Date stone wastes have been utilized for production of activated carbon by chemical activation with phosphoric acid using a fluidized-bed reactor. The effects of the activation time, activation temperature, impregnation ratio, and particle size on the yield and the adsorptive capacity towards iodine were studied.
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Original Title
Utilization of Date Stones for Production of Activated Carbon
Date stone wastes have been utilized for production of activated carbon by chemical activation with phosphoric acid using a fluidized-bed reactor. The effects of the activation time, activation temperature, impregnation ratio, and particle size on the yield and the adsorptive capacity towards iodine were studied.
Date stone wastes have been utilized for production of activated carbon by chemical activation with phosphoric acid using a fluidized-bed reactor. The effects of the activation time, activation temperature, impregnation ratio, and particle size on the yield and the adsorptive capacity towards iodine were studied.
Utilization of date stones for production of activated carbon
using phosphoric acid
N.M. Haimour a, * , S. Emeish b,1 a Department of Chemical Engineering, University of Jordan, Amman 11942, Jordan b Department of Chemical Engineering, Faculty of Engineering Technology, Al-Balqa Applied University, P.O. Box (15008), 11134 Marka, Amman, Jordan Accepted 23 August 2005 Available online 26 October 2005 Abstract Date stone wastes have been utilized for production of activated carbon by chemical activation with phosphoric acid using a uidized- bed reactor. The eects of the activation time, activation temperature, impregnation ratio, and particle size on the yield and the adsorp- tive capacity towards iodine were studied. The yield and the quality of the activated carbon prepared by using H 3 PO 4 were compared with that prepared from date stones using the same equipment, and under similar conditions by using ZnCl 2 as an oxidizing agent. The maximum value of the iodine number of the activated carbon produced using H 3 PO 4 in this work was about 495 under the following conditions: impregnation ratio 0.4, activation time 60 min, activation temperature 800 C, particle size 0.60 mm. The iodine number for the produced activated carbon was higher when phosphoric acid was used, compared to that when zinc chloride was used as impreg- nation reagent; however, the yield obtained when H 3 PO 4 was used was lower than the yield when ZnCl 2 was used. The iodine number increases signicantly with increasing the activation temperature. By increasing the impregnation ratio at the same temperature, the iodine number decreased sharply and an oscillation is noticed for all the cases but it was clearer at 800 C. The average variation of the iodine number for the whole range of particle size used in this work is 10%. 2005 Elsevier Ltd. All rights reserved. 1. Introduction Active carbon is the nal product of an activation pro- cess of carbonaceous materials from dierent sources and with carbon contents in the range 7290%. The activation sequence usually commences with an initial carbonization of the raw material to obtain samples with high carbon content (Daza et al., 1986). The most concise denition of an activated carbon, which includes a wide range of amorphous-based materi- als, is a material prepared to exhibit a high degree of porosity and an extended inter-particulate surface area. These qualities dene an activated carbon with excellent adsorbent characteristics useful for a wide variety of pro- cesses including ltration, purication, deodorization, decolorization and separation (Bansal et al., 1988). Activated carbon is dened by its properties as well as by its source, and it can be produced from almost any or- ganic substance with high carbon content. Many agricul- tural byproducts have been used as sources for activated carbon such as coconut shells (Kirubakaran et al., 1991), wood (Benaddi et al., 1998; Jagtoyen and Derbyshire, 1998), almond shells (Rodriguez-Reinoso et al., 1989; Toles et al., 2000), olive stones (Al-Khalid et al., 1998; Bacaoui et al., 2001), pecan shells (Shawabkeh et al., 2002; Bansode et al., 2003; Dastgheib and Rockstraw, 2002), nutshells (Toles et al., 1998; Abdi et al., 2001) and other agricultural byproducts (Wu et al., 1997; Tsai et al., 2001). Few studies have been done for activation of date stones (Abdulkarim et al., 2002; Girgis and El-Hendawy, 2002). The physical properties and the chemical composition of the precursor, as well as the methods and process condi- tions employed for activation, determine the nal pore size 0956-053X/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.wasman.2005.08.004 * Corresponding author. Tel.: +962 6 535 5000; fax: +962 6 535 5588. E-mail addresses: nomanhaimour@hotmail.com (N.M. Haimour), s_emiesh@yahoo.com (S. Emeish). 