CN111874881B - Method for purifying xenon by using DD3R molecular sieve membrane - Google Patents
Method for purifying xenon by using DD3R molecular sieve membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 91
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 81
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- 229910052724 xenon Inorganic materials 0.000 title claims abstract description 67
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- 238000000034 method Methods 0.000 title abstract description 27
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- 239000007789 gas Substances 0.000 description 43
- 238000011084 recovery Methods 0.000 description 15
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- 239000012535 impurity Substances 0.000 description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 2
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- 101001001642 Xenopus laevis Serine/threonine-protein kinase pim-3 Proteins 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003994 anesthetic gas Substances 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
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- 239000013316 polymer of intrinsic microporosity Substances 0.000 description 1
- OUTLDGKNVWHDMO-UHFFFAOYSA-M potassium;propan-2-one;hydroxide Chemical compound [OH-].[K+].CC(C)=O OUTLDGKNVWHDMO-UHFFFAOYSA-M 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B23/00—Noble gases; Compounds thereof
- C01B23/001—Purification or separation processes of noble gases
- C01B23/0036—Physical processing only
- C01B23/0042—Physical processing only by making use of membranes
- C01B23/0047—Physical processing only by making use of membranes characterised by the membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/18—Noble gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/102—Nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0009—Physical processing
- C01B2210/001—Physical processing by making use of membranes
- C01B2210/0012—Physical processing by making use of membranes characterised by the membrane
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- C01B2210/00—Purification or separation of specific gases
- C01B2210/0029—Obtaining noble gases
- C01B2210/0037—Xenon
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- C01B2210/0043—Impurity removed
- C01B2210/0051—Carbon dioxide
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Abstract
The invention provides a method for purifying xenon by using a DD3R molecular sieve membrane. We develop an online recycling technology of xenon in a closed-circuit medical xenon anesthesia process by using a DD3R molecular sieve membrane. Single component carbon dioxide permeability of 1.5X 10 ‑7 mol·m ‑2 ·s ‑1 ·Pa ‑1 The selectivity for separation of carbon dioxide to xenon is 570. The permeation flux is an order of magnitude higher than that of conventional membrane materials. CO due to the all-silicon nature of the DD3R molecular sieve membrane 2 The permeability of the membrane is slightly influenced by water vapor, which is different from that the aluminum-containing molecular sieve membrane pore channel is easily blocked by water adsorption. High CO content 2 Flux and high CO 2 the/Xe selectivity and the long-time stability ensure the good prospect of the hollow fiber DD3R molecular sieve membrane in the on-line recycling of xenon for medical anesthesia.
Description
Technical Field
The invention relates to a method for purifying xenon by using a DD3R molecular sieve membrane, belonging to the technical field of gas separation.
Background
The preparation and purification of noble gases is a very challenging process. Xenon, as an extremely precious rare gas, has wide applications in the fields of semiconductor manufacturing, photovoltaic power, aviation, medical imaging and anesthesia, etc. Currently, xenon gas can only be obtained by further cryogenic rectification of the air separation tail gas. Because the abundance of xenon in air is very low (0.087 ppmv), the energy consumption for separation is very high, and the selling price of xenon is between $30,000 and $60,000/m 3 gas,STP . In addition, the increasing industrial demand is limited by the limited supply of the xenon market. It is estimated that even if all air separation units around the world are equipped with xenon extraction units, the supply amount thereof is insufficient84,000m 3 gas,STP . Therefore, the development of the xenon online recycling technology is the only way for ensuring the effective supply of xenon.
