Process, characterized by the ça having properties and properties according to the fact that the ca 1% by weight according to the fact that the ca 1% by weight according to the fact that the desired hearing of selectivity.
claim 1, modifying agent and about 95% by weight claim 2, modifying agent and about 50% by weight claim 3, modifying agent
Petition 870160023992, of 05/30/2016, p. 94/116
2/7 comprises between about 5% by weight and about 25% by weight of the solution.
[5]
5. Process according to claim 1, characterized by the fact that the modifying agent is a compound having the general formula R ¹ R ² R ³ R ' ¹ Si, where each of R *, R, R, and R e, independently, Cr-Ce alkyl or alkenyl, alkoxy, or halogen; with the proviso that the compound contains at least one C 1 -C 6 alkyl or alkenyl substituent, and at least one alkoxy or halogen substituent.
Process according to the claim characterized by the fact that the modifying agent is vinyl trimethoxy silane.
Process, of the color d <
with the
1, characterized by the fact that the modifying agent is a compound having the general formula R ⁱ R ² R ' ^, R ^ M, where M is a metal and where each of R ¹ , R ² , R', and R ⁴ is, independently, Ci
Cg alkyl or alkenyl, alkoxy, or halogen; with the proviso that the compound contains at least one C 1-6 alkyl or alkenyl substituent and at least one alkoxy or halogen substituent.
8. Process, according to claim 7, by the fact that M is selected from the group consisting of Ge, B, Al, Ti, V, Fe, and combinations thereof.
9. Process, according to claim 1, characterized by the fact that the solution still comprises a branched or linear aliphatic hydrocarbon,
Cs or greater.
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3/7
10. Process, according with claim 9, characterized by the fact that the aliphatic hydrocarbon branched or straight chain, C ₅ or greater is n-hexane. 11. Process, according with claim 1, characterized by the fact that the solution comprises vinyl
trimethoxy silane and n-hexane.
12. Process, according with claim 1,
characterized by the fact that the asymmetric hollow polymer fiber comprises a polyimide.
13. Process, according with claim 12,
characterized by the fact that the polyimide is selected from the group consisting of Matrimid® 5218 and 6FDA / BPDADAM.
14. Process, according with claim .1,
characterized by the fact that the concentration of the modifying agent in the. solution is selected to obtain an asymmetric modified CMS hollow fiber membrane having a gas permeability property that is at least a 300% increase over a CMS hollow fiber membrane
asymmetric equivalent that does is subjected to treatment
aa step o.
15. Process, according with claim 14, characterized by the fact that 2 agent concentration
solution modification is selected to obtain an asymmetric modified CMS hollow fiber membrane having a
selectivity which is at least 85% of the selectivity of a
equivalent asymmetric CMS hollow fiber membrane that is not
submitted to the treatment of the stage B. 16. Process, according with claim 1, characterized by the fact that < the concentration of the
Petition 870160023992, of 05/30/2016, p. 96/116
4 / Ί
modification in the solution is selected to get a
asymmetric modified CMS hollow fiber membrane which is useful for the separation of gases selected from the group consisting of C0 ₂ and CH ₄ , H ₂ S and CH ₄ , CO ₂ / H ₂ S and CH ₄ , C0 ₂ and N ₂ , 0 ₂
and N ₂ , N ₂ and CH ₄ , He and CH ₄ , H ₂ and CH ₄ , H ₂and C ₂ H ₄ , ethylene and ethane, propylene and propane, and ethane, '' propane and
lene / propylene.
17. Process, according to claim 1, characterized by the fact that the ration of the modification in the solution is selected to get a
asymmetric modified CMS hollow fiber membrane that is useful for separating acid gases from a natural gas stream.
18. Process, according to r e i vi ndication 1,
characterized by the fact that the concentration of the
modification in. solution is selected to get a
hollow fiber membrane. Asymmetric modified CMS which is useful
for the separation of CO ₂ from a i gas stream
nt e n do hid r o c a rbone t
19. Process, according to claim 1, characterized by the fact that the agent action modification in the solution is selected to get a modified CMS hollow fiber membrane asymmetric having
C0 ₂ permeability of at least 50 GPU and a selectivity of CO ₂ / CH ₄ of at least 60 when subjected to a mixed feed containing 50 mol% of CO ₂ and 50 mol% of CH ₄ at 150 psi (1.03x10 ^s Pa) and 35 ° C.
20. Process, according to claim 1,
characterized by the feeling that the precursor fiber of
treated polymer is supplied with other precursor pounds
