Micro Process Technology - Welkom bij NWO · - focussing on lessons learnt ... Chemical Engineering, BASF SE . Outline 1 Micro Process Technology @ BASF history and motivation 2 Lessons

Micro Process Technology and bulk chemical industry

- focussing on lessons learnt

PoaC Symposium

The Dutch process on a chip and micro reactor meeting

May 22, 2013

Conference Center ‘The Strip’, Eindhoven, Netherlands

Dr. Ralf Böhling

Chemical Engineering, BASF SE

Outline

1 Micro Process Technology @ BASF

history and motivation

2 Lessons learnt

Deydrogenation, Mercaptoethanol,

Cyclohexane Oxidation

3 Applications and outlook

Heat exchanger, Reactor, Evaporator, Mixer

Inherently safe – enables operation in the

explosive regime

No hot spot – improved selectivity

Numbering up instead of scale up – easy

transfer to production scale

Fast mixing for improving selectivity

Some Advantages commonly

attributed to micro reactors ...

Micro Process Technology

Motivation

. . . .

Source: Presentation of F. Lippert, Process Intensification @ BASF, Sep 7 - 10, 2008, Kyoto/Japan

History of Micro Process Technology

World and BASF

0

100

200

300

400

2006

2004

2002

2000

1998

1996

1994

1992

1990

Publications

Patents

Dr. Wörz (BASF)

starts cooperation

with IMM (Prof. Ehrfeld)

and FZK (Prof. Schubert)

Fast liquid phase reactions,

Oxy-dehydrogenation

1. IMRET

in Frankfurt

Chairman

Dr. Jäckel BASF

Start of SOLEMIO

a BMBF founded project

Focus on

wall coated micro reactors

2008

Implementation of a

Heatric PCHE

as compact heat exchanger

Start of Operation

of a Heatric PCHE

as reactor for

fine chemicals

BMBF-Project

µ.Pro.Chem

BASF, Degussa,

IMM, BAM,

TU-Chemnitz

Bringing µ-reactors

into technical scale

EU-Projekt

F³-Factory

BASF, Bayer, Evonik,

KIT, Astra Zeneca….

Development of

modular continuous plant


Outline

1 µ-Process-Technology @ BASF


2 Lessons learnt and bad luck



3 Applications and outlook

Heat exchanger, Reactor, Evaporator


Strong exothermic heterogeneous gas phase reaction:

Quelle: O.Wörz et al., Microreactors a new efficient tool for reactor development, Cem. Eng. Technol 24, 2 (2001) 138-143

Dehydrogenation (heterogeneous gas phase)

Laboratory

microreactor

S = 96%

T: 390 °C

Q

P

Laboratory

reactor

S = 90%

d: 50 mm

current plant reactor

S = 80-85%

d: 3m

Tmax = 450°C

Hot spot: 60 °C

former

plant reactor

S = 45 %

d > 1m

T = 550 °C

Q: heat flow

P: mass flow

Pilot plant operation

Silver micro reactor become leaky

Structural failure

Catalytically active material is not

suitable as construction material

Source: IMVT of KIT

500 h

10 Vol.-% O2

450 °C

Dehydrogenation


Cooling channels


Cyclohexane Oxidation (gas – liquid phase)


OOH + O2

OH

O

+ H2O

BMBF Förderkennzeichen 16SV1992

Large scale industrial processes:

T < 180 °C / p < 20 bar / = 15 - 60 min

Cyclohexane conversion only < 6 %

Selectivity: 70 - 90 %

Source: Presentation of R. Böhling, µ.pro.chem,

ACHEMA Kongress 2009, 12 -13 May, Frankfurt am Main

Expectations in using a microreactor

high mass and heat transfer

increasing selectivity and/or conversion

lowering reaction volume

Space-time-yield of up to 10 t/m3·h achieved, impact of wall eliminated

but: Selectivity decreases at higher temperatures project terminated

Results of µ-experiments



Uncatalyzed cyclohexane oxidation in capillary tubes D = 0.25-2.1 mm / p = 40-60 bar / conversion of cyclohexane 5 %

Source: Presentation of R. Böhling, µ.pro.chem, ACHEMA Kongress 2009, 12 -13 May, Frankfurt am Main

Existing BASF Process

Long residence time (>> 1 h)

Low temperature and low pressure

Byproduct TDG (up to 20 %), TDG is essential as catalyst

highly exothermic gas-liquid reaction

Potential for micro reactor ?

