JP2010137174A - Detoxifying agent for halogen gas and method for detoxifying halogen gas using the same - Google Patents
Detoxifying agent for halogen gas and method for detoxifying halogen gas using the same Download PDFInfo
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- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 62
- 150000002367 halogens Chemical class 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000010457 zeolite Substances 0.000 claims abstract description 53
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 52
- 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 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 23
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 22
- 150000001768 cations Chemical class 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 239000012013 faujasite Substances 0.000 claims abstract description 14
- 239000002516 radical scavenger Substances 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000001784 detoxification Methods 0.000 description 16
- 239000011734 sodium Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- -1 etc.) Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000004927 clay Substances 0.000 description 7
- 239000000575 pesticide Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229910052811 halogen oxide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 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
- 229910003691 SiBr Inorganic materials 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 238000004065 wastewater treatment Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
【課題】高効率でハロゲン系ガスを除害できるゼオライトからなる除害剤及びそれを用いたハロゲン系ガスの除害方法を提供する。
【解決手段】ＳｉＯ２／Ａｌ２Ｏ３モル比が２．０〜２．３であり、少なくともＫカチオンを３０ｍｏｌ％以上含有するフォージャサイト型ゼオライトを除害剤として用いる。Ｋカチオンは５０ｍｏｌ％以上、さらには８０ｍｏｌ％以上であることが好ましい。バインダーを用いて成型する場合、バインダーをゼオライト化して用いることが好ましい。
【選択図】なしA detoxifying agent comprising a zeolite capable of detoxifying a halogen-based gas with high efficiency and a halogen-based gas detoxifying method using the same.
A faujasite type zeolite having a SiO 2 / Al 2 O 3 molar ratio of 2.0 to 2.3 and containing at least 30 mol% of a K cation is used as a detoxifying agent. The K cation is preferably 50 mol% or more, more preferably 80 mol% or more. When molding using a binder, it is preferable to use the binder after zeoliticization.
[Selection figure] None
Description
本発明は半導体・液晶製造におけるエッチング工程、ＣＶＤ（化学気相蒸着）プロセス及びクリーニング工程などから排出されるハロゲン系ガスを含む排ガスを無害化する、ハロゲン系ガスの除害剤及びそれを用いるハロゲン系ガスの除害方法に関するものである。 The present invention relates to a halogen-based gas detoxifying agent that detoxifies exhaust gas containing a halogen-based gas discharged from an etching process, a CVD (chemical vapor deposition) process, a cleaning process, etc. in semiconductor / liquid crystal manufacturing, and a halogen using the same. The present invention relates to a system gas removal method.
半導体・液晶製造におけるエッチング工程、ＣＶＤ（化学気相蒸着）プロセス及びクリーニング工程などから排出されるハロゲン系ガスを含む排ガス無害化する方法として、熱分解法、湿式法及び乾式法が知られている。熱分解法は加熱または燃焼して前記排ガスを分解するものである。熱分解法では可燃性ガスを多く取扱う半導体工場内で高温を使用する問題がある。また熱分解ガスは水などで処理されるが、排水処理が問題となる。 Thermal decomposition methods, wet methods, and dry methods are known as methods for detoxifying exhaust gases containing halogen-based gases discharged from etching processes, CVD (chemical vapor deposition) processes, and cleaning processes in semiconductor / liquid crystal manufacturing. . In the thermal decomposition method, the exhaust gas is decomposed by heating or combustion. In the pyrolysis method, there is a problem of using high temperature in a semiconductor factory that handles a large amount of combustible gas. The pyrolysis gas is treated with water or the like, but wastewater treatment becomes a problem.
湿式法は苛性ソーダ水溶液などのアルカリ水溶液や水に吸収させるものである。前記排ガスをアルカリ水溶液に吸収させる場合、ナトリウムによるウエハーの汚染、ハロゲン系ガスとアルカリ水溶液との反応によって生成する固形物が処理装置の排気ラインを閉塞するなどの問題がある。また、水を使用する場合、排水量を抑制するために洗浄水を循環使用されることが多く、前記排ガスが十分に洗浄されない問題がある。 In the wet method, an aqueous alkali solution such as an aqueous caustic soda solution or water is absorbed. When the exhaust gas is absorbed in an alkaline aqueous solution, there are problems such as contamination of the wafer by sodium and solid matter produced by the reaction between the halogen-based gas and the alkaline aqueous solution clogging the exhaust line of the processing apparatus. Moreover, when using water, in order to suppress the amount of waste_water | drain, in many cases, the wash water is circulated and used, There exists a problem in which the said waste gas is not fully wash | cleaned.
乾式法は固体の除害剤と前記排ガスを接触させて処理する簡便であり、熱分解法及び湿式法の問題点を改善できる方法として多く採用されている。これまで提案されている多くの除害剤は多量の活性炭を使用しているが、活性炭はハロゲン系ガスの急激な吸着・反応に伴う発熱による発火及び爆発などが発生する危険性があるため、不燃性であるゼオライトを使用した除害剤及び除害方法が提案されている。ゼオライトには数多くの結晶構造があり、組成、細孔径も多種多様である。 The dry method is a simple method in which a solid detoxifying agent and the exhaust gas are brought into contact with each other for treatment, and is often employed as a method that can improve the problems of the thermal decomposition method and the wet method. Many abatement agents that have been proposed so far use a large amount of activated carbon, but activated carbon has a risk of ignition and explosion due to heat generation due to rapid adsorption and reaction of halogen gas, A detoxifying agent and a detoxifying method using a nonflammable zeolite have been proposed. Zeolite has a large number of crystal structures, and the composition and pore size are also diverse.
