KR101516448B1 - Uv uv cross-linked mixed matrix membranes of polymer functionalized molecular sieve and polymer - Google Patents

Abstract

The present invention relates to a process for preparing high performance UV cross-linked mixed matrix membranes (MMM) of polymeric functionalized molecular sieves and polymers which have no macropores or have voids less than a few angstroms at the interface of the polymer matrix and the molecular sieve And a method of using the same. Such UV crosslinked MMM is prepared by incorporating the polymeric functionalized molecular sieve into a continuous UV crosslinkable polyimide polymer matrix and then UV crosslinking. UV crosslinked MMM in the form of a symmetrical dense film, an asymmetric flat sheet membrane or an asymmetric hollow fiber membrane has excellent flexibility and high mechanical strength and has a corresponding continuous polyimide polymer matrix for carbon dioxide / methane and hydrogen / Lt; RTI ID = 0.0 > and / or < / RTI > MMM is suitable for various liquid, gas and vapor separations.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to UV cross-linked mixed matrix membranes of polymeric functionalized molecular sieves and polymers.

The present invention relates to high performance UV crosslinked mixed matrix membranes of polymeric functionalized molecular sieves and polymers having no macropores or at pores of less than a few angstroms at the interface of the polymer matrix and the molecular sieve ). The present invention also relates to methods of making and using UV crosslinked MMM.

Membrane-based gas separation processes have undergone major developments since the original membrane-based industrial hydrogen separation process approximately 20 years ago. The design of novel materials and effective methods will continue to advance the membrane gas separation process.

The gas transport properties of many glassy and rubbery polymers have been measured as part of a study on materials with high permeability and high selectivity for potential applications as gas separation membranes. Unfortunately, an important limitation of the development of new membranes for gas separation applications is the trade-off between the permeability and selectivity of the well-known polymers. Robeson compared the data of hundreds of different polymers so that the selectivity and permeability of the polymer membrane seemed to be inseparably linked to each other and in this relationship the selectivity increased as the permeability decreased and also in the opposite case I have proved that.

Despite the concentrated effort to tailor the polymer structure to improve separation properties, current polymeric membrane materials seem to have reached a limit in the trade-off between productivity and selectivity. For example, many polyimides and polyetherimide glassy polymers such as Ultem ^® 1000 have significantly higher intrinsic CO ₂ / CH ₄ selectivity than cellulose acetate (22 at 50 ° C. and 690 kPa (100 psig) pure gas test α _{CO2 / CH4} ) (30 at 50 ° C and 690 kPa (100 psig) pure gas test) and is more attractive for practical gas separation applications. However, such polyimide and polyetherimide polymers do not have outstanding permeability for commercial use as compared to current commercial cellulose acetate membrane products, consistent with the trade-off reported by Robeson. Also, although some inorganic membranes, such as Si-DDR zeolites and carbon molecular sieve membranes, which provide much higher permeability and selectivity than separation polymer membranes are present, these membranes are found to be too expensive and difficult to produce in large scale . It is therefore highly desirable to provide an alternative cost effective membrane having improved separation characteristics and, if possible, separation characteristics that surpass the trade-off curve between permeability and selectivity.

Based on the need for more effective membranes than polymers and inorganic membranes, new types of membranes, mixed matrix membranes (MMM) have recently been developed. MMM is a hybrid membrane containing an inorganic filler, such as molecular sieve, dispersed in a polymer matrix.

Mixed matrix membranes have the potential to achieve higher selectivity with equal or better permeability compared to conventional polymeric membranes while maintaining the advantages of low cost and easy processability. Most of the work done so far for mixed matrix membranes has focused on a combination of dispersed solid molecular sieve phases, such as zeolite molecular sieves or carbon molecular sieves and easily processed continuous polymer matrices. For example, U.S. 4,705,540; U.S. 4,717,393; U.S. 4,740,219; U.S. 4,880,442; U.S. 4,925,459; U.S. 4,925,562; U.S. 5,085,676; U.S. 5,127,925; U.S. 6,500,233; U.S. 6,503,295; U.S. 6,508,860; US 6,562,110; U.S. 6,626,980; U.S. 6,663,805; US 6,755,900; U.S. Patent No. 7,018,445; U.S. Patent No. 7,109,140; U.S. Patent No. 7,166,146; US 7,250,545; US 7,268,094; US 2005/0230305; US 2005/0268782; U.S. 7,306,647; And US 2006/0117949. Scenarios of the sieving phase within the solid / polymer blend matrix can have significantly higher selectivity than pure polymers. Thus, theoretically, the addition of a small volume ratio of molecular sieve to the polymer matrix significantly increases the overall separation efficiency. Conventional inorganic body phases in MMM include various molecular sieves, carbon molecular sieve, and silica. Many organic polymers, including cellulose acetate, polyvinylacetate, polyetherimide (commercial Ultem ^® ), polysulfone (commercial Udel ^® ), polydimethylsiloxane, polyethersulfone and polyimide (including commercial Matrimid ^® ) .

The use of solid / polymer MMM surpasses the polymer "upper limit" curve, but there are still many issues that still need to be addressed for large industrial production of this new type of MMM. For example, in the case of most molecular sieves and polymeric MMMs reported in the literature, voids and defects at the interface of the inorganic molecular sieve and the organic polymer matrix were observed due to poor interfacial adhesion and poor material compatibility. This pore, which is much larger than the permeating molecules, consequently reduces the overall selectivity of the MMM. Studies have shown that interfacial areas between the continuous polymer and the dispersed phase are particularly important in forming successful MMMs.

More recently, considerable research efforts have focused on material compatibility and adhesion at the inorganic molecular sieve / polymer interface of MMM to achieve improved separation properties for conventional polymers. For example, Kulkarni et al. And Marand et al. Have reported the use of organosilicon coupling agent functionalized molecular sieves to improve the adhesion of MMM at the body particle / polymer interface. US 6,508,860 and US 7,109,140 B2. Kukanai et al. Also report the use of electrostatically stabilized suspensions to form MMM with minimal macropores and defects. US 2006/0117949.

Despite all these research efforts, the issues of material compatibility and adhesion at the inorganic molecular sieve / polymer interface of MMM have not been completely solved.

No. 11 / 300,775, entitled " Cross-Linkable and Cross-Linked Mixed Matrix Membranes and Methods of Making the Same " ), Filed December 15, 2005, which is hereby incorporated by reference in its entirety. In this prior art, a novel type of UV crosslinkable and UV crosslinked, molecular sieve-polymer mixed matrix membrane (MMM) using a polymer as a dispersed filler as a porous molecular sieve and a continuous polymer matrix was first disclosed . The present invention is an improvement on this prior art. In accordance with the present invention, a high selectivity UV crosslinked MMM that does not have macropores or has voids less than a few angstroms in the interface between the polymer matrix and the molecular sieve has a polymeric functionalized molecular sieve, such as AlPO-14 or UZM-25 Can be successfully prepared by incorporation into a continuous polyimide polymer matrix followed by UV cross-linking. Polyethersulfone (PES) has been found to be a particularly useful polymer for providing polymeric functionalized molecular sieves. Thus, a large scale membrane manufacturing process is disclosed for the preparation of UV cross-linked MMMs of polymeric functionalized molecular sieves and polymers without pores and defects.

Summary of the Invention

SUMMARY OF THE INVENTION The present invention is directed to a UV crosslinked mixed matrix membrane (MMM) of polymeric functionalized molecular sieves and polymers free of new voids and defects. More particularly, the present invention relates to a novel process for making and using UV cross-linked MMMs of such polymeric functionalized molecular sieves and polymers.

The present invention relates to polymeric functionalized molecular sieves containing polymeric (e.g., polyethersulfone) functionalized molecular sieves as dispersed fillers and a continuous UV crosslinkable polymer (e.g., polyimide) matrix, and UV cross-linkable MMM UV crosslinked mixed matrix membranes (MMM) of polymeric functionalized molecular sieves and polymers that do not have macropores at the interface of the polymer matrix and molecular sieve by UV crosslinking or have pores of less than 5 A (0.5 nm) . UV cross-linked MMM in the form of a symmetric dense film, an asymmetric flat sheet membrane or an asymmetric hollow fiber membrane prepared by the process described herein has excellent flexibility and high mechanical strength and is suitable for use in a variety of applications including carbon dioxide / methane (CO ₂ / CH ₄ ) And hydrogen / methane (H ₂ / CH ₄ ) separations for polymer membranes prepared from corresponding continuous polyimide polymer matrices. The UV crosslinked MMMs of the present invention can also be used in a variety of liquid, gas and vapor separations such as depth desulfurization of gasoline and diesel fuels, ethanol / water separation, aqueous / organic mixtures, CO ₂ / CH ₄ , CO ₂ / N ₂ , H ₂ / CH ₄ , O ₂ / N ₂ , pervaporation dehydration of olefins / paraffins, iso / normal paraffin separation and other light gas mixture separations.

The present invention relates to stable polymeric functionalized molecular sieves containing polymeric functionalized molecular sieve particles dispersed in a mixture of organic solvents and a dissolved continuous UV crosslinkable polymer matrix and pores using a suspension of polymer (or so-called "casting dope & And UV-crosslinked MMM of polymer with functionalized molecular sieves without defects. The method for producing the membrane includes the steps of (a) dispersing molecular sieve particles in a mixture of two or more organic solvents by ultrasonic mixing and / or mechanical stirring or other methods to form a molecular sieve slurry, (b) Dissolving a suitable polymer to effect functionalization of the surface of the molecular sieve particles; (c) dissolving the UV crosslinkable polymer acting as a continuous polymer matrix in the polymeric functionalized molecular sieve slurry to form a stable polymer functionalized molecular sieve (Fig. 1), asymmetric flat sheet (Fig. 2), a thin film film composite (TFC, Fig. 3) or asymmetric flat film (Fig. 2) using a suspension of the polymeric functionalized molecular sieve and polymer. (E) cross-linking the MMM under UV radiation. ≪ Desc / Clms Page number 7 >

In some cases, the membrane post-treatment step may be added to improve selectivity, but this post-treatment step should not significantly alter or damage the membrane or cause the membrane to lose its performance over time ). Such a membrane post-treatment step may include coating the top surface of the MMM with a thin layer of UV radiation curable epoxy silicone material, followed by UV cross-linking the surface coated MMM under UV radiation. The membrane post-treatment step may also include coating the top surface of the UV crosslinked MMM with a thin layer of a material such as polysiloxane, fluoropolymer, or thermosetting silicone rubber.

The molecular sieve in the MMM provided in the present invention may have significantly higher selectivity and / or permeability than the UV crosslinkable polymer matrix. Thus, adding less weight percent molecular sieve to the UV crosslinkable polymer matrix increases the overall separation efficiency. UV crosslinking can further improve the overall separation efficiency of the UV crosslinkable MMM. Molecular sieves used in the UV crosslinked MMM of the present invention include microporous molecular sieves, mesoporous molecular sieves, carbon molecular sieves, and porous metal-organic structures (MOF). The microporous molecular sieve may be a microporous alumino-phosphate molecular sieve such as AlPO-18, AlPO-14, AlPO-52 and AlPO-17, microporous microporous aluminosilicate molecular sieves such as UZM- 25 and UZM-9, microporous microporous silica-alumino-phosphate molecular sieves such as, but not limited to SAPO-34, SAPO-56 and mixtures thereof.

