JP2017019721A - Modified titanium oxide-based fine particle powder for honeycomb extrusion molded body, composition for honeycomb extrusion molded body and honeycomb molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified titanium oxide-based fine particle powder for honeycomb extrusion molded body capable of manufacturing a honeycomb molded body capable of reducing thickness and weight even increasing pitch number and excellent in moldability, strength, abrasion resistance and crack resistance or the like.SOLUTION: There is provided a modified titanium oxide-based fine particle powder for honeycomb extrusion molded body consisting of titanium oxide-based fine particle powder which is modified by a modifier consisting of aliphatic acid and/or aliphatic acid ester and having average particle diameter of 0.03 to 2.5 μm. There is provided a modified titanium oxide-based fine particle powder for honeycomb extrusion molded body where the aliphatic acid is saturated aliphatic acid represented by the following formula (1) and/or unsaturated aliphatic acid represented by the following formula (2). CH-COH (1) CH-COH (2), where n is an integer of 4 to 23, n' is an integer of 13 to 23 and m is an integer of 1 to 6 showing the number of double bond.SELECTED DRAWING: None

Description

  The present invention relates to a modified titanium oxide-based fine particle powder for a honeycomb extruded body, a composition for a honeycomb extruded body using the fine powder, and a honeycomb molded body.

  The ceramic molded body is formed by molding a ceramic molding composition containing ceramic powder by a molding method such as extrusion molding, casting molding, and compression molding (also referred to as tableting molding), followed by a drying step and further firing. It is manufactured through a process.

Various shapes such as a tablet shape, a ring shape, a pipe shape, and a honeycomb (honeycomb) shape are known as the shape of the extrusion-molded body, and it is used as a catalyst carrier or a catalyst.
For example, pollutants, particularly NO _x , emitted from fixed sources such as power plants and mobile sources such as automobiles are treated using a honeycomb catalyst as a selective reduction type NO _x catalyst (hereinafter referred to as SCR catalyst). .

  Conventionally, a honeycomb molded body is manufactured by extruding a ceramic powder with a composition containing a catalyst component source through a die, drying, and then firing. However, there are cases where extrusion is difficult or exfoliation may occur during extrusion molding, and then there is a problem of significant shrinkage or cracking during drying and firing.

  For this reason, the applicant of the present application discloses that shrinkage during drying can be reduced by blending a saturated fatty acid into the honeycomb molding composition. (Patent Document 1: JP 2009-226583 A)

  JP-A-2011-240618 (Patent Document 2) contains (a) a polyalkylene glycol fatty acid ester and (b) a linear unsaturated fatty acid having 12 to 22 carbon atoms, and the ratio is expressed in mass ratio. (A) :( b) = 96: 4 to 99: 1 An additive for ceramic extrusion is disclosed. In Patent Document 2, there is no particular limitation on the method for adding and using the ceramic extrusion additive, and the addition method may be added to the ceramic raw material powder or may be added during kneading. In addition, it is disclosed that it may be added after the preparation of the clay. However, only an example using cordierite as a ceramic raw material powder is disclosed. Regarding the use of titanium oxide particles, particularly the effect when an additive for extrusion molding is added to titanium oxide fine particles in advance. There is no description or suggestion. In addition, there is no description as to what particle size ceramic raw material powder is used.

JP 2009-226583 A JP 2011-240618A

  Honeycomb catalysts are required to increase the number of pitches for further performance improvement or economic improvement, as well as to improve moldability, crack suppression, strength, wear resistance, etc., and catalyst performance. There is a need for weight reduction and thinning.

  Therefore, in order to solve such problems, the present inventors have intensively studied. As a result, when a predetermined amount of a specific modifier is supported in advance on the titanium oxide-based fine particle powder, the moldability is improved and cracks are improved. It has been found that effects such as suppression, strength, wear resistance, etc. can be obtained, and on the other hand, by improving the moldability, it can be made thinner and the number of pitches can be increased without lowering strength, wear resistance, etc. The present invention has been completed.

[1] Honeycomb extrusion molding comprising titanium oxide-based fine particles, and the titanium oxide-based fine particles are modified with a modifier comprising a fatty acid and / or a fatty acid ester, and the average particle diameter is 0.03 to 2.5 μm. Modified titanium oxide fine particle powder for body.

[2] The honeycomb extruded body according to [1], wherein the fatty acid is a saturated fatty acid represented by the following formula (1) and / or an unsaturated fatty acid represented by the following formula (2): Modified titanium oxide fine particle powder.
_{C n H 2n + 1 -CO 2} H ················ (1)
(Where n is an integer from 4 to 23)
_{C n 'H 2n'-2m +} 1 -CO 2 H ······ (2)
(Where n ′ is an integer from 13 to 23, m is an integer from 1 to 6 representing the number of double bonds)

[3] The modified titanium oxide fine particle powder for a honeycomb extruded body according to [1], wherein an average particle size of the titanium oxide fine particles is in a range of 0.03 to 2.0 μm.
[4] Titanium oxide fine particles contain at least one oxide selected from tungsten oxide (WO ₃ ), molybdenum oxide (MoO ₃ ), silicon oxide (SiO ₂ ), and zirconium oxide (ZrO ₂ ) together with titanium oxide. The modified titanium oxide-based fine particle powder for honeycomb extruded bodies according to [1], wherein the content in the titanium oxide-based fine particles is in the range of 0.5 to 40% by weight as an oxide.
[5] The weight reduction rate (W (%)) when the temperature was raised from 30 ° C. to 100 ° C. in the differential thermal analysis of the titanium oxide fine particles whose water content was adjusted to 15% by weight, and the water content was adjusted to 15% by weight. and said honeycomb extrusion producing molded modified titanium oxide-based fine powder weight loss when heated to 100 ° C. from 30 ° C. in differential thermal analysis (W _ST (%)) and weight loss ratio (W _ST ( %)) / (W (%)) is in the range of 1.02-1.20, the modified titanium oxide system for honeycomb extruded bodies according to any one of [1] to [4] Fine powder.

[6] (i) Modified titanium oxide-based fine particle powder for honeycomb extruded body according to any one of [1] to [5],
(ii) reinforcement,
(iii) a composition containing an active ingredient precursor compound,
In the composition, the content of (i) the modified titanium oxide-based fine particle powder for honeycomb extrusion molding is in the range of 33 to 80.8% by weight, and (ii) the content of the reinforcing material is 1.8 to In the range of 12.8 wt%, (iii) the content of the active ingredient precursor compound is in the range of 0.0006 to 12.8 wt% in terms of oxide,
A composition for extruded honeycomb bodies, wherein the total solid content is in the range of 60 to 85% by weight.
[7] The composition for extruded honeycomb bodies according to [6], further comprising a filler, wherein the filler content is in the range of 0.6 to 12.8% by weight as a solid content. object.
[8] The composition for extruded honeycomb bodies according to [6], further comprising an organic additive other than the modifier in a range of 0.03 to 4.5% by weight.
[9] The active component precursor compound is at least one selected from the group consisting of V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir. The composition for extruded honeycomb bodies according to [6], which is a compound of a seed element.

[10] (i) Modified titanium oxide-based fine particle powder for honeycomb extruded body according to any one of [1] to [5],
(ii) reinforcement,
(iii) including active ingredients
(i) The content of the modified titanium oxide-based fine particle powder for honeycomb extrusion molding is in the range of 55 to 95% by weight, (ii) the content of the reinforcing material is in the range of 3 to 15% by weight, ) A honeycomb molded body characterized in that the content of the active ingredient is in the range of 0.001 to 15% by weight as an oxide.
[11] The honeycomb molded body according to [10], further including a filler, wherein the filler content is in the range of 1 to 15% by weight.
[12] The outer diameter of the molded body is in the range of 30 to 400 mm, the length is in the range of 3 to 1500 mm, the pitch is in the range of 6 to 500 cpsi, and the wall thickness is 0.1 to 1.5 mm. The honeycomb molded body according to [10] or [11], which is in a range.
[13] The active component is a metal of at least one element selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir, or The honeycomb molded body according to any one of [10] to [12], which is a metal oxide.
[14] The honeycomb molded body according to [12], wherein the thickness is in a range of 0.1 to 0.3 mm.