例えば特許文献１はハロゲン系ガスをアルミナおよび／またはゼオライトとソーダライムを組み合せて除害する方法が開示されている。特許文献２には、ハロゲン系ガスを平均孔径９Å以上のゼオライトを使用することが記載されている。特許文献３、４にはハロゲン系ガスをゼオライト等の除害剤と接触させる工程を含むハロゲン系ガスの除害方法が記載されており、ゼオライトとしてＭＳ−５Ａ（ＣａＡ型ゼオライト）及びＭＳ−１３Ｘ（ＮａＸ型ゼオライト）等が例示されている。特許文献５には、固体塩基と炭素質材料と無機酸化物の多孔質体からなる造粒物によりハロゲン系ガスを除供する方法が記載されており、ゼオライトとしてはＡ型ゼオライトが例示されている。 For example, Patent Document 1 discloses a method of detoxifying a halogen-based gas by combining alumina and / or zeolite and soda lime. Patent Document 2 describes that a halogen-based gas having an average pore diameter of 9 mm or more is used. Patent Documents 3 and 4 describe a halogen-based gas removal method including a step of contacting a halogen-based gas with a detoxifying agent such as zeolite. MS-5A (CaA-type zeolite) and MS-13X are used as zeolites. (NaX type zeolite) and the like are exemplified. Patent Document 5 describes a method of removing a halogen-based gas by using a granulated product made of a porous body of a solid base, a carbonaceous material, and an inorganic oxide, and examples of zeolite include A-type zeolite. .
特許文献６には、カチオンとしてアルカリ金属および／またはアルカリ土類金属を少なくとも１種を含有しているＳｉＯ２／Ａｌ２Ｏ３モル比が２．０〜２．３のフォージャサイト型ゼオライトのハロゲン系ガス除害剤が例示されているが、いずれもＫカチオンは３０ｍｏｌ％以下のものであった。 Patent Document 6 discloses a faujasite-type zeolite having a SiO 2 / Al 2 O 3 molar ratio of 2.0 to 2.3 containing at least one alkali metal and / or alkaline earth metal as a cation. Halogen-based gas scavengers are exemplified, but in all cases, K cation was 30 mol% or less.
これまで開示されているものは、ハロゲン系ガスの除害性能は必ずしも十分なものではなかった。 What has been disclosed so far has not always been sufficient in the halogen gas removal performance.
本発明は、これまで以上に高効率でハロゲン系ガスを除害できるゼオライトを含んでなる除害剤及びそれを用いたハロゲン系ガスの除害方法を提供するものである。 The present invention provides a detoxifying agent comprising a zeolite capable of detoxifying a halogen-based gas with higher efficiency than ever, and a method for detoxifying a halogen-based gas using the same.
本発明者は上記目的を達成するために鋭意検討した結果、従来のゼオライトを使用した除害剤よりもハロゲン系ガスを安全に高効率で除害できる除害剤および除害方法を見出した。 As a result of intensive studies to achieve the above object, the present inventor has found a detoxifying agent and a detoxifying method capable of detoxifying a halogen-based gas safely and more efficiently than a detoxifying agent using a conventional zeolite.
以下、本発明のハロゲン系ガスの除害剤及びそれを使用するハロゲン系ガスの除害方法について説明する。 Hereinafter, the halogen-based gas scavenger of the present invention and the halogen-based gas scavenging method using the same will be described.
本発明のハロゲン系ガスの除害剤は、ＳｉＯ２／Ａｌ２Ｏ３モル比が２．０〜２．３であり、少なくとも３０ｍｏｌ％を超えるＫカチオンを含有するフォージャサイト型ゼオライトを含んでなるものであり、Ｋカチオンは特に５０ｍｏｌ％以上、さらには８０ｍｏｌ％以上含有しているものが好ましい。 Detoxifying agents of halogen-containing gas of the present invention, SiO 2 / Al 2 O 3 molar ratio is 2.0 to 2.3, contains a faujasite-type zeolite containing K cations in excess of at least 30 mol% In particular, the K cation is preferably contained in an amount of 50 mol% or more, and more preferably 80 mol% or more.
残りのカチオンについては特に限定はないが、例えばＮａカチオンを用いれば良い。 The remaining cations are not particularly limited, but for example, Na cations may be used.
本発明の除害剤のゼオライト種としては、ＳｉＯ２／Ａｌ２Ｏ３モル比２．０〜２．３のフォージャサイト型ゼオライトが用いられるが、特にＳｉＯ２／Ａｌ２Ｏ３モル比は特に２．０〜２．２、さらには２．０〜２．１が好ましい。 As the zeolite species of the present pesticide, a faujasite type zeolite having a SiO 2 / Al 2 O 3 molar ratio of 2.0 to 2.3 is used, and in particular, the SiO 2 / Al 2 O 3 molar ratio is In particular, 2.0 to 2.2, more preferably 2.0 to 2.1 is preferable.
