KR101320600B1 - Diesel oxidation catalyst composition for diesel vehicles using high-sulfur fuel - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxidation catalyst composition for a diesel vehicle using a high sulfur fuel, and comprises a composite carrier made of titania-silica, zeolite and aluminosilicate in a flow-through type support made of ceramic or metal. And 0.1 to 10% by weight of at least one platinum group catalyst component selected from platinum (Pt) based, palladium (Pd) based or rhodium (Rh) based components and 0.1 to 20% by weight of vanadium (V) based catalyst components. Characterized in that it is supported.

The oxidation catalyst according to the present invention effectively burns the soluble organic fraction by the interaction of the composite carrier, and the vanadium metal compound inhibits the generation of sulfate by oxidation of sulfur compounds in the exhaust gas. The soot reduction efficiency can be improved.

Diesel Engine, Oxidation Catalyst, Soluble Organic Fraction

Description

Diesel oxidation catalyst composition for diesel vehicles using high-sulfur fuel}

1 is a graph showing a comparison of sulfur dioxide oxidation temperature and particulate matter (PM) reduction rate for an oxidation catalyst according to Examples 1 to 4 and Comparative Example 1. FIG.

The present invention relates to an oxidation catalyst composition for a diesel automobile using high sulfur fuel.

Diesel cars have been applied to large vehicles such as trucks and buses because they have lower fuel consumption and better output than gasoline vehicles. However, demand for diesel vehicles continues to increase in advanced countries. However, in developed countries, such large and small diesel vehicles account for 40% of the total air pollution, and are recognized as the main causes of air pollution, mainly caused by nitrogen oxides (NOx) and particulate matter (PM). . Nitrogen oxides and particulate matter have trade-offs with each other, so developed countries are adjusting their incidence according to policy requirements. In order to reduce the emission of air pollutants, advanced countries are tightening emission regulations of diesel engines.

As a countermeasure for satisfying the exhaust gas regulation of diesel engines, there are a method of improving a diesel engine and developing a post-treatment technology and mounting them on exhaust gas. Such post-treatment technology,

(1) Oxidation catalyst for purifying unburned hydrocarbons in particulate matter (PM)

(2) Diesel Particulate Filter (DPF) for filtering particulate matter (PM) through a filter

(3) DeNOx catalyst systems for decomposing or reducing nitrogen oxides (NOx) in a reducing atmosphere.

Among the post-treatment techniques, the first oxidation catalyst is known to have a lower particle reduction rate than the DPF, but it has advantages such as low cost, high reliability due to a simple structure, and no regeneration cycle. The operation principle of the oxidation catalyst is to reduce total particulate matter by purifying soluble organic fraction (SOF), which is about 40-50% of total diesel particulate matter. It is known.

However, oxidation catalysts with too high oxidation activity are not suitable for diesel vehicles using high sulfur fuels. This is because the sulfur dioxide generated during engine combustion of the high sulfur fuel is oxidized to sulfur trioxide while passing through an oxidation catalyst, and at the same time, sulfuric acid reacts with moisture present in the exhaust gas to form sulfuric acid.

(1) SO ₂ + 1 / 2O ₂ → SO ₃ (catalytic reaction)

(2) SO ₃ + H ₂ O → H ₂ SO ₄

It is known that the oxidation catalyst using a general platinum occurs by the above equation (1) from 300 degrees.

Removal of particulate matter (PM) by the oxidation catalyst is usually carried out in the engine or chassis dynamometer by adopting the CVS-75, D-13, ESC test mode, and the like. Sulfuric acid (H ₂ SO ₄ ) is detected in the state of being adsorbed with a certain amount of water. In general, the particulate matter (PM) is composed of soluble organic fraction, char and sulfate, which is higher than that when the oxidation catalyst is not used due to the increase of sulfuric acid particles. In addition, the reduction effect of particulate matter due to the removal of the soluble organic fraction is offset, and the phenomenon of increasing particulate matter is often found. Particularly, in D-13 and ESC test mode including high speed and high load operating conditions, particulate matter increases when using an oxidation catalyst.

