JPH06134455A - Method for coagulating photochemically and ionizing microp articulate impurities in liquid - Google Patents
Method for coagulating photochemically and ionizing microp articulate impurities in liquidInfo
- Publication number
- JPH06134455A JPH06134455A JP30627392A JP30627392A JPH06134455A JP H06134455 A JPH06134455 A JP H06134455A JP 30627392 A JP30627392 A JP 30627392A JP 30627392 A JP30627392 A JP 30627392A JP H06134455 A JPH06134455 A JP H06134455A
- Authority
- JP
- Japan
- Prior art keywords
- liquid
- impurities
- photochemical
- treatment
- aggregation
- 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.)
- Granted
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 55
- 239000012535 impurity Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims description 15
- 230000001112 coagulating effect Effects 0.000 title abstract 2
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 238000005259 measurement Methods 0.000 claims abstract description 12
- 238000005342 ion exchange Methods 0.000 claims abstract description 7
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 7
- 239000010419 fine particle Substances 0.000 claims description 44
- 230000002776 aggregation Effects 0.000 claims description 28
- 238000004220 aggregation Methods 0.000 claims description 27
- 241000894006 Bacteria Species 0.000 claims description 20
- 239000007800 oxidant agent Substances 0.000 claims description 17
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- 239000002510 pyrogen Substances 0.000 claims description 10
- 230000015271 coagulation Effects 0.000 claims description 6
- 238000005345 coagulation Methods 0.000 claims description 6
- 238000000108 ultra-filtration Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 40
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 3
- 239000010935 stainless steel Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 26
- 239000012498 ultrapure water Substances 0.000 description 26
- 239000000377 silicon dioxide Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- -1 LSI Substances 0.000 description 15
- 239000004065 semiconductor Substances 0.000 description 15
- 230000001590 oxidative effect Effects 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 201000007902 Primary cutaneous amyloidosis Diseases 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/32—Details relating to UV-irradiation devices
- C02F2201/322—Lamp arrangement
- C02F2201/3223—Single elongated lamp located on the central axis of a turbular reactor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/32—Details relating to UV-irradiation devices
- C02F2201/324—Lamp cleaning installations, e.g. brushes
-
- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、液体中の微粒子状不純
物の光化学凝集、イオン化処理方法に関するもので、液
体に含有されている微量なコロイド物質、バクテリア、
パイロジェン、細菌等の微粒子状不純物、イオンを測定
または除去することに特徴がある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochemical agglomeration and ionization treatment method for fine particle impurities in a liquid, which contains a trace amount of colloidal substances, bacteria,
It is characterized by measuring or removing particulate impurities and ions such as pyrogens and bacteria.
【０００２】[0002]
【従来の技術】最近、半導体、液晶、医薬品業界や原子
力発電所等においては、超純水を始めとする高純度の液
体が使用されている。例えば、ＬＳＩ等の半導体を製造
する際には、半導体の洗浄水として超純水が使用されて
いるが、通常の場合、この分野で用いられる超純水は、
イオン交換装置、超濾過膜装置、逆浸透膜装置等を適宜
組み合わせた超純水製造システムによって製造されてい
る。2. Description of the Related Art Recently, high purity liquids such as ultrapure water have been used in the semiconductor, liquid crystal, pharmaceutical industry and nuclear power plants. For example, when manufacturing semiconductors such as LSI, ultrapure water is used as cleaning water for semiconductors, but normally, ultrapure water used in this field is
It is manufactured by an ultrapure water manufacturing system that appropriately combines an ion exchange device, an ultrafiltration membrane device, a reverse osmosis membrane device, and the like.
【０００３】しかし、この超純水製造システムは、被処
理対象である原水中に含まれている各種の不純物イオ
ン、有機物、懸濁粒状物等の除去には有効であるが、微
量なコロイド物質（コロイドシリカ、コロイド鉄）、バ
クテリア、パイロジェン（発熱性物質）、細菌等の微粒
子状不純物の除去には不適当であり、処理液である超純
水中にリークすることが多かった。However, this ultrapure water production system is effective for removing various impurity ions, organic substances, suspended particulate matter, etc. contained in the raw water to be treated, but a trace amount of colloidal substance. It is unsuitable for removing particulate impurities such as (colloidal silica, colloidal iron), bacteria, pyrogens (pyrogenic substances) and bacteria, and often leaks into the ultrapure water which is the treatment liquid.
【０００４】そして、これらの微粒子状不純物は微量で
あると、簡単、容易な測定機器では測定できず、見逃さ
れて超純水中に残留したままであることが多く、このよ
うな超純水を半導体の洗浄水として使用すると、これら
の微粒子状不純物が半導体にスケールとして付着し、半
導体の汚染、回路破壊等のトラブルを発生することもあ
った。If the amount of these fine particulate impurities is very small, they cannot be measured by a simple and easy measuring instrument, and they are often overlooked and remain in the ultrapure water. When used as washing water for semiconductors, these fine particles of impurities may adhere to the semiconductor as a scale, causing troubles such as semiconductor contamination and circuit breakage.
