Process Analytical Technology:
How much oxygen is inside?
150
years
150
years
Dr. Alexander Schocker
BASF SE, Task Force Process Analytical Technology
27. Oktober 2015, ETH Zurich, Switzerland
150 years
Verbund site Ludwigshafen
The largest integrated chemical complex
in the world
Headquarters
Employees BASF SE
Site area
Sales products
Road
Rail
Site traffic
Shipment
Pipeline system
Production facilities
* As of December 31, 2014
35,848*
10 km²
about 8.5 million metric tons p.a.
106 km
230 km
2,100 trucks daily
100,000 containers p.a.
about 2,800 km
around 110 production facilities
with around 200 production
plants
2
150 years
Process Analytical Technology
Center of Technical Expertise
Process Analytical Technology
Employees
125
Education
Chemists
Physics
Engineers
Lab Technicans
Tasks
* As of December 31, 2014
Consulting
Applications
Studies
Engineering
Maintenance
R&D
3
150 years
Process Analytical Technology
– what is online-analysis?
Offline:
Sampling & external
analysis in laboratory
Courtesy of Dr. Claudia Lohmann, Competence Center Analytics, BASF SE
Online/Inline
Direct analysis
(24h /7d)
150 years
What is Process Analytical Technology ?
Process Analytical Technology (PAT) comprises
all methods for the continuous in-process
measurement of
 Properties
Chromatography
Humidity,
ultrasound
pH, Titration
Gas
monitoring
 Concentrations
 Compositions
O2
measurements
TOC, VOC,
environmental
PAT = basis for process optimization
Laser and Raman
spectroscopy
10.11.2014
5
150 years
102 Years Process Analytical Technology: First Patent for
Pipe Analyzer granted in 1913
02.04.2015
INTERNAL
6
150 years
Development of PAT Instruments by the Process Industry
URAS:
First IR process
photometer
BASF, 1938
Magnos:
Thermomagnetic
process
oxygen analyzator
Process
gas chromatograph
Fast process
titration apparatus
BASF, 1940
BASF, 1957
BASF, 2014
150 years
Process Analytical Technology
More than 50 Methods in BASF Group
Ludwigshafen
Schwarzheide (Germany)
11000 Instruments
750 Instruments
6
Mass spectrometers
Gas chromatographs
184
Optical spectrometers
50
On-line titrators
80
Laser-spectrometers
110
TOC (Total Organic Carbon)
400
Oxygen (paramagnetic)
200
Thermal conductivity
170
Humidity
Complexity
291
1
3
2
18
22
18
1.200
Photometer
29
3.500
Gas warning systems
310
4.500
pH, redox, conductivity
260
150 years
Process Analytical Technology:
How much oxygen is inside?
Lecture “Analytical Strategy”
Process Analytical Technology
Questions
0 Chemical Process
1 Analytical methods for oxygen
Analytical strategy requires the
understanding the chemical
process
2 Advantages/Disadvantages
3 Inline/online & atline
4 Link of instrument to process
5 Explosion protection
6 Your choice
9
150 years
Why is the Oxygen Concentration important ?
Raw Materials – Products – Side Products
Main reaction
H
H
H
+ ½ O2
C=C
H
Silver Catalyst
C―C
200 – 280 °C, 10 – 20 bar
H
H
H
O
H
Selectivity 80% - 85%
+ Methane
+ Chlorethane (Traces)
Side Reaction (will be the main reaction at higher oxygen concentrations)
H
H
+ 3 O2
C=C
H
H
2 CO2 +2 H2O
Ethylen Oxide Production at BASF
What is made of Ethylene Oxide?
ethylene glycol (ethanediol)
for example, main
compound of Glysantin®
Glysantin® is much more
than just an antifreeze. The
premium-grade coolant
from BASF provides
threefold protection from
corrosion, overheating and
frost.
150 years
150 years
Process Analytical Technology:
How much oxygen is inside?
Lecture “Analytical Strategy”
Process Analytical Technology
Questions
0 Chemical Process
1 Analytical methods for oxygen
Which analytical methods for
online/inline monitoring of oxygen
concentration are suitable at all?
2 Advantages/Disadvantages
3 Inline/online & atline
4 Link of instrument to process
5 Explosion protection
6 Your choice
13
150 years
Which analytical methods for online/inline monitoring of
oxygen concentration are suitable at all?
Paramagnetic
Absorption Spectroscopy
Zirconia Sensor
Electrochemical
Fluorescence
O2
O2 NO
NO2
Gas chromatography
14
Process Analytical Technology:
How much oxygen is inside?