本発明のハロゲン系ガスの除害剤は、フォージャサイト型ゼオライトとして特にＳｉＯ２／Ａｌ２Ｏ３モル比が低いフォージャサイト型ゼオライト｛通常ＬＳＸ（Ｌｏｗ Ｓｉｌｉｃａ Ｘ）ゼオライトと呼ばれている｝を用いた場合、そのカチオン量の化学量論的な増大から予想される性能向上をはるかに超えた性能向上を発揮するものである。 The halogen-based gas scavenger of the present invention is a faujasite type zeolite having a low SiO 2 / Al 2 O 3 molar ratio as a faujasite type zeolite {usually called LSX (Low Silica X) zeolite} Is used, the performance improvement far exceeds that expected from the stoichiometric increase in the cation content.
本発明のハロゲン系ガス除害剤にはバインダーが含有されても良いが、更に除害能力を高めるためにバインダー成分（粘土鉱物、シリカ、アルミナなど）をバインダーレス化してゼオライトに転換していることが好ましく、特に残存するバインダーが０〜１０％なるまで、ゼオライト結晶に変性転化する（通常「バインダーレス化」といわれる）ことが好ましい。 The halogen-based gas abatement agent of the present invention may contain a binder, but the binder component (clay mineral, silica, alumina, etc.) is converted to a zeolite by making it binderless in order to further enhance the abatement capability. In particular, it is preferable to modify and convert to zeolite crystals until the remaining binder is 0 to 10% (usually referred to as “binderless”).
ゼオライト粉末はミクロンオーダーの粉末であり、吸着用途などで使用する場合は成形体として使用される。しかしゼオライト粉末は自己結合性がないため成形する時にはバインダーが添加され、バインダーとしては粘土鉱物（カオリン、アタパルジャイト、セピオライト、モンモリロナイトなど）、シリカ、アルミナなどが代表的に使用される。これらのバインダーは吸着能力が極めて低く、その添加量だけ吸着容量は低下するため、本発明の除害剤はバインダー成分をバインダーレス化することによってさらに吸着容量を高めて用いることが好ましい。 Zeolite powder is a micron-order powder, and is used as a molded body when used in adsorption applications. However, since zeolite powder does not have self-bonding properties, a binder is added during molding. As the binder, clay minerals (kaolin, attapulgite, sepiolite, montmorillonite, etc.), silica, alumina and the like are typically used. Since these binders have extremely low adsorption capacity and the adsorption capacity is reduced by the amount of the binder added, it is preferable to use the detoxifying agent of the present invention by further increasing the adsorption capacity by making the binder component binderless.
本発明のハロゲン系ガス除害剤は、低いＳｉＯ２／Ａｌ２Ｏ３モル比のフォージャサイト型ゼオライトを用いること、カチオンとして少なくともＫカチオンを３０ｍｏｌ％を超えて含有（好ましくは５０ｍｏｌ％以上、さらに８０ｍｏｌ％以上）含有していること、更にバインダー成分をバインダーレス化することによって、期待される除害剤中のゼオライト成分の増大率から予想されるハロゲン系ガスの除害性能の増大率を超えた除害性能が発揮されるものである。 The halogen-based gas scavenger of the present invention uses a faujasite type zeolite having a low SiO 2 / Al 2 O 3 molar ratio, and contains at least K cation as a cation exceeding 30 mol% (preferably 50 mol% or more, Furthermore, by making the binder component binder-free, the increase rate of the halogen gas detoxification performance expected from the expected increase rate of the zeolite component in the detoxifying agent can be increased. Excess detoxification performance is demonstrated.
バインダー成分のバインダーレス化は、粘土等のバインダーで成形したゼオライト成形体のバインダー成分をアルカリ処理することでゼオライトへ転換することによって実施できる。バインダーから転換されるゼオライトは、ハロゲン系ガスの除害に有効なＳｉＯ２／Ａｌ２Ｏ３モル比が２．０〜２．３のフォージャサイト型ゼオライトが好適である。 The binder-less binder component can be carried out by converting the binder component of the zeolite molded body molded with a binder such as clay into zeolite by alkali treatment. Zeolite is converted from the binder is effective SiO 2 / Al 2 O 3 molar ratio abatement of halogen-containing gas is preferably faujasite zeolite of 2.0 to 2.3.
使用されるバインダーは、ＳｉＯ２／Ａｌ２Ｏ３モル比が２．０〜２．３のフォージャサイト型ゼオライトへ転換できるものであれば特に限定されないが好ましくは粘土鉱物が使用され、そのなかでもカオリン粘土が好適である。カオリン粘土はゼオライトと同様にＳｉＯ２及びＡｌ２Ｏ３で構成されており、ＳｉＯ２／Ａｌ２Ｏ３モル比は２．０であり、ＳｉＯ２／Ａｌ２Ｏ３モル比が２．０〜２．３のフォージャサイト型ゼオライトと組成が近いためである。 The binder used is not particularly limited as long as it can be converted into a faujasite type zeolite having a SiO 2 / Al 2 O 3 molar ratio of 2.0 to 2.3, but a clay mineral is preferably used. However, kaolin clay is preferred. Kaolin clay is composed of SiO 2 and Al 2 O 3 like zeolite, SiO 2 / Al 2 O 3 molar ratio is 2.0, and SiO 2 / Al 2 O 3 molar ratio is 2.0 to This is because the composition is similar to that of 2.3 faujasite type zeolite.
