Microwave assisted processing at commercial scale

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1 Microwave assisted processing at commercial scale ZING CONFERENCE, NAPPA 23 TH OF JULY 2013 MORSCHHÄUSER; SCHOLZ; FAIRWEATHER 2) ; GIBSON 2) ; KRULL; KAPPE 1) Public Detergents & Intermediates ) 2)

2 2 Table of Contents Introduction Microwave processing in continuous flow kg/h - scale Biodiesel Biodiesel and microwave Microwave processing in continuous flow large - scale

3 Introduction Morschhäuser. Scholz, Fairweather, Gibson, Krull, Kappe Public Detergents & Intermediates

4 Technical landscape GHz? 915 MHz Slide 4

Shikoku (6.5 L) Issues penetration depth (2.

5 5 Scale-Up in Batch Multimode Reactors (Prototype Reactors, state of the art) UltraCLAVE (3.5 L) Milestone AccelBeam Reactor (13 L) Shikoku (6.5 L) Issues penetration depth (2.45 GHz) volumetric heating? heating/cooling profiles temperature/pressure limits safety, energy efficiency.. Review: Moseley, J. D. in Microwave Heating as a Tool for Sustainable Chemistry, Leadbeater, N. E. (Ed.), CRC Press, Boca Raton, 2011; chapter 5, pp

6 6 State of the art technology Multi mode design Single mode design Major drawback: - slow energy transfer - limited throughput Major drawback: - very low energy efficiency - no scalability (fixed to wave length)

7 Microwave processing in continuous flow kg/h - scale Morschhäuser. Scholz, Fairweather, Gibson, Krull, Kappe Public Detergents & Intermediates

8 8 Hybrid concept

9 Energy efficiency from power plug to process heat Single mode (lab use) 2.45 GHz 100% from power plug Overall efficiency [%] 10-12% MW heat transfer 40% transformation loss 5-8% Multi mode (lab use) 2.45 GHz % MW heat transfer 40% transformation loss 20-25% Hybrid resonator 2.45 GHz % MW heat transfer 40% transformation loss 50-55% Slide 9

10 10 Clariant's Hybrid reactor flow heater approx. 12 cm Al 2 O 3 -tube after 1 year of use 2.45 GHz continuous flow Operates at 25 to 300 C Up to 70 bars tested Advanced safety concept (proved by German TüV)

11 11 Example Reactions 2.45 GHz / < 6/10 kw Flow Heater

12 12 Clariant's Hybrid reactor flow heater Situation: reliable and robust cont. flow system established feasibility proven for many reaction types under MW conditions how can we leverage this technology???

wt% KOH batch- and continuous mode entry reaction conditions energy consumption 1 Conventional heating 94,3 2

13 13 Biodiesel and Microwave Energy consumption estimations for the preparation of biodiesel using conventional systems and microwave heating Reaction characteristics Methanol/Triglyceride 6:1 temperature 50 C catalyst: 1 wt% KOH batch- and continuous mode entry reaction conditions energy consumption 1 Conventional heating 94,3 2 3 MW-continuous flow at 7.2 liters MW-continuous flow at 2.0 liters 26,0 60,3 4 MW-batch at 4.6 liters 90,1

14 14 Biodiesel and Microwave It is evident that, while the energy consumption of the batch process may be on the order of that of the conventional methodology, the continuous-flow processes are more energy efficient. Microwave continuous-flow processes

15 Biodiesel Morschhäuser. Scholz, Fairweather, Gibson, Krull, Kappe Public Detergents & Intermediates

16 16 World Biodiesel Production [Mio tons] 16,4 Mio tons Lamers, P.; Internationale Biodieselmärkte; UFOP Schriften (2011) 4.

