WO2001019731A1 - Novel compound and microporous material and method for production thereof - Google Patents

Abstract

A microporous material comprising a 3-valent element and a silicon skeleton, which has an adsorbing part capable of adsorbing H2O or NH3 and holding it and exhibits strong solid acidity, wherein the adsorbing part can stably hold H2O at a temperature of 500°C or lower and the adsorbed H2O can be desorped at a temperature higher than 500°C; and a method for producing the microporous material which comprises a mixing step of preparing a liquid inorganic material mixture comprising a crystalization adjusting agent, a silicon component and a 3-valent element component, a solid-liquid separation step of separating fine particles deposited in the liquid inorganic material mixture from the liquid mixture, a heating step of heating the solid component obtained in the separation step and a copper addition treatment step of adding a copper compound to the resultant product for treatment. A microporous material thus obtained exhibits catalytic activity for a long period of time even at a low temperature, has high thermal stability, and exhibits a high catalytic activity even under a condition of a relatively low reaction temperature, in a variety of chemical reactions in the field of petrochemical industry.

Description

 Description Novel compound, microporous material and method for producing the same

 The present invention relates to a novel compound, a microporous body, and a method for producing the same, comprising an adsorbent, a catalyst, and a material for separation, that is, a CFC-based refrigerant, sulfur fluoride gas as an insulating medium for high-voltage power equipment, and As a desiccant for air in vehicle air brakes, an adsorbent for nitrogen compounds in wastewater and an adsorbent for radioactive substances in radioactive wastewater, and as a catalyst for supporting various metals by supporting various metals, Such as microporous materials used in the field of petrochemical industry, etc., and their production methods; and microporous materials as catalysts that contain silicon components and can be used for reduction reactions of nitrogen oxides and the like in wastewater and exhaust gas. The present invention relates to a body and a method for producing the same. Background art

 In the fields of petroleum refining and petrochemical industry, catalytic cracking, catalytic reforming, hydrodesulfurization, catabolism, alkylation, polymerization, cyclization, dehydration or dehydrogenation of aliphatic and aromatic hydrocarbons, etc. The chemical reaction is often performed. In particular, isomerization of hydrocarbons such as esterification and alkylation, which are said to proceed under acidic conditions, is an important technology in organic synthetic chemistry that has been widely used in the petroleum refining and petrochemical industries. is there. For example, cyclic compounds such as methylcyclopentene are isomerized and converted into cyclohexane, which is used in the production of nylon and the like as an organic industrial raw material, or n-paraffin which has a chain skeleton and is liquid at room temperature isomerized. Is known to produce highly lubricated blended base materials necessary for improving the octane number of fuel oil for automobiles and aircraft by converting into iso-paraffins with branched chains. .

Chemical reactions such as catalytic cracking, catalytic reforming, hydrodesulfurization, isomerization, alkylation, polymerization, cyclization, dehydration or dehydrogenation of aliphatic and aromatic hydrocarbons include sulfuric acid and aluminum chloride. , Antimony trichloride, hydrogen fluoride, phosphoric acid and other acid catalysts, Metal oxide-supported catalysts composed of tungsten oxide or molybdenum oxide and zirconium are often used. Typical isomerization catalysts therein, a noble metal such as platinum or palladium catalyst and which is supported on a carrier such as alumina, O started solid strong acid catalyst consisting of _{P t / Z r 0 2 /} S 0 4 Solid acid catalysts are known. On the other hand, in the petroleum refining and other fields mentioned above, chemical reactions such as catalytic cracking, hydrocracking, paraffin isomerization, dewaxing, and dimerization of olefins, etc. Zeolites such as zeolite, mordenite, and ZSM-5 are also widely used as catalysts.

It is well known that nitrogen oxides (NO X) emitted from various combustion engines cause serious global environmental problems such as air pollution and acid rain. In order to eliminate such NO _x, it thus purifying treatment in the reduction of NO _x using a predetermined reducing agent such as ammonia are well known. Catalysts used in the reduction reaction of the NO _x, for example, as the inorganic compound catalyst V- W- T i 0 has _two catalysts are used in thermal power plants and the like.

Here, there is a case to be carried out a reduction reaction of the NO _x from the safety and energy cost at a low temperature, the V- W- T i 0 In the reduction reaction of the NO _x using _two catalysts, anti応温degree conditions When the temperature was set to a low temperature of about 150 to 25 CTC, the catalyst activity was relatively low, and as a result, there was a disadvantage that NO _x could not be removed sufficiently.

Therefore, micro-porous body containing Kei Ingredient, i.e., Zeorai bets catalyst using Zeorai bets is the V- W- compared to T i 0 ₂ based catalyst, the catalyst activity is compared to definitive to such low temperatures target high and Ri due to reasons such as deterioration for a certain force Li is small, it was used in the catalyst of the reduction reaction of NO _x.

 As zeolite, there are many natural products such as mordenite and huelierite, and also as artificial zeolite, zeolite A, zeolite X, and ZSM-5 (Japanese Patent Publication No. 46-100664) And various types such as ZSM-11 (see Japanese Patent Publication No. 53-23280).

In the case of producing an artificial zeolite as described above, after performing a mixing step of forming an alkaline mixed solution containing a silicon dioxide component, an aluminum oxide component, and an organic ammonium salt, a high pressure is applied. In the inorganic material mixture by heating It was manufactured by the so-called hydrothermal synthesis method, which carries out a crystallization step to crystallize zeolite.

 Since the above-described hydrothermal synthesis method generally requires intense reaction conditions at a high temperature and for a long time, an alkaline inorganic material mixed solution containing a crystallization modifier and a silicon component is prepared, and the inorganic material is prepared. There has been proposed a method for producing a microporous body obtained by separating fine particles precipitated in a mixed liquid from a mixed liquid of an inorganic material and heating a solid component subjected to solid-liquid separation (Japanese Patent Application Laid-Open No. Hei 8-3-1191). 2). The microporous body thus obtained is synthesized with energy saving and has good caking properties.

However, conventionally, in the fields of petroleum refining and petrochemical industry, when the above-mentioned acid catalyst is used as an isomerization reaction catalyst, most of the reaction takes place in a relatively high temperature range of about 400 to 600 ° C. This was not desirable in terms of safety, energy and cost. Further, in the conventional sulfuric acid supported super acid catalyst, when exposed to a temperature or a reducing atmosphere exceeds 6 5 0 ° C, there may lose sulfate ion (S 0 ₄ ² I) is scattered and decomposition and activity.

 In addition, a metal oxide-supported catalyst comprising tungsten oxide or molybdenum oxide and zirconium has a problem that the production cost of the catalyst is high because zirconia is used as a base.

Further, as the application for reduction of the NO _x in the prior art described above, in terms of the total resistance and energy costs Bok cheap, they are more anxious be carried out at a low temperature reduction reaction of the NO _x. However, in the conventional Zeorai bets catalyst, reaction temperature if with reduced tendency for the catalytic activity decreases with sufficient NO _x removal can not be achieved is known.

On the other hand, even when the above-mentioned zeolite is used as a catalyst for the isomerization reaction, most of the reactions are carried out in a relatively high temperature range of about 250, so that safety and energy It was also unfavorable in terms of cost. In addition, in a zeolite catalyst synthesized by a hydrothermal synthesis method, as the reaction temperature is increased, active metals involved in the development of catalytic ability tend to move easily. That is, as the reaction temperature rises, the active metal (eg, Cu) dispersed on the zeolite catalyst separates from the exchange site and aggregates to form an aggregate (cluster 1) composed of a plurality of Cu cations. Tend to form. When the active metal is dispersed, it effectively functions as a catalytic active site, but when the active metal is agglomerated, the activity of the zeolite catalyst decreases because it approaches ascending to show bulk properties . In such a case, even if the reaction condition temperature was lowered again, the catalyst activity was not initially shown, and as a result, there was a problem in thermal stability. Therefore, an object of the present invention is to provide a microporous body that is hard to exhibit the above-mentioned problems and is useful for various uses, and more specifically, is advantageous in terms of energy such as room temperature. At low temperatures, new compounds and microporous materials with long-term catalytic activity have been produced in various chemical reactions in the petroleum refining and petrochemical industries, including isomerization reactions of aliphatic hydrocarbons and aromatic hydrocarbons. to provide a method for producing it provides and its Mi black porous body, in case of performing the reduction reaction such as NO _x, the reaction temperature relatively high catalytic activity even in the cold, and changing the reaction temperature conditions An object of the present invention is to provide a microporous body having high thermal stability without any change in catalytic activity even when it is made to react. Disclosure of the invention

Features of the present invention for achieving the above object, as described in claim 1, wherein, with having a suction portion for sucking and holding the H ₂ 0 or NH _3, wherein the suction portion is H ₂ 0 5 0 0 ° stable to be held in C or less, H ₂ 0 which is maintained are new compounds 5 0 0 comprising a Aruminiumu component and Kei ingredient it can be eliminated under temperatures exceeding state.

 Further, the features of the microporous body of the present invention for achieving the above object, as described in claim 2,

In addition to having an adsorbing portion for adsorbing and holding H ₂ 0 or NH ₃ ammonia, the adsorbing portion can stably hold H ₂で at 500 ° C. or less, and the held H ₂ 0 is 50 ° It is a microporous material that can be desorbed at high temperatures exceeding 0 ° C.

In addition, a method for producing a microporous body according to the present invention for achieving the above-mentioned object includes, as described in claim 3, ammonium ion (R ₄ N ⁺ : R is hydrogen, having 10 or less carbon atoms). At least one selected from an alkyl group or an aryl group) and a phosphonium ion (R 4 P +: R is hydrogen, an alkyl group having 10 or less carbon atoms or an aryl group) A crystallization regulator selected from amines or diamines, an aluminum component, and a silicon component. Performing, after the mixing step, performing a solid-liquid separation step of separating fine particles precipitated in the mixed liquid from the inorganic material mixed liquid, and performing a heating step of heating the solid component separated into solid and liquid. To obtain an intermediate, and after the ion exchange step of ion-exchanging the intermediate with ammonium ions, a desorption step of desorbing ammonia and water is performed.

 A method for producing a microporous body according to the present invention for achieving the above object, as described in claim 4, comprises at least one kind selected from ammonium ions, phosphonium ions, amines or diamines. Performing a mixing step of forming an inorganic material mixed solution containing a crystallization modifier and a silicon component; and after the mixing step, a solid-liquid separation step of separating fine particles precipitated in the inorganic material mixed solution After that, the solid component subjected to the solid-liquid separation is subjected to a heating step of heating and a copper addition treatment step of adding copper.

 In addition, a method for producing a microporous body according to the present invention for achieving the above object, as described in claim 5, is a liquid mixture of an inorganic material containing a silicon component and a trivalent element component. After the mixing step, a solid-liquid separation step of separating fine particles precipitated in the inorganic material mixed liquid is performed, and then the solid component subjected to the solid-liquid separation is heated. And a copper addition treatment step of adding copper.

 Further, the method for producing a microporous body according to the present invention for achieving the above object, as described in claim 6, comprises at least one selected from ammonium ions, phosphonium ions, amines and diamines. Performing a mixing step of forming an inorganic material mixed solution containing a kind of crystallization modifier and a silicon component; and after the mixing step, solid-liquid separation for separating fine particles precipitated in the inorganic material mixed solution Performing a heating step of heating the solid component subjected to the solid-liquid separation to obtain an intermediate, and performing a copper addition treatment step of adding copper to the intermediate.

Further, a method for producing a microporous body according to the present invention for achieving the above object is as described in claim 7, wherein in the invention according to claim 6, In the process, the addition of the trivalent element component is performed.

 Further, the method for producing a microporous body according to the present invention for achieving the above object, as described in claim 8, is a mixed liquid of an inorganic material containing a silicon component and a trivalent element component. After the mixing step, a solid-liquid separation step of separating fine particles precipitated in the inorganic material mixed liquid is performed, and a heating step of heating the solid-liquid separated solid component is performed. An intermediate is obtained, and a copper addition treatment step of adding copper to the intermediate is performed.

 Further, the method for producing a microporous body according to the present invention for achieving the above object, as described in claim 9, in the invention according to claims 6 to 8, in the copper addition process, And performing a copper ion exchange treatment step of subjecting the intermediate to ion exchange treatment with copper ions.

 Further, the method for producing a microporous body according to the present invention for achieving the above object, as described in claim 10, is characterized in that, in the invention according to claim 9, the copper ion exchange treatment step is performed. Before performing the method, a pretreatment step of exchanging the intermediate with ammonium ions is performed.

 Further, a method for producing a microporous body according to the present invention for achieving the above object, as described in claim 11, in the invention according to any one of claims 3 to 10, The silicon component is kanemite, TEOS (tetraethyl orthosilicate), colloidal silica, or fumed silica.

