JPS63194792A - Process for purifying drinking water - Google Patents
Process for purifying drinking waterInfo
- Publication number
- JPS63194792A JPS63194792A JP2560987A JP2560987A JPS63194792A JP S63194792 A JPS63194792 A JP S63194792A JP 2560987 A JP2560987 A JP 2560987A JP 2560987 A JP2560987 A JP 2560987A JP S63194792 A JPS63194792 A JP S63194792A
- Authority
- JP
- Japan
- Prior art keywords
- water
- adsorbent
- drinking water
- chlorine
- treated
- 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
- 238000000034 method Methods 0.000 title claims abstract description 14
- 235000020188 drinking water Nutrition 0.000 title claims abstract description 13
- 239000003651 drinking water Substances 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003463 adsorbent Substances 0.000 claims abstract description 28
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 26
- 239000000460 chlorine Substances 0.000 claims abstract description 26
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 5
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000000746 purification Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 39
- 230000002829 reductive effect Effects 0.000 abstract description 4
- 230000001954 sterilising effect Effects 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 3
- 238000001179 sorption measurement Methods 0.000 description 15
- 235000019645 odor Nutrition 0.000 description 10
- 239000011148 porous material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- LFYXNXGVLGKVCJ-FBIMIBRVSA-N 2-methylisoborneol Chemical compound C1C[C@@]2(C)[C@](C)(O)C[C@@H]1C2(C)C LFYXNXGVLGKVCJ-FBIMIBRVSA-N 0.000 description 1
- LFYXNXGVLGKVCJ-UHFFFAOYSA-N 2-methylisoborneol Natural products C1CC2(C)C(C)(O)CC1C2(C)C LFYXNXGVLGKVCJ-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- GZSOSUNBTXMUFQ-NJGQXECBSA-N 5,7,3'-Trihydroxy-4'-methoxyflavone 7-O-rutinoside Natural products O(C[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](Oc2cc(O)c3C(=O)C=C(c4cc(O)c(OC)cc4)Oc3c2)O1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@H](C)O1 GZSOSUNBTXMUFQ-NJGQXECBSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 activated carbon Chemical compound 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- GZSOSUNBTXMUFQ-YFAPSIMESA-N diosmin Chemical compound C1=C(O)C(OC)=CC=C1C(OC1=C2)=CC(=O)C1=C(O)C=C2O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@H]2[C@@H]([C@H](O)[C@@H](O)[C@H](C)O2)O)O1 GZSOSUNBTXMUFQ-YFAPSIMESA-N 0.000 description 1
- 229960004352 diosmin Drugs 0.000 description 1
- IGBKNLGEMMEWKD-UHFFFAOYSA-N diosmin Natural products COc1ccc(cc1)C2=C(O)C(=O)c3c(O)cc(OC4OC(COC5OC(C)C(O)C(O)C5O)C(O)C(O)C4O)cc3O2 IGBKNLGEMMEWKD-UHFFFAOYSA-N 0.000 description 1
- 231100000676 disease causative agent Toxicity 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VUYDGVRIQRPHFX-UHFFFAOYSA-N hesperidin Natural products COc1cc(ccc1O)C2CC(=O)c3c(O)cc(OC4OC(COC5OC(O)C(O)C(O)C5O)C(O)C(O)C4O)cc3O2 VUYDGVRIQRPHFX-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 150000002634 lipophilic molecules Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、浄水場での浄水処理、或いは給水栓から得ら
れる飲用水の脱臭のための処理に際して、消毒目的で用
いられている遊離有効塩素（以下、単に遊離塩素という
ことがある）の損失をできるだけ抑えながら、“カビ臭
”等の感覚上の不快感を与える原因となる極微量の溶存
有機物質を除去することのできる飲用水の浄水処理方法
に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to a free effective disinfectant used for the purpose of disinfection during water purification treatment at a water treatment plant or treatment for deodorizing drinking water obtained from a water tap. Drinking water that can remove trace amounts of dissolved organic substances that cause sensory discomfort such as "mold odor" while minimizing the loss of chlorine (hereinafter sometimes simply referred to as free chlorine). Regarding water purification treatment methods.
飲用水中に極微量溶存し、“カヒ臭″゛等の原因とされ
る有機物質として、ジオスミンや２−メチルイソボルネ
オール等のテルペン類が知られている。これらの有機物
質は塩素処理によってもある程度除去できるが、除去対
象物質濃度が希薄であり、大量の水を処理する必要があ
るため、一般に活性炭による吸着除去が行われている（
水道協会誌 第５３巻 第１２号 ５７〜５９頁）。Terpenes such as diosmin and 2-methylisoborneol are known as organic substances that are dissolved in extremely small amounts in drinking water and are said to be the cause of a "mushy odor". These organic substances can be removed to some extent by chlorination, but since the concentration of the substances to be removed is dilute and a large amount of water needs to be treated, adsorption removal using activated carbon is generally used.
