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Journal of the Japan Petroleum Institute, 46, (6), 379382 (2003)

[Research Note]

379

Immobilized Tungstophosphoric Acid-catalyzed Oxidative Desulfurization of Diesel Oil with Hydrogen Peroxide

Kazumasa YAZU*, Takeshi FURUYA, and Keiji MIKI

Institute for Energy Utilization, National Institute of Advanced Industrial Science and Technology, AIST Tsukuba West, 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, JAPAN

(Received May 13, 2003)

An immobilized 12-tungstophosphoric acid on an anion exchange resin (TPA/AER) catalyzes the oxidation of dibenzothiophene and 4,6-dimethyldibenzothiophene with H2O2 in acetonitrile (MeCN) to give the corresponding sulfones as the major product. The oxidation rates increased with increasing amounts of H2O2 and TPA/AER.

TPA/AER is reusable since the catalytic activity was not reduced even during the fifth cycle of use.

TPA/AER

acts as a catalyst for the oxidation of dibenzothiophenes in an octane/MeCN biphasic system as well.

The major

oxidation products were also the sulfones, which were mainly distributed in the MeCN phase. In TPA/AER-cat- alyzed oxidative desulfurization of diesel oil containing 330 ppm sulfur, the reduction of the sulfur content was enhanced with increasing amounts of immobilized TPA per unit weight of AER and the sulfur content was reduced to below 50 ppm. The sulfur content was further decreased by solvent extraction with MeCN.

Keywords Immobilized catalyst, Tungstophosphoric acid, Hydrogen peroxide, Dibenzothiophene, Oxidative desulfurization, Diesel oil

1.

Introduction

The removal of sulfur compounds from diesel oil is necessary for the reduction of NOx and particulate con- tents in the emission from diesel engines. New legis- lation in Japan and Europe will limit the sulfur content to a maximum of 50 ppm by 2005. Alkylated diben- zothiophenes substituted at the 4 and/or 6 positions in diesel oil are difficult to be removed by the convention- al hydrodesulfurization method because of their steric hindrance 1),2) . Therefore, a new method for removing these hindered dibenzothiophenes is needed. Oxidative desulfurization is one of the best methods because hindered dibenzothiophenes in diesel oil are oxidized effectively with peroxy-acids 3),4) , H2O2 5) and t- BuOCl 6) , or by photooxidation 7),8) , and the oxidation products are easily removed from the diesel oil by extraction and adsorption. We recently found that the hindered dibenzothiophenes were oxidized smoothly with H2O2 in the presence of 12-tungstophosphoric acid (TPA) in a hydrocarbon/acetonitrile (MeCN) biphasic system and that the sulfur content of a diesel oil was effectively reduced 9) . To further develop this oxida- tion system, we have used immobilized TPA on a strongly basic anion exchange resin as the catalyst.

* To whom correspondence should be addressed.

* E-mail: yazu-k@aist.go.jp

J. Jpn. Petrol. Inst.,

* E-mail: yazu-k@aist.go.jp J. Jpn. Petrol. Inst., Scheme 1 Here we report that the immobilized TPA

Scheme 1

Here we report that the immobilized TPA catalyzes the oxidation of dibenzothiophenes in the presence of H2O2 (Scheme 1) and is effective for the oxidative desulfurization of diesel oil in the diesel oil/MeCN biphasic system.

2.

Experimental

2. 1. Preparation of Immobilized TPA Catalyst Amberlyst A-26 (AER) used as an anion exchange resin was obtained from Organo Corp. The ion exchange capacity of AER is 3.8 meq/g dry resin. To prepare the immobilized TPA on AER (TPA/AER), an AER (0.5 g dry resin) suspension in an aqueous TPA solution (100 ml) was stirred at room temperature for 24 h. Then, the resin was filtered off, washed with distilled water and MeCN, and stored in MeCN. TPA/AER-1, TPA/AER-2, TPA/AER-3, and TPA/AER- 4 were the immobilized catalysts prepared with 1, 2, 4,

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380

Table 1

Immobilized TPA-catalyzed Oxidation of 5 mM (1 M = 1 moldm 3 ) Dibenzothiophenes with H2O2 in MeCN at 60°C

Entry

Substrate

TPA/AER [mmol/g dry resin]

35 wt% H2O2

Conversion [mol%]

 
 

[ml]

0.5 h

1 h

2 h

1

1a

TPA/AER-3 (0.12/0.25)

1.0

70

93

99

2

AER (0/0.25)

