Strategies for the Direct and Real-time Measurement of Gases by Mass Spectrometry for new Fuel Development

Dr. Terry Ramus, Diablo Analytical Inc.

Agenda
16:00 -16:05 16:05 -16:10 16:10 -16:45 Welcome & Introductions, Logistics, Agenda Review About Diablo Analytical and the RTGA Strategies for the Direct and Real-time Measurement of Gases by Mass Spectrometry for new Fuel Development Questions & Answers

16:45- 17:00

About Diablo Analytical Inc.

Strategies for the Direct and Real-time Measurement of Gases by Mass Spectrometry for new Fuel Development
Dr. Terry Ramus, Principal Diablo Analytical, Inc.

Energy sources
Hydrocarbon
Cru

Bio
m ss) (bioipalaolids Waste , Munic S
ul tu re Fo od

de

as

Oil sands

al Co

il le o a Sh

ure h g ultose, switc ic Agr Cellul

d foo n -no rass

Fermentation, PY Refinery Methane, pyro-oil, FT-diesel, bio-diesel, alcohols

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

Alg

Na tur al g

ae

oil

Ag ric

Wood,

Ag

Syngas Related Products & Mix with Traditional HCs

H2, CO, CH4, H2O

Hydrocarbon

SynGas

Biomass
ME FA ls Oi

High CO

Refinery

ig h

Transesterfication
C H 4

2 hH Hig

HC Fuels FT-diesel, alcohols Fuel Cell Hydrogen

Biodiesel (FAME) Methane Gas Mixtures

Syngas and related Energy Strategy

Fuel Cell: hydrocarbons to H2 Coal Gasification: C to CH4, etc. Biomass Pyrolysis: Waste to fuel Other Inputs ??: Water, air, temp, pressure, catalysts Fuel Cell Operation: H2 to electric power Alcohol Production: Syngas to MeOH Diesel Production: Fischer-Tropsch
7

Syngas: H2, CO
with H20, CH4, CO2

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

8

Why MS ?
Rich in information Separation by mass Very fast

Why, traditionally, NOT MS ?

Expensive and delicate ? Requires experts ? Hard to interface ?
9

Why RTGA MS ?
Very robust Moderate cost Designed for Engineers Interface = flexible, quantitative

Not just qualitative trend data anymore

10

What is an RTGA-How does it work?

MS Interface
Pressure Transducer
Isolation Valve

Process Stream in

To MSD

Orifice 50

Orifice 30

Out to vent

Molecular flow

Sonic Flow To LV12 pump

 Proven platform -reversible adaptation of Agilent 5975C Engineers Software Ready for direct gas measurements Fast response Pressure or vacuum samples Heated Interface Compensate for pressure changes Quantitative results Calibration
12

Natural Gas- Hydrogen

methane

CH4

C3-C5 C2C5 Hydrogen Carbon dioxide

C2

C3C5

CO2

13

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
14

Which Tools for Measurements? - Traditional Categories Lab Equipment Option? Laboratory Type off-line Instruments: Results are delayed Slow to adapt/optimize process Samples change before analysis On-line Option? Production Type On-line Instruments: Dedicated equipment Robust for any environment Less flexible bad for development
15

Third Option (MS): Rapid and Flexible Real-time Measurement Tools On-line (few units) Traditional On-line Systems High-end
Dedicated process Quads and Sectors, vacuum system Quads API-TOF

More Robust

Engineering Lab System RGA (vac.) MS Systems - Low cost, trend tool

Traditional Lab Systems Quads, TOFs, Triple-Quads, Sectors, Hyphenated MS Agilent 5973/75 MSD
16

RTGA (modified Lab Quad) - Best performance

Increase in complexity for users

Real-time Process Software

17

Fuel Cell Gas Calibration:

Dynamic Dilution with MFC manifold
100 90 100% H2 50

Hydrogen balance gas

45 100% H2 Gas Comp N2=33.25% +CO=3.5% O2=3.5% CO2=7.5% H2=50% CH4=2.25% 40

80

70

Concentratio n (%)

60

Gas Comp N2=16.63% +CO=1.75% O2=1.75% CO2=3.75% H2=75% CH4=1.12%

Nitrogen
Gas Comp N2=16.63% +CO=1.75% O2=1.75% CO2=3.75% H2=75% CH4=1.12%

35

30 N2+CO CO2 H2 O2 CH4

50 Gas Comp N2=49.88% +CO=5.25% O2=5.25% CO2=11.25% H2=25% CH4=3.37%

25

40

30

20

Oxygen CO2 Methane

45 55 65

20

15

10

10

0 5 15 25 35

Time (min.)

