JP2000093957A - Water purifying membrane and method - Google Patents
Water purifying membrane and methodInfo
- Publication number
- JP2000093957A JP2000093957A JP10265074A JP26507498A JP2000093957A JP 2000093957 A JP2000093957 A JP 2000093957A JP 10265074 A JP10265074 A JP 10265074A JP 26507498 A JP26507498 A JP 26507498A JP 2000093957 A JP2000093957 A JP 2000093957A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- water
- org
- matter
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000012528 membrane Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000010457 zeolite Substances 0.000 claims abstract description 58
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims description 21
- 239000005416 organic matter Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 10
- 230000000266 injurious effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 229920000592 inorganic polymer Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 101150091051 cit-1 gene Proteins 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000012690 zeolite precursor Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、浄水膜及び浄水方
法に関し、更に詳しくは、水中の分子サイズの比較的小
さいトリハロメタン等の微量の有機分子を除去する浄水
膜及び浄水方法に関する。特に、人間の体内に直接はい
る飲料、料理用の水の処理に有用である。水中の微量の
有機成分は、人間の体に悪いので除去されることが望ま
れている。The present invention relates to a water purification membrane and a water purification method, and more particularly to a water purification membrane and a water purification method for removing trace amounts of organic molecules such as trihalomethane having a relatively small molecular size in water. In particular, it is useful for the treatment of drinking water and cooking water directly in the human body. It is desired that trace organic components in water be removed because they are bad for the human body.
【０００２】[0002]
【従来の技術】近年、おいしい水、安全な水を作るため
に種々の浄水器が開発されている。水中の微量の有機物
を除去するために活性炭などと水を接触する方法はすで
にしられている。活性炭は確かに、有機物を除去するこ
とは可能であるががその吸着力は強く、吸着できなくな
った後の再生は難しい。再生のためには一度取り出して
熱処理するなど連続的に処理再生を繰り返すことは難し
い。2. Description of the Related Art In recent years, various water purifiers have been developed for producing delicious water and safe water. A method of contacting water with activated carbon or the like in order to remove a trace amount of organic matter in water has already been performed. Activated carbon can certainly remove organic matter, but its adsorptive power is so strong that it is difficult to regenerate it after it can no longer be adsorbed. For regeneration, it is difficult to repeat the process regeneration continuously, such as taking out once and performing heat treatment.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、上記
の従来の技術の欠点を解消しようとするものであり、連
続的に水中の微量有機物を有効に除去する浄水膜及び浄
水方法を提供するものであるSUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned disadvantages of the prior art, and to provide a water purification membrane and a water purification method for continuously and effectively removing trace organic substances in water. To do
【０００４】[0004]
【課題を解決するための手段】本発明は、上記目的を達
成するために下記の構成を有する。The present invention has the following arrangement to achieve the above object.
【０００５】「１％未満の有機物を含む水から有機物を
選択的に透過して除去するゼオライトを含む浄水膜」及
び「１％未満の有機物を含む水と該浄水膜を接触させる
ことを特徴とする浄水方法。」すなわち、本発明者等
は、ゼオライト膜の性質について鋭意検討を重ねた結
果、これらが、水中の非常に低濃度の有機物を選択的に
吸着し透過することを見いだし本発明に到達した。[0005] A "water purification membrane containing zeolite for selectively permeating and removing organic matter from water containing less than 1% of organic matter" and "contacting the water purification membrane with water containing less than 1% of organic matter". That is, the present inventors have conducted intensive studies on the properties of zeolite membranes, and as a result, have found that they selectively adsorb and permeate very low-concentration organic substances in water. Reached.
【０００６】[0006]
【発明の実施の形態】以下に本発明の浄水膜及び浄水方
法について詳述する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The water purification membrane and the water purification method of the present invention will be described below in detail.
