Composite membranes for olefin/paraffin separation

Abstract

This invention presents a metal-doped zeolite membrane-based apparatus containing molecular sieving zeolite thin film on the seeded porous substrate. The metal-doped zeolite membrane exhibits high selectivity to olefin over paraffins. The membrane is synthesized by seed coating and secondary growth method, followed by metal doping and post treatment processes.

Claims

1. An apparatus for olefin separation from an olefin/paraffin mixture, comprising: (a) a source of fluid which includes an olefin and a paraffin; (b) a closed container body having an inlet coupled to said source, a first outlet for discharge of an olefin enriched fluid, and a second outlet for discharge of an olefin depleted fluid; and (c) a plurality of membranes disposed in said body between said inlet and second outlet, wherein the at least one of said membranes comprises a porous substrate and a metal-doped zeolite layer thereon having pores with metal clusters in the zeolite pores, wherein the clusters comprise a metal or metal alloy of at least one transition metal selected from the group consisting of copper, silver, gold, cobalt, nickel, ruthenium, and palladium.

2. The apparatus of claim 1, wherein said at least one membrane comprises one or two seed layers and one or two continuous zeolite layers on the porous substrate.

3. The apparatus of claim 2, wherein a seed layer is prepared by coating a zeolite seed suspension onto the porous substrate by rubbing, spraying, dip-coating, or slip-coating.

4. The apparatus of claim 3, wherein the seed suspension is made from a homogenous precursor through hydrothermal synthesis.

5. The apparatus of claim 2, wherein the continuous zeolite layer comprises Y-type zeolite.

6. The apparatus of claim 2, wherein the continuous zeolite layer comprises ETS-10 type zeolite.

7. The apparatus of claim 2, wherein the continuous zeolite layer is synthesized by a process comprising the steps of: a) placing seed substrate vertically in a polytetrafluoroethylene container; b) adding a homogeneous precursor containing sodium chloride, sodium hydroxide, potassium chloride, potassium fluoride, sodium silicate solution, and a source of titanium to the container; c) putting the polytetrafluoroethylene container into an autoclave with good sealing; and d) heating the autoclave in an oven for hydrothermal synthesis at a temperature in the range of from 180 to 240 C. for from 24 to 72 hours to form a continuous zeolite layer on the seeded substrate.

8. The apparatus of claim 7, wherein the source of titanium is titanium dioxide, titanium chloride, or titanium butoxide.

9. The apparatus of claim 1, wherein metal doping of the zeolite layer is achieved by vapor deposition, plasma treatment, or ion-exchange or a combination of two or more thereof.

10. The apparatus of claim 9, wherein the continuous zeolite layer is subjected to additional treatment selected from the group consisting of temperature programmed reduction, temperature programmed calcination, and UV-irradiation.

11. The apparatus of claim 1, wherein the continuous zeolite layer is fabricated in the shape of a flat-sheet, a tubular member, or a hollow fiber.

12. The apparatus of claim 1, wherein the container body comprises a canister or cylindrical structure coupled to receive a gas or liquid stream containing olefin, paraffin, and other components.

13. The apparatus of claim 12, wherein the canister or cylindrical structure is coupled to receive a gas stream containing an olefin.

14. The apparatus of claim 13, wherein the olefin-containing gas is mixed in a feedstock containing paraffin and other components.

15. The apparatus of claim 12, which comprises a canister or cylindrical structure coupled to receive a gas or liquid stream containing ethylene and ethane, propylene and propane, or butylene and butane, and other components.

16. The apparatus of claim 13, which is used to enrich or recycle the olefins in the gas stream from a refinery gas, steam cracking plant, a gas stream from an oil field, or a venting gas from a propylene polymerization plant.

17. The apparatus of claim 16, wherein the olefins are light hydrocarbons obtained from fluidized catalytic cracking.

18. The apparatus of claim 1, further comprising an inlet for receipt of a sweep gas.

19. The apparatus of claim 1, wherein the porous substrate is coated with one or more nanoparticle seed layers suspended in an aqueous solution having a pH between six and eight, wherein the nanoparticle seeds comprise at least one of sodium chloride, potassium chloride, potassium fluoride, titanium oxide, sodium silicate, and water.