  According to the present invention, since a predetermined amount of a specific modifier is supported in advance on the titanium oxide fine particle powder, the moldability is improved, and even if the number of pitches is increased, it is possible to reduce the thickness and weight. Thus, it becomes possible to manufacture a honeycomb molded body excellent in strength, wear resistance, crack resistance and the like.

The weight reduction curve of the sample of Example 1, Example 6, the comparative example 1, and the comparative example 4 is shown. The endothermic curves of the samples of Example 1, Example 6, Comparative Example 1 and Comparative Example 4 are shown.

Hereinafter, first, the modified titanium oxide-based fine particle powder for a honeycomb extruded body of the present invention will be specifically described.
[Modified titanium oxide fine particle powder for honeycomb extrusion molding]
The modified titanium oxide-based fine particle powder for honeycomb extrusion molding according to the present invention is composed of titanium oxide-based fine particles, and the titanium oxide-based fine particles are modified with a modifier composed of fatty acid and / or fatty acid ester. .

Titanium oxide fine particles Titanium oxide fine particles are used as the titanium oxide fine particles used in the present invention. Further, composite titanium oxide-based fine particles containing at least one oxide selected from tungsten oxide (WO ₃ ), molybdenum oxide (MO ₃ ), silicon oxide (SiO ₂ ), and zirconium oxide (ZrO ₂ ) can be used. . When tungsten oxide (WO ₃ ), molybdenum oxide (MO ₃ ), silicon oxide (SiO ₂ ), zirconium oxide (ZrO ₂ ), etc. are contained, the content of oxide other than titanium oxide is 40 wt% or less as an oxide, Furthermore, it is preferable that it exists in the range of 30 weight% or less.
If the content of oxide other than titanium oxide in the titanium oxide fine particles is too large, molding may be difficult even if the modified titanium oxide fine particle powder is used.

Modifiers As the modifiers used in the present invention, fatty acids and / or fatty acid esters are used.
The fatty acid is preferably a saturated fatty acid represented by the following formula (1) and / or an unsaturated fatty acid represented by the following formula (2).
_{C n H 2n + 1 -CO 2} H ················ (1)
(Where n is an integer from 4 to 23)
_{C n 'H 2n'-2m +} 1 -CO 2 H ······ (2)
(Where n ′ is an integer from 13 to 23, m is an integer from 1 to 6 representing the number of double bonds)

Specific examples of the saturated fatty acid include stearic acid, lauric acid, myristic acid, behenic acid, arachidic acid, lignoceric acid, palmitic acid and the like, and mixtures thereof.
Examples of unsaturated fatty acids include oleic acid, arachidonic acid, linoleic acid, linolenic acid, icosapentaenoic acid, docosahexaenoic acid, and the like, and mixtures thereof.
As the fatty acid ester, glycerin fatty acid ester is preferable, and is represented by the following formula.

具体的にはステアリン酸モノグリセライド、パルミチン酸モノグリセライド、オレイン酸モノグリセライド、ステアリン酸ジグリセライド、オレイン酸ジグリセライド、ベヘニン酸モノグリセライド、カプリル酸モノグリセライド、カプリル酸ジグリセライド、カプリル酸トリグリセライド等およびこれらの混合物が挙げられる。

Specific examples include stearic acid monoglyceride, palmitic acid monoglyceride, oleic acid monoglyceride, stearic acid diglyceride, oleic acid diglyceride, behenic acid monoglyceride, caprylic acid monoglyceride, caprylic acid diglyceride, caprylic acid triglyceride, and the like.

The content of the modifier in the modified titanium oxide fine particle powder for honeycomb extrusion molding is preferably 0.01 to 1.5% by weight, more preferably 0.02 to 1.0% by weight. .
If the content of the modifying agent in the modified titanium oxide fine particle powder for honeycomb extrusion molding is low, the effect of improving the moldability during extrusion molding may not be sufficiently obtained. When the content of the modifier is too large, the pore volume of the molded body obtained when a molded body described later is prepared tends to be large, and the compression strength may be insufficient.

  If the content of the modifier in the modified titanium oxide fine particle powder for honeycomb extrusion molding is within the above range, a molding having excellent moldability, compression strength, abrasion resistance, crack resistance, etc. is prepared. can do. In particular, since it is excellent in moldability, it is possible to prepare a molded body having a complicated structure such as a honeycomb molded body. For this reason, it is possible to prepare a lightweight honeycomb molded body having a small thickness.

  The modified titanium oxide-based fine particle powder for honeycomb extrusion molding is an aggregate of modified titanium oxide-based fine particles, and the average particle diameter of the modified titanium oxide-based fine particles before modification is 0.03 to 2.0 μm, It is preferably in the range of 0.30 to 1.50 μm.

The average particle size of the modified titanium oxide fine particles is preferably in the range of 0.03 to 2.5 μm, more preferably 0.30 to 2.0 μm.
Depending on the content of the modifier and the average particle diameter of the titanium oxide fine particles, the surface of the titanium oxide fine particles is coated when the modifier is large, or the surface of the titanium oxide fine particles is coated when the modifier is small. It is adsorbed on the part. Thus, the moldability is improved by the presence of the modifier on the surface of the titanium oxide-based fine particles.

If the average particle diameter of the modified titanium oxide fine particles is in the above range, the moldability is excellent, and the resulting molded article is excellent in compressive strength, wear resistance, crack resistance and the like.
Such a modified titanium oxide-based fine particle powder for a honeycomb extruded body is produced as follows.

A modified titanium oxide-based fine particle powder for a molded body can be prepared by mixing a predetermined amount of a modifier with the titanium oxide-based fine particles having the predetermined average particle diameter.
The mixing method is not particularly limited as long as it can be uniformly mixed with titanium oxide-based fine particles as much as possible, and a conventionally known mixing method can be employed.

For example, a kneader, a blender, a mixer, etc. are mentioned.
When mixing, it is preferable to heat, and the heating temperature is generally in the range of 40 to 120 ° C., although it varies depending on the type of the modifier (melting point etc.). Further, a volatile solvent such as ethanol may be used at the time of reforming.

Moreover, although mixing time changes also with temperature, it is 0.25 to 5 hours in general.
In the differential thermal analysis of the titanium oxide fine particles whose water content was adjusted to 15% by weight, the weight reduction rate (W (%)) accompanying water desorption when the temperature was raised from 30 ° C. to 100 ° C., and 15% by weight of water. % Weight reduction rate (W _ST (%)) accompanying water desorption when the temperature was raised from 30 ° C. to 100 ° C. in the differential thermal analysis of the modified titanium oxide-based fine particle powder for honeycomb extruded body adjusted to% The weight loss rate ratio (W _ST (%)) / (W (%)) is 1.02 to 1.20, preferably 1.03 to 1.15.

  Here, it is not clear why the weight reduction ratio in the differential thermal analysis of the modified titanium oxide fine particle powder for honeycomb extrusion molding is increased. When preparing the composition, even if the moisture of the raw material mixture is the same at the time of kneading and kneading around 100 ° C., the moisture desorbed by heating around 100 ° C. causes the apparent moisture to be It is presumed that a composition for a honeycomb extruded body that exhibits a large number of states, increases kneading and kneading effects, and has excellent moldability can be prepared.