【０００７】本発明の浄水膜は、主成分がゼオライトで
ある。特にハイシリカ及び／又は純シリカ質のゼオライ
トであることが好ましい。 ゼオライトとは分子サイズ
の細孔径の細孔を有した結晶性無機酸化物である。本発
明において、ゼオライトとは、結晶性アルミノシリケー
ト、結晶性メタロシリケートを言うが、本発明において
ゼオライトの組成は珪素及び４価の金属とそれ以外の金
属の原子比が２５以上が好ましい。更に好ましくは、５
０以上であり、特に好ましい例は純シリカ質である。純
シリカ質のゼオライトとは、実質的に珪素と酸素だけで
構成されたゼオライトである。４価の金属の例として
は、チタンやゲルマニウムが挙げられ、結晶性チタノシ
リケートは好ましく用いられる。結晶性チタノシリケー
ト中のチタンは４価であり、他の骨格中に金属成分がな
ければ純シリカ質と、同等と思われる。分子サイズと
は、世の中に存在する分子のサイズの範囲であり、一般
的には、２から２０オングストローム程度の範囲を意味
する。結晶性シリケート、結晶性メタロシリケート、結
晶性アルミノシリケートの種類は特に制限が無く、例え
ば、Atlas of Zeolite Structure types(W. M. Meier,
D. H. Olson, Ch. Baerlocher, Zeolites, 17(1/2), 19
96)に掲載されている構造を持つ結晶性無機多孔性物質
が挙げられる。細孔径、細孔構造には特に制限はない
が、細孔径は大きいほどまた細孔構造は多次元ほど好ま
しい。それは吸着容量が大きくなるからである。結晶の
大きさは特に制限なく、小さいものは接触面積が大きく
拡散の点で有利であり、大きいものはより疎水性になり
吸着選択性の点で好ましい。ゼオライトでは、細孔の大
きさをしばしば、酸素ｎ員環という表現を使うが、１０
員環から１４員環が好ましく用いられる。上記したよう
なゼオライトの例としては、ハイシリカMFI型ゼオライ
ト、シリカライト、ハイシリカＹ型ゼオライト、ハイシ
リカベータ型ゼオライト、純シリカベータ型ゼオライ
ト、CIT-1,CIT-5,SSZ-26,SSZ-31,SSZ-33等が挙げられる
が、この例に限られるものではない。[0007] The main component of the water purification membrane of the present invention is zeolite. Particularly, high silica and / or pure siliceous zeolite is preferable. Zeolite is a crystalline inorganic oxide having pores having a pore size of a molecular size. In the present invention, zeolite refers to crystalline aluminosilicate and crystalline metallosilicate. In the present invention, the composition of zeolite is preferably such that the atomic ratio of silicon and a tetravalent metal to other metals is 25 or more. More preferably, 5
It is 0 or more, and a particularly preferred example is pure silica. Pure silica zeolite is a zeolite substantially composed of only silicon and oxygen. Examples of the tetravalent metal include titanium and germanium, and crystalline titanosilicate is preferably used. Titanium in the crystalline titanosilicate is tetravalent, and is considered to be equivalent to pure silica if there is no metal component in the other skeleton. The molecular size is a range of the size of a molecule existing in the world, and generally means a range of about 2 to 20 angstroms. There are no particular restrictions on the types of crystalline silicate, crystalline metallosilicate, and crystalline aluminosilicate, for example, Atlas of Zeolite Structure types (WM Meier,
DH Olson, Ch. Baerlocher, Zeolites, 17 (1/2), 19
96) include crystalline inorganic porous substances having the structure described in (96). There is no particular limitation on the pore diameter and the pore structure, but the larger the pore diameter and the more the multi-dimensional pore structure, the better. This is because the adsorption capacity increases. The size of the crystal is not particularly limited, and a small one has a large contact area and is advantageous in terms of diffusion, and a large one is more hydrophobic and is preferable in terms of adsorption selectivity. In zeolites, the pore size is often referred to as the oxygen n-membered ring.
A membered ring to a 14-membered ring is preferably used. Examples of zeolites as described above, high silica MFI zeolite, silicalite, high silica Y zeolite, high silica beta zeolite, pure silica beta zeolite, CIT-1, CIT-5, SSZ-26, SSZ-31 , SSZ-33 and the like, but are not limited to this example.