【０００５】また、これらの微量な微粒子状不純物は、
かなり高度で、精密な測定機器で慎重に測定すると、測
定が可能であるが、しかし、これらの微量な微粒子状不
純物の除去は非常に難しく、適切な除去手段がないのが
実情であった。Further, these minute amounts of fine particulate impurities are
Although it is possible to perform the measurement by careful measurement with a highly sophisticated and precise measuring instrument, it is very difficult to remove these minute amounts of particulate impurities, and there is no suitable removal means.
【０００６】前述した半導体、液晶、医薬品業界や原子
力発電所等においては、近年の技術革新、技術の高度化
に伴い、この微量なコロイド物質、バクテリア、パイロ
ジェン、細菌等の微粒子状不純物の液体よりの除去を簡
単、容易に、かつ正確に測定することによって、事前に
トラブルを回避したり、適切な対応をとることが求めら
れており、さらに技術課題としては、この微量の微粒子
状不純物を液体より完全に除去することが切望されてい
る。In the semiconductor, liquid crystal, pharmaceutical industry, nuclear power plant, etc. described above, with the recent technological innovation and sophistication of technology, this minute amount of colloidal substances, liquids of fine particulate impurities such as bacteria, pyrogens and bacteria are used. It is required to avoid troubles and take appropriate measures in advance by measuring the removal of impurities easily, easily and accurately. There is a strong desire for more complete removal.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、液体中の微
量なコロイド物質、バクテリア、パイロジェン、細菌等
の微粒子状不純物を、簡単、容易に測定し、これに応じ
て適切に対処することによって、これらの微量な微粒子
状不純物に起因して発生する各種のトラブルを事前に回
避することにある。DISCLOSURE OF THE INVENTION The present invention provides a simple and easy method for measuring minute amounts of colloidal substances, bacteria, pyrogens, bacteria and other particulate impurities in a liquid, and taking appropriate measures accordingly. In order to avoid various troubles caused by these minute amounts of fine particulate impurities in advance.
【０００８】また、本発明は、液体中の微量なコロイド
物質、バクテリア、パイロジェン、細菌等の微粒子状不
純物を、簡単、容易に除去し、この純度の高い処理液体
を各種の産業分野で使用して、高品質の製品を製造する
ことにある。Further, the present invention can easily and easily remove minute amounts of colloidal substances, fine particles of impurities such as bacteria, pyrogens and bacteria in a liquid, and use the treated liquid with high purity in various industrial fields. To produce high quality products.
【０００９】[0009]
【課題を解決するための手段】本発明は、液体中の微粒
子状不純物の光化学凝集、イオン化処理方法に関するも
のであり、微量なコロイド物質、バクテリア、パイロジ
ェン、細菌等の微粒子状不純物を含有する液体に、紫外
線（望ましくは２２０ｎｍの紫外線）、太陽光線等の光
照射を行い、液体中の微粒子状不純物を光化学凝集、イ
オン化処理することによって、液体中の微粒子状不純
物、イオンの測定を可能にしたことに特徴がある。The present invention relates to a method for photochemical aggregation and ionization treatment of particulate impurities in a liquid, which contains a trace amount of particulate impurities such as colloidal substances, bacteria, pyrogens and bacteria. Ultraviolet rays (preferably 220 nm ultraviolet rays), sunlight, etc. are irradiated to the particles to perform photochemical aggregation and ionization treatment of fine particle impurities in the liquid, thereby enabling measurement of fine particle impurities and ions in the liquid. It is characterized by this.
【００１０】また、本発明は、前述した液体の光化学凝
集、イオン化処理方法に関するもので、光化学凝集、イ
オン化処理した液体中の微量な微粒子状不純物を、イオ
ン交換装置、超濾過膜装置、逆浸透膜装置等の液体処理
装置のいずれか、またはこれらの液体処理装置を組み合
わせたシステムで除去することに特徴がある。The present invention also relates to the above-described photochemical aggregation and ionization treatment method for a liquid, in which a trace amount of fine particulate impurities in the liquid subjected to the photochemical aggregation and ionization treatment are ion exchange device, ultrafiltration membrane device, reverse osmosis device. It is characterized in that it is removed by any of the liquid treatment devices such as a membrane device or a system in which these liquid treatment devices are combined.
