JP2000102734A - Fibrous catalyst for decomposition of organic chlorine compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fibrous catalyst which is hardly oxidized and poisoned by SOx contained in a waste gas and efficiently makes organic chlorine compounds harmless at a low temperature. SOLUTION: This fibrous catalyst contains multiple oxide A and 1-40 wt.% metal vanadium or vanadium oxide B based on the amount of the component A as effective components. The multiple oxide A consists of titanium dioxide (a) and 2-40 wt.% zirconium oxide and/or silicon dioxide (b) based on the amount of the component (a). The metal vanadium or vanadium oxide B is the composition of metal tungsten or tungsten oxide B' in a B' to B weight ratio of <=10 and/or the composition of metal molybdenum or molybdenum oxide B'' in a B'' to B weight ratio of <=10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fibrous catalyst for decomposing aliphatic and aromatic organic chlorine compounds and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, an electrostatic precipitator (EP), a bag filter, and the like have been used to remove dust in exhaust gas.
Organochlorine compounds represented by nitrogen oxides and dioxins have been removed by a catalytic decomposition method, an activated carbon blowing method, an activated coke adsorption method, or the like. Among these, the catalyst decomposition method is known as a catalyst for decomposing dioxins, a catalyst comprising titanium oxide, vanadium pentoxide, and tungsten trioxide, which has a honeycomb shape, a pellet shape, a bead shape. It has been generally used as a honeycomb catalyst for removing nitrogen oxides contained in exhaust gas from a refuse incinerator using ammonia as a reducing agent (see JP-A-2-35914). As a decomposition catalyst for halogen-containing organochlorine compounds, for example, aliphatic organochlorine compounds such as chlorofluorocarbons, trichlene, and perchrene, acidic zeolites or the second to sixth groups of the periodic table can be used.
A metal-substituted zeolite belonging to a period is known (see JP-A-4-250825). Further, methylene chloride, as a decomposition catalyst for methyl bromide, such as organic halogen compounds, precious metal TiO ₂ -ZrO ₂ composite oxide support (P
t, Pd) is known (Japanese Unexamined Patent Publication No.
173760).

On the other hand, a method using a fibrous catalyst is effective for causing a more efficient reaction as a catalyst. However, as a fibrous exhaust gas treatment catalyst, a cloth made of glass fibers impregnated with titanium oxide sol is used. A method has been proposed in which a nitrogen oxide is treated with a filter that has been heat-treated at 150 ° C. and further impregnated with ammonium metavanadate (see JP-A-9-220466). In addition, the catalyst preparation solution containing anatase-type titanium oxide, ammonium metavanadate, and oxalic acid solution contains E
A glass fiber is immersed, dried, and calcined at 190 to 200 ° C. to obtain a denitration catalyst filter (see JP-A-1-258746). Also, titania,
Using alkoxide of silica and vanadyl trichloride, an amorphous fiber is produced by a sol-gel method, blended with an E glass fiber monofilament, and woven to produce a catalyst fiber (see JP-A-5-184923). Further, water is added to a catalyst composition powder containing one or more oxides of TiO ₂ and V, Mo, and W obtained by calcining to form a slurry, which is impregnated into an inorganic fiber sheet,
It is dried and calcined to obtain a catalyst for removing nitrogen oxides (see JP-A-2-169028).

[0004]

In the above-mentioned catalyst utilizing a catalyst for removing nitrogen oxides contained in exhaust gas from a refuse incinerator using ammonia as a reducing agent, polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans are used. The efficiency of removing organic chlorine compounds such as (PCDFs) is as follows: temperature is 280 ° C, space velocity (SV) is 9600h
^Under conditions such as ^-1, it was as low as 30 to 48%. Further, such a catalyst had inferior processing ability in a practically low concentration range. Further, in the case where the H-type mordenite-type zeolite used as an aliphatic organochlorine compound decomposition treatment catalyst is replaced with Co, Cu, Ni, and Fe, the removal efficiency of dichloromethane (CH ₂ Cl ₂ ) at 350 ° C. is 49 to 49%. It was as low as 58%. Also,
Such a catalyst is suitable for treating a halogen-containing organic compound having a relatively low molecular weight, but there is no example of a polymer having a benzene ring. In addition, durability against acidic substances such as Cl ₂ and HCl generated by the reaction and sulfur oxides present in the exhaust gas is poor, which is a problem. Further, in Pt.Pd / TiO ₂ —ZrO ₂ used as a decomposition catalyst for organic halogen compounds, the decomposition rate of methylene chloride (CH ₂ Cl ₂ ) is as good as 71 to 88% at 350 ° C. Since it is used, the production cost of the catalyst is increased, and the durability to acidic substances is poor, which is a problem.

