JP2009198497A - Indirect measuring method for ozone concentration - Google Patents
Indirect measuring method for ozone concentration Download PDFInfo
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- JP2009198497A JP2009198497A JP2009011097A JP2009011097A JP2009198497A JP 2009198497 A JP2009198497 A JP 2009198497A JP 2009011097 A JP2009011097 A JP 2009011097A JP 2009011097 A JP2009011097 A JP 2009011097A JP 2009198497 A JP2009198497 A JP 2009198497A
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 238000000034 method Methods 0.000 title claims abstract description 37
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 55
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 35
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 229910052734 helium Inorganic materials 0.000 claims abstract description 6
- 239000001307 helium Substances 0.000 claims abstract description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 33
- 239000012530 fluid Substances 0.000 claims description 15
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052743 krypton Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 4
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 4
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052704 radon Inorganic materials 0.000 claims description 3
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 82
- 239000007788 liquid Substances 0.000 abstract description 19
- 238000004880 explosion Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005949 ozonolysis reaction Methods 0.000 abstract description 4
- 239000003085 diluting agent Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010790 dilution Methods 0.000 description 21
- 239000012895 dilution Substances 0.000 description 21
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 16
- 229910001882 dioxygen Inorganic materials 0.000 description 16
- 238000004821 distillation Methods 0.000 description 8
- 238000000691 measurement method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001739 density measurement Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 208000035404 Autolysis Diseases 0.000 description 1
- 206010057248 Cell death Diseases 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000028043 self proteolysis Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 150000003736 xenon Chemical class 0.000 description 1
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Abstract
Description
この発明は、オゾンを含有する流体が存在する試験設備や生産プロセスにおいて、高濃度に濃縮したオゾンの濃度を、間接的に測定する方法に関する。 The present invention relates to a method of indirectly measuring the concentration of ozone concentrated to a high concentration in a test facility or production process in which a fluid containing ozone exists.
液体オゾンを安全に取扱う方法として、Ｈｅ、Ｎｅ、Ａｒ、Ｋｒ、Ｒｎ、ＣＦ４、ＣＨＦ３、ＣＣｌＦ３などの不活性ガス（以下、希釈ガスと言う)を液化した液化不活性ガス（以下、希釈液化ガスと言う）中にオゾンを溶解、混合し、これら不活性ガスを爆発抑制用ガスとして利用する方法がある。
しかし、希釈ガスの種類によって、その爆発抑制効果が異なっており、その効果は実際にそれぞれの条件で着火試験、自己分解試験を行ってみなければならない。
希釈ガスのうち、分子量の大きなものや比熱の大きなものは、爆発抑制効果が高いが、その分、高濃度にオゾンを濃縮しても自己分解または着火源があっても爆発、燃焼をおこさない。
このため、比較的爆発抑制効果の高いと推定される希釈ガスの効果を確認するためには、高濃度にオゾンを濃縮する必要がある。
As a method for safely handling liquid ozone, a liquefied inert gas (hereinafter referred to as a dilution gas) liquefied with an inert gas (hereinafter referred to as a dilution gas) such as He, Ne, Ar, Kr, Rn, CF 4 , CHF 3 , or CClF 3 is used . There is a method in which ozone is dissolved and mixed in a dilute liquefied gas), and these inert gases are used as explosion suppressing gases.
However, the explosion suppression effect differs depending on the type of dilution gas, and the effect must actually be subjected to an ignition test and a self-decomposition test under each condition.
Among dilution gases, those with large molecular weight and large specific heat have a high explosion-suppressing effect. However, even if ozone is concentrated to a high concentration, it will explode and burn even if there is an autolysis or ignition source. Absent.
For this reason, in order to confirm the effect of the dilution gas estimated to have a relatively high explosion suppression effect, it is necessary to concentrate ozone to a high concentration.