1 Fax: +962 6 489 4292. www.elsevier.com/locate/wasman Waste Management 26 (2006) 651660 distribution and the adsorption properties of the activated carbon (Bota et al., 1997). The activation of the carbon provides it with many of its useful properties. The type and degree of activation aect its physical and chemical properties. Processes used for activation are broadly divided into: (a) Physical activation processes, in which steam, nitro- gen or carbon dioxide are used for mild oxidation of the carbonaceous matter. The process is usually carried out in two stages. The rst stage is the carbon- ization stage followed by an activation stage. (b) Chemical activation processes in which a dehydrating agent is used, such as H 2 SO 4 , H 3 PO 4 , ZnCl 2 , and KCl (Al-Khalid, 1995). The worldwide demand for activated carbon is increas- ing. The raw materials used are nonrenewable. Therefore, all possible sources should be investigated. Palm trees are abundant in several countries in the world such as Iraq, Saudi Arabia, Iran, Egypt and other Mediterranean coun- tries. The world annual production of the dates was about 3.4 million tons in 1990 (Barreveld, 1993) and it is expected to be more than 5 million tons in 2004. Date stones repre- sent about 10% of the date weight. The chemical composi- tion of the date stones is shown in Table 1. The crude ber and carbohydrates consists of hemicellulose (23%), lignin (15%), cellulose (57%) and ash (5%). Date stones are re- moved from dates during manufacturing and considered harmful to the environment. It has been shown by many researchers (Kirubakaran et al., 1991; Al-Khalid, 1995; Toles et al., 1998; Shawabkeh et al., 2002; Dastgheib and Rockstraw, 2001) that lignocellulosic agricultural wastes are good precursors for the production of activated carbon. Therefore, the possibility of using date stones as a source for activated carbon production should be investigated. The objective of this paper was to utilize date stones for the production of activated carbon by chemical activation with H 3 PO 4 in a uidized bed reactor. The eects of the u- idization time, temperature, particle size, and the impreg- nation ratio (IR) were studied. The eect of the above- mentioned parameters on the yield and the iodine number of the activated carbon was studied. The results were com- pared with that for activated carbon produced from date stones using the same equipment, and under similar operat- ing conditions with activation achieved by use of ZnCl 2 (Al-Qaessi, 2001). 2. Experimental setup A schematic diagram illustrating the experimental setup of the reactor furnace system is shown in Fig. 1. The system consists of a furnace and a uidized-bed reactor. The fur- nace (F21100) is an electrical tube furnace and is mounted vertically. It has a maximum power of 5.8 KW (230 V in- put) and a maximum operating temperature of 1200 C. It is controlled by an electronic single set point. The uid- ized-bed reactor is inserted through the furnace-heating unit, as shown in Fig. 2. The reactor was constructed from a carbon-steel tube with an inside diameter of 2.54 cm, an outside diameter of 3.14 cm and a length of 50.0 cm. Its upper edge rises 12.5 cm above the upper surface of the heated length in the furnace and its lower end is 7.5 cm be- low the bottom of the heated length. Two mesh screens (0.2500.355 mm) were placed 20.0 cm apart in the lower part of the column. This distance was lled with ceramic packing to heat the incoming gas stream to the temperature of the tube furnace. The bed temperature was measured by a thermocouple that was positioned about 1 cm above the upper screen. The uidizing gas (nitrogen) was passed through a rotameter and then admitted into the reactor in- let at the lower end of the column. The material is intro- duced through an opening at the upper end of the column using a funnel. The nal product is collected by a cyclone tted at the top of the system. 3. Procedure 3.1. Sample preparation Date stones were received isolated from dates. With vig- orous agitation, any oated particulates were easily sepa- rated by decanting. The process of washing, agitation, and decantation was continued and the remaining hard stones were used in the experiments. The clean stones were then dried at 130 C for about 24 h, then they were crushed Table 1 Chemical composition of date stones (Barreveld, 1993) Compound % Moisture 510 Protein (N 6.25) 57 Oil 710 Ash 12 Crude ber 1020 Carbohydrates 5565 Fig. 1. Experimental set-up. 652 N.M. Haimour, S. Emeish / Waste Management 26 (2006) 651660 using a jaw crusher and sieved to the desired particle size. The resultant sieve cut was soaked in 98% ethanol for about 24 h to extract any oil content, after which the col- lected fractions were used to study the eect of the dierent parameters. 