WO2016125709A1 - 内燃機関の排気浄化装置 - Google Patents
内燃機関の排気浄化装置 Download PDFInfo
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- WO2016125709A1 WO2016125709A1 PCT/JP2016/052739 JP2016052739W WO2016125709A1 WO 2016125709 A1 WO2016125709 A1 WO 2016125709A1 JP 2016052739 W JP2016052739 W JP 2016052739W WO 2016125709 A1 WO2016125709 A1 WO 2016125709A1
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- Prior art keywords
- supported
- exhaust
- combustion catalyst
- amount
- exhaust gas
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Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0081—Preparation by melting
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/065—Surface coverings for exhaust purification, e.g. catalytic reaction for reducing soot ignition temperature
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/40—Engine management systems
Definitions
- the present invention relates to an exhaust purification device for an internal combustion engine. Specifically, the present invention relates to an exhaust gas purification apparatus for an internal combustion engine including a NOx purification catalyst and a particulate combustion catalyst.
- NSC NOx purification catalyst
- engine compression ignition type internal combustion engine
- CSF catalyzed soot filter
- the NSC oxidizes and purifies CO and HC contained in the exhaust gas, and captures NOx when the exhaust gas is lean, then desorbs and enriches the captured NOx to reduce it to N 2 To do.
- the CSF captures particulates contained in the exhaust gas, and oxidizes and purifies the captured particulates by the particulate combustion catalyst.
- a particulate combustion catalyst As the particulate combustion catalyst, a particulate combustion catalyst is proposed in which an alloy composed of 75 to 25% by mass of Ag and 25 to 75% by mass of Pd is supported on an Al 2 O 3 carrier (for example, patents). Reference 1). According to this particulate combustion catalyst, the particulates can be oxidized and purified regardless of the NOx concentration in the exhaust gas.
- S component sulfur components such as SOx (hereinafter referred to as “S component”) contained in a trace amount in the exhaust gas and the purification performance is lowered. Therefore, a so-called sulfur purge (hereinafter referred to as “S purge”) for desorbing the S component from the noble metal by increasing the temperature of the NSC to about 500 to 600 ° C. and enriching the exhaust gas is performed. At this time, the desorbed S component reacts with hydrogen generated by the steam reforming reaction that proceeds by enrichment, and hydrogen sulfide (H 2 S) is generated. The produced H 2 S has a specific odor and causes a bad odor, so that purification is a problem.
- S purge sulfur purge
- Patent Document 1 the particulate combustion catalyst of Patent Document 1 has not been studied at all for the purification of H 2 S.
- expensive noble metals are used in large quantities, resulting in high costs. Therefore, it is desired to develop an exhaust emission control device including an inexpensive particulate combustion catalyst having excellent purification performance for both particulates and H 2 S.
- the present invention has been made in view of the above, and an object of the present invention is to provide an exhaust emission control device including an inexpensive particulate combustion catalyst having an excellent purification performance for both particulates and H 2 S. It is in.
- the present invention provides an exhaust purification device (for example, an exhaust purification device 1 to be described later) of an internal combustion engine (for example, an engine 2 to be described later), and an exhaust passage (for example, an exhaust gas to be described later) of the internal combustion engine.
- an exhaust purification device for example, an exhaust purification device 1 to be described later
- an internal combustion engine for example, an engine 2 to be described later
- an exhaust passage for example, an exhaust gas to be described later
- a particulate combustion catalyst that is provided in a part (for example, a NOx purification part 4 described later) and an exhaust passage downstream of the NOx purification part, captures particulates in the inflowing exhaust gas, and burns the captured particulates.
- a supported exhaust purification filter (for example, CSF 5 described later) and exhaust gas flowing into the NOx purification catalyst are controlled to be rich, and the NOx purification catalyst is kept at a predetermined temperature.
- the reproducing device for the sulfur component trapped in the NOx purification catalyst desorb (e.g., comprising a, and ECU 7) described later, the particulate combustion catalyst, Al 2 O 3 carrier Ag and Pd is supported in a state of being alloyed, the a Al 2 O 3 supported amount of Ag relative to the carrier is 1.2g / L ⁇ 2.5g / L, the Al 2 O 3 carrier
- An exhaust emission control device for an internal combustion engine is provided, in which the amount of Pd supported is 0.7 g / L or less, and the ratio Ag / Pd of the amount of Ag supported to the amount of Pd is 1.7 to 8.3. .
- an NOx purification unit having a NOx purification catalyst is provided in an upstream exhaust passage, an exhaust purification filter having a particulate combustion catalyst is provided in an exhaust passage downstream thereof, and NOx Regeneration means for desorbing the sulfur component trapped by the NOx purification catalyst is provided by controlling the exhaust gas flowing into the purification catalyst to be rich and raising the temperature of the NOx purification catalyst to a predetermined temperature.
- an alloy of Ag and Pd is supported on an Al 2 O 3 carrier, the supported amount of Ag is 1.2 g / L to 2.5 g / L, and the supported amount of Pd is 0.7 g.
- the ratio Ag / Pd of the supported amount of Ag to the supported amount of Pd is set to 1.7 to 8.3.
- excellent particulate purification performance can be achieved while suppressing costs by setting the supported amount of Ag and the supported amount of Pd in the particulate combustion catalyst within the above ranges. can get.
- the ratio of the supported amount of Ag and the supported amount of Pd in the particulate combustion catalyst within the above range the H 2 S generated in the upstream side in the rich atmosphere is mainly made up of Ag while suppressing the cost. Can be efficiently captured by forming sulfides and sulfides.
- the desorption of the S component from the sulfide or sulfate of Ag produced by the capture of H 2 S can be promoted by Pd. Therefore, according to the exhaust gas purification apparatus for an internal combustion engine according to the present invention, excellent purification performance can be obtained for both particulates and H 2 S while suppressing costs.
