JP2016068083A - Silanol compound removal equipment - Google Patents

Abstract

A silanol compound removal facility capable of efficiently removing silanol compounds in a fluid is provided. SOLUTION: The silanol compound removal equipment of the present invention uses an inorganic silica-based porous material having a pH of 7 or less in a water mixture (content ratio: 5 wt%) obtained by mixing with pure water as an adsorbent. and a chemical filter for removing inhibitors, which is installed upstream of the chemical filter for removing silanol compounds and removes inhibitors that reduce the ability of the chemical filter for removing silanol compounds to remove silanol compounds. It is characterized by [Selection figure] None

Description

  The present invention relates to an installation for removing a silanol compound from a fluid (particularly in the air). The present invention also relates to a fluid purification method using the equipment.

  It is known that a disilazane compound such as hexamethyldisilazane (HMDS) is used as a photoresist adhesive in the exposure process of the semiconductor manufacturing process. HMDS, for example, is sprayed as a gas on the wafer surface to replace the hydroxyl group on the wafer surface with a trimethylsilanol group, thereby hydrophobizing the wafer surface and improving the adhesion with the resist agent on the wafer surface. . However, HMDS may be hydrolyzed to a low molecular weight trimethylsilanol (TMS), which may float in the gaseous state in the exposure equipment. The floating TMS may be bonded to the surface of the lens or the like to cause fogging of the lens, which may cause exposure failure or the like.

  Air that has passed through a chemical filter having an adsorbent such as activated carbon is usually supplied into the chamber of the exposure equipment where the exposure process is performed. In general, gaseous impurities such as TMS are removed by a chemical filter, so that the inside of the chamber is maintained at a certain level of cleanliness, thereby preventing exposure failure and the like (see, for example, Patent Document 1).

  However, TMS is a low-molecular-weight, volatile substance that is difficult to adsorb on activated carbon, which is a general chemical filter adsorbent, and is desorbed immediately after adsorption. It is difficult to remove. Therefore, conventionally, in order to remove the necessary amount of TMS, it has been necessary to use a large amount of activated carbon such as thickening the chemical filter or increasing the capacity.

  Patent Document 2 discloses a chemical filter using an acidic additive. In this chemical filter, silanol compounds contained in the air are dimerized by an acidic additive and adsorbed. However, when the concentration of the silanol compound in the air is very low, the dimerization reaction is unlikely to occur, so this method does not necessarily provide sufficient removal efficiency.

JP 2008-181968 A International Publication No. 2011/099616

Accordingly, an object of the present invention is to provide a silanol compound removal facility capable of efficiently removing silanol compounds such as TMS.
Another object of the present invention is to provide a fluid purification method capable of efficiently removing silanol compounds such as TMS present in a fluid (particularly in the air).

  As a result of intensive studies to achieve the above object, the present inventors have found that a silanol compound removing chemical filter using an inorganic silica-based porous material having a pH of 7 or less as a water mixture with pure water as an adsorbent, According to the equipment having a chemical filter for removing an inhibitor that lowers the silanol compound removing ability of the silanol compound removing chemical filter installed upstream thereof, silanol such as TMS in fluid (particularly in the air) The present inventors have found that the compound can be removed extremely efficiently and completed the present invention.

  That is, the present invention is a silanol compound removal chemical filter using an inorganic silica-based porous material having a pH of 7 or less as a water mixture obtained by mixing with pure water (content ratio: 5 wt%) as an adsorbent, A silanol compound having an inhibitor removal chemical filter installed upstream of the silanol compound removal chemical filter, for removing an inhibitor that reduces the silanol compound removal ability of the silanol compound removal chemical filter. Provide removal equipment.

  The inhibitor removing chemical filter may be at least one selected from the group consisting of a basic substance removing chemical filter and a siloxane compound removing chemical filter.

  The inorganic silica-based porous material is zeolite, silica gel, silica alumina, aluminum silicate, porous glass, diatomaceous earth, hydrous magnesium silicate clay mineral, allophane, imogolite, acidic clay, activated clay, activated bentonite, mesoporous silica, It may be at least one inorganic silica-based porous material selected from the group consisting of aluminosilicate, fumed silica, fly ash, and clinker ash.

  As the adsorbent, another adsorbent may be used together with the inorganic silica-based porous material whose pH of the water mixture (content ratio: 5 wt%) is 7 or less.

  The inorganic silica-based porous material includes a synthetic zeolite having a water mixture (content ratio: 5 wt%) having a pH of 7 or less, and the content of the synthetic zeolite in the adsorbent is based on the total weight of the adsorbent. It may be 10% by weight or more.

  The inorganic silica-based porous material includes a synthetic zeolite having a water mixture (content ratio: 5 wt%) having a pH of 7 or less, and the synthetic zeolite is A-type, ferrierite, MCM-22, ZSM-5, ZSM- 11, synthetic zeolite having at least one kind of framework structure selected from the group consisting of SAPO-11, mordenite, beta type, X type, Y type, L type, chabazite, and offretite.

  Moreover, this invention provides the fluid purification | cleaning method characterized by removing a silanol compound using the said silanol compound removal equipment.

  According to the silanol compound removal equipment of the present invention, especially for a silanol compound such as TMS, once adsorbed TMS or the like does not desorb again, the removal effect lasts longer than that of activated carbon. That is, the removal efficiency does not decrease in a short time, but decreases gently, and TMS is released like activated carbon and does not have a negative effect (a phenomenon in which the concentration on the downstream side is higher than that on the upstream side of the filter). . Moreover, since the silanol compound removing ability is not lowered by an inhibitor that reduces the silanol compound removing ability, the removal effect of the silanol compound lasts for a long time.

  Furthermore, according to the chemical filter of the present invention, in particular, since silanol compounds in the air can be removed extremely efficiently, the amount of adsorbent used can be made very small, and the number of filter base materials can be reduced. Energy saving, low cost, and space saving.

It is the schematic of the aeration test apparatus used in the Example. It is a partial schematic sectional drawing of the aeration test apparatus used in the Example. It is a graph (relationship between pH of a water mixture of zeolite and removal efficiency) showing aeration test results of Example 1. It is a graph (The relationship between the pH and removal efficiency of the water mixture of silica gel, acid clay, activated clay, diatomaceous earth, fumed silica, and talc) of the air permeability test result of Example 1. It is a graph (relationship (time change) between pH of zeolite water mixture and removal efficiency) showing the aeration test result of Example 2. It is a graph (The relationship (time change) of pH and removal efficiency of the water mixture of silica gel, acid clay, activated clay, and diatomaceous earth) which shows the aeration test result of Example 2. FIG. 5 is a schematic view of an aeration test apparatus used in Example 4. It is a graph (time change of the removal efficiency of TMS) which shows the ventilation test result of Example 4. 6 is a graph showing the aeration test results of Example 5 (relationship between pH and removal efficiency of binder water mixture (time change)). 10 is a graph showing the results of an aeration test in Example 6 (relationship between content of synthetic zeolite and removal efficiency (time change)). It is a graph (time change of the removal efficiency of TMS) which shows an aeration test result of Example 7. It is a graph which shows the extraction test result (extraction amount of TMS and HMDSO) of Example 8. It is a graph (time change of the removal efficiency of TMS) which shows the ventilation test result of Example 9. It is a graph (The removal efficiency (time change) before and behind ammonia treatment of a synthetic zeolite) which shows the aeration test result of Example 11. It is a graph (The removal efficiency (time change) before and behind ammonia treatment of silica gel, activated clay, and diatomaceous earth) which shows the aeration test result of Example 12. It is a graph which shows the aeration test result of Example 13 (removal efficiency (time change) before and after D4 treatment of synthetic zeolite).

  The silanol compound removing equipment of the present invention is a silanol compound removing chemical using as an adsorbent an inorganic silica-based porous material whose pH of a water mixture (content ratio: 5 wt%) obtained by mixing with pure water is 7 or less. At least a filter and an inhibitor removal chemical filter for removing an inhibitor that reduces the silanol compound removal ability of the silanol compound removal chemical filter. In the present specification, the above-mentioned “chemical filter for removing silanol compounds using as an adsorbent an inorganic silica-based porous material whose pH of a water mixture (content ratio: 5 wt%) obtained by mixing with pure water is 7 or less” May be referred to as “the chemical filter of the present invention”. Further, in the present specification, the above-mentioned “chemical filter for removing an inhibitory substance that removes an inhibitory substance that lowers the silanol compound removing ability of the chemical filter for removing a silanol compound”, that is, “the silanol compound removing ability of the chemical filter of the present invention is lowered. The “inhibitory substance removing chemical filter for removing the inhibiting substance” may be simply referred to as “inhibitory substance removing chemical filter”.

[Chemical filter of the present invention]
The chemical filter of the present invention is a silanol compound removing chemical filter using as an adsorbent an inorganic silica-based porous material whose pH of a water mixture (content ratio: 5 wt%) obtained by mixing with pure water is 7 or less. It is. In the present specification, an adsorbent using an inorganic silica-based porous material whose pH of a water mixture (content ratio: 5 wt%) obtained by mixing with pure water is 7 or less is referred to as “adsorbent of the present invention”. Sometimes called. In the present specification, “pH of water mixture” means “pH of water mixture (content ratio: 5 wt%)” unless otherwise specified.

(Adsorbent of the present invention)
The chemical filter of the present invention uses an inorganic silica-based porous material as an essential adsorbent. As for the said inorganic silica type porous material, only 1 type may be used and 2 or more types may be used.

  The inorganic silica-based porous material has a pH of a water mixture (content ratio: 5 wt%) obtained by mixing with pure water of 7 or less (for example, 3 to 7), preferably less than 7 (for example, 3 or more). Less than 7), more preferably 3 to 6.5, and still more preferably 4 to 6. When the pH is 7 or less, the silanol compound can be removed with high efficiency.

  In this specification, the pH of the water mixture (content ratio: 5 wt%) obtained by mixing with pure water is the content ratio of the substance (target substance) mixed in the water mixture with respect to the entire water mixture. The pH when measured under the condition of 5 wt%. For example, when the pH of the water mixture (content ratio: 5 wt%) obtained by mixing the inorganic silica porous material with pure water is measured under the condition that the content ratio of the inorganic silica porous material is 5 wt%. Of pH. The pH of the water mixture can be measured using, for example, a pH meter. In addition, when using the above-described inorganic silica-based porous material with an additive or the like as the adsorbent of the present invention, the above “pH of water mixture obtained by mixing with pure water (content ratio: 5 wt%)” is A water mixture (content ratio: 5 wt%) obtained by mixing inorganic silica based porous material in a state before adhering an additive or the like (that is, no adhering agent or the like) with pure water. Let us say pH.

  In the present specification, the water mixture (content ratio: 5 wt%) can be produced, for example, by the following “method for producing water mixture (content ratio: 5 wt%)”.

Preparation method of water mixture (content ratio: 5 wt%) The above water mixture (content ratio: 5 wt%) is, for example, a sample (“object” for measuring the pH of the water mixture so that the content ratio is 5 wt%. The sample may be referred to as “sample”) and mixed with pure water, stirred sufficiently, and allowed to stand for preparation. Although pure water is used for preparation of the water mixture, a mixed solvent of an organic solvent and pure water may be used. However, when an organic solvent is used, the acid dissociation constant varies greatly depending on the type and concentration of the organic solvent. Therefore, it is generally a water-soluble organic solvent such as alcohol and does not have a large effect on pH. Concentration. The “wt%” has the same meaning as “wt%”. In order to prepare a water mixture having a content ratio of 5 wt%, specifically, for example, 5 g of the target sample is weighed using a scale, and pure water is added to make the whole 100 g, and the liquid is sufficiently mixed. It can be produced by stirring. For example, the inorganic silica-based porous material water mixture (content ratio: 5 wt%) can be produced using the inorganic silica-based porous material as the target sample.

The inorganic silica-based porous material is not particularly limited, but the specific surface area (BET specific surface area) may be 10 m ² / g or more (for example, 10 to 800 m ² / g), preferably 50 m ² / g or more. (For example, 50 to 750 m ² / g), more preferably 100 m ² / g or more (for example, 100 to 700 m ² / g).

The inorganic silica-based porous material is not particularly limited, but the content of SiO ₂ in the porous material may be 5% by weight or more (for example, 5 to 100% by weight), preferably 10% by weight or more. More preferably, it is 20% by weight or more, and further preferably 50% by weight or more.

  The inorganic silica-based porous material is not particularly limited. For example, zeolite (for example, synthetic zeolite, natural zeolite, etc.), silica gel, silica alumina, aluminum silicate, porous glass, diatomaceous earth, hydrous magnesium silicate clay Minerals (for example, talc), allophane, imogolite, acid clay, activated clay, activated bentonite, mesoporous silica, aluminosilicate, fumed silica, fly ash, clinker ash and the like can be mentioned. By using the inorganic silica-based porous material as the adsorbent, the silanol compound can be removed with high efficiency. Among these, zeolite is preferable, and synthetic zeolite is particularly preferable. When zeolite (especially synthetic zeolite) is used as the adsorbent, the silanol compound can be efficiently removed over a longer period of time. Only 1 type may be used for the said inorganic silica type porous material, and 2 or more types may be used for it. The synthetic zeolite includes artificial zeolite.