20. A method of separating olefin from an olefin/paraffin mixture, comprising the steps of: (a) injecting an olefin/paraffin fluid into a container comprising a porous membrane; (b) applying the fluid to one side of the membrane, (c) discharging an olefin enriched portion of the fluid that passes through the membrane; (d) discharging an olefin depleted fluid that remains on said one side of the membrane, wherein the membrane is a metal-doped zeolite membrane comprising a porous substrate and a zeolite layer thereon having pores with metal clusters in the zeolite pores, wherein the clusters comprise a metal or metal alloy of at least one transition metal selected from the group consisting of copper, silver, gold, cobalt, nickel, ruthenium, and palladium.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) This invention may be more readily understood by reference to the following drawings wherein:

(2) FIGS. 1(a) and 1(b) represent x-ray diffraction patterns of Y-type zeolite and ETS-10 zeolite, respectively;

(3) FIG. 2 represents a scanning electron microscopy (SEM) image of the ETS-10 zeolite membrane;

(4) FIG. 3 is a graphical representation of the separation performance of the ETS-10 membrane without metal doping;

(5) FIG. 4 is a graphical representation of the separation performance of the metal-doped ETS-10 membrane; and

(6) FIG. 5 is a schematic representation of a zeolite membrane-containing device for olefin/paraffin separation.

DETAILED DESCRIPTION OF THE INVENTION

(7) In accordance with this invention, a composite zeolite membrane is prepared by the following procedure: (1) zeolite membrane is grown on a treated porous substrate (either uncoated or nano-scale zeolite seed coated); (2) a template removal step (if necessary); and (3) metal doping of the membrane. It should be noted that each step mentioned above involves a unique technique specially employed to obtain a composite membrane in which specific molecules permeate through the membrane with high selectivity as well as high permeability.

(8) With reference to the above-mentioned procedure, the porous substrates include a disk shaped, tubular, or hollow fiber porous ceramic, porous silica, metal mesh, or a sintered porous metallic support. Ceramic porous materials are preferred to be the substrates in this invention because of their good affinity to the zeolite materials. Optional seed materials include various zeolite nano-particles, zirconia, and titania. Transition metals or metal alloys with absorption/adsorption property and structure integrity can be selected as doping materials to be dispersed in the zeolitic pores by means of ion-exchange, melt salt vaporization, plasma irradiation, or photo-assisted irradiation.

(9) The following examples are presented to better describe this invention. These examples are used to illustrate the process for zeolite membrane preparation, and not necessarily represent the best formula. It is noted that, this invention is not limited by the following examples. The chemicals used in this work included potassium chloride (99%, Aldrich), potassium fluoride (99%, Aldrich), sodium chloride (99.995%, Aldrich), sodium hydroxide (98%, Aldrich), sodium silicate solution (Na.sub.2SiO.sub.3: 27% SiO.sub.2, 8% Na.sub.2O, Aldrich), sodium alum Mate (50-56% Al+40-45% Na (Fe<0.05%), Riedel-de Haen), titanium(III) chloride solution (TiCl.sub.3/HCl, >12%, Aldrich), anatase (P-25, Aldrich), and titanium butoxide. The propylene (99.5%), propane (ACS grade) gases were obtained from Airgas.

EXAMPLES

Example 1. Preparation of Zeolite Nanoparticle Suspension

(10) (a) Y-Type Zeolite Nano-Particles.

(11) The Y-type zeolite nanoparticle seeds were prepared by hydrothermal synthesis. Amounts of NaAlO.sub.2 (2.78 g)+NaOH (12.67 g)+distilled water (149.91 g) were mixed and then stirred for 30 minutes. Water glass (41.83 g) was added, and the mixture was stirred for 12 hours. The resulting mixture was transferred into a bottle made of polytetrafluoroethylene (hereinafter, TEFLON) for hydrothermal synthesis at 90 C. for 12 hours. After the hydrothermal synthesis, the resulting seed suspension was washed to a pH of 89 for further use.

(12) (b) ETS-10 Zeolite Nanoparticles.

