Sustainable Chemicals Industry
Process Intensification
Dr. Jean-Marie Bassett
General introduction to TNO
EXPERTISE
CENTERS
TNO organization
Technical Sciences
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1800
950
850
Employees:
General introduction to TNO
Our position in innovation
Demand or
Opportunity
Fundamental
Research
Research
Ideas
Feasibility
& Concept
design
Research
Production
preparation
Proof of
principle
R&D
Functional
Model
Prototype
Pilot
Product
development
Technical aspects
Regulatory aspects
Commercial aspects
TNO
Universities
TNO and/or company R&D
Company and/or manufacturer
Trials
Tests
Production
Sales
General introduction to TNO
TNO as your partner in R&D
 Business models
Fee-for-service
Open innovation:
 Dual party program: TNO-Co financing
 Multiple party program: Consortium
 Project- & account-management
Multi-disciplinary project teams
Collaborate directly with partner
Multi-level contact
 Confidentiality
 Intellectual Property
Sustainable Chemicals Industry
Process Intensification
TNO’s vision on Chemicals Industry
The chemicals industry in Europe needs to reduce its dependency on fossil
resources by 50% in 2030
The chemical industry in Europe wants to double its added value by:
Reducing operating costs
Increasing raw material efficiency
Creating more high added value products
Enabling the industry’s ambition by working on 3 innovation lines:
1. Biobased economy: biomass refinery, white biotech, chain improvement
2. Small Scale Chemistry: process intensification, flow chemistry
3. Innovative Industrial Risk Management
Sustainable Chemicals Industry
Process Intensification
Process Intensification at TNO
Continuous process technology that replaces batch technology for economical
and ecological efficiency.
 Mainly in specialties, fine chemicals & pharmaceuticals.
Technical hurdles
Downstream processing and integrated process control
Multi-phase / multi-purpose processes
Cost-effective Scale up
Sustainable Chemicals Industry
Process Intensification
Our position in process development
Chemical process development chain:
Laboratory
Bench
Pilot/Demo
TNO Focus
TNO competences:
- Multi-phase flow, separation technology, sensor technology
- Track record in development, scale-up and implementation
- Multi-disciplinary approach
- (Access to) pilot facilities
Production
Sustainable Chemicals Industry
Process Intensification
Continuous technologies portfolio
Separation technologies
Reactor technologies
Crystallization based
Sensor technologies
Multi-phase TNO Helix® reactor
TNO
HWC®
Analytical technologies
Flowmeters
purification
Ultrasonic particle monitors
TNO HWC® solvent switch
Micro-reactor manifolding
Optical spectroscopy
Membrane based
Interpret, model & control
Membrane reactors
Pertraction (l-l)
Chemometrics & data processing
MGA (g-l)
Pervaporation (l-g)
Spray Printing / Drying /
Encapsulation
Modelling & Predictive control
Sustainable Chemicals Industry
Process Intensification
Piloting & demonstration track record
Sustainable Chemicals Industry
Process Intensification – Continuous reactors
Axel Lexmond, Dirk Verdoes
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Process Intensification with continuous reactors
TNO’s aim:
Replace batch with continuous reactors
Bring technology into practice
Reduce costs and/or improve efficiency
Main competences
Micro Reactor technology
Tubular Reactor Technology
Integrated Reaction - Separation
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Platform approach continuous reactors
Technology platforms
TNO Helix® reactor
Membrane Slurry Reactor
Examples
TNO Helix reactor (TNO Helix) for multiphase exothermic reactions
Integration of heterogeneous catalysis, reaction and separation in a
Membrane Slurry Reactor
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
The TNO Helix Reactor:
A tubular continuous reactor ideally suited
for exothermal and multiphase reactions
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Characteristics of the Helix reactor
Helical structure results in secondary Dean vortices
Improved radial mixing
Minimal axial mixing
Near plug-flow conditions in laminar flow regime!
