DE19519137A1 - Catalyst comprising residue from exhausted desulphurisation catalyst - Google Patents

Abstract

A catalyst compsn. comprises a residue obtd. in the discharge of an exhausted catalyst used in an oil refinery for desulphurisation of crude oil. The catalyst contains no above 80% of V, not above 80% of Mo, not above 20% of Ni, not above 30% of Co, not above 99% of Al2O3, and traces of impurities. A catalyst for cleaning diesel waste gases is prepd. by heating the catalytically active compsn. obtd. on discharging the exhausted oil refinery catalyst at 400-1000 deg. C for 0.5-5 h, and grinding to a 100-800 mesh powder. A filter for cleaning diesel waste gases is prepd. by slurrying the catalyst compsn., alone or with known filter material powders, with a binder, a caustic material, an active material and water, casting the slurry to form a filter structure, and sintering at 200-1000 deg. C. The slurry contains 10-100 wt.% of catalyst compsn. and 90-10% of filter material. The filter material is cordierite, mullite, ZrO2 or SiO2, and the filter is a ceramic foam, an open honeycomb, a ceramic fibre filter, a ceramic honeycomb or a honeycomb monolith with flow-through wall.

Description

The invention relates generally to a catalyst composition tion and a catalyst that is suitable for diesel exhaust clean, and more specifically, the use of a catalytic effect the composition during or after desulfurization is discharged from crude oil as a catalyst composition, or egg NEN catalyst to remove the particles in the exhaust gas Diesel vehicle are included, both thermally and chemically has great stability and when burning parti distinguishes. The present invention is also concerned with Manufacturing process for this.

Particles contained in the exhaust gas of diesel vehicles have Average diameter of about 0.3 microns and include in general incompletely burned carbon particles, soluble  organic materials, sulfides, etc. These consist of particles the materials are very harmful to the human body. At first, they are visually very unpleasant and can be carcinogenic Act. For these reasons, environmental standards apply to diesel exhaust gases been set up. In Korea, where the share of diesel vehicles 42%, more than in any other country, is diesel vehicles a major cause of air pollution. It is therefore necessary to clean the exhaust gases and remove the particles.

Emission standards for particles are becoming stricter every year, e.g. B. 0.67 g / HP.Hour (0.67 g / HP hour) in Korea in 1996 and 0.1 g / HP hour in the United States, 1994. In response to these strict regulations intensive research and development efforts on that was contained in the exhaust gas of diesel vehicles to eliminate any particles.

The techniques for removing the particles develop in three Directions: Reduce the production of unburned particles by improving engine performance; Improve the burn efficiency through the use of fuel additives; and after treatment of the exhaust gas to filter out particles. The first two Techniques essentially aim to remove the harmful mate rialien essentially by improving the combustion blue to avoid fes. However, they require high production costs and can also create harmful materials due to their obviously technical limits not completely ver prevent. That is why post-treatment methods have become more important.

An aftertreatment method essentially consists of a fil ter process for collecting the exhaust gas particles in a filter and a treatment process for removing the retained Particles from the filter to regenerate it. For this ver driving it is necessary to choose a filter that has a high Has aggregate yield, and it actually corrected on led vehicles to apply. Because particles are returned in the filter will hold, the back pressure of the exhaust pipe increases what can damage the filter and continue to affect engine performance  belittles. Combustion of the collected material at high temperatures ratures stresses the filter with thermal stresses, and affects its life span is harmful. Accordingly, the Regenera tion process in the direction of improved combustion developed further at low temperatures. The most Most regeneration methods used include temperature increase of the exhaust gas by an auxiliary energy from an external Heat source, such as a burner or by throttling of the engine, and a reduction in the necessary activation Energy for the oxidation by adding additives or by impregnating the filter with a catalyst, whereby the Oxidation takes place at lower temperatures.

The present invention uses a catalytic action the activation energy of the oxidation process of the particle mass reduce terials so that they operate under normal operating conditions be burned against a diesel engine, namely at conven Chen exhaust gas conditions including the exhaust gas composition and Temperature. The catalytic effect is essentially achieved by using a suitable filter material with a heat-resistant three-dimensional structure, such as ceramic foam, Wire mesh, metal foam, ceramic honeycomb structures or similar be impregnated with a catalytically active substance.

The following are the general requirements for a Kataly sator for cleaning diesel exhaust gases explained.

First, the catalyst should be harmful with high efficiency Components like unburned hydrocarbons at low Remove temperatures from the exhaust just like small coals fabric particles.