(13) Sodium silicate solution was mixed with 15.4 g distilled water, 2.47 g sodium hydroxide, 2.33 g sodium chloride, and 3.63 g potassium chloride. This mixture was thoroughly stirred until a solution was obtained. Titanium dioxide (1.7 g) was then added with stirring, and a homogeneous gel formed. Static crystallization was carried out in TEFLON-lined autoclaves at 220 C. for 24 hours. The products were then washed with distilled water to a pH between 9-10. The gel composition was 4.7 Na.sub.2O:1.5 K.sub.2O:TiO.sub.2:5.5 SiO.sub.2:122 H.sub.2O.

(14) The resultant zeolite nano-particle suspension was re-dispersed in distilled water to obtain a suspension with a dry solid concentration ranging from 0.1-10 wt %, 0.1 wt % hydroxyl propyl cellulose (HPC, Mw=100,000, Aldrich) solution was used as binder. The final stable colloidal suspension contained 0.1-10 wt %, preferably 0.5-2 wt %, of dry particles. The nanoparticle suspension was coated onto the polished side of a disc substrate by dip-coating. The contact time of the dip-coating process was 3-5 seconds or 3-5 minutes, dependent upon the affinity of seeds and substrates. After dip-coating, the disc was dried at room temperature and stored in an oven.

Example 2. Preparation of Membrane #Y-1, and Separation Performance

(15) This example is directed to the preparation of zeolite membrane #Y1. The precursor solution for secondary growth was prepared in a TEFLON beaker by dissolving 1.235 g NaAlO.sub.2 and 6.965 g NaOH in 88.86 g de-ionized water, under rigorous stirring. After addition of 15.5 g water glass and stirring for another six hours at room temperature, the precursor was transferred into the TEFLON-lined synthesis vessels. The seeded alumina disc was placed vertically at the bottom of the vessel and completely immersed in the synthesis solution about 1 cm below the liquid surface. The container was then moved into an oven to perform hydrothermal synthesis at 100 C. for 12 hours. The membrane was taken out, washed with distilled water, and dried at 70 C. overnight. The membrane was then subjected to a second hydrothermal synthesis. This membrane was characterized by X-ray diffraction (XRD, Rigaku D/MAX-II), showing the pattern set forth in FIG. 1(a).

(16) For ion-exchange, the membrane prepared was placed into 0.04 M AgNO.sub.3 solution (10 ml) at room temperature for one hour. The membrane was then dried overnight at room temperature in a vacuum oven. After drying, the membrane was subjected to temperature program reduction under 5% (v) H.sub.2 (balanced with nitrogen) environment. This membrane showed a propylene selectivity of 1.29 over propane.

Example 3. Membrane #Y-2 Synthesis and Separation Performance

(17) Membrane #Y-2 preparation and ion-exchange process were the same as in Example 2, except that the membrane was subjected to calcination under a nitrogen environment. After calcination, the membrane was subjected to UV irradiation. This membrane showed a propylene selectivity of 1.31 over propane.

Example 4. #M-1 Zeolite Membrane Synthesis and Separation Performance

(18) This example shows the preparation procedure for ETS-10 zeolite membrane. ETS-10 zeolite membrane (#M-1) was synthesized by secondary growth method with the following procedure: 2.47 g NaOH was added into 20.0 g Na.sub.2SiO.sub.3 solution with additional water of 15.4 g, stirring at room temperature for 30 minutes. Amounts of 3.63 g KCl, 2.33 g NaCl, and 1.5 g KF were added into 15.4 g de-ionized water, and the resulting solution was stirred for five minutes. The two solutions were mixed, and the solution mixture was stirred for another 30 minutes. TiCl.sub.3 solution (10.7 g 15% TiCl.sub.3 solution) was added to the solution mixture, with stirring at room temperature for 30 minutes. The precursor was transferred into an autoclave with seeded substrate, and sealed with a TEFLON liner. The autoclave was placed in an oven for secondary growth synthesis at 200 C. for 24 hours. After cooling down to room temperature, the membrane was taken out and rinsed with de-ionized water. The membranes were dried at 80 C. in an oven overnight, and further dried at 300 C. with both heating rate and cooling rate of 1 C./min for eight hours. This membrane showed a propylene selectivity of 4.5 over propane.

