TW200836828A - Catalyst for exhaust gas treatment and exhaust gas treatment method - Google Patents

Abstract

This invention provides a waste gas treating catalyst which possessing sufficient mechanical strength and catalytic activity and also light weight. Since the waste gas treating catalyst is light weight, so less charge is need for construct the waste gas treating equipment, and decreased the cost of manufacturing the equipment. This invention relates to a kind of waste gas treating catalyst. The catalyst is made by carrying metal composition on Ti - Si compound oxide particles and then molding to a honey-comb shape. The Ti - Si compound oxide particles having the average particle size of 12 to 50μm, which is determined by laser diffraction method after the particle is irradiated by ultrasonic wave of 46 to 48kHz, 34 to 36W for 55 to 65 seconds. The density of the catalyst of the present invention is 0.7 to 1.8g/cm<SP>3</SP>.

Description

200836828 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a catalyst for exhaust gas treatment. More specifically, it relates to a lightweight catalyst for exhaust gas treatment and an exhaust gas treatment method using the catalyst. [Prior Art] There are many catalysts for exhaust gas treatment that decompose harmful substances such as nitrogen oxides (NOx) and organic halogen compounds such as dioxin (dioxine, dioxins) in the exhaust gas to make them harmless. Catalyst proposed. In the catalysts used in the related art, the catalyst density is as follows: JP-A-8-131829 discloses that silver or silver oxide is supported on a bulk density and a true density measured by a mercury intrusion method. (true density) alumina-titanium oxide carriers each of 0.60 g/cc or less and 1.80 g/cc or less, which removes nitrogen oxides in the exhaust gas by hydrogen in an oxygen excess environment. Nitrogen catalyst. JP-A-2001-70803 discloses that a noble metal is supported on a honeycomb structure having a bulk density of 0.5 to 1.2 g/cc, and the catalyst for exhaust gas purification of carbon monoxide, hydrocarbons and nitrogen oxides in the exhaust gas of an internal combustion engine can be simultaneously purified. JP-A-2001-129406 discloses a low-temperature denitration catalyst composed of a modified manganese oxide having a specific gravity of 0.1 to 0.7 ml/g. JP-A-2001-129428 discloses a specific gravity of 26.26g/cm3 6 200836828. The following study of the Honeycomb Hive will carry a 20-2-370032 Shanghai publication, and the silver and tin will be carried on the real 2 Reporting σ 己, can be purified to thin air;: transport media. Special opening 2002_5δ963: The exhaust gas treatment agent of the gas turbine exhaust gas is about the same as the exhaust gas treatment agent. Please have a specific gravity of 0.1 to 〇.3. [Invention] The exhaust gas treatment catalyst, the light-duty exhaust gas treatment device, can obtain (4) reduced simplification and reinforcement, and can reduce the thickness of the steel plate. It is easy to load and transport: 2. The manufacturing cost of the two devices; (8) The amount of raw materials required for the media is small, and the manufacturing cost of the source media can be reduced. A catalyst for exhaust gas treatment, and an exhaust gas treatment method using the catalyst. The content of the present invention is as follows: (1) A catalyst for exhaust gas treatment characterized by containing a component and having a density of OH.Sg/cy. (2) The catalyst for exhaust gas treatment according to (1) above, wherein the component contains a compound selected from the group consisting of titanium and a mixture of materials.穣7^ (3) The catalyst for exhaust gas treatment according to (1) or (2) above, wherein the pore size distribution measured by the mercury intrusion method has a peak value in the case of G plus ~Q, and The pore volume of the fine pore group 200836828 of 0.003~〇.〇5_ range is 0.37~〇e6ml/g. (4) The catalyst for exhaust gas treatment according to any one of the above items (1) to (3), wherein the catalyst substrate component is directly irradiated by a laser diffraction method at 46 to 48 kHz and 34 to 36 w for 55 to 65 seconds. : Metal oxides with a particle size of 12 to 50 (iv) are used as raw materials. (5) The catalyst for exhaust gas treatment according to any one of the above (1) to (4), wherein the catalyst of any one of (1) to (4) is extruded and burned, and the integrally formed porous honeycomb catalyst is burned, and The mass per gram (g) divided by the compressive strength of the catalyst (N/cm 100 or more. m (6) - an exhaust gas treatment method' is characterized by using the catalyst for exhaust gas treatment according to any one of the above (1) Since the exhaust gas treatment catalyst of the present invention is lightweight, it is possible to reduce the (m) degree of the exhaust gas treatment device and reduce the thickness of the steel sheet, thereby reducing the manufacture of the exhaust gas treatment device. Cost; (8) Catalyst can be easily loaded and moved. When comparing, there is a need for modulation catalyst, and there are fewer originals, which can save resources and reduce the cost of catalyst manufacturing. When the catalyst for the treatment is compared with the catalyst for industrial use, the exhaust gas treatment can be performed at a low cost. [Embodiment] The catalyst for exhaust gas treatment of the present invention (hereinafter referred to as "the invention 8 200836828 catalyst" ) containing a catalyst component and a catalyst substrate component, and the touch of the present invention The media check degree is 〇·7~i 8g/cm3, and is better than 〇·8~ l/g/cm, 〇9~丄5g/cm3 is better, 丄〇~工知/(五) The most child' The density of the above-mentioned catalyst is in the range of 〇·· 18 g/cm 3 , and the composition of the catalyst is not particularly limited. Basically, the conventionally known components constitute a catalyst for exhaust gas treatment. Refers to the density obtained by dividing the mass of the catalyst by the volume of the body. For example, in the case of a granular catalyst, = the value obtained by dividing the mass of the catalyst by the volume of the catalyst. Another example is the honeycomb type = medium or ring. When the catalyst of an open shape such as a catalyst is used, it is the volume of the catalyst of the catalyst mass port portion (ie, the gap portion), and the mass of the catalyst is divided by the mass of the catalyst divided by the pores of the catalyst. Volumetric touch volume, /, packing density "different. Accumulate the true density of the piece" or "Method of obtaining the density of the honeycomb-like catalyst. (a) Cut out the plate-like fragments, will be 曰 /, rainbow" The brothers are as follows: Determine the quality of the honeycomb-like catalyst itself|~$, rough product or (8) calculation. 胄^里(四)Product, then according to the formula of T column [Math 1] Catalyst density=(Hive-like catalyst per 1 Cm3 cake, 触 touch media product) χ {1 (honeycomb media open 11 [(hive (here, "honey-like touch media gap") apparent volume.) 'including the opening part (ie Empty 9 200836828 The catalyst component of the present invention is not particularly limited, and for example, it is preferably contained in at least two elements selected from the group consisting of 鈒, 铌, 翻, and crane, and the sub-containing element is selected from the group consisting of 鈒, 锐, pin, and town. The oxygen of at least the working species in the group is more a woman; specifically, for example, cerium oxide (V2〇3, p〇5), oxidized crane (W〇3), cerium oxide (10)A), oxygen scent _, etc. In the raw material of the catalyst component of the present invention, in addition to various oxides, oxides formed by combustion may be used. For example, hydroxides, ammonium salts, oxalates, halides, and nitric acid may be used. Sulfate and the like. Further, in the catalyst component of the present invention, the above-mentioned enumerated elements may be used singly or in a plurality of kinds, and the above-mentioned oxides may be used alone or in combination, or may be solid solution (10). )use. In particular, the addition of cerium oxide as a catalyst component is preferred. Further, when two or more kinds of catalyst components according to the present invention are used, it is particularly preferable to use vanadium oxide (V2〇5) and tungsten oxide (W03) in a mass ratio of 10:1 to 1::10. (4) An example of the catalyst component of the present invention, that is, a content of at least one type of catalyst component selected from the group consisting of vanadium, niobium, molybdenum, and tungsten (in terms of an oxide), which is 0.1 to 20 in the total mass of the catalyst. The mass% is preferably 0.5 to 15% by mass, more preferably 5% to 5% by mass. If the activity of the catalyst is reduced if it is less than ι mass%, and the catalyst density may be increased when it exceeds 2 mass%. 200836828 The composition of the catalyst substrate of this month is not particularly limited, but it is better to use the oxide of chin, such as titanium oxide (τω2), = or oxide (10) 2), or the enthalpy of such oxides. 5 emulsions and combinations of these, and the like. Among the above, from the viewpoint of the catalyst activity 11 and the durability, it is preferable to use a catalyst containing titanium oxide as a catalyst substrate. Use a mixture of oxides such as titanium, tantalum or hammer as the relevant

