Fuel 88 (2009) 885889

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Catalysis of SO2 =ZrO2 solid acid for the liquefaction of coal 4

Zhicai Wang a,*, Hengfu Shui a, Yanni Zhu a, Jinsheng Gao b
a b

School of Chemistry and Chemical Engineering, Anhui Key laboratory of Clean Coal Conversion & Utilization, Anhui University of Technology, 243002 Maanshan, China College of Resource and Environmental Engineering, East China University of Science and Technology, 200273 Shanghai, China

a r t i c l e

i n f o

a b s t r a c t
In order to study the catalysis of SO2 =ZrO2 solid acid for the liquefaction of coal, a series of SO2 =ZrO2 4 4 solid acids were synthesized by the method of precipitationimpregnation. The catalytic behaviours of the SO2 =ZrO2 solid acids for the hydro-liquefaction of Shenhua coal and model compounds, such as 4 diphenylmethane, bibenzyl and phenyl ethyl ether, were investigated. In addition, non-catalytic liquefaction and the catalytic liquefaction under N2 were further compared with the catalytic liquefaction under H2 in order to understand the catalytic mechanism of SO2 =ZrO2 solid acid. The results indicate that 4 hydro-liquefaction conversions of coal and model compounds are related to the strength, amount and 2 nature of acid sites on the surface of SO4 =ZrO2 , and the strong acid site responds to their catalytic activities. The SO2 =ZrO2 solid acid catalyzes mainly the hydro-cracking, ring-opening and hydrogenation 4 reactions of coal to produce oil and gas during the coal liquefaction. The hydro-cracking reactions in the liquefaction of model compounds and coal catalyzed by SO2 =ZrO2 involved via carbenium ion inter4 mediate instead of traditional radicals intermediate. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 9 May 2008 Received in revised form 29 October 2008 Accepted 30 October 2008 Available online 18 November 2008 Keywords: SO2 =ZrO2 solid acid 4 Hydro-liquefaction Coal Model compound Catalysis

1. Introduction As a viable option of the production of transportation fuels, the direct liquefaction of coal is an issue of the higher efciency and cleaner utilization of coal in China. For direct liquefaction of coal, catalyst plays an important role and attracts extensive attention. However, most of researchers only concerned on the hydrogenation activity of catalyst, in order to stabilize the fragments formed during coal pyrolysis and remove the heteroatoms of liqueed products. Fe, Mo and Ni based catalysts are usually used [17]. Traditional coal liquefaction processes require high temperature above 400 C because the fragment of coal is produced by thermal cleavage [8,9]. Therefore, a novel coal liquefaction catalyst to be used under moderate conditions is very attractive in order to reduce the cost of operation [10,11]. Liquid acids such as CF3SO3H [11,12], HF + BF3 [13,14] and molten salt [1517], have been widely studied in a moderate liquefaction of coal at temperatures ranging from 100 C to 350 C with low hydrogen pressure. However, these liquid acids are difcult to be recovered and regenerated, and their corrosive nature and instability may exclude their practical application [18]. Recently, SO2 =Mx Oy solid acids with strong acidity and less corrosive are 4 found to be good catalyst for the synthetic reactions such as esterication, etherication and alkylation, and the cracking reaction [19]. In addition, the synergistic action between acid site and base
* Corresponding author. Tel.: +86 13955530691; fax: +86 555 2311822. E-mail address: zhicaiw@ahut.edu.cn (Z. Wang). 0016-2361/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2008.10.040