【０００８】本発明浄水膜は、上記のようなゼオライト
の多結晶を膜状にしたものである。その形状、形態は特
に制限はないが、できるだけ緻密にした方がよい。膜状
にする方法は、例えば、多孔質支持体にゼオライトをコ
ーティングするかまたは有機及び／又は無機のポリマー
の膜に含有させてコーティングする。勿論、単独の膜で
あっても構わないが、強度の点では、支持体にコーティ
ングした方が好ましい。多孔性の支持体の材質は、特に
限定されないが、金属又は金属酸化物である。耐熱性、
耐薬品性の観点から、金属酸化物が好ましく用いられ
る。金属酸化物としては、特に限定されないが、アルミ
ナ、ジルコニア、シリカ、ムライト等が好ましく用いら
れる。支持体の形状も特に限定されること無く、球状、
平板状、チューブ状、モノリス状、ハニカム状等通常市
販で得られるものが利用できる。支持体に直接ゼオライ
トをコーティングしても良いが、通常はそのコーティン
グ性能を高めるために、支持体上に、中間層を一層以上
設け、その上にゼオライトをコーティングしても良い。
中間層は例えば、比較的粒径の小さい粒子を、支持体に
コーティングし、必要に応じて、乾燥や、焼成を加えて
形成する。中間層には、支持体表面を滑らかにしたり、
支持体の細孔径を小さくしたり、ゼオライト膜相との親
和性を良好にするなどの効果がある。中間層やゼオライ
ト膜は支持体のどちらの面にコーティングされても良
く、両方にコーティングされても良い。支持体がチュー
ブ状、モノリス状、ハニカム状であるときは、内側にコ
ーティングされることが好ましい。The water purification membrane of the present invention is obtained by forming the above-mentioned zeolite polycrystal into a membrane. The shape and form are not particularly limited, but it is better to be as dense as possible. As a method for forming a film, for example, a porous support is coated with zeolite or contained in a film of an organic and / or inorganic polymer for coating. Of course, a single film may be used, but from the viewpoint of strength, it is preferable to coat the support. The material of the porous support is not particularly limited, but is a metal or a metal oxide. Heat-resistant,
From the viewpoint of chemical resistance, metal oxides are preferably used. The metal oxide is not particularly limited, but alumina, zirconia, silica, mullite and the like are preferably used. The shape of the support is also not particularly limited, and is spherical,
A commercially available product such as a flat plate, a tube, a monolith, and a honeycomb can be used. The support may be directly coated with zeolite, but usually, in order to enhance the coating performance, one or more intermediate layers may be provided on the support, and zeolite may be coated thereon.
The intermediate layer is formed, for example, by coating particles having a relatively small particle diameter on a support, and drying or baking the particles as necessary. For the intermediate layer, smooth the surface of the support,
There are effects such as reducing the pore diameter of the support and improving the affinity with the zeolite membrane phase. The intermediate layer or the zeolite membrane may be coated on either side of the support, or may be coated on both sides. When the support is in the form of a tube, a monolith, or a honeycomb, it is preferable to coat the inside of the support.
【０００９】膜状のゼオライトの製造方法は、特に限定
されないが、一般に知られている方法が適用できる。例
えば支持体上に、ゼオライト膜を支持体上にコーティン
グする場合ゼオライトを合成するための前駆体ゲル中
に、支持体をつけて、水熱処理する方法（例：特開昭６
３ー２９１８０９）、支持体に予めゼオライトの種結晶
を、コートしてから前駆体ゲルにつけ水熱処理する方法
（例：特開平７ー１０９１１６）、前駆体ゲルを支持体
表面にコーティングしたあと乾燥し、その後水蒸気で処
理する方法（例：特開平７ー８９７１４）、あるいはハ
イシリカ及び／又は純シリカ質のゼオライトをそのまま
コーティングする方法などの方法（特公平５ー５０３３
１）が適用できる。ゼオライトの種結晶、ゼオライトの
前駆体ゲル、ゼオライト微粒子を支持体にコーティング
する方法は、特に限定されず公知のいかなる方法も適用
できる。例えば、支持体をスラリー中、浸した後、その
まま引き上げる方法、塗布する方法、支持体の片側をス
ラリーに接触させ、もう一方から減圧する方法、支持体
の片側からスラリーを圧力を加えて押し込む方法が考え
られる。ハイシリカ及び／又は純シリカ質のゼオライト
膜のコーティングは２回以上行っても良い。また２回以
上行った方が緻密性の点で好ましい。ゼオライト膜は、
生成した後、水洗、乾燥、焼成等の処理を加えても良
い。ゼオライト膜が形成したかどうかは、薄膜用のＸ線
回折装置を用いて確認できる。The method for producing the film-form zeolite is not particularly limited, but a generally known method can be applied. For example, when a zeolite membrane is coated on a support, a method of subjecting the support to a precursor gel for synthesizing zeolite and subjecting the support to hydrothermal treatment (for example,
3-291809), a method in which a support is coated with a zeolite seed crystal in advance and then applied to a precursor gel and subjected to hydrothermal treatment (eg, JP-A-7-109116). The precursor gel is coated on the support surface and dried. And then a method of treating with steam (for example, JP-A-7-89714) or a method of directly coating high silica and / or pure silica zeolite (Japanese Patent Publication No. 5-5033).
