Available online at http://ijcpe.uobaghdad.edu.iq and www.iasj.net Iraqi Journal of Chemical and Petroleum Engineering Vol.20 No.4 (December 2019) 15 – 20 EISSN: 2618-0707, PISSN: 1997-4884 Corresponding Authors: Name: Shafaa D. Mohammed , Email: shafaadhyaa@gmail.com , Name: Muthana J. Ahmed, Email: muthannaj@yahoo.com IJCPE is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License. Enhanced conversion of Glycerol to Glycerol carbonate on modified Bio-Char from reed plant Shafaa D. Mohamme and Muthana J. Ahmed University of Baghdad - College of Engineering –chemical engineering department Abstract The surplus glycerol produced from biodiesel production process as a by-product with high quantity can be considered as a good source to prepare glycerol carbonate (GC) whereas with each 1000 kg from biodiesel obtains 100 kg from glycerol. The aim of this paper is studying the possibility of converting the glycerol to glycerol carbonate using the bio-char prepared from reed plant as a catalyst. The catalyst was prepared at different temperatures ranging from 400-800°C. The results show that the bio- char prepared at 700 ᴼC gives a best one among the others types of bio-char, but the yield was increased to 67.80% using prepared bio-char and when the catalyst promoted by sodium hydroxide, the obtained yield reached to 98.3% and complete conversion. In this study, the complete conversion was achieved at optimum conditions which were 60ᴼC, 90 min, 3:1 DMC:G , 3%wt. catalyst loading and using bio-char modified with 3 molar NaOH . Keywords: Glycerol Carbonate, Glycerol, Pyrolysis, Trans esterification reaction, Biochar Received on 07/07/2019, Accepted on 15/09/2019, published on 30/12/1029 https://doi.org/10.31699/IJCPE.2019.4.3 1- Introduction Biodiesel has involved significant consideration as an alternative to the fossil fuel resources. U.S. government and European Union have broadcast obligatory rules for the use of biodiesel in transportation on-road diesel and fuel. Though, production of biodiesel by plant oil methanolysis produces large quantity of glycerol (about 10 wt. %) as an inevitable by-product that has to be valorized to progress the monetary attractiveness of biodiesel. Consequently, transformation of glycerol into valuable products is of excessive significance. So far, numerous routes for glycerol translation have been stated like: reduction, selective oxidation, esterification, etherification, transesterification, and polymerization ‎[1]. Biodiesel is a harmless fuel with great biodegradability, better lubrication, and combustion efficiency. It can be formed from animal fats, oils, algal, and plant ‎[2]. Usually, 1 mol of triglyceride containing fats and oils reacted with 3 mol of alcohol particularly methanol to provide 3 mol of fatty acid methyl ester fame that is named biodiesel, and 1 mol of glycerol result ‎[3]. Therefore, the creation of every 1000 kg of biodiesel yields by-product of glycerol around 100 kg ‎[4]. Biodiesel production in 2016 reached 37 billion gallons as indicated by Oil World's gauge. So, around 4 billion gallons of glycerol will be delivered that year ‎[5]. It is usually recognized that glycerol has an extensive diversity of applications and usages like: pharmaceutical, perfumery, food, cosmetic, and coating ‎[6]. Furthermore, glycerol itself is very inexpensive and most use needs added refining process. Later, the glycerol transformation to other important synthetic substances like esters of glycerol, glycerol carbonate, propane diols, glyceric acid, and acrolein will create included an incentive for glycerol, yet additionally advance biodiesel generation ‎[5] ‎[7] ‎[8]. Glycerol is a non-flammable, non-toxic, readily biodegradable, water-soluble viscous liquid which is produced in the modern oleo chemical industry as a coproduct via a variety of processes including alcoholysis, saponification, as well as dedicated synthesis processes from propene and fermentation of sugars ‎[9],‎[10]. Lately, scientists