process analytical technology: how much oxygen is inside? · how much oxygen is inside? dr....

150 years

Process Analytical Technology: How much oxygen is inside?

Dr. Alexander SchockerBASF SE, Task Force Process Analytical Technology

27. Oktober 2015, ETH Zurich, Switzerland

150 years

150 years

Verbund site Ludwigshafen

2* As of December 31, 2014

HeadquartersEmployees BASF SE 35,848*Site area 10 km² Sales products about 8.5 million metric tons p.a.Road 106 km Rail 230 kmSite traffic 2,100 trucks dailyShipment 100,000 containers p.a.Pipeline system about 2,800 kmProduction facilities around 110 production facilities

with around 200 production plants

The largest integrated chemical complex in the world

150 years

Process Analytical TechnologyCenter of Technical Expertise

3* As of December 31, 2014

Process Analytical TechnologyEmployees 125Education Chemists

PhysicsEngineersLab Technicans

Tasks ConsultingApplicationsStudiesEngineeringMaintenance R&D

150 years

Process Analytical Technology – what is online-analysis?

Offline:Sampling & external analysis in laboratory

Online/InlineDirect analysis

(24h /7d)

Courtesy of Dr. Claudia Lohmann, Competence Center Analytics, BASF SE

150 years

What is Process Analytical Technology ?

Process Analytical Technology (PAT) comprises all methods for the continuous in-process measurement of

Properties

Concentrations

Compositions

PAT = basis for process optimization

510.11.2014

Chromatography

pH, Titration

Laser and Raman spectroscopy

TOC, VOC, environmental

Gas monitoring

O2 measurements

Humidity, ultrasound

150 years

102 Years Process Analytical Technology: First Patent for Pipe Analyzer granted in 1913

6INTERNAL02.04.2015

150 years

Development of PAT Instruments by the Process Industry

URAS:First IR processphotometer

BASF, 1938

Process gas chromatograph

BASF, 1957

Magnos:Thermomagneticprocessoxygen analyzator

BASF, 1940

Fast processtitration apparatus

BASF, 2014

150 years

Process Analytical TechnologyMore than 50 Methods in BASF Group

Ludwigshafen Schwarzheide (Germany)11000 Instruments 750 Instruments

6 Mass spectrometers291 Gas chromatographs 1184 Optical spectrometers 350 On-line titrators 280 Laser-spectrometers 18

110 TOC (Total Organic Carbon) 22400 Oxygen (paramagnetic) 18200 Thermal conductivity 170 Humidity

1.200 Photometer 293.500 Gas warning systems 3104.500 pH, redox, conductivity 260

Complexity

150 yearsLecture “Analytical Strategy”Process Analytical TechnologyQuestions

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Analytical methods for oxygen

Advantages/Disadvantages

Inline/online & atline

Link of instrument to process

Explosion protection

Your choice

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Analytical strategy requires the understanding the chemical process

Chemical Process0

150 years

Why is the Oxygen Concentration important ? Raw Materials – Products – Side Products

2 CO2 +2 H2O+ 3 O2C=CH

H H

H

C=CH

H H

H

C―CH

H H

HO+ ½ O2

Silver Catalyst200 – 280 °C, 10 – 20 bar

+ Methane+ Chlorethane (Traces)

Selectivity 80% - 85%

Main reaction

Side Reaction (will be the main reaction at higher oxygen concentrations)

150 yearsEthylen 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.


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Which analytical methods for online/inline monitoring of oxygen concentration are suitable at all?

Chemical Process0

150 years

Which analytical methods for online/inline monitoring of oxygen concentration are suitable at all?

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Paramagnetic

Gas chromatography

Zirconia SensorAbsorption Spectroscopy

Fluorescence

O2

O2

NONO2

Electrochemical


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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).