In the case of the catalyst substrate component of the invention, the mixing ratio of titanium oxide (in terms of the shell ratio of the oxide) is preferably 3% by mass or more, more preferably 5% by weight or more, more preferably 70% or more. Further, the catalyst base component of the present invention may be a composite oxide of titanium, ruthenium or iridium, for example, a titanium-ruthenium composite oxide (Ti-Si composite oxide) or a titanium-ruthenium composite oxide (Ti_). Zr composite oxide), or titanium_矽_鍅 composite oxide (Ti-Si_Zr composite oxide), etc., among which Ti-Si composite oxide having high BET specific surface area and strong solid acidity is particularly good. . Further, in the catalyst base component of the present invention, not only the above composite oxide but also a plurality of composite oxides may be used in combination, and a titanium-cerium composite oxide (Ti-si composite telluride) may be selected. At least one composite oxide composed of a titanium-zirconium composite oxide (Ti-Zr composite oxide) and a titanium-ruthenium-iridium composite oxide (Ti-y-Zr composite oxide), and remote auto-oxidation At least one of the oxides of the group consisting of titanium (Τι〇2), yttrium oxide (si〇2), and yttrium oxide (Zr〇2) is mixed and kneaded, and used as a catalyst substrate component of the present invention. Further, 'mixing the above composite oxide and the compound, when used as the catalyst substrate component of the present invention, the mixing ratio of the above-mentioned = emulsion to the above oxide (in terms of the mass ratio of the oxide) is 60: 40 to 95. : 5 is better. The above-mentioned titanium-;Ti-Si composite oxide has a titanium-zhen (η-Si) ratio in the mass ratio of the conversion to the oxide in the range of 3〇: 70 to 99:1, and 50:50. ~95 ·· 5 is better, 70 ·· 3〇~9〇·· 1〇 is better. The BET specific surface area of the catalyst substrate component of the present invention is preferably from 3 Å to 300 m 2 /g, more preferably from 50 〜 25 〇 m 2 /g, and most preferably from 1 〇〇 〜. The content of the catalyst substrate component of the present invention is 80 to 99.9% by mass of the total mass of the catalyst when converted into an oxide, and is preferably 85 to 99.8% by mass, and 9 to 99.5 mass%. better. When the content of the catalyst substrate component is less than 8% by mass, the dispersibility of the catalyst component such as vanadium is lowered, which leads to a decrease in durability and an improvement in the degree of contact with the catalyst. When the amount is more than 99.9% by mass, the catalyst component content is small and sufficient catalyst activity cannot be obtained. Further, the catalyst substrate component and the catalyst component may be combined, and if the titanium-rhenium composite oxide and the catalyst component are combined, the titanium-niobium-vanadium composite oxide or the titanium-ruthenium-ruthenium composite oxide may be used. , titanium-bismuth-molybdenum composite oxide, titanium-niobium-tungsten composite oxide, and the like. When a composite of a catalyst substrate component and a catalyst component is used, the content of the catalyst component is preferably 〇1 12 200836828. "", and 〇5~15% by mass is better, ::: invention, containing at least one compound selected from the group consisting of narcissus, bismuth, and the like, is called (4) a metal oxide which is fresh, and such a , a knife, a shovel or a knot, etc., is referred to as a catalyst substrate component./or a composite oxide of the present invention. The catalyst of the present invention has a porous catalyst substrate component having a composition of 0.003~ The fineness of the range of 0.05 (4) is good. Further, the catalyst of the present invention has the above-mentioned (4) thinning pores of the (4) substrate component, and the finer pores of the substrate are better than ο ^ ^, and the catalyst of the present invention is used. Detailed description of the pores. The composition of the catalyst substrate of the invention is preferably formed by using a porous catalyst substrate. Specifically, the catalyst of the present invention is finely formed by using a mercury intrusion method. The pore size distribution has a peak in the range of 0 to G05, and the pore volume (hereinafter also referred to as PV2) of the pore group in the range of 0.003 to 〇〇5_ is 〇3 to 〇6mi/g, and is (U4~) 〇.6m1/g is better, 〇.37~〇6 is better than the catalyst substrate component. PV2 does not reach 〇.3ml/g, low density of the catalyst cannot be obtained. Since 6ml/g has been used, the catalyst strength may be reduced. Moreover, the catalyst of the present invention has a peak value in addition to 0.003~〇.〇—Fanyuan and is in the range of 〇.