JP7471863B2 - Method for cleaning an oxidation catalyst device for a diesel vehicle - Google Patents
Method for cleaning an oxidation catalyst device for a diesel vehicle Download PDFInfo
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- 238000004140 cleaning Methods 0.000 title claims description 57
- 239000003054 catalyst Substances 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 17
- 230000003647 oxidation Effects 0.000 title claims description 17
- 238000007254 oxidation reaction Methods 0.000 title claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 96
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 33
- 229910052698 phosphorus Inorganic materials 0.000 claims description 33
- 239000011574 phosphorus Substances 0.000 claims description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 24
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- 239000011593 sulfur Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 description 36
- 238000000746 purification Methods 0.000 description 30
- 229930195733 hydrocarbon Natural products 0.000 description 22
- 150000002430 hydrocarbons Chemical class 0.000 description 22
- 239000007789 gas Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000011084 recovery Methods 0.000 description 9
- 238000004453 electron probe microanalysis Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 5
- 238000004445 quantitative analysis Methods 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000007096 poisonous effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 206010021198 ichthyosis Diseases 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
本発明は、ディーゼル自動車用の酸化触媒装置の洗浄方法に関する。 The present invention relates to a method for cleaning an oxidation catalyst device for diesel vehicles.
自動車から排出された排ガスには、炭化水素（ＨＣ）、一酸化炭素（ＣＯ）、窒素酸化物（ＮＯｘ）、粒子状物質（ＰＭ）等の環境汚染物質が含まれている。これらの環境汚染物質を除去するために、各種の排ガス浄化用触媒が開発されている。このような排ガス浄化用触媒として、ディーゼル自動車用の酸化触媒装置（Ｄｉｓｅｌ Ｏｘｉｄａｔｉｏｎ Ｃａｔａｌｙｓｔ。以下、「ＤＯＣ」）がある。 Exhaust gas emitted from automobiles contains environmental pollutants such as hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NOx), and particulate matter (PM). In order to remove these environmental pollutants, various exhaust gas purification catalysts have been developed. One such exhaust gas purification catalyst is the Diesel Oxidation Catalyst (DOC) for diesel automobiles.
ＤＯＣは、ディーゼルエンジンからの排ガス中に含まれる有害成分のうち、ＨＣ及びＣＯを、白金（Ｐｔ）やパラジウム（Ｐｄ）を含有した触媒を用いて浄化処理することで、無害な二酸化炭素や水に変換する装置である。 DOC is a device that converts the harmful components contained in the exhaust gas from diesel engines, HC and CO, into harmless carbon dioxide and water by purifying them using catalysts containing platinum (Pt) and palladium (Pd).
ここで、自動車から排出された排ガスには、燃料や潤滑油由来の被毒成分が含まれている。被毒成分は、リン（Ｐ）、硫黄（Ｓ）等である。被毒成分がＤＯＣに付着すると、ＤＯＣが持っているＨＣ等を浄化して無害化する性能（以下、「浄化性能」）が低下する。よって、浄化性能を回復するために様々な処理が行われる。 Here, the exhaust gas emitted from an automobile contains poisonous components derived from fuel and lubricating oil. The poisonous components are phosphorus (P), sulfur (S), etc. When the poisonous components adhere to the DOC, the DOC's ability to purify and detoxify HC and other substances (hereinafter referred to as "purification performance") decreases. Therefore, various treatments are carried out to restore the purification performance.
たとえば、特許文献１には、気体及び液体を使用してＤＯＣに堆積した粒子状物質を除去する装置が開示されている。また洗浄効果を増大させるために溶液を加熱するための加熱器を組み込むことが開示されている。 For example, Patent Document 1 discloses an apparatus that uses gas and liquid to remove particulate matter that has accumulated in a DOC. It also discloses incorporating a heater to heat the solution to increase the cleaning effect.