Secondly, the catalyst should be suitable for the oxidation of SO₂, that in the engine when burning sulfur components containing fuel arises to prevent SO₃ to the To minimize SO₃ content in the exhaust gas.  

Third, the activity of the catalyst should go through the property unit of toxic components, such as SO₂, not we be significantly influenced.

Fourthly, it should have a long service life, so that it can high temperatures is active for a long period of time.

There are several ways to increase the efficiency of the catalyst Techniques have been proposed. With these techniques, a large surface area provided so that the catalytically active Ingredients come into contact with the particles and the big one Area is created by a layer of a catalyst carrier, such as aluminum oxide or titanium dioxide on a fil termaterial is deposited and a platinum group metal, the is known as a combustion catalyst for particulate matter, is integrated into the filter using a metal salt solution. The However, these techniques have not produced the desired results brought. Typical alumina is sta at high temperatures bil, e.g. B. at about 800 ° C and has sufficient stability to be used continuously at such high temperatures. However, it reacts with sulfur trioxide that occurs during combustion of sulfur-rich oil, so that aluminum sulfate is formed, which worsens the surface and pore structure of the Catalyst generated, reducing the activity of the catalyst falls. In contrast to aluminum oxide, titanium dioxide is chemically ge stable to sulfur trioxide, so that its activity is not degraded. However, it is sensitive to high Temperatures, e.g. B. 500 ° C. It is in practice in an exhaust gas temperature range thermally decomposed between 300 and 600 ° C lies, which is completely normal for diesel vehicles. Especially when the particles are burned to regenerate the filter material the temperature rises steeply and therefore the upper area by phase transformation from the anatase state to the rutile state stood reduced. As a result, the pore structure is destroyed interferes, which leads to a decrease in activity and durability. The preparation of a catalyst that introduced the four above has not yet become known.  

It is therefore an object of the present invention to provide a catalyst sator composition for cleaning diesel exhaust gases, the regarding the combustion of the particles contained in the exhaust gas is improved.

It is another object of the present invention, a kata Specify analyzer composition for cleaning diesel exhaust gas, the is able to effect the catalyst because of its chemical and thermal stability for a long time right to maintain.

It is another object of the present invention, a kata to provide the analyzer composition for cleaning diesel exhaust gas, the catalytic effect of which is not generated in the diesel engine Sulfur oxides is reduced.

It is another object of the present invention to provide a ver drive to manufacture the catalyst composition.

It is another object of the present invention to provide a fil ter using the catalyst composition and the superior properties when removing particles from Has diesel exhaust.

It is another object of the present invention to provide a me specify the method for making the filter.

It is another object of the present invention to provide a fil ter with a coating using the catalyst together to create the superior qualities when removing of particles from diesel exhaust.

It is another object of the present invention to provide a ver drive to manufacture the filter.  

It is another object of the invention to provide a catalyst for To clean the exhaust gas of diesel vehicles to create the Filter material or the filter is used.

It is another object of the present invention to provide a ver drive to manufacture the catalyst.

During the intensive investigations the inventor has come up with issued that the composition following the Ent sulfurization process of crude oil is discharged in an oil refinery, contains a variety of catalytically active ingredients that outstanding qualities in terms of particle removal from diesel exhaust. The inventors also found out that a filter material or a filter made from this together is made alone for cleaning smoke can be useful. In addition, the experiments showed that a catalyst in which at least one platinum group metal evenly introduced into the filter material or into the filter is, conventional filters that use alumina or titanium dioxide Use support structure with regard to temperature resistance and is superior to sulfur trioxide resistance.

Catalysts used for the desulfurization of heavy crude oil Oil refineries are useful generally 30 to 50 Ge weight percent aluminum on, 0 to 10% molybdenum, 0 to 3 Ge weight percent nickel and 0 to 3% phosphorus. You will be using a Discharge composition that is different from the original composition very different because they are during desulfurization process with vanadium, cobalt and other catalytically active Ingredients are enriched for the combustion of in Particles containing diesel exhaust are very suitable.

Although the following information depends on the operating conditions of the Desulfurization process, the duration and the composition of the Crude oil and the catalyst originally charged, has the catalyst composition after desulfurization unloading process (hereinafter referred to as the "unloaded Kataly  sator ") generally about 80% or less of Vanadi to, 80% or less of molybdenum, 20% or less of nickel, 30% or less of cobalt, 99% or less of alumina and Traces of the impurities after the cleaning of the crude oil too lag behind.

