microwave assisted processing at commercial scale · detergents & intermediates, 23.07.2013...

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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

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23.07.2013

Introduction

Morschhäuser. Scholz, Fairweather,

Gibson, Krull, Kappe


Technical landscape 2012

Slide 4

2.45 GHz

915 MHz

?

Public, Microwave assisted processing at commercial scale


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



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


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Microwave processing in continuous flow kg/h - scale




“Hybrid concept”



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

[%]



Clariant's Hybrid reactor “flow heater”


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

http://www.fraunhofer.de/



Example Reactions – 2.45 GHz / < 6/10 kW 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 ???


Biodiesel and Microwave


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


“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


Microwave

Microwave

continuous-flow processes

continuous-flow processes

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Biodiesel




World Biodiesel Production


16,4 Mio tons

[Mio tons]

Lamers, P.; Internationale Biodieselmärkte; UFOP Schriften (2011) 4.


International bioenergy trade


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





Reviews. 15 (2011) 2655-2676.

Significant subsidies for use of

Biodiesel in many EU countries



Volumetric Excise Tax Credit

in US extended till 2009





Reviews. 15 (2011) 2655-2676.



Penalty tax for US Biodiesel imports

into EU countries

Indonesia

increases

production for EU





Reviews. 15 (2011) 2655-2676.



Indonesia

increases

production for EU

Half of EU Biodiesel consumption

based on imports



• Issue water

Classical FAME synthesis basic route


Classical FAME synthesis basic route


• Issue free fatty acid (FFA)


Classical FAME synthesis acidic route


• Issue reactivity

fast √

slow !!


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


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



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)


Key messages from Zang et. al. (2003) Summary of economical considerations


• 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$



Biodiesel

data origin: http://www.indexmundi.com/commodities

450 US$ per ton

1100 US$ per ton



Feedstock cost development

2006 2013

100 kt/year unit,

soybean based

500

1.000

US $/t

Soy bean oil


Biodiesel


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


Biodiesel price and margin 2009-12


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


Cost driven decision of process route


• 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)


Concept for proof of principle


can we combine the

acidic route

with

MW cont. processing ?

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23.07.2013

Biodiesel and microwave




Biodiesel production in continuous flow - basic route -


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%


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


0,5 wt% water

2,6 wt% FFA


MW assisted esterification of FFA Stearic acid methyl ester


Catalyst: MeSO3H, 1 wt%

Max. Temp: 180°C


pressure: 18 bar

• very high conversion

observed for long chain FA

• no product degradation a

b c

c

d

yield: > 98%



Catalyst: MeSO3H, 1 wt%

Max. Temp: 175°C


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%


Kinetics of acid catalyzed transesterification


What is common understanding

on acidic route ??

What is known in literature ??




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..



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)


8:1

MeOH/FFA

2-3 hours


FAME via acidic processing cont. microwave processing – lab data


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


• high temperature




FAME via acidic processing Summary






• easy to achieve √

• 2 :1 molar ratio sufficient (MeOH/FFA) √

• only seconds necessary √

• Pressure no issue √













Classical acidic route MW processing

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Microwave processing in continuous flow t/day - scale






915 MHz continuous flow

operates at 25 to 300°C

up to 40 bars tested

approval under “pressurized equipment guideline”

(proved by German TüV)


MW assisted continuous process for making Biodiesel



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


acidic

process


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


Hybrid resonator 2.45 GHz




20-25%

50-55%

70–75%

5-8%

Overall efficiency

[%]

99 % 81%

found



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



Slide 50

Heat transfer classical systems


• bigger equipment size

• numbering up

Scale up strategy:

V = 1000 cm3

D = 2,75 cm

L = 100 cm



Slide 51

Energy transfer 915 MHz MW reactor


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:



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, tresidence)

• Overall energy efficiency competitive to classical systems

• Combination of MW processing and renewable electricity

potentially superior to standard processing


Technical landscape 2013

Slide 53

2.45 GHz

915 MHz

“several

tons/day

realized”



Remark

54

…..from 1881 ……..

The Kings of steam and coal with worries

clouded face asking themselves:

“What will the infant electricity grow to ?”



Many thanks to….


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

http://www.uni-duesseldorf.de/

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23.07.2013

Thank you very much for your audience



microwave assisted processing at commercial scale · detergents & intermediates, 23.07.2013...

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