- the present invention can provide an exhaust gas purification apparatus having an inexpensive particulate combustion catalyst having a particulate and H 2 conversion performance superior to any of S.
- the particulate combustion catalyst according to the present embodiment it is a diagram showing a change in the 1st_SOx peak area value when the amount of Ag supported is changed.
- it is a diagram showing a change in the total SOx peak area value when the amount of Ag supported is changed. It is a figure which shows the relationship between Ag carrying amount and Pd carrying amount obtained by the statistical analysis process, and particulate purification performance (T90 / min). It is a diagram showing the relationship between the Ag carrying amount obtained by statistical analysis and amount of supported Pd and H 2 S purification performance ( ⁇ H 2 S /%). It is an X-ray diffraction spectrum figure of the particulate combustion catalyst concerning this example.
- FIG. 1 is a diagram illustrating an example of an exhaust purification device 1 including a particulate (hereinafter referred to as “PM”) combustion catalyst according to the present embodiment.
- the exhaust purification device 1 includes a NOx purification unit 4 provided in an exhaust pipe 3 directly under the engine 2, a CSF 5 provided on the downstream side of the NOx purification unit 4, and an ECU 7. .
- the NOx purification unit 4 and the CSF 5 are accommodated in a single casing 6.
- the PM combustion catalyst according to the present embodiment is supported on CSF5.
- Engine 2 is a diesel engine. Exhaust gas discharged from the diesel engine contains a large amount of NOx and PM in addition to CO and HC. The exhaust purification device 1 efficiently purifies these CO, HC, NOx, and PM.
- the NOx purification unit 4 is configured by supporting NSC on a honeycomb carrier. Therefore, the NOx purification unit 4 oxidizes and purifies CO and HC contained in the exhaust gas. Further, NOx purification section 4, after the exhaust was captured NOx when the lean, by enriching the exhaust, the trapped NOx desorbed to reduce and purify the N 2.
- a conventionally known NSC containing a noble metal such as Pt is used as the NSC constituting the NOx purification unit 4.
- the precious metal such as Pt contained in the NSC captures NOx and also captures S components such as SOx contained in the exhaust gas. Therefore, the noble metal is poisoned by the S component, and the purification performance for NOx and the like is lowered. Since the adsorption force of this S component to NSC is greater than that of NOx, the NSC is heated to a high temperature of 500 to 600 ° C. and S purge is performed to enrich the exhaust. Thereby, the S component is desorbed from the noble metal. At this time, the desorbed S component reacts with hydrogen generated by the steam reforming reaction that proceeds by enrichment, and hydrogen sulfide (H 2 S) is generated. The generated H 2 S flows into a CSF 5 described later provided on the downstream side of the NSC.
- H 2 S hydrogen sulfide
- the S purge is executed by the ECU 7 that includes a regeneration unit as a regeneration means.
- the ECU 7 shapes input signal waveforms from various sensors (not shown), corrects the voltage level to a predetermined level, converts an analog signal value into a digital signal value, and a central processing unit (Hereinafter referred to as “CPU”).
- the ECU 7 includes a storage circuit that stores various calculation programs executed by the CPU, calculation results, and the like, and an output circuit that outputs a control signal to the engine 2 and the like.
- the ECU 7 performs the S purge by raising the temperature of the NSC constituting the NOx purification unit 4 to a high temperature of 500 to 600 ° C. and enriching the exhaust gas flowing into the NSC.
- the ECU 7 enriches exhaust by enriching the air-fuel ratio in the combustion chamber by fuel injection control and enriching exhaust, and supplying unburned fuel into the combustion chamber and the exhaust pipe 3 after combustion.
- the temperature of the NSC is raised by the heat generated by the oxidation reaction of the NSC that is enriched and the exhaust gas is enriched by either the post-rich that becomes rich or the exhaust rich that directly injects fuel into the exhaust pipe 3 to enrich the exhaust.
- the CSF 5 captures PM contained in the exhaust.
- the CSF 5 is configured by supporting a PM combustion catalyst of the present embodiment on a diesel particulate filter (hereinafter referred to as “DPF”).
- DPF diesel particulate filter
- a conventionally known DPF is used as the DPF.
- a DPF such as a wall-through type, a flow-through honeycomb type, a wire mesh type, a ceramic fiber type, a metal porous body type, a particle filling type, and a foam type can be used.
- Examples of the material of the base material constituting the DPF include cordierite, ceramics such as SiC, Fe—Cr—Al alloy, stainless steel alloy and the like.
- the PM combustion catalyst according to the present embodiment has a function of oxidizing and purifying PM by burning PM, and also has a function of oxidizing and purifying H 2 S.
- the PM combustion catalyst according to the present embodiment is configured by being supported on an Al 2 O 3 carrier in a state where Ag and Pd are alloyed.
- the PM combustion catalyst according to the present embodiment will be described in detail.
- the carrier of the PM combustion catalyst according to the present embodiment is composed of Al 2 O 3 .
- Al 2 O 3 is excellent in heat resistance, the pores are not crushed even at high temperatures, and the decrease in specific surface area is small. Therefore, in the PM combustion catalyst according to the present embodiment, it is possible to prevent the catalytic metal made of an alloy of active species Ag and Pd from being buried, and a high purification performance is maintained even at a high temperature.
- Al 2 O 3, ⁇ -Al 2 O 3, ⁇ -Al 2 O 3, ⁇ -Al 2 O 3 various Al 2 O 3, such as is used.
- the preferred specific surface area of Al 2 O 3 is 80 to 160 m 2 / g.
- a binder layer made of a binder component such as SiO 2 , TiO 2 , ZrO 2, or Al 2 O 3 is provided on the surface of the Al 2 O 3 carrier.
- a Ag acts as the main active species for PM combustion.
- Ag since Ag has a low melting point, it causes aggregation of the PM combustion catalyst at high temperatures.
