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Carbon 45 (2007) 30423059 www.elsevier.com/locate/carbon

Letters to the Editor

Selective dibenzothiophene adsorption on modied activated carbons

Yongxing Yang
a

a,b

, Hongying Lu

a,b

, Pingliang Ying a, Zongxuan Jiang

a,*

, Can Li

a,*

State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China b Graduate Schools of the Chinese Academy of Sciences, Beijing 100039, China Received 2 September 2007; accepted 17 October 2007 Available online 25 October 2007

World rening industry is facing new and more stringently environmental regulations on the sulfur content in diesel fuel. Hydrodesulfurization (HDS) has been widely used in current industry to remove the sulfur from the diesel fuel. However, HDS has diculty in reducing the refractory sulfur-containing compounds such as dibenzothiophene (DBT) and its derivatives to an ultra low level. Therefore, new strategies [14] for desulfurization have been explored to meet the urgent needs to produce cleaner diesel fuel in current years. Among them, selective adsorption is regarded as one of the most promising strategies to remove the refractory sulfur-containing compounds from diesel fuels. Carbon materials, particularly activated carbons (ACs) are potential adsorbents for the removal of the sulfur-containing compounds in the fuels [57]. However, ACs usually have poor adsorption capacity and selectivity for the refractory sulfur-containing compounds. Therefore, it is still a challenging subject to increase the adsorption capacity and selectivity for the sulfur-containing compounds on ACs to meet the industrial demands. In the present work, a series of modication approaches such as steam and concentrated H2SO4 have been employed to tune the textural structure and surface chemical properties of AC. It is found that the adsorption performance of the modied ACs for DBT from the model diesel is greatly improved. The commercial granulated AC (Beijing Guanghua Woods Plant, China) was used in this work. The carbon was dashed with concentrated hydrochloric and hydrouoric acids and then dried in air at 120 C overnight. This sample was denoted as AC. The AC sample treated by steam at 900 C for 25 min was denoted as ACW900. The
* Corresponding authors. Fax: +86 411 84694447 (Z. Jiang), fax: +86 411 84694447 (C. Li). E-mail addresses: zxjiang@dicp.ac.cn (Z. Jiang), canli@dicp.ac.cn (C. Li).

AC sample treated by concentrated H2SO4 (96%) at 250 C for 4 h was denoted as ACS250. For a combination treatment by steam and H2SO4, the AC sample was rst treated by steam at 900 C for 25 min and subsequently treated by concentrated H2SO4 at 250 C for 4 h. The sample obtained was denoted as ACWS. For further heat treatment, ACWS was heated at a rate of 10 C/min under owing nitrogen from room temperature to 900 C and was kept at 900 C for 12 h. The sample obtained was denoted as ACWSN. All samples were characterized by N2 sorption and base titration (Boehms method). The dynamic adsorption tests of DBT on the modied ACs were carried out using a xed-bed ow reactor at ambient temperature and pressure. A model diesel fuel containing DBT in heptane (sulfur concentration: 220 mg/dm3) was used. Adsorption operating conditions were as follows: ow rate: 10 cm3/h; amount of adsorbents: 0.3 g. Sulfur content of the euent was analyzed by microcoulometry every 30 min until saturation was achieved (i.e. the euent sulfur concentration was equal to the feed sulfur concentration). Table 1 lists the physicochemical properties of dierent samples. The steam treatment at 900 C could greatly enhance the porosity of AC. The microporous volumes (Vmic) and total pore volumes (Vtotal) of ACW900 are increased by 50% and 83% as compared with the unmodied AC, respectively. The steam treatment at 900 C hardly produces the surface acidic-oxygenated groups, because these groups are unstable at high temperature. The decrease in Vmic of ACS250 is attributed to the opening of micropores through the reaction between the AC and H2SO4 at 250 C. However, the H2SO4 treatment can greatly increase the surface acidic-oxygenated groups. The two-step modication by steam at 900 C and subsequently by H2SO4 at 250 C can produce the maximum amount of these acidic-oxygenated groups on AC surface. ACWS is posttreated by N2 at 900 C to remove the acidic-oxygenated groups and keep the textural structure unchanged. By