have changed Glycerol into a multitude of high valuable substances like propanediols, ethers, glycerol carbonate (GC), and bulk chemicals ‎[11]. (GC) is an important multi-functional complex used as additive, solvent, and creates a block in substitute chlorine-free procedures ‎[12]. GC is such a substance that has been extensively used in gas-separation membranes, paints, and solvent for therapeutic research and personal care products due to its low flammability, worthy bio-degradability, low toxicity, slight viscosity, high boiling point, and water solubility. Also, GC has strained greatly care in the few last year’s owing to its possible manufacturing uses in the preparation of polyurethanes ‎[13]. For these significant features, it detections many uses in diverse industrial parts, particularly as a glacial great hot solvent or middle in organic syntheses (i.e., synthesis of additional polymeric and polycarbonates constituents in https://doi.org/10.31699/IJCPE.2019.4.3 S. D. Mohammed and M. J. Ahmed / Iraqi Journal of Chemical and Petroleum Engineering 20,4 (2019) 15 - 20 61 the plastics arena employed in plastics, textile, cosmetics, and pharmaceutical industries), as a forerunner in biomedical uses and as a protection group in carbohydrate chemistry. It is also used as a constituent in membranes for instead of ethylene, in the synthesis of polyurethanes, gas separation, and in the production of surfactants, propylene carbonates. Finally, glycerol carbonate and its derivatives it reflected to be a green extra for significant petro- derivative compounds (propylene carbonate or ethylene carbonate) ‎[14]. As described previously in the previous studies, glycerol can also directly or indirectly be converted to glycerol carbonate via a number of routes reacting with a “CO” source. These sources include, urea, ethylene carbonate, alkyl carbonates, as well as CO2 ‎[10]. The drawbacks of formation GC from urea and glycerol achieved by creation great quantities of ammonia and the difficulty in extrication the undesired by-products such as: biuret and isocyanic acid. Glycerol carbonate may be produced from ethylene carbonate and glycerol via transesterification reaction but the high boiling points of ethylene glycol as a by-product which makes the separation of products hard. Comparison with these ways, transesterification of dimethyl carbonate (DMC) with glycerol for GC preparation is reflected as the talented and most preferable method for industrial use due to the easy separation of byproduct, mild reaction conditions, high GC produce, and simple process ‎[1]. A wide range of catalytic systems have demonstrated effective synthesis of glycerol carbonate, including both heterogeneous and homogeneous catalysts as well as enzymatic processes. The development of heterogeneous catalysts with worthy strength and high action is extremely wanted ‎[15]. Between the probable catalysts which can be used, bio-char achieve high performance for valorization, prepared by pyrolysis method from utilization of renewable source (reed plant) was used to catalyze transesterification reaction and it can be considered a highly efficient heterogeneous catalyst easy to separate and recycle. Fig. 1. Transesterification reaction to produce glycerol carbonate 2- Experimental Work 2.1. Char Manufacturing Catalyst produced depending on pyrolysis technique, char was used to activate the reaction which was manufactured from reed plant as raw material. Firstly, Reed plant was washed twice with deionized water instead of raw water to prevent increasing impurities in pore sites then dried for 6 hr by dryer under (110 ˚C) before uses. Then it was cut, crushed and grind, after grinding the reed plant particles sieved by sieve size (600 and 1200) micrometer to obtain the particle size around (600 – 1200) micrometer, bio-char prepared by pyrolysis process under different temperature from 400 - 800 ˚C for 1 hr in absence or very low oxygen . Grinding and sieving to size (600 