Tgd Rtgacust Final 3-3-11

8/6/2019 Tgd Rtgacust Final 3-3-11

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1

Strategies for the Direct andReal-time Measurement

of

Gases by Mass Spectrometry fornew Fuel Development

Dr. Terry Ramus, Diablo Analytical Inc.


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Agenda

16:00 -16:05 Welcome & Introductions, Logistics, Agenda Review

16:05 -16:10 About Diablo Analytical and the RTGA

16:10 -16:45 Strategies for the Direct and Real-time Measurement ofGases by Mass Spectrometry for new Fuel Development

16:45- 17:00 Questions & Answers


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About Diablo Analytical Inc.


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4

Strategies for the Directand Real-time

Measurement of Gases

by Mass Spectrometryfor new FuelDevelopment

Dr. Terry Ramus,

Principal Diablo Analytical, Inc.


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Hydrocarbon Bio

Crudeoil

Oilsands

Shale

oil

Coal

Naturalgas

Agriculture

-Food

Agricu

lture-n

onfoo

d

Cellulo

se,swi

tchgra

ss

Alg

ae

Waste(biomas

s)

Wood,Ag,Muni

cipalSolids

Energy sources

Refinery

Gasoline, jet fuel, diesel, heating oil, mfg goods, nat gas

Fermentation, PY

Methane, pyro-oil, FT-diesel, bio-diesel, alcohols


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Hydrocarbon Biomass

Methane Gas Mixtures

Biodiesel (FAME)HC Fuels

Refinery Transesterfication

FAM

EOils

SynGas

FT-diesel, alcohols

Syngas Related Products & Mix with Traditional HCs

High

CH4High

CO

Fuel Cell Hydrogen

HighH

2

H2, CO, CH4, H2O


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Syngas and related Energy Strategy

Syngas: H2, CO

with H20, CH4,CO2

Fuel Cell:hydrocarbons to

H2

Coal Gasification:C to CH4, etc.

Other Inputs ??:Water, air, temp,pressure,catalysts

BiomassPyrolysis: Waste

to fuel

Fuel CellOperation: H2 toelectric power

AlcoholProduction:

Syngas to MeOH

DieselProduction:

Fischer-Tropsch


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What is Real time?

IR, MS, Probes - seconds Not GC, LC - many minutes

(note: GC is very common not real-time)

Answer = Depends on the Process


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Why MS ?

Rich in information

Separation by mass

Very fast

Why, traditionally, NOT MS ?

Expensive and delicate ?

Requires experts ?

Hard to interface ?


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Why RTGA MS ?

Very robust

Moderate cost Designed for Engineers

Interface = flexible,quantitative

Not just qualitative trend data anymore


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To LV12 pump

ToMSD

PressureTransducer Process

Stream in

Out tovent

Molecular flow

Orifice 50

Sonic Flow

Orifice 30

IsolationValve

..

What is an RTGA-How does it work?MS Interface


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Proven platform -reversibleadaptation of Agilent 5975C

Engineers Software

Ready for direct gasmeasurements

Fast response

Pressure or vacuum samples

Heated Interface

Compensate for pressure changes

Quantitative results

Calibration


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13

Natural Gas- Hydrogen

methane

C3-C5

Hydrogen

Carbon dioxide

C2C5

C2

CH4

C3C5

CO2


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Where is the Sample?

Typically, Testing begins in the lab May be Real-time ? - off a bed or reactor

Moves to engineering development

Research reactors, still indoors

NOT out doors yet for RTGA! Traditional Production on-line Equipment


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Which Tools for Measurements?

- Traditional Categories -

Laboratory Type off-lineInstruments:

Results are delayed

Slow to adapt/optimizeprocess

Samples change

before analysis

Lab Equipment Option? On-line Option?

Production Type On-lineInstruments:

Dedicated equipment

Robust for anyenvironment

Less flexible bad for

development


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Third Option (MS): Rapid andFlexible Real-time Measurement

Tools

Increase in complexity for users

More

Robust

Traditional Lab Systems

Quads, TOFs, Triple-Quads,

Sectors, Hyphenated MS

Traditional On-line Systems

Dedicated process Quadsand Sectors, vacuum

system Quads

High-end On-line (few units)

API-TOF

Engineering Lab System

RGA (vac.) MS Systems

- Low cost, trend tool

RTGA (modified Lab Quad)