1) is applicable. The method for coating the support with the zeolite seed crystal, the zeolite precursor gel, and the zeolite fine particles is not particularly limited, and any known method can be applied. For example, a method in which a support is immersed in a slurry and then pulled up as it is, a method of applying, a method in which one side of the support is brought into contact with the slurry and the pressure is reduced from the other side, and a method in which the slurry is pressed from one side of the support by applying pressure Can be considered. The coating of the high silica and / or pure siliceous zeolite membrane may be performed twice or more. Further, it is preferable to perform the measurement twice or more in terms of denseness. The zeolite membrane is
After generation, treatments such as washing with water, drying and baking may be added. Whether or not a zeolite membrane has been formed can be confirmed using an X-ray diffractometer for a thin film.
【００１０】ゼオライト膜を無機及び／又は有機のポリ
マーとの複合膜にする場合は、予め公知の方法でゼオラ
イトを作った後その粒子をポリマーと混合しその後製膜
する。方法はこれに限られるものではなくゼオライトが
混入したポリマーができればそれでよい。この場合も、
無機や有機の多孔質支持体上に製膜しても良い。混合さ
せるポリマーの種類は、特に限定されないが例えばシリ
コーンゴム、ポリスルホン系ポリマーなどである。When a zeolite membrane is formed into a composite membrane with an inorganic and / or organic polymer, zeolite is prepared in advance by a known method, the particles are mixed with the polymer, and then a film is formed. The method is not limited to this, but any method can be used as long as a polymer containing zeolite is formed. Again,
A film may be formed on an inorganic or organic porous support. The type of the polymer to be mixed is not particularly limited, and examples thereof include a silicone rubber and a polysulfone-based polymer.
【００１１】上記したゼオライト膜は、場合によって
は、焼成を加える。焼成温度は通常４００〜７００℃で
ある。The above-mentioned zeolite membrane is optionally subjected to calcination. The firing temperature is usually 400 to 700 ° C.
【００１２】本発明のゼオライト膜は、ゼオライトの多
結晶膜であるが、そのゼオライト自体の水の吸着量は、
３重量％以下であることが好ましい。更に好ましくは、
２重量％、特に好ましくは１重量％以下である。その測
定方法は、まず生成したゼオライト膜を削り落とし、石
英バランス式の吸着装置に本ゼオライトを充填し、500
℃で１時間真空下で焼成した後、２５℃で０℃の水の蒸
気圧下におき、その飽和吸着量を、石英製のバネを用い
て、測定する。このような水吸着特性を得るために、ゼ
オライト膜をシランカップリング剤などで疎水化処理を
しても構わない。The zeolite membrane of the present invention is a zeolite polycrystalline membrane. The amount of water absorbed by the zeolite itself is as follows:
It is preferably at most 3% by weight. More preferably,
It is 2% by weight, particularly preferably 1% by weight or less. The measurement method is as follows: first, the generated zeolite membrane is scraped off, and the zeolite is filled in a quartz-balanced adsorption device,
After sintering under vacuum at 1 ° C. for 1 hour, the sample is placed under a vapor pressure of water at 25 ° C. and 0 ° C., and the saturated adsorption amount is measured using a quartz spring. In order to obtain such water adsorption characteristics, the zeolite membrane may be subjected to a hydrophobic treatment with a silane coupling agent or the like.