and 1200) micrometer biochar (400-800) ᴼC Fig. 2. Reed plant particles and prepared bio-char 2.2. Characterization a. BET and pore volume The surface area and pore volume measurement were performed by the Ministry of Oil, Petroleum R and D center by using ASTM D1993 accelerated surface area and porosimetry system. The knowledge of the specific surface, is of great importance in the characterization of a powder or a solid (extruded or beads), regardless of the areas of application. It helps to improve the control of the reactivity of a sample when it is in the presence of other materials. In the BET measurement, the mixture of nitrogen with helium will pass through a channel for thermal conductivity detector, the detector to sample flow through a glass cell and then pass into analytical channel that is a thermal conductivity detector. Sign of detector was indicated by microprocessor control board, and then saved in a memory file. The procedure of test began when degassing the sample by a carrier gas at a programming temperature. During the drying of operator transfer the holder of the sample to the analytical port and then fitted them with specified place by basis quick fit connectors. Turning on the bottom should raise the nitrogen flask carriage will initiate the analysis. Desorption and adsorption of the gas measured with a highly sensitive thermal conductivity detector. High sensitivity will be used for a low surface area begin from 0.1 m2/g. If the sample with the large surface area, then the thermal conductivity detector give wide range of signal response. S. D. Mohammed and M. J. Ahmed / Iraqi Journal of Chemical and Petroleum Engineering 20,4 (2019) 15 - 20 61 2.3. Glycerol Carbonate Production Procedure The reaction of glycerol and dimethyl carbonate was performed in a three neck around bottom flask reactor ( of 50 ml) equipped with a condenser, and established in a water bath over hot plate with magnetic stirrer stirring with (150 rpm), and two thermometer for monitoring temperature one of them in flask and the another one in water bath. Char prepared at various pyrolysis temperatures used to catalyze the reaction. The mixture of biochar catalyst and glycerol was heated to reach the reaction temperature and then added dimethyl carbonate. The reaction performed at conditions 3:1 DMC :G ratio,60 ˚C ,90 min ,150 rpm and 3% weight percent catalyst loading ,these conditions selected as a mid-points in the studied variables 5:1 DMC :G ratio, (40 - 80) ˚C , (30 -150) min , (1 – 5)% weight percent catalyst loading and 150 rpm. HPLC (high performance liquid chromatography) was used for analyzing purpose. Fig. 3. Photographic picture of Experimental work for GC synthesis 2.4. Catalyst Modification Procedure Modification of catalyst was required in case of want to meet complete conversion and highly yield due to enhance the surface area of active sites. It is important to investigate the effect of base molar concentration on improvement the catalyst activity ‎[16] to give high glycerol carbonate yield, different molar concentration (1, 2 and 3) M from NaOH was used in char modification. Bio-char was modified as described in ‎[16] by immersing (1.0 g) of bio-char in 20 mL of different molar concentration (1 - 3) Molarity sodium hydroxide solution, then was shaked for 24 hr at 120 rpm. Filtration was performed for solid separation from liquid, after that washed with deionized water till neutral pH was obtained and dried for 24 hr at 110 ᴼC. The modified bio-char used in the study with operating condition (3:1 ratio DMC: Glycerol, 60˚C, 90 min, 150 rpm and 3% weight per cent catalyst) these conditions selected as a mid-points in the studied variables 5:1 DMC :G ratio, (40 - 80) ˚C , (30 -150) min , (1 – 5)% weight percent catalyst loading and 150 rpm to investigate which molar concentration of NaOH have more effect increase the catalytic activity of bio-char. 3- Results and discussion 3.1. Effect of Pyrolysis Temperature on Bio-Char Yield% Fig. 