一方、オゾンの製造は通常、オゾナイザーを用い、常温で乾燥した酸素ガスに無声放電を行うなどの方法によって製造されるが、常温では一般的に高濃度のオゾンを製造することができず、多くはオゾン濃度が７容積％程度のオゾン・酸素混合ガスが得られるにすぎない。
オゾンをこれ以上の濃度に希釈液化ガス中に濃縮するためには、オゾナイザーからの混合ガスを希釈液化ガス中に導入し、オゾンを液化し、液化しない酸素ガスを真空ポンプ等で系外に排気する操作を繰り返す必要がある。
しかし、この操作では、酸素ガスの排出に伴って、オゾンガス、希釈液化ガスが気化した気化ガスが系外に微量排出され、また濃縮操作を繰り返すことで、最終的に希釈液化ガス中のオゾン濃度が不明確になってしまう。
On the other hand, ozone is usually manufactured by a method such as using an ozonizer and performing silent discharge on oxygen gas dried at room temperature. Only produces an ozone / oxygen mixed gas having an ozone concentration of about 7% by volume.
In order to concentrate ozone in diluted liquefied gas to a higher concentration, the mixed gas from the ozonizer is introduced into the diluted liquefied gas, ozone is liquefied, and oxygen gas that is not liquefied is exhausted out of the system by a vacuum pump or the like. It is necessary to repeat the operation.
However, in this operation, along with the discharge of oxygen gas, a small amount of vaporized gas vaporized from ozone gas and diluted liquefied gas is discharged out of the system, and the concentration of ozone in the diluted liquefied gas is finally achieved by repeating the concentration operation. Becomes unclear.
オゾンを濃縮する際に、オゾン濃縮槽の上部または前段において蒸留塔などを用いて液体オゾンと酸素ガスを完全に分離し、オゾン混合液体中に酸素ガスが全く入っていない混合液を作ることも可能であるが、これらオゾン中から酸素ガスを完全に取り除くための設備は非常に大型、高コストであり、また連続的に運転をしなければ酸素分離は達成できないため、単に希釈ガスの爆発抑制効果を計測する目的に合致しない。
ところで、オゾン含有ガス中のオゾン濃度の測定方法には、非特許文献１に記載のヨウ化カリウム溶液を用いた滴定による方法（ヨウ素法）、紫外線吸収による方法（紫外線吸収法）、インジゴ法（特許文献３）などがある。
その他、混合ガス密度測定値あるいは混合液密度測定値からの推定方法、または温度・圧力測定から気液平衡曲線を利用した推定方法などがある。
When concentrating ozone, liquid ozone and oxygen gas can be completely separated using a distillation column or the like in the upper part of the ozone concentrating tank, or a mixture containing no oxygen gas in the ozone mixture can be made. Although it is possible, the equipment for completely removing oxygen gas from ozone is very large and expensive, and oxygen separation cannot be achieved without continuous operation. It does not meet the purpose of measuring the effect.
By the way, as a measuring method of the ozone concentration in the ozone-containing gas, there are a titration method (iodine method), an ultraviolet absorption method (ultraviolet absorption method), an indigo method (non-patent document 1) described in Non-Patent Document 1. Patent Document 3) and the like.
In addition, there are an estimation method from a mixed gas density measurement value or a mixed liquid density measurement value, an estimation method using a gas-liquid equilibrium curve from a temperature / pressure measurement, and the like.
これら測定方法は、測定可能なオゾン濃度域が比較的低濃度であったり、人為的操作が複雑であったり、十分な精度で測定ができないものが多い。
手軽に濃度を測定する方法としては、サンプリングしたオゾン混合液体を気化させ、酸化マンガン、金属銅などのオゾン分解触媒を用いてオゾンを酸素に温和な条件で分解した後に、酸素濃度計で計測してオゾン濃度を推算する方法があるが、この方法では、オゾン混合液中に酸素が溶解している場合には使用できない。
また、質量分析計を利用する方法もあるが、同様に酸素とオゾンの区別はつけることができないため、酸素の溶解分だけ、オゾン濃度が高く計測される。
In many of these measuring methods, the measurable ozone concentration range is relatively low, man-made operations are complicated, and measurement cannot be performed with sufficient accuracy.