【００１１】さらに、本発明は、前述した液体の光化学
凝集、イオン化処理方法に関するもので、液体中の微量
な微粒子状不純物を紫外線、太陽光線等の光照射を行う
について、光照射とともにオゾンを添加して、微粒子状
不純物の光化学凝集、イオン化処理を一段と促進するこ
とに特徴がある。Further, the present invention relates to the above-mentioned photochemical aggregation and ionization treatment method for a liquid, in which a minute amount of fine particulate impurities in the liquid are irradiated with light such as ultraviolet rays and sun rays, and ozone is added together with the light irradiation. Then, the photochemical aggregation and ionization treatment of the particulate impurities are further promoted.
【００１２】さらに、本発明は、前述した液体の光化学
凝集、イオン化処理方法に関するもので、液体中の微量
な微粒子状不純物を紫外線、太陽光線等の光照射を行う
について、光照射とともに酸化剤を添加して、微粒子状
不純物の光化学凝集、イオン化処理を一段と促進するこ
とに特徴がある。Further, the present invention relates to the above-described photochemical aggregation and ionization treatment method for a liquid, in which a minute amount of fine particulate impurities in the liquid are irradiated with light such as ultraviolet rays or sunlight, and an oxidizing agent is added together with the light irradiation. It is characterized by being added to further promote photochemical aggregation and ionization treatment of fine particle impurities.
【００１３】[0013]
【作用】以上のように、液体中の微量なコロイド物質、
バクテリア、パイロジェン、細菌等の微粒子状不純物
に、紫外線、太陽光線等の光照射を行うと、微量な微粒
子状不純物は、相互に光化学反応によって凝集して増粒
化することによって、さらに光化学反応によってイオン
化（例えばコロイド状シリカはイオン化する）すること
によって、簡単、容易に測定、除去し易くなる。[Function] As described above, a minute amount of colloidal substance in the liquid,
When minute particles of impurities such as bacteria, pyrogens, and bacteria are irradiated with light such as ultraviolet rays and sun rays, minute amounts of minute particles of impurities are aggregated by photochemical reaction to increase the particle size. Ionization (for example, colloidal silica is ionized) facilitates easy and easy measurement and removal.
【００１４】本発明の液体中の微粒子状不純物の光化学
凝集、イオン化処理方法を実施する装置の一例について
説明すると、図１に示すように、周知の紫外線照射装置
のステンレス製の処理筒１内に紫外線ランプ２を配設す
るが、この紫外線ランプ２は紫外線透過率が高く、かつ
被照射体に溶出物が流出しない材質、たとえば石英ガラ
スよりなる透過筒３に収めることが通常である。以上の
ように、処理筒１を構成することによって、処理筒１内
に流入する液体中の微量な微粒子状不純物に紫外線照射
することによって、微粒子状不純物の光化学凝集、イオ
ン化処理を行う流路４を形成し、さらに処理筒１には、
液体の流入管５と処理液の流出管６を接続し、そして、
この液体の流入管５には、必要に応じて、オゾン発生機
（図示せず）または酸化剤貯槽（図示せず）を接続する
とよい。An example of an apparatus for carrying out the photochemical coagulation and ionization treatment method of the particulate impurities in the liquid of the present invention will be explained. As shown in FIG. Although the ultraviolet lamp 2 is provided, the ultraviolet lamp 2 is usually housed in a transparent cylinder 3 made of a material such as quartz glass, which has a high ultraviolet transmittance and in which the eluate does not flow out to the irradiated body. As described above, by configuring the processing cylinder 1, by irradiating the minute amount of fine particle impurities in the liquid flowing into the processing cylinder 1 with ultraviolet rays, the flow path 4 for performing photochemical aggregation and ionization processing of the fine particle impurities. Is formed, and further, in the processing cylinder 1,
The liquid inflow pipe 5 and the processing liquid outflow pipe 6 are connected, and
If necessary, an ozone generator (not shown) or an oxidant storage tank (not shown) may be connected to the liquid inflow pipe 5.
【００１５】[0015]
【実施例１】公知のイオン交換装置、超濾過膜装置、逆
浸透膜装置等を組み合わせた超純水製造システムによっ
て製造した超純水を、（イ）株式会社堀場製作所製の微
粒子測定装置、ＰＬＣＡ−３１０（０．０７μｍ以上の
微粒子測定可能）、（ロ）ＤＫＫ株式会社製のシリカモ
ニター、ＳＬＣ−１６０５によって、微粒子とシリカイ
オンを測定したところ、以下のような測定結果になっ
た。[Example 1] Ultrapure water produced by an ultrapure water production system combining a known ion exchange device, ultrafiltration membrane device, reverse osmosis membrane device, etc. Fine particles and silica ions were measured by PLCA-310 (measuring fine particles of 0.07 μm or more), (b) silica monitor manufactured by DKK Co., Ltd., SLC-1605, and the following measurement results were obtained.