[0005] The above-mentioned conventional fibrous catalyst is mainly used for denitration, and has not been used as a catalyst for removing organic chlorine compounds such as PCDDs and PCDFs. Furthermore, in any of the catalysts, the fibrous advantage of increasing the geometric area was not utilized, and sufficient removal efficiency was not obtained.

[0006] The present invention solves the above-mentioned problems, and the deterioration of the catalyst can be suppressed even for an exhaust gas containing an acidic substance which is a main cause of deterioration of the catalyst, or an exhaust gas generated by processing and affecting the catalyst itself. The catalyst component can be used stably, the removal efficiency of organochlorine compounds at that time can be increased, and the catalyst component can be uniformly used in a fibrous form by utilizing the advantage of the fiber having a large geometric area in order to use the catalyst efficiently. It is an object of the present invention to provide an attached fibrous catalyst and a method for producing the same.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve such problems, and as a result, a fibrous catalyst having a specific composition or a composite oxide having a specific composition has been used as a carrier. The present inventors have found that a fibrous catalyst supporting a specific metal or metal oxide is effective, and have reached the present invention.

That is, the first aspect of the present invention is the following A
A fibrous catalyst for decomposition treatment of organochlorine compounds, characterized in that the component and the B component are effective components, the B component is 1 to 40 wt% with respect to the A component, and the shape is fibrous. It is. (A): a binary or more complex oxide composed of (a) titanium oxide and (b) zirconium oxide and / or silicon oxide, provided that (b) is 2 to 40% by weight based on (a) is there. (B): a composition comprising (a) a metal or metal oxide of vanadium, or (b) a composition comprising a metal or metal oxide of (b) tungsten and / or (c) a metal or metal oxide of molybdenum. Object, but
(B) or (c) has a weight ratio of 10 or less to (a). The second aspect of the present invention is characterized in that a spinning dope comprising a component A raw material is prepared, and a fiber obtained by spinning the solution is impregnated or coated with a solution comprising a component B raw material, followed by baking. The first aspect of the present invention is a method for producing a fibrous catalyst for decomposition treatment of an organic chlorine compound according to the present invention. The third aspect of the present invention is the first aspect of the present invention, characterized in that a raw material of the component A and a raw material of the component B are mixed to prepare a spinning dope, and a fiber obtained by spinning it is fired. The gist of the present invention is a method for producing a fibrous catalyst for decomposition treatment of an organic chlorine compound. A fourth aspect of the present invention is the first method for decomposing an organic chlorine compound according to the first aspect of the present invention, wherein the inorganic fiber is impregnated or coated with a solution composed of a raw material of the component A and a raw material of the component B, and then firing. The gist is a method for producing a fibrous catalyst. The fifth aspect of the present invention is characterized in that the inorganic fiber is impregnated or coated with a solution composed of the component A material, dried, impregnated or coated with a solution composed of the component B material, and then fired. The gist of the present invention is a first method for producing a fibrous catalyst for decomposition treatment of an organochlorine compound according to the present invention.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
First, the first fibrous catalyst for decomposition treatment of an organic chlorine compound of the present invention will be described. The organic chlorine compounds in the present invention include polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) contained in exhaust gas from an incinerator. Further, it includes chlorinated organic compounds such as monochlorobenzene, dichlorobenzene, and o-chlorophenol, which are precursors of these dioxins, and also includes aliphatic organic chlorine compounds such as freon, trichlene, and perchrene.

[0010] The fibrous catalyst of the present invention comprises the A component and the B component as active components, wherein the B component is 1 to 1 component to the A component.
40 wt%, preferably 5 to 3%.
0 wt%. If the amount of the component B is too small relative to the component A, the activity as a catalyst will be low. Conversely, if the component B is too large, it will not be uniformly dispersed in the component A, and will form aggregates and block pores. It is not preferable because it causes a decrease in the value.

The component A in the present invention is a binary or more complex oxide composed of (a) titanium oxide and (b) zirconium oxide and / or silicon oxide.
It is necessary to be 2 to 40% by weight, preferably 2 to 20% by weight based on (a). (b) is 2w for (a)
If it is less than t%, it is difficult to mold, and the strength is reduced, resulting in a problem of durability as a catalyst. On the other hand, if the content is more than 40 wt%, the catalytic activity is lowered, so that it cannot be adopted.