More importantly, the molecular sieve particles dispersed in the thickening suspension are functionalized by a suitable polymer, such as polyethersulfone (PES), which results in the formation of hydroxyl (-OH) groups on the surface of the molecular sieve, O-molecular sieve through reaction between hydroxyl (-OH) group at the polymer side chain of the self-stabilizing agent or at the end of the polymer chain covalent bond or hydroxyl group on the surface of the molecular sieve and ether And a hydrogen bond between the functional groups such as a tether. Functionalization of the surface of the molecular sieve using a suitable polymer provides a substantially void-free, non-deficient interface and excellent compatibility in the molecular sieve / polymer used to functionalize the molecular sieve / polymer matrix interface. Thus, polymeric functionalized molecular sieves which are prepared from suspensions containing the same molecular sieves as the conventional polymeric membranes and which are identical to the polymeric matrix but which have significantly improved separation characteristics compared to polymeric non-functionalized polymeric membranes, The UV cross-linkable MMM of the polymer is successfully prepared using such a stable polymeric functionalized molecular sieve and a suspension of the polymer. UV crosslinking of such MMM further improves overall separation efficiency. Without voids and defects at the interface, there is an increased likelihood that the permeate will be separated by passing through the pores of the molecular sieve in the MMM rather than passing through the pores and defects in the membrane non-segregated. The UV crosslinked MMMs prepared using the present invention combine the molecular sieving and sorption mechanism of the molecular sieve with the solution-diffusion mechanism of the polymer membrane (Fig. 5) and can be obtained from different membrane samples containing the same molecular sieve / polymer composition Ensuring maximum selectivity and consistent performance. The function of the polymer used to functionalize the molecular sieve particles in the UV crosslinked MMMs of the present invention is (1) molecular sieves used to functionalize the molecular sieve interface via hydrogen bonding or molecular sieve-O- (2) the intermediate improves the compatibility of the molecular sieve with the continuous polymer matrix, and (3) stabilizes the molecular sieve particles in the thickening suspension so that they remain uniformly suspended do.

The stabilized suspension containing the polymeric functionalized molecular sieve particles is uniformly dispersed in the continuous UV crosslinkable polymer matrix. UV crosslinked MMMs, in particular symmetrical dense film MMM, asymmetric flat sheet MMM or asymmetric hollow fiber MMM, are prepared from a stabilized suspension. The UV crosslinked MMM prepared by the present invention comprises polymeric functionalized molecular sieve particles uniformly dispersed throughout the continuous UV crosslinked polymer matrix. Continuous UV crosslinked polymeric matrices are formed by UV cross-linking UV crosslinkable glassy polymers, such as UV crosslinkable polyimides, under UV radiation. The polymer used to vaporize the molecular sieve particles is selected from polymers different from the UV crosslinked polymer matrix.

The process of the present invention is suitable for large-scale membrane production and can be integrated into a commercial polymer membrane manufacturing process.

The present invention further provides a method of separating at least one gas from a gaseous mixture using the UV crosslinked MMM described herein, comprising the steps of: (a) providing a homogeneously dispersed Providing a UV cross-linked MMM comprising a polymeric functionalized molecular sieve filler material; (b) contacting the mixture on one side of a UV cross-linked MMM so that the at least one gas passes through a UV cross-linked MMM And (c) removing the permeate gas composition comprising a portion of the at least one gas that has permeated the membrane from the opposite side of the membrane.

UV cross-linking of the present invention combined MMM various liquid, gas and vapor separation, for example, gasoline, and the depth desulfurization, ethanol / water separation of the diesel fuel, an aqueous / organic _{mixture, CO 2 / CH 4, CO} 2 / N 2, H 2 / CH ₄ , O ₂ / N ₂ , pervaporation dehydration of olefins / paraffins, iso / normal paraffin separation and other light gas mixture separations.

The invention may be better understood with reference to the following drawings and the accompanying description.

Brief Description of Drawings

Figure 1 is a schematic diagram of a symmetric UV crosslinked mixed matrix dense film containing a dispersed polymer coated molecular sieve and a continuous UV crosslinked polymer matrix.

Figure 2 is a schematic diagram of an asymmetric UV cross-linked mixed matrix membrane containing a dispersed polymer-coated molecular sieve and a continuous UV crosslinked polymer matrix, prepared on a porous support substrate.

3 is a schematic diagram of an asymmetric thin film film composite UV crosslinked mixed matrix membrane containing a dispersed polymer coating molecular sieve and a continuous UV crosslinked polymer matrix prepared on a porous support substrate.

4 is a schematic diagram of a post-treated asymmetric UV crosslinked mixed matrix membrane comprising a dispersed polymer coating molecular sieve and a continuous UV crosslinked polymer matrix, prepared on a porous support substrate and coated with a thin polymer layer.

Figure 5 is a schematic diagram showing the separation mechanism of a UV cross-linked mixed matrix membrane of a polymer-coated molecular sieve and a polymer, combining a solution-diffusion mechanism of a UV cross-linked polymer membrane and a molecular sieving mechanism of a molecular sieve membrane.

Figure 6 is a schematic diagram showing the formation of polymeric functionalized molecular sieves through covalent bonds.

7 is a chemical structural diagram of poly (BTDA-PMDA-ODPA-TMMDA).

8 is a chemical structural diagram of poly (DSDA-TMMDA).

9 is a chemical structural diagram of poly (DSDA-PMDA-TMMDA).

FIG. 10A shows the structure and preparation of UV cross-linkable microporous polymers showing reaction and hydroxyl group containing monomers "Al to A12 ".

FIG. 10B shows the structure of "B1 to B1O" used in the reaction shown in FIG. 10A.

Figure 11 is a plot showing CO ₂ / CH ₄ separation performance of P1, control 1, MMM 1 and MMM 2 membranes.

Figure 12 is a plot showing H ₂ / CH ₄ separation performance of P1, control 1 and MMM 1 membranes.

Figure 13 is a plot showing the CO ₂ / CH ₄ separation performance of the P2 and MMM 3 membranes.

Figure 14 is a plot showing CO ₂ / CH ₄ separation performance of P3, control 2, and MMM 5 membranes.

DETAILED DESCRIPTION OF THE INVENTION

Mixed matrix membranes (MMM) containing molecular sieve fillers dispersed in a continuous polymer matrix can possess polymer processability due to the better molecular sieve and sorption properties of the molecular sieve material and can improve selectivity for separation. MMM has been around the world for the last 20 years. However, in the case of most types of MMMs, consequent aggregation of molecular sieve particles in the polymer matrix resulting in poor mechanical and processing properties and poor permeation performance and poor aggregation of the molecular sieve particles and polymer matrix in the MMM Adhesion still needs to be resolved. Material compatibility and good adhesion of polymer matrix and molecular sieve particles are needed to achieve improved selectivity of MMM. The poor adhesion that results in voids and defects as a result of molecular sieve particulate removal, which is larger than pores in the molecular sieve, reduces the overall selectivity of the MMM by bypassing the pores of the paper molecular sieve to be separated. Thus, MMM slightly improves the selectivity of the continuous polymer matrix at best.

The present invention relates to novel, UV-crosslinked mixed matrix membranes (MMM) of polymeric functionalized molecular sieves and polymers without voids and defects. More particularly, the present invention relates to a novel method of making and using UV crosslinked polymeric MMM with such polymeric functionalized molecular sieves. The UV crosslinked MMM is a polymeric functionalized molecular sieve prepared from a stabilized thick suspension (also referred to as "casting dope ") containing a uniformly dispersed polymeric functionalized molecular sieve and a continuous UV crosslinkable polymer matrix, By UV crosslinking. The term "mixed matrix" as used in the present invention means that the membrane comprises a continuous UV crosslinkable polymer matrix and an optional transparent layer comprising discontinuous polymeric functionalized molecular sieve particles uniformly dispersed throughout the continuous UV crosslinkable polymer matrix . ≪ / RTI > As used herein, the term "UV crosslinkable polymer matrix" refers to a UV-crosslinkable polymer matrix that can be linked together to form an interpolymer-chain-linked crosslinked polymer structure when all of the polymeric matrices used in the present invention are exposed to UV radiation Quot; functional group ". As used herein, the term "UV crosslinked" means that an interpolymer-chain-linked crosslinked polymer structure is formed under UV radiation.

The present invention relates to a UV crosslinked mixed matrix membrane (MMM), in particular a UV crosslinking of a dense film, using a stabilized concentrated suspension containing polymeric functionalized molecular sieve particles and a dissolved continuous polymer matrix dispersed in a mixture of organic solvents UV crosslinked MMM of asymmetric flat sheets, MMM of asymmetric thin film composites, or UV crosslinked MMM of asymmetric hollow fibers. The method comprises the steps of (a) dispersing molecular sieve particles in a mixture of two or more organic solvents by ultrasonic mixing and / or mechanical stirring or otherwise to form a molecular sieve slurry, (b) dissolving a suitable polymer in the molecular sieve slurry (C) dissolving the UV crosslinkable polymer which acts as a continuum polymer matrix in the polymeric functionalized molecular sieve slurry to form a stable polymeric functionalized molecular sieve and a suspension of the polymer (Fig. 1), an asymmetric flat sheet (Fig. 2), an asymmetric thin film film composite (Fig. 3), or asymmetric hollow fibers using a suspension of the polymeric functionalized molecular sieve and polymer , And (e) crosslinking said MMM under UV radiation to form a UV crosslinked MMM.

In some cases, the membrane post-treatment step may be added to improve selectivity, but this post-treatment step should not alter or damage the membrane or cause the membrane to lose performance over time (Figure 4) . Such a membrane post-treatment step may comprise coating the top surface of the UV cross-linkable MMM with a thin layer of UV radiation curable epoxy silicone material, followed by UV cross-linking the surface coated UV cross-linkable MMM under UV radiation . The membrane post-treatment step may also include coating the top surface of the UV crosslinked MMM with a thin layer of a material such as polysiloxane, fluoropolymer, or thermosetting silicone rubber.

The design of UV cross-linked MMMs containing the uniformly dispersed polymeric functionalized molecular sieves described herein includes the molecular sieve, the polymer used to functionalize the molecular sieve, the UV cross-linkable polymer that acts as a continuous polymer matrix And the appropriate choice of solvent used to dissolve the polymer.

The molecular sieve in the UV crosslinked MMM provided in the present invention may have significantly higher selectivity than the polymer matrix for separation. Thus, adding a small percentage by weight of molecular sieve to the polymer matrix increases the overall separation efficiency. UV crosslinking can further improve the overall separation efficiency of the UV crosslinkable MMM. Molecular sieves used in the UV crosslinked MMM of the present invention include microporous molecular sieves, mesoporous molecular sieves, carbon molecular sieves, and porous metal-organic structures (MOF).

The molecular sieve includes optional holes / pores that allow gases such as carbon dioxide to pass through but do not allow other gases such as methane to pass through or allow the other gases to pass at a significantly lower rate Thereby improving the performance of the polymer matrix. The molecular sieve must have a higher selectivity to the desired separation than the original polymer to improve the performance of the MMM. To obtain the desired gas separation in the UV crosslinked MMM, it is preferred that the steady state permeability of the faster permeating gas component in the molecular sieve is at least equal to the steady state permeability of the faster permeating gas in the original polymer matrix phase. The molecular sieve has a structure that can be characterized by a unique broad X-ray diffraction pattern. Zeolites are a sub-class of molecular sieves based on aluminosilicate compositions. Non-zeolitic molecular sieves are based on other compositions such as aluminophosphates, silica-aluminophosphates and silicas. Molecular sieves of different chemical compositions may have the same structure.

