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Energy Conversion and Management 49 (2008) 107112 www.elsevier.com/locate/enconman

Conversion of asphalt into distillate products

Mohammad Shakirullah a, Imtiaz Ahmad a,*, Mohammad Arsala Khan b, Amjad Ali Shah a, Mohammad Ishaq a, Habib-ur-Rehman a
a

Institute of Chemical Sciences, University of Peshawar, N. W. F. P., Pakistan b Yanbu Industrial College, Yanbu Al Sinayah, Saudi Arabia

Received 23 February 2006; received in revised form 6 October 2006; accepted 20 May 2007 Available online 10 July 2007

Abstract This paper reports the conversion of asphalt in a micro-autoclave under an inert atmosphere of nitrogen to lighter products. The inuence of temperature, contact time and some catalysts, i.e. clay type; UTIMAC, HZSM-5 and sodium silicate, acidic type; phospho-tungstic acid, oxide type; ammonium hepta molybdate, silica gel, nickel oxide and alumina powder, chloride type; stannous chloride and aluminum chloride and modiers like methyl iodide and coal, on the yield of liquid and gas products was studied. A marked eect of temperature on the yield of liquid as well as gas products was observed. Employment of clay type catalysts was found to be benecial in term of yields of liquid products. Among the catalysts used; UTIMAC clay caused the maximum conversion to desired products. The other catalysts caused a decline in the yield of desired products because of coke formation due to condensation reactions catalyzed by these catalysts. The eect of concentration in the case of clay as catalyst was also studied, and synergistic eects were observed in terms of desired product yield. The study will be helpful in planning asphalt conversion processes into light oil fractions. 2007 Elsevier Ltd. All rights reserved.
Keywords: Asphalt; Resource recovery; Auto cleaving; Catalysts; Zeolite; Clay

1. Introduction With the rapid growth in global population, energy demand grows rapidly, particularly the demand for lighter oil fractions like gasoline and diesel. Petroleum resources are limited, and due to warnings of a foreseen shortage, the new upgrading technologies that are sought by rening engineers today are aimed at conversion of the bottom of the barrel to distillate oils [1]. This eort is being much intensied by the fact that rening processes should be much more ecient due to environmental restrictions [2]. While using conventional methods of rening, vacuum residues production persists to be a great problem for the renery. Very heavy crude oils are found, yielding more
Abbreviations: IP, Institute of petroleum; ASTM, American system for testing and material; BS, British standard; UTIMAC, Utimanzai clay; T, Temperature; P.S, Pentane soluble; P.I, Pentane insoluble; V, Volatiles; TC, Total conversion; RT, Residence time. * Corresponding author. Tel./fax: +92 091 9216652. E-mail address: patwar2001@yahoo.co.in (I. Ahmad). 0196-8904/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.enconman.2007.05.012

than 50% of the weight of the vacuum residue [3]. Also, it is not necessarily easy to upgrade heavy residual oils, since they contain large quantities of metals and asphaltenes whose characteristics are not suciently known [4]. Although these residues are modied to dierent grades of asphalts and various other materials, still these are vital energy resources and should be modied into valuable commodities like diesel and gasoline. Research about asphalt characterization and conversion into light oil fractions is underway worldwide. Many processes have been developed [57]. However, there are still bottlenecks for these processes to be in the centre of the scene. The pyrolytic pathway for conversion of asphalt has been the focus of many researchers [811]. Pyrolysis of asphalt results in thermal dissociation of the asphaltene fraction, which breaks the cross links, resulting in sets of straight chain alkanes and alkenes and a large number of isomers of alkylated mono and polycyclic aromatic hydrocarbons [12]. Maltene in such asphalt evaporates in the