Further, a method for producing a microporous body according to the present invention for achieving the above object, as described in claim 12, in the invention according to any one of claims 3 to 11, the crystallization modifier, tetra n- Petit Ruan monitor ©-ion _{((n- C 4 H 9)} 4 N +), tetra-n- propyl ammonium Niu-ion _{((n- C 3 H 7)} 4 N +), Te Traethylammonium ion ((C ₂ H ₅ ) ₄ N +), tetramethylammonium ion ((CH ₃ ) ₄ N +), n-propyltrimethylammonium ion ((n—C ₃ H ₇ ) (CH ₃ ) ₃ N +), benzyltrimethylammonium ion ((C ₇ H ₇ ) (CH ₃ ) ₃ N +), tetra-n-butylphosphonium ion ((n—C ₄ H ₉ ) ₄ P ⁺ ), Benzyltriphenylphosphonium ion ((C ₇ H ₇ ) (C ₆ H ₅ ) ₃ P +), 1,4-monodimethyl-1,4-diazobicyclo (2,2,2) Butane, pyrrolidine, n-propylamid Down _{(n- C 3 H 7 NH 2} ), Mechirukinuku lysine, Echirenjiamin lies in at least selected piperidine from one type of cationic crystallization modifiers. Further, a microporous body according to the present invention for achieving the above object, as described in claim 13, fills the reaction tube with the microporous body, and at a predetermined temperature, nitrogen oxides together with a reducing agent. Flowing through the reaction tube, measuring an inlet nitrogen oxide concentration and an outlet nitrogen oxide concentration of the reaction tube, and calculating a difference between the inlet nitrogen oxide concentration and the outlet nitrogen oxide concentration; Is calculated as a denitration rate, and in a denitration evaluation test for evaluating the catalytic activity of the microporous material based on the denitration rate, a denitration rate of 50% or more under a temperature of 450 ° C. It is characterized by showing.

 The present inventors performed a mixing step of forming an inorganic material mixed liquid containing a crystallization modifier, an aluminum component, and a silicon component, and after the mixing step, fine particles precipitated in the mixed liquid A solid-liquid separation step of separating the mixture from the inorganic material mixed liquid, and a heating step of heating the solid-liquid separated solid component to obtain an intermediate, wherein the intermediate is ion-exchanged with ammonium ions. Based on the fact that a novel compound comprising an aluminum component and a silicon component obtained by performing a desorption step of desorbing ammonia and water after the exchange step has a very strong solid acidity, Completed the invention.

 That is, a mixing step of forming an inorganic material mixed liquid containing a crystallization modifier, an aluminum component, and a silicon component is performed, and after the mixing step, the fine particles precipitated in the mixed liquid are removed from the inorganic material. Performing a solid-liquid separation step of separating from the material mixture, performing a heating step of heating the solid component subjected to solid-liquid separation to obtain an intermediate, after the ion exchange step of ion-exchanging the intermediate with ammonium ions, The microporous Miku α obtained by performing the desorption step of desorbing ammonia and water has a very strong solid acidity. Further, due to its porous structure, aliphatic and aromatic hydrocarbons The present invention has been completed based on the fact that the catalyst has a long-term catalytic activity even at a low temperature such as room temperature in various chemical reactions such as an isomerization reaction of hydrogen and the like.

In the present invention, the term “adsorbed water” refers to only those in which water molecules are adsorbed by the electric affinity to the acid points indicating the solid acidity in the porous structure. In which water molecules are structurally held in a porous structure, or where adjacent sites such as Si SH are easily bonded to release water molecules. Shall be included.

When a novel compound containing an aluminum component and a silicon component obtained by the production method according to the present invention was subjected to measurement with a heat conduction detector using an NH ₃ —TPD device, it was found that the temperature was 100 ° C. It was confirmed as an experimental fact that the amount of desorbed substances in the high-temperature region in the range of 500 ° C or more and 800 ° C or less was 30% or more of the total desorbed substances in the range of 800 ° C or less.

That is, when the microporous body obtained by the production method according to the present invention was subjected to measurement with a heat conduction detector using an NH ₃ —TPD device, the amount of the desorbed material in the high-temperature region relative to the total amount of the desorbed material was determined. Was found to be 30% or more as an experimental fact.

Here, NH ₃ - T PD device is a device which includes a vacuum pump for evacuation of the pretreatment and the carrier first gas, and the thermal conductivity detector, a mass spectrometer, NH ₃ - T It quantifies the amount of ammonia desorbed according to the PD program. The NH ₃ -TPD measurement method mainly includes a method for quantifying the amount of ammonia using a thermal conductivity detector and a method for quantifying the amount of ammonia using a mass spectrometer (hereinafter referred to as NH ₃ — TCD method when determined by the thermal conductivity detector of the TPD device, NH ₃ — MAS method when determined by the TPD mass spectrometer).

In other words, first, the microporous sample is heated from room temperature to 500 ° C in a helium atmosphere, and then maintained at that temperature for a predetermined time (usually 30 minutes) to obtain a porous structure of the microporous material. To remove the moisture contained in the helium (helium treatment step). Next, the hemi-processed microporous body is cooled to 10 ° C. and then exposed to an ammonia atmosphere at that temperature for a predetermined time (usually one hour), so that the acid point of the microporous body is reduced to an ammonia point. The near is fixed (fixing step). Further, when the temperature of the microporous body on which ammonia is fixed is raised (desorption step), the ammonia once fixed is gradually desorbed. At this time, since the temperature range in which ammonia is desorbed varies depending on the strength of the acid point, if the temperature range in which ammonia desorption is observed is high under the same heating rate, the acid point becomes It is known that the solid acidity is higher. According to this, by the above-mentioned heliming treatment step, it was usually adsorbed to the adsorbing portion such as an acid point of a microporous body or the like. Moisture is once desorbed, ammonia is adsorbed to the acid sites in the fixing step, and the ammonia is observed in the desorption step. If the desorbed gas is obtained in terms of ammonia, the microporous material, etc. It is reported that data indicating solid acidity can be obtained.

On the other hand, when the microporous material obtained by the hydrothermal synthesis method was similarly subjected to NH ₃ -TPD measurement, no result showing strong solid acidity was obtained.

 The fact that the ratio of the high-temperature region desorbed substance to the total desorbed substance amount is 30% or more is that the high-temperature range desorbed substance amount is higher than that of a microporous material obtained by a general hydrothermal synthesis method. It shows that the amount is remarkably large, and proves that the microporous body according to the present invention exhibits strong solid acidity.

Further, the present inventors have an adsorbing portion for adsorbing and holding H ₂₀ or NH _{3 according} to the present invention, and the adsorbing portion can stably hold H ₂₀ at 500 ° C. or less, The retained H ₂₀ is a microporous material containing an aluminum component and a silicon component that can be desorbed at a high temperature exceeding 500 ° C. It has been further found that water is contained as a substance other than monium, and the presence of water that is not desorbed even in the preceding helium treatment step makes the microporous material of the present invention a new solid acidic substance. Was proved to be an important substance.

 It is considered that the use of the production method according to the present invention provides microporous materials exhibiting extremely strong solid acidity for the following reasons. In other words, usually, the acid point showing the catalytic activity of the microporous material is the A1 portion in the crystal skeleton, and the acid point is strongly affected by the distribution of A1 atoms in the microporous material and the surrounding conditions. For example, when the A 1 atom and the Si atom are uniformly dispersed, a difference in electronegativity between Si and A 1 occurs, so that a Brenstead acid point or a Lewis acid point is generated at such a place, and a strong acidity is generated. However, it is considered that acidity does not appear at the places where the A1 atoms are located close to each other.

By the way, the microporous material obtained by the known hydrothermal synthesis method has a step of heating and crystallizing an aqueous raw material slurry having a large amount of water. In the initial stage of crystallization, a small amount of heteroatom A 1 atom is inhibited compared to S i · 0 atom, and S i. 〇 It is considered that there is a strong tendency to form a microporous skeleton structure using only atoms and to crystallize. Therefore, it is considered that the distribution of A 1 atoms in the microporous body obtained after crystallization tends to be biased.For example, the inside of the crystal has a high percentage of Si atoms and approaches the crystal surface. As the distribution of A1 atoms increases, there may be a case where A1 atoms that are not involved in the acidic expression described above are present at positions close to each other, and therefore, the solid acidity, that is, the activity of the catalyst, Is likely to be low.

 On the other hand, the microporous body manufactured by the manufacturing method according to the present invention is considered to exhibit strong solid acidity and a large amount of acid for the following reasons.

 That is, a mixing step of forming an inorganic material mixed liquid containing a crystallization modifier, an aluminum component, and a silicon component is performed, and after the mixing step, the fine particles precipitated in the mixed liquid are removed from the inorganic material. An intermediate obtained by performing a solid-liquid separation step of separating from the material mixture and performing a heating step of heating the solid-liquid separated solid component is a solid phase in which the solid-liquid separated solid component remains in powder form Therefore, it is considered that A1 is an intermediate which is uniformly dispersed and held. That is, in the heating step, the diffusion and movement of A1 species is restricted, so that the position of the A1 atom remains uniformly dispersed, and the A1 atom and the Si atom are uniformly dispersed. It is considered that an intermediate having a modified skeleton structure is easily produced. In other words, it is possible to form an intermediate having a skeletal structure that easily develops solid acidity.

 Then, as shown in FIG. 1, the intermediate having such a structure is subjected to an ion exchange step and a desorption step of desorbing ammonia and water, so that A 1 atoms and S i atoms are uniform. It is possible to further increase the solid acidity while maintaining the dispersed skeleton itself. In FIG. 1, A 1 atoms and Si atoms are alternately arranged in the skeletal structure. This is a schematic representation of the skeleton itself in which A 1 atoms and Si atoms are uniformly dispersed. is there.

Therefore, the microporous body manufactured by the manufacturing method according to the present invention is considered to exhibit strong solid acidity.

Further, the present inventors include at least one crystallization regulator selected from ammonium ions, phosphonium ions, amines or diamines, and a silicon component. After the mixing step, a solid-liquid separation step of separating fine particles precipitated in the mixed liquid from the inorganic material mixed liquid is performed. A heating step of heating the separated solid component, a copper addition step of adding copper, and a microporous body obtained by a production method including the steps of: The present invention has obtained a new finding that, when used as a catalyst for thermal treatment, it has high thermal stability and high catalytic activity even at relatively low reaction temperature conditions, and has completed the present invention based on that finding. .

 When a trivalent element component is allowed to coexist in the mixed solution containing the silicon component, the inorganic material mixed solution in which the trivalent element component is coexisted contains fine particles of the composite containing the trivalent element component. Easy to form. After performing a solid-liquid separation step of separating fine particles precipitated in the inorganic material mixture from the inorganic material mixture, a heating step of heating the solid-liquid separated solid component, and adding copper Compared to the copper addition treatment process and the production method that includes the process, when used as a catalyst for the reduction reaction of nitrogen oxides, the thermal stability is high and the reaction temperature conditions are compared. Even when the temperature is very low, a microporous body having high catalytic activity can be obtained.

 Here, as the trivalent element component, aluminum, boron, iron (trivalent), titanium or the like can be used.

 Performing a mixing step of forming an inorganic material mixed liquid containing at least one crystallization modifier selected from ammonium ions, phosphonium ions, amines or diamines, and a silicon component; Thereafter, by performing a solid-liquid separation step of separating the composite fine particles precipitated in the mixed liquid from the inorganic material mixed liquid, the composite fine particles can be isolated as a solid component. By performing a heating step of heating the solid component that has been subjected to solid-liquid separation, the solid component of the isolated complex undergoes a phase change due to the heat treatment, so that an intermediate that is a porous substance can be obtained. By subjecting the obtained intermediate to a copper addition step of adding copper, the microporous body of the present invention can be obtained. Further, in the mixing step, a trivalent element component such as aluminum, boron, iron (trivalent), and titanium can be added.

Performing a mixing step of forming an inorganic material mixed solution containing a silicon component and a trivalent element component, and after the mixing step, dispersing the fine particles precipitated in the mixed solution into the inorganic material A solid-liquid separation step of separating the mixture from the raw material mixture, and a heating step of heating the solid-liquid separated solid component to obtain an intermediate, and a copper addition step of adding copper to the intermediate Even with the production method including the above, it is possible to obtain the microporous body according to the present invention.

 In the case where the trivalent element component is mixed in the mixing step, a copper ion exchange treatment step of ion-exchanging the intermediate with copper ions may be performed in the copper addition treatment step.

 In the heating step, since the solid component subjected to solid-liquid separation is heated in a solid phase in a powder form, diffusion and movement of the trivalent element component are restricted, and a skeleton in which the trivalent element component is uniformly dispersed and held. It is considered that an intermediate having a structure is easily produced. Then, the intermediate having such a structure is subjected to an ion-exchange treatment step of performing an ion-exchange treatment with copper ions, so that it is considered that copper involved in the expression of catalytic activity can be uniformly dispersed in the skeleton.

 On the other hand, a microporous material obtained by a known hydrothermal synthesis method has a step of heating and crystallizing an aqueous raw material slurry having a large amount of water. Diffusion and migration of the aluminum component (trivalent element component) occur freely, and in the initial stage of crystallization, the aluminum component (trivalent element component), which is a heterogeneous atom in a smaller amount than the Si0 atom, is inhibited. It is considered that there is a strong tendency to form a microporous skeletal structure using only Si · 0 atoms and try to crystallize. Therefore, it is considered that the distribution of the aluminum component (trivalent element component) in the microporous body obtained after crystallization tends to be biased. For example, the ratio of Si atoms is high inside the crystal, It is considered that the distribution of the aluminum component (trivalent element component) increases as the crystal surface is approached, and that the copper involved in the development of the catalytic activity is relatively unevenly dispersed. That is, in the microporous body according to the present invention, copper involved in the expression of catalytic activity is uniformly dispersed in the skeleton of the microporous body, which means that high catalytic activity is obtained even at relatively low reaction temperature conditions. It is thought that it has contributed to having.

Further, the method may include performing a pretreatment step of ion-exchanging the intermediate with ammonia before performing the copper ion exchange treatment step. In other words, it is considered that the compound functions as the novel compound and exhibits high denitration catalyst performance. It is.