Mercaptoethanol (MCE) from EO and H2S



BMBF Förderkennzeichen 16SV1992



Lab results with several µ-reactors

(T = 110-140 °C / p = 30-90 bar / = 2 min)

- Capillary tubes (d<1 mm)

- Parallel channel structure (IMM)

- Mingatec reactor

STY up to 16 t/m3h achieved

high selectivity only in liquid phase

Selectivity up to 95 % achieved

Pilot plant tests planned


Lab results

Flow chart pilot plant at EVONIK site Hanau-Wolfgang



H2S

EO

TDG

EO; H2S; N2 MCE

N2

Mixer (CSTR)

25 °C

1.

Sambay

1 bar

µ-Reactor 2.

Sambay

vacuum

recycle TDG

Mixing zone

Mingatec only

TDG


IMM

reactor

Mingatec

reactor

Front view (work-up section on back side)

Exchangeable

microstructured

reaction module

Pilot plant (start up III/07 at Evonik site Hanau-Wolfgang)




µ-Reactors tested in pilot plant


Mingatec-reactor (Miprova®, 2 types)

20 ml lab. reactor

(1 channel / 1,7 x 12 mm / 3 x 0,5 mm N comb layers)

100 ml pilot reactor

(12 channels / 1,2 x 12 mm / 2 x 0,5 mm N comb layers)

IMM – type


Heatric-type

130 ml pilot reactor

(4 channels / 1.0 mm) Lab reactor 3 ml reactor volume

Pilot reactor 90 ml (30 fold stack)

Major step during

manufacturing:

brazing of the wet

chemically etched plates

Enlarged view: cut through

the (BASF) reactor stack


During start-up period:

STY of up to 16 t/m3h

confirmed

Sel. 90-94 % at EO

conversion of

> 95 % achieved

Pilot plant results




MCE-Pilotanlage

110°C / 80 bar( 1,3 mol/mol H2S/EO)

84

86

88

90

92

94

96

98

100

70 75 80 85 90 95 100

Conversion %

Sel.

%

Mingatec Labor IMM

Mingatec 100 ml Mingatec (+TDG)

Heatric II Kinetic 1 mm RohrKinetic 1 mm lab tube

With closed TDG-recycle:

Fast plugging of all micro reactors

Decrease in reactor performance

Results



recycle TDG

**A-Reactor

* fresh TDG

**B-Reactor

* fresh TDG from the Lu-site BASF plant

synthesis by addition of MCE and EO

** A and B-Reactor are two identical Heatric PCHE


Results


Continuous process only with additional TDG-work-up feasible

Instable process due to oligomer formation



Heatric A-Reactor

running with recycle TDG

Heatric B-Reactor

running with fresh TDG

IMM Reactor

running with recycle TDG

scrubbing solutions after operation

Alkane Nitration (hom. gas phase)

State of the art: DOW process with an adiabatic multi stage reactor with

HNO3 feeding between the stages – operation up to 400°C

broad product spectrum with nitromethane, nitroethane, 1- and 2- nitropropane......

Low conversion with the need of propane recycle

2-nitropropane selectivity around 25 - 30 %

Target: > 50% propane selectivity, nearly full conversion to avoid the propane recycle

Idea: Using a micro reactor to ensure isothermal conditions for shifting product

mix to the kinetically preferred 2-nitropropan


Gas-Phase Alkane Nitration Background


Challenge: Optimum reaction condition are in an explosive regime and elevated pressure range.