4. Effect of pyrolysis temperature on bio-char yield% Preliminarily the influence of pyrolysis temperature on the yield of bio-char must be investigated by study effect of different temperatures on prepared char from reed plant. Fig. 4 shows the results of the present study and show the effect of difference in pyrolysis temperature on 2 g of reed particles, obviously there is a continuous reduction in the weight of char and this is observed at each 100ᴼ C which was increased. When the reed particles combusted at pyrolysis temperature 400ᴼ C the char yield gained 33.75% and when the pyrolysis temperature increased to 500ᴼ C and the yield obtained which decreased dramatically to 31.55%. This gives an indication that when the pyrolysis temperature increased the volatile element like hydrogen, nitrogen decreased also the water content will decrease with temperature increasing. When the pyrolysis temperature became 600ᴼC the char yield slightly decreased to 29.59%, In temperature 700ᴼC and 800ᴼC the yield obtained was 21.36% ,9.27% respectively, so approximately the char yield reached to the quarter yield of char which was prepared at 400ᴼC. Increasing in pyrolysis temperature causes a in rise the ash and fixed C contents, also lowering of volatile materials content (hydrogen and oxygen) readily due to the weaker bonds in the volatile constituents ‎[17]. Optimum bio char yield obtained in this study at the lower pyrolysis temperature 400ᴼ C. 0.00% 5.00% 10.00% 15.00% 20.00% 25.00% 30.00% 35.00% 40.00% 400 600 800 1000 C h a r Y ie ld % Temperature,ᴼC S. D. Mohammed and M. J. Ahmed / Iraqi Journal of Chemical and Petroleum Engineering 20,4 (2019) 15 - 20 61 Bio-char yield% The yield of char used for indication the process efficiency for the chemical activation process. The char yield was calculated as the weight percentage of the manufactured char divided by the weight of the grinded reed. Y𝑖𝑒𝑙𝑑% = wei/weig ×100 𝑤𝑒𝑖 (𝑔) is weight of char 𝑤𝑒𝑖𝑔 (g) is weight of 𝑟𝑎𝑤 material 3.2. Effect of Prepared Char at Various Pyrolysis Temperatures on GC Yield% and G Conversion% Fig. 5. Effect of prepared char at various pyrolysis temperatures on GC yield% and G conversion% After preparation of char at different pyrolysis temperature from 400ᴼC to 800ᴼC, the catalytic activity of the prepared char was investigated by transesterification process of glycerol with dimethyl carbonate and to show the influence of prepared bio-char on glycerol carbonate yield and glycerol conversion. The reaction was carried out under mild conditions temperature 60ᴼ C, 3:1 DMC: G ratio, 150 rpm and 3% wt. catalyst loading in time of 90 min ,all results illustrate in Fig. 5. When the char was manufactured at 400 ᴼC , the obtained GC yield and G conversion was very low (below 20%),after that char was prepared with 500ᴼC used in catalyze the reaction to make a slight increasing in GC yield (19.683%) and G conversion (26.53%). GC yield and G conversion was obtained from catalyze the reaction with char prepared at pyrolysis temperature 600ᴼC were 20.48%, 34.17% respectively. The prepared char at 700ᴼC has been shown a dramatic increasing in yield and conversion until reach 54.16%, 69.81% respectively. In each increasing in bio-char preparation temperature causes dramatic increase in GC yield an G conversion this can belong to increasing the active sites numbers and catalytic surface area of bio-char catalyst causes increment in GC yield an G conversion . The Highest values for yield and conversion were obtained when the reaction catalyze with bio-char prepared with 800 ᴼC pyrolysis temperature but the difference in values of GC yield and G conversion between the two bio-char prepared at temperature (700 ᴼC and 800 ᴼC) is very slight and to reduce in energy and cost , the bio-char prepared at 700ᴼC used for catalyzing transesterification reaction .Finally to enhance the char activity ,the selected bio-char immersed in (0.1 M) HCL for 24 hr to remove impurities from char pores after