2. Biodiesel Technologies and Plant Design Farizul Kasim April 2014 acknowledgments to: 1. Jon Van Gerpen (whose PPT was the basis for this talk) 2. Institut Francais du Pétrol 3. Journeytoforever.org

3. In this talk … n First half: n Background, general info, common knowledge, useful stuff n Second half: n Design considerations and class examples n Choices of technology and feedstocks n Commercial examples

4. Biodiesel Benefits and Processes n Greenhouse n Definition and standards n Transesterification n Fatty acid chains n Standard recipes n Competing reactions n Process issues

5. Biodiesel and Greenhouse n Australia uses 14 billion litres/year of diesel n Australian Renewbale Fuels total capacity 88.8 million litres/year n equals 0.63% of total n © not much of a dent. n Biodiesel is a niche product until petroleum gets much more expensive

6. Biodiesel and Greenhouse LOCAL SCENE n Use palm oil as raw material n B5 mix will be implemented fully by July 2014 n Government also looking at B7 and B10 mix n 2011-29 Biodiesel plant were registered under Malaysian Oil Palm Industry

7. If biodiesel replaced Petroleum Diesel completely using Canola or Rapeseed Crop yield: 2 tonnes per ha (ha=0.01 km 2 ) To make 14 billion litres of biodiesel Use 30 million tonnes of canola Area needed: 15 million ha = 0.15 million km 2 Area of Australia = 7.7 million km 2 40% increase in crop area needed Big problem: water for irrigation!

8. Definition of Biodiesel n Biodiesel – a fuel composed of mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats. FAME = Fatty Acid Methyl Ester FAME is not Biodiesel unless it meets the relevant standards

9. ASTM D 6751-02 PropertyMethodLimitsUnits Flash point, closed cupD 93130 min° C Water and sedimentD 27090.050 max% volume Kinematic viscosity, 40 ° CD 4451.9 – 6.0mm 2 /s Sulfated ashD 8740.020 maxwt. % Total SulfurD 54530.05 maxwt. % Copper strip corrosionD 130No. 3 max Cetane numberD 61347 min Cloud pointD 2500Report to customer° C Carbon residueD 45300.050 maxwt. % Acid numberD 6640.80 maxmg KOH/g Free glycerinD 65840.020wt. % Total glycerinD 65840.240wt. % PhosphorusD 49510.0010wt. % Vacuum distillation end pointD 1160360 °C max, at T-90 % distilled

10. Transesterification

11. Triglyceride Sources n Rendered animal fats: beef tallow, lard n Vegetable oils: soybean, canola, palm, rapeseed etc. n Chicken, pork fat n Rendered greases: yellow grease (= waste cooking oil) n Recovered materials: brown grease (=grease-trap waste), soapstock, etc. n NB Prices vary a lot!

12. Standard Recipe 100 kg oil + 21.7 kg methanol 1.5 kg NaOH (or KOH) 100 kg biodiesel + 10.4 kg glycerol + 11.3 kg xs methanol

13. Amateurs’ Page Batch homebrew Thanks to “Journey to Forever” and Mike Pelley Melted fat Methanol and Sulfuric acid stage After acid esterification

14. Second stage MeOH and NaOH addition Glycerol layer settles out More glycerol settles out First wash

15. After first wash After third wash

16. Free Fatty Acids (FFAs) n FFAs are present in oils and fats. Low in virgin and high in low-grade or waste. (i.e. hydrocarbon chain)

17. O ||+ KOH HO - C - (CH 2 ) 7 CH=CH(CH 2 ) 7 CH 3 Oleic Acid Potassium Hydroxide O || →K + - O -C - (CH 2 ) 7 CH=CH(CH 2 ) 7 CH 3 + H 2 O Potassium oleate (soap)Water Free Fatty Acids react with alkali catalyst to form soap

18. Water is a problem Water hydrolyses fats to form free fatty acids, which then form soap. Dry feedstocks best.

19. Soap generation n Can cause the entire product mixture to gel into a semi-solid mass, giving headaches with separation and washing. n Increased water use and treatment costs n Loss of biodiesel product

20. Free Fatty Acid (FFA) levels in Feedstocks Biodiesel feedstocks vary from edible oils to stinking wastes n Refined vegetable oils< 0.05% n Crude soybean oil0.3-0.7% n Restaurant waste grease2-7% n Animal fat5-30% n Trap grease75-100% Price decreases as FFAs increase High FFA feeds need special processing to avoid soap. But certain processes use FFA as the feed.