  The zeolite is a porous material having a skeleton mainly composed of silicon element (Si), aluminum element (Al), and oxygen element (O), but a part or all of aluminum element ( Al) may be replaced with a trivalent metal element such as iron element (Fe), boron element (B), gallium element (Ga); or a divalent metal element such as zinc element (Zn). .

  The pore structure of the zeolite is not particularly limited. Although the number of member rings of zeolite is not specifically limited, For example, it is 4-20, Preferably it is 8-20, More preferably, it is 8-12. The number of member rings of zeolite is generally represented by the number of O atoms in the pore ring structure. Moreover, the pore connection (channel system) of zeolite is not particularly limited, but is preferably 1 to 3 dimensions, and more preferably 3 dimensions. In particular, a zeolite (particularly a synthetic zeolite) having a pore structure with 12 member rings and three-dimensional pore connection is preferable.

  Although it does not specifically limit as said synthetic zeolite, For example, A type, ferrierite, MCM-22, ZSM-5, ZSM-11, SAPO-11, mordenite, beta type, X type, Y type, L type, chabazite And synthetic zeolite having a skeletal structure such as offretite. In addition, the said synthetic zeolite may use the zeolite of 1 type of frame structure, and may use it in combination of 2 or more types of zeolite. Moreover, the synthetic zeolite may be prepared in a powder form or may be used in a film form.

  Examples of the artificial zeolite generally include zeolite produced from waste containing silicon and aluminum, such as coal ash discharged from a coal-fired power plant and papermaking sludge incinerated ash discharged from a paper mill. The artificial zeolite may be used alone or in combination of two or more.

  The natural zeolite is not particularly limited, and examples thereof include clinoptilolite (clinoptilolite), mordenite (mordenite), chabazite, natrolite, gonnardite, edding tonite, analsim, leucite, yugawaralite, gismondine, porinite. , Philipsite, Chabazite, Elionite, Haujasite, Ferrierite, Mutinaite, Chernihito, Huerudite, Stillebite, Koureite, Aluminosilicate, Berylsilicate (Rogianite, Shanhalite, etc.), Zinccosilicate (Gaultite) ) And the like. The natural zeolite may be used alone or in combination of two or more.

  The zeolite has a pH of a water mixture (content ratio: 5 wt%) obtained by mixing with pure water of 7 or less (for example, 3 to 7), preferably less than 7 (for example, 3 or more and less than 7), more Preferably it is 3-6.8, More preferably, it is 3.5-6.7, Most preferably, it is 4-6.5. In addition, the water mixture (content ratio: 5 wt%) of zeolite can be prepared using zeolite as a target sample by the above “method for preparing water mixture (content ratio: 5 wt%)”. When the pH is 7 or less, the silanol compound can be removed with high efficiency. This is because the silanol group is sufficiently present in the zeolite due to the pH of the zeolite water mixture being 7 or less, and this silanol group is closely related to the removal of the silanol compound in the fluid. Guessed.

The ratio of SiO ₂ and Al ₂ O ₃ in the composite zeolite (molar _{ratio) [SiO 2 / Al 2 O} 3] is not particularly limited, from the viewpoint of the removal efficiency of the silanol compound may be 4-2000 Preferably, it is 10-1500, More preferably, it is 15-1000, More preferably, it is 100-500. The above [SiO ₂ / Al ₂ O ₃ ] is considered as an index indicating the hydrophilicity or hydrophobicity of zeolite. When [SiO ₂ / Al ₂ O ₃ ] is high (that is, the silica ratio is high and the alumina ratio is low), the hydrophobicity tends to increase. On the other hand, when [SiO ₂ / Al ₂ O ₃ ] is low (that is, the silica ratio is low and the alumina ratio is high), the hydrophilicity tends to be high. If the hydrophilicity is too high (that is, the hydrophobicity is too low), the surface of the skeleton is covered with water molecules, and it becomes difficult for the hydrophobic silanol compound to approach the adsorption site (adsorption site). If the hydrophilicity is too low (that is, the hydrophobicity is too high), the acid sites in the zeolite are reduced, and the removal efficiency of the silanol compound tends to decrease. For this reason, for example, by setting [SiO ₂ / Al ₂ O ₃ ] within the above range, the hydrophilicity or hydrophobicity of the zeolite can be appropriately adjusted, and the silanol compound removal efficiency can be further improved.

The zeolite is not particularly limited, but may contain a cation in the framework structure. Examples of the cation include, but are not limited to, hydrogen ion (H ⁺ ); ammonium ion (NH ₄ ⁺ ); alkyl-substituted ammonium ion (for example, methylammonium ion ((CH ₃ ) H ₃ N ⁺ )) Dimethylammonium ion ((CH ₃ ) ₂ H ₂ N ⁺ ), trimethylammonium ion ((CH ₃ ) ₃ HN ⁺ ), tetramethylammonium ion ((CH ₃ ) ₄ N ⁺ ), etc.); aryl or aralkyl-substituted ammonium Ions; alkali metal ions such as lithium ion (Li ⁺ ), sodium ion (Na ⁺ ), potassium ion (K ⁺ ); magnesium ion (Mg ²⁺ ), calcium ion (Ca ²⁺ ), barium ion (Ba ²⁺⁾ ) an alkaline earth metal such as ion; zinc ion (Zn ^2+), tin ions (Sn ^2+, Sn ^4+), Ions (Fe ^2+, Fe ^3+), a platinum ion (Pt ^2+), palladium ion (Pd ^2+), titanium ions (Ti ^3+), silver ions (Ag ^+), copper ion (Cu ^+, Cu ^{2 +} ), Manganese ions (Mn ²⁺ , Mn ⁴⁺ ), transition metal ions such as cobalt ions (Co ²⁺ ); gallium ions (Ga ⁺ ) and the like. One kind of the cation may be contained, or two or more kinds may be contained. The content of the cation in the zeolite is not particularly limited. In particular, a zeolite called a proton type zeolite having a high content of hydrogen ions (H ⁺ ) as cations contained in the skeleton structure is preferable.

  The specific surface area (BET specific surface area), average particle diameter (average particle diameter), average pore diameter (diameter), total pore volume, etc. of the zeolite are not particularly limited. Moreover, the said zeolite may use only 1 type and may use 2 or more types.

  As the zeolite, an acid-treated product obtained by acid treatment of natural zeolite or synthetic zeolite, a hydrothermal treatment product obtained by hydrothermal treatment of natural zeolite or synthetic zeolite, an ammonium-treated product obtained by calcining ammonium type zeolite, Proton type zeolite may be used.

  The acid-treated product and the hydrothermally treated product are presumed to be because silanol groups in the zeolite increase due to desorption of cations and aluminum elements in the zeolite by acid in acid treatment or heated steam in hydrothermal treatment. The pH of the water mixture becomes 7 or less, and the removal efficiency of the silanol compound is increased.

  Examples of the proton type zeolite include, for example, at least a part of cations other than hydrogen ions in natural zeolite or synthetic zeolite (for example, metal ions, ammonium ions, etc.) replaced with hydrogen ions, Examples thereof include synthetic zeolite prepared so as to contain a large amount of hydrogen ions. The proton-type zeolite can also be produced by, for example, a method in which a cation such as sodium ion in natural zeolite or synthetic zeolite is ion-exchanged with ammonium ion and then calcined. In general, a proton type zeolite in which the cation in the zeolite is replaced with a hydrogen ion is called a proton type zeolite. In the above proton type zeolite, at least a part of the cation in the zeolite is replaced with a hydrogen ion. It is not limited to those in which all cations in the zeolite are replaced with hydrogen ions.

  Although proton type zeolite is sometimes used as a catalyst, it is not generally used as an adsorbent. Note that zeolite may be used as an adsorbent, but most of the zeolite used as the adsorbent is basic, that is, the pH of the water mixture exceeds 7. As a specific embodiment in which zeolite is used as an adsorbent, for example, molecular sieve is well known, but the substance removed by molecular sieve is water, which is present in the molecular sieving function of zeolite and in zeolite. It is mainly removed by coordinating water to metal ions such as Na ions. Thus, when utilizing Na ion in zeolite, the pH of the water mixture of zeolite used exceeds 7. Furthermore, examples in which solid acid zeolite is used as an adsorbent are very rare. For example, there is one that removes a basic compound such as ammonia by a neutralization reaction utilizing the acid of the solid acid type zeolite and ion exchange ability. However, the removal target is currently limited to inorganic compounds and basic compounds. That is, there has never been an example of using a zeolite whose pH of a water mixture is 7 or less to remove an organic compound, particularly a silanol compound which is an acidic organic compound.

  The acid clay is not particularly limited, and acid clay produced in various places can be used. Examples include acid clay from Niigata Prefecture and acid clay from Yamagata Prefecture. Only 1 type may be used for the said acid clay, and 2 or more types may be used for it.

  The activated clay is obtained by acid-treating the acid clay. For example, the acid clay is acid-treated with a mineral acid such as sulfuric acid so as not to destroy all of the basic structure of montmorillonite. Examples include those in which a metal oxide such as an oxide is eluted and the specific surface area and pore volume are increased. Only 1 type may be used for the said activated clay, and 2 or more types may be used for it.

  The diatomaceous earth is not particularly limited, and diatomaceous earth produced in various places can be used. For example, diatomaceous earth (diatom shale) from Wakkanai, Hokkaido, diatomaceous earth from Tsukiko, Akita Prefecture, diatomaceous earth from Ulsan, Okayama Prefecture, diatomaceous earth from Kuju, Oita Prefecture, diatomaceous earth (diatomaceous mudstone) from Noto, Ishikawa Prefecture, etc. May be. Only 1 type may be used for the said diatomaceous earth, and 2 or more types may be used for it.

  The inorganic silica-based porous material other than the synthetic zeolite (other inorganic silica-based porous material) has a pH of a water mixture (content ratio: 5 wt%) obtained by mixing with pure water of 7 or less (for example, 3 to 3 7), preferably less than 7 (for example, 3 or more and less than 7), more preferably 3 to 6.5, still more preferably 3.5 to 6.3, and particularly preferably 4 to 6. In addition, the water mixture (content ratio: 5 wt%) of other inorganic silica-based porous materials is a target sample of other inorganic silica-based porous materials according to the above “method for producing water mixture (content ratio: 5 wt%)”. Can be produced.

In the inorganic silica-based porous material other than the synthetic zeolite, the content of SiO ₂ is not particularly limited, but is 50% by weight or more with respect to the total weight (100% by weight) of the inorganic silica-based porous material (for example, 50 to 100% by weight), preferably 60% by weight or more, more preferably 70% by weight or more.

  Although the said inorganic silica type porous material is not specifically limited, It is preferable that the additive etc. are not attached. That is, it is preferable that the inorganic silica-based porous material to which an additive or the like is added is excluded from the inorganic silica-based porous material. Examples of the additive include an acidic substance additive, a basic substance additive, and an oxidizing agent. For example, when an acidic substance additive is added, the skeleton of the inorganic silica porous material may change.

  The adsorbent of the present invention is not particularly limited, but may contain an adsorbent (other adsorbent) other than the inorganic silica-based porous material whose pH of the water mixture is 7 or less, if necessary. That is, as the adsorbent of the present invention, other adsorbents may be used together with the inorganic silica-based porous material whose pH of the water mixture is 7 or less. Examples of the other adsorbent include porous materials other than inorganic silica-based porous materials whose pH of the water mixture is 7 or less, other silicas, clay minerals, activated carbon, alumina, and glass. By using the other adsorbents as the adsorbent, in addition to the effects of the present invention, a chemical filter having the effects of other adsorbents can be obtained.

  The content of the inorganic silica-based porous material in which the pH of the water mixture in the adsorbent of the present invention (in all adsorbents) is 7 or less is not particularly limited, but from the viewpoint of the silanol compound removal efficiency, the adsorbent Is preferably 10% by weight or more (for example, 10 to 100% by weight), more preferably 30% by weight or more, still more preferably 50% by weight or more, and particularly preferably 70% by weight. That's it.

  In the adsorbent of the present invention (in all adsorbents), the content of the synthetic zeolite whose pH of the water mixture is 7 or less is not particularly limited, but from the viewpoint of silanol compound removal efficiency, the total weight of the adsorbent ( 100% by weight) is preferably 10% by weight or more (for example, 10 to 100% by weight), more preferably 50% by weight or more, and still more preferably 70% by weight or more.

  The chemical filter of this invention will not be specifically limited if the inorganic silica type porous material whose pH of a water mixture (content rate: 5 wt%) is 7 or less is used as an adsorbent. Examples of the chemical filter include a chemical filter in which the adsorbent of the present invention is attached (fixed) to a filter base material. In addition, when the adsorbent of the present invention also has a function as a binder, the adsorbent can be attached to the filter base material without using a binder, but the adsorbent of the present invention uses a binder to filter base. It is preferable that it adheres to the material. That is, the chemical filter may be a chemical filter in which the adsorbent of the present invention is attached to the filter substrate without using a binder (or only the adsorbent of the present invention is attached). A chemical filter in which the adsorbent of the present invention is attached to a filter base material using a binder is preferable.

  The adsorbent of the present invention is not particularly limited, but may be pelletized. That is, the adsorbent of the present invention may be a pelletized adsorbent. That is, the chemical filter of the present invention may contain the pelletized adsorbent of the present invention. The pelletization can be performed, for example, by granulating the adsorbent powder of the present invention using the binder.

