ICAC/EPA Round-table

Meeting

Peter G. Zemek, PhD

CTO, MKS Instruments

Peter_Zemek@MKSinst.com

Boston, USA

May 2015

An Optical Sensor for

Real-Time, Speciated

Gas and Liquid Measurement

Electromagnetic Spectrum

Optical Instruments

Light – Particles and Waves

Higgs Boson particle

Photon spin is not constant

Double Slit “Wavicles” Higgs-Boson Particle

Quantum gets both impacts like

particles and interference patterns

like wavesCourtesy of Youtube

Courtesy of Wiki

MKS Instruments

$1.6B

4900+ employees

https://www.mksinst.com/

MKS Instruments

Fourier Transform Infrared (FTIR)

Spectrometry– SO3/H2SO4 SCR, Scrubber (H2O 40% by Vol)

– NH3 Slip

– NOx, SO2, CO/CO2, CH4, any dipole

Solid State Laser– Ultralow trace level

Non-Dispersive Infrared (NDIR)

Tunable Filter Spectrometer (TFS)

Do

wn

str

eam

M

idstr

eam

Up

str

eam

Innovative Optical Device Developed for HPI

>2700 Installations

Designed for Purpose

Shock, Vibration, Unattended

On-line & /or Portable

Ambient temperature

Delta

Sample temperature

Vibration & shock

Humidity

Wet-Gas

Easy Installation

Quick Warm-Up time

Fast Response Time 5

sec

High Accuracy

Good Repeatability

Great Linearity

Stability

Remote control

No Calibration

Zero-Drift

Ruggedness

Price

Cost of Ownership

What are we talking about?

Tunable Filter Spectrometer (TFS)

Key customers:

• Saudi Aramco, Gasco, ADGAS

• BP (UK and Germany)

• BASF

• Shell

• Wartsilla

• SinoPec Guangzhou Petroleum

• CNPC Jiangyou Plant

• CNPC Dalian West Pacific

+ Fiber Based Liquid (Cryogenic) Probes

OEM Design – Customized Needs, Gases, LOD

CE, ATEX, CSA, UL, Class I DIV I or II

IECEx,NEMA4X, IP66

TFS Technology Differentiation

Comparison to other major competitorsTFS FTIR NDIR Laser

Based

Sensor

GC Significance

Specificity High High Low High High Ability to measure target compound in

complex real-world mixes

Sensitivity High High Med High High Ability to measure trace components

accurately

Multi Compound

Monitoring

Med Multi Single Single Multi Ability to monitor multiple components with

one instrument. Requirements of most

applications.

Reponse time Fast Fast Fast Fast Slow Ability to response to the variation of the

monitor gas promptly

Cost of

Ownership

Low Med to High Low Low High Low cost of ownership is a prerequisite for

wide industrial deployment of technology

FTIR: Fourier Transform Infrared Spectroscopy

NDIR: Non-Dispersive Infrared Spectroscopy

GC: Gas Chromatography

FID: Flame Ionization Detector

CRDS: Cavity Ring-down Spectroscopy - * Depending on the LOD needed but typically 1 cmpd for CRDS

CLD: Chemi-luminescent Detector - NOx

1 TFS Replaces – FID, NDIR, CRDS*, CLD

Expanding into all Markets

Total BTU, Wobbe, MN, Sp Grav. C1-C6+

Speciation, Blending, Olefins, LNG/LPG

Semi-Endpoint, Etch, and Clean Detection

HRVOC – Highly Reactive VOCs (Propylene,

Ethylene, 1,3-Butadiene, Butenes)(0-100ppm)

Air Separation Units (ASU)

CO+CO2+CH4+H2O+N2O+THC(alkanes)

------------------------

Acid Gases- HCl, HBr, H2SO4, etc

CEM Criteria Pollutants – NOx (NO2, NO), SO2

Air Toxics/HAPs – HCN, Carbonyls, etc.MKS Confidential 11

Real-time, On-Line, All-Optical

Speciated Gas Analyzer

OEM Fuel Feed

Gas analyzer, providing:

Individual alkane component concentration, such as C1 – C6+ & CO2

BTU/CV calculated value (ISO6976)

Wobbe Index calculated value (ISO6976)

Hydrocarbon dew point

Real-time measurement in seconds

Unaffected by N2, O2, H2 and CO2

Any dipole gas measurement (IR, UV)

Low-cost installation and operation:

– No carrier gas requirement

– No calibration gases or “clean” air requirement

– Minimal “sheltering” requirement

• GC-like speciation (C1-nC6, alkanes, alkynes, alkenes, etc.)

• Fast update rate (< 5 seconds)

• Total BTU/HV from C1 to C6+ in natural gas (0-3000 BTU

linear response)

• Repeatability <+/- 0.01 MJ/m3 T(+/- 0.3 BTU/1000)

• Accuracy <+/- 0.04 MJ/m3 (+/- 1 BTU/1000) (5 x RMS noise)

• No carrier gas required

• No H2 instrument fuel gas required

• Permanently calibrated (easy to span-adjust)

• Alternative or fast-response transmitter/sensor to GC-TCD

GC Alternative

How does it work?