site on the surface of MxOy may catalyze the hydrogenation reaction by ion mechanism [2022]. Therefore, it is worthy to be used as a novel catalyst for the hydro-liquefaction of coal. Since Tanabe et al. [23] discovered that SO2 promoted the cat4 alytic ability of Fe2O3 for direct liquefaction of coal in 1982, Kotanigawa and Yokoyama et al. [2427] had also studied the catalytic behaviour of sulfated Fe2O3 catalysts. For example, Kotanigawa et al. [27] speculated that Fe2O3 (SO2 ) might be a active form of 4 conventional FeS2 catalyst, and H2 adsorbed on the surface of Fe2O3 (SO2 ) may be decomposed into H+ and H by heterolysis. 4 But they only studied the transformation of sulfur and the effect of acid properties of catalyst on its catalytic cracking ability. The distribution of the products was not discussed. Although Pradhan et al. [28] considered Fe2O3 (SO2 ) as a super acid, and speculated 4 that the super acidity of the catalyst catalyzed coal liquefaction to some extent, they attributed such enhance to the suppress of the agglomeration of metal oxide and the dispersity of catalyst. Matsuhashi et al. [29] studied the catalysis of metal oxide promoted by SO2 for the cracking of model compounds, but relation4 ship of the catalytic properties of catalysts with their acid properties was not found. In China, Zhu [30] prepared a highly dispersed SO2 =Fe2 O3 solid acid from NH4Fe(SO4)2, and studied the ef4 fects of acid properties of SO2 =Fe2 O3 on coal liquefaction with 4 sulfur as promoter. Bronsted acid site of catalyst was found to be the active sites for coal liquefaction, which can catalyze the hydro-cracking of asphaltene to oil. Because Fe2O3 will be transformed into sulde iron under 300 C while sulfur is used as promoter [18], the acid properties of SO2 =Fe2 O3 surface changed 4

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during coal liquefaction. Therefore, it is disadvantage to study the catalytic mechanism of SO2 =Fe2 O3 with sulfur as promoter for 4 coal liquefaction. In order to avoid the catalysis of FeS1x, which maybe generated from SO2 =Fe2 O3 , and to study the catalysis of SO2 =Mx Oy solid 4 4 acids for the liquefaction of coal, sulfated ZrO2 solid acids had been used to catalyze the liquefaction of Shenhua coal in our previous work [31]. The results showed that the conversion of coal catalyzed by solid acid was higher than that by FeS or FeS + S. In this paper, the acid property of the sulfated ZrO2 was characterized and its catalytic mechanism was probed by direct liquefactions of coal and model compounds. 2. Experimental 2.1. Coal and solvent Shenhua coal (Chinese subbituminous coal) used in this study was provided by 973 Program (National Basic Research Program of China) research group. It was ground to less than 200 mesh, stored under nitrogen atmosphere and used by drying under vacuum at 353 K overnight. The ultimate and proximate analyses of coal are shown in Table 1. All solvents were used without further purication. 2.2. Preparation of SO2 =ZrO2 4 The hydroxide of Zr was obtained by hydrolization of ZrOCl2 with aqueous ammonia at room temperature, and then the precipitated solution was ltered, washed and dried. The hydroxide of Zr was further impregnated with aqueous sulfuric acid, dried and calcined at specied temperature and time. A detailed description can be found elsewhere [31]. All chemicals used as above were of reagent grade. 2.3. Liquefaction procedure of coal and model compounds The liquefaction experiments were carried out in a 30 mL tubing reactor shaken vertically. Dried coal (2.0 g) and catalyst (0.5 g) were charged into the reactor together with 5 mL of tetralin (THN) solvent. Before liquefaction, the reactor was purged with H2 for several times and pressurized to the desired initial pressure of 5.0 MPa with H2. The reactor was submerged into an eutectic salt bath, which had been heated to a temperature of 405 C in order to keep the reactor to the desired working temperature (400 C) in 10 min with agitating vertically at 120 times/min, and maintained at the temperature for 30 min. Then the reactor was quenched to ambient temperature in a water bath, and the overhead pressure in the reactor was released slowly. The liquid and solid products of coal liquefaction were recovered from the autoclave by washing out and Soxlet extraction with tetrahydrofuran (THF) [32]. The overall conversion was calculated from the amount of THF-insoluble material (THFI). After THF was removed by evaporation, the THF-solubles were extracted with hexane to separate into hexane-insoluble (HI) and hexane-soluble (HS) fractions. The HI was further fractionated into toluene soluble (HITS) and toluene-insoluble (TITHFS) by extraction with toluene. The HITS and TITHFS were dened as asphaltene and preasphalTable 1 Ultimate and proximate analyses of Shenhua coal. Sample Ultimate analysis (wt%, daf) C Shenhua coal
*