(Filter base material)
It does not specifically limit as said filter base material, What is generally used as a filter base material of a chemical filter can be used. Examples of the filter base material include fibrous base materials (woven fabric or non-woven fabric) composed of fibers such as organic fibers and inorganic fibers, foams composed of paper, polyurethane foam, refractory metal oxides, and the like. Examples thereof include a filter base material using a refractory inorganic material (for example, a metal such as aluminum, ceramics, etc.). The shape of the woven fabric of the fibrous base material is not particularly limited, and examples thereof include those in which fibers are woven in a mesh shape. Among these, a fibrous substrate is preferable as the filter substrate.

  Examples of the fiber in the fibrous base material include inorganic fibers such as silica alumina fiber, silica fiber, alumina fiber, mullite fiber, glass fiber, rock wool fiber, and carbon fiber; polyethylene fiber, polypropylene fiber, nylon fiber, and polyester fiber. (For example, polyethylene terephthalate fiber, etc.), polytetrafluoroethylene fiber, polyvinyl alcohol fiber, aramid fiber, pulp fiber, rayon fiber, and other organic fibers. Among these, inorganic fibers are preferable, and glass fibers are more preferable from the viewpoint of increasing the strength of the chemical filter and less contamination due to outgas from the fibers. That is, as the filter substrate, a fibrous substrate (glass cloth (glass cloth)) using glass fibers is preferable. The said fiber may use only 1 type and may use it in combination of 2 or more type. Moreover, the shape of the said inorganic fiber and the said organic fiber is not specifically limited.

(Binder)
The binder can be used for promoting adhesion of the adsorbent to the filter base material or pelletizing the adsorbent. The binder is not particularly limited, and a known or commonly used binder for a filter (for example, for an air filter or a chemical filter) can be used. The binder may be an organic binder or an inorganic binder. The binder is not particularly limited, but is preferably an inorganic binder. The said binder may use only 1 type and may use 2 or more types.

  The binder may be acidic or basic, but is preferably acidic. When the binder is acidic, the removal efficiency of the silanol compound tends to be higher than when a basic binder is used. The acidic binder has a pH of a water mixture (content ratio: 5 wt%) obtained by mixing with pure water of 7 or less (for example, 3 to 7), preferably less than 7 (for example, 3 or more and less than 7), More preferably, it is 3-6.8, More preferably, it is 3.5-6.7, Most preferably, it is 4-6.5. In addition, the water mixture (content ratio: 5 wt%) of the binder can be manufactured using the binder as a target sample by the above-described “method for manufacturing the water mixture (content ratio: 5 wt%)”. In addition, when the said binder is a binder containing solvents, such as colloidal silica, the said content rate is a content rate of the solid content in the said binder with respect to the said water mixture.

  Examples of the organic binder include polyethylene resins, polypropylene resins, acrylic resins such as methyl methacrylate, ABS resins, polyester resins such as PET, phenol resins, epoxy resins, urethane resins, vinyl acetate resins, and polyvinyl resins. Examples thereof include cellulose such as alcohol and carboxymethylcellulose, and arabic gum. The said organic binder may use only 1 type and may use 2 or more types.

  The inorganic binder is preferably in the form of particles that do not completely cover the surface of the inorganic silica-based porous material. For example, sodium silicate, silica sol, alumina sol, colloidal silica, colloidal alumina, colloidal tin oxide, colloidal Examples thereof include inorganic oxide particles such as titanium oxide. Among them, colloidal inorganic oxide particles such as colloidal silica, colloidal alumina, colloidal tin oxide and colloidal titanium oxide are preferable. Of these, colloidal silica is preferable. The said inorganic binder may use only 1 type and may use 2 or more types.

  The average particle diameter (primary particle diameter), specific surface area (BET specific surface area), average pore diameter (diameter), total pore volume, and the like of the inorganic binder are not particularly limited.

(Chemical filter structure)
The structure of the chemical filter of the present invention is not particularly limited, and examples thereof include a honeycomb structure, a pleat structure, a pellet filling structure, a three-dimensional network structure, and a sheet packaging structure. Among these, a honeycomb structure, a pleated structure, and a three-dimensional network structure are preferable, and a honeycomb structure is particularly preferable from the viewpoint of suppressing pressure loss. When the pelletized adsorbent (pellet) is used as the adsorbent of the present invention, it is not particularly limited, but a pleated structure, a pellet filling structure, or a three-dimensional network structure is preferable. The chemical filter of the present invention may have only one type of structure, or may have a combination of two or more types of structures.

  In addition to the so-called honeycomb structure, the honeycomb structure includes, for example, a lattice shape, a circular shape, a wave shape, a polygonal shape, an indefinite shape, a shape having a curved surface in whole or in part, and a fluid (particularly , Air) includes all structures that can pass through the cells that are the elements of the structure.

  Examples of the honeycomb structure include a structure obtained by alternately laminating corrugated sheets and flat sheets formed by corrugating (corrugated honeycomb structure), and includes a pleated sheet and a flat sheet. Examples of the structure include a structure in which a pleated sheet and a flat sheet are sequentially laminated at right angles to the ventilation direction.

  As the chemical filter of the present invention having a honeycomb structure, for example, a filter base material using a fibrous base material has a corrugated honeycomb structure, and a filter base material using a fibrous base material has a honeycomb structure. Examples thereof include a chemical filter having a honeycomb structure in which a metal filter substrate made of metal such as aluminum has a honeycomb structure.

  The pleated structure includes, for example, a structure having a bellows shape processed so that a waveform or a V shape is continuous in order to efficiently expand a filtration area in a limited space.

  Examples of the pellet filling structure include a structure in which the pelletized adsorbent is filled in a casing having a structure in which a fluid (particularly gas) can pass therethrough. In addition, when the particle size of the adsorbent powder is large enough to be held in the casing, instead of the pellet filling structure, the powder is not pelletized and the powder is filled in the casing. You can also

  The three-dimensional network structure is, for example, a mesh formed by three-dimensionally processing a foam composed of the polyurethane foam or the like, glass fiber (glass wool or the like), rock wool fiber, or fiber of the fibrous base material. A structure having a filter base material of the structure or polytetrafluoroethylene made into needle-like fibers is preferably exemplified.

  Examples of the sheet packaging structure include a structure in which an air-permeable sheet such as a non-woven fabric or PTFE is molded into a bag of any size and filled with an adsorbent. Further, the particle size of the adsorbent may be pelletized so that the adsorbent particles do not leak out of the sheet, but depending on the sheet, it can be used as a powder.

(Method for producing chemical filter of the present invention)
The manufacturing method of the chemical filter of this invention is not specifically limited, The manufacturing method of the chemical filter which has a well-known thru | or usual adsorption agent can be used. Although the chemical filter of this invention is not specifically limited, For example, it has at least the process (adsorbent adhesion process) which makes the adsorbent of this invention adhere to a filter base material. Although the manufacturing method of the chemical filter of this invention is not specifically limited, You may have processes (other processes) other than the said adsorption agent adhesion process. Moreover, the said filter base material may purchase a commercially available filter base material, and may use it as it is.

  In the adsorbent adhering step, the adsorbent of the present invention is adhered to, for example, the filter substrate, the adsorbent of the present invention, a solvent (for example, water), and a suspension containing the binder as necessary. After dipping in, it can be carried out by removing from the suspension and drying. The suspension may contain an antisettling agent as long as the effects of the present invention are not impaired.

  In addition, the adsorbent of the present invention is attached to the filter base material after being immersed in a suspension containing the solvent and, if necessary, the binder, then taken out from the suspension, dried, and then filtered. It can also be carried out by dispersing and adsorbing the adsorbent of the present invention on the substrate surface.

  In addition, the adsorbent of the present invention is attached to the filter base material (particularly, non-woven fabric) by spraying the mixed solution containing the adsorbent of the present invention, the solvent, and, if necessary, the binder. It can also be performed by applying and adhering.

  In addition, the adsorbent of the present invention can be attached to the above filter base material by adhering pellets produced by granulating the adsorbent powder of the present invention with an adhesive or filling the inside of the filter base material. It can also be done. When granulating the adsorbent powder of the present invention, the binder may be mixed as necessary. When the adsorbent powder of the present invention, the binder, and the solvent (preferably water) are mixed in an appropriate amount, the clay-like viscosity and plasticity are exhibited, and granulation becomes possible.

  In addition, the adsorbent of the present invention can be attached by using a polytetrafluoroethylene resin that has been made into acicular fibers and capturing and adsorbing the adsorbent of the present invention on the acicular fibers.

  In addition, the adsorbent of the present invention may be attached in a state where the adsorbent of the present invention is contained in nanofibers. As said nanofiber, well-known thru | or usual nanofiber can be used. Moreover, the said nanofiber can also be produced with the manufacturing method of well-known thru | or a usual nanofiber. Examples of the method for producing the nanofiber include an electrospinning (ES) method (electrospinning, electrostatic spinning), a melt blow method, a composite melt spinning method, and the like. In the ES method, a high voltage is applied to a suspension in which the adsorbent of the present invention is dispersed in a polymer solution, and the suspension is sprayed on a ground surface (for example, a filter substrate (for example, a non-woven fabric) having a zero surface potential). Do. In the ES method, when the suspension is sprayed at a high voltage, nanofibers containing the adsorbent of the present invention are formed.

  In the case of a chemical filter using a filter base material (for example, a metal filter base material) to which the adsorbent is difficult to adhere, the adsorbent of the present invention is attached to the filter base material using an adhesive. You may go.

  In the pleated structure chemical filter, the adsorbent of the present invention is adhered to, for example, by adhering the adsorbent powder or pelletized adsorbent of the present invention between two non-woven filter substrates. It can also be performed by sandwiching with an agent or the like.

  As said other process, the process (filter base material processing process) etc. which process a filter base material are mentioned, for example. The order of the filter base material processing step and the adsorbent attachment step is not particularly limited, but the order of the filter base material processing step and the adsorbent attachment step is preferable from the viewpoint of workability.

  Examples of the filter base material processing step include a step of corrugating the filter base material, a step of forming a honeycomb structure, and a step of providing pores in the filter base material as described above. The said filter base-material processing process may perform only 1 process, and may perform the same or different 2 processes or more. Also when performing the said filter base-material process process 2 steps or more, the order is not specifically limited.

  The chemical filter of the present invention may be a chemical filter manufactured by a papermaking method. The chemical filter manufactured by the papermaking method is, for example, a chemical filter having at least a fibrous base material and the adsorbent of the present invention, and contains the fibers constituting the fibrous base material and the adsorbent of the present invention. A substance (floc) produced by adding a flocculant to the suspension is formed into a sheet by a wet papermaking method and then heat-treated.

  The chemical filter of the present invention may be a ceramic type chemical filter. The ceramic-type chemical filter can be produced by a known or common processing method for ceramic materials. For example, the adsorbent of the present invention can be produced by molding and firing together with a ceramic raw material. Specifically, for example, after preparing the clay by weighing and kneading the adsorbent of the present invention, the binder, the pore former, and other ceramic raw materials as required, the clay is extruded by screw type extrusion. Extrusion is performed by an extruder such as a machine to produce a molded body. The obtained molded body is dried and fired to obtain a porous ceramic type chemical filter. The ceramic type chemical filter is not particularly limited, but a ceramic type chemical filter having a honeycomb structure is preferable. The ceramic-type chemical filter can be processed into a predetermined length by a grinding tool such as a diamond cutter or a diamond saw as appropriate.

  Among the above, the chemical filter of the present invention is particularly preferably a chemical filter having a honeycomb structure in which a plurality of corrugated sheets each having the adsorbent of the present invention attached to its surface with an inorganic binder are laminated via thin sheet sheets.

  Although not particularly limited, it is preferable that the chemical filter of the present invention does not include an adsorbent to which an additive (for example, an acidic substance, a basic substance, an oxidizing agent, or the like) is attached. That is, the chemical filter of the present invention is preferably excluded from those having an adsorbent to which an additive is attached.

  The chemical filter of the present invention uses an inorganic silica-based porous material whose pH of the water mixture is 7 or less as an adsorbent. Thereby, in the chemical filter of the present invention, since the silanol group (—Si—OH) is present in the inorganic silica-based porous material acting as a solid acid, the silanol group (—Si—OH) and the fluid (particularly, It is assumed that Si-O-Si bonds are formed by dehydration condensation with silanol compounds in the air), mainly due to chemical adsorption, but the silanol compounds adsorbed firmly and once adsorbed It becomes difficult to detach. In addition, the formed Si—O—Si bond has a significantly stronger binding force than ionic bonds formed by a neutralization reaction or physical adsorption using activated carbon. In addition, although it is estimated that the chemical filter of this invention removes a silanol compound mainly by chemical adsorption, it does not exclude removing partially by physical adsorption.

  The chemical filter disclosed in Patent Document 2 discloses that an acidic substance additive is attached to the adsorbent. However, the acidic material additive is a protonic acid, its function is to dimerize the silanol compound, and the function of adsorbing this dimerized compound is not the acidic material additive but the adsorbent. . Thus, even if it is generally referred to as an acidic substance, a general low-molecular proton acid such as sulfuric acid and a solid acid having a silanol group (—Si—OH) have completely different properties.