RTGA Calibration
Methane calibration (repeat for each component): n 3 point linear calibration (percent range) n Non-zero intercept

19

Hydrogen Cal in Fuel Cell Mix

Hydrogen Calibration
35000 30000 25000 20000 15000 10000 5000 0 0 10 20 30 40 50 60 y = 676.02x - 876.4 R2 = 0.9976

20

Trace Contaminants in Hydrogen

120000

Use Stream Selection Valve:

Nitrogen (64 ppm) 10 ppm CO, CO2, methane 10 ppm CO, CO2, methane
100000

n Blank Hydrogen (getter) n Gas Standard #1 n Gas Standard #2

Fuel Cell Hydrogen H2 Blank

80000

Fuel Cell Hydrogen

RTGA Response

n Fuel Cell Hydrogen Sample

10 ppm N2, O2

60000

40000

H2 Blank

H2 Blank

H2 Blank

H2 Blank

20000

0 90 100 110 120 130 140 150 160 170 180

H2 Blank

10 ppm N2, O2

Carbon Dioxide Methane Nitrogen Oxygen

21

Time (min.)

Compare RTGA and GC-PDID

Trace Contaminants in Hydrogen
Component Water GC System ND 0.5 ppm 5 ppm 54 ppm ND NA ND NA NA RTGA 5000A 4.5 ppm 0.9 ppm 6 ppm 64 ppm 2 ppm ND NA ND ND RTGA Mass 18 44 32 28 15 40 28 34 27,42,43

Carbon Dioxide
Oxygen Nitrogen Methane Argon Carbon Monoxide Hydrogen Sulfide C2 C3 Hydrocarbons

GC System: Valco Pulsed Discharge Ionization Detector in HID mode Gas Sampling Valve and Column Switching Valve (three columns)
22

Show Percent/ppm in Real-time

methane

CH4

C3-C5 C2C5 Hydrogen Carbon dioxide

C2

C3C5

CO2

23

O2
Water Gas Shift

Fuel Cell Characterization

Exhaust Heat Water

CO Oxidation

CO

CO<10ppm

Fuels

Fuel Processor

H2 Rich H2,CO CO2,H2O O2, N2 Sulfur CH4, C2+

Fuel Cell Stack

DC

Inverter

Oxidant [Impurities, SO2]

Natural Gas Gasoline Diesel Landfill Gas Synthesis Gas Methanol

H2
H2O Anode

Crossover Anode/Cathode Rxns O2 Characterize CO poisoning

Cathode
24

Fuel Cell Poisons lower concentration

Sulfur Harmful to all systems [voltage loss, rxn with electrolyte] 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
25

Packed Bed for Sulfur Removal from Gas Stream breakthrough study

Before Treatment Desulfurizer on-line Breakthrough

1 ppm

26

Sulfur Poisons in Fuel Cell H2 Mix

H2S + MeSH + DMS + EtSH

Sulfur off

450 ppb

775 ppb

27

Inert System- Fast Response for Sulfur

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

5 4 3 2 1

28

Conclusions & Benefits

Flexibility Quantitation Proven Platform Support and flexible configurations Easy to Use Applications -- FAST response Fuel Cell, Catalyst, Syngas Reaction Optimizations Packed Bed Studies

Questions?
Contact Details:
tlramus@diabloanalytical.com www.diabloanalytical.com P: +1 925 755 1005 ext. 115 F: +1 925 755 1007

deborah.burton@transglobaldistributors.com www.transglobaldistributors.com P: + 31 10 258 1870 F: + 31 10 258 1879