 According to experiments, the microporous body obtained in this manner was subjected to a solid component after a mixing step of forming an inorganic material mixed solution containing a crystallization modifier, a trivalent element component, and a silicon component. A solid-liquid separation step is performed to separate the intermediate, and a pretreatment step is performed in which the intermediate obtained by performing the heating step is ion-exchanged with ammonium ions, and then ion-exchanged with copper ion It has been confirmed that the microporous body thus obtained has a higher catalytic activity than the microporous body obtained without performing the pretreatment step. The silicon component may be kanemite, TEOS (tetraethylorthosilicate), colloidal silica, or fumed silica.

That is, as long as the microporous body is manufactured using the manufacturing method according to the present invention, the silicon components are kanemite, which is a layered silicate, TE〇S, which is a Si alkoxide, and colloidal silica. Colloidal silica or fumed silica, which is a powdered silica, can be used. When a microporous body produced using these as a silicon component source is subjected to NH ₃ -TPD measurement, the type of the silicon component source is determined. Regardless, the results show properties of strong solid acidity, and the microporous body produced by the production method of the present invention using these as a silicon component source is thermally degraded when used as a catalyst for the reduction reaction of nitrogen oxides. Experimental results have shown that the catalyst has high stability and high catalytic activity even at relatively low reaction temperature conditions.

Further, the crystallization modifier, tetra n- Petit Ruan monitor ©-ion _{((n- C 4 H g)} 4 N +), tetra-n- propyl ammonium Niu-ion _{((n- C 3 H 7)} 4 N +) , Tetraethylammonium ion ((C ₂ H ₅ ) ₄ N ⁺ ), tetramethylammonium ion ((CH ₃ ) ₄ N +), n-provided trimethylammonium ion ((n—C ₃ H ₇ ) (CH ₃ ) ₃ N +), benzyltrimethylammonium ion ((C ₇ H ₇ ) (CH ₃ ) ₃ N +), tetra n-butylphosphonium ion ((n—C ₄ Hg) ₄ P +), benzyl triphenylphosphonium ion ((C ₇ H ₇ ) (C ₆ H ₅ ) ₃ P ⁺ ), 1,4-dimethyl-1,4, diazabicyclo (2,2,2) octane, pyrrolidine, n - Puropiruami emissions _{(n- C 3 H 7 NH 2} ), Mechirukinuku lysine, Echirenjiami down, one mosquito least selected piperidine from Even on of crystallization modifier is expected a similar effect. Further, the reaction tube is filled with a microporous body, and at a predetermined temperature, nitrogen oxides are passed through the reaction tube together with a reducing agent, and the nitrogen oxide concentration at the inlet and the nitrogen oxide concentration at the outlet of the reaction tube are measured. Calculate the percentage of the difference between the inlet nitrogen oxide concentration and the outlet nitrogen oxide concentration with respect to the inlet nitrogen oxide concentration as a denitration rate, and evaluate the catalytic activity of the microporous body based on the denitration rate. In the test, it was confirmed as an experimental fact that the microporous body obtained by the production method according to the present invention exhibited a denitration rate of 50% or more under a temperature of 450 ° C.

 In the denitration evaluation test, a reaction tube set at a predetermined temperature is filled with a predetermined amount of a catalyst to be measured, and a predetermined concentration of nitric oxide (NO) is flown together with a predetermined concentration of a reducing agent at a predetermined space velocity. After a lapse of a predetermined time, the inlet NO concentration and outlet NO concentration of the reaction tube were measured by a nitrogen oxide analyzer, and the difference between the inlet NO concentration and outlet NO concentration was divided by the inlet NO concentration. This is a test in which a value multiplied by 100 is calculated as a denitration rate, and the catalytic ability of the catalyst to be measured is evaluated based on the denitration rate. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a view illustrating some steps of a method for producing a microporous body according to the present invention.

 FIG. 2 is an X-ray diffraction diagram of the microporous body according to the present invention.

FIG. 3 is a view showing the measurement results of the microporous body and the intermediate according to the present invention in the TCD method using an NH ₃ —TPD apparatus.

FIG. 4 is a diagram showing the measurement results of the ZMS-5 type zeolite measured by the MAS S method using an NH ₃ —TPD apparatus.

FIG. 5 is a diagram showing a measurement result by the TCD method using an NH ₃ —TPD device when the silicon component is kanemite.

Figure 6 is a Kei-containing component Kanemai _{bets, H 2 0 / S i 0} 2 is NH in the case of 0.5 ₃ - a diagram showing the measurement results of the NH ₃ desorption amount of TPD MAS S method by device is there.

Figure 7 is a Kei-containing component Kanemai _{bets, H 2 0 / S i 0} 2 is ◦ in the case of 5 NH ₃ -. TPD device measurements of the amount of released NH ₃ and H ₂ 0 in the MASS method by To FIG.

Figure 8 is a Kei-containing component Kanemai _{bets, H 2 0 / S i 0} 2 is 1. NH ₃ in the case of 0 - a diagram showing the NH ₃ measurement results of the desorption amount of TPD MA SS method by device is there.

Figure 9 shows the measurement of the desorption amount of NH ₃ and H ₂₀ in the MAS S method using NH ₃ —TPD when the silicon component is kanemite and H ₂ 〇 / Si 0 ₂ is 1.0. It is a figure showing a result.

 FIG. 10 is an X-ray diffraction diagram of the intermediate when the silicon component is kanemite.

FIG. 11 shows the results of the NH ₃ —TPD measurement method when the silicon component is TEOS.

Fig. 12 shows the measurement results of NH ₃ desorption amount in MAS S method using NH ₃ — TPD device when the silicon component is TEOS and H ₂ 0 / Si ₂ is 1.0. It is.

The first 3 figures in Kei-containing component _{TE 0 S, H 2 0 /} S i 0 2 is 1. NH ₃ in the case of 0 - desorption amount of TPD apparatus NH ₃ and H ₂ 0 in the MAS S method by It is a figure showing the measurement result of.

FIG. 14 is an X-ray diffraction diagram of the intermediate when the silicon component is TE〇S. FIG. 15 is a diagram showing the results of the TCD method using an NH ₃ —TPD apparatus when the silicon component is colloidal silica.

 FIG. 16 is an X-ray diffraction diagram of the intermediate when the silicon component is colloidal silica.

FIG. 17 shows the results of the NH ₃ —TPD measurement method when the silicon component is fumed silica.

 FIG. 18 is an X-ray diffraction diagram of the intermediate when the silicon component is fumed silica.

FIG. 19 is a diagram showing the results of the NH ₃ —TPD measurement method when H ₂ O / Si _{2 in} the white powder sample after the solid-liquid separation step is 4.0.

FIG. 20, the solid-liquid separation H ₂ O / S i 0 ₂ white powder sample after step field 7.0 FIG. 10 is a view showing a result of an NH ₃ —TPD measurement method in the above-mentioned case.

 FIG. 21 is a view showing the results of a denitration test of a microporous body according to the present invention in an ammonia reduction reaction.

 FIG. 22 is a view showing a denitration test result of the microporous body according to the present invention in a propane reduction reaction.

 FIG. 23 is a view showing a deodorization test result of the microporous body according to the present invention in a pyridine oxidation reaction.

 FIG. 24 is a diagram showing a result of a denitration test of the microporous body according to the present invention. FIG. 25 is a diagram showing the results of a denitration test of the microporous body according to the present invention when the silicon component is kanemite.

 FIG. 26 is a diagram showing the results of a denitration test of the microporous body according to the present invention when the silicon component is TEOS.

 FIG. 27 is a diagram showing a denitration test result of the microporous body according to the present invention when the silicon component is colloidal silica.

 FIG. 28 is a view showing a denitration test result of the microporous body according to the present invention when the silicon component is fumed silica.

 FIG. 29 is a diagram showing an X-ray diffraction pattern of the microporous body according to the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.

 [Embodiment 1]

1,000 liters of layered sodium silicate (Hoechst SKS-6 (trademark)) was dispersed in 4 liters of deionized water to precipitate the generated kanemite (Kanemite), and then the supernatant was removed. did. Add deionized water again to make up to 4 liters, add 20.6 g of sodium aluminate (manufactured by Wako Pure Chemical Industries, Ltd.) and tetrapropylammonium bromide (Wako Pure Chemical Industries, Ltd.) as a crystallization regulator. 250 g) (manufactured by Kogyo Co., Ltd.) and stirred (mixing step). The pH of this solution was about 11.8. This was heated to 45 ° C and stirred for 3 hours. After allowing to cool to room temperature, add 1 Omo1 / liter of concentrated hydrochloric acid. PH 9.5. The resulting slurry was washed with deionized water and then dried to obtain a white powder (solid-liquid separation step). Incidentally, H ₂ H / S i O ₂に お け る 0.8 in the white powder was 0.8. This white powder was sealed in a stainless steel hermetically sealed container with a tube inside a Tef mouth, and subjected to a heat treatment for 150 to 48 hours to obtain a product I. The product I was calcined in an electric furnace (produced by Isuzu Corporation) at 500 ° C for 24 hours to obtain a product II as an intermediate (heating step). Next, 1.134 g of the product II was dispersed in 1 liter of pure water, stirred at room temperature for 10 hr, and left as it was until precipitation. Thereafter, the supernatant was removed, and the mixture was boiled for 3 hr while stirring in an aqueous NH ₄ NO ₃ solution (ion exchange step), and then subjected to solid-liquid separation to obtain a product III. Subsequently, the product III was calcined at 500 ° C. for 24 hours to obtain a product IV (desorption step). The diffraction pattern of this product IV was measured using a powder X-ray diffractometer (RINT 2500, manufactured by Rigaku Denki Co., Ltd.). As shown in FIG. 2, the MF I of ZSM-5 was obtained. It was similar to the diffraction pattern of a microporous material having a structure.

The products II and IV were measured using an NH ₃ —TPD (temperature program desorption) device. NH ₃ — TPD device is a device used to measure the properties of catalytic acids. It absorbs ammonia, which is a basic substance, at the acid sites, then raises the temperature of the catalyst layer at a constant rate and measures the desorbed ammonia . In NH 3 -TPD measurement, the number of solid acid sites (which may be catalytically active sites) can be obtained from the amount of NH ₃ desorbed, and information on acid strength (solid acidity) can be obtained from the desorption temperature. The phenomenon in which NH ₃ molecules once adsorbed and constrained to solid acid sites are desorbed in a high temperature region indicates that the solid acid sites have strong acidity. NH ₃ -TPD has been measured for microporous materials synthesized by the main types of hydrothermal synthesis methods. Forces Various types of microporous materials (eg, ZSM-5 type zeolite) in each case, the ratio of total desorption amount of substance in 5 00 or 80 0 hand 80 0 ° C or less over a 00-hand high-temperature range desorbed substance amount in the following is not more than about 25%, NH ₃ adsorbed Most of them are desorbed below 500 ° C (see Fig. 4). The measurement procedure is as follows: First, fill the sample tube with the sample and set it in the instrument. Next, as a pretreatment, vacuum degassing was performed at 500 ° C for 1 hour.First, a helm treatment step was performed to remove H ₂ 〇 adhering to the adsorption points, and the temperature was reduced to 100 ° C, and ammonia was removed. To 1 3. A fixing step of performing saturated adsorption at 3 kPa for 1 hour is performed. Then, the non-adsorbed ammonia is degassed under vacuum, and the temperature is raised under a He carrier (13.3 kPa) (heating rate 10 / min) (desorption step), and the temperature is reduced to 800 ° C. Confirm that the peak of the desorbed gas has ended, and end the measurement. This TPD program has been standardized by the Catalysis Society of Japan.

The results of measuring the products II and IV by the TCD method using an NH ₃ -TPD device are shown in FIG. Here, the amount of desorbed substances in the high-temperature region is obtained as an ammonia equivalent amount by a thermal conductivity detector. As a result, the ratio of the amount of desorbed substances in the high-temperature region at 500 ° C or more and 800 ° C or less to the total amount of desorbed substances at 100 ° C or more and 800 or less is 55.3%. It was confirmed that there were active sites adsorbing substances up to the region.

 On the other hand, for the above-mentioned product II, the ratio of the amount of high-temperature desorbed substances to the total desorbed substances was 28.3%.

Further, when the substance desorbed at 500 ° C. or higher in the product IV was determined by the MAS method using an NH ₃ —TPD apparatus, it was found that most of the product IV was H ₂ 〇. syneresis amount is very large as 1 0-20%, eliminated water content is in the conventional normal microporous body, considering that a small amount of less than 1 0% NH ₃ - TPD device according at 500 ° C This indicates that the adsorbed water was stably retained even in the helm treatment step, and it is considered that the point at which this water can be retained serves as an acid point indicating strong solid acidity. In other words, it can be seen that the substance produced in this manner is a novel compound having characteristics not known until now, and has a structure as a microporous body.

 For the measurement by the TCD method, KCR-1 TPD-1 manufactured by Kyushu Ceramics Research Co., Ltd. was used, and for the measurement by the MASS method, TPD-66 made by Nippon Bell Co., Ltd. was used.

Therefore, a mixing step of forming an inorganic material mixed solution containing a crystallization modifier, an aluminum component, and a silicon component is performed, and after the mixing step, the fine particles precipitated in the mixed solution are removed. An intermediate obtained by performing a solid-liquid separation step of separating from the inorganic material mixed liquid, and performing a heating step of heating the solid component separated from the solid-liquid separation is a conventional water Although the acidity of the solid acid point is stronger than that of the microporous material synthesized by the thermal synthesis method, in order for the microporous material according to the present invention to exhibit extremely strong solid acidity, it is necessary to use an ion with ammonium ions. It is understood that an essential requirement is to pass a desorption step of desorbing ammonia and water after the ion exchange step of exchanging.

