Basset.ppt

Sustainable Chemicals Industry
Process Intensification
Dr. Jean-Marie Bassett

TNO organization
1800
Technical
Sciences
Behavioural
&
Societal
sciences
Earth,
Environmental
&
Life
Sciences
950 850
Employees:
EXPERTISE
CENTERS
General introduction to TNO

Our position in innovation
Feasibility
& Concept
design
Proof of
principle
Functional
Model
Prototype
Pilot
Trials
Tests
Production
preparation
Production
Sales
Fundamental
Research
Research
Ideas
Demand or
Opportunity
Technical aspects
Regulatory aspects
Commercial aspects
Research R&D Product
development
Universities
TNO and/or company R&D
Company and/or manufacturer
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

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

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

Our position in process development
Chemical process development chain:
TNO competences:
- Multi-phase flow, separation technology, sensor technology
- Track record in development, scale-up and implementation
- Multi-disciplinary approach
- (Access to) pilot facilities
TNO Focus
Laboratory Bench Pilot/Demo Production

Continuous technologies portfolio
Separation technologies Reactor technologies Analytical technologies
Multi-phase TNO Helix® reactor
TNO HWC® purification
Crystallization based
Membrane based
Micro-reactor manifolding
TNO HWC® solvent switch
Pertraction (l-l)
Pervaporation (l-g)
MGA (g-l)
Flowmeters
Optical spectroscopy
Ultrasonic particle monitors
Modelling & Predictive control
Chemometrics & data processing
Sensor technologies
Interpret, model & control
Membrane reactors
Spray Printing / Drying /
Encapsulation

Piloting & demonstration track record

Process Intensification – Continuous reactors
Axel Lexmond, Dirk Verdoes

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
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
Continuous Reactors

The TNO Helix Reactor:
A tubular continuous reactor ideally suited
for exothermal and multiphase reactions
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!
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
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
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
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
Continuous Reactors

Optimization Process conditions Ionic Liquid
Tuning the process parameters
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
Red colour
indicates by-
product formation
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
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.
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, …….
Continuous Reactors

The TNO Membrane Slurry Reactor:
Integration of heterogeneous catalysis,
reaction and separation
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
Continuous Reactors

Case study: enzymatic-catalyzed
transesterification
Experimental
Catalyst: Lipozyme TL IM
Temperature: 70 °C
Feed: Palm oil/coconut oil 60:40
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
Continuous production with MSR
30
35
40
45
50
0 50 100 150 200 250
Time [hr]
melting
point
[°C]
Continuous Reactors

Case-study: MSR-CLEA hydrolysis of Penicillin G
Conditions
Feed: 10% K-Pen G
[CLEA]: 5, 7.5 & 10 %
Conversion: 65, 75 & 82 %
Vreactor = 400 ml
T=20 C, pH=8.0
1M NaOH to maintain pH
100 mM Phosphate buffer
MSR
PenG
feed
APA-
Precipitation
MSR CLEA Overview Continuous experiments
0
0,2
0,4
0,6
0,8
1
1,2
0 20 40 60 80 100 120 140 160 180
time (min)
Rate
APA
(mmol/min)
cumulative
Rate APA cumulative 5% CLEA
Rate APA cumulative 7.5% CLEA
Rate APA cumulative 10% CLEA
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
Continuous Reactors

Process Intensification – Separation Technology
Mark Roelands, Dirk Verdoes

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
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

The TNO Hydraulic Wash Colum:
A versatile solid-liquid separator for high
purity products

Conventional process high purity products
Better:use a TNO wash column = solid-liquid separation and
washing (with no nett use of wash liquid)

Principle of the TNO Hydraulic Wash Column
Photograph of a 15 cm TNO
Hydraulic Wash Column
operating with para-xylene.

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).
S-L
separation
counter current
washing
ice crystals in
salt water (-8 °C) position filter
wash front
ice crystals in
pure water (0 °C)
Two bottom zones
of the wash column
EXAMPLE

Illustrative results for purification of para-xylene
A simulated industrial para-xylene feed was purified in a melt
crystallization – TNO HWC process
Compound [impurity]
mother liquor
[impurity]
product
Distribution
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
distribution coefficient = [impurity, product]/[impurity, mother liquor]

Solvent switch in TNO Hydraulic Wash Column
Feed slurry
(solids in
solvent A)
Filtrate (solvent A with
Small amount of B)
Product slurry
Solids in
solvent B
Wash liquid
unwashed crystal bed
washed crystal bed
filter
counter-current
washing process
slurry feed pump
Solvent B
filtrate recycle pump

