JPH07328445A - Catalytic composition for removing particulate substance of diesel vehicle - Google Patents

Abstract

PURPOSE: To prepare a catalyst composition having superior performance to remove particulate materials of diesel vehicles and to obtain a filter medium, a filter body and a catalyst body prepared from the catalyst composition. CONSTITUTION: The catalyst composition is prepared from a spent catalyst and consists of <=80% vanadium, <=80% molybdenum, <=20% nickel, <=30% cobalt, <=99% alumina and a trace of impurities included in ordinary crude oil refining.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst composition for purifying exhaust gas discharged from a diesel vehicle, a filter material, a filter body and a catalyst for removing particulate and gaseous substances in exhaust gas using the catalyst composition. The present invention relates to a medium and a manufacturing method thereof.

[0002]

2. Description of the Related Art Particulate matter of exhaust gas emitted from a diesel vehicle is unburned carbon particles having an average diameter of about 0.3 μm, soluble organic substances and sulfides, and the concentration of the particulate matter is an environmental standard value ( When the smog regulation value in the case of the 1993 heavy duty vehicle: 40%) is exceeded, it not only causes visually unpleasant discomfort, but also induces cancer and is very harmful to the human body. Especially in Korea, where the ownership ratio of diesel vehicles is 42%, which is higher than any other country in the world, it is emerging as a major cause of air pollution. Therefore, strict emission regulations and purification of such particulate matter are required. Has been done.

The emission control standard for particulate matter is 0.67 g in 1996 for heavy-duty diesel vehicles.
/ HP. Hour (USA: 0.1 g / H since 1994)
P. Hour), the trend is to strengthen gradually every year,
Various studies have been actively conducted to remove particulate matter emitted from diesel vehicles. The development direction of particulate matter removal technology can be broadly divided into the suppression of unburned matter generation by engine improvement, the improvement of combustion efficiency using fuel additives, and the post-treatment of particulate matter.

While engine improvements and fuel additive utilization methods can improve combustion efficiency within the engine and can fundamentally reduce harmful substances such as particulate matter or soot,
Since the cost is excessively high and it is difficult to completely suppress it due to the technical limit, the removal method by the post-treatment technology is generally used. The post-treatment technology is composed of a filtration technology that filters particulate matter in exhaust gas and a regeneration technology that burns the filtered particulate matter to regenerate the filter material. We are focusing on research to select a filtering material with excellent performance that can effectively collect water, and apply it to an actual vehicle.

On the other hand, the filter medium is damaged by the increase of the back pressure in the engine exhaust passage due to the filtration of the particulate matter, the performance of the engine is deteriorated, and when the collected particulate matter is burned at a high temperature condition, the filter medium becomes a filter medium. Due to the serious problem of durability due to thermal shock, it was necessary to develop a regeneration technique for effectively burning particulate matter at low temperatures. The most widely known regeneration technology to date is to supply secondary energy from the outside using a burner, heater, etc. or to raise exhaust gas temperature by throttling, and to add a catalyst to fuel or a catalyst. There is a method in which the carbon dioxide is supported on a filter medium to reduce the activation energy of the oxidation reaction and thereby regenerate at a relatively low temperature.

In the present invention, among these techniques, a method for removing particulate matter by a catalytic action has been studied, which is a ceramic foam, wire mesh, metal foam, wall flow ceramic honeycomb, open flow ceramic honeycomb or metal honeycomb. A filter material containing a refractory three-dimensional structure such as the one described above is loaded with a catalyst material capable of burning particulate matter, and fine particulate matter contained in the exhaust gas of a diesel engine is filtered, and the diesel engine is normally operated. That is, the particulate matter is burned under the exhaust gas discharge conditions (gas composition and temperature).

The general required performance of a catalyst for purifying exhaust gas of a diesel engine is as follows. First of all, not only fine carbon particles but also harmful components of human body such as unburned hydrocarbons can be removed with high efficiency by combustion even at low temperature. Second,
As SO ₂ generated from a sulfur component contained in large amounts diesel in the engine used is less active that is oxidized to SO ₃ fuel, be less emissions of SO ₃ in the exhaust gas, the third The catalyst is not deactivated by poisoning agents such as SO ₂ and SO 4 and fourthly, it has durability that is not deactivated even when continuously used at high temperature.

Various methods have been proposed to enhance the efficiency of particulate matter removal by combustion. In these conventional methods, a platinum group metal, which is known as a catalyst for burning particulate matter, is prepared by pre-depositing a deposition support such as activated alumina or titania as a catalyst carrier on a filter material in order to provide a large reaction surface area. Is uniformly supported on the filter with an aqueous platinum group salt solution.

[0009]

However, the types and amounts of the deposition support and the catalyst component and the production method have not always provided a satisfactory catalytic effect. That is,
In the case of the general alumina, it is thermally stable at a high temperature of about 800 ° C. and has sufficient durability for continuous use at a high temperature, but is discharged by burning a large amount of sulfur component contained in light oil. There is a problem that it reacts with the sulfur trioxide to form aluminum sulfate and causes a change in surface area and pore structure, which causes a rapid decrease in activity of the catalyst having alumina as a carrier.

