Thermogravimetric Analysis under Application Relevant ... · PDF fileThermogravimetric...

Rubotherm GmbH Konrad-Zuse-Str. 4 44801 Bochum Germany

Thermogravimetric Analysis under Application Relevant Conditions –

High Pressure, Vapours and Corrosive Atmospheres

Thomas Paschke Rubotherm

Technology Days

May 7th 2015, Ghelamco Arena Gent


• Company Overview

• Product Line “Gravimetric Instruments” Magnetic Suspension Balance, ISOSORP, DYNTHERM, FLEXIDOSE

• TGA Application Examples

• New Gravimetric Product NANOMSB

Outline


• Founded 1990 as spin-off of the chair of Thermodynamics, Ruhr-University Bochum

• Develops, manufactures & installs specialized analytical instruments and laboratory testing installations worldwide

• Subsidiary companies in USA and China

• Office and manufacturing facilities at two locations in Bochum, Germany

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

Rubotherm - Company Facts


• Complete separation between balance and measuring atmosphere -> vacuum to high pressures, corrosive gases

• Complete reactor (including magnetic suspension coupling) heatable to 200°C -> measurements with vapors possible

• Zero point function -> correction of base line drift in long term measurements

Magnetic Suspension Balance – Unique Features

Inert Gas

Balance

Inert and

Measuring Gas

Sample

(Adsorbent)

Thermostat

(high/low T)

Measuring Gas

(UHV ... high pressure)


Gravimetric instruments with Magnetic Suspension Balance for analysis of: - Sorption - Thermogravimetry - Thermophysical

Properties

Product Line “Gravimetric Instruments”


Typically used for isothermal gas and/or vapor ad- or absorption measurements.

Sample temperature range: -196°C up to 400°C

Pressure range: vacuum up to 700 bar (depending on chosen temperature range)

ISOSORP - MSB for Sorption Measurements


ISOSORP - Pressure Ranges & Thermostation


Forced flow through bulk material bed

Sample container is set down on a by-pass free support. Gas flow must pass through the sample and leaves container through “sieve like” bottom.

Weighing in certain time intervals by lifting up sample container.

ISOSORP - Unique Options


ISOSORP - Application Examples

Estimation of the potential of CO2 enhanced coal bed CH4 recovery

Adsorption of CH4 and CO2 on Sardinian coal sample at 45°C and 60°C

S. Ottiger, R. Pini, G. Storti, M. Mazzotti, R. Bencini, F. Quattrocchi, G. Sardu and G. Deriu: Adsorption of Pure Carbon Dioxide and Methane on Dry Coal from the Sulcis Coal Province (SW Sardinia, Italy); Environmental Progress; 25 (2006) 355-364


Typically used for high pressure TGA and/or measurements with vapor or corrosive atmospheres.

Sample temperature range: RT up to 1550°C

Pressure range: vacuum up to 350 bar (depending on chosen temperature range)

DYNTHERM - MSB for Thermogravimetry


Low Pressure (LP) versions for highest temperatures

Medium pressure (MP) versions with cold wall reactor

High pressure (HP) versions for highest pressures

DYNTHERM - Pressure & Temperature Ranges


Anti condensation heating of all parts of the reactor

Convenient sample loading by electrical lifting of the balance

DYNTHERM - Operation

Fast sample heating device > 1000 K/min Introducing the sample into the pre-heated furnace Available with DynTHERM LP at ambient pressure

DYNTHERM - Operation

DynTHERM LP

• Maximum Sample Temperature: up to 1550 °C • Vacuum to 1 bar • Al2O3 measuring cell tube and convection flow tubes: no metal

parts in hot reaction zone • Electrical Heating to 1100°C or 1550°C (optional)

• HighTemp corrosion and reaction studies:

– Siegen University, Werkstoffkunde – Wacker Chemie München – Pohang University of Science and Technology – Oak Ridge National Lab – Ural State University Russia – GE Research, NY, USA

• TGA with gas and vapor – Institut Francais du Petrol – RUB Bochum, Rubokat – DOW

DynTHERM MP

• Cold wall reactor design: – ST: 40 bar/1100°C, HT: 30 bar/1200°C, HT-II: 20 bar/1300°C

– Al2O3 flow separator tube for reaction gas atmosphere: no metal parts in contact with hot reaction gas