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)

Practical example: results for solvent switch NaCl
60
70
80
90
100
0 1 2 3 4 5 6
flowrate wash liquid(wt%)
wash
efficiency
(%)
99% wash efficiency
Results for the
washing of
NaCl in a HWC.
The impurity to
be removed
was SO4
2- and
the applied
wash liquid was
a saturated
NaCl-solution.
Wash column
capacity = ±
21.2 ton/m2•hr

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

Background Information HWC-55 skid
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
Close up of the HWC-55

TNO Hydraulic Wash Column HWC-55 pilot plant

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

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

Pertraction
A hybrid membrane liquid-liquid extraction
process for the purification of process and
waste water streams

Principle Pertraction for Removal of Organics
Economical Advantages
 low investments
 low maintenance and operational
costs
 small foot print & compact equipment
Technical Advantages
 flexible process operation
 small extractant volume
 no density difference needed
between liquids
 no emulsion formation
PRINCIPLE
Extractant
water
Membrane module

Solvent selection: medium throughput screening
Shaker
unit
Robotic arm
Samples
Solvents
Analysis
HPLC

Solvent selection: predicted vs measured Kd
 
 aq
solv
phenol
phenol

d
K
0
1
10
100
1000
0 1 10 100 1000
predicted phenol Kd
measured
phenol
Kd
y = 0.9778x
R2 = 0.9799
Hydrophobic interaction
Hydrogen bonding
Complexation
Very good prediction
of removal efficiency!

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
Effective membrane surface: 1.2 m2
Specific area/volume = 280 m2/m3
Width liquid channel = ± 2 mm
Small full scale module
Effective membrane surface: 40 m2
Specific area/volume = 450 m2/m3
Width liquid channel = ± 2 mm

Case-study: Aromatics from waste water
process
feed-
stock
biological
waste
water
treatment
waste water
10 m3/h
Invista (former Hoechst ) - Vlisssingen
aromatics
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
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

Process flow diagram

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)

Emulsion Pertraction installation for passivating
baths in galvanic industry
Installation
contains 26 m2
membranes.
Investment costs
± 50 k€
Distribution
coefficient for Zn
is ± 100
Candle filter
Emulsion
Feed acid
Spent acid
with Zn, Fe
Membranes

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.

Process Intensification – Inline Process Analysis
Leon Geers

Classical process and quality control
Feedstock
Waste
Product
T & p control
During production: typically only T, p and sometimes flow monitoring
After production: product quality assessment in lab
Process control: keep
process parameters (p,T)
within a fixed window
Product quality
Price
/
kg
waste
profit
rework / purify
or dump
Consequence: money is lost here!
Source: http://www.cartoonnetwork.com
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
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
Feedstock
Waste
Product
On-line measurements
of CTQ quantities
Operator or
control system
Data modeling

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

Examples of TNO sensor technology
Developed with/for equipment manufacturers
Mass & volume flow meters
Chemical concentration sensors
Fibre Bragg Gratings
Integrated nano-photonics
Micro IR-spectrometers
Particle monitoring systems
Micro gas chromatograph
Micro IR-spectrometer Flowmeters
Integrated nano-photonics Fiber Bragg Grating Electrochemical sensors
Ultrasonic particle monitor Ultrasonic transmission
spectroscopy
Micro gas chromatograph

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
Process model: Batch reaction
Goals
Determine end time of process
Determine process kinetics
NIR spectrometer
Probe
Stirring motor
Three necked flask
Access for
chemicals

Spectra of aspirin production monitoring
Due to similarities in molecular
structure of reactants and products,
their NIR spectra are similar
Hence, there is no one-to-one relation
between the height of peaks and
concentrations of present species
Chemometrics are necessary to
calculate the correlation between
species concentration and spectra 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000
-0.5
0
0.5
1
1.5
2
2.5
3
Wavelength (nm)
Absorbance
(-)
Changing spectra during reaction
t=0
t = tend

Results
Experimental spectra acquired during
aspirin synthesis is used for
determination of rate constant
Second order rate equation:
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
Disappearing
reactants
Appearing
products
]
[
]
[ SalOH
AcOAc
k
rAspirin 
Result:
• process time appears to be
only 300 s (=5 min)
• rate constant k=3.0 l/mol.s

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.

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

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