Patent Application
20120228213
The present invention relates to a separation membrane unit wherein a feed is filtrated to generate a permeate, and a separation membrane element provided with this unit.
As manners of filtrating feed water (feed) , such as waste water or seawater, by use of a reverse osmosis process or some other process, the total filtration manner and the cross flow filtration manner are generally known. The total filtration manner is a manner of filtrating the total amount of supplied water. For example, the feed water is supplied to a separation membrane in a direction perpendicular to the membrane. The cross flow filtering manner is a manner of supplying feed water to a separation membrane in a direction parallel to the membrane, filtrating a portion of the feed water through the separation membrane, and optionally circulating the feed water simultaneously with the filtration, thereby making it possible to filtrate the feed water while the clogging of the separation membrane is restrained.
As an example of a separation membrane unit usable when feed water is filtrated by the cross flow filtrating method, known is a separation membrane unit having a separation membrane folded plural times into the form of pleats in such a manner that folds are formed to be arranged alternately at one side face and an opposite side face of the unit, as disclosed in Patent Document 1 listed up below. According to the structure disclosed in Patent Document 1, the separation membrane, which is a single membrane, is folded plural time into the form of pleats, and between regions of the separation membrane that are made adjacent to each other by the folding, a channel member (net-like spacer) for making a channel is arranged.
In the separation membrane, a separation active layer (skin layer) is formed on, for example, one surface of a sheet-form porous substrate. Feed water is supplied to this separation active layer side to be passed through the separation active layer and the porous substrate, whereby permeated water can be obtained.
Patent Document 1: JP-A-S54-17378
When a separation membrane wherein a separation active layer is formed on one surface of a porous substrate is folded plural times into the form of pleats as described above, the separation active layer comes to be exposed to either one side face or the opposite side face at which folds are formed. Thus, when the separation membrane unit is handled, the separation active layer may be damaged. According to Patent Document 1, the outside of the separation membrane folded into the pleat form is covered with a protecting layer (plastic film) , so that the separation active layer can be prevented from being damaged. However, this technique has a problem that the layout of this protecting layer makes the structure complicated so that costs for the production increase.
Moreover, when a separation membrane wherein a separation active layer is formed only on one of the two surfaces of a porous substrate is folded plural times into the form of pleats as described above, the separation membrane unit has an asymmetric structure. In this case, bias current is easily caused, so that the unit may not satisfactorily attain filtration in the cross flow filtration manner.
In light of the situation, the present invention has been made. An object thereof is to provide a separation membrane unit which has a simple structure and can prevent its separation active layer from being damaged, and a separation membrane element having this unit. Another object of the invention is to provide a separation membrane unit which can satisfactorily attain filtration in the cross flow filtration manner, and a separation membrane element having this unit.
A separation membrane unit of the present invention is a separation membrane unit for filtrating a feed to generate a permeate, and comprises two separation membranes each having a separation active layer formed on one surface of a porous substrate in a sheet form, the two separation membranes being superposed over each other while the separation active layers face each other, wherein the two separation membranes are folded plural times into the form of pleats, whereby forming folds alternately at one side face and an opposite side face.
According to this structure, the two separation membranes, in each of which the separation active layer is formed on the one surface of the sheet-form porous substrate, are superposed over each other while the separation active layers face each other; thus, the separation active layers are not exposed to the one side face nor the opposite side face where the folds are formed. Thus, according to this simple structure, the separation active layers can be prevented from being damaged.
Moreover, the two separation membranes, which are superposed over each other, while the separation active layers face each other, have a symmetric structure. Although the two separation membranes are in the state of being folded plural times into the pleat form, the two separation membranes have this symmetric structure. Accordingly, as compared with an asymmetric structure wherein a single separation membrane having a surface on which a separation active layer is formed is folded plural times into the form of pleats, bias current is less caused so that the feed can be more satisfactorily filtrated in the cross flow filtration manner.
The separation membrane unit of the present invention is characterized in that between the two separation membranes a supply side channel is made as a channel for supplying the feed.
According to this structure, by supplying the feed into the supply side channel made between the two separation membranes, the feed can be filtrated through the two separation membranes to produce the permeate outside the two separation membranes.
The separation membrane unit of the present invention is characterized by comprising a supply side channel member for making the supply side channel, the supply side channel member being arranged between the two separation membranes.
According to this structure, the supply side channel can be certainly made by means of the supply side channel member laid between the two separation membranes. Thus, the feed can be satisfactorily filtrated at the folds and others also.
The separation membrane unit of the present invention is characterized in that a permeate side channel is made as a channel for the permeate at each of the one side face and the opposite side face of the two separation membranes.