Because of the problems described above, the prior art has approached in two ways, a method for improving a carrier and a method for improving a catalyst. In the method of improving the carrier, there are known methods of using titania and silica carriers to minimize the adsorption of sulfur dioxide while maintaining the adsorption of the soluble organic fraction in the flue gas. According to the SAE 940240 paper published by Ogura et al., The amount of sulfate adsorbed to alumina and titania left in the sulfur dioxide discharge stream is 55 mg / g for alumina and 5 mg / g for titania, more than 10 times. It is reported that there is a difference. However, in this case, there is a disadvantage that the surface area of titania cannot be effectively expected to disperse the platinum group catalyst, which is a noble metal, at a level of 1/4 or less as compared with the conventional alumina. In the method of improving the catalyst, calcium (Ca), iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), vanadium (V), chromium (Cr), and niobium (Nb) in the noble metal catalyst A method of suppressing the production of sulfate (sulfate) by reducing the oxidation activity of the platinum group by adding a promoter having an oxide structure such as molybdenum (Mo).

Korean Patent Publication No. 10-0387862 attempts to solve the above problem by stacking a titania layer containing vanadium on a platinum catalyst layer supported on alumina having a high surface area, but sulfur dioxide gas is diffused between carriers ( Since it can be diffused into, it can be said that the adsorption potential of sulfur dioxide by alumina still exists.

Therefore, there is an urgent need for the development of an oxidation catalyst capable of suppressing the generation of sulfate while sufficiently burning the soluble organic fraction component in diesel vehicles using high sulfur fuel.

Accordingly, an object of the present invention is to provide an oxidation catalyst composition for a diesel engine that can suppress the production of sulfate while sufficiently burning the soluble organic fraction component in a diesel vehicle using high sulfur fuel.

The present inventors have continued to study the above limitations of the prior art, and as a result, there is a composite support composed of titania-silica, zeolite, silica-alumina, and the catalyst of platinum (Pt) series As a result of preparing an oxidation catalyst impregnated with the compound and the vanadium salt, it was confirmed that the interaction of the composite carrier effectively burns the volatile organic fraction and the vanadium metal compound inhibits the formation of sulfate by the oxidation of sulfur compounds in the exhaust gas. The present invention was completed.

Accordingly, the present invention is a composite carrier made of titania-silica, zeolite and aluminosilicate in a flow-through type support made of ceramic or metal, and platinum (Pt) based on the composite carrier, palladium (Pd). Oxidation catalyst for exhaust gas purification of high-activity diesel engines carrying 0.1 to 10% by weight of at least one platinum group catalyst component and 0.1 to 20% by weight of vanadium (V) catalyst component selected from In particular, the present invention provides an oxidation catalyst composition that effectively acts on diesel vehicles using high sulfur fuels.

The working principle of the oxidation catalyst according to the present invention is as follows. The main component of the carrier consists mainly of titania-silica to minimize the adsorption of sulfur dioxide, and includes zeolite and aluminosilicate in addition to titania-silica disclosed in Korean Patent Application No. 2005-124588 filed by the present inventors. In the case of using a composite carrier, the PM reduction performance is better because combustion of the soluble organic fraction is more effective.

The zeolite used as a carrier component of the oxidation catalyst according to the present invention means a specific crystalline form having an apparent pore structure, and the aluminosilicate contains less aluminum oxide (Al ₂ O ₃ ) than silicon oxide (SiO ₂ ). That is, it means that it does not have a specific crystal structure and more preferably is amorphous.

In order to effectively show the performance of the platinum catalyst in titania with a relatively small surface area, it is advantageous to keep the phase of the platinum in metal form and minimize its size. It is also well known that the platinum metal form is more effective than the platinum oxide form in the combustion of soluble organic fractions. For this reason, it is more effective to prepare a catalyst impregnation solution by the platinum colloid method and to carry out nano-sized platinum metal particle forms on a carrier, but is not limited thereto.