  In addition, the modified titanium oxide fine particle powder for honeycomb extrusion molded body according to the present invention not only has a large amount of water desorption when the temperature is raised from 30 ° C. to 100 ° C., but also the endotherm accompanying the desorption of water. There is a tendency for the bottom temperature of the peak to shift to a higher temperature.

  The weight reduction rate was measured by a differential thermal analyzer (manufactured by Rigaku Corporation: differential type differential thermal balance: TG8120 high temperature type, high sensitivity differential scanning calorimeter: DSC8230 standard type). Measurement was performed under conditions of 5.0 ° C./min in an air atmosphere, and a weight reduction rate from 30 ° C. to 100 ° C. was obtained.

[Composite composition]
A composition for a honeycomb extruded body according to the present invention is a composition containing (i) the modified titanium oxide fine particle powder for a honeycomb extruded body, (ii) a reinforcing material, and (iii) an active component precursor compound. .

Modified titanium oxide-based fine particle powder for honeycomb extruded body The above-described modified titanium oxide-based fine particle powder for honeycomb extruded body is used.
The content of the modified titanium oxide-based fine particle powder for honeycomb extrusion molding in the composition for honeycomb extrusion molding is preferably in the range of 33 to 80.8% by weight, more preferably 40 to 75% by weight as the solid content. .

When the content of the modified titanium oxide fine particle powder for honeycomb extrusion molding in the composition for honeycomb extrusion molding is small, molding becomes difficult and catalyst performance, for example, NO _x removal of the selective reduction type NO _x catalyst is removed. The rate may be insufficient.

  Even if the content of the modified titanium oxide fine particle powder for honeycomb extrusion molded body in the composition for honeycomb extrusion molded body is too much, the usage amount of other reinforcing materials, fillers and active ingredient precursors described later is limited. Therefore, moldability, compressive strength, crack resistance, and catalyst performance may be insufficient.

As the reinforcing material reinforcing material, a fibrous reinforcing material such as glass fiber or ceramic fiber can be used.

  When such a reinforcing material is included, generation of cracks due to shrinkage during drying after extrusion molding can be suppressed, and a honeycomb molded body excellent in compressive strength and wear resistance can be prepared.

The content of the reinforcing material in the composition for honeycomb extrusion molding is preferably in the range of 1.8 to 12.8% by weight, more preferably 3 to 10% by weight as the solid content.
If the content of the reinforcing material in the composition for a honeycomb extruded body is small, cracks due to shrinkage may occur during drying after extrusion molding. Even if the content of the reinforcing material in the molded body composition is too large, the reinforcing material may be clogged in the molding die during extrusion molding, which may impair the moldability.

Active component precursor compound The active component precursor compound is selected from the group consisting of V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir. A compound of at least one element is used. Since the active component functions as a catalyst, it is appropriately selected according to the purpose.

  Specifically, ammonium metavanadate, vanadyl sulfate, ammonium paratungstate, ammonium metatungstate, tungstic acid, ammonium molybdate, chromium nitrate, chromium acetate, manganese nitrate, manganese acetate, palladium nitrate, iron sulfate, nickel nitrate, Examples thereof include copper nitrate, silver nitrate, yttrium nitrate, cerium nitrate, gold chloride, and iridium chloride.

The content of the active component precursor compound in the composition for a honeycomb extruded body is preferably 0.0006 to 12.8% by weight, more preferably 0.3 to 10% by weight.
If the content of the active component precursor compound is small, the NO _x removal rate may be insufficient when used as a selective reduction type NO _x catalyst.
When the content of the active component precursor compound is large as an oxide, the moldability is lowered, and the compression strength and crack resistance of the resulting honeycomb extruded body are insufficient.

Filler In the present invention, a filler may be included. When such a filler is contained, it is possible to continuously perform extrusion molding and to prepare a molded body having excellent compressive strength and wear resistance.

As the filler, ceramic powder such as cordierite, alumina, zirconia, silicon nitride, silicon carbide, clay mineral can be used.
The filler content in the composition for extruded honeycomb bodies is preferably in the range of 0.6 to 12.8% by weight, more preferably 3 to 10% by weight as the solid content.

  If the content of the filler in the honeycomb extrusion molded body composition is low, the continuous extrusion moldability is lowered, and it may be difficult to mold a long-sized molded body, particularly a long-sized honeycomb molded body. The molding die may be frequently cleaned or replaced, which may reduce productivity and economy. Even if there is too much content of the filler in the composition for shaping | molding bodies, catalyst performance may become inadequate.

Organic additive The composition for a honeycomb extruded body of the present invention may contain an organic additive other than the modifier.

  Examples of the organic additive include carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, crystalline cellulose, polyethylene glycol, polypropylene glycol, polyethylene oxide and the like.

When such an organic additive is contained, an effect of improving the peelability from the molding die, moldability, and the like can be obtained.
The content of the organic additive in the honeycomb extruded body composition may be in the range of 0.03 to 4.3% by weight, more preferably 0.5 to 2% by weight, in the honeycomb extruded body composition. preferable.

  If the content of the organic additive in the honeycomb extrusion molded composition is low, the moldability becomes insufficient, and if it is too much, the pore volume of the resulting molded catalyst becomes large and the compression strength is insufficient. In addition, cracks may occur during the firing of the molded body.

The composition for a composition honeycomb molded body includes a solvent in addition to the above components. The solvent is appropriately selected depending on the purpose of use and the molding method.
Specific examples include volatile solvents such as water, methanol, ethanol, propanol, and methyl ethyl ketone. Specifically, water is preferable.
The total solid content of such a composition for extruded honeycomb bodies is preferably in the range of 60 to 85% by weight, more preferably 65 to 75% by weight.

When the total solid content concentration of the composition for a honeycomb extruded body is too low, the shape retaining property of the molded body before the drying after the extrusion molding is weak and may be deformed.
Even when the total solid content concentration of the composition for a honeycomb extruded body is too large, the slip property when passing through the molding die is small, and the moldability, particularly the continuous moldability may be lowered.

The composition for a honeycomb extruded body according to the present invention can be prepared in the same manner as in the prior art except that the modified titanium oxide fine particle powder for a honeycomb extruded body is used.
For example, in the example of the selective reduction type NOx catalyst, the modified titanium oxide fine particle powder for a honeycomb extrusion molded body, a reinforcing material, an active ingredient precursor compound, water, a filler used as necessary, and an organic additive are included. It can be prepared by mixing, kneading, kneading, etc. so that it may become the range of the above-mentioned predetermined amount.

  Kneading and kneading are preferably performed under heating. The temperature at this time is preferably in the range of about 80 to 140 ° C, more preferably 90 to 130 ° C. By performing kneading and kneading in such a temperature range, it is possible to prepare a honeycomb molded body composition having excellent moldability.

[Molded body]
The honeycomb molded body according to the present invention includes (i) the modified titanium oxide fine particle powder for the honeycomb extruded molded body, (ii) a reinforcing material, and (iii) an active component.

The content of the modified titanium oxide-based fine particle powder for honeycomb extrusion molding in the honeycomb molding is preferably in the range of 55 to 95% by weight, more preferably 70 to 80% by weight.
If the content of the modified titanium oxide fine particles for the honeycomb extruded body in the honeycomb molded body is small, the molding becomes difficult and the catalyst performance, for example, the NOx removal rate of the selective reduction type NOx catalyst becomes insufficient. There is a case.

  Even if the content of the modified titanium oxide fine particle powder for honeycomb extrusion molded body in the honeycomb molded body is too large, the content of other reinforcing materials, fillers, and active ingredient precursors is limited, so the moldability and compression The strength, crack resistance and catalyst performance may be insufficient.