[Embodiment 2]

N—C ₄ H using the product IV as a catalyst. An isomerization reaction was attempted, and evaluation for an isomerization reaction catalyst was performed. 0.1 lg of the product IV, which is a microporous material, was charged into a reaction tube and treated at 400 ° C. in a He gas flow, and then the reaction temperature was set to 20 CTC to obtain n—C ₄ H. Was subjected to a pulse reaction using 1 ml, and its conversion was determined to be 16.4%.

On the other hand, in the above isomerization reaction catalyst for evaluation under the same conditions, the catalyst as W0 ₃ - with Z r 0 _2, was attempted isomerization reaction. The conversion was determined to be 6.2%. Further, under the same conditions as for evaluation the isomerization catalyst, S i 0 ₂ as catalyst - with A 1 ₂ 0 _3, tried to isomerization reaction. The conversion was determined to be 10.3%. The present invention is not limited to butane, as is generally the catalyst for isomerizing a low C ₅ ~ about ₆ octane positive paraffin, W_〇 ₃ - Z R_〇 _{2, S i 0 2 - A} 1 2 0 3 Etc. are commonly used. _{Further, S i 0 2 - A 1} 2 0 3 of NH ₃ - percentage against the total desorption amount of substance was measured by TPD device 5 00 ° hot zone desorbed substance amount in the C or 800 ° C or less, 27. 8%.

As described above, the substance of the present invention exhibits high activity for isomerization of hydrocarbons (n—C ₄ H ^ 0) at low temperature (200 ° C.) due to its strong acidic active site, and shows high activity with existing catalysts. In comparison, it was confirmed that high activity was exhibited at a low temperature.

The industrial applicability of the substance of the present invention is to lower the isomerization temperature of hydrocarbons (isomerization reaction of xylene (a main starting material of polyester), synthesis of ethylbenzene (a main starting material of polystyrene)). , Cyclohexene (a major starting material for nylon), etc.). These fields are industrially very important and the production volume of the products is enormous. In such a reaction system, it contributes to the improvement such as lowering the reaction temperature and improving the activity, so that the profits are immense. [Embodiment 3]

When using the Kanemai bets as Kei Ingredient, it is H ₂ 0 / S I_〇 ₂ in white powder sample after solid-liquid separation step is about 0.8. After the solid-liquid separation step, the H ₂ 0 / S i 0 ₂ is adjusted to 0.5, 1.0, 2.0, 4.0, 7 by making the white powder sample contain water or drying. . We prepared 0, 20 cases. FIG. 5 shows the measurement results of the microporous material according to the present invention in these cases using an NH ₃ -TPD apparatus. The manufacturing method, except for adjusting the manufacturing method in the first embodiment, and H ₂ 〇 / S i 0 ₂ white powder sample after solid-liquid separation isolation step, the same. Fig. 5 also shows the results of measurement of the control using an NH ₃ -TPD device using the microporous material produced by the hydrothermal synthesis method as a control. The above control involves dispersing the silicon component, the aluminum component and the tetrabutyl pyrammonium salt in the aqueous solution so that S i / A 1 = 33, and then bringing the entire aqueous solution to 150 ° C for 6 days. Place in a heated state, and then remove the water by filtration to obtain a solid.The solid is dried at 40 to 50 ° C for 6 hours, and then calcined at 500 ° C for 4 hours. Obtained by. The S i / A 1 of the microporous body produced by the hydrothermal synthesis method was 33.

In the microporous body according to the present invention, H ₂ O / S i 0 _{2 in} the white powder sample after the solid-liquid separation step is 0.5, 1.0, 2.0, 7.0, Table 1 shows the ratio of the amount of desorbed substances in the high-temperature range by the TCD method at 500 ° C or more and 80 CTC or less to the total amount of desorbed substances at 100 ° C or more and 800 ° C or less using NH ₃ TPD equipment for 20 Show. Table 1 also shows the ratio of the amount of desorbed substances in the high-temperature region to the total amount of desorbed substances by the NH ₃ _TPD device of the control. The control is shown in the case where H ₂ 0 / S i 02 is 100, but when H ₂ O / S i〇 ₂ is 100, the amount of 11 ₂ mass is very much smaller than that of 3:10 ₂ mass. Means more. table 1

Figure 5 and as will be understood from Table 1, even H 20 / S i 0 ₂ white powder sample after solid-liquid separation step is different, as long as the production of micro-porous material in the present invention production process, The ratio of the amount of desorbed substances in the high temperature region to the total desorbed substances in the temperature range from 500 ° C to 800 ° C was 30% or more. Therefore, it has been experimentally proved to have strong solid acidic active sites, and it is considered that the catalytic activity is sufficiently expressed and maintained even at low temperatures. Furthermore, when the amount of NH ₃ desorbed and the total amount of desorbed substances when H ₂ 0 / S i 0 ₂ was 0.51.0 were determined by the MAS S method, the results shown in FIGS. 6 to 9 were obtained. Became. To together the desorption substances high temperature range even in each case as can be seen the main component is water, extremely high temperature (H ₂ 0 / S i 0 if the ₂ 0. 5 628 ° C (Figure 7) it can be seen that H ₂ 0 / S I_〇 ₂ 1. 6 1 0 ° C (Figure 9) to a peak) suction holdable acid sites moisture until zero is present.

As the amount of H ₂ 0 / Si _{2 in} the white powder sample after the solid-liquid separation step becomes relatively large, the method for producing the microporous material is considered to be similar to the hydrothermal synthesis method as a control. . However, the catalyst activity of the microporous material is high even at a low temperature as long as the ratio of the amount of desorbed substances in the high-temperature region at 500 ° C or more and 800 ° C or less is 30% or more. If the ratio of the amount of high-temperature desorbed substances to the total desorbed substances by the TCD method using NH ₃ — TPD is 35% or more, the solid-state active sites are stronger, so even at low temperatures. Express and maintain sufficient catalytic ability. In addition, if the acid site as an adsorption part that adsorbs water by the MAS S method can stably hold water up to 60 CTC or more and can desorb at a temperature higher than that, the solid acidity is particularly high. It is considered something.

When using the Kanemai bets as Kei Ingredient, solid-liquid separation step white powder H ₂ in the sample 0 / S I_〇 ₂ 0.5 after, 1.0, 2.0, 4.0, 7.0 In either case, as shown in FIG. 10, the intermediate was a crystalline substance. Further, the microporous body obtained by performing the ion exchange step and the desorption step on the intermediate also has a H ₂ 〇 / S i 0 ₂ of 0.5, 1 in the white powder sample after the solid-liquid separation step. In any of the cases of 0.0, 2.0, 4.0, 7.0 and 20, it was a crystalline microporous material. When the intermediate is a crystalline substance, the microporous body is crystalline because the skeleton itself is considered to have no structural change even after the ion exchange step and the desorption step. . Similarly, when the intermediate is an amorphous substance, the microporous body is amorphous even after an ion exchange step and a desorption step.

When using the Kanemai bets as Kei Ingredient, even solid-liquid separation H of a white powder in the sample after the step ₂ O / S i 0 ₂ is any of 0.5 to 20, the microporous body crystalline Yes, it has shape selectivity, and therefore has excellent properties such as improved reaction selectivity and suppression of side reactions.

[Embodiment 4]

Then, in the case of using the TEO S as Kei Ingredient, the NH ₃ one TPD device microporous body when of H ₂ 〇_ZS I_〇 ₂ white powder sample after solid-liquid separation step was variously changed The measurement results by the TCD method used are shown in FIG. The manufacturing method includes adjusting the production process in the first embodiment, the H ₂ O / S i 0 2 white powder sample after solid-liquid separation step, but using TE_〇 S, the same It is. Solid-liquid separation H ₂ 0 / S i 0 ₂ white powder samples after step 2.0, 4.0, in either case of 7.0 is also a high-temperature range in the following 500 ° C or higher 800 ° C Desorption material amount The ratio to the total amount of desorbed substances was 30% or more. Therefore, even when TEOS is used as the silicon component, it is experimentally proved that it has a strong solid acidic active site, and the catalyst ability is sufficiently expressed and maintained even at a low temperature.

Further, when the amount of NH ₃ desorbed and the total amount of desorbed substances were determined by MAS S method when ^ 1 ₂ 〇 / 3: 10 ₂ was 1.0, as shown in Figs. 12 and 13, became. In each case, the main component of the desorbed material in the high-temperature region is water, and the acid point at which the water can be adsorbed and retained at very high temperature (the peak is at 657 at high temperature (Fig. 13)). It can be seen that exists.

When using the TE 0 S as Kei Ingredient, solid-liquid H ₂ 〇 / S i 0 of a white powder in the sample after the separation step ₂ is 2.0, 4.0, be any one of 7.0, As shown in FIG. 14, the intermediate was a crystalline substance. Further, the intermediate ion exchange step及beauty desorption step the microporous body obtained by performing also the H ₂ 0 / S i 0 ₂ in white powder specimen after the solid-liquid separation step 2.0, In either case of 4.0 or 7.0, it was a crystalline microporous body. Therefore, when using TE 0 S as Kei Ingredient, solid-liquid separation step H ₂ 0 / S i 0 ₂ white powder samples after the 2.0 to 7.0 either Der connexion also, microporosity The body is crystalline and has shape selectivity.

[Embodiment 5]

Then, in the case of using colloidal silica as Kei Ingredient, NH microporous body when the H ₂ O / S i 0 ₂ white powder sample after solid-liquid separation step was variously changed ₃ - T PD Fig. 15 shows the measurement results of the device by the TCD method. The manufacturing method includes adjusting the production process in the first embodiment, and H ₂ 〇 / S i 0 ₂ white powder sample after solid-liquid separation step, except using colloidal silica, the same It is. Colloidal silica is a colloid liquid in which spherical silica having a particle diameter of 10 to 14 μm is dispersed in water. As the colloidal silica, Cata 1oid (trademark) · Si-30 manufactured by Catalysis Chemical Industry Co., Ltd. was used. The composition is S i 0 ₂ 3 0-3 1 by weight%, N a ₂ 0 is not less 0.5 wt% or less, the specific gravity is 1. a 1 9-1.22. High-temperature desorption when the H ₂ O / S i〇 _{2 in} the white powder sample after the solid-liquid separation step is 0.5, 1.0, 2.0, 4.0, or 7.0 Substance amount to total desorbed substance amount The ratio was more than 30%. Therefore, even when the colloidal silicide force is used as the silicon component, it is experimentally proved that it has a strong solid acidic active site, and it is considered that the catalytic activity is sufficiently expressed and maintained even at a low temperature.

Here, in the case of using colloidal silica as Kei Ingredient, white powder samples after the solid-liquid separation isolation step H ₂ 0 / S I_〇 ₂ 0.5, 1.0, 2.0, 4. For the cases of 0, 7.0, 20, 50, and 100, the X-ray diffraction pattern of the intermediate was examined as shown in FIG. The case where the H ₂ O / S i 0 _{2 in} the white powder sample after the solid-liquid separation step is 100 means that the amount of H ₂₀ in the white powder sample is much higher than the amount of S i 0 ₂ It means more. In FIG. 16, 96 hr at H ₂ O / S i O ₂ = 0.5 and 96 hr means that the heat treatment time of the white powder after the solid-liquid separation step is 96 hours. It is.

According to Fig. 16, when H ₂ 0 / S i〇 ₂ is 0.5, the amorphous substance does not crystallize even if the heat treatment time of the white powder after the solid-liquid separation step is 48 hours or 96 hours. Is confirmed.

Therefore, when using colloidal silica as Kei Ingredient, solid-liquid separation step H ₂ 0 / S i 0 ₂ of white powder in the sample later that's a relatively small amount, if the intermediate is amorphous material It is understood that there is. However, from the results of FIGS. 15 and 16, when colloidal silica is used as the silicon component, regardless of whether the microporous body is crystalline or amorphous, the microporous body is manufactured by the manufacturing method of the present invention. As long as it has a strong solid acidic active site, it has been experimentally proved, and it is thought that the catalytic activity is sufficiently expressed and maintained even at low temperatures. When the intermediate is a crystalline substance, the microporous body is crystalline even after an ion exchange step and a desorption step, and when the intermediate is an amorphous substance, As described above, the microporous body is considered to be amorphous even after the step and the desorption step.

[Embodiment 6]

Then, in the case of using fumed silica as Kei Ingredient, NH microporous body when the H ₂ O / S i 0 ₂ white powder sample after solid-liquid separation step was variously changed ₃ - TPD Fig. 17 shows the measurement results of the device. The production method is A manufacturing method in the serial Embodiment 1, and adjusting the H ₂ 0 / S I_〇 ₂ white powder sample after solid-liquid separation step, except using fumed silica, are identical. Further, fumed silica, the composition is a powdery silica S i 0 ₂ 9 9.8 wt%, 2 average particle diameter is 0. ~ 0. 3 m. As the fumed silica, CAB-0 manufactured by CABOT, USA, CAB-0-Si1 (trademark) M-5 was used.

Regardless of the H ₂ 0 / S i 0 _{2 in} the white powder sample after the solid-liquid separation step was 0.5, 1.0, 4.0, or 7.0, the total The ratio to the amount of desorbed substances was 30% or more. Therefore, even when fumed silica is used as the silicon component, it has been experimentally proved that it has a strong solid acidic active site, and it is considered that the catalytic activity is sufficiently expressed and maintained even at a low temperature.