- the PM combustion catalyst of the present embodiment has a catalyst metal in which Ag and Pd are alloyed. Therefore, the catalyst metal has a higher melting point than Ag in a pure metal state, and aggregation at a high temperature is prevented. ing. That is, the PM combustion catalyst of this embodiment has high heat resistance, and excellent PM purification performance is maintained even at high temperatures.
- Pd acts as an active species for PM combustion.
- the heat resistance of the PM combustion catalyst according to the present embodiment is enhanced by alloying this Pd together with Ag.
- whether or not Ag and Pd are alloyed can be confirmed by performing X-ray diffraction measurement on the PM combustion catalyst according to the present embodiment and analyzing the obtained X-ray diffraction spectrum. is there.
- the X-ray diffraction spectrum obtained by measurement when a peak is observed at a position slightly shifted to a higher angle side than the X-ray diffraction peak derived from pure metal Ag metal, such peak is observed. Is a peak derived from alloyed Ag metal, and it can be determined that Ag and Pd are alloyed (see FIG.
- a peak is recognized at a position slightly shifted to the high angle side
- the X-ray diffraction spectrum of the PM combustion catalyst according to the present embodiment is based on the X-ray diffraction peak position derived from a pure metal Ag metal. Also means that a peak is observed at a position shifted to the high angle side by 0.1 degree (deg) or more.
- FIG. 2 is a diagram showing the relationship between the SOx concentration in the exhaust gas supplied to the PM combustion catalyst of the present embodiment and the SOx concentration in the exhaust gas discharged from the PM combustion catalyst of the present embodiment.
- FIG. 3 is a diagram showing the relationship between the H 2 S concentration in the exhaust gas supplied to the PM combustion catalyst of the present embodiment and the H 2 S concentration in the exhaust gas discharged from the PM combustion catalyst of the present embodiment. is there.
- a PM combustion catalyst having an Ag loading amount of 2.5 g / L and a Pd loading amount of 0.7 g / L is used as an example of the PM combustion catalyst according to the present embodiment.
- the measurement data when the S purge is performed on the upstream NSC is shown.
- the H 2 S concentration in the exhaust at this time is as shown in FIG. That is, compared to the H 2 S concentration in the exhaust gas supplied to the PM combustion catalyst (broken line in FIG. 3), the H 2 S concentration in the exhaust gas discharged from the PM combustion catalyst (solid line in FIG. 3) is large. It can be seen that there is a reduction. Therefore, it can be seen that H 2 S in the exhaust is captured by Ag and Pd as the above reaction formulas (1) and (2) proceed.
- the catalyst metal of the present embodiment made of an alloy of Ag and Pd has a characteristic that it is easy to generate sulfide as compared with other noble metals such as Pt and Rh or alloys thereof. Therefore, the catalytic metal of the present embodiment having the alloy of Ag and Pd is the H 2 S efficiently capture, have excellent H 2 S purification performance.
- reaction formula (3-1) when the exhaust gas is changed from rich to lean, O 2 contained in a large amount in the exhaust gas reacts with the sulfide Ag 2 S, so that the sulfide Ag 2 S is converted to the sulfate as shown in the reaction formula (3-1). As well as being converted to Ag 2 SO 4 , SO 2 is desorbed from the sulfide Ag 2 S to produce Ag as shown in the reaction formula (3-2).
- the reaction ratios of these reaction formulas (3-1) and (3-2) vary depending on the oxygen partial pressure, temperature, and the like.
- the SOx concentration in the exhaust at this time is as shown in FIG. That is, it can be seen that the SOx concentration (solid line in FIG. 2) in the exhaust discharged from the PM combustion catalyst is greatly increased (see 2nd_SOx peak in FIG. 2). Therefore, it can be seen that SOx is desorbed from the sulfides Ag 2 S and PdS by the progress of the above reaction formulas (3) and (4).
- the SOx concentration in the exhaust at this time is as shown in FIG. That is, it can be seen that the SOx concentration (solid line in FIG. 2) in the exhaust discharged from the PM combustion catalyst is greatly increased (see the 1st_SOx peak in FIG. 2). Therefore, it can be seen that SOx is desorbed from the sulfated Ag 2 SO 4 by the progress of the above reaction formula (5).
- the reaction formulas (1) to (5) are repeatedly advanced as the exhaust lean / rich control is executed. Thereby, the PM combustion catalyst according to the present embodiment can purify H 2 S.
- FIG. 4 shows the PM combustion catalyst according to the present embodiment, in which the supported amount of Ag is fixed at 2.5 g / L, and the supported amount of Pd is three stages of 0, 0.7, and 1.4 g / L. It is a figure which shows the change of 1st_SOx peak area value when making it fluctuate by. As is clear from FIG. 4, it can be seen that when the ratio of Pd to Ag is increased, the 1st_SOx peak area value increases accordingly. Therefore, it can be seen that in the PM combustion catalyst of the present embodiment, Pd promotes the progress of the above reaction formula (5) and promotes the desorption of SOx from Ag 2 SO 4 .
- FIG. 5 shows the PM combustion catalyst according to the present embodiment, in which the supported amount of Ag is fixed at 2.5 g / L, and the supported amount of Pd is three steps of 0, 0.7, and 1.4 g / L. It is a figure which shows the change of the total value (total SOx peak area value) of 1st_SOx peak area value and 2nd_SOx peak area value when making it fluctuate.
- total SOx peak area value total SOx peak area value
- the Ag carrying amount and the Pd carrying amount in the PM combustion catalyst of the present embodiment will be described in detail.
- the amount of Ag supported on the Al 2 O 3 carrier (hereinafter referred to as “Ag supported amount”) is 1.2 g / L to 2.5 g / L. If the Ag loading is within this range, excellent PM purification performance can be obtained. On the other hand, if the Ag loading is less than 1.2 g / L, sufficient PM purification performance cannot be obtained. Moreover, even if the Ag loading exceeds 2.5 g / L, no further effect is obtained and the cost increases.