【００１６】 超純水中の微粒子とシリカイオンの測定結果 （イ）微粒子量（個／ｍｌ） ０ （ロ）微粒子径（μｍ） ０ （ハ）シリカイオン（μｇ（Ｓｉ０2 ／ｌ）） ０Measurement results of fine particles and silica ions in ultrapure water (a) Fine particle amount (pieces / ml) 0 (b) Fine particle diameter (μm) 0 (c) Silica ions (μg (Si 0 2 / l)) 0
【００１７】前述した超純水製造システムによって製造
した超純水を、次の三種類の実験装置に流速２ｔ／ｈｒ
で通液して光化学凝集、イオン化処理を行った。 （Ａ）実験装置 ステンレス製の処理筒（１０００ｍｍ(L) ×２０００ｍ
ｍ(W) ×２０００ｍｍ(H））の内部に、株式会社日本フ
ォトサイエンス製の１８５ｎｍの波長、６５Ｗの紫外線
ランプ（ＡＹ−６）を内蔵した石英ガラス製の透過筒を
２０本配置したもの。 （Ｂ）実験装置 前述した（Ａ）実験装置に、株式会社日本フォトサイエ
ンス製のオゾン発生装置（ＮＰＳ−０３）を付設し、超
純水にオゾンを１０ｐｐｍ添加したもの。 （Ｃ）実験装置 前述した（Ａ）実験装置に、酸化剤貯槽を付設し、超純
水に酸化剤として過酸化水素を７ｐｐｍ添加したもの。 以上の実験装置によって超純水を処理した結果、半導体
の洗浄水中の微粒子とシリカイオンは、以下に示すよう
な状態になった。The ultrapure water produced by the above-mentioned ultrapure water production system was flowed into the following three types of experimental equipment at a flow rate of 2 t / hr.
Then, photochemical aggregation and ionization treatment were carried out. (A) Experimental equipment Stainless steel processing cylinder (1000mm (L) x 2000m
m (W) × 2000 mm (H)), in which 20 transmission tubes made of quartz glass having a 185 nm wavelength, 65 W ultraviolet lamp (AY-6) made by Nippon Photoscience Co., Ltd. built therein are arranged. (B) Experimental Device An ozone generator (NPS-03) manufactured by Nippon Photoscience Co., Ltd. was attached to the experimental device (A) described above, and 10 ppm of ozone was added to ultrapure water. (C) Experimental device The above-mentioned (A) experimental device was provided with an oxidant storage tank, and 7 ppm of hydrogen peroxide was added to ultrapure water as an oxidant. As a result of treating the ultrapure water with the above experimental apparatus, the fine particles and silica ions in the semiconductor washing water were in the following states.
【００１８】 本発明法で処理した超純水中の微粒子とシリカイオンの測定結果 実験装置 （Ａ） （Ｂ） （Ｃ） （イ）微粒子量（個／ｍｌ） ４０ ４５ ６０ （ロ）微粒子径（μｍ） 0.07 以上 0.07以上 0.07 以上 （ハ）シリカイオン ５〜１７ ６〜１８ ９〜２５ （μｇ（Ｓｉ０2 ／ｌ）） 以上の結果で明なように、本発明の紫外線照射、紫外線
照射とオゾン添加、紫外線照射と酸化剤添加を行うと、
超純水の微量な微粒子は光化学凝集によって増粒（０．
０７μｍ以上の微粒子径に増粒）したため、またシリカ
は光化学イオン化によってイオン化したため、前述した
微粒子測定装置、シリカモニターで簡単、容易に測定で
きた。Measurement results of fine particles and silica ions in ultrapure water treated by the method of the present invention Experimental apparatus (A) (B) (C) (a) Fine particle amount (pieces / ml) 40 45 60 (b) Fine particle diameter (Μm) 0.07 or more 0.07 or more 0.07 or more (C) Silica ion 5 to 176 to 189 to 25 (μg (Si0 2 / l)) As is clear from the above results, the ultraviolet irradiation and the ultraviolet irradiation of the present invention are When ozone is added, UV irradiation and oxidizer are added,
Trace amount of ultrapure water particles are increased by photochemical aggregation (0.
Since the particle size was increased to 07 μm or more) and the silica was ionized by photochemical ionization, it was possible to easily and easily measure with the above-described particle measuring device and silica monitor.
【００１９】[0019]
【実施例２】公知のイオン交換装置、超濾過膜装置、逆
浸透膜装置等を組み合わせた超純水製造システムで製造
した超純水によって半導体を洗浄し、その洗浄水を回収
し、前述した（イ）の微粒子測定装置、（ロ）のシリカ
モニターによって、微粒子とシリカイオンを測定したと
ころ、以下のような結果になった。Example 2 A semiconductor was washed with ultrapure water produced by an ultrapure water production system combining a known ion exchange device, ultrafiltration membrane device, reverse osmosis membrane device, etc., and the washing water was collected and was used as described above. When the fine particles and silica ions were measured by the fine particle measuring device (a) and the silica monitor (b), the following results were obtained.