Vanadium salts were also added with the platinum metal to inhibit sulfate production. As the vanadium salt is added, the production of sulfate is greatly reduced, and the activity of the platinum catalyst due to the addition of the vanadium salt may be slightly lowered, but this problem can be overcome by using the composite carrier as described above.

Hereinafter, the oxidation catalyst for a diesel engine of the present invention will be described in detail.

Another oxidation catalyst for a diesel engine according to the present invention is a composite carrier composed of titania-silica, zeolite and aluminosilicate in a flow-through type support made of ceramic or metal, and platinum (Pt) based on the composite carrier, palladium 0.1 to 10% by weight of at least one platinum group catalyst component selected from (Pd) or rhodium (Rh) based components and 0.1 to 20% by weight of vanadium (V) based catalyst components.

The support of the oxidation catalyst according to the present invention is preferably made of a material having high heat resistance and high mechanical strength in a flow-through type, specifically, cordierite, SiC, mullite, or α. It is preferable to use a ceramic material selected from alumina or a metal material selected from iron-chromium alloy, nickel-chromium alloy, and nickel-chromium-aluminum alloy. In addition, the shape of the support may be used in the form of a monolith honeycomb structure, mesh (mesh), foam (foam) or fiber (fiber).

Titania-silica in the components of the carrier is derived from a mixture of titania and silica sol having a particle size of 10 mm or less, and the mixing ratio of silica and titania is preferably 1: 2 to 4 weight ratio. If the mixing ratio of silica and titania is less than 1: 2, the specific surface area for uniformly supporting the catalyst is insufficient, and if it exceeds 4: 1, there is a problem that the adhesion to the support is significantly reduced. Preferably, the zeolite is a beta zeolite having a silica / alumina molar ratio of 10 to 400. When the molar ratio of SiO ₂ / Al ₂ O ₃ is less than or equal to 10 in the beta zeolite, aluminum ions are released under a mixed vehicle exhaust gas. Zeolite activity is greatly reduced by "de-alumination", and at a molar ratio of 400 or more, the adsorption of the soluble organic fraction adsorbed is not easy, so that regeneration is difficult and sometimes coking occurs. May occur. Said aluminosilicate is SiO ₂ 70 to 95% by weight and Al ₂ O ₃ as consisting of 5 to 30% by weight of silica (SiO ₂₎ to the main component as, and the Al ₂ O ₃ is substituted by from 5 to 30% by weight of surface acidity Is preferably a high aluminosilicate. This is because the hydrogen ions present for charge balance around the substituted Al ₂ O ₃ act as strong Bronsted acid, which has a strong surface acidic property that is different from that of silica. ) Cracking It is judged because In the case of using aluminosilicate in which Al ₂ O ₃ is substituted in the above range, the surface acidity is high, so that adsorption and decomposition of the soluble organic fraction present in the exhaust gas are more effective. The surface acidity can be confirmed from the temperature range of the ammonia desorbed by the ammonia-TPD (Temperature Programmed Desorption) method and the amount of desorption.

The oxidation catalyst according to the present invention washwashes a composite carrier composed of titania-silica, zeolite and aluminosilicate on the support, and allows the composite carrier to be coated by a process of drying or drying and firing. The catalyst coating solution containing the platinum group catalyst component and the vanadium catalyst component is impregnated with the support coated with the composite carrier, and the catalyst component is supported on the composite carrier component, followed by drying and firing. In another manufacturing method, the platinum carrier catalyst component and the vanadium catalyst component are previously supported on a composite carrier composed of titania-silica, zeolite and aluminosilicate, and then the composite carrier on which the catalyst component is supported is washed on the support, followed by drying and It can be manufactured through a calcination process.