- the amount of Pd supported on the Al 2 O 3 carrier (hereinafter referred to as “Pd supported amount”) is 0.7 g / L or less. If the amount of Pd supported is within this range, excellent PM purification performance can be obtained. On the other hand, even if the amount of Pd supported exceeds 0.7 g / L, no further effect is obtained and the cost increases.
- the unit (g / L) in this specification means the weight per unit volume. Accordingly, the Ag supported amount means weight of Ag per unit volume of Al 2 O 3 carrier, the amount of Pd supported means the weight of Pd per unit volume of Al 2 O 3 carrier.
- FIG. 6 is a diagram showing the relationship between the Ag carrying amount and the Pd carrying amount obtained by the statistical analysis process and the PM purification performance (T90 / min).
- T90 represents the time (minutes) until the PM combustion rate reaches 90%. That is, as T90 is smaller, it means that the PM purification performance is higher.
- the numerical value in FIG. 6 represents T90 (minute), and the darker the region, the smaller T90 means that the PM purification performance is higher.
- the region defined by the present embodiment in which the Ag loading is 1.2 g / L to 2.5 g / L and the Pd loading is 0.7 g / L or less has a small T90 and a high PM. It turns out that purification performance is obtained.
- region where T90 is small and high PM purification performance is acquired is seen also in the Pd carrying amount of 2.0 g / L vicinity.
- high PM purification performance can be obtained in this region, it is necessary to use a large amount of Pd, which increases costs.
- the ratio Ag / Pd of the Ag loading amount to the Pd loading amount (hereinafter referred to as “Ag / Pd ratio”) is 1.7 to 8.3.
- Ag / Pd ratio is within this range, excellent H 2 S purification performance can be obtained while suppressing costs.
- the Ag / Pd ratio is less than 1.7, an excellent H 2 S purification performance can be obtained, but a large amount of Pd is required and the cost is increased.
- the Ag / Pd ratio exceeds 8.3, further improvement in H 2 S purification performance cannot be expected, and excellent PM purification performance cannot be obtained.
- the H 2 S purification performance itself becomes maximum when the Ag / Pd ratio is 1.7. This is considered to be due to the following reason.
- the purification of H 2 S in the present embodiment is performed such that Ag adsorbs H 2 S, passes through Ag 2 S, becomes Ag 2 SO 4 , captures the S component, and Pd becomes Ag 2. This is done by promoting the desorption of SOx from SO 4 . Therefore, in order to adsorb H 2 S, Ag needs to be exposed to some extent on the surface of the catalyst, and Pd also needs to be exposed to some extent on the surface of the catalyst and be present in the vicinity of Ag. is there.
- the existence balance of Ag and Pd on the catalyst surface is important, and when the Ag / Pd ratio is 1.7, the existence balance of Ag and Pd on the catalyst surface is optimized. As a result, the H 2 S purification performance is maximized. It is considered that.
- FIG. 7 is a diagram showing the relationship between the Ag loading amount and the Pd loading amount obtained by the statistical analysis process and the H 2 S purification performance ( ⁇ H 2 S /%).
- ⁇ H 2 S represents the H 2 S purification rate.
- the numerical value in FIG. 7 represents ⁇ H 2 S (%), and the lighter the region, the larger ⁇ H 2 S and the higher the H 2 S purification performance.
- the powder of the PM combustion catalyst according to the present embodiment obtained as described above is mixed with a binder component such as SiO 2 and alumina sol and water as required, and finely wet pulverized with a pulverizer such as a ball mill to obtain a slurry. Then, CSF5 is obtained by apply
- a binder component such as SiO 2 and alumina sol and water
- the total supported amount of the PM combustion catalyst of the present embodiment with respect to the DPF substrate is, for example, 5 to 100 g / L in the case of a wall flow type DPF. It is preferable that When the total amount of the PM combustion catalyst supported on the DPF substrate is less than 5 g / L, sufficient PM purification performance and H 2 S purification performance cannot be obtained. Further, if the total amount of the PM combustion catalyst supported on the DPF substrate exceeds 100 g / L, the back pressure against the exhaust becomes high, which is not preferable. A more preferable total loading is 10 to 40 g / L.
- the present invention is not limited to the above-described embodiment, and modifications and improvements within the scope that can achieve the object of the present invention are included in the present invention.
- PM combustion catalyst was carry
- the PM combustion catalyst of this embodiment may be carried on a gasoline particulate filter (GPF) provided in the exhaust pipe of a gasoline engine.
- GPF gasoline particulate filter
- the PM combustion catalyst was provided in the downstream of NSC, it is not limited to this. For example, what is necessary is just to be the downstream side of the catalyst that adsorbs the S component in a lean atmosphere and releases the adsorbed S component in a rich atmosphere.
- Examples 1 to 4 and Comparative Examples 1 to 4 First, a silver nitrate aqueous solution containing Ag ions and a palladium nitrate aqueous solution containing Pd ions with respect to the Al 2 O 3 carrier are as shown in Table 1 with respect to the Ag loading amount, the Pd loading amount, and the Ag / Pd ratio, respectively. It was impregnated.
- each PM combustion catalyst powder obtained as described above 100 g of alumina sol (20 wt%), and 320 g of water were mixed, and finely wet pulverized with a ball mill pulverizer to prepare a slurry.
- the prepared slurry was applied to a SiC DPF substrate, dried at 120 ° C. for 30 minutes, and then fired at 800 ° C. for 20 hours to obtain CSFs of Examples 1 to 4 and Comparative Examples 1 to 4. .
- the total supported amount of each catalyst was 30 g / L.
- Comparative Example 5 In Comparative Example 5, a platinum nitrate aqueous solution containing Pt ions was used in place of the silver nitrate aqueous solution containing Ag ions, and the Pt carrying amount and the Pd carrying amount were adjusted as shown in Table 1, except that the above was prepared. The PM combustion catalyst and CSF of Comparative Example 5 were obtained.