According to this structure, the permeate produced by the filtration of the feed through the two separation membranes can be efficiently transported through the permeate side channel formed at each of the one side face and the opposite side face of the two separation membranes. In the case of symmetrically arranging, for the two separation membranes folded particularly to give a symmetric structure, the permeate side channels at the one side face and the opposite side face thereof, the separation membrane unit has a symmetric structure as a whole. As a result, the feed can be more stably filtrated. In a case where the separation membrane unit is held inside, for example, an exterior member having a cylindrical cross section, or in other cases, the permeate side channel can be laid in a space which is made at each of the one side face and the opposite side face of the two separation membranes, and which is positioned between each of these side faces and the internal circumferential surface of the exterior member: therefore, spaces where the two separation membranes are to be set can be certainly gained at a maximum level. Thus, the feed can be more efficiently filtrated.
The separation membrane unit of the present invention is preferable in the case where the separation active layer comprises a polyamide type resin.
A separation membrane element of the present invention is characterized by comprising the above separation membrane unit and an exterior member that covers an outside of the separation membrane unit.
The two separation membranes 1 have structures identical with each other, and each of the membranes 1 has a sheet-form porous substrate 3, and a separation active layer (skin layer) 4 formed on one of the two surfaces of the porous substrate 3. The separation membrane 1 may contain not only the porous substrate 3 and the separation active layer 4 but also some other layer. These two separation membranes 1 are superposed onto both sides of the channel member 2, respectively, to sandwich the member 2 therebetween in such a manner that their separation active layers 4 face each other. In this manner, the two separation membranes 1 and the channel member 2 are stacked onto each other in the state that the separation active layers 4 of the separation membranes 1 contact opposed surfaces of the channel member 2, respectively.
The porous substrates 3 may each be made of, for example, polysulfone, polyethersulfone, PVDF, polyethylene, polyimide, or epoxy. The porous substrate 3 may have a structure reinforced with a reinforcing material, such as nonwoven fabric, woven fabric, knitting or a net, used together with such a material. The thickness of the porous substrate 3 is from about 20 to 1000 μm. The separation active layers 4 are each a dense and nonporous thin film, and the forming material thereof is not particularly limited. Examples thereof include cellulose acetate, ethylcellulose, polyether, polyester, polyamide, and silicon. The channel member 2 may be made of, for example, knitting or a net.
In the invention, the separation active layers 4 are each preferably a separation active layer 4 containing a polyamide type resin obtained by polymerizing a polyfunctional amine component and a polyfunctional acid halide component.
The polyfunctional amine component is a polyfunctional amine having two or more reactive amine groups, and examples thereof include aromatic, aliphatic and alicyclic polyfunctional amines.
Examples of the aromatic polyfunctional amine include m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2,6-diaminotoluene, N,N′-dimethyl-m-phenylenediamine, 2,4-diaminoanisole, amidol, and xylylenediamine.
Examples of the aliphatic polyfunctional amine include ethylenediamine, propylenediamine, tris(2-aminoethyl)amine, and n-phenyl-ethylenediamine.
Examples of the alicyclic polyfunctional amine include 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, and 4-aminomethylpiperazine.
These polyfunctional amines may be used alone or in a combination of two or more thereof. In order to yield the separation active layers 4 that have a high salt-rejection performance, it is preferred to use an aromatic polyfunctional amine.
The polyfunctional acid halide component is a polyfunctional acid halide having two or more reactive carbonyl groups.
Examples of the polyfunctional acid halide include aromatic, aliphatic, and alicyclic polyfunctional acid halides.
Examples of the aromatic polyfunctional acid halide include trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyldicarboxylic acid dichloride, naphthalenedicarboxylic acid dichloride, benzenetrisulfonic acid trichloride, benzenedisulfonic acid dichloride, and chlorosulfonylbenzenedicarboxylic acid dichloride.
Examples of the aliphatic polyfunctional acid halide include propanedicarboxylic acid dichloride, butanedicarboxylic acid dichloride, pentanedicarboxylic acid dichloride, propanetricarboxylic acid trichloride, butanetricarboxylic acid trichloride, pentanetricarboxylic acid trichloride, any glutaryl halide, and any adipoyl halide.
Examples of the alicyclic polyfunctional acid halide include cyclopropanetricarboxylic acid trichloride, cyclobutanetetracarboxylic acid tetrachloride, cyclopentanetricarboxylic acid trichloride, cyclopentanetetracarboxylic acid tetrachloride, cyclohexanetricarboxylic acid trichloride, tetrahydrofurantetracarboxylic acid tetrachloride, cyclopentanedicarboxylic acid dichloride, cyclobutanedicarboxylic acid dichloride, cyclohexanedicarboxylic acid dichloride, and tetrahydrofurandicarboxylic acid dichloride.