The catalyst solution containing the platinum group catalyst component according to the present invention may be prepared in solution or colloidal reduction method in which the platinum group compound is treated with a water-soluble polymer compound and a reducing agent. The method of preparing in solution phase is more preferable because the platinum particles are more likely to become platinum oxides than the platinum metal during the firing process, and in this case, the selectivity to the reactants is increased while the activity may be slightly decreased. . The water-soluble high molecular compound contained in the catalyst solution may be polyvinyl alcohol, polyvinylpyrrolidone or polymethyl acrylate, and the like, and as the reducing agent, a mixture of methanol, ethanol, hydrazine or methanol / sodium hydroxide may be used. In addition, the catalyst solution may be used by appropriately adjusting the required concentration by using water or alcohol as a diluent.

Among the catalyst components included in the oxidation catalyst of the present invention, the platinum group component is supported by 0.1 to 10% by weight of one or more catalyst components selected from platinum (Pt) based, palladium (Pd) based or rhodium (Rh) based components. do. If the catalyst component is less than 0.1% by weight, no catalytic performance appears, and if it exceeds 10% by weight, no further catalyst performance is improved, which is economically disadvantageous. In addition, the vanadium-based catalyst component is supported by 0.1 to 20% by weight based on the weight of the carrier. When the content of the vanadium-based catalyst component is less than 0.1% by weight, the production of sulfate is increased, and when the content is more than 20% by weight, it may cause a problem of lowering the activity of the platinum group catalyst. The weight ratio of the platinum group catalyst component and the vanadium catalyst component need not be limited, but is preferably 1: 0.5 to 10. If the weight ratio is less than 0.5, sulfate production is increased, and if it exceeds 10, the PM reduction rate is significantly reduced.

The platinum-based catalyst component is H ₂ PtCl ₆ , H ₂ PtCl ₄ , (NH ₄ ) ₂ PtCl ₆ , (NH ₄ ) ₂ PtCl ₄ , (NH ₄ ) ₂ PtCl ₆ , (NH ₄ ) ₂ PtCl ₄ , K ₂ PtCl ₆ , K ₂ PtCl ₄ , (NH ₄ ) ₂ Pt (CN) ₄ , (NH ₄ ) ₂ Pt (SCN) ₄ , (NH ₄ ) ₂ Pt (NO ₃ ) ₄ , K ₂ Pt (CN) ₄ , K ₂ Pt (SCN) ₄ , K ₂ Pt (NO ₃ ) ₄ , Pt (NH ₃ ) ₂ Cl ₄ , Pt (NH ₃ ) ₂ (NO ₃ ) ₄ or (R-NH ₃ ) ₂ Pt (OH) ₆ Derived from at least one platinum-based compound and hydrates thereof selected from (R-NH ₃ ) ₂ Pt (OH) ₆ is an amine-water soluble platinum hydroxide, R is C _It is an alkyl or cycloalkyl group of ₁ to C ₈ , and may be substituted with a hydroxy group or an amino group. The palladium-based catalyst component is derived from one or more palladium-based compounds or hydrates thereof consisting of Pd (NO ₃ ) ₂ , PdCl ₂ or Pd (NH ₃ ) ₄ Cl ₂ , and the rhodium-based catalyst component is Rh (NO ₃ ) Derived from one or more rhodium-based compounds consisting of ₃ , RhCl ₃ or Rh (NH ₃ ) ₃ Cl ₆ or a hydrate thereof.

In addition, the vanadium catalyst component used with the platinum group catalyst is vanadium (V) oxide (V ₂ O ₅ ), vanadium (III) oxide (V ₂ O ₃ ), vanadium (II) chloride (VCl ₂ ), vanadium (III) Selected from chloride (VCl ₃ ), vanadium (IV) chloride (VCl ₄ ), ammonium metavanadate (NH ₄ VO ₃ ), sodium metavanadate (NaVO ₃ ) or sodium orthovanadate (Na ₃ VO ₄ ) It is derived from at least one vanadium compound.

