SEPARATION SYSTEM
20230108642 · 2023-04-06
Assignee
Inventors
Cpc classification
C01B39/02
CHEMISTRY; METALLURGY
B01D53/228
PERFORMING OPERATIONS; TRANSPORTING
Y02C20/40
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
Abstract
A separation system includes first and second separation parts each having a separation membrane and provided with a fluid supply port, a permeate fluid exhaust port, and a non-permeate fluid exhaust port, an intermediate connecting part for connecting the permeate fluid exhaust port of the first separation part and the fluid supply port of the second separation part, a supply pipe connected to the fluid supply port of the first separation part, in which a mixed fluid flows at a pressure higher than an atmospheric pressure, and a pressure reducing part connected to the permeate fluid exhaust port of the second separation part, for reducing a pressure inside the permeate fluid exhaust port to a pressure lower than the atmospheric pressure. A pressure inside the intermediate connecting part is lower than a pressure inside the supply pipe and not lower than the atmospheric pressure.
Claims
1. A separation system, comprising: a first separation part having a separation membrane and provided with a fluid supply port, a permeate fluid exhaust port, and a non-permeate fluid exhaust port; a second separation part having a separation membrane and provided with a fluid supply port, a permeate fluid exhaust port, and a non-permeate fluid exhaust port; an intermediate connecting part for connecting said permeate fluid exhaust port of said first separation part and said fluid supply port of said second separation part; a supply pipe connected to said fluid supply port of said first separation part, in which a mixed fluid containing a plurality of types of fluids flows at a pressure higher than an atmospheric pressure; a pressure reducing part connected to said permeate fluid exhaust port of said second separation part, for reducing a pressure inside said permeate fluid exhaust port to a pressure lower than the atmospheric pressure, and a pressure adjustment part for adjusting a pressure inside said permeate fluid exhaust port of said second separation part so that a flow rate and/or component composition of a fluid exhausted from said permeate fluid exhaust port or said non-permeate fluid exhaust port of said second separation part can fall within a predetermined range, wherein said intermediate connecting part is not provided with any device for pressure rising nor any device for pressure reduction, and a pressure inside said intermediate connecting part is lower than a pressure inside said supply pipe and not lower than the atmospheric pressure.
2. The separation system according to claim 1, wherein a pressure difference between said fluid supply port and said permeate fluid exhaust port in said second separation part is not higher than 0.8 times said pressure difference in said first separation part.
3. The separation system according to claim 1, wherein said mixed fluid is a mixed gas containing a plurality of types of gases.
4. The separation system according to claim 3, further comprising: a condensation prevention part provided at a predetermined position on a path from said supply pipe to said separation membrane of said second separation part, for heating or keeping warm a gas flowing in said path, to thereby prevent condensation of said gas.
5. The separation system according to claim 1, further comprising: a preprocessing part provided at a predetermined position between a supply source of said mixed fluid and said first separation part, for removing at least part of a predetermined component contained in said mixed fluid.
6. The separation system according to claim 1, wherein said separation membrane of said first separation part and/or said separation membrane of said second separation part each contain an inorganic material.
7. The separation system according to claim 1, wherein said separation membrane of said first separation part and/or said separation membrane of said second separation part are each a zeolite membrane.
8. The separation system according to claim 7, wherein said mixed fluid contains a fluid having a molecular size smaller than a pore diameter of zeolite forming said zeolite membrane and a fluid having a molecular size larger than said pore diameter.
9. The separation system according to claim 7, wherein a zeolite forming said zeolite membrane is an eight-membered ring zeolite.
10. The separation system according to claim 1, wherein said pressure adjustment part is provided between said permeate fluid exhaust port of said second separation part and said pressure reducing part in a permeate fluid collection pipe connected to said permeate fluid exhaust port of said second separation part.
11. The separation system according to claim 1, further comprising: a return pipe for leading part of a fluid exhausted from said non-permeate fluid exhaust port of said first separation part and/or at least part of a fluid exhausted from said non-permeate fluid exhaust port of said second separation part to said fluid supply port of said first separation part.
12. The separation system according to claim 1, further comprising: an energy conversion part for converting pressure energy of a fluid exhausted from said non-permeate fluid exhaust port of said first separation part into different energy.
13. The separation system according to claim 1, further comprising: an exhaust fluid pressure rising part for raising a pressure of a fluid exhausted from said non-permeate fluid exhaust port of said second separation part, wherein the fluid whose pressure is raised by said exhaust fluid pressure rising part is mixed with a fluid exhausted from said non-permeate fluid exhaust port of said first separation part.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DETAILED DESCRIPTION
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[0045] The mixed fluid may be a mixed gas containing a plurality of types of gases (including vapors), may be a mixed liquid containing a plurality of types of liquids, or may be a gas-liquid two-phase fluid containing both a gas and a liquid. The mixed fluid may contain a slight amount of solids such as particles or the like.
[0046] The mixed fluid contains at least one of, for example, hydrogen (H.sub.2), helium (He), nitrogen (N.sub.2), oxygen (O.sub.2), water (H.sub.2O), water vapor (H.sub.2O), carbon monoxide (CO), carbon dioxide (CO.sub.2), nitrogen oxide, ammonia (NH.sub.3), sulfur oxide, hydrogen sulfide (H.sub.2S), sulfur fluoride, mercury (Hg), arsine (AsH.sub.3), hydrogen cyanide (HCN), carbonyl sulfide (COS), C1 to C8 hydrocarbons, organic acid, alcohol, mercaptans, ester, ether, ketone, and aldehyde.
[0047] The nitrogen oxide is a compound of nitrogen and oxygen. The above-described nitrogen oxide is, for example, a gas called NOx such as nitric oxide (NO), nitrogen dioxide (NO.sub.2), nitrous oxide (also referred to as dinitrogen monoxide) (N.sub.2O), dinitrogen trioxide (N.sub.2O.sub.3), dinitrogen tetroxide (N.sub.2O.sub.4), dinitrogen pentoxide (N.sub.2O.sub.5), or the like.
