KR100904531B1 - Particualte Matter and Hydrocarbon Reduction Catalyst Coating Soultion and Preparation Method The Same - Google Patents

Abstract

The present invention relates to a composite catalyst coating solution for oxidizing and removing a Particulate Matter (PM), soot, hydrocarbons, carbon monoxide, etc. with carbon dioxide and water at a relatively low temperature with a BPT (Balance Point Temperature) of 270 ° C. or less, According to the present invention, one or more metals of titanium, platinum group metal (A), platinum, iridium, ruthenium, and palladium, and one or more metals of lanthanum (La), cerium (Ce), and samarium (Sm) Ti-AB composite catalyst coating solution with and coated with a porous foam or ceramic filter made of metal such as Fe-Cr-Al alloy or stainless steel, etc. to manufacture a catalyst device, and the catalyst device for automobile exhaust gas treatment When applied to has a superior oxidation effect such as PM, hydrocarbons, carbon monoxide at a relatively low temperature than conventional.

Low temperature oxidation, PM, hydrocarbon, carbon dioxide, catalyst

Description

Particualte Matter and Hydrocarbon Reduction Catalyst Coating Soultion and Preparation Method The Same}

In the present invention, a composite catalyst including titanium, a platinum group metal, and a lanthanum-based metal is applied to oxidize and remove PM (Particulate Matter), soot, etc. with carbon dioxide at a lower temperature of BPT at a lower temperature than a conventional catalyst. The present invention relates to a composite catalyst coating liquid having excellent low temperature oxidation power removed by water and carbon dioxide, and a method of manufacturing the same.

Conventional diesel exhaust gas treatment technology was used to wash coat alumina, a refractory inorganic compound, and to carry platinum on it. However, after collecting soot, it is rapidly oxidized at about 350 ° C or higher. In addition, local overheating causes melting of the ceramic filter (melting) to melt or break often occurs so that the smoke is discharged to the outside as it was, there was a disadvantage that does not achieve the original purpose of reducing the smoke.

The object of the present invention is to eliminate the drawbacks of the prior art, to continuously oxidize the collected soot from low temperatures, to reduce the collection load of soot on metal foam or ceramic filters, and to balance the collected soot with the removed soot. BPT (Balance Point Temperature) is made before 270 ℃, so it is possible to remove PM and Particulate Matter continuously at low temperature without damaging metal foam or ceramic filter, and to oxidize hydrocarbon and carbon monoxide. And to provide a method for producing the same.
Still another object of the present invention is to provide a composite catalyst coating liquid having excellent catalytic activity and a method of preparing the titanium since titanium may act as a component of a catalyst rather than a conventional carrier.

In the present invention, a Ti-AB composite catalyst coating liquid, wherein A is a platinum group metal, and at least one of platinum (Pt), ruthenium (Ru), iridium (Ir), and palladium (Pd), and B is lanthanum ( La), cerium (Ce), samarium (Sm) to provide a catalyst coating liquid for removing the PM (PM, Particulate Matter) and hydrocarbon characterized in that at least one metal.

In addition, as a method of preparing the catalyst coating liquid, one of platinum (Pt), ruthenium (Ru), iridium (Ir), and palladium (Pd) metal is used as TiCl ₄ or titanium tetraisopropoxide and platinum group metal (A) as Ti metal. The above metal compound and at least one metal compound of lanthanum (La), cerium (Ce), and samarium (Sm) metals are mixed with the lanthanum-based metal (B) and 60 rpm or more at 60 ° C to 150 ° C in an aqueous hydrochloric acid, sulfuric acid, or nitric acid solution. A Ti-AB composite catalyst was prepared while stirring for 3 hours or more, and a method of preparing Ti-AB composite catalyst coating solution for removing PM and Particulate Matter and hydrocarbons, which was prepared by mixing alcohol and an inorganic binder thereto. To provide.