A simple method to measure the concentration is to vaporize the sampled ozone mixture liquid, decompose ozone into oxygen under a mild condition using an ozone decomposition catalyst such as manganese oxide or metallic copper, and then measure with an oximeter. Although there is a method for estimating the ozone concentration, this method cannot be used when oxygen is dissolved in the ozone mixture.
In addition, there is a method using a mass spectrometer, but similarly, since it is impossible to distinguish between oxygen and ozone, the ozone concentration is measured as high as the dissolved oxygen.
本発明における課題は、オゾンを安全に取り扱うために用いられるヘリウム、ＣＦ４などからなる希釈ガスの爆発抑制効果を確認するためのオゾンを高濃度に濃縮する試験設備や、生産プロセスなどのオゾンを濃縮する工程が含まれるプロセスにおいて、このプロセス中の濃縮されたオゾンの濃度を正確、簡便、安全に知ることができるようにすることにある。 The problem in the present invention is that test equipment for concentrating ozone at a high concentration for confirming the explosion suppression effect of dilution gas composed of helium, CF 4, etc. used for safely handling ozone, ozone for production process, etc. In the process including the step of concentrating, the object is to make it possible to know the concentration of concentrated ozone in the process accurately, simply and safely.
かかる課題を解決するため、
請求項１にかかる発明は、オゾンを濃縮した流体中のオゾン濃度を間接的に測定する方法であって、
前記流体は、酸素からオゾナイザ−により製造された希薄オゾンに、該希薄オゾンの濃度と等量もしくは等量比のキセノンとヘリウム、ネオン、アルゴン、クリプトン、ラドン、テトラフルオロメタン、トリフルオロメタン、クロロトリフルオロメタンのうち少なくともいずれか１つの希釈ガスを添加してからオゾンが高濃度になるように濃縮したものであり、
前記流体中のキセノン濃度を測定することにより、オゾン濃度を間接的に測定することを特徴とするオゾン濃度の間接測定方法である。
To solve this problem,
The invention according to claim 1 is a method for indirectly measuring the ozone concentration in a fluid enriched with ozone,
The fluid includes dilute ozone produced from oxygen by an ozonizer, and xenon and helium, neon, argon, krypton, radon, tetrafluoromethane, trifluoromethane, chlorotrifluoromethane in the same or equivalent ratio to the concentration of the dilute ozone. After adding at least one dilution gas of romethane, it is concentrated so that ozone becomes high concentration,
An ozone concentration indirect measurement method, wherein the ozone concentration is indirectly measured by measuring the xenon concentration in the fluid.
本発明によれば、希釈ガス中でオゾンが高濃度に濃縮されてなる流体中のオゾン濃度を正確に、簡便に、かつ安全に測定することができる。 According to the present invention, it is possible to accurately, simply and safely measure the ozone concentration in a fluid obtained by concentrating ozone in a dilution gas to a high concentration.
本発明は、図２に示すような温度変化に伴う飽和蒸気圧力がオゾンとほとんど同じである不活性希ガスのキセノンを濃度指標用のガスとして用い、これの既知量をオゾンを含む流体に添加し、ついでこの混合流体を希釈ガス中においてオゾンを濃縮し、得られた濃縮オゾン混合流体中のキセノン濃度を計測することにより前記濃縮オゾン混合流体中のオゾン濃度を推定する方法である。 In the present invention, an inert rare gas xenon having a saturated vapor pressure accompanying the temperature change as shown in FIG. 2 is almost the same as ozone is used as a concentration indicator gas, and a known amount thereof is added to a fluid containing ozone. Then, this mixed fluid is a method of estimating the ozone concentration in the concentrated ozone mixed fluid by concentrating ozone in a dilution gas and measuring the xenon concentration in the obtained concentrated ozone mixed fluid.
