New High Pressure TGA Instrument for Coal Pyrolysis and … · • Integration with TA Zs TRIOS software simplifies HP-TGA measurements drastically • Applied new HP-TGA for coal

New High Pressure TGA Instrument for Coal Pyrolysis and Gasification Measurement under Application Relevant Conditions

Frieder Dreisbach, Thomas Paschke, Cornelia WillTA Instruments – Waters GmbH, Bochum, Germany

[email protected], www.tainstruments.com

Outline

▪ Working principle

▪ Unique features

▪ Company history

▪ Motivation

▪ Setup and functional parts

▪ Specifications

▪ Influence of heating rate on pyrolysis

▪ Influence on pressure on pyrolysis and gasification

▪ Summary

NEW MAGNETIC LEVITATION BALANCE

BACKGROUND

NEW DISCOVERY HP-TGA

COAL PYROLYSIS AND GASIFICATION

CONCLUSION

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• Rubotherm was founded 1990 as spin-off of the Thermodynamics Department at Ruhr-University Bochum, Germany

• Key technology: Magnetic Suspension Balance instruments for thermogravimetric measurements under extreme conditions (high temperature, high pressure, vapor, corrosive atmospheres)

• Continuous collaboration with Universities and Research Organizations in the framework of research projects

• More than 1000 instruments installed worldwide

• Main markets: Europe, Asia, North America

• Acquisition of Rubotherm by TA Instruments effective September 2016

• All operations in Germany: R&D, laboratory, and product management in Bochum, manufacturing facilities in Hüllhost

Company HistoryRubotherm is part of TA Instruments

MotivationSimplify operation of high pressure TGA

PROBLEM

HP-TGA are large and expensive custom made experimental installations. Standard TGA

instruments are much smaller and easier to operate but do not offer the possibility to

work under realistic process

conditions.

IDEA

Bring the HP-TGA features to the

“benchtop”. Developing a HP-TGA with

comparable size and ease of operation as standard TGA instruments.

MotivationSimplify operation of high pressure TGA

DEVELOPMENT

Invention of new magnetic

levitation balance with high

resolution and small internal

volume by ETH Zürich.

R&D effort to integrate the new

balance into a compact HP-TGA by Rubotherm / TA Instruments.

INNOVATION

Discovery HP-TGA instrument.

High pressure TGA in benchtop size.

Operation with TA’s TRIOS

software as simple as a

standard TGA instrument.

Magnetic Levitation BalanceInventor of the Patented New Working Principle

Dr. Heinrich Baur

New Magnetic Levitation Balance

Sample crucible(top-loading)

Working Principle & Setup

Some µm wide “positioning window”without change in vertical force! Holding force only dependent on electric

current on coils Current is linearly proportional to levitated mass Electric current measurement = weight measurement

New Magnetic Levitation BalanceWorking Principle & Setup

Position sensor resolution is ≤ 250 nm

New Magnetic Levitation BalanceWorking Principle & Setup

New Magnetic Levitation BalanceWorking Principle & Setup

▪ Minimized drift – excellent base line stability

▪ Highest reproducibility

▪ Higher resolution than all other HP-TGA

▪ Perfect for low mass (change) samples & fast kinetics

▪ High pressure and vacuum capable, safe

▪ Quick & clean gas changing, low gas consumption

▪ Can perform TGA with application relevant gases

▪ Extensive list of gases to select from in the software

ACCURATE BALANCE T-CONTROL

HIGHEST RESOLUTION

SMALL INTERNAL VOLUME

CORROSION RESISTANT

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New Magnetic Levitation BalanceUnique Features

New Discovery HP-TGAFunctional Parts

Magnetic Levitation Balance

High Pressure Furnace

Pressure Controller

Reaction Gas Dosing

New Discovery HP-TGASetup

0.1 mg weighing resolution

500 mg weighing range / sample mass

Magnetic Levitation Balance

High Pressure Furnace

Up to 1100°C, 250°C/min heating and cooling rate

Integrated Curie-Point T-calibration

Gas Dosing &PressureController

3 reaction gas MFC for gas switching and blending

Vacuum…80 bar, EGA sampling for QMS

New Discovery HP-TGASpecifications

Calcium OxalateInfluence of Pressure on DecompositionAtmosphere: Ar, Heating Rate: 4°C/min, Maximum Temperature: 900°C

Mass changesteps areindependent ofpressure and canbe measuredaccurately.

Lignite PyrolysisInfluence of Heating Rate on Reaction KinecticsAtmosphere: N2, Pressure: 2 bar, Maximum Temperature: 1100°C

Selected 10°C/min heating rate for all lignite measurements

Lignite Pyrolysis in N2Influence of Pressure on Reaction KinecticsAtmosphere: N2, Heating Rate: 10°C/min, Maximum Temperature: 1100°C

No significant influence of pressure

Lignite GasificationInfluence of Pressure on Reaction KinecticsAtmosphere: Ar, switch to 30% CO2 in Ar, Heating Rate: 10°C/min, Maximum Temperature: 1000°C

𝑑𝑚

𝑑𝑡≤ 3.0 %/𝑚𝑖𝑛

𝑑𝑚

𝑑𝑡≤ 5.9 %/𝑚𝑖𝑛

𝑑𝑚

𝑑𝑡≤ 5.8 %/𝑚𝑖𝑛

𝑚∞ = 3.5%

𝑚∞ = 7.3%

𝑚∞ = 4.4%

EGA of Lignite GasificationQMS coupled to TGAAtmosphere: 30% CO2 in Ar, Pressure: 2 bar, Temperature: 1000°C

Anthracite GasificationInfluence of Pressure on Reaction KinecticsAtmosphere: 30% CO2 in Ar, Heating Rate: 100°C/min, Maximum Temperature: 1100°C

𝑑𝑚

𝑑𝑡≤ 3.1 %/𝑚𝑖𝑛

𝑑𝑚

𝑑𝑡≤ 6.6 %/𝑚𝑖𝑛

𝑚∞ = 8.1 %

𝑚∞ = 6.0 %

ConclusionSummary

• New Magnetic Levitation Balance integrated in Discovery HP-TGA

• Top loading balance with high resolution allows measurements with small samples

• High heating and cooling rate improves the sample throughput

• Integration with TA‘s TRIOS software simplifies HP-TGA measurements drastically

• Applied new HP-TGA for coal pyrolysis and gasification measurement with lignite and anthracite samples

• Pyrolysis showed no dependence on pressure

• At higher pressure gasification can be performed at lower temperature and/or with higher reaction rates

• Product gas analysis with QMS for gasification of lignite showed mainly CO but also CH4

Thank You

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