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Public
Detergents & Intermediates
23.07.2013
Microwave assisted processing at commercial scale
ZING CONFERENCE, NAPPA 23TH OF JULY 2013
MORSCHHÄUSER; SCHOLZ; FAIRWEATHER2); GIBSON2);
KRULL; KAPPE1)
2) 1)
Detergents & Intermediates, 23.07.2013
Table of Contents
Public, Microwave assisted processing at commercial scale 2
– Introduction
– Microwave processing in continuous
flow kg/h - scale
– Biodiesel
– Biodiesel and microwave
– Microwave processing in continuous
flow large - scale
Public
Detergents & Intermediates
23.07.2013
Introduction
Morschhäuser. Scholz, Fairweather,
Gibson, Krull, Kappe
Detergents & Intermediates, 23.07.2013
Technical landscape 2012
Slide 4
2.45 GHz
915 MHz
?
Public, Microwave assisted processing at commercial scale
Detergents & Intermediates, 23.07.2013
Shikoku (6.5 L)
Scale-Up in Batch Multimode Reactors (Prototype Reactors, state of the art)
5
UltraCLAVE (3.5 L)
Milestone
AccelBeam
Reactor (13 L)
• penetration depth (2.45 GHz)
• volumetric heating?
• heating/cooling profiles
• temperature/pressure limits
• safety, energy efficiency
• …………..
Issues
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. 105-147
Public, Microwave assisted processing at commercial scale
Detergents & Intermediates, 23.07.2013
State of the art technology
6
Major drawback:
- very low energy efficiency
- no scalability (fixed to wave length)
Multi mode design
Major drawback:
- slow energy transfer
- limited throughput
Single mode design
Public, Microwave assisted processing at commercial scale
Public
Detergents & Intermediates
23.07.2013
Microwave processing in continuous flow kg/h - scale
Morschhäuser. Scholz, Fairweather,
Gibson, Krull, Kappe
Detergents & Intermediates, 23.07.2013
“Hybrid concept”
Public, Microwave assisted processing at commercial scale 8
Detergents & Intermediates, 23.07.2013
Energy efficiency from power plug to process heat
Slide 9
Multi mode (lab use) 2.45 GHz
Single mode (lab use) 2.45 GHz 100% from power plug
40% transformation loss 10-12% MW→heat transfer
40% transformation loss 30-40 % MW→heat transfer
90-95 % MW→heat transfer
Hybrid resonator 2.45 GHz
40% transformation loss
20-25%
50-55%
5-8%
Overall efficiency
[%]
Public, Microwave assisted processing at commercial scale
Detergents & Intermediates, 23.07.2013
Clariant's Hybrid reactor “flow heater”
Public, Microwave assisted processing at commercial scale 10
approx. 12 cm
2.45 GHz continuous flow
Operates at 25 to 300°C
Up to 70 bars tested
Advanced safety concept
(proved by German TüV)
Al2O3-tube after 1 year of use
Detergents & Intermediates, 23.07.2013
Public, Microwave assisted processing at commercial scale 11
Example Reactions – 2.45 GHz / < 6/10 kW Flow Heater
Detergents & Intermediates, 23.07.2013
Clariant's Hybrid reactor “flow heater”
Public, Microwave assisted processing at commercial scale 12
Situation:
• reliable and robust cont. flow system
established ……
• feasibility proven for many reaction types under
MW conditions ……
how can we leverage
this technology ???
Detergents & Intermediates, 23.07.2013
Biodiesel and Microwave
Public, Microwave assisted processing at commercial scale 13
Energy consumption estimations for the preparation of biodiesel
using conventional systems and microwave heating
entry reaction conditions energy
consumption
1 Conventional heating 94,3
2 MW-continuous flow at 7.2
liters 26,0
3 MW-continuous flow at 2.0
liters 60,3
4 MW-batch at 4.6 liters 90,1
Reaction characteristics
Methanol/Triglyceride 6:1
temperature 50°C
catalyst: 1 wt% KOH
batch- and continuous mode
Detergents & Intermediates, 23.07.2013
“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”.
Biodiesel and Microwave
Public, Microwave assisted processing at commercial scale 14
Microwave
Microwave
continuous-flow processes
continuous-flow processes
Public
Detergents & Intermediates
23.07.2013
Biodiesel
Morschhäuser. Scholz, Fairweather,
Gibson, Krull, Kappe
Detergents & Intermediates, 23.07.2013
World Biodiesel Production
Public, Microwave assisted processing at commercial scale 16
16,4 Mio tons
[Mio tons]
Lamers, P.; Internationale Biodieselmärkte; UFOP Schriften (2011) 4.