The discharged catalyst impurities such as Contains moisture and / or oil, it is heated to prevent contamination to remove cleaning agents and so make a suitable material for the to manufacture the present invention. It is preferred that the Heating at temperatures from about 400 to 1000 ° C for about 0.5 up to 5 hours. Insufficient heating at tem temperatures lower than 400 ° C lead to insufficient ent removal of impurities. On the other hand, heating leads at temperatures higher than 1000 ° C for thermal decomposition of the catalytically active components contained in the discharged kata lysator are included, as well as a waste of energy. There the heated catalyst then becomes particles in a mill powdered. The size of the particles preferably moves in the Range between 100 to 800 mesh. Excessively large particles, large larger than 100 mesh, have difficulty making one homogeneous slurry as used to make a filter mat rials is necessary according to the present invention, as in fol will still be described. On the other hand, if the through If the particle is too small, smaller than 800 mesh, the Resistance to high temperatures and the Manufacturing costs increase excessively. According to one aspect of The present invention provides a catalyst composition represents by the discharged catalyst by means of heating is treated and the heated catalyst to a powder is ground.

The powder obtained from the discharged catalyst is a very high one useful substance (hereinafter referred to as "YK-R") for manufacturing put a filter, a coating and a catalyst, in accordance with the present invention.  

According to another aspect of the present invention, a filter material for cleaning diesel exhaust gases is produced by means of a method, which has the following method steps:
Mixing YK-R powder, either alone or together with conventional filter material powders, to produce a homogeneous slurry; Pouring the slurry into a filter mold; and sintering the filter structure to produce a filter. The slurry or slurry for the filter material is made by mixing either YK-R powder alone or in combination with conventional filter materials with a binder, an attacking agent, active materials and water.

The conventional filter materials described in the present Er are used include ceramic materials such as Cordierite, mullite, zirconium dioxide, silicon dioxide and the like chen. However, there are all ceramic materials that act as filters materials are known, available and there are no special ones Exclusions. It is preferred that conventional filter media can be combined with YK-R up to a quantity of 90%. If the content of YK-R powder drops below 10%, the result is Filter material only slightly active, which is directly from the low Concentration of the above-mentioned catalytically active components comes from.

In the slurry, the glues or binders serve to to bind ceramic filter materials and any of the prior art Binders known in the art can be used.

The attack agent (etchant) prevents the ceramic Ma material forms foam and all known means can be used become.

The active material is intended to increase the porosity of the kerami to control the filter body. It can all known materia lien can be used.  

Using a known method suitable for this is to form ceramic material, such as by In injection or extrusion, the filter material pulp is converted into a Filter structure shaped, which is then at a temperature between about 25 and 150 ° C, followed by sintering at one Temperature between about 200 to 1000 ° C. The filter structure can adopt any known three-dimensional design as suitable for cleaning diesel exhaust gas is known, such as white ceramic foam, open honeycomb structures, ceramic fiber fil ceramic honeycombs and honeycomb monoliths with wall currents mung, and there are no special requirements for this.

YK-R powder can also be used for a coating structure which is suitable for creating a filter for collecting and burning the particles contained in diesel exhaust gases. According to a further aspect of the present invention, a filter for cleaning diesel exhaust gases is therefore produced by a method which has the following method steps:
Mixing YK-R powder either alone or in combination with conventional powders to make coatings to form a slurry; Applying the slurry to the surface of a filter structure; and sintering the coated filter. Any zeolite can be used as the general coating as used in the present invention. Examples are alumina (aluminum oxide), titanium de (titanium dioxide) and silica (silicon dioxide). It is preferred that the normal coatings be combined with the YK-R powder up to 90%. If the content of YK-R powder falls below 10%, the resulting coating material has only an insignificant activity, which is directly due to the low concentrations of the above-mentioned, catalytically active ingredients.

To create the slurry for making the coating, YK-R powder is used either alone or in combination with conventional coating powder evenly mixed with water and  with such an amount of acid or base that a Vis of 400 cps or less is set. The Beschich tion powder, including the YK-R powder, and if available that, including the conventional coating powder preferably between 3 and about 50 percent by weight of the pulp or the slurry. If the absolute proportion of the coating powder drops below 3% by weight are those mentioned above too little represented catalytically active ingredients to a Ka trigger analysis. If on the other hand the absolute share of the deposition aid powder is over 50%, this is too much to adjust the slurry to a lower viscosity. A viscosity of 400 cps or less is necessary to get one uniform coating on the conventional filter material to reach.