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M. Shakirullah et al. / Energy Conversion and Management 49 (2008) 107112 Table 1 Properties of asphalt used Penetration grade 80/90 Density (gm/cm3) 0.987 Carbon residue (%) 24.458 Ash (%) 0.512 Acid no. (mg KOH/g) 0.370 Pentane insoluble (%) 45

low-temperature pyrolysis experiments [13]. Pyrolysis of asphalt has been studied by Song et al. [14] using thermogravimetric analysis at atmospheric pressure and with nitrogen as the ambient gas with slow heating rate method and a two stage rst order model was established to describe the pyrolysis of asphalt. Walendziewski and Steininger [15] have studied thermal and catalytic conversion of waste polyolens with hydrogen in closed autoclaves. At a cracking temperature of 400 C or higher process temperature, some quantities of hydrocarbon mixtures in the form of gas and liquid products (gasoline and diesel fuel boiling range), as well as higher boiling liquid residue or solid can be obtained [16,17]. Ali et al. [18] have studied the eect of clay based catalysts, and commercial hydrocracking catalysts were evaluated for hydrocracking activity using vacuum gas oil from Saudi Arabian light crude oil. At present, an insignicant part of petroleum is distilled into lighter oil frictions, while the rest is either cracked or reformed. These processes mostly use hydrogen for conversion of the high residual oils into lighter oil fractions, but hydrogen, being a costly commodity, cannot provide the ultimate solution. If heavy residue is cracked under an inert atmosphere like nitrogen, signicant enhancement in the yield of distillates could be achieved. The present work deals with the conversion of asphalt sample obtained from the Attock oil renery into useful products in a stream of nitrogen. The eect of pyrolysis temperature, residence time and some catalysts on its conversion to useful products has been discussed. 2. Experimental procedure 2.1. Sample collection Penetration grade of asphalt (90/80) (obtained from Attock oil renery, Rawilpindi, Pakistan) was used in the current investigation. Other chemicals employed were of analytical grade (Merck and BDH) and used without further purication. 2.2. Characterization Various properties such as carbon residue, ash contents, acidity and asphaltene contents were determined using ASTM methods. Conradson carbon residue was determined by the IP 13/82 (ASTM D189-81) method [19]. Ash was determined by the IP 4/81 (ASTM D482-80) method [20]. The acidity of the asphalt understudy was determined by the IP 213/82 method [21]. The asphaltene contents were determined following the well documented IP 143/84 method [22]. The data is provided in Table 1. 2.2.1. Determination of conradson carbon residue The sample was heated in order to attain uidity, and then 5 g were taken in a silica crucible. This crucible was

placed in the centre of the Skidmore crucible. The sand in the large sheet iron crucible was leveled, and the Skidmore crucible was set in the exact center of the iron crucible. Covers were applied to both the Skidmore and the iron crucible, and the same were mounted on a suitable stand arranged on the bare niche chrome wire triangle. The sheet iron crucible in the insulator with its bottom resting on the top of the triangle was centered, and then it was covered with the whole sheet iron hood in order to distribute the heat uniformly during the process. The heat was applied with a high, strong ame from the gas burner for 10 min. When the smoke appeared above the chimney, the burner was adjusted in a way so that the gas ame ushing the sides of the crucible would ignite the vapors. When the vapors ceased to burn and there was no further blue smoke observed, the burner was readjusted and the heat was held as at the beginning to make the bottom and lower part of the sheet iron crucible a cherry red, and this arrangement was maintained for 7 min. The total period of heating was about 32 min. The burner was then removed, and the apparatus was cooled until there evolved no smoke. Then the cover of the Skidmore crucible was removed. The silica crucible was removed with heated tongs and placed in a desiccator, cooled and weighed. The percentage of the Conradson carbon residue was calculated on the basis of the original sample. Percentage of carbon residue A 100 W

where A = mass of carbon residue, in grams, and W = mass of sample, in grams. 2.2.2. Determination of ash Ash of the asphalt samples, i.e. of the virgin samples and the residues, after conversion was determined using the IP method No. 4/81. A crucible was heated at 700800 C for 10 min, cooled to room temperature in a desiccator and weighed. Five grams of the sample under study were taken in the preheated, cooled and weighed crucible. The crucible and sample was heated till sample ignition, leaving only ash and carbon when the burning ceased. The residue was subsequently placed in a mue furnace and heated at 775 25 C until all carbonaceous material had disappeared. The crucible was cooled to room temperature in a desiccator and then weighed. The crucible was reheated at 775 C for 2030 min and was cooled again in the desiccator and was re-weighed. The heating and weighing was repeated until constant mass was attained.