The main separation system involved in the medical xenon recovery applied in the present application is N 2 、O 2 、CO 2 And a mixed gas of Xe. German Dragerwek Aktiengesellschaft discloses a method for recovering xenon from anesthetic tail gas by using a high-pressure liquefaction method (US 005520169) and pressurizing the gas to>60bar, liquefying xenon to separate it from other non-condensable gases, and regasifying to obtain a mixture with a content of 80% xenon, 12% oxygen and 8% nitrogen; the carbon dioxide can be removed by coupling technologies such as activated carbon and molecular sieve adsorption. Italy SIAD SOCIETA' ITALIANA ACETILENE&Derivatii S.P.A. discloses a method for cryogenic recovery of xenon in anesthetic tail gas (WO 98/18718), firstly absorbing carbon dioxide by using 5-30% acetone potassium hydroxide solution, and then carrying out cryogenic separation, wherein the recovery rate of xenon is 90-92%. Smetannikov et al also disclose a cryogenic recovery process for xenon gas (RU 2238113). The cryogenic process was optimized by Messer Griesheim GmbH and uwsvents LTD in uk, disclosing cryogenic solidification for recovery of xenon (US 006134914) and two-stage cryogenic process (WO 2004/060459), respectively. Although recovery can be realized by utilizing the difference of phase change temperatures of xenon and gas components, the problems of complicated separation process, extremely high energy consumption and high cost exist.
Hargasser discloses an anesthetic breathing system (US 2010/0258117), and proposes to recover xenon from anesthetic tail gas by using solid adsorbing materials such as activated carbon, silica, alumina or molecular sieves. U.S. Advanced Technology Materials discloses a method for recovering xenon by activated carbon adsorption (US 2013/0112076). Air Products and Chemicals in the united states disclose a method for recovering xenon by vacuum pressure swing adsorption (US 8535414) which can be used for recovering 0.1-2.5% of xenon in nitrogen. Sagetech Medical Equipment Limited, UK discloses a separation method in which porous material adsorption is coupled with supercritical carbon dioxide extraction (GB 2574208). Zhejiang xenon department medical equipment limited company discloses a method for removing carbon dioxide in anesthetic xenon by using a mixture of solid sodium hydroxide and calcium oxide (CN 108837253). The solid adsorption or absorption method can realize the recovery of xenon at normal temperature, but the regeneration process needs high-temperature treatment, the energy consumption is higher, and the recovery rate of xenon is lower.
The membrane separation technology does not relate to phase inversion, and can obviously reduce the energy consumption of xenon recycling; meanwhile, the membrane separation technology can realize the continuous separation of the mixed gas, the operation is simpler, and the method is a more economic and reliable technical route. Klaus Schmidt, germany, discloses a method for recovering anesthetic xenon by using a carbon membrane (US 2010/0031961), but the membrane flux is only-5 × 10 -9 (J.Membr.Sci.2007, 301, 29-38), the technical requirements of miniaturization and portability of the anesthesia respirator cannot be met. French Air Liquide discloses a method for recycling anesthetic xenon with an organic membrane (US 2009/0126733).
Disclosure of Invention
At present, the preparation and recovery technology of xenon mainly comprises high-energy consumption refrigeration rectification. The increasing market demand and the upper limit of capacity force the development of highly efficient and energy-saving xenon recycling technologies, such as membrane separation technologies. The invention develops an online recycling technology of xenon in a closed-circuit medical xenon anesthesia process by using a DD3R molecular sieve membrane. Single component carbon dioxide permeability of 1.5X 10 -7 mol·m -2 ·s -1 ·Pa -1 The selectivity for separation of carbon dioxide to xenon is 570. The permeation flux is an order of magnitude higher than that of conventional membrane materials. The membrane separation performance is mainly formed by CO 2 And the difference of the diffusion coefficient of Xe molecules in the DD3R molecular sieve. However, CO 2 The mass transfer rate of (A) is remarkably reduced due to the existence of Xe, which is the same as that of the prior eight-membered ring molecular sieve membrane in CO 2 /N 2 And CO2/CH 4 The separation structure of the binary components varies widely. The molecular dynamics simulation result shows that the Xe molecules are adsorbed on the surface of the molecular sieve membrane to form CO 2 Surface resistance to adsorption and diffusion. Under the relevant conditions of medical xenon anesthesia, namely the carbon dioxide content is lower than 5 percent and the water vapor exists, CO 2 Permeability and CO 2 The selectivity of/Xe separation was 2.0X 10, respectively -8 mol·m -2 ·s -1 ·Pa -1 And 67. Because of the DD3R molecular sieveThe membrane has the all-silicon characteristic, and the permeability of CO2 is slightly influenced by water vapor, which is different from that the pore channels of the membrane containing aluminum molecular sieves are easily blocked by water adsorption. High CO2 flux and high CO 2 The selectivity of/Xe and the long-term stability ensure the good prospect of the hollow fiber DD3R molecular sieve membrane in the on-line recycling of xenon in medical anesthesia.