3.2. Impregnation One hundred grams of specied size particles was mixed with 300 ml solution of H 3 PO 4 of 85% concentration. The mixture was shaken for homogenization, and then it was left for 24 h at room temperature using impregnation ratios from 0.20 to 1.40, similar to the procedure followed by Caturla et al. (1991). The solid particles were then washed with distilled water and ltered using vacuum ltration. The particles were then dried at 85 C for about 24 h to en- sure complete drying. 3.3. Activation The furnace was preheated to the desired temperature for a minimum of 3 h prior to the start of the experiment to obtain a steady state temperature. The required nitrogen ow rate that would correspond to the minimum uidiza- tion velocity was determined by sight using a plexiglas u- idized bed column (Al-Khalid, 1995). The reactor was purged with nitrogen at a ow rate of 45 L/min, prior to the addition of the date stones. The ow rate was reduced to 18 L/min during date stones addition, then it was increased to a value between one- and twofold of the minimum uidization velocity (Kirubakaran et al., 1991). Flow rates of 47.6, 45, 35 and 28.0 L/min were se- lected for particles of an average size of 1.20, 0.78, 0.605 and 0.428 mm, respectively. Activation temperatures of 200, 300, 400, 500, 600, 700 and 800 C for 60 min with an average particle size and impregnation ratio of 0.780 mm and 0.40, respectively, were used to study temperature eect. The eect of activation time was studied at 800 C for 15, 30, 60, 90 and 120 min with the same particle size of 0.780 mm and impregnation ratio of 0.40. Samples of average particle size of 0.428, 0.605, 0.780 and 1.20 mm were used for 60 min during activation and 0.40 impregnation ratio at 800 C to study the eect of par- ticle size. Impregnation ratios of 0.2, 0.40, 0.6, 0.8, 1.0, 1.2 and 1.4 were used to investigate the eect of impregnation ratio; runs were performed at 400 and 800 C for 60 min with the same particle size of 0.780 mm. At the end of the experimental time, the product in the reactor was cooled to 150200 C by passing a nitrogen ow at 1618 L/min into the reactor at room temperature to prevent oxidation in the cyclone. The activated carbon obtained was removed from the reactor. It was then thor- oughly washed with 500 ml solution of 0.10 N HCl, and then rewashed thoroughly with distilled water and soaked in distilled water for 24 h at room temperature. The solu- tion was decanted and the activated carbon was dried at 120 C for about 24 h, and then weighed and stored for characterization. It is expected that this procedure is en- ough for removing any phosphoric acid and any soluble phosphate salts in the activated product because of the high solubility of phosphoric acid in water. This procedure has been used by several researchers (Bevia et al., 1984; Kirubakaran et al., 1991; Wu et al., 1997; Jagtoyen and Derbyshire, 1998; Macias-Garcia et al., 2003). Other researchers (Bansode et al., 2003; Shawabkeh et al., 2002; Toles et al., 1998) used lead acetate or lead nitrate solution to assure phosphate removal is complete. 3.4. Characterization The prepared activated carbon was characterized by its adsorptive capacity of iodine, which is referred to as iodine number. The iodine number is dened as the milligrams of iodine adsorbed by 1 g of carbon when the iodine concen- tration of the residual ltrate is 0.02 N (Robinson and Hansen, 1978). The procedure of the iodine number deter- mination is as follows: 1. A dry sample of the activated carbon is weighed and added to 10 ml of 5% HCl acid and mixed until the sam- ple is wetted them the mixture is boiled for 30 s then cooled. 2. 100 ml of standardized iodine solution of normality N 1 is added to the mixture and the contents were shaken for 30 s then ltered through Whatmann No. 2 V lter paper. 3. A volume of 50 ml of the ltrate is titrated with stan- dardized 0.1 N sodium thiosulfate solution using starch as indicator. Fig. 2. Dimensions of reactor and furnace (cm). N.M. Haimour, S. Emeish / Waste Management 26 (2006) 651660 653 4. The amount of iodine adsorbed = N 1* 100 N 2* V * 110/ 50 g mol. 5. The iodine number of the activated carbon is then calcu- lated by using the following equation: Iodine Number X m A; 1 where A is the correction factor obtained after the calcu- lation of the residual ltrate normality, m the weight of activated Carbon in grams, X the weight of adsorbed io- dine in milligrams and is given by: X N 1 100 N 2 V 110=50 126:93; 2 where N 1 is the normality of iodine solution, N 2 the normality of thiosulfate solution, V the volume of thio- sulfate solution used for titration. The percentage yield of activated carbon is calculated as: %Yield weight of the end product= weight of the impregnated powder weight of the reagent impregnated. 