Example 5. #M-2 Zeolite Membrane Synthesis and Separation Performance

(19) This example shows the preparation procedure for metal-doped ETS-10 zeolite membrane and its separation performance. ETS-10 zeolite membrane (#M-2) was synthesized by secondary growth method with the following procedure: 1.3 g KCl, 6.9 g NaCl, and 1.5 g KF were added into 20.0 de-ionized water with stirring for five minutes. An amount of 20.0 g Na.sub.2SiO.sub.3 solution was then added to the above mixture with stirring at room temperature for 30 minutes. An amount of 1.3 g anatase was added with stirring at room temperature for 3-4 hours. The precursor was then transferred into an autoclave with seeded substrates, sealed with a TEFLON liner. The autoclave was placed in an oven for hydrothermal synthesis at 220 C. for 24 hours. After cooling down to room temperature, the membrane was taken out and rinsed with the de-ionized water. The membranes were dried overnight in an oven at 80 C. before ion-exchange. The process of ion-exchange was conducted over the membranes by using silver nitrate solution (0.125 N) to ensure a certain amount of Ag ions doping in the zeolitic channels. The ion-exchanged membrane was subjected to post-treatment by UV irradiation.

(20) The crystal growth was examined by x-ray diffraction, as shown in FIG. 1(b). The membrane integrity was observed by using scanning electron microscope (SEM, Philips XL30), a pictograph of which is shown in FIG. 2, Upon Ag ion modification and post treatment, this zeolite composite membrane gave separation performance with propylene selectivity of 106.5.

Example 6. #M-3 Zeolite Membrane Synthesis and Separation Performance

(21) This example shows the preparation procedure for metal-doped ETS-10 zeolite membrane. ETS-10 zeolite membrane (#M-3) was synthesized by secondary growth method with the following procedure: 2.47 g NaOH was added into 20.0 g Na.sub.2SiO.sub.3 solution with additional water of 15.4 g, under stirring at room temperature for 30 minutes. Amounts of 3.63 g, KCl, 2.33 g NaCl, and 1.5 g KF were added into 15.4 g de-ionized water, under stirring for five minutes. The above two solutions were mixed, and the mixed solutions were stirred for another 30 minutes. TiCl.sub.3 solution (10.7 g 15% TiCl.sub.3 solution) was added to the solution mixture, under stirring at room temperature for 30 minutes. The precursor was transferred into an autoclave with seeded substrate, and sealed with a TEFLON liner. The autoclave was placed in an oven for secondary growth synthesis at 200 C. for 24 hours. After cooling down to room temperature, the membrane was taken out and rinsed with the de-ionized water. The membranes were dried overnight in an oven at 80 C. before ion-exchange.

(22) The process of ion-exchange was conducted over the membranes by using Ag(NH.sub.3).sub.2NO.sub.3 solution. The ion-exchange process was similar to one with AgNO.sub.3 solution. The ETS-10 membrane was placed into above mentioned Ag(NH.sub.3).sub.2NO.sub.3 solution (10 ml) at room temperature for 12 hours. The ion-exchanged membrane was subjected to post-treatment by UV irradiation.

(23) Upon Ag ion modification and post treatment, this zeolite composite membrane gave separation performance with propylene selectivity as high as 98.6.

Example 7. #M-4 Zeolite Membrane Synthesis and Separation Performance

(24) This example shows the preparation procedure for metal-doped ETS-10 zeolite membrane and its separation performance. ETS-10 zeolite membrane (#M-4) was synthesized by secondary growth method with the following procedure: 1.3 g KCl, 6.9 g NaCl, and 1.5 g KF were added into 20.0 de-ionized water with stirring for five minutes. An amount of 20.0 g Na.sub.2SiO.sub.3 solution was then added in the above mixture with stirring at room temperature for 30 minutes. An amount of 5.6 g titanium butoxide was added with stirring at room temperature for 3-4 hours. The precursor was then transferred into an autoclave with seeded substrates, sealed with a TEFLON liner. The autoclave was placed in an oven for hydrothermal synthesis at 220 C. for 24 hours. After cooling down to room temperature, the membrane was taken out and rinsed with the de-ionized water. The membranes were dried overnight in an oven at 80 C. before ion-exchange.