〇〇3~〇〇5_ The fine pores of the fine pore group (PV2) are 〇.3~〇.6ml/g, and if there is a pore group having a peak in the range of 20082008 1336828~4 // m, the catalytic activity can be enhanced. Further, in the catalyst of the present invention, the pore volume (pv2) of the pore group of the range of 〇〇〇3 to 〇〇5 is used for the fine pore group of the range of 〇1 to 4#m. The ratio of the pore volume (hereinafter also referred to as pVl) (pV1/pV2) is 0·1 to 0.4, and is preferably 〇·1~〇·35, and 〇·15~〇3 is better, '0·15~〇· 25 special catalyst substrate components are suitable. When PV1/PV2 exceeds 〇·4, low-density catalyst cannot be obtained, and if it is less than 0.1, the catalyst activity may be reduced. The above PV2 is derived from the catalyst substrate component. The pores are themselves, and the PV1 is derived from pores which occur during the formation of the catalyst. Therefore, it has a peak in the range of 0.003 to 0.05 #m, and the fine pore group of the range of 〇〇〇3 to 〇〇5 is fine. The pore volume (pv2) is 〇 The catalyst of 3 to 〇6 ml/g is essentially a pore volume (PV2) of a fine pore group having a peak value in the range of 0·003 to 0.05/zm and having a range of 〇·〇〇3 to 〇〇5. It is obtained as a catalyst substrate component of 〇3~〇.6ml/g. 'PV2 means that the catalyst substrate component is porous. Further, according to the method of preparing a catalyst according to the following, The ratio of PV1 to PV2 (PV1/PV2) can be obtained as 〇·; [above 〇4 or less of the catalyst. Further, in the catalyst relating to the present invention, the total pore volume product measured by the mercury intrusion method is 〇·43 to QMml/g, and is 0.46 to 0.60 ml/g. 乂 47 47 47 〇 〇 47 47 47 better. When the total pore volume is less than 0.43 ml/g, a low-density catalyst cannot be obtained. If it exceeds 200836828, 0.65 ml/g, the catalyst strength may be reduced. In the present invention, the pore size distribution is measured by a mercury intrusion method, and the measurement is carried out by using a Micrometrics AutoPorelll apparatus manufactured by Shimadzu, Japan. In relation to the catalyst of the present invention, the catalyst substrate component of the present invention is irradiated by ultrasonic irradiation using a 46 to 48 kHz, 34 to 36 W ultrasonic wave for 55 to 65 seconds, and then has an average particle diameter of 12 to 5 by laser diffraction. ) #m, preferably 15 to 50//m, more preferably 18 to 5 Å//m, and the catalyst substrate component can improve the void ratio of the catalyst. That is, increasing the void ratio of the catalyst results in a reduction in the density of the catalyst. As for the method of increasing the void ratio of the catalyst, a particle having a certain degree of particle size, a strong cohesive f〇rce, and a particle which is not easily dissipated even if it is pressurized is preferably 0. A particle having a small cohesive force, such as when irradiating an ultrasonic wave. The average particle diameter is changed to J, and the sound emission is an index for evaluating the cohesive force of the particles. Further, the catalyst substrate component may be irradiated by ultrasonic irradiation at 46 to 48 kHZ or 34 to 36 W for 55 to 65 seconds, and the average particle diameter measured by a laser diffraction method is 12 to 50/zm and 15 to 5 〇//m is better, 18 50 is better, the range of the catalyst substrate component (catalytic substrate component a), and 46~48 kHz, 34~36W ultrasonic irradiation "~" seconds after the laser diffraction method The average particle diameter measured is a mixture of catalyst substrate components (catalyst substrate components... At this time, the ratio of the two 15 200836828 is such that the total pore volume of the catalyst is determined by mercury intrusion method 0.43~ In the present invention, the particle diameter is measured by a laser diffraction method, and the measurement is carried out by using SALD-11 manufactured by Shimadzu Corporation of Japan. The material composition is preferably a density reducing agent = at least - part is preferred. The density reducing agent is oxidized. 2), the cerium oxide of one of the above density reducing agents may be used in any of the following cases: (A) and the catalyst of the present invention The substrate components are used in combination, and U is used as a composite with the catalyst substrate component of the present invention, or jMA), (B) The combination. The ruthenium oxide is not particularly limited in any use, and the use of granularity, flakes, powders, and the like::% may be used, but it is preferable to use amorphous fine particles for the purpose of reducing the density of the catalyst. When the powdered cerium oxide is used, its apparent bulk density is the best. 〇3g/ml is better 'not up to 2g/ml. It is not as good as O.ig/m1. The total amount of oxygen cut is better with the catalyst substrate. 2~nTf Dan ^~5〇 % is better, 1~20% by mass, and it is good. When the amount used is less than 0.5% by mass, there is no two = salt: the effect of the catalyst density, and conversely, the excess activity of the medium is reduced or the strength is reduced. The complex shape is compounded with titanium (Ti_Si &gt; good use. The content of the oxidized dream in the titanium-germanium (Ti-Si) 16 200836828 composite emulsion is converted into oxide as a buffer. The mass % is better, more preferably 5 to 5 % by mass, and most preferably 1 to 3 % by mass. As a result of using such a titanium-bismuth (Ti_si) composite oxide, not only the catalyst density can be reduced, but also Catalysts with excellent activity and strength can be obtained. If the content of oxidized dreams is less than i% by mass, the effect of reducing the catalyst density cannot be obtained, and if the content of super positive 7G f is %, the catalytic activity is obtained.