A method for purifying xenon by using a DD3R molecular sieve membrane comprises the following steps:
the gas containing xenon is separated by DD3R, and the xenon is remained on the interception side.
In one embodiment, the xenon-containing gas refers to a gas containing N 2 、Xe、CO 2 The gas of (2).
In one embodiment, the xenon-containing gas has a composition of 5% 2 ,30％N 2 And 65% Xe gas mixture.
In one embodiment, the xenon-containing gas further contains H 2 O。
In one embodiment, said H 2 The partial pressure of O was 2.3kPa.
In one embodiment, the separation is carried out at a feed gas pressure of 1-3bar and a temperature of 10-30 ℃.
The invention also provides:
the DD3R molecular sieve membrane contains N 2 、Xe、CO 2 In the separation of Xe from gases.
In one embodiment, the application is to CO 2 the/Xe selectivity is 60 or more.
Advantageous effects
The molecular sieve membrane method for circularly using the anesthetic xenon can obviously improve the membrane permeation flux; meanwhile, the molecular sieve membrane is a pure inorganic material, has better biocompatibility and antibacterial property, and has higher safety when being used in a medical process.
DD3R is a molecular sieve with oval 8-membered ring channels, and the effective channel size is 0.36nm multiplied by 0.44nm. Moreover, the DD3R molecular sieve has certain hydrophobicity due to the all-silicon characteristic, and can effectively weaken the blockage of water vapor on the pore passages of the molecular sieve.
Drawings
FIG. 1 is SEM pictures of the surface (left column) and the cross section (right column) of the DD3R molecular sieve membrane used in the present invention. Wherein the meaning of the respective regions is: different SDA/H 2 DD3R molecular sieve membrane synthesized under O proportioning condition, SDA/H 2 O＝16/4000(a-b),8/4000(c-d),3/4000(e-f).
Fig. 2 is the permeability and separation performance of hollow fiber DD3R molecular sieve membranes. Wherein (a) the permeability of a single component and the DD3R molecular sieve [4 ] 3 5 12 6 1 8 3 ]Cage (operating conditions at 25 ℃ C. And 1bar pressure); (b) CO in Single component (open legend) and binary component (solid legend) 2 The permeability varies with pressure (operating conditions were temperature 25 ℃ C., pressure 1bar increased to 3 bar); (c) Xe molar composition to CO 2 Influence of/Xe mixture gas separation Performance (feed pressure: 3 bar).
FIG. 3 shows the separation performance of DD3R molecular sieve membrane. (a) Separation of CO from DD3R molecular sieve membrane 2 Xe performance compared to other membrane materials; (b) DD3R molecular sieve membrane to CO at different temperatures 2 Single component, CO 2 /H 2 Binary component of O and CO 2 /H 2 O/Xe ternary component separation performance; (c) The DD3R molecular sieve membrane has stable membrane separation performance under the condition of simulating medical anesthesia xenon.
FIG. 4 is an XRD pattern of DD3R molecular sieve membrane prepared under different SDA content conditions.
FIG. 5 is an SEM photograph of DD3R molecular sieve membrane prepared under different synthesis time conditions. (a-b) 12h; (c-d) 24h; (e-f) 36h.
FIG. 6 is an XRD pattern of DD3R molecular sieve membrane prepared under different synthesis time conditions.
Fig. 7 knudsen diffusion selectivity (right) and ideal state selectivity (left).
FIG. 8 is a performance characterization of DD3R molecular sieve prepared by the secondary growth method, wherein, (a) SEM photograph; (b) XRD pattern using Co target K α radiation (wavelength 0.178897 nm); (c) N at 77K 2 Adsorption-desorption curve.