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The weight of the ash was calculated as a percentage of the original sample as follows: w Ash % 100 W where w = weight of ash, in grams and W = weight of sample, in grams. 2.2.3. Acidity of asphalt/neutralization value Virgin asphalt sample (5 g) was taken in a 250 ml conical ask. The sample was dissolved in about 60 ml of toluene by boiling and swirling the contents of the ask, and the hot solution was transferred to the titration vessel. Then, 160 ml of diluted alcohol were added, followed by 20 ml of alkali blue solution and one drop of 0.1 N standard acid. The mixture was neutralized with potassium hydroxide solution (0.1 N). This mixture was then added to the solution of the sample in the titration vessel. The mixture was titrated with standard alkali solution by shaking vigorously after each addition of alkali until a colour change was observed, then an excess of 0.5 ml of alkali was added. It was back titrated with the standard acid. The neutralization value (NV) was calculated as follows: NV 56:1A1 B1N 1 A2 B2N 2 W

Table 2 Experimental conditions used for conversion of asphalt under study Parameter Temperature Nitrogen pressure (cold) Residence timeb Rate of stirring Heating rate
a b a

Level 300 20 C 10 atm 1.0 h 250300 rpm 5 C/min

Temperature was varied in case of eect of temperature. Residence time was varied in case of eect of residence/contact time.

until clearance of the thimble compartment. The cake from the thimble was dried in a vacuum oven at 70 C until constant mass and weighed. The conversion was calculated as: Conversion 100 cake wt% All the experimental determinations were performed in triplicate and mean values were reported in tables. 2.3.1.1. Temperature optimization. In order to optimize the temperature, the asphalt was thermally cracked by varying the temperature between 250 C and 450 C. Charges were autoclaved at 250 C, 300 C, 350 C, 400 C and 450 C. 2.3.1.2. Contact time optimization. The time was varied between 00 and 2.0 h. The charges were autoclaved for a residence or contact time of 00 h, 0.5 h, 1.00 h and 2.00 h. 2.3.1.3. Catalytic cracking of asphalt. A desired amount of each catalyst was mixed separately with the asphalt and each charge was autoclaved. 2.3.2. Product separation The crackate was separated into three fractions according to solubility in n-pentane and tetrahydrofuran. The product was heated on a steam bath for a few minutes in order to obtain a uniform solution. A 50 cm3 aliquot of n-pentane was then added and shaken vigorously. The asphaltene (PI) was precipitated by n-pentane and separated by ltration. The ltrates were collected as distillate (PS). The residual asphaltene was dried for 30 min at 50 C in a vacuum oven, cooled and weighed. 3. Results and discussion Cracking experiments of asphalt were conducted at different temperatures. The product distribution as a function of temperature is provided in Table 3. The eect of temperature is clearly seen. It is evident from the data that the total conversion calculated as [100 cake (wt%)] is increasing with the increase in temperature with the highest being at 450 C (70%). The yield of desired products, i.e. pentane soluble (PS), is increasing with the increase in temperature from 250 C to 300 C but beyond 300 C, it is decreasing. The yield of PS at 250 C is 0%, at 300 C; 18%, at 350 C; 7.0%, at 400 C; 1.3% and at 450 C; 0%. The gas yield