  As described above, the chemical filter of the present invention is considered to remove the silanol compound mainly by chemical adsorption by using an inorganic silica-based porous material having a pH of 7 or less as the adsorbent. Therefore, unlike the physical adsorption using an adsorbent such as activated carbon, the once adsorbed silanol compound is not desorbed. Therefore, the adsorption capacity is easier to estimate than the chemical filter using activated carbon as the adsorbent, and the life analysis is relatively easy. Further, as will be described later, since it is difficult to desorb even when the pressure is returned from high pressure to normal pressure, it is useful to dispose the chemical filter of the present invention in the pressure pipe in the silanol compound removing equipment of the present invention.

  Furthermore, since the chemical filter using activated carbon as the adsorbent removes the silanol compound by physical adsorption, when VOC is present in addition to the silanol compound in the fluid, the removal of the silanol compound competes with the removal of the VOC. For this reason, the removal ability of a silanol compound falls. In contrast, the adsorbent of the present invention removes the silanol compound mainly by silanol groups in the inorganic silica-based porous material as described above. It can be removed efficiently.

[Chemical filter for removing inhibitory substances]
The inhibitor removing chemical filter is a chemical filter for removing an inhibitor that reduces the silanol compound removing ability of the chemical filter of the present invention. The inhibitor removing chemical filter is installed upstream of the chemical filter of the present invention.

  The chemical filter for removing an inhibitory substance is not particularly limited as long as it is a chemical filter that removes a substance (inhibitor substance) that reduces the silanol compound removing ability of the chemical filter of the present invention. Examples of such chemical filters for removing inhibitory substances include basic substances removing chemical filters that adsorb basic substances such as ammonia and amines; acidic substances such as hydrogen sulfide, sulfur oxides, nitrogen oxides, and organic acids. Examples include chemical filters for removing acidic substances that adsorb organic substances; chemical filters for removing organic substances that adsorb organic substances such as benzene, toluene, and cyclohexanone; and chemical filters for removing siloxane compounds that adsorb siloxane compounds. As the chemical filter for removing the inhibitory substance, a chemical filter for removing a basic substance and a chemical filter for removing a siloxane compound are preferable. If the chemical filter for removing an inhibitory substance is a chemical filter for removing a basic substance, the basicity may reduce the acidic point of the inorganic silica porous material in the adsorbent of the present invention in the chemical filter of the present invention. It is preferable because the substance can be efficiently removed, and the silanol compound removing ability of the chemical filter of the present invention is not lowered and can be maintained for a long time. Further, when the chemical filter for removing an inhibitory substance is a chemical filter for removing a siloxane compound, there is a possibility of reducing silanol groups and pores of the inorganic silica-based porous material in the adsorbent of the present invention in the chemical filter of the present invention. It is preferable because a certain siloxane compound can be efficiently removed and the silanol compound removing ability of the chemical filter of the present invention is not lowered and can be maintained for a long time.

  Although it does not specifically limit as said siloxane compound, For example, the compound which has at least Si-O-Si frame | skeleton in a molecule | numerator is mentioned. Examples of the siloxane compound include cyclic siloxane compounds (for example, D3-D20 cyclic siloxane compounds such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, etc.), linear siloxane compounds (for example, Straight chain siloxane compounds having 2 to 20 silicon atoms such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, etc.), branched siloxane compounds, and the like. Among these, a cyclic siloxane compound and a linear siloxane compound are preferable. The siloxane compound is preferably volatile.

  The chemical filter for removing the inhibitory substance may be any chemical filter that removes the inhibitory substance, and the material and shape of the chemical filter for removing the inhibitory substance are not particularly limited.

  For example, when the chemical filter for removing an inhibitory substance has an adsorbent or an ion exchange resin, the adsorbent or the ion exchange resin is not particularly limited, and can be appropriately selected depending on the kind of the inhibitor to be removed. Examples of the adsorbent and ion exchange resin include adsorbents (for example, activated carbon) and ion exchange resins that are used in known or conventional chemical filters. Further, the adsorbent may be non-added, and basic substances such as potassium hydroxide, sodium hydroxide and potassium carbonate; acidic substances such as phosphoric acid, sulfuric acid, sulfate, nitric acid and nitrate are attached. It may be. The inhibitor removing chemical filter is not limited to the one having the adsorbent or the ion exchange resin, and includes, for example, a filter base material having an ion exchange function (for example, a nonwoven fabric having an ion exchange function). The chemical filter used may be used.

  As the adsorbent in the chemical filter for removing the inhibitory substance, specifically, when the inhibitory substance is a basic substance, an adsorbent to which an acidic substance is attached (particularly, activated carbon to which an acidic substance is attached) When the inhibitor is an acidic substance, the adsorbent to which a basic substance is attached (particularly, activated carbon to which a basic substance is attached) is adsorbed without adhesion when the inhibitor is an organic substance or a siloxane compound. An agent (particularly non-attached activated carbon) is preferred. The non-adsorbing adsorbent may have an adsorbing agent added to such an extent that removal of the organic substance or the siloxane compound is not significantly inhibited.

  The structure of the inhibitor removing chemical filter is not particularly limited, and examples thereof include those illustrated and described as the structure of the chemical filter of the present invention.

[The Silanol Compound Removal Equipment of the Present Invention]
The silanol compound removal equipment of the present invention has the chemical filter of the present invention. The chemical filter of the present invention acts as a solid acid by the presence of the surface of an inorganic silica-based porous material having a pH of the water mixture of 7 or less in the chemical filter, and the silanol compound is strongly consolidated by dehydration condensation of the silanol compound. It is presumed that the silanol compound can be effectively removed due to adsorption. Even when another adsorbent is used in combination as the adsorbent, the silanol compound is effectively removed because the surface of the inorganic silica-based porous material having a pH of the water mixture of 7 or less exists in the chemical filter. The effect that it can be removed can be maintained. For this reason, the silanol compound removal equipment of the present invention having the chemical filter of the present invention can efficiently remove the silanol compound.

  Furthermore, the silanol compound removal equipment of the present invention has the inhibitor removing chemical filter upstream of the chemical filter of the present invention. The chemical filter of the present invention may have a reduced silanol compound removal ability depending on the substance to be adsorbed. For this reason, the silanol compound removal system of the present invention has a chemical filter that removes a substance (inhibitory substance) that reduces the silanol compound removal ability upstream of the chemical filter of the present invention, so that the inhibitor is removed from the inhibitor. By being removed by the chemical filter for use, the silanol compound removing ability of the chemical filter of the present invention is not lowered by the inhibitory substance and can be maintained for a long time.

  The silanol compound removal equipment of the present invention is not particularly limited, but may have a chemical filter (other chemical filter) other than the chemical filter of the present invention and the chemical filter for removing the inhibitory substance. In this case, the silanol compound removing equipment of the present invention may have the chemical filter of the present invention next to the chemical filter for removing the inhibitor, or the chemical filter for removing the inhibitor and the chemical filter of the present invention. You may have the said other chemical filter in between.

  The silanol compound removal equipment of the present invention may have only one chemical filter or inhibitor removal chemical filter of the present invention, or may have two or more. Further, when two or more chemical filters for removing an inhibitory substance are included, the two or more chemical filters for removing an inhibitory substance may remove the same inhibitory substance or remove different inhibitory substances. Also good. Further, when two or more inhibitory substance removal chemical filters are provided, it is only necessary that at least one inhibitory substance removal chemical filter is located upstream of the chemical filter of the present invention.

  In the silanol compound removal facility of the present invention, the position of the inhibitor removing chemical filter may be upstream of the chemical filter of the present invention. That is, the silanol compound removal equipment of the present invention has a structure in which a fluid (particularly air) containing a silanol compound passes through the chemical filter of the present invention after passing through the chemical filter for removing an inhibitory substance. That's fine. Therefore, in the silanol compound removal equipment of the present invention, each chemical filter (the chemical filter of the present invention, the chemical filter for removing an inhibitory substance, etc.) may be partly or entirely disposed separately, All may be arranged continuously (for example, stacked). In the case where a part or all of them are arranged separately, the separation interval is not particularly limited. As an example in which a part or the whole is continuously arranged, for example, a chemical filter (a panel type filter, a cell type filter, a chemical filter for piping, which will be described later) a part or all of the chemical filter is collectively framed. Etc.). As an example in which a part or all of the chemical filters are arranged separately, for example, a chemical filter in which some or all of the chemical filters are respectively framed, and each of the framed chemical filters has one long flow. For example, a device that is arranged on the road in isolation. The inhibitor removing chemical filter may be installed immediately before the chemical filter of the present invention, or upstream of the chemical filter of the present invention in a passage through which the fluid containing the silanol compound (especially air) passes. In addition, it may be installed away from the chemical filter of the present invention.

  As a method of using the silanol compound removal equipment of the present invention, for example, using a power such as a ventilation fan, the substance to be removed is introduced into the inside of the apparatus equipped with the chemical filter for removing the inhibitor and the chemical filter of the present invention in this order. In addition to the aeration method that forcibly introduces air containing air and removes the substance to be removed, air is used to power the inside of the apparatus equipped with the chemical filter for removing the inhibitory substance and the chemical filter of the present invention in this order. Rather than introducing the method, there is a stationary method in which the substance to be removed is removed by contact only with natural diffusion or natural convection. That is, the silanol compound removal equipment of the present invention can be used by either the aeration method or the stationary method. As the silanol compound removal equipment using the ventilation method, for example, a ventilation fan (for example, a device for taking in air, a device for discharging air), the chemical filter of the present invention, and the chemical filter for removing an inhibitory substance are integrated. A unit (sometimes referred to as a “fan filter unit (FFU)”). The FFU can be attached to a ceiling or a clean booth, or provided in the middle of a duct.

  In the silanol compound removal facility of the present invention, each chemical filter (the chemical filter of the present invention, the chemical filter for removing an inhibitor, etc.) is a chemical filter (framed chemical filter) in a framed state. Also good. Moreover, the chemical filter with which all the chemical filters in the silanol compound removal equipment of this invention were put into a frame may be sufficient, and the chemical filter with which some chemical filters were put into a frame may be sufficient. Further, it may be framed for each chemical filter, or a part or all of the chemical filters may be collectively framed.

  The framed chemical filter is obtained, for example, by putting a chemical filter (filter medium) in which an adsorbent is attached to a filter base material. Examples of the framed chemical filter include a panel type filter, a cell type filter, a piping chemical filter, and the like. In addition, both the said filter medium and the said framed chemical filter correspond to the chemical filter in this specification.

  Examples of the panel type filter include a chemical filter in which the edge of a plate-shaped filter medium is fitted in a frame like a frame. The panel-type filter is generally used so that a fluid containing a silanol compound passes in the thickness direction of a plate-shaped filter medium. The shape of the frame is not particularly limited and can be appropriately selected depending on the usage mode. Examples of the shape of the frame include a polygonal shape (for example, a triangular shape, a quadrangular shape, a hexagonal shape, a frame shape, etc.), a circular shape, an elliptical shape, a shape in which some or all of the corners of the polygon are rounded, The shape etc. which combined these shapes are mentioned. Further, the plate-shaped filter medium may be a single sheet, or may be a stack of a plurality of filter mediums.

  Examples of the cell-type filter include a filter in which a filter medium is disposed inside a cell having a hexahedral shape (cube, rectangular parallelepiped, etc.) so that a fluid containing a silanol compound passes through the filter medium. Examples of the cell-type filter include a chemical filter in which the filter medium has a series of bent portions so that the filter medium has a continuous V shape, and the bent portions are arranged to face the aeration direction. The cell type filter may be a chemical filter arranged in a folding screen so that each of the bent portions is cut, that is, a plurality of filter media have a V-shaped structure. In the cell type filter in which the filter medium is arranged to have a V-shaped structure, the fluid containing the silanol compound is arranged to pass in the thickness direction of the filter medium arranged to have the V-shaped structure.

  Examples of the pipe chemical filter include a chemical filter in which a filter medium is packed in a part of a pipe (for example, a cylinder, a square cylinder, etc.). In the portion where the filter medium is packed, it is preferable that the filter medium is packed over the entire cross section of the tubular pipe so that all the fluid containing the silanol compound passes through the filter medium. The chemical filter for piping can be preferably used in pressure piping.

  In the silanol compound removal equipment of the present invention, when each chemical filter is arranged separately, the environment in which each chemical filter is installed may be the same or different.

(Usage environment of silanol compound removal equipment of the present invention)
The silanol compound removal equipment of the present invention can be used in various environments where chemical filters can be used. For example, since the chemical filter of the present invention can be used in a high temperature environment where activated carbon cannot be used, or in an environment such as various concentration environments and humidity environments, the chemical filter of the present invention in the silanol compound removal facility of the present invention can be used. The chemical filter can be used in these environments.

  The chemical filter of the present invention can be used in a wide temperature environment (for example, an environment of 0 to 500 ° C.). A chemical filter using activated carbon as an adsorbent cannot be used because activated carbon gradually oxidizes in a high-temperature environment, and the activation progresses and the pores widen, resulting in a decrease in removal performance. In contrast, the chemical filter of the present invention does not require the use of activated carbon as an adsorbent, and therefore can be used in a wide temperature environment including a high temperature environment. Therefore, the chemical filter of the present invention can be used in these environments in the silanol compound removing equipment of the present invention. Although the temperature of the environment where the chemical filter of this invention is used in the silanol compound removal equipment of this invention is not specifically limited, 10-300 degreeC is preferable, More preferably, it is 15-100 degreeC, More preferably, it is 15-50 degreeC It is.

