Catalytic cracking of vegetable oil sludge by HY catalyst

Journal of Chemistry, Vol. 45 (6A), P. 285 - 291, 2007<br /> <br /> <br /> Catalytic cracking of vegetable oil sludge by HY<br /> catalyst<br /> Received 15 October 2007<br /> Van Dinh Son Tho1, Le Van Hieu1, Nguyen Anh Vu1, Nguyen Ngoc Triu2,<br /> Nguyen Dinh Tuyen2, Le Thi Hoai Nam*<br /> 1<br /> Faculty of Chemical Technology – Hanoi University of Technology<br /> 2<br /> Institute of Chemistry – Vietnam Academic of Science and Technology<br /> <br /> <br /> summary<br /> The alternative fuels that are derived from non-fossil source are very promising fuels for the<br /> future. Catalytic cracking of vegetable oil sludge is an advanced method for obtaining of bio-<br /> fuels. The huge waste in the vegetable oil manufacture could be converted to bio-fuel. Cracking of<br /> vegetable oil sludge by HY catalyst using MAT5000 instrument is a precious method for studying<br /> this catalytic cracking reaction. By catalytic cracking, the LPG gas, gasoline product, LCO and<br /> HCO products are also formed of vegetable oil sludge.<br /> <br /> <br /> I - Introduction II - Experimental<br /> <br /> Transportation fuels derived from renewable The vegetable oil sludge was obtained from<br /> sources are potentially good alternatives for Van Dao Company. Their composition is of<br /> conventional fossil-derived fuels [1]. Bio-fuel 61% of triglyceride and 37% of free fatty acid<br /> can be obtained from biomass (e.g. pyrolysis, and 2% impurities. The hydrocarbon chain of<br /> gasification) and from agricultural sources such triglyceride and free fatty acid is mainly C16<br /> as vegetable oil, cat fish, rubber seed oil, (30%) and C18 (36%) hydrocarbons. The others<br /> soybean oil … One of the potential sources consisted of C12-C17 hydrocarbon chain.<br /> could be able to convert to biofuel is a vegetable Micro-activity test MAT 5000 of Zeton-<br /> oil sludge. This waster is a major by-product of Canada was used for catalytic cracking of the<br /> vegetable oil factory. Transesterification method vegetable oil sludge. The procedures of catalytic<br /> of vegetable oil sludge could be able to convert cracking were done according to ASTM D5154<br /> into bio-fuel. The requirement of this method is testing method [8] and main parameters of<br /> required large amount of methanol [1]. The catalytic cracking condition were described in<br /> alternative method for the conversion of table 1.<br /> vegetable oil sludge to bio-fuel is catalytic<br /> cracking [2]. The objective of this paper is to The coke formation was in-situ evaluated by<br /> carried out the catalytic cracking of vegetable combustion with air and was quantified by CO2<br /> oil sludge using HY catalyst and using advanced infrared analyzer (1440 Gas Analyzer –<br /> analysis method to evaluate the products of the Servomex). The gas product was collected in a<br /> cracking reaction such as dry gas, LPG gas, brine water glass bottle and was analyzed by<br /> LCO (light cycle oil), HCO (high cycle oil) and Refinery gas analyzer – Trace GC -<br /> coke formation of catalytic cracking process ThermoElectro. The boiling distribution of the<br /> <br /> 285<br /> liquid product was determined by SIMDIST GC MESA International Technologies, Inc<br /> ThermoElectro system, detector FID integrated The calibration liquid for distillation<br /> TriPlus auto-sampler [8]. simulation is ASTM D2887 Calibration mix<br /> The calibration gas is RGA standard of (RESTEK).