The filter material structure can be any three-dimensional Have structure as it is known to clean diesel exhaust conditions, such as ceramic foam, open honeycomb structure doors, ceramic fiber filters, ceramic honeycombs, metal foam, honeycomb monoliths with wall flow and metal grille, and it are no special boundary conditions.

5 to about 200 grams of the coating slurry is about Given 1 liter of the filter structure, which was then dried and made to about 400 to about 1000 ° C is heated. If the slurry in an amount of less than 5 g per liter of the filter material sufficient surface is not assured to to enable the catalytically active ingredients to To clean diesel exhaust. On the other hand, if the coating in an amount of more than 200 g / l filter material is used, the exhaust back pressure is unnecessarily increased, which leads to a deterioration the efficiency of the engine leads. To be big enough To provide surface, the coating is preferably on applied to the surface of a filter structure made from YK-R according to the present invention.  

The filter material or filter made from YK-R according to the present invention is used to build a catalyst. The filter material or filter is immersed in a catalytic metal solution and then sintered at a temperature between approximately 400 and 800 ° C. According to a further aspect of the invention, therefore, a catalyst for purifying diesel exhaust gas is produced by a process which has the following process steps:
Impregnating the filter material or the filter according to the invention with catalytic metal; and sintering the thus obtained in the impregnated filter material or filter at a temperature between approximately 400 and 800 ° C.

At least one of the catalytic metals is made of platinum group selected. Specific examples of catalytically active Me platinum, rhodium and palladium. Per liter of filter media terials or filters are preferably used with platinum 0 to 7.07 g, 0 to 2 g for rhodium and 0 to 7.07 g for palladium, with at least one of the metals in sufficient concentration should be present to cause catalysis.

At least one precious metal from the group consisting of platinum, Rho dium and palladium are on the coating, in a mass rela tion between 0.001 and 0.1. If the mass ratio between the precious metal and the coating drops below 0.001, there is too little precious metal to have a catalytic effect cause. If the mass ratio on the other hand is over 0.1 increases, the catalytic effect is increased only slightly However, the costs are increased considerably.

After the catalyst or filter with a coating of YK-R been installed in the filter device of a diesel vehicle the engine was running. The exhaust gas was examined, whereby it turned out that the catalyst or filter with regard to has superior qualities to the combustion of particles. It was also exceptionally stable, not only at high ones  Temperatures, but also generated by the diesel engine Sulfur oxides. This chemical and thermal stability enables makes it clear to him about the operating conditions of diesel vehicles withstand a long time and so it is suitable to parti remove from the exhaust gas of diesel vehicles.

The invention is illustrated below with the aid of a few examples explained.

example 1 Process for the preparation of the catalyst substance YK-R 1-1. Analysis of the composition of originally loaded Origi catalyst and discharged catalyst (YK-R)

Having a catalyst for the desulfurization of heavy crude oil has been loaded, as shown in Table 1 below, in a refinery of Yukong, Ltd., in Korea, became the descriptor development process over 250 days. 2 g of the discharged catalytic converter Tors were removed and then analyzed using ICP. The he Results of the analysis are given in Table 2, along with the Composition of the original catalytic converter.

Table 1

Composition of the originally charged original desulphurization catalyst

Table 2

Composition of originally loaded and unloaded catalysts

As shown in Table 2, the discharged differs Catalyst in terms of its composition significantly different from that originally charged catalyst.

1-2. Change in specific surface depending on Heating temperatures

10 g of the discharged catalyst were as in Table 3 below indicated heated and the specific surface was measured. The results are shown in Table 3.  

Table 3

Specific surface area depending on the heating temperature of the discharged catalyst

This table shows that insufficient heating to less than 400 ° C for incomplete removal of impurities leads and that heating to over 1000 ° C decomposes the causes catalytically active ingredients, causing the pores structure is destroyed.

1-3. Preparation of the catalyst composition (YK-R) powder

100 kg of the discharged catalyst were heated to 800 ° C with a Heating rate of 20 ° C / min. heated and at this temperature for two Held for hours. After cooling, the catalyst became powder ground with a size of 200 mesh.

Example 2 Reaction tests of YK-R compositions 2-1. Sample preparation

15 g each according to Example 1-3. produced YK-R powder, from Alumi nium oxide and titanium dioxide were used as sample 1 (for example), Sample 2 and Sample 3 (both for comparison purposes) used.  

2-2. CO oxidation

1 g of each sample according to Example 2-1. was loaded into a reactor and the reaction temperature was controlled. While air with containing 200 ppm CO with a volume velocity of 50,000 / h (50 l / h) was sent through the reactor, the Concentration of CO₂ analyzed at the outlet of the reactor and the CO content calculated. The temperature at which the conversion rate of CO reached 50% was measured.