Lecture “Analytical Strategy”
Process Analytical Technology
Questions
0 Chemical Process
1 Analytical methods for oxygen
2 Advantages/Disadvantages
150 years
Please discuss the advantages/disadvantages
of the individual analytical methods in
combination with economic impact of each
measurement (cross sensitivities, response
time, calibration, investment, maintenance
costs).
3 Inline/online & atline
4 Link of instrument to process
5 Explosion protection
6 Your choice
15
150 years
Paramagnetic Oxygen Analyzer
Advantages / Disadvantages
Advantage
 Very high sensitivity
 Very limited cross sensitivity (no
influence of 99 % of background
compounds)
 High reliability and precision of
the signal
 Long operation period
 Linear response of the sensor
Disadvantage
 Not applicable in case of
presence of NO, NO2 und ClO2
 Sensitive against impurities
(solid & liquid)
 Precision mechanical system
 Sensitive against shock
pressure of the sample
gas
 Sensitive against
vibrations- or impact load
 Complex setup using different
materials
 Medium maintenance effort
Operational
 Operation mode:
on-line (sample preparation is required)
 Investment:
approx. 10 -20 k€
 Maintenance interval: approx. 1- 3 month
16
150 years
Zirconia Sensor (ZrO2)
Measuring Principle
Advantage
Disadvantage
 Simple testing method
 Dynamic range staring from trace level
(ppm) up to percent range
 Perfect for combustion systems due to
high temperature of the sample gas, inline installation is possible
 Not suitable for flammable mixtures
(potential source of ignition)
 Negative cross sensitivity at presence
of flammable gas (even at low
concentrations)
 Impact by presence of low
concentrations of reducing gas
 Medium maintenance effort
Operational
 Operation mode:
 Investment:
 Maintenance Intervals:
in-line and/or on-line
approx. 9 k€
approx. 1- 3 Month
17
150 years
Gas Chromatography using molecular sieve
Advantages / Disadvantages
Advantage
 Applicable to complex matrix's
 Robust for changes in pressure
and temperature
 High reliability and precision of
the signal
 Long operation period
 High dynamic and linear range
of thermal conductivity
detectors
Disadvantage
 Measuring interval: discrete
(every 3-5 min)
 High invest
 High maintenance effort
Operational
 Operation mode:
 Investment:
 Maintenance interval:
on-line (sample preparation is required)
approx. 50-100 k€
approx. 1- 3 month
18
150 years
Fluorescence Quenching
Advantage
Disadvantage
 Real-time inline technology
 Suitable for gaseous and liquid
samples
 Applicable for
 Leak detection of vacuum
systems
 Inertisation of vessels,
tanks
 Nitrogen purge of storage
tanks
 Cross sensitivity to other
quenchers
Operational
 Operation:
 Investment
 Maintenance interval
on-line / in-line
approx. 30 T€
approx. xx month
19
150 years
Tunable Diode Laser Spectroscopy (TDLS)
Advantage
 High sensitivity and high
selectivity for oxygen (even in
complex matrix)
 Quantitative detection is feasible
for Temperatures up to 1500 °C
 Real-time detection
 Calibration during plant
operation possible
 Maintenance of instrument
without any impact to the
process and plant operation
 Influence by pressure and/or
temperature can be adjusted
 Minor maintenance effort
Disadvantage
 High initial investment
Operational
 Operation mode:
 Investment:
 Maintenance interval:
in-line without sample preparation
approx. 40-60 T€
approx. 6 month
20
Process Analytical Technology:
How much oxygen is inside?
Lecture “Analytical Strategy”
Process Analytical Technology
Questions
150 years
0 Chemical Process
1 Analytical methods for oxygen
2 Advantages/Disadvantages
3 Inline/online & atline
What are differences between inline, online,
atline and offline analyses?
4 Link of instrument to process
5 Explosion protection
6 Your choice
21
150 years
Process Analytical Technology (PAT)
– definitions
Offline
Atline
Online
Inline
Q
Q
Q
Q
measurement after
manual sampling
measurement after
automated sampling
measurement in
a by-pass
measurement within
the reactor
 In-Process Control
 Automated/manual
sample handling
 no sample handling
 no sample handling
 measurement very
close to the process
(short time delay)
 real-time
 real-time
 constancy of p/T
 constancy of p/T
 In-situ in
homogeneous
systems
 space-resolved
 Analysis in laboratory
 In-situ in general
 non-invasive
Process Analytical Technology:
How much oxygen is inside?