<br /> Table 1<br /> Vegetable oil catalytic cracking conditions<br /> Weight of catalyst 4.0600 (g)<br /> Catalyst Bed temperature 483.0 (oC)<br /> Total N2 Flowrate (Prepurge) 50(ml/s)<br /> Total N2 Flowrate (Reaction) 5 (ml/s)<br /> Total N2 Flowrate (Stripping) 25(ml/s)<br /> Oil Feed Temperature 50.0 (°C)<br /> Oil Feed Density @ 50.0°C 0.8747 (g/ml)<br /> Actual Volumetric Oil Feed 1.1600 (ml)<br /> N2 Pre-purge Time 15.0 (min)<br /> N2 Reaction Time 75 (sec)<br /> N2 Stripping Time 10.0 (min)<br /> <br /> III - Results and discussion<br /> <br /> The main results of catalytic cracking of vegetable oil sludge was showed in table 2<br /> (Catalytic cracking data), table 3 (the data of gas collection) and table 4 (Catalytic generation<br /> condition).<br /> <br /> Table 2<br /> Catalytic cracking data of vegetable oil sludge<br /> Catalyst Charge (g) 4.0600 Liquid product (g) 0.5964<br /> Oil Feed (g) 1.0147 Gas volume (ml) 1103.9<br /> Cat./ Oil (C/O)<br /> Ratio 4.001 Ambient temp. (°C) 30.0<br /> Catalyst Temp (°C) 483.0 Press of Collected Gas (torr) 788.1<br /> Oil Injection Time (sec) 75 Feed density (g/ml) 0.8747<br /> WHSV (1/h) 11.9959 Liq. prod. Density (g/ml) -----<br /> Corrected Gas Vol. (sml) 1031.4 Coke on catalyst (%) 1.4860<br /> Weight of carbon (g) 0.05724 Liq. hold-up (g) 0.0000<br /> Liquid yield (%) 58.779<br /> <br /> <br /> <br /> <br /> 286<br />  Table 3<br /> <br /> Conditions of gas collection<br /> Atm. Pressure 765.0 (torr abs)<br /> Room Temp. 30.0 (°C)<br /> Brine Weight 1304.0 (g)<br /> Brine Density 1.189 (g/ml)<br /> Gas Volume 1103.9 (ml)<br /> (cm) After gas sample<br /> Head of Brine Above Level in Gas Collection 26.3<br /> is collected.<br /> Pressure of Collected Gas 788.0 (torr abs)<br /> <br /> Table 4:<br /> Generation conditions of the catalyst<br /> Temperature 600oC<br /> Standard Volume of CO2 115.06(scm3,1 atm, 70F)<br /> Weight of Carbon, g 0.05724(g)<br /> Coke, Weight % of Oil Feed 6.036(%)<br /> Weight % Coke on Catalyst 1.468(%)<br /> <br /> The figure 1 is a chromatogram of gas products of cracking process and their components<br /> were shown in table 5. The first column was detected gas; the third column is a mole percent of each<br /> gas. The 4th column is a mole weight of the gas. The 5th column is a correction factor of gases. This<br /> factor was corrected to subtract out O2 and N2 from air. Cracked gas products exclude CO, CO2, O2,<br /> N2. CO and CO2 were excluded because of difficulty distinguishing between that from the<br /> atmosphere and that from the oil feed.