The zeolite may further be broadly described as a molecular sieve which is assembled to define a three-dimensional structure structure in which the complexed aluminosilicate molecule surrounds the pore occupied by water molecules and ions capable of moving to a considerable degree of freedom in the zeolite matrix. In commercially useful zeolites, water molecules can be removed or replaced without destroying the structure structure. The zeolite composition has the following formula: M _{2 / n} O: Al ₂ O ₃ : xSiO ₂ : yH ₂ O, where M is a cation of valence n, x is greater than or equal to 2, y is the porosity of the zeolite And the number measured by the hydration state, and is generally 0 to 8). In natural zeolites, M is expressed primarily as Na, Ca, K, Mg and Ba in proportions that generally reflect the geochemical abundance ratio. The cation M can be loosely bound to the structure and can be replaced in whole or in part by other cations or hydrogen, usually by conventional ion exchange. The acid form of the molecular sieve sorbent can be prepared by a variety of techniques, including ammonium exchange followed by calcination or direct exchange of alkali ions to protons using inorganic acids or ion exchangers.

The microporous molecular sieve material is a microporous crystal having pores of a very limited size of 0.2 to 2 nm. These distinct degrees of porosity provide molecular characterization properties for these materials with a wide range of applications as catalysts and sorbent media. The molecular sieve structure type can be identified by the structural form code assigned to it by the IZA structural committee in accordance with the rules established by the IUPAC committee for the zeolite nomenclature. Each unique structure topology is referred to as a structured type code consisting of three uppercase letters. Preferred molecular sieves used in the present invention include molecular sieves having the IZA structure designations AEI, CHA, ERI, LEV, AFX, AFT and GIS. Exemplary compositions of such small pore alumina containing molecular sieves include, but are not limited to, specific aluminophosphates (AlPO), silicoaluminophosphates (SAPO), metallo-aluminophosphates (MeAPO), elemental aluminophosphates (ElAPO) Zeolite molecular sieve (NZMS) comprising silicoaluminophosphate (MeAPSO) and elemental silicoaluminophosphate (ElAPSO). Preferably, the microporous molecular sieve used in the preparation of the UV crosslinked MMM in the present invention comprises a small pore molecular sieve such as SAPO-34, Si-DDR, UZM-9, AlPO-14, AlPO- 17, SSZ-62, SSZ-13, AlPO-18, LTA, ERS-12, CDS-1, MCM-65, MCM-47, 4A, 5A, UZM-5, UZM- 34, SAPO-44, SAPO-47, SAPO-17, CVX-7, SAPO-35, SAPO-56, AlPO- MEL and the airborne per se, such as FAU, OFF, zeolite L, NaX, NaY and CaY.

More preferably, the microporous molecular sieve used in the preparation of the UV crosslinked MMM in the present invention is a microporous microporous aluminophosphate molecular sieve such as AlPO-18, AlPO-14, AlPO-52 and AlPO-17 , Microporous aluminosilicate molecular sieves such as UZM-5, UZM-25, UZM-9 and microporous microporous silico-alumino-phosphate molecular sieves such as SAPO-34, SAPO-56 and mixtures thereof But are not limited to these.

Another type of molecular sieve used in the UV crosslinked MMM provided herein is the mesoporous molecular sieve. Examples of preferred mesoporous molecular sieves include the MCM-41 type of mesoporous materials, SBA-15 and surface functionalized MCM-41 and SBA-15.

Metal-organic structures (MOF) can also be used as molecular sieves in the UV cross-linked MMM described in the present invention. MOF is a novel type of highly porous crystalline zeolitic material and is composed of hard organic units assembled by metal-ligands. MOF has a surface area that is widely accessible per unit mass. Yaghi et al., SCIENCE, 295: 469 (2002); Yaghi et al., J. Solid State Chem., 152: 1 (2000); Eddaoudi et al., ACC. CHEM. RES., 34: 319 (2001); Russell et al., SCIENCE, 276: 575 (1997); Kiang et al., J. Am. CHEM. SOC., 121: 8204 (1999); Hoskins et al., J. Am. CHEM. SOC, 111: 5962 (1989); Li et al., NATURE, 402: 276 (1999); Serpaggi et al., J. MATER. CHEM., 8: 2749 (1998); Reineke et al., J. Am. CHEM. SOC., 122: 4843 (2000); Bennett et al., MATER. RES. BULL., 3: 633 (1968); Yaghi et al., J. Am. CHEM. SOC., 122: 1393 (2000); Yaghi et al., MICROPOR. MESOPOR. MATER., 73: 3 (2004); Dybtsev et al., ANGEW. CHEM. INT. ED., 43: 5033 (2004). MOF-5 is a prototype of a new class of porous materials consisting of octagonal Zn-OC clusters and benzene linkages. Most recently, Yaghi et al. Have reported the regular design and construction of a series of structures (IRMOF) based on the framework of MOF-5. In MOF-5, It changes without changing the structure. For example, IRMOF-1 (Zn ₄ O (R ₁ -BDC) ₃ ) has the same structure as that of MOF-5, but is synthesized by a simplified method. Millward and Yagi first reported Cu ₃ (BTC) ₂ MOF materials in JACS in 2005, and BASF (Basolite ^® C 300 BASF brand name) was the first to commercialize. The Cu ₃ (BTC) ₂ MOF material has a fixed diameter of 6.9 A and a BET surface area of 1800 m ² / g, which can be used as an adsorbent for propylene / propane separation with high propylene loading capacity. In 2001, Yagi et al. Reported a porous metal-organic polyhedron (MOP) Cu ₂₄ (m-BDC), which is composed of 12 paddle-wheel units bridged by m- ) ₂₄ (DMF) ₁₄ (H ₂ O) _5O (DMF) ₆ (C ₂ H ₅ OH) ₆ to produce a large metal-carboxylate polyhedron. See Yaghi et al., 123: 4368 (2001). Such MOF, IR-MOF, and MOP materials exhibit behavior similar to that of conventional microporous materials, such as large and accessible surface areas with interconnected intrinsic micropores. In addition, such MOF, IR-MOF and MOP materials can reduce the hydrocarbon fouling problem of the polyimide membrane due to the relatively larger pore size than the zeolite material. MOF, IR-MOF, and MOP materials are also expected to allow the polymer to penetrate into the pores, thereby improving the interface and mechanical properties and subsequently affecting the permeability. Thus, such MOF, IR-MOF and MOP materials (all referred to herein as "MOF") are used as molecular sieves in the preparation of UV crosslinked MMMs in the present invention.

The particle size of the molecular sieve dispersed in the continuum polymer matrix of the UV crosslinked MMM in the present invention should be small enough to form a uniform particle dispersion in the concentrated suspension in which the UV crosslinked MMM is prepared. The median particle size should be 10 [mu] m, preferably less than 5 [mu] m, more preferably less than 1 [mu] m. Most preferably, nano-molecular sieves (or "molecular sieve nanoparticles") should be used within the UV cross-linked MMM of the present invention.

The nano-molecular sieves described herein are submicron sized molecular sieves having a particle size in the range of 5 to 1000 nm. The choice of nano-molecular sieves for the preparation of UV crosslinked MMM is dependent on the degree of dispersion of the nano-molecular sieve in the organic solvent, porosity of the nano-molecular sieve, particle size and surface functionalization, ≪ / RTI > adhesion or wetting properties. The nano-molecular sieves for the preparation of the UV crosslinked MMM must have a suitable pore size to allow selective permeation of a smaller size gas and also have an appropriate particle size in the nanometer range to prevent defects in the membrane do. The nano-molecular sieve must be readily dispersed in the polymer matrix without aggregation to maximize transport properties.

The nano-molecular sieves described herein are originally synthesized from a clear solution. Representative examples of nano-molecular sieves suitable for incorporation into UV crosslinked MMMs described herein include silicate-1, SAPO-34, Si-MTW, Si-BEA, Si-MEL, LTA, FAU, , AlPO-14, AlPO-34, SAPO-56, AlPO-52, AlPO-18, SSZ-62, UZM-5, UZM-9, UZM-25 and MCM-65.

In the present invention, the molecular sieve particles dispersed in the thickened suspension in which the UV crosslinked MMM is formed are functionalized by a suitable polymer, which results in the formation of hydroxyl (-OH) groups on the surface of the molecular sieve and molecular sieves O-molecular sieve covalent bond (Fig. 6) or a hydroxyl group on the surface of the molecular sieve by reaction between the hydroxyl (-OH) group at the polymer side chain of the stabilizer or at the end of the polymer chain Or a hydrogen bond between functional groups such as an ether group in the molecule. The surface of the molecular sieve in the thickening suspension contains a large number of hydroxyl groups attached to silicon (if present), aluminum (if present) and phosphate (if present). These hydroxyl groups in the molecular sieve in the thickening suspension can affect the long term stability of the suspension and the phase separation kinetics of MMM. The stability of the thickened suspension is related to the characteristics of the remaining molecular sieve particles uniformly dispersed in the suspension. An important factor in determining if agglomeration of molecular sieve particles can be prevented and whether a stable suspension can be formed is the compatibility of the polymer matrix and solvent in such a molecular sieve surface with the suspension. The functionalization of the surface of the molecular sieve using a suitable polymer described in the present invention provides a substantially void free, defect-free interface and excellent compatibility in the molecular sieve / polymer used to functionalize the molecular sieve / polymer matrix interface . Thus, there is a need for a polymeric functionalized polymeric membrane that is prepared from a suspension containing conventional molecular sieves and the same molecular sieve as the same UV crosslinkable polymeric matrix, but with significantly improved separation properties for the polymeric non- UV cross-linked MMMs of molecular sieves and polymers are successfully prepared using such stable polymeric functionalized molecular sieves and suspensions of polymers. The absence of voids and defects at the interface increases the likelihood of separation by passing through the pores of the molecular sieve in the UV crosslinked MMM rather than through the permeate paper through the voids and defects and not segregated. Thus, the UV crosslinked MMMs prepared using the present invention combine the molecular sieving and sorption mechanism of the molecular sieve with the solution-diffusion mechanism of the polymer membrane (Fig. 5), and the different membranes containing the same molecular sieve / Ensuring maximum selectivity and consistent performance among the samples.

The function of the polymer used to functionalize the molecular sieve particles in the UV crosslinked MMMs of the present invention is (1) molecular sieves used to functionalize the molecular sieve interface via hydrogen bonding or molecular sieve-O- (2) the intermediate improves the compatibility of the molecular sieve with the continuous polymer matrix, and (3) stabilizes the molecular sieve particles in the thickening suspension so that they remain uniformly suspended do. Any polymer having this function may be used to functionalize molecular sieve particles in a thickened suspension in which UV crosslinked MMM is formed. Preferably, the polymer used to functionalize the molecular sieve contains a functional group such as an amino group capable of forming a hydrogen bond with the hydroxyl group on the surface of the molecular sieve. More preferably, the polymer used to functionalize the molecular sieve contains a functional group such as a hydroxyl group or isocyanate group that can react with the hydroxyl group on the surface of the molecular sieve to form a polymer-O-molecular sieve covalent bond do. Thus, excellent adhesion between the molecular sieve and the polymer is achieved. Such representative polymers include, but are not limited to, hydroxyl groups or amino group terminations or ether polymers such as polyethersulfone (PES), poly (hydroxyl styrene), sulfonated PES, polyethers such as hydroxyl terminated poly (ethylene oxide) (Vinyl acetate), an amino group-terminated poly (ethylene oxide) or an isocyanate group-terminated poly (ethylene oxide), a hydroxyl terminated poly (propylene oxide), a hydroxyl terminated co- (Ethylene oxide) -block-poly (propylene oxide), tri-block-poly (propylene oxide) -poly (propylene oxide), hydroxyl terminated tri-block- ) -Block-poly (ethylene glycol) -block-poly (propylene glycol) bis (2-aminopropyl ether), poly (aryl ether ketone) (Ethyleneimine), poly (amido amine), poly (vinyl alcohol), poly (allylamine), poly (vinylamine), and polyetherimide, for example Ultem (or produced by the GE Plastics and marketed under the trademark Ultem ^® Ultem 1000) as well as cellulose polymers including hydroxyl group-containing glassy polymers such as cellulose acetate, cellulose triacetate, cellulose acetate-butyrate, cellulose propionate, ethylcellulose, methylcellulose and nitrocellulose.