Further, in the case of the above-mentioned ordinary titania, it is chemically stable to sulfur trioxide and the activity decrease due to sulfur trioxide is small, but it is thermally unstable at 500 ° C. or more and is practically not practical. 300-60, which is the operating condition of a diesel vehicle
Deterioration at exhaust gas temperature of around 0 ° C, especially when repeatedly exposed to combustion of soot, that is, rapid rise in temperature during regeneration of filter media, causes a decrease in surface area and phase change of titania (that is, from anatase form to crystalline rutile). There is a drawback that the activity and durability are deteriorated by the destruction of the pore structure due to the morphology.

As explained above, no catalyst has yet been reported that completely satisfies the above four performances required as a diesel engine exhaust gas purification catalyst. Therefore,
The object of the present invention is, firstly, that it is thermally stable at high temperatures and can maintain a high catalytic effect for a long period of time, and the activity of the catalyst does not decrease due to the sulfur oxides produced in the engine, and it can be used alone in diesel vehicles. Disclosed is a catalyst composition having excellent combustion performance of particulate matter discharged from a catalyst, and a method for producing the same.

Secondly, it is to provide a filter medium having excellent performance for removing particulate matter of diesel vehicles using the catalyst composition and a method for producing the same. Thirdly, when the particulate matter of the diesel vehicle is to be removed by using the existing filter medium, the filter medium having the deposited support, which has the same effect as the filter medium for the second purpose, is deposited. And a method for manufacturing the same. Fourth,
It is an object of the present invention to provide a diesel engine particulate matter removing catalyst body using the filter medium or the filter body described above for the above purpose, and a method for producing the same.

[0013]

As a result of a number of experiments and researches conducted by the present inventors, a catalyst having an excellent catalytic effect for removing particulate matter discharged from a diesel vehicle and having the above-mentioned catalytic requirements Since a large amount of such catalyst components were found in the waste catalyst discharged in the desulfurization process in the heavy oil cracking facility of the refinery plant after the discovery of the components, filtration produced using such waste catalyst as a raw material The material or the deposition support alone exerts excellent performance in burning soot, and such a filter material or the deposition support has at least one platinum group metal selected from platinum group metals dispersed and supported thereon. The present invention was completed by discovering the fact that the medium can significantly improve the thermal stability at high temperature and the chemical stability to sulfur trioxide as compared with the existing catalyst bodies produced by using alumina or titania as a deposition support. .

The catalyst used in the desulfurization process in the heavy oil cracking facility of the refinery is generally aluminum 30-50.
%, Molybdenum 0-10%, nickel 0-3%, phosphorus 0-
It is composed of a weight ratio of 3%, etc., but by using it in the desulfurization process, catalyst components such as vanadium and cobalt which have an excellent effect on combustion of particulate matter are added in addition to such catalyst components. It is discharged as a waste catalyst with a completely new composition. The composition of the waste catalyst varies depending on the operating conditions of the desulfurization process, the period of use, the composition of crude oil and the desulfurization catalyst, etc., but generally 80% or less of vanadium, 80% or less of molybdenum, 20% or less of nickel and 30 % Or less, 99% or less of aluminum, and impurities during ordinary crude oil refining.

The method for producing a catalyst composition for removing particulate matter of a diesel vehicle for achieving the first object of the present invention comprises a) a step of heating and pre-treating a waste catalyst used as a raw material, and b. A) grinding the waste catalyst of step a) to produce a waste catalyst powder. The waste catalyst used as the raw material is a waste catalyst that is generally discharged in the desulfurization process in the heavy oil cracking facility of an oil refinery and contains impurities such as moisture or oil. The waste catalyst in an oxygen atmosphere of 400 to 1000
The waste catalyst powder is manufactured by heating at 0 ° C. for 0.5 to 5 hours and pulverizing it to 100 to 800 mesh particles with a pulverizer.

The waste catalyst thus pretreated is used as a raw material (hereinafter referred to as YK-R) for producing a filter medium, a deposition support and a catalyst body for achieving the object of the present invention. At this time, if the heating temperature is 400 ° C. or lower, the heating is insufficient and impurities are not completely removed. If the heating temperature is 1000 ° C. or higher, not only energy is wasted but also deterioration of the catalyst component in the waste catalyst is accelerated. Also, if the particle size is too large, it is difficult to obtain a uniformly mixed slurry at the time of slurry production in the next step, and if the particle size is too small, not only the manufacturing cost increases, but also the durability at high temperature is high. Sex decreases.

The method for producing a diesel vehicle particulate matter removing filter material for achieving the second object of the present invention is as follows: a) YK-R powder alone or YK-R powder mixed with an existing filter material powder. To produce a filter medium slurry, b) forming the filter medium slurry into a filter medium structure, and c) sintering the product resulting from the step b) to produce a filter medium.