Specific examples of the titanium oxide used in the present invention include TiO ₂ , TiO _2n-1 (n = 4 to 9), Ti ₂ O ₅ ,
₂ O ₃ and TiO. Of these, TiO ₂ having three types of transformations of rutile, brookite, and anatase is preferable, particularly an anatase form is preferable, and it is most preferable that 95 wt% or more of anatase type is contained in titanium oxide. Further, specific examples of the zirconium oxide used in the present invention include ZrO ₂ . Further, specific examples of the silicon oxide used in the present invention include SiO 2,
SiO ₂ may be mentioned. Of these, SiO ₂ is preferred. In the fibrous catalyst of the present invention, each oxide in the component A is not necessarily limited to the above crystal form, and may be Ti-O-Si, Ti-O-Zr, Zr
It is preferable to include an amorphous structure containing -O-Si bonds.

The component B of the fibrous catalyst of the present invention comprises (a) a composition comprising a metal or metal oxide of vanadium, or (a) and (b) a metal or metal oxide of tungsten and / or (c) A composition comprising a metal or metal oxide of molybdenum, (b) or (c)
However, it is necessary that the weight ratio is not more than 10 with respect to (a). Preferably, the weight ratio is 5 or less.

In the present invention, the metal oxide of vanadium
Specific examples are VO, V_TwoO_Three, VO_Two, V_TwoO_Five, V_nO_2n-1(n =
4-8), V_nO_{2n + 1}(n = 3, 6). these
V in_TwoO_FiveIs preferred. Tungsten in the present invention
Specific examples of metal oxides include WO_Two, WO_Three, W_{1 8}O₄₉, W
₂₀O₅₈, W₅₀O₁₄₈, W₄₀O₁₁₉Is mentioned. Among these
In WO_ThreeIs preferred. Molybdenum metal acid in the present invention
As a specific example of the compound, MoO_Two, MoO_Three, Mo_ThreeO ₈, Mo₉O₂₆,
Mo_FourO₁₁, Mo₁₇O₄₇, Mo_FiveO₁₄Is mentioned. Among these
MoO_ThreeIs preferred.

In the fibrous catalyst of the present invention, component (B) in component B
The crystallinity of (b) or (c) is preferably 60% or less, and more preferably 50% or less. Not all of the metal of the component B is supported in the form of a crystalline oxide. That is, it is considered that the activity is high because the compound A is present in an unstable state in terms of energy on the composite oxide. The crystallinity here is determined as follows. All V ₂ O ₅ metal in the B component, respectively, WO _3, X-ray theoretical diffraction intensity I _i, assuming that a crystalline oxide represented by MoO ₃ (i) is expressed by the following equation.

[0016]

(Equation 1)

I _ip is the X-ray diffraction intensity of the pure i component, (μ /
ρ) _i is the mass absorption coefficient of the i component, (μ ′ / ρ) is the average mass absorption coefficient of the sample, and W _i is the weight fraction of the i component in the sample. This is a value when the amount of metal is measured by ICP or the like and all detected metals are assumed to be crystalline oxides. Then, the X-ray diffraction intensity (I) of the i component of the sample is measured, and the crystallinity of the i component in the sample is defined as I / I _i .
The diffraction intensity is assumed to be an intensity appearing in a range of a diffraction angle (2θ) of 5 to 90 °, preferably 10 to 40 °.

The fibrous catalyst of the present invention may be formed into a fibrous form by spinning the above-mentioned active ingredient. Alternatively, the above-mentioned active ingredient may be fixed to the surface of a conventional inorganic fiber to obtain a fibrous form. It may be a catalyst. Also,
The fibrous catalyst of the present invention also includes a knitted fabric and a woven fabric obtained by knitting or weaving a fiber composed of an active ingredient or a fiber having an active ingredient fixed on an inorganic fiber. Examples of the inorganic fibers used here include fibers obtained from alumina, glass, silica, silica alumina, silica alumina zirconium, and the like. Among them, silica alumina fibers are preferable from the viewpoint of versatility. The diameter of the inorganic fiber is set to 0.
It is preferably from 1 to 50 μm, more preferably from 1 to 20 μm. Exceeding this range is not preferred because the surface area is reduced and the activity is reduced, and the elasticity is reduced and the material is easily broken. If it is less than this range, it is difficult to handle and it is not preferable.
When the above-mentioned active ingredient is fixed to the surface of the inorganic fiber, the active ingredient is preferably 3 to 200 wt%, more preferably 10 to 100 w%, based on the inorganic fiber.
t%, most preferably 20 to 50 wt%. If it is less than this range, sufficient activity cannot be obtained, and if it exceeds this range, the active ingredient will be peeled off over a long period of use.

The diameter of the fibrous catalyst of the present invention is preferably 0.1 to 50 μm, and 1 to 20 μm.
μm is more preferred. Exceeding this range is not preferred because the surface area is reduced and the activity is reduced, and the elasticity is reduced and the material is easily broken. If it is less than this range, it is difficult to handle and it is not preferable.