ここで、従来から被毒成分が付着したＤＯＣに対して熱処理を行うことで、硫黄成分を除去できることが知られている。一方、硫黄成分を除去しただけではＤＯＣの浄化性能が十分に回復しない例もあり問題となっていた。 Here, it has been known that sulfur components can be removed by performing heat treatment on DOCs that have poisoning components attached to them. However, there have been cases where the purification performance of DOCs has not been fully restored by simply removing the sulfur components, which has been a problem.
本発明の目的は、ＤＯＣの浄化性能を回復することが可能な洗浄方法を提供することにある。 The object of the present invention is to provide a cleaning method that can restore the purification performance of DOC.
上記目的を達成するための発明は、付着物としてリン成分が付着したディーゼル自動車用の酸化触媒装置を、クエン酸を含有する洗浄液に浸漬することにより、当該酸化触媒装置から当該リン成分を除去する、ディーゼル自動車用の酸化触媒装置の洗浄方法である。
本発明の他の特徴については、後述する明細書及び図面の記載により明らかにする。
The invention for achieving the above-mentioned object is a method for cleaning an oxidation catalyst device for a diesel vehicle, which removes phosphorus components from an oxidation catalyst device having phosphorus components attached thereto as deposits by immersing the oxidation catalyst device in a cleaning solution containing citric acid.
Other features of the present invention will become apparent from the following specification and drawings.
本発明によれば、ＤＯＣの浄化性能を回復することができる。 According to the present invention, it is possible to restore the purification performance of DOC.
＜実施形態＞
本実施形態に係る洗浄方法は、付着物としてリン成分が付着したディーゼル自動車用の酸化触媒装置を、クエン酸を含有する洗浄液に浸漬することにより、当該酸化触媒装置から当該リン成分を除去する。
<Embodiment>
In the cleaning method according to the present embodiment, an oxidation catalyst device for a diesel vehicle to which phosphorus components have adhered as deposits is immersed in a cleaning solution containing citric acid, thereby removing the phosphorus components from the oxidation catalyst device.
＝＝酸化触媒装置＝＝
酸化触媒装置は、ディーゼル自動車用の装置（ＤＯＣ）である。本実施形態に係る洗浄方法が実施されるＤＯＣは、所定時間使用された結果（すなわち、ディーゼル自動車が所定距離走行した結果）、浄化性能が基準を満たさなくなったものである。
Oxidation Catalyst Device
The oxidation catalyst device is a device for a diesel automobile (DOC). The DOC on which the cleaning method according to the present embodiment is performed is one whose purification performance no longer satisfies the standard as a result of being used for a certain period of time (i.e., as a result of the diesel automobile traveling a certain distance).
＝＝付着物＝＝
付着物は、ディーゼル自動車の走行に伴ってＤＯＣに付着するものである。付着物が付着することにより、ＤＯＣの浄化性能が低下する。本実施形態における付着物は少なくともリン（Ｐ）成分を含む。リン成分は、たとえばＰ2Ｏ5（五酸化二リン）のようなリンの酸化物である。
==Attachments==
The deposits are deposited on the DOC as the diesel vehicle travels. The deposition of the deposits reduces the purification performance of the DOC. In this embodiment, the deposits contain at least a phosphorus (P) component. The phosphorus component is, for example, an oxide of phosphorus such as P2O5 ( diphosphorus pentoxide).
付着物は、硫黄（Ｓ）成分を含んでいる場合もある。硫黄成分は、たとえばＳＯ3（三酸化硫黄）のような硫黄の酸化物である。 The deposits may also contain sulfur (S) components, which are oxides of sulfur, such as SO 3 (sulfur trioxide).
＝＝洗浄液＝＝
洗浄液は、水にクエン酸を溶解させたものである。クエン酸の水溶液は毒性が少ないため取扱いが容易である。なお、本実施形態におけるクエン酸は、クエン酸の塩（たとえばクエン酸ナトリウム）を含む。
==Cleaning Solution==
The cleaning solution is citric acid dissolved in water. The aqueous solution of citric acid is easy to handle because it has low toxicity. Note that the citric acid in this embodiment includes a salt of citric acid (e.g., sodium citrate).