The filter medium slurry is the YK-R produced as described above.
It is manufactured by thoroughly mixing a powder or a powder of YK-R powder and a powder of an existing filter medium with an adhesive, a molding stabilizer (Attacking Agent), an active substance and water. As the existing filter medium powder used in the present invention, all known substances such as cordierite, mullite, zirconia, and silica can be used as raw materials for producing ceramic filter medium, and there is no particular limitation. Further, the mixed composition of the YK-R powder and the existing filter medium powder is preferably 10 to 100% in the case of the YK-R powder and 0 to 90% in the case of the existing filter medium powder. YK-R
If the content of the powder is less than 10%, the concentration of the above-mentioned catalyst substance is small and the activity is lowered.

As the adhesive used in the present invention, any of the substances known in the art which are useful for curing ceramic materials can be used without any particular limitation. The molding stabilizer used in the present invention is useful for preventing a cylindrical foam (TubularFoam) of a ceramic material, and all the substances known in the art can be used without any particular limitation. As the active substance used in the present invention, any substance known in the art that is useful for controlling the pores of the ceramic material can be used, and there is no particular limitation.

The produced filter medium slurry is molded into a filter body structure by a known method useful for molding ceramic materials such as injection and extrusion, and is completely dried at 25 to 150 ° C. A filter medium is manufactured by sintering at ˜1000 ° C. The filter material of the present invention includes ceramic foam, open flow honeycomb, ceramic fiber filter,
Ceramic honeycomb, wall flow honeycomb monolith, etc. useful for filtering particulate matter in diesel vehicles,
All known three-dimensional structures can be used, without particular restrictions.

To achieve the third object of the present invention, a method for producing a filter body having a deposition support for removing particulate matter of a diesel vehicle deposited is as follows: a) YK-R powder alone or YK-R powder To prepare a deposited support slurry by mixing with the existing deposited support powder into b), b) depositing the deposited support slurry onto the existing filter media structure, and c) heating the resulting product of step b). To produce a filter body.

According to the present invention, even when the particulate matter of a diesel vehicle is to be removed by using the existing filter medium, the deposition support having the same excellent performance as that of the YK-R produced filter medium described above. Provide the body. The existing deposition support powder used in the present invention can be any substance known as a raw material for producing a deposition support, such as zeolite such as alumina, titania and silica, and there is no particular limitation.
In addition, the composition of the YK-R powder and the existing deposition support powder is preferably 10 to 100% in the case of the YK-R powder,
In the case of existing deposition supports, 0 to 90% is suitable. YK
When the content of -R powder is less than 10%, the concentration of the above-mentioned catalyst substance is small and the activity is lowered.

The depositing support slurry is prepared by adding water to the YK-R powder or a mixture of the YK-R powder and the depositing support powder and mixing them uniformly, and then adding an acid or a base to give a viscosity of 40.
It is manufactured by adjusting it to 0 cps or less. The composition of the deposition support powder in the deposition support slurry was 3 by weight.
-50% is suitable. In the slurry, when the content of the deposition support powder is less than 3%, the content of the catalyst component is small and it is difficult to exert a catalytic effect, and when the content of the deposition support powder is 50% or more, the deposition support powder is excessively dispersed and the viscosity is increased. It is difficult to produce low deposition support slurries. Further, when the viscosity is 400 cps or more, it is difficult to uniformly coat the deposition support on the filter body.

The form of the filter medium used in the present invention is ceramic foam, open flow honeycomb, ceramic fiber filter, ceramic honeycomb, metal foam, wall flow honeycomb monolith, metal mesh, etc., as a particulate matter filter medium for diesel vehicles. All three-dimensional structures which are useful and already known can be used without any special limitation.

5 to 200 g of the deposited support slurry is deposited on the filter medium per liter of the filter medium, dried, and sintered at 400 to 1000 ° C. to produce a filter body. At this time, if the amount of the deposited support slurry is 5 g / liter or less, a sufficient surface area cannot be provided and the concentration of the catalyst substance is low, so that the catalytic performance is deteriorated, and if it is 200 g / liter or more, the exhaust gas pressure is excessively increased. Operation efficiency is reduced. It is also possible to deposit the deposition support on the YK-R-manufactured filter media described above to provide sufficient surface area.

The method for producing a diesel vehicle particulate matter removing catalyst body of the present invention for achieving the fourth object of the present invention comprises: a) a method for producing the second and third objects. The step of supporting the catalyst metal on the filter material or the filter body, and the step of b) baking the product of the step a) to produce the catalyst body. After supporting the solution containing the catalytic metal on the filter material or the filter body, the catalyst material is heated to, for example, 400 to 800 ° C. and calcined to finally produce the metal or metal oxide form catalyst body.

The catalyst metal of the present invention is a solution of at least one platinum group metal selected from platinum group metal compounds such as platinum, rhodium or palladium. The content of platinum, rhodium or palladium is preferably platinum per liter of the filter medium. 0-7.07 g, rhodium 0-2 g, palladium 0-
7.07 g (but the total amount of these metals is greater than 0).

Further, the ratio of the amount of at least one noble metal selected from platinum, rhodium and palladium deposited on the deposition support (nonmetal / deposition support weight ratio) is 0.00.
The range of 1/1 to 0.1 / 1 is desirable. If the ratio of the amount of the noble metal supported on the deposition support is 0.001 / 1 or less, the amount of the supported noble metal is too small to expect the catalytic effect of the noble metal, and if it is 0.1 / 1 or more, the catalyst of the noble metal is used. Since there is almost no increase in effect and only the cost of precious metals is increased,
It is disadvantageous both economically and effective use of resources.