Reduce or reduce strength. Such a Ti-Si composite oxide can be prepared by a conventional method. , &quot;The above titanium-bismuth (Ti-Si) composite oxide may also be used in combination with oxidized stone and/or titanium oxide. The above titanium-bismuth (Ti-Si) composite oxide has a specific surface area of from 140 to 250 m2/g, preferably from 160 to 25 Åm2/g, more preferably from 17 Å to 25 Åm2/g. The titanium-tellurium (Ti-Si) composite oxide is irradiated by 47 kHz and 35 w ultrasonic waves for 60 seconds, and the average particle diameter measured by a laser diffraction method is 12 to 50 #m, and preferably 15 to 50/zm. 18~5〇#m better. The shape of the catalyst of the present invention is not particularly limited, and may be appropriately selected from the shape of the catalyst for exhaust gas treatment such as honeycomb, granules, and powder. Taking a honeycomb-like catalyst as an example, it is suitable for users such as: the mass per hcm3 of the hive is 〇"~〇.&amp;, and is preferably 15~ο% better '0.2~0.38g; hole spacing or caliber (10) The ratio of fh〇(4) is 0.15~1.2cm' and is preferably 0.2~i.0cm; the aperture ratio is 〜85%, and 70~85% is better, 75~85% is better; the wall thickness of 200836828 in the honeycomb is 〇i~9 0.5 is better. It is also a good axis, and it is better to use Q.2~U coffee, 〇·2~ contains the quality of the hive per 1cm3 of the honeycomb void, which means the mass per km3 of the volume (apparent volume) of 邛. The brittle of the catalyst of the present invention (4) has an area of 70 to 200: 2/g. Two Γ: 92 〇 ~ 180 mVg is better, 110 to 160 mVg is better, 120 to 140 m2 / esoteric 5 ft. r low, It right # . When the temperature is less than 70 m, the catalytic activity is reduced, and the sub-cavity sometimes causes the catalyst to be in the exhaust gas of the catalyst, such as exceeding the fineness... The durability is reduced. There is a - increase in the amount of animal stocks, the fear of the catalyst, the true density of the catalyst is 2 ~ 3 5_3 range, and: Erguang is better, 2.5 ~ 3.3 gW is better. If it is less than 2g/cm (4), sufficient catalyst activity cannot be obtained, and if it is less than 3.5 g/cm, a low-density catalyst cannot be obtained. In the present specification, "the direct sound is squeaky, the cake b is n 〃 」" is the mass of the catalyst minus the honeycomb 〆 U to) the open part of the void and the micro hole: after the hole part, divided by the catalyst Real volume gain. The true density is measured by the density measuring device, and is determined by the so-called pycnometer (4) (10) which is measured by the gas gas instead of the gas sample (the true density) = weight / catalyst entity in this specification. product). The representative modulation method of the catalyst of the human body, the present invention, describes the catalyst substrate component of the present invention, and the titanium source used in addition to the 200836828 titanium alloy, as long as the titanium oxide is produced by combustion, the inorganic and organic Any compound can be used. For example, an inorganic compound such as titanium tetrachloride 'titanium sulfate and an organic titanium compound such as titanium oxalate or tetraisopropyl titanium can be used. Further, the source of lanthanum may be appropriately selected from the group consisting of inorganic ruthenium compounds such as colloidal ruthenium, water glass, fine particle ruthenium, ruthenium tetrachloride, ruthenium ruthenium, and the like. Further, the catalyst substrate component of the present invention is used for preparing a titanium source of a titanium-bismuth (Ti-Si) composite oxide, and any of the above inorganic and organic compounds can be used, and the same is true for Shi Xiyuan. Further, in addition to cerium oxide, an inorganic cerium compound such as cerium hydroxide, zirconium chloride or cerium sulfate or an organic cerium compound such as cerium oxalate can be used. When the catalyst substrate component is used, two or more kinds of metal oxides may be used. (1) The oxide or compound may be mixed as a solid and then burned as needed; (2) solids and water-soluble oxides may be used. (3) adding a test or the like to a liquid in which two or more kinds of compounds are dissolved and mixed, performing hydrolysis co-precipitation, washing and then burning; (1) to (3) combination, etc. The method is capable of modulating a mixture of oxides, composite oxides, and composites thereof. In the method for preparing a catalyst substrate component which is particularly suitable for obtaining the effects of the present invention, the method of the above (2) and (3) is combined to easily prepare a composite oxide, and the specific method is Ti-Si. The compound oxide 200836828 is used as an example to illustrate the following method for dispersing the cerium oxide powder in the aqueous oxidized