3 4. Results and discussion Date stones are composed of a low-porosity and com- pact cellular structure (Girgis and El-Hendawy, 2002). Its composition is shown in Table 1. It has the lowest lignin content, highest cellulose and hemicellulose contents com- pared with almond shells, pecan shells, walnut shells, and macadamia (Toles et al., 1998). When concentrated H 3 PO 4 is mixed with date stones at high temperature, it ap- pears to function both as an acid catalyst to promote bond cleavage reactions and formation of cross-links via pro- cesses such as cyclization and condensation and to combine with organic species to form phosphate and polyphosphate bridges that connect and crosslink biopolymer fragments (Jagtoyen and Derbyshire, 1998). Dastgheib and Rock- straw (2001) proposed that various surface acidic func- tional groups (oxygen- and/or phosphorus-containing groups) are developed through the surface oxidation as well as attachment of dierent oxygen/phosphorous groups to the surface, while developing required porosity. Benaddi et al. (1998) suggested that dehydration of cellulose by phosphoric acid is similar to dehydration of alcohols and at higher temperatures the phosphorous oxides act as Le- wis acids and can form COP bonds. At temperatures higher than 900 C phosphorus-bearing species leave the carboneous surface (Labruquere et al., 1997). Character- ization of the activated carbon could be done from measur- ing the surface area using N 2 adsorption, iodine number, phenol number, etc. In this work, the eciency and the quality of the pro- duced activated carbon from date stones were character- ized by measuring the percentage yield and the iodine number. These characteristics were plotted and analyzed for the variables of activation time, activation temperature, impregnation ratio and particle size of the date stones to nd the optimum conditions at which the maximum yield and iodine number of the activated carbon is obtained. The results were compared with results obtained by Al- Qaessi (2001) for activation of date stones by ZnCl 2 using the same equipment and similar operating conditions. Yield of the activated carbon. The yield can be dened as the mass ratio of activated carbon produced to the mass of the raw material used. The eects of activation time, activa- tion temperature, impregnation ratio, and particle size on yield were studied. Eect of activation time on yield. It was noticed that, as the activation time increases from 15 to 120 min, the per- centage yield decreases from 20% to 8.5% as shown in Fig. 3. The other parameters (temperature, impregnation Fig. 3. Eect of activation time on yield. 654 N.M. Haimour, S. Emeish / Waste Management 26 (2006) 651660 ratio and particle size) were kept constant. A steep decrease occurs within the rst 30 min from 20% to about 9%. This is due to rapid evolution of volatile compounds to form stable compounds. As the activation time increases, the percentage yield de- creases after 30 min. The loss in the yield is proportional to the rate of activation as shown by Edwards et al. (1993) and Kirubakaran et al. (1991). The yield obtained when H 3 PO 4 was used is lower than the yield when ZnCl 2 was used. The dierence between the yields increases with increasing the activation time. During short contact time, less than 30 min, H 3 PO 4 acts as an oxi- dation inhibitor of carbon oxidation; however, for long contact time (3060 min) the phosphorus-bearing species leave the carboneous surface and degradation of the acti- vated carbon becomes severe; therefore, the yield decreases, while for ZnCl 2 this behavior does not occur. After contact time of 60 min a stable activated carbon is formed and the yield becomes almost constant. Eect of activation temperature on yield. In can be seen from Fig. 4 that, as the activation temperature increases from 200 to 800 C, the percentage yield decreases from 58% to 9.5%. This is due to the loss of the volatile materials with increasing temperature. Beyond 700 C a lower rate of yield decrease was noticed where a stable structure is formed. This behavior agrees with results obtained from TGA of date stones activated with H 3 PO 4 studied by Girgis and El-Hendawy (2002). Kirubakaran et al. (1991) found also that the yield decreases as the temperature in- creases up to 700 C. Since H 3 PO 4 can