すなわち、オゾンとキセノンとは上述のように温度変化に伴う飽和蒸気圧力のほぼ同じであるので、オゾンの希釈液化ガス中での液化、濃縮のプロセスを経てもキセノンはオゾンと同様の挙動を取ることになる。このため、このようなプロセスの途中においてオゾンがプロセス系外に放散されたとしても、キセノンも同様にその同量が放散されることになって、プロセス後の流体中のキセノン濃度を知れば、間接的にオゾン濃度を正確に知ることができる。 That is, since ozone and xenon have substantially the same saturated vapor pressure as the temperature changes as described above, xenon behaves like ozone even after the process of liquefaction and concentration in diluted liquefied gas of ozone. It will be. For this reason, even if ozone is diffused out of the process system in the middle of such a process, the same amount of xenon will be diffused as well, and knowing the xenon concentration in the fluid after the process, The ozone concentration can be accurately known indirectly.
図１は、本発明のオゾン濃度の間接測定方法の一例を示すものである。
図１中、符号１は液化濃縮槽を示し、この液化濃縮槽１には冷凍機２が付設されており、液化濃縮槽１に導入されたガスを液化できるようになっている。
希釈ガス供給源３からは希釈ガスとして例えばテトラフルオロメタン（以下、ＣＦ４と表記する）が常温ガス状で液化濃縮槽１に導入される。液化濃縮槽１内は冷凍機２により予め、例えば１３０Ｋに冷却されており、導入されたＣＦ４ガスは液化して、液化状態で液化濃縮槽１に溜められる。
希釈ガスには、これ以外にヘリウム、ネオン、アルゴン、クリプトン、ラドン、トリフルオロメタン、クロロトリフルオロメタンのうち少なくともいずれか１つが用いられる。
FIG. 1 shows an example of an indirect method for measuring ozone concentration according to the present invention.
In FIG. 1, reference numeral 1 denotes a liquefaction concentration tank. A refrigeration machine 2 is attached to the liquefaction concentration tank 1 so that the gas introduced into the liquefaction concentration tank 1 can be liquefied.
From the dilution gas supply source 3, for example, tetrafluoromethane (hereinafter referred to as CF 4 ) is introduced into the liquefaction and concentration tank 1 in the form of a normal temperature gas as a dilution gas. The inside of the liquefaction concentration tank 1 is cooled to, for example, 130 K in advance by the refrigerator 2, and the introduced CF 4 gas is liquefied and stored in the liquefaction concentration tank 1 in a liquefied state.
In addition, at least one of helium, neon, argon, krypton, radon, trifluoromethane, and chlorotrifluoromethane is used as the dilution gas.
液化濃縮槽１に導入されるＣＦ４量は、液化濃縮槽内が許容する量であればよいが、液化濃縮槽１内が一定圧力になったら、ＣＦ４が液化するまで一旦導入を停止することが望ましい。
液化濃縮槽１内に必要量のＣＦ４液が溜まったならば、酸素ガス供給源４からの高純度酸素ガスが常温でオゾナイザー５に送られる。オゾナイザー５では供給された酸素の一部がオゾンに変換され、例えばオゾン濃度３〜７容積％のオゾンが希薄なオゾン・酸素混合ガスが生成され、このオゾン・酸素混合ガスは液化濃縮槽１に導入される。
The amount of CF 4 introduced into the liquefying and concentrating tank 1 may be an amount allowed in the liquefying and concentrating tank, but once the inside of the liquefying and concentrating tank 1 reaches a constant pressure, the introduction is temporarily stopped until CF 4 is liquefied. It is desirable.
When a necessary amount of CF 4 liquid is accumulated in the liquefaction concentration tank 1, high-purity oxygen gas from the oxygen
この際、オゾナイザー５から導出されるオゾン・酸素混合ガス中のオゾン濃度を紫外吸収スペクトル法などによるオゾン濃度計６で計測する。計測されたオゾン濃度は調節計７に送られ、調節計７からの制御信号がキセノン流量調整弁８に送られる。
キセノン流量調整弁８には、キセノンガス供給源９からのキセノンガスが送られ、その流量が前記オゾン濃度に対応して調整されたうえ、オゾン・酸素混合ガスに添加される。
At this time, the ozone concentration in the ozone / oxygen mixed gas derived from the
Xenon gas from a xenon
キセノンガスの添加濃度は、オゾン・酸素混合ガス中のオゾン濃度と等量もしくは等量比とされる。ここでの等量比とは、例えばオゾン濃度が５容積％であれば、キセノンガスの添加量を０．５容量％となるようにすること言う。キセノンの濃度はオゾン濃度１〜１／１０とされ、酸素が共存する場合には、キセノン濃度を２０モル％以下とすることが好ましい。 The addition concentration of the xenon gas is equal to or equal to the ozone concentration in the ozone / oxygen mixed gas. The equivalence ratio here means that, for example, if the ozone concentration is 5% by volume, the amount of xenon gas added is 0.5% by volume. The concentration of xenon is set to an ozone concentration of 1 to 1/10. When oxygen coexists, the xenon concentration is preferably 20 mol% or less.