domain of the above-mentioned titanium-cerium composite oxide by using the powdery oxygen domain, and then adding a sulfuric acid aqueous solution of titanium sulfate, and adding τ Killing things, to 80~20丄; "Xin Shen Dian" wash. &lt;: burning roasting ~ in L red 1~24 hours after 300~7 〇〇: 疋~0 hours, then use hammer mill When pulverized, it is prepared into the most::: the catalyst substrate component of the invention. When the titanium-aspartate compound is prepared by the method, the titanium content is 3〇% to 9% by mass, and %~:=°1 It is better to make '70~85 mass%, ^ ray diffraction right, Ϊ see the obvious natural peak of titanium oxide (Ti〇2) and oxygen cut (10) 2) and have a wide diffraction peak, (4) confirmed to have A titanium-cerium composite oxide having an amorphous fine structure. The titanium-stone composite oxide thus obtained is entangled by a mercury pressing method. The pore size distribution has a peak in the range of 0.003 to 〇.〇5#m. Next, a method for producing a honeycomb catalyst may be, for example, kneading a catalyst substrate component and then extruding it into an integrated honeycomb shape. Drying and burning. The combustion temperature is 40〇~6〇〇. The range of combustion is ~10 hours. In the extrusion process, forming aids (such as organic binders) and reinforcing agents (such as fiberglass) can be added. And an auxiliary agent such as a density reducing agent (such as cerium oxide). The forming aid may be polyethylene glycol, polyethylene glycol, sulfhydryl cellulose, glycerin, starch, etc. 20 200836828 Measured by law - tft: 裘 之 蜂Catalyst, which is pressed into the range of 〜·7~1.8g/cm3 with mercury. Door M, and then, through the composition of the base material of the catalyst, the preformed moon peas are prepared in advance, the second pass, the net pan, the upper The physique can also be. A temple method supports the catalyst component in Cheng Xi:: The catalyst of the present invention is extruded and burned to obtain an integrally formed two-hole honeycomb honeycomb catalyst, and the compressive strength (N/cm 2 ) of the catalyst is divided. The value obtained by the amount per ounce of honeycomb (8) is (10) (N/cm2 or more, and preferably 120 (N/Cm2·g) or more, u〇 (N/cm is better, 150 (Ν/Μ) · The best of the magic. When handling the exhaust, usually the catalyst is first loaded in # (cassette), and then the caliper is set to the T catalyst reaction tower. Since the catalyst is loaded in the cassette, there is pressure, so The compressive strength (N/Cm2) is divided by the mass per 2 cm3 of the honeycomb. If the value obtained is less than 100, the catalyst is loaded in the cassette when it is destroyed. Also, since the cassette is placed in the catalyst reaction tower Or in operation, there is impact or vibration, so the catalyst has better strength. ♦ The catalyst of the invention is suitable for removing nitrogen oxides discharged from boilers, thermal power plants, ironworks, garbage incinerators and various equipments. : (N〇x) and other harmful substances in the exhaust gas, and the removal of various chemical factories and incinerators, such as dioxin (dioxine, crocodile) and other organic By using the catalyst of the present invention, it is possible to decompose and remove the harmful substances in the exhaust gas as described in 21 200836828 with good efficiency. As for the system, it can be used in general treatment for the content of the content = no special restrictions. Under the gas condition [Examples] Hereinafter, the present invention will be described in detail, and the present invention will be described in detail. (Example 1) <Preparation of Ti-Si composite oxide powder> Dioxotomy (Si〇2) powder [product name········································································· (4) In this state, a sulfuric acid solution (calculated as titanium oxide (Ti〇2) of 70 g/L and a sulfuric acid concentration of 285 g/L] of 45 〇L was added dropwise thereto to form a precipitate. The slurry was aged, After filtration and washing, it was dried at 150 ° C for 10 hours, and this was burned at 5 ° C for 5 hours, and then pulverized by a hammer mill to obtain a titanium-ruthenium (Ti - Si) composite oxide. Τι - Si) When the composition of the composite oxide is converted into an oxide of each element, titanium dioxide (Ti〇2): cerium oxide Si〇2)= 76: 24 (mass ratio), BET specific surface area is 193 m2/g. After dispersing the above titanium-dream (Ti-Si) composite oxide powder in water, the same apparatus as the particle size is used. (SALD - 11〇〇), when the particle size of titanium-bismuth (Ti-Si) composite oxide particles after 47 kHz, 35 W ultrasonic irradiation for 60 seconds and 22 200836828 is measured by laser diffraction method, the average particle diameter is IMm. X' corresponds to a pore volume of pV2 of 〇.44ml/g 〇&lt;modulation catalyst&gt;