remove more volatile materials from the particles compared to ZnCl 2 , the percentage yield was lower when H 3 PO 4 was used compared with ZnCl 2 as shown in Fig. 4. Eect of impregnation ratio on yield. Fig. 5 shows the ef- fect of increasing impregnation ratio, from 0.2 to 1.4 at 400 and 800 C, respectively. As the impregnation ratio (IR) in- creases, the percentage yield of the activated carbon de- creases gradually for activation at 400 C due to the continuous removal of tar material from the pores. At 800 C it was found that the yield increases from 8% to about 13%, and a step increase in yield occurs at an impregnation ratio of 1.0. This behavior agrees with results obtained by Qasem et al. (2004) for chemical activation of olive seeds using KCl and ZnCl 2 and with Girgis and El- Hendawy (2002) who noticed that increasing impregnation ratio has a higher eect at higher temperatures, and by increasing the impregnation ratio after a certain value probably forms an insulating layer covering the particles, thus reducing the activation process. The yield obtained when ZnCl 2 was used is higher than that when H 3 PO 4 was used. Kirubakaran et al. (1991) and Wu et al. (1997) obtained similar results for activation of coconut shells and extruded corn under operating conditions similar to this work. This may be due to the combustion reactions, which are more pronounced with H 3 PO 4 because of its low- er temperature stability (boiling point 213 C). Eect of particle size on yield. It was noticed that, as the particle size increases the percentage yield decreases, as shown in Fig. 6. The other parameters (temperature, impregnation ratio and time) were kept constant. This abnormal behavior could be attributed to the low poros- ity and compact cellular structure of date stones and the high viscosity and low diusion coecient of concen- trated H 3 PO 4 through the particles. For particles of small size, the resistance to diusion is lower than that for large-size particles. Therefore, H 3 PO 4 does not diuse to the core of the large particles. When H 3 PO 4 reacts Fig. 4. The relation between activation temperature and yield using chemical activation. N.M. Haimour, S. Emeish / Waste Management 26 (2006) 651660 655 with the lignocelulosic structure, it imparts protection from oxidation as shown by Lu and Chung (2001); there- fore, for large particles at high temperature the core of the particles degrades and the yield decreases more com- pared with small size particles. Another reason for the high yield of small particles compared with large parti- cles is that by decreasing the particle size, better contact occurs between H 3 PO 4 and the organic species. This leads to formation of phosphate and polyphosphate es- ters (Moreno-Castilla et al., 2001). So the yield will in- crease relative to the larger particles. 4.1. Iodine number of the activated carbon Iodine number gives an estimation of the relative surface area of two samples and is usually used to measure poros- ity for pores greater than 1.0 nm in diameter. Thus the io- dine number was measured to evaluate the adsorptive capacity of the activated carbon produced (Moreno-Castil- la et al., 2001; Bacaoui et al., 2001; Girgis and El-Hen- dawy, 2002). Eect of activation time on the iodine number. Fig. 7 shows that as the activation time increases, the iodine num- Fig. 5. Eect of impregnation ratio on yield using chemical activation at t a = 60 min, dp = 0.710.85 mm. Fig. 6. The relation between particle size and yield by activation at T a = 800 C, t a = 60 min and IR = 0.4. 656 N.M. Haimour, S. Emeish / Waste Management 26 (2006) 651660 ber increases with increasing time up to 60 min; then it de- creases slightly for the time period of 60120 min. This means that there is a pronounced decline in micro-porosity with lower total surface area for activation. When H 3 PO 4 is used as an impregnation reagent, phosphorus-bearing spe- cies (COP) are linked at carbon active sites (Labruquere et al., 1997). By increasing activation time, some of the C OP species leave the carboneous surface and therefore the iodine number of the activated carbon decreases. The io- dine number for the produced activated carbon was higher when phosphoric acid was used, compared to that when zinc chloride was used as an impregnation reagent. This is because of the strong dehydration anity of phosphoric, which leads to a greater surface area and hence greater adsorptive capacity represented by the iodine number. The average value for the iodine number was 360, which is in agreement with the average value obtained by Girgis and El-Hendawy (2002), compared with an average of 300 when ZnCl 2 was used. Eect of activation temperature on the