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Eect of mechanochemical treatment on petroleum cokeCO2 gasication

Jianhui Zou a, Boli Yang a, Kaifeng Gong a, Shiyong Wu b, Zhijie Zhou a, Fuchen Wang a,*, Zunhong Yu a
a b

Key Laboratory of Coal Gasication of Ministry of Education, East China University of Science and Technology, Shanghai 200237, China Department of Chemical Engineering for Energy Resources, East China University of Science and Technology, Shanghai 200237, China Received 17 March 2007; received in revised form 12 July 2007; accepted 19 July 2007 Available online 14 August 2007

Abstract The eect of mechanochemical treatment during the grinding of petroleum coke on its gasication by CO2 was studied. An additive derived by drying the black liquor in papermaking industry is adopted in grinding process. Results show that the gasication reactivity of petroleum coke is eectively improved by grinding, and the activation by wet grinding is more noticeable than that by dry grinding. Besides, by wet grinding petroleum coke and additive together, the active metal species in additive are not easily volatilized in gasication, and retain a high catalytic reactivity to the cokeCO2 reaction throughout most of the conversion range. Changes in crystal structure of the petroleum coke induced by mechanochemical treatment is related to its gasication reactivity. In general, the crystalline amorphous phase transition is the tendency of long time mechanical grinding, while a crystal structure re-formation stage is observed after wet grinding of petroleum coke with and without additive for some time. Similar phenomenon has also been found in the reported data, but not given attention. Some discussion is made in the paper, and more work should be undertaken to disclose the mechanism. 2007 Elsevier Ltd. All rights reserved.
Keywords: Petroleum coke; Gasication; Grinding; X-ray diraction; Crystal structure

1. Introduction With the continuous increase of heavy crude supply, the output of petroleum coke, as the nal by-product of rening, is steadily increasing. The gasication of petroleum coke for the production of hydrogen, power, and steam has generated much interest in the petroleum industry [1]. It is reported that the proportion of petroleum coke, as one of gasication feedstock, is increasing constantly, and will rise from 3% to 8% in the future 5 years. Crushing and grinding processes are obligatory steps in the preparation of gasication feedstock, in which some modication of the surface layer of particles is virtually
Corresponding author. Fax: +86 21 64252521. E-mail addresses: raymond_2007@126.com (J.H. Zou), wfch@ecust. edu.cn (F.C. Wang). 0016-2361/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2007.07.021
*

inevitable. Research on the changes on surface, crystal structure and chemical reactions induced by mechanical energy are termed mechanochemistry. It has been developed to a useful method to activate some properties of particles. Research on the mechanochemical activation of carbon materials has become an important issue in recent decades, and it has been proved that mechanochemical treatment has notable impact on some properties of coal and petroleum coke [211]. Redkina et al. [2] found the adsorption of surfactants on the surface of coal particles was remarkably activated by mechanical grinding, and the viscosity of highly concentrated coalwater slurries was decreased several times consequently. Turcaniova et al. [3,4] investigated the coal mechanochemical activation eect as disintegration in the nano-submicron range and destruction of carbon structure, and presented a possible method of

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arsenic removal and desulfurization for anthracite and brown coal. Khrenkova et al. [57] have undertaken a series of research on mechanochemical activation of coals. Some changes in the structure of a number of coals containing from 79% to 90% of carbon on ne grinding and vibromilling have been conrmed by various physicochemical methods (IR, ESR, and X-ray structural phase and chemical functional analyses). It was shown that the proportion of amorphous carbon rose as the result of a breakdown of the carbon packets and the carbon layers. Mechanical grinding was also employed to improve the formability and sintering ability of petroleum coke and obtained carbon materials with high density and high compressive strength [8,9]. But there is still no reported research on the inuence of mechanochemical treatment on the gasication reactivity of carbon materials. The aim of the present work is to investigate the eect of mechanochemical treatment on the gasication reactivity of petroleum coke by dry grinding and wet grinding, and trying to reveal the mechanochemical activation mechanism by X-ray diraction analysis. 2. Experimental 2.1. Sample preparation The petroleum coke sample came from Jing Ling Renery Plant. Its proximate analysis and ultimate analysis are given in Table 1. An industry waste, black liquor in papermaking industry is used as additive in the experiment. The black liquor is mainly composed of lignosulfonate. Lignosulfonate as a kind of dispersant has already been used in the preparation of coalwater slurries in some studies. And the alkali metal species in the lignosulfonate have been veried for then catalytic ability to the gasication reaction of carbon material. So, the black liquor can be used as a dispersant in the preparation of cokewater slurries and a catalyst in the gasication of petroleum coke meanwhile. The additive is derived by drying the black liquor for 4 h at 105 C. The content of metal species in the dried additive is measured by ICP-AES, and results show that there are 7.27% sodium and 1.25% magnesium. Grinding process was carried out in a planetary ball-mill (XQM, Nanjing Kexi Instrument Institute) with stainless steel container (1070 ml) and balls. 40 big balls (1.93 mm diameter) and 200 small balls (0.93 mm diameter) were used together in grinding process. All tests were run at 280 rpm. Dry grinding and wet grinding were carried out for the activation of petroleum coke. In dry grinding, petroleum coke or the mixture of petroleum coke and additive was
Table 1 Proximate analysis and ultimate analysis of petroleum coke Proximate analysis (wt.%) Mad 0.79 Adaf 0.56 Vdaf 10.12 FCdaf 89.32