2-3. C₃H₈ oxidation

The temperature at which the conversion rate of C₃H₈ reached 50% was measured in the same manner as in Example 2-2, except that air with a content of 1000 ppm of C₃H₈ by Reactor was headed.

2-4. SO₂ oxidation

1 g of each of the samples according to Example 2-1 was in one Reactor loaded and the reaction temperature was checked. While air containing 50 ppm of SO₂ with a volume speed of 50,000 / h (50 l / h) passed through the reactor was, the concentration of SO₂ was analyzed at the outlet of the reactor siert. The conversion rates of SO₂ were measured at 450 ° C.

2-5. Smoke combustion test

Each of the three samples according to Example 2-1 was evenly ver mixes with 1 g of particulate matter from the exhaust gas of a die was removed and then loaded into a reactor. The temperature of the reactor was raised at a rate of 10 ° C / min. increased to 200 ° C. During the temperature of the reactor then at a rate of 1 ° C / min. was further increased, the Temperatures at which the particles ignited (smoke combustion temperature).  

The measurement results in Example 2, the temperatures of the 50% wall lungs rates of CO and C₃H₈, the conversion rates of SO₂ at 450 ° C. and smoke combustion temperatures are given in Table 4.

Example 3 Attempted stability at high temperatures

5 g of each catalyst composition was placed in an oven according to samples 1, 2 and 3 according to example 2-1 at 800 ° C at egg ner heating rate of 20 ° C / min. heated and at this temperature for held for five hours. After that, the three samples were the same Oxidation tests for CO, C₃H₈ and SO₂ and the same Rauchver subjected to combustion test as in Example 2. The measurement results are shown in Table 4 below.

Example 4 Analysis of chemical stability against sulfur oxides

In an oven, 5 g of each of Samples 1, 2 and 3 were placed in accordance with Example 2-1 with a heating rate of 20 ° C / min. raised to 500 ° C heats and nitrogen with a content of 100 ppm SO₃ was at a rate of 2 l / min. passed into the oven for 50 hours. There after the three samples were subjected to the same oxidation tests for CO, C₃H₈ and SO₂ and the same smoke combustion test as in Subject to Example 2. The results are shown in Table 4 below poses.

Table 4

Reaction tests

Table 4 shows that the discharged catalyst composition (YK-R) superior in smoke combustion temperature alone and is also very stable thermally at high temperatures bil and chemically stable to SO₃ and therefore over a long time Period can be used for cleaning diesel exhaust.

Example 5 Manufacture of filter materials 5-1. Production of a foam type filter

10 ppi polyurethane foam was sized to 2 cm x 2 cm x 2 cm cut and then into a solution of water and methyl alcohol hol (1: 1 mass ratio) dipped and dried.

100 g of YK-R according to Example 1-3 became 15 g of dextrin as a binder added and then 7 g of monoethanolamine as an attacking agent. 60 g of water and 6 ml of ethylene glycol were also added, that served as active material. By stirring up a slurry or porridge produced. The polyurethane foam was made with sufficiently soaked this slurry. Then 80% of the Slurry removed from the polyurethane foam which then was dried. This impregnation was repeated three times and then an impregnated or impregnated filter material with a Obtained a total weight of 6 g. After drying for 24 hours The impregnated filter material became 50 ° C at 300 ° C for three Sintered for hours at a heating rate of 0.5 ° C / min. and then, at 900 ° C for one hour at a heating rate of 1 ° C / min. When As a result, foam 1 (filter material 1) was produced.  

Regardless of this, foam 2 (filter material 2) was used as a reference prepared, using cordierite powder instead of YK-R powder was applied.

5-2. Production of a flow honeycomb type filter

A honeycomb filter material was produced by an extrusion process as follows:
100 g of YK-R powder according to Example 1-3, 4 g of methyl cellulose as a binder and 15 g of a pore-forming additive were beige added and then dry-milled and mixed in a ball mill. A suitable amount of water was added to the mixture thus obtained to produce a slurry whose strength was between 0.8 to 1 mg / mm 3. It was loaded into a screw extruder to produce a honeycomb structure with a diameter of 5 mm. This honeycomb was dried in an oven at 70 ° C for 36 hours. It was then subjected to sintering, the temperature being raised in various stages as shown below (filter material 3).

Regardless, the filter material 4 was used as a reference provides, using cordierite powder instead of YK-R powder has been.