iodine number. As can be seen from Fig. 8, the iodine number increases signif- icantly with increase in activation temperature. The in- crease in activation temperature increases the micro-pore development (Bacaoui et al., 2001), which increases the adsorptive capacity of the activated carbon. Similar results were obtained by other researchers (Girgis and El-Hen- dawy, 2002; Moreno-Castilla et al., 2001). Eect of impregnation ratio on the iodine number. Fig. 9 shows the eect of changing the impregnation ratio on the iodine number for two dierent temperatures and two Fig. 7. The relation between activation time and iodine number using chemical activation at T a = 800 C, dp = 0.710.85 and IR = 0.4. Fig. 8. The relation between activation temperature and iodine number using H 3 PO 4 . N.M. Haimour, S. Emeish / Waste Management 26 (2006) 651660 657 dierent particle size ranges. The highest iodine number was obtained at an impregnation ratio of 0.4 and a temper- ature of 800 C, when phosphoric acid was used as the impregnation reagent. By increasing the impregnation ratio at the same temperature, the iodine number decreased sharply and an oscillation is noticed for all of the cases but more clearly for a temperature of 800 C. The experi- ment of IR = 0.4 was repeated twice because the results seem to be abnormal; however, similar results were ob- tained. This trend was obtained by Abdi et al. (2001) for activation of nutshells using ZnCl 2 . This trend means that by increasing the impregnation ratio there is a transfer from one type of pores to another. For the high tempera- ture case and when using H 3 PO 4 , another phenomena could have occurred where phosphorus-bearing species leave the carboneous surface and a disintegration of the structure of the activated carbon occurs; therefore, the iodine number of the activated carbon has been decreased. The development of the microporosity of the activated car- bon is aected, mainly, by temperature and IR. At a higher temperature (800 C), the maximum iodine number was obtained at a lower IR of 0.4. By decreasing the activation temperature to 400 C, a higher IR of 1.2 is required to obtain the maximum iodine number. Eect of particle size on the iodine number. By increasing the average particle size from 0.428 to 0.60 mm, the iodine number increased from 474 to 495. By further increasing the particle size to 0.78 mm, a decrease in iodine number to a value of 374 was obtained. By increasing the particle size to 1.2 mm, the iodine number increased to 458 as can be seen from Fig. 10. The decrease in iodine number with increasing particle size is due to increasing external surface area and decreasing of the diusion path; therefore, easier penetration of the viscous H 3 PO 4 to the core of the smaller particles compared with larger particles occurs. Further increase in the particle size does not have an appre- ciable eect on the iodine number. The average variation of the iodine number for the range of particle sizes from 0.78 to 1.2 mm is 6%, which is not abnormal for this type of experiment. The average variation of the iodine number for the whole range of particle sizes studied is 10%. The highest iodine number was 495 and was obtained when the average particle size was 0.60 mm and at an impregna- tion ratio of 0.6. Fig. 9. The relation between impregnation ratio and iodine number using H 3 PO 4 at t a = 60 min. Fig. 10. The relation between particle size and iodine number using H 3 PO 4 at T a = 800 C, t a = 60 min and IR = 0.4. 658 N.M. Haimour, S. Emeish / Waste Management 26 (2006) 651660 5. Conclusions Waste date stones were used as raw materials for the production of activated carbon using H 3 PO 4 as an activa- tion agent. The maximum value of the iodine number of the activated carbon produced in this work was about 495 under the following conditions: impregnation ratio 0.4, activation time 60 min, activation temperature 800 C, particle size 0.60 mm. The maximum iodine num- ber in this work is higher than the iodine number obtained by other researchers using ZnCl 2 . The iodine number in- creases signicantly with an increase in activation temper- ature. An oscillation in the value of the iodine number has been noticed with increasing impregnation ratio at the same temperature. The average variation of the iodine number for the whole range of particle sizes studied is 10%. The iodine number for the produced activated carbon was higher when phosphoric acid was used, compared to that when zinc chloride was used as impregnation reagent. How- ever, the yield obtained when H 3 PO 4 was used for acti- vation is lower than the yield obtained when ZnCl 2 was used. 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