[0048] The sulfur oxide is a compound of sulfur and oxygen. The above-described sulfur oxide is, for example, a gas called SO.sub.X such as sulfur dioxide (SO.sub.2), sulfur trioxide (SO.sub.3), or the like.
[0049] The sulfur fluoride is a compound of fluorine and sulfur. The above-described sulfur fluoride is, for example, disulfur difluoride (F—S—S—F, S═SF.sub.2), sulfur difluoride (SF.sub.2), sulfur tetrafluoride (SF.sub.4), sulfur hexafluoride (SF.sub.6), disulfur decafluoride (S.sub.2F.sub.10), or the like.
[0050] The C1 to C8 hydrocarbons are hydrocarbons with not less than 1 and not more than 8 carbon atoms. The C3 to C8 hydrocarbons may be any one of a linear-chain compound, a side-chain compound, and a ring compound. Further, the C2 to C8 hydrocarbons may either be a saturated hydrocarbon (i.e., in which there is no double bond nor triple bond in a molecule), or an unsaturated hydrocarbon (i.e., in which there is a double bond and/or a triple bond in a molecule). The C1 to C4 hydrocarbons are, for example, methane (CH.sub.4), ethane (C.sub.2H.sub.6), ethylene (C.sub.2H.sub.4), propane (C.sub.3H.sub.8), propylene (C.sub.3H.sub.6), normal butane (CH.sub.3(CH.sub.2).sub.2CH.sub.3), isobutane (CH(CH.sub.3).sub.3), 1-butene (CH.sub.2═CHCH.sub.2CH.sub.3), 2-butene (CH.sub.3CH═CHCH.sub.3), or isobutene (CH.sub.2═C(CH.sub.3).sub.2).
[0051] The above-described organic acid is carboxylic acid, sulfonic acid, or the like. The carboxylic acid is, for example, formic acid (CH.sub.2O.sub.2), acetic acid (C.sub.2H.sub.4O.sub.2), oxalic acid (C.sub.2H.sub.2O.sub.4), acrylic acid (C.sub.3H.sub.4O.sub.2), benzoic acid (C.sub.6H.sub.5COOH), or the like. The sulfonic acid is, for example, ethanesulfonic acid (C.sub.2H.sub.6O.sub.3S) or the like. The organic acid may either be a chain compound or a ring compound.
[0052] The above-described alcohol is, for example, methanol (CH.sub.3OH), ethanol (C.sub.2H.sub.5OH), isopropanol (2-propanol) (CH.sub.3CH(OH)CH.sub.3), ethylene glycol (CH.sub.2(OH)CH.sub.2(OH)), butanol (C.sub.4H.sub.9OH), or the like.
[0053] The mercaptans are an organic compound having hydrogenated sulfur (SH) at the terminal end thereof, and are a substance also referred to as thiol or thioalcohol. The above-described mercaptans are, for example, methyl mercaptan (CH.sub.3SH), ethyl mercaptan (C.sub.2H.sub.5SH), 1-propanethiol (C.sub.3H.sub.7SH), or the like.
[0054] The above-described ester is, for example, formic acid ester, acetic acid ester, or the like.
[0055] The above-described ether is, for example, dimethyl ether ((CH.sub.3).sub.2O), methyl ethyl ether (C.sub.2H.sub.5OCH.sub.3), diethyl ether ((C.sub.2H.sub.5).sub.2O), or the like.
[0056] The above-described ketone is, for example, acetone ((CH.sub.3).sub.2CO), methyl ethyl ketone (C.sub.2H.sub.5COCH.sub.3), diethyl ketone ((C.sub.2H.sub.5).sub.2CO), or the like.
[0057] The above-described aldehyde is, for example, acetaldehyde (CH.sub.3CHO), propionaldehyde (C.sub.2H.sub.5CHO), butanal (butylaldehyde) (C.sub.3H.sub.7CHO), or the like.
[0058] In the following description, it is assumed that the mixed fluid to be separated by the separation system 4 is a mixed gas containing a plurality of types of gases. The mixed gas may contain particles, droplets, or the like as impurities.
[0059] The separation system 4 shown in
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[0062] The support 11 is a porous member that gas and liquid can permeate. In the exemplary case shown in
[0063] The length of the support 11 (i.e., the length in the left and right direction of
[0064] As the material for the support 11, various materials (for example, ceramics or a metal) may be adopted only if the materials ensure chemical stability in the process step of forming the zeolite membranes 12 on the surface thereof. In the present preferred embodiment, the support 11 is formed of a ceramic sintered body. Examples of the ceramic sintered body which is selected as a material for the support 11 include alumina, silica, mullite, zirconia, titania, yttria, silicon nitride, silicon carbide, and the like. In the present preferred embodiment, the support 11 contains at least one type of alumina, silica, and mullite.
[0065] The support 11 may contain an inorganic binder. As the inorganic binder, at least one of titania, mullite, easily sinterable alumina, silica, glass frit, a clay mineral, and easily sinterable cordierite can be used.
[0066] The average pore diameter of the support 11 is, for example, 0.01 μm to 70 μm, and preferably 0.05 μm to 25 μm. The average pore diameter of the support 11 in the vicinity of the surface on which the zeolite membrane 12 is formed is 0.01 μm to 1 μm, and preferably 0.05 μm to 0.5 μm. The average pore diameter can be measured by using, for example, a mercury porosimeter, a perm porometer, or a nano-perm porometer. Regarding the pore diameter distribution of the entire support 11 including the surface and the inside thereof, D5 is, for example, 0.01 μm to 50 μm, D50 is, for example, 0.05 μm to 70 μm, and D95 is, for example, 0.1 μm to 2000 μm. The porosity of the support 11 in the vicinity of the surface on which the zeolite membrane 12 is formed is, for example, 20% to 60%.