5-3. Manufacture of a wall flow type honeycomb filter

In a flow-through honeycomb filter according to Example 5-2 was a added slurry, which comes from the same substance was like the flow-through honeycomb filter itself, with a mask from an easily pourable polymer was used, as well as in U.S. Patent 4,411,856 to selectively fill the pores.  

As a result, a wall flow honeycomb type filter material 5 became testifies.

In the same way, a slurry of YK-R and cordierite was used (1: 1 mass ratio) used to filter material 6 from Wall flow honeycomb type. Regardless of this, a Filter material 7 of the wall flow honeycomb type made for reference, using cordierite powder instead of YK-R powder.

Example 6

A 400 cpi ceramic honeycomb monolith was sized cut 2 cm × 2 cm × 2 cm. 1000 g of YK-R powder was mixed with 900 g Mixed water and then ground for 24 hours. After stirring the resulting slurry became concentrated acetic acid and ammonia spirit added to pH 4.5 and a vis to set a viscosity of 95 cps. The prepared honeycomb monolith was soaked in the slurry and compressed air at 40 psi Blown off (2.75 bar). It was then at 120 ° C for ten hours dried at a rate of 20 ° C / min. and according to white heating at 500 ° C for two hours with the same increase rate. A filter 8 was produced in which 1.3 g of YK-R Be layer was impregnated.

In the same way, a slurry of YK-R and an alumi was made nia powder (1: 1 mass ratio) used to filter 9 to produce. Regardless, filters 10 and 11 were used as a reference made the alumina and titanium dioxide powders instead of YK-R powder used.

Example 7 Reaction tests for filter material and filters 7-1. CO oxidation

Each of the filter materials 1 to 7 and filters 8 to 11 according to the  Examples 5 and 6 were placed in a reactor and the reac tion temperature was checked. While air with a content of 200 ppm of CO at a volume rate of 50,000 / h flowing through the reactor became the concentration of CO at the end let the reactor determine. The temperature at which the conversion CO rate was 50% was measured.

7-2. C₃H₈ oxidation

The temperatures at which the conversion rate of C₃H₈ 50% were measured in the same way as in Example 7-1, except for the fact that the air contains 100 ppm of C₃H₈ flowed into the reactor.

7-3. SO₂ oxidation

Each of the filter materials 1 to 7 and the filters 8 to 11 were placed in the reactor and the reaction temperature became controlled liert. While air containing 50 ppm of SO₂ with a Volume velocity of 50,000 ml / h flowed through the reactor, the concentration of SO₃ at the outlet of the reactor was calculated certainly. The conversion rates of SO₂ were measured at 450 ° C.

7-4. Smoke combustion test

1 g of particulate matter from diesel exhaust was evenly applied each of the filter materials 1 to 7 and the filters 8 to 11 gela and then put it in the reactor. The temperature of the reactor was increased at a rate of 1 ° C / min starting from 200 ° C. The temperature at which the particles ignited (smoke burning temperatures) were measured.

The measurements in Example 7, the temperatures of the 50% conversion advise of CO and C₃H₈, the conversion rates of SO₂ at 450 ° C and the smoke combustion temperatures are shown in Table 5.  

Example 8 Endurance test at high temperatures

Each of the filter materials 1 to 7 and the Filters 8 to 11 at a heating rate of 20 ° C / min to 800 ° C heats and held at this temperature for five hours. After that the catalytic materials became the same oxidation craze tion tests for CO, C₃H₈ and 502 and the same Rauchverbren subjected to the same test as in Example 7. The results are shown in Table 5 shown below.

Example 9 Endurance test at high temperatures

Each of the filter materials 1 to 7 and the Filters 8 to 11 at a heating rate of 20 ° C / min to 500 ° C heats. Thereafter, nitrogen gas with a content of 1000 ppm of SO₂ through the furnace at a rate of 2 l / min for 50 hours headed. The catalytic materials were the same Oxyda tion reaction tests for CO, C₃H₈ and SO₂ and the same smoke subjected to combustion test as in Example 7. The results are shown in Table 5.

Table 5

Reaction tests

Table 5 shows that the filter materials or filters made from YK-R powders are produced alone or in combination with them conventional filter materials or the corresponding coating against conventional coatings in terms of smoke combustion temperature are superior and also at high Temperatures and chemically very stable to sulfur oxide and therefore for a long time to clean diesel exhaust sen can be used.