- FIG. 8 shows an X-ray diffraction spectrum of the PM combustion catalyst according to this example obtained by measurement.
- Apparatus “Mini Flex600” manufactured by Rigaku X-ray source: CuK ⁇ Measurement range: 5 to 80 deg. Step: 0.02 deg. Speed: 10 deg. / Min
- PM purification performance evaluation The PM purification performance of each PM combustion catalyst according to each example and comparative example was evaluated according to the following procedure. First, after depositing 3 g / L of PM (actually carbon black as an alternative, the same applies hereinafter) on each CSF carrying each PM combustion catalyst powder according to each example and comparative example, A PM purification performance test was conducted according to the following test conditions. From the resulting CO and CO 2 concentrations, the amount of PM burned was calculated, and T90 (min) until the PM combustion rate reached 90% was calculated.
- PM actually carbon black as an alternative, the same applies hereinafter
- H 2 S purification performance evaluation The H 2 S purification performance of the PM combustion catalyst according to each example and comparative example was evaluated according to the following procedure.
- lean / rich control was performed on the NSC of the above embodiment carrying Pt under the following test conditions in a state where no CSF was installed on the downstream side.
- the lean / rich control was repeated until the H 2 S emission concentration from NSC was stabilized at 300 ppm.
- the average discharge concentration (ppm) of 5 cycles in which the discharge concentration of H 2 S was stabilized at 300 ppm was defined as the H 2 S supply amount to the CSF.
- each CSF according to each example and comparative example was installed downstream of the NSC, and lean / rich control was performed under the following conditions.
- the lean / rich control was repeatedly performed until the maximum discharge concentration of H 2 S from each CSF was stabilized.
- the average emission concentration (ppm) of 5 cycles in which the maximum emission concentration of H 2 S was stabilized was defined as the amount of H 2 S emission from each CSF.
- the material prices in Table 1 are values when the unit price of Ag is 0.76 $ / g, the unit price of Pt is 60.91 $ / g, and the unit price of Pd is 26.79 $ / g. .
- the PM determination, H 2 S determination, and cost determination in Table 1 were determined based on the following determination criteria based on T90, ⁇ H 2 S, and material price, respectively.
- “not yet” in the column of ⁇ H 2 S of Comparative Example 4 means unmeasured, and for the reason described later, the H 2 S determination of Comparative Example 4 describes an estimated value.
- FIG. 8 is an X-ray diffraction spectrum diagram of the PM combustion catalyst according to this example.
- the X-ray diffraction spectrum of the PM combustion catalyst according to Example 1 is shown as a representative of this example.
- X-ray diffraction of 150 ° C. dry product before firing obtained in the preparation process.
- the spectrum is shown.
- a 150 ° C. dried product of Ag / Al 2 O 3 before firing, in which only Ag is supported on an Al 2 O 3 carrier a 150 ° C. dried product of Ag and Pd physically mixed, and Ag X-ray diffraction spectrum of a 150 ° C. dry product obtained by mixing Pd and Pd in a liquid.
- the X-ray diffraction peak of the 150 ° C. dried product before baking of Ag / Al 2 O 3 is 38.1 degrees
- the 150 ° C. dried product peak of Example 1 is It is 38.3 degrees. That is, in the X-ray diffraction spectrum of the PM combustion catalyst according to Example 1, all of the 150 ° C. dry product, the fresh product, and the aging product were derived from Ag metal compared to the X-ray diffraction peak of Ag / Al 2 O 3. It can be seen that the peak is shifted to the high angle side by 0.1 degree (deg) or more.
- FIG. 9 is a diagram showing the relationship between the amount of Ag carried by the PM combustion catalyst according to this embodiment and T90.
- the horizontal axis represents the amount of Ag supported (g / L), and the vertical axis represents T90 (minutes).
- T90 of Example 2, Example 4, and Comparative Example 4 in which the Pd loading is 0.7 g / L is shown.
- T90 of only DPF and T90 of Comparative Example 5 of the Pt-based PM combustion catalyst are shown.
- the PM combustion catalysts of Example 2 and Example 4 had small PM90 and excellent PM purification performance as compared with the conventional Pt-based PM combustion catalyst. Further, from the results of FIG.
- T90 increases rapidly when the amount of Ag supported is less than 1.2 g / L (Example 2), and excellent when the amount of Ag supported is 1.2 g / L or more. It was found that PM purification performance can be obtained. In addition, even if the Ag loading amount exceeds 2.5 g / L (Example 4), considering that PM purification performance is not improved anymore and is wasted, the Ag loading amount is 1.2 g / L to 2.5 g. It was confirmed that it should be set within the range of / L.
- FIG. 10 is a diagram showing the relationship between the Pd carrying amount of the PM combustion catalyst according to this embodiment and T90.
- the horizontal axis represents the amount of Pd supported (g / L), and the vertical axis represents T90 (minutes).
- FIG. 10 shows T90 of Example 3, Example 4, and Comparative Examples 1 to 3 in which the Ag loading is 2.5 g / L.
- T90 of Comparative Example 5 of the Pt-based PM combustion catalyst is also shown.
- the PM combustion catalysts of Examples 3 and 4 had a small T90 and an excellent PM purification performance as compared with the conventional Pt-based PM combustion catalyst.
- the amount of Pd supported exceeds 0.7 g / L (Example 4)
- the cost becomes high. From the result of FIG. 10, the amount of Pd supported should be set to 0.7 g / L or less. It was confirmed.
- FIG. 11 is a graph showing the relationship between the Ag / Pd ratio and ⁇ H 2 S of the PM combustion catalyst according to this example.
- the horizontal axis represents the Ag / Pd ratio
- the vertical axis represents ⁇ H 2 S (%).