このオゾン・酸素・キセノン混合ガスは液化濃縮槽１に回分供給される。液化濃縮槽１に導入されたオゾン・酸素・キセノン混合ガスは冷却され、沸点の高いオゾンおよびキセノンは液化し、液化濃縮槽１内に溜まっているＣＦ４液中に溶解し、沸点の低い酸素は液化濃縮槽１の気相に残り、液化濃縮槽１の底部には、ＣＦ４・オゾン・キセノン混合液体が溜まる。液化濃縮槽１の気相の酸素ガスは、液化濃縮槽１に接続された真空ポンプ１０により系外に排出される。
この操作を複数回繰り返すことで、オゾンの濃縮が行われ、液化濃縮槽１に導入したオゾン・酸素・キセノン混合ガス中のオゾン濃度、例えば５容量％よりも高い濃度、例えば５０〜７０容積％の濃縮が可能となる。
This ozone / oxygen / xenon mixed gas is supplied to the liquefaction concentration tank 1 in batches. The ozone / oxygen / xenon mixed gas introduced into the liquefying and concentrating tank 1 is cooled, and ozone and xenon having a high boiling point are liquefied and dissolved in the CF 4 liquid accumulated in the liquefying and concentrating tank 1, and oxygen having a low boiling point. Remains in the gas phase of the liquefaction concentration tank 1, and a mixed liquid of CF 4 , ozone, and xenon accumulates at the bottom of the liquefaction concentration tank 1. The gaseous oxygen gas in the liquefaction concentration tank 1 is discharged out of the system by the
By repeating this operation a plurality of times, ozone is concentrated and the ozone concentration in the ozone / oxygen / xenon mixed gas introduced into the liquefied concentration tank 1 is higher than, for example, 5% by volume, for example, 50 to 70% by volume. Can be concentrated.
液化濃縮槽１でのオゾンおよびキセノンの液化は液化濃縮槽１内の圧力が一定になったことで完了したかどうかを判別可能であるが、本発明では液化が十分ではない状態で気相の酸素ガスを真空ポンプで排気しても、オゾン濃度の推定には影響がない。 Although it is possible to determine whether or not the liquefaction of ozone and xenon in the liquefaction concentration tank 1 has been completed when the pressure in the liquefaction concentration tank 1 has become constant, in the present invention, in the state where the liquefaction is not sufficient, Exhausting oxygen gas with a vacuum pump does not affect the estimation of ozone concentration.