Water Works Association Journal, Vol. 53, No. 12, pp. 57-59).
飲用水には有害菌を殺したり増殖を抑える目的で塩素が
加えられ、因に、水道水に係わる法規によれば水道水中
の塩素の濃度は、末端給水栓で遊離塩素として０．１
ｐｐｍ以上と規定されている。しかしながら遊離塩素を
含む水中の有機物質の吸着処理用吸着剤として活性炭を
用いた場合、水中の遊離塩素が殆ど失われ、有機物質の
吸着処理後の水については殺菌機能、静菌機能がなくな
る。このため浄水場における浄水処理の過程で、殺菌以
外の目的も有する塩素を、活性炭による有機物質の吸着
処理後に添加しなければならないという問題がある。ま
た水道蛇口において、活性炭を吸着剤とする浄水器を用
いた場合にも処理後の水の殺菌能力が欠如し衛生上の問
題となる。この活性炭の存在による遊離塩素の損失は、
活性炭の元素状炭素の触媒的作用による塩素の還元分解
によるものであることが知られており、有機物質を吸着
するために用いる活性炭に吸着機能が残存する限り、活
性炭による塩素の還元分解を防止することは不可能であ
る。Chlorine is added to drinking water for the purpose of killing harmful bacteria and suppressing their growth.According to the laws regarding tap water, the concentration of chlorine in tap water is 0.1 as free chlorine at the end tap.
It is defined as ppm or more. However, when activated carbon is used as an adsorbent for adsorption treatment of organic substances in water containing free chlorine, most of the free chlorine in the water is lost, and the water after the adsorption treatment of organic substances loses its bactericidal and bacteriostatic functions. Therefore, in the water purification process at a water purification plant, there is a problem in that chlorine, which has purposes other than sterilization, must be added after the organic substances are adsorbed by activated carbon. Furthermore, when a water purifier using activated carbon as an adsorbent is used in a water tap, the water after treatment lacks the ability to sterilize, which poses a sanitary problem. The loss of free chlorine due to the presence of this activated carbon is
It is known that this is due to the reductive decomposition of chlorine due to the catalytic action of the elemental carbon in activated carbon, and as long as the activated carbon used to adsorb organic substances remains capable of adsorption, the reductive decomposition of chlorine by activated carbon can be prevented. It is impossible to do so.
更に活性炭は吸着剤として極めて大きな比表面積を有し
、吸着容量は大きいか、“カビ臭”の原因となる比較的
分子量の大きい有機物質に対して選択性を有していると
は言い鋪い。即ち活性炭は細孔分布上でミクロな細孔が
多く、このため処理原水中の比較的分子量の小さい化合
物の方が吸着速度が大きく、“カビ臭゛等の原因となる
比較的分子量の大きい有機物質に対する吸着容量が制限
されるという問題があった。Furthermore, activated carbon has an extremely large specific surface area as an adsorbent, and it cannot be said that it has a large adsorption capacity or selectivity for organic substances with relatively large molecular weights that cause "musty odor". . In other words, activated carbon has many microscopic pores in its pore distribution, and as a result, compounds with relatively small molecular weights in the treated raw water have a higher adsorption rate, and organic compounds with relatively large molecular weights that cause mold odors etc. There was a problem in that the adsorption capacity for substances was limited.
本発明者らは、糖類や蛋白質等の選択的吸着分離に使用
されている樹脂吸着剤か、比表面積は活性炭に比べて小
さく約１／２であるが、細孔分布上では活性炭に比べて
マクロな細孔が多く、比較的大きな分子の吸着に有利で
あること、更には活性炭のように元素状炭素を有してい
ないので、活性炭のように積極的に遊離塩素を還元分解
しないことが期待できる点に着目して鋭意研究した結果
、本発明を完成するに至った。The present inventors discovered that a resin adsorbent used for selective adsorption separation of sugars and proteins, has a specific surface area smaller than that of activated carbon, about 1/2, but has a pore distribution that is smaller than that of activated carbon. It has many macroscopic pores and is advantageous for adsorbing relatively large molecules, and since it does not contain elemental carbon like activated carbon, it does not actively reduce and decompose free chlorine like activated carbon. As a result of intensive research focusing on promising points, we have completed the present invention.