tene, respectively. The conversion and the yield of asphaltene and preasphaltene were, respectively, calculated on dry and ash-free (daf) basis coal. The combined oil-plus-gas yield was obtained by the difference, i.e. Gas + oil = conversion-AS-PA. Most of the runs were made in duplicate and the reproducibility was better than 2%. The liquefaction procedure of model compounds was the same as that of coal. In the runs, 10% model compounds in THN solutions were substituted into coal and solvent. The liqueed products of model compound were characterized by GC/MS and quantied by GC with standard curve method. 2.4. Characterization of liquefaction derivatives The IR spectra of liquefaction residue (THFI), AS and PA coming from liquefaction of coal were measured by PE-Spectrum One IR spectrometer. The solid-state product was mixed with KBr and the mixture was pressed into a pellet. The liquid product was determined by lm coating method. The spectra were recorded at room temperature. 1 H-NMR spectra of AS and PA, which were dissolved in d5-pyridine solvent, were obtained using Brucker AM500 (500 MHz). The element analysis was carried out in Elementar Vario EL III. 3. Results and discussion 3.1. Hydro-liquefaction of coal catalyzed by SO2 =ZrO2 solid acids 4 The distributions of acid sites of the SO2 =ZrO2 solid acids pre4 pared at different calcination conditions are quite different; therefore, the catalytic properties of the solid acids are varied. In order to explore the catalysis of SO2 =ZrO2 solid acids for coal liquefac4 tion, the SO2 =ZrO2 solid acids calcined at different conditions 4 were used. Table 2 shows the conversions and the liqueed product distributions of Shenhua coal catalyzed by SO2 =ZrO2 . 4 From Table 2, it can be found that the conversion of Shenhua coal liquefaction increases with the increase of calcination temperature of SO2 =ZrO2 up to 650 C, at which the conversion reaches 4 76.8%, and then the conversion decreases with the increased calcination temperature. According to our recent work [33], there are two types of acid sites on the surface of SO2 =ZrO2 solid acid. 4 The SO2 =ZrO2 calcinated above 550 C shows most of Lewis acid 4 site. The intensity of acid site and the percent of strong acid site of SO2 =ZrO2 increase with the increased calcination temperature. 4 The SO2 =ZrO2 calcinated at 650 C shows not only a lot of stronger 4 acid sites but also higher density of acid site compared to the other SO2 =ZrO2 calcinated at 450750 C. The result suggests that the 4 conversion of coal liquefaction is related to the strength, amount, and nature of acid site of SO2 =ZrO2 , and the Lewis acid site re4 sponds to the catalytic activity of SO2 =ZrO2 for coal liquefaction. 4 The more the amount of stronger acid sites, the higher the activity of SO2 =ZrO2 and the conversion of coal liquefaction. 4 Table 2 also shows that the effects of SO2 =ZrO2 properties on 4 the distributions of liquefaction products are very complicated. There are a lot of reactions during the coal liquefaction, such as hydrogenation, decomposition, condensation, dealkylation and
Table 2 Results of the liquefaction of coal catalyzed by SO2 =ZrO2 solid acid. 4 Preparation conditions of catalyst Conversion/ % 56.5 59.2 69.9 76.8 67.0 Distribution of products/% Preasphaltene 37.1 28.5 32.9 36.1 38.8 Asphaltene 35.9 39.7 24.3 30.5 26.3 Oil + gas 27.0 31.8 42.8 33.4 35.0

Proximate analysis (wt%) O* 13.51 Ad 5.52 Vdaf 38.24 Mad 9.34

H 4.88

N 1.06

S 0.42

80.13

By difference.

