1 Data Update Effect of Water and FFA on Transeseterification Using Zn x La y O z as Catalyst Shuli Yan

2 Outline Introduction Experiments Results and Discussion Biodiesel Effect of water in homogeneous catalysis for biodiesel production Effect of FFA in homogeneous catalysis for biodiesel production Catalyst synthesis and Transesterification Catalytic activity of Zn and La mixture oxides Effect of FFA Effect of water

3 Introduction Biodiesel

4 High production Cost  Food grade vegetable oils( soybean oil $0.27/lb) FFA content is lower than 0.5 % (wt) Water content is lower than 0.06% (wt) Introduction  Crude oils and yellow grease( about 30 % of refined oils) FFA content is in the range of 0.5 ~ 15 % (wt) Water content is higher than 0.06% (wt)

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6 Introduction Prices of some inexpensive materials (Rudbeck, 2000)Rudbeck, 2000 BulkPrice range (per pound)Average price Animal/livestock feed$0.09–$0.14$0.12 Tallow$0.10–$0.20$0.17 Grease$0.07–$0.20$0.16 Blood$0.20 Hydrolyzed feather meal$0.125

7 Introduction Effect of FFA in homogeneous catalysis for biodiesel production B. Freedman, R.O. Butterfield and E.H. Pryde, Transesterification kinetics of soybean oil, J Am Oil Chem Soc 63 (1986), pp. 1375–1380

8 Introduction Effect of water in homogeneous catalysis for biodiesel production B. Freedman, R.O. Butterfield and E.H. Pryde, Transesterification kinetics of soybean oil, J Am Oil Chem Soc 63 (1986), pp. 1375–1380

9 Introduction Comparisons between homogeneously catalytic methanol (MeOH) process and supercritical methanol (SCM) method for biodiesel from vegetable oils by transesterification Catalytic MeOH processSCM method Methylating agentMethanol CatalystAlkaliNone Reaction temperature (K)303– Reaction pressure (MPa) Reaction time (min)60–3607–15 Removal for purificationMethanol, catalyst, glycerol, soapsMethanol Free fatty acidsSaponified productsMethyl esters, water

10 Simultaneous transesterification and esterification Minimizing hydorlysis  Developing a heterogeneous catalyst with high activity in feedstocks with high content of FFA and water Objective

11 Experiments Catalyst preparation Homogeneous-coprecipitation method using urea as precipitant 1.Prepare a mixture solution of Zn(NO 3 ) 2, La(NO 3 ) 3 and urea 2.Heat to 100 o C and hold for 6 hr 3.With vigorous stir 4.Filter or not 5.Dry at 150 o C for 8 hr 6.Use step-rising calcination method at 250, 300, 350, 400, 450 o C

12 Experiments Transesterification Temperature controller Sampling device Molar ratio of methanol to soybean oil-42:1 Catalyst dosage %(wt) Stir speed rpm

13 Experiments FAME yield Water content FFA content Clarus 500 GC-MS, Perkin-Erlmer 831 KF Coulometer 809 KF Coulometer

14 Results and discussion Blank experiments

15 Results and discussion Catalytic activity of mixed metal oxides

16 Results and discussion Effect of water

17 Results and discussion Effect of FFA

18 Results and discussion Effect of FFA

19 Results and discussion Effect of water and FFA

20 Results and discussion Effect of water and FFA

21 Results and discussion Comparison with homogeneous catalysts

22 Results and discussion Comparison with homogeneous catalysts

23 Results and discussion × ×