where A1 = milliliters of alkali used in the determination; B1 = milliliters of alkali used in the blank; N1 = normality of alkali; A2 = milliliters of acid used in the determination; B2 = milliliters of acid used in the blank; N2 = normality of acid; and W = grams of sample. The result was reported as the neutralization value. 2.2.4. Determination of asphaltenes Original asphalt sample (5 g) was weighed into a clean and well dried ask and 150 ml aliquot of n-pentane was added. The mixture was boiled for 1 h under reux. The ask was then cooled, stoppered and stored in a dark cupboard for 2 1 h. The contents were ltered. The ltrates 2 were collected as oil. The residue on the lter paper was washed with successive quantities of n-pentane until free of oil. The lter paper was dried in an oven at 50 C and weighed to calculate the % asphaltene. 2.3. Cracking 2.3.1. Cracking protocol Cracking was undertaken under the conditions provided in Table 2. A portion of the asphalt (40 g) was placed in a pyrex brand glass insert tted tightly in the autoclave. The autoclave was bolted tightly and lled with nitrogen at room temperature after purging twice to remove air and then pressure tested to 10 atm with N2. The furnace temperature was increased incrementally (heated at 5 C min1) to the desired temperature, held there for 1 h, and cooled to room temperature over night (18 h). The residual asphalt, along with the distillates was collected and subsequently soxhletly extracted with n-pentane

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Table 3 Eect of temperature on product distribution T (C) 250 300 350 400 450 P.S (%) 18 7 1.348 P.I (%) 81.178 46 30 35.03 29.80 V (%) 19 36 46 64 70 TC (%) 19 40 50 65 70

Residence time: 0.5 h.

at the temperature of 250 C is 19%, at 300 C; 36%, at 350 C; 46%, at 400 C; 64% and at 450 C; 70%. Cracking at 250 C and 450 C gave no liquid products. It can be seen that as the temperature was increased from 250 C, the liquid formation starts and attains its highest yield at 300 C, and then starts to decline with the increase in temperature. The gas yield increased with the increase in temperature, the highest being at 450 C. This is due to the fact that the more volatile compounds evaporate when the temperature is increased as well as due to the onset of more frequent cleavages of the whole asphalt and crackate molecules upon increasing the temperature. The chemistry of the asphalt is playing a vital role during cracking. The side chains (alkyl substituents) are important congurations in heavy distillates and may suer from cracking, yielding lower molecular weight fragments. The feed with higher amount of side chains across all of the aromatic fractions are more likely to yield favorable products like gasoline and distillate range materials. Product distribution as a function of residence time was also studied. The data is displayed in Table 4. The contact time was varied between 0.0 and 2 h. The yield of liquid products, i.e. PS, is increasing with the increase in contact time from 0.0 h up to 1.0 h, but beyond 1.0 h, a decreasing trend can be noticed. The yield of PS at 0.0 h is 8%, at 0.5 h is 18 0%, at 1.0 h is 20% and at 2.0 h is 14%. The gas yield obtained at contact time of 0.0 h is 36%, at 0.5 h is 36%, at 1.0 h is 37% and at 2.0 h is 44%. An increase can be observed in the yield of desired products up to 1.0 h, but beyond 1.0 h, the yield is decreased. The reason is that coking occurs by dierent mechanisms in the vapor and liquid phases of the products upon extended times. The coke formation can be inhibited by preventing condensation [23] and, hence, decreasing the residence time of the products in the rector [24]. In order to enhance the conversion of asphalt into the desired products, the treatment was undertaken in the pres-