【００２０】 洗浄水中の微粒子とシリカイオンの測定結果 （イ）微粒子量（個／ｍｌ） ５００ （ロ）微粒子径（μｍ） 0.07以上 （ハ）シリカイオン（μｇ（Ｓｉ０2 ／ｌ）） ３〜６Measurement results of fine particles in washing water and silica ion (a) Fine particle amount (pieces / ml) 500 (b) Fine particle diameter (μm) 0.07 or more (c) Silica ion (μg (Si 0 2 / l)) 3 to 6
【００２１】前述した半導体の洗浄水を、次の三種類の
実験装置に流速１ｔ／ｈｒで通液して光化学凝集、イオ
ン化処理をおこなった。 （Ａ）実験装置 ステンレス製の処理筒（１０００ｍｍ(L) ×１０００ｍ
ｍ(W) ×１０００ｍｍ(H) ）の内部に、株式会社日本フ
ォトサイエンス製の２２０ｎｍ以下の波長、７８０Ｗの
紫外線ランプ（ＡＶ−９）を内蔵した石英ガラス製の透
過筒を２本配置したもの。 （Ｂ）実験装置 前述した（Ａ）実験装置に、株式会社日本フォトサイエ
ンス製のオゾン発生装置（ＮＰＳ−０３）を付設し、超
純水にオゾンを１１ｐｐｍ添加したもの。 （Ｃ）実験装置 前述した（Ａ）実験装置に、酸化剤貯槽を付設し、超純
水に酸化剤として過酸化水素を８ｐｐｍ添加したもの。 以上の実験装置によって半導体の洗浄水を処理した結
果、その洗浄水中の微粒子とシリカイオンは、以下に示
すような状態になった。The above-mentioned semiconductor washing water was passed through the following three types of experimental equipment at a flow rate of 1 t / hr to perform photochemical aggregation and ionization treatment. (A) Experimental equipment Stainless steel processing cylinder (1000mm (L) x 1000m
m (W) × 1000 mm (H)) with two quartz glass transmission tubes with a UV lamp (AV-9) of 780 W and a wavelength of 220 nm or less manufactured by Nihon Photo Science Co., Ltd. . (B) Experimental Device An ozone generator (NPS-03) manufactured by Nippon Photoscience Co., Ltd. was attached to the experimental device (A) described above, and 11 ppm of ozone was added to ultrapure water. (C) Experimental device The above-mentioned (A) experimental device was provided with an oxidant storage tank, and 8 ppm of hydrogen peroxide as an oxidant was added to ultrapure water. As a result of treating the semiconductor washing water with the above experimental apparatus, the fine particles and silica ions in the washing water were in the following states.
【００２２】 本発明法で処理した洗浄水中の微粒子とシリカイオンの測定結果 実験装置 （Ａ） （Ｂ） （Ｃ） （イ）微粒子量（個／ｍｌ） ６９５ ８１５ ８８０ （ロ）微粒子径（μｍ） 0.07以上 0.07以上 0.07以上 （ハ）イオン状シリカ ８〜１７ ９〜１８ ９〜２５ （μｇ（Ｓｉ０2 ／ｌ）） 以上の結果で明なように、本発明の紫外線照射、紫外線
照射とオゾン添加、紫外線照射と酸化剤添加を行うと、
洗浄水の微粒子は光化学凝集によって増粒（０．０７μ
ｍ以上の微粒子径に増粒）したため、またシリカは光化
学イオン化によってイオン化したため、前述した微粒子
測定装置、シリカモニターで簡単、容易に測定できた。Measurement Results of Fine Particles and Silica Ions in Wash Water Treated by the Method of the Present Invention Experimental apparatus (A) (B) (C) (a) Fine particle amount (pieces / ml) 695 815 880 (b) Fine particle diameter (μm) ) 0.07 or 0.07 or 0.07 or higher (c) an ion-like silica 8~17 9~18 9~25 (μg (Si0 2 / l)) Ming that as in the above results, the ultraviolet irradiation, ultraviolet irradiation and ozone present invention Addition, UV irradiation and oxidant addition,
Fine particles of washing water are increased by photochemical aggregation (0.07μ
Since the particle size was increased to m or more) and the silica was ionized by photochemical ionization, it was possible to easily and easily measure with the above-described particle measuring device and silica monitor.
【００２３】次いで、以上の実験装置（Ａ）、（Ｂ）、
（Ｃ）で処理した光化学凝集した微粒子とイオン化した
シリカを含む洗浄水を、公知のイオン交換装置と逆浸透
膜装置等を組み合わせた超純水製造システムに流速１ｔ
／ｈｒで通液して処理したところ、その処理結果は、以
下に示す通りであった。Next, the above experimental devices (A), (B),
The washing water containing the photochemically agglomerated fine particles treated in (C) and the ionized silica was introduced into an ultrapure water production system in which a known ion exchange device and a reverse osmosis membrane device were combined with a flow rate of 1 t.