[0067] The support 11 has, for example, a multilayer structure in which a plurality of layers with different average pore diameters are layered in a thickness direction. In the exemplary case shown in
[0068] The zeolite membrane 12 is a porous membrane having micropores. The zeolite membrane 12 can be used as a separation membrane for separating a specific substance from a mixed substance in which a plurality of types of substances are mixed, by using a molecular sieving function. As compared with the specific substance, any one of the other substances is harder to permeate the zeolite membrane 12. In other words, the permeance of any other substance through the zeolite membrane 12 is smaller than that of the above specific substance.
[0069] The thickness of the zeolite membrane 12 is, for example, 0.05 μm to 30 μm, preferably 0.1 μm to 20 μm, and more preferably 0.5 μm to 10 μm. When the thickness of the zeolite membrane 12 is increased, the separation performance increases. When the thickness of the zeolite membrane 12 is reduced, the permeance increases. The surface roughness (Ra) of the zeolite membrane 12 is, for example, 5 μm or less, preferably 2 μm or less, more preferably 1 μm or less, and further preferably 0.5 μm or less.
[0070] The pore diameter of a zeolite crystal contained in the zeolite membrane 12 (hereinafter, also referred to simply as “the pore diameter of the zeolite membrane 12”) is not smaller than 0.2 nm and not larger than 0.8 nm, preferably not smaller than 0.3 nm and not larger than 0.7 nm, and more preferably not smaller than 0.3 nm and not larger than 0.45 nm. When the pore diameter of the zeolite membrane 12 is smaller than 0.2 nm, there are some cases where the amount of substance permeating the zeolite membrane becomes smaller, and when the pore diameter of the zeolite membrane 12 is larger than 0.8 nm, there are some cases where the selectivity of a substance by the zeolite membrane becomes insufficient. The pore diameter of the zeolite membrane 12 refers to a diameter (i.e., a short diameter) of the pore in a direction substantially perpendicular to the maximum diameter (i.e., a long diameter which is the maximum value of a distance between oxygen atoms) of the pore of a zeolite crystal forming the zeolite membrane 12. The pore diameter of the zeolite membrane 12 is smaller than the average pore diameter in the surface of the support 11 on which the zeolite membrane 12 is arranged.
[0071] When the maximum number of membered rings of the zeolite forming the zeolite membrane 12 is n, the short diameter of an n-membered ring pore is defined as the pore diameter of the zeolite membrane 12. Further, when the zeolite has a plurality of types of n-membered ring pores having the same n, the short diameter of the n-membered ring pore having the largest short diameter is defined as the pore diameter of the zeolite membrane 12. Furthermore, an n-membered ring refers to a portion in which the number of oxygen atoms constituting a framework forming a pore is n and each oxygen atom is bonded to later-described T atoms to form a ring structure. Further, the n-membered ring refers to a portion in which a through hole (channel) is formed and does not include any portion in which no through hole is formed. The n-membered ring pore refers to a pore formed of an n-membered ring. In terms of improvement of selectivity, it is preferable that the maximum number of membered rings of the zeolite contained in the zeolite membrane 12 described above should be eight. In other words, it is preferable that the zeolite forming the zeolite membrane 12 should be an 8-membered ring zeolite.
[0072] The pore diameter of the zeolite membrane is uniquely determined depending on the framework structure of the zeolite and can be obtained from values disclosed in “Database of Zeolite Structures” [online], internet <URL: http://www.iza-structure.org/databases/> of the International Zeolite Association.
[0073] There is no particular limitation on the type of the zeolite forming the zeolite membrane 12, but the zeolite membrane 12 may be formed of, for example, AEI-type, AEN-type, AFN-type, AFV-type, AFX-type, BEA-type, CHA-type, DDR-type, ERI-type, ETL-type, FAU-type (X-type, Y-type), GIS-type, IHW-type, LEV-type, LTA-type, LTJ-type, MEL-type, MFI-type, MOR-type, PAU-type, RHO-type, SOD-type, SAT-type zeolite, or the like. In the case where the zeolite is an eight-membered ring zeolite, for example, the zeolite may be AEI-type, AFN-type, AFV-type, AFX-type, CHA-type, DDR-type, ERI-type, ETL-type, GIS-type, IHW-type, LEV-type, LTA-type, LTJ-type, RHO-type, SAT-type zeolite, or the like. In the present preferred embodiment, the type of the zeolite forming the zeolite membrane 12 is DDR-type zeolite.
[0074] The zeolite membrane 12 contains, for example, silicon (Si). The zeolite membrane 12 may contain, for example, any two or more of Si, aluminum (Al), and phosphorus (P). As the zeolite forming the zeolite membrane 12, a zeolite in which atoms (T-atoms) located at the center of an oxygen tetrahedron (TO.sub.4) constituting the zeolite include only Si or Si and Al, an AlPO-type zeolite in which T-atoms include Al and P, an SAPO-type zeolite in which T-atoms include Si, Al, and P, an MAPSO-type zeolite in which T-atoms include magnesium (Mg), Si, Al, and P, a ZnAPSO-type zeolite in which T-atoms include zinc (Zn), Si, Al, and P, or the like can be used. Some of the T-atoms may be replaced by other elements.
[0075] When the zeolite membrane 12 contains Si atoms and Al atoms, the ratio of Si/Al in the zeolite membrane 12 is, for example, not less than 1 and not more than 100,000. The Si/Al ratio is a molar ratio of Si element to Al element contained in zeolite membrane 12. The Si/Al ratio is preferably 5 or more, more preferably 20 or more, and further preferably 100 or more. In short, the higher the ratio is, the better. By adjusting the mixing ratio of an Si source and an Al source in a starting material solution used in the manufacture of the zeolite membrane 12, or the like, it is possible to adjust the Si/Al ratio in the zeolite membrane 12. The zeolite membrane 12 may contain an alkali metal. The alkali metal is, for example, sodium (Na) or potassium (K).
[0076] The ratio (permeance ratio) of the permeance of CO.sub.2 through the zeolite membrane 12 to the permeance of N.sub.2 therethrough is, for example, not lower than 5, preferably not lower than 10, more preferably not lower than 15, and further preferably not lower than 25. The permeance ratio is a ratio in a case where a single-component cylinder gas is used as a supply gas and the pressure on the supply side is 300 kPaG, the pressure on the permeate side is an atmospheric pressure, and the temperature is 25° C.