液化濃縮槽１に溜まったＣＦ４・オゾン・キセノン混合液体中のオゾン濃度の測定は、この混合液体の一部を抜き出し、気化器１１に送って気化し、さらにこれをオゾン分解槽１２に送って、酸化マンガン、金属銅などの分解触媒によってこれに含まれるオゾンを分解して酸素とする。オゾン分解槽１２からの混合ガスはガス分析計１３に送られ、これに含まれるキセノン濃度が計測される。ガス分析計１３には、質量分析計などが用いられる。
Measurement of the ozone concentration in the CF 4 / ozone / xenon mixed liquid accumulated in the liquefying and concentrating tank 1 is carried out by extracting a part of the mixed liquid, sending it to the
さらに、ガス分析計１３で計測されたキセノン濃度からオゾン濃度を換算する。キセノンガスの添加濃度がオゾン濃度と等量であれば、キセノン濃度がそのままオゾン濃度となり、等量比であればその比を乗ずればオゾン濃度が得られる。
キセノン濃度の測定は、質量分析計でおこなうことができるが、そのほかの方法でもかまわない。またオゾンによる影響がなければ、ガス分析計１３の前段でオゾンを分解する必要は必ずしもない。
Further, the ozone concentration is converted from the xenon concentration measured by the
Xenon concentration can be measured with a mass spectrometer, but other methods are also acceptable. Moreover, if there is no influence by ozone, it is not always necessary to decompose ozone at the front stage of the
一般に販売されているオゾン濃度計の測定濃度範囲は最大でも１５容積％程度であるが、この測定方法では、キセノンを導入するオゾン・酸素混合ガス中のオゾン濃度の１／１０量のキセノンを導入することで、ＣＦ４・オゾン・キセノン混合液体中のオゾン濃度が５０容積％以上の場合もその濃度を推定することができる。 The measurement concentration range of a commercially available ozone densitometer is about 15% by volume at the maximum, but this measurement method introduces xenon that is 1/10 of the ozone concentration in the ozone / oxygen mixed gas into which xenon is introduced. By doing so, even when the ozone concentration in the CF 4 / ozone / xenon liquid mixture is 50% by volume or more, the concentration can be estimated.
ところで、キセノンをオゾン・酸素混合ガスに添加しない場合には、液化濃縮槽１の気相の酸素ガスを真空ポンプ１０で排気する際に、酸素ガスに同伴して、希釈ガスの一部や液化しなかったオゾンが系外に排出され、真空排気操作とオゾン導入操作が複数回重なることで、液化濃縮槽１底部の前記混合液体中のオゾン濃度が正確に推定できない。
さらに、前記混合液体中に酸素ガスが微量溶解するため、質量分析計や該混合液体をオゾン分解槽を通したあとに酸素ガスを計測すると、該混合液体中に溶解している酸素ガスもオゾンとして加算されてしまう。
By the way, when xenon is not added to the ozone / oxygen mixed gas, when the gas phase oxygen gas in the liquefying and concentrating tank 1 is exhausted by the
Furthermore, since a small amount of oxygen gas is dissolved in the mixed liquid, when the oxygen gas is measured after passing the mass spectrometer or the mixed liquid through the ozonolysis tank, the oxygen gas dissolved in the mixed liquid is also ozone. Will be added.
これに対して、本発明では、キセノンを等量または等量比で予めオゾン・酸素混合ガスに添加させておくと、オゾンと飽和圧力がほぼ同じキセノンの混合液中の濃度を測定することで、オゾンの濃度を推定することが可能となる。
キセノンの飽和蒸気圧力は、オゾンのそれよりわずかに小さいため、液化に際してキセノンの方が若干液化しやすい。そのため、流体中の実際のオゾン濃度は、測定されたキセノン濃度よりもわずかに小さい値になる。しかし、キセノン濃度をオゾン濃度と読み替えた場合、実際のオゾン濃度がそれ以下であるので、安全側になり、プロセス管理に使用した場合にも、保安上の問題とはならない。
On the other hand, in the present invention, when xenon is added to the ozone / oxygen mixed gas in an equal amount or an equal ratio in advance, the concentration in the mixed liquid of xenon having substantially the same saturation pressure as ozone is measured. The ozone concentration can be estimated.
Since the saturated vapor pressure of xenon is slightly smaller than that of ozone, xenon is slightly liquified when liquefied. Therefore, the actual ozone concentration in the fluid is slightly smaller than the measured xenon concentration. However, when xenon concentration is read as ozone concentration, since the actual ozone concentration is lower than that, it becomes safer and does not pose a safety problem when used for process management.
以上のようにしてオゾンが濃縮され、かつそのオゾン濃度が求められたＣＦ４・オゾン・キセノン混合液体は、希釈ガスであるＣＦ４の爆発抑制効果の測定に供される。 The CF 4 / ozone / xenon mixed liquid in which ozone is concentrated and the ozone concentration is determined as described above is used for measurement of the explosion suppression effect of CF 4 as a dilution gas.