Detergents & Intermediates, 23.07.2013
International bioenergy trade
Public, Microwave assisted processing at commercial scale 17
Lamers P et al.; International bioenergy trade – a review of past developments in the liquid biofuels market. Renewable and Sustainable; Energy
Reviews. 15 (2011) 2655-2676.
Low production cost for
Biodiesel in Argentina
Volumetric Excise Tax Credit
in US extended till 2009
Detergents & Intermediates, 23.07.2013
International bioenergy trade
Public, Microwave assisted processing at commercial scale 18
Lamers P et al.; International bioenergy trade – a review of past developments in the liquid biofuels market. Renewable and Sustainable; Energy
Reviews. 15 (2011) 2655-2676.
Significant subsidies for use of
Biodiesel in many EU countries
Low production cost for
Biodiesel in Argentina
Volumetric Excise Tax Credit
in US extended till 2009
Detergents & Intermediates, 23.07.2013
International bioenergy trade
Public, Microwave assisted processing at commercial scale 19
Lamers P et al.; International bioenergy trade – a review of past developments in the liquid biofuels market. Renewable and Sustainable; Energy
Reviews. 15 (2011) 2655-2676.
Low production cost for
Biodiesel in Argentina
Penalty tax for US Biodiesel imports
into EU countries
Indonesia
increases
production for EU
Detergents & Intermediates, 23.07.2013
International bioenergy trade
Public, Microwave assisted processing at commercial scale 20
Lamers P et al.; International bioenergy trade – a review of past developments in the liquid biofuels market. Renewable and Sustainable; Energy
Reviews. 15 (2011) 2655-2676.
Low production cost for
Biodiesel in Argentina
Indonesia
increases
production for EU
Half of EU Biodiesel consumption
based on imports
Detergents & Intermediates, 23.07.2013
Public, Microwave assisted processing at commercial scale 21
• Issue water
Classical FAME synthesis basic route
Detergents & Intermediates, 23.07.2013
Classical FAME synthesis basic route
Public, Microwave assisted processing at commercial scale 22
• Issue free fatty acid (FFA)
Detergents & Intermediates, 23.07.2013
Classical FAME synthesis acidic route
Public, Microwave assisted processing at commercial scale 23
• Issue reactivity
fast √
slow !!
Detergents & Intermediates, 23.07.2013
Basic and acidic treatment of oleo feedstock - basic catalysis -
Public, Microwave assisted processing at commercial scale 24
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
Detergents & Intermediates, 23.07.2013
Basic and acidic treatment of oleo feedstock - acidic catalysis -
Public, Microwave assisted processing at commercial scale 25
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
Detergents & Intermediates, 23.07.2013
Public, Microwave assisted processing at commercial scale 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)
Detergents & Intermediates, 23.07.2013
Key messages from Zang et. al. (2003) Summary of economical considerations
Public, Microwave assisted processing at commercial scale 27
• Capital costs favor the basic route versus the acid catalyzed process
• 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) 229-240
Capital cost estimate from Zhang et.al. for a 8.000 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
All values are given in 106 US$
Capital cost estimate from Zhang et.al. for a 8.000 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 106 US$
Detergents & Intermediates, 23.07.2013
Public, Microwave assisted processing at commercial scale 28
Biodiesel
data origin: http://www.indexmundi.com/commodities
450 US$ per ton
1100 US$ per ton
Detergents & Intermediates, 23.07.2013
Public, Microwave assisted processing at commercial scale 29
Feedstock cost development
2006 2013
100 kt/year unit,
soybean based
500
1.000
US $/t
Soy bean oil
Detergents & Intermediates, 23.07.2013
Biodiesel
Public, Microwave assisted processing at commercial scale 30
Soybeans and Biodiesel: Key Price Relationships United Soybean Board (2009), p. 3
Historical feedstock costs for Biodiesel production
RBD-grade
waste oils (high FFA) 50-70% of RBD
Detergents & Intermediates, 23.07.2013
Biodiesel price and margin 2009-12
Public, Microwave assisted processing at commercial scale 31
US $ per liter
0,32 U$/l
0,84 U$/l
+262%
0,83 U$/l
1,16 U$/l
+139%
U.S. Department of Energy; Biofuels Issues and Trends; (October 2012) p.19
Detergents & Intermediates, 23.07.2013
Cost driven decision of process route
Public, Microwave assisted processing at commercial scale 32
• 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
• low temperature
• Methanol/Oil ratio
• processing time
• no pressure
How can we utilize benefits of both routes ??