洗浄液は、ＤＯＣに付着した付着物を水に可溶化させる役割を果たす。付着物を水に可溶化させることにより、ＤＯＣから付着物が除去される。具体的には、付着物がクエン酸と反応して塩や錯体を形成する。そして、その塩や錯体が水中に溶け出すことにより、ＤＯＣから除去される。 The cleaning solution serves to solubilize the deposits attached to the DOC in water. By solubilizing the deposits in water, the deposits are removed from the DOC. Specifically, the deposits react with citric acid to form salts or complexes. These salts or complexes then dissolve in the water and are removed from the DOC.
付着物を除去するためには、洗浄液の温度は２～９８℃が好ましく、クエン酸の濃度は、０．１～２．０ｍｏｌ／Ｌであることが好ましい。更に、リン成分を除去するための温度としては、２５～９８℃がより好ましい。 To remove the deposits, the temperature of the cleaning solution is preferably 2 to 98°C, and the concentration of citric acid is preferably 0.1 to 2.0 mol/L. Furthermore, the temperature for removing phosphorus components is more preferably 25 to 98°C.
また、洗浄方法を室温で実施する場合、クエン酸の濃度は１．０～２．０ｍｏｌ／Ｌであることが好ましい。一方、洗浄液の温度を高くすることによりクエン酸の濃度を低くする（すなわち水に添加するクエン酸の量を少なくする）ことができる。具体的には、洗浄液の温度が５０℃～８０℃の場合、クエン酸の濃度を０．１～１．０ｍｏｌ／Ｌとすることができる。 When the cleaning method is carried out at room temperature, the concentration of citric acid is preferably 1.0 to 2.0 mol/L. On the other hand, the concentration of citric acid can be lowered (i.e., the amount of citric acid added to water can be reduced) by increasing the temperature of the cleaning solution. Specifically, when the temperature of the cleaning solution is 50°C to 80°C, the concentration of citric acid can be set to 0.1 to 1.0 mol/L.
なお、洗浄液には、付着物を除去する役割を損ねない範囲で、他の任意成分を添加してもよい。 Other optional ingredients may be added to the cleaning solution as long as they do not impair its function of removing deposits.
＝＝洗浄方法＝＝
本実施形態に係る洗浄方法は、付着物が付着したＤＯＣを、クエン酸を含有する洗浄液に浸漬することにより、ＤＯＣからリン成分を除去する。
== Cleaning method ==
In the cleaning method according to the present embodiment, the phosphorus component is removed from the DOC by immersing the DOC having the deposits in a cleaning solution containing citric acid.
ＤＯＣに付着した付着物を除去する場合、洗浄液にＤＯＣを浸漬する。浸漬は、たとえば洗浄液で満たされた容器内にＤＯＣを配することにより行う。洗浄液にＤＯＣを浸漬することで、洗浄液中のクエン酸が付着物と確実に反応し、付着物を水に可溶化させることができる。 When removing the deposits attached to the DOC, the DOC is immersed in a cleaning solution. Immersion is performed, for example, by placing the DOC in a container filled with the cleaning solution. By immersing the DOC in the cleaning solution, the citric acid in the cleaning solution can react reliably with the deposits, solubilizing the deposits in water.
なお、洗浄液による洗浄が完了したＤＯＣに対して、更に水による洗浄を行うことが好ましい。水による洗浄の方法としては、高圧洗浄機からの水をＤＯＣに直接噴霧する方法等、通常用いられている方法で行うことができる。 It is preferable to further wash the DOC with water after cleaning with the cleaning solution has been completed. Washing with water can be done by a commonly used method, such as spraying water from a high-pressure washer directly onto the DOC.
＜実施例１＞
ＤＯＣによるＨＣの浄化性能を回復する際のリン成分及び硫黄成分の影響について実験を行った。
Example 1
An experiment was carried out to examine the effects of phosphorus and sulfur components on the recovery of the HC purification performance of DOC.
（ＤＯＣ）
ＤＯＣは、所定期間、走行済みのディーゼル自動車から回収したもの（以下、「回収品（１）」）を使用した。
(DOC)
The DOC used was recovered from a diesel vehicle that had been driven for a certain period of time (hereinafter, "recovered product (1)").