(25) A process of ion-exchange was conducted over the membranes by using Ag(NH.sub.3).sub.2NO.sub.3 solution. The ion-exchanged membrane was subjected to temperature programmed calcination at 450 C. in air for eight hours with a heating and cooling rate of 1 C./min. before LTV irradiation.

(26) Upon Ag ion modification and UV irradiation, this zeolite composite membrane gave separation performance with propylene selectivity as high as 9.8.

Example 8. #M-5 Zeolite Membrane Synthesis and Separation Performance

(27) This example shows the preparation procedure for metal-doped ETS-10 zeolite membrane. ETS-10 zeolite membrane (#M-5) was synthesized by secondary growth method with the following procedure: 2.47 g NaOH was added into 20.0 g Na.sub.2SiO.sub.3 solution with additional water of 15.4 g, stirring at room temperature for 30 minutes. Amounts of 3.63 g KCl, 2.33 g NaCl, and 1.5 g KF were added into 15.4 g de-ionized water, under stirring for five minutes. The two solutions were mixed and then stirred for another 30 minutes. TiCl.sub.3 solution (10.7 g 15% TiCl.sub.3 solution) was added into the mixture, and the mixture was stirred at room temperature for 30 minutes. The precursor was transferred into an autoclave with seeded substrate, and sealed with a TEFLON liner. The autoclave was placed in an oven for secondary growth synthesis at 200 C. for 24 hours. After cooling down to room temperature, the membrane was taken out and rinsed with the de-ionized water. The membranes were dried overnight in an oven at 80 C. before ion-exchange.

(28) The process of ion-exchange was conducted over the membranes by using Ag(NH.sub.3).sub.2NO.sub.3 solution. The ion-exchanged membrane was then thermally treated in nitrogen at 300 C. with a heating rate and cooling rate of 1 C./min. for eight hours. The thermally treated membrane was subjected to UV irradiation.

(29) Upon Ag ion modification, thermal treatment and UV-irradiation, this zeolite composite membrane gave separation performance with propylene selectivity as high as 123.7.

(30) Separation performance of the ETS-10 membrane is set forth in FIGS. 3 and 4. In FIG. 3, which represents the separation performance of the ETS-10 membrane without metal doping, the propylene/propane selectivity is about 4.5 (triangle dot), and propylene permeance is about 0.3410.sup.8 mol/m.sup.2.Math.s.Math.Pa (square dot).

(31) In FIG. 4, which represents the separation performance of the metal-doped ETS-10 membrane, the propylene/propane selectivity is about 120 (triangle dot) and propylene permeance is about 0.8510.sup.8 mol/m.sup.2.Math.s.Math.Pa (square dot).

(32) FIG. 5 is a schematic representation of a zeolite membrane-based device or apparatus useful for olefin/paraffin separation according to the invention. A device such as a cartridge 2 has a cylindrical body 4 closed with closed ends 6 and 8. Closed end 6 has an inlet 12 for receipt of olefin/paraffin feed mixture 14, and closed end 8 has an outlet 16 for retentate 20, that is, olefin depleted mixture. Cylindrical body 4 has at least one outlet 22 for permeate 24, that is, olefin enriched mixture. Cylindrical body 4 comprises zeolite membrane material, preferably arranged in cylindrical porous structures 28 of alumina covered with a metal doped zeolite layer. The cylinders 28 are arranged adjacent and parallel to each other within cylindrical body 4. Optionally a sweep gas 30 may enter cylindrical body 4 at inlet 32 to assist in collecting the permeate 24.

(33) Although the invention has been described in detail for the purpose of illustration based on what is currently considered to be the most practical and preferred embodiments, it is to be understood that such detail is solely for that purpose and that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover modifications and equivalent arrangements that are within the spirit and scope of the appended claims. For example, it is to be understood that the present invention contemplates that, to the extent possible, one or more features of any embodiment can be combined with one or more features of any other embodiment.