[0029]

EXAMPLES The constitution and effects of the present invention will be specifically described below with reference to examples. However, the following examples do not limit the scope of the invention.

[0030]

【Example】

Example 1. Method for producing catalyst component (YK-R) 1-1. Composition analysis of raw catalyst and waste catalyst (YK-R) After the catalyst was filled in the hydrodesulfurization process in the heavy oil cracking facility of Yuko Co., Ltd. as shown in Table 1 below and the process was operated for 250 days, ICP (Induct)
The results are shown in Table 2 below, in which the components are analyzed by ion coupled plasma and compared with the composition of the catalyst initially filled.

[0031]

[Table 1]

[0032]

[Table 2]

1-2. Change in Specific Surface Area with Heating Temperature After taking 10 g of each of the waste catalysts and heating them as shown in Table 3 below, the specific surface area was measured and shown in Table 3 below. It can be seen that when the heating temperature is 400 ° C. or lower, the heating is insufficient and impurities are not completely removed, and when the heating temperature is 1000 ° C. or higher, the pores are destroyed due to the deterioration of the catalyst component.

[0034]

[Table 3]

1-3. Production of catalyst composition (YK-R) powder 100 kg of the waste catalyst was heated in a furnace at a heating rate of 20 ° C./min to 800 ° C., heated for 2 hours, cooled, and then pulverized by a pulverizer. To produce 200 mesh powder.

Example 2. Reaction test (YK-R composition) 2-1. Sample Preparation 15 g each of the YK-R powder prepared in Example 1-3, alumina, and titania were taken and the composition 1 was prepared.
(For implementation) and Compositions 2 and 3 (for comparison) were prepared. 2-2. CO Oxidation Reaction Each of the composition samples 1 to 3 prepared in Example 2-1 was charged in a reactor in an amount of 1 g and fixed, and then the reaction temperature was adjusted. While allowing air containing 200 ppm of CO to flow into the reactor at a space velocity of 50,000 / h, the concentration of CO at the outlet of the reactor is subjected to combustion analysis based on the time-resolved results to investigate the temperature at which the conversion rate becomes 50%.

2-3. C ₃ H ₈ Oxidation reaction Using the same method as the CO oxidation reaction test, 1000 ppm of C ₃
The temperature at which the conversion of C ₃ H ₈ is 50% is measured while injecting a mixed gas of H ₈ and air. 2-4. SO ₂ Oxidation Reaction The SO ₂ conversion rate is measured at 450 ° C. while introducing a mixed gas of 50 ppm SO ₂ and air in the same manner as in the CO oxidation reaction test.

2-5. Soot combustion test Each of the composition samples 1 to 3 prepared in Example 2-1 was uniformly mixed with 1 g of the particulate matter in the smoke, and then charged into the reactor. Increase temperature by 10 ° C per minute to 200 ° C
When the temperature reached, the temperature at which ignition was performed (soot combustion temperature) was measured while increasing the temperature by 1 ° C. per minute. The measured C
Table 4 below shows the 50% conversion of O and C ₃ H ₈ , the SO ₂ conversion at 450 ° C. and the soot burning temperature.

Example 3. Durability Evaluation at High Temperature 5 g of each of the catalyst compositions 1-3 created in Example 2-1 was placed in a furnace and heated to 800 ° C. at a heating rate of 20 ° C./min. Left for 5 hours.
This catalyst composition was treated in the same manner as in Example 2 with CO, C ₃ H ₈ ,
The results of measuring the SO ₂ oxidation reaction activity and the soot burning temperature are shown in Table 4 below.

Example 4. Evaluation of Chemical Stability to Sulfur Oxide After taking 5 g of each of the catalysts 1-3 produced in Example 2-1 and putting them in a furnace, 50 at a heating rate of 20 ° C./min.
The mixture was heated to 0 ° C., and nitrogen gas containing 100 ppm of SO ₃ was flown at 2 liter / min for 50 hours. The results of measurement of CO, C ₃ H ₈ , SO ₂ oxidation reaction activity and soot burning temperature of this catalyst by the same method as in Example 2 are shown in Table 4 below.

[0041]

[Table 4] Note) CO means temperature (° C) at 50% CO conversion. HC means temperature (° C.) at 50% C ₃ H ₈ conversion. SO ₂ means SO ₂ conversion (%) at 450 ° C. T means a soot burning temperature (° C.).

As shown in Table 4, YK-R (waste catalyst composition) powder (Sample 1) not only excels in soot combustion performance by itself, but also has high thermal stability at high temperature and sulfur oxidation. It can be seen that the chemical stability of the catalyst is excellent and that it actually has excellent durability as a catalyst composition for removing particulate matter of diesel vehicles.

Example 5. Manufacturing of filtration material 5-1. Manufacture of Foam filter media 2 cm x 2 cm x 2 of 10 ppi polyurethane foam
After being cut to a size of cm, the solution was allowed to stand for 10 minutes in a solution having a weight ratio of water and methyl alcohol of 1: 1 and then dried.

