sustainable chemicals industry process intensification dr. jean-marie bassett

Sustainable Chemicals IndustryProcess Intensification

Dr. Jean-Marie Bassett

TNO organization

1800

Technical S

ciences

Behavioural &

Societal sciences

Earth, E

nvironmental &

Life Sciences

950 850Employees:

EXPERTISECENTERS

General introduction to TNO

Our position in innovation

Feasibility& Concept

design

Proof of principle

Functional Model

PrototypePilot

TrialsTests

Productionpreparation

ProductionSales

FundamentalResearch

ResearchIdeas

Demand orOpportunity

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 modelsFee-for-serviceOpen innovation: Dual party program: TNO-Co financing Multiple party program: Consortium

Project- & account-managementMulti-disciplinary project teamsCollaborate directly with partnerMulti-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

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 hurdlesDownstream processing and integrated process control Multi-phase / multi-purpose processesCost-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 manifoldingTNO 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


Sustainable Chemicals IndustryProcess 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

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


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


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!


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


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


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


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


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


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


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.


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, …….


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


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


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]

me

ltin

g p

oin

t [°

C]


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

PenGfeed

APA-Precipitation


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 IndustryProcess 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

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


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 TNOHydraulic 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).

aa

S-Lseparation

counter currentwashing

ice crystals in

salt water (-8 °C) position filter

wash frontice crystals in

pure water (0 °C)

Two bottom zones

of the wash columnEXAMPLE


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 slurrySolids 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

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


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 tubesdiameter ± 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 80C• Different operating options possible

Close up of the HWC-55


TNO Hydraulic Wash Column HWC-55 pilot plant

Sold


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: 7-8C

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


PertractionA 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

SamplesSolvents

Analysis

HPLC


Solvent selection: predicted vs measured Kd

aq

solv

phenol

phenoldK

0

1

10

100

1000

0 1 10 100 1000

predicted phenol Kd

me

as

ure

d p

he

no

l Kd

y = 0.9778xR2 = 0.9799

Hydrophobic interaction

Hydrogen bonding

Complexation

Very good prediction of removal efficiency!


TNO Membrane Modules

Lab scale test moduleLength * Height * Width = 0.1 m * 0.1 m * 0.05 mEffective membrane surface: 0.05 m2

Pilot scale moduleLength * Height * Width = 0.2 m * 0.3 m * 0.05 mEffective membrane surface: 1.2 m2

Specific area/volume = 280 m2/m3

Width liquid channel = ± 2 mm

Small full scale moduleLength * Height * Width = 1.5 m * 0.5 m * 0.14 mEffective membrane surface: 40 m2Specific area/volume = 450 m2/m3Width liquid channel = ± 2 mm


Case-study: Aromatics from waste water

process

feed-stock

biologicalwaste 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/hrImpurity-1, in: 2200 ppmImpurity-1, out: < 40 ppmImpurity-2, in: 830 ppmImpurity-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€

Distributioncoefficient for Zn is ± 100

Candle filter

Emulsion

Feed acidSpent acidwith 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.


Sustainable Chemicals IndustryProcess 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

Pric

e /

kg

waste

profit

rework / purifyor dump

Consequence: money is lost here!

Source: http://www.cartoonnetwork.com

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

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 measurementsof CTQ quantities

Operator orcontrol system

Data modeling


Process monitoring toolbox

Sensor / Analytical Equipment:Temperature, pressure, flow sensorsChemical composition sensors (e.g. spectroscopy, electrochemical sensors)Phase distribution sensorParticle monitor (size distribution & concentration)

Data Analysis Methodologies:InversionChemometrics

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)

Abs

orba

nce

(-)

Changing spectra during reaction

t=0

t = tend


ResultsExperimental 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

Disappearingreactants

Appearingproducts

][][ SalOHAcOAckrAspirin

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 BassettBusiness Development [email protected]+31 (0)88 866 8118+31 (0)6 104 804 73

Ir. Martijn P. de GraaffBusiness Development [email protected]+31 (0)88 866 6437+31 (0)6 222 608 71


sustainable chemicals industry process intensification dr. jean-marie bassett

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