JP3230799B2 - Exhaust gas purification equipment for diesel engines - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an exhaust gas from a diesel engine which is passed through a catalytic device, where unburned components in the exhaust gas, particularly HC and SO in particulates, are passed through the catalytic device.
The present invention relates to an exhaust gas purification device in which F is oxidized and purified.

[0002]

2. Description of the Related Art Exhaust gas discharged from a diesel engine is usually unburned as HC (hydrocarbon), soot or SO.
Fine particles composed of F (organic solvent-soluble component) and the like (hereinafter referred to as “particulates”). Since these pollute the atmosphere, conventionally, a method has been proposed in which a filter is provided in an exhaust system of a diesel engine, particulates in exhaust gas are captured by the filter, and ignited and burned by a burner or a heater. However, the method using a burner or a heater has a disadvantage that a large amount of cost is required because fuel and electric power are used.

[0003] An exhaust gas treatment device that uses a filter carrying an oxidation catalyst without using a burner or a heater and burns unburned components according to the temperature of the exhaust gas itself of a diesel engine has been proposed.
For example, it is known from JP-A-3-210008. That is, Japanese Patent Application Laid-Open No. Hei 3-210008 discloses an exhaust gas treatment apparatus in which exhaust gas is passed through a catalyst device, and unburned components in the exhaust gas are oxidized and purified. A first filter composed of a fine filter and a second filter composed of a coarse filter carrying a noble metal-based oxidation catalyst are combined in series in the flow direction of exhaust gas. Fine filters that catch particulates and cause clogging and require replacement should be filters that carry inexpensive base metal oxidation catalysts, and expensive filters that carry precious metal oxidation catalysts should be replaced without clogging Disclosed is an unnecessary coarse filter.

[0004] Also, Japanese Patent Application Laid-Open No. Hei 3-210008 discloses that
Disclosed is that a heat storage structure made of a ceramic honeycomb formed body is arranged on the exhaust gas upstream side of the first and second filters to assist the combustion of particulate carbon in a noble metal-based oxidation catalyst. However, in the apparatus disclosed in Japanese Patent Application Laid-Open No. Hei 3-210008, the heat storage body accumulates the heat of the exhaust gas discharged from the exhaust pipe of the diesel engine and, when the temperature of the exhaust gas falls, radiates heat to heat the exhaust gas, and the noble metal When the temperature of the exhaust gas discharged from the exhaust pipe of the diesel engine is low because it assists the combustion of particulate carbon in the system oxidation catalyst and cannot utilize the combustion heat generated in the catalyst device However, there was a disadvantage that unburned components in exhaust gas, particularly SOF in HC and particulates, were not sufficiently oxidized.

FIG. 5 is a graph showing the effect of a Pt-based oxidation catalyst device using a simulated gas simulating exhaust gas from a diesel engine. In the graph of FIG. 5, the horizontal axis represents the temperature (° C.) of the exhaust gas at the inlet of the Pt-based oxidation catalyst device, and the vertical axis represents the conversion of the HC component (propylene) in the simulated gas. The simulated gas, as shown on the right side of FIG.
00 ppm, C ₃ H ₆ (propylene) 300 ppm, O
₂ 10%, 20 ppm of SO _2, comprises a H ₂ O 4%, the simulated gas throughput per unit volume of the unit time the catalyst (S
V) is 20,000 per hour (20,000 hr ^-1 ).

As shown in FIG. 5, in the Pt-based oxidation catalyst device, the temperature of the exhaust gas at the catalyst device inlet is 220 ° C.
At this time, the conversion of HC exceeds 20%, and the increase in the conversion with respect to the rise in the inlet temperature becomes steep, and a practical effect of reducing the HC component in the exhaust gas is produced. However, when the inlet temperature is 220 ° C. or lower, the reduction rate (conversion rate) of HC in the exhaust gas is only 20% or lower. Therefore, in the Pt-based oxidation catalyst device, in order to reduce HC in the exhaust gas, it is necessary to set the exhaust gas temperature at the catalyst device inlet to 220 ° C. or more.