The on-fiber catalyst of the present invention comprises the A component and the B component as active components.
a, IIa, IIIa, IVa, Va, VIa, VIIa, VIII, Ib, IIb
, IIIb, IVb, Vb, VIb, and VIIb may be contained as long as they do not affect the catalytic activity, even if they contain atoms, molecules or compounds composed of elements belonging to the respective groups.

Next, the production method of the present invention will be described.
The production method of the present invention is a method for producing the above-mentioned fibrous catalyst. The method for producing a fibrous catalyst comprising the active ingredients of the A component and the B component, and the method for producing the fibrous catalyst in which the active ingredients of the A component and the B component are inorganic fibers In some cases, a fibrous catalyst fixed thereon is produced. First, a method for producing a fibrous catalyst comprising the active ingredients of the component A and the component B (the second and third production methods of the present invention) will be described. The raw material for the component A is preferably an alkoxide, and the raw materials for the titanium oxide include tetramethoxytitanium, tetraethoxytitanium, tetra-i-propoxytitanium, tetra-n-propoxytitanium, tetra-n-butoxytitanium, and tetra-i-titanium. Butoxy titanium, tetra-
sec-butoxytitanium, tetra-t-butoxytitanium and the like. Of these, tetra-i-propoxytitanium is preferred. As a raw material of the zirconium oxide, tetramethoxy zirconium, tetraethoxy zirconium, tetra-i-propoxy zirconium, tetra-n-propoxy zirconium, tetra-i-butoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium , Tetra-
t-butoxyzirconium and the like. Of these, tetra-n-butoxyzirconium is preferred.
As raw materials for silicon oxide, tetramethoxysilane,
Tetraethoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-i-butoxysilane, tetra-n-butoxysilane, tetra-s
ec-butoxysilane, tetra-t-butoxysilane and the like. Of these, tetraethoxysilane is preferred.

The raw materials for V, W, and Mo as the component B are not particularly limited. Examples of the raw materials for V include vanadyl sulfate, ammonium vanadate, vanadyl oxalate,
Vanadyl chloride, vanadium oxychloride, triethoxyvanadyl and the like are used. As a raw material of W, ammonium tungstate, tungstic acid, silicotungstic acid, tungsten chloride, tungsten bromide, pentaethoxytungsten and the like are used, and a raw material of Mo is used. For example, molybdic acid, silicomolybdic acid, phosphomolybdic acid, ammonium molybdate, molybdenum chloride, pentaethoxymolybdenum, or the like is used. Among these, ammonium vanadate, ammonium tungstate, and ammonium molybdate are preferred.

In the second production method of the present invention, the above-mentioned A
The raw materials of the components are mixed so as to have a predetermined weight ratio to prepare a spinning dope. At that time, it is preferable to mix the raw material of the component A and the alcohol, and further mix with a solution containing water, a strong acid and an alcohol. The alcohol used here is represented by the general formula ROH (R is an alkyl group), and the OH group is a single monohydric alcohol having no other functional group. Examples of the strong acid include hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, sulfonic acid and the like. Heat treatment of the spinning stock solution in air is preferable because hydrolysis is promoted and the solution is concentrated to form a viscous gel. The heating temperature is preferably 30 to 80C, more preferably 40 to 60C. If the temperature is lower than this temperature range, it takes a long time to have spinnability and the efficiency is poor. On the other hand, if the temperature is higher than this temperature range, gelation proceeds rapidly, which is not preferable. Next, the spinning solution is spun to obtain fibers. As spinning conditions, it is preferable to use a nozzle having a temperature of 5 to 80 ° C. and a nozzle diameter of 0.01 to 0.5 mm, but there is no particular limitation. When the yarn coming out of the nozzle is drawn at a ratio of 1 to 50 times using a suction gun, a roller or the like, finer fibers can be obtained. Next, a solution containing a predetermined amount of the ingredient B is prepared. At this time, the raw material of the component B may be dissolved using a boric acid aqueous solution, an oxalic acid aqueous solution, a methylamine solution, or the like. The solutions used as the raw materials of the component B may be separately prepared or mixed. Next, impregnating or applying a solution as a raw material of the B component to the fiber composed of the A component,
dry. Thereafter, firing is performed in an oxidizing atmosphere.

As for the fibrous catalyst comprising the active ingredients of the component A and the component B, as described above, a method comprising obtaining the fiber comprising the component A and adhering the component B to the fiber (the second method of the present invention). In addition to the (production method), it can also be produced by the third method of the present invention in which the component A and the component B are mixed to form a fiber. As the raw material, the same one as in the second production method of the present invention is used. However, the raw material of the component B may be any as long as it is soluble in the alcohol used as the solvent, and in particular, vanadium chloride, tungsten chloride, chloride Molybdenum is preferred. In the third production method of the present invention, a raw material of the component A and a raw material of the component B are mixed in a predetermined amount to prepare an alkoxide solution, which is spun as a spinning solution to obtain a fiber,
Thereafter, drying and firing are performed.