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Advantages of the Helix reactor
Very good mixing
Very high heat transfer rate
Narrow residence time distribution
Good multiphase handling, especially solids
No internals  Less clogging/fouling
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Straightforward scale-up strategy
Combination of:
Changing diameter and pitch (keeping the Dean effect)
Parallelization of Helix reactors
Depending on:
Expected throughput
Reaction kinetics & residence time
Thermal behaviour
Cost profile (CAPEX vs. OPEX)
Parallel Helix pilot unit
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Case-study: Exothermic reaction in Helix-reactor
Old situation
Highly exothermic
Fast reaction
Cooling capacity limits addition rate of
reactant B
Advantages Helix reactor
Production rate equals reaction velocity
Inherently safe
Easier control
Higher selectivity
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Case-study: Ionic Liquid production
Alkylation of methylimidazol using ethylbromide @ 6 bar and 93 ˚C
Highly exothermic reaction (~70 kJ/mole); high initial temperature
required (>80°C)
Too high temperatures (>120oC) will result in side reactions and
product contamination
Conventional production: 90% solvent / 10% reactants
Helix: Enables operation without solvent due to superior mixing
behaviour and excellent heat transfer properties
Plug flow character helix reactor reduces residence time from 45 min
to 2 minutes!
Small contents Helix Reactor: intrinsically safer process
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Optimization Process conditions Ionic Liquid
Tuning the process parameters
Red colour
indicates byproduct formation
To obtain the desired product
Perfect control of process conditions/product quality in helix reactor
No solvent and 20 times shorter : > 200 * higher specific production
capacity for Helix compared to conventional batch reactor
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Advantages after pilot phase
From batch to continuous
3 times higher production capacity
30 % less raw materials
75 % less energy
30 % less waste
Inherently safe plant
Decrease operational costs
R.O.I. < 1 year
Scale-out easy
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Case-study: Emulsion polymerization of MMA
Mixing behavior and plug flow:
Demonstration of production of mono
disperse nano-particles
Reaction time reduced from 4 hours in
batch reactor to 15 minutes.
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Conclusions Helix reactor
Dean vortices contribute to efficient and fast mixing in Helix Reactor.
The Helix reactor is ideally suited for multi-phase reactions.
Fast implementation possible by applying the scale out principle.
The Helix Reactor is a promising plug-flow “Micro”-Reactor for
applications like highly exothermic chemical reactions, polymerization
reactions, cooling crystallization, precipitation, …….
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
The TNO Membrane Slurry Reactor:
Integration of heterogeneous catalysis,
reaction and separation
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Principle of the MSR
Product can pass membrane or filter, while catalyst particles are
retained in reactor which is operated in fed-batch mode
Advantages
Suited as add-on to batch reactors
Continuous operation
Low hold up of catalyst in system
Mild mechanical treatment of catalyst
Suited for chemical and bio-catalysis
Increased activity catalyst
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Case study: enzymatic-catalyzed
transesterification
Continuous production with MSR
Catalyst: Lipozyme TL IM
Temperature: 70 °C
Feed: Palm oil/coconut oil 60:40
melting point [°C]
Experimental
50
45
40
35
30
0
50
100
150
Time [hr]
Results
Highly permeable membranes selected
Stable production over 200 hrs demonstrated
Catalyst activity increase with factor 4
Cost reduction MSR: 50% compared to batch reactor
200
250
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Case-study: MSR-CLEA hydrolysis of Penicillin G
PenG
feed
Conditions
Feed: 10% K-Pen G
[CLEA]: 5, 7.5 & 10 %
MSR
Conversion: 65, 75 & 82 %
APAPrecipitation
Vreactor = 400 ml
T=20 C, pH=8.0
MSR CLEA Overview Continuous experim ents
1,2
1M NaOH to maintain pH
100 mM Phosphate buffer
Rate APA (mmol/min) cumulative
1
0,8
0,6
Rate APA cumulative 5% CLEA
Rate APA cumulative 7.5% CLEA
Rate APA cumulative 10% CLEA
0,4
0,2
0
0
20
40
60
80
100
tim e (m in)
120
140
160
180
Sustainable Chemicals Industry
Process Intensification
Continuous Reactors
Conclusions Membrane Slurry Reactor
Concept for a continuous process which combines
heterogeneous catalysis, reaction and separation
Low hold-up of catalyst in MSR and no pumping/external
handling needed
Suited as add on for batch reactor
CLEAs are interesting biocatalysts suited for use in MSR
Proof of Principle delivered for hydrolysis of Penicillin by CLEA
Sustainable Chemicals Industry
Process Intensification – Separation Technology
Mark Roelands, Dirk Verdoes
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Process Intensification in Separation Technology
TNO’s aim:
Replace batch with continuous separations
Bring technology into practice
Reduce costs and/or improve efficiency of separation processes by
making smart combinations of functionalities
Main competences
Crystallization based separations
Membrane based separations
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Platform approach separation technology
Technology platforms
TNO Hydraulic Wash Column
Membrane contactor modules
Micro-evaporator technology
Examples
TNO Hydraulic Wash Column (TNO HWC) for solid-liquid
separation and counter current washing
Pertaction for liquid-liquid extraction and phase separation
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
The TNO Hydraulic Wash Colum:
A versatile solid-liquid separator for high
purity products
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Conventional process high purity products
Better:use a TNO wash column = solid-liquid separation and
washing (with no nett use of wash liquid)
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Principle of the TNO Hydraulic Wash Column
Photograph of a 15 cm TNO
Hydraulic Wash Column
operating with para-xylene.