The step of fixing the coated catalyst composition is usually by calcination but may be accomplished by any other method known in the art.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are only for illustrating the present invention in more detail, it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples. .

Example 1

Pt-V / ( Titania Silica + Zeolite Beta + Aluminosilicate ) Preparation of Catalyst

1.5 kg of silica sol (solid% = 40%, manufactured by Grace Davison) was added to 6.1 kg of distilled water and stirred for 30 minutes. Here, 0.8 kg of titania (from Degussa), 0.8 kg of beta zeolite (mole ratio of SiO ₂ / Al ₂ O _{3 from} Geolyst: 24), 0.8 kg of aluminosilicate (10% by weight of Al ₂ O ₃ from Grace Davison) The mixture was stirred for 1 hour to prepare a composite carrier mixed solution. Then, the composite carrier mixture was coated on a cordierite honeycomb having a diameter of 11.25 inches, a length of 3 inches, and a cell density of 400 cpsi, dried at 120 ° C. for about 3 hours, and calcined at 550 ° C. for about 3 hours to washcoated honeycomb. Was prepared.

After adding 550 g of polyvinylpyrrolidone (number average molecular weight 10000) to 1,734 g of distilled water and stirring for 30 minutes, 200 g of chloroplatinic acid (H ₂ PtCl _{6 ·} 6H ₂ O) was stirred and completely dissolved. 450 g of methanol was added thereto, stirred, and reacted for 4 hours at reflux under reduced temperature to prepare a platinum catalyst solution. At the same time, 136 g of vanadium oxide (V ₂ O ₅ ) was added to 952 g of distilled water, and oxalic acid was added to completely dissolve vanadium oxide to prepare a vanadium salt solution. Then, the platinum catalyst solution and the vanadium salt solution were stirred and mixed thoroughly, coated on the wash-coated honeycomb, dried at 120 ° C. for about 3 hours, and calcined at 550 ° C. for about 3 hours, so that the platinum-based catalyst component weighed as carrier. An oxidation catalyst having 2.4% by weight and 2.4% by weight of vanadium component was completed.

[Examples 2 to 4]

In the same manner as in Example 1, except that the washcoat solution and the catalyst solution were prepared using the amount of each component described in Table 1 below.

[Comparative Example]

In the same manner as in Example 1, except that the washcoat solution and the catalyst solution were prepared using the amount of each component described in Table 1 below.

[Table 1]

Wash coat liquid  Usage amount by ingredient according to manufacture

Of catalyst liquid  Usage amount by ingredient according to manufacture

[Test Example 1]

The degree of sulfate formation by SO ₂ oxidation was evaluated for the oxidation catalysts of Examples 1 to 4 and Comparative Examples. The evaluation method is equipped with the oxidation catalyst of the Examples and Comparative Examples, respectively, after passing the model exhaust gas of 200ppm CO, 900ppm decane, 300ppm NO, 300ppm SO ₂ 200ppm through the reactor and raising the temperature of the reactor SO ₂ The temperature at which 10% is oxidized was measured and the results are summarized in Table 2. As shown in Table 2, it was confirmed that the SO ₂ oxidation temperature increased as the vanadium catalyst content was increased, which means that SO ₂ oxidation is inhibited by the vanadium catalyst component. In addition, the configuration of the carrier showed better results than the three-component composite carrier according to the present invention.

[Test Example 2]

In order to measure the particulate matter reduction characteristics and durability between the catalysts of the Examples and Comparative Examples, it was measured by the CVS-75 test mode method of the domestic emission control method in Chassis Dynamo Mita, and the results are summarized in Table 3.

As shown in Table 2, the composition of the carrier under various platinum and vanadium content catalyst combinations and carrier combination conditions, when the three-component composite carrier and platinum vanadium mixed catalyst combination according to the present invention, SO ₂ oxidation temperature characteristics and PM reduction rate Better results were obtained.