YK-R1 produced in Examples 1-3 above
After adding 15 g of dextrin as a binder to 00 g, 7 g of monoethanolamine is added as a molding stabilizer. Then, 60 g of water and 6 ml of ethylene glycol, which is an active substance, were added, and the mixture was stirred and put into a slurry so that it was sufficiently supported on the foam, and about 80% of the slurry supported on the foam was added. Remove and dry. The process of supporting the slurry on the polyurethane foam is repeated three times to obtain a substance in which YK-R is supported on the polyurethane foam having a total weight of 6 g. After drying this at 50 ° C for 24 hours, 0.5 ° C /
3 hours after heating to 300 ℃ at a heating rate of 1 minute, 1 ℃
Form 1 (filter material 1) is manufactured by heating to 900 ° C. at a heating rate of 1 minute / minute and then sintering for 1 hour. Foam 2 (filter material 2 / comparative) was made using cordierite powder alone.

5-2. Flow-slow honeycomb
-Through Honeycomb) Manufacturing Flow of Filter Media-The slow honeycomb filter media is manufactured by the extrusion method, and the manufacturing process is as follows. To 100 g of YK-R powder, 4 g of methyl cellulose is added as a binder, 15 g of a pore-forming material is added, and dry pulverization and mixing are performed with a ball mill for 1 hour. An appropriate amount of water is added to the mixed raw materials to produce a slurry having a strength of 0.8 to 1 mg / mm ² . While injecting this slurry into a screw extrusion molding machine, a honeycomb having a diameter of 5 mm was molded. The molded product was dried in a drying oven at 70 ° C. for 36 hours, and then sintered while being heated in multiple stages as shown in FIG. 1 to complete (filter material 3). In addition, filter medium 4 (for comparison) was manufactured by using cordierite powder alone.

5-3. Wall Flow Honeycomb (Wall-F
Production of low honey comb) type filter medium The flow-throw type honeycomb produced from YK-R as a raw material in Example 5-2 was prepared according to US Pat. No. 4,411,85.
Easy castable polymer (Ea
A wall-flow honeycomb filter material 5 was manufactured by a method in which a slurry made of the same material as that of the honeycomb was pressed in using a mask made of sy Castable Polymer) to selectively close the holes. The YK-R and cordierite powder were mixed in a ratio of 1: 1 to prepare a filter medium 6 by the same method as described above. (For comparison) was manufactured.

Example 6. Manufacture of filter body 2 cm x 400 cpi ceramic honeycomb monolith
Cut into 2 cm x 2 cm pieces. YK-R powder 1000
g and 900 g of water were mixed and then pulverized into a slurry state by a pulverizer for 24 hours. The slurry was transferred to a stirring tank, concentrated acetic acid and aqueous ammonia were added thereto with stirring, and the pH was adjusted to 4.
5, the viscosity was adjusted to 95 cps. The ceramic honeycomb monolith prepared here is dipped, blown with compressed air of 40 psi, heated to 120 ° C. at a heating rate of 20 ° C./min, heated for 10 hours, and heated at 500 ° C. for 2 hours, and then Y
A filter body 8 carrying 1.3 g of KR deposition support was produced. Also, the YK-R and alumina powder were mixed in a ratio of 1: 1 to manufacture a filter body 9 by the same method as described above, and the alumina powder and titania powder were used alone to obtain filter bodies 10 and 11 (comparative). Manufactured).

Example 7. Reaction test (filter material and filter body) 7-1. CO oxidation reaction Filter media and filters 1 to 11 produced in Examples 5 and 6 above.
After each was attached to the reactor, the reaction temperature was adjusted.
Air containing 200 ppm CO was passed through a space velocity of 50,000
CO at the outlet of the reactor while flowing into the reactor at 0 / h
Combustion analysis is performed on the concentration based on the time-resolved result to investigate the temperature at which the conversion rate becomes 50%. 7-2. C ₃ H ₈ oxidation reaction 100 ppm of C ₃ H in the same manner as the CO oxidation reaction test
_The temperature at which the C ₃ H ₈ conversion rate was 50% was measured while introducing a mixed gas of ₈ and air.

7-3. SO ₂ Oxidation Reaction The SO ₂ conversion rate is measured at 450 ° C. while introducing a mixed gas of 50 ppm SO ₂ and air in the same manner as in the CO oxidation reaction test. 7-4. Soot burning test Filter media 1 to 7 and filter body 8 produced in Examples 5 and 6 above.
1 to 11 g of soot are evenly charged and then loaded into the reactor. Increase the temperature by 10 ° C per minute to 200
When the temperature reached 0 ° C, the temperature was raised by 1 ° C per minute and the ignition temperature (soot combustion temperature) was measured. The measured CO and C ₃
Table 5 below shows 50% conversion of H ₈ , SO ₂ conversion at 450 ° C. and soot burning temperature.

