OSAKA GAS FOUNDATION OF INTERNATIONAL CULTURAL EXCHANGE RESEARCH CENTER FOR SCIENCE AND TECHNOLOGY UNIVERSITY OF INDONESIA RESEARCH GRANT PROGRAM FINAL REPORT A Sustainable Production of C 3 Hydrocarbons from a Renewable Resource with Zeolite Catalyst Principle Investigator Setiadi Department Of Chemical Engineering Faculty Of Engineering - University Of Indonesia
Resources Non-renewable Source Renewable Source Fossil Resources (Petroleum crude Oil) Scope of this Research Work Biomass Source Catalytic Cracking Unit (FCC) Target Compounds C 3 hydrocarbons Acetone, Butanol Biomass-derived liquid From fermentation Products Fuel Polypropylene Aromatics products Refrigerant MTBE Catalytic Reaction Process? Catalyst? HZSM-5 & Nat. Zeolite Reaction condition? A schematic route of C 3 hydrocarbons production from a renewable resource
Pore Dimension for some Zeolites Similar pore channel Structure Zeolite Y Mordenite Offreite ZSM-5 Ferrierite Erionite Pore size, nm.72.67 x.7.64.54 x.56.43 x.55.52 x.36 Natural Zeolite Malang, East Java High mordenite-zeolite type Structure (Melia-ITB, 1999)
Reactor for C 3 production
Characterization of Fresh Zeolite RESULTS AND DISCUSSION Amount of N2 adsorbed (cc/g, STP) 12 1 8 6 4 2..2.4.6.8 1. Relative Pressure, p/po Amount of N 2 adsorbed vs relative pressure as the result of the N 2 adsorption technique for HZSM-5 catalyst
1 75 NZM 25wt%B2O3/NZM 15wt%B2O3/NZM 5wt%B2O3 addition Amount of N2 Adsorbed (ml/g, STP) 5 25,2,4,6,8 1 Relative Pressure, p/p o Amount of N 2 adsorbed vs relative pressure as the result of the N 2 adsorption technique for all sample HNZ modified by boron oxide addition.
Amount of N2 adsorbed ( cc/g STP) 12 1 8 6 4 2 5 1 15 2 Adsorbed layer, t(å) The slope of straigt line to determine the external surface Halsey equation, t(nm)= 3.54 x (-ln-5/(ln(p/po)) 1/3 x 1-1 Fig. 6 The plot between adsorbed layer (t) vs Amount of N2 adsorbed for determining the total area, micropore area for HZSM-5 catalyst sample
1 NZM Amount of N2 adsorbed ( cc/g STP) 75 5 25 5wt% B2O3 addition 15wt% B2O3 addition 25wt%B2O 3 addition 5 1 15 2 Thickness of adsorbed layer, t (angstroom) The plot between adsorbed layer (t) vs Amount of N 2 adsorbed for determining the total area, micropore area for natural zeolite sample
4 3 Surface area, m 2 /g 2 1 1 2 3 % B 2 O 3 content (%wt) The decreasing of the Total Surface Area ( ) or Micropore Area ( ) due to the Boron Oxide impregnation onto Natural Zeolite
SEM photograph of HZSM-5 with magnification of 5x
Table 3 Effect of Temperature on the Reaction for C 3 Production over H-ZSM-5 Temperature [ o C] 45 4 35 Acetone conversion [%] 98.6 98.9 7.8 Product distribution [ % w ] CO 1.27 1.19.36 CO 2 5.3 3.88 7.56 CH 4.35.4.15 C 2 H 4 2.59.69.38 C 2 H 6.67.93. C 3 H 6 3.94.7 1.34 C 3 H 8 9.2 13.22.11 C 4 aliphatics 13.2 6.89 48.16 C 3 Hydrocarbons 25.98 2.81 49.61 Liquid Hydrocarbon 63.84 71.4 58.6
1 Selectivity [ % Carbon] 8 6 4 2 2 4 6 8 1 Time on stream [h] C 3 and liquid oil selectivity during 1 h time of stream resulted from acetone conversion using HZSM-5. Symbols:, Liquid oil selectivity and, C 3 - selectivity