Here, when fumed silica was used as the silicon component, the H 2 O / S i 02 in the white powder sample after the solid-liquid separation step was 0.5, 1.0, 2.0, 4. For the cases of 0 and 7.0, the X-ray diffraction pattern of the intermediate was examined as shown in FIG. In FIG. 18, 96 hours at H ₂ O / S i O ₂ = 0.5 and 96 hours means that the heat treatment time of the white powder after the solid-liquid separation step is 96 hours. The taste.

According to FIG. 18, when H ₂₀ / S i 0 ₂ is 0.5, the time for heating the white powder after the solid-liquid separation step at 150 ° C is 48 hours or 96 hours. It is confirmed to be a crystalline substance. Also, when H ₂ O / S i O ₂ is 1.0, it is confirmed that the peak intensity indicating crystallinity is weak and the crystalline portion is relatively small in structure.

Therefore, when using fumed silica as Kei _{Ingredient, H 2 O / S i 0} 2 white powder sample after solid-liquid separation step is that's relatively small, intermediate becomes amorphous material It is understood that there are cases. However, from the results shown in FIGS. 17 and 18, when fumed silica was used as the silicon component, regardless of whether the microporous body was crystalline or amorphous, it was manufactured by the manufacturing method of the present invention. As far as possible, it has been experimentally proved that it has a strong solid acidic active site, and it is considered that the catalytic activity is sufficiently expressed and maintained even at low temperatures. [Embodiment 7]

Next, Kanemai preparative as Kei Ingredient, TE_〇 S, colloidal silica, a case of using a fume _{Doshirika, H 2 0 / S i 0} 2 is white powder in the sample after the solid-liquid separation step 4.0 Fig. 19 shows the results of measurement of the microporous material with the NH ₃ -TPD device in the case of. The manufacturing method is the same as the manufacturing method in the first embodiment. Moreover, microporous body produced by the hydrothermal synthesis method as a control, NH ₃ for that control - are shown in TPD first 9 Figure also measurements by the device.

 Colloidal silica is indicated by Cataloid, and fumed silica is indicated by CAB-Sil. The controls are the same as those used in the third embodiment. In all cases, the ratio of high-temperature desorbed substances to total desorbed substances was more than 30%.

Next, Kanemai preparative as Kei Ingredient, TE0S, colloidal silica, a case of using a fume Doshirika, when the H ₂ 〇 / S i 0 ₂ is 7.0 of the solid-liquid white powder sample after the separation step Fig. 20 shows the results of measurement of the microporous material using the NH ₃ -TPD device. The manufacturing method is the same as the manufacturing method in the first embodiment. Fig. 20 also shows the measurement results of the microporous body produced by the hydrothermal synthesis method as a control, measured by the TCD method using an NH ₃ -TPD device for the control. The controls are the same as those used in the third embodiment. In each case, the ratio of high-temperature desorbed substances to total desorbed substances was more than 30%.

 Therefore, it was experimentally proved that a strong solid acidic active site was obtained regardless of the use of any one of kanemite, TEOS, colloidal silica, and humid silica as the silicon component. Express and maintain sufficient catalytic ability.

[Embodiment 8]

1000 g of layered sodium silicate (Hoechst. SKS-6 (trademark)) is dispersed in 4 liters of deionized water to precipitate the generated kanemite and remove the supernatant. did. Add deionized water again to this to make 4 liters, and 20.6 g of sodium aluminate (manufactured by Wako Pure Chemical Industries, Ltd.) and 250 g of tetrapropylammonium bromide (manufactured by Wako Pure Chemical Industries, Ltd.) as a crystallization regulator were added and stirred (mixed). Process). The pH of this solution was about 11.8. This was heated to 45 ° C and stirred for 3 hours. After cooling to room temperature, the pH was lowered to 9.5 by adding 1 Omo1 / liter of concentrated hydrochloric acid. The resulting slurry was washed with deionized water, and then dried to obtain white powder A (solid-liquid separation step). Incidentally, the white powder A to your Keru H ₂ 0 / S i 0 ₂ was 0.8.

This white powder A was sealed in a stainless steel sealed container with a Teflon inner cylinder, and subjected to a heat treatment at 150 ° C. for 48 hours to obtain a product I-A. This product I-A was calcined in an electric furnace (manufactured by Isuzu Corporation) at 500 ° C for 24 hours to obtain a product II-A as an intermediate (heating step). Next, 1.134 g of product II-A was dispersed in 1 liter of pure water, stirred at room temperature for 10 hr, and left as it was until precipitation. After that, the supernatant was removed, and the mixture was boiled for 3 hr with stirring in an aqueous NH ₄ NO ₃ solution (pretreatment step), and then subjected to solid-liquid separation to obtain a product III-A. Subsequently, the product III-A was calcined at 500 ° C. for 24 hours to obtain a product IV-A.

The product III an _{A Cu (N0 3) 2 ·} 3 H 2 〇 in 0. 087 g / 1 00m l, overnight at 60 ° C and stirred (copper ion-exchange process). The reason why the ion exchange reaction was carried out while heating at 60 ° C was that at a temperature different from room temperature, the water of hydration on the Cu ^{2 +} cation tended to be in a relatively separated state. This is because it is considered that the ion exchange reaction can be performed in a state where the ion exchange rate is small and the ion exchange rate increases. To this, a 5.6 wt% NH ₃ aqueous solution was slowly added dropwise at room temperature, and the pH was adjusted to pH 7.0 to 7.5 (deposition process). Here, since the unexchanged Cu ²⁺ cation remains in the aqueous solution, the entire aqueous solution is adjusted to pH 7.0 to 7.5 by the residual Cu ²⁺ This is done to incorporate cations into product III-A.

Immediately after the pH adjustment, the solution was suction-filtered, thoroughly washed with pure water, and then dried in air at 80 ° C. This was compression-molded into a pellet, crushed, sieved to 10 to 20 mesh, and fired at 500 to obtain a product VA as a microporous body according to the present invention. Here, the firing at 500 ° C is the result of the addition performed in the mixing step. The purpose is to remove tetrapropylammonium bromide as a crystallization regulator and to improve the mechanical strength of the microporous body as the final product.

 When the product VA was measured by ICP analysis (inductively coupled plasma emission spectrometry), it was found that Cu was contained at 1.98 wt%.

(Embodiment 9)

 Using the product VA as the microporous body of the present invention as a catalyst, the denitration catalytic ability in a selective reduction reaction when a predetermined reducing agent was used was measured.

 Further, the product VA was used as a catalyst, and the deodorizing catalytic ability of the test substance was measured.

(Evaluation 1)

The product VA was used as a catalyst as a microporous body of the present invention, and a reduction reaction of N 0 with a reducing agent NH ₃ was performed, and the denitration catalytic ability of the product VA was measured. The product V—A was packed in a 2 m 1 catalyst layer, and the denitration rate was measured under the following conditions: l OOO p pmNO—Ι Ο Ο Ο ρρ mNH ₃ — 3% 〇 ₂ , SV 10000 h- ¹ However, a value of 99.6% was observed at 250 ° (:).

On the other hand, the existing V- W- T i 0 ₂ was used as a catalyst, subjected to a reduction reaction of NO by a reducing agent NH _3, was measured denitration catalyst performance under the same conditions, the denitration rate 99.6% value It was necessary to raise the reaction temperature condition to about 300 ° C in order to show When the reaction temperature was 250 ° C, the denitration rate was about 85%. The results are shown in FIG. Denitrification efficiency of the present invention the microporous body, indicating the value of the denitrification rate 9 9.6% realizes a low temperature of about 50 ° C than the existing V- W- T i 0 _2. Further, NOx removal efficiency of the present invention the microporous body, if the reaction temperature conditions 2 50, it is also a high value of about 1 0% or more than the existing V- W_ T i 0 _2.

(Evaluation 2)

The product V- A use as a catalyst, subjected to a reduction reaction of NO by a reducing agent C ₃ H _8, were tested denitration catalyst performance of the product V- A. Touch the product V—A with 2 m1 Filling the medium _{layer, 1 OO ppmNO- 2000 p pmC 3} H 8 - l 0% O 2 - 6% C 0 2 - 1 0% H 2 O, SV 1 5 00 0 conditions h ^1, reaction temperature conditions The denitration rate was measured at 300 to 500 ° C.

On the other hand, using the existing zeolite Co / Z SM-5 (S i / A 1 = 25), which is regarded as champion data, as a catalyst, a reduction reaction of NO with a reducing agent C ₃ H ₈ was performed, and The denitration catalytic activity was tested under the following conditions. The results are shown in FIG.

 The denitration rate of the microporous body of the present invention was 75.2% at a reaction temperature of 450 ° C. This is 6% better than that of the existing zeolite Co / Z SM-5 (Si / Al = 25) under the same reaction temperature conditions.

 In the case of Co / Z SM-5 (S i / A 1 = 25), when the reaction temperature condition is increased, the active metal involved in the expression of catalytic activity moves, and the reaction temperature condition is decreased again. Also tend to degrade without exhibiting the original catalytic activity.

 On the other hand, in the microporous body of the present invention, even when the reaction temperature was changed to 350 ° C, 500, and 400 ° C, there was no change in the catalytic activity.

 This is probably due to the following. That is, since the Co / Z SM-5 (S i / A 1 = 25) is produced by a hydrothermal synthesis method, the distribution of the aluminum component tends to concentrate on the surface of the microporous body, and the aluminum component It is easy to form a state where the distance between Cu cations existing at the site is relatively short. Therefore, when Co / Z SM-5 (S i / A 1 = 25) is used under relatively high temperature conditions, the tendency to form Cu cation aggregates (cluster 1) is likely to occur. However, when a cluster is formed, the catalytic activity is reduced due to the active metal being uniformly dispersed. Then, once a cluster is formed, even if the temperature condition is lowered, the formation of the cluster one is not canceled and the Cu cation cannot be dispersed uniformly again.

On the other hand, according to the production method according to the present invention, the distribution of the aluminum component becomes uniform, so that the dispersion distance of the aluminum component tends to be relatively long. The dispersion distance is also relatively long. Therefore, even if used under relatively high temperature conditions, it is considered that the above-mentioned cluster formation is unlikely to occur. Accordingly, the present invention microporous body, thermal stability is high, is understood to be an excellent material for holding the long activity, practical to denitrification (NO _x stationary sources such as boilers, automobile exhaust gas or the like) It can be expected that (Evaluation 3)

 The product VA was used as a catalyst to oxidize pyridine in air, and the product VA was tested for its catalytic ability for deodorization.

The above product VA is packed in a 2 ml catalyst layer, and the pyridine oxidation activity is performed at a reaction temperature of 100 to 300 ° C under the conditions of 60 ppm pyridine / air, SV 60000 h- ^1. The conversion due to the reaction was measured. The catalyst layer of the reaction tube was filled with 2 ml of the product VA, and 60 pm pyridine / air was passed at a space velocity SV of 60,000 h- ^1. The inlet pyridine concentration and the outlet pyridine concentration were measured, and the value obtained by dividing the difference between the inlet pyridine concentration and the outlet pyridine concentration by the inlet pyridine concentration and multiplying by 100 was calculated as the conversion.

 On the other hand, pyridine oxidation reaction was carried out in the air under the same conditions using Cu-Mn (Hopcalite), which is a representative example of a catalyst having strong oxidation activity even at room temperature, as a catalyst. Figure 23 shows the results.

Note that, Cu- Mn (Ho pcalite) in the presence of oxygen at room temperature, a strong catalyst of higher oxidizing activity that can be C_〇 ₂ by burning C_〇, M n 0 _2: 60 % + CuO: A composition obtained by mixing 40% hopcalite and pentasilzeolite (manufactured by Sudohemi Co., Ltd.) in a weight ratio of 1: 2.

 The microporous body of the present invention exhibited a conversion rate of 84.5% due to pyridine oxidation reaction at a reaction temperature of 100 ° C, and a conversion of 91.6% at a reaction temperature of 300 ° C. showed that. Therefore, it is shown that the microporous body of the present invention has an excellent deodorizing catalytic ability as compared with the existing deodorizing catalyst, and has a stable and high deodorizing catalytic ability even when the reaction temperature conditions are changed. It is understood that.

[Embodiment 10]

The product V—A of Embodiment 8 described above was filled in a 2 ml catalyst layer, and 200 p _{pmNO- 1 000 p pmC 3 H 8} - l 0% O 2 - 6% C0 2 - 1 0% H 2 O, under the conditions of SV ¹ 5000 h 1, denitration ratio at a reaction temperature 300 to 500 ° C under Was measured.

Moreover, the product II one A in the eighth embodiment described _{above, Cu (N0 3) 2.} 3 H 2 0, in 0. 087 g / 1 00 m 1 , and stirred overnight at 60 ° C (copper ions Replacement process). A 5.6 wt% NH ₃ aqueous solution was slowly added dropwise at room temperature, and the pH was adjusted to pH 7.0 to 7.5 (deposition step). Immediately after the pH adjustment, the solution was suction-filtered, sufficiently washed with pure water, and dried in air in air. This was compression-molded into a pellet, crushed, sieved to 10 to 20 mesh, and fired at 500 ° C to obtain a product V_A-1 as a microporous body according to the present invention. . Further, the product IV-A in Embodiment 8 described above was stirred for 24 hours at 60 ° C. in Cu (N0 ₃ ) ₂ · 3H ₂ ·, 0.087 g / 100 ml (copper ion exchange treatment). Process). A 5.6 wt% NH ₃ aqueous solution was slowly added dropwise at room temperature, and the pH was adjusted to pH 7.0-7.5 (deposition step). Immediately after the pH was adjusted, the solution was subjected to suction filtration, sufficiently washed with pure water, and dried in air at 80 ° C. This was compression-molded into a pellet, crushed, sieved to 10 to 20 mesh, and fired at 500 ° C to obtain a product V—A-2 as a microporous body according to the present invention. Was. Then, the product V- A- 1 and the product V- A- 2 and for also be it its, filled into 2 m 1 catalyst layer, 200 p pmNO, one 1 000 p pmC ₃ H _8, one _{1 0% O 2, - 6} % C0 2, - 1 0% H 2 O, under the conditions of SV ¹ 5000 h- 1, was measured NOx removal efficiency under 300 -500 ° C. These results are shown in FIG.