17 17 International bioenergy trade Volumetric Excise Tax Credit in US extended till 2009 Low production cost for Biodiesel in Argentina Lamers P et al.; International bioenergy trade a review of past developments in the liquid biofuels market. Renewable and Sustainable; Energy Reviews. 15 (2011)

18 International bioenergy trade Significant subsidies for use of Biodiesel in many EU countries Volumetric Excise Tax Credit in US extended till 2009 Low production cost for Biodiesel

18 18 International bioenergy trade Significant subsidies for use of Biodiesel in many EU countries Volumetric Excise Tax Credit in US extended till 2009 Low production cost for Biodiesel in Argentina Lamers P et al.; International bioenergy trade a review of past developments in the liquid biofuels market. Renewable and Sustainable; Energy Reviews. 15 (2011)

19 19 International bioenergy trade Penalty tax for US Biodiesel imports into EU countries Low production cost for Biodiesel in Argentina Indonesia increases production for EU Lamers P et al.; International bioenergy trade a review of past developments in the liquid biofuels market. Renewable and Sustainable; Energy Reviews. 15 (2011)

20 20 International bioenergy trade Half of EU Biodiesel consumption based on imports Low production cost for Biodiesel in Argentina Indonesia increases production for EU Lamers P et al.; International bioenergy trade a review of past developments in the liquid biofuels market. Renewable and Sustainable; Energy Reviews. 15 (2011)

21 21 Classical FAME synthesis basic route Issue water

22 22 Classical FAME synthesis basic route Issue free fatty acid (FFA)

23 23 Classical FAME synthesis acidic route Issue reactivity fast slow!!

24 Basic and acidic treatment of oleo feedstock - basic catalysis -

water content (< 0,1 wt%) anhydrous Catalyst and Methanol mandatory

conversion (98%) moderate Methanol/Oil ratio (4-8 mol/mol) simple and

24 24 Basic and acidic treatment of oleo feedstock - basic catalysis - Reaction characteristics * ) low free fatty acid content (< 0,5 wt%) low water content (< 0,1 wt%) anhydrous Catalyst and Methanol mandatory Advantages versus acidic route short processing time (5-90 min) high conversion (98%) moderate Methanol/Oil ratio (4-8 mol/mol) simple and relatively (stainless 304, 316) cheap process equipment * ) Freedman et al., 1984; Jeromin et al., 1987

25 Basic and acidic treatment of oleo feedstock - acidic catalysis - Reaction characteristics * ) large excess Methanol mandatory (9-40 mol/mol) moderate processing times (15 min 8 h) use of large

25 25 Basic and acidic treatment of oleo feedstock - acidic catalysis - Reaction characteristics * ) large excess Methanol mandatory (9-40 mol/mol) moderate processing times (15 min 8 h) use of large and expensive (Monel, Hastelloy) equipment Advantages versus basic route tolerates traces of water (< 2 % wt/wt) use of low value feedstock (>> 5 % wt/wt FFA) (high FFA content) no metal containing catalyst (no soap formation) * ) Biodiesel Handbook

26 26 Biodiesel (FAME) feedstock Two different grades of feedstock crude or refined vegetable oil (degummed, bleached, deodorized) waste cooking oil, grease (low value and quality feedstock) Refined Vegetable Oil (RBD) Waste Cooking Oil (WCO)

27 27 Key messages from Zang et. al. (2003) Summary of economical considerations Capital costs favor the basic route versus the acid catalyzed process Capital cost estimate from Zhang et.al. for a mt/y production unit * ) basic route Acidic pretreatment/ basic route Acidic route / continuous (reactor cascade) Acidic route / continuous + hexane extraction 1,34 2,68 2,55 3,19 1,98 3,97 3,77 4,72 All values are given in 10 6 US$ Capital costs still offset advantages in raw material sourcing for acidic route Nevertheless, acidic route becomes more attractive with increasing feedstock cost for basic route * ) Y. Zhang, M. A. Dubé, D.D. Mc.Lean, M. Kates: Bioresource Technology 90 (2003)

28 28 Biodiesel 1100 US$ per ton 450 US$ per ton data origin:

29 29 Feedstock cost development 100 kt/year unit, soybean based US $/t Soy bean oil

30 30 Biodiesel Historical feedstock costs for Biodiesel production RBD-grade waste oils (high FFA) 50-70% of RBD Soybeans and Biodiesel: Key Price Relationships United Soybean Board (2009), p. 3

31 31 Biodiesel price and margin US $ per liter +139% 1,16 U$/l 0,83 U$/l 0,84 U$/l +262% 0,32 U$/l U.S. Department of Energy; Biofuels Issues and Trends; (October 2012) p.19

32 Cost driven decision of process route low temperature Methanol/Oil

low catalyst cost FFA sensitivity water tolerance costly catalyst

pressure required How can we utilize benefits of both routes?