バインダーレス化する際のアルカリ濃度、ＳｉＯ２濃度、温度、反応時間などの条件は、バインダーレス化が十分に進行し不純物が生成しないで、使用する時に成形体が粉化しない強度を保持できる条件であればよい。例えばアルカリ濃度０．５〜１０ｍｏｌ／Ｌ、特にＬＳＸゼオライトへ転化する場合は６〜１０ｍｏｌ／Ｌ、ＳｉＯ２濃度０〜１．５ｗｔ％、温度７０〜９５℃、反応時間３〜１０時間が例示できる。 Conditions such as alkali concentration, SiO 2 concentration, temperature, reaction time, etc. when making binderless are conditions under which binderlessness is sufficiently advanced and impurities are not generated, and the strength at which the molded body does not become powdered when used. If it is. For example, an alkali concentration of 0.5 to 10 mol / L, particularly 6 to 10 mol / L when converted to LSX zeolite, an SiO 2 concentration of 0 to 1.5 wt%, a temperature of 70 to 95 ° C., and a reaction time of 3 to 10 hours can be exemplified. .
次に本発明の除害剤を用いたハロゲン系ガスの除害方法について説明する。 Next, the halogen gas removal method using the remover of the present invention will be described.
本発明の除害方法は、ハロゲン系ガスと接触させる除害剤として本発明の除害剤を使用する以外は、従来の乾式法によるハロゲン系ガスの除害方法と同様に実施できる。例えば、一端にハロゲン系ガスの入口及び他端にガス出口を有する除害塔（吸着塔）に本発明の除害剤を充填して、ガス入口よりハロゲン系ガスを導入すると、除害塔内の本発明の除害剤にハロゲン系ガスが吸着され、ガス出口よりハロゲン系ガスの濃度が許容濃度以下となったガスが放出される。 The detoxifying method of the present invention can be carried out in the same manner as the detoxifying method for halogen-based gas by the conventional dry method, except that the detoxifying agent of the present invention is used as a detoxifying agent to be brought into contact with the halogen-based gas. For example, when a detoxification tower (adsorption tower) having a halogen-based gas inlet at one end and a gas outlet at the other end is filled with the detoxifying agent of the present invention and the halogen-based gas is introduced from the gas inlet, The halogen-based gas is adsorbed by the detoxifying agent of the present invention, and a gas having a halogen-based gas concentration below an allowable concentration is released from the gas outlet.
本発明の除害剤の充填量、除害剤の形状と粒子径、除害塔の大きさ、ハロゲン系ガスの流量（線速度）、ハロゲン系ガスの濃度、除害温度、除害圧力などの処理条件は、除害能力が低下しない条件が適宜選択される。通常、使用される除害剤は球状あるいは円柱状などの成形体であり、好ましくは球状が使用される。球状の場合では粒子直径は０．１〜５ｍｍ、円柱状の場合では直径０．５〜３ｍｍ、長さ１〜１０ｍｍ程度のものを使用することができる。極端に粒子径が小さい場合は除害塔の圧力損失が大きくハロゲン系ガスの流通が困難となり、粒子径が大きくなりすぎると除害効率の低下を引き起こす。ハロゲン系ガスの濃度は０．１〜１０体積％、線速度は０．０１〜１０ｍ／秒の範囲となるように調整される。除害温度は特に加温及び冷却の必要はなく常温（２０〜３０℃）で、除害圧力は大気圧でよい。 Packing amount of the detoxifying agent of the present invention, shape and particle size of the detoxifying agent, size of the detoxifying tower, halogen gas flow rate (linear velocity), concentration of halogen gas, detoxifying temperature, detoxifying pressure, etc. The treatment conditions are appropriately selected so that the abatement ability does not decrease. Usually, the detoxifying agent used is a molded body such as a spherical shape or a cylindrical shape, and preferably a spherical shape is used. In the case of a spherical shape, a particle diameter of 0.1 to 5 mm can be used, and in the case of a cylindrical shape, a diameter of about 0.5 to 3 mm and a length of about 1 to 10 mm can be used. When the particle size is extremely small, the pressure loss of the detoxification tower is large and the circulation of the halogen-based gas becomes difficult. When the particle size is too large, the detoxification efficiency is lowered. The concentration of the halogen-based gas is adjusted to be in the range of 0.1 to 10% by volume, and the linear velocity is in the range of 0.01 to 10 m / second. The detoxification temperature is not particularly required to be heated and cooled, and is normal temperature (20 to 30 ° C.), and the detoxification pressure may be atmospheric pressure.
本発明でいうハロゲン系ガスとして、ハロゲン（Ｆ２、Ｃｌ２、Ｂｒ２、Ｉ２）、ハロゲン化水素（ＨＦ、ＨＣｌ、ＨＢｒ、ＨＩ）、ハロゲン化珪素（ＳｉＦ４、ＳｉＣｌ４、ＳｉＢｒ４）、ハロゲン化ホウ素（ＢＣｌ３）、ハロゲン化タングステン（ＷＦ６、ＷＣｌ６）、ハロゲン化カルボニル（ＣＯＦ２、ＣＯＣｌ２）及び酸化ハロゲン（ＯＦ２）などが挙げられる。 As the halogen-based gas in the present invention, halogen (F 2 , Cl 2 , Br 2 , I 2 ), hydrogen halide (HF, HCl, HBr, HI), silicon halide (SiF 4 , SiCl 4 , SiBr 4 ) Boron halide (BCl 3 ), tungsten halide (WF 6 , WCl 6 ), carbonyl halide (COF 2 , COCl 2 ), and halogen oxide (OF 2 ).