  Furthermore, chemical filters using activated carbon as an adsorbent are presumed to be because the molecular movement of the silanol compound is activated in a high-temperature environment by removing the silanol compound by physical adsorption. Tends to decrease. On the other hand, since the adsorbent of the present invention is considered to remove silanol compounds with strong bonds mainly as in chemical adsorption, the silanol compound removal equipment of the present invention is effective even in a high temperature environment. Can be removed.

The chemical filter of the present invention can be used in a wide range of humidity environments (for example, in an environment with a relative humidity of 0 to 99% RH) as long as no condensation occurs. A chemical filter using activated carbon as an adsorbent is known to promote TMS dimerization at, for example, a relative humidity of 33% RH or less (for example, JP 2012-30163 A). However, in an environment where a chemical filter is actually used, the concentration of TMS in the fluid is thin, and in this case, dimerization is unlikely to occur. On the other hand, since the chemical filter of the present invention can be removed without dimerizing the silanol compound, the silanol compound can be efficiently removed under a wide range of humidity. For this reason, in the silanol compound removal equipment of the present invention, the chemical filter of the present invention can also efficiently remove silanol compounds in the purge gas by dry gas or inert gas such as N ₂ gas. The relative humidity at which the chemical filter of the present invention is used in the silanol compound removing facility of the present invention is not particularly limited, but is preferably 0 to 95% RH, more preferably 0 to 60% RH, and still more preferably 0 to 40. % RH.

  When a zeolite having a pH of 7 or less is used as the inorganic silica-based porous material having a pH of 7 or less in the water mixture, the amount of hydrogen ions in the zeolite is large and the amount of other cations is relatively small. Because of its relatively high hydrophobicity, it is difficult to adsorb moisture in the fluid even in a high humidity environment, and is less susceptible to humidity. For this reason, a silanol compound can be efficiently removed even in a high humidity environment.

The chemical filter of the present invention can be used under a wide pressure environment (for example, an environment of 10 ^{−11 to} 100 MPa). A chemical filter using activated carbon as an adsorbent has a high removal capability in a high-pressure environment because the concentration of the substance to be removed is high, but when it is returned to normal pressure, the substance that has adhered excessively due to the pressure. There is a tendency to detach. In contrast, the chemical filter of the present invention strongly adsorbs and removes the silanol compound, so that it does not desorb when used under a high pressure environment and then returned to normal pressure. For this reason, in the silanol compound removal equipment of the present invention, the chemical filter of the present invention can be used under a wide pressure environment including a high pressure environment. Although the pressure of the environment where the chemical filter of this invention is used is not specifically limited, 10 < ^-7 > -1MPa is preferable, More preferably, it is 10 < ^-4 > -1MPa, More preferably, it is 0.05-1MPa. For this reason, the chemical filter of this invention can be preferably used also in pressure piping in the silanol compound removal equipment of this invention. In addition, you may have the chemical filter of this invention and the chemical filter for inhibitory substance removal in one chemical filter for piping.

  The chemical filter of the present invention can be preferably used even under a wide range of silanol compound concentration environments (for example, 0.001 ppb to 10 ppm). For example, Patent Document 2 discloses a chemical filter using an adsorbent with an acidic substance adhering agent, and dimerizing and dimerizing a silanol compound with an acidic substance adhering agent. The adsorbent is removed. However, in an environment where a chemical filter is actually used, the concentration of TMS in the air is low, and in this case, dimerization hardly occurs. On the other hand, the chemical filter of the present invention in the silanol compound removal facility of the present invention can remove the silanol compound without dimerizing it, so that the concentration of the silanol compound in the fluid is extremely low (for example, one digit). Silanol compounds can be removed with high efficiency even at ppb or less). In particular, the silanol compound removal equipment of the present invention (particularly the chemical filter of the present invention) has a silanol compound concentration in the fluid (particularly in the air) of 100 ppb or less (preferably 50 ppb or less, more preferably 10 ppb or less). It can be preferably used in an extremely low concentration environment. Although not particularly limited, the concentration of the silanol compound in the fluid is preferably 0.001 ppb or more.

  In addition, when using the silanol compound removal equipment of the present invention (particularly, the chemical filter of the present invention) in an environment where the concentration of the silanol compound in the fluid is extremely low, the temperature of the environment is not particularly limited, but is 0 to 500. ° C is preferred, more preferably 15 to 50 ° C.

  The chemical filter of the present invention can be used under various wind speed environments (for example, the filtration wind speed is 0 to 5 m / s). In particular, it can be used even in a high wind speed environment (for example, in an environment where the filtration wind speed is 1 to 5 m / s). A chemical filter using activated carbon as an adsorbent tends to have a lower removal ability as the wind speed of the passing air is higher. On the other hand, the chemical filter of the present invention can efficiently remove the silanol compound even under a high wind speed environment. Although the wind speed of the environment in which the chemical filter of the present invention is used in the silanol compound removal facility of the present invention is not particularly limited, the filtration wind speed is preferably 0 to 5 m / s, more preferably the filtration wind speed is 0 to 3 m / s, More preferably, the filtration wind speed is 0 to 1 m / s.

  Moreover, the silanol compound removal equipment of the present invention (particularly, the chemical filter of the present invention) is used in an environment where the content of gas other than the silanol compound is low (low gas environment) and in an environment where the concentration of air is low (for example, vacuum It can be used even in the environment). In addition, since the chemical filter of the present invention does not necessarily use activated carbon as an adsorbent, the chemical filter of the present invention is preferably used in an environment where flame retardancy is required in the silanol compound removal facility of the present invention. it can.

The silanol compound removal equipment of the present invention is equipment for removing a silanol compound. The silanol compound is a compound having at least a silanol group (—Si—OH) as represented by R _4-n Si (OH) _n . N is an integer of 1 to 3. R represents a hydrogen atom; a halogen atom such as a fluorine atom or a chlorine atom; an optionally substituted hydrocarbon group (preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms), and the like. It is done. When there are a plurality of Rs, two or more of the plurality of Rs may be the same or different. The silanol compound is preferably volatile. As the silanol compound, trimethylsilanol (TMS) is particularly preferable.

[Fluid purification method]
Furthermore, the fluid can be purified by removing the silanol compound in the fluid using the silanol compound removing equipment of the present invention. As described above, the method of removing the silanol compound in the fluid using the silanol compound removing equipment of the present invention and purifying the fluid may be referred to as “the fluid purification method of the present invention”. For this reason, the silanol compound removal equipment of the present invention can be installed at an appropriate place in order to remove the silanol compound in the fluid (for example, in the air). For example, the silanol compound removal equipment of the present invention includes equipment in a clean room (in particular, equipment inside a semiconductor manufacturing process such as an internal equipment of an exposure equipment, an internal equipment of a coating and developing equipment, a equipment around a semiconductor chip cutting process), As applications that require removal of silanol compounds, such as equipment inside magnetic disk storage devices (eg, equipment inside HDDs), equipment around the manufacturing process of liquid crystal displays, equipment at sewage treatment plants, equipment at landfill sites, etc. It can be preferably used.

  In the clean room (for example, a clean room in which gaseous pollutants are controlled, especially a clean room in a semiconductor manufacturing factory, etc.), various gaseous organic compounds such as silanol compounds exist. Silanol compounds may be adsorbed on the surface of a semiconductor silicon wafer or the surface of a liquid crystal glass substrate, causing problems in these products. In the sewage treatment plant, the digestion gas generated from the digestion tank contains a trace amount of silanol compound due to the silicone oil contained in the shampoo and cosmetics. Furthermore, in the above landfill, siloxane compounds and silanol compounds contained in biogas in mud (active sludge and the like) used for landfill may be problematic. Therefore, the silanol compound removal equipment of the present invention can be used particularly preferably for fluid (especially air) purification for such applications.

  Moreover, it can be preferably used also for applications that require avoidance of poisoning by silanol compounds such as gas sensors and reaction catalysts. In addition, it can also be used in the vicinity of various analyzers, gas supply lines, the periphery where cell regeneration processing is performed, the periphery where micropore processing is performed, a nuclear power plant, and the like. Silanol compounds can also be preferably used in fuel cell manufacturing processes and the like because they may reduce the electromotive force of the fuel cell. Furthermore, silanol compounds may accumulate in gas turbines, boiler burners, heat exchangers, etc., reducing efficiency and causing malfunctions and failures, so they can also be used in such places. .

  The silanol compound removing equipment in the clean room is preferably used as a silanol compound removing equipment for a semiconductor manufacturing apparatus. Especially, it is preferable that they are the silanol compound removal equipment for the inside of the exposure apparatus used in the exposure process of a semiconductor manufacturing process, and the silanol compound removal equipment for the inside of a coating and developing apparatus (coater developer). TMS may occur in the exposure apparatus used in the exposure process of the semiconductor manufacturing process, or in the coating and developing apparatus, etc., and the floating TMS is combined with a lens or the like to cause fogging and cause exposure troubles. There is a fear. In addition, it can be set as the clean room of this invention by using the silanol compound removal equipment of this invention in the said clean room. Moreover, it can be set as the semiconductor manufacturing equipment of this invention by using the silanol compound removal equipment of this invention inside a semiconductor manufacturing apparatus. Further, by using the silanol compound removing facility of the present invention in the above exposure apparatus or in a coating and developing apparatus, the exposure apparatus of the present invention or the coating and developing apparatus of the present invention can be obtained.

[Semiconductor manufacturing equipment]
The semiconductor manufacturing facility of the present invention includes the silanol compound removing facility of the present invention. The said semiconductor manufacturing equipment will not be specifically limited if it is a semiconductor manufacturing equipment which has the silanol compound removal equipment of this invention. According to the semiconductor manufacturing equipment of the present invention, since the chemical filter of the present invention is used as an internal chemical filter, it is in a fluid compared with a semiconductor manufacturing apparatus using a conventional chemical filter using activated carbon as an adsorbent. The silanol compound (especially in the air) can be efficiently removed. Further, the removal efficiency of the silanol compound does not decrease in a short time, and the silanol compound is not released as in the case of activated carbon and does not become negative efficiency (higher concentration on the downstream side than on the upstream side of the filter). Furthermore, since the silanol compound can be adsorbed without dimerization, it can be efficiently removed even if the silanol compound in the fluid (particularly in the air) has a low concentration. For this reason, it is possible to remarkably suppress an exposure failure caused by a silanol compound in the fluid (particularly in the air).

[Exposure equipment, coating and developing equipment]
The exposure equipment of the present invention includes the silanol compound removal equipment of the present invention. The said exposure equipment will not be specifically limited if it is exposure equipment which has the silanol compound removal equipment of this invention. Moreover, the coating and developing equipment of the present invention includes the silanol compound removing equipment of the present invention. The coating and developing equipment is not particularly limited as long as it is a coating and developing equipment having the silanol compound removing equipment of the present invention. According to the exposure equipment of the present invention and the coating and developing equipment of the present invention, the chemical filter of the present invention using an inorganic silica-based porous material having a pH of a water mixture of 7 or less as an adsorbent as the internal equipment, Since the silanol compound removal equipment which has the chemical filter for inhibitor removal which removes the inhibitor which reduces the silanol compound removal ability of the chemical filter of the present invention is used upstream of the chemical filter of the invention, activated carbon is used as an adsorbent. Compared with exposure equipment and coating and development equipment using conventional chemical filters, silanol compounds such as TMS in fluid (especially in air) can be efficiently removed. In particular, the removal efficiency of the silanol compound does not decrease in a short time, and TMS is not released like activated carbon, resulting in a negative efficiency (higher concentration on the downstream side than on the upstream side of the filter). Further, since the silanol compound can be adsorbed without dimerization, it can be efficiently removed even if the silanol compound in the fluid (particularly in the air) has a low concentration. And even if the substance which reduces the removal ability with respect to the silanol compound of the chemical filter of this invention exists, the said removal ability does not fall. For this reason, it is possible to remarkably suppress an exposure failure caused by a silanol compound in the fluid (particularly in the air).

  The silanol compound removing equipment of the present invention is preferably used as a silanol compound removing equipment for a laser processing apparatus. Silanol compounds may be generated inside or around the laser processing equipment, and laser light impinges on the silanol compounds and scatters, preventing laser irradiation or adhering to the laser optical system, especially the lens surface. As a result, the laser irradiation may become a hindrance, and laser processing may fail or may adhere to the surface of the workpiece and contaminate the workpiece. Moreover, it can be set as the laser processing equipment of this invention by using the silanol compound removal equipment of this invention inside a laser processing apparatus.