- Best performance

Agilent 5973/75MSD


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Real-time Process Software


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0

10

20

30

40

50

60

70

80

90

100

5 15 25 35 45 55 65

0

5

10

15

20

25

30

35

40

45

50

N2+CO

CO2

H2

O2

CH4

Gas Comp

N2=16.63%+CO=1.75%

O2=1.75%

CO2=3.75%

H2=75%

CH4=1.12%

100% H2

Gas Comp

N2=33.25%

+CO=3.5%

O2=3.5%

CO2=7.5%H2=50%

CH4=2.25%

Gas Comp

N2=49.88%

+CO=5.25%

O2=5.25%

CO2=11.25%H2=25%

CH4=3.37%

Gas Comp

N2=16.63%

+CO=1.75%

O2=1.75%

CO2=3.75%

H2=75%

CH4=1.12%

100% H2

Fuel Cell Gas Calibration:Dynamic Dilution with MFC manifold

Hydrogen balance gas

Nitrogen

OxygenCO2Methane

Time (min.)

C

oncentratio

n

(%)


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RTGA Calibration

Methane calibration (repeat for each component):n 3 point linear calibration (percent range)

n Non-zero intercept


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Hydrogen Cal in Fuel Cell Mix

Hydrogen Calibration y = 676.02x - 876.4

R2 = 0.9976

0

5000

10000

15000

20000

25000

30000

35000

0 10 20 30 40 50 60


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Trace Contaminants in Hydrogen

0

20000

40000

60000

80000

100000

120000

90 100 110 120 130 140 150 160 170 180

Carbon Dioxide

Methane

Nitrogen

Oxygen

Time (min.)

RTG

A

Response

10ppm

CO,

CO2,me

thane

10ppm

CO,

CO2,me

thane

FuelCellHydrogen

FuelCellHydrogen

10ppm

N2,

O2

10ppm

N2,

O2

H2Blank

H2Blank

H2Blank

H2Blank

H2Blank

H2Blank

Use Stream Selection Valve:

n Blank Hydrogen (getter)

n Gas Standard #1

n Gas Standard #2

n Fuel Cell Hydrogen Sample

Nitrogen (64 ppm)


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Compare RTGA and GC-PDID

Trace Contaminants in HydrogenComponent GC System RTGA 5000A RTGA Mass

Water ND 4.5 ppm 18

Carbon Dioxide 0.5 ppm 0.9 ppm 44

Oxygen 5 ppm 6 ppm 32

Nitrogen 54 ppm 64 ppm 28

Methane ND 2 ppm 15

Argon NA ND 40

Carbon Monoxide ND NA 28

Hydrogen Sulfide NA ND 34

C2 C3 Hydrocarbons NA ND 27,42,43

GC System:

Valco Pulsed Discharge Ionization Detector in HID mode

Gas Sampling Valve and Column Switching Valve (three columns)


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Show Percent/ppm in Real-time

methane

C3-C5

HydrogenCarbon dioxide

C2C5

C2

CH4

C3C5

CO2


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Anode Cathode

CrossoverAnode/Cathode Rxns

FuelProcessor

Fuel CellStack

InverterFuels H2 Rich

Natural GasGasolineDieselLandfill GasSynthesis GasMethanol

H2,CO

CO2,H2OO2, N2SulfurCH4, C2+

DC

Water Gas

Shift

CO

Oxidation

CO


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Fuel Cell Poisons lower concentration

Sulfur

Harmful to all systems [voltage loss, rxn withelectrolyte]

Carbon Monoxide

Harmful to Pt catalysts

Carbon Dioxide

Detrimental to alkaline systems

Halides [corrosion, rxn with electrolyte]

Hydrocarbons [carbon deposition]

Nitrogen Oxides [rxn with electrolyte]

SO2 in oxidant to cathode


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Packed Bed for Sulfur Removal from Gas Stream

breakthrough study

Before Treatment

Desulfurizer on-line

Breakthrough

1 ppm


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Sulfur Poisons in Fuel Cell H2 Mix

450 ppb775 ppb

H2S + MeSH + DMS + EtSH

Sulfur off


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Inert System- Fast Response for Sulfur

12

3

4

5

Step 1: 1.0 ppm (mercaptans) to Step 5: 4.0ppm (mercaptans)


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Conclusions & Benefits

Flexibility

Quantitation

Proven Platform

Support and flexible configurations

Easy to Use

Applications -- FAST responseFuel Cell, Catalyst, Syngas

Reaction Optimizations

Packed Bed Studies


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Questions?

Contact Details:[email protected]

www.diabloanalytical.com

P: +1 925 755 1005 ext. 115 F: +1 925 755 1007

[email protected]

www.transglobaldistributors.comP: + 31 10 258 1870F: + 31 10 258 1879
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Tgd Rtgacust Final 3-3-11

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