When the solution was passed through at a rate of / hr for treatment, the treatment results were as shown below.
【００２４】 超純水製造システムで処理した洗浄水の微粒子とシリカイオンの除去結果 実験装置 （Ａ） （Ｂ） （Ｃ） （イ）微粒子量（個／ｍｌ） ０〜２ ０〜１ ０ （ロ）微粒子径（μｍ） 0.28 〜0.2 0.24〜0.2 0.2〜0.15 （ハ）シリカ（μｇ（Ｓｉ０2 ／ｌ）） 0.4〜0.5 0.35〜0.4 0.3〜0.4 以上の結果で明なように、本発明の紫外線照射、紫外線
照射とオゾン添加、紫外線照射と酸化剤添加を行うと、
超純水の微量な微粒子は光化学凝集によって増粒し、ま
たシリカは光化学イオン化によってイオン化した結果、
超純水製造システムで洗浄水中の微粒子とシリカイオン
を除去することができた。Results of Removal of Fine Particles and Silica Ions of Wash Water Treated by Ultrapure Water Production System Experimental apparatus (A) (B) (C) (a) Fine particle amount (pieces / ml) 0 to 20 to 10 ( b) fine diameter (μm) 0.28 ~0.2 0.24~0.2 0.2~0.15 (c) silica (μg (Si0 2 / l) ) 0.4~0.5 0.35~0.4 0.3~0.4 Ming that as in the above results, the present invention UV irradiation, UV irradiation and ozone addition, UV irradiation and oxidant addition,
The ultrafine particles of ultrapure water are increased in size by photochemical aggregation, and silica is ionized by photochemical ionization.
The ultrapure water production system was able to remove fine particles and silica ions in the wash water.
【００２５】前述した実施例においては、被処理対象液
に含まれている微粒子状不純物のうち、微粒子とコロイ
ド物質について言及したが、バクテリア、パイロジェ
ン、細菌等の微粒子状不純物微粒子の測定、除去につい
ても同様である。Although the fine particles and colloidal substances among the fine particle impurities contained in the liquid to be treated are mentioned in the above-mentioned embodiments, the measurement and removal of fine particle impurities such as bacteria, pyrogens and bacteria are described. Is also the same.
【００２６】光照射手段としては紫外線照射が一般的あ
り、この場合に使用される紫外線ランプとしては、波長
１８５ｎｍの低圧ランプ、波長２２０ｎｍ以下の中・高
圧ランプが最適であり、これ以外の主波長２５４ｎｍの
低圧殺菌ランプ、主波長３６５ｎｍの中・高圧ランプ
は、光化学凝集、イオン化処理効果が落ちる。またが紫
外線ランプ以外にも、光化学凝集、イオン化処理の目的
に応じて、太陽光ランプ、ケミカルランプ、ブラックラ
イトランプ、メタルライトランプ、ナトリウムランプ等
の各種ランプを使用してもよい。Ultraviolet irradiation is generally used as the light irradiation means. As the ultraviolet lamp used in this case, a low pressure lamp with a wavelength of 185 nm and a medium / high pressure lamp with a wavelength of 220 nm or less are optimal, and other main wavelengths. The low pressure sterilization lamp of 254 nm and the medium / high pressure lamp of the main wavelength of 365 nm have poor photochemical coagulation and ionization treatment effects. In addition to the ultraviolet lamp, various lamps such as a solar lamp, a chemical lamp, a black light lamp, a metal light lamp, and a sodium lamp may be used depending on the purpose of photochemical aggregation and ionization treatment.
【００２７】光化学凝集、イオン化処理を促進するため
に液体に添加するオゾンとしては、オゾン発生機によっ
て発生したオゾンを用いることが一般的であり、オゾン
の添加量は３〜２０ｐｐｍの範囲であればよく、３ｐｐ
ｍ未満であると所期の処理効果があがらず、また２０ｐ
ｐｍを超えても、オゾン添加量の増加に応じた処理効果
があがらない。Ozone generated by an ozone generator is generally used as ozone to be added to the liquid in order to promote photochemical coagulation and ionization treatment, and the amount of ozone added is in the range of 3 to 20 ppm. Well, 3pp
If it is less than m, the desired treatment effect will not be obtained, and it will be 20p.
Even if it exceeds pm, the treatment effect corresponding to the increase in the amount of ozone added does not increase.