[0077] As shown in
[0078] There is no particular limitation on the shape of the housing 22, but the housing 22 is, for example, a tubular member having a substantially cylindrical shape. The housing 22 is formed of, for example, stainless steel or carbon steel. The longitudinal direction of the housing 22 is substantially in parallel with the longitudinal direction of the zeolite membrane complex 1. A supply port 221 is provided at an end portion on one side in the longitudinal direction of the housing 22 (i.e., an end portion on the left side in
[0079] The two sealing members 23 are arranged around the entire circumference between an outer peripheral surface of the zeolite membrane complex 1 and an inner peripheral surface of the housing 22 in the vicinity of both end portions of the zeolite membrane complex 1 in the longitudinal direction. Each of the sealing members 23 is a substantially annular member formed of a material that gas and liquid cannot permeate. The sealing member 23 is, for example, an O-ring formed of a flexible resin. The sealing members 23 come into close contact with the outer peripheral surface of the zeolite membrane complex 1 and the inner peripheral surface of the housing 22 around the entire circumferences thereof. In the exemplary case shown in
[0080] In the separation membrane module 2, a mixed fluid (herein, mixed gas) containing a plurality of types of fluids having different permeabilities to the zeolite membrane 12 is supplied into the inside of the housing 22 as indicated by an arrow 251. For example, a main component of the mixed fluid includes CO.sub.2 gas and N.sub.2 gas. The mixed fluid may contain any substance other than CO.sub.2 and N.sub.2. The mixed fluid supplied to the housing 22 is fed from the left end of the zeolite membrane complex 1 in this figure into the inside of each through hole 111 of the support 11. A fluid with high permeability (which is, for example, CO.sub.2 gas, and hereinafter is referred to as a “high permeability fluid”) in the mixed fluid permeates the zeolite membrane 12 provided on the inner surface of each through hole 111 and the support 11, and is led out from the outer peripheral surface of the support 11. The high permeability fluid is thereby separated from a fluid with low permeability (which is, for example, N.sub.2 gas, and hereinafter is referred to as a “low permeability fluid”) in the mixed fluid.
[0081] The fluid (hereinafter, referred to as a “permeate fluid”) which has permeated the zeolite membrane complex 1 and has been led out from the outer peripheral surface of the support 11 is exhausted from the housing 22 through the second exhaust port 223 as indicated by an arrow 253. The permeate fluid may include the low permeability fluid permeating the zeolite membrane 12, as well as the above-described high permeability fluid.
[0082] Further, in the mixed fluid, a fluid (hereinafter, referred to as a “non-permeate fluid”) other than the fluid which has permeated the zeolite membrane 12 and the support 11 passes through each through hole 111 of the support 11 from the left side to the right side in this figure. The non-permeate fluid is exhausted from the housing 22 though the first exhaust port 222 as indicated by an arrow 252. A pressure of the non-permeate fluid to be exhausted from the housing 22 is, for example, substantially the same as the pressure (feed pressure) of the fluid to be fed into the inside of the housing 22. The non-permeate fluid may include the high permeability fluid that has not permeated the zeolite membrane 12, as well as the above-described low permeability fluid.
[0083] As described earlier, each separation part 41 or 42 shown in
[0084] The first separation part 41 includes a fluid supply port 411, a non-permeate fluid exhaust port 412, and a permeate fluid exhaust port 413. In the first separation part 41, the supply port 221 of the first separation membrane module 2, i.e., the separation membrane module 2 on the most upstream side serves as the fluid supply port 411. The first exhaust port 222 of the M-th separation membrane module 2, i.e., the separation membrane module 2 on the most downstream side serves as the non-permeate fluid exhaust port 412. Further, a group of M second exhaust ports 223 in the first to M-th separation membrane modules 2 serves as the permeate fluid exhaust port 413. The first separation part 41 may include only one separation membrane module 2, and in this case, the supply port 221, the first exhaust port 222, and the second exhaust port 223 of the separation membrane module 2 serve as the fluid supply port 411, the non-permeate fluid exhaust port 412, and the permeate fluid exhaust port 413, respectively.
[0085] Like the first separation part 41, the second separation part 42 includes a fluid supply port 421, a non-permeate fluid exhaust port 422, and a permeate fluid exhaust port 423. In the second separation part 42, the supply port 221 of the first separation membrane module 2, i.e., the separation membrane module 2 on the most upstream side serves as the fluid supply port 421. The first exhaust port 222 of the M-th separation membrane module 2, i.e., the separation membrane module 2 on the most downstream side serves as the non-permeate fluid exhaust port 422. Further, a group of M second exhaust ports 223 in the first to M-th separation membrane modules 2 serves as the permeate fluid exhaust port 423. The second separation part 42 may include only one separation membrane module 2, and in this case, the supply port 221, the first exhaust port 222, and the second exhaust port 223 of the separation membrane module 2 serve as the fluid supply port 421, the non-permeate fluid exhaust port 422, and the permeate fluid exhaust port 423, respectively.
[0086] The separation system 4 further includes a supply pipe 43, an intermediate connecting part 44, a first non-permeate fluid collection pipe 45, a second non-permeate fluid collection pipe 46, and a permeate fluid collection pipe 47. The supply pipe 43 is connected to the fluid supply port 411 of the first separation part 41. The supply pipe 43 is provided with a supply fluid pressure rising part 431. The intermediate connecting part 44 is a connecting pipe and connects the permeate fluid exhaust port 413 of the first separation part 41 to the fluid supply port 421 of the second separation part 42. The first non-permeate fluid collection pipe 45 is connected to the non-permeate fluid exhaust port 412 of the first separation part 41. The second non-permeate fluid collection pipe 46 is connected to the non-permeate fluid exhaust port 422 of the second separation part 42. The permeate fluid collection pipe 47 is connected to the permeate fluid exhaust port 423 of the second separation part 42. The permeate fluid collection pipe 47 is provided with a pressure reducing part 471.