500 C, 550 C, 600 C, 650 C, 700 C,

3h 3h 3h 3h 3h

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etc., dependent on the strength of acid sites. For example, the strong acid site is favorable for catalyzing the decomposition and isomerization of carbon skeleton, the medium strong acid site is favorable for the dealkylation of alkyl aromatics. The hydrogenation and hydrogen transfer reaction are catalyzed by the bifunctional catalyst with acid and base sites together [34,35]. The distribution of liquefaction products shows that the yield of Oil + gas increases with the calcination temperature of SO2 =ZrO2 up 4 to 600 C, and the lowest value is obtained when the SO2 =ZrO2 4 was calcinated at 500 C. It suggests that weaker acid site formed by calcination at lower temperature only catalyzes the breakage of weak covalent bond such as ether and ester bonds to give higher yields of PA and AS, and lower yield of Oil + gas. The increased strength of acid sites of SO2 =ZrO2 is advantageous to improve 4 the catalytic activity for the dealkylation and fragmentation of hydroaromatic ring resulting in the increase yields of Oil + gas, PA and AS. However, the stronger acid site can also catalyze the condensation of coal fragments to promote the regressive reactions. When the SO2 =ZrO2 was calcinated at 650 C, the PA and 4 AS yields markedly increased, and the Oil + gas yield decreased compared to that the liquefaction of coal catalyzed by the SO2 =ZrO2 calcinated at 600 C. For the SO2 =ZrO2 prepared at 4 4 700 C for 3 h, the total amount of acid site reduced sharply compared to that of the other catalysts [33], and the decreased amount of acid site results in the decrease of the conversion and the variation of the product distribution. 3.2. Characterization of liquefaction products catalyzed by SO2 =ZrO2 4 solid acids Figs. 1 and 2 show the IR spectra of PAs and liqueed residues catalyzed by the SO2 =ZrO2 prepared under different conditions. 4 It can be observed from the IR spectra of PAs that the absorption peak of OH (near to 3400 cm1) increases with the increasing calcination temperature for catalyst except at 650 C for 3 h. However, the absorption peak of OH in the liquefaction residues decreases with the increase of the calcination temperature of the catalyst. It indicates that the OH content of the residue decreases and that of PA increases with the increased calcination temperature for the catalyst. Weaker acid site formed at lower calcination temperature can only catalyze the breakage of weaker covalent bonds of coal to product PA, so the residue contains more OH groups. With the increased calcination temperature, the SO2 =ZrO2 shows higher ratio 4 of strong acid site to weaker acid site [33], and can catalyze the

Fig. 2. FTIR spectra of liqueed residues catalyzed by SO2 =ZrO2 solid acid: ae 4 calcinated at 500 C, 550 C, 600 C, 650 C and 700 C, respectively.

pyrolysis of carbon skeleton of coal to PA, so the OH content of PA increases simultaneously with the decreased content of OH in the residue. The SO2 =ZrO2 calcinated at 650 C for 3 h, which 4 exhibits the highest acid strength and more strong acid site [33], can catalyze the decomposition of coal and PA into lower molecular weight products, so the contents of OH in the residue and PA are both low. Therefore, it can be speculated that the OH groups in the residue and PA are mainly phenolic one, which is in accordance with the existence of OH in Shenhua coal we found before [36], besides a little of OH may come from the breakage of ether and ester functional group. In addition, the relative absorption peak of aromatic carbonyl (1650 cm1) to that of aromatic ring (1610 cm1) in the IR spectra of PAs and liqueed residues catalyzed by the SO2 =ZrO2 calcinated at 650 C and 700 C is weaker 4 than that calcinated at other temperatures. The absorption peak of aromatic carbonyl in the IR spectrum of liqueed residue catalyzed by the SO2 =ZrO2 calcinated at 600 C almost disappears. In 4 our previous work, the absorption peaks of aromatic carbonyl in PAs are stronger while FeS was used as catalyst [31]. It suggests that strong acid site is also favorable for catalyzing the decomposition of carbonyl structure in coal and PA to give more Oil + gas. Thus, the results of IR spectra characterization of liqueed products further support that the strong acid site is responsible for the coal liquefaction by catalytic cracking reaction. 3.3. Effects of liquefaction atmosphere on the liquefaction of coal catalyzed by SO2 =ZrO2 solid acids 4 In order to further explore the catalytic activities of the SO2 =ZrO2 , the liquefaction of coal catalyzed by SO2 =ZrO2 under 4 4 different atmospheres were carried out. Fig. 3 shows the conversions and distributions of the liquefaction products of Shenhua coal under N2 and H2 catalyzed by the SO2 =ZrO2 , which was prepared 4 at 650 C for 3 h, and the liquefaction under H2 without catalyst, respectively. Compared to the non-catalytic liquefaction, the increment of liquefaction conversion is near to 16% when the SO2 =ZrO2 4 was used as catalyst. Meanwhile, the conversion under N2 is the lowest but the Oil + gas yield is similar to that under H2, and the lower yields of AS and PA are respond for the decreased conversion under N2 compared to that under H2. It suggests that the SO2 =ZrO2 shows obvious catalytic activity for coal liquefaction, 4 especially for the decomposition of coal to give higher yields of the oil and gas. In addition, H2 also shows a promotion for the liquefaction of coal resulting in distinct increase of PA yield.