(Favorable capital cost from basic route and low feedstock costs from acidic process)
Detergents & Intermediates, 23.07.2013
Concept for proof of principle
Public, Microwave assisted processing at commercial scale 33
can we combine the
acidic route
with
MW cont. processing ?
Public
Detergents & Intermediates
23.07.2013
Biodiesel and microwave
Morschhäuser. Scholz, Fairweather,
Gibson, Krull, Kappe
Detergents & Intermediates, 23.07.2013
Biodiesel production in continuous flow - basic route -
Public, Microwave assisted processing at commercial scale 35
Increasing efficiency
Rapeseed oil
1:4 Oil /Methanol
1:8 Oil /Methanol
Catalyst: NaOCH3, 1 wt%
Max. Temp: 180°C
Flow: 6-8 L/h (27 sec)
after 1st run;
no further treatment
90 mol%
> 95 mol%
Detergents & Intermediates, 23.07.2013
Slide 36
Biodiesel production in continuous flow - acidic route - Catalyst: CH3-SO3H, 1 wt%
Max. Temp: 170°C
Flow: 6,5 L/h (30 sec)
first pass
second pass
crude coconut oil
90 mol%
> 98 mol%
virgin grade coconut oil
(cold pressed)
coconut oil methyl ester
(after processing)
crude glycerol
containing phase
Public, Microwave assisted processing at commercial scale
0,5 wt% water
2,6 wt% FFA
Detergents & Intermediates, 23.07.2013
MW assisted esterification of FFA Stearic acid methyl ester
Public, Microwave assisted processing at commercial scale 37
Catalyst: MeSO3H, 1 wt%
Max. Temp: 180°C
Flow: 6-7 L/h (27 sec)
pressure: 18 bar
• very high conversion
observed for long chain FA
• no product degradation a
b c
c
d
yield: > 98%
Detergents & Intermediates, 23.07.2013
Public, Microwave assisted processing at commercial scale 38
Catalyst: MeSO3H, 1 wt%
Max. Temp: 175°C
Flow: 6-7 L/h (27 sec)
pressure: 18 bar
a
d
c,c`
b,b`
MW assisted esterification of FFA Benzoic acid methyl ester
• very high conversion
observed for aromatic FA
• no product degradation
yield: 96%
Detergents & Intermediates, 23.07.2013
Kinetics of acid catalyzed transesterification
Public, Microwave assisted processing at commercial scale 39
What is common understanding
on acidic route ??
What is known in literature ??
Detergents & Intermediates, 23.07.2013
Kinetics of acid catalyzed transesterification
Public, Microwave assisted processing at commercial scale 40
Temperature dependency1) Catalyst conc. dependency1)
source: 1) J.M. Marchetti; M.N. Pedernera; N.S. Schbib : Int. J. Low-Carbon Tech. (2011) 6 (1): 38-43.
more heat beneficial... more catalyst beneficial..
Detergents & Intermediates, 23.07.2013
Public, Microwave assisted processing at commercial scale 41
source: 1) J.M. Marchetti; M.N. Pedernera; N.S. Schbib : Int. J. Low-Carbon Tech. (2011) 6 (1): 38-43.