[0087]
[0088] In the separation system 4 of
[0089] In the first separation part 41, a fluid (hereinafter, referred to as a “first non-permeate fluid”) which has not permeated the zeolite membrane 12 of any separation membrane module 2 is exhausted to the first non-permeate fluid collection pipe 45 through the non-permeate fluid exhaust port 412 and then collected. A pressure of the first non-permeate fluid (the pressure on a non-permeate side of the first separation part 41) is substantially the same as the pressure P1 of the supply fluid supplied to the first separation part 41. In the first separation part 41, a fluid (hereinafter, referred to as a “first permeate fluid”) which has permeated the zeolite membrane 12 of one separation membrane module 2 is led to the intermediate connecting part 44 through the permeate fluid exhaust port 413. As described later, in the exemplary case shown in
[0090] The intermediate connecting part 44 is not provided with any device for pressure rising, such as a compressor or the like, nor any device for pressure reduction, such as a vacuum pump or the like, and in the exemplary case shown in
[0091] The pressure reducing part 471 is, for example, a vacuum pump or the like, and as shown in
[0092] In the second separation part 42, a fluid (hereinafter, referred to as a “second permeate fluid”) which has permeated the zeolite membrane 12 of one separation membrane module 2 is exhausted to the permeate fluid collection pipe 47 through the permeate fluid exhaust port 423. In the separation system 4 of
[0093] In the second separation part 42, a fluid (hereinafter, referred to as a “second non-permeate fluid”) which has not permeated the zeolite membrane 12 of any separation membrane module 2 is exhausted to the second non-permeate fluid collection pipe 46 through the non-permeate fluid exhaust port 422 and then collected. In the separation system 4, a pressure inside the second non-permeate fluid collection pipe 46 (a pressure on the non-permeate side of the second separation part 42) is the substantially atmospheric pressure. The pressure inside the intermediate connecting part 44 thereby becomes the substantially atmospheric pressure (i.e., the atmospheric pressure P0 or a pressure slightly higher than the atmospheric pressure P0). Actually, pressures of all the portions inside the intermediate connecting part 44 are lower than the pressure inside the supply pipe 43 and not lower than the atmospheric pressure.
[0094] Next, description will be made on a separation test performed on respective separation systems in Example and Comparative Examples. The separation system 4 in Example has the same configuration as that shown in
[0095] In the separation system 9b of Comparative Example 2 shown in
[0096] The separation system 9d of Comparative Example 4 shown in
[0097] In the separation systems 4 and 9a to 9d of Example and Comparative Examples 1 to 4, respectively, the same separation membrane module 2 (see
[0098] In the separation systems 4 and 9a to 9d of Example and Comparative Examples 1 to 4, respectively, it is assumed that the pressure of the supply fluid is 800 kPaG. In the separation system 4 of Example, it is assumed that the pressure of the permeate fluid exhaust port 413 of the first separation part 41 is 0 kPaG and the pressure of the permeate fluid exhaust port 423 of the second separation part 42 is −100 kPaG. In the separation systems 9a and 9b of Comparative Examples 1 and 2, it is assumed that the pressure of the permeate fluid exhaust port 913 of the separation part 91 is 0 kPaG, and in the separation system 9b, it is assumed that the flow rate of the permeate fluid returned by the return pipe 98 is 2.3 Nm.sup.3/h. In the separation system 9c of Comparative Example 3, it is assumed that the pressure of the permeate fluid exhaust port 913 of the separation part 91 is −100 kPaG. In the separation system 9d of Comparative Example 4, it is assumed that the pressure of the permeate fluid exhaust port 913 of the first separation part 91 is 0 kPaG, the pressure of the fluid supply port 921 of the second separation part 92 is 200 kPaG, and the pressure of the permeate fluid exhaust port 923 of the second separation part 92 is 0 kPaG.
[0099] In the separation test, the CO.sub.2 concentration of the permeate fluid collected by the permeate fluid collection pipe 47 or 97 is evaluated. This is because it becomes important to increase the CO.sub.2 concentration of the permeate fluid in order to extend the range of uses of the permeate fluid. The separation test is performed at 25° C., where the mixed fluid consisting of CO.sub.2 of 15% (mol %, the same applies to the following) and N.sub.2 of 85% is used as the supply fluid. The mixed fluid is generated by mixing a cylinder gas of CO.sub.2 and a cylinder gas of N.sub.2. The flow rate of the supply fluid is 30 Nm.sup.3/h. Further, the test is performed by adjusting the number of separation membrane modules 2 used in each of the separation systems 4 and 9a to 9d (in other words, by adjusting the membrane surface area) so that the CO.sub.2 collection rate of the permeate fluid to be collected by the permeate fluid collection pipe 47 or 97 may be 30%. Furthermore, the CO.sub.2 collection rate is a percent obtained by dividing the amount of CO.sub.2 in the permeate fluid in the permeate fluid collection pipe 47 or 97 by the amount of CO.sub.2 in the supply fluid ((the amount of CO.sub.2 in the permeate fluid/the amount of CO.sub.2 in the supply fluid)×100). Table 1 shows a result of the separation test.