that washed with deionized water for neutralization purpose to be ready for catalyzing glycerol transesterification reaction then found a good increasing in GC yield happened reach it to 67.8% and G conversion reached to 76.3%, the increment in GC yield and G conversion belonged to clearance the active sites from impurities when the char washed with (0.1 M) HCL. 3.3. Effect of Modified Bio-Char by Different NaOH Molar Concentration on GC Yield% and G Conversion% Fig. 6. Effect of different NaOH molar concentration on catalytic activity Fig. 6 explain all results of glycerol carbonate yield and glycerol conversion at different molar concentrations of NaOH under time 90 min , temperature 60 ᴼC, Dimethyl Carbonate : Glycerol ratio 3:1 DMC:G ratio and 3%wt. used from catalyst loading. From the figure observed that each increasing in NaOH concentration which was used for catalyst modification there was increasing in GC yield and G conversion. complete conversion of glycerol was achieved by enhancing the catalyst with 3 M NaOH also high yield of GC obtained 98.32%,the increment in yield belonged to enhancing the activity of catalyst when modified with sodium hydroxide base by increasing the number of hydroxyl group OH as described in ‎[18] and this was regarded as a major reason to initiate the reaction between the proton of weak acid from one of the two primary hydroxyl group of glycerol with the base catalyst ,this is mean in each increasing in NaOH concentration the hydrouxyl groups number increment and the GC yield and G conversion also increased . S. D. Mohammed and M. J. Ahmed / Iraqi Journal of Chemical and Petroleum Engineering 20,4 (2019) 15 - 20 61 3.4. Surface Area and Pore Volume The obtained BET surface area and total pores volume of prepared bio-char from reed plant particles are 214.1487 m 2 /g and 0.1204 cm 3 /g respectively, so the results show good surface characterization for transesterification process .The surface area and pore volume of char produced from different feedstock clarified in the table below: Table 1. Specifications of char from different feedstock Feedstock Surface Area Pore Volume References Cotton stalk 224 0.070 ‎[19] Pine wood 209.6 0.009 ‎[20] Bamboo 351 0.130 ‎[21] 4- Conclusion Reaction of glycerol with dimethyl carbonate is performed by catalyzing the reaction with bio-char as a heterogeneous catalyst. Char catalyst prepared from reed plant as a natural source by pyrolysis technique under different temperatures from 400°C to 800°C, in each increasing in pyrolysis temperatures the yield of char decrease. The Highest values for GC yield and G conversion were obtained when the reaction catalyze with bio-char prepared at 800 ᴼC pyrolysis temperature but the difference in values of GC yield and G conversion between the two prepared bio-char at temperatures (700 ᴼC and 800 ᴼC) is very slight also to reduce the energy cost select bio-char prepared at 700ᴼC. The char prepared at 700ᴼC give 54.16 % GC yield and 69.81% G conversion. when the selected catalyst immersed in (0.1 M) HCL for 24 hr and washed with deionized water for neutralization purpose found a good increasing in GC yield happened reach it to 67.8% and conversion reached to 76.3%. The catalyst modification with 3 M NaOH shows enhance in catalyst activity to give high yield of GC reached to 98.32% and complete conversion achieved, all the reactions carried out under conditions 90 min, 60 ᴼC, 3:1 DMC:G ratio and 3%wt. used from catalyst loading. References [1] Liu, Z., Wang, J., Kang, M., Yin, N., Wang, X., Tan, Y. and Zhu, Y., 2014. Synthesis of glycerol carbonate by transesterification of glycerol and dimethyl carbonate over KF/γ-Al2O3 catalyst. Journal of the Brazilian Chemical Society, 25(1), pp.152-160. [2] Witoon, T., Bumrungsalee, S., Vathavanichku, P., Palitskun, S., Saisriyoot, M. and Faungnawakij, K. (2014). Biodiesel production from transesterification of palm oil with methanol over CaO supported on bimodal meso-macroporous silica catalyst. Bioresource Technology. 