 Mixing process, solid-liquid separation process, microprocessed by performing a pre-treatment process of performing ion exchange with ammonium ions on the intermediate obtained by performing the heating process, and then performing a copper ion exchange treatment process It is understood that the porous body has a high denitration rate. In addition, the microporous body obtained by performing the copper ion exchange treatment step without performing the pretreatment step on the intermediate obtained by performing the mixing step, the solid-liquid separation step, and the heating step, It is understood that the denitration rate is relatively low.

On the other hand, the pretreatment step is performed on the intermediate obtained by performing the mixing step, the solid-liquid separation step, and the heating step, followed by firing at a predetermined temperature, and the copper ion exchange treatment step is performed. It is understood that the microporous body obtained by this method has a lower denitration ratio than the case where no baking is performed after the pretreatment step.

 This is thought to be due to the fact that the product VA, the product VA-1, and the product VA-2 have different copper ion exchange rates, respectively, and thus have different denitration rates. .

 Therefore, it is better to perform ion exchange treatment with copper ions after the pretreatment process in which ion exchange treatment with ammonium ions is performed on the intermediate obtained by performing the mixing step, solid-liquid separation step, and heating step. It was experimentally proved that the denitration rate of the microporous body was improved as compared with the case where the pretreatment step was not performed.

[Embodiment 11]

 In Embodiment 8 described above, the embodiment in which the microporous body according to the present invention is manufactured by using kanemite as a silicon component is described. However, in addition to kanemite, TE〇S, colloidal silica, or By using fumed silica, the microporous body according to the present invention can be produced.

(White powder B)

1,000 liters of layered sodium silicate (Hoechst SKS-6 (trademark)) was dispersed in 4 liters of deionized water, and the resulting kanemite was precipitated. Removed. Deionized water was again added to this to make up to 4 liters, and 250 g of tetrapropylammonium bromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a crystallization regulator and stirred (mixing step). The pH of this solution was about 11.8. This was heated to 45 ° C and stirred for 3 hours. Thereafter, the mixture was allowed to cool to room temperature, and the pH was lowered to 9.5 by adding concentrated hydrochloric acid of 10 mol / liter. The slurry thus formed was washed with deionized water and then dried to obtain white powder B (solid-liquid separation step). Incidentally, the Netsukasane measuring analysis, H ₂ 〇 / S i 0 ₂ in the white powder B according it was 0.8.

(White powder C)

42 g TEOS (tetraethyl orthosilicate) and aluminum tree A solution of 2.5 g of ec-butoxide in 20 g of ethanol and a solution of 0.9 g of sodium hydroxide (NaOH) in 10 g of deionized water were mixed, and mixed well. A gel-like inorganic material mixture was obtained (mixing step). After sufficiently washing the gel-like substance with deionized water, (this phenomenon is considered to be caused by the hydrolysis of the tetraethyl orthosilicate and the condensation with the elimination of ethanol.) The inorganic material mixture was recovered by filtration under reduced pressure, and then naturally dried at room temperature to obtain white powder C (solid-liquid separation step). This white powder C is considered to be a complex of amorphous silicon dioxide and aluminum oxide. Incidentally, by thermal gravimetric _{analysis, H 2 0 / S i 0} 2 in the engagement Ru white powder C was 0.6.

(White powder D)

31.3 g of TE 0 S (tetraethyl orthosilicate), 9.8 g of tetrapropylammonium hydroxide ((n—C ₃ H ₇ ) ₄ N 0 H) aqueous solution, When 34.2 g of deionized water was mixed and heated at 80 ° C, a gel-like inorganic material mixture was obtained (mixing step). (This phenomenon is considered to be because the tetraethyl orthosilicate hydrolyzed and condensed with the elimination of ethanol.) The inorganic material mixture was filtered under reduced pressure to obtain a solid component. It was air-dried to obtain white powder D (solid-liquid separation step). This powder is considered to be a composite of amorphous silicon dioxide and tetrapropylammonium ((n—C ₃ H ₇ ) ₄ N +). Incidentally, the Netsukasane measuring _{analysis, H 2 O / S i 0} 2 in the white powder D according was 0.6.

(White powder E)

45. was added to 2 g of tetrapropylammonium hydroxide ammonium Niu beam _{((n- C 3 H 7)} 4 NO H) aqueous solution 1. 2 6 g of aluminate San'naboku Riumu (N a A 10 ₂₎ After making the solution homogeneous, it was added to 100.52 g of colloidal silica (Cata 1oid (trademark) Si-30, manufactured by Catalyst Chemical Industry Co., Ltd.) and stirred for about 30 minutes. The slurry-like substance thus formed was spread thinly on a stainless steel batter, and was then allowed to stand in an air-heating oven (manufactured by Tapa's Yespec) and dried overnight at a temperature of 40. As a result of crushing, a white powder E was obtained (solid-liquid separation step). The white color was determined by thermogravimetric analysis. H ₂ 0 / Si ₂ in Powder E was 0.7. (White powder F)

45.2 g of tetrapropylammonium hydroxide ((n—C ₃ H ₇ ) ₄ NOH) aqueous solution was added to 100.52 g of colloidal silica (Cata 1 oid (trademark), manufactured by Katsushi Kasei Kogyo Co., Ltd.) ) Si-30) was added and stirred for about 30 minutes. The resulting slurry was spread thinly on a stainless steel batter, then placed in an air-heating oven (Tabayspeck) and dried at 40 ° C for 24 hours. This was crushed to obtain white powder F (solid-liquid separation step). Incidentally, by thermal gravimetric analysis, H ₂ 0 / S I_〇 ₂ in white powder E according was 0.7.

(White powder G)

45. 3 g of tetrapropylammonium hydroxide ammonium Niu beam _{((n- C 3 H 7)} 4 NOH) well enough by adding 1. 2 5 g aluminate sodium of the (N a A 10 ₂₎ to the aqueous solution After stirring to obtain a transparent homogeneous solution, 10 g of fumed silica (CAB-0-Sil (trademark) M-5, manufactured by CAB〇T, USA) was added thereto, and gelatinized by stirring. (Although the gel becomes a viscous gel in the middle, water is generated if the stirring is continued as it is, indicating a fluid state.) 60.7 g of deionized water was added thereto, followed by further stirring. While adding 20 g of fumed silica, the mixture was sufficiently stirred for about 30 minutes. (After the addition of 20 g of fumed silica and stirring well, it showed a slightly cloudy and uniform paste-like liquid. The slurry-like substance thus formed was spread thinly on a stainless steel bag, and then air-cooled. It was allowed to stand in a single-tinging oven (manufactured by Tabai Espec) and dried all day and night at a temperature of 40 ° C. As a result of crushing, a white powder G was obtained (solid-liquid separation process). As a result, H ₂ 0 / Si ₂ in the white powder G was ◦.

(White powder H)

45. 3 g of the hydroxide Te tiger propyl ammonium Niu beam into _{((n- C 3 H 7)} 4 NOH) aqueous solution, 1 0 g of fumed silica (US CABOT Co. CAB-O-S i 1 (TM ) M-5) was added and stirred to gelatinize. (Although the gel becomes a viscous gel on the way, water is generated if the stirring is continued as it is, indicating a fluid state.) 60.7 g of deionized water was added thereto, followed by further stirring. While adding 20 g of fumed sili force, the mixture was stirred well for about 3 minutes. (After the addition of 20 g of fumed silica, the mixture was sufficiently stirred and showed a slightly cloudy and uniform paste-like liquid. The resulting slurry-like substance was spread thinly on a stainless steel batt. Thereafter, it was allowed to stand in an air-heating oven (manufactured by Tabai Espec) and dried overnight at a temperature of 40 ° C. As a result of crushing, white powder H was obtained (solid-liquid separation step). In addition, according to the thermogravimetric analysis, H ₂ O / Si ₂ of the white powder H was 0.8.

 Using the white powder C, the white powder E, or the white powder G to produce a microporous body by the same method as described in the above-described Embodiment 8, the ICP analysis (inductive coupling type) was performed. Plasma emission spectroscopy) experimentally confirmed that Cu was contained in a predetermined amount.

 Therefore, even when TE〇S, colloidal silica, or fumed silica is used as the silicon component, it is possible to obtain a microporous body to which copper is added, as in the case of using kanemite. I found it. Therefore, when such a microporous material is used as a catalyst, it is considered that a denitration catalytic ability and a denitration catalytic ability are exhibited. [Embodiment 12]

The white powder C obtained in the above-described embodiment 10 was sealed in a stainless steel sealed container with a Teflon inner cylinder, and subjected to a heat treatment at 150 ° C for 48 hours to obtain a product I-C. Was. This product I-C was calcined in an electric furnace (made by Isuzu Corporation) at 500 for 24 hours to obtain a product II-C as an intermediate (heating step). Next, 1.134 g of product II-C was dispersed in 1 liter of pure water, stirred at room temperature for 10 hr, and left as it was until precipitation. The supernatant was removed thereafter, NH ₄ N 0 ₃ After while stirring grounds 3 hr boiling in an aqueous solution (pretreatment step), solid-liquid separation to give the product III-C. Next, the product III-C was stirred at 60 ° C. for 3 hours in Cu (N〇 ₃ ) ₂ '3 H ₂₀ , 0.087 g / 100 ml (copper ion exchange treatment step). , Filter immediately with suction, After washing thoroughly with pure water, it was dried at 80 ° C in air. This was compression-molded into a pellet, then crushed, sieved to 10 to 20 mesh, and fired at 500 ° C to obtain a product VC. The product V—C was analyzed by ICP analysis (inductively coupled plasma emission spectrometry) and found to be 1.40 wt% of 1.

 Further, when a microporous body was manufactured using the white powder A, the white powder E, or the white powder G by the same method as that described in the above-described Embodiment 12, an ICP analysis was performed. It was experimentally confirmed that a predetermined amount of Cu was contained by (inductively coupled plasma emission analysis).

 Even in such a case, even when kanemite, colloidal silica, or fumed silica is used as the silicon component, a microporous body to which copper is added can be obtained as in the case of using TEOS. It turned out to be possible. Therefore, when such a microporous material is used as a catalyst, it is conceivable that a denitration catalytic activity and a denitration catalytic activity are exhibited.

In the case of the microporous body obtained in Embodiment 12, the amount of copper contained in the microporous body as a final product is determined by the microporous body obtained by the production method described in Embodiment 8. This is considered to be due to the fact that the time required for the copper ion exchange treatment step is short and that the above-mentioned deposition treatment step is not performed. In addition, it is also effective to repeat the copper ion exchange treatment step in order to increase the copper addition rate of the final product. That is, in Embodiment 1 the second embodiment described above, the product III-C u (N0 ₃₎ in ₂ · 3 H ₂ 0 solution of C a given amount, after stirring a predetermined time (copper ion-exchange process), the filtrate The solution is replenished with a predetermined amount of Cu (NO ₃ ) ₂ .3H ₂ 〇 aqueous solution, stirred for a predetermined time, and the process of suction-filtrating the filtrate is repeated several times. By washing with, the ion exchange rate can be increased. Further, after stirring the product III-C in a predetermined amount of Cu (NO ₃ ) ₂ .3H ₂₀ aqueous solution for a predetermined time (copper ion exchange treatment step), the filtrate was removed by decantation, and the filtrate was removed again. After replenishing the fixed amount of 〇1 (^ 10 ₃ ) ₂ · 3H ₂ 0 aqueous solution, stirring for a predetermined time, removing the filtrate by decantation several times, finally wash with pure water Can increase the ion exchange rate. (Embodiment 13)

(Impregnation process)

The white powder C obtained in the above-described Embodiment 11 was sealed in a stainless steel sealed container having a Teflon inner cylinder, and subjected to a heat treatment at 150 ° C for 48 hours to obtain a product I-C. Was. This product I-C was calcined at 500 in an electric furnace (manufactured by Isuzu Co., Ltd.) for 24 hours to obtain a product II-C as an intermediate (heating step). Next, 1.134 g of product II-C was dispersed in 1 liter of pure water, stirred at room temperature for 10 hr, and left as it was until precipitation. Thereafter the supernatant was removed, NH ₄ N0 ₃ after with stirring grounds 3 is hr boil in an aqueous solution (pretreatment step), solid-liquid separation to give the product III one C. By performing an impregnation step of impregnating the product III-Ic with an aqueous solution containing copper ions as a copper addition treatment step of adding copper to the product III-Ic, a microporous body to which copper is added is also obtained. It is possible.

That is, the product III one C the _{Cu (N0 3) 2 '3} H 2 〇 in 0. 087 g / 1 0 Oml, After stirring for 3 h at 60 ° C, concentrated' dried, the present invention The final product VI-C, which is a microporous material according to the above, was obtained. Therefore, when such a microporous material is used as a catalyst, a denitration catalytic activity and a denitration catalytic activity are exhibited by performing an impregnation process as a copper addition process of adding copper to the product III-C. It is possible that it will be done.

It is also effective to repeat this operation to increase the copper addition rate. Immediate Chi, C u (N0 ₃₎ in ₂ · 3 H ₂ 0 aqueous solution having a predetermined concentration the product III one C, After stirring for a predetermined time, after concentrated to dryness, again, a predetermined concentration (: 1 ( ^^ 0 _{3) 2.} immersed in 3 H ₂ 〇 solution, by repeating a series of operations of concentration and drying, it is possible to increase the addition rate of copper definitive in microporous material.

 In the above-described embodiment, the microporous body of the present invention was obtained by performing the impregnation process using the white powder C, but not only the white powder C but also the white powders A, B, Even when D to H are used, the microporous body of the present invention can be obtained under the same conditions as in the above-described embodiment.

(Embodiment 14) (Kneading process)

 Performing a mixing step of forming an inorganic material mixed liquid containing at least one crystallization modifier selected from ammonium ions, phosphonium ions, amines or diamines, and a silicon component; Thereafter, after performing a solid-liquid separation step of separating fine particles precipitated in the mixed liquid from the inorganic material mixed liquid, a copper addition processing step of adding copper to the solid component subjected to the solid-liquid separation is performed. It is possible to obtain the microporous material of the present invention also in a manufacturing method including performing a heating step of performing heating after performing.

 That is, as a copper addition treatment step of adding copper to the solid-liquid separated solid component, a kneading treatment step of dry-mixing copper or a copper-containing substance with the solid-liquid separated solid component is performed, and then the kneading treatment is performed. By performing a heating step of heating the kneaded product obtained in the step, a microporous body to which copper has been added can be obtained.

 Take 5.165 g of the white powder B, crush it in an agate mortar for 10 minutes, and then add copper chloride dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.14 45 g Was similarly crushed in an agate mortar for 10 minutes. This was dry-mixed well with the crushed white powder B, and crushed for another 10 minutes (copper addition treatment step).

 Next, the mixed powder thus obtained was sealed in a stainless steel sealed container having a Teflon inner cylinder, and subjected to a heat treatment at 150 ° C. for 72 hours to obtain a product VIIB. The product VII-B was calcined at 500 ° C for 24 hours in an electric furnace (manufactured by Isuzu Corporation) to obtain a product VIIIB (heating step).

 After the kneading treatment step of dry-mixing the solid component separated into solid and liquid with copper chloride dihydrate is performed, the heating step of heating the kneaded treatment product obtained in the kneading treatment step is performed. This makes it possible to obtain a microporous body to which copper has been added. When such a microporous body is used as a catalyst, it is conceivable that a denitration catalytic activity and a denitration catalytic activity are exhibited.

The diffraction pattern of this product VIII-B was measured using a powder X-ray diffractometer (RINT 250, manufactured by Rigaku Corporation). As shown in FIG. 29, the MFI of ZSM-5 type was obtained. It was similar to the diffraction pattern of a microporous material having a structure. In the above-described embodiment, by performing the impregnation process using the white powder B, The microporous body of the present invention was obtained. Not only in the case of the white powder B, but also in the case of using the white powders A and C to H, the microporous body of the present invention was used under the same conditions as in the above-described embodiment. It is possible to get a body. (Embodiment 15)

 (Evaluation method by denitration evaluation test)

 A denitration evaluation test was performed on the microporous body when the silicon component was kanemite, TEOS, colloidal silica, and fumed silica, and the copper addition process was a copper ion exchange process.

Here, the the denitration evaluation test, to the analyte 2 ml in an ordinary-pressure flowing-type reactor tube Filling, In contrast, 200 PpmN_〇 one _{1 000 p pmC 3 H 8 -} l 0% 0 2 - 6 % C 02-10% H ₂ O SV 1 5000 h ¹ Under the condition of 5000 h ¹ , the concentration of N 0 at the inlet and the concentration of NO at the outlet of the reaction tube (however, the outlet concentration is the value 10 minutes after the start of the reaction) This is an evaluation test in which measurement is performed using an analyzer, and from this measurement result, “denitration rate (%) 2 (inlet NO concentration-outlet NO concentration) Z inlet NO concentration X 100” is calculated.

(Kanemite)

In Embodiment 1 the fifth embodiment described above, the H ₂ 0 / S i 0 ₂ of the obtained white powder A by performing a solid-liquid separation step was adjusted to 0.5, the other conditions the same manner as in the eighth embodiment Thus, the product VA (0.5) was obtained as a microporous body. FIG. 25 shows the results of the denitration evaluation test of the product VA (0.5) in such a case. As a comparative example, a commercially available microporous material (pentasil-type zeolite manufactured by Zudhemi Co., Ltd.) produced by a hydrothermal synthesis method containing copper by the same treatment was used. It is also shown in Fig. 25. (TE 0 S)

In Embodiment 1 1 described above, the solid-liquid of H ₂ white powder C obtained by performing the separation step O / S i◦ ₂ to 0.8, 1.0, 1. was adjusted to 5, and other The conditions were the same as in Embodiment 8 to obtain products V—C (0.8), V—C (1.0), and V—C (1.5) as microporous materials. Fig. 26 shows the results of the denitration evaluation test. still, As a comparative example, in the same manner as shown in FIG. 25, a commercially available microporous body (pencil type zeolite manufactured by Sudohemi Co., Ltd.) was treated with copper in the same manner as shown in FIG. The data for the inclusions are also shown in FIG. 26.

In both cases of FIG. 25 and FIG. 26, the zeolite of the present invention shows a higher denitration ratio in all temperature ranges than the comparative example. In some samples, including the comparative example, a decrease in the denitrification rate was observed in the temperature range exceeding 450 ° C, which is presumed to be due to oxygen oxidation of the reducing agent C ₃ H ₈ itself. Is done.

(Colloidal silica)

In Embodiment 1 1 described above, the H ₂ 0 / S i 0 ₂ white powder E obtained by performing solid-liquid separation step was adjusted to 0.5, the other conditions the same manner as in the eighth embodiment Thus, the product V—E (0.5) as a microporous material was obtained. Further, by incorporating an appropriate water against a white powder sample H ₂ O / S i 0 ₂ was adjusted to _{0. 5, H 2 0 / S} i O 2 is prepared 20, 50, 1 00 state, Thereafter, products V—E (20), V—E (50), and V—E (100) were obtained as microporous materials after each heating step. Note that H ₂ O / S i O ₂ > 50 was prepared and measured on the assumption of a (quasi-hydrothermal) system substantially similar to a hydrothermal synthesis reaction of a known technique. Figure 27 shows the results of each of the denitration evaluation tests. As a comparative example, a commercially available microporous material (pentasil type zeolite manufactured by Sudohemi Co., Ltd.) containing copper in the same manner as shown in Fig. 25 as a comparative example. Figure 27 shows the data of the test.

(Fumed silica)

In the above-described Embodiment 11, H ₂ O / S i 0 ₂ of the white powder G obtained by performing the solid-liquid separation step was adjusted to 0.5, and other conditions were the same as those of Embodiment 8. The product VG (0.5) was obtained as a microporous material. FIG. 28 shows the results of the denitration evaluation test of the product VG (0.5) in such a case. Further, by incorporating an appropriate water against a white powder sample H ₂ O / S i 0 ₂ was adjusted to 0. 5, H 20ZS I_〇 ₂ prepared state of 20, 50, 1 00, then, respectively Micro with heating process The products VG (20), VG (50) and VG (100) as porous bodies were obtained. In addition, H ₂ O / S i 0 ₂ > 50 was prepared and measured assuming that it is substantially similar to a hydrothermal synthesis reaction of a known technique (pseudo-hydrothermal system). As a comparative example, in the same manner as shown in FIG. 25, a commercially available microporous body (a pentasil type zeolite manufactured by Zudhemi Co., Ltd.) produced by hydrothermal synthesis was treated with copper in the same manner. Figure 28 also shows the data for the case where

In both FIG. 27 and FIG. 28, when H ₂ 0 / S i 0 ₂ = 20, the denitration rate is higher than that of the comparative example in almost all temperature ranges. Note that, in both of FIGS. 27 and 28, when H ₂₀ / S i 02 = 50 and 100, the denitration rate tends to be lower than that in the comparative example, and in particular, H ₂ O / The sample with Si ₂ = 50, 100 shows almost no significant denitration rate.

 Performing a mixing step of forming an inorganic material mixed solution containing a crystallization modifier and a silicon component; separating the fine particles precipitated in the mixed solution from the inorganic material mixed solution after the mixing step; After performing the solid-liquid separation step, the solid component subjected to the solid-liquid separation is subjected to a heating step of heating and a copper addition treatment step of adding copper. According to the results of FIGS. 25, 26, 27 and 28, the porous body tends to show a denitration rate of 50% or more under the condition of a temperature of 450 ° C. in the denitration evaluation test. Understood.

 Further, a mixing step of forming an inorganic material mixed liquid containing a silicon component and a trivalent element component is performed. After the mixing step, fine particles precipitated in the mixed liquid are mixed with the inorganic material mixed liquid. After performing a solid-liquid separation step of separating from the solid component, a solid component separated from the solid component is subjected to a heating step of heating, and a copper addition treatment step of adding copper, and a copper addition treatment step. Even if the microporous body is prepared, a microporous body to which copper has been added can be obtained, so that in the above-described denitration evaluation test, a denitration rate of 50% or more is obtained at a temperature of 450 ° C. It is considered that there is a tendency.

 In FIG. 27 and FIG. 28, the microporous body according to the present invention tends to show a higher denitration rate in the above-mentioned denitration evaluation test, as compared with a microporous body produced by a hydrothermal synthesis method. It is considered that the reason is as follows.

That is, in the case of H ₂ O / S i O ₂ = 50, 100, the state is close to that of a hydrothermal synthesis reaction system In general, a commercially available microporous material obtained by such a method has a step of heating and crystallizing a water-based raw material slurry having a large amount of water. In the initial stage of crystallization, the trivalent element, which is a heterogeneous atom in a smaller amount than the Si0 atom, is hindered, and the microporous is formed only by the Si0 atom. It is thought that there is a strong tendency to crystallize by forming the skeleton structure of the body. Therefore, it is considered that the distribution of the trivalent element in the microporous body obtained after crystallization tends to be biased.For example, the ratio of Si atoms is high in the inside of the crystal, and the closer to the crystal surface, the closer to the crystal surface. The distribution of trivalent elements increases.

 On the other hand, a mixing step of forming an inorganic material mixed liquid containing a silicon component and a trivalent element component is performed, and after the mixing step, fine particles precipitated in the mixed liquid are removed from the inorganic material mixed liquid. The intermediate obtained by performing the solid-liquid separation step of separating and then performing the heating step of heating the solid-liquid separated solid component heats the solid-liquid separated solid component in a solid phase in powder form. This is considered to be an intermediate in which the trivalent element is uniformly dispersed and held. That is, in the heating step, the diffusion and movement of the trivalent element species are restricted, so that the position of the trivalent element remains uniformly dispersed, and the trivalent element and the Si atom are uniformly dispersed. It is considered that an intermediate having a skeletal structure is easily produced. Since the trivalent element components are uniformly dispersed in the skeleton, it is considered that copper involved in the development of the catalytic activity is relatively uniformly dispersed in the catalyst. It is considered that the function can be expressed.

When H ₂ O / S i / ₂ = 50, 100, the colloidal silicide force was used as the silicon component over the entire temperature range compared to the case where fumed silica was used. The higher denitration rate is due to the fact that the colloidal silicide force has a smaller particle size than fumed silica and has higher reactivity, and the trivalent element is easily distributed uniformly in the intermediate skeleton structure. it is conceivable that.

[Embodiment 16

An aqueous solution of trimethylbenzylammonium hydroxide (40% inwater, manufactured by Tokyo Chemical Industry Co., Ltd.) (14.2 g) was added to 31.77.3 g of distilled water, and the mixture was sufficiently stirred. To this aqueous solution, add sodium hydroxide (Wako 95%> manufactured by Junyaku Kogyo Co., Ltd. 1 1 3.57 g was added little by little. To the aqueous solution thus obtained, 98.66 g of sodium aluminate (manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little with sufficient stirring to prepare an aqueous solution as a whole. To this aqueous solution, 2024.2 g of colloidal silica (Catalyst Chemical Industry Co., Ltd., Cataloid SI-30) was further added little by little, and the mixture was stirred well enough to make the whole homogeneous (mixing step). The aqueous solution thus obtained was powder-dried with a spray dryer (LT-8, manufactured by Okawara Kakoki Co., Ltd.) to obtain a white powder (solid-liquid separation step). _{Incidentally, H 2 O / S i 0} 2 in the white powder was 0.3.

 Next, 7 g of this white powder and 1.2 g of distilled water were mixed well enough to be uniform, and sealed in a stainless steel pressure-resistant container (Model 4749, manufactured by Parr, USA) containing a Teflon inner cylinder. Heating was performed at 180 ° (: 48 hours) in a single oven (manufactured by Tabai Espec Corp.). After the heat treatment, the contents were taken out, and the contents were taken out with the above-mentioned air-heating oven at 40 ° C for 24 hours. The product I-1k thus obtained was calcined in an electric furnace (manufactured by Isuzu Corporation) at 500 ° C for 24 hours to obtain a product II-k as an intermediate. (Heating step).

 Next, 1.2 g of the product I Ik was dispersed in 1 liter of distilled water, stirred at room temperature for 1 Ohr, and allowed to stand until precipitation. Thereafter, the supernatant was removed, and the mixture was boiled for 3 hr while stirring in an aqueous NH 4 NO 3 solution (ion exchange step), and then subjected to solid-liquid separation to obtain a product II I-k. Subsequently, the product IIIk was calcined at 500 ° C for 24 hours to obtain a product IVk (desorption step). This product IV-k was measured with a powder X-ray diffractometer (RINT 2500, manufactured by Rigaku Denki Co., Ltd.). The powder X-ray diffraction of a microporous material having a Mordenite type M〇R structure was measured. It turned out to be similar to the folding pattern.

In addition, the amount of NH ₃ desorbed and the total desorbed material were determined by the MAS S method. As a result, it was found that the main component of the desorbed material in the high-temperature region was water, and the water content was extremely high (800 ° C). It was found that there was an acid site capable of adsorbing and holding. At this time, the ratio of the amount of high-temperature desorbed substances to the total desorbed substances was 50.3%. [Another embodiment]

 In order to express strong solid acidity in the microporous body according to the present invention, it is essential to add an atomic species A1 other than Si as the second component. In the embodiment, aluminate is used as the A1 source. Although sodium is added, aluminum chloride can also be added as an A1 source.

 In the above-described embodiment, the pH of the inorganic material mixed solution in the mixing step of forming the inorganic material mixed solution containing the crystallization modifier, the aluminum component, and the silicon component was 9.5. However, it is preferable that the pH of the inorganic material mixed solution is adjusted in the range of 9.0 or more and 12.5 or less. This is because if the pH is adjusted to a range smaller than 9.0, the caking property of the microporous body decreases. Under a highly alkaline condition of about PH13, the yield of the intermediate decreases and the intermediate decreases. This is because the enrichment of amorphous is promoted.

 In the above embodiment, the temperature of the inorganic material mixture is adjusted to 45 ° C. in the mixing step of forming the inorganic material mixture containing the crystallization modifier, the aluminum component, and the silicon component. It is preferable to stir the mixture of inorganic materials at a temperature of 60 ° C. or lower, and more preferable to stir the mixture under a liquid condition of 30 ° C. or lower. . This is because if the inorganic material mixture is stirred under a low temperature condition of 6 (TC or less), the intermediate can be produced in a short time and in an extremely high yield.

Ammonia ion (R ₄ N +: R is hydrogen, at least one selected from an alkyl group having 10 or less carbon atoms or aryl group), phosphonium ion (R ₄ P ⁺ : R is hydrogen, carbon atom 1 At least one selected from an alkyl group or aryl group of 0 or less), at least one crystallization modifier selected from amines, an inorganic component, and an inorganic material containing colloidal silica or fumed silica. Performing a mixing step of forming a liquid; and after the mixing step, performing a solid-liquid separation step of separating fine particles precipitated in the mixed liquid from the inorganic material mixed liquid. the H ₂ O / S i 0 ₂ weight ratio 0.5 yielding intermediate by performing a heating step of heating after adjusting below, the intermediate of i O-exchange step of ion-exchanged with ammonium Niu-ion The manufacturing method comprising the elimination step of the ammonia and water elimination, non A crystalline microporous body can also be obtained.

In the TCD method using an NH ₃ -TPD device, such an amorphous microporous material can be used at a temperature of 500 ° C or more and 80 (TC or less) with respect to the total amount of desorbed substances at 100 ° C or more and 800 ° C or less. It is a microporous material containing an amorphous region in which the amount of desorbed substances in a high temperature region is 30% or more.

In the TCD method using the NH ₃ —TPD device, the mass of high-temperature desorbed substances at 500 to 800 ° C was 30% or more of the total desorbed substances at 100 ° C to 8 ° 0 ° C. The method for producing a certain microporous body is not limited to the method described in the above embodiment.

 In Embodiment 8 described above, the p of the inorganic material mixed solution in the mixing step of forming the inorganic material mixed solution containing the crystallization modifier, the aluminum component, and the silicon component is described.

H was a force of 9.5 It is preferable to adjust the pH of the inorganic material mixed solution in a range of 9.0 or more and 12.5 or less. If the pH is adjusted to a range smaller than 9.0, the caking property of the microporous body is reduced, and the yield of the intermediate is reduced under conditions of high resistance to PH13. This is because the enrichment of the intermediate in the amorphous state is promoted.

 In Embodiment 8 described above, in the mixing step of forming the inorganic material mixed solution containing the crystallization modifier, the aluminum component, and the silicon component, the temperature of the inorganic material mixed solution is adjusted to 45 ° C. It is preferable to stir the mixture of inorganic materials at a temperature of 60 ° C. or lower, and more preferable to stir the mixture under a liquid condition of 30 or lower. This is because, when the inorganic material mixture is stirred at a low temperature of 60 or less, the intermediate can be produced in a short time and in an extremely high yield.

In the eighth of the above embodiment, the copper additive _{process, Cu (N0 3) 2.} 3 was added H ₂ 0, the form of the metal salt,齚酸salts other than the nitrate, forms such as chlorides are possible, for example, can be _{Cu C l 2, C u (} acac) 2 and the like.

In the present invention, after performing the mixing step, a solid-liquid separation step of separating fine particles precipitated in the mixed liquid from the inorganic material mixed liquid is performed, and the solid component subjected to the solid-liquid separation is heated. Performing a heating step and a copper addition processing step of adding copper. Although it is a method for producing a microporous body, it has an effective predetermined catalytic activity even when a metal other than copper is added. Examples of metals other than copper include Ga, Co, Mn, Ni, In, Pd, Pt, Rh, V, Ru, Ir, and Au. The yo Ri Specifically, P t (N_〇 _{2) 2 (NH 3) 2} + HN0 3, Rh ( N_〇 _{3) 3, VO C 2 0} 4, P d [(NH 3) 4] (N0 3 ) _2, Ru (NO) (N_〇 _{3) 3, I r (acac} ) 3, HA u C 1 4/4 H 2 0 , etc. of the metal salt is effective. It is also possible to add copper in combination with a metal other than copper.

 After performing the mixing step, a solid-liquid separation step of separating fine particles precipitated in the mixed liquid from the inorganic material mixed liquid is performed, and the solid component subjected to the solid-liquid separation is heated. After performing the copper addition treatment step of adding, and, the molding can be performed freely by an appropriate molding technique, for example, compression, extrusion molding, or the like. Further, after performing the mixing step, a solid-liquid separation step of separating fine particles precipitated in the mixed liquid from the inorganic material mixed liquid is performed, and a solid component subjected to solid-liquid separation is formed. A heating step to be performed and a copper addition processing step to add copper may be performed.

 In the denitration evaluation test, a method for producing a microporous body characterized by exhibiting a denitration rate of 50% or more at a temperature of 450 ° C is described by the method described in the above embodiment. However, the present invention is not limited to this. Industrial applicability

 As a result, a novel compound having an extremely strong solid acidity and containing an aluminum component and a silicon component could be obtained. In other words, at a low temperature that is advantageous in terms of energy such as room temperature, the catalytic activity is long in various chemical reactions in the petroleum refining and petrochemical industries, including the isomerization reaction of aliphatic hydrocarbons and aromatic hydrocarbons. A microporous body having a long time was obtained. Also, a method for producing the microporous body was obtained.

In addition, even when the reaction temperature conditions for simultaneously performing the N 0 _x reduction reaction are changed, there is no change in the catalyst activity, the thermal stability is high, and the reaction temperature conditions are relatively low. Even so, a microporous body having high catalytic activity could be obtained.

That is, the substance of the present invention can be used for the isomerization reaction of hydrocarbons such as xylene at low temperature, It has sufficient catalytic activity in the synthesis of benzene, the synthesis of cyclohexene, and the denitration.

 Since these fields are industrially very important and the production volume of the products is enormous, in the reaction system or denitration of exhaust gas, etc., the reaction temperature is lowered, the activity is improved, and environmental pollution is reduced. Since it contributes to improvements such as reduction of substances, it is extremely advantageous in terms of energy, and the benefits of the microporous body according to the present invention are immeasurable.

Claims

The scope of the claims

1. It has an adsorbing section for adsorbing and holding H ₂ 0 or NH _3, and the adsorbing section can stably hold H ₂ 0 at 500 ° C. or less, and the held H ₂ 0 is 50 0 A novel compound comprising an aluminum component and a silicon component that can be desorbed at high temperatures exceeding 0 ° C.

2. And has a H ₂ 0 or NH ₃ ammonia adsorption portion for holding suction, the suction unit is stable can hold H ₂ 0 at 5 0 CTC hereinafter, H ₂ 0, which is held, 5 0 0 A microporous material that can be desorbed at high temperatures exceeding ° C.

3. Ammonia ion (R ₄ N +: R is hydrogen, at least one selected from an alkyl group or an aryl group having 10 or less carbon atoms), phosphonium ion (R ₄ P +: R is At least one selected from hydrogen, an alkyl group having 10 or less carbon atoms or an aryl group), at least one crystallization modifier selected from amines or diamines, an aluminum component, and a silicon component. A mixing step of forming an inorganic material mixture is performed. After the mixing step, a solid-liquid separation step of separating fine particles precipitated in the mixture from the inorganic material mixture is performed. An intermediate is obtained by performing a heating step of heating the solid component, and after an ion exchange step of ion-exchanging the intermediate with ammonium ions, a desorption step of desorbing ammonia and water is performed. A method for producing a microporous body.

4. Ammonia ions (R ₄ N +: R is hydrogen, at least one selected from alkyl or aryl groups having 10 or less carbon atoms), phosphonium ions (R ₄ P +: R is hydrogen, carbon Forming an inorganic material mixture comprising at least one crystallization modifier selected from amines or diamines and at least one crystallization modifier selected from alkyl groups or aryl groups having a number of 10 or less, and a silicon component. After the mixing step, a solid-liquid separation step of separating fine particles precipitated in the inorganic material mixed liquid is performed, and then a heating step of heating the solid component subjected to the solid-liquid separation is performed. And a copper addition treatment step of adding and treating copper.

5. A mixing step is performed to form an inorganic material mixed solution containing a silicon component and a trivalent element component. After the mixing step, fine particles precipitated in the inorganic material mixed solution are removed. A method for producing a microporous body, comprising: performing a heating step of heating a solid component subjected to solid-liquid separation after performing a solid-liquid separation step of separating, and a copper addition treatment step of adding copper. .

 6. performing a mixing step of forming an inorganic material mixed liquid containing at least one crystallization modifier selected from ammonium ions, phosphonium ions, amines or diamines, and a silicon component; After the step, an intermediate is obtained by performing a solid-liquid separation step of separating fine particles precipitated in the inorganic material mixed liquid, and a heating step of heating the solid component subjected to solid-liquid separation. A method for producing a microporous body, comprising performing a copper addition treatment step of adding copper.

7. The method for producing a microporous body according to claim 6, wherein a trivalent element component is added in the mixing step.

 8. A mixing step is performed to form an inorganic material mixed solution containing a silicon component and a trivalent element component. After the mixing step, solid-liquid separation for separating fine particles precipitated in the inorganic material mixed solution is performed. Performing a heating step of heating the solid component subjected to solid-liquid separation to obtain an intermediate, and performing a copper addition step of adding copper to the intermediate. .

 9. The method for producing a microporous body according to claim 6, wherein the copper addition treatment step includes performing a copper ion exchange treatment step of subjecting the intermediate to ion exchange treatment with copper ions.

10. The method for producing a microporous body according to claim 9, further comprising performing a pretreatment step of ion-exchanging the intermediate with ammonia before performing the copper ion exchange treatment step.

 1 1. The method for producing a microporous body according to claim 3, wherein the silicon component is kanemite, TEOS (tetraethyl orthosilicate), colloidal silica, or fumed silica.

1 2. The crystallization modifier, tetra n- Petit Ruan monitor ©-ion _{((n- C 4 H 9)} 4 N +), tetra-n- propyl ammonium Niu-ion _{((n_C 3 H 7) 4} N +), Te tiger E chill ammonium Niu-ion _{((C 2 H 5) 4} N +), Te tetramethyl ammonium Niu Mui oN ^{_{((CH 3) 4 N +}} ), n- propyl DOO trimethyl ammonium Niu-ion ((n-C ₃ H _{7) (CH 3) 3 N} +), Benjiruto trimethyl ammonium Niu-ion _{((C 7 H 7) (} CH 3) 3 N +), tetra-n- butyl phosphonyl ©-ion _{((n- C 4 H g)} 4 P +), benzyltriphenylphosphonium ion ((C ₇ H ₇ ) (C ₆ H ₅ ) ₃ P +), 1,4-dimethyl-1,4 diazobicyclo (2,2,2) octane, pyrrolidine, n Claims ₃ to 11 which are at least one kind of cationic crystallization regulator selected from —propylamine (n—C ₃ H ₇ NH ₂ ), methylquinuclidine, ethylenediamine, and piperidine. 13. The method for producing a microporous body according to the above item.

 1 3. Fill the reaction tube with the microporous material, flow nitrogen oxide together with the reducing agent through the reaction tube at a predetermined temperature, and measure the concentration of nitrogen oxide at the inlet and the concentration of nitrogen oxide at the outlet of the reaction tube. Calculating the percentage of the difference between the inlet nitrogen oxide concentration and the outlet nitrogen oxide concentration with respect to the inlet nitrogen oxide concentration as a denitration rate, and evaluating the catalytic activity of the microporous body based on the denitration rate. A microporous body characterized by exhibiting a denitration ratio of 50% or more at a temperature of 450 ° C in an evaluation test.