The weight ratio of the polymer used to functionalize the molecular sieve versus the molecular sieve in the UV crosslinked MMM of the present invention can be varied depending on the desired properties as well as the degree of dispersion of the particular molecular sieve in a particular suspension, Based on the polymer, from 1: 2 to 100: 1, i.e. from 5 parts by weight of molecular sieve per 100 parts by weight of the polymer used for functionalizing the molecular sieve to molecular sieves per part by weight of the polymer used to functionalize the molecular sieve But not limited to, 100 parts by weight. Preferably the weight ratio of polymer used to functionalize the molecular sieve to the molecular sieve in the UV crosslinked MMM of the present invention is in the range of from 10: 1 to 1: 2.

The stabilized suspension contains uniformly dispersed polymeric functionalized molecular sieve particles in the continuous polymer matrix. The UV crosslinked MMM, in particular the dense film MMM, the asymmetric flat sheet MMM, the asymmetric thin film film composite MMM or the asymmetric hollow fiber MMM, are produced from the stabilized suspension and UV crosslinked. The UV crosslinked MMM prepared by the present invention comprises polymeric functionalized molecular sieve particles uniformly dispersed throughout the continuous UV crosslinked polymer matrix. The polymers that serve as the continuum polymer matrix in the UV crosslinked MMMs of the present invention are a type of UV crosslinkable polymer and provide a wide range of properties important for separation, and altering it can improve membrane selectivity. Materials with a high glass transition temperature (T _g ), high melting point and high crystallinity are preferred for most gas separation. Glassy polymers (i.e., low polymer than its T _g) has a more rigid polymer backbone and thus a larger molecule, such as and the hydrocarbon is smaller molecules such as hydrogen and helium to permeate the membrane more quickly so as to passes through the membrane more slowly . In the case of the UV crosslinked MMM application in the present invention, the polymer matrix is capable of forming a crosslinked structure that provides a wide range of properties important for membrane separation, such as low cost and ease of processing, and further improves membrane selectivity Should be selected from polymeric materials. A comparable membrane made from a pure polymer preferably exhibits a carbon dioxide or hydrogen selectivity over methane of 10 or greater, more preferably of 15 or greater. Preferably, the polymer used as the continuous polymer matrix phase in the crosslinked MMM is a UV crosslinkable rigid glassy polymer. The weight ratio of the polymer serving as the molecular sieve to the continuous polymer matrix in the UV crosslinked MMM of the present invention is 1: 100 (acting as a continuous polymer matrix, depending on the desired properties as well as the degree of dispersion of the particular molecular sieve in the particular continuous polymer matrix (1 part by weight of molecular sieve per 100 parts by weight of polymer to be polymerized) to 1: 1 (100 parts by weight of molecular sieve per 100 parts by weight of polymer acting as a continuous polymer matrix).

Conventional polymers that serve as a continuous polymer matrix phase suitable for the preparation of UV crosslinked MMMs comprise polymeric chain fractions and at least a portion of such polymeric chain fractions are exposed to UV radiation to be UV crosslinked . The UV cross-linkable polymer may be a UV crosslinkable nitrile (-C? N), benzophenone (-C ₆ H ₄ -C (═O) -C ₆ H ₄ -), acrylic (CH ₂ ═C (COOH) or -CH = C (COOH) -) , vinyl (CH ₂ = CH-), styrene (C ₆ H ₅ -CH = CH- or _{-C 6 H 4 -CH = CH 2} ), styrene-acrylic, aryl sulfonyl _{(-C 6 H 4 -SO 2 -C} 6 H 4 -), 3,4- and 2,3-epoxycyclohexyl group, or a dihydro-furan may be selected from any of the polymers containing a combination of these groups . For example, such polymers include polysulfones; Sulfonated polysulfone; Polyethersulfone (PES); Sulfonated PES; Polyacrylates; Polyetherimide; Poly (styrene) including styrene-containing copolymers such as acrylonitrile styrene copolymer, styrene-butadiene copolymer and styrene-vinylbenzyl halide copolymer; Polyimides such as poly [l, 2,4,5-benzenetetracarboxylic acid dianhydride-ko-3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride- Methylene bis (2,6-dimethylaniline)] imide (e.g., 1,2,4,5-benzenetetracarboxylic acid dianhydride and 3,3 ', 4,4'-benzophenonetetracarboxylic acid the acid dianhydride 1:01 polyimide having a ratio), Matrimid (Matrimid ^® 5218 which is sold under the trademark Matrimid ^® by Huntsman Advanced Materials are speaking a particular polyimide polymer sold under ^® trademark Matrimid) and respectively from HP polymers GmbH P84 or P84HT, sold under the trademarks P84 and P84HT; A mixture of polyamide and polyimide; But are not limited to, polyketones, polyether ketones, and the like.

Some preferred polymers that serve as a continuous polymer matrix phase suitable for the preparation of UV crosslinked MMMs include polyethersulfone (PES); Sulfonated PES; Polyimide, e.g., P84 or respectively sold under the trademark P84 and P84HT Matrimid as marketed under the trademark Matrimid ^® by Huntsman Advanced Materials (Matrimid ^® 5218 is referring to a particular polyimide polymer sold under ^® trademark Matrimid), from HP Polymers GmbH P84HT , Poly (3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride-pyromellitic acid dianhydride-4,4'-oxydiphthalic anhydride-3,3', 5,5'-tetramethyl (BTDA-PMDA-ODPA-TMMDA) (FIG. 7), poly (3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride- 3 ', 5,5'-tetramethyl-4,4'-methylene dianiline) (poly (DSDA-TMMDA), FIG. 8), poly (3,3', 4,4'-diphenylsulfonetetracarboxyl Acid dianhydride-pyromellitic acid dianhydride-3,3 ', 5,5'-tetramethyl-4,4'-methylene dianiline) (poly (DSDA-PMDA-TMMDA), FIG. 9); And UV cross-linkable microporous polymers (Figures 10a and 10b).

The most preferred polymers acting as a continuous polymer matrix phase suitable for the preparation of UV crosslinked MMMs include PES; Polyimide, e.g., Matrimid ^®, poly (BTDA-PMDA-ODPA-TMMDA ), poly (DSDA-TMMDA), poly (DSDA-PMDA-TMMDA), and P84 or P84HT; And UV cross-linkable microporous polymers.

UV crosslinkable microporous polymers (or so-called "polymers of intrinsic microporosity ", McKeown, et al., CHEM. COMMUN., 2780 (2002); McKeown, et al, CHEM. COMMUN Budd, et al., ADV (2001), " Budd, et al., J. < RTI ID = 0.0 & (See, for example, McKeown, et al., CHEM, EUR, J., 11: 2610 (2005)) have micropurity degrees unique to their molecular structures Also, a polymeric material comprising a polymeric chain fraction, wherein at least a portion of the polymeric chain fraction is UV crosslinked to one another via direct covalent bonds when exposed to UV radiation. UV crosslinkable microporous polymers include UV crosslinkable nitrile (-C? N), benzophenone (-C ₆ H ₄ -C (═O) -C ₆ H ₄ -), acrylic (CH ₂ ═C ) - or -CH = C (COOH) -), vinyl (CH ₂ = CH-), styrene (C ₆ H ₅ -CH═CH- or -C ₆ H ₄ -CH═CH ₂ ), styrene- From any microporous polymer containing arylsulfonyl (-C ₆ H ₄ -SO ₂ -C ₆ H ₄ -), 3,4-epoxycyclohexyl and 2,3-dihydrofuran groups or combinations of these groups Can be selected. The structures of some exemplary UV crosslinkable microporous polymers and their preparation are shown in Figures 10a and 10b. This type of UV crosslinkable microporous polymer can be used as a continuous polymer matrix in UV crosslinked MMMs in the present invention. UV crosslinkable microporous polymers have irregularly distorted rigid rod-like structures, resulting in intrinsic microporosity. Such UV crosslinkable microporous polymers exhibit similar behavior to conventional microporous molecular sieve materials, such as high chemical and thermal stability, as well as large and accessible surface area, interconnected intrinsic micropores of size 2 nm or less, But retains the properties of conventional polymers such as good solubility and easy processability. In addition, such UV crosslinkable microporous polymers possess polyether polymer chains with favorable interactions between the carbon dioxide and the ether.

The solvent used to dissolve the polymer used to disperse the molecular sieve particles in the concentration suspension and to function as the polymer and the polymer used to functionalize the molecular sieve and the polymer acting as the continuous polymer matrix mainly depends on its ability to dissolve the polymer entirely, Choose for ease of removal. Other considerations in solvent selection include low toxicity, low corrosive activity, low environmental risk potential, availability and cost. Representative solvents for use in the present invention include most of the amide solvents commonly used in the formation of polymeric membranes such as N-methylpyrrolidone (NMP) and N, N-dimethylacetamide (DMAC), methylene chloride, THF, Acetone, DMF, DMSO, toluene, dioxane, 1,3-dioxolane, mixtures thereof, other solvents known to those skilled in the art, and mixtures thereof.

In the present invention, the UV crosslinked MMM can be prepared from a stabilized thickening suspension containing a solvent mixture, a polymeric functionalized molecular sieve and a continuous polymer matrix, into various membrane structures such as UV crosslinked mixed matrix dense films, UV of asymmetric flat sheets Crosslinked MMM, UV crosslinked MMM of asymmetric thin film film composites or UV crosslinked MMM of asymmetric hollow fibers. For example, the suspension may be sprayed on top of a clean glass plate, spin coated, poured into a sealed glass loop, or cast with a doctor knife. In another method, the porous substrate can be dip coated with a suspension. One solvent removal technique used in the present invention is to ventilate the atmosphere above the membrane formed of the dilute dry gas and to withdraw the vacuum to evaporate the volatile solvent. Other solvent removal techniques used in the present invention require that the cast thin layer of a thickening suspension (pre-cast on a glass plate or on a porous or transparent substrate) is immersed in the non-solvent for a polymer that is miscible with the solvent of the suspension. To facilitate the removal of the solvent, it is possible to heat the non-solvent in which the substrate and / or the thin layer of the air or dispersion liquid is immersed. If the UV crosslinkable MMM is substantially free of solvent, the UV crosslinkable MMM can be separated from the glass plate to form a free-standing (or independent) structure, or UV crosslinkable MMM May be left in contact with the porous or permeable support substrate to form an integrated composite assembly. A further manufacturing step that may be used is to wash the UV crosslinkable MMM in a bath of a suitable liquid to extract residual solvent and other foreign materials from the membrane and dry the washed UV crosslinkable MMM to remove the residual liquid . In some cases, the UV cross-linkable MMM can be coated with a thin layer of material such as UV radiation curable epoxy silicone to fill the surface voids and defects on the UV cross-linkable MMM.