【００２８】光化学凝集、イオン化処理を促進するため
に液体に添加する酸化剤としては、Ｈ2 Ｏ2 以外にＢｒ
Ｏ3 、Ｏ2 、Ｏ3 等を用いるとよく、これらの一種また
は二種以上を光化学凝集、イオン化処理目的に応じて適
宜選択して使用する。酸化剤の添加量は５〜１０ｐｐｍ
の範囲であればよく、５ｐｐｍ未満であると所期の処理
効果があがらず、また１０ｐｐｍを超えると、これに応
じた処理効果があがらず、酸化剤の添加量が過剰とな
り、かえって不純物が増加する結果にもなるので不都合
である。なお酸化剤を併用する場合には、酸化剤の濃度
により紫外線等の光吸収係数が異なるために、酸化剤の
濃度と光吸収係数との関係を考慮して液体の光化学凝
集、イオン化処理を行う必要がある。In addition to H 2 O 2 , Br is used as an oxidizing agent added to the liquid for promoting photochemical aggregation and ionization treatment.
It is preferable to use O 3 , O 2 , O 3 and the like, and one or more of these are appropriately selected and used according to the purpose of photochemical aggregation or ionization treatment. Addition amount of oxidizer is 5-10ppm
If it is less than 5 ppm, the desired treatment effect will not be obtained, and if it exceeds 10 ppm, the treatment effect corresponding to this will not be obtained, and the amount of oxidant added will be excessive, which will rather increase impurities. This is also inconvenient because it will result in When an oxidant is used in combination, the optical absorption coefficient of ultraviolet rays and the like varies depending on the concentration of the oxidant, so photochemical aggregation and ionization of the liquid are performed in consideration of the relationship between the concentration of the oxidant and the optical absorption coefficient. There is a need.
【００２９】[0029]
【考案の効果】本発明によると、液体中の微量なコロイ
ド物質（コロイドシリカ、コロイド鉄）、バクテリア、
パイロジェン（発熱性物質）、細菌等の微粒子状不純物
を、簡単、容易な測定機器で測定して、除去することが
可能であり、これらの微粒子状不純物を含有しない高純
度の処理液を得ることができる。According to the present invention, a trace amount of colloidal substances (colloidal silica, colloidal iron), bacteria,
It is possible to measure and remove fine particle impurities such as pyrogens (pyrogenic substances) and bacteria with a simple and easy measuring device, and obtain a high-purity treatment liquid that does not contain these fine particle impurities. You can
【００３０】したがって、処理液である超純水中に微粒
子状不純物が残留することがないために、たとえば半導
体の洗浄水として使用しても、微粒子状不純物が半導体
にスケールとして付着し、半導体の汚染、回路破壊等の
トラブルを発生することはなく、高品質の半導体を歩留
りよく製造することができる。Therefore, since the fine particle impurities do not remain in the ultrapure water as the processing liquid, the fine particle impurities adhere to the semiconductor as a scale even when it is used as cleaning water for the semiconductor. Problems such as contamination and circuit destruction do not occur, and high quality semiconductors can be manufactured with high yield.
【００３１】特に、光照射とともにオゾンまたは酸化剤
を併用添加した場合は、液体中微粒子状不純物の光化学
凝集、イオン化処理が促進して処理効率が一段と向上
し、より純度の高い処理液体を得ることができる。In particular, when ozone or an oxidant is added together with light irradiation, photochemical aggregation and ionization treatment of fine particle impurities in the liquid are promoted, the treatment efficiency is further improved, and a treated liquid having a higher purity is obtained. You can
【００３２】本発明は、半導体、液晶、医薬品の製造工
程や原子力発電所等において使用する用水の処理の他
に、飲料水の浄化等にも活用することができる。The present invention can be utilized not only for the treatment of water used in the manufacturing process of semiconductors, liquid crystals, pharmaceuticals and nuclear power plants, but also for the purification of drinking water.
【図１】本発明の光化学凝集、イオン化処理を行う紫外
線ランプを円筒状の透過筒に内蔵させて配設した処理筒
の断面図である。FIG. 1 is a cross-sectional view of a processing tube in which an ultraviolet lamp for performing photochemical coagulation and ionization processing of the present invention is installed in a cylindrical transmission tube.
１ 処理筒 ２ 紫外線ランプ ３ 透過筒 ４ 流路 1 treatment cylinder 2 ultraviolet lamp 3 transmission cylinder 4 flow path
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０２Ｆ 1/52 ＺＡＢ Ｚ 7824−4Ｄ 1/72 ＺＡＢ 9045−4Ｄ １０１ 9045−4Ｄ 1/78 ＺＡＢ 9045−4Ｄ 9/00 ＺＡＢ Ｚ 7446−4Ｄ // Ｇ０１Ｎ 15/00 Ｃ 2107−2Ｊ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Internal reference number FI Technical indication C02F 1/52 ZAB Z 7824-4D 1/72 ZAB 9045-4D 101 9045-4D 1/78 ZAB 9045 -4D 9/00 ZAB Z 7446-4D // G01N 15/00 C 2107-2J
Claims (5)
ロジェン、細菌等の微粒子状不純物を含有する液体に、
紫外線、太陽光線等の光照射を行い、液体中の微粒子状
不純物を光化学凝集、イオン化処理することによって、
液体中の微粒子状不純物、イオンの測定を可能にした液
体中の微粒子状不純物の光化学凝集、イオン化処理方
法。1. A liquid containing a trace amount of colloidal substances, particulate impurities such as bacteria, pyrogens and bacteria,
By irradiating light such as ultraviolet rays and sun rays, and photochemical aggregation and ionization treatment of fine particle impurities in the liquid,
A method for photochemical aggregation and ionization of fine particle impurities in a liquid, which enables measurement of fine particle impurities and ions in the liquid.