【００１３】本発明の浄水膜は、１％未満の有機物を含
有する水から有機物を選択的に透過しなければならな
い。この意味は、１％未満の有機物を含む水に本発明の
浄水膜を接触させ、反対側から真空にひいて、透過して
きた蒸気を分析したときに、有機物の濃度が、元の液よ
り高くなることをいう。本発明において、処理する水の
有機物の濃度が１％未満であることは必須である。ゼオ
ライト膜は、非常に細孔が小さいためそれほど多くの透
過量を稼ぐことができない。従って、水中に含まれる微
量の有機物を透過して除去するという用途には非常に適
している。[0013] The water purification membrane of the present invention must selectively permeate organic matter from water containing less than 1% organic matter. This means that when the water purification membrane of the present invention is brought into contact with water containing less than 1% of an organic substance, and a vacuum is applied from the opposite side to analyze the permeated vapor, the concentration of the organic substance is higher than that of the original liquid. It means becoming. In the present invention, it is essential that the concentration of organic matter in the water to be treated is less than 1%. Zeolite membranes cannot gain so much permeation because of their very small pores. Therefore, it is very suitable for the use of permeating and removing a trace amount of organic substances contained in water.
【００１４】本発明は、上記したようなゼオライトを含
む浄水膜と１％未満の有機物を接触させることを特徴と
する浄水方法も含む。具体的には、１％未満の有機物を
含む水とゼオライト膜を接触させる。有機物を透過させ
る方法としては、圧力差を付ける方法、透過してきた有
機物を、蒸発させて除去する方法が考えられる。蒸発さ
せて除去する場合は、水と接触していない側を減圧にす
る方法、キャリアガスを流す方法、加熱する方法などが
考えられる。除去された有機物が何らかの方法で再利用
できる場合は再利用しても良い。The present invention also includes a water purification method characterized by contacting a water purification membrane containing zeolite as described above with an organic substance of less than 1%. Specifically, the zeolite membrane is brought into contact with water containing less than 1% of an organic substance. As a method of permeating an organic substance, a method of applying a pressure difference and a method of evaporating and removing the permeated organic substance are considered. In the case of removing by evaporation, a method of reducing the pressure on the side not in contact with water, a method of flowing a carrier gas, a method of heating, and the like can be considered. If the removed organic matter can be reused by any method, it may be reused.
【００１５】本発明を以下の実施例によりさらに詳細に
説明する。The present invention will be described in more detail with reference to the following examples.
【００１６】[0016]
【実施例】実施例１ ２０ｇのテトラプロピルアンモニウムハイドロオキサイ
ド（TPAOH）の２０％水溶液（東京化成２０〜２５％水
溶液）に０．２８ｇのNaOH（片山化学試薬１級）を添加
して攪拌した。それに５ｇのヒュームドシリカ（Aldric
h)を添加し８０℃に加熱し透明な水溶液を得た。これを
テフロンラインのオートクレーブに入れ、シリカライト
の微粒子（平均粒径80 nm）をα−アルミナの多孔性セ
ラミックス板（日本碍子、平均粒径100 nm）の上に、コ
ーティングした後、乾燥し、５５０℃で３時間焼成し
た。このシリカライトの微粒子をコーティングしたセラ
ミックス１２５℃で８時間加熱したところ、シリカライ
トの微粒子（約８０nm）が得られた。このシリカライト
の微粒子（平均粒径80 nm）をα−アルミナの多孔性セ
ラミックス板（平均粒径100 nm）の上に、コーティング
した後、乾燥し、５５０℃で３時間焼成した。このシリ
カライトの微粒子をコーティングしたセラミックスの平
板を40 SiO2 : 12 TPAOH（テトラプロピルアンモニウム
ハイドロオキサイド） : 16800 H2Oの組成のゲル中に入
れ、オートクレーブ中で１３０℃で２４時間加熱した。
シリカライトの約２ミクロンの薄膜が、セラミックスの
平板上に形成していることを、Ｘ線回折と電子顕微鏡で
確認した。約１ミクロン分のシリカライト部分を削り、
石英バランス式の吸着装置に本シリカライトを充填し、
500℃で１時間真空下で焼成した後、２５℃で０℃の水
の蒸気圧下におき、その飽和吸着量を、石英製のバネを
用いて、測定した。水の吸着量は、２．９重量％であっ
た。EXAMPLE 1 0.28 g of NaOH (Katayama Chemical Reagent 1st grade) was added to 20 g of a 20% aqueous solution of tetrapropylammonium hydroxide (TPAOH) (20-25% aqueous solution of Tokyo Kasei) and stirred. And 5g of fumed silica (Aldric
h) was added and heated to 80 ° C. to obtain a clear aqueous solution. This is placed in a Teflon line autoclave, coated with fine particles of silicalite (average particle size of 80 nm) on a porous alumina plate of α-alumina (Nippon Insulator, average particle size of 100 nm), and dried. Baking was performed at 550 ° C. for 3 hours. When the ceramic coated with the silicalite fine particles was heated at 125 ° C. for 8 hours, silicalite fine particles (about 80 nm) were obtained. The silicalite fine particles (average particle size: 80 nm) were coated on an α-alumina porous ceramic plate (average particle size: 100 nm), dried, and fired at 550 ° C. for 3 hours. The ceramic plate coated with the silicalite fine particles was placed in a gel having a composition of 40 SiO 2 : 12 TPAOH (tetrapropyl ammonium hydroxide): 16800 H 2 O, and heated at 130 ° C. for 24 hours in an autoclave.