Lecture “Analytical Strategy”
Process Analytical Technology
Questions
150 years
0 Chemical Process
1 Analytical methods for oxygen
2 Advantages/Disadvantages
3 Inline/online & atline
4 Link of instrument to process
5 Explosion protection
6 Your choice
23
150 years
PAT Installations Involve Complex Systems
Carrier gas
Combustion gas
Calibration gas
Recirculation
02.04.2015
Sample preparation
INTERNAL
24
150 years
PAT Installations Involve Complex Systems
Sample Preparation
Physical
condition
Device
Removal of particles
Liquid, gaseous
Fine filter / coarse filter
gaseous
Carrier gas
Recirculation
02.04.2015
Removal of droplets
Water/condensate separator
Adjustment sample
Liquid, gaseous
Combustion gas
pressure
Pressure reduction station
Adjustment sample
Liquid, gaseous
Calibration
gas
temperature
Cooler / Heater
(electrical/process steam)
Accumulation of sample
Liquid, gaseous
Dynamic stripping (open-loop headspace), static stripping (closed-loop),
adsorbent materials
Switching between different
process streams/calibration
substance
Liquid, gaseous
Valve (manual/automized)
Adjustment sample flow
rate
Liquid, gaseous
Needle valve, Flow controller
Sample preparation
INTERNAL
25
150 years
PAT Installations Involve Complex Systems
Distributed Control System (DCS)
Carrier gas
Combustion gas
Calibration gas
Recirculation
Integration
Control
Communication
(Profibus / Modbus)
02.04.2015
Sample preparation
INTERNAL
Remote Diagnostics
26
Process Analytical Technology:
How much oxygen is inside?
Lecture “Analytical Strategy”
Process Analytical Technology
Questions
150 years
0 Chemical Process
1 Analytical methods for oxygen
2 Advantages/Disadvantages
3 Inline/online & atline
4 Link of instrument to process
5 Explosion protection
An installation directly inside the petro-chemical
production plant requires special conditions.
The atmosphere inside the plant might classify
as "explosion protected and preventive area".
Instruments known from the research lab
cannot be installed directly in a chemical plant.
Consider safety precautions that have to be
addressed to place the analytical instrument
inside the plant.
6 Your choice
27
150 years
5. Explosion Protection (ATEX = atmosphere explosive)
An area in which an
explosive mixture is ..
Zone 0
… continuously present or
present for long periods
Zone 1
… likely to occur in normal
operation
Zone 2
… not likely to occur in
normal operation and if it
occurs it will exist only for
a short time.
28
150 years
Process Analytical Technology
Sample Preparation & Analyzer houses
Sample Preparation
Analyzer house / room
Process Analytical Technology:
How much oxygen is inside?
Lecture “Analytical Strategy”
Process Analytical Technology
Questions
150 years
0 Chemical Process
1 Analytical methods for oxygen
2 Advantages/Disadvantages
3 Inline/online & atline
4 Link of instrument to process
5 Explosion protection
6 Your choice
30
150 years
6. Your Choice – the solution!
Paramagnetic
Electrochemical
Zirconium
Oxide
GC
TDLS
Fluorescence
concentration
6 – 8 Vol. %

Real Time
High Reliability
Gas is consisting
organic compounds



Fluctuations of gas
pressure
Installation in explosive
protected area
31
150 years
Tunable Diode Laser Spectroscopy (TDLS)
Quantification of Oxygen
σp*
π*
2p
2p
π
σp
σs*
2s
2s
σs
O
O
Atom-Orbital
O
O
Molekül-Orbital
Atom-Orbital
MO diagram of Oxygen
R-branch
1 +
Σg

Σ g - Transition
3
-
Ground state:
3
Σg
-
32
150 years
Tunable Diode Laser Spectroscopy (TDLS)
“Process Windows” developed at BASF SE
PLT 4192
PLT 4193
PLT 3809
with flush connection
heatable with process steam
Size:
Material:
Max. design pressure:
Max. admissible design temperature:
DN 50 / PN 10-40
1.4571, N-BK7
PS 16 bar
TS 200 oC
33
150 years
Tunable Diode Laser Spectroscopy (TDLS)
Heatable Cuvette using Process Steam
In-house development by BASF SE
Sample gas
(outlet)
Steam
Diode laser
Steam
Detector
Sample gas (Inlet)
34
150 years
Tunable Diode Laser Spectroscopy (TDLS)
35
150 years
Questions ?
19.10.2015
INTERNAL
36
150 years
INTERNAL