[Laser processing equipment]
The laser processing equipment of the present invention includes the silanol compound removing equipment of the present invention. The said laser processing equipment will not be specifically limited if it is a laser processing equipment which has the silanol compound removal equipment of this invention. According to the laser processing equipment of the present invention, since the chemical filter of the present invention is used as an internal chemical filter, it can be used in a fluid as compared with a laser processing apparatus using a conventional chemical filter using activated carbon as an adsorbent. The silanol compound (especially in the air) can be efficiently removed. Further, the removal efficiency of the silanol compound does not decrease in a short time, and TMS is not released like activated carbon, and the negative efficiency (the concentration on the downstream side of the filter upstream is higher). Furthermore, since the silanol compound can be adsorbed without dimerization, it can be efficiently removed even if the silanol compound in the fluid (particularly in the air) has a low concentration. Therefore, the malfunction of the laser processing resulting from the silanol compound in fluid (especially in air) can be suppressed significantly.

  Examples of the laser processing apparatus in the laser processing equipment of the present invention include known or conventional laser processing apparatuses, such as an apparatus that cuts glass or film with a laser, an apparatus that performs fine metal processing with a laser, and the like. The various processing apparatuses to be used are mentioned. Examples of the laser include known or commonly used lasers such as carbon dioxide laser and YAG (yttrium / aluminum / garnet) laser, and are not particularly limited.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to them. “Ppb” is based on weight unless otherwise specified.

  In addition, the VOC used in the following Examples 1-10 does not contain the inhibitor which reduces the silanol compound removal ability of a test sample. That is, Examples 1 to 10 below are based on the assumption that an inhibitor removal chemical filter is provided upstream of the silanol compound removal chemical filter.

Example 1
The gas removal efficiency of the adsorbent was measured using an aeration test apparatus as shown in FIG. In Example 1, two series of acrylic cylindrical test columns (inner diameter: 50 mm, length: 30 cm) 1 connected in series are arranged in parallel in six lines, and a gas supply tube 2 is arranged upstream of the column. The flow meter 3, the flow rate adjusting valve 4, and the pump 5 were attached in this order on the downstream side of the column. The nonwoven fabric 6 was sandwiched between two columns connected in series, a test sample (adsorbent) 7 was laid on the nonwoven fabric 6 with a thickness of 5 mm, and the flow rate was adjusted so that the filtration wind speed of the test sample was 5 cm / s. Air was blown. As the air flowing through the column, TMS3 ppb and VOC 250 ppb were mixed with air adjusted to a temperature of 23 ° C. and a humidity of 50% using a constant temperature and humidity chamber. A schematic cross-sectional view (for one series) of the aeration test apparatus is shown in FIG.
As a test sample (adsorbent), a plurality of zeolites (synthetic zeolites) (average particle diameter: 3 to 20 μm) having different pHs in the water mixture (content ratio: 5 wt%) shown in Table 1, and a water mixture (containing) A plurality of silica gels, acid clay, activated clay, diatomaceous earth, fumed silica, and talc (average particle diameter: 5 to 30 μm) having different pH at a ratio of 5 wt% were used. In addition, the fumed silica used what was processed into the pellet form. The removal efficiency was measured for every six test samples, and each of the six test samples to be measured was used for each column 1 arranged in parallel in six series.
On the third day after the start of the aeration test, air on the upstream and downstream sides of the column is collected by an adsorption tube, and the adsorption tube that collects the air is subjected to gas analysis by ATD (heat desorption device) -GC / MS. The gas concentration of TMS was measured. The removal efficiency of TMS was calculated from the measured gas concentration of TMS on the upstream side and downstream side of the column by the following formula, and a graph of the relationship between the pH of the water mixture of the test sample and the removal efficiency was created.
Removal efficiency (%) = {(Upstream gas concentration−Downstream gas concentration) / Upstream gas concentration} × 100
The results are shown in FIG. 3 (zeolite) and FIG. 4 (silica gel, acid clay, activated clay, diatomaceous earth, fumed silica, talc). In FIG. 4, square marks (□) indicate silica gel data, triangle marks (△) indicate acid clay data, circle marks (◯) indicate active clay data, cross marks (×) indicate diatomaceous earth data, diamond marks (◇ ) Indicates fumed silica data, and asterisk (*) indicates talc data. The horizontal axis of the graph is the pH of the water mixture of the test sample, and the vertical axis is the removal efficiency (%).

  As shown in Table 1 and FIG. 3, the zeolite whose pH of the water mixture is 7 or less has significantly higher TMS removal efficiency than the zeolite whose pH of the water mixture exceeds 7. Also, the zeolite with lower pH of the water mixture tends to have higher TMS removal efficiency. As shown in Table 2 and FIG. 4, the inorganic silica-based porous material having a lower pH tends to have higher TMS removal efficiency.

Example 2
As the air flowing through the column, a mixture of TMS7 ppb and VOC 200 ppb mixed with air adjusted to a temperature of 23 ° C. and a humidity of 50% using a constant temperature and humidity chamber is used so that the filtration wind speed of the test sample is 3 cm / s. The gas removal efficiency of the adsorbent was measured using an aeration test apparatus as shown in FIG. 1 in the same manner as in Example 1 except that air with an adjusted flow rate was flowed.
As a test sample (adsorbent), among those shown in Tables 1 and 2, specific zeolite, silica gel, acid clay, activated clay, and diatomaceous earth were used.
The upstream and downstream air of the column was collected by an adsorption tube, and the adsorption tube that collected the air was subjected to gas analysis by ATD (thermal desorption apparatus) -GC / MS to measure the gas concentration of TMS. The removal efficiency of TMS was calculated from the measured TMS gas concentration on the upstream side and downstream side of the column by the following formula, and a graph of the time change of the test sample was created.
Removal efficiency (%) = {(Upstream gas concentration−Downstream gas concentration) / Upstream gas concentration} × 100
The results are shown in FIG. 5 (zeolite) and FIG. 6 (silica gel, acid clay, activated clay, diatomaceous earth). In FIG. 5, the cross mark (×) is the data of zeolite A, the diamond mark (◇) is the data of zeolite B, the asterisk mark (*) is the data of zeolite C, the triangle mark (Δ) is the data of zeolite D, and the square mark (□) shows the data of zeolite G, respectively. In FIG. 6, rhombus marks (◇) indicate data for silica gel A, square marks (□) indicate data for silica gel C, triangle marks (Δ) indicate data for acid clay A, cross marks (×) indicate data for acid clay B, An asterisk mark (*) indicates data of activated clay B, and a circle mark (◯) indicates data of diatomaceous earth A. 5 and 6, the horizontal axis of the graph is the number of days elapsed (day), and the vertical axis is the removal efficiency (%).

  As shown in FIG. 5, the zeolite (zeolite A, zeolite B, zeolite C, zeolite D) whose pH of the water mixture is 7 or less is compared with the zeolite (zeolite G) whose pH of the water mixture is more than 7. Even after the elapse of time, the removal efficiency of TMS is remarkably large. In addition, as shown in FIG. 6, silica gel (silica gel A), acid clay (acid clay A), activated clay (active clay B), and diatomaceous earth (diatomaceous earth A) having a pH of 7 or less are mixed with the water mixture. Compared with silica gel (silica gel C) and acidic clay (acid clay B) having a pH of more than 7, the removal efficiency of TMS is large even after days.

Example 3
Zeolite A after completion of the aeration test of Example 2 was placed in 30 ml of acetone solvent and shaken for 2 hours. Thereafter, the supernatant was subjected to GC-FID analysis. Table 3 shows the area values measured by GC-FID of TMS. In addition, as a comparison object, a coconut shell activated carbon (trade name “Dazai CB”, manufactured by Futamura Chemical Co., Ltd.) was used as an adsorbent, and the same aeration test as in Example 2 was performed. The area values measured by GC-FID are shown in Table 3.

  As shown in Table 3, in the case of coconut shell activated carbon, the adsorbed TMS is desorbed by acetone extraction, but in the case of zeolite A, the adsorbed TMS is not desorbed by acetone extraction. From this, it can be seen that TMS is adsorbed to zeolite with a water mixture having a pH of 7 or less with an extremely strong force as compared with activated carbon.

Example 4
After the glass cloth (filter base material) is formed into a corrugated shape, it is laminated via a sheet-like glass cloth (fixed with an adhesive), and this laminate is made of zeolite A and an inorganic binder (colloidal silica, Nissan Chemical Industries ( The product was made in a suspension containing a product name “Snowtex O”) and water, taken out from the suspension, and dried to prepare a filter structure A having a honeycomb structure. The cross section of the vent hole (ventilation path) of the filter structure A is corrugated, the length of the bottom of the corrugation is 1 to 5 mm, and the height is 1 to 5 mm. The pulverized filter structure A was immersed in pure water to prepare an immersion liquid (the ratio of the filter structure A: 5 wt%), and the pH of the immersion liquid was measured to be 4.81. As a comparative material, a filter structure B in which a coconut shell activated carbon (trade name “Dazai CB” manufactured by Futamura Chemical Co., Ltd.) was similarly formed into a honeycomb structure was used.
The gas removal efficiency of the filter structure was measured using a ventilation test apparatus as shown in FIG.
That is, two rectangular test columns (19 mm × 19 mm × length 20 cm) 8 made of acrylic are arranged in parallel, a tube 2 for gas supply is attached on the upstream side of the column, and a flow rate is provided on the downstream side of the column. A total of 3, a flow rate adjusting valve 4 and a pump 5 were attached in this order. A filter structure (length 80 mm) 9 was placed in the column. Air whose flow rate was adjusted to flow so that the filtration wind speed of the filter structure was 0.5 m / s was flowed. As the air flowing through the column, TMS7 ppb and VOC 250 ppb were mixed with air adjusted to a temperature of 23 ° C. and a humidity of 50% using a constant temperature and humidity chamber.
As the filter structure, the filter structure A and the filter structure B produced above were used. The two filter structures described above were used for each column 1 arranged in parallel.
The upstream and downstream air of the column was collected by an adsorption tube, and the adsorption tube that collected the air was subjected to gas analysis by ATD (thermal desorption apparatus) -GC / MS to measure the gas concentration of TMS. The TMS removal efficiency was calculated from the measured TMS gas concentration on the upstream side and downstream side of the column by the following formula, and a graph of time change was created.
Removal efficiency (%) = {(Upstream gas concentration−Downstream gas concentration) / Upstream gas concentration} × 100
The results are shown in FIG. In the figure, a triangle mark (Δ) indicates data of the filter structure A, and a diamond mark (（) indicates data of the filter structure B. The horizontal axis of the graph is the elapsed days (days), and the vertical axis is the removal efficiency (%).

  As shown in FIG. 8, the filter structure A using zeolite A has a much lower rate of TMS removal efficiency over time than the filter structure B using activated carbon. In the case of activated carbon, the removal efficiency becomes negative after a certain number of days. That is, once adsorbed TMS is desorbed and released. On the other hand, in the case of the filter structure A, the removal efficiency does not become negative even after 40 days.

Example 5
60 parts by weight of zeolite A as an inorganic silica-based porous material, 25 parts by weight of kaolinite which is clay as a binder and 15 parts by weight of colloidal silica were mixed, and pure water was added to prepare a clay-like sample. This clay-like sample is threaded through a mesh, thoroughly dried in an oven, pulverized in a mortar, and collected with a sieve having a particle size of 200 to 500 μm to obtain a pelletized adsorbent (pellet). It was. In addition, three types of pellets (pellets A to C) were prepared using three colloidal silicas having different pHs as the colloidal silica.
Except that the pellets A to C shown in Table 4 obtained above were used as test samples, the gas removal of the adsorbent was performed in the same manner as in Example 2 using a ventilation test apparatus as shown in FIG. Efficiency was measured.
The upstream and downstream air of the column was collected by an adsorption tube, and the adsorption tube that collected the air was subjected to gas analysis by ATD (thermal desorption apparatus) -GC / MS to measure the gas concentration of TMS. The removal efficiency of TMS was calculated from the measured TMS gas concentration on the upstream side and downstream side of the column by the following formula, and a graph of the time change of the test sample was created.
Removal efficiency (%) = {(Upstream gas concentration−Downstream gas concentration) / Upstream gas concentration} × 100
The results are shown in Table 4 and FIG. In FIG. 9, rhombus marks (◇) indicate data for pellet A, square marks (□) indicate data for pellet B, and triangle marks (Δ) indicate data for pellet C. In FIG. 9, the horizontal axis of the graph is the elapsed days (days), and the vertical axis is the removal efficiency (%).

  As shown in Table 4 and FIG. 9, the adsorbent pelletized with zeolite (zeolite A) having a water mixture pH of 7 or less passed the number of days regardless of the pH value of the binder water mixture. Also, the removal efficiency of TMS is large. In particular, pellets produced using a binder having a low pH of the water mixture tend to have higher TMS removal efficiency.

Example 6
Adsorption using a ventilation test apparatus as shown in FIG. 1 in the same manner as in Example 2 except that a mixture of zeolite A, which is a synthetic zeolite, and natural zeolite (mixed zeolite) was used as a test sample. The gas removal efficiency of the agent was measured. In addition, mixed zeolite A (mixing ratio: 10% by weight of zeolite A, 90% by weight of natural zeolite) and mixed zeolite B (mixing ratio: 15% by weight of zeolite A, 85% by weight of natural zeolite) are used as mixed zeolite as a test sample. It was.
The upstream and downstream air of the column was collected by an adsorption tube, and the adsorption tube that collected the air was subjected to gas analysis by ATD (thermal desorption apparatus) -GC / MS to measure the gas concentration of TMS. The removal efficiency of TMS was calculated from the measured TMS gas concentration on the upstream side and downstream side of the column by the following formula, and a graph of the time change of the test sample was created.
Removal efficiency (%) = {(Upstream gas concentration−Downstream gas concentration) / Upstream gas concentration} × 100
The results are shown in Table 5 and FIG. In FIG. 10, the triangle mark (Δ) indicates the data of the mixed zeolite A, and the square mark (□) indicates the data of the mixed zeolite B. In FIG. 10, the horizontal axis of the graph is the elapsed days (days), and the vertical axis is the removal efficiency (%).