21. Methods for High FFA feeds: Acid catalysis followed by base catalysis 1. Acid catalysis methylates FFAs to methyl esters, until FFA < 0.5%. – Alkaline esterification of FFA is relatively fast (1 hour) but acid-catalyzed transesterification is slow – Water formed by FFA + methanol ==> methyl ester + water can be a problem. 2. Then separate, add additional methanol and base catalyst to transesterify the triglycerides.

22. Feedstocks n Common to all processes n “Triglygeride” or fats and oils soybean oil – vegetable oils, animal fats, greases, waste VO, soapstock, etc. n Primary alcohol: usu. methanol or ethanol (typically in stoichiometric excess) n … for conventional process n Catalyst (sodium or potassium hydroxide) n Neutraliser (sulfuric or hydrochloric acid) n Washwater

23. Rough Reaction rates n Transesterification reaction is too slow, at ambient temps i.e. 4-8 hours. n Reaction time can be shortened to 1-2 hours at 60°C. n For higher temperatures pressure vessels needed. Methanol boils at 65°C. n Normally a two-phase mixture, ergo… n High-shear mixing or use of co-solvents to accelerate reaction rate. n Reverse reaction occurs, ergo two-stage processes with two reactors are commonly seen.

24. Process Evolution n Batch mixing at < 60 deg C n Continuous < 60 deg C n Continuous pressurised homogenous catalyst, at say 120 deg C, 6 bar (most common) n Continuous pressurised heterogeneous catalyst (State of the art?) n Co-solvent (commercialised as BIOX) n Supercritical (not commercial) n Supercritical co-solvent (not commercial)

25. Batch Processes Good for smaller plants (<4 million litres/yr). n Does not require continuous operation. n Provides greater flexibility wrt feedstock variations. n Higher labour costs. n Physically large plant cf continuous. n Heat integration awkward. n Greater risk levels:

26. Continuous Processes Better safety, lower risks n Lower unit labour costs n Better economies of scale as capacity goes up n More compact plant n Heat recovery inherent n Allows better use of high-volume separation systems (e.g. centrifuges) n High capex at small scale but ROI better at larger scale

27. Innovative Processes Supercritical Heterogeneous catalysts

28. Supercritical Methanol n SC methanol is a high-density chemically-labile vapour that cannot be compressed into the liquid state. (80 bar 240 deg C) n It is miscible with oils and fats or FFAs n It reacts without catalyst to form FAME, glycerol and water. Fast reaction (  = 4 mins) n See Saka and Kusdiana Kyoto U n However … n Not commercial as yet. n Large xs methanol required 42:1 mole ratio. n MeOH recycle costs are significant

29. Heterogeneous Catalysis WHY ? 1.Homogenous catalysts are used up 2.They make soap with FFAs 3.Product needs lots of washing, ergo wastewater costs Can we use a solid that has catalytic properties that will stay in the reactor? YES we can … enter the Heterogeneous Catalyst. More later …

30. Summary (so far) n Biodiesel can be made from virtually any oil or fat. n The technology choice must consider: capacity, feedstock type and quality, catalyst consumption, methanol:oil ratio etc. n Biodiesel is regarded as a “green” fuel but there is not enough oil and fat made to replace more than 20% of petroleum diesel. n Sustainability of biodiesel is >> petroleum diesel but it is a niche product for the time being.

31. Summary cont. Biodiesel from Waste Oil is much more “green” because it can be reasonably regarded as having near zero embodied energy debt. BUT There is not enough of it to make a great difference. Compare what you consume: (i) ? Litres per year of petrol vs (ii) ? Litres/year of cooking oil

32. Part 2: Class Exercises Kinetics Commercial Examples

33. Kinetics of Transesterification n Class Exercise: n Consider vegetable oil and methanol n Write down the relevant parameters for designing a reactor! n 3 minutes then show and tell.