TABLE-US-00001 TABLE 1 Membrane Permeate CO.sub.2 Performance CO.sub.2 Collection CO.sub.2/N.sub.2 Concentration Rate Structure of Separation System Perm. Ratio [%] [%] Comparative 1 Stage Pressure Rising on Supply Side 27 66 30 Example 1 Comparative 1 Stage Pressure Rising on Supply Side 27 70 30 Example 2 Permeate Fluid Recycle Comparative 1 Stage Pressure Rising on Supply Side 27 80 30 Example 3 Pressure Reduction on Permeate Side Comparative 2 Stages First Separation Part: Pressure 27 90 30 Example 4 Rising on Supply Side Second Separation Part: Pressure Rising on Supply Side Example 2 Stages First Separation Part: Pressure 27 96 30 Rising on Supply Side Second Separation Part: Pressure Reduction on Permeate Side Reference 1 Stage Pressure Rising on Supply Side 1013 96 30 Example
[0100] In the separation system 9a of Comparative Example 1, the CO.sub.2 concentration of the permeate fluid in the permeate fluid collection pipe 97 is 66% and sufficient CO.sub.2 concentration is not obtained. In the separation system 9b of Comparative Example 2, the CO.sub.2 concentration of the permeate fluid is slightly increased (up to 70%) by returning half of the permeate fluid in the permeate fluid collection pipe 97 to the supply pipe 93, but sufficient CO.sub.2 concentration is not still obtained. In the separation system 9c of Comparative Example 3, the CO.sub.2 concentration of the permeate fluid is increased up to 80% by raising the pressure on the supply side of the separation part 91 and reducing the pressure on the permeate side thereof, but this is not sufficient. In the separation system 9d of Comparative Example 4, the CO.sub.2 concentration of the permeate fluid is increased up to 90% by raising the pressure on the supply side of the first separation part 91 and also raising the pressure on the supply side of the second separation part 92, but the two compressors 931 and 942 are needed. Since the compressor is expensive, the manufacturing cost of the separation system 9d increases.
[0101] In contrast to this, in the separation system 4 of Example, the CO.sub.2 concentration of the permeate fluid is significantly increased (up to 96%) by raising the pressure on the supply side of the first separation part 41 and reducing the pressure on the permeate side of the second separation part 42, and the separation accuracy can be improved. Since the number of expensive compressors (supply fluid pressure rising parts 431) to be needed is one, it is possible to suppress an increase in the manufacturing cost of the separation system 4. In comparison between the separation system 4 of Example and the separation system 9d of Comparative Example 4, in the separation system 9d of Comparative Example 4, it is necessary to raise the pressure of all the permeate fluids which have permeated the first separation part 91. On the other hand, in the separation system 4 of Example, since the pressure of only the second permeate fluid which has permeated the second separation part 42 among the first permeate fluid which has permeated the first separation part 41 is reduced, it is possible to reduce the consumption energy as compared with that in the separation system 9d of Comparative Example 4.
[0102] Like in the separation system 9a of Comparative Example 1, in order to increase the CO.sub.2 concentration on the permeate side up to 96% in the case of raising the pressure on the supply side of the separation part, according to calculations, a separation membrane having a permeance ratio of CO.sub.2/N.sub.2 of 1000 or more is needed. In Table 1, the permeance ratio and the like in this case are shown as Reference Example. In contrast to this, in the separation system 4 of Example, by using the separation membrane having a permeance ratio of CO.sub.2/N.sub.2 which is sufficiently lower than that of the separation membrane in Reference Example, it is possible to concentrate the CO.sub.2 concentration of the permeate fluid to 96%.
[0103] As described above, the separation system 4 includes the first separation part 41 and the second separation part 42 each have the separation membrane (the zeolite membrane 12 in the above-described exemplary case). The intermediate connecting part 44 connects the permeate fluid exhaust port 413 of the first separation part 41 and the fluid supply port 421 of the second separation part 42 to each other. The supply pipe 43 is connected to the fluid supply port 411 of the first separation part 41, and the mixed fluid is thereby supplied at a pressure higher than the atmospheric pressure. To the permeate fluid exhaust port 423 of the second separation part 42, connected is the pressure reducing part 471 for reducing the pressure inside the permeate fluid exhaust port 423 to a pressure lower than the atmospheric pressure. In the separation system 4, the pressure inside the intermediate connecting part 44 is lower than the pressure inside the supply pipe 43 and is not lower than the atmospheric pressure. In the above-described separation system 4, it is possible to improve the separation accuracy by using a simple structure capable of suppressing the consumption energy. Further, since the intermediate connecting part 44 is not provided with any expensive component such as a compressor, a vacuum pump, or the like, it is possible to reduce the manufacturing cost of the separation system 4.
[0104] Herein, like in the separation system of FIG. 2 in Japanese Patent Application Laid Open Gazette No. 2008-137847 (the above-described Document 4), assumed is a separation system of one other Comparative Example in which each of the first separation part 91 and the second separation part 92 is provided with a compressor on the supply side and a vacuum pump on the permeate side.
[0105] As shown in
[0106] In the separation system 9e, it is premised on using a polymer membrane (organic membrane) as the separation membrane. The polymer membrane has a permeance ratio lower than that of the zeolite membrane and a permeance of the permeate fluid which is lower than that of the zeolite membrane. Therefore, in order to both improve the separation accuracy and increase the permeance of the permeate fluid, it is necessary to set a large pressure difference for each of these separation parts by providing the compressor and the vacuum pump on the upstream side and the downstream side of each of the separation parts, respectively.
[0107] On the other hand, in each of the separation parts 41 and 42 of the separation system 4, preferably a separation membrane containing an inorganic material such as a zeolite membrane, a carbon membrane, a silica membrane, or the like is used, or more preferably the zeolite membrane 12 is used as the separation membrane. Such a separation membrane has a permeance ratio higher than that of the polymer membrane and a permeance of the permeate fluid which is higher than that of the polymer membrane. Therefore, it is easily possible to both improve the separation accuracy and increase the permeance of the permeate fluid without setting a large pressure difference for each separation part 41 or 42.
[0108] Depending on the design of the separation system 4, different types of separation membranes may be provided in the first separation part 41 and the second separation part 42. Preferably, the separation membrane of the first separation part 41 and/or the separation membrane of the second separation part 42 contain an inorganic material. More preferably, the separation membrane of the first separation part 41 and/or the separation membrane of the second separation part 42 are each the zeolite membrane 12. In a case where it is not necessary to increase the permeance of the permeate fluid or the like case, in the separation system 4, the polymer membrane (organic membrane) may be used. As the separation membrane, not only a membrane using molecular sieving but also a facilitated transport membrane may be used. In the separation system 4, even in a case of using a separation membrane having not high separation performance, such as the polymer membrane or the like, it is possible to attempt improvement of the separation accuracy.