The content of the reinforcing material in the honeycomb molded body is preferably in the range of 3 to 15% by weight, more preferably 3 to 10% by weight as the solid content.
If the content of the reinforcing material in the honeycomb molded body is small, the strength is low, and even if it is increased, the productivity is poor, and the active ingredient that functions as a catalyst decreases.

  The filler content in the honeycomb molded body is preferably in the range of 1 to 15% by weight, more preferably 3 to 10% by weight as the solid content. If the filler content in the honeycomb molded body is small, the strength is low, and if the filler content is too large, the catalyst performance may be insufficient.

  The active component is derived from the precursor and is selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir. At least one elemental metal or metal oxide is included.

Specifically, metals such as V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir, and / or V ₂ O ₅ , WO ₃ , MO ₃ , Cr ₂ O ₃ , MnO ₂ , Mn ₂ O ₃ , Fe ₂ O ₃ , NiO, CuO, Ag ₂ O, AuO, PdO, Y ₂ O ₃ , CeO ₂ , Nd ₂ O ₅ , In ₂ O ₃ And oxides such as IrO and mixtures thereof.

The content of the active ingredient in the honeycomb molded body is preferably in the range of 0.001 to 15% by weight, more preferably 0.3 to 12% by weight as an oxide. If the content of the active component is small, the NO _x removal rate may be insufficient when used as a selective reduction type NO _x catalyst. Even if there is too much content of an active ingredient, the compressive strength and crack resistance of a molded object will become inadequate.

  In the present invention, the use of the modified titanium oxide fine particle powder for a honeycomb extruded body greatly improves the moldability, so that it is suitable as a honeycomb molded body, particularly a thin-walled honeycomb molded body, which has been difficult to mold. Can be used.

  In the present invention, since the above-described composition is used, the moldability is high, and the obtained honeycomb molded body is excellent in strength and wear resistance. A molded product having a large number of pitches can be obtained.

The outer diameter of the honeycomb molded body is preferably in the range of 30 to 400 mm.
Here, the external shape of the honeycomb is not particularly limited, such as a quadrangle, a hexagon, a polygon more than an octagon, a circle, and an ellipse, and can be appropriately selected depending on the application and usage.

  There is no effect of reducing the outer diameter of the honeycomb molded body to less than 30 mm, and when used as a honeycomb type selective reduction type NOx catalyst, only the number of production increases and it is not economical. There is no effect of increasing the outer diameter of the honeycomb molded body beyond 400 mm, and therefore there is no extrusion molding apparatus.

The length of the honeycomb molded body is preferably in the range of 3 to 1500 mm, more preferably 50 to 1300 mm.
When the length of the honeycomb molded body is less than 3 mm, it is difficult to manufacture.

When the length of the honeycomb molded body exceeds 1500 mm, the usage is small.
The pitch of the honeycomb formed body is preferably in the range of 6 to 500 cpsi, more preferably 15 to 200 cpsi.

When the pitch of the honeycomb formed body is less than 6 cpsi, the mesh opening is large and the shape retaining property is weak, which makes it difficult to manufacture.
When the pitch of the honeycomb molded body exceeds 500 cpsi, pressure loss becomes large at the time of molding, and molding may be difficult.

The thickness of the honeycomb molded body is preferably in the range of 0.1 to 1.5 mm, more preferably 0.1 to 0.3 mm.
A honeycomb molded body having a thickness of less than 0.1 mm is difficult to obtain even if the above-described modified titanium oxide-based fine particles are used.

When the thickness of the honeycomb formed body exceeds 1.5 mm, it can be formed by a conventionally known method without using the modified titanium oxide-based fine particles.
In the present invention, the thickness of the honeycomb molded body is particularly preferably in the range of 0.1 to 0.3 mm.

According to the present invention, it can be suitably used as a honeycomb that is thin and lightweight, has a large number of pitches, is excellent in strength, wear resistance, and compressive strength, is lightweight, and is economical.
The molded body according to the present invention can be prepared by a conventionally known method using the aforementioned molded body composition.

  The shape of the molded body can be obtained by obtaining a molded body having a conventionally known shape such as pellets, beads, rings, and honeycombs, and can be prepared by appropriately selecting a mold for extrusion molding at the time of molding.

  In the present invention, it is possible to obtain a thin-walled honeycomb molded body particularly excellent in strength and wear resistance, but at this time, if a vacuum extrusion molding machine is used, there is no crack, and the strength and wear resistance are more excellent. A thin honeycomb molded body can be obtained stably.

[Example]
Hereinafter, although an example explains, the present invention is not limited by these examples.
[Example 1]
Preparation of Modified Titanium Oxide Fine Particle Powder (1) for Honeycomb Extruded Molded Body 78.3 kg of metatitanic acid slurry (manufactured by Ishihara Sangyo Co., Ltd.) was charged into a stirring tank equipped with a heating reflux, and 2.82 kg of ammonium paratungstate was further added. After adding and mixing, 30.5 kg of 15% by weight ammonia water was added to adjust the pH to 9.5, and the mixture was aged with stirring at 95 ° C. for 1 hour. Then, this mixed slurry was cooled to 40 ° C., then filtered, and washed with water to prepare a washed cake having a solid content concentration (TiO ₂ · WO ₃ ) of 49% by weight. The washed cake contained 3.0 wt% SO ₄ and 0.03 wt% Na ₂ O on a dry basis.

Next, the washed cake was dried at 110 ° C. for 20 hours, further calcined at 550 ° C. for 5 hours, and then pulverized by using a pulverizer to obtain a composite oxide of titanium oxide and tungsten oxide (TiO ₂ —WO ₃ , weight ratio TiO 2). ₂ / WO ₃ = 90/10) to obtain a titanium oxide fine particle powder (1).

The average particle size of the titanium oxide fine particle powder (1) was measured by the following method, and the results are shown in the table. The composition (preparation standard) is shown in the table.
The average particle size and particle size distribution were measured using a laser diffraction / scattering particle size distribution measuring apparatus (Horiba, Ltd .: LA-300). The conditions at this time were dispersed in an aqueous dispersion medium, irradiated with ultrasonic waves for 3 minutes, and the concentration was adjusted so that the laser light transmittance was 85%.

Further, the moisture desorption rate (W%) was measured, and the results are shown in the table, and the weight loss curve is shown in FIG. 1, and the endothermic curve is shown in FIG. 1).
Next, 23.5 kg of the obtained titanium oxide-based fine particle powder (1) and 23.5 g of stearic acid as a modifier were mixed and mixed with a kneader for 20 minutes while heating to 120 ° C. to form a honeycomb extruded body. Modified titanium oxide fine particle powder (1) was prepared.

The average particle size and moisture desorption rate (W _ST %) of the modified titanium oxide fine particle powder (1) for honeycomb extrusion molding were measured. The results are shown in the table, and the weight loss curve is shown in FIG. 2 shows an endothermic curve.

At this time, the content of the modifier in the modified titanium oxide fine particle powder (1) for the honeycomb extruded body is 0.1% by weight based on the amount used.
The average particle size was measured in the same manner as the titanium oxide fine particle powder (1).

Preparation of Composition for Honeycomb Extrudate (1) 1. Modified titanium oxide fine particle powder for honeycomb extrudate (1) 23.5 kg, monoethanolamine 0.375 kg and ammonium metavanadate as V ₂ O ₅ . A solution in which 28 kg was dissolved was added, then aqueous ammonia and water were added to adjust the pH of the mixed slurry to 9, and the mixture was kneaded for 0.5 hours while heating to 120 ° C. with a kneader. Thereafter, glass fiber (made by Owens Corning Co., Ltd .: chopped strand 03 DE, length 3 mm, fiber diameter 5 μm) 1.25 kg as a reinforcing material, acid clay 1.25 kg as a filler, and polyethylene oxide 0. 5 kg was added and the mixture was further kneaded for 1.5 hours to prepare a honeycomb extruded body composition (1).
The contents (usage standard) of each component in the composition for honeycomb extruded body (1) are shown in the table.
The moisture content was measured with an infrared moisture meter (Ketto Chemical Laboratory: FD-610).