[0007]

In order to combust and purify unburned components, particularly HC, in exhaust gas of a diesel engine in an oxidation catalyst device, the temperature of the exhaust gas at the inlet of the catalyst device is generally higher than a certain temperature (see FIG. 1). In the case of the Pt-based oxidation catalyst device of No. 5, the temperature must be 220 ° C. or higher. However, in a diesel engine, generally, under operating conditions with a small engine load, for example, an idling operation and a low-speed operation, the temperature of the exhaust gas decreases, and a temperature may occur in which the HC component does not decrease in the oxidation catalyst device. An object of the present invention is to provide an exhaust gas purifying apparatus in which exhaust gas is passed through an oxidation catalyst device, and the unburned components in the exhaust gas are oxidized and purified, even when the exhaust gas temperature decreases, without using expensive fuel. It is to heat and raise the temperature of exhaust gas, thereby efficiently purifying HC components in an oxidation catalyst device.

A more specific object of the present invention is to measure the amount of heat of exhaust gas discharged to an exhaust manifold and the amount of heat generated by oxidation of unburned components in exhaust gas in a preceding oxidation catalyst device (first oxidation catalyst device). Both are accumulated in the heat storage structure,
When the low-temperature exhaust gas flows, the amount of heat accumulated in the heat storage structure is released, the temperature of the exhaust gas is raised, and the exhaust gas is supplied to the subsequent oxidation catalyst device (second oxidation catalyst device), and the combustion heat of the unburned portion in the exhaust gas is reduced. The purpose of the present invention is to make it possible to effectively purify HC components in exhaust gas.

Another object of the present invention is to exchange heat between exhaust gas discharged from an exhaust manifold of a diesel engine and a heat exchange structure capable of exchanging heat. By lowering the exhaust gas temperature and releasing heat from the heat storage structure to the exhaust gas when the temperature of the exhaust gas is low, the temperature of the exhaust gas is increased, thereby reducing the change in the exhaust gas temperature and reducing the difference between the maximum temperature and the minimum temperature. To reduce the thermal load on the catalyst device on the downstream side of the catalyst to reduce the thermal degradation of the catalyst. Other objects and advantages of the present invention will become apparent in the following description.

[0010]

The exhaust gas purifying apparatus of the present invention is of a type in which exhaust gas of a diesel engine is passed through a catalytic device, and unburned components in the exhaust gas are oxidized and purified. A first oxidation catalyst device disposed upstream of the first oxidation catalyst device, a second oxidation catalyst device disposed downstream of the first oxidation catalyst device, and a heat storage structure disposed between the first oxidation catalyst device and the second oxidation catalyst device. The heat storage structure is heated and stored by the exhaust gas when the exhaust gas passing through the heat storage structure is at a high temperature, and releases heat when the exhaust gas passing through the heat storage structure is at a relatively low temperature to heat the exhaust gas. The temperature of the exhaust gas at the inlet of the oxidation catalyst device is maintained at or above a predetermined value, and the unburned portion in the exhaust gas,
In particular, HC and SOF in particulates are oxidized and purified.

In the exhaust gas purifying apparatus of the present invention, preferably, the first oxidation catalyst device and the second oxidation catalyst device can independently oxidize and purify unburned components in the exhaust gas when the exhaust gas temperature is equal to or higher than a predetermined value. In each case, a metal carrier such as a metal honeycomb made of ferritic stainless steel is coated with Pt-metal oxide, Pd-metal oxide or Pt-Pd-metal oxide. The heat storage structure may be any material having a heat storage function and a structure through which exhaust gas can freely pass. Preferably, the heat storage structure is a ceramic honeycomb or a ceramic filter made of cordierite, SiC, SiN, or the like. The heat storage structure has an appropriate heat storage capacity and heat exchange so that the temperature of the exhaust gas flowing out of the heat storage structure becomes 220 ° C or more by absorbing heat from the high-temperature exhaust gas passing therethrough and releasing heat when the low-temperature exhaust gas passes. It shall have performance.