– Electrical Heating

– Argon purge gas

– One pressure controller for reaction gas and purge gas: no pressure gradient at hot flow separator tube

– Cold steel wall holds the pressure

• MP-ST is very popular for Coal gasification

• latest orders: – 2 units Poland, mining applications

– KIT Karlsruhe: IPI MS and Agilent GC connected

– Alstom Power US

– TU Bergakademie Freiberg: View Cell for Spectroscopy

DynTHERM HP

• Hot wall reactor: special high strength alloy for high temperature applications, electrically heated from the outside – HPII-LT: 350bar/750°C, HP-LT: 150bar/750°C, ST: 100bar/1000°C

– Dyntherm-Reactor with metal parts in contact with reaction mixture at operating temperature

• New: Hot wall reactor, double wall version – Stainless steel reactor with corrosion resistant inlay

– Al2O3 or quartz glass

– Argon as purge gas

between the walls

– HP-LT: 50 bar/750°C


Customizable, flexible gas and/or vapor dosing systems and pressure controllers for operation with ISOSORP and DYNTHERM instruments.

Working principles: Static: P-control Flow: Gas & vapor flow and P-control

Pressure ranges: LP: vacuum up to 1 bar MP: vacuum up to 50 bar HP: vacuum up to 150 bar HPII: vacuum up to 350 bar

FLEXIDOSE - Gas/Vapor Dosing Systems & P-Controller


Static P-controller for gases in the pressure range from vacuum up to 150 bar

Static P-controller for gases and sub-critical fluids (vapors) in the pressure range from vacuum up to 700 bar

Anti condensation heating up to 150°C

FLEXIDOSE Static - Gas P-Controller


Gas flow controller and dynamic P-controller for gases in the pressure range from vacuum up to 300 bar

FLEXIDOSE G Flow – Gas Flow and P-Controller


Gas & vapor flow controller and dynamic P-controller for gases in the pressure range from vacuum up to 150 bar

FLEXIDOSE G&V Flow – Gas&Vapor Flow and P-Controller


-1.00

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0.00

300 400 500 600 700 800

Temperature／℃

Rel

. W

eig

ht

Ch

an

ge D

m(t

)/D

m(t

) /

-

0.1MPa

3.3MPa

Coal gasification research: effect of pressure on kinetics Sample: anthracite, reaction gas: 2% O2 in N2

Application Examples I: Gasification of Coal and Biomass


Coal gasification research:TGA measurement of coal gasification



Coal gasification research:


TGA + MS: Simultaneous MS gas analysis of coal gasification

Temperature profile as shown in previous slide


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300 400 500 600 700 800

Temperature／℃

Rel

. W

eig

ht

Ch

an

ge D

m(t

)/D

m(t

) /

-

0.1MPa

3.3MPa


Catalyst research: carbon formation of steam reformation catalyst under process conditions (20 bar, 650°C)

y = 0.0921x + 3870.7

3900

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3960

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Time / min

Sa

mp

le M

ass

/ m

g

0

50

100

150

200

250

Flo

w / m

l/m

in

Weight

Weight selected

CH4 Flow

H2O(V) Flow

Linear (Weight selected)

y = 0.4004x + 3751.2

3900

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Time / min

Sa

mp

le M

ass

/ m

g

0

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Flo

w / m

l/m

in

Weight

Weight selected

CH4 Flow

H2O(V) Flow


S:C – Ratio 1.0 S:C – Ratio 0.8

Gasification of rice husk: Material conversion is slow in nitrogen but increased with 10% water vapor



-1.00

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-0.40

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0.00

300 400 500 600 700 800

Temperature／℃

Rel

. W

eig

ht

Ch

an

ge D

m(t

)/D

m(t

) /

-

0.1MPa

3.3MPa



y = 0.0921x + 3870.7

3900

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3960

345 350 355 360 365 370 375 380 385

Time / min

Sa

mp

le M

ass

/ m

g

0

50

100

150

200

250

Flo

w / m

l/m

in

Weight

Weight selected

CH4 Flow

H2O(V) Flow


y = 0.4004x + 3751.2

3900

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Time / min

Sa

mp

le M

ass

/ m

g

0

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120

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Flo

w / m

l/m

in

Weight

Weight selected

CH4 Flow

H2O(V) Flow



KIT

Gasification of wood char: Reactivity increases with pressure and pCO2


KIT, Engler Bunte Institut



y = 0.0921x + 3870.7

3900

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345 350 355 360 365 370 375 380 385