A specific method for preparing an alkoxide solution composed of the raw material of the component A and the raw material of the component B is preferably as follows. Titanium alkoxide / silicon alkoxide / alcohol mixed solution, water / strong acid /
An alcohol mixed solution, a tungsten compound / alcohol mixed solution, and a vanadium compound are separately prepared. At this time, the amount of water used was
It is preferably used in the range of 0.5 to 4.0 mol per mol. If the amount is less than 0.5 mol, a viscous gel can be obtained after the heat concentration treatment, but it is difficult to maintain the shape of the gel fiber after spinning. If it is more than 4.0 mol, the reaction proceeds rapidly during hydrolysis, and even if a powdery precipitate precipitates or a viscous sol is obtained, the gelation is rapid and the sol having a viscosity suitable for spinning operation is obtained. Not suitable for synthesis. As the strong acid, hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, sulfonic acid and the like are used, and the amount of use is in the range of 0.01 to 0.5 mol based on 1 mol of all alkoxides. If the amount is less than 0.01 mol, the reaction proceeds rapidly during the hydrolysis, and a powdery precipitate is deposited, or even if a viscous sol is obtained, the gelation is fast and the sol having a viscosity suitable for spinning operation is obtained. Not suitable for synthesis. 0.5mo
If it is more than 1, a sol having viscosity can be obtained after the heat concentration treatment, but spinning becomes difficult. The alcohol is represented by the general formula ROH (R is an alkyl group).
As the H group, only one monohydric alcohol having no other functional group is used. The amount of the H group used is 0.1 to 3 mol based on 1 mol of the total alkoxide. desirable. In the case of mixing with less than 0.1 mol, the reaction proceeds rapidly, and a precipitate is easily deposited. On the other hand, if the amount is more than 3 mol, it takes a long time for concentration, which is not efficient. About the above, what is necessary is just the quantity required to melt | dissolve a tungsten compound, and 5-20 mol of alcohols are suitable for 1 mol of tungsten compounds.

The above (1) is mixed to prepare an alkoxide solution to be a spinning solution. The order of mixing them is not particularly limited, but it is particularly preferable to mix pulp and then mix in order to easily prepare a spinning dope having good spinnability. When heat is mixed, heat is generated, so it is desirable to mix while cooling in an ice bath or the like.

Next, the spinning solution is preferably subjected to heat treatment in the air, whereby hydrolysis is promoted, and the solution is concentrated to form a viscous gel, which is preferable. The heating temperature is 30-8
0 ° C is preferred, and 40-60 ° C is more preferred. If the temperature is lower than this temperature range, it takes a long time to have spinnability and the efficiency is poor. On the other hand, if the temperature is higher than this temperature range, gelation proceeds rapidly, which is not preferable. The spinning solution can be spun in the same manner as in the above-described second production method of the present invention, and a fibrous catalyst can be obtained by drying and firing the obtained fiber.

Next, a method for producing a fibrous catalyst in which the active ingredients of the components A and B are fixed on inorganic fibers (fourth aspect of the present invention)
Fifth manufacturing method) will be described. The raw material of component A is
As the titania oxide, titania sol, tetra-i-
Propoxy titanium, titanyl sulfate, titanium tetrachloride, etc. are used.As zirconium oxide, zirconia sol, tetra-n-butoxy zirconium, etc. are used.As silicon oxide, silica sol, tetraethoxysilane, water glass, etc. Used. Among these,
Preferred are titania sol, zirconia sol and silica sol. As a raw material of the component B, V is preferably ammonium vanadate, vanadyl chloride, W is ammonium tungstate, tungsten chloride, and Mo is preferably ammonium molybdate or molybdenum chloride. In the fourth production method of the present invention, the above-mentioned raw materials are mixed so as to have a predetermined weight ratio, and the mixed solution is impregnated or applied to inorganic fibers and dried. Thereafter, firing is performed in an oxidizing atmosphere.

In order to produce a fibrous catalyst in which the active ingredients of the component A and the component B are fixed on inorganic fibers, a solution obtained by mixing the materials of the components A and B is used as described above. It may be, first, after fixing the component A on the inorganic fiber,
Furthermore, the fifth method of the present invention of impregnating and applying the component B can be adopted. That is, the same raw material is used for both the A component and the B component, and the inorganic fiber is impregnated or coated with the solution of the A component, and then dried. Thereafter, the component B is impregnated or applied, dried, and fired in an oxidizing atmosphere.