Preparation of Molded Body (1) The honeycomb structure (1) was prepared by extruding the honeycomb extruded body composition (1) into a honeycomb shape with a vacuum extruder.
At this time, moldability was evaluated according to the following criteria, and the results are shown in the table.

<Moldability>
The case where the flow from the die surface during extrusion molding was stable and no defect occurred inside the honeycomb catalyst during extrusion molding for 10 minutes continuously was marked as と し た. In addition, the initial flow was stable, but a case where a defect occurred inside the honeycomb catalyst during the continuous 10-minute molding was marked as ◯. On the other hand, when the initial flow was unstable and a defect was generated inside the honeycomb catalyst, Δ was given. The thing which did not come out from a die surface was set as x.

Next, the honeycomb structure (1) was dried at 60 ° C. for 48 hours and then fired at 530 ° C. for 3 hours to prepare a honeycomb structure molded body (1).
Each dimension of the molded body (1) was measured, and the results are shown in the table. In addition, the content (usage standard) of each component in the molded body (1) is shown in the table. (The weight ratio of TiO ₂ / WO ₃ / V ₂ O ₅ / GF / acid clay is 77.4 / 8.6 / 4/5/5.)
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (1) were measured by the following methods, and the results are shown in the table.

<Specific surface area>
The specific surface area of the honeycomb-shaped exhaust gas treatment catalyst is determined by a specific surface area measuring device based on the BET method using a mixed gas of 30% nitrogen and 70% helium as an adsorbed gas.

<Pore volume>
The pore volume was measured with a mercury intrusion method pore distribution measuring device (manufactured by QANTA CROME: PM-33GT1LP). The pressure range is 32 to 32200 psi.

<Compressive strength>
Using a compressive strength machine (manufactured by Tokyo Test Machine Manufacturing Co., Ltd .: model AL / B30P), a sample obtained by cutting the molded body (1) into a cube or a rectangular parallelepiped, and the direction through which the honeycomb holes penetrate and perpendicular to this direction (hereinafter, A compressive load is applied at a constant speed to the specimen (also referred to simply as “orthogonal direction”), the maximum load (N) until the sample is broken is read, and the compressive strength is obtained from the following equation (4).
Compressive strength: (N / cm ² ) = W (N) / {a (cm) × c (cm)} (4)
Here, a (cm) and c (cm) indicate the dimensions of the two sides of the pressing surface of the sample. W (N) indicates the maximum load until the sample is completely destroyed by applying a load gradually.

<Denitration catalyst performance test>
The molded body (1) was cut into a honeycomb sample having 5 × 5 honeycomb holes and a length of 200 mm to obtain a test sample, and this test sample was filled in a flow reactor. A model gas having the following composition was passed through this flow reactor, and the denitration rate was measured. The denitration rate of nitrogen oxides (NO _x ) in the gas before and after contact with the catalyst was determined by the following equation (5). At this time, the concentration of NO _x was measured with a chemiluminescent nitrogen oxide analyzer.
Denitration rate (%) = {(NO _{x in} non-contact gas (ppm by mass) −NO _x in gas after contact (mass ppm)) / NO _{x in} non-contact gas (mass ppm)} × 100・ (5)
Test conditions Catalyst shape: Honeycomb pore number 5 × 5, length 200mm
Reaction temperature: 350 ° C., SV = 40,000 hr −1
Model gas composition: NOx = 100 mass ppm, NH ₃ = 100 mass ppm, O ₂ = 7 wt%, H ₂ O = 10 wt%, N ₂ = balance

[Example 2]
Preparation of Modified Titanium Oxide Fine Particle Powder (2) for Honeycomb Extruded Body Modified Example of Modified Titanium Oxide Fine Particle for Honeycomb Extruded Body Except that 4.7 g of stearic acid was used as a modifier. Powder (2) was prepared.
The average particle diameter and moisture desorption rate (W _ST %) of the modified titanium oxide fine particle powder (2) for honeycomb extruded body were measured, and the results are shown in the table. The content of the modifier is shown in the table.

Preparation of Composition for Extruded Honeycomb (2) Composition for Extruded Honeycomb (2) in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (2) for honeycomb extruded is used. Was prepared.
The content of each component in the composition for honeycomb extruded body (2) is shown in the table.

Preparation of molded body (2) A molded body (2) was prepared in the same manner as in Example 1 except that the composition for extruded honeycomb body (2) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (2) was measured, and the results are shown in the table. In addition, the content of each component in the molded body (2) is shown in the table.
Further, the specific surface area, pore volume, compressive strength, and denitration catalyst performance of the molded body (2) were measured, and the results are shown in the table.

[Example 3]
Preparation of Modified Titanium Oxide Fine Particle Powder (3) for Honeycomb Extrusion Molded Modified Titanium Oxide Fine Particle for Honeycomb Extrusion Molded Example 1 except that 11.8 g of stearic acid was used as a modifier. Powder (3) was prepared.
The average particle diameter and moisture desorption rate (W _ST %) of the modified titanium oxide fine particle powder (3) for honeycomb extruded body were measured, and the results are shown in the table. The content of the modifier is shown in the table.

Preparation of Composition for Extruded Honeycomb (3) Composition for Honeycomb Extruded Body (3) was the same as in Example 1 except that modified titanium oxide fine particle powder (3) for honeycomb extruded body was used. Was prepared.
The content of each component in the composition for honeycomb extruded body (3) is shown in the table.

Preparation of molded body (3) A molded body (3) was prepared in the same manner as in Example 1 except that the composition for extruded honeycomb body (3) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (3) was measured, and the results are shown in the table. Further, the content of each component in the molded body (3) is shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (3) were measured, and the results are shown in the table.

[Example 4]
Preparation of Modified Titanium Oxide Fine Particle Powder (4) for Honeycomb Extrusion Molded Modified Titanium Oxide Fine Particle for Honeycomb Extrusion Molded Example 1 except that 47.0 g of stearic acid was used as a modifier. Powder (4) was prepared.
The average particle diameter and moisture desorption rate (W _ST %) of the modified titanium oxide fine particle powder (4) for honeycomb extruded body were measured, and the results are shown in the table. The content of the modifier is shown in the table.

Preparation of Composition for Extruded Honeycomb (4) Composition for Extruded Honeycomb (4) in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (4) for extruded honeycomb is used. Was prepared.
The content of each component in the composition for honeycomb extruded body (4) is shown in the table.

Preparation of molded body (4) A molded body (4) was prepared in the same manner as in Example 1 except that the composition for extruded honeycomb body (4) was used.
At this time, while evaluating moldability, each dimension of the obtained molded object (4) was measured, and a result is shown to a table | surface. Further, the content of each component in the molded body (4) is shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (4) were measured, and the results are shown in the table.

[Example 5]
Preparation of Modified Titanium Oxide Fine Particle Powder (5) for Honeycomb Extrusion Molded Modified Titanium Oxide Fine Particle for Honeycomb Extrusion Molded Example 1 except that 117.5 g of stearic acid was used as a modifier. Powder (5) was prepared.
The average particle diameter and moisture desorption rate (W _ST %) of the modified titanium oxide fine particle powder (5) for honeycomb extruded body were measured, and the results are shown in the table. The content of the modifier is shown in the table.