Table 5 Effect of Boron oxide loading into HNZ catalyst on Product Reaction Catalyst HNZ 5 wt% B 2 O 3 -HNZ 15 wt%b 2 O 3 - HNZ 25 wt%b 2 O 3 - HNZ Temperature [ o C] 4 4 4 Conversion [%] 98.9 98.4 95.8 2.3 Product distribution (% w) CO.31.63.65.36 CO 2 2.93 3.66 5.45 4.85 CH 4.21.27.3.1 C 2 H 4 1. 2.96 4.11.17 C 2 H 6.31.24.1. C 3 H 6 1.55 5.82 12.6 1.26 C 3 H 8 6.9 4.2 1.84. C 4 aliphatics 7.35 9.69 2.3 61.7 C 3 Hydrocarbons 15.8 19.53 34.74 62.96 Liquid Hydrocarbon 77.3 72.8 54.7 31.5
5 4 C3-C4 Yield, %wt 4 3 2 1 3 2 1 Area, m 2 /g 1 2 3 % B 2 O 3 content (%wt) Plot of B 2 O 3 content vs C 3 yield and replotted surface area micropore area. Symbols: C 3 -yield, Total surface area, Micropore Area
1 8 C3-C4 sel. Liq. Product Sel Selectivity, wt% 6 4 2 2 4 6 8 1 12 Time On Stream, h Fig. 16 C 3 and liquid oil selectivity during 12 h time of stream resulted from acetone/butanol conversion using 15 wt%b 2 O 3 -HNZ.
Conclusions 1. An innovative way to establish a catalytic process for production of C 3 hydrocarbons from a mixture of acetone/butanol using H-ZSM-5 and Natural Zeolite with its modification by boron oxide addition has been systematically studied. 2. The characterization of HZSM-5 sample by XRD measurement indicates that this catalyst has a high crystallinity and microcrystal structure with the crystallites size 43 nm. The total surface area 321.8 m 2 /g, micropore area 29.4 m2/g with the external surface area 112.5 m 2 /g (total 426 m 2 /g) 3. The addition of boron oxide into the natural zeolites, however, have made the catalysts underwent a loss of surface area (both total or micropore area). It may be explained that the pore filling phenomenon of boron oxide which penetrates into the pore of HNZ, so that the total area or micropore area of impregnated HNZ will decrease with the increasing of the amount of boron oxide addition. 4. The C3-C4 hydrocarbons formation over HZSM-5 proceeded effectively at the 4 oc and acetone space velocity 4 h-1. Acetone conversion was close to 1 % with the selectivity around 2 %. The best catalyst for natural Zeolite should be decided on 15 wt% B2O3-HNZ, because the highest yield for C3-C4 hydrocarbons attain 33.3 %. Even, this result surpasses the result of the reaction using HZSM-5 which just reaches 2.6 % yield. So, the boron oxide addition can significantly improve the catalytic performance of natural Zeolites.
The shift selectivity between the change of C 3 hydrocarbons and liquid oil selectivity during the progressing the time on stream over HZSM-5 or 15 wt% B 2 O 3 -HNZ catalyst that is to show the curves lead to relative symmetry in the opposite direction between the increasing of C3-C4 hydrocarbons and the decreasing of liquid oil selectivity with reaction time. The catalyst deactivation by coking which is effect on the occurance of the narrowing of pore dimension during the progress of the reaction time. But, this condition gives to the favourable condition for the formation of C3-C4 hydrocarbons. The loss of surface area are due to the deactivation catalyst was for HZSM-5 about 3 % for total area and 23 % for micropore area, The loss area of HNZ was 2.1 % for total area and 35 % for micropore area, and the loss area of 15 wt% B2O3-HNZ was 33 % and 24,2 % for total area and micropore area, irrespectively. The reaction pathway of C3-C4 hydrocarbons formation from acetone/butanol over zeolite catalysts is discussed in detail. The reaction is initially generated by aldol condensation reaction mechanism.