<br /> 50000<br /> <br /> <br /> <br /> 40000<br /> <br /> <br /> <br /> 30000<br /> Signal (micromol)<br /> <br /> <br /> <br /> <br /> 20000<br /> <br /> <br /> <br /> 10000<br /> <br /> <br /> <br /> 0<br /> <br /> <br /> 0 10 20 30 40 50<br /> Retention time (minutes)<br /> <br /> Figure 1: Chromatogram of gas products<br /> <br /> 287<br />  Table 5<br /> GAS ANALYSIS<br /> Components in the MOLE<br /> gas products MOLE % MOL % GRAMS WEIGHT%<br /> OF OIL<br /> WT CORR. FEED<br /> <br /> 2-Methyl-2-<br /> Butene 2M2C4= 0.0000 70.13520 0.000 0.0000 0.000<br /> C6+ C6+ 0.5698 85.17021 0.570 0.0223 3.097<br /> Hydrogen H2 0.8076 2.01594 0.808 0.0007 0.104<br /> Propane C3 0.2455 44.09706 0.246 0.0050 0.691<br /> Propylene C3= 1.8508 42.08112 1.851 0.0358 4.971<br /> iso-Butane iC4 0.0687 58.12410 0.069 0.0018 0.255<br /> Propadiene Propadiene 0.0000 40.06533 0.000 0.0000 0.000<br /> n-Butane nC4 0.0651 58.12410 0.065 0.0017 0.242<br /> 1-Butene + iso-<br /> Butene 1C4= + iC4= 0.8050 56.10816 0.805 0.0208 2.883<br /> trans-2-Butene T2C4= 0.3924 56.10816 0.392 0.0101 1.405<br /> cis-2-Butene C2C4= 0.2673 56.10816 0.267 0.0069 0.957<br /> 1,3-Butadiene 1,3Butadiene 0.0136 54.09222 0.014 0.0003 0.047<br /> iso-Pentane iC5 0.0434 72.15114 0.043 0.0014 0.200<br /> n-Pentane nC5 0.0275 72.15114 0.028 0.0009 0.127<br /> Trans/Cis-2- T2C5= +<br /> Pentene ,C2C5= 0.0433 70.13520 0.043 0.0014 0.194<br /> 1-Pentene 1C5= 0.2532 70.13520 0.253 0.0082 1.133<br /> 3-Methyl-1-<br /> Butene 3M1C4= 0.0976 70.13520 0.098 0.0031 0.437<br /> Carbon Dioxide CO2 1.9608 44.00990 1.961 0.0397<br /> Ethylene C2= 0.8103 28.05408 0.810 0.0105 1.451<br /> Ethane C2 0.1754 30.07002 0.175 0.0024 0.337<br /> Oxygen O2 0.0000 31.99880 0.000<br /> Nitrogen<br /> (Total) N2 89.5309 28.01340 89.531<br /> Methane CH4 0.5573 16.04298 0.557 0.0041 0.571<br /> Carbon Monoxide CO 1.2712 28.01050 1.271 0.0164<br /> Cracked gas<br /> products) 7.094 0.1377 19.101<br /> Total (All) 99.86 28.0732<br /> Factor 1.00000 1.40734<br /> N2/O2 Ratio in Air 3.7619<br /> <br /> Figure 2 is a chromatogram of liquid products simulated distillation according to ASTM<br /> D2887. The horizontal axes are retention time and the temperature and the horizontal time is a TCS<br /> signal. Based on the results of figure 2, the evaluation the distillation distribution of liquid product<br /> used the software SIMDIST and the data is mentioned in Fig. 3 and table 6.<br /> <br /> 288<br />  Figure 3: Distillated distribution of liquid products<br /> Figure 2: Chromatogram of liquid<br /> products simulated distillation<br /> <br /> Table 6:<br /> <br /> Liq. Prod, IBP less than 200 °C<br /> Simulated Distillation (Wt% of Liquid Product) 16.5%<br /> Liq. Prod, IBP less than 221 °C<br /> (Wt% of Liquid Product) 19.5%<br /> Liq. Prod, IBP less than 343 °C<br /> (Wt% of Liquid Product) 65.9%<br /> <br /> Based on the tables and the data, the final results of catalytic cracking of vegetable oil<br /> sludge are shown in table 7. The material balance of the reaction is calculated by the quantity of the<br /> feed stock converted into gas, liquid and coke. The materials balance of catalytic cracking is 83.9%.<br /> Cause of the error of the analysis and experiments therefore it is not to reach 100%. The normalized<br /> results of this table were converted based on the real materials balance and theoretically value<br /> (100%).<br /> Dry gas = Total (H2, CO, CO2, C1, C2 and C2=)<br /> LPG = Total ( C3, C3=, iC4, nC4, C4=, Propandien)<br /> Gasoline ={[((IBP(