The Ti-A-B composite catalyst coating liquid used in the present invention has excellent oxidation effects such as PM (Particulate Matter), hydrocarbons, carbon monoxide and the like at low temperatures. In addition, the composite catalyst of the present invention provides continuous PM and hydrocarbon removal effect even at a low temperature of BPT (Balance Point Temperature) of 270 ° C. or lower than the conventional catalyst. Therefore, it is possible to obtain excellent automotive exhaust gas treatment effect by applying to Diesel Particulate Filter (DPF), Partial Diesel Particulate Filter (DPF) or Diesel Oxidation Catalyst (DOC).

Hereinafter, the term "low temperature" used in the present invention means that BPT (Balance Point Temperature) is about 270 ° C or less, and BPT is about 80 ° C or more lower than a conventional catalyst (or catalyst coating liquid).
The catalyst for removing hydrocarbons at low temperature used in the present invention is a Ti metal, TiCl ₄ or titanium tetraisopropoxide, platinum group metal (A) of at least one metal compound of platinum, ruthenium, iridium, palladium metal, and lanthanum Mixing one or more metal compounds of lanthanum, cerium, and samarium metals with the series metal (B) to form a Ti-AB composite catalyst while stirring at 60 rpm or more at 60 ° C. to 150 ° C. in hydrochloric acid, sulfuric acid, or nitric acid solution for at least 3 hours, and The catalyst coating liquid is prepared by mixing hexamethyldisilane or phenylmethylsilane or methyltrimethoxysilane with an alcohol such as ethanol, isopropyl alcohol or propanol and an inorganic binder such as silane.
The catalyst coating solution thus prepared is impregnated with a foam or filter made of Fe-Cr-Al material, stainless steel, metal or alloy, SiC, or ceramic material, dried at 110 ° C for at least 6 hours, and then dried at 300 ° C to 600 ° C. Firing for at least time to obtain a Ti-AB composite catalyst foam or Ti-AB composite catalyst filter for reducing PM at low temperature. Examples of the metal compound include platinum chloride or dinitrodiamineplatinate as a platinum metal compound, ruthenium chloride as a ruthenium metal compound, iridium chloride as an iridium metal compound, palladium chloride or palladium nitrate as a palladium metal compound, and (B) metal. As the compound, it is preferable to use lanthanum nitrate as the lanthanum metal compound, cerium nitrate as the cerium metal compound, and samarium nitrate as the samarium metal compound, but not limited to the examples listed above.

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The ratio of the metal used in the Ti-A-B composite catalyst is used by mixing the ratio of Ti metal to A and B in a weight ratio of 1: 1 to 1: 100. And mix A: B = 10: 1 to 1:10 by weight. When the weight ratio between the metals is out of the reaction, the oxidation reaction force is reduced in the catalyst, so the effect of converting the smoke or PM to carbon dioxide is significantly reduced. (A) When two or more metal materials are used, the weight ratio between (A) metal materials is not limited within the weight ratio of Ti-A-B composite catalyst. (B) When two or more metal materials are used, the weight ratio between (B) metal materials is not limited within the weight ratio of Ti-A-B composite catalyst.

An aqueous solution of hydrochloric acid, sulfuric acid, or nitric acid is used in a weight ratio of 100: 1 to 1: 1 by weight with respect to Ti, (A) metal, and (B) metal. It is difficult to obtain the object of the present invention.

The amount of ethanol, isopropyl alcohol or propanol used as the alcohol may be mixed in a weight ratio of 50: 1 to 1:50 for hexamethyldisilane or phenylmethylsilane or methyltrimethoxysilane as an inorganic binder, for example, silane. The amount of hexamethyldisilane or phenylmethylsilane or methyltrimethoxysilane as ethanol or isopropyl alcohol or propanol and silane as an alcohol for a catalyst coating liquid consisting of a Ti-AB complex catalyst and an aqueous solution of hydrochloric acid or sulfuric acid or nitric acid. Silver is used in a mixture with a weight ratio of 50: 1 to 1:50. When the weight ratio is out of the above, the coating liquid of the composite catalyst is significantly reduced in adhesion to a Fe-Cr-Al material, or a stainless steel metal or alloy, SiC, or ceramic foam or filter, which causes problems in durability.