- FIG. 11 shows ⁇ H 2 S of the PM combustion catalysts according to Examples 1 to 4 and Comparative Examples 1 to 3.
- ⁇ H 2 S of Comparative Example 5 of the Pt-based PM combustion catalyst is also shown.
- it is confirmed that the PM combustion catalysts of Examples 1 to 4 have a large H 2 S purification performance with a large ⁇ H 2 S compared to the conventional Pt-based PM combustion catalyst of Comparative Example 5. It was done.
- Example 2 when the Ag / Pd ratio is less than 1.7 (Example 2), the cost becomes high as in Comparative Example 2 and Comparative Example 3, and when the Ag / Pd ratio exceeds 8.3 (Example 3), the comparative example. It was confirmed that the Ag / Pd ratio should be set within the range of 1.7 to 8.3 because the excellent PM purification performance as in 1 cannot be obtained.
- Comparative Example 4 although ⁇ H 2 S has not been measured, it corresponds to a case where the Ag / Pd ratio is in the range of 1.7 to 8.3, and only the amount of Ag in Example 4 is increased. The H 2 S purification performance was estimated to be 4 as in Example 4.
- the Ag supported amount is 1.2 g / L to 2.5 g / L
- the Pd supported amount is 0.7 g / L.
- the PM combustion catalyst according to the present invention having an L / L ratio and an Ag / Pd ratio of 1.7 to 8.3, excellent PM purification performance and excellent H 2 S purification performance can be achieved while reducing costs. It was confirmed that it was obtained.
Abstract
Description
本発明に係る内燃機関の排気浄化装置によれば、パティキュレート燃焼触媒中のAgの担持量とPdの担持量を上記範囲内とすることで、コストを抑制しつつ優れたパティキュレート浄化性能が得られる。また、パティキュレート燃焼触媒中のAgの担持量とPdの担持量の比率を上記範囲内とすることで、コストを抑制しつつ、リッチ雰囲気下において上流側で発生したH2Sを、主としてAgが硫化物や硫酸化物となることで効率良く捕捉できる。さらには、H2Sの捕捉により生成したAgの硫化物や硫酸化物からのS成分の脱離を、Pdにより促進できる。従って、本発明に係る内燃機関の排気浄化装置によれば、コストを抑制しつつ、パティキュレート及びH2Sのいずれに対しても優れた浄化性能が得られる。
またこのとき、脱離したS成分と、リッチ化することで進行する水蒸気改質反応により生成した水素とが反応し、硫化水素(H2S)が生成する。生成したH2Sは、NSCの下流側に設けられた後述のCSF5に流入することとなる。
このECU7は、NOx浄化部4を構成するNSCを、500~600℃の高温まで昇温するとともに、NSCに流入する排気をリッチ化することにより、Sパージを実行する。具体的には、ECU7は、燃料噴射制御により燃焼室内の空燃比をリッチ化して排気をリッチ化する燃焼リッチ、燃焼後の燃焼室や排気管3内に未燃燃料を供給して排気をリッチ化するポストリッチ、あるいは排気管3内に燃料を直接噴射して排気をリッチ化する排気リッチのいずれかによって、排気をリッチ化するとともに進行するNSCの酸化反応による発熱により、NSCを昇温する。
DPFとしては、従来公知のものが用いられる。例えば、ウォールスルー型、フロースルーハニカム型、ワイヤメッシュ型、セラミックファイバー型、金属多孔体型、粒子充填型、フォーム型等のDPFを用いることができる。DPFを構成する基材の材質としては、コージェライト、SiC等のセラミック、Fe-Cr-Al合金、ステンレス合金等が挙げられる。
本実施形態に係るPM燃焼触媒は、Al2O3担体に、AgとPdが合金化された状態で担持されて構成される。以下、本実施形態に係るPM燃焼触媒について、詳しく説明する。
ここで、AgとPdが合金化されているか否かは、本実施形態に係るPM燃焼触媒に対してX線回折測定を実施し、得られたX線回折スペクトルを解析することにより確認可能である。具体的には、測定して得られたX線回折スペクトルにおいて、純金属状態のAgメタル由来のX線回折ピークよりもやや高角側にシフトした位置にピークが認められた場合には、かかるピークは合金化されたAgメタル由来のピークであり、AgとPdが合金化されていると判断できる(後段で詳述する図8参照)。
なお、上述の「やや高角側にシフトした位置にピークが認められ」とは、本実施形態に係るPM燃焼触媒のX線回折スペクトルにおいて、純金属状態のAgメタル由来のX線回折ピーク位置よりも0.1度(deg)以上、高角側にシフトした位置にピークが認められることを意味する。