Chemical Process0

150 years

Paramagnetic Oxygen AnalyzerAdvantages / Disadvantages

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Advantage Disadvantage 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

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

150 years

Zirconia Sensor (ZrO2)Measuring Principle

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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, in-line 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: in-line and/or on-line Investment: approx. 9 k€ Maintenance Intervals: approx. 1- 3 Month

150 years

Gas Chromatography using molecular sieve Advantages / Disadvantages

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Advantage Disadvantage 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

Measuring interval: discrete (every 3-5 min)

High invest High maintenance effort

Operational Operation mode: on-line (sample preparation is required) Investment: approx. 50-100 k€ Maintenance interval: approx. 1- 3 month

150 years

Fluorescence Quenching

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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: on-line / in-line Investment approx. 30 T€ Maintenance interval approx. xx month

150 years

Tunable Diode Laser Spectroscopy (TDLS)

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Advantage Disadvantage 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

High initial investment

Operational Operation mode: in-line without sample preparation Investment: approx. 40-60 T€ Maintenance interval: approx. 6 month


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What are differences between inline, online, atline and offline analyses?

Chemical Process0

150 years

Process Analytical Technology (PAT)– definitions

Inline

Q

Online

Q

Offline

Q

Atline

Q

measurement in a by-pass no sample handling

real-time

constancy of p/T

In-situ in homogeneoussystems

measurement withinthe reactor no sample handling

real-time

constancy of p/T

space-resolved

In-situ in general

non-invasive

measurement after automated sampling Automated/manual

sample handling

measurement veryclose to the process(short time delay)

measurement after manual sampling In-Process Control

Analysis in laboratory


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Chemical Process0

150 years

PAT Installations Involve Complex Systems

24INTERNAL02.04.2015

Recirculation

Carrier gas

Combustion gas

Calibration gas

Sample preparation

150 years



Recirculation

Carrier gas

Combustion gas

Calibration gas

Sample preparation

Sample Preparation Physical condition

Device

Removal of particles Liquid, gaseous Fine filter / coarse filter

Removal of droplets gaseous Water/condensate separator

Adjustment sample pressure

Liquid, gaseous Pressure reduction station

Adjustment sample temperature

Liquid, gaseous Cooler / Heater (electrical/process steam)

Accumulation of sample Liquid, gaseous Dynamic stripping (open-loop head-space), 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

150 years



Remote Diagnostics

Distributed Control System (DCS)

IntegrationControl

Communication(Profibus / Modbus)

Recirculation

Carrier gas

Combustion gas

Calibration gas

Sample preparation


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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.

Chemical Process0

150 years

5. Explosion Protection (ATEX = atmosphere explosive)

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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.

150 years

Sample Preparation Analyzer house / room

Process Analytical TechnologySample Preparation & Analyzer houses


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Chemical Process0

150 years

6. Your Choice – the solution!

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Para-magnetic

Electro-chemical

ZirconiumOxide 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

150 years

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1Σ+

g 3Σ-

g - Transition

2s 2s

σs

σs*

σp

2p 2p

π

π *

σ*p

O OO OAtom-Orbital Molekül-Orbital Atom-Orbital

MO diagram of Oxygen Ground state: 3Σ-

gR-branch

Tunable Diode Laser Spectroscopy (TDLS)Quantification of Oxygen

150 years

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Tunable Diode Laser Spectroscopy (TDLS)“Process Windows” developed at BASF SE

PLT 4192 PLT 4193 PLT 3809with flush connection heatable with process steam

Size: DN 50 / PN 10-40Material: 1.4571, N-BK7Max. design pressure: PS 16 barMax. admissible design temperature: TS 200 oC

150 years

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Tunable Diode Laser Spectroscopy (TDLS)Heatable Cuvette using Process SteamIn-house development by BASF SE

Sample gas (Inlet)

Sample gas (outlet)Steam

Diode laser

DetectorSteam

150 years

Tunable Diode Laser Spectroscopy (TDLS)

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150 years

Questions ?

3619.10.2015 INTERNAL

150 years

INTERNAL

process analytical technology: how much oxygen is inside? · how much oxygen is inside? dr....

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