A homogeneous solution was prepared by mixing and dissolving 0.69 kg of ammonium metavanadate, 3 kg of oxalic acid lokg and 1 kg of ethanolamine and 3 L of water. Adding a vanadium-containing solution, an aqueous solution of ammonium tungstate to a mass% of methylamine (converted to tungsten oxide (w〇3) ^ 400 g/L] 3.4 L, a molding aid (starch), glass fiber, and water of suitable form. 25.0 kg of the titanium-cerium (Ti_Si) composite oxide powder prepared as described above was kneaded by a kneading machine and then extruded into an outer diameter of 80 mm square, a length of 500 mm, a hole pitch of 6 mm, a thickness of 〇7 mm, and an opening ratio of 79%. Honeycomb. This molded product was dried at 8 ° C and burned at 450 ° C for 3 hours to obtain a catalyst a. The composition of the catalyst A is [titanium-tellurium (Ti__Si) composite oxide]·pentaoxide (V2〇5): oxidized crane (W〇3) = 93 : 2 : 5 (mass ratio). The pore size distribution of the catalyst A measured by the mercury intrusion method has a peak in the range of 0.1 to 4//m and 〇·〇1 to 0.05 am. (Example 2) &lt;Preparation of titanium-based composite oxide powder&gt; The same titanium-bismuth (Ti-Si) composite oxide powder was obtained in the same manner as in Example 1. &lt;Modulating Catalyst&gt; A homogeneous solution was prepared by mixing and dissolving 0.70 kg of ammonium metadecanoate, i. 〇 kg of oxalic acid and monoethanolamine 〇. 3 kg 23 200836828 and 3 L of water. Adding a vanadium-containing solution, a 10% by mass aqueous solution of methylammonium tungstate (400 g/L of tungsten oxide (W03)), 3.4 L of a molding aid, a glass fiber, and a flux of water to the titanium prepared as described above. -矽(Ti - Si) composite oxide powder 19.91^ and titanium oxide powder (trade name: 0! 1-51, 1^ 〇风0 ug 1^ Company system, measured by laser diffraction method 47kHz, 35W After 60 seconds of ultrasonic irradiation, the average particle size: 4 μπι) 5.5 kg of mixed powder, after kneading by kneading machine, extruded into an outer diameter of 80 mm square, length 500 mm, hole pitch 6 mm, thickness 0.7 mm, aperture ratio 79 % of the honeycomb. After the molded product is dried at 80 ° C and burned at 450 ° C for 3 hours, the catalyst B is obtained. The composition of the catalyst B is titanium-bismuth (Ti - Si) composite oxide: Titanium dioxide (Ti〇2): pentoxide Two vanadium (V2〇5): tungsten oxide (W03) = 73 : 20 : 2 : 5 (mass ratio). The pore size distribution of the catalyst B measured by the mercury intrusion method has a peak in the range of 0·1 to 4/zm and 0.01 to 0·05//ιη. (Example 3) <Preparation of titanium-bismuth (Ti-Si) composite oxide powder> Mixing of ruthenium sol (containing cerium oxide (SiO2) 30 mass%/〇) 16 kg, 25 mass% ammonia water 270 kg, and water 180 L The solution was slowly added dropwise with a sulfuric acid solution of titanium sulfate (70 g/L of titanium oxide (Ti〇2) and a sulfuric acid concentration of 285 g/L) under stirring to form a precipitate. The slurry was aged, filtered, washed and dried at 150 ° C for 24 hours. This was burned at 500 ° C for 5 hours, and then pulverized with a hammer mill to transfer a titanium-叾 复合 composite emulsion. When the composition of the compound oxide is changed to the oxide of each element, 'dioxide (Tj〇2) · · dioxide dioxide (Si〇2) = 88: 12 (mass ratio), BET ratio The surface area is 146 m2/g. After dispersing the above-mentioned titanium-niobium (Ti-Si) composite oxide powder in water*, the device having the same particle diameter (SALD-lioo) and φ were used to measure 47 kHz, 35 W ultrasonic irradiation by laser diffraction method. When the particle size of the Ti-Si composite oxide particles after 6 sec., the average particle diameter is 14 m. Further, the pore volume corresponding to PV2 was 〇.36 ml/g. &lt;Modulating Catalyst&gt; A homogeneous solution was prepared by mixing and dissolving 0.77 kg of ammonium metavanadate, 1.2 kg of oxalic acid, 0.3 kg of monoethanolamine, and 3 L of water. Adding a vanadium-containing solution, an aqueous solution of 1% by mass of ammonium phthalate to ammonium tungstate (converted to 40 g of tungsten trioxide 10 (W03)), a forming aid, glass fiber, and water suitable for the above-mentioned preparation. Titanium-bismuth (Ti-Si) composite oxidation powder 25.0ks and cerium oxide (Si〇2) powder [product name··New Jinlu (two V彳シ一小) LP, Dongsu The mixed powder of 西kg, which is made by the lyrics of 西 一 东 东 , , , , , , , , 混 混 混 混 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合7mm, a honeycomb with an opening rate of 79%. After the molded product was dried at 80 ° C, it was burned at 45 ° C for 3 hours to obtain a catalyst c. 25 200836828 The composition of this catalyst c is [titanium-niobium (Ti-Si) composite oxide]·titanium dioxide (Τι〇2): vanadium pentoxide (v2〇5): tungsten oxide (WO3) = 83 : 1〇 : 2 : 5 (mass ratio). The pore size distribution of the catalyst C measured by the mercury intrusion method has a peak in the range of 〇^~‘^ melon and 0 01 to 〇〇5. (Example 4) • <Preparation of Ti-Si composite oxide powder> φ The same titanium-bismuth (Ti - was obtained in the same manner as in Example 3.