[0012]

In the exhaust gas purifying apparatus of the present invention, the exhaust gas discharged from the diesel engine body is introduced from the exhaust manifold into the first oxidation catalyst device of the catalyst device, and the exhaust gas is heated to a predetermined temperature (about 220 ° C.) or higher. In the first oxidation catalyst device, unburned components such as HC in exhaust gas and SOF in particulates are oxidized and purified by the presence of the oxidation catalyst. In this case, since the amount of heat is generated substantially in proportion to the content of the unburned portion, the temperature of the exhaust gas discharged from the first oxidation catalyst device is increased. The heated exhaust gas is then introduced into the heat storage structure to heat and heat the heat storage structure, and then the unburned portion is oxidized by the second oxidation catalyst device disposed downstream. Purified and released to the atmosphere.

When the temperature of the exhaust gas discharged from the engine body at the inlet of the first oxidation catalyst device is lower than a predetermined temperature (about 220 ° C.), the oxidation reaction of the unburned portion in the first oxidation catalyst device is slight, and the purification is not performed. Although insufficient, the exhaust gas exchanges heat when passing through the first oxidation catalyst device and the heat storage structure, is supplied with the amount of heat accumulated therein, and is heated and heated. Therefore, the temperature of the exhaust gas at the entrance of the second oxidation catalyst device is increased, and the unburned components in the exhaust gas are oxidized and purified in the second oxidation catalyst device and released to the atmosphere.

[0014] In the exhaust gas purifying apparatus of the present invention, the first oxidation catalyst device and the second oxidation catalyst device include Pt on the metal carrier.
-When coated with Al ₂ O ₃ , the predetermined temperature is about 220 ° C., and it is possible to maintain the predetermined temperature in a wide operating range of the diesel engine;
It is advantageous. Since the storage structure is a ceramic honeycomb or a ceramic filter made of cordierite, SiC or SiN, the storage structure can have heat resistance and durability.

[0015]

FIG. 1 is a layout diagram schematically showing an exhaust system of a diesel engine provided with an exhaust gas purifying apparatus 14 according to an embodiment of the present invention. In the exhaust system shown in FIG. 1, exhaust gas generated in the diesel engine main body 10 is discharged from the exhaust manifold 12 to the atmosphere through the purification device 14 and the muffler 16. The purification device 14 includes a cylindrical first oxidation catalyst device 22 disposed on the upstream side of the flow of the exhaust gas, and a cylindrical second oxidation catalyst device 2 disposed on the downstream side.
4, the first oxidation catalyst device 22 and the second oxidation catalyst device 24
The catalyst device 20 includes a cylindrical heat storage structure 23 disposed between the two.

FIG. 2 schematically shows a cylindrical heat storage structure 23 incorporated in the purification device of FIG. 1, FIG. 2A is a side view of the cylindrical heat storage structure, and FIG. 2B is a cylindrical heat storage structure. FIG. 2C is a partial enlarged view of FIG. 2B. The length L of the cylindrical heat storage structure 23 is, for example, 17.
8 cm (7 inches) and the diameter M is 19.1 cm
(7.5 inches). The cylindrical thermal storage structure 23 comprises a number of axially extending cells (cavities) 32 defined by a thin partition wall 34, the partition wall 34 having a thickness u of about 0.15 mm (6 milliinches). , 2.54cm
For example, a total of 400 cavities are arranged in a (1 inch) square, each of which is 20 in length and width. The material forming the cylindrical heat storage structure 23 is a ceramic such as cordierite, SiC, or SiN. The cylindrical heat storage structure 23 in FIG. 2 has a filter structure in which the longitudinal vertical cross sections of a large number of cavities are rectangular, but may also have a honeycomb structure in which the longitudinal vertical cross sections of the cavities are regular hexagons.