In all the production methods of the present invention described above, the drying step after impregnation or coating is performed in the range of 80 to 160
C., preferably 100 to 140.degree. C., for 8 to 16 hours, preferably 10 to 14 hours. The firing step is performed at 300 to 800 ° C., preferably 350 to 700 ° C.
The heat treatment may be performed at a temperature of ° C. for 1 to 10 hours, preferably 2 to 6 hours, in an oxidizing atmosphere. If the calcination time is too long or the calcination temperature is too high, anatase-type titanium oxide cannot be obtained, and rutile-type crystals of titanium oxide grow, resulting in a decrease in activity.

[0031]

Next, the present invention will be described specifically with reference to examples. The measurement of the amount of crystalline oxide in the obtained catalyst by X-ray diffraction was performed as follows. The sample was packed in a glass cell having a depth of 0.2 mm, and wide-angle X-ray measurement was performed. The X-ray diffractometer is Rigaku Denki RAD-rB.
The slit configuration is DS (divergent slit) = 1.0 °, R
S (receiving slit) = 0.3 mm, RS _M = a (no), was used with monochromatic with curved graphite monochromator Cu-K [alpha line output of 50 kV / 200 mA.
The measuring method was a symmetrical reflection method. Scanning was performed at 3 ° / min, steps were measured at 0.01 °, and 2θ range was from 3 to 90 °. V
The diffraction angles of the crystalline substances of ₂ O ₅ , WO ₃ and MoO ₃ are 20.2 °, 23.5 ° and 27.3 °, respectively.
At that time, the peak intensity, the X-ray diffraction intensity and the mass absorption coefficient of the pure crystalline substance, and the average mass coefficient of the sample were measured.
Further, the amount of metal in the catalyst was measured by IPC and used for calculating the crystallinity. The diffraction angle of the anatase type titanium oxide was set to 25.3 °, and the ratio of the anatase type titanium oxide was calculated in the same manner.

Example 1 A fibrous catalyst containing a titania oxide, a silicon oxide, a vanadia oxide and a tungsten oxide was prepared by the following method. Silica sol (manufactured by Nissan Chemical Industries, Ltd.: Snow Tex O; SiO ₂ solids concentration 20wt of particle size 10~20nm
%) To 1 g of titania sol (manufactured by Nissan Chemical Industries, Ltd .: titania sol TA-15; Ti having a particle size of 2 to 20 nm)
O ₂ solid concentration of 15.2wt%) 26.3g were mixed,
This mixed solution is impregnated with short silica alumina fibers,
Dry at 0 ° C. for 12 hours, then impregnate the fibers with a solution of 0.3 g of ammonium vanadate and 0.81 g of ammonium tungstate parapentahydrate in oxalic acid,
It was dried at 0 ° C. for 12 hours and calcined at 500 ° C. for 2 hours in air. The anatase titanium oxide in the titanium oxide was 98%. The catalyst composition is V ₂ O ₅ / WO ₃ / TiO ₂ / Si in terms of oxide weight ratio
O ₂ = 4.5 / 13.5 / 77/4, and the crystallinity of V ₂ O ₅ and WO _{3 in} the catalyst was 38% and 42%, respectively.

Example 2 16.3 g of silica sol, 26.3 g of titania sol, 0.42 g of vanadyl trichloride and tungsten (VI) chloride
1.23 g was mixed to obtain a solution. The mixed solution was impregnated with short silica alumina fibers, dried at 120 ° C. for 12 hours, and calcined at 500 ° C. for 2 hours in air. The anatase titanium oxide in the titanium oxide was 98%. The catalyst composition is V ₂ O ₅ / WO ₃ / TiO ₂ / SiO ₂ = 4.6 / 13.5 / 77 / by oxide equivalent weight ratio.
The crystallinity of V ₂ O ₅ and WO _{3 in} the catalyst was 37% and 40%, respectively.

Example 3 1 mol of tetra-i-propoxytitanium, tetraethoxy
0.1 mol of silane, 1.0 mol of ethanol, distillation
2 mol of water and 0.2 mol of hydrochloric acid were stirred and mixed at 0 ° C.
Then, while stirring at 40 ° C., the alcohol was removed.
A spinnable viscous solution was prepared. This solution is 20μ in diameter.
m, and dried at 120 ° C. for 12 hours.
Calcination was performed in air at 0 ° C. for 2 hours. This fiber, vanadin
Ammonium acid 0.053mol, tungstic acid
Oxalic acid solution in which 0.0052 mol of monium is dissolved
And dried at 120 ° C. for 12 hours.
Fired in air for hours_TwoO_Five-WO_Three-TiO_Two-SiO_TwoGet the fiber
Was. This fiber was processed into a non-woven fabric. Ana in titanium oxide
Titanium oxide was 98%. The catalyst composition is oxide
V in converted weight ratio_TwoO_Five/ WO_Three/ TiO_Two/ SiO_Two= 4.5 / 13.7 / 78/4
And V in the catalyst_TwoO_FiveAnd WO _ThreeHas a crystallinity of 40
And 42%.