1.0

0

0

0

3

TPA/AER-1 (0.04/0.25)

1.0

63

88

94

4

TPA/AER-2 (0.07/0.25)

1.0

71

93

98

5

TPA/AER-4 (0.17/0.25)

1.0

70

94

100

6

TPA/AER-3 (0.12/0.25)

0.5

57

79

88

7

TPA/AER-3 (0.12/0.25)

2.0

88

100

100

8

TPA/AER-3 (0.04/0.08)

1.0

34

65

92

9

TPA/AER-3 (0.24/0.50)

1.0

87

98

99

10

1b

TPA/AER-3 (0.12/0.25)

1.0

48

77

92

11

TPA/AER-3 (0.12/0.25)

2.0

78

100

100

and 8 mM (1 M = 1 moldm 3 ) TPA aqueous solution,

respectively. The amount of TPA retained on AER

was calculated from the decrease in the amount of TPA

estimated from tungsten analyses by inductively cou- pled plasma (ICP) spectrometry using Thermo Jarrell Ash IRIS/AP. The values for TPA/AER-1, TPA/ AER-2, TPA/AER-3, and TPA/AER-4 were 0.16, 0.29, 0.49, and 0.66 mmol/g dry resin, respectively.

2. 2. Oxidation of Dibenzothiophenes in MeCN

TPA/AER (or AER) was added to 50 ml of a MeCN solution of dibenzothiophene (1a) (0.25 mmol) or 4,6- dimethyldibenzothiophene (1b) (0.25 mmol) and kept

at 60°C with stirring, and then the required amount of 35% aqueous H2O2 was added. High performance liq-

uid chromatography (HPLC) analysis for the oxidation

of 1a or 1b was conducted as reported previously 10) . Consumption of H2O2 was followed by iodometry. Experiments for the reuse of TPA/AER were carried out as follows. TPA/AER-3 (0.12 mmol/0.25 g dry resin) was added to 50 ml of a MeCN solution of 1a (0.25 mmol) and kept at 60°C with stirring, and then 2

ml of 35% aqueous H2O2 (23.2 mmol) was added.

The oxidation was similarly monitored with HPLC.

After 1.5 h, the catalyst was filtered off, washed with MeCN three times, and stored in MeCN. The catalyst was then used in the next run. This procedure was repeated as required.

2. 3. Oxidation of Dibenzothiophenes in an Organic

Biphasic System TPA/AER-3 (0.12 mmol/0.25 g dry resin) was added to 50 ml of an octane solution of 1a (0.25 mmol) or 1b (0.25 mmol) and 50 ml of MeCN. The mixture was kept at 60°C and 2 ml of 35% aqueous H2O2 (23.2

mmol) was added. The decay of 1a or 1b was mea- sured as described above.

2. 4. Oxidative Desulfurization of Diesel Oil

Hydrodesulfurized diesel oil was supplied by Japan Energy Corp. The sulfur content was 330 ppm. TPA/AER (0.25 g dry resin) was added to 25 ml of the diesel oil, 25 ml of hexane and 50 ml of MeCN. The

J. Jpn. Petrol. Inst.,

MeCN phase formed the upper layer without hexane since the densities of the diesel oil, hexane and MeCN are 0.83, 0.65 and 0.78, respectively. The biphasic mixture was kept at 60°C and 2 ml of 35% aqueous H2O2 (23.2 mmol) was added. The oil phase was sep- arated, washed with water, and dehydrated with CaCl2 and the sulfur content was measured as reported previ- ously 10) after evaporation of hexane.

3. Results and Discussion

3. 1. Immobilized TPA-catalyzed Oxidation of Dibenzothiophenes in MeCN The results of TPA/AER-catalyzed oxidation of

dibenzothiophenes in MeCN are summarized in Table

1. The oxidation of 1a proceeded rapidly in the pres-

ence of TPA/AER to give the corresponding sulfoxide and sulfone (2a) as the major products (e.g., 2a was formed in 90 mol% yield at 1 h under the conditions of entry 7). On the other hand, no oxidation was observed when intact AER was used (entry 2). The amount of immobilized TPA per unit weight of AER was TPA/AER-1 < TPA/AER-2 < TPA/AER-3 < TPA/ AER-4 (entries 1, 3-5). The increase in the immobi- lized TPA had little effect on the oxidation under the conditions employed. The difference in the conver- sion after 1 h was important since complete oxidation is essential for the oxidative desulfurization. Therefore, an increase in the immobilized TPA would be useful for the oxidation. This was consistent with the results for the oxidative desulfurization of diesel oil. The oxidation rates increased with higher amounts of H2O2 (entries 1, 6, 7) and immobilized catalyst (entries 1, 8, 9), but an increase in the immobilized catalyst was not effective for complete oxidation. Oxidation to the sulfone needs two moles of H2O2 per one mole of dibenzothiophene (Scheme 1). Excess H2O2 was necessary in this oxidation system since most H2O2 was consumed by non-reactive decomposition; 84% of the added H2O2 was consumed during 1 h oxidation but

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Fig. 1 Removal of 1a ( ● ) or 1b ( ○ ) in Octane

Fig.