ground for 0.5 h. In wet grinding, petroleum coke and de-ionized water (or the de-ionized water dissolved additive) were ground together for 0.56.0 h. Where petroleum coke accounted for 65 wt.% of the slurry, and the load of additive was 5 wt.% of the petroleum coke on air-dried basis. After grinding, the resulting products were dried for 1 h at 105 C and sieved to generate the 6174 lm size fraction for the evaluation of gasication reactivity. In wet grinding, block was derived by drying the slurry, so it should be crashed manually rst, and then it could be sieved to get the required size fraction. Because the average particle size decreases with the increasing grinding time, the 6174 lm size fraction may not represent the reactivity of the whole particles. But if we use the average size fraction to measure the gasication reactivity, it will take into consideration the inner diusion due to dierent particle size (although the factor can be eliminated by involving eective diusion factor). Moreover, it is hard to separate the eect of crystal structure and the eect of particle size or specic surface area. Thus, the paper will be meaningless because there are many related research. We just want to investigate the eect of mechanochemical treatment on the gasication reactivity from the aspect of crystal structure. So, we used the same size fraction in the measurement of gasication reactivity. As to whether the samples with same particle size have the same specic surface area, the BET specic surface area of the samples in 6174 lm size fraction derived by wet grinding for dierent time was determined. Result shows that the BET specic surface areas are almost same (about 3.15 m2 g1) for all samples. It means the eect of specic surface area on gasication rate could be neglected. 2.2. Gasication procedure Evaluation of gasication reactivity was performed in a SETARAM TG-DTG/DSC thermogravimetric analyzer by the isothermal method. Before gasication reactivity measurements, it is essential to judge whether reaction is not inuenced by the external and intragranular diusion. Experiment results show that reaction rates did not increase any more when sample weight was less than 10 mg, particle size was smaller than 74 lm, and gas ow was faster than 60 ml min1. It means the eects of external and intragranular diusion could be eliminated in this condition. The gasication procedure is described as follow: A weighed petroleum coke (around 8 mg) sample placed on crucible (5 mm diameter and 3 mm height) was heated

Ultimate analysis (wt.%) Cdaf 90.25 Hdaf 3.75 Ndaf 1.74 Sdaf 3.03 Odaf 0.67

HHV (MJ kg1)

36.24

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under N2 stream up to 1273 K at 30 K min1. When the desired temperature was reached, N2 was replaced by CO2 at the ow rate of 60 ml min1. Then, gasication reaction was started at the constant temperature until no evident weight loss was observed. The system recorded automatically the weight loss by a highly sensitive analytical balance located in the casing of apparatus. Thermocouples for determination of sample temperatures were connected to the bottom part of crucible, precisely underneath the sample layer. The purity of N2 and CO2 is 99.99% and 99.8%, respectively. 2.3. Calculation of conversion and gasication rate The additive is mainly composed of gasiable hydrocarbon, which would be gasied together during gasication. Presume the weight loss of the additive were synchronous as that of petroleum coke. Then, the conversion for both non-catalytic and catalytic gasication can be written as m0 m x 100% 1 m0 m0 Adaf where m0, m is the initial mass and instantaneous mass of sample, respectively, g; Adaf is ash content of dried basis of petroleum coke, wt.%. Gasication rate is dened as differential of conversion to gasication time, r dx dt 2

Fig. 1. Gasication reactivity of petroleum coke activated by dierent methods. 1, dry grinding without additive; 2, dry grinding with additive; 3, wet grinding without additive; 4, wet grinding with additive.

2.4. X-ray diraction analysis The crystal structure of the milled sample was investigated by a Rigaku X-ray diractometer with CuKa radiation. The interlayer spacing d(002) and crystallite size Lc can be used to describe the evolution of crystal structure under mechanochemical treatment. The Scherrer equation Lc 0: 9k b cos h 3

was used to calculate crystallite size Lc in c-direction (0 0 2) from the X-ray diraction pattern (k is wave length, 0.154056 nm; b is structural broadening (full width at half maximum intensity = FWHM), h = diraction angle), which is calculated by b = bobservedbstandard. 3. Results and discussion 3.1. Eect of dierent mechanochemical treatments on gasication reactivity It is shown in Fig. 1. that the gasication reactivity of petroleum coke after wet grinding is always superior to that activated by dry grinding for both non-catalytic and catalytic gasication. As to non-catalytic gasication, the gasication kinetic characteristics of petroleum coke activated by the two activation methods are similar, which all

increase with increasing conversion and then decrease after reaching a maximal gasication rate at around x = 0.3 (curve 1 and curve 3). Zou et al. [12] studied the kinetic characteristics of petroleum cokeCO2 gasication by analyzing the evolution of pore structure with conversion, and found the poor initial pore structure of petroleum coke was the main reason of the emergence of the maximal gasication rate. However, the catalytic gasication kinetics is quite dierent for the two activation methods. The gasication rate decreases sharply with conversion in dry grinding, while retains a high catalytic reactivity throughout most of the conversion range in wet grinding (curve 2 and curve 4). These phenomena can be explained as follows. At rst, the mechanochemical interaction in grinding process will lead to the decrease of particle size and the increase of specic surface area. Then, with the constant increase of mechanical energy adsorbed by particles, some defects like lattice distortion, lattice deformation and lattice dislocation will occur in the surface layer of particles [13]. The particles with crystal defeats can be called activated carbon. They have higher energetic level and are easier to adsorb oxygen atom in contact with CO2 and then form carbon active site C(O), as shown in the carbon active site mechanism (Eqs. (4) and (5)) proposed by Elgun [14]. So, more activated carbon will lead to increasing gasication rate. CO2 Cf
CO CO CO ! CO 4 5

Second, the mechanochemical interaction is dierent for the two activation methods. Research shows that the energy adsorbed by particles in wet grinding was higher than that in dry grinding [5]. Consequently, more activated carbons with lattice defects are generated. That is the reason why the mechanochemical activation by wet grinding is more notable in non-catalytic gasication. But the variation of carbon active site with conversion is still mainly

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inuenced by the evolution of pore structure, so the gasication kinetic characteristics of petroleum coke activated by the two activation methods is still similar to each other. When additive is loaded, the contact between additive and petroleum coke particles resulting from the two activation methods is quite dierent. In dry grinding, the newly generated interface has much higher free energy, which will make petroleum coke particles aggregate spontaneously, thereby resisting the contact with additive. According to the oxidationreduction mechanism for catalytic carbon gasication, gasication rate is controlled by the content of active metal species and its existing form [15]. So, the relative looser contact will result in the volatilization of active metal species in additive during gasication, and the rapid decrease of gasication rate with conversion. While in wet grinding, the newly generated interface will be wrapped by solution instantaneously, and the active metal cations of additive dissolved in aqueous solution will be adsorbed on the surface of particles. So, the active metal species have a stronger contact with petroleum coke, and are not easily volatilized in the process of gasication, and retain a high catalytic reactivity throughout most of the conversion range. 3.2. Eect of mechanochemical treatment time on gasication reactivity The eect of mechanochemical treatment time on gasication reactivity was measured by wet grinding petroleum coke with and without additive for dierent times. Because the gasication rate curve is similar for dierent grinding times, the xt curve and the rx curve are not listed here. The gasication time at half conversion, t0.5 is adopted to represent the gasication reactivity of petroleum coke. It can be seen in Fig. 2. that, all t0.5 decreases rapidly with the increasing wet grinding time and then increases gradually after reaching a minimum. While the turn-around point in the two cases is dierent, it lies in 2 h for wet grind-

ing with additive and 3 h for wet grinding without additive. So, there is the critical time for the improvement of gasication reactivity by mechanochemical activation. In order to specify the causative factor of the variation of gasication reactivity, the crystalline structure of ground petroleum coke is measured by X-ray diraction. The evolution of the interlayer spacing d(002) and crystallite size Lc of the samples ground with grinding time is shown in Fig. 3a and b. It can be seen that, for wet grinding with additive when the grinding time is less than 2 h, the d(002) spacing increases gradually from 0.348 nm to 0.351 nm and crystallite size Lc is reduced from 54.41 nm to 52.38 nm correspondingly, which means disordered structures are produced. However, with prolonged grinding time, the decreasing d(002) spacings and increasing crystallite size Lc are found, which indicates there is a crystal structure re-formation stage with the longer time of mechanochemical activation. Same behaviors are also found in the wet grinding process without additive. But the occurrence of turn-around point is delayed to 3 h. The evolution of the interlayer spacing d(002) and crystallite size Lc with grinding time is in accordance with the variation of t0.5 in

Fig. 2. Gasication reactivity of petroleum coke activated by wet grinding for dierent times.

Fig. 3. The evolution of interlayer spacing d(002) and crystallite size Lc with grinding time

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Fig. 2. So, the crystalline transformation is the causative reason of the evolution of gasication reactivity. Another phenomenon shown in Fig. 3. is that the evolution of d(002) and Lc for wet grinding with additive is more acute than that without additive. It can be explained by the function of dispersant in comminution process. On the one hand, the solution with dispersant is less viscous, which improves the uidity of the cokewater slurry; on the other hand, dispersant will penetrate into the cracks of particles and then enhance the breakage of particles. So, the existence of additive decreases the energy consumption of comminution. Namely, for same energy consumption (same wet grinding time), petroleum coke can absorb more mechanical energy in the existence of additive, and is more advantageous for crystalline transformation. The crystallineamorphous phase transition has also been found in the preparation of nanostructured carbon materials by long time mechanical grinding of graphite [1628]. And for example, reactivity of graphite for some chemical reactions are signicantly enhanced by mechanical milling, e.g. the increase of combustion reactivity and the decrease of ignition temperature [16,17], and even self-ignition was observed after strong grinding [18]. It should be noted that the crystallineamorphous phase transition is the tendency of long time mechanical grinding. Tidjani et al. [19] considered that the changes in d(002) are attributed to the introduction of interstitial carbon atoms into the initial pristine graphite structure. Meanwhile, Nakamizo et al. [20] attributed the change observed in d(002) to the introduction of structural defects, on the basis of Raman spectroscopy measurements. The two dierent explanations, however, indicate the same thing that mechanochemical treatment causes structural defects or crystalline distortion of the coke, and results in the improvement of the gasication reactivity of petroleum coke. The evolution of d(002) spacings and crystallite size Lc after 2 h of wet grinding in the experiment, signifying a crystal structure re-formation stage, is hard to understand. But similar phenomenon has also been found in the reported data [9,2123], as shown in Fig. 4a and b. The d(002) spacings and crystallite size Lc also have a small uctuation in the initial grinding period. (The time of this turnaround point is dierent because the raw materials and the power of mills adopted in experiments are dierent.) The tiny uctuation has not impressed most people because it is very small as compared to the whole tendency in long time grinding, which is the highlight of most research. However, in studying the eect of atmosphere on the mechanical grinding of natural graphite, Ong et al. [21] found that in air and oxygen, the d(002) spacings and crystallite size Lc remained fairly constant when the sample was milled for less than 7 h and 10 h, respectively; while in argon, they changed greatly even in the beginning of grinding (in Fig. 4a and b), the lled legends denote grinding in oxygen or air, the unlled legends denote grinding in inert atmosphere.). He stated that the presence of oxygen helped to preserve the crystalline nature of the milled samples until

Fig. 4. Evolution of d(002) and Lc with grinding time in reported data. Ong [21], Aladekomo [22]: natural graphite; Francke [23]: high purity graphite; Cheng [9]: petroleum coke after graphitization at 1673 K for 1 h.

the depletion of oxygen inside the vial. But this still cannot explain the crystal structure re-formation stage in the grinding of many carbon materials. It seems hard to explain, and more related research should be undertaken. As the feedstock of gasier, particles in the nano-size fraction derived by long time grinding are not suitable in preparation of the highly concentrated coal/cokewater slurries with low viscosity (less than 1000 MPa s), although these carbon materials with totally amorphous crystal structure might have high chemical reactivity. Actually, the main purpose of grinding in gasication industry is to get an appropriate particle size distribution for the preparation of coal/cokewater slurries. The aim of the research is to investigate the mechanochemical impact on the gasication reactivity of petroleum coke in a short time grinding. Because the planetary ball-mill used in the investigation is dierent to the mill in actual process, and it is hard to conduct such experiments in actual process since it is a continuous process. We can only say there must be a mechanochemical activation in the actual grinding process, but are not sure whether there is also a turnaround point in the evolution of crystal structure. If same phenomenon also existed in actual process, the occurrence

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time of the turn-around point could be regarded as a constraint in operation. 4. Conclusions The gasication reactivity of petroleum coke is eectively improved by grinding, and the activation by wet grinding is more noticeable than that by dry grinding. Besides, by wet grinding petroleum coke and additive together, the active metal species in additive are not easily volatilized in gasication, and retain a high catalytic reactivity to the cokeCO2 reaction throughout most of the conversion range. Changes in crystal structure of the petroleum coke induced by mechanochemical treatment is related to its gasication reactivity. In general, the crystallineamorphous phase transition is the tendency of long time grinding, while a crystal structure re-formation stage is observed after wet grinding of petroleum coke with and without additive for some time. Acknowledgements The research is supported by the program for New Century Excellent Talents in University (NCET-05-0413), National Key State Basic Research Development Program of China (973 Program, 2004CB217700) and Program for Changjiang Scholars and Innovative Research Team in University (PCSIRT-IRT0620). The authors would like to thank Prof. Gao JS for technical assistance. References
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