[0109] In the case where the zeolite membrane 12 is used as the separation membrane, it is preferable that the mixed fluid should include a fluid having a molecular size smaller than the pore diameter of the zeolite forming the zeolite membrane 12 (CO.sub.2 gas in the above-described exemplary case) and a fluid having a molecular size larger than the pore diameter thereof (N.sub.2 gas in the above-described exemplary case). It is thereby possible to more reliably improve the separation accuracy.
[0110]
[0111] The fluid storage part 441 is, for example, a buffer tank or the like, and can adjust a variation of the flow rate of the first permeate fluid and stabilize the performance of the second separation part 42. In the separation system 4 of
[0112] Herein, it can be thought that the intermediate connecting part 44 is provided with a compressor and the pressure of the first permeate fluid is thereby significantly raised, to thereby stabilize the performance of the second separation part 42. Since the compressor is expensive and the consumption energy is large, however, the manufacturing cost and the running cost of the separation system disadvantageously increase. Further, in the case where the intermediate connecting part 44 is provided with the compressor, depending on the temperature of the first permeate fluid which is increased due to pressure rising by the compressor, there is a possibility that an effect may be produced on the separation performance of the zeolite membrane 12 of the second separation part 42.
[0113] In contrast to this, in the separation system 4 of
[0114]
[0115] The thermal insulation material 481 is, for example, a fibrous thermal insulation material such as glass wool or the like or a foam thermal insulation material such as urethane foam or the like and suppresses a decrease in the temperature of the supply fluid supplied to the first separation part 41 (herein, the mixed gas) and that of the first permeate fluid exhausted from the first separation part 41. The thermal insulation material 481 is a condensation prevention part for keeping warm a gas flowing in the path from the supply pipe 43 to the second separation part 42, to thereby prevent condensation of the gas. The condensation prevention part can prevent a decrease in the permeability of the zeolite membrane 12 (particularly, the zeolite membrane 12 of the second separation part 42) due to condensation of the gas.
[0116] The thermal insulation material 481 does not necessarily need to cover both the supply pipe 43 and the intermediate connecting part 44, and has only to be provided at a predetermined position on the path from the supply pipe 43 to the separation membrane of the second separation part 42 (the zeolite membrane 12 in the above-described exemplary case). Further, the condensation prevention part may include a heating part, and also in this case, the heating part is provided at a predetermined position on the path from the supply pipe 43 to the separation membrane of the second separation part 42. In
[0117]
[0118] The preprocessing part 480 is, for example, a filter, a washing tower, an absorption tower, an adsorption tower, a condenser, or the like, and removes at least part of a predetermined component from the mixed fluid flowing from the supply source of the mixed fluid toward the first separation part 41. The component to be removed is, for example, a component damaging the separation membrane (herein, the zeolite membrane 12) included in each of the separation parts 41 and 42 or a component affecting the permeability of the separation membrane, specifically, a solid content, a fine droplet, a condensed component, a slight amount of gas component, or the like. Further, the component to be removed may be the high permeability fluid or the low permeability fluid in the first separation part 41 and/or the second separation part 42. In the exemplary case shown in
[0119] Thus, in the separation system 4 of
[0120]
[0121] The fluid analysis part 473 measures a component composition of the second permeate fluid exhausted from the permeate fluid exhaust port 423 of the second separation part 42. The pressure adjustment part 472 is, for example, a vacuum regulator or the like and adjusts the pressure inside the permeate fluid exhaust port 423 of the second separation part 42. Actually, the fluid analysis part 473 and the pressure adjustment part 472 are electrically connected to a control part 40, and a measurement result of the fluid analysis part 473 is outputted to the control part 40. To the control part 40, for example, a target range of the CO.sub.2 concentration of the second permeate fluid is set in advance, and when the CO.sub.2 concentration indicated by the measurement result of the fluid analysis part 473 is lower than the target range, the control part 40 controls the pressure adjustment part 472 to cause the pressure inside the permeate fluid exhaust port 423 to be lower than a current pressure. Further, when the CO.sub.2 concentration indicated by the measurement result of the fluid analysis part 473 is higher than the target range, the control part 40 controls the pressure adjustment part 472 to cause the pressure inside the permeate fluid exhaust port 423 to be higher than the current pressure. Furthermore, the fluid analysis part 473 may be provided in the second non-permeate fluid collection pipe 46. Further, the pressure adjustment part 472 may be provided in the second non-permeate fluid collection pipe 46 and may be, for example, a back pressure valve or the like.
[0122] In the separation system 4 of
[0123] Thus, in the pressure adjustment part 472, the pressure inside the permeate fluid exhaust port 423 of the second separation part 42 is adjusted on the basis of the flow rate and/or the component composition of the second permeate fluid or the second non-permeate fluid. It thereby becomes easily possible to cause the flow rate of the fluid exhausted from the permeate fluid collection pipe 47 and/or the concentration of the predetermined component (CO.sub.2 in the above-described exemplary case) of the fluid to become substantially constant within the target range.
[0124]
[0125] In the separation system 4 of
[0126] In the separation system 4 of
[0127]
[0128] The energy conversion part 484 is, for example, a turbine or the like, and converts pressure energy of the first non-permeate fluid flowing in the first non-permeate fluid collection pipe 45 into different energy such as electrical energy, mechanical energy, or the like. The energy obtained by the energy conversion part 484 may be used by the supply fluid pressure rising part 431, the pressure reducing part 471, or the like. As described earlier, the first non-permeate fluid exhausted from the non-permeate fluid exhaust port 412 of the first separation part 41 has substantially the same pressure as that of the supply fluid whose pressure is raised by the supply fluid pressure rising part 431. As shown in
[0129]
[0130] The exhaust fluid pressure rising part 485 is, for example, a compressor or the like, and raises a pressure of the second non-permeate fluid flowing in the second non-permeate fluid collection pipe 46. As described earlier, the second non-permeate fluid exhausted from the non-permeate fluid exhaust port 422 of the second separation part 42 has a pressure lower than that of the first non-permeate fluid exhausted from the non-permeate fluid exhaust port 412 of the first separation part 41. Therefore, the exhaust fluid pressure rising part 485 raises the pressure of the second non-permeate fluid and the second non-permeate fluid is mixed with the first non-permeate fluid, and it is thereby possible to obtain a large amount of high-pressure non-permeate fluid.