本発明のハロゲン系ガスの除害剤では、半導体・液晶製造におけるエッチング工程、ＣＶＤ（化学気相蒸着）プロセス及びクリーニング工程などから排出される排ガス中のハロゲン、ハロゲン化水素、ハロゲン化珪素、ハロゲン化ホウ素、ハロゲン化タングステン、ハロゲン化カルボニル及び酸化ハロゲン等のハロゲン系ガスを効率良く除害することが可能である。その中でもハロゲンガス、特にＣｌ２に対しての非常に高い効率で除害することが可能である。本発明のハロゲン系ガスの除害剤は従来よりも除害性能が高いため、除害塔の交換頻度を少なくすることができる。 The halogen-based gas scavenger of the present invention is a halogen, hydrogen halide, silicon halide, halogen in exhaust gas discharged from an etching process, a CVD (chemical vapor deposition) process and a cleaning process in semiconductor / liquid crystal manufacturing. It is possible to efficiently remove halogen-based gases such as boron halide, tungsten halide, carbonyl halide, and halogen oxide. Among them, it is possible to perform detoxification with very high efficiency against halogen gas, particularly Cl 2 . Since the halogen-based gas detoxifying agent of the present invention has a higher detoxifying performance than before, the replacement frequency of the detoxifying tower can be reduced.
以下、実施例及び比較例を用いて本発明について説明する。 Hereinafter, the present invention will be described using examples and comparative examples.
実施例１
ゼオライト粉末としてＬＳＸゼオライト（ＳｉＯ２／Ａｌ２Ｏ３モル比２．０のフォージャサイト型ゼオライト）を使用してハロゲン系ガスの除害剤を調製した。ＬＳＸゼオライトの合成は以下のようにして行った。
Example 1
A halogen-based gas scavenger was prepared using LSX zeolite (a faujasite type zeolite having a SiO 2 / Al 2 O 3 molar ratio of 2.0) as the zeolite powder. LSX zeolite was synthesized as follows.
反応容器にケイ酸ナトリウム水溶液（Ｎａ２Ｏ＝３．８重量％、ＳｉＯ２＝１２．６重量％）１０７７０ｇ、水１３３０ｇ、水酸化ナトリウム（純度９９％）１３１０ｇ、工業用水酸化カリウム水溶液（純度４８％）３６３０ｇを入れ１００ｒｐｍで撹拌しながら４５℃に保った。当該溶液に４０℃のアルミン酸ナトリウム水溶液（Ｎａ２Ｏ＝２０．０重量％、Ａｌ２Ｏ３＝２２．５重量％）５３９０ｇを投入した。次にＬＳＸ粉末４．２２ｇを小量の水に分散し添加した。添加終了後のスラリーの組成は、３．３９Ｎａ２Ｏ・１．３１Ｋ２Ｏ・１．９０ＳｉＯ２・Ａｌ２Ｏ３・７４．１Ｈ２Ｏであった。１００ｒｐｍで撹拌し、４５℃で１時間熟成を行った。熟成後、撹拌を継続しながら１時間かけて７０℃に昇温した後、撹拌を停止し、７０℃で８時間結晶化を行った。得られた結晶を濾過し、純水で洗浄した後、７０℃で１晩乾燥してＬＳＸゼオライトを得た。得られたＬＳＸゼオライトは、Ｘ線回折からフォージャサイト型ゼオライトであり、また化学組成は０．７２Ｎａ２Ｏ・０．２８Ｋ２Ｏ・Ａｌ２Ｏ３・２．０ＳｉＯ２であった。 A reaction vessel was charged with sodium silicate aqueous solution (Na 2 O = 3.8 wt%, SiO 2 = 12.6 wt%) 10770 g, water 1330 g, sodium hydroxide (purity 99%) 1310 g, industrial potassium hydroxide aqueous solution (purity 48 %) 3630 g was added and kept at 45 ° C. with stirring at 100 rpm. To the solution, 5390 g of a 40 ° C. sodium aluminate aqueous solution (Na 2 O = 20.0 wt%, Al 2 O 3 = 22.5 wt%) was added. Next, 4.22 g of LSX powder was dispersed in a small amount of water and added. The composition of the slurry after the addition was 3.39Na 2 O · 1.31K 2 O · 1.90SiO 2 · Al 2 O 3 · 74.1H 2 O. The mixture was stirred at 100 rpm and aged at 45 ° C. for 1 hour. After aging, the temperature was raised to 70 ° C. over 1 hour while continuing stirring, and then the stirring was stopped and crystallization was performed at 70 ° C. for 8 hours. The obtained crystals were filtered, washed with pure water, and then dried at 70 ° C. overnight to obtain LSX zeolite. The obtained LSX zeolite was a faujasite type zeolite from X-ray diffraction, and the chemical composition was 0.72Na 2 O · 0.28K 2 O · Al 2 O 3 · 2.0SiO 2 .