These polyfunctional acid halides may be used alone or in a combination of two or more thereof. In order to yield the separation active layers 4 that have a high salt-rejection performance, it is preferred to use an aromatic polyfunctional acid halide. It is also preferred to use plural polyfunctional acid halide components, and use, as at least one of the components, a trivalent or higher-multivalent polyfunctional acid halide to form a crosslinked structure.
In order to improve performances of the separation active layers 4 that contain a polyamide type resin, it is allowable to copolymerize therewith, for example, a polymer such as polyvinyl alcohol, polyvinyl pyrrolidone or polyacrylic acid, or a polyhydric alcohol such as sorbitol or glycerin.
The method for forming the polyamide-type-resin-containing separation active layers 4 onto the respective surfaces of the porous substrates 3 is not particularly limited, and may be any known method. Examples thereof include an interfacial condensation method, a phase separation method, and a thin-film painting method. The interfacial condensation method is specifically a method of bringing an aqueous amine solution containing a polyfunctional amine component into contact with an organic solution containing a polyfunctional acid halide component to cause interfacial polymerization, thereby forming the separation active layers 4, and then putting the separation active layers 4 onto the porous substrates 3, respectively, or a method of causing the interfacial polymerization on the porous substrates 3, thereby forming the separation active layers 4 of a polyamide type resin directly onto the porous substrates 3, respectively. Details of conditions for the interfacial condensation method, and others are described in JP-A-S58 (or 1983)-24303, JP-A-H1 (or 1989)-180208, and others. These known techniques may be appropriately adopted.
In the invention, preferred is the method of forming aqueous solution coated layers made of an aqueous amine solution containing a polyfunctional amine component onto the porous substrates 3, respectively, and next bringing the aqueous solution coated layers into contact with an organic solution containing a polyfunctional acid halide component to cause interfacial polymerization, thereby forming the separation active layers 4.
In the interfacial polymerization method, the concentration of the polyfunctional amine component in the aqueous amine solution is not particularly limited, and is preferably from 0.1 to 5% by weight, more preferably from 1 to 4% by weight. If the concentration of the polyfunctional amine component is too low, defects such as pinholes are easily generated in the separation active layers 4, and further the layers 4 tend to be easily deteriorated in salt-rejection performance. On the other hand, if the concentration of the polyfunctional amine component is too high, the separation active layers become too large in film thickness to turn large in resistance against permeate, so that the present separation membrane unit tends to be declined in permeate flux.
The concentration of the polyfunctional acid halide component in the organic solution is not particularly limited, and is preferably from 0.01 to 5% by weight, more preferably from 0.05 to 3% by weight. If the concentration of the polyfunctional acid halide component is too low, an unreacted fragment of the polyfunctional amine component remains easily or defects such as pinholes are easily generated in the separation active layers 4, so that the layers 4 tend to be easily deteriorated in salt refection performance. On the other hand, if the concentration of the polyfunctional acid halide component is too high, an unreacted fragment of the polyfunctional acid halide component remains easily or the separation active layers become too large in film thickness to turn large in resistance against permeate, so that the present separation membrane unit tends to be declined in permeate flux.
In the above-mentioned organic solution, the used organic solvent is not particularly limited as far as the solvent is a solvent which is low in solubility in water, does not deteriorate the porous substrates 3, and dissolves the polyfunctional acid halide component. Examples thereof include saturated hydrocarbons, such as cyclohexane, heptane, octane, and nonane; and halogen-substituted hydrocarbons, such as 1,1,2-trichlorotrifluoroethane. The organic solvent is preferably a saturated hydrocarbon having a boiling point of 300° C. or lower, and is more preferably one having a boiling point of 200° C. or lower.
Various additives may be added to the aqueous amine solution or the organic solution to make the formation of the films easy or improve the resultant composite semipermeable membranes in performance. Examples of the additives include surfactants such as sodium dodecylbenzenesulfonate, sodium dodecylsulfate and sodium laurylsulfate, sodium hydroxide, which removes halogenated hydrogen generated by the polymerization, basic compounds such as trisodium phosphate and triethylamine, an acylated catalyst, and compounds having a solubility parameter of 8 to 14 (cal/cm3)1/2 and disclosed in JP-A-H8(or 1996)-224452.
The thickness of each of the separation active layers 4 formed on the porous substrates 3, respectively, is not particularly limited, and is usually from about 0.05 to 2 μm, preferably from 0.1 to 1 μm.