ここで、図2は、本実施形態のPM燃焼触媒に供給される排気中のSOx濃度と本実施形態のPM燃焼触媒から放出される排気中のSOx濃度との関係を示す図である。また、図3は、本実施形態のPM燃焼触媒に供給される排気中のH2S濃度と本実施形態のPM燃焼触媒から放出される排気中のH2S濃度との関係を示す図である。なお、図2及び図3では、本実施形態に係るPM燃焼触媒の一例として、Agの担持量が2.5g/LでPdの担持量が0.7g/LであるPM燃焼触媒を用い、上流側のNSCに対してSパージを実施したときの測定データを示している。
また同時に、反応式(2)に示すように、後段で詳述する通りAgに比べると極少量であるものの、PdもH2Sを吸着し、硫化物(PdS)となることでS成分を捕捉する。
[化1]
(リッチ)
H2S+2Ag→Ag2S+H2・・・反応式(1)
H2S+Pd→PdS+H2・・・反応式(2)
また同時に、反応式(4)に示すように、排気中に多量に含まれるO2が硫化物PdSと反応することで、硫化物PdSからSO2が脱離し、硫化物PdSがPdに変換されて元の状態に戻る。これにより、再びPdによるH2Sの捕捉が可能となる。
[化2]
(リッチ→リーン)
Ag2S+2O2→Ag2SO4・・・反応式(3-1)
Ag2S+O2→2Ag+SO2・・・反応式(3-2)
PdS+O2→Pd+SO2・・・反応式(4)
[化3]
(リーン→リッチ)
Ag2SO4→2Ag+SOx・・・反応式(5)
図4から明らかであるように、Agに対するPdの比率を増加させると、1st_SOxピーク面積値もそれに伴い増加することが分かる。従って、本実施形態のPM燃焼触媒では、Pdが、上記反応式(5)の進行を促進し、Ag2SO4からのSOxの脱離を促進していることが分かる。
図5から明らかであるように、Agに対するPdの比率を増加させても、総SOxピーク面積値に大きな変化は見られない。従って、本実施形態のPM燃焼触媒では、PdによるH2Sの吸着は極少量であり、主としてAgがH2Sを吸着して捕捉していることが分かる。
本実施形態では、Al2O3担体に対するAgの担持量(以下、「Ag担持量」という。)は、1.2g/L~2.5g/Lである。Ag担持量がこの範囲内であれば、優れたPM浄化性能が得られる。これに対してAg担持量が1.2g/L未満であると、十分なPM浄化性能が得られない。また、Ag担持量が2.5g/Lを超えても、それ以上の効果は得られずコストが嵩む。
なお、本明細書における単位(g/L)は、単位体積当たりの重量を意味する。従って、上記Ag担持量はAl2O3担体の単位体積当たりのAgの重量を意味し、上記Pd担持量はAl2O3担体の単位体積当たりのPdの重量を意味する。
なお図6では、Pd担持量が2.0g/Lの付近にも、T90が小さく高いPM浄化性能が得られる領域が見られる。しかしながら、この領域は高いPM浄化性能は得られるものの、Pdを多量に用いる必要があり、コストが嵩む。これに対して本実施形態で規定する上記領域では、コストを抑制しつつ、高いPM浄化性能が得られるようになっている。
即ち、上述したように本実施形態におけるH2Sの浄化は、AgがH2Sを吸着し、Ag2Sを経てAg2SO4となることでS成分を捕捉するとともに、PdがAg2SO4からのSOxの脱離を促進することで行われる。そのため、H2Sを吸着するためには、Agはある程度触媒の表面に露出していることが必要であるとともに、Pdもある程度触媒の表面に露出してAgの近傍に存在することが必要である。従って、触媒表面におけるAgとPdの存在バランスが重要であり、Ag/Pd比率が1.7のときに触媒表面におけるAgとPdの存在バランスが最適化される結果、H2S浄化性能が極大となるものと考えられる。
この図7から明らかであるように、例えば、Ag/Pd=0.5(g/L)/0.5(g/L)のときとAg/Pd=2.5(g/L)/2.5(g/L)のときとを比べると、Ag/Pd比率は同じ1.0であるものの、Ag及びPdの各担持量が少な過ぎるとH2S浄化性能が極端に低下することが分かる。即ち、この図7から、Ag/Pd比率の最適化によりH2S浄化性能は高まるものの、一定以上の担持量が必要であることが分かる。
先ず、Al2O3担体に対して、Agイオンを含有する例えば硝酸銀水溶液と、Pdイオンを含有する例えば硝酸パラジウム水溶液を、Ag担持量が1.2g/L~2.5g/L、Pd担持量が0.7g/L以下、及び、Ag/Pd比率が1.7~8.3の範囲内となるように、含侵させる。
次いで、例えば120~150℃で蒸発乾固させた後、空気中で800±100℃×20±10時間焼成することにより、AgとPdとを確実に合金化させる。これにより、本実施形態に係るPM燃焼触媒の粉末が得られる。
上記実施形態では、ディーゼルエンジの排気管に設けられたDPFにPM燃焼触媒を担持させたが、これに限定されない。例えば、ガソリンエンジンの排気管に設けられたガソリンパテュキュレートフィルタ(GPF)に本実施形態のPM燃焼触媒を担持させてもよい。
また、上記実施形態では、NSCの下流側にPM燃焼触媒を設けたが、これに限定されない。例えば、リーン雰囲気でS成分を吸着し、吸着したS成分をリッチ雰囲気で放出する触媒の下流側であればよい。
先ず、Al2O3担体に対して、Agイオンを含有する硝酸銀水溶液と、Pdイオンを含有する硝酸パラジウム水溶液を、Ag担持量、Pd担持量及びAg/Pd比率がそれぞれ表1に示す通りとなるように、含侵させた。
なお、DPF基材としては、円筒状であり、径が2.54cmで長さが30mmの容量15mLの基材を用いた。各触媒の総担持量は、30g/Lとした。
比較例5では、Agイオンを含有する硝酸銀水溶液の代わりに、Ptイオンを含有する硝酸白金水溶液を用い、Pt担持量及びPd担持量が表1に示す通りとなるように調製した以外は、上記と同様に調製を行い、比較例5のPM燃焼触媒及びCSFを得た。
各実施例及び比較例で得られた各PM燃焼触媒に対して、以下の測定条件に従って、X線回折測定を実施した。測定により得られた本実施例に係るPM燃焼触媒のX線回折スペクトルを図8に示す。
(X線回折測定条件)
装置:Rigaku製「Mini Flex600」
X線源:CuKα
測定範囲:5~80deg.
ステップ:0.02deg.