1

Removal of 1a () or 1b () in Octane during Oxida- tion with Hydrogen Peroxide and TPA/AER at 60°C in an Octane/MeCN Biphasic System

only about 2% of the consumed H2O2 was used for the oxidation of 1a under the conditions of entry 7. The consumption of H2O2 should be minimized by the improvement of the catalytic activity since more than 80% of the consumed H2O2 was utilized for the oxida- tion of 1a in a homogeneous TPA catalyzed reaction. 4,6-Dimethyldibenzothiophene (1b), one of the most unreactive sulfur compounds during hydrodesulfuriza- tion 1),2) , was also oxidized effectively to the correspond- ing sulfoxide and sulfone (2b); the yield of 2b was 86 mol% at 1 h under the conditions of entry 11. However, the rate of oxidation of 1b was a little slower than that of 1a in this oxidation system (entries 1, 7, 10, 11). This difference in oxidation rates may result from the difference in the accessibilities of 1a and 1b to the active sites of TPA/AER because the two substrates were oxidized at a similar rate in homogeneous TPA- catalyzed oxidations. TPA/AER is reusable, since recovery can be easily achieved by simple filtration and the catalytic activity was not reduced even after the fifth cycle of use; the extents of the conversion after 0.5 h and 1 h oxidation were 92 mol% and 100 mol%, respectively, in the fifth run (see entry 7 in Table 1). Consequently, these results indicate that TPA/AER can act effectively as a catalyst for the oxidation of diben- zothiophenes with H2O2 in MeCN. 3. 2. Immobilized TPA-catalyzed Oxidation of Dibenzothiophenes in an Organic Biphasic System Oxidation of dibenzothiophenes was investigated in the presence of TPA/AER in an organic biphasic sys- tem using octane as the model for the diesel oils. Figure 1 shows that 54% of 1a was transferred into the MeCN phase from the octane phase prior to oxida-

J. Jpn. Petrol. Inst.,

381

the octane phase prior to oxida- J. Jpn. Petrol. Inst., 381 Scheme 2 tion and the

Scheme 2

tion and the concentration of 1a in octane phase decreased as 1a was oxidized in the MeCN phase (Scheme 2). Compared with 1a, a lesser amount (36%) of 1b was transferred into the MeCN phase from the octane phase prior to oxidation due to the substitu- tion with methyl groups. The oxidation of 1b pro- ceeded similarly, but more slowly than that of 1a. This may be ascribed to the lower reactivity of 1b (Table 1) and the lower partition constant in the MeCN phase. In addition, the rates of TPA/AER-cat- alyzed oxidation of 1a and 1b were much smaller than those observed in the TPA-catalyzed reactions 9) . Accordingly, improvement of the catalytic activity is necessary for application to the oxidative desulfuriza- tion of diesel oil. The design of AER may be effec- tive for the improvement; the molecular weights of the support polymers influence the catalytic activities of the supported heteropoly oxometalates 11) . The major oxidation products were the sulfones, as observed in MeCN. This biphasic system would be useful for desulfurization of diesel oil since the sulfones are much more soluble in MeCN than in octane due to their polarity: 2a and 2b partition 99% and 96%, respective- ly, into the MeCN phase. 3. 3. Immobilized TPA-catalyzed Oxidative Desul- furization of Diesel Oil TPA/AER was applied to the oxidative desulfuriza- tion of diesel oil containing 330 ppm sulfur. A small reduction in sulfur content (ca. 60 ppm) was observed prior to the oxidation (Fig. 2) since the organic sulfur compounds in diesel oil were extracted with MeCN. There was little decrease in the sulfur content in the absence of TPA/AER. In contrast, the sulfur content was reduced with time in the presence of TPA/AER and the reduction was enhanced by increasing the amount of immobilized TPA per unit weight of AER. After 5 h of oxidation, the sulfur content was reduced to 43 ppm with TPA/AER-4 and to 97 ppm with TPA/ AER-1. These results indicate that TPA/AER-cat- alyzed oxidation is applicable to the oxidative desulfur- ization of diesel oil. Since a small amount of oxidized sulfur compounds still remained in the oil phase, addi- tional solvent extraction was effective for further reduction of the sulfur content in the oil: the sulfur con-