156: 329-334. [3] Roschat, W., Siritanon, T., Yoosuk, B. and Promarak, V. (2016). Biodiesel production from palm oil using hydrated lime-derived CaO as a low-cost basic heterogeneous catalyst. Energy Conversion and Management. 108: 459-467. [4] Malyaadri, M., Jagadeeswaraiah, K., Sai-Prasad, P. S. and N. Lingaiah. (2011). Synthesis of glycerol carbonate by transesterification of glycerol with dimethyl carbonate over Mg/Al/Zr catalysts. Applied Catalysis A: General. 401: 153-157. [5] Rastegari, H. and Ghaziaskar, H. S. (2015). From glycerol as the byproduct of biodiesel production to value-added monoacetin by continuous and selective esterification in acetic acid. Journal of Industrial and Engineering Chemistry. 21: 856-861. [6] Roschat, W., Kacha, M., Yoosuk, B., Sudyoadsuk, T. and Promarak, V. (2012). Biodiesel production based on heterogeneous process catalyzed by solid waste coral fragment. Fuel. 98:194-202. [7] Zheng, L., Xia, S., Lu, X. and Hou, Z. (2015). Transesterification of glycerol with dimethyl carbonate over calcined Ca-Al hydrocalumite. Chinese Journal of Catalysis. 36: 1759-1765. [8] Zhou, Y., Ouyang, F., Song, Z. B., Yang, Z. and Tao, D. J. (2015). Facile one-pot synthesis of glycidol from glycerol and dimethyl carbonate catalyzed by tetraethylammonium amino acid ionic liquids. Catalysis Communications. 66: 25-29. [9] Dibenedetto, A., Angelini, A., Aresta, M., Ethiraj, J., Fragale, C. and Nocito, F. (2011). Converting wastes into added value products: from glycerol to glycerol carbonate, glycidol and epichlorohydrin using environmentally friendly synthetic routes. Tetrahedron. 67: 1308-1313. [10] Stewart, J.A., 2015. Towards Green Cyclic Carbonate Synthesis: Heterogeneous and Homogeneous Catalyst Development (Doctoral dissertation, Utrecht University). [11] Du, Y., Gao, J., Kong, W., Zhou, L., Ma, L., He, Y., Huang, Z. and Jiang, Y., 2018. Enzymatic Synthesis of Glycerol Carbonate Using a Lipase Immobilized on Magnetic Organosilica Nanoflowers as a Catalyst. ACS Omega, 3(6), pp.6642-6650. [12] Chiappe, C. and Rajamani, S., 2011. Synthesis of glycerol carbonate from glycerol and dimethyl carbonate in basic ionic liquids. Pure And Applied Chemistry, 84(3), pp.755-762. [13] Algoufi, Y. T., Akpan, U. G., Asif, M. and Hameed, B. H. (2014). One-pot synthesis of glycidol from glycerol and dimethyl carbonate over KF/sepiolite catalyst. Applied Catalysis A: General. 487: 181-188. [14] Wang, S., Hao, P., Li, S., Zhang, A., Guan, Y. and Zhang, L., 2017. Synthesis of glycerol carbonate from glycerol and dimethyl carbonate catalyzed by calcined silicates. Applied catalysis a: general, 542, pp.174-181. [15] Wang, Y., Liu, C., Sun, J., Yang, R. and Dong, W., 2015. Ordered mesoporous BaCO 3/C-catalyzed synthesis of glycerol carbonate from glycerol and http://www.scielo.br/scielo.php?pid=S0103-50532014000100019&script=sci_arttext&tlng=pt http://www.scielo.br/scielo.php?pid=S0103-50532014000100019&script=sci_arttext&tlng=pt http://www.scielo.br/scielo.php?pid=S0103-50532014000100019&script=sci_arttext&tlng=pt http://www.scielo.br/scielo.php?pid=S0103-50532014000100019&script=sci_arttext&tlng=pt http://www.scielo.br/scielo.php?pid=S0103-50532014000100019&script=sci_arttext&tlng=pt https://www.sciencedirect.com/science/article/pii/S0960852414001011 https://www.sciencedirect.com/science/article/pii/S0960852414001011 https://www.sciencedirect.com/science/article/pii/S0960852414001011 https://www.sciencedirect.com/science/article/pii/S0960852414001011 https://www.sciencedirect.com/science/article/pii/S0960852414001011 https://www.sciencedirect.com/science/article/pii/S0960852414001011 https://www.sciencedirect.com/science/article/pii/S0196890415010560 https://www.sciencedirect.com/science/article/pii/S0196890415010560 https://www.sciencedirect.com/science/article/pii/S0196890415010560 https://www.sciencedirect.com/science/article/pii/S0196890415010560 https://www.sciencedirect.com/science/article/pii/S0196890415010560 