The UV crosslinked MMM can then be further crosslinked by UV crosslinking using a UV lamp from a certain distance for a selected period of time based on the desired separation characteristics of the UV crosslinkable MMM with UV crosslinkable MMM or coating of the thin layer . For example, UV crosslinked MMM can be prepared using UV light of 254 nm wavelength generated from a UV lamp with a distance of 1.9 cm (0.75 inch) from the membrane surface to the UV lamp for 30 minutes of irradiation time at 50 ° C or less Can be prepared from MMM by exposure to UV radiation. The UV lamp described herein is a low pressure mercury arc immersion UV quartz 12-watt lamp with a 12-watt power supply from Ace Glass Incorporated. Optimization of the degree of crosslinking in UV crosslinked MMM facilitates customization of the membrane to a wide range of gas and liquid separations with improved permeation characteristics and environmental stability. The crosslinking degree of the UV crosslinked MMM of the present invention can be controlled by adjusting the distance between the UV lamp and the membrane surface, the UV irradiation time, the wavelength and intensity of the UV light, and the like. Preferably, the distance from the UV lamp to the membrane surface is in the range of 0.8 to 25.4 cm (0.3 to 10 inch) with UV light provided from a low pressure or medium pressure mercury arc lamp of 12 to 450 watts and the UV irradiation time is 1 to 1 Time range. More preferably, the distance from the UV lamp to the membrane surface is in the range of 1.3 to 5.1 cm (0.5 to 2 inches) with UV light provided from a low pressure or medium pressure mercury arc lamp from 12 to 450 watts, and the UV irradiation time is from 1 to 40 Min.

In some cases, the UV cross-linked MMM is further coated with a thin layer of a material such as polysiloxane, fluoropolymer, or thermosetting silicone rubber to fill the surface voids and defects on the UV cross-linked MMM.

One preferred embodiment of the present invention is a UV crosslinked MMM in the form of an asymmetric flat sheet for gas separation comprising a smooth, thin dense, selective layer on top of the porous support layer. Another preferred embodiment of the present invention is a UV cross-linked MMM in the form of an asymmetric hollow fiber for gas separation comprising a smooth, thin dense, selective layer on top of the porous support layer.

The process of the present invention for producing high performance UV crosslinked MMM is suitable for large scale membrane production and can be integrated into commercial polymer membrane manufacturing processes. The UV crosslinked MMMs produced by the process described in the present invention, particularly the MMMs of dense films, the MMM of the asymmetric flat sheet, the MMM of the asymmetric thin film composite or the UV crosslinked MMM of the asymmetric hollow fibers, Exhibit significantly improved selectivity and / or permeability for polymeric membranes prepared from polymeric matrices and for membranes which are prepared from suspensions containing the same molecular sieves and the same polymeric matrix but which are not polymeric functionalized.

The present invention is a process for separating one or more gases from a gaseous mixture using UV crosslinked MMM as described herein, comprising the steps of: (a) providing a homogeneously dispersed polymer in a continuous UV crosslinked polymer matrix permeable to said at least one gas Providing a UV cross-linked MMM comprising a functionalized molecular sieve filler material; (b) contacting the gas mixture to one side of a UV cross-linked mixed matrix membrane such that the at least one gas passes through UV cross-linked MMM And (c) removing the permeate gas composition comprising the at least one gas that has permeated the membrane from the opposite side of the membrane.

The UV cross-linked MMM of the present invention is suitable for a wide range of gases, vapors, and liquid separation and gas and vapor separation, for example, _{CO 2 / CH 4, H 2} / CH 4, O 2 / N 2, CO 2 / N 2, Olefins / paraffins and iso / normal paraffins.

The UV crosslinked MMMs of the present invention are particularly useful for the purification, separation or absorption of certain species in liquid or gas phases. In addition to separation of the gas pairs, such UV crosslinked MMM can be used, for example, for the separation of proteins or other thermally unstable compounds, for example in the pharmaceutical and biotechnological industries. The UV crosslinked MMM can also be used in a fermenter and a bioreactor to transport the gas to a reaction vessel and transfer the cell culture medium from the vessel. In addition, UV crosslinked MMM can be used for the removal of microorganisms from air or water streams, water purification, ethanol production in continuous fermentation / membrane pervaporation systems and for the detection or removal of trace compounds or metal salts in air or water streams have.

The UV crosslinked MMMs of the present invention are particularly useful in gas separation processes in the air purification, petrochemical, refinery and natural gas industries. Examples of such separation include the separation of volatile organic compounds (e.g., toluene, xylene, and acetone) from atmospheric gases such as nitrogen or recovery of oxygen and nitrogen from air. Additional examples of such separation include separation of CO ₂ from natural gas, separation of H ₂ from N ₂ , CH ₄ and Ar in the ammonia purge gas stream, recovery of H ₂ from the refinery, olefin / paraffin separation such as propylene / And iso / normal paraffin separation. Any predetermined pair or group of gases of different molecular size, such as nitrogen and oxygen, carbon dioxide and methane, hydrogen and methane or carbon monoxide, helium and methane, may be separated using UV cross-linked MMM as described herein . Two or more gases can be removed from the third gas. For example, some of the gas components that can be selectively removed from natural gas feeds using the membranes described herein include carbon dioxide, oxygen, nitrogen, water vapor, hydrogen sulfide, helium, and other trace gases. Some of the gas components that may optionally be retained include hydrocarbon gases.

The UV crosslinked MMM described in the present invention can also be used in gas / vapor separation processes in chemical, petrochemical, pharmaceutical and allied industries to remove organic vapors from a gas stream, for example by satisfying clean air regulation In the exhaust stream for the recovery of volatile organic compounds, or in the process stream in the production plant such that important compounds (e.g., vinyl chloride monomers, propylene) can be recovered. Further examples of gas / vapor separation processes in which such UV cross-linked MMMs may be used include those for reducing the hydrocarbon dew point of the natural gas (i. E., The hydrocarbon dew point to the lowest possible exhaust transport pipe Temperature), vapor separation of hydrocarbons from hydrogen in oil and gas refineries for the regeneration of methane in fuel gas for gas engines and gas turbines, and for recovery of gasoline. UV cross-linked MMM incorporates species that strongly adsorb to this gas (e.g., cobalt porphyrin or phthalocyanine for O ₂ or (I) for ethane) to facilitate transport of specific gases across the membrane can do.

These UV crosslinked MMMs can also be used in the separation of liquid mixtures by pervaporation, for example in the removal of organic compounds (e.g., alcohols, phenols, chlorinated hydrocarbons, pyridines, ketones) from water such as aqueous effluents or process oils have. Selective membranes for ethanol are used to increase the concentration of ethanol in a relatively dilute ethanol solution (5 to 10% ethanol) obtained by the fermentation process. Examples of other liquid phase separations using such UV crosslinked MMMs include depths of gasoline and diesel fuel by a pervaporation membrane process similar to that described in US 7,048,846 B2, incorporated herein by reference in its entirety There is desulfurization. UV crosslinked MMM selective to sulfur containing molecules is used to selectively remove sulfur containing molecules and other naphtha hydrocarbon streams from fluid catalytic cracking (FCC). Examples of further liquid phases include, for example, the separation of one organic component from another organic component to separate the isomers of the organic compound. The mixture of organic compounds which can be separated by using the membrane of the present invention may be selected from the group consisting of ethyl acetate-ethanol, diethyl ether-ethanol, acetic acid-ethanol, benzene-ethanol, chloroform-ethanol, chloroform-methanol, acetone- Butanol-1-butyl ether, ethanol-ethyl butyl ether, propyl acetate-propanol, isopropyl ether-isopropanol, methanol-ethanol-isopropanol and ethyl acetate- isopropyl alcohol, allyl alcohol-allyl ether, allyl alcohol-cyclohexane, Ethanol-acetic acid.

UV crosslinked MMM can be used for the separation of organic molecules from water (for example, the separation of ethanol and / or phenol from water by pervaporation) and the removal of metals and other organic compounds from water.

A further use for UV crosslinked MMM is to increase the yield of the equilibrium limiting reaction by selective removal of a particular product in a manner similar to the use of a hydrophilic membrane in a chemical reactor to increase the esterification yield by the removal of water will be.

The present invention relates to a novel, void-free, defect-free, UV-cross-linked mixed matrix membrane of polymeric functionalized molecular sieves and polymers made from a stable thickening suspension containing a uniformly dispersed polymeric functionalized molecular sieve and a continuous polymer matrix MMM). These novel UV crosslinked MMMs have immediate use for the separation of gas mixtures, including the removal of carbon dioxide from natural gas. UV crosslinked MMM allows carbon dioxide to diffuse at a faster rate than methane in natural gas. Carbon dioxide has a higher permeation rate than methane due to higher solubility, higher diffusion, or both. Thus, the carbon dioxide is rich in the permeate side of the membrane, and methane is rich in the supply (or rejection) of the membrane.

Any other predetermined pairs of gases of different sizes, such as nitrogen and oxygen, carbon dioxide and methane, carbon dioxide and nitrogen, hydrogen and methane or carbon monoxide, helium and methane, can be prepared using UV crosslinked MMM as described herein Can be separated. Two or more gases can be removed from the third gas. For example, some of the components that can be selectively removed from natural gas feeds using the membranes described herein include carbon dioxide, oxygen, nitrogen, water vapor, hydrogen sulfide, helium, and other trace gases. Some of the optional components that may be retained include hydrocarbon gases.

The following examples are provided to illustrate one or more preferred embodiments of the invention, but are not intended to limit the embodiments thereof. Various modifications may be made to the following embodiments, which are within the scope of the present invention.

Example  One:

Poly ( DSDA - PMDA - TMMDA ) - PES  polymer Of the membrane (abbreviated as P1)  quite

5.4 g of poly (DSDA-PMDA-TMMDA) polyimide polymer (FIG. 9) and 0.6 g of polyethersulfone (PES) were mechanically stirred and mixed with a certain amount of organic solvent or a mixture of several organic solvents (eg NMP, acetone, 3-dioxolane) to form a homogeneous casting dope. The obtained homogeneous casting dope was degassed overnight. Poly (DSDA-PMDA-TMMDA) polymer membranes were prepared from bubble-free casting dope using a doctor knife with 20-millimeter spacing on clean glass plates. The film was then placed in a vacuum oven with a glass plate. The solvent was removed by slowly increasing the vacuum and temperature of the vacuum oven. Finally, the membrane was dried under vacuum at 200 [deg.] C for at least 48 hours to completely remove the residual solvent to form the P1 polymer membrane described in Tables 1 and 2 and Figs. 11 and 12.

Example  2:

UV Crosslinked Poly ( DSDA - PMDA - TMMDA ) - PES  polymer Membrane (abbreviated as control 1) of  quite

The Control 1 polymer membranes described in Tables 1 and 2 and Figures 11 and 12 were prepared from UV lamps with a distance of 1.9 cm (0.75 inch) from the membrane surface to the UV lamp at a time of 10 minutes at 50 ° C By further UV crosslinking the P1 polymer membrane by exposure to UV radiation using UV light at 254 nm wavelength. The UV lamp described herein is a low pressure mercury arc immersion UV quartz 12-watt lamp with a 12-watt power supply from Aisle Glass Inc.