ence of various cracking catalysts. Many catalysts like clay type; UTIMAC, HZSM-5 and sodium silicate, acidic type; phospho-tungstic acid, oxide type; ammonium hepta molybdate, nickel oxide, alumina powder and silica, chloride type; stannous chloride and aluminum chloride and some modiers like methyl iodide and coal were used. The product distribution as a function of various catalysts is provided in Table 5. It is evident from the data compiled that conversion to desired products in the case of UTIMAC, HZSM-5 and sodium silicate is 25%, 28% and 12%, respectively. In the case of the acidic type catalyst; phospho-tungstic acid, the yield is 16%. In the case of the oxide type catalysts; ammonium hepta molybdate, silica gel, nickel oxide, and alumina powder, the yield is 19%, 18%, 6% and 6%, respectively. In the case of chloride type catalysts; AlCl3 and stannous chloride, the yield is 4% and 3%, respectively, while in the case of modiers; methyl iodide and coal, the yield is 7% and 14%, respectively. The yields of desired products in some cases were enhanced, but in other cases, declined. Maximum yield was obtained in the cases of UTIMAC and HZSM-5. Both are zeolite catalysts having cracking activities. It is also evident from the data that the yield pattern of volatiles obtained in the case of catalytic runs is almost similar to that of the uncatalyzed charge. Meaningless enhancement in total conversion compared to the uncatalyzed run can be observed. Thus, it is established that most of the catalysts have caused cracking of the PI-BS comprising congurations. On the contrary, the decline in the yields with some catalysts might be due to deactivation of these catalysts or their poor selectivity for cracking of asphaltenes or their decay, erosion or lumping at the temperature of operation. Catalyst decay at the temperature of operation can inuence the product distribution [25]. In order to view the eect of concentration of the catalyst, the UTIMAC catalyst was used in 1%, 2% and 20%
Table 5 Eect of catalysts on product distribution Catalyst type Clay UTIMAC HZSM Sodium silicate Acidic Phospho-tungstic acid Oxide Ammonium hepta molybdate Silica gel NiO2 Alumina powder Chloride AlCl3 Stannous chloride Modiers Methyl iodide Hungu coal P.S (%) 25 28 12 16 19 18 6 6 4 3 7 14 P.I (%) 33 41 48 34 40 52 58 59 51 60 49 43 V (%) 42 31 40 50 41 30 36 35 45 37 44 43 TC (%) 67 59 52 66 60 47 42 41 49 40 51 23

Table 4 Eect of contact time on product distribution RT (h) 0 0.5 1 2 P.S (%) 8 18 20 14 P.I (%) 56 46 43 42 V (%) 36 36 37 44 TC (%) 34 39 57 58

Reaction temperature: 400 C.

M. Shakirullah et al. / Energy Conversion and Management 49 (2008) 107112 Table 6 Eect of concentration of UTIMAC (catalyst) on product distribution Catalyst loading (%) 1 2.5 20 P.S (%) 25 26 38 P.I (%) 33 31 26 V (%) 42 43 33 TC (%) 67 69 74

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loadings. The data is displayed in Table 6. The yield of desired product (PS) at 1% loading is 25%, at 2.5% loading is 26% and at 20% loading is 38%. The gas yield in the case of 1% of catalyst is 42%, in the case of 2.5% of catalyst is 43% and in the case of 20% catalyst is 33%. An increase in the yield of desired products can be seen with the highest in the case of the charge loaded with 20% catalyst. Catalyst concentration greatly inuences the product distribution [26,27]. Several reasons can be responsible for this high conversion. Among them, the surface area and pore structure of the catalyst is a strong argument [28]. Because of the availability of sucient surface area, the remnant whole asphalt molecules are cleaved. Moreover, frequent coke formation, which is not desired, usually results in uncatalyzed reactions as a consequence of retrogressive reactions. In the presence of a highly porous catalyst, coke formation is inhibited with the result of increased yield of the desired product. Pyrolysis equipment, feedstock properties, catalyst types and operating conditions are the major inuencing factors on catalytic pyrolysis processes and their product distribution [29]. All of these factors have signicant eects on the catalytic pyrolysis processes and their product distributions. Operating conditions and employment of a catalyst are the key inuencing factors. Our yields in the presence of a cheap local catalyst, i.e. UTIMAC, are quite comparable with the commercial catalysts reported elsewhere for cracking of hydrocarbons [3032]. 4. Conclusions It is concluded from the current study that asphalt can be converted into desired liquid products via cracking in a nitrogen environment. In order to avoid formation of PI-BS in the product slate, catalysts, particularly UTIMAC and HZSM-5, proved very eective. The other catalysts employed were found unsatisfactory and caused deleterious eects on the formation of desired products due to coke formation. The eect of concentration of the catalyst was also studied in the case of UTIMAC, and the yields were found to be concentration dependent. UTIMAC is a locally available, cheap clay, therefore, the process will be cost eective. References
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