即ち本発明は吸着剤を用いて飲用水中の微量有機物質を
除去する方法において、スチレンージビニルベセン系高
架橋樹脂を母体とする吸着剤であって、親水基を有さな
い疎水性の樹脂吸着剤を用い、遊離有効塩素の共存下で
処理することを特徴とする飲用水の浄水処理方法を要旨
とするものである。That is, the present invention provides a method for removing trace amounts of organic substances from drinking water using an adsorbent, which is an adsorbent based on a styrene-divinylbecene-based highly crosslinked resin, which is a hydrophobic resin having no hydrophilic groups. The gist of the present invention is a method for purifying drinking water, which is characterized by using an adsorbent and treating it in the coexistence of free available chlorine.
本発明において用いる吸着剤の母体となる樹脂は比表面
積が大きく、且つ機械的強度が大きいものが望ましく、
本発明ではスチレン−ジビニルヘンセン系高架橋樹脂を
母体とするものを用い、特にジビニルヘンゼン含有量が
１０％以上の高架橋樹脂を用いることが好ましい。It is desirable that the resin serving as the base of the adsorbent used in the present invention has a large specific surface area and high mechanical strength.
In the present invention, a resin based on a styrene-divinylhensen-based highly crosslinked resin is used, and it is particularly preferable to use a highly crosslinked resin having a divinylhensen content of 10% or more.
吸着剤の茫本的物性として、被吸着物質との親和性が挙
げられる。本発明の処理方法において処理の対象とする
、“カビ臭゛の原因となる有機物質の全てが確認されて
いるわけてはないが、現在“カビ臭”の原因物質として
確認されているテルペン類の如く、一般的には親油性化
合物と考えられている。従って本発明において用いる樹
脂吸着剤は実質的に疎水性でなければならない。即ちカ
ルボキシル基、アミノ基、ヒドロキシル基等の親水性基
を実質的に有さない樹脂吸着剤である。上記の如き親水
基を有する樹脂吸着剤を用いた場合には塩素の損失の改
善がなされないばかりでなく、テルペン類の除去効率が
小さい。Isomoto's physical properties of adsorbents include affinity with adsorbed substances. Although not all of the organic substances that cause "mold odor" that are targeted for treatment in the treatment method of the present invention have been confirmed, terpenes that are currently confirmed as the causative agent of "mold odor" It is generally considered to be a lipophilic compound. Therefore, the resin adsorbent used in the present invention must be substantially hydrophobic. When a resin adsorbent having a hydrophilic group as described above is used, not only is the loss of chlorine not improved, but the removal efficiency of terpenes is low.
樹脂吸着剤の比表面積は、“カビ臭″′の原因となる有
機物質の除去という観点からは大きい方が好ましいが、
塩素が吸着されるごとによる塩素の損失を小さくする観
点からは、比表面積が８００１７ ｇ以下、好ましくは
４００〜６００ｍ／ｇである。また“カヒ臭゛の原因と
なる有機物質の選択吸着性を高める観点からは、細孔容
積の細孔径分布はマクロ側にシフトしていることが好ま
しく、上記の如き比表面積を有するものでは細孔容積が
０．５〜１．２、好ましくは０．７以上であり、平均細
孔径は３５人程度以上となる。It is preferable for the specific surface area of the resin adsorbent to be large from the viewpoint of removing organic substances that cause "mold odor";
From the viewpoint of reducing the loss of chlorine each time it is adsorbed, the specific surface area is 80017 g or less, preferably 400 to 600 m/g. In addition, from the viewpoint of increasing the selective adsorption of organic substances that cause "mushy odor," it is preferable that the pore size distribution of the pore volume is shifted toward the macro side. The pore volume is 0.5 to 1.2, preferably 0.7 or more, and the average pore diameter is about 35 or more.
本発明方法では上記の樹脂吸着剤を用いた固定方式によ
る処理方法が採用できるが、遊離塩素が樹脂に吸着され
たり、還元されることによる遊離塩素の損失をできるだ
け小さくするために、大きな空間速度で水を処理するこ
とが好ましい。処理原水の空間速度は原水中の遊離塩素
濃度と吸着処理後に期待する残存率、“カビ臭゛の程度
及び樹脂吸着剤の物性等によっても異なるが、実施例に
よれば一般的な水処理用活性炭の５倍程度でも樹脂吸着
剤の方に優位性があることが認められた。In the method of the present invention, a fixed treatment method using the resin adsorbent described above can be adopted, but in order to minimize the loss of free chlorine due to adsorption or reduction of free chlorine to the resin, a large space velocity is required. It is preferable to treat the water with The space velocity of treated raw water varies depending on the free chlorine concentration in the raw water, the expected residual rate after adsorption treatment, the degree of mold odor, the physical properties of the resin adsorbent, etc., but according to the examples, it is suitable for general water treatment. It was recognized that the resin adsorbent is superior even at about 5 times that of activated carbon.