Si) composite oxide powder. &lt;Modulating Catalyst&gt; A homogeneous solution was prepared by mixing and dissolving 0.79 kg of ammonium metavanadate, 12 kg of oxalic acid, and 3 kg of monoethanolamine and 3 L of water. Adding a vanadium-containing solution, an aqueous solution of ammonium tungstate (% by weight of tungsten oxide (w〇3) of 400 g/L), 3.8 L, a molding aid, glass fiber, and an appropriate amount of water, as described above. Titanium-tellurium (Ti _ Si) composite oxide powder • 23.9kg, titanium oxide powder (trade name: DT 51, εΥ〇ΝΙ) ει^ • company made of 3" 4 and yttrium oxide (SiOJ powder [ Product Name: Xinpu, Xilu (two 7 7シ-small) LP, East Susilijia (East y — · シy Li) Co., Ltd.] 1.5kg mixed powder, after kneading machine, after extrusion, squeeze It was formed into a honeycomb shape having an outer diameter of 80 mm square, a length of 500 mm, a hole pitch of 6 mm, a thickness of 〇.7 mm, and an opening ratio of 79%. The molded product was dried at 8 ° C and then burned at 450 ° C for 3 hours to obtain a catalyst D. The composition of the catalyst D is titanium-bismuth (Ti-si) composite oxide·· 26 200836828 titanium dioxide m〇2) ··cerium dioxide (Si〇2) ··vanadium pentoxide (v205): tungsten oxide ( W〇3)=78: 1〇·· 5·· 2: 5 (mass ratio). The pore size distribution of the catalyst D measured by the mercury intrusion method has a peak in the range of 〇1 to 4#m and 〇.〇1 to 〇.〇5//m. (Comparative Example 1) Commercially available titanium oxide (trade name: .DT-51, manufactured by LYONDELL Co., Ltd.) was used as the catalyst substrate component. _ Mixing 12 kg of ammonium vanadate, oxalic acid 174 and monoethanolamine 〇 5 kg and water 5 L to prepare a homogeneous solution. This vanadium-containing solution, a 10% by mass aqueous solution of methylamine recorded in tartaric acid (converted oxidized crane (w〇3) of 400 g/L] 5.6 L, a molding aid, glass fiber, and an appropriate amount of water were added to titanium oxide (trade name) : DT_ 51, ly〇ndell company made of powder, after mixing with a kneading machine, (4) forming a honeycomb with an outer diameter of 8 square faces, a length of 5 mm, a hole spacing of 6 mm, a thickness of 7 faces, and an opening ratio of 79%. shape. After the TC is dried, the catalyst is burned at 450 &gt; t: for 3 hours. The composition of the catalyst E is titanium dioxide (Ti〇2): antimony pentoxide: tungsten oxide (W03) == 93:2:5 (mass ratio is measured by the mercury intrusion method. The pore size distribution of the catalyst E is a peak in the range of 0.01 to 〇05 (four), but there is no peak in the range of Q1 to 4_. (Example 5) The following exhaust treatment is performed using the catalysts A to E. &lt;Gas composition&gt; 27 200836828 N〇 (ppm, dry): 200 NH2 (ppm ^ dry) : 200 S〇2 (ppm, dry): 500 〇 2 (%, dry) : 4 H20 (%) : 8 N2 : Balance ' &lt;Processing conditions> • Gas temperature (°C) : 380 Line speed (m/s (Normal)) : 2·0 SV value (1/h): 10000 The denitration rate is obtained by the following formula: [Math 2] Denitration rate (%) = [(reactor inlet N〇x concentration) 1 (reactor outlet N〇x concentration) ]+(reactor inlet NOx concentration) χ100 The density of the catalyst Α~Ε, the mass per 1 cm3 of the honeycomb, the _ specific surface area, the pore volume (total pore volume, PV1, PV2), &quot; PV1/PV2 And the true density is shown in Table 1. Again, the density, the quality of the bee per 1 cm3 The pressure resistance and the denitration rate are shown in Table 2. From the results of Tables 1 and 2, it is understood that the catalyst of the present invention is low in density and light in weight, and is excellent in mechanical strength and catalytic activity. For the measurement, an automatic pycnometer (AUTO PYCNOMETER 1320) of the density measuring device of Shimadzu Corporation was used. 28 200836828