Fig. 1. FTIR spectra of preasphaltene catalyzed by SO2 =ZrO2 solid acid: ae 4 calcinated at 500 C, 550 C, 600 C, 650 C and 700 C, respectively.

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Oil+Gas

80 70 60 50

Asphaltene Preasphaltene

25.6

22.2 23.4 25.7 16.1 14.8 27.3 10.6 20.6

40 30 20 10 0

H2

N2

H2 without catalyst

Fig. 3. Distributions of liqueed products under N2, H2 and non-catalyst.

Tables 3 and 4 show the results of element analyses and structural parameters of liquefaction products, respectively, under different conditions. H/C ratio of liquefaction residue under H2 with or without catalyst is similar to 0.62, but the H/C ratio of liquefaction residue under N2 increases to 0.67. The transformation of coal matrix to PA is mainly ascribed to the hydro-cracking, predominated by the capacity of hydrogen donation. The liquefaction under N2 yields lower PA, and gives higher H/C ratio of the residue due to lower capacity of hydrogen donation. However, the PA is easy to contact with the catalyst and solvent (hydrogen donator) and be catalyzed into AS or Oil + gas. So, the lower H/C ratio of the PA and higher yield of the AS were obtained during the catalytic liquefaction.
Table 3 Results of element analysis of Shenhua coal liquefaction products. Samples Asphaltene Liquefaction conditions H2 catal N2 catal H2 non-catal H2 catal N2 catal H2 non-catal H2 catal N2 catal H2 non-catal Cdaf/% 83.0 82.2 80.6 82.3 80.6 80.7 62.0 64.1 68.5 79.6 Hdaf/% 6.6 6.3 6.2 5.4 5.4 5.6 3.2 3.6 3.6 4.8 H/C 0.95 0.92 0.92 0.79 0.80 0.83 0.62 0.67 0.63 0.72

The aromaticity of the PA from the catalytic liquefaction is higher than that from the non-catalytic liquefaction, as shown in Table 4. It suggests that the alkyl side chains in the PA were removed by the catalytic decomposition. Meanwhile, the hydrogen distribution shows that the percentage of Hc is the highest in the AS coming from the non-catalytic liquefaction, and is the second highest from the catalytic liquefaction under N2. It suggests that these ASs contain some longer alkyl side chains due to the weaker cracking during the non-catalytic liquefaction. Meanwhile, the HAU/CA (condensation index of aromatic ring) of AS coming from the catalytic liquefaction under H2 is distinctly higher than that from the catalytic liquefaction under N2 and the non-catalytic liquefaction under H2. It indicates that the ring-opening reaction occurs during the transformation from PA and/or coal to AS when the SO2 =ZrO2 and hydrogen gas are simultaneously used. Because the 4 intermediates of ring-opening reaction catalyzed by the SO2 =ZrO2 4 can be immediately stabilized by the hydrogenation. Meanwhile, HAU/CA of PA coming from the catalytic liquefaction under H2 is the lowest in comparison with those of other PAs. It further conrms that the PA in the liquefaction catalyzed by the SO2 =ZrO2 4 under H2 is mainly high condensation aromatic fragments with lower reactivity. In addition, the catalytic hydrogenation occurs obviously in the process of AS formation so as to give the AS with higher H/C ratio in the catalytic liquefaction under H2. The structural parameters of AS also indicate that the catalytic hydrogenation is favorable for decreasing the aromaticity of AS under H2. Therefore, the catalytic activity for the ring-opening and hydro-cracking reaction is the main catalysis of SO2 =ZrO2 in the liquefaction of coal and the 4 catalysis for the hydrogenation can also be observed, especially for the hydrogenation of AS. 3.4. Hydro-liquefaction of model compounds Based on the structure of coal, diphenylmethane (DPM), bibenzyl (DPE) and ethoxylbenzene (PEE) were selected as model compounds of coal. They were hydro-liqueed in THN solvent in order to further probe the catalytic mechanism of SO2 =ZrO2 for the 4 liquefaction of coal. Table 5 shows that the conversions of all model compounds increase with the increased calcination temperature of SO2 =ZrO2 4 from 500 C to 650 C, and the highest conversion is obtained at 650 C for all the model compounds. Further, the conversions of all the model compounds decrease when the catalyst was calcined at 700 C. Thus the effects of calcination temperature on catalytic activity of SO2 =ZrO2 during the hydro-liquefaction of the model 4 compounds are in accordance with that of the liquefaction of coal. The catalysis of SO2 =ZrO2 maybe attributed to the strong acid site 4 on the surface of SO2 =ZrO2 . The stronger the acidity of acid site 4 and the more the strong acid site, the higher the catalytic activity of SO2 =ZrO2 during the liquefaction of coal. It was found by the 4 GC/MS characterization that the liqueed products of model compounds consist of the crackates by the rupture of the bridging bond along with a few of hydrogenated products. Therefore, it also
Table 5 Hydro-liquefaction conversion of model compounds with SO2 =ZrO2 solid acid 4 prepared under different calcining temperature. Preparation conditions of catalyst Conversion/% DPM 500 C, 550 C, 600 C, 650 C, 700 C, 3h 3h 3h 3h 3h 21.7 26.3 34.3 53.9 26.5 DPE 1.7 2.1 2.7 4.3 4.1 PEE 15.1 17.2 27.1 40.6 26.0