→ Micro structure can not avoid explosion – a multiplication factor for pressure rise in case

of explosion of around 50 is taken into account

Dependency of quenching distance and pressure Quenching distance for stochiom.

combustible air mixture

Quench distance

[mm]

1,50

0,64

1,17

2,03

0,58

Gas - componente

Methanol

Acetylene

Ethylenoxide

Methane

Hydrogen

Gas-Phase Alkane Nitration Challenge

→ Using an inherent safe reactor concept with pressure resistant > 500 bar and

do not forget all other parts with reaction mixture inside must also pressure resistant > 500 bar


Lab scale down:

60 m capillary inside a hot air oven

– for example

HEATRIC heat exchangers

Gas-Phase Alkane Nitration Results


Gas-phase nitration under thermal

control is within micro structured

devices feasible

for high selectivity inter stage feeding

of O2 is necessary to suppress side

reaction of O2

High temperature leads to the

thermodynamically preferred products

Avoid explosive liquid phase - strictly

Gas-Phase Alkane Nitration Results


Reactor concept: Cascade of Heatric heat exchangers with O2 feeding between them

25 °C

100 bar

280 °C

55 °C

280 °C 110 bar

270 °C

285 °C 311 °C

Project status: Stopped due to decrease of marked scenario from several thousends to

some hundred tons per year

Bi-phasic Substitution (liquid-liquid phase) Corning reactor


State of the art: Batch process with a complex temperature management

Target: Increasing selectivity, saving cooling costs and

reducing toxic hold up

Idea: Using a Corning micro reactor to ensure isothermal

conditions and good mixing to get a stable emulsion

during the operation

Bi-phasic Substitution Corning reactor


Project status: Stopped - investment due to capital costs uneconomically

Results:

Stable emulsion formed

inside Corning - fast phase

separation at Corning

outlet

Residence time < 1min

feasible

Temperature 60°C higher

than batch

Selectivity comparable to

batch process

Saving of cooling shown

Temperature profiles

batch

conti Corning

Corning lab plant

Glucose Dehydration (super critical phase)


OOH

OH

OH

OH

OH

O

O

OH

OHH2O

p = 400 barT ~ 450°C

Zeit < 1sec

Quelle: Alois Kindler BASF SE, GCN

C1 ID: 250 µm Heating rate: 10000 - 100000 K/sec

Heating time: 3 – 30 ms

C2 ID: 800 µm Reaction tube

W3 ID: 800 µm Cooling rate 2000 - 10000 K/sec

Heat transfer coefficient: 9000 – 27000 W/m²/K

Glucose Dehydration (super critical phase) Results


0

10

20

30

40

50

60

70

0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70

VWZ_nom in s (rho=0,4)

Yie

ld D

HD

in

mo

l%

450 °C - 5% Glucose 425°C - 5% Glucose

475°C - 10% Glucose 450°C - 10 % Glucose

425°C - 10% Glucose

Dehydration of glucose under

super critical conditions is

feasible without formation of

brown colored waste

An extremly short residence time

avoids plugging of the reactor

Project stopped

work up is uneconomically

Lack of demand for DHD

Outline

1 µ-Process-Technology @ BASF


2 Lessons learnt


Cyclohexane Oxidation, Propane Nitration…..

3 Applications and Conclusion

Heat exchange, Evaporation, Reaction, Mixing

Heat exchange

Located on 3rd deck of the plant Compact design – small footprint


Heatric heat exchanger at BASF plant

Source: Presentation of R. Böhling / S.Schirrmeister Micro Process Technology, April 25,—April 27 2008, German-American Frontiers of Engineering Symposium Irvine, California

Source:http://www.heatric.com/index.html

49.2 52.8 Heat Duty (MW)

1.8 1.5 P (bar)

38.4 117.5 37.9 120.2 T cool (°C)

555 555 Flow (t/h)

1.9 1.5 P (bar)

131.0 46.5 131.0 42.9 T hot (°C)

526 526 Flow (t/h)