Preparation of composition for honeycomb extruded body (5) A composition for molded body (5) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (5) for honeycomb extruded body was used. did.
The content of each component in the composition for a honeycomb extruded body (5) is shown in the table.

Preparation of molded body (5) A molded body (5) was prepared in the same manner as in Example 1, except that the composition for extruded honeycomb body (5) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (5) was measured, and the results are shown in the table. Further, the content of each component in the molded body (5) is shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (5) were measured, and the results are shown in the table.

[Example 6]
Preparation of Modified Titanium Oxide Fine Particle Powder (6) for Honeycomb Extrusion Molded Example 1 Modified titanium oxide fine particle powder for honeycomb extrudate ( except for the use of 188 g of stearic acid as a modifier ). 6) was prepared.
The average particle diameter and moisture desorption rate (W _ST %) of the modified titanium oxide fine particle powder (6) for honeycomb extrusion molding were measured. The results are shown in the table, and the weight loss curve is shown in FIG. Shows the endothermic curve.
Moreover, a composition (usage amount basis) is shown in the table.

Preparation of honeycomb extruded body composition (6) Preparation of honeycomb extruded body composition (6) in Example 1 except that the modified titanium oxide fine particle powder (6) for honeycomb extruded body was used. Was prepared.
The contents (usage basis) of each component in the composition for extruded honeycomb body (6) are shown in the table.

Preparation of molded body (6) A molded body (6) was prepared in the same manner as in Example 1 except that the composition for extruded honeycomb body (6) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (6) was measured, and the results are shown in the table. In addition, the content (usage standard) of each component in the molded body (6) is shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (6) were measured, and the results are shown in the table.

[Example 7]
Preparation of Modified Titanium Oxide Fine Particle Powder (7) for Honeycomb Extrusion Molded Titanium oxide fine particle powder (7) was obtained in the same manner as in Example 1. In a thermostatic bath adjusted to 40 ± 5 ° C. after mixing for 20 minutes with 23.5 kg of the resulting titanium oxide fine particle powder (7) and 100 ml of a solution of 23.5 g of stearic acid dissolved in ethanol as a modifier. And dried to prepare a modified titanium oxide fine particle powder (7) for a honeycomb extruded body.
The average particle diameter and moisture desorption rate (W _ST %) of the modified titanium oxide fine particle powder (7) for honeycomb extruded body were measured, and the results are shown in the table. The content of the modifier is shown in the table.

Preparation of honeycomb extruded body composition (7) Preparation of honeycomb extruded body composition (7) in Example 1 except that the modified titanium oxide fine particle powder (7) for honeycomb extruded body was used. Was prepared.
The content of each component in the composition for a honeycomb extruded body (7) is shown in the table.

Preparation of molded body (7) A molded body (7) was prepared in the same manner as in Example 1 except that the composition for extruded honeycomb body (7) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (7) was measured, and the results are shown in the table. Further, the content of each component in the molded body (7) is shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (7) were measured, and the results are shown in the table.

[Example 8]
Preparation of Modified Titanium Oxide Fine Particle Powder (8) for Honeycomb Extruded Body Modified Example of Modified Titanium Oxide Fine Particle Powder for Honeycomb Extruded Body in Example 1 except that 23.5 g of lauric acid was used as a modifier. (8) was prepared.
The average particle diameter and moisture desorption rate (W _ST %) of the modified titanium oxide fine particle powder (8) for honeycomb extruded body were measured, and the results are shown in the table. The content of the modifier is shown in the table.

Preparation of composition for honeycomb extruded body (8) Preparation of honeycomb extruded body composition (8) in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (8) for honeycomb extruded body was used. Was prepared.
The content of each component in the composition for honeycomb extruded body (8) is shown in the table.

Preparation of molded body (8) A molded body (8) was prepared in the same manner as in Example 1 except that the composition for honeycomb extruded body (8) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (8) was measured, and the results are shown in the table. In addition, the content of each component in the molded body (8) is shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (8) were measured, and the results are shown in the table.

[Example 9]
Preparation of modified titanium oxide fine particle powder (9) for honeycomb extruded body Modified titanium oxide fine particle powder for honeycomb extruded body was the same as in Example 1 except that 23.5 g of myristic acid was used as a modifier. (9) was prepared.
The average particle diameter and moisture desorption rate (W _ST %) of the modified titanium oxide fine particle powder (9) for honeycomb extruded body were measured, and the results are shown in the table. The content of the modifier is shown in the table.

Preparation of Composition for Extruded Honeycomb (9) Composition for Extruded Honeycomb (9) in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (9) for honeycomb extruded is used. Was prepared.
The content of each component in the composition for honeycomb extruded body (9) is shown in the table.

Preparation of molded body (9) A molded body (9) was prepared in the same manner as in Example 1, except that the composition for honeycomb extruded body (9) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (9) was measured, and the results are shown in the table. Further, the content of each component in the molded body (9) is shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (9) were measured, and the results are shown in the table.

[Example 10]
Preparation of Modified Titanium Oxide Fine Particle Powder (10) for Honeycomb Extrusion Molded Example 1 Modified titanium oxide fine particle powder for honeycomb extruded model, except that 23.5 g of palmitic acid was used as a modifier. (10) was prepared.
The average particle diameter and moisture desorption rate (W _ST %) of the modified titanium oxide fine particle powder (10) for honeycomb extrusion molding were measured, and the results are shown in the table. The content of the modifier is shown in the table.

Preparation of Composition for Extruded Honeycomb (10) Composition for Extruded Honeycomb (10) in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (10) for honeycomb extruded is used. Was prepared.
The content of each component in the composition for honeycomb extruded body (10) is shown in the table.

Preparation of molded body (10) A molded body (10) was prepared in the same manner as in Example 1, except that the composition for extruded honeycomb body (10) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (10) was measured, and the results are shown in the table. In addition, the content of each component in the molded body (10) is shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (10) were measured, and the results are shown in the table.

[Example 11]
Preparation of Modified Titanium Oxide Fine Particle Powder (11) for Honeycomb Extruded Body Modified Example of Modified Titanium Oxide Fine Particle Powder for Honeycomb Extruded Body Except that 23.5 g of oleic acid was used as a modifier. (11) was prepared.
The average particle diameter and moisture desorption rate (W _ST %) of the modified titanium oxide fine particle powder (11) for honeycomb extrusion molding were measured, and the results are shown in the table. The content of the modifier is shown in the table.

Preparation of composition for honeycomb extruded body (11) A composition for molded body (11) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (11) for honeycomb extruded body was used. did. The content of each component in the composition for honeycomb extruded body (11) is shown in the table.

Preparation of molded body (11) A molded body (11) was prepared in the same manner as in Example 1 except that the composition for extruded honeycomb body (11) was used.
At this time, the moldability was evaluated, the dimensions of the obtained molded body (11) were measured, and the results are shown in the table. Further, the content of each component in the molded body (11) is shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (11) were measured, and the results are shown in the table.

[Example 12]
Preparation of Modified Titanium Oxide Fine Particle Powder (12) for Honeycomb Extrusion Molded Modified Titanium Oxide Fine Particle for Honeycomb Extrusion Molded Example 1 except that 23.5 g of stearic acid monoglyceride was used as a modifier. Powder (12) was prepared.
The average particle diameter and moisture desorption rate (W _ST %) of the modified titanium oxide fine particle powder (12) for the honeycomb extruded body were measured, and the results are shown in the table. The content of the modifier is shown in the table.

Preparation of honeycomb extruded body composition (12) Preparation of honeycomb extruded body composition (12) in Example 1 except that the modified titanium oxide fine particle powder (12) for honeycomb extruded body was used. Was prepared.
The content of each component in the composition for honeycomb extruded body (12) is shown in the table.