Example  3:

UV Crosslinked  30% AlPO -14 / PES / Poly ( DSDA - PMDA - TMMDA ) Mixed Matrix The membrane lane( MMM  1)

UV crosslinked polyethersulfone (PES) functionalized containing 30 wt.% Of AlPO-14 molecular sieve filler dispersed in a UV crosslinked poly (DSDA-PMDA-TMMDA) polyimide continuity matrix AlPO-14 / poly -PMDA-TMMDA) Mixed matrix membranes (abbreviated as MMM 1) were prepared as follows:

1.8 g of AlPO-14 molecular sieve was mechanically stirred for 1 hour and sonicated to disperse it in a mixture of NMP and 1,3-dioxolane to form a slurry. Then 0.6 g of PES was added to functionalize the AlPO-14 molecular sieve in the slurry. The slurry was stirred for at least 1 hour to completely dissolve the PES polymer and functionalize the surface of AlPO-14. Thereafter, 5.6 g of poly (DSDA-PMDA-TMMDA) polyimide polymer was added to the slurry and the resulting mixture was stirred for an additional 2 hours to form a PES functionalized dispersed in a continuous poly (DSDA-PMDA-TMMDA) polymer matrix 30% by weight of AlPO-14 molecular sieve (weight ratio of AlPO-14 to poly (DSDA-PMDA-TMMDA) and PES is 30: 100 and weight ratio of PES to poly (DSDA-PMDA-TMMDA) is 1: 9) To form a stable casting doping. This stable casting dope was degassed overnight.

The mixed matrix membrane was prepared from a stable casting dope without bubbles using a doctor knife with 20-millimeter spacing on a clean glass plate. The film was then placed in a vacuum oven with a glass plate. The solvent was removed by slowly increasing the vacuum and temperature of the vacuum oven. Finally, the membrane was dried under vacuum at 200 [deg.] C for at least 48 hours to remove all residual solvent to form a 30% AlPO-14 / PES / poly (DSDA-PMDA-TMMDA) mixed matrix membrane.

The MMM 1 membranes described in Tables 1 and 2 and Figures 11 and 12 were prepared from UV lamps with a distance of 1.9 cm (0.75 inch) from the membrane surface to the UV lamp at 50 ° C for 10 minutes of irradiation, and 254 14 / PES / poly (DSDA-PMDA-TMMDA) mixed matrix membrane was further UV cross-linked by exposure to UV radiation using UV light of a wavelength of 30 nm. The UV lamp described herein is a low pressure mercury arc immersion UV quartz 12-watt lamp with a 12-watt power supply from Aisle Glass Inc.

Example  4:

UV Crosslinked  40% AlPO -14 / PES / Poly ( DSDA - PMDA - TMMDA ) Mixed Matrix The membrane lane( MMM  2)

UV crosslinked polyethersulfone (PES) functionalized containing 40 wt% of AlPO-14 molecular sieve filler dispersed in a UV crosslinked poly (DSDA-PMDA-TMMDA) polyimide continuity matrix AlPO-14 / poly -PMDA-TMMDA) Mixed matrix membranes (abbreviated as MMM 2) were prepared as follows:

2.4 g of AlPO-14 molecular sieves were mechanically stirred and sonicated to form a slurry by dispersion in a mixture of NMP and 1,3-dioxolane. Then 0.6 g of PES was added to functionalize the AlPO-14 molecular sieve in the slurry. The slurry was stirred for at least 1 hour to completely dissolve the PES polymer and functionalize the surface of AlPO-14. Thereafter, 5.6 g of poly (DSDA-PMDA-TMMDA) polyimide polymer was added to the slurry and the resulting mixture was stirred for an additional 2 hours to form a PES functionalized dispersed in a continuous poly (DSDA-PMDA-TMMDA) polymer matrix 40 wt% of AlPO-14 molecular sieve (weight ratio of AlPO-14 to poly (DSDA-PMDA-TMMDA) and PES is 40: 100 and weight ratio of PES to poly (DSDA-PMDA-TMMDA) is 1: 9) To form a stable casting doping. This stable casting dope was degassed overnight.

A 40% AlPO-14 / PES / poly (DSDA-PMDA-TMMDA) mixed matrix membrane was prepared from a stable bubble-free casting dope using a doctor knife with 20-millimeter spacing on a clean glass plate. The film was then placed in a vacuum oven with a glass plate. The solvent was removed by slowly increasing the vacuum and temperature of the vacuum oven. Finally, the membrane was dried under vacuum at 200 [deg.] C for at least 48 hours to completely remove the residual solvent to form a 40% AlPO-14 / PES / poly (DSDA-PMDA-TMMDA) mixed matrix membrane.

The MMM 2 membranes described in Tables 1 and 2 and Figures 11 and 12 were prepared from a UV lamp with a distance of 1.9 cm (0.75 inch) from the membrane surface to the UV lamp at 50 占 폚 for 10 minutes of irradiation. 14 / PES / poly (DSDA-PMDA-TMMDA) mixed matrix membrane by further UV crosslinking using UV light of a wavelength of 40 nm. The UV lamp described herein is a low pressure mercury arc immersion UV quartz 12-watt lamp with a 12-watt power supply from Aisle Glass Inc.

Example  5:

P1 , Control group 1, MMM  1 and MMM  2 Membrane CO ₂ / CH ₄  Separation characteristic

Embodiment permeability of Example 1 P1 polymer membrane in Example 2, the MMM prepared in the control group 1, Example 3 produced in the first and carrying an MMM 2 of CO ₂ and CH ₄ prepared in Example 4 prepared in (P _CO2 and P _CH4 ) And CO ₂ / CH ₄ selectivity (? _{CO2 / CH4} ) were measured by pure gas measurement at 5O < 0 _{& gt} ; C and 690 kPa (100 psig) pressure. The results for CO ₂ / CH ₄ separation are shown in Table 1 and FIG.

Table 1 and from Figure 11, Control 1 polymer membrane with UV crosslinking as compared with the membrane polymer P1 represents a 27% increase in the α _{CO2 / CH4,} can be seen to represent a 60% reduction in P _CO2. The .alpha..sub.CO2 _{/ CH.sub.4} of the UV crosslinked MMM.sub.1 membrane was increased to 43 and improved by 80% compared to the P1 polymer membrane. The UV cross-linked poly (DSDA-PMDA-TMMDA) UV cross-linked MMM 2 membrane containing AlPO-14 molecular sieve fillers 40% by weight in the polymer matrix compared to the P1 polymer membrane for the CO ₂ / CH ₄ separation α represents a _{CO2 / CH4} 50% increase and P _CO2 40% increase at the same time, which the AlPO-14 a CO ₂ / CH ₄ molecular sieving mechanism for the production of high minute of the selectivity itself and the polymer mixed matrix membrane of for gas separation (Micro pore size: 1.9 x 4.6 A, 2.1 x 4.9 A and 3.3 x 4.0 A). These test results show that the molecular sieving mechanism of the AlPO-14 molecular sieve filler for CO ₂ / CH ₄ gas separation and the solution-diffusion mechanism of the UV cross-linked poly (DSDA-PMDA-TMMDA) polyimide matrix in this mixed matrix membrane Represents a successful combination.

Figure 11 shows the CO ₂ / CH ₄ separation performance of P1, control 1, MMM 1 and MMM 2 at 5O < 0 > C and 690 kPa (100 psig) (1991) for CO ₂ / CH ₄ separation at 35 ° C and 345 kPa (50 psig). It can be seen that the CO ₂ / CH ₄ separation performance of the P1 polymer membrane and the UV crosslinked control 1 polymer membrane is well below the polymer upper limit of Robeson (1991) for CO ₂ / CH ₄ separation. However, UV cross-linked MMM 1 and MMM 2 mixed matrix membrane shows a nearly CO ₂ / CH ₄ separation performance of the polymer upper limit of Kurobe hand (1991) for the CO ₂ / CH ₄ separation significantly. These results indicate that the new voids and defect free UV crosslinked MMM 1 and MMM 2 membranes are highly promising membrane candidates for CO ₂ removal from natural gas or flue gas. The improved performance of MMM 1 and MMM 2 for P1 and control 1 polymer membranes is due to the molecular sieving mechanism of the AlPO-14 molecular sieve filler and the solution-diffusion mechanism of the UV cross-linked poly (DSDA-PMDA-TMMDA) polyimide matrix It is due to a successful combination.

Pure gas permeation test results of P1, control 1, MMM 1 and MMM 2 membranes for CO ₂ / CH ₄ separation ^a Membrane P _CO2
(Barrer) ΔP _CO2
(Barrer) alpha _{CO2 / CH4} Δα _{CO2 / CH4} P1 29.3 0 23.6 0 Control 1 12.0 -59% 30.0 27% MMM 1 23.7 -19% 43.1 83% MMM 2 41.6 42% 35.3 50%

^a Tested at 50 캜 under a pure gas pressure of 690 kPa (100 psig);

1 Barrer = 10 ^-10 (cm3 (STP) 占) m) / (cm3 占 sec 占 H Hg)

Example  6:

P1 , Control 1 and MMM  One Membrane H ₂ / CH ₄  Separation characteristic

(P _H2 and P _CH4 ) of the P1 polymer membrane prepared in Example 1, the H ₂ and CH ₄ of the UV crosslinked MMM 1 mixed matrix membrane prepared in Example 2 and the control 1 prepared in Example 2, and selection of the H ₂ / CH ₄ is also the (α _{H2 / CH4)} at 5O ℃ were measured by pure gas measurements under 690 kPa (100 psig) pressure. The results for H ₂ / CH ₄ separation are shown in Table 2 and FIG.

From Table 2 and Figure 12, it can be seen that the UV cross-linked control 1 polymer membrane exhibits a 178% increase in alpha _{H2 / CH4} with a 10% reduction in P _H2 compared to the P1 membrane. However, the UV crosslinked MMM 1 containing 30 wt% of AlPO-14 molecular sieve filler in the UV crosslinked poly (DSDA-PMDA-TMMDA) polymer matrix exhibited a significantly lower molecular weight as compared to the P1 polymer membrane for H ₂ / CH ₄ separation alpha _{H2 / CH4} 190% increase and P _H2 30% increase, indicating the molecular sieving mechanism of the AlPO-14 molecular sieve filler for H ₂ / CH ₄ gas separation and the UV cross-linked poly (DSDA -PMDA-TMMDA) polyimide matrix.

Figure 12 shows the H ₂ / CH ₄ separation performance of P1, control 1 and MMM 1 at 5O < 0 > C and 690 kPa (100 psig) (1991) for H ₂ / CH ₄ separation at 35 ° C and 345 kPa (50 psig). It can be seen that the H ₂ / CH ₄ separation performance of the P1 polymer membrane is well below the polymer upper limit of Robeson (1991) for CO ₂ / CH ₄ separation. Control 1 polymer membranes exhibit improved H ₂ / CH ₄ separation performance as compared to the Pl polymer membrane and its H ₂ / CH ₄ separation performance reaches the upper polymer limit of Robeson (1991) for H ₂ / CH ₄ separation. UV cross-linked MMM 1 mixed matrix membrane is added to indicate a significantly improved H ₂ / CH ₄ separation performance compared to the Control 1 polymer membrane H ₂ / CH counter ₄ separation performance is Kurobe hand for the H ₂ / CH ₄ separation (1991). ≪ / RTI > These results show that the novel voids and defect free UV cross-linked MMM 1 mixed matrix membranes are highly promising membrane candidates for H ₂ removal from natural gas.