（実験手順）
１．回収品（１）に対し、ＨＣを含む模擬ガスを用いたＨＣの浄化性能の測定、及び付着物の付着量の定量分析を行った。
２．回収品（１）に対して大気中、７００℃×５０時間の熱処理を加えた後、ＨＣを含む模擬ガスを用いたＨＣの浄化性能の測定、及び付着物の付着量の定量分析を行った。
３．熱処理を行った回収品（１）に対してクエン酸を含有する洗浄液（濃度１ｍｏｌ／Ｌ）により洗浄処理（８０℃の洗浄液に３０分浸漬）を行った後、ＨＣを含む模擬ガスを用いたＨＣの浄化性能の測定、及び付着物の付着量の定量分析を行った。
(Experimental Procedure)
1. For the recovered product (1), the HC purification performance was measured using a simulated gas containing HC, and the amount of attached matter was quantitatively analyzed.
2. The recovered product (1) was subjected to a heat treatment at 700° C. for 50 hours in the atmosphere, and then the HC purification performance was measured using a simulated gas containing HC, and the amount of attached matter was quantitatively analyzed.
3. The recovered product (1) that had been subjected to the heat treatment was subjected to a cleaning treatment (immersion in a cleaning solution at 80° C. for 30 minutes) using a cleaning solution containing citric acid (concentration 1 mol/L), and then the HC purification performance was measured using a simulated gas containing HC, and the amount of attached matter was quantitatively analyzed.
なお、ＨＣの浄化性能の測定は、模擬ガスを使用した触媒反応装置を用いて行った。この例では１５％浄化温度を測定した。定量分析は、蛍光Ｘ線分析（ＸＲＦ）により行った。使用した模擬ガスの構成及び条件は、表２に示すとおりである。 The measurement of HC purification performance was carried out using a catalytic reaction device with a simulated gas. In this example, the 15% purification temperature was measured. Quantitative analysis was carried out using X-ray fluorescence analysis (XRF). The composition and conditions of the simulated gas used are as shown in Table 2.
表１に示す除去率は、処理の前後で付着物がどれだけ除去できているかを示す割合である。除去率は、以下の式を用いて算出した。除去率は、リン成分（Ｐ2Ｏ5）及び硫黄成分（ＳＯ3）それぞれについて求めた。なお、新品には付着物は無いため、付着量を「０」として計算を行った。また、回収品（１）におけるリン成分の付着量は７．２であり、硫黄成分の付着量は４．９である。 The removal rate shown in Table 1 is the ratio indicating how much of the attached matter was removed before and after the treatment. The removal rate was calculated using the following formula. The removal rate was determined for each of the phosphorus component ( P2O5 ) and the sulfur component ( SO3 ). Since there was no attached matter on the new product, the amount of attachment was set to "0" in the calculation. The amount of attached phosphorus component in the recovered product (1) was 7.2, and the amount of attached sulfur component was 4.9.
除去率（％）＝１００－（（新品と処理後の回収品との付着量の差／新品と回収品との付着量の差）×１００） Removal rate (%) = 100 - ((difference in adhesion amount between new and recovered products after processing / difference in adhesion amount between new and recovered products) x 100)
表１に示す回復率は、処理の前後でＨＣの浄化性能がどれだけ回復しているかを示す割合である。回復率は以下の式を用いて算出した。 The recovery rate shown in Table 1 is the percentage that indicates how much HC purification performance has been recovered before and after treatment. The recovery rate was calculated using the following formula.
回復率（％）＝１００－（（新品と処理後の回収品との１５％浄化温度の差／新品と回収品との１５％浄化温度の差）×１００） Recovery rate (%) = 100 - ((15% purification temperature difference between new and recovered products after processing / 15% purification temperature difference between new and recovered products) x 100)
図１は、表１に示したリン成分及び硫黄成分の除去率と、ＨＣの浄化性能の回復率を示したグラフである。表１及び図１から明らかなように、熱処理を行うことにより硫黄成分を約７６％取り除くことができたが、リン成分を取り除くことはできなかった。また熱処理を行っただけではＤＯＣの浄化性能は回復しなかった。 Figure 1 is a graph showing the removal rate of phosphorus and sulfur components shown in Table 1, and the recovery rate of HC purification performance. As is clear from Table 1 and Figure 1, the heat treatment was able to remove approximately 76% of the sulfur components, but it was not possible to remove the phosphorus components. Furthermore, the DOC purification performance was not restored by just performing the heat treatment.