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382

382 △ , TPA/AER-1; ▽ , TPA/AER-2; □ , TPA/AER-3; ○ , TPA/ AER-4; ● ,

, TPA/AER-1; , TPA/AER-2; , TPA/AER-3; , TPA/ AER-4; , no TPA/AER.

Fig. 2 Oxidative Desulfurization of Diesel Oil Induced by Hydrogen Peroxide and TPA/AER at 60°C in a Light Oil/MeCN Biphasic System

tent was decreased to 21 ppm by the treatment of the oxidized diesel oil containing 43 ppm sulfur with an equal volume of MeCN.

4.

Conclusion

TPA/AER catalyzed the oxidation of dibenzothio-

phenes with H2O2 not only in MeCN but also in an organic biphasic system. The immobilized catalyst was useful for the oxidative desulfurization of diesel oil in the diesel oil/MeCN biphasic system. The applica- tion of TPA/AER would simplify oxidative desulfuriza- tion, although the catalytic activity requires further improvement.

References

1) Kabe, T., Ishihara, A., Tajima, H., Ind. Eng. Chem. Res., 31, 1577 (1992).

2) Ma, X., Sakanishi, K., Mochida, I., Ind. Eng. Chem. Res., 33,

218 (1994).

3) Aida, T., Yamamoto, D., Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem., 39, 623 (1994). 4) Bonde, S. E., Gore, W., Dolbear, G. E., Skov, E. R., Prepr. Pap.-Am. Chem. Soc., Div. Petrol. Chem., 45, 364 (2000).

5) Collins, F. M., Lucy, A. R., Sharp, C., J. Mol. Catal. A, 117, 397

(1997).

6) Otsuki, S., Nonaka, T., Qian, W., Ishihara, A., Kabe, T., Sekiyu Gakkaishi (J. Jpn. Petrol. Inst.), 44, (1), 18 (2001). 7) Shiraishi, Y., Hirai, T., Komasawa, I., Ind. Eng. Chem. Res., 37,

203 (1998).

8) Shiraishi, Y., Taki, Y., Hirai, T., Komasawa, I., Chem. Commun., 1998, 2601. 9) Yazu, K., Yamamoto, Y., Furuya, T., Miki, K., Ukegawa, K., Energy & Fuels, 15, 1535 (2001). 10) Yazu, K., Yamamoto, Y., Miki, K., Ukegawa, K., J. Oleo Sci., 50, 521 (2000). 11) Ogawa, M., Tanaka, H., Ishii, Y., Sekiyu Gakkaishi (J. Jpn. Petrol. Inst.), 36, (1), 27 (1993).

……………………………………………………………………

要   旨

固定化タングストリン酸触媒を用いた過酸化水素による軽油の酸化脱硫

矢津 一正,古屋  武,三木 啓司

産業技術総合研究所 エネルギー利用研究部門,305-8569 茨城県つくば市小野川 16-1 つくば西

アセトニトリル(MeCN)中,陰イオン交換樹脂上に固定化

した 12-タングストリン酸触媒(TPA/AER)を用いた H2O2

よるジベンゾチオフェンおよび 4,6-ジメチルジベンゾチオフェ

ンの酸化反応について検討した。主酸化生成物は,ともに相当

するスルホンであった。酸化速度は H2O2 および TPA/AER

添加量の増加に伴い増大した。TPA/AER は,5 回目の使用に

おいても触媒活性が低下しなかったことから,再使用可能であ

った。TPA/AER は,オクタン/MeCN 二相系中においても,ジ

ベンゾチオフェン類の酸化触媒として作用した。主酸化生成物

は,同様に,それらのスルホンであり,それらのほとんどは

MeCN 相中に分配した。TPA/AER を用いた硫黄分 330 ppm

軽油の酸化脱硫においては,AER 単位重量あたりの TPA 固定

化量の増加に伴い硫黄分の減少量が増大し,硫黄分を 50 ppm

以下に削減することができた。硫黄分は MeCN での溶媒抽出

によりさらに削減可能であった。

……………………………………………………………………

J. Jpn. Petrol. Inst.,

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