  As shown in Table 5 and FIG. 10, the higher the content of the synthetic zeolite in the adsorbent, the higher the removal efficiency of TMS.

Example 7
The gas removal efficiency of the adsorbent was measured using an aeration test apparatus as shown in FIG. In Example 7, two series of acrylic cylindrical test columns (inner diameter: 19 mm, length: 30 cm) 1 connected in series are arranged in 6 series in parallel, and gas supply is provided upstream of the column. A tube 2 was attached, and a flow meter 3, a flow rate adjustment valve 4, and a pump 5 were attached in this order on the downstream side of the column. A non-woven fabric 6 is sandwiched between two columns connected in series, and a test sample (adsorbent) 7 is laid on the non-woven fabric 6 in a thickness of 1 cm (2.8 cc), and the surface wind speed of the test sample is 58.8 cm / s. The air whose flow rate was adjusted so as to flow. As the air flowing through the column, TMS9ppb was mixed with air adjusted to a temperature of 23 ° C. and a humidity of 50% using a constant temperature and humidity chamber.
The following samples A to C were used as test samples (adsorbents), respectively.
A: Activated carbon impregnated with potassium hydrogen sulfate (addition amount of the additive to the activated carbon: 6% by weight)
B: Granulated product of zeolite D (pH of water mixture: 6.04)
C: Unattached activated carbon The particle size of the samples A to C is around 600 μm. Sample B is 60 parts by weight of zeolite D in Table 1, 25 parts by weight of kaolinite as a binder and 15 parts by weight of colloidal silica are mixed, and pure water is added to prepare a clay-like sample. This clay-like sample was threaded through a mesh, dried sufficiently in an oven, pulverized in a mortar, and collected with a sieve having a particle size of about 600 μm.
The upstream and downstream air of the column was collected by an adsorption tube, and the adsorption tube that collected the air was subjected to gas analysis by ATD (thermal desorption apparatus) -GC / MS to measure the gas concentration of TMS. The removal efficiency of TMS was calculated from the measured TMS gas concentration on the upstream side and downstream side of the column by the following formula, and a graph of the time change of the test sample was created.
Removal efficiency (%) = {(Upstream gas concentration−Downstream gas concentration) / Upstream gas concentration} × 100
The results are shown in Table 6 and FIG. In FIG. 11, diamond marks (◇) indicate data of sample A, square marks (□) indicate data of sample B, and triangle marks (Δ) indicate data of sample C. In FIG. 11, the horizontal axis of the graph represents elapsed days (days), and the vertical axis represents removal efficiency (%).

  As shown in Table 6 and FIG. 11, Sample B, that is, a granulated product of zeolite (zeolite D) whose pH of the water mixture is 7 or less, is extremely large without reducing the TMS removal efficiency even after the number of days. . In contrast, sample A, ie, activated carbon impregnated with potassium hydrogensulfate, gradually decreases the efficiency of removing TMS as the number of days elapses, and decreases to 30% after 22 days. In the case of sample C, that is, unattached activated carbon, after a certain number of days, the removal efficiency becomes negative, and once adsorbed TMS is desorbed and released. As described above, the adsorbent of the present invention using the inorganic silica-based porous material in which the pH of the water mixture is 7 or less under an extremely low concentration environment of 9 ppb where the concentration of the silanol compound in the air is single digit ppb. Clearly shows that the silanol compound can be removed more efficiently than the porous material to which the acidic substance is added.

Example 8
Samples A to C after the elapse of 18 days in Example 7 were collected for 1% (about 0.02 g) of the entire adsorbent. 1 ml of acetone was added to the collected sample, and extraction was performed by applying ultrasonic waves for 20 minutes in an ultrasonic cleaner. Thereafter, the extracted solution was measured by GC / MS. The area values (extraction amounts) of the detected TMS and hexamethyldisiloxane (TMS dimer, sometimes referred to as “HMDSO”) are shown in Table 7 and FIG. 12, respectively.

  As shown in Table 7 and FIG. 12, when samples A and C, that is, activated carbon were used, the adsorbed TMS was eluted in a large amount by acetone extraction, but in the case of sample B, the adsorbed TMS was acetone. Little elution occurs by extraction. From this, it can be seen that TMS is adsorbed to zeolite with a water mixture having a pH of 7 or less with an extremely strong force as compared with activated carbon. In addition, it is considered that samples A and C using activated carbon mainly removed TMS by physical adsorption, whereas sample B mainly removed TMS by chemical adsorption. Sample A, which is activated carbon impregnated with an acidic substance, has a larger amount of HMDSO extraction than sample C, which is activated carbon without impregnation. This is considered that the activated carbon impregnated with an acidic substance has a higher conversion efficiency from TMS to HMDSO than non-added activated carbon. From this, it can be seen that the acidic material additive has a catalytic action to efficiently convert TMS to HMDSO.

Example 9
The gas removal efficiency of the adsorbent was measured using an aeration test apparatus as shown in FIG. In Example 9, six acrylic test columns (inner diameter 19 mm, length 30 cm) 1 connected in series are arranged in parallel in six lines, and gas supply is provided upstream of the column. A tube 2 was attached, and a flow meter 3, a flow rate adjustment valve 4, and a pump 5 were attached in this order on the downstream side of the column. A non-woven fabric 6 is sandwiched between two columns connected in series, and a test sample (adsorbent) 7 is laid on the non-woven fabric 6 at a thickness of 1 cm (2.8 cc), and the filtration wind speed of the test sample is 58.8 cm / s. The air whose flow rate was adjusted so as to flow. As the air flowing through the column, TMS9ppb was mixed with air adjusted to a temperature of 23 ° C. and a humidity of 50% using a constant temperature and humidity chamber.
The following samples A to E were used as test samples (adsorbents), respectively.
A: Activated carbon impregnated with potassium hydrogen sulfate (addition amount of the additive to the activated carbon: 6% by weight)
B: Granulated product of zeolite D (pH of water mixture: 6.04)
C: Unattached activated carbon (pH of water mixture: 10.57)
D: Unattached activated carbon (pH of water mixture: 4.48)
E: Granulated product of zeolite L (pH of water mixture: 9.47)
The particle sizes of the samples A to E are around 600 μm. Samples B and E were mixed with 60 parts by weight of zeolite D or zeolite L in Table 1, 25 parts by weight of kaolinite, which is clay as a binder, and 15 parts by weight of colloidal silica. A sample was prepared, and the clay-like sample was passed through a mesh to form a thread. After sufficiently drying in an oven, the sample was pulverized in a mortar and collected with a sieve having a particle size of about 600 μm.
The upstream and downstream air of the column was collected by an adsorption tube, and the adsorption tube that collected the air was subjected to gas analysis by ATD (thermal desorption apparatus) -GC / MS to measure the gas concentration of TMS. The removal efficiency of TMS was calculated from the measured TMS gas concentration on the upstream side and downstream side of the column by the following formula, and a graph of the time change of the test sample was created.
Removal efficiency (%) = {(Upstream gas concentration−Downstream gas concentration) / Upstream gas concentration} × 100
The results are shown in FIG. In FIG. 13, rhombus marks (◇) indicate data for sample A, asterisk marks (*) indicate data for sample B, circle marks (◯) indicate data for sample C, square marks (□) indicate data for sample D, triangle marks (Δ) indicates data of sample E, respectively. In FIG. 13, the horizontal axis of the graph is the elapsed days (days), and the vertical axis is the removal efficiency (%).

  As shown in FIG. 13, Sample B, that is, a granulated product of zeolite (zeolite D) whose pH of the water mixture is 7 or less, is extremely large without decreasing the TMS removal efficiency even if the number of days elapses. On the other hand, samples A, C to E gradually decrease the removal efficiency of TMS as the number of days elapses. In particular, samples A, C, and E using activated carbon as an adsorbent are finally obtained. The removal efficiency becomes negative, and once adsorbed TMS is desorbed and released. It is clearly shown that this phenomenon occurs with activated carbon regardless of pH.

Example 10
Samples A to C after 25 days in Example 9 and Sample D at the time when the TMS aeration test was completed were each collected for 1% (about 0.02 g) of the entire adsorbent. 1 ml of acetone was added to the collected sample, and extraction was performed by applying ultrasonic waves for 20 minutes in an ultrasonic cleaner. Thereafter, the extracted solution was measured by GC / MS. The area values (extraction amount) of the detected TMS and HMDSO are shown in Table 8, respectively.

  As shown in Table 8, when Samples A, C, and D, ie, activated carbon were used, the adsorbed TMS was eluted in a relatively large amount by acetone extraction, but in the case of Sample B, the adsorbed TMS was Is relatively little eluted by acetone extraction. From this, it can be seen that TMS is adsorbed to zeolite with a water mixture having a pH of 7 or less with an extremely strong force as compared with activated carbon. In addition, samples A, C, and D using activated carbon do not depend on the pH of the water mixture, and TMS is removed mainly by physical adsorption, but easily desorbed, whereas the pH of the water mixture is low. It is considered that Sample B using 7 or less zeolite mainly removes TMS by chemical adsorption and is firmly bonded to the silanol compound.

  From Examples 9 and 10, when the zeolite whose pH of the water mixture is 7 or less is used when the activated carbon to which the acidic substance is added is used, and when the unadsorbed activated carbon is used regardless of the pH of the water mixture. In comparison, it clearly shows that the silanol compound can be removed more efficiently. Furthermore, when activated carbon is used as an adsorbent regardless of whether an acidic substance is added, the water mixture has a pH of 7 or less, or the water mixture has a pH of more than 7, once adsorbed TMS is used. It is clearly shown that the zeolite having a pH of 7 or less in the activated carbon and water mixture exhibits a completely different action in the removal of the silanol compound because of desorption.

Example 11
(Production example of ammonia-treated product of synthetic zeolite)
Using an aeration test apparatus as shown in FIG. 1, an ammonia-treated product of synthetic zeolite was produced. That is, two acrylic cylindrical test columns (inner diameter 50 mm, length 30 cm) 1 connected in series are arranged in 6 series in parallel, and a gas supply tube 2 is attached to the upstream side of the column, On the downstream side of the column, a flow meter 3, a flow rate adjustment valve 4, and a pump 5 were attached in this order. A nonwoven fabric 6 is sandwiched between two columns connected in series, and zeolite for performing ammonia treatment is placed on the nonwoven fabric 6 in place of the test sample 7 in a thickness of 2.5 mm (bulk volume: 4.8 mL). The air containing ammonia gas was flowed so that the flow rate was adjusted to 3.0 cm / s.
Zeolite A, zeolite D, and zeolite N shown in Table 1 were used as zeolites for the ammonia treatment. Three synthetic zeolites to be treated with ammonia were respectively used in three columns 1 of six columns arranged in parallel.
Air containing ammonia gas on the upstream side and downstream side of each column was collected, and the concentration of ammonia gas was measured. The concentration of upstream ammonia gas was 5.5 ppm. After 12 hours from the start of aeration of air containing ammonia gas, it was confirmed that the concentration of ammonia gas on the downstream side of each column was 5.5 ppm, which was the same as that on the upstream side, so the ammonia treatment to each synthetic zeolite was completed. As a result, the ventilation of air containing ammonia gas was terminated. In this way, an ammonia-treated product of synthetic zeolite was produced. In addition, the density | concentration of ammonia gas was measured using 3 L of detection tubes by Gastec Corporation.

(TMS ventilation test)
4.8 mL of test sample (adsorbent) 7 is laid on the nonwoven fabric 6 in a thickness of 2.5 mm, and the air flowing through the column is adjusted to a temperature of 23 ° C. and a humidity of 50% using a thermostatic chamber, TMS6 ppb 1 was used in the same manner as in Example 1 except that air having a flow rate adjusted so that the filtration wind speed of the test sample was 3.0 cm / s was used. The gas removal efficiency of the adsorbent was measured using a test apparatus.
As test samples (adsorbents), zeolite A, zeolite D, zeolite N, an ammonia-treated product of zeolite A, an ammonia-treated product of zeolite D, and an ammonia-treated product of zeolite N shown in Table 1 were used. The weight of the test sample was 1.9 g of zeolite A and its ammonia-treated product, 2.0 g of zeolite D and its ammonia-treated product, and 1.6 g of zeolite N and its ammonia-treated product, respectively. In addition, when an ammonia-treated product of synthetic zeolite is used as a test sample, when a silanol compound removal facility that does not have a filter for removing the inhibitor is used (that is, the basic substance ammonia, which is an inhibitor, is used for removing the inhibitor). It is assumed that the filter is not removed.
The upstream and downstream air of the column was collected by an adsorption tube, and the adsorption tube that collected the air was subjected to gas analysis by ATD (thermal desorption apparatus) -GC / MS to measure the gas concentration of TMS. The removal efficiency of TMS was calculated from the measured TMS gas concentration on the upstream side and downstream side of the column by the following formula, and a graph of the time change of the test sample was created.
Removal efficiency (%) = {(Upstream gas concentration−Downstream gas concentration) / Upstream gas concentration} × 100
The results are shown in Table 9 and FIG. In FIG. 14, circles (◯) indicate zeolite A data, crosses (×) indicate zeolite A processed ammonia, triangles (Δ) indicate zeolite D, diamonds (◇) indicate zeolite D. Data on the ammonia-treated product, square mark (□) shows data on zeolite N, and asterisk mark (*) shows data on ammonia-treated product of zeolite N, respectively. In FIG. 14, the horizontal axis of the graph represents elapsed days (days), and the vertical axis represents removal efficiency (%).