32 32 Cost driven decision of process route low temperature Methanol/Oil ratio processing time no pressure FFA not critical tolerates water very low catalyst cost FFA sensitivity water tolerance costly catalyst higher temperature unfavorable Methanol/Oil ratio long processing time pressure required How can we utilize benefits of both routes?? (Favorable capital cost from basic route and low feedstock costs from acidic process)

33 33 Concept for proof of principle can we combine the acidic route with MW cont. processing?

34 Biodiesel and microwave Morschhäuser. Scholz, Fairweather, Gibson, Krull, Kappe Public Detergents & Intermediates

35 35 Biodiesel production in continuous flow - basic route - Catalyst: Max. Temp: 180 C Flow: NaOCH 3, 1 wt% 6-8 L/h (27 sec) after 1 st run; no further treatment Increasing efficiency 1:4 Oil /Methanol 1:8 Oil /Methanol 90 mol% > 95 mol% Rapeseed oil

36 Biodiesel production in continuous flow - acidic route - coconut oil methyl ester (after processing) Catalyst: CH 3 -SO 3 H, 1 wt% Max. Temp: 170 C Flow: 6,5 L/h (30 sec) virgin grade coconut oil (cold pressed) crude glycerol containing phase crude coconut oil 0,5 wt% water 2,6 wt% FFA first pass second pass 90 mol% > 98 mol% Slide 36

37 37 MW assisted esterification of FFA Stearic acid methyl ester yield: > 98% c Catalyst: MeSO 3 H, 1 wt% Max. Temp: 180 C Flow: 6-7 L/h (27 sec) pressure: 18 bar a very high conversion observed for long chain FA no product degradation d b c

38 38 MW assisted esterification of FFA Benzoic acid methyl ester Catalyst: MeSO 3 H, 1 wt% Max. Temp: 175 C Flow: 6-7 L/h (27 sec) pressure: 18 bar yield: 96% a very high conversion observed for aromatic FA no product degradation b,b` c,c` d

39 39 Kinetics of acid catalyzed transesterification What is common understanding on acidic route?? What is known in literature??

.. more catalyst beneficial.. source: 1) J.

40 40 Kinetics of acid catalyzed transesterification Temperature dependency 1) Catalyst conc. dependency 1) more heat beneficial... more catalyst beneficial.. source: 1) J.M. Marchetti; M.N. Pedernera; N.S. Schbib : Int. J. Low-Carbon Tech. (2011) 6 (1):

Pedernera; N.S. Schbib : Int. J. Low-Carbon Tech. (2011) 6 (1): 38-43.

41 41 Kinetics of acid catalyzed transesterification Molar ratio MeOH/FFA 1) Reaction time 2) 8:1 MeOH/FFA 2-3 hours source: 1) J.M. Marchetti; M.N. Pedernera; N.S. Schbib : Int. J. Low-Carbon Tech. (2011) 6 (1): ) Siddharth Jain, M.P. Sharma, Shalini Rajvanshi: Fuel Processing Technology 92 (2011) 32 38

42 42 FAME via acidic processing cont. microwave processing lab data Classical versus MW processing of FFA containing feedstock using acidic catalysis Classical 1) MW 2) reaction temperature C 170 C Methanol / FFA 8:1 2:1 [on FFA] processing time 2-3 h s pressure requirement atmospheric to 4 bar 18 bar Remark: data generated using cont. flow MW 2.45 GHz flow: 5.5-6,0 l/h source 1) Biodiesel Handbook 2) Lab data Clariant

43 43 FAME via acidic processing Summary Classical acidic route MW processing high temperature unfavorable Methanol/Oil ratio long processing time pressure required easy to achieve 2 :1 molar ratio sufficient (MeOH/FFA) only seconds necessary Pressure no issue