[I硌]

True density ^Η m CN cn inch cn 卜 PV1 / PV2 0.21 0.23 0.29 0.29 1 pore volume (ml/g) PV 2 0.43 0.39 0.35 0.34 0.28 Τ-Η &gt; 0.09 0.09 o rH • oo T—( o total Pore volume 0.53 0.49 0.46 0.45 0.29 Specific surface area 138 125 104 107 in v〇W η Steel 0.269 0.273 0-298 0.307 0.452 Density 1·28 〇cn rH CN Inch 1.46 (N Catalyst &lt; WUDW ^^^lwiirlw# Ridge Pity Ίί:·!杷杷S 缄日ττ/sd~20d^:(NAdt 无妗Ίί:4回奢怜令^篇杷砘®缄STyt,~ro-^: I ΛΡΗ ”m3 / 3:衂锲Η b£&gt;/ ~日:"§ / g 29 200836828

Denitration rate (%) CM On On rH On rH On On 00 2+1 (N / cm2 · g) ί 167 tH 148 140 v〇00 Compressive strength (N / cm2) • · . © inch inch inch inch inch ON Quality per 1 cm3 of honeycomb (g) • · · CD 0.269 0.273 0,298 0.307 0.452 Density! (g / cm3) 00 CN TH ο c〇CN Inch v〇 inch r—4 mr—&lt; CN Catalyst &lt; PQ u QW

</ RTI> </ RTI> <RTIgt;

31 200836828 [Simple description of the diagram] None [Key component symbol description]

32

Claims (1)

200836828 X. Patent application scope: L = a catalyst for exhaust gas treatment, characterized in that it contains a catalyst substrate knives and has a density of 〇·7 to 1.8 g/cm 3 . 2. The catalyst for exhaust gas treatment according to item ith of the patent application of the present invention, wherein the catalyst base component contains a compound selected from at least one element selected from the group consisting of titanium, erbium and ytterbium. Declare the exhaust treatment touch of item 1 or 2 of the patent scope In the m medium, the pore size distribution measured by the mercury intrusion method has a peak in the range of 0 〇 3 〇 05 05 μπι, and the pore volume of the pore group in the range of 〇〇〇 3 〇 〇 is 〇 · 3~〇, 6 ml/g 〇· 4. For the exhaust gas treatment catalyst of any one of the first to third aspects of the patent application, the 'catalytic substrate component is used at 46 to 48 kHz, 34 After ~36W ultrasonic irradiation for 55~65 seconds, the metal oxide with an average particle size of 12~5 〇# m is measured by laser and '% shot method. 5. The catalyst for exhaust gas treatment according to any one of the first to fourth aspects of the patent application, wherein the catalyst of any one of the items i to 4 of the patent application is extruded and burned It is formed into a liter-type honeycomb honeycomb catalyst, and the value of the compressive strength (N/crn2) of the catalyst per 1 cm3 of the honeycomb quality (g) is 100 (N/cm2 · g) )the above. 33 200836828 6. An exhaust gas treatment method characterized by using the catalyst for exhaust gas treatment according to any one of claims 1 to 5 to treat the exhaust gas. 寥 34 200836828 VII. Designated representative map: (1) The representative representative of the case is: (). (2) A brief description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: