Process Safety and Environmental Protection 8 7 ( 2 0 0 9 ) 323330

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Process Safety and Environmental Protection

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Differences in physical properties and CO2 gasication reactivity between coal char and petroleum coke
Youqing Wu, Shiyong Wu, Jing Gu, Jinsheng Gao
Department of Chemical Engineering for Energy Resources and Key Laboratory of Coal Gasication of Ministry of Education, East China University of Science and Technology, 200237 Shanghai, China

a b s t r a c t
This paper mainly investigated the physical properties and gasication reactivity of coal char and petroleum coke, separately at the high temperature pyrolysis (9501400 C) with slow heating rate and pyrolysis pressure of the atmospheric pressure and at the pressurized pyrolysis (the atmospheric pressure to 3 MPa) with rapid heating rate and the pyrolysis temperature of 950 C. Some signicant differences in those between coal chars and petroleum coke were found. The high temperature pyrolysis caused more easily the graphitization of petroleum coke than that of coal char, especially in the higher temperature range. The increasing pyrolysis temperature resulted in the decrease of surface areas of coal char and the increase of surface areas of petroleum coke. As the pyrolysis pressure was elevated from the atmospheric pressure to 3 MPa, surface areas of petroleum coke initially increased and then decreased, while those of coal chars presented an opposite tendency. The increasing pyrolysis temperature was adverse to the gasication activity of coal chars and was favorable for the gasication activity of petroleum coke. Also, the effects of the pyrolysis pressure on the gasication activity of coal char and petroleum coke were signicantly different. The gasication activity of petroleum coke was obviously lower than that of coal chars, and even lower than that of the natural graphite. 2009 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved. Keywords: Coal char; Petroleum coke; Physical property; Gasication reactivity; Pressurized pyrolysis

1.

Introduction

Petroleum coke is a byproduct of delayed coking. With the development of crude oil rening technology and the continuous increasing of crude oil in worldwide supply, its output is steadily increasing (Liu, 2006). Consequently, the feasible, efcient and clean utilization of petroleum coke, especially those with high sulfur content, has risen as an urgent problem (Cheng, 1999; Zhang and Gong, 2004; Ding, 2004) and some efcient utilization technologies for petroleum coke are worthy to be explored in depth. Thereinto, one of the most efcient utilizations is that it can be used as fuels in an entrained-ow gasier, due to its particular characteristics which are high caloric value, low volatile content, high carbon content and low ash content (Marano et al., 2003). It is well-known that the main reactions are the interactions between carbon and gasifying agents during gasication process and the generation process of petroleum coke is dif-

ferent from that of coal chars (here, coal chars belong to those resulted from non-coking coals). The carbon from petroleum coke is formed at the condition of liquid phase carbonization (during the heat-treatment, carbonaceous mesophase appears typically in the temperature range of 350500 C) and the carbon from coal char is mainly formed at the condition of solid phase carbonization (some in coal char also contain a quite small quantity of those at the condition of liquid phase carbonization). Thereby, when petroleum coke is used as fuel in gasiers, the gasication characteristics of coal chars cannot be completely used for reference. Reports on physical properties (such as carbon crystalline structure, BET surface area and so on) and gasication characteristics of coal chars were abundant (Liu et al., 2004; Yeasmin et al., 1999; Messenbock et al., 1999; Russell et al., 1999; Liu et al., 2000; Gadiou et al., 2002; Roberts et al., 2003; Davis et al., 1995; Valix et al., 1992; Schoening, 1983), while studies on those of petroleum coke were very scarce, especially at

Corresponding author. Tel.: +86 21 64252058; fax: +86 21 64252058. E-mail address: gjs@ecust.edu.cn (J. Gao). Received 21 September 2008; Received in revised form 12 April 2009; Accepted 10 May 2009 0957-5820/$ see front matter 2009 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved. doi:10.1016/j.psep.2009.05.001

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Table 1 Proximate and ultimate analysis of ve raw materials. Raw materials A

SH YZ PM PH GP 6.50 12.90 0.21 0.21 0.12

Proximate analysis (wt%, dry basis) V

35.21 38.82 10.09 7.77 2.16

Ultimate analysis (wt%, dry basis) C

75.30 66.17 89.89 95.25 99.08

FC
58.29 48.28 89.70 92.02 97.72

H
4.49 4.70 3.67 3.27

St
0.33 2.83 3.85 0.34 0.54

N
0.83 0.94 1.51 1.00

A: ash content; V: volatile matter content; FC: xed carbon content; () not be detected; St : total sulphur content.

the high temperature pyrolysis condition. Only few studies were reported (Zhou et al., 2007; Zhou et al., 2008; Tyler and Smith, 1975; Kocaefe et al., 1995; Alcantara et al., 1996; Tyler, 1986; Lee and Choi, 2000; Jung, 1987) and these reports were also quite dispersive. Besides, there were almost no studies on the physical properties and gasication characteristics of petroleum coke at the pressurized pyrolysis condition with rapid heating rate. Accordingly, it appears very necessary to investigate physical properties and gasication characteristics of petroleum coke, which aims to further enrich the knowledge of liquid phase carbonization materials, understand well physical properties and gasication characteristics of different carbonaceous materials and provide valuable information for proper design and operation of gasiers, in which petroleum coke is used as fuel.

2.
2.1.

Experimental
Raw materials

Five kinds of raw materials which are two non-coking coals, petroleum coke, pitch coke and natural graphite, are used in the study. Pitch coke and graphite are used for a comparison purpose. Non-coking coals (two typical Chinese coals) are Shenhua coal (SH) and Yanzhou coal (YZ). Petroleum coke (PM) and pitch coke (PH) are respectively from Qilu Petrochemical Co. Ltd. and Baosteel Co. Ltd. in China, and differ from other samples according to raw material and heat-treatment process. During heat-treatment, the carbonaceous mesophase appears typically in the temperature range of 350500 C (liquid phase carbonization). Graphite (GP) from Shanghai Colloid Chemical Plant is a kind of natural carbon. The proximate and ultimate analysis data of the ve raw materials are listed in Table 1.

atures of 950 C, 1200 C and 1400 C are termed respectively as S-X950, S-X1200 and S-X1400. R chars were prepared using a pressurized pyrolysis set-up (Fig. 1) designed independently by the authors. The preparation processes of R chars are as follows. Raw samples are put in the sample cell. The sample cell is upgraded to the top of the reactor, and then the reactor is closed. A N2 ow of about 300 ml/min as a sweeping gas enters separately into the reactor from its top and bottom (the N2 ow from its top is slightly larger than that from its bottom). After about 5 min, the reactor is heated by a programmed-temperature controller. When the temperature is up to the desired pyrolysis temperature of 950 C, the reactor is pressurized up to the desired pyrolysis pressure (if the desired pyrolysis pressure is the ambient pressure, the reactor does not need to be pressurized). When the desired pressure is leveled off in the interior of the reactor, the sample cell drops to the place where the samples are heat-treated. Here, the time is termed as the beginning of the thermal history. When the thermal history is up to 2 min, the sample cell is upgraded again to the top of the reactor, the internal pressure of the reactor is adjusted up to the atmo-

2.2.

Preparation of char samples

In the study, two species of char samples were prepared separately at the high temperature pyrolysis (9501400 C) with slow heating rate and pyrolysis pressure of the atmospheric pressure and at the pressurized pyrolysis (the atmospheric pressure to 3 MPa) with rapid heating rate and the pyrolysis temperature of 950 C. The char samples prepared at the two different pyrolysis conditions were named correspondingly as S and R chars. S chars were prepared in the temperature range of 9501400 C by de-volatilization of the corresponding raw materials (the particle size of 0.400.63 mm) in the mufe. Raw materials are heated up to a desired temperature at a heating rate of 6 C/min, and then held at this temperature for 20 min. S chars from X (X is SH, YZ, PM or PH) at the pyrolysis temper-

Fig. 1 Schematic diagram of the pressurized pyrolysis set-up. 1: gas cylinder; 2: needle valve; 3: stale pressure valve; 4: mass owmeter; 5: protection gas inlet; 6: balance system; 7: gas outlet; 8: reaction gas inlet; 9: reactor system; 10: temperature control system; 11: pressure control system; 12. data collection system.

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Fig. 2 XRD spectra of S chars at different pyrolysis temperatures.

spheric pressure and the heat-treatment process of samples is stopped. When the temperature descends to about 50 C, the reactor is opened, and then the char samples in the sample cell are taken out. According to the above all, the preparation conditions of R chars are summarized as follows: the mass weight of samples, about 0.4 g; the particle size of samples, 0.400.63 mm; the pyrolysis atmosphere, a total N2 (99.999 v/v%) ow of about 600 ml/min; the pyrolysis temperature, 950 C; the estimated heating rate, above 650 C/s (The interval that the samples drops from the top of the reactor to the place where the raw samples are heat-treated, is only about 1.5 s); the thermal history, 2 min; the pyrolysis pressure, 0.13 MPa. R chars from X (X is YZ or PM) at pyrolysis pressures of 0.1 MPa (the ambient pressure), 1 MPa, 2 MPa and 3 MPa, are separately termed as R-X0, R-X1, R-X2 and R-X3. Prior to all experiments, all S and R chars are crushed up to below 73 m and stored for experimental samples.

Lc =

0.89 002 cos(002 )

(2)

where d002 and Lc are respectively the interplanar spacing and the stacking height of the carbon crystal, is the wavelength of the X-ray radiation, 002 is the position of the (0 0 2) peak and 002 is the angular width at half-maximum intensity of the (0 0 2) peak. The analysis of BET surface areas of various samples (the particle size <73 m) was conducted by N2 adsorption techniques using the pore structure analyzer (ASAP 2400) produced by Micrometrics Instrument Co.

2.4. Measurement of the CO2 gasication reactivity of samples

Measurement of CO2 gasication reactivity for various samples (the particle size <73 m) was carried out using an isothermal method by a thermo-gravimetric analyzer (SETARAM TG-DTG/DSC). The detailed description of the analyzer, the detailed procedure of measurement and the detailed experimental conditions could be seen in our previous paper (Wu et al., 2006a; Wu et al., 2008). The carbon conversion (X) and the gasication reaction rate (R, min1 ) of samples were calculated using Eqs. (3) and (4): W0 W W0 Wash dW 1 dX = dt dt W0 Wash

2.3. Analysis of carbon crystalline structure and BET surface area of samples
An X-ray diffraction (JSM-6360LV XRD, D/max-rA12 kW; 12 kW; 40 kV; 100 mA; Cu K radiation) analysis was employed to analyze the variation trend of the carbon crystalline structure of samples (the particle size <73 m) during the pyrolyis process. The carbon crystalline structure parameters of samples can be calculated from X-ray spectra using Eqs. (1) and (2) (Short and Walker, 1963; Roberts et al., 2003):

X=

(3)

d002 =

2 sin(002 )

(1)

R=

(4)

Fig. 3 The effects of the pyrolysis temperature on carbon crystalline structures of S chars from SH, YZ, PM and PH (*original samples; pyrolysis temperature: 950 C (PT950), 1200 C (PT1200), 1400 C (PT1400)).

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Fig. 4 XRD spectra of R chars from YZ and PM at different pyrolysis pressures. where W0 is the initial mass of the sample, W is the instantaneous mass of the sample, Wash is the mass of the ash in the sample and t is the gasication reaction time. especially above 1200 C. These indicate that the graphitization of petroleum coke and pitch coke is easier than that of coals, especially in the higher temperature range. At the pressurized pyrolysis with rapid heating rate, the effects of the pyrolysis pressure on the carbon crystalline structures of R chars from YZ and PM were also investigated. Fig. 4 shows XRD spectra of R chars from YZ and PM at different pyrolysis pressures and Fig. 5 reects the quantitative data regarding the carbon crystalline structure parameters (d002 , Lc ) of these samples. From the gure, it can be seen that with the increase of the pyrolysis pressure, the variations of the carbon crystalline structure parameters of R-chars from PM or YZ are very small and do not present systematical. This illustrates that the carbon crystalline structures of R chars obtained at the pressurized pyrolysis with rapid heating rate are hardly affected by the pyrolyis pressure. Roberts et al. (2003) investigated the effects of the pyrolysis pressure on the carbon crystalline structure of coal chars obtained at the pressurized pyrolysis with rapid heating rate and pyrolysis temperature of 1100 C and also found the similar results.

3.

Results and discussion

3.1. Comparison of effects of pyrolysis temperature and pressure on carbon crystalline structure
S chars prepared at high temperature pyrolysis with slow heating rate were analyzed by XRD. Fig. 2 shows that XRD spectra of S chars from SH, YZ, PM and PH. Analyses of these (0 0 2) peaks in XRD spectra yield quantitative data regarding the carbon crystalline structure parameters (d002 , Lc ) of the samples, which are presented in Fig. 3. From the gure, it can be seen that with the increase of pyrolysis temperature, d002 of S chars from PM or PH becomes smaller and smaller and Lc of those becomes larger and larger, which suggests that the increasing pyrolysis temperature results in the more ordered carbon crystalline structure of PM or PH. Sun and Shen (2004) investigated the variations of carbon crystalline structure of petroleum coke (from Gaoqiao Petrochemical Co., Shanghai, China) with the change of carbonization temperature, and found that above 800 C, the carbon crystalline structure similar to graphite was formed again and the carbon structure became more ordered with the increase of the carbonization temperature. This is in accord with the result of this investigation. Besides, it can be also concluded that with the increase of pyrolysis temperature, the variation trend of carbon crystalline structure of S chars from both SH and YZ is similar to that of S chars from PM and PH. Separately comparing d002 and Lc of S chars from coals with those from PM and PH, two results are obtained: at the same pyrolysis temperature, the carbon crystalline structures of S chars from PM or PH are more ordered than those from coals; as the pyrolysis temperature increases, the variation degree (especially Lc ) of the former is larger than that of the latter,

3.2. Comparison of effects of pyrolysis temperature and pressure on BET surface area
Fig. 6 shows the variations of BET surface areas of S chars from SH, YZ, PM and PH with the change of the pyrolysis temperature at the high temperature pyrolysis with slow heating rate. From the gure, it can be found that with the increase of the pyrolysis temperature, BET surface areas of R chars from both PM and PH increase as a whole, while those from coals present an opposite variation trend. Up till now, almost no literatures reported that the increasing pyrolysis temperature led to the increase of BET surface area of petroleum coke and pitch coke at high temperature pyrolysis. However, many literatures (Chiche et al., 1965; Lu et al., 2002; Wu et al., 2006b; Alcantara et al., 1996; Alonso et al., 2001) reported the similar

Fig. 5 Effects of the pyrolysis pressure on the carbon crystalline structures of R chars from YZ and PM.

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Fig. 6 The effects of the pyrolysis temperature on BET surface area of S chars from SH, YZ, PM and PH (*original samples; pyrolysis temperature: 950 C (PT950), 1200 C (PT1200), 1400 C (PT1400)).

rate. For coal chars, many literatures also reported the similar results and gave the explanations as follows. The tars can be easily produced in coal chars and jammed the pores of resultant chars at the pressurized pyrolysis condition (Cetin et al., 2004; Yeasmin et al., 1999; Messenbock et al., 1999), so surface areas of coal chars produced at pressurized pyrolysis are less than those produced at ambient pressure. Besides, the elevated pressure is favorable to the secondary pyrolysis of tars. As the pyrolysis pressure is elevated, the more tars are redecomposed and re-polymerized and the less tars adhere to the surface of pores, resulting in the increase of surface areas of coal chars (Gadiou et al., 2002; Wall et al., 2002). Comparing the BET surface areas of chars from petroleum coke with those of chars from coals in both Figs. 6 and 7, it is found that the former, as a whole, is larger than the latter at the same pyrolysis conditions. This is probably attributed to their different nature. In addition, comparing the data in Fig. 6 and those in Fig. 7, it is found that the BET surface areas of chars prepared at the high temperature pyrolysis with slow heating rate, as a whole, are larger than those of chars prepared at the pressurized pyrolysis with rapid heating rate. However, Roberts et al.s (2003) study indicated that the chars produced at high heating rate had signicantly larger surface areas than those produced at low heating rate. This seems to be inconsistent with the result of the study. In fact, resulting in this discrimination are probably due to the differences in the experimental conditions, the preparation methods of samples and the measurement (or analysis) method, etc. Accordingly, the above all problems need to be further investigated and discussed in depth and detail for the future.