In the present embodiment, the two separation membranes 1 and the channel member 2, which are superposed on each other as described above, are used in the state of being folded plural times into the form of pleats (bellows). Thus, the two separation membranes 1, and the channel member 2 each preferably have flexibility, and preferably have such a crack resistance that when the superposed members are subjected to 180°-bending three or more times, the members are not cracked.
In the two separation membranes 1, and the channel member 2 folded plural times into the pleat form, the folds are adjacent to each other to be stacked onto each other into a specified direction A. The individual folds 5 are extended to a direction B perpendicular to the stack direction A in the separation membranes 1 and the channel member 2. The adjacent folds out of the folds 5 are arranged in the stack direction A.
In this separation membrane unit 10, the cross flow filtration manner is adopted wherein feed water such as waste water or seawater is supplied to the separation membranes 1 along the direction B parallel to the separation membranes 1. The feed water is supplied from an end of the two separation membranes 1 and the channel member 2 folded plural times into the pleat form, this end being an end thereof at the upstream side of the supply direction B. The supplied feed water passes through a channel, for the feed water (supply side channel), that is made by means of the channel member 2 between the two separation membranes 1, so as to advance between the two separation membranes 1 and flow in the direction (supply direction B) parallel to the separation membranes 1. In this process, the feed water is filtrated through the separation membranes 1. At this time, the channel member 2 functions as a supply side channel member for forming the supply side channel, and this supply side channel member makes it possible to form the supply side channel certainly. For this reason, at the folds 5 and other regions also, the feed water can be satisfactorily filtrated.
At both sides of a direction (C) perpendicular not only to the stack direction A in the two separation membranes 1 and the channel member 2 folded plural times in the pleat form, but also to the supply direction B (at the upper and the lower in
The permeated water, which is generated by the matter that the feed water flowing in the supply direction B between the two separation membranes 1 is filtrated through the separation membranes 1, flows to the outside of the two separation membranes 1, more specifically, flows out to the upper side and the lower side of
In this example, sealing regions 8 are formed between the two separation membranes 1 and the channel member 2 folded plural times in the pleat form, and the water collecting pipe 6 laid at the one side face thereof, and formed between the same folded members, and the water collecting pipe 6 at the opposite side face, respectively. The sealing regions 8 are regions for separating the feed water passing between the two separation membranes 1 from the permeated water generated outside the two separation membranes 1, and only the permeated water passes through the sealing regions 8 to be introduced into the water collecting pipes 6. This water collecting mechanism may be formed in the sealing regions 8, or may be formed separately from the sealing regions 8.
In the embodiment, the two separation membranes 1, in each of which one of the separation active layers 4 is formed on one of the two surfaces of one of the sheet-form porous substrates 3, are superposed over each other to cause the separation active layers 4 to face each other; thus, the separation active layers 4 are not exposed to the one side face, nor the opposite side face (to the upper nor the lower in
Moreover, the two separation membranes 1, which are superposed over each other to cause the separation active layers 4 to face each other, have a symmetric structure. Although the two separation membranes 1 are in the state of being folded plural times into the pleat form as illustrated in
Additionally, the permeated water generated by filtrating the feed water through the two separation membranes 1 can be efficiently transported through the water collecting pipes 6 laid at the one side face of the two separation membranes 1 and at the opposite side face (at the upper and the lower in
In the above-mentioned embodiment, the description has been made about the structure wherein the channel member 2 is sandwiched between the two separation membranes 1. However, the channel member 2 maybe omitted as far as a channel for the feed water can be certainly gained between the two separation membranes 1. As attained in an example illustrated in, for example,
In this example, the sealing regions 8 are laid at the one side face of the two separation membranes 1 and the channel member 2 folded plural times into the pleat form and at the opposite side face, respectively, (the upper and the lower in
In each of the examples in
As illustrated in each of
However, the exterior member 9 is not limited to any member having a circular cross section, and may be an exterior member having a cross section of a different shape, for example, a rectangular shape. The exterior member 9 may be omitted. Even when the exterior member 9 is omitted, the two separation membranes 1 are superposed over each other in the present embodiment to cause the separation active layers 4 to face each other, so that the separation active layers 4 are not naked. As a result, it is not feared that the separation active layers 4 are damaged.
In the above-mentioned embodiments, the description has been made about the cases where the feed is feed water. However, the feed may be not any feed water but any other raw liquid such as raw oil. The feed may be a gas or some other.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2009-258334 | Nov 2009 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2010/060536 | 6/22/2010 | WO | 00 | 5/10/2012 |