Time / min

Sa

mp

le M

ass

/ m

g

0

50

100

150

200

250

Flo

w / m

l/m

in

Weight

Weight selected

CH4 Flow

H2O(V) Flow


y = 0.4004x + 3751.2

3900

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3960

375 380 385 390 395 400 405 410 415

Time / min

Sa

mp

le M

ass

/ m

g

0

20

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100

120

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Flo

w / m

l/m

in

Weight

Weight selected

CH4 Flow

H2O(V) Flow



Application Examples II: Catalyst Performance



Catalyst Optimization for Dry Reforming of Methane: Ni/MgAlOx Catalyst: Documentation of Catalyst Activation



Catalyst Optimization for Dry Reforming of Methane: Ni/MgAlOx Catalyst: Coking behaviour depending on reaction conditions (Temperature, Gas Flow Rates)

Fritz Haber Institute Berlin DynTHERM Application Note 1, Tarasov et. al. CIT 2014, 86, 1916-1924


Application Examples III: Chemical Looping Combustion

Reaction kinetics of a CLC process using a copper based oxygen carrier: Reduction: 50 ml/min Methane 60 min, Oxidation: 100 ml/min Air 60 min

Mass change (left) and conversion rate curves at different reaction temperatures. Qingdao Institute of Bioenergy and Bioprocess Technology Liu et. al. AMR 2013, 724-725, 1140-1144


Application Examples IV: High temperature Corrosion

Improved materials for aerospace turbines – Oxidation of Mo-Si-B alloys at 750 – 1300°C in air: catastrophic oxidation, evaporation of volatile MoO3, formation of protective borosilicate layers

Mass change in mg/cm3 of Mo-9Si-8B-35Ti oxidized in air DynTHERM LP system with oxygen sensor and bellows protected lift for fast sample introduction into hot reactor.


Application Examples IV: High temperature Corrosion

Oxidation of various Mo alloys in air

Mass change over time for three alloys at temperatures of 1100°C (left) and 1300°C (right) Steffen Burk, 2011, Ph.D. thesis Siegen University


-1.00

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-0.60

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0.00

300 400 500 600 700 800

Temperature／℃

Rel

. W

eig

ht

Ch

an

ge D

m(t

)/D

m(t

) /

-

0.1MPa

3.3MPa



y = 0.0921x + 3870.7

3900

3910

3920

3930

3940

3950

3960

345 350 355 360 365 370 375 380 385

Time / min

Sa

mp

le M

ass

/ m

g

0

50

100

150

200

250

Flo

w / m

l/m

in

Weight

Weight selected

CH4 Flow

H2O(V) Flow


y = 0.4004x + 3751.2

3900

3910

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3960

375 380 385 390 395 400 405 410 415

Time / min

Sa

mp

le M

ass

/ m

g

0

20

40

60

80

100

120

140

160

180

Flo

w / m

l/m

in

Weight

Weight selected

CH4 Flow

H2O(V) Flow



Oil exploration research: TGA of crude oil gasification (destillation & pyrolysis) at 50 bar

-100

-80

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0

20

0 100 200 300 400 500 600

Temperature / °C

Sa

mp

le M

ass

Ch

an

ge

/ %

0

10

20

30

40

50

60

Pre

ssu

re /

ba

r

Sample Mass Change

Pressure

Application Examples V: Petrochemistry: Crude Oil Destillation


Reaction Chamber with 4 Windows

Dyntherm MP HTIII: 40 bar 1400°C

Application Examples VI: Spectroscopic Investigation of Gasification Process


Magnetic Suspension Balance for high resolution weighing

New Gravimetric Product NANOMSB


Working principle & basic setup (Patented in Europe and USA)

Product Line News NANOMSB

Maxwell coils

Balance heating

Position sensor

Diamagnet

2D quadrupole


Hanging sample version for highest P & moderate T applications

mSample 200 mg 1000 mg Dm 0.01 mg 0.1 mg


Small volume / inner diameter -> highest pressures possible (> 1000 bar)


Toploading version for high T & high P TGA application

mSample 200 mg 500 mg Dm 0.01 mg 0.1 mg


Reduced convection -> improved balance stability

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