Fig. 7 Effects of the pyrolysis pressure on BET surface area of R chars from YZ and PM. results on coal chars and considered that the increasing pyrolysis temperature could result in the decrease of BET surface area of coal chars at the high temperature pyrolysis with slow heating rate. Fig. 7 shows the effects of the pyrolysis pressure on the BET surface areas of R chars from YZ and PM at the pressurized pyrolysis with rapid heating rate. From the gure, it can be found that with the change of the pyrolysis pressure, the variation trend of surface areas of R chars from coal is opposite to that of R chars from petroleum coke, and that as a whole, the surface areas of R chars from coal prepared at the atmospheric pressure are larger than those prepared at pressurized pyrolysis, while those from petroleum coke presented an opposite phenomena. For petroleum coke, almost no studies reported the effects of the pyrolysis pressure on the BET surface areas of petroleum coke at the pressurized pyrolyis with rapid heating

3.3. Comparison of effects of pyrolysis temperature and pressure on the CO2 gasication activity
At the high temperature pyrolysis with slow heating rate, the effects of pyrolysis temperature on the CO2 gasication activity of S chars from SH and PM were investigated at the gasication temperature of 950 C. Fig. 8 shows the data of the carbon conversion versus the gasication reaction time for S chars at different pyrolysis temperatures. From Fig. 8A, it can be seen that at the same gasication time, the carbon conversions of S chars from SH decrease with the increase of pyrolysis temperature. This indicates that increasing the pyrolysis temperature is adverse to the gasication activity of S chars from coal, which is in accord with those reported in literatures (Kajitani et al., 2002; Ochoa et al., 2001; Bayarsaikhan et al., 2005). From Fig. 8B, the result can be obtained that at the same gasication time of 100 min, the carbon conversions (X) of PM, S-PM950, S-PM1200 and S-PM1400 are respectively up to 0.13, 0.26, 0.33 and 0.51. According to this result, the gasication activity ordering of S chars from PM is as

Fig. 8 Carbon conversion versus reaction time for S chars from SH and PM at different pyrolysis temperature.

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Fig. 9 Reaction rate versus carbon conversion for R chars from YZ and PM at different pyrolysis pressure. follows: S-PM1400 > S-PM1200 > S-PM950 > PM, which suggests that there is a signicant effect of pyrolysis temperature on the gasication activity of petroleum coke and the increasing pyrolysis temperature is favorable for the gasication activity of S chars from PM. This conclusion was not almost reported by previous literatures. One of the reasons for this result probably is that the increasing pyrolysis temperature leads to the increase of BET surface areas of S chars from PM (seen in Fig. 6). Above all, the effect of pyrolysis temperature on the gasication activity of petroleum coke is opposite to the effect of pyrolysis temperature on that of coal chars. At the pressurized pyrolysis with rapid heating rate, the effects of pyrolysis pressure on the CO2 gasication activity of R chars from YZ and PM were also investigated at the gasication temperature of 950 C. Fig. 9 shows the data of the reaction rate versus the carbon conversion for R chars at different pyrolysis pressures. From Fig. 9A, it can be found that the gasication reaction rate of R-YZ0 is higher than those of R-YZ1, R-YZ2 and R-YZ3, and at the pressurized pyrolysis, the ordering of the gasication reaction rates of R chars produced at different pressures is R-YZ3 > R-YZ2 > R-YZ1. From Fig. 9B, it could be found that the gasication reaction rate of R-PM0 is higher than those of R-PM1, R-PM2 and R-PM3, and at the pressurized pyrolysis, the gasication reaction rates of R chars seem to present almost unchanging as the pyrolysis pressure increases from 1 MPa to 3 MPa. According to the above results, the following conclusions can be reached: at the pyrolysis with rapid heating rate, the gasication activity of resultant chars produced from both coal or petroleum coke at pressurized pyrolysis are lower than that of those at the atmospheric pressure; at the pressurized pyrolysis with rapid heating rate, the increasing pyrolysis pressure results in the increase of the gasication activity of coal chars, while it almost has no effects on the gasication activity of resultant chars from petroleum coke. The consistent result on coal char has been reported by some literatures (Gadiou et al., 2002; Cetin et al., 2004; Fan et al., 2005), while there are almost no similar studies on petroleum coke. The above conclusions illustrate that the effects of the pyrolysis pressure on the gasication activity of coal chars are different from those of petroleum coke. The different effects of the pyrolysis pressure on their gasication activity are probably due to their different quantities of active sites resulted from the variations of surface area and carbon crystalline structure at pressurized pyrolysis (seen in Figs. 7 and 5). Generally, it is considered that the carbon crystalline structure and the surface area are two main factors which affect the gasication activity of carbonaceous materials (Alonso et al., 2001; Lu et al., 2002; Zolin et al., 2002; Gadiou et al., 2002; Wall et al., 2002). If the BET surface area is less or the carbon crystalline structure is more ordered, the gasication activity is lower. Otherwise, the gasication activity is higher.