44 Microwave processing in continuous flow t/day - scale Morschhäuser. Scholz, Fairweather, Gibson, Krull, Kappe Public Detergents & Intermediates

45 45 Clariant's Hybrid reactor flow heater 915 MHz continuous flow operates at 25 to 300 C up to 40 bars tested approval under pressurized equipment guideline (proved by German TüV)

46 46 MW assisted continuous process for making Biodiesel

47 FAME on large scale (5 t/day) Palm Kernel Fatty Acid Distillate acidic process single MW run Methyl-Ester content: 91% double pass Methyl-Ester content: > 98%

48 Energy efficiency from power plug to process heat Single mode (lab use) 2.45 GHz 100% from power plug Overall efficiency [%] 10-12% MW heat transfer 40% transformation loss 5-8% Multi mode (lab use) 2.45 GHz % MW heat transfer 40% transformation loss 20-25% Hybrid resonator 2.45 GHz % MW heat transfer 40% transformation loss 50-55% Hybrid resonator 915 MHz % MW heat transfer 99 % 20% transformation loss 81% found 70 75% Slide 48

MHz, 2.45 GHz) Total energy efficiency: 43% 23% twice as efficient 35% (915 MHz) * ) L.A.

49 Total energy efficiency steam heated systems/ 915 MHz MW reactor primary energy 50% Gas green electricity Electricity Steam 50-65% MW energy 82% (915 MHz) 85% Reaction mixture 90% 99% (915 MHz, 2.45 GHz) Total energy efficiency: 43% 23% twice as efficient 35% (915 MHz) * ) L.A.Hulshof; Right First Time in Fine Chem. Process Scale-up; Scientific update LLP; (2013) p.121 Slide 49

50 Heat transfer classical systems V = 1000 cm 3 D = 2,75 cm L = 100 cm Scale up strategy: bigger equipment size numbering up * ) L.A.Hulshof; Right First Time in Fine Chem. Process Scale-up; Scientific update LLP; (2013) p.121 Slide 50

Energy transfer 915 MHz MW reactor dielectric constant E- field strength P MW = 2 π f ε 0 ε E 2 V P MW E 2 frequency dielectric loss Volume Scale up strategy:

51 Energy transfer 915 MHz MW reactor dielectric constant E- field strength P MW = 2 π f ε 0 ε E 2 V P MW E 2 frequency dielectric loss Volume Scale up strategy: increase power release of the magnetron increase tube diameter * ) L.A.Hulshof; Right First Time in Fine Chem. Process Scale-up; Scientific update LLP; (2013) p.121 Slide 51

52 52 Summary and outlook Chemical MW-assisted processing feasible in tons scale per day Transfer from 915 MHz -> 2.45 GHz successfully done Very efficient volumetric heating in the order of seconds High flexibility in reaction controls (T, P, Flow, t residence ) Overall energy efficiency competitive to classical systems Combination of MW processing and renewable electricity potentially superior to standard processing

53 Technical landscape GHz 915 MHz several tons/day realized Slide 53

54 54 Remark The Kings of steam and coal with worries clouded face asking themselves: What will the infant electricity grow to?..from

55 55 Many thanks to. Clariant Dr. Hans Jürgen Scholz DI Said Kchirid Team members Procter & Gamble Chemicals Dr. Neil Fairweather Dr. Mike Gibson Püschner GmbH Dr. Peter Püschner Team Scientific advisers Prof. Dr. Oliver Kappe (University of Graz) Prof. Dr. Helmut Ritter (University of Düsseldorf) Dr. Sarah Schmitz (Evonik)

56 Thank you very much for your audience Morschhäuser. Scholz, Fairweather, Gibson, Krull, Kappe Public Detergents & Intermediates

Abstract Process Economics Program Report 251 BIODIESEL PRODUCTION (November 2004)

Abstract Process Economics Program Report 251 BIODIESEL PRODUCTION (November 2004) Biodiesel is an ester of fatty acids produced from renewable resources such as virgin vegetable oil, animal fats and used