Preasphaltene

Residue

Raw coal

Table 4 Results of 1H NMR analysis and structure parameters of Shenhua coal liquefaction products. Sample Liquefaction conditions Hydrogen distribution/% HA Asphaltene H2 catal N2 catal H2 non-catal H2 catal N2 catal H2 non-catal 21.5 22.2 23.1 22.0 30.4 21.0 Ha 26.6 22.8 21.7 33.6 29.0 32.4 Hb 42.2 39.5 35.1 24.2 21.1 29.9 Hc 9.8 15.5 20.0 5.4 6.1 5.7 Structure parameters fa 0.63 0.65 0.65 0.75 0.77 0.72 d 0.38 0.34 0.32 0.43 0.32 0.44 HAU/CA 0.53 0.48 0.48 0.41 0.47 0.43

Preasphaltene

Yield/%

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proved that SO2 =ZrO2 shows not only better catalytic cracking 4 activity but also great catalytic hydrogenation activity during the coal liquefaction. Meanwhile, Table 5 also shows that the conversions of model compounds catalyzed by SO2 =ZrO2 increase in turn DPE, PEE 4 and DPM. For example, conversions of DPE, PEE and DPM are 4.25%, 40.56% and 53.89%, respectively, when the catalyst is calcinated at 650 C for 3 h. During the liquefaction of coal and the hydro-cracking of model compounds, it is generally thought that the homolysis of linkage bond in coal or model compounds rstly gives the free radical. Then it is stabilized by hydrogenation transformation or catalytic hydrogenation. Shimizu et al. [37] found that BPE and DPM show higher reactivity in superacidic medium compared to biphenyl ether, and thought that the cracking reaction of model compounds catalyzed by acid followed the carbenium ion mechanism due to higher stability of benzyl cation. According to the free radical mechanism, the activity of DPE reaction should be higher than that of DPM because the bond of CalkCalk of ethylene in DPE is weaker than the bond of CalkCar in DPM. However, our results show that the conversion of DPM is much higher than that of DPE. Therefore, it is suggested that the cracking reactions of model compounds and coal catalyzed by SO2 =ZrO2 may take place via 4 carbenium ion intermediate instead of radical intermediate. 4. Conclusion Catalytic properties of SO2 =ZrO2 solid acids for coal liquefaction 4 are related to their acid strength, amount and nature of acid sites. The strong acid site dominates their catalytic activities. Catalytic activity of SO2 =ZrO2 and liquefaction conversion of coal increase 4 with increasing of the amount of strong acid sites. SO2 =ZrO2 mainly 4 catalyzes the hydro-cracking, ring-opening and the hydrogenation to generate the oil and gas during the liquefaction of coal. Effects of catalyst acidity on the liquefaction of the model compounds are accordance with the liquefaction of the coal. The hydro-cracking reaction of model compounds catalyzed by SO2 =ZrO2 is via carbe4 nium ion intermediate instead of radical intermediate. Acknowledgements This study was supported by the National Natural Science Foundation of China (20776001, 20676001). The authors gratefully acknowledge the 863 Program of China (2006AA05Z314, 2007AA06Z113) and the International Cooperative Project of Anhui Province (07080703001). The authors also appreciated the nancial support of innovative group of Anhui Province Coal Resource Processing & Cleaning Utilization. Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.fuel.2008.10.040. References
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