Hereinafter, the present invention will be described in more detail with reference to the following examples.

Examples 1 to 5 were tested for the reduction efficiency of BPT, PM, hydrocarbons and carbon monoxide by varying the composition of the Ti-AB composite catalyst, Comparative Example 1 is a Ti-A catalyst, Comparative Example 2 is a Ti-B catalyst , Comparative Example 3 is in the form of an AB catalyst, Comparative Example 4 in the form of a Ti-AB catalyst, but unlike Examples 1 to 4, ethanol or isopropyl alcohol or propanol and silane as hexamethyldisilane or phenylmethylsilane or methyltri The reduction efficiency of BPT, PM, hydrocarbons and carbon monoxide was tested without the use of methoxysilane.

The present invention is explained in more detail by the following examples, which are not intended to limit the present invention.

Example  One

To prepare a Ti-AB composite catalyst, as a Ti metal, 100 g of TiCl ₄ was mixed with 5 g of chloroplatinic acid as a platinum group (A) metal, 5 g of lanthanum nitrate as a lanthanide metal (B), and 500 g of an aqueous 10% hydrochloric acid solution. Ti-Pt-La composite catalyst was prepared while stirring at 90 ° C. at 60 rpm for 3 hours, and 10 g of ethanol with alcohol and 10 g of hexamethyldisilane were mixed with silane to form a Ti-Pt-La composite catalyst coating solution. This 7-inch, 1-inch thick Fe-Cr-Al foam impregnated with two 30PPI and three 50PPI voids, dried at 110 ° C for 6 hours, and calcined at 400 ° C for 2 hours Obtain a reduction Ti-Pt-La composite catalyst foam, connect two 30PPI foams and three 50PPI foams in series, operate the engine dynamometer using a 3900cc engine for 200 hours in Engelhard deterioration mode, and then use the BPT. Measure and operate in ND-13 mode Hydrogen, carbon monoxide removal rate was measured.

Example  2

To prepare a Ti-AB composite catalyst, as a Ti metal, 100 g of titanium tetraisopropoxide, 5 g of ruthenium chloride as a platinum group (A) metal, 5 g of cerium nitrate as a lanthanide metal (B), and a 10% sulfuric acid aqueous solution Ti-Ru-Ce composite catalyst was prepared by mixing 500g and stirring at 90 ° C. at 60 rpm for 3 hours, and mixing 10 g of isopropyl alcohol with alcohol and 10 g of phenylmethylsilane with silane to mix the Ti-Ru-Ce composite catalyst coating solution. A stainless steel foam with a diameter of 7 inches and a thickness of 1 inch was impregnated with two 30PPI porosity and three 50PPI porosity, dried at 110 ° C for 6 hours and baked at 400 ° C for 2 hours at low temperature. After obtaining Ti-Ru-Ce composite catalyst foam for reducing PM, two porosity foams and two 50PPI foams were connected in series. T was measured and PM, hydrocarbon, and carbon monoxide removal rates were measured by operating in ND-13 mode.

Example  3

To prepare a Ti-AB composite catalyst, as a Ti metal, 100 g of titanium tetraisopropoxide, 5 g of iridium chloride as a platinum group (A) metal, 5 g of samarium nitrate as a lanthanide metal (B), and a 10% aqueous solution of nitric acid Ti-Ir-Sm composite catalyst was prepared by mixing 500g and stirring at 90 ° C. at 60 rpm for 3 hours, and mixing 10 g of propanol with alcohol and 10 g of methyltrimethoxysilane with silane to Ti-Ir-Sm composite catalyst coating solution. Stainless steel foam with a diameter of 7 inches and a thickness of 1 inch, impregnated with two 30PPI and three 50PPI porosity, dried at 110 ℃ for 6 hours and fired at 400 ℃ for 2 hours Obtain a reduction Ti-Ir-Sm composite catalyst foam, connect two 30PPI foams and three 50PPI foams in series, and operate in Engelhard deterioration mode for 200 hours with engine dynamometer using 3900cc engine. Measurement, by operating with ND-13 mode to measure the PM, hydrocarbons, carbon monoxide removal rate.