一方、クエン酸を含有する洗浄液による洗浄処理を行った結果、リン成分を取り除くことができ、ＤＯＣの浄化性能が大幅に回復した。この結果から、ＤＯＣの浄化性能を回復するためには、リン成分を除去することが有効であることが理解できる。 On the other hand, when cleaning was performed using a cleaning solution containing citric acid, the phosphorus components were removed and the purification performance of the DOC was significantly restored. From this result, it can be seen that removing the phosphorus components is effective in restoring the purification performance of the DOC.
なお、表１及び図１から明らかなように、クエン酸を含有する洗浄液による洗浄処理を行うことにより、リン成分と併せて硫黄成分も取り除くことができる。 As is clear from Table 1 and Figure 1, by performing a cleaning process using a cleaning solution containing citric acid, it is possible to remove sulfur components in addition to phosphorus components.
図２Ａは回収品（１）をＳＥＭ／ＥＰＭＡで測定した写真である。白い部分がリン成分である。一方、図２Ｂは洗浄処理した回収品（１）をＳＥＭ／ＥＰＭＡで測定した写真である。この図からも明らかなように、洗浄液による洗浄処理を行った回収品はリン成分を確実に取り除くことができる。 Figure 2A is a photograph of recovered product (1) measured with SEM/EPMA. The white parts are phosphorus components. Meanwhile, Figure 2B is a photograph of recovered product (1) after cleaning treatment, measured with SEM/EPMA. As is clear from this figure, the phosphorus components can be reliably removed from recovered products that have been cleaned with a cleaning solution.
また、図３Ａは回収品（１）をＳＥＭ／ＥＰＭＡで測定した写真である。白い部分が硫黄成分である。一方、図３Ｂは洗浄処理した回収品（１）をＳＥＭ／ＥＰＭＡで測定した写真である。この図からも明らかなように、洗浄液による洗浄処理を行った回収品は硫黄成分を確実に取り除くことができる。 Figure 3A is a photograph of recovered product (1) measured with SEM/EPMA. The white parts are sulfur components. Meanwhile, Figure 3B is a photograph of recovered product (1) after cleaning treatment, measured with SEM/EPMA. As is clear from this figure, sulfur components can be reliably removed from recovered products that have been cleaned with a cleaning solution.
＜実施例２＞
洗浄液の温度について実験を行った。
Example 2
An experiment was carried out on the temperature of the cleaning solution.
（ＤＯＣ）
ＤＯＣは、所定期間、走行済みのディーゼル自動車から回収したもの（以下、「回収品（２）」）を使用した。回収品（２）は回収品（１）と異なる。
(DOC)
The DOC used was recovered from a diesel vehicle that had been driven for a certain period of time (hereinafter, "recovered product (2)"). Recovered product (2) is different from recovered product (1).
（実験手順）
１．回収品（２）の一部をサンプリングした部分に対し、ＨＣを含む模擬ガスを用いたＨＣの浄化性能の測定、及び付着物の付着量の定量分析を行った。
２．サンプリングした部分に対してクエン酸を含有する洗浄液（濃度１ｍｏｌ／Ｌ）により洗浄処理を行った後、ＨＣを含む模擬ガスを用いたＨＣの浄化性能の測定、及び付着物の付着量の定量分析を行った。
(Experimental Procedure)
1. A portion of the recovered product (2) was sampled, and the HC purification performance was measured using a simulated gas containing HC, and the amount of attached matter was quantitatively analyzed.
2. The sampled area was washed with a washing solution containing citric acid (concentration 1 mol/L), and then the HC purification performance was measured using a simulated gas containing HC, and the amount of attached matter was quantitatively analyzed.