得られたＬＳＸゼオライト１００重量部に対して、バインダーとしてアタパルジャイト粘土２０重量部と混合混練し、水を適宜加えながら最終的にＬＳＸゼオライト１００重量部に対して６５重量部の水を加えた後、十分に捏和した。この捏和物を直径１．２〜２．０ｍｍのビーズ状に造粒成形し、１００℃で１晩乾燥した。ついで空気流通下において、６００℃で２時間焼成した後、大気中で冷却して、水分が２０〜２５％になるように加湿した。 After mixing and kneading 20 parts by weight of attapulgite clay as a binder with respect to 100 parts by weight of the obtained LSX zeolite, and finally adding 65 parts by weight of water with respect to 100 parts by weight of LSX zeolite while appropriately adding water, He was sufficiently relaxed. This kneaded product was granulated and formed into beads having a diameter of 1.2 to 2.0 mm and dried at 100 ° C. overnight. Subsequently, after calcination at 600 ° C. for 2 hours under air circulation, the mixture was cooled in the air and humidified so that the water content was 20 to 25%.
当該成形体をＫ交換を行い、水で洗浄した。成形体を乾燥した後、乾燥空気流通下において、５３０℃で３時間活性化処理し、吸湿させないように冷却して本発明の除害剤とした。得られた除害剤のＳｉＯ２／Ａｌ２Ｏ３モル比は２．０であり、カチオンはＫ５５ｍｏｌ％及びＮａ４５ｍｏｌ％であった。 The molded body was subjected to K exchange and washed with water. After the molded body was dried, it was subjected to an activation treatment at 530 ° C. for 3 hours under a flow of dry air, and cooled to prevent moisture absorption, thereby obtaining a detoxifying agent of the present invention. The obtained scavenger had a SiO 2 / Al 2 O 3 molar ratio of 2.0, and the cations were K55 mol% and Na 45 mol%.
得られた除害剤を用いてハロゲン系ガスの除害評価を行った。除害塔としては下端にガス入口及び上端にガス出口を備えており、内径２８ｍｍ、高さ２８０ｍｍ、内容積１７２ｍｌのステンレス製を使用した。該除害塔を垂直に設置し、本発明の除害剤を充填した。ハロゲン系ガスとしてはＮ２でＣｌ２濃度を０．５体積％に調整したガスを使用し、大気圧下、２５℃、空塔線速０．０８ｍ／秒で処理を行った。除害塔の上端のガス出口から流出したガスのＣｌ２濃度は、電気化学式センサー（ドレーゲル・セイフティージャパン製、ポリトロン７０００）を用いて測定し、Ｃｌ２濃度が１ｐｐｍに達した時点で破過として、吸着剤単位重量当たりの吸着量を求めた。除害剤の除害能力の結果を表１に示す。 Using the obtained detoxifying agent, the detoxification of the halogen-based gas was performed. As the detoxification tower, a gas inlet at the lower end and a gas outlet at the upper end were used, and a stainless steel having an inner diameter of 28 mm, a height of 280 mm, and an internal volume of 172 ml was used. The abatement tower was installed vertically and filled with the abatement agent of the present invention. As the halogen-based gas, a gas in which the Cl 2 concentration was adjusted to 0.5% by volume with N 2 was used, and the treatment was performed at 25 ° C. and a superficial linear velocity of 0.08 m / sec under atmospheric pressure. The Cl 2 concentration of the gas flowing out from the gas outlet at the upper end of the detoxification tower is measured using an electrochemical sensor (Dregel Safety Japan, Polytron 7000), and breakthrough occurs when the Cl 2 concentration reaches 1 ppm. As a result, the amount of adsorption per unit weight of the adsorbent was determined. Table 1 shows the results of the detoxifying ability of the pesticide.
Ｃｌ２の除害能力は、フォージャサイト型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比が２．５から２．０に増大することによるカチオンサイトの増大率をはるかに上回る除害性能であった。更には特許文献６で開示されている除害剤よりも高い能力であった。 The detoxification ability of Cl 2 was a detoxification performance far exceeding the rate of increase of cation sites due to the increase in SiO 2 / Al 2 O 3 molar ratio of faujasite type zeolite from 2.5 to 2.0. It was. Furthermore, the ability was higher than the detoxifying agent disclosed in Patent Document 6.
実施例２
カチオンの組成をＫ８２ｍｏｌ％及びＮａ１８ｍｏｌ％とした以外は、実施例１と同じ方法で除害剤を調製し、除害能力を評価した。除害剤の除害能力の結果を表１に示す。
Example 2
A detoxifying agent was prepared in the same manner as in Example 1 except that the composition of the cation was K82 mol% and Na 18 mol%, and the detoxifying ability was evaluated. Table 1 shows the results of the detoxifying ability of the pesticide.
実施例３
カチオンの組成をＫ９９ｍｏｌ％及びＮａ１ｍｏｌ％とした以外は、実施例１と同じ方法で除害剤を調製し、除害能力を評価した。除害剤の除害能力の結果を表１に示す。
Example 3
A detoxifying agent was prepared in the same manner as in Example 1 except that the cation composition was K99 mol% and Na 1 mol%, and the detoxifying ability was evaluated. Table 1 shows the results of the detoxifying ability of the pesticide.