34. Kinetics of Transesterification n Temperature n Oil/fat type n Ratio of methanol to oil/fat n Catalyst concentration n Catalyst type n Mixing (esp. if single phase system) n Water content of feed

35. Kinetics of  Dissakou, et al No catalyst, high temps. Co-solvent

36. This is curve fitting not “Prediction” as stated

37. Kinetics of transesterification of soybean oil Noureddini, H. and Zhu, D., Journal of the American Oil Chemists' Society, 74, n11, 1997, 1457-1463 Abstract rewritten by WD with apologies Three stepwise and reversible reactions are believed to occur. The effect of variations in mixing intensity and temperature on the rate of reaction were studied at constant molar ratio (methanol:triglyceride = 6:1) and constant concentration of catalyst (0.20 wt% based on soybean oil). Variations in mixing intensity appeared to affect the reaction as did variations in temperature. A 2-step reaction mechanism consisting of an initial mass transfer-controlled step followed by a kinetically controlled step is proposed. Experimental data for the latter step were consistent with second-order kinetics. The reaction rate constants and the activation energies were determined for all the forward and reverse reactions. WAD suggests: compare rate constants with Dissakou et al.

38. Transesterification of vegetable oil to biodiesel using heterogeneous base catalyst Kim, Hak-Joo (Department of Chemical Engineering, Korea University) ;Kang, Bo-Seung ;Kim, Min-Ju ;Park, Young Moo ;Kim, Deog-Keun ;Lee, Jin-Suk ;Lee, Kwan-Young : Catalysis Today, v 93-95, Sep 1, 2004. WAD rewritten Abstract: Na/NaOH/gamma-Al 2O3 heterogeneous base catalyst was adopted for the production of biodiesel. A study of the reaction conditions: reaction time, stirring speed, use of co-solvent, oil to methanol ratio, and amount of catalyst, was performed. The heterogeneous base catalyst showed almost the same activity under the optimized reaction conditions compared to conventional homogeneous NaOH catalyst. WAD notes: 80% of the yield is not “almost the same”. Large ratio of co-solvent and excess methanol suggest significant recycle costs. Slow rates of reaction. Why did they not heat it up and run under pressure?

39. Design a Reactor n Your task: to design a continuous plug flow reactor for 160,000 tonnes per year of biodiesel. n Density 0.88 tonne/m3 n 320 days/year n Determine: length of pipe for “best diam.” n Pipe sizes available (mm): n 50, 100, 150, 200, 300 n Two alternative residence times: n A: Low temp: 2 hours n B: Hi temp: 20 mins n 10 minutes to do this then show and tell.

40. REACTOR DESIGN FOR A CONTINUOUS PLANT Based on Esterfip plant capacity (Sête France) Capacitytonne per year160000 Flowratem3 per year188235 Flowratem3/hour23.8 Reactor Volumes WAD's intuition Residence time 2 hoursm347.5too big 20 minutesm37.9still pretty big 4 minutesm31.6too good to be true

41. Design pipe reactor (cont. a) ConditionsLength (m)WAD’s intuition 2 hours, 50 mm ID24209not feasible 20 minutes, 50 mm ID4034still too long 20 minutes, 150 mm ID448more practical 4 minutes, 50 mm ID807a bit long 4 minutes, 75 mm ID359you wish

42. Design pipe reactor (cont. b) no. of 6-m Dimensions* pipe runsW and H (m) Conditions 2 hours 50 mm ID40356.4 20 minutes 50 mm ID6722.6 20 minutes 150 mm ID752.6 4 minutes 50 mm ID1351.16 4 minutes 75 mm ID601.16 * Allows for insulation thickness = (guess) half pipe diam.

43. Reactor Optimisation A small high-temperature reactor is desirable because it saves CAPEX (less metal, fabrication and installation costs, footprint) Temp up, rate up, reactor size down, CAPEX down BUT both CAPEX and OPEX can increase when… Heating to greater temperatures -> OPEX up as fuel consumption (and cooling water) up. Bigger heat exchanger -> CAPEX up Reactor wall thickness up as pressure up -> CAPEX up Thicker insulation -> CAPEX up. Bigger pump for increased pressure -> CAPEX up. Heterogeneous catalyst life down -> OPEX up.