この例において、洗浄処理は、洗浄液の温度（２℃、１０℃、２５℃、５０℃、８０℃、９８℃）を変えて行った。各温度において使用したサンプリングした部分におけるリン成分及び硫黄成分の付着量は表３に示した通りである。 In this example, the cleaning process was performed by changing the temperature of the cleaning solution (2°C, 10°C, 25°C, 50°C, 80°C, 98°C). The amount of phosphorus and sulfur components adhering to the sampled parts used at each temperature is shown in Table 3.
なお、ＨＣの浄化性能の測定、及び付着量の定量分析は実施例１と同様の方法により行った。但し、この例では５０％浄化温度を測定した。また、除去率及び回復率は実施例１で示した式を用いて算出した。使用した模擬ガスの構成及び条件は、表４に示すとおりである。 The measurement of HC purification performance and quantitative analysis of the amount of adhesion were performed in the same manner as in Example 1. However, in this example, the 50% purification temperature was measured. The removal rate and recovery rate were calculated using the formula shown in Example 1. The composition and conditions of the simulated gas used are as shown in Table 4.
図４は、表３に示した温度の変化に伴うリン成分の除去率を示したグラフである。図５は、表３に示した温度の変化に伴うＨＣの浄化性能の回復率を示したグラフである。図６は、表３に示した温度の変化に伴う硫黄成分の除去率を示したグラフである。 Figure 4 is a graph showing the removal rate of phosphorus components with the change in temperature shown in Table 3. Figure 5 is a graph showing the recovery rate of HC purification performance with the change in temperature shown in Table 3. Figure 6 is a graph showing the removal rate of sulfur components with the change in temperature shown in Table 3.
図４及び図５から明らかなように、洗浄液の温度が２℃～９８℃の範囲において、リン成分を除去することができ、ＤＯＣの浄化性能が回復した。また、図６から明らかなように、洗浄液の温度が２℃～９８℃の範囲において、硫黄成分についても除去することができた。 As is clear from Figures 4 and 5, when the temperature of the cleaning solution was in the range of 2°C to 98°C, phosphorus components were removed and the purification performance of the DOC was restored. In addition, as is clear from Figure 6, when the temperature of the cleaning solution was in the range of 2°C to 98°C, sulfur components were also removed.
＜実施例３＞
洗浄液の温度と、クエン酸の濃度の関係について実験を行った。
Example 3
An experiment was conducted on the relationship between the temperature of the cleaning solution and the concentration of citric acid.
（ＤＯＣ）
ＤＯＣは、所定期間、走行済みのディーゼル自動車から回収したもの（以下、「回収品（３）」）を使用した。回収品（３）は回収品（１）及び回収品（２）と異なる。
(DOC)
The DOC used was recovered from a diesel vehicle that had been driven for a certain period of time (hereinafter, “recovered product (3)”). Recovered product (3) is different from recovered product (1) and recovered product (2).
（実験手順）
１．回収品（３）の一部をサンプリングした部分に対し、付着物の付着量の定量分析を行った。
２．サンプリングした部分に対してクエン酸を含有する洗浄液により洗浄処理を行った後、付着物の付着量の定量分析を行った。
(Experimental Procedure)
1. A portion of the recovered product (3) was sampled and a quantitative analysis of the amount of attached matter was performed.
2. The sampled area was washed with a washing solution containing citric acid, and then the amount of attached matter was quantitatively analyzed.
この例において、洗浄処理は、洗浄液の温度（２５℃、５０℃、８０℃）、及びクエン酸の濃度（０．１ｍｏｌ／Ｌ、０．５ｍｏｌ／Ｌ、１．０ｍｏｌ／Ｌ、１．５ｍｏｌ／Ｌ、２．０ｍｏｌ／Ｌ）を変えて行った。各温度及び濃度において使用したサンプリングした部分のリン成分及び硫黄成分の付着量は表４に示した通りである。 In this example, the cleaning process was performed by changing the temperature of the cleaning solution (25°C, 50°C, 80°C) and the concentration of citric acid (0.1 mol/L, 0.5 mol/L, 1.0 mol/L, 1.5 mol/L, 2.0 mol/L). The amount of phosphorus and sulfur components adhering to the sampled portions used at each temperature and concentration is shown in Table 4.