また、１７Ｏなどの酸素同位体の濃縮方法においては、図３に示すように、高純度酸素を管２１からオゾナイザー２２に導入して、オゾン・酸素混合ガスとし、これに管２３からのＣＦ４などの希釈ガスを混合したうえ、これを第１蒸留塔２４に送り、酸素を分離、除去する。第１蒸留塔２４からのオゾン・希釈ガス混合ガスはついで光セル２５に送られ、ここで特定波長のレーザ光が照射されて１７Ｏを含むオゾンが選択的に分解されて、１７Ｏを含む酸素となり、１７Ｏを含む酸素とオゾンと希釈ガスとの混合ガスが第２蒸留塔２６に送られ、１７Ｏを含む酸素が分離されてその塔頂から導出され、塔底からは残余のオゾンと希釈ガスとの混合ガスが導出されるプロセスが、例えば特開２００５−４０６６８号公報に開示されている。
In addition, in the method for concentrating oxygen isotopes such as 17 O, as shown in FIG. 3, high-purity oxygen is introduced into the ozonizer 22 from the
このプロセスでは、第１蒸留塔２４から導出されるオゾン・希釈ガス混合ガス中のオゾン濃度あるいは第２蒸留塔２６から導出されるオゾン・希釈ガス混合ガス中のオゾン濃度が高濃度になると予想される。これらの混合ガス中のオゾン濃度を測定する場合においても、本発明の間接測定方法が適用できる。
In this process, it is expected that the ozone concentration in the ozone / dilution gas mixed gas derived from the
すなわち、オゾナイザー２２から導出されるオゾン・酸素混合ガス中のオゾン濃度を計測し、このオゾン濃度と等量または等量比のキセノンを管２８から添加する。そして、第１蒸留塔２４から導出されるオゾン・希釈ガス・キセノン混合ガス中のキセノン濃度あるいは第２蒸留塔２６から導出されるオゾン・希釈ガス・キセノン混合ガス中のキセノン濃度を先と同様にして計測し、このキセノン濃度からオゾン濃度を算出する。
That is, the ozone concentration in the ozone / oxygen mixed gas derived from the ozonizer 22 is measured, and xenon having the same amount or an equivalent ratio as this ozone concentration is added from the
１・・液化濃縮槽、２・・冷凍機、３・・希釈ガス供給源、４・・酸素ガス供給源、５・・オゾナイザー、６・・オゾン濃度計、７・・調節計、８・・キセノン流量調整弁、９・・キセノンガス供給源、１０・・真空ポンプ、１１・・気化器、１２・・オゾン分解槽、１３・・ガス分析計 1 .... Liquefaction concentrating tank, 2 .... Refrigerator, 3 .... Dilution gas supply source, 4 .... Oxygen gas supply source, 5 .... Ozonizer, 6 .... Ozone concentration meter, 7 .... Regulator, 8 .... Xenon flow control valve, 9 ... xenon gas supply source, 10 ... vacuum pump, 11 ... vaporizer, 12 ... ozonolysis tank, 13 ... gas analyzer
Claims (1)
前記流体は、酸素からオゾナイザ−により製造されたオゾンに、該オゾンの濃度と等量もしくは等量比のキセノンとヘリウム、ネオン、アルゴン、クリプトン、ラドン、テトラフルオロメタン、トリフルオロメタン、クロロトリフルオロメタンのうち少なくともいずれか１つの流体を添加してからオゾンが高濃度になるように濃縮したものであり、
前記流体中のキセノン濃度を測定することにより、オゾン濃度を間接的に測定することを特徴とするオゾン濃度の間接測定方法。 A method for indirectly measuring ozone concentration in a fluid enriched with ozone,
The fluid is composed of oxygen produced by an ozonizer from oxygen, and xenon and helium, neon, argon, krypton, radon, tetrafluoromethane, trifluoromethane, and chlorotrifluoromethane in the same or equivalent ratio as the ozone concentration. After adding at least one of these fluids, the ozone is concentrated to a high concentration,
A method for indirectly measuring ozone concentration, wherein the ozone concentration is indirectly measured by measuring the xenon concentration in the fluid.
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