https://www.sciencedirect.com/science/article/abs/pii/S0926860X11002882 https://www.sciencedirect.com/science/article/abs/pii/S0926860X11002882 https://www.sciencedirect.com/science/article/abs/pii/S0926860X11002882 https://www.sciencedirect.com/science/article/abs/pii/S0926860X11002882 https://www.sciencedirect.com/science/article/abs/pii/S0926860X11002882 https://www.sciencedirect.com/science/article/abs/pii/S1226086X14002214 https://www.sciencedirect.com/science/article/abs/pii/S1226086X14002214 https://www.sciencedirect.com/science/article/abs/pii/S1226086X14002214 https://www.sciencedirect.com/science/article/abs/pii/S1226086X14002214 https://www.sciencedirect.com/science/article/abs/pii/S1226086X14002214 https://www.sciencedirect.com/science/article/pii/S0016236112002736 https://www.sciencedirect.com/science/article/pii/S0016236112002736 https://www.sciencedirect.com/science/article/pii/S0016236112002736 https://www.sciencedirect.com/science/article/pii/S0016236112002736 https://www.sciencedirect.com/science/article/pii/S1872206715609159 https://www.sciencedirect.com/science/article/pii/S1872206715609159 https://www.sciencedirect.com/science/article/pii/S1872206715609159 https://www.sciencedirect.com/science/article/pii/S1872206715609159 https://www.sciencedirect.com/science/article/pii/S1566736715001065 https://www.sciencedirect.com/science/article/pii/S1566736715001065 https://www.sciencedirect.com/science/article/pii/S1566736715001065 https://www.sciencedirect.com/science/article/pii/S1566736715001065 https://www.sciencedirect.com/science/article/pii/S1566736715001065 https://www.sciencedirect.com/science/article/abs/pii/S0040402010017461 https://www.sciencedirect.com/science/article/abs/pii/S0040402010017461 https://www.sciencedirect.com/science/article/abs/pii/S0040402010017461 https://www.sciencedirect.com/science/article/abs/pii/S0040402010017461 https://www.sciencedirect.com/science/article/abs/pii/S0040402010017461 https://www.sciencedirect.com/science/article/abs/pii/S0040402010017461 https://dspace.library.uu.nl/handle/1874/325586 https://dspace.library.uu.nl/handle/1874/325586 https://dspace.library.uu.nl/handle/1874/325586 https://dspace.library.uu.nl/handle/1874/325586 https://pubs.acs.org/doi/abs/10.1021/acsomega.8b00746 https://pubs.acs.org/doi/abs/10.1021/acsomega.8b00746 https://pubs.acs.org/doi/abs/10.1021/acsomega.8b00746 https://pubs.acs.org/doi/abs/10.1021/acsomega.8b00746 https://pubs.acs.org/doi/abs/10.1021/acsomega.8b00746 https://www.degruyter.com/view/j/pac.2012.84.issue-3/pac-con-11-07-06/pac-con-11-07-06.xml https://www.degruyter.com/view/j/pac.2012.84.issue-3/pac-con-11-07-06/pac-con-11-07-06.xml https://www.degruyter.com/view/j/pac.2012.84.issue-3/pac-con-11-07-06/pac-con-11-07-06.xml https://www.degruyter.com/view/j/pac.2012.84.issue-3/pac-con-11-07-06/pac-con-11-07-06.xml https://www.sciencedirect.com/science/article/abs/pii/S0926860X14005687 https://www.sciencedirect.com/science/article/abs/pii/S0926860X14005687 https://www.sciencedirect.com/science/article/abs/pii/S0926860X14005687 https://www.sciencedirect.com/science/article/abs/pii/S0926860X14005687 https://www.sciencedirect.com/science/article/abs/pii/S0926860X14005687 https://www.sciencedirect.com/science/article/abs/pii/S0926860X17302193 https://www.sciencedirect.com/science/article/abs/pii/S0926860X17302193 https://www.sciencedirect.com/science/article/abs/pii/S0926860X17302193 https://www.sciencedirect.com/science/article/abs/pii/S0926860X17302193 https://www.sciencedirect.com/science/article/abs/pii/S0926860X17302193 https://link.springer.com/article/10.1007/s11426-014-5173-0 https://link.springer.com/article/10.1007/s11426-014-5173-0 https://link.springer.com/article/10.1007/s11426-014-5173-0 S. D. Mohammed and M. J. Ahmed / Iraqi Journal of Chemical and Petroleum Engineering 20,4 (2019) 15 - 20 02 dimethyl carbonate. Science China Chemistry, 58(4), pp.708-715. [16] Wan, M.-W., Petrisor, I. G., Lai, H.