この樹脂吸着剤は、稀酸、稀アルカリ、あるいはアルコ
ール溶液等の溶剤で再生できる。This resin adsorbent can be regenerated with a solvent such as a dilute acid, dilute alkali, or alcohol solution.
本発明の使用態様としては、活性炭と同様に、浄水場に
於いて吸着処理装置に使用する場合と、各家庭で蛇口に
取り付ける浄水器に使用する場合とがある。As with activated carbon, the present invention can be used in adsorption treatment devices at water purification plants, and in water purifiers attached to faucets in households.
以下、実施例を挙げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１〜２、比較例１〜６
ガラス製の吸着カラム（内径３０龍×充填長７０ｍｍ）
に第１表に示す性状の粒状の樹脂吸着剤及び水処理用活
性炭（比較例１〜２）とイオン交換樹脂（比較例３〜６
）５０ｃｃを充填した。処理原水として水道蛇白水（遊
離塩素をｏ−トリジン法で約１ ｐｐｍ含有）に、“カ
ビ臭”物質としてカンファーをｌｐｐｍ配合したものを
用い、第２表に示ず液空間速度で処理した。結果を第２
表にあわせて示す。Examples 1-2, Comparative Examples 1-6 Glass adsorption column (inner diameter 30 mm x packing length 70 mm)
Particulate resin adsorbents with properties shown in Table 1, activated carbon for water treatment (Comparative Examples 1 to 2) and ion exchange resins (Comparative Examples 3 to 6)
) 50cc was filled. As treated raw water, tap water (containing about 1 ppm of free chlorine by the o-tolidine method) mixed with 1 ppm of camphor as a "musty odor" substance was used, and treated at a liquid hourly space velocity not shown in Table 2. Second result
Also shown in the table.
尚、破過時間から求めた吸着容量は、吸着剤Ａ、吸着剤
Ｂでは吸着剤Ｃ及び吸着剤りと同等以上であった。In addition, the adsorption capacity determined from the breakthrough time was equal to or higher than that of adsorbent C and adsorbent B for adsorbent A and adsorbent B.
第１表 第２表 ものど巴われる。Table 1 Table 2 Something is lost.
本発明によれば、従来の活性炭を用いる処理方法に比べ
、還元分解等による遊離塩素の損失が少なく、また比較
的分子量の大きい物質の選択吸着性に優れ、“カビ臭゛
の原因となる微量の）容存有機物質を確実に吸着除去で
き、ごの結果、遊離塩素を含有する原水を処理しても処
理水の殺菌能力を保持することができるとともに、゛′
カカビ”を効果的に除去できる。According to the present invention, compared to the conventional treatment method using activated carbon, there is less loss of free chlorine due to reductive decomposition, etc., and it also has excellent selective adsorption of substances with relatively large molecular weights, so that trace amounts of ) The organic substances present in the water can be reliably adsorbed and removed, and as a result, even when raw water containing free chlorine is treated, the sterilizing ability of the treated water can be maintained, and the
Can effectively remove mold.
Claims (1)
において、スチレン−ジビニルベゼン系高架橋樹脂を母
体とする吸着剤であって、親水基を有さない疎水性の樹
脂吸着剤を用い、遊離有効塩素の共存下で処理すること
を特徴とする飲用水の浄水処理方法。In a method for removing trace amounts of organic substances from drinking water using an adsorbent, a hydrophobic resin adsorbent having no hydrophilic groups and having a styrene-divinylbenzene-based highly cross-linked resin adsorbent is used to remove trace amounts of organic substances from drinking water. A drinking water purification method characterized by treating water in the coexistence of available chlorine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2560987A JPS63194792A (en) | 1987-02-06 | 1987-02-06 | Process for purifying drinking water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2560987A JPS63194792A (en) | 1987-02-06 | 1987-02-06 | Process for purifying drinking water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63194792A true JPS63194792A (en) | 1988-08-11 |
Family
ID=12170636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2560987A Pending JPS63194792A (en) | 1987-02-06 | 1987-02-06 | Process for purifying drinking water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63194792A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6443389A (en) * | 1987-08-12 | 1989-02-15 | Kao Corp | Water purifier |
| JPH0290989A (en) * | 1988-09-26 | 1990-03-30 | Kao Corp | Water purifier |
-
1987
- 1987-02-06 JP JP2560987A patent/JPS63194792A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6443389A (en) * | 1987-08-12 | 1989-02-15 | Kao Corp | Water purifier |
| JPH0290989A (en) * | 1988-09-26 | 1990-03-30 | Kao Corp | Water purifier |
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