2) Siddharth Jain, M.P. Sharma, Shalini Rajvanshi: Fuel Processing Technology 92 (2011) 32–38
Molar ratio MeOH/FFA1) Reaction time2)
Kinetics of acid catalyzed transesterification
8:1
MeOH/FFA
2-3 hours
Detergents & Intermediates, 23.07.2013
FAME via acidic processing cont. microwave processing – lab data
Public, Microwave assisted processing at commercial scale 42
Classical versus MW processing of
FFA containing feedstock using acidic
catalysis
Classical1) MW2)
reaction temperature 65 – 100°C 170°C
Methanol / FFA 8:1 2:1 [on FFA]
processing time 2-3 h 10-30 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
Detergents & Intermediates, 23.07.2013
• high temperature
• unfavorable Methanol/Oil ratio
• long processing time
• pressure required
FAME via acidic processing Summary
Public, Microwave assisted processing at commercial scale 43
• 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 √
• high temperature
• unfavorable Methanol/Oil ratio
• long processing time
• pressure required
• high temperature
• unfavorable Methanol/Oil ratio
• long processing time
• pressure required
• high temperature
• unfavorable Methanol/Oil ratio
• long processing time
• pressure required
Classical acidic route MW processing
Public
Detergents & Intermediates
23.07.2013
Microwave processing in continuous flow t/day - scale
Morschhäuser. Scholz, Fairweather,
Gibson, Krull, Kappe
Detergents & Intermediates, 23.07.2013
Clariant's Hybrid reactor “flow heater”
Public, Microwave assisted processing at commercial scale 45
915 MHz continuous flow
operates at 25 to 300°C
up to 40 bars tested
approval under “pressurized equipment guideline”
(proved by German TüV)
Detergents & Intermediates, 23.07.2013
MW assisted continuous process for making Biodiesel
Public, Microwave assisted processing at commercial scale 46
Detergents & Intermediates, 23.07.2013
Methyl-Ester content: > 98%
double pass
FAME on large scale (5 t/day) Palm Kernel Fatty Acid Distillate
Methyl-Ester content: 91%
single MW run
Public, Microwave assisted processing at commercial scale
acidic
process
Detergents & Intermediates, 23.07.2013
Energy efficiency from power plug to process heat
Slide 48
Multi mode (lab use) 2.45 GHz
Hybrid resonator 915 MHz
Single mode (lab use) 2.45 GHz 100% from power plug
40% transformation loss 10-12% MW→heat transfer
40% transformation loss 30-40 % MW→heat transfer
90-95 % MW→heat transfer
Hybrid resonator 2.45 GHz
40% transformation loss
20% transformation loss
90-95 % MW→heat transfer
20-25%
50-55%
70–75%
5-8%
Overall efficiency
[%]
99 % 81%
found
Public, Microwave assisted processing at commercial scale
Detergents & Intermediates, 23.07.2013
Slide 49
Total energy efficiency steam heated systems/ 915 MHz MW reactor
*) L.A.Hulshof; Right First Time in Fine Chem. Process Scale-up; Scientific update LLP; (2013) p.121
Gas
50%
Electricity
Steam MW energy
Reaction
mixture
50-65%
90% 85%
Total energy
efficiency: 43% 23%
82% (915 MHz)
99% (915 MHz, 2.45 GHz)
35% (915 MHz)
“twice as efficient”
primary energy
”green” electricity
Public, Microwave assisted processing at commercial scale
Detergents & Intermediates, 23.07.2013
Slide 50
Heat transfer classical systems
*) L.A.Hulshof; Right First Time in Fine Chem. Process Scale-up; Scientific update LLP; (2013) p.121
• bigger equipment size
• numbering up
Scale up strategy:
V = 1000 cm3
D = 2,75 cm
L = 100 cm
Public, Microwave assisted processing at commercial scale
Detergents & Intermediates, 23.07.2013
Slide 51
Energy transfer 915 MHz MW reactor
*) L.A.Hulshof; Right First Time in Fine Chem. Process Scale-up; Scientific update LLP; (2013) p.121
𝑷𝑀𝑊 = 𝟐 ∗ 𝝅 ∗ 𝒇 ∗ 𝜺𝟎 ∗ 𝜺′′ ∗ 𝑬𝟐 ∗ V frequency
dielectric constant
dielectric loss
E- field strength
Volume
𝑷𝑀𝑊 ≈ 𝑬𝟐
• increase power release
of the magnetron
• increase tube diameter
Scale up strategy:
Public, Microwave assisted processing at commercial scale
Detergents & Intermediates, 23.07.2013
Summary and outlook
Public, Microwave assisted processing at commercial scale 52
• 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, tresidence)
• Overall energy efficiency competitive to classical systems
• Combination of MW processing and renewable electricity
potentially superior to standard processing
Detergents & Intermediates, 23.07.2013
Technical landscape 2013
Slide 53
2.45 GHz
915 MHz
“several
tons/day
realized”
Public, Microwave assisted processing at commercial scale
Detergents & Intermediates, 23.07.2013
Remark
54
…..from 1881 ……..
The Kings of steam and coal with worries
clouded face asking themselves:
“What will the infant electricity grow to ?”
Public, Microwave assisted processing at commercial scale
Detergents & Intermediates, 23.07.2013
Many thanks to….
Public, Microwave assisted processing at commercial scale 55
Clariant
Dr. Hans Jürgen Scholz
DI Said Kchirid
Team members
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)
Procter & Gamble Chemicals
Dr. Neil Fairweather
Dr. Mike Gibson
Public
Detergents & Intermediates
23.07.2013
Thank you very much for your audience
Morschhäuser. Scholz, Fairweather,
Gibson, Krull, Kappe