3.4. Comparison of coal char and petroleum coke in the gasication activity
Due to the signicant differences in the properties of various carbonaceous materials, the average gasication reaction rate (0.5/t0.5 ) is used to represent their gasication activity indexes. t0.5 is the half-time, which is the time at the carbon conversion of 0.5. The CO2 gasication activities of S-SH1400, S-YZ1400, PM, PH and GP were measured at the gasication temperature of 1000 C, as shown in Fig. 10. From the gure, the ordering for the gasication activity indexes of various carbonaceous materials is as follows: S-SH1400 > S-YZ1400 > GP > PM > PH. According to the result, it is concluded that the activity of resultant carbons at the liquid phase carbonization is obviously lower than those at the solid phase carbonization (i.e., those resulting form non-coking coals), and even lower than those from natural graphite.

4.

Conclusions

Fig. 10 Comparison of the gasication activity of various carbonaceous materials.

(1) At the high temperature pyrolysis with slow heating rate, the differences between coal char and petroleum coke in physical properties and gasication activities are presented as follows. The graphitization degree of petroleum coke is larger than that of coal char, especially in the higher temperature range. The increasing pyrolysis temperature leads to the decrease of BET surface areas of coal chars, while those of petroleum coke present an opposite variation trend. The increasing pyrolysis temperature leads to the decrease of gasication activities of coal chars, while

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the high pyrolysis temperature is favorable for the gasication activity of petroleum coke. (2) At the pressurized pyrolysis with rapid heating rate, the differences between coal char and petroleum coke in the physical properties and gasication activities are presented as follows. The effects of pyrolysis pressure on the carbon crystalline structures of both coal chars and petroleum coke are very small and do not present systematical. With the increase of the pyrolysis pressure, surface areas of coal chars initially decrease and then increase, while those of resultant chars from petroleum coke present an opposite tendency. The increasing pyrolysis pressure results in the increase of the gasication activity of coal chars and almost has no effects of the gasication activity of petroleum coke. (3) Comparing the gasication activities of various carbonaceous materials, it is found that the gasication activity of petroleum coke is lower than that of coal char and even lower than that of natural graphite. At the same time, it suggests that the gasication activity of carbons formed at the liquid phase carbonization is obviously lower than that of those formed at the solid phase carbonization.

Acknowledgement
The work is supported by Program for Changjiang Scholars and Innovative Research Team in University (PCSIRT). The authors thank Special Fund for Excellent Young Teachers of East China University of Science and Technology (YB0157108), National Basic Research Program of China (2004CB217704), State Natural Science Foundation of China (20876050) and China Renewable Energy Scale-up Program (A1-B09-Subgrant2008-001) for nancial support.

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