Example 10 Production of a catalyst from YK-R

Using an aqueous platinum chloride solution, 1 Ge weight percent catalytic metal in each of the filter materials 1 to 7 and the filter 8 to 11 introduced, which then at 120 ° C. dried for 12 hours and for two hours at 500 ° C with a Heating rate of 20 ° C / min was sintered. As a result, the Obtain catalysts 12 to 22.

Example 11 Reaction tests of the catalysts

The catalysts 12 to 22 prepared in Example 10 were the same oxidation tests for CO, C₃H₈, SO₂ and the same Smoke combustion test as in Example 7 subjected. The result These are shown in Table 6 below.  

Example 12 Endurance test for catalysts at high temperatures

Each of the catalysts 12 to 22 according to Example 10 or in the Atmosphere sintered at 600 ° C for seven days. After that, the Catalysts the same oxidation tests for CO, C₃H₈ and SO₂ and subjected to the same smoke combustion test as in Example 7. The Results are shown in Table 6 below.

Example 13

Investigation of the chemical stability of the catalysts against Sulfur oxide.

In dry air with a content of 200 ppm of SO₂ everyone was the catalysts 12 to 22 sintered at 600 ° C for seven days. After that, the catalysts were subjected to the same oxidation reaction tests for CO, C₃H₈ and SO₂ and the same smoke combustion test as subject in Example 7. The results are in Table 6 below shown.

Table 6

Reaction tests

As can be seen from Table 6, the catalysts thus prepared are gates are both thermally stable at high temperatures and che are stable to sulfur oxide and show excellent kata analyzer effect, so that the particles at very low temperature can be ignited.

Example 14 Preparation of a catalyst for the engine test

100 g of the coatings as shown in Table 7 per liter of a single ceramic filter, such as egg such as that sold by Corning Incorporated, U.S.A. under the Brand "EX-54" is distributed. Then a catalytic Me tall in an amount of 1 percent by weight calculated on the Ge weight of the coating applied. After drying at 120 ° C for The air was sintered for 12 hours at 500 ° C for two hours Catalysts 1 to 6 produced. To the fatigue strength too test, Catalysts 2 and 4 were on for seven days Aged 800 ° C. To increase resistance to poisoning test, the catalysts 3, 5 and 6 were 200 ppm SO₂ at 200 ° C. suspended for seven days.  

Table 7

Catalysts for the engine test

Example 15 Attempt to determine the renewability of the catalyst

Each of the catalysts according to Example 14 was in an engine Installed. The engine was a supercharged single cylinder diesel, Model "Petter AV-B", distributed by Petters limited, in England. The engine was computer controlled and on following Values set: speed 2,250 rpm, 100 ° C coolant temperature, 90 ° C oil temperature, 2.5 bar oil pressure and 2,230 mbar La dedruck, the bypass valve was closed and the filter valve was open. The throttle was slightly open and if none The aim was to open the regeneration a little further Exhaust temperature increase. When it was regenerated, they were returned held particles burned due to catalyst ignition where was reduced by the exhaust back pressure of the exhaust pipe and the temperature at the rear end of the filter trap increases.

A was used for an analysis of the sulfur trioxide content in the exhaust gas predetermined exhaust gas volume in a mixture of isopropyl alcohol  and water (volume ratio 60:40) for two minutes by one Vacuum pump collected and using ion-liquid chromatogra compared to a standard solution.

The regeneration temperatures and the sulfur trioxide content with respect to the six catalysts according to Example 14 is in Table 8 shown.

Table 8

Engine test

As can be seen from Table 8, catalysts 1, 2 and 3 show all made from YK-R-1, excellent long-term egg properties without inactivation, even when they are high temperatures and / or exposed to sulfur oxide for a long time. Table 8 also shows that when the catalysts are high temperatures exposed for a long time, the one made from YK-R-1 Catalyst 2 is better than Catalyst 4, which is made of titanium dioxide exists, both with regard to the regeneration temperature and susceptibility to sulfur trioxide. The comparison of the Catalysts 3, 5 and 6 shows that Catalyst 3, which consists of YK-R-1 is produced, a lower renewal temperature and one has lower sulfur trioxide content than the other two ren catalysts, both made of aluminum iodide.

As described above, those can be obtained from YK-R-1 put the retained particles at very catalysts burn much lower temperatures than conventional Kataly and are also very stable, both thermally high temperatures as well as chemically against sulfur oxides and  are so very useful to contribute to diesel exhaust for long periods of time normal operating conditions of a diesel engine.

In the context of this description, the term denotes "Particle material" Particles that occur in the exhaust gas of a diesel engine.