Preparation of molded body (12) A molded body (12) was prepared in the same manner as in Example 1, except that the composition for extruded honeycomb body (12) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (12) was measured, and the results are shown in the table. Further, the content of each component in the molded body (12) is shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (12) were measured, and the results are shown in the table.

[Example 13]
Preparation of Modified Titanium Oxide Fine Particle Powder (13) for Honeycomb Extruded Molded Body 78.3 kg of metatitanic acid slurry (manufactured by Ishihara Sangyo Co., Ltd.) was charged into a stirring tank equipped with a heating reflux, and 1.97 kg of ammonium paratungstate was further added. After adding 18.8 kg of an acidic silicic acid solution having a SiO ₂ concentration of 4.0 wt% prepared by dealkalizing the water glass solution with a cation exchange resin, 30.5 kg of ammonia water having a concentration of 15 wt% was mixed. Was added to adjust the pH to 9.5, and the mixture was further aged with stirring at 95 ° C. for 1 hour. Then, this mixed slurry was cooled to 40 ° C., then filtered, and washed with water to prepare a washing cake having a solid content concentration (TiO ₂ · WO ₃ · SiO ₂ ) of 50% by weight. The washed cake contained 3.0 wt% SO ₄ and 0.03 wt% Na ₂ O on a dry basis.

Next, the washed cake was dried at 110 ° C. for 20 hours, and further calcined at 550 ° C. for 5 hours to be a composite oxide of titanium oxide, tungsten oxide and silica (TiO ₂ —WO ₃ —SiO ₂ , weight ratio: TiO ₂ / A titanium oxide fine particle powder (13) composed of WO ₃ / SiO ₂ = 90/7/3) was obtained.

The average particle diameter of the titanium oxide fine particle powder (13) was measured, and the results are shown in the table. The composition (preparation standard) is shown in the table. Further, the moisture desorption rate (W%) was measured, and the results are shown in the table.
Hereinafter, a modified titanium oxide fine particle powder (13) for a honeycomb extruded body was prepared in the same manner except that the titanium oxide fine particle powder (13) was used in Example 1.
The average particle diameter and moisture desorption rate (W _ST %) of the modified titanium oxide fine particle powder (13) for honeycomb extruded body were measured, and the results are shown in the table. The content of the modifier is shown in the table.

Preparation of composition for honeycomb extruded body (13) In Example 1, a composition for molded body (13) was prepared in the same manner except that the modified titanium oxide fine particle powder (13) for honeycomb extruded body was used. did.
The content of each component in the composition for honeycomb extruded body (13) is shown in the table.

Preparation of molded body (13) A molded body (13) was prepared in the same manner as in Example 1 except that the composition for honeycomb extruded body (13) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (13) was measured, and the results are shown in the table. In addition, the content of each component in the molded body (13) is shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (13) were measured, and the results are shown in the table.

[Comparative Example 1]
Preparation of Titanium Oxide Fine Particle Powder (R1) for Honeycomb Extrusion Molded Titanium oxide fine particle powder (R1) for honeycomb extrudate was prepared in the same manner as in Example 1 except that no modifier was used.
The average particle diameter of the titanium oxide-based fine particle powder (R1) for the molded body for the honeycomb extruded body was measured, and the results are shown in the table.

Preparation of composition for honeycomb extruded body (R1) In Example 1, a composition for honeycomb extruded body (R1) was prepared in the same manner as in Example 1 except that the titanium oxide fine particle powder (R1) for honeycomb extruded body was used. did.
The content of each component in the honeycomb extruded body composition (R1) is shown in the table.

Preparation of molded body (R1) Extrusion molding was started in the same manner as in Example 1 except that the composition for extruded honeycomb body (R1) was used, but it was soon clogged and could not be molded.

[Comparative Example 2]
Preparation of Titanium Oxide Fine Particle Powder (R2) for Honeycomb Extruded Body A titanium oxide fine particle powder (R2) for a honeycomb extruded body was prepared in the same manner as in Example 13 except that no modifier was used.
The average particle diameter of the titanium oxide fine particles (R2) for honeycomb extrusion-molded bodies was measured, and the results are shown in the table.

Preparation of composition for honeycomb extruded body (R2) A composition for molded body (R2) was prepared in the same manner as in Example 1 except that the titanium oxide fine particle powder (R2) for honeycomb extruded body was used.
The content of each component in the honeycomb extruded body composition (R2) is shown in the table.

Preparation of molded body (R2) Extrusion molding was started in the same manner as in Example 1 except that the composition for honeycomb extruded body (R2) was used, but it was soon clogged and could not be molded.

[Comparative Example 3]
Preparation of composition for honeycomb extruded body (R3) 23.5 kg of titanium oxide fine particle powder (1) prepared in the same manner as in Example 1, 0.375 kg of monoethanolamine and V ₂ O ₅ of ammonium metavanadate as V ₂ O ₅ A solution in which 1.28 kg was dissolved was added, then 23.5 g of stearic acid was added, then ammonia water and water were added to adjust the pH of the mixed slurry to 9, and kneaded while heating to 110 ° C. with a kneader.

Then, glass fiber (made by Owens Corning Co., Ltd .: chopped strand 03 DE, length 3 mm, fiber diameter 5 μm) 1.25 kg as reinforcing material, 1.25 kg of acid clay as (filler), and polyethylene oxide as organic additive 0.5 kg was added and further kneaded to prepare a honeycomb extruded body composition (R3).
The content of each component in the composition for honeycomb extruded body (R3) is shown in the table.

Preparation of molded body (R3) A molded body (R3) was prepared in the same manner as in Example 1 except that the composition for extruded honeycomb body (R3) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (R3) was measured, and the results are shown in the table. Further, the content of each component in the molded body (R3) is shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (R3) were measured, and the results are shown in the table.

[Comparative Example 4]
Preparation of Titanium Oxide Fine Particle Powder (R4) for Honeycomb Extrusion Molded Titanium oxide fine particle powder (R4) for molded body was prepared in the same manner as in Example 1 except that 1175 g of stearic acid was used as a modifier. The average particle diameter and moisture desorption rate (W _ST %) of the titanium oxide fine particle powder (R4) for molded bodies were measured. The results are shown in the table, the weight loss curve is shown in FIG. 1, and the endothermic curve is shown in FIG. Show. The content of the modifier is shown in the table.

Preparation of honeycomb extruded body composition (R4) A honeycomb extruded body composition (R4) was prepared in the same manner as in Example 1 except that the titanium oxide fine particle powder (R4) for honeycomb extruded body was used. did.
The content of each component in the composition for extruded honeycomb bodies (R4) is shown in the table.

Preparation of molded body (R4) A molded body (R4) was prepared in the same manner as in Example 1 except that the composition for extruded honeycomb body (R4) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (R4) was measured, and the results are shown in the table. In addition, the content of each component in the molded body (R4) is shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (R4) were measured, and the results are shown in the table.

[Comparative Example 5]
Preparation of Titanium Oxide Fine Particle Powder (R5) for Honeycomb Extrusion Molded Titanium oxide fine particle powder (R5) for honeycomb extrudate in the same manner as in Example 1 except that 1.2 g of stearic acid was used as a modifier. Was prepared.
The average particle diameter and moisture desorption rate (W _ST %) of the titanium oxide fine particle powder (R5) for honeycomb extrusion molding were measured, and the results are shown in the table. The content of the modifier is shown in the table.

Preparation of composition for honeycomb extruded body (R5) In Example 1, a composition for honeycomb extruded body (R5) was prepared in the same manner as in Example 1 except that the titanium oxide fine particle powder (R5) for honeycomb extruded body was used. did.
The content of each component in the composition for honeycomb extruded body (R5) is shown in the table.