Example  4

To prepare a Ti-AB composite catalyst, 100 g of TiCl ₄ as a Ti metal, ₅ g of palladium chloride as a platinum group (A) metal, 5 g of samarium nitrate as a lanthanide metal (B), and 500 g of a 10% aqueous solution of nitric acid were mixed and 90 Ti-Pd-Sm composite catalyst was prepared while stirring at 60 rpm for 3 hours at 10 ° C., and 10 g of propanol with alcohol and 10 g of methyltrimethoxysilane were mixed with silane to form a Ti-Pd-Sm composite catalyst coating solution. Impregnating three honeycombs of stainless steel, 7 inches thick and 6 inches thick, dried at 110 ° C. for 6 hours and calcined at 400 ° C. for 2 hours to obtain a low temperature PM-reduced Ti-Ir-Sm composite catalyst honeycomb catalyst. Three coated stainless honeycombs were connected in series, and the BPT was measured after operating in Engelhard deterioration mode for 200 hours using an engine dynamometer using a 3900cc engine, and the PM, hydrocarbon and carbon monoxide removal rates were measured by operating in ND-13 mode. Measured.

Example  5

To prepare a Ti-AB composite catalyst, 3 g of dinitrodiamineplatinate as a platinum group (A) metal, 2 g of iridium chloride, 3 g of samarium nitrate as lanthanide metal (B), and 100 g of titanium tetraisopropoxide as a Ti metal were prepared. 2 g of lanthanum nitrate and 500 g of 10% aqueous nitric acid solution were mixed and stirred for 3 hours at 90 ° C. at 60 rpm to form a Ti-Pt-Ir-Sm-La composite catalyst, wherein 10 g of propanol as alcohol and methyl tri with silane were added thereto. 10 g of methoxysilane was mixed to form a Ti-Pt-Ir-Sm-La composite catalyst coating solution, impregnated into a filter containing 30 mesh-size SiC particles in an outer diameter of 10.5 inches and a depth of 15 inches. 6 hours at 400 ℃ and fired for 2 hours at 400 ℃ to produce a Ti-Pt-Ir-Sm-La composite SiC filter for reducing the PM at low temperature, the engine dynamometer using a 3900cc engine 200 hours in Engelhard degradation mode Measure BPT after driving And, by operating with ND-13 mode to measure the PM, hydrocarbons, carbon monoxide removal rate.

Comparative example  One

A Ti-A composite catalyst was prepared in the same manner as in Example 1, except that 100 g of TiCl ₄ was used as the Ti metal, ₅ g of chloroplatinic acid was used as the platinum group (A) metal, and B metal was not used. .

Comparative example  2

A Ti-B composite catalyst was prepared in the same manner as in Example 2 except that 5 g of cerium nitrate was used as a lanthanide metal (B) for 100 g of titanium tetraisopropoxide as a Ti metal, and no A metal was used. Prepared.

Comparative example  3

AB composite catalyst was prepared using the same production method as in Example 1 except that 5 g of chloroplatinic acid as the platinum group (A) metal and 5 g of lanthanum nitrate as the lanthanide metal (B) were used, and nothing was used as the Ti metal. It was.

Comparative example  4

A Ti-A-B composite catalyst was prepared in the same manner as in Example 1 except for not using both ethanol and hexamethyldisilane as alcohol.

Experimental Example

Table 1 shows the composition of Ti-AB composite catalyst and 3,900cc engine, and operated in Engelhard deterioration mode for 200 hours with Engine Dynamometer, PM in BPT (Balance Point Temperature) and ND-13 mode. , Removal rate of hydrocarbon, carbon monoxide is shown. The lower the BPT (Balance Point Temperature), the lower the PM (PM) at low temperatures, indicating that the ability to remove soot and hydrocarbons is excellent.