  For measurement of the GC / MS, a product name “JMS-Q1000GC MKII” manufactured by JEOL Ltd. was used.

  As shown in Table 9 and FIG. 14, when a synthetic zeolite whose pH of the water mixture is 7 or less is used and the synthetic zeolite is not attached with ammonia, which is a basic gas, the pH of the water mixture is 7 or less. Compared with the case where the synthetic zeolite is treated with ammonia, the removal efficiency of TMS is remarkably large even if the number of days elapses. That is, in the case of having an inhibitor removal chemical filter upstream of a silanol compound removal chemical filter using a synthetic zeolite whose pH of the water mixture is 7 or less as an adsorbent, when there is no inhibitor removal chemical filter In comparison, it is clear that the removal efficiency of TMS is remarkably large even after days.

Example 12
(Production example of ammonia-treated product of silica gel, activated clay, diatomaceous earth)
Using an aeration test apparatus as shown in FIG. 1, ammonia-treated products of silica gel, activated clay, and diatomaceous earth were prepared. That is, two acrylic cylindrical test columns (inner diameter 50 mm, length 30 cm) 1 connected in series are arranged in 6 series in parallel, and a gas supply tube 2 is attached to the upstream side of the column, On the downstream side of the column, a flow meter 3, a flow rate adjustment valve 4, and a pump 5 were attached in this order. A nonwoven fabric 6 is sandwiched between two columns connected in series, and an inorganic silica-based porous material for carrying out ammonia treatment instead of the test sample 7 on the nonwoven fabric 6 is 2.5 mm thick (bulk volume: 4.8 mL). ), And air containing ammonia gas was flowed so that the flow rate of the inorganic silica-based porous material was adjusted to 3.0 cm / s.
Silica gel A, activated clay B, and diatomaceous earth A shown in Table 2 were used as the inorganic silica-based porous material for the ammonia treatment. Three inorganic silica-based porous materials to be treated with ammonia were respectively used for three columns 1 out of six columns arranged in parallel.
Air containing ammonia gas on the upstream side and downstream side of each column was collected, and the concentration of ammonia gas was measured. The concentration of upstream ammonia gas was 5.5 ppm. After 12 hours from the start of aeration of air containing ammonia gas, it was confirmed that the concentration of ammonia gas on the downstream side of each column was 5.5 ppm, the same as that on the upstream side, so ammonia to each inorganic silica-based porous material Judging that the treatment was completed, the ventilation of air containing ammonia gas was terminated. In this way, an ammonia-treated product of silica gel, an ammonia-treated product of activated clay, and an ammonia-treated product of diatomaceous earth were produced. In addition, the density | concentration of ammonia gas was measured using 3 L of detection tubes by Gastec Corporation.

(TMS ventilation test)
4.8 mL of a test sample (adsorbent) 7 is laid on the nonwoven fabric 6 in a thickness of 2.5 mm, and the air flowing through the column is adjusted to a temperature of 23 ° C. and a humidity of 50% using a thermostatic chamber. 1 was used in the same manner as in Example 1 except that air having a flow rate adjusted so that the filtration wind speed of the test sample was 3.0 cm / s was used. The gas removal efficiency of the adsorbent was measured using a test apparatus.
As test samples (adsorbents), silica gel A, activated clay B, diatomaceous earth A, treated ammonia of silica gel A, treated ammonia of activated clay B, and treated ammonia of diatomaceous earth A shown in Table 2 were used. . The weights of the test samples were 0.7 g for silica gel A and its ammonia treated product, 3.9 g for activated clay B and its ammonia treated product, and 3.0 g for diatomaceous earth A and its ammonia treated product, respectively. In addition, when an ammonia-treated product of an inorganic silica-based porous material is used as a test sample, when a silanol compound removal facility that does not have an inhibitor removal filter is used (that is, the basic gas ammonia as an inhibitor is removed). It is assumed that the substance is not removed by the inhibitor removal filter.
The upstream and downstream air of the column was collected by an adsorption tube, and the adsorption tube that collected the air was subjected to gas analysis by ATD (thermal desorption apparatus) -GC / MS to measure the gas concentration of TMS. The removal efficiency of TMS was calculated from the measured TMS gas concentration on the upstream side and downstream side of the column by the following formula, and a graph of the time change of the test sample was created.
Removal efficiency (%) = {(Upstream gas concentration−Downstream gas concentration) / Upstream gas concentration} × 100
The results are shown in Table 10 and FIG. In FIG. 15, circles (◯) indicate data for silica gel A, triangles (Δ) indicate data for activated clay B, and squares (□) indicate data for diatomaceous earth A. In addition, white indicates an untreated product, and black indicates an ammonia-treated product. In FIG. 15, the horizontal axis of the graph represents elapsed days (days), and the vertical axis represents removal efficiency (%).

  As shown in Table 10 and FIG. 15, silica gel, activated clay, and diatomaceous earth whose pH of the water mixture is 7 or less are used, and these inorganic silica-based porous materials do not attach ammonia, which is a basic gas. In this case, the removal efficiency of TMS is remarkably large even when the number of days elapses, compared to the case where silica gel, activated clay, and diatomaceous earth whose pH of the water mixture is 7 or less are treated with ammonia. That is, when a chemical filter for removing an inhibitory substance is provided upstream of a silanol compound removing chemical filter using silica gel, activated clay, and diatomaceous earth having a pH of 7 or less as an adsorbent, the inhibitory substance removing chemical filter It is clear that the removal efficiency of TMS is remarkably large even if the number of days elapses as compared with the case where no s.

Example 13
(Production example of D4 processed product of synthetic zeolite)
A synthetic zeolite octamethylcyclotetrasiloxane (D4) -treated product was produced using an aeration test apparatus as shown in FIG. That is, two acrylic cylindrical test columns (inner diameter 50 mm, length 30 cm) 1 connected in series are arranged in 6 series in parallel, and a gas supply tube 2 is attached to the upstream side of the column, On the downstream side of the column, a flow meter 3, a flow rate adjustment valve 4, and a pump 5 were attached in this order. A nonwoven fabric 6 is sandwiched between two columns connected in series, and zeolite for D4 treatment is placed on the nonwoven fabric 6 in place of the test sample 7 in a thickness of 2.5 mm (bulk volume: 4.8 mL). The air containing D4 gas was flowed with the flow rate adjusted to be 3.0 cm / s.
As zeolites to be subjected to the D4 treatment, zeolite A, zeolite D, zeolite K, and zeolite O shown in Table 1 (pH of water mixture: 4.52, framework structure: beta type, specific surface area: 400 m ² , [SiO ₂ / Al ₂ O ₃ ]: 500) was used. Each of the four synthetic zeolites to be subjected to the D4 treatment was used in four columns 1 of six columns arranged in parallel.
Air containing D4 gas on the upstream side and downstream side of each column was collected, and the concentration of D4 gas was measured. The concentration of the upstream D4 gas was 3 ppm. After 12 hours from the start of aeration of air containing D4 gas, it was confirmed that the concentration of D4 gas on the downstream side of each column was 3 ppm, the same as that on the upstream side, so that D4 treatment to each synthetic zeolite was completed. Judgment was made and the ventilation of air containing D4 gas was terminated. In this way, a D4 treated product of synthetic zeolite was produced. The concentration of D4 gas was measured using a PID volatile organic compound concentration meter.

(TMS ventilation test)
4.8 mL of a test sample (adsorbent) 7 is laid on the nonwoven fabric 6 in a thickness of 2.5 mm, and the air flowing through the column is adjusted to a temperature of 23 ° C. and a humidity of 50% using a thermostatic chamber. 1 was used in the same manner as in Example 1 except that air having a flow rate adjusted so that the filtration wind speed of the test sample was 3.0 cm / s was used. The gas removal efficiency of the adsorbent was measured using a test apparatus.
As a test sample (adsorbent), the zeolite A, the zeolite D, the zeolite K, the zeolite O, the D4-treated product of the zeolite A, the D4-treated product of the zeolite D, the D4-treated product of the zeolite K, and the above A D4 treated product of zeolite O was used. The weights of the test samples were 1.9 g for zeolite A and its D4 treated product, 2.0 g for zeolite D and its D4 treated product, 1.9 g for zeolite K and its D4 treated product, zeolite O and its D4 treated product, respectively. The product was 3.2 g. In addition, when the D4 treated product of synthetic zeolite is used as a test sample, when a silanol compound removal facility that does not have an inhibitor removal filter is used (that is, D4 of a siloxane compound that is an inhibitor is removed by an inhibitor removal filter) Is assumed to be removed).
The upstream and downstream air of the column was collected by an adsorption tube, and the adsorption tube that collected the air was subjected to gas analysis by ATD (thermal desorption apparatus) -GC / MS to measure the gas concentration of TMS. The removal efficiency of TMS was calculated from the measured TMS gas concentration on the upstream side and downstream side of the column by the following formula, and a graph of the time change of the test sample was created.
Removal efficiency (%) = {(Upstream gas concentration−Downstream gas concentration) / Upstream gas concentration} × 100
The results are shown in Table 11 and FIG. In FIG. 16, circles (◯) indicate zeolite A data, triangles (Δ) indicate zeolite D data, diamonds (◇) indicate zeolite K data, and squares (□) indicate zeolite O data. . In addition, a white outline shows an untreated thing and black painting shows a D4 processed thing. In FIG. 16, the horizontal axis of the graph represents elapsed days (days), and the vertical axis represents removal efficiency (%).

  For measurement of the GC / MS, a product name “JMS-Q1000GC MKII” manufactured by JEOL Ltd. was used.

  As shown in Table 11 and FIG. 16, when a synthetic zeolite whose pH of the water mixture is 7 or less is used and the synthetic zeolite does not adhere D4 which is a siloxane compound, the pH of the water mixture is 7 or less. Compared with the case where a certain synthetic zeolite is treated with D4, the removal efficiency of TMS is remarkably large even if the number of days elapses. That is, in the case of having an inhibitor removal chemical filter upstream of a silanol compound removal chemical filter using a synthetic zeolite whose pH of the water mixture is 7 or less as an adsorbent, when there is no inhibitor removal chemical filter In comparison, it is clear that the removal efficiency of TMS is remarkably large even after days.

1 Column 2 Tube 3 Flowmeter 4 Flow Control Valve 5 Pump 6 Nonwoven Fabric 7 Test Sample (Adsorbent)
8 columns 9 filter structure

Claims (7)

  A silanol compound removing chemical filter using an inorganic silica-based porous material having a pH of 7 or less as a water mixture (content ratio: 5 wt%) obtained by mixing with pure water, and the silanol compound removing chemical A silanol compound removal facility, comprising an inhibitor removal chemical filter that removes an inhibitor that lowers the silanol compound removal ability of the silanol compound removal chemical filter installed upstream of the filter.   The silanol compound removing equipment according to claim 1, wherein the inhibitor removing chemical filter is at least one selected from the group consisting of a basic substance removing chemical filter and a siloxane compound removing chemical filter.   The inorganic silica-based porous material is zeolite, silica gel, silica alumina, aluminum silicate, porous glass, diatomaceous earth, hydrous magnesium silicate clay mineral, allophane, imogolite, acidic clay, activated clay, activated bentonite, mesoporous silica, The silanol compound removal equipment according to claim 1 or 2, which is at least one inorganic silica-based porous material selected from the group consisting of aluminosilicate, fumed silica, fly ash, and clinker ash.   The adsorbent according to any one of claims 1 to 3, wherein another adsorbent is used together with the inorganic silica-based porous material having a pH of 7 or less as the water mixture (content ratio: 5 wt%) as the adsorbent. Silanol compound removal equipment.   The inorganic silica-based porous material includes a synthetic zeolite having a water mixture (content ratio: 5 wt%) having a pH of 7 or less, and the content of the synthetic zeolite in the adsorbent is based on the total weight of the adsorbent. It is 10 weight% or more, The silanol compound removal installation of any one of Claims 1-4.   The inorganic silica-based porous material includes a synthetic zeolite having a water mixture (content ratio: 5 wt%) having a pH of 7 or less, and the synthetic zeolite is A-type, ferrierite, MCM-22, ZSM-5, ZSM- 11. A synthetic zeolite having at least one skeletal structure selected from the group consisting of 11, SAPO-11, mordenite, beta-type, X-type, Y-type, L-type, chabazite, and offretite. The silanol compound removal equipment according to claim 1.   A fluid purification method, wherein the silanol compound is removed using the silanol compound removal equipment according to claim 1.

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