Example 8. Durability evaluation at high temperature Filter media 1 to 7 and filter body 8 produced in Examples 5 and 6 above.
After putting ~ 11 into the furnace, 800 at a heating rate of 20 ° C / min
After heating to ℃, it was left for 5 hours. The results of measurement of CO, C ₃ H ₈ , SO ₂ oxidation reaction activity and soot combustion temperature of this catalyst by the same method as in Example 7 are shown in Table 5 below.

Example 9. Evaluation of chemical stability against sulfur oxides Catalysts 1 to 7 and filters 8 to 8 produced in Examples 5 and 6 above
After putting 11 in the furnace, 500 ℃ at a heating rate of 20 ℃ / min
After heating, nitrogen gas containing 1,000 ppm of SO ₃ was passed at 2 liters / minute for 50 hours. The results of measurement of CO, C ₃ H ₈ , SO ₂ oxidation reaction activity and soot combustion temperature of this catalyst by the same method as in Example 7 are shown in Table 5 below.

[0052]

[Table 5] Note) CO means temperature (° C) at 50% CO conversion. HC means temperature (° C.) at 50% C ₃ H ₈ conversion. SO ₂ means SO ₂ conversion (%) at 450 ° C. T means a soot burning temperature (° C.).

As shown in Table 5, the YK-R-made filter medium or filter body not only excels in the soot-smoke combustion performance as compared with the existing filter medium or filter body, but also heat at high temperature. The chemical stability and chemical stability due to sulfur oxides are excellent, and it can be seen that it actually has excellent durability as a catalyst for removing particulate matter of diesel vehicles.

Example 10. Production of catalyst body from YK-R Using chloroplatinic acid aqueous solution for each of the filtration media 1 to 7 and the filtration media 8 to 11 produced in Examples 5 and 6,
After supporting the catalyst metal content to be 1 wt%, 12
After being dried at 0 ° C. for 12 hours and then calcined at a heating rate of 20 ° C./min to 500 ° C. for 2 hours, catalyst bodies 12 to 22 were manufactured.

Example 11. Reaction test (catalyst body) With respect to the catalyst bodies 12 to 22 produced in Example 10, CO, C ₃ H ₈ and SO ₂ were produced in the same manner as in Example 7.
The conversion rate and the soot burning temperature were measured, and the results are shown in Table 8 below.
Shown in.

Example 12 Durability evaluation at high temperature (catalyst body) The catalyst materials 12 to 22 produced in Example 10 were treated at 600 ° C.
Baked in air for 7 days. These catalysts were subjected to a CO, C ₃ H ₈ and SO ₂ oxidation reaction and a soot combustion test in the same manner as in Example 7, and the results are shown in Table 6 below.

Example 13. Evaluation of chemical stability to sulfur oxides (catalyst body) The catalyst bodies 12 to 22 produced in Example 10 were heated to 400 ° C.
Calcination in dry air containing 200 ppm SO ₂ for 7 days. Using these catalysts in the same manner as in Example 7, CO, C ₃
H ₈ and SO ₂ oxidation reaction and soot combustion test were conducted, and the results are shown in Table 6 below.

[0058]

[Table 6] Note) CO means temperature (° C) at 50% CO conversion. HC means temperature (° C.) at 50% C ₃ H ₈ conversion. SO ₂ means SO ₂ conversion (%) at 450 ° C. T means a soot burning temperature (° C.).

As shown in Table 6 above, the catalyst body produced by using the filter medium or the deposition support produced from the waste catalyst burns the particulate matter at a much lower temperature than the conventional catalyst body. It has an excellent catalytic effect to regenerate the filter material by
It can be seen that the thermal stability at high temperatures and the chemical stability against sulfur oxides are excellent.

Example 14 Manufacture of catalyst body for engine test After depositing 100 g / l of the deposition support as shown in Table 7 below on EX-54 ceramic single-body filter manufactured by Corning Incorporated in the United States, the metal support was deposited. The catalyst metal was supported so as to be 1 wt% based on the above. This is dried at 120 ℃ for 12 hours, then 500 ℃
It was calcined in air for 2 hours to produce six catalyst bodies 1-6. The catalyst bodies 2 and 4 were aged at 800 ° C. for 7 days to evaluate the durability of the catalyst bodies, and the catalyst bodies 3, 5 and 6 were exposed to 200 ° C. for 7 days to investigate the SO ₂ poisoning resistance. Two
Exposed to 00 ppm SO ₂ .

[0061]

[Table 7]

Example 15. Evaluation of Regeneration Performance of Catalyst Body Each of the catalyst bodies produced in Example 14 was putter AV-B (Petter AV-B) manufactured by Petters Ltd.
B) After installed in a supercharged single cylinder diesel engine, operating speed 2250 rpm, cooling water temperature 1
00 ° C, oil temperature 90 ° C, oil pressure 2.5 bar,
The bypass valve of the engine is closed and the filtration trap valve is opened under the operation conditions of air input of 2230 mbar and computer operation. When the throttle was slightly opened and the regeneration phenomenon did not occur, the catalyst was regenerated while the exhaust temperature was raised by further opening the throttle. When regeneration occurs, the collected particulate matter burns due to catalyst ignition, the back pressure of the engine exhaust pipe decreases, and the temperature at the rear end of the filter trap rises.