Pure gas permeation test results of P1, control 1 and MMM 1 membranes for H ₂ / CH ₄ separation ^a Membrane P _H2
(Barrer) ΔP _H2
(Barrer) alpha _{H2 / CH4} DELTA alpha _{H2 / CH4} P1 65.6 0 52.9 0 Control 1 58.6 -11% 147.0 178% MMM 1 85.0 30% 154.2 191%

^a Tested at 50 캜 under a pure gas pressure of 690 kPa (100 psig);

1 Barrer = 10 ^-10 (cm3 (STP) 占) m) / (cm3 占 sec 占 H Hg)

Example  7:

Poly ( DSDA - TMMDA ) - PES  polymer Membrane (abbreviated as P2) of  quite

7.2 g of poly (DSDA-TMMDA) polyimide polymer (FIG. 8) and 0.8 g of polyethersulfone (PES) were mechanically stirred and dissolved in a solvent mixture of NMP and 1,3-dioxolane to form a homogeneous casting dope . The obtained homogeneous casting dope was degassed overnight. The P2 polymer membrane was prepared from a bubble-free casting dope using a doctor knife with 20-millimeter spacing on a clean glass plate. The membrane was then placed in a vacuum oven with a glass plate. The solvent was removed by slowly increasing the vacuum and temperature of the vacuum oven. Finally, the membrane was dried under vacuum at 200 [deg.] C for at least 48 hours to completely remove the residual solvent to form P2 as shown in Table 3 and Fig.

Example  8:

Preparation of a mixed matrix membrane (abbreviated as MMM 3) of UV crosslinked 40% AlPO-14 / PES / poly (DSDA-TMMDA)

UV crosslinking of polyethersulfone (PES) functionalized AlPO-14 / poly (DSDA-TMMDA) containing 40% by weight of AlPO-14 molecular sieve filler dispersed in UV crosslinked poly (DSDA- TMMDA) polyimide continuity matrix A combined mixed matrix membrane (MMM 3) was prepared as follows:

3.2 g of AlPO-14 molecular sieves were mechanically stirred for 1 hour and sonicated to form a slurry by dispersing in a mixture of NMP and 1,3-dioxolane. 0.8 g of PES was then added to functionalize the AlPO-14 molecular sieve in the slurry. The slurry was stirred for at least 1 hour to completely dissolve the PES polymer and functionalize the surface of AlPO-14. Thereafter, 7.2 g of poly (DSDA-TMMDA) polyimide polymer was added to the slurry and the resulting mixture was stirred for an additional 2 hours to form a PES functionalized AlPO-14 minute dispersed in a continuous poly (DSDA-TMMDA) polymer matrix A stable casting dope containing 40 wt% of itself (weight ratio of AlPO-14 to poly (DSDA-TMMDA) and PES of 40: 100 and PES to poly (DSDA-TMMDA) in a weight ratio of 1: 9) . This stable casting dope was degassed overnight.

A 40% AlPO-14 / PES / poly (DSDA-TMMDA) mixed matrix membrane was prepared from a bubble-free stable casting dope using a doctor knife with 20-millimeter spacing on a clean glass plate. The film was then placed in a vacuum oven with a glass plate. The solvent was removed by slowly increasing the vacuum and temperature of the vacuum oven. Finally, the membrane was dried under vacuum at 200 [deg.] C for at least 48 hours to completely remove the residual solvent to form a 40% AlPO-14 / PES / poly (DSDA-TMMDA) mixed matrix membrane.

MMM 3 was exposed to UV radiation using UV light of 254 nm wavelength generated from a UV lamp with a distance of 1.9 cm (0.75 inch) from the membrane surface to the UV lamp at 10 minutes irradiation time at 50 占 폚, The AlPO-14 / PES / poly (DSDA-TMMDA) mixed matrix membrane was further prepared by UV cross-linking. The UV lamp described herein is a low pressure mercury arc immersion UV quartz 12-watt lamp with a 12-watt power supply from Aisle Glass Inc.

Example  9:

P2  And MMM  3 Membrane CO ₂ / CH ₄  Separation characteristic

Exemplary selection of P2 polymer membrane and in Example 8 the UV crosslinking in a combined MMM 3 permeability of the mixed matrix membrane CO ₂ and CH ₄ (P _CO2 and P _CH4) and CO ₂ / CH ₄ prepared in Example 7. Fig. ( alpha _{CO2 / CH4} ) was measured by pure gas measurement at 5O < 0 _> C and 690 kPa (100 psig) pressure. The results for CO ₂ / CH ₄ separation are shown in Table 3 and FIG.

Table 3 and from the Figure 13, UV cross-linked poly (DSDA-TMMDA) UV cross-linked MMM 3 membranes containing AlPO-14 molecular sieve fillers 40% by weight in the polymer matrix is P2 polymer for the CO ₂ / CH ₄ separation as compared to the membrane represents a 60% increase in α _{CO2 / CH4} and P _CO2 at the same time, which is a poly combined UV crosslinking of AlPO-14 bun such mixed matrix membrane and the molecular sieving mechanism of self-filler for the CO ₂ / CH ₄ gas separation ( DSDA-TMMDA) polyimide matrix. ≪ / RTI >

Figure 13 shows the CO ₂ / CH ₄ separation performance of P2 polymer membranes and UV crosslinked MMM 3 mixed matrix membranes at 5O < 0 > C and 690 kPa (100 psig), as well as in the literature (see Robeson, J. Membr. Sci. (1991) for CO ₂ / CH ₄ separation at 35 ° C and 345 kPa (50 psig). It can be seen that the CO ₂ / CH ₄ separation performance of the P2 polymer membrane is well below the polymer upper limit of Robeson (1991) for CO ₂ / CH ₄ separation. However, UV cross-linked MMM 3 shows a nearly CO ₂ / CH ₄ separation performance of the polymer upper limit of Kurobe hand (1991) for the CO ₂ / CH ₄ separation significantly.

Pure gas permeation test results of P2 and MMM 3 membranes for CO ₂ / CH ₄ separation ^a Membrane P _CO2
(Barrer) ΔP _CO2
(Barrer) alpha _{CO2 / CH4} Δα _{CO2 / CH4} P2 18.5 0 24.8 0 MMM 3 29.4 59% 39.8 60%

^a Tested at 50 캜 under a pure gas pressure of 690 kPa (100 psig);

1 Barrer = 10 ^-10 (cm3 (STP) 占) m) / (cm3 占 sec 占 H Hg)

Example  10:

UV Crosslinked  30% UZM -25 / PES / Poly ( DSDA - TMMDA ) Mixed matrix membrane ( MMM  4)

UV crosslinked polyethersulfone (PES) functionalized UZM-25 / UZM-25 containing 30 wt% UZM-25 (pure silica type) molecular sieve filler dispersed in UV crosslinked poly (DSDA- TMMDA) polyimide continuity matrix UZM- A poly (DSDA-TMMDA) mixed matrix membrane (abbreviated as MMM 4) was prepared as follows:

1.8 g of UZM-25 molecular sieves were mechanically stirred for 1 hour and sonicated to form a slurry by dispersion in a mixture of NMP and 1,3-dioxolane. Subsequently, 0.6 g of PES was added to functionalize the UZM-25 molecular sieve in the slurry. The slurry was stirred for at least 1 hour to completely dissolve the PES polymer and functionalize the surface of UZM-25. Thereafter, 5.6 g of poly (DSDA-TMMDA) polyimide polymer was added to this slurry and the resulting mixture was stirred for an additional 3 hours to give a PES functionalized UZM-25 minute dispersed in a continuous poly (DSDA-TMMDA) polymer matrix A stable casting dope was formed containing 30 wt% of itself (weight ratio of UZM-25 to poly (DSDA-TMMDA) and PES is 30: 100 and weight ratio of PES to poly (DSDA-TMMDA) is 1: 9) . This stable casting dope was degassed overnight.

A 30% UZM-25 / PES / poly (DSDA-TMMDA) mixed matrix membrane was prepared from a stable bubble-free casting dope using a doctor knife with 20-millimeter spacing on a clean glass plate. The film was then placed in a vacuum oven with a glass plate. The solvent was removed by slowly increasing the vacuum and temperature of the vacuum oven. Finally, the membranes were dried under vacuum at 200 캜 for at least 48 hours to remove all residual solvent to form a 30% UZM-25 / PES / poly (DSDA-TMMDA) mixed matrix membrane.

MMM 4 was exposed to UV radiation using UV light of 254 nm wavelength generated from a UV lamp with a distance of 1.9 cm (0.75 inch) from the membrane surface to the UV lamp at 10 minutes irradiation time at 50 占 폚, The UZM-25 / PES / poly (DSDA-TMMDA) mixed matrix membrane was further prepared by UV cross-linking. The UV lamp described herein is a low pressure mercury arc immersion UV quartz 12-watt lamp with a 12-watt power supply from Aisle Glass Inc.

Example  11:

P2  And MMM  4 Membrane CO ₂ / CH ₄  Separation characteristic

Exemplary selection of Example 7. The MMM prepared in the P2 polymer membrane, and Example 10, prepared from 4-permeability of the mixed matrix membrane of CO ₂ and CH ₄ (P _CO2 and P _CH4) and CO ₂ / CH _4, also (α _{CO2 / CH4} ) Was measured by pure gas measurement at 5O < 0 > C and 690 kPa (100 psig) pressure. The results for CO ₂ / CH ₄ separation are shown in Table 4.

From Table 4 it can be seen that the UV crosslinked MMM 4 mixed matrix membrane prepared in Example 10 containing 30% by weight of UZM-25 molecular sieve filler in the UV crosslinked poly (DSDA-TMMDA) polymer matrix has CO ₂ / CH ₄ the α _{CO2 / CH4} is increased to 39 from 25 in the P2 polymer membrane, α _{CO2 / CH4} represents a hayeoteum 60% increase, which UZM-25, the CO ₂ / CH ₄ gas separation as compared to P2 polymer membrane for the separation (Micro pore size: 2.5 x 4.2 A and 3.1 x 4.2 A) with a molecular sieving mechanism for preparing a mixed matrix membrane of molecular sieve with a high selectivity for molecular sieves.

Pure gas permeation test results of P2 and MMM 4 membranes for CO ₂ / CH ₄ separation ^a Membrane P _CO2
(Barrer) alpha _{CO2 / CH4} Δα _{CO2 / CH4} P2 18.5 24.8 0 MMM 4 15.3 39.2 58%

^a Tested at 50 캜 under a pure gas pressure of 690 kPa (100 psig);

1 Barrer = 10 ^-10 (cm3 (STP) 占) m) / (cm3 占 sec 占 H Hg)

Example  12:

UV Crosslinkability Poly ( BTDA - PMDA - ODPA - TMMDA ) - PES  polymer Membrane (shortened to P3)  quite

5.4 g of poly (BTDA-PMDA-ODPA-TMMDA) polyimide polymer (FIG. 7) and 0.6 g of polyethersulfone (PES) were mechanically stirred for 3 hours and dissolved in a solvent mixture of NMP and 1,3-dioxolane A homogeneous casting dope was formed. The obtained homogeneous casting dope was degassed overnight. The P3 polymer membrane was prepared from a bubble-free casting dope using a doctor knife with 20-millimeter spacing on a clean glass plate. The film was then placed in a vacuum oven with a glass plate. The solvent was removed by slowly increasing the vacuum and temperature of the vacuum oven. Finally, the membrane was dried at 200 < 0 > C under vacuum for at least 48 hours to remove the residual solvent altogether to form the P3 membrane as described in Table 5 and Fig.