44. Actual Commercial Processes

45. BIOX Process n Uses co-solvent usually MTBE n Low temperature operation n Claimed 7 min residence time n Needs alkaline homog. catalyst (and acid) n Requires large ratios of methanol to oil n Commercialised at 67 million litres/annum n Inventor Em. Prof. D. Boocock Toronto Canada

46. Energea Process n Pressurised continuous n Elevated temperature n Residence time probably 20 mins n Uses alkaline catalyst and acid n Low ratios of methanol to oil n Chosen by ARF (SA and WA) n Look for Dr Richard Gapes at Vienna Tech. U

47. Lurgi Process n Similar to Energea n Two stage CSTR reactor (?) n 100,000 tonne per annum plant in California n Flowsheet (for PR purposes) has washwater in but not out

48. Institut Francais du Pétrol, n Hetero aluminate catalyst (no caustic soda, potash) n Clean glycerol, little washing needed n Temperature ca 200 deg C (? ex patent) n Pressure ca 62 bar (?) n Residence time 2 hours (? ouch!) n Max water allowed in = 1000 ppm n 160,000 tonne per year at Sete France See Bournay, et al. Inventor US Patents

53. Cao et al. (not commercial) n Supercritical process no catalyst n Temps 260 to 300 deg C n Propane:methanol = 0.05 to lower SC temp n Large ratio methanol:oil n High pressure (>100 bar) Fast reaction   n Not costed (methanol recycle might be a worry)

54. Local Manufacturers n Australian Biodiesel Group (also see Australian Biodiesel Consultancy. Plant at Berkeley Vale NSW (home made, conventional) n Australian Renewable Fuels (ARF) floated $20 M. Total capacity 88.8 million litres/year in SA and WA (Uses Energea technology)

55. Economics (ex ARF prospectus) Revenue: 0.96 $A/litre biodiesel n Feedstock tallow: 560 A$/tonne n Methanol: 443 $A/tonne n Converter margin on feedstocks only n $960*0.86 - $560 - $0.11*443 = $217 per tonne n Equals 19 cents per litre. n Total income/year $16.9 million n Cf prospectus $37 million n (what the…?)

56. Relevant Unit Operations n Phase separation (gravity, ‘fuges) n Washing (cc gravity, ‘fuges etc) n Evaporation (distillation less relevant) n Heat exchange n Drying

57. Summary and conclusions n Feedstocks are a major cost component. n Oils and tallows more available but expensive. n Waste VO, yellow grease limited supply n Design plant to be cheap to run: energy costs, labour costs and utilities.Robots might be useful. n Capex is important too but it should make less impact on a large-scale plant. n You must optimise your design for it to have any engineering significance.

58. References n John Duncan “Costs of biodiesel production” (use Google to find) n Barry Judd “Biodiesel from Tallow” (use Google to find) n Nelson and Schrock “Economics of biodiesel production from tallow” n Anneliese Niederl and Michael Narodoslawsky “. LCA study of biodiesel from tallow and used vegetable oil (use Google to find) n Australian Renewable Fuels prospectus (use Google to find) n Ma, F. and Hanna, M.A. “Biodiesel production: A review”Bioresource Technology, 70, 1999, 1-15 n Dissakou, M et al. “Kinetics of the non-catalytic transesterification of soybean oil” Fuel, 77 1998, 1297-1302 Noureddini, H. and Zhu, D., “Kinetics of transesterification of soybean oil Journal of the American Oil Chemists' Society, 74, n11, 1997, 1457-1463 n http://journeytoforever.org/biofuel_supply.html#biodiesel

59. References cont. n Van Gerpen et al. “Biodiesel production technology: Aug 02-Jan 04” NREL/SR-510-36244 (use Google) [PDF] “Biodiesel Report Outline” n Cao et al. “Preparation of biodiesel from soybean oil using supercritical methanol and co-solvent” Fuel, 84, 2005 p347-351 n TIP: Visit US Patent Office for kinetic data described in patents and not in the general literature.

60. “Assessment of biodiesel and ethanol diesel blends, greenhouse gas emissions, exhaust emissions, and policy issues” prepared by Levelton Engineering Ltd. (NB good for costing processes and energy usage etc) References cont.