実施例４
実施例１で合成されたＬＳＸゼオライト１００重量部に対してカオリン粘土を２５重量部、ＣＭＣ（カルボキシメチルセルロース）４重量部を混合し、水を適宜加えながら最終的にＬＳＸ粉末１００重量部に対して７５重量部となるように調整した後、１時間混練した。この混練物を直径１．５ｍｍの円柱状に成形し、長さは３〜５ｍｍに調整した後に、２００℃で乾燥した。次いで乾燥空気流通下において、６００℃で３時間焼成した後に、大気中で冷却して水分が２０〜２５％になるように加湿した。得られた成形体を内径１０８ｍｍ、高さ１５００ｍｍのカラムに充填してバインダーレス化を行った。バインダーレス化には、ＮａＯＨ濃度２．２ｍｏｌ／Ｌ、ＳｉＯ２濃度１．０ｗｔ％の溶液を３０リットル使用し、溶液を循環させながら温度９０℃で６時間反応させて、全てのバインダー成分（カオリン粘土）をフォージャサイト型ゼオライトへ転化した。次いでカラムに充填したまま水で十分に洗浄した。その後Ｋ交換を行い、Ｋ６５ｍｏｌ％、Ｎａ３５ｍｏｌ％とした。得られた除害剤のＳｉＯ２／Ａｌ２Ｏ３モル比は２．１であった。活性化処理及び除害評価は実施例１と同様に行った。除害剤の除害能力の結果を表１に示す。
Example 4
25 parts by weight of kaolin clay and 4 parts by weight of CMC (carboxymethylcellulose) are mixed with 100 parts by weight of the LSX zeolite synthesized in Example 1, and finally 100 parts by weight of LSX powder is added while adding water appropriately. The mixture was adjusted to 75 parts by weight and then kneaded for 1 hour. The kneaded product was molded into a cylindrical shape having a diameter of 1.5 mm, the length was adjusted to 3 to 5 mm, and then dried at 200 ° C. Subsequently, after baking at 600 ° C. for 3 hours under a flow of dry air, the mixture was cooled in the air and humidified so that the water content was 20 to 25%. The obtained molded body was filled in a column having an inner diameter of 108 mm and a height of 1500 mm to make it binderless. In the binder-less process, 30 liters of a solution having a NaOH concentration of 2.2 mol / L and a SiO 2 concentration of 1.0 wt% was used, and the reaction was performed at a temperature of 90 ° C. for 6 hours while circulating the solution. Clay) was converted to faujasite type zeolite. Next, the column was thoroughly washed with water while being packed in the column. Thereafter, K exchange was performed to obtain K65 mol% and Na 35 mol%. The scavenger obtained had a SiO 2 / Al 2 O 3 molar ratio of 2.1. Activation treatment and detoxification evaluation were performed in the same manner as in Example 1. Table 1 shows the results of the detoxifying ability of the pesticide.
比較例１
実施例１と同様にＬＳＸゼオライトを合成した。得られたＬＳＸゼオライト１００重量部に対して、バインダーとしてセピオライト粘土２０重量部と混合混練し、水を適宜加えながら最終的にＬＳＸゼオライト１００重量部に対して６５重量部の水を加えた後、十分に捏和した。この捏和物を直径１．２〜２．０ｍｍのビーズ状に造粒成形し、１００℃で１晩乾燥した。ついで空気流通下において、６００℃で２時間焼成した後、大気中で冷却して、水分が２０〜２５％になるように加湿した。
Comparative Example 1
LSX zeolite was synthesized in the same manner as in Example 1. After mixing and kneading 20 parts by weight of sepiolite clay as a binder with respect to 100 parts by weight of the obtained LSX zeolite, finally adding 65 parts by weight of water to 100 parts by weight of LSX zeolite while adding water appropriately, He was sufficiently relaxed. This kneaded product was granulated and formed into beads having a diameter of 1.2 to 2.0 mm and dried at 100 ° C. overnight. Subsequently, after calcination at 600 ° C. for 2 hours under air circulation, the mixture was cooled in the air and humidified so that the water content was 20 to 25%.
当該成形体をＮａ交換を行い、水で洗浄した。成形体を乾燥した後、乾燥空気流通下において、５３０℃で３時間活性化処理し、吸湿させないように冷却して本発明の除害剤とした。得られた除害剤のＳｉＯ２／Ａｌ２Ｏ３モル比は２．０であり、カチオンはＮａ９８ｍｏｌ％及びＫ２ｍｏｌ％であった。除害評価は実施例１と同様に行い、除害剤の除害能力の結果を表１に示す。 The shaped body was exchanged with Na and washed with water. After the molded body was dried, it was subjected to an activation treatment at 530 ° C. for 3 hours under a flow of dry air, and cooled to prevent moisture absorption, thereby obtaining a detoxifying agent of the present invention. The obtained detoxifying agent had a SiO 2 / Al 2 O 3 molar ratio of 2.0 and cations of Na 98 mol% and K 2 mol%. The detoxification evaluation is carried out in the same manner as in Example 1, and the results of the detoxifying ability of the detoxifying agent are shown in Table 1.