Example  13:

UV Crosslinked Poly ( BTDA - PMDA - ODPA - TMMDA ) - PES  polymer Membrane (abbreviated as control 2)  quite

Control 2 membranes were exposed to UV radiation using a 254 nm wavelength UV light generated from a UV lamp with a distance of 1.9 cm (0.75 inch) from the membrane surface to the UV lamp at 10 minutes irradiation time at 50 ° C to form P3 The polymer membrane was further prepared by UV cross-linking. The UV lamp described herein is a low pressure mercury arc immersion UV quartz 12-watt lamp with a 12-watt power supply from Aisle Glass Inc.

Example  14:

UV Crosslinked  30% AlPO -14 / PES / Poly ( BTDA - PMDA - ODPA - TMMDA ) Mixed Matrix Membrane (abbreviated as MMM 5) of  quite

UV Crosslinked Polyethersulfone (PES) Functionalized Containing 30 wt% AlPO-14 Molecular Sieve Filler Dispersed in a UV Crosslinked Poly (BTDA-PMDA-ODPA-TMMDA) Polyimide Continuity Matrix [ (BTDA-PMDA-ODPA-TMMDA) (abbreviated as MMM 5) was prepared as follows: < tb >

1.8 g of AlPO-14 molecular sieve was mechanically stirred for 1 hour and sonicated to disperse it in a mixture of NMP and 1,3-dioxolane to form a slurry. Then 0.6 g of PES was added to functionalize the AlPO-14 molecular sieve in the slurry. The slurry was stirred for at least 1 hour to completely dissolve the PES polymer and functionalize the surface of AlPO-14. Thereafter, 5.6 g of poly (BTDA-PMDA-ODPA-TMMDA) polyimide polymer was added to this slurry and the resulting mixture was stirred for an additional 2 hours to disperse into the continuous poly (BTDA-PMDA-ODPA-TMMDA) polymer matrix (Weight ratio of AlPO-14 to poly (BTDA-PMDA-ODPA-TMMDA) and PES is 30: 100 and the weight ratio of PES to poly (BTDA-PMDA-ODPA-TMMDA) is 1 : 9) to form a stable casting dope containing 30 wt%. This stable casting dope was degassed overnight.

A 30% AlPO-14 / PES / poly (BTDA-PMDA-ODPA-TMMDA) mixed matrix membrane was prepared from a stable casting dope without bubbles using a doctor knife with 20-millimeter spacing on a clean glass plate. The film was then placed in a vacuum oven with a glass plate. The solvent was removed by slowly increasing the vacuum and temperature of the vacuum oven. Finally, the membrane was dried under vacuum at 200 [deg.] C for at least 48 hours to remove all residual solvent to form a 30% AlPO-14 / PES / poly (BTDA-PMDA-ODPA-TMMDA) mixed matrix membrane.

The MMM 5 mixed matrix membrane was exposed to UV radiation using UV light of 254 nm wavelength generated from a UV lamp with a distance of 1.9 cm (0.75 inch) from the membrane surface to the UV lamp at 10 minutes of irradiation time at 50 ° C Was prepared by further UV crosslinking a 30% AlPO-14 / PES / poly (BTDA-PMDA-ODPA-TMMDA) mixed matrix membrane. The UV lamp described herein is a low pressure mercury arc immersion UV quartz 12-watt lamp with a 12-watt power supply from Aisle Glass Inc.

Example  15:

P3 , Control 2 and MMM  5 Membrane CO ₂ / CH ₄  Separation characteristic

Example 12 The P3 polymer membrane, carried the MMM prepared in Control 2 polymer membrane, and Example 14, prepared in example 13 produced from 5 mixture permeability of the matrix membrane CO ₂ and CH ₄ (P _CO2 and P _CH4) and CO ₂ / choice of CH ₄ is also the (α _{CO2 / CH4)} at 5O ℃ were measured by pure gas measurements under 690 kPa (100 psig) pressure. The results for CO ₂ / CH ₄ separation are shown in Table 5 and FIG.

From Table 5 and Figure 14, it can be seen that the control 2 polymer membrane shows a 199% increase in a _{CO2 / CH4} compared to a P3 polymer membrane, but a 60% reduction in P _CO2 . The α _{CO2 / CH4} of the MMM 5 mixed matrix membrane prepared in Example 14 was increased to 51 and the α _{CO2 / CH4} was 201% improved and the P _CO2 was reduced by 43% as compared with the P3 polymer membrane.

Figure 14 shows the CO ₂ / CH ₄ separation performance of P3, control 2 and MMM 5 at 5O < 0 > C and 690 kPa (100 psig) (1991) for CO ₂ / CH ₄ separation at 35 ° C and 345 kPa (50 psig). It can be seen that the CO ₂ / CH ₄ separation performance of the P3 polymer membrane is well below the polymer upper limit of Robeson (1991) for CO ₂ / CH ₄ separation. The control 2 polymer membrane exhibits improved CO ₂ / CH ₄ separation performance and reaches the upper polymer limit of Robeson (1991) for CO ₂ / CH ₄ separation. MMM 5 mixed matrix membrane represents a CO ₂ / CH ₄ separation performance that exceeds the upper limit of the polymer Kurobe hand (1991) for the CO ₂ / CH ₄ separation. These results show that the new voids and defect-free MMM 5 mixed matrix membranes are good membrane candidates for CO ₂ removal from natural gas or flue gas. The improved performance of the MMM 5 mixed matrix membrane for the P3 polymeric and control 2 polymer membranes is due to the molecular sieving mechanism of the AlPO-14 molecular sieve filler and the solution of the UV crosslinked poly (BTDA-PMDA-ODPA-TMMDA) polyimide matrix - due to a successful combination of diffusion mechanisms.

Pure gas permeation test results of P3, control 2 and MMM 5 membranes for CO ₂ / CH ₄ separation ^a Membrane P _CO2
(Barrer) ΔP _CO2
(Barrer) alpha _{CO2 / CH4} Δα _{CO2 / CH4} P3 55.5 0 17.0 0 Control group 2 22.4 -60% 50.9 199% MMM 5 31.6 -43% 51.1 201%

^a Tested at 50 캜 under a pure gas pressure of 690 kPa (100 psig);

1 Barrer = 10 ^-10 (cm3 (STP) 占) m) / (cm3 占 sec 占 H Hg)

Claims (15)

A process for the preparation of UV cross-linked mixed matrix membranes of polymeric functionalized molecular sieves and UV cross-linkable polymers, (a) dispersing a predetermined amount of molecular sieve particles having an outer surface in a mixture of two or more organic solvents to form a molecular sieve slurry, (b) dissolving the polymer in the molecular sieve slurry to functionalize the outer surface of the molecular sieve particle, (c) dissolving the UV crosslinkable polymer acting as a continuum polymer matrix in the polymeric functionalized molecular sieve slurry to form a suspension of the stable polymeric functionalized molecular sieve and the UV crosslinkable polymer, (d) preparing a UV crosslinkable mixed matrix membrane using the suspension of the stable polymeric functionalized molecular sieve and UV crosslinkable polymer, and (e) crosslinking said UV crosslinkable mixed matrix membrane under UV radiation ≪ / RTI > The method of claim 1, wherein the suspension of the polymeric functionalized molecular sieve and the UV crosslinkable polymer is used to prepare a mixed matrix membrane in the form of a symmetrical dense film, a thin film composite, an asymmetric flat sheet or an asymmetric hollow fiber membrane RTI ID = 0.0 > 1, < / RTI > The UV crosslinkable polymer according to claim 1, wherein the UV crosslinkable polymer is at least one member selected from the group consisting of a nitrile group, a benzophenone group, an acryl group, a vinyl group, a styrene group, a styrene-acryl group, an arylsulfonyl group, a 3,4-epoxycyclohexyl group, - dihydrofuran group and combinations of these groups. The UV cross-linkable polymer of claim 1, wherein the UV cross-linkable polymer acting as the continuum polymer matrix is selected from the group consisting of polysulfone, sulfonated polysulfone, polyethersulfone (PES), sulfonated PES, polyacrylate, polyether imide, poly , Polyimide, a mixture of polyamide and polyimide, polyketone, polyether ketone, and mixtures thereof. The polymer of claim 1, wherein the polymer used to functionalize the outer surface of the molecular sieve particles comprises a functional group selected from the group consisting of a hydroxyl group, an amino group, an isocyanato group, a carboxylic acid group, an ether group, ≪ / RTI > The composition of claim 1, wherein the polymer used to functionalize the outer surface of the molecular sieve particles is selected from the group consisting of polyethersulfone, poly (hydroxyl styrene), sulfonated polyethersulfone, hydroxyl terminated poly (ethylene oxide) (Ethylene oxide) -poly (propylene oxide), hydroxyl terminated poly (propylene oxide), hydroxyl terminated co-block-poly (ethylene oxide) (Ethylene oxide) -block-poly (propylene oxide), block-poly (propylene oxide) -block-poly Poly (vinyl alcohol), poly (vinyl alcohol), poly (vinylidene chloride), poly (ethylene oxide), poly Cellulose acetate, cellulose triacetate, cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, nitrocellulose, and mixtures thereof, as well as mixtures of these materials, such as polyvinylpyrrolidone, poly (allylamine) ≪ RTI ID = 0.0 > and / or < / RTI > The method of claim 1, further comprising coating the mixed matrix membrane with a thin layer of a material selected from the group consisting of polysiloxane, fluoropolymer, and thermosetting silicone rubber. 3. The method of claim 1, wherein the UV crosslinkable mixed matrix membrane is coated with a layer of a UV radiation curable epoxy silicone material and then the UV radiation curable epoxy silicone material is exposed to UV radiation for a time sufficient to crosslink the curable epoxy silicone material. ≪ / RTI > further comprising the step of exposing the substrate to radiation. A UV cross-linked mixed matrix membrane of a polymeric functionalized molecular sieve and a UV cross-linkable polymer, prepared according to any one of claims 1 to 8. A method for separating at least one gas from a gas mixture, (a) providing a UV cross-linked mixed matrix membrane of a UV cross-linkable polymer and a polymeric functionalized molecular sieve of claim 9 that is permeable to said at least one gas, (b) contacting the gas mixture to one side of the UV cross-linked mixed matrix membrane so that the at least one gas passes through the UV cross-linked mixed matrix membrane; and (c) removing the permeate gas composition comprising the at least one gas that has permeated the UV cross-linked mixed matrix membrane from the opposite side of the UV cross-linked mixed matrix membrane ≪ / RTI > 11. The process of claim 10, wherein the UV cross-linked mixed matrix membrane of the polymeric functionalized molecular sieve and the UV cross-linkable polymer is in the form of a symmetric dense film, an asymmetric flat sheet, an asymmetric thin film film composite or an asymmetric hollow fiber membrane Separation method. 11. The method of claim 10 wherein the gas mixture is selected from at least one gas pair and wherein the gas pair comprises carbon dioxide / methane, hydrogen / methane, oxygen / nitrogen, water vapor / methane and carbon dioxide / . 11. The method of claim 10, wherein the gas mixture comprises air and at least one volatile organic compound, wherein the at least one volatile organic compound is selected from the group consisting of acetone, xylene, and toluene. delete 11. The process according to claim 10, wherein the gas mixture comprises olefins and paraffins or comprises isoparaffins and normal paraffins.

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