なお、付着量の定量分析は実施例１と同様の方法により行った。また、除去率は実施例１で示した式を用いて算出した。一方、使用した模擬ガスの構成及び条件は、実施例２と同様である。 The quantitative analysis of the amount of adhesion was performed in the same manner as in Example 1. The removal rate was calculated using the formula shown in Example 1. The composition and conditions of the simulated gas used were the same as in Example 2.
図７は、表５に示した洗浄液の温度、及びクエン酸の濃度の変化に伴うリン成分の除去率を示したグラフである。図８は、表５に示した洗浄液の温度、及びクエン酸の濃度の変化に伴う硫黄成分の除去率を示したグラフである。 Figure 7 is a graph showing the removal rate of phosphorus components with changes in temperature and citric acid concentration of the cleaning solution shown in Table 5. Figure 8 is a graph showing the removal rate of sulfur components with changes in temperature and citric acid concentration of the cleaning solution shown in Table 5.
図７から明らかなように、洗浄液の温度を５０℃以上にすることにより、クエン酸の濃度が低い場合であってもリン成分を除去することができた。すなわち、水に対するクエン酸の添加量を抑制できた。一方、クエン酸の濃度を１．０ｍｏｌ／Ｌ以上とすることにより、常温であってもリン成分を除去できることが明らかとなった。 As is clear from Figure 7, by setting the temperature of the cleaning solution to 50°C or higher, phosphorus components could be removed even when the concentration of citric acid was low. In other words, the amount of citric acid added to the water could be reduced. On the other hand, it was revealed that by setting the concentration of citric acid to 1.0 mol/L or higher, phosphorus components could be removed even at room temperature.
また図８から明らかなように、硫黄成分については、洗浄液の温度やクエン酸の濃度の影響を受けることなく除去することができた。 As is also clear from Figure 8, sulfur components could be removed without being affected by the temperature of the cleaning solution or the concentration of citric acid.
上記実施形態及び実施例は、例として提示したものであり、発明の範囲を限定するものではない。上記の構成は、適宜組み合わせて実施することが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。上記実施形態やその変形は、発明の範囲や要旨に含まれると同様に、特許請求の範囲に記載された発明とその均等の範囲に含まれる。 The above embodiments and examples are presented as examples and do not limit the scope of the invention. The above configurations can be implemented in appropriate combinations, and various omissions, substitutions, and modifications can be made without departing from the gist of the invention. The above embodiments and their modifications are included in the scope of the invention and its equivalents as described in the claims, as well as in the scope and gist of the invention.
Claims (2)
前記洗浄液の温度は、２５～５０℃であり、前記クエン酸の濃度は、１．０～２．０ｍｏｌ／Ｌであるディーゼル自動車用の酸化触媒装置の洗浄方法。 A method for cleaning an oxidation catalyst device for a diesel vehicle, comprising the steps of: immersing an oxidation catalyst device for a diesel vehicle having phosphorus components attached thereto as deposits in a cleaning solution containing citric acid to remove the phosphorus components from the oxidation catalyst device, the method comprising the steps of:
A method for cleaning an oxidation catalyst device for a diesel vehicle, wherein the temperature of the cleaning solution is 25 to 50° C., and the concentration of the citric acid is 1.0 to 2.0 mol/L.
前記酸化触媒装置を、前記クエン酸を含有する洗浄液に浸漬することにより、当該酸化触媒装置から前記リン成分及び前記硫黄成分を除去することを特徴とする、請求項１に記載のディーゼル自動車用の酸化触媒装置の洗浄方法。2. The method for cleaning an oxidation catalyst device for a diesel vehicle according to claim 1, characterized in that the phosphorus components and the sulfur components are removed from the oxidation catalyst device by immersing the oxidation catalyst device in a cleaning solution containing citric acid.
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