Preparation of molded body (R5) A molded body (R5) was prepared in the same manner as in Example 1 except that the composition for extruded honeycomb body (R5) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (R5) was measured, and the results are shown in the table. The contents of each component in the molded body (R5) are shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (R5) were measured, and the results are shown in the table.

[Example 14]
Preparation of Modified Titanium Oxide Fine Particle Powder (14) for Extruded Honeycomb Molded Body 87.0 kg of metatitanic acid slurry (manufactured by Ishihara Sangyo Co., Ltd.) was charged into a stirring tank equipped with a heating reflux, and ammonia water having a concentration of 15% by weight. The pH was adjusted to 9.5 by adding 5 kg, and further aged with stirring at 95 ° C. for 1 hour. Thereafter, the mixed slurry was cooled to 40 ° C., then filtered and washed with water to prepare a washing cake having a solid content concentration (TiO ₂ ) of 49% by weight. The washed cake contained 3.0 wt% SO ₄ and 0.03 wt% Na ₂ O on a dry basis.

Next, the washed cake was dried at 110 ° C. for 20 hours, and further calcined at 540 ° C. for 5 hours to obtain titanium oxide fine particle powder (14) made of titanium oxide oxide (TiO ₂ ). The average particle diameter of the titanium oxide fine particle powder (14) was measured, and the results are shown in the table. The composition (preparation standard) is shown in the table. Further, the moisture desorption rate (W%) was measured, and the results are shown in the table.

Hereinafter, a modified titanium oxide-based fine particle powder (14) for a honeycomb extruded body was prepared in the same manner except that the titanium oxide-based fine particle powder (14) was used in Example 1. The average particle diameter and moisture desorption rate (W _ST %) of the modified titanium oxide fine particle powder (14) for honeycomb extruded molded body were measured, and the results are shown in the table. The content of the modifier is shown in the table.

Preparation of honeycomb extruded body composition (14) Preparation of honeycomb extruded body composition (14) in Example 1 except that the modified titanium oxide fine particle powder (14) for honeycomb extruded body was used. Was prepared. The content of each component in the composition for a honeycomb extruded body (14) is shown in the table.

Preparation of molded body (14) A molded body (14) was prepared in the same manner as in Example 1 except that the composition for honeycomb extruded body (14) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (14) was measured, and the results are shown in the table. In addition, the content of each component in the molded body (14) is shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (14) were measured, and the results are shown in the table.

[Comparative Example 6]
Preparation of Titanium Oxide Fine Particle Powder (R6) for Honeycomb Extruded Body A titanium oxide fine particle powder (R6) for a honeycomb extruded body was prepared in the same manner as in Example 14 except that no modifier was used. The average particle diameter of the titanium oxide fine particle powder (R6) for honeycomb extrusion-molded bodies was measured, and the results are shown in the table.

Preparation of composition for honeycomb extruded body (R6) A composition for honeycomb extruded body (R6) was prepared in the same manner as in Example 1 except that the titanium oxide fine particle powder (R6) for honeycomb extruded body was used. did. The content of each component in the honeycomb extruded body composition (R6) is shown in the table.

Preparation of molded body (R6) A molded body (R6) was prepared in the same manner as in Example 1 except that the composition for extruded honeycomb body (R6) was used.
At this time, the moldability was evaluated, each dimension of the obtained molded body (R6) was measured, and the results are shown in the table. The contents of each component in the molded body (R6) are shown in the table.
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (R6) were measured, and the results are shown in the table.

Claims (14)

  The modified honeycomb extruded body is composed of titanium oxide-based fine particles, and the titanium oxide-based fine particles are modified with a modifier comprising a fatty acid and / or a fatty acid ester, and have an average particle size of 0.03 to 2.5 μm. Titanium oxide fine particle powder. The modified oxidation for a honeycomb extruded body according to claim 1, wherein the fatty acid is a saturated fatty acid represented by the following formula (1) and / or an unsaturated fatty acid represented by the following formula (2): Titanium fine particle powder.
_{C n H 2n + 1 -CO 2} H ················ (1)
(Where n is an integer from 4 to 23)
_{C n 'H 2n'-2m +} 1 -CO 2 H ······ (2)
(Where n ′ is an integer from 13 to 23, m is an integer from 1 to 6 representing the number of double bonds)   2. The modified titanium oxide fine particle powder for a honeycomb extruded body according to claim 1, wherein an average particle size of the titanium oxide fine particles is in a range of 0.03 to 2.0 μm. The titanium oxide fine particles contain at least one oxide selected from tungsten oxide (WO ₃ ), molybdenum oxide (MoO ₃ ), silicon oxide (SiO ₂ ), and zirconium oxide (ZrO ₂ ) together with titanium oxide. The modified titanium oxide fine particle powder for a honeycomb extruded body according to claim 1, wherein the content in the titanium fine particle is in the range of 0.5 to 40% by weight as an oxide. Weight reduction rate (W (%)) when the temperature was raised from 30 ° C. to 100 ° C. in the differential thermal analysis of the titanium oxide fine particles adjusted to 15% by weight, and the honeycomb adjusted to 15% by weight weight loss ratio of the weight loss rate when the temperature was raised from 30 ° C. to 100 ° C. in differential thermal analysis of the extrusion producing molded modified titanium oxide-based fine particles _{(W ST (%)) (} W ST (%)) / (W (%)) is in the range of 1.02-1.20, modified titanium oxide-based fine particle powder for a honeycomb extruded body according to any one of claims 1 to 4. (i) Modified titanium oxide fine particle powder for honeycomb extruded body according to any one of claims 1 to 5,
(ii) reinforcement,
(iii) a composition containing an active ingredient precursor compound,
In the composition, the content of (i) the modified titanium oxide-based fine particle powder for honeycomb extrusion molding is in the range of 33 to 80.8% by weight, and (ii) the content of the reinforcing material is 1.8 to In the range of 12.8 wt%, (iii) the content of the active ingredient precursor compound is in the range of 0.0006 to 12.8 wt% in terms of oxide,
A composition for extruded honeycomb bodies, wherein the total solid content is in the range of 60 to 85% by weight.   The composition for a honeycomb extruded body according to claim 6, further comprising a filler, wherein the content of the filler is in the range of 0.6 to 12.8% by weight as a solid content.   The composition for extruded honeycomb bodies according to claim 6, further comprising an organic additive other than the modifier in a range of 0.03 to 4.5% by weight.   The active component precursor compound is at least one element selected from the group consisting of V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir. The composition for extruded honeycomb bodies according to claim 6, wherein the composition is a compound of (i) Modified titanium oxide fine particle powder for honeycomb extruded body according to any one of claims 1 to 5,
(ii) reinforcement,
(iii) including active ingredients
(i) The content of the modified titanium oxide-based fine particle powder for honeycomb extrusion molding is in the range of 55 to 95% by weight, (ii) the content of the reinforcing material is in the range of 3 to 15% by weight, ) A honeycomb molded body characterized in that the content of the active ingredient is in the range of 0.001 to 15% by weight as an oxide.   The honeycomb molded body according to claim 10, further comprising a filler, wherein the filler content is in the range of 1 to 15 wt%.   The outer diameter of the molded body is in the range of 30 to 400 mm, the length is in the range of 3 to 1500 mm, the pitch is in the range of 6 to 500 cpsi, and the wall thickness is in the range of 0.1 to 1.5 mm. The honeycomb molded body according to claim 10 or 11, wherein   The active component is a metal or metal oxide of at least one element selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir The honeycomb formed body according to any one of claims 10 to 12, wherein   The honeycomb molded body according to claim 12, wherein the thickness is in a range of 0.1 to 0.3 mm.

Images