FIG. 3 shows a cylindrical first oxidation catalyst device 22 or a cylindrical second oxidation catalyst device 24 formed in the purification device of FIG. 1, and FIG. 3A shows a cylindrical oxidation catalyst device. FIG. 3B is a partially enlarged view of a cross section perpendicular to the axis of the cylindrical oxidation catalyst device. The length L and diameter M of the cylindrical oxidation catalyst device 22 are the same as those of the cylindrical heat storage structure 23.
The same dimensions are selected as, for example, the length L is 17.8c
m (7 inches) and diameter M is 19.1 cm (7.5 inches). In the cylindrical oxidation catalyst device 22, the metal support supporting the oxidation catalyst includes a large number of cells (cavities) 36 defined by a ferritic stainless steel foil 38 and extending in the axial direction. 50μ
m and a cavity 36 in a 2.54 cm (1 inch) square.
Are arranged, for example, 400 pieces.

The cylindrical oxidation catalyst devices 22 and 24 shown in FIG.
Although a honeycomb structure having a large number of cavities 36 is provided, a honeycomb structure having a rectangular or regular hexagonal vertical cross section in the longitudinal direction of the cavities may be used as in the case of the cylindrical heat storage structure 23. Each of the first oxidation catalyst device and the second oxidation catalyst device is provided with Pt on a metal carrier having a large number of cavities as described above.
It is coated with an oxidation catalyst of —Al ₂ O ₃ , Pd—Al ₂ O ₃ or Pt—Pd—metal oxide.

FIG. 4 is a graph schematically showing a change in the temperature of the exhaust gas. The horizontal axis H indicates time, and the vertical axis T indicates temperature (° C.). 4, the curve T ₁ shows the exhaust gas temperature in the exhaust manifold 12 (FIG. 1), the curve T ₂ are, shows the exhaust gas temperature after passing through the heat storage structure 23 (FIG. 1). As shown in FIG. 4, the temperature T ₂ of the exhaust gas passing through the heat storage structure has a shape in which the undulation of the curve of the temperature T ₁ is smoothed, and even when the temperature T ₁ temporarily becomes 220 ° C. or less. Exhaust gas temperature T ₂ after passing through the heat storage structure,
That is, the inlet temperature of the second oxidation catalyst device 24 of the exhaust gas purifying device of FIG. 1 can be set to 220 ° C. or higher, and this temperature is set within a range where the HC conversion rate of FIG. belongs to.

[0020]

In the exhaust gas purifying apparatus of the present invention, when the temperature of the exhaust gas discharged from the engine body is equal to or higher than a predetermined value, most of the unburned components in the exhaust gas are oxidized and purified in the first oxidation catalyst device. At the same time, the exhaust gas temperature is raised. In the first oxidation catalyst device, the heated exhaust gas is
Next, it passes through the heat storage structure and the second oxidation catalyst device, heats both, and is discharged to the atmosphere.

When the temperature of the exhaust gas discharged from the engine body is lower than a predetermined value, the exhaust gas discharged from the engine body hardly undergoes an oxidation reaction of unburned components while passing through the first oxidation catalyst device. Is heated by exchanging heat with the heat storage structure when passing through the heat storage structure. Therefore, by performing an oxidation reaction in the second oxidation catalyst device, unburned components in exhaust gas, particularly HC And the SOF in the particulates is oxidized and removed. That is, in the exhaust gas purifying apparatus of the present invention, both the amount of heat of the exhaust gas discharged to the exhaust manifold and the amount of heat generated by the oxidation of unburned components in the exhaust gas in the first oxidation catalyst device are accumulated in the heat storage structure. When the low-temperature exhaust gas flows, the amount of heat accumulated in the heat storage structure is released and heats the exhaust gas to increase the temperature of the exhaust gas at the second oxidation catalyst device inlet, thereby causing the exhaust gas in the second oxidation catalyst device to be heated. HC components can be effectively purified.