[Table 2] SO ₂ Oxidation and Particulate Matter Reduction by Various Catalyst Compositions

As described above, the present invention relates to an oxidation catalyst for exhaust gas purification of a diesel engine. The oxidation catalyst according to the present invention effectively burns a soluble organic fraction by interaction of a composite carrier, and the vanadium metal compound is a sulfur compound in the exhaust gas. While suppressing the production of sulfate by oxidation of diesel fuel, it is possible to improve the soot reduction efficiency of diesel vehicles using high sulfur fuel.

Claims (9)

A composite carrier consisting of titania-silica, zeolite and acid aluminosilicate in a flow-through type support made of ceramic or metal and platinum (Pt), palladium (Pd) or rhodium (Rh) 0.1-10% by weight of at least one platinum group catalyst component selected from the system component and 0.1-20% by weight of vanadium (V) -based catalyst component are supported, and the acidic aluminosilicate is 70-95% by weight of SiO ₂ and Al ₂ O. _{3. An} oxidation catalyst for exhaust gas purification of a diesel engine, comprising 5 to 30 wt%. The method of claim 1, The oxidation catalyst is an oxidation catalyst for exhaust gas purification of a diesel engine, characterized in that after the wash-coating a composite support (support) on the support, the platinum group catalyst component and the vanadium catalyst component is carried. The method of claim 1, The oxidation catalyst is an oxidation catalyst for purification of exhaust gas of a diesel engine, characterized in that the composite support (support) is supported by a platinum group catalyst component and a vanadium catalyst component supported on the support. The method of claim 1, The zeolite is an oxidation catalyst for exhaust gas purification of a diesel engine, characterized in that the beta zeolite having a molar ratio of SiO ₂ / Al ₂ O ₃ is 10 ~ 400. delete The method according to any one of claims 1 to 4, The method of supporting a platinum group catalyst component is an oxidation catalyst for exhaust gas purification of a diesel engine, wherein the platinum group compound is a colloidal reduction method of treating the platinum group compound with a water-soluble polymer compound and a reducing agent. The method according to claim 6, The platinum group catalyst component is H ₂ PtCl ₆ , H ₂ PtCl ₄ , (NH ₄ ) ₂ PtCl ₆ , (NH ₄ ) ₂ PtCl ₄ , (NH ₄ ) ₂ PtCl ₆ , (NH ₄ ) ₂ PtCl ₄ , K ₂ PtCl ₆ , K ₂ PtCl ₄ , (NH ₄ ) ₂ Pt (CN) ₄ , (NH ₄ ) ₂ Pt (SCN) ₄ , (NH ₄ ) ₂ Pt (NO ₃ ) ₄ , K ₂ Pt (CN) ₄ , K _{From 2} Pt (SCN) ₄ , K ₂ Pt (NO ₃ ) ₄ , Pt (NH ₃ ) ₂ Cl ₄ , Pt (NH ₃ ) ₂ (NO ₃ ) ₄ or (R-NH ₃ ) ₂ Pt (OH) ₆ Oxidation catalyst for exhaust gas purification of a diesel engine, characterized in that it is derived from one or more selected platinum-based compounds or hydrates thereof (wherein R is a C ₁ to C ₈ alkyl or cycloalkyl group and is substituted with a hydroxy or amino group). Can be.) 8. The method of claim 7, The vanadium catalyst component is vanadium (V) oxide (V ₂ O ₅ ), vanadium (III) oxide (V ₂ O ₃ ), vanadium (II) chloride (VCl ₂ ), vanadium (III) chloride (VCl ₃ ), vanadium ( IV) derived from one or more vanadium compounds selected from chloride (VCl ₄ ), ammonium metavanadate (NH ₄ VO ₃ ), sodium metavanadate (NaVO ₃ ) or sodium orthovanadate (Na ₃ VO ₄ ) An oxidation catalyst for exhaust gas purification of a diesel engine, characterized in that. An exhaust gas purification apparatus for a diesel engine having the oxidation catalyst according to any one of claims 1 to 4.

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