Table 1. BPT and PM / hydrocarbon / carbon monoxide removal rate according to the embodiment

Claims (9)

A Ti-AB composite catalyst coating liquid, wherein A is a platinum group metal, at least one of platinum (Pt), ruthenium (Ru), iridium (Ir), and palladium (Pd), and B is lanthanum (La), At least one metal of cerium (Ce) and samarium (Sm), and the Ti-AB composite catalyst coating liquid for removing PM and Particulate Matter, which is characterized in that the mixture of alcohol and inorganic binder to the catalyst component. In claim 1, The weight ratio of the metal used in the Ti-AB composite catalyst coating liquid is (A + B): Ti = 1: 1 to 100, A: B = 10: 1 to 1:10 to use by mixing in a weight ratio Characterized by PM (PM, Particulate Matter) and hydrocarbon-free Ti-AB composite catalyst coating liquid. TiCl ₄ or titanium tetraisopropoxide as a Ti metal and a platinum group metal (A), at least one metal compound of platinum (Pt), ruthenium (Ru) iridium (Ir), palladium (Pd) metal, and lanthanum-based metal (B Ti-AB complex while mixing at least one metal compound among lanthanum (La), cerium (Ce), and samarium (Sm) metal at 60 ° C to 150 ° C for at least 3 hours in hydrochloric acid, sulfuric acid, or nitric acid solution A method for preparing Ti-AB composite catalyst coating liquid for PM and PM, characterized in that the catalyst is prepared, and the mixture is prepared by mixing alcohol and inorganic binder. In claim 3, PM (PM) characterized by using any one of ethanol, isopropyl alcohol or propanol as the alcohol and silane of any one of hexamethyldisilane, phenylmethylsilane or methyltrimethoxysilane as the inorganic binder. , Particulate Matter) and Ti-AB composite catalyst coating solution for hydrocarbon removal. In claim 3, For hydrochloric acid, sulfuric acid, or nitric acid aqueous solution based on 1 part by weight of the total Ti, (A) metal and (B) metal, 1 to 100 parts by weight of PM (Particulate Matter) and hydrocarbon removal for Method for preparing Ti-AB composite catalyst coating liquid. In claim 4, The amount of the alcohol is prepared by mixing in a weight ratio of 50: 1 to 1:50 with respect to the amount of the silane, PM (Particulate Matter) and a method for producing a Ti-A-B composite catalyst coating solution for hydrocarbon removal. In claim 4,  PM, Particulate, characterized in that the total amount of the alcohol and silane to the total of the aqueous solution consisting of the Ti-AB complex catalyst and hydrochloric acid, sulfuric acid or nitric acid is mixed in a weight ratio of 50: 1 to 1:50 Matter) and Ti-AB composite catalyst coating solution for hydrocarbon removal. As Ti metal, among TiCl ₄ or titanium tetraisopropoxide, at least one metal compound among platinum, ruthenium, iridium, palladium metal as platinum group metal (A), and lanthanum, cerium and samarium metal as lanthanide metal (B) One or more metal compounds are mixed to form a Ti-AB complex catalyst while stirring at 60 rpm to 60 rpm or more at 60 ° C. to 150 ° C. in an aqueous hydrochloric acid solution or sulfuric acid solution or nitric acid solution, wherein the alcohol is either ethanol, isopropyl alcohol or propanol. Alcohol and an inorganic binder were mixed with silane of hexamethyldisilane, phenylmethylsilane or methyltrimethoxysilane to form a catalyst coating solution, and made of Fe-Cr-Al or stainless metals or alloys, SiC, ceramics Impregnated into a foam or filter of material, dried at 110 ° C for at least 6 hours, and fired at 300 ° C to 600 ° C for at least 2 hours. Wherein W get piem (PM, Particulate Matter) and a hydrocarbon to remove Ti-AB complex catalyst apparatus. In claim 8, The composite catalyst device is any one of Diesel Particulate Filter (DPF), Partial Diesel Particulate Filter (DPF), or Diesel Oxidation Catalyst (DOC), and Ti-AB for hydrocarbon removal. Compound catalyst device.