Example 4 1 mol of tetra-i-propoxytitanium, 0.1 mol of tetraethoxysilane, 0.053 mol of vanadyl sulfate
l, 0.0046 mol of tungsten chloride, 1.0 mol of ethanol, 2 mol of distilled water, 0.2 mol of hydrochloric acid
After stirring and mixing at 40 ° C., the alcohol was removed while stirring at 40 ° C. to prepare a viscous solution capable of spinning. This solution is spun into a fiber having a diameter of 20 μm,
After drying for 2 hours, baking in air at 500 ° C for 2 hours,
To obtain a _{V 2 O 5 -WO 3 -TiO 2} -SiO 2 fibers. This fiber was processed into a non-woven fabric. 98% of anatase titanium oxide in titanium oxide
was. The catalyst composition was V ₂ O ₅ / WO ₃ / TiO ₂ /
SiO ₂ = 4.5 / 13.6 / 77/4, and the crystallinity of V ₂ O ₅ and WO _{3 in} the catalyst was 38% and 40%, respectively.

Example 5 A solution was prepared by dissolving 1.04 g of tetraethoxysilane in 0.58 g of ethanol based on 14.2 g of titanium isopropoxide. 1 g of 36% hydrochloric acid solution, 1.16 water
g and 0.58 g of ethanol were mixed to prepare a solution. The solution was slowly added dropwise while stirring the solution in an ice bath. At this time, titanium isopropoxide, tetraethoxysilane, ethanol, hydrochloric acid, the molar ratio of water,
1: 0.1: 0.5: 0.2: 2. To the above solution, 0.7 g of tungsten hexachloride was added to 1.15 of ethanol.
g was added. Next, 0.75 g of vanadyl sulfate was mixed in powder form. Thereafter, stirring was continued at 40 ° C. until the viscosity became suitable for spinning. The obtained spinning dope exhibited excellent spinnability. After drying at 120 ° C. for 12 hours, the obtained fibrous catalyst precursor was calcined at 500 ° C. for 2 hours. Anatase type titanium oxide in titanium oxide is 9
8%. The catalyst composition ratio is V ₂ O ₅ / W in weight ratio in terms of oxide.
O ₃ / TiO ₂ / SiO ₂ = 5.5 / 8 / 80.4 / 6, and the crystallinity of V ₂ O ₅ and WO _{3 in} the catalyst was 39% and 40%, respectively.

Comparative Example 1 1.3 weight parts of titania sol was mixed with 1 weight part of silica sol, and a fibrous catalyst was prepared in the same manner as in Example 1. The anatase titanium oxide in the titanium oxide was 98%. The catalyst composition is V ₂ O ₅ / WO ₃ / TiO ₂ / Si in terms of oxide weight ratio
O ₂ = 4.4 / 13.5 / 40/40, and the crystallinity of V ₂ O ₅ and WO _{3 in} the catalyst was 38% and 42%, respectively.

Comparative Example 2 The viscous solution prepared in Example 3 was dried at 120 ° C. for 12 hours and calcined at 500 ° C. for 2 hours in air.
The particles were sized to 00 μm to obtain a TiO ₂ —SiO ₂ composite oxide. This composite oxide was treated with ammonium vanadate 0.053mo.
1, impregnated with an oxalic acid solution in which 0.0052 mol of ammonium tungstate is dissolved, dried at 120 ° C. for 12 hours, and calcined in air at 500 ° C. for 2 hours to obtain V ₂ O ₅ / WO ₃
A / TiO ₂ / SiO ₂ granular catalyst was obtained. The anatase titanium oxide in the titanium oxide was 98%. The catalyst composition was V ₂ O ₅ / WO ₃ / TiO ₂ / SiO ₂ = 4.5 / 13.7 / 78/4 in terms of weight in terms of oxide, and the crystallinity of V ₂ O ₅ and WO _{3 in} the catalyst was 41% each. And 4
2%.

Comparative Example 3 The viscous solution prepared in Example 4 was dried at 120 ° C. for 12 hours, calcined at 500 ° C. for 2 hours in air, sized to 300 μm, and V ₂ O ₅ − WO ₃ -TiO ₂ -SiO ₂ granular catalyst was obtained. The anatase titanium oxide in the titanium oxide was 98%. The catalyst composition was V ₂ O ₅ / WO ₃ / TiO ₂ /
SiO ₂ = 4.5 / 13.6 / 77/4, and the crystallinity of V ₂ O ₅ and WO _{3 in} the catalyst was 39% and 41%, respectively.