化処理した微粒子状不純物を、イオン交換装置、超濾過
膜装置、逆浸透膜装置等の液体処理装置のいずれか、ま
たはこれらの液体処理装置を組み合わせたシステムで除
去して処理液体を製造する液体の光化学凝集、イオン化
処理方法。2. A liquid treatment device such as an ion exchange device, an ultrafiltration membrane device, or a reverse osmosis membrane device, or the liquid treatment of the fine particle impurities obtained by photochemical aggregation and ionization treatment in the liquid according to claim 1. A photochemical coagulation and ionization treatment method for a liquid, which is produced by removing a treated liquid by a system including a combination of devices.
子状不純物を光化学凝集、イオン化処理するについて、
光照射とともにオゾンを添加する液体の光化学凝集、イ
オン化処理方法。3. Regarding the photochemical aggregation and ionization treatment of the particulate impurities in the liquid according to claim 1 or 2,
A photochemical aggregation and ionization treatment method of a liquid in which ozone is added together with light irradiation.
子状不純物を光化学凝集、イオン化処理するについて、
光照射とともに酸化剤を添加する液体の光化学凝集、イ
オン化処理方法。4. Regarding photochemical aggregation and ionization treatment of fine particle impurities in the liquid according to claim 1 or 2,
A photochemical aggregation and ionization treatment method of a liquid in which an oxidizing agent is added together with light irradiation.
子状不純物を光化学凝集、イオン化処理するについて、
光照射として、２２０ｎｍ以下の紫外線の照射を行う液
体の光化学凝集、イオン化処理方法。5. The photochemical coagulation and ionization treatment of the particulate impurities in the liquid according to claim 1 or 2,
A method of photochemical aggregation and ionization treatment of a liquid, which comprises irradiating ultraviolet rays of 220 nm or less as light irradiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30627392A JP3315447B2 (en) | 1992-10-20 | 1992-10-20 | Photochemical agglomeration and ionization treatment method for particulate impurities in liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30627392A JP3315447B2 (en) | 1992-10-20 | 1992-10-20 | Photochemical agglomeration and ionization treatment method for particulate impurities in liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06134455A true JPH06134455A (en) | 1994-05-17 |
| JP3315447B2 JP3315447B2 (en) | 2002-08-19 |
Family
ID=17955102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30627392A Expired - Fee Related JP3315447B2 (en) | 1992-10-20 | 1992-10-20 | Photochemical agglomeration and ionization treatment method for particulate impurities in liquid |
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| Country | Link |
|---|---|
| JP (1) | JP3315447B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1112965A3 (en) * | 1999-12-28 | 2002-03-13 | Sociedad Espanola De Carburos Metalicos S.A. | Process for the degradation of organic compounds in aqueous solution by means of ozonisation and sunlight irradiation |
| JP2007209856A (en) * | 2006-02-07 | 2007-08-23 | Toshiba Corp | Agglomerator and its flocculation process of particle |
| CN108097648A (en) * | 2016-11-25 | 2018-06-01 | 宁德市凯欣电池材料有限公司 | Material wash mill |
-
1992
- 1992-10-20 JP JP30627392A patent/JP3315447B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1112965A3 (en) * | 1999-12-28 | 2002-03-13 | Sociedad Espanola De Carburos Metalicos S.A. | Process for the degradation of organic compounds in aqueous solution by means of ozonisation and sunlight irradiation |
| ES2170626A1 (en) * | 1999-12-28 | 2002-08-01 | Soc Es Carburos Metalicos Sa | Process for the degradation of organic compounds in aqueous solution by means of ozonisation and sunlight irradiation |
| JP2007209856A (en) * | 2006-02-07 | 2007-08-23 | Toshiba Corp | Agglomerator and its flocculation process of particle |
| JP4660390B2 (en) * | 2006-02-07 | 2011-03-30 | 株式会社東芝 | Fine particle aggregating apparatus and aggregating method thereof |
| CN108097648A (en) * | 2016-11-25 | 2018-06-01 | 宁德市凯欣电池材料有限公司 | Material wash mill |
| CN108097648B (en) * | 2016-11-25 | 2021-02-12 | 宁德市凯欣电池材料有限公司 | Material washing device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3315447B2 (en) | 2002-08-19 |
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