The sulfur trioxide content in the exhaust gas was measured by ionic liquid phase chromatography by collecting a certain amount of exhaust gas with a vacuum pump for 2 minutes in a mixed solution having a volume ratio of isopropyl alcohol and water of 60:40. Compared with standard solution by chromatography,
analyzed. By the above test method, the emission amount of sulfur trioxide at the regeneration temperature was measured for the six catalyst bodies produced in Example 14, and the results are shown in Table 8 below.

[0064]

[Table 8]

Comparing the catalyst bodies 1, 2, and 3 in Table 8 above, it can be seen that the catalyst bodies prepared from YK-R-1 have the activity of the catalyst bodies even when exposed to high temperature or sulfur oxide for a long time. It can be seen that it has excellent durability that does not decrease. Also, comparing the catalyst bodies 2 and 4, when exposed at high temperature for a long time,
It can be seen that the catalyst body 2 made from YK-R-1 has a lower regeneration temperature and lower sulfur oxide emissions than the catalyst body 4 made from titania.

Further, comparing the catalyst bodies 3, 5, and 6,
When exposed to sulfur oxides for a long time, the catalyst body 3 made of YK-R-1 becomes a catalyst body 5 made of alumina,
It can be seen that it has a lower regeneration temperature and sulfur oxide emission amount as compared with No. 6. As described above, the catalyst body produced from YK-R-1 has an excellent catalytic effect of regenerating the filter medium by burning the particulate matter even at a very low temperature as compared with the conventional catalyst body, and at a high temperature. It can be seen that the thermal stability and the chemical stability with respect to sulfur oxides are excellent, and the catalyst exhibits excellent performance for a long time as a catalyst for removing particulate matter even under the operating conditions of diesel vehicles.

[0067]

[Effects of the Invention] When the filter medium or the catalyst body containing the filter body produced by YK-R by the above-mentioned method is mounted on the filter device to remove the particulate matter of the diesel vehicle, the particulate matter is removed. It has excellent combustion performance with respect to diesel fuel and has excellent thermal stability at high temperatures and chemical stability against sulfur oxides generated during diesel combustion, which makes it possible to maintain the diesel particulate matter removal performance for a long period of time. So it is suitable for the removal of diesel vehicle particulate matter.

[Brief description of drawings]

1 shows the sintering conditions at the time of manufacturing the filter medium 3 of Example 5. FIG.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location B01D 53/94 B01J 23/88 ZAB A 23/96 ZAB A (72) Inventor Kim Yong Woo South Korea, Dae Jeong, Sugu, Samsung-dong, Dong-sung Kwa Apartment 1-505 (72) Inventor Choi Yong-taek, Republic of Korea, Daejeung, Yusung, Jun-min Dong 460-1, Samsung Plung Apartment 113-503 (72) Inventor Lee Ki-ho, Republic of Korea, Daejeung, Yousung, Jun Min Dong 460-1, Samsung Prung Apartment 113-501 (72) Inventor Min Kyung Chul Republic of Korea, Daejeung, Sugu, Well Pyeong Dong Dong San 285-2 Block, Saeville Apartment 102-307 (72) Invention Eun Jae Eun Korea, Dae Jeung, Yu Sung, Ae Eun Dong, Hanbit A Part 118-104

Claims (30)