[0131] In the purification of the biogas having a main component of CH.sub.4 and CO.sub.2, it is necessary to increase the CH.sub.4 concentration by removing CO.sub.2. As described earlier, in the separation system 4, the CO.sub.2 concentration in the permeate fluid (second permeate fluid) collected by the permeate fluid collection pipe 47 becomes high. Therefore, in the case where the biogas having a main component of CH.sub.4 and CO.sub.2 is used as the supply fluid, the CH.sub.4 concentration becomes high in the non-permeate fluid collected by the first non-permeate fluid collection pipe 45 and the second non-permeate fluid collection pipe 46. In the separation system 4 of
[0132] In the above-described separation system 4, various modifications can be made.
[0133] In the separation system 4, three or more stages of separation parts may be arranged. In this case, the separation part other than the first or second separation part 41 or 42 is arranged, for example, on an upstream side of the supply pipe 43.
[0134] In the first separation part 41, the plurality of separation membrane modules 2 may be connected in parallel. In this case, in M separation membrane modules 2 (M is an integer not smaller than 2) connected in parallel to one another, a group of M supply ports 221 serve as the fluid supply port 411, a group of M first exhaust ports 222 serve as the non-permeate fluid exhaust port 412, and a group of M second exhaust ports 223 serve as the permeate fluid exhaust port 413. The same applies to the second separation part 42.
[0135] In the intermediate connecting part 44, it is not necessary that all the first permeate fluid exhausted from the permeate fluid exhaust port 413 of the first separation part 41 is supplied to the fluid supply port 421 of the second separation part 42, and depending on the design of the separation system 4, only part of the first permeate fluid may be supplied to the fluid supply port 421. In this case, the first permeate fluid which is not supplied to the fluid supply port 421 may be returned to an upstream side of the supply fluid pressure rising part 431 of the supply pipe 43.
[0136] It is not necessary that the pressure inside the intermediate connecting part 44 (i.e., the pressure of the first permeate fluid) is the substantially atmospheric pressure, and the pressure inside the intermediate connecting part 44 may be a pressure which is sufficiently higher than the atmospheric pressure only if the pressure is lower than the pressure of the supply fluid.
[0137] Though part of the fluid supplied to the second separation part 42 permeates the zeolite membrane 12 and is led to the permeate side (permeate fluid exhaust port 423) by the pressure reducing operation of the pressure reducing part 471 in the above-described separation system 4, instead of the pressure reducing part 471, by carrying a sweep gas to the permeate side of the second separation part 42, it is also possible to construct the separation system of Reference Example which leads part of the fluid supplied to the second separation part 42 to the permeate side.
[0138] The maximum number of membered rings of the zeolite forming the zeolite membrane 12 may be any number other than 8. In the separation membrane complex 1, as described above, the zeolite membrane 12 may be formed of any one of various types of zeolites.
[0139] The zeolite membrane complex 1 may further include a function layer or a protective layer laminated on the zeolite membrane 12, additionally to the support 11 and the zeolite membrane 12. Such a function layer or a protective layer may be an inorganic membrane such as a zeolite membrane, a silica membrane, a carbon membrane, or the like or an organic membrane such as a polyimide membrane, a silicone membrane, or the like. Further, a substance that is easy to adsorb specific molecules such as CO.sub.2 or the like may be added to the function layer or the protective layer laminated on the zeolite membrane 12.
[0140] In the first separation part 41 and/or the second separation part 42, the separation membrane module 2 may be a membrane reactor including a catalyst for further promoting a chemical reaction.
[0141] In the separation membrane complex 1, instead of the zeolite membrane 12, a separation membrane (for example, the above-described inorganic membrane or organic membrane) other than the zeolite membrane 12 may be formed on the support 11.
[0142] Though the case has been described where one type of high permeability fluid (e.g., CO.sub.2) is concentrated and extracted as the second permeate fluid in the above-discussed preferred embodiment, in a case where the mixed fluid contains three or more types of components, two or more types of high permeability fluids may be concentrated and extracted. In other words, in the separation system 4, at least one type of high permeability fluid may be concentrated and extracted. Further, as described earlier, the separation system 4 may be used for the purpose of concentrating at least one type of low permeability fluid.
[0143] In the above-discussed preferred embodiment, though separation of gases (including vapors) is performed in the separation system 4, there may be a case where the supply fluid is a mixed liquid containing a plurality of types of liquids and liquid separation or pervaporation is performed.
[0144] In the above-described separation system 4, any substances other than the substances exemplarily shown in the above description may be separated from the mixed fluid.
[0145] The configurations in the above-discussed preferred embodiment and variations may be combined as appropriate only if those do not conflict with one another.
[0146] While the invention has been shown and described in detail, the foregoing description is in all aspects illustrative and not restrictive. It is therefore understood that numerous modifications and variations can be devised without departing from the scope of the invention.
INDUSTRIAL APPLICABILITY
[0147] The separation system of the present invention can be used for separation of various substances in various fields.
REFERENCE SIGNS LIST
[0148] 4 Separation system [0149] 12 Zeolite membrane [0150] 41 First separation part [0151] 42 Second separation part [0152] 43 Supply pipe [0153] 44 Intermediate connecting part [0154] 411, 421 Fluid supply port [0155] 412, 422 Non-permeate fluid exhaust port [0156] 413, 423 Permeate fluid exhaust port [0157] 441 Fluid storage part [0158] 471 Pressure reducing part [0159] 472 Pressure adjustment part [0160] 480 Preprocessing part [0161] 481 Thermal insulation material [0162] 481a Heating part [0163] 482, 483 Return pipe [0164] 484 Energy conversion part [0165] 485 Exhaust fluid pressure rising part