-T., Kim, D., & Yen, T. F., (2004)," Copper Adsorption Through Chitosan Immobilized On Sand To Demonstrate The Feasibility For In Situ Soil Decontamination", Carbohydrate Polymers, 55(3), 249–254. [17] Paethanom, A., & Yoshikawa, K., (2012),"Influence Of Pyrolysis Temperature On Rice Husk Char Characteristics And Its Tar Adsorption Capability", Energies, 5(12), 4941–4951. [18] Paul,J. and Shunnian,Wu.,2004,"Acid/Base- Treated Activated Carbon:Characterization of Functional Groups and Metal Adsorptive Properties",Langmuir,vol 20,pp. 2233-2242. [19] Zhang, X., Zhang, S., Yang, H., Feng, Y., Chen, Y., Wang, X., Chen, H., 2014. Nitrogen enriched biochar modified by high temperature CO2-ammonia treatment: characterization and adsorption of CO2. Chem. Eng. J. 257, 20-27. [20] Wang, S., Gao, B., Zimmerman, A.R., Li, Y., Ma, L., Harris, W.G., Migliaccio, K.W., 2015b. Removal of arsenic by magnetic biochar prepared from pinewood and natural hematite. Bioresour. Technol. 175, 391-395. [21] Yao, Y., Gao, B., Fang, J., Zhang, M., Chen, H., Zhou, Y., Creamer, A.E., Sun, Y., Yang, L., 2014. Characterization and environmental applications of clayebiochar composites. Chem. Eng. J. 242, 136-143. تحسين تحويل الكميسرول الى كميسرول كاربونيت بأستخدام الفحم الحيوي المحسن نبات القصبوالمنتج من شفاء ضياء و مثنى جبار قسم اليندسة الكيمياوية-كمية اليندسة-جامعة بغداد الخالصة النتاج مادة عد الكميسرول الفائض من عمميات انتاج البايوديزل كمنتج ثانوي بكميات ىائمو مصدر جيد ي .كيموغرام من الكميسرول 011قريبا كيموغرام من البايوديزل يصاحبيا ت 0111الكميسرول كاربونيت حيث ان كل اليدف من ىذا البحث ىو دراسة احتمالية تحويل الكميسرول الى كميسرول كاربونيت بأستخدام الفحم الحيوي وقد درجة مئوية °800الى400.يتم تحضير العامل المساعد بحرارات مختمفو من المحضر من نبات القصب درجة مئوية يعد االفضل من بين انواع الفحم ° 700اظيرت النتائج ان الفحم المحضر بالدرجو الحراريو % بأستخدام الفحم الحيوي المحضر وعندما تم تحسين العامل 67 ,01.لكن االنتاجية زادت الى المحضره % وتحول تام .في ىذه الدراسة يتم 98.3المساعد باستخدام ىيدروكسيد الصوديوم فأن االنتاجية وصمت الى % نسبة 3, نسبة الكميسرول:الداي مثيل كاربونيت 1:3دقيقة ، 90درجة مئوية ،°60تحقيق تحول تام بظروف .من ىيدروكسيد الصوديوم موالري 3واستخدام الفحم الحيوي المحسن ب تحميل العامل المساعد حمل الحراري, الفحم الحيوي.الكممات الدالة: كميسرول كاربونيت, كميسرول, الت https://link.springer.com/article/10.1007/s11426-014-5173-0 https://link.springer.com/article/10.1007/s11426-014-5173-0 https://www.sciencedirect.com/science/article/pii/S0144861703002777 https://www.sciencedirect.com/science/article/pii/S0144861703002777 https://www.sciencedirect.com/science/article/pii/S0144861703002777 https://www.sciencedirect.com/science/article/pii/S0144861703002777 https://www.sciencedirect.com/science/article/pii/S0144861703002777 https://www.mdpi.com/1996-1073/5/12/4941 https://www.mdpi.com/1996-1073/5/12/4941 https://www.mdpi.com/1996-1073/5/12/4941 https://www.mdpi.com/1996-1073/5/12/4941 https://pubs.acs.org/doi/abs/10.1021/la0348463 https://pubs.acs.org/doi/abs/10.1021/la0348463 https://pubs.acs.org/doi/abs/10.1021/la0348463 https://pubs.acs.org/doi/abs/10.1021/la0348463 https://www.sciencedirect.com/science/article/pii/S1385894714009036 https://www.sciencedirect.com/science/article/pii/S1385894714009036 https://www.sciencedirect.com/science/article/pii/S1385894714009036 https://www.sciencedirect.com/science/article/pii/S1385894714009036 https://www.sciencedirect.com/science/article/pii/S1385894714009036 https://www.sciencedirect.com/science/article/pii/S0960852414015363 https://www.sciencedirect.com/science/article/pii/S0960852414015363 https://www.sciencedirect.com/science/article/pii/S0960852414015363 https://www.sciencedirect.com/science/article/pii/S0960852414015363 https://www.sciencedirect.com/science/article/pii/S0960852414015363 https://www.sciencedirect.com/science/article/pii/S1385894713016434 https://www.sciencedirect.com/science/article/pii/S1385894713016434 https://www.sciencedirect.com/science/article/pii/S1385894713016434 https://www.sciencedirect.com/science/article/pii/S1385894713016434