Reference Example 1 [Decomposition rate of monochlorobenzene] Monochlorobenzene as a model compound of organochlorine compound
Zen (MCB: C₆H _FiveCl) 120 ppm, hydrogen chloride
(HCl) and sulfur oxide (SO _Two ) 50
Air containing ppm is used as the gas to be treated, and the fibrous catalyst (implemented
Examples 1 to 5) or granular catalysts (Comparative Examples 1 to 3) with an inner diameter of 8 m
m glass tube to a height of 25mm
1.25cm^Three 200 ° C, gas throughput
It was passed at 100 ml / min. The analysis of the processing gas
Chromatograph [Shimadzu GC-8A (FID)]
And the value calculated by the following equation was defined as the decomposition rate. Decomposition rate (%) = (1- (MCB concentration after reaction) / (before reaction)
MCB concentration)) × 100 The results are shown in Table 1. The fibrous catalyst of the present invention is referred to as a particulate catalyst.
In comparison, the activity was shown to increase.

[0041]

[Table 1]

REFERENCE EXAMPLE 2 [Evaluation of catalyst life] A gas to be treated having the same composition as that of Reference example 1 was used as the fibrous catalyst 1.25.
cm ³ to 200 ° C., through successively 1000 hours gas throughput 100 ml / min, analyzes the process gases for each Time-calculates the decomposition ratio of monochlorobenzene, S
The degree of activity deterioration due to catalyst poisoning of O ₂ , NO, NH ₃ , and HCl was evaluated. The catalyst used was that obtained in Example 1 and Comparative Example 1. The results are shown in FIG. It was shown that the catalyst of the present invention was not significantly affected by SO ₂ and maintained a stable and high activity.

[0043]

According to the present invention, a fibrous catalyst having a large contact area is used for decomposing and removing an organic chlorine compound contained at a low concentration together with an acidic substance which is a main cause of deterioration of a catalyst in an exhaust gas from an incinerator. As a result, the catalyst can be used stably with little deterioration of the catalyst, the treatment at the exhaust gas temperature can be realized at a high removal rate, and the cost is reduced because the amount of the used catalyst is small as compared with catalysts of other shapes.

[Brief description of the drawings]

FIG. 1 is a view showing the results of a life evaluation test of a fibrous catalyst of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B01J 23/30 B01D 53/36 ZABG (72) Inventor Ichiro Ninomiya 23 Uji Kozakura, Uji City, Kyoto Unitika Unitika (72) Inventor Riko Wada 23 Uji Kozakura, Uji-shi, Kyoto Unitika Ltd.F-term in the Central Research Laboratory (reference) BA04B BA05A BA05B BB02A BB02B BB04A BB04B BC54A BC54B BC59A BC59B BC60A BC60B CA19 EA03X EA03Y FA01 FB14 FB23 FB30 FB66

Claims (5)

[Claims] Claims: 1. An A component and a B component shown below as active ingredients, wherein the B component is 1 to 40% by weight based on the A component,
A fibrous catalyst for organochlorine compound decomposition treatment, which is fibrous in shape. (A): a binary or more complex oxide composed of (a) titanium oxide and (b) zirconium oxide and / or silicon oxide, provided that (b) is 2 to 40% by weight based on (a) is there. (B): a composition comprising (a) a metal or metal oxide of vanadium, or (b) a composition comprising a metal or metal oxide of (b) tungsten and / or (c) a metal or metal oxide of molybdenum. Object, but
(B) or (c) has a weight ratio of 10 or less to (a). 2. A spinning dope comprising a component A raw material is prepared, and a fiber obtained by spinning the solution is impregnated or coated with a solution comprising a component B raw material, and then fired. Item 1. A method for producing a fibrous catalyst for treating an organic chlorine compound according to Item 1. 3. The organochlorine compound according to claim 1, wherein a raw material for component A and a raw material for component B are mixed to prepare a spinning solution, and the fiber obtained by spinning the solution is baked. A method for producing a fibrous catalyst for cracking treatment. 4. The fibrous catalyst for organic chlorine compound decomposition treatment according to claim 1, wherein the inorganic fiber is impregnated or coated with a solution comprising a raw material of the component A and a raw material of the component B, and then calcined. Manufacturing method. 5. An inorganic fiber impregnated or coated with a solution composed of a component A raw material, dried, impregnated or coated with a solution composed of a component B raw material, and then fired. 2. The method for producing a fibrous catalyst for decomposing organic chlorine compounds according to 1.