FIG. 9 is CO 2 (a) And Xe (b) at 273K and 2Adsorption and desorption curves at 98K (data points are original experimental data, and the curve is single-point Langmuir model fitting data)
FIG. 10 shows a DD3R molecular sieve membrane vs. CO 2 (a) And a visual numerical fitting of the adsorption and desorption curves of Xe (b)
FIG. 11 shows a DD3R molecular sieve membrane vs. CO 2 And isothermal heat of adsorption curve of Xe
FIG. 12 shows a DD3R molecular sieve membrane vs. CO 2 And Xe separation performance. (a) Equal molar CO of DD3R molecular sieve membrane at different temperatures 2 Xe separation performance, feed pressure 1.2bara; (b) Xe and steam to CO 2 Analysis of the contribution of the decrease in permeability (operating conditions at a temperature of 25-150 ℃ C.)
FIG. 13 shows a DD3R molecular sieve membrane pair N under different pressure conditions 2 Separation performance of/Xe.
Fig. 14 is a schematic diagram of a DD3R zeolite membrane used in the separation of anesthetic xenon.
Detailed Description
The DD3R molecular sieve membrane used in the following examples can be prepared by referring to the prior art, for example, CN110745839A "A process for activating a defect-free DD3R molecular sieve membrane".
Evaluation of Single component gas Permeability DD3R Membrane separation Performance
For He, H 2 ,CO 2 ,N 2 ,CH 4 Xe and SF 6 Equal single component gas, CO 2 The highest permeability characteristic is shown and is 1.5 multiplied by 10 -7 mol·m -2 ·s -1 ·Pa -1 (region a of FIG. 2). Because the wall thickness of the hollow fiber carrier is thin, the supported DD3R molecular sieve membrane is in a tubular form (about 0.84X 10) -7 mol·m -2 ·s -1 ·Pa -1 ) Sum sheet type (1.12X 10) -7 mol·m -2 ·s -1 ·Pa -1 ) The carrier flux is high (microporouus and mesorouus Materials,68 (2004) 71-75 and Journal of Membrane Science,505 (2016) 194-204). In addition, the packing density of the hollow fibers is higher. For CO 2 /He，CO 2 /H 2 ，CO 2 /N 2 ，CO 2 /CH 4 ，CO 2 /Xe，CO 2 /SF 6 The ideal selectivity for this is 9.1,5.1, 68, 201, 570 and 1914, respectively, which far exceed the knudsen diffusion selectivity. CO of hollow fiber DD3R molecular sieve membrane 2 The single component permeability is slightly higher than that of 8-membered ring SAPO-34 molecular sieve membrane (CO) 2 Permeability of-1.0X 10 -7 mol·m -2 ·s -1 ·Pa -1 ,CO 2 the/Xe ideal selectivity was 500, AIChE journal,63 (2017) 761-769), probably due to the elliptical pore size of the DD3R molecular sieve (0.36 nm. Times.0.44 nm, region a of FIG. 2).
CO when the feed pressure increased from 1bara to 3bara 2 Slight decrease in permeability of the monocomponent (<15%, region b of fig. 2). This is mainly due to CO 2 The diffusion coefficient is decreased with the increase of the loading amount. However, CO 2 The permeability of the steel is reduced by 50 percent to 0.76 multiplied by 10 -7 mol·m -2 ·s -1 ·Pa -1 Possibly due to competitive adsorption of Xe. To further quantify this effect, the gas separation performance at different feed pressures was tested. When CO is present 2 CO when Xe feed pressure increased to 2bara 2 The permeability is continuously reduced to 0.54X 10 -7 mol·m -2 ·s -1 ·Pa -1 . At the same time, CO 2 The decrease in permeability is more pronounced with increasing Xe composition (region c of fig. 2). Finally, when CO is present 2 When the content is reduced to 5%, CO 2 Permeability of 0.24X 10 -7 mol·m -2 ·s -1 ·Pa -1 (ii) a However, CO 2 The separation selectivity of/Xe was always around 43, showing CO 2 Good separation selectivity at low concentration.
The membrane separation performance under the medical anesthesia xenon condition is simulated. Separation of CO by membrane 2 There are fewer reports of/Xe. Currently, only carbon and MFI molecular sieve membranes are used for CO 2 Separation of/Xe gas mixture (Journal of Membrane Science,301 (2007) 29-38 and ACS Applied Materials&Interfaces,10(2018)33574-33580)。
CO of hollow fiber DD3R molecular sieve membrane reported in this application 2 The permeability of the single component is 1.5X 10 -7 mol·m -2 ·s -1 ·Pa -1 And is an order of magnitude higher than the results reported in the previous literature (area a of fig. 3). Therefore, DD3R will be CO 2 Ideal membrane separation material for Xe separation. The high permeability of the hollow fiber DD3R molecular sieve membrane can obviously reduce the investment and the occupied area of membrane separation equipment, and has good application prospect for the on-line recycling of xenon in medical anesthesia.