0008-6223/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2007.10.016

Letters to the Editor / Carbon 45 (2007) 30423059

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comparing ACWSN with ACWS, we observe the dramatic decrease of all types of acidic-oxygenated groups and slight change in pore volumes (Vmic and Vtotal). Fig. 1 shows the variance of sulfur removal with euent volume and the total adsorption capacity of DBT on the modied ACs calculated from the breakthrough curves. Both ACW900 and ACS250 show enhanced adsorption performance as compared with the unmodied AC. As shown in Table 1, ACW900 has dramatic increase in the total pore volumes (Vtotal) as compared with AC. Thus higher DBT adsorption performance of ACW900 is directly related to its improved Vtotal. Adsorption of DBT on AC is governed by the dispersion interactions (pp interactions) in the micropores [6]. The enhanced DBT adsorption performance of ACW900 is attributed to its largest Vmic (as shown in Table 1). The acidic-oxygenated groups on the surface might act as adsorption sites for selective adsorption of DBT [5,6]. The signicant increase in adsorption performance of ACS250 may be due to the increase in surface acidic-oxygenated groups as a result of H2SO4 treatment. ACWS has the highest adsorption capacity in all the investigated samples because it has the maximum amount of surface acidic-oxygenated groups. ACWSN with similar pore volumes (Vtotal and Vmic) to ACWS shows higher adsorption performance as compared with AC, because its pore volumes are lager than AC. On the other hand, ACWSN shows rather lower adsorption performance as compared with ACWS. This result is ascribed to the loss of the surface acidic-oxygenated groups due to N2 treatment at 900 C. This suggests that the surface acidic-oxygenated groups play an important role in enhancing DBT adsorption performance on the modied ACs. The arenes present in diesel fuel strongly compete with the sulfur-containing compound in the adsorption process [2]. Therefore, it is important to investigate the adsorption selectivity for sulfur-containing compound on ACs in the presence of arenes. The tetrahydronaphthalene is added to the heptane to mimic the arenes in the model diesel and its content is set to 5 and 30 wt%. Fig. 2 shows the effect of arene on the DBT adsorption performance of ACWS and ACWSN. The DBT adsorption performance of ACWSN
Table 1 Physicochemical properties of activated carbon samples Samplea SBETb (m2/g) 1106 1979 1271 1570 1516 Vtotalb (cm3/g) 0.617 1.138 0.740 0.922 0.912 Smicc (m2/g) 716 1091 543 990 985

a
100

ACWS ACS250 ACWSN ACW900 AC

Sulfur removal (%)

80 60 40 20 0

50

100

150

200

250

300

Effluent volume (cm3- elution/g-adsorbent)

b
Total adsorption capacity (mg/g)

50 40 33.3 30 20.6 20 10.9 10 0

47.1

23.6

AC

ACW900

ACS250

ACWS

ACWSN

Fig. 1. Adsorption of dibenzothiophene (DBT) on the dierent activated carbons. (a) The variance of sulfur removal with euent volume for the dierent samples, (b) comparison of the total adsorption capacity on the dierent samples. AC: unmodied activated carbon, ACW900: AC treated by steam at 900 C, ACS250: AC treated by H2SO4 at 250 C, ACWS: AC treated by steam at 900 C and subsequently treated by H2SO4 at 250 C, ACWSN: ACWS treated by N2 at 900 C.

is declined dramatically by the addition of arene. However, the eect of arene on the DBT adsorption performance of ACWS is very little. After 5 wt% of arene is added, the adsorption capacity of ACWSN is decreased by 60%. In contrast, the adsorption capacity of ACWS is decreased by only 10%, and decreased by only 30% even after 30 wt% of arene

Vmicc (cm3/g) 0.369 0.553 0.308 0.428 0.422

Surface acidity (mmol/g)d Phenol Lactone 0.010 0.018 0.381 0.522 0.047 Carboxyl 0.030 0.036 1.271 1.433 0.052 Total 0.058 0.094 1.953 2.410 0.141

AC ACW900 ACS250 ACWS ACWSN

0.018 0.040 0.301 0.455 0.042

a AC: Untreated activated carbon, ACW900: AC treated by steam at 900 C, ACS250: AC treated by H2SO4 at 250 C, ACWS: AC treated by steam at 900 C and subsequently treated by H2SO4 at 250 C, ACWSN: ACWS treated by N2 at 900 C. b The specic surface areas calculated using the BET equation by assuming the section area of nitrogen molecule to be 0.162 nm. The total pore volumes estimated to be the liquid N2 volume at relative pressure of 0.98. c The micropore volumes and micropore areas calculated using the t-plot method. d NaHCO3 (carboxyl), Na2CO3 (carboxyl and lactonic), NaOH (carboxyl, lactonic and phenolic).

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Letters to the Editor / Carbon 45 (2007) 30423059

a
100

ACWS/No arene ACWS/5% arene ACWS/30% arene ACWSN/No arene ACWSN/5% arene

Sulfur removal (%)

80 60 40 20 0

functional groups appear to play an important role in enhancing adsorption selectivity for DBT on the modied ACs. The specic interaction between the adsorbed DBT molecules and surface acidic-oxygenated groups on ACWS may be responsible for the high selectivity for DBT on the modied ACs. Acknowledgements We acknowledge the nancial support from the National Science Foundation of China (NSFC Grant No. 20673114) and the State Key Project of China (Nos. 2006CB202506). Appendix A. Supplementary material

50

100

150
3

200

250

300

Effluent volume (cm - elution/g-adsorbent)

Total adsorption capacity (mg/g)

50 40 30
No arene 5% arene 30% arene

47.1 43.8

32.4

Supplementary data associated with this article can be found, in the online version, at <doi:10.1016/j.carbon. 2007.10.016>. References

23.6
20 10 0

10.4

ACWSN

ACWS

Fig. 2. Adsorption of dibenzothiophene (DBT) on the dierent activated carbons. (a) Eect of arene on the DBT adsorption performance on ACWSN and ACWS, (b) comparison of the arene eect on the total adsorption capacity of ACWS and ACWSN. ACWS: AC treated by steam at 900 C and subsequently treated by H2SO4 at 250 C, ACWSN: ACWS treated by N2 at 900 C.

is added (as shown in Fig. 2b). These results indicate that ACWS exhibits higher selectivity for DBT in the presence of arene than ACWSN does. Since ACWS and ACWSN have similar pore volumes (Vtotal and Vmic), the adsorption contribution from the dispersion interactions (pp interactions) in the pore channel is similar. The acidic-oxygenated

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