Petition 870160023992, of 05/30/2016, p. 97/116
5/7 polymer treated prior to pyrolysis to form a bundle of asymmetric modified CMS hollow fibers and wherein the asymmetric modified CMS hollow fibers are substantially free to adhere to one another.
21. Process for forming an asymmetric modified CMS hollow fiber membrane, characterized by the fact that it comprises:
The. form a hollow asymmetric polymer fiber,
B. contacting the hollow polymer fiber with one or more solvent exchange materials, and
ç. pyrolyzing the hollow polymer fiber to form an asymmetric CMS hollow fiber membrane, wherein at least one of the solvent exchange materials comprises a modifying agent in an amount effective to improve the gas permeability of the CMS hollow fiber membrane asymmetric.
22. Process, according to claim 21, CêlXsiCtêXXZâLdO by the fact that it still comprises, after step c, put in contact a. hollow polymer fiber with an atmosphere containing moisture.
23. Process according to claim 21, characterized by the fact that at least one of the solvent exchange materials is a solution comprising an organic compound and a modifying agent.
24. Process according to claim 23, m ü ss in that the organic compound is a branched or straight chain aliphatic hydrocarbon, C ₅ or greater.
Petition 870160023992, of 05/30/2016, p. 98/116
[6]
6 / Ί
25. Process, in wake up with the r e i v i n d i c action 24, characterized by fat < s that the comp · I'm organic it's n- hexane. 26. Process, in wake up with the claim 21, characterized by fact that the agent modification it is a
compound having the general formula R ¹ R ² R ^, R ' ¹ Si, where each of R *, R _f R, and R ^{1 is} , independently, C 1 -C 6 alkyl or alkenyl, alkoxy, or halogen; with the proviso that the compound contains at least one C 1 -C 6 alkyl or alkenyl substituent, and at least one alkoxy or halogen substituent.
27. Process, according with cl claim 26, characterized by fact of what the agmodification is vinyl trimethoxy sil .year. 28. Process, from ac ordo with The claim 21, characterized by fact of that the now you modification is a compound having the formula general f or rmu the general R ¹ R ^z R''R ⁴ Si, where M is a metal and where each a D .and R ¹ , R ² , R ', and R ^ is, independently, C 1 -Cg alkyl or alkenyl, alkoxy, or
halogen; with the proviso that the compound contains at least one C 1-6 alkyl or alkenyl substituent and at least one alkoxy or halogen substituent.
29. Process, according to claim 28, by the fact that M is selected from the group consisting of Ge, B, Al, Ti, V, Fe, and combinations thereof.
30. Asymmetrical modified CMS hollow fiber membrane, Î ”1 (251. is» 32 JL because it is produced by the process, defined according to claim 1.
Petition 870160023992, of 05/30/2016, p. 99/116
[7]
7/7
31. Asymmetric modified CMS hollow fiber membrane, characterized by the fact that it is produced by the process, defined according to claim 21.
32. Process for the preparation of a thermally rearranged polymeric material having improved gas separation performance properties, characterized by the fact that it comprises
The. provide a precursor polymer material,
B. contacting the precursor polymer material with a solution comprising a modifying agent,
ç. contact the precursor polymer material of step b. with an atmosphere containing moisture to form a treated precursor polymer material, and
d. heating the treated precursor polymer material to form a thermally rearranged polymer having an improved gas permeability.
33. The method of claim 32, which is thermally rearranged, is selected from the group consisting of polybenzoxazoles, polybenzothiazoles, polybenzimidazoles, and combinations thereof.
34. Thermally rearranged polymer, characterized by the fact that it is prepared by the method, defined according to claim 32.

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-03-10| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.21 NA RPI NO 2553 DE 10/12/2019 POR TER SIDO INDEVIDA. |

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2020-08-04| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-08-31| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-10-19| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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2021-12-07| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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US201361884548P| true| 2013-09-30|2013-09-30|

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PCT/US2014/058329|WO2015048754A1|2013-09-30|2014-09-30|Asymmetric modified carbon molecular sieve hollow fiber membranes having improved permeance|

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