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
The counter current washing process
Bottom zone: Crystal bed moves down and the pure wash liquid
moves up
Wash Front: Recrystallization of the pure wash liquid on cold crystals
in the bed (see example water).
EXAMPLE
ice crystals in
salt water (-8 °C)
ice crystals in
pure water (0 °C)
Two bottom zones
of the wash column
S-L
separation
position filter
wash front
counter current
washing
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Illustrative results for purification of para-xylene
A simulated industrial para-xylene feed was purified in a melt
crystallization – TNO HWC process
distribution coefficient = [impurity, product]/[impurity, mother liquor]
Compound
[impurity]
[impurity]
Distribution
mother liquor
product
coefficient
o-xylene
2.0 wt%
0.002 wt%
0.001
ethylbenzene
1.5 wt%
0.001 wt%
0.0007
toluene *
5.3 wt%
0.115 wt%
0.02
mixture
10.8 wt%
0.07 wt%
0.006
* Solid
solution forming impurity
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Solvent switch in TNO Hydraulic Wash Column
filtrate recycle pump
Feed slurry
(solids in
solvent A)
slurry feed pump
Filtrate (solvent A with
Small amount of B)
filter
counter-current
washing process
unwashed crystal bed
washed crystal bed
Product slurry
Solids in
solvent B
Wash liquid
Solvent B
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Differences between solvent switch and melt
crystallization
No recrystallization at the wash front
Wash front always at the position of the filters
HWC product is typically a suspension instead
of a melt
Difference in layout of bottom section (e.g. no
melter)
Photo of a 15 cm TNO
HWC during solvent
switch of Carnalite
(KMgCl3.6 H20)
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Practical example: results for solvent switch NaCl
wash efficiency (%)
100
99% wash efficiency
90
80
70
60
0
1
2
3
4
flow rate wash liquid (wt% )
5
6
Results for the
washing of
NaCl in a HWC.
The impurity to
be removed
was SO42- and
the applied
wash liquid was
a saturated
NaCl-solution.
Wash column
capacity = ±
21.2 ton/m2•hr
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Scale-up strategy of a Hydraulic Wash Column
Case-study Para Xylene
diameter column =
1.13 m = 1 m2
effective height column
 1-2 m
200 filter tubes
(with d = 2.5 cm)
capacity > 15 tonnes/m2.hr
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Background Information HWC-55 skid
Close up of the HWC-55
Dimensions Skid and Wash Column
• Skid ± 2 * 3 * 8 m, turn key
• Wash column: height ± 1.5 m
± 50 filter tubes
diameter ± 0.55 m
Certifications
• Explosion proof: ATEX zone 2,
Group IIA,T3
• CE-certified (PED)
Design parameters
• Target capacity HWC-55:
1.5-5 tonne purified product/hour
• Maximum operating pressure: 10 bar
• T-range: -15 to 80C
• Different operating options possible
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
TNO Hydraulic Wash Column HWC-55 pilot plant
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Overview test results HWC-55
Easy start up (on day 2) and stable operation
Illustrative process conditions:
feed and wash pressures: ± 3 en ± 1.5 bar
bed en wash front heights: 30 cm and 10 cm
T wash front: 7-8C
High production capacity: up to 5 ton pure product per hour = 20 ton
per hour per m2 wash column !!