Fig. 3 shows the industrial separation performance of the hollow fiber DD3R molecular sieve membrane. Wherein, the (a) area is a hollow fiber DD3R molecular sieve membrane and other reported membranes, including a carbon molecular sieve membrane (CMS), a b-oriented MFI membrane, a DD3R membrane PIMs membrane (PIM-1 and PIM-7 membrane) with SAPO-34 membrane treated by PDMS and a CO of PDMS membrane 2 Comparison of the/Xe separation Performance, equimolar CO2/Xe mixtures are separated. (b) The zones being single CO at different temperatures 2 Permeation and saturated steam separation of CO 2 a/Xe binary mixture. (c) The region is the composition of DD3R molecular sieve membrane at 3bara of 0.76% 2 O、4.96％CO 2 、29.77％N 2 And 64.51% Xe by weight the long term stability of the recovered Xe.
Water vapor is often present in the anesthetic exhaled breath. Due to the presence of water vapor, CO 2 The permeability of the single component decreases by 37-45% (region b of FIG. 3); however, the gas permeability of the aluminum-containing 8-membered ring molecular sieve membrane is more significantly reduced under the same conditions, for example: SSZ-13 decreased by 75% (Journal of Materials Chemistry A,2 (2014) 13083-13092) and SAPO-34 decreased by 99.2% (Journal of Membrane Science,186 (2001) 25-40). The aluminum-containing molecular sieve framework has strong adsorption capacity to water vapor, and water molecules are adsorbed in pore channels of the DDR molecular sieve to block the diffusion of gas molecules. The DD3R molecular sieve membrane has better hydrophobic property, and can effectively weaken CO brought by water vapor adsorption 2 The permeability is reduced. For example, the full-silicon CHA molecular sieve Membrane decreased by 88% under the water vapor environment (Separation and Purification Technology,197 (2018) 116-121), and the DD3R molecular sieve Membrane decreased by 68% under the water vapor environment (Journal of Membrane Science,505 (2016) 194-204). Because the synthesis of the all-silicon CHA molecular sieve membrane and the literature report DD3R molecular sieve membrane uses a cationic template agent N, N, N-trimethyl-1-adamantyl oxyhydrogenAmmonium iodide and methyl tropyl iodide; this will result in the cleavage of the Si-O-Si bonds in the framework of the molecular sieve during synthesis to form Si-OH bonds to charge balance with the positively charged templating agent ions. In this application, we used an aprotic templating agent and an ion-free synthesis solution for preparing more hydrophobic DD3R molecular sieve films for CO in a humid environment 2 Separation of/Xe. The water vapor adsorption characteristics of DD3R molecular sieves synthesized by using the template agent are reported to be even lower than those of Silicalite-1 molecular sieves (Zeolites, 19 (1997) 353-358).
Further study of water vapor on CO 2 The effect of permeability and selectivity is shown in region b of fig. 3 and region a of fig. 12. In a water vapor environment, the separation selectivity of the membrane is higher than that of the dry gas. Si-OH at the grain boundary of the molecular sieve film layer can strongly adsorb water molecules, thereby blocking the diffusion of gas molecules at the pore canals. Therefore, in a moisture environment, the permeability of Xe is lower than in dry gas. The adsorption of water vapor gradually decreases with increasing temperature, e.g., by 55% at 100 ℃; the temperature is reduced by 52 percent at 125 ℃; the reduction was 42% at 150 ℃. However, in both wet and dry gases, CO 2 The permeability of the molecule is mainly contributed by the DD3R molecular sieve. Therefore, the selectivity in a wet gas environment is higher than in a dry gas. From the above, it can be seen that both Xe molecules and water molecules have some blocking effect on DD3R molecular sieves. To dry CO 2 Based on gas permeability, we compared the plugging effect of Xe and water molecules on DD3R molecular sieves, respectively (region b of fig. 12): according to Xe + water ≈ Xe>The sequence of water decreases in turn. This is illustrated in CO 2 In the/Xe separation process, the blockage of the transmission channels mainly comes from the adsorption of Xe molecules, and the influence of water vapor is basically negligible.