スピード:10deg./分
各実施例及び比較例に係る各PM燃焼触媒のPM浄化性能について、以下の手順に従って評価を行った。
先ず、各実施例及び比較例に係る各PM燃焼触媒粉末が担持された各CSFに対して、PM(実際には代替品としてのカーボンブラック。以下同じ。)を3g/L堆積させた後、以下の試験条件に従ってPM浄化性能試験を実施した。その結果得られたCO及びCO2濃度から、燃焼されたPM量を算出し、PM燃焼率が90%に達するまでのT90(分)を算出した。
試験温度:550℃
エージング条件:750℃×16時間
昇温中ガス:N2
試験ガス組成:O2=6%、NO=400ppm、N2=バランスガス
試験ガス速度:空間速度SV=60000/時
測定時間:30分
評価方法:2分燃焼速度(反応開始2分間の燃焼量を、0.1秒間隔で連続的に測定したCO及びCO2濃度から燃焼速度として算出したもの)
各実施例及び比較例に係るPM燃焼触媒のH2S浄化性能について、以下の手順に従って評価を行った。
先ず、Ptを担持した上記実施形態のNSCに対して、下流側にCSFを設置しない状態で、以下の試験条件でリーン/リッチ制御を実施した。リーン/リッチ制御は、NSCからのH2Sの排出濃度が300ppmで安定化するまで、繰り返し実施した。H2Sの排出濃度が300ppmで安定化した5サイクルの平均排出濃度(ppm)を、CSFへのH2S供給量とした。
[数1]
ηH2S(%)={(H2S供給量-H2S排出量)/H2S供給量}×100
・・・数式(1)
試験温度:620℃
エージング条件:750℃×16時間
昇温中ガス:N2
リーン試験ガス組成:O2=7%、NO=280ppm、CO2=10%、SO2=120ppm、H2O=7%、N2=バランスガス
リーン試験時間:20秒
リッチ試験ガス組成:CO=16000ppm、C3H6=10000ppm、O2=0.33%、NO=280ppm、CO2=10%、SO2=120ppm、H2O=7%、N2=バランスガス
リッチ試験時間:10秒
(判定基準)
4:比較例5に対して特に優れる。
3:比較例5に対して優れる。
2:比較例5に対して同等である。
1:比較例5に対して劣る。
なお、X線回折スペクトルでは、シンタリング(凝集)が進んでおらず粒子径が小さい場合には、ピークが観測され難い傾向がある。従って、図8から明らかであるように、本実施例に係るフレッシュ品やエージング実施品は、ピークが非常に小さいことから、凝集が進んでいないことが分かる。
図9に示すように、実施例2及び実施例4のPM燃焼触媒は、従来のPt系PM燃焼触媒と比べて、T90が小さく優れたPM浄化性能を有することが確認された。また、図9の結果から、Ag担持量が1.2g/L(実施例2)を下回ると急激にT90が大きくなることが分かり、Ag担持量が1.2g/L以上であれば優れたPM浄化性能が得られることが分かった。また、Ag担持量が2.5g/L(実施例4)を超えてもそれ以上PM浄化性能は向上せず無駄となることを踏まえると、Ag担持量は1.2g/L~2.5g/Lの範囲内に設定すべきであることが確認された。
図10に示すように、実施例3及び実施例4のPM燃焼触媒は、従来のPt系PM燃焼触媒と比べて、T90が小さく優れたPM浄化性能を有することが確認された。また、Pd担持量が0.7g/L(実施例4)を超えると高コストとなることを踏まえると、図10の結果から、Pd担持量は0.7g/L以下に設定すべきであることが確認された。
図11に示すように、実施例1~4のPM燃焼触媒は、比較例5の従来のPt系PM燃焼触媒と比べて、ηH2Sが大きく優れたH2S浄化性能を有することが確認された。また、Ag/Pd比率が1.7(実施例2)を下回ると比較例2や比較例3のように高コストとなり、Ag/Pd比率が8.3(実施例3)を超えると比較例1のように優れたPM浄化性能が得られなくなることから、Ag/Pd比率は1.7~8.3の範囲内に設定すべきであることが確認された。
なお、比較例4については、ηH2Sは未測定であるものの、Ag/Pd比率が1.7~8.3の範囲内で実施例4のAgを増量しただけのものに相当するため、H2S浄化性能は実施例4と同様の4と推定された。
2…エンジン
3…排気管
4…NOx浄化部
5…SCF(排気浄化フィルタ)
7…ECU(再生手段)
Claims (1)
- 内燃機関の排気浄化装置であって、
前記内燃機関の排気通路に設けられ、流入する排気がリーンのときに排気中のNOxを捕捉し、捕捉したNOxを流入する排気がリッチのときに脱離して還元浄化するNOx浄化触媒が担持されたNOx浄化部と、
前記NOx浄化部の下流側の排気通路に設けられ、流入する排気中のパティキュレートを捕捉し、捕捉したパティキュレートを燃焼させるパティキュレート燃焼触媒が担持された排気浄化フィルタと、
前記NOx浄化触媒に流入する排気をリッチに制御するとともに前記NOx浄化触媒を所定温度まで昇温することにより、前記NOx浄化触媒に捕捉された硫黄成分を脱離させる再生手段と、を備え、
前記パティキュレート燃焼触媒は、
Al2O3担体にAgとPdが合金化された状態で担持され、
前記Al2O3担体に対するAgの担持量が1.2g/L~2.5g/Lであり、
前記Al2O3担体に対するPdの担持量が0.7g/L以下であり、
前記Pdの担持量に対する前記Agの担持量の比率Ag/Pdが1.7~8.3である内燃機関の排気浄化装置。
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JP2005090760A (ja) * | 2003-09-12 | 2005-04-07 | Matsushita Electric Ind Co Ltd | 熱交換器 |
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US20180023436A1 (en) | 2018-01-25 |
JP6626010B2 (ja) | 2019-12-25 |
EP3254748A1 (en) | 2017-12-13 |
EP3254748B1 (en) | 2019-08-28 |
KR101931510B1 (ko) | 2018-12-24 |
KR20170110653A (ko) | 2017-10-11 |
BR112017016511A2 (ja) | 2018-04-10 |
BR112017016511B1 (pt) | 2022-02-08 |
CN107206317A (zh) | 2017-09-26 |
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