The term "discharged catalyst" is used to refer to a composite designation to be used in a refinery after the Ent sulfurization of crude oil occurs.

Claims (20)

1. Catalyst composition for cleaning diesel exhaust gases, characterized in that it consists essentially of a residue which is obtained when discharging a spent catalyst which has been used in an oil refinery for desulfurization of crude oil, the catalyst composition comprising the following ingredients has: 80% or less of vanadium; 80% or less of molybdenum; 20% or less of nickel; 30% or less of cobalt; 99% or less of alumina; and traces of contaminants. 2. A method for producing a catalyst composition for purifying diesel exhaust gases according to claim 1, comprising the following process steps:

• - heating a catalytically active composition, which is obtained when unloading spent catalyst material from an oil refinery, which has been used for the desulfurization of crude oil, to a temperature between 400 and 1000 ° C for 0.5 to 5 hours; and
• - Grinding the composition into powder with a size of 100 to 800 mesh.

3. A process for producing a filter for cleaning diesel exhaust gases, with the following process steps:

• - Mixing a catalyst composition either alone or in combination with conventional filter material powders with a binder, an attacking agent, an active material and water to produce a homogeneous slurry, the catalyst composition being one according to claim 1;
• - Pour the slurry into a filter structure and
• - Sintering the filter structure at a temperature of about 200 to about 1000 ° C.

4. The method of claim 3, wherein the catalyst composition is obtained in a method according to claim 2. 5. The method according to claim 3 or 4, characterized in that at least one of the conventional filter powders from the following group is selected: Cordierite, Mullite, Zirkoni dioxide and silicon dioxide. 6. The method according to any one of claims 3 to 5, wherein the on slurry between 10 and 100 percent by weight of the catalytic converter gate composition contains and between 0 and 90% from ago conventional filter material powders. 7. The method according to any one of the preceding claims, characterized characterized in that the filter structure from the following Group selected: ceramic foam, open honeycomb structure, ceramic fiber filter, ceramic honeycomb structure and honeycomb structure monolith with wall flow.   8. Filter for cleaning diesel exhaust gases, thereby ge indicates that it uses a method according to a or more of the preceding claims. 9. A process for producing a coated filter for cleaning diesel exhaust gases, characterized by the following process steps:

• - Mixing a catalyst composition according to claim 1 either alone or in combination with conventional coating powders with water and an amount of acid or base such that a viscosity of 400 cps or less is set to produce a slurry suitable for coating;
• - depositing the coating slurry on the upper surface of a filter structure; and
• - Sintering the resulting filter material structure at a temperature between about 400 to about 1000 ° C.

10. The method according to claim 9, characterized in that the A catalyst composition in a process according to claim 2 is generated. 11. The method according to claim 9 or 10, characterized in that that at least one of the conventional coating powders is selected from the following group: aluminum oxide, Ti tan dioxide and silicon dioxide. 12. The method according to any one of claims 9 to 11, characterized records that the coating slurry has a content of 10 to 100 percent by weight of catalyst composition and a content of 0 to 90% of conventional coating contains powder.   13. The method according to any one of claims 9 to 12, characterized records that the filter material structure from the following group pe is selected: ceramic foam, open honeycomb structure, kera mix fiber filter, ceramic honeycomb structure and honeycomb structure monolith with wall flow. 14. The method according to any one of claims 9 to 12, characterized records that the amount of coating deposit deposited slurry is 5 to 200 g / l filter material structure. 15. Filters for cleaning diesel exhaust gases, produced by a method according to one or more of claims 9 to 14. 16. A process for producing a catalyst for cleaning diesel exhaust gases, characterized by the following process steps:

• - Applying at least one catalytically active metal selected from the group consisting of platinum, palladium and rhodium on a filter having a coating or a filter material consisting of a catalyst composition according to claim 1; and
• - Sintering of the filter material or filter impregnated with the catalytic metal at a temperature between 400 ° C and 800 ° C.

17. The method according to claim 1, characterized in that the A catalyst composition with a process according to claim 2 is produced. 18. The method according to claim 16 or 17, characterized in that that the catalytically active material 0 to 7.07 g of platinum, 0 up to 7.07 g palladium and / or 0 to 2 g rhodium per liter of Has filter material or filter.   19. The method according to any one of claims 16 to 18, characterized records that the mass ratio between the catalytic acting metal and the coating in the range of 0.001 and 0.1. 20. Catalyst for cleaning diesel exhaust gas, manufactured according to a method according to one or more of claims 16 until 19.