High product purity: 99.94 wt% (> specs) for 85 wt% mother liquor.
I.e. distribution coefficient = ± 0.004.
CONCLUSION:
Scale up proven and HWC implemented at industrial scale
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Conclusions Hydraulic Wash Column
Technical feasibility for use of TNO Hydraulic Wash Column in
suspension-based melt crystallization and solvent switch proven for
various systems
Impurity concentration in product is 100 – 1000* lower than in mother
liquor. Good perspectives in final purification i.e. product purity and
recovery
TNO wash column concept offers:
- a straight forward scale-up potential, proven up to 55 cm
- a broad turn down ratio
- control strategies for automatic operation
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Pertraction
A hybrid membrane liquid-liquid extraction
process for the purification of process and
waste water streams
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Principle Pertraction for Removal of Organics
PRINCIPLE
water
Extractant
Economical Advantages
 low investments
 low maintenance and operational
costs
 small foot print & compact equipment
Membrane module
Technical Advantages
 flexible process operation
 small extractant volume
 no density difference needed
between liquids
 no emulsion formation
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Solvent selection: medium throughput screening
Robotic arm
Analysis
Shaker
unit
Samples
Solvents
HPLC
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Solvent selection: predicted vs measured Kd
y = 0.9778x
R2 = 0.9799
1000
measured phenol Kd

phenol solv
Kd 
 phenol aq
100
Complexation
10
Hydrogen bonding
1
0
0
1
10
predicted phenol Kd
100
Hydrophobic interaction
1000
Very good prediction
of removal efficiency!
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
TNO Membrane Modules
Lab scale test module
Length * Height * Width = 0.1 m * 0.1 m * 0.05 m
Effective membrane surface: 0.05 m2
Pilot scale module
Length * Height * Width = 0.2 m * 0.3 m * 0.05 m
Effective membrane surface: 1.2 m2
Specific area/volume = 280 m2/m3
Width liquid channel = ± 2 mm
Small full scale module
Length * Height * Width = 1.5 m * 0.5 m * 0.14 m
Effective membrane surface: 40 m2
Specific area/volume = 450 m2/m3
Width liquid channel = ± 2 mm
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Case-study: Aromatics from waste water
Original process
• Waste water polluted with
aromatic impurities was
incinerated (5 Mm3 gas/yr)
Pertraction option
• Use feedstock of process as
extractant in pertraction
• Replace incineration by
biological waste water
treatment
• Increase yield of the process
Invista (former Hoechst ) - Vlisssingen
waste water
10 m3/h
biological
waste
water
treatment
aromatics
process
Waste water flow: 10 m3/hr
Impurity-1, in: 2200 ppm
Impurity-1, out: < 40 ppm
Impurity-2, in: 830 ppm
Impurity-2, out: <15 ppm
feedstock
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Process flow diagram
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Pertraction full scale unit for the removal of
aromatics from waste water
Information full scale plant
 3 membrane modules in series (35
m2/module)
 In operation since 1998
 Critical unit operation in process
 Realised benefits:
 stable and robust
 process integrated solution
increasing process yield
 Energy friendly alternative for
incinerator (5 Mm3 less gas per
year)
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Emulsion Pertraction installation for passivating
baths in galvanic industry
Membranes
Emulsion
Installation
contains 26 m2
membranes.
Investment costs
± 50 k€
Candle filter
Feed acid
Spent acid
with Zn, Fe
Distribution
coefficient for Zn
is ± 100
Sustainable Chemicals Industry
Process Intensification
Continuous Separation Technology
Conclusions membrane contactors
TNO has proven processes using membrane technology for
continuous separation of organics and in-organics.
Lab-scale, pilot-scale and production-scale applications.
Pertraction, pervaporation & Membrane Gas Absorption.