Separation and permeability of mixed gas
During the anesthesia process, the impurities of the expired anesthetic gas are except CO 2 In addition, human tissues and organs release nitrogen during the initial phase of anesthesia. Generally, in the initial phase of anesthesia, CO is released 2 And N 2 The rates of (A) are 0.25L/min and 0.02L/min, respectively. To realizeOn-line Xe recycling, CO 2 And N 2 Need to be removed. The nitrogen permeability of our hollow fiber DD3R molecular sieve membrane was 3.25X 10 -9 mol·m -2 ·s -1 ·Pa -1 The separation selectivity was 95.3 (fig. 13). Although Carreon et al reported that ZIF-8 membranes could also achieve N 2 Separation of/Xe, but in water vapor and CO 2 In the presence of ZIF-8, the separation performance of the crystals is lost by the decomposition of carbonate (Angewandte Chemie International Edition,53 (2014) 7471-7474).
For xenon recovery in a closed loop system for respiratory anesthesia, we proposed an on-line recycling system based on DD3R molecular sieve membranes (FIG. 14) and used it for 5% CO 2 ,30％N 2 And 65% by weight of xenon gas in the Xe gas mixture. After introduction of 2.3kP steam, CO 2 And N 2 All slightly decreased (fig. 3 c) finally, the permeability of carbon dioxide stabilized at 2.0 x 10 - 8 mol·m -2 ·s -1 ·Pa -1 ，CO 2 the/Xe selectivity is 67 +/-12; n is a radical of 2 Permeability of 2.4X 10 -9 mol·m -2 ·s -1 ·Pa -1 ，N 2 the/Xe selectivity was 8. + -.2. In other words, after selectively removing impurities such as carbon dioxide and nitrogen, more than 99% of Xe can be effectively recycled. The operating cost of the process is $1.5/m, based on an economic balance 3 gas,STP And the price is four orders of magnitude cheaper than the current xenon market. However, for medical Anesthesia of xenon, the recovery rate of other conventional recovery processes is very low, for example, the recovery rate of cryogenic liquefaction is 8.95% (Anesthesia)&Analgesia,110 (2010) 101-109), the recovery rate of cryogenic crystallization is 70% (Anesthesia)&Analgesia,105 (2007) 1312-1318), the recovery rate of pressure swing adsorption is 87.5% (US 8535414 B2). The high separation performance and long-term stability of the DD3R molecular sieve membrane will significantly reduce the recycling cost of medical anesthesia xenon, making the xenon anesthesia process economically more competitive.
We verified that DD3R molecular sieve membranes can be separated from CO with a certain humidity 2 /N 2 The characteristic of recovering xenon from Xe mixed gas. Separation performance of the membraneMainly composed of CO 2 And the difference in diffusion coefficient of Xe molecules in DD3R molecular sieves.
As can be seen from the above experiments, based on CO 2 The difference between the molecular kinetic sizes of (0.33 nm) and Xe (0.41 nm), the Deca-Dodecasil 3 Rhombohedral (DD 3R) molecular sieve would be an ideal membrane separation material. DD3R is a molecular sieve with oval 8-membered ring channels, and the effective channel size is 0.36nm multiplied by 0.44nm. Moreover, the DD3R molecular sieve has certain hydrophobicity due to the all-silicon characteristic, and can effectively weaken the blockage of water vapor on the pore passages of the molecular sieve.
Claims (1)
1.D 3R molecular sieve membrane containing N 2 、Xe、CO 2 The use in the separation of Xe from a gas, characterized in that it comprises the following steps: the DD3R molecular sieve membrane is adopted to separate the gas containing xenon, the xenon is retained on the interception side, and N 2 And CO 2 Permeating the DD3R molecular sieve membrane;
the gas containing xenon contains 5% CO 2 , 30% N 2 And 65% Xe, and then 2.3kPa steam is introduced;
in the separation, the pressure of the feed gas is 1-3bar and the temperature is 10-30 ℃.
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