Actual Design Parameter

Heatric heat exchanger in

operation at BASF since 2002

Decreasing performance

after 2 ½ years

Micro reactor fouling

Heat exchange



Gas puffing for cleaning of Heatric PCHE

Heat exchange



Offsite gas puffing

(Heatric)

View into feed header

Debris from gas puffing


Gas puffing for cleaning of Heatric PCHE

Heat exchange


Decomposition

within the miniplant evaporator at

different pressure

0

5

10

15

20

25

30

35

0 200 400 600

Pressure [mbar]

Co

nte

nt o

f d

eco

mp

ositio

n g

ase

s

in th

e e

xh

au

st va

po

r [V

ol.-%

]

Background

Evaporation


Evaporation with technical evaporator leads to

a brown colored waste stream and

could plug the evaporator even under vacuum conditions at 100 - 200 mbar

increasing pressure and temperature leads to non selective starting material cleavage

high cost for vacuum pumps and electrical power supply

used tube bundle of a technical evaporator

8 cm³ KIT-Cube discont. lab

distillation*

Temperature of

exhaust vapor

[°C] 225 198

Decomposition

fraction

[%] < 0,5 50,5

Evaporation at lab with a micro evaporator compared to a discontinuous

distillation at atmospheric pressure

Nearly no decomposition with a micro evaporator

Up to 50 % decomposition with usual lab equipment

* Source: Dr. Achhammer BASF SE

Micro vs. macro

Evaporation


The micro evaporator (1 cm³ KIT-Cube) operates at 1,2 - 2,6 bar up to more than 1000 h without plugging

Lab tests (8 cm³ “KIT-Cube”) with cycles of evaporation and condensation showed no formation of colored byproducts

fresh

starting

material

16-fold

evaporated ↔

condensed

1 cm³ “KIT-Cube”

capacity: 1 kg/h

channel wide: 200 µm

channel length: 1,4 cm

Lab plant with a

sectional view of the

used micro evaporator

capacity: 5 kg/h

Source: FZK

KIT micro evaporator

Evaporation


The heat transfer coefficient is only secondary for the feed material

decomposition within a technical evaporator

The crucial point is the residence time. In a micro evaporator it is less than

one thousandth compare to a technical evaporator.

1 cm³ KIT-Cube 10 l KIT-Cube tech.

evaporator

tube length cm 1,4 12 200

hyd. diameter mm 0,15 0,15 21

heat trans. coefficient W/(m²K) 4600 4600 300

Heat power kW 0,05 1000 1000

residence time sec 0,1 0,1 700

Characteristic data for micro and technical evaporators

Micro vs. macro

Evaporation


Source: http://www.basf.de/en/pharma/inside/2010-09/microreactors.htm

Smale scale production

Reaction


BASF operates two Heatric microreactors at its

Ludwigshafen site

One to produce samples of up to about 20 kilograms

One can manufacture quantities ranging from 1 to 50

tons for market launches of new products

The microreactors are used for reactions that require

high pressure, high temperatures or/and are strong

exothermic

The continuous mode of operation and the short

reactor residence time of the reaction media ensure

end products of consistently high quality

batch process

stirred vessel

space time yield

8 kg m-3 h-1

- BASILTM

continuous process

jet reactor

space time yield

69000 kg m-3 h-1

> 8 x 103

nucleophilic

catalysis/

Ionic liquid

Source: http://www.dechema.de/dechema_media/Downloads/fachsektionen/FS_PI/Workshop_2006_05_29-p-1798/Strohrmann_M_Prozessintensivierung_in_der_BASF.pdf

Large scale production

Mixing


Micro reactors are versatile

lab devices

Refrain from improper

generalizations

Operation in explosive regime

needs careful consideration

Corrosion, fouling and scale up pose

severe problems for production

applications

BASF already uses micro devices

and explores further applications

Conclusions



Thank you for your attention

Documents

Micro Process Technology - Welkom bij NWO · - focussing on lessons learnt ... Chemical Engineering, BASF SE . Outline 1 Micro Process Technology @ BASF history and motivation 2 Lessons