In the exhaust gas purifying apparatus of the present invention, heat is exchanged between the exhaust gas discharged from the exhaust manifold of the diesel engine and the heat storage structure, and the change of the exhaust gas temperature over time is moderated. By reducing the difference between the temperature and the minimum temperature, it is possible to reduce the thermal deterioration of the catalyst in the device portion downstream of the heat storage structure.

[Brief description of the drawings]

FIG. 1 is a layout diagram schematically showing an exhaust system of a diesel engine provided with an exhaust gas purifying apparatus of the present invention.

2 schematically shows a cylindrical thermal storage structure incorporated in the purification device of FIG. 1, FIG. 2A is a side view of the cylindrical thermal storage structure, and FIG. 2B is perpendicular to the axis of the cylindrical thermal storage structure. 2C is a partially enlarged view of FIG. 2B.

FIG. 3 shows a cylindrical first oxidation catalyst device or a cylindrical second oxidation catalyst device formed in the same shape as the cylindrical oxidation catalyst device incorporated in the purification device of FIG. 1, and FIG. 3A is a side view and a view of the cylindrical oxidation catalyst device. 3B
FIG. 3 is a partially enlarged view of a cross section perpendicular to the axis of the cylindrical oxidation catalyst device.

FIG. 4 is a graph schematically showing a change in temperature of exhaust gas.

FIG. 5 is a graph showing the relationship between the temperature of exhaust gas and the effect of the Pt-based oxidation catalyst device.

[Explanation of symbols]

10: diesel engine body, 12: exhaust manifold, 1
4: Exhaust gas purifier, 16: muffler, 20: oxidation catalyst device, 22: first oxidation catalyst device, 23: heat storage structure, 2
4: second oxidation catalyst device, 32, 36: cavity, 34, 3
8: Partition wall.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI F01N 3/28 ZAB F01N 3/28 ZAB (56) References JP-A-5-141228 (JP, A) JP-A-5-65817 (JP, A) JP-A-4-116619 (JP, A) JP-A-60-190614 (JP, A) JP-A-59-79025 (JP, A) JP-A-50-64625 (JP, A) Kaisho 64-36517 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) F01N 3/24 F01N 3/02 F01N 3/28

Claims (3)

(57) [Claims] 1. An exhaust gas purifying apparatus in which exhaust gas of a diesel engine is passed through a catalytic device and an unburned component in the exhaust gas is oxidized and purified, wherein a first oxidation catalytic device disposed upstream of a flow of the exhaust gas;
A second oxidation catalyst device disposed on the downstream side; and a heat storage structure disposed between the first oxidation catalyst device and the second oxidation catalyst device, wherein the heat storage structure has an exhaust gas passing through the heat storage structure. When the temperature is high, the exhaust gas is heated by the exhaust gas to accumulate heat, and when the exhaust gas passing through the storage structure is relatively low temperature, heat is released and the exhaust gas is heated, whereby the exhaust gas temperature at the inlet of the second oxidation catalyst device is equal to or higher than a predetermined value. An exhaust gas purifying apparatus characterized in that unburned components in exhaust gas, particularly HC and SOF in particulates are oxidized and purified. 2. The exhaust gas purifying apparatus according to claim 1, wherein each of the first oxidation catalyst device and the second oxidation catalyst device has Pt-metal oxide, Pd-metal oxide or Pt-Pd- An exhaust gas purifying apparatus which is coated with a metal oxide and has a catalytic ability to oxidize and purify unburned components in exhaust gas alone when the temperature of exhaust gas passing therethrough is equal to or higher than a predetermined value. 3. The exhaust gas purifying apparatus according to claim 1, wherein the heat storage structure is in the form of a ceramic honeycomb or a ceramic filter, and can maintain the exhaust gas temperature at the inlet of the second oxidation catalyst device at 220 ° C. or higher. An exhaust gas purifying device having heat storage capacity and heat exchange capacity.