比較例２
実施例４と同様の方法でバインダーレス化のみを行ったＬＳＸゼオライト成形体を調製した。カチオンはＮａ８９ｍｏｌ％及びＫ１１ｍｏｌ％であった。活性化処理及びハロゲン系ガスの除害評価は実施例１と同じ操作を行った。除害剤の除害能力の結果を表１に示す。
Comparative Example 2
An LSX zeolite molded body in which only the binder-less process was performed in the same manner as in Example 4 was prepared. The cation was 89 mol% Na and 11 mol% K. The same operation as in Example 1 was performed for the activation treatment and the halogen gas removal evaluation. Table 1 shows the results of the detoxifying ability of the pesticide.
比較例３
ゼオライト粉末として東ソー製Ｆ−９粉末（ＳｉＯ２／Ａｌ２Ｏ３モル比２．５、カチオンがＮａであるフォージャサイト型ゼオライト）を使用して実施例２と同様の操作を行い、バインダーレス化は行わなかった。ハロゲン系ガスの除害評価は実施例１と同じ操作を行った。除害剤の除害能力の結果を表１に示す。
Comparative Example 3
The same operation as in Example 2 was carried out using Tosoh F-9 powder (SiO 2 / Al 2 O 3 molar ratio 2.5, faujasite type zeolite whose cation is Na) as the zeolite powder, and binderless There was no conversion. The detoxification evaluation of the halogen-based gas was performed in the same manner as in Example 1. Table 1 shows the results of the detoxifying ability of the pesticide.
Claims (6)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016155072A (en) * | 2015-02-24 | 2016-09-01 | 宇部興産株式会社 | Halogen-based gas treatment agent and halogen-based gas treatment method |
| CN108430924A (en) * | 2015-12-29 | 2018-08-21 | 环球油品公司 | The method of binder free zeolite adsorbents and manufacture binder free zeolite adsorbents |
| JP2018149508A (en) * | 2017-03-14 | 2018-09-27 | 大陽日酸株式会社 | Ethylene oxide removal method |
| JP2018149509A (en) * | 2017-03-14 | 2018-09-27 | 大陽日酸株式会社 | Ethylene oxide removal method |
| US11033879B2 (en) | 2015-12-29 | 2021-06-15 | Uop Llc | Binderless zeolitic adsorbents |
| US11885681B2 (en) | 2018-05-30 | 2024-01-30 | Pendar Technologies, Llc | Methods and devices for standoff differential Raman spectroscopy with increased eye safety and decreased risk of explosion |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0256242A (en) * | 1988-08-19 | 1990-02-26 | Agency Of Ind Science & Technol | Adsorbent for gaseous organic halogen compound |
| JPH08206494A (en) * | 1995-02-06 | 1996-08-13 | Tosoh Corp | Desiccant and use of desiccant |
| JP2001219056A (en) * | 2000-02-14 | 2001-08-14 | Miura Co Ltd | Adsorbent for dioxins |
| JP2008229610A (en) * | 2007-02-21 | 2008-10-02 | Tosoh Corp | Halogen-based gas scavenger and halogen-based gas scavenging method using the same |
-
2008
- 2008-12-12 JP JP2008316548A patent/JP5309945B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0256242A (en) * | 1988-08-19 | 1990-02-26 | Agency Of Ind Science & Technol | Adsorbent for gaseous organic halogen compound |
| JPH08206494A (en) * | 1995-02-06 | 1996-08-13 | Tosoh Corp | Desiccant and use of desiccant |
| JP2001219056A (en) * | 2000-02-14 | 2001-08-14 | Miura Co Ltd | Adsorbent for dioxins |
| JP2008229610A (en) * | 2007-02-21 | 2008-10-02 | Tosoh Corp | Halogen-based gas scavenger and halogen-based gas scavenging method using the same |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016155072A (en) * | 2015-02-24 | 2016-09-01 | 宇部興産株式会社 | Halogen-based gas treatment agent and halogen-based gas treatment method |
| CN108430924A (en) * | 2015-12-29 | 2018-08-21 | 环球油品公司 | The method of binder free zeolite adsorbents and manufacture binder free zeolite adsorbents |
| JP2019501766A (en) * | 2015-12-29 | 2019-01-24 | ユーオーピー エルエルシー | Binderless zeolite adsorbent and method for producing binderless zeolite adsorbent |
| JP2021007944A (en) * | 2015-12-29 | 2021-01-28 | ユーオーピー エルエルシー | Binderless zeolite adsorbent and method for producing binderless zeolite adsorbent |
| US10981143B2 (en) | 2015-12-29 | 2021-04-20 | Uop Llc | Binderless zeolitic adsorbents |
| US11033879B2 (en) | 2015-12-29 | 2021-06-15 | Uop Llc | Binderless zeolitic adsorbents |
| JP2018149508A (en) * | 2017-03-14 | 2018-09-27 | 大陽日酸株式会社 | Ethylene oxide removal method |
| JP2018149509A (en) * | 2017-03-14 | 2018-09-27 | 大陽日酸株式会社 | Ethylene oxide removal method |
| US11885681B2 (en) | 2018-05-30 | 2024-01-30 | Pendar Technologies, Llc | Methods and devices for standoff differential Raman spectroscopy with increased eye safety and decreased risk of explosion |
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