[Claims] 1. Vanadium 80% or less, molybdenum 80
% Of nickel, 20% or less of nickel, 30% or less of cobalt, 99% or less of alumina, and trace impurities contained during ordinary crude oil refining, and used catalyst composition for removing particulate matter of diesel engine. 2. A waste catalyst used as a raw material is heated and pretreated, and then crushed to obtain 80% or less of vanadium,
Particulates of a diesel engine characterized by producing a waste catalyst composition consisting of 80% or less of molybdenum, 20% or less of nickel, 30% or less of cobalt, 99% or less of alumina, and trace impurities contained during ordinary crude oil refining. A method for producing a waste catalyst composition for removing a substance. 3. The heating temperature of the waste catalyst is 400 to 100.
The method for producing a waste catalyst composition for removing particulate matter of a diesel engine according to claim 2, wherein the temperature is 0 ° C. 4. The particle size of the waste catalyst is 100-80.
The method for producing a waste catalyst composition for removing particulate matter of a diesel engine according to claim 2, which is pulverized to 0 mesh. 5. Vanadium 80% or less, molybdenum 80
% Or less, nickel 20% or less, cobalt 30% or less, alumina 99% or less, and a trace amount of impurities contained in a usual crude oil refining alone, or the waste catalyst composition is used as an existing filter medium. A method for producing a filter material for removing particulate matter of a diesel engine, which comprises producing a filter medium slurry by using a mixed substance of powders as a raw material, molding this into a filter medium structure, and incinerating this. 6. The method for producing a particulate matter removing filter material for a diesel engine according to claim 5, wherein the waste catalyst composition is produced by heating the waste catalyst and then pulverizing the waste catalyst. 7. The heating temperature of the waste catalyst is 400 to 100.
It is 0 degreeC, The manufacturing method of the filter material for particulate matter removal of the diesel engine of Claim 6 characterized by the above-mentioned. 8. The particle size of the waste catalyst is 100-80.
The method for producing a filter material for removing particulate matter of a diesel engine according to claim 6, wherein the filter material is pulverized to 0 mesh. 9. The method for producing a particulate matter removing filter material for a diesel engine according to claim 5, wherein the existing filtering material powder is cordierite, mullite, zirconia, silica or the like. 10. The composition of the filtering medium slurry is 10 to 100% by weight of the waste catalyst composition and 0 to 9 of the existing filtering medium powder.
The method for producing a particulate matter removing filter material for a diesel engine according to claim 5, wherein the method comprises a content of 0%. 11. The form of the filter medium is ceramic foam,
The method for producing a particulate matter removing filter material for a diesel engine according to claim 5, which is an open flow honeycomb, a ceramic fiber filter, a ceramic honeycomb, a wall flow honeycomb monolith, or the like. 12. A filter material for removing particulate matter from a diesel engine, which is manufactured by the method according to any one of claims 5 to 11. 13. Vanadium 80% or less, molybdenum 8
0% or less, nickel 20% or less, cobalt 30% or less,
Deposition support produced by using a waste catalyst composition consisting of 99% or less of alumina and a trace amount of impurities usually included in the refining of crude oil alone, or a mixed substance of the waste catalyst composition and an existing deposition support powder as a raw material. A method for producing a filter body on which a deposition support for removing particulate matter of a diesel engine is deposited, which is produced by producing a body slurry, depositing it on the surface of a filter medium, and then firing it. 14. The filter body having the deposition support for removing diesel engine particulate matter according to claim 13, wherein the waste catalyst composition is produced by heating the waste catalyst and then pulverizing the waste catalyst. Manufacturing method. 15. The heating temperature of the waste catalyst is 400 to 10
The method for producing a filter body having a deposition support for removing particulate matter of a diesel engine according to claim 14, wherein the temperature is 00 ° C. 16. The particle size of the spent catalyst is 100-8.
The method for producing a filter body according to claim 14, wherein the filter body has a deposition support for removing particulate matter of a diesel engine, which is pulverized to a size of 00 mesh. 17. The filter body having a deposition support for removing particulate matter of a diesel engine according to claim 13, wherein the existing deposition support powder is a zeolite such as alumina, titania or silica. Production method. 18. The composition of the deposition support slurry comprises 10 to 100% by weight of the waste catalyst composition and 0 to 90% of the existing deposition support powder.
A method for producing a filter body on which a deposition support for removing particulate matter of a diesel engine described above is deposited. 19. The firing temperature of the filter is 400 to 10
The method for producing a filter body having a deposition support for removing particulate matter of a diesel engine according to claim 13, wherein the temperature is 00 ° C. 20. The form of the filter medium is ceramic foam,
The filter with deposited support for removing particulate matter of a diesel engine according to claim 13, which is an open flow honeycomb, a ceramic fiber filter, a ceramic honeycomb, a metal mesh, a metal foam, a worm flow honeycomb monolith, or the like. Body manufacturing method. 21. The deposition support for removing particulate matter of a diesel engine according to claim 13, wherein the deposition support deposited on the filter medium is 5 to 200 g per liter of the filter medium. A method for manufacturing a filter body. 22. A filter body having a deposition support for removing particulate matter of a diesel engine deposited by the method according to any one of claims 13 to 21. 23. Vanadium 80% or less, molybdenum 8
0% or less, nickel 20% or less, cobalt 30% or less,
Platinum, palladium, rhodium, or other platinum on the surface of a filter material on which a filter material or a deposition support is deposited, which is produced by using a waste catalyst composition containing 99% or less of alumina and trace impurities contained in ordinary crude oil refining as a raw material. A method for producing a catalyst body for removing particulate matter of a diesel engine, which comprises producing at least one platinum group metal selected from the group metals and then firing it. 24. The method for producing a particulate matter removing catalyst body for a diesel engine according to claim 23, wherein the waste catalyst composition is produced by heating the waste catalyst and then pulverizing the waste catalyst. 25. The heating temperature of the waste catalyst is 400 to 10
The method for producing a particulate matter removing catalyst body for a diesel engine according to claim 24, wherein the temperature is 00 ° C. 26. The particle size of the waste catalyst is 100-8.
25. The method for producing a catalyst body for removing particulate matter of a diesel engine according to claim 24, wherein the catalyst body is pulverized to 00 mesh. 27. At least one metal selected is
0 to 7.07 g per liter of the filter medium or filter body
24. Platinum of 0, 7.07 g of palladium and 0-2 g of rhodium are contained, and the total amount of these is greater than 0. . 28. The weight ratio of the platinum group metal to the deposition support (platinum group metal / deposition support) is 0.001 / 1 to 0.1.
24. The method for producing a particulate matter removing catalyst body for a diesel engine according to claim 23, wherein 29. The calcination temperature of the catalyst body is 400-80.
The method for producing a particulate matter removing catalyst body for a diesel engine according to claim 23, wherein the temperature is 0 ° C. 30. A catalyst body for removing diesel engine particulate matter, which is produced by the method according to any one of claims 23 to 29.