Sustainable Chemicals Industry
Process Intensification – Inline Process Analysis
Leon Geers
Sustainable Chemicals Industry
Process Intensification
Inline Process Analysis
Classical process and quality control
During production: typically only T, p and sometimes flow monitoring
Product
Feedstock
Waste
Process control: keep
process parameters (p,T)
within a fixed window
T & p control
Price / kg
After production: product quality assessment in lab
profit
rework / purify
or dump
waste
Source: http://www.cartoonnetwork.com
Product quality
Consequence: money is lost here!
Sustainable Chemicals Industry
Process Intensification
Inline Process Analysis
Idea behind PAT: on-line monitoring
During production: monitoring of quantities that are critical to quality
(CTQ) and taking appropriate control actions
Product
Operator or
control system
Feedstock
Waste
Data modeling
On-line measurements
of CTQ quantities
Better understanding of process
Variability managed by the process
Product quality predicted reliably over the design space of process
parameters
BUT
Before process control comes process monitoring
Sustainable Chemicals Industry
Process Intensification
Inline Process Analysis
Process monitoring toolbox
Sensor / Analytical Equipment:
Temperature, pressure, flow sensors
Chemical composition sensors (e.g. spectroscopy, electrochemical sensors)
Phase distribution sensor
Particle monitor (size distribution & concentration)
Data Analysis Methodologies:
Inversion
Chemometrics
Process Model:
Reaction model (order)
Mass & energy balances
Sustainable Chemicals Industry
Process Intensification
Inline Process Analysis
Examples of TNO sensor technology
Developed with/for equipment manufacturers
Mass & volume flow meters
Chemical concentration sensors
Fibre Bragg Gratings
Micro IR-spectrometer
Flowmeters
Integrated nano-photonics
Micro IR-spectrometers
Particle monitoring systems
Micro gas chromatograph
Integrated nano-photonics
Fiber Bragg Grating
Ultrasonic particle monitor
Ultrasonic transmission
spectroscopy
Electrochemical sensors
Micro gas chromatograph
Sustainable Chemicals Industry
Process Intensification
Inline Process Analysis
Example process: Production of aspirin
Aspirin from salicylic acid and acetic anhydride (sulphuric acid cat.)
Batch reactor at different temperatures and different catalyst
concentrations
In-line sensor: Near infra-red spectroscopy
Stirring motor
Process model: Batch reaction
Access for
chemicals
Probe
Goals
NIR spectrometer
Determine end time of process
Determine process kinetics
Three necked flask
Sustainable Chemicals Industry
Process Intensification
Inline Process Analysis
Spectra of aspirin production monitoring
Due to similarities in molecular
3
structure of reactants and products,
their NIR spectra are similar
t=0
2.5
Hence, there is no one-to-one relation
2
concentrations of present species
Absorbance (-)
between the height of peaks and
1.5
t = tend
1
0.5
Chemometrics are necessary to
calculate the correlation between
species concentration and spectra
0
-0.5
1000
1100
1200
1300
1400 1500 1600
Wavelength (nm)
1700
1800
1900
Changing spectra during reaction
2000
Sustainable Chemicals Industry
Process Intensification
Inline Process Analysis
Results
Experimental spectra acquired during
aspirin synthesis is used for
determination of rate constant
Appearing
products
Second order rate equation:
rAspirin  k [ AcOAc] [ SalOH ]
Disappearing
reactants
Solid lines present model data
Symbols present data reconstructed
from reaction spectra
At 95°C and 0.029M catalyst, the recipe
states a process time of 10 min, k is
unknown
Result:
• process time appears to be
only 300 s (=5 min)
• rate constant k=3.0 l/mol.s
Sustainable Chemicals Industry
Process Intensification
Inline Process Analysis
Conclusions Inline Process Analysis
Development of sensors together with equipment suppliers for various
applications
Application of existing and new measurement technology for in-line
analysis at bench-scale for measurement of kinetics
Development of in-line analysis tools at plant-scale for monitoring and
control of continuous reactors/separators.
Sustainable Chemicals Industry
Process Intensification
For more information please contact:
Dr. Jean-Marie Bassett
Business Development Manager
jean-marie.bassett@tno.nl
+31 (0)88 866 8118
+31 (0)6 104 804 73
Ir. Martijn P. de Graaff
Business Development Manager
martijn.degraaff@tno.nl
+31 (0)88 866 6437
+31 (0)6 222 608 71