It was confirmed by X-ray diffraction and an electron microscope that a thin film of about 2 microns of silicalite was formed on a ceramic flat plate. We cut off silicalite part for approximately one micron,
Fill this silica light into a quartz balance type adsorption device,
After calcination at 500 ° C. for 1 hour under vacuum, the sample was placed at 25 ° C. under a vapor pressure of water of 0 ° C., and the saturated adsorption amount was measured using a quartz spring. The amount of water absorbed was 2.9% by weight.
【００１７】０．５％のエタノール水溶液に、上記方法
で合成した膜を接触させ、膜の反対側から、真空に引
き、液体窒素温度で透過してきた蒸気をトラップした。
トラップした液のエタノール濃度は、１％より大きかっ
た。The membrane synthesized by the above method was brought into contact with a 0.5% aqueous ethanol solution, and the other side of the membrane was evacuated to trap the vapor permeating at the temperature of liquid nitrogen.
The ethanol concentration of the trapped liquid was greater than 1%.
【００１８】[0018]
【発明の効果】本発明の水処理装置は、健康上有害な、
水中の微量の有機成分を効率よく除去でき連続的に浄水
できる。EFFECT OF THE INVENTION The water treatment apparatus of the present invention is
A trace amount of organic components in water can be efficiently removed and water can be continuously purified.
Claims (4)
択的に透過して除去するゼオライトを含む浄水膜。1. A water purification membrane containing zeolite for selectively permeating and removing organic matter from water containing less than 1% of organic matter.
金属とそれ以外の金属の原子比が２５以上であるハイシ
リカ及び／又は純シリカ質のゼオライトであることを特
徴とする請求項１記載の浄水膜。2. The zeolite according to claim 1, wherein the zeolite is a high-silica and / or pure-silica zeolite having an atomic ratio of silicon and a tetravalent metal to the other metal in the skeleton of 25 or more. Water purification membrane.
小さいことを特徴とする請求項１または２記載の浄水
膜。3. The water purification membrane according to claim 1, wherein the water adsorption of the zeolite is less than 3% by weight.
のいずれか１項記載の浄水膜を接触させることを特徴と
する浄水方法。4. Water containing less than 1% of organic matter and water as claimed in claim 1.
A water purification method comprising contacting the water purification membrane according to any one of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10265074A JP2000093957A (en) | 1998-09-18 | 1998-09-18 | Water purifying membrane and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10265074A JP2000093957A (en) | 1998-09-18 | 1998-09-18 | Water purifying membrane and method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000093957A true JP2000093957A (en) | 2000-04-04 |
Family
ID=17412243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10265074A Pending JP2000093957A (en) | 1998-09-18 | 1998-09-18 | Water purifying membrane and method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000093957A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7662295B2 (en) | 2004-11-05 | 2010-02-16 | Hitachi, Ltd. | Method for removing organic material in oilfield produced water and a removal device therefor |
| JP2017018880A (en) * | 2015-07-09 | 2017-01-26 | 三菱化学株式会社 | Removal method of minute amount of alcohol |
-
1998
- 1998-09-18 JP JP10265074A patent/JP2000093957A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7662295B2 (en) | 2004-11-05 | 2010-02-16 | Hitachi, Ltd. | Method for removing organic material in oilfield produced water and a removal device therefor |
| JP2017018880A (en) * | 2015-07-09 | 2017-01-26 | 三菱化学株式会社 | Removal method of minute amount of alcohol |
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