TFS Principle of Operation

Sample

λ

Filter FunctionFabry-Perot Etalon

Metric The TFS Advantage

Simplicity • Delivers low-cost and rugged hardware design

Wavelength Sweep • Enables multi-component analysis (4 regions 100-300 cm-1 wide)

• Provides higher selectivity and improved speciation

Larger Etendue • Higher optical throughput

• Delivers high sensitivity and low LDL capability per path length

Field proven technology. We have 2700+ delivered

sensor products based on this technology

I

TFS™ Sensor Wavelength Scanning Technology

2500 3000 3500 4000 4500 5000

0

0.5

1

1.5

2

2.5

x 10-4

3 separate regions

H2O

THC

CO2

CO

• Custom designed Fabry-Perot element

• Focused on relevant band(s)

• Wavelength scanning within the band(s) (up to 4 regions)

Light Absorption Spectroscopy with Advanced

Spectral Decomposition Algorithm

Speciated and

Quantified

Compounds

Chemometrics

Ch. # Compound Range Accuracy

1 Methane 0 - 100% +/- 0.2%

2 Ethane 0 – 25% +/- 0.2%

3 Propane 0 – 25% +/- 0.2%

4 iso-Butane 0 – 10% +/- 0.1%

5 n-Butane 0 – 10% +/- 0.1%

6 Propylene 0 – 10% +/- 0.2%

7 Ethylene 0 – 10% +/- 0.2%

Example Configuration

Challenges of Hydrocarbon

Spectroscopic Analysis

Source: www.camo.com

“A data collection task involves many measurements made on

many samples. Such multivariate data has traditionally been

analyzed using one or two variables at a time. However, this

approach fails to discover the relationships among all variables and

samples efficiently. To overcome this,we must process all of the

data simultaneously. Chemometrics is the tool for extracting

information from multivariate chemical data using tools of

statistics and mathematics.”

Effects of Light Intensity Drift to

Span Accuracy

Test Procedure:

1. Zero the instrument (pure N2)

2. Flow sample mixture

3. Reduced light intensity by 50%

4. Flow back N2

Results:

Span drift due to ~50% light

intensity reduction: < 0.03%

on all channels

Zero drift: virtually zero on all

channels (< 0.01%) without

re-zeroing the instrument

CH4: 49.72% CH4: 49.74%

=> Error: 0.03% (due to a

50% drop in light intensity)

=> Zero Drift <0.01%

Optical Throughput Advantage

with TFSTM

platforms

• Low detection limit (high sensitivity)

• Highly overlapping spectra

• Rapid measurement response

3200 3300 3400 3500 3600 3700

0

0.5

1

1.5

2

2.5

3

3.5

x 10-4

3200 3300 3400 3500 3600 3700

0.5

1

1.5

2

2.5

3

3.5

4

4.5

5

x 10-4

TFS Grating / diode array

Spectral quality difference:

Yields high optical throughput

Installs, Studies and Field Tests

Saudi-Aramco MKS-TFS Evaluation

Use ISO 6976

For Total BTU

GPA Standard 2261 in Section 2 Summary of Method the following

Note is found:

NOTE 2 – Modern technology has brought many advances in the

way natural gas can be analyzed. These advances are now

available for traditional laboratory as well as portable and on-line

gas chromatographs. Any gas chromatograph is acceptable for

analysis of natural gas as long as the specifications for repeatability

and reproducibility in Section 9 over the component ranges listed in

Table 1 are met or exceeded.

Field Trial – Pipeline Gas Analysis

• Test performance against an ‘industry-standard’ Gas Chromatograph (GC)

• Performed in a natural gas & oil well in Eastern Colorado

• Data represents a well run of over a 3-day period

0

5

10

15

20

25

30

35

40

45

1 2891 5781 8671 11561 14451 17341 20231 23121 26011

Data point

Co

ncen

trati

on

(%

)

0

5

10

15

20

25

30

35

40

45

1 3243 6485 9727 12969 16211 19453 22695 25937 29179

Data point

Co

ncen

trati

on

(%

)

Total HC gas plot from a GC-TCD

Total HC gas plot from an IR with

TFS-equipped optical analyzer

Field Trial – Data Analysis

Speciated Methane plots

0

50000

100000

150000

200000

250000

300000

1 3059 6117 9175 12233 15291 18349 21407 24465 27523

Data point

Co

ncen

trati

on

(p

pm

)

GC measurement

0

50000

100000

150000

200000

250000

300000

1 3567 7133 10699 14265 17831 21397 24963 28529

Data point

Co

ncen

trati

on

(p

pm

)

IR measurement

y = 1.0209x

R2 = 0.9886

0

50000

100000

150000

200000

250000

300000

0 50000 100000 150000 200000 250000 300000

IR reading (ppm)G

C r

ead

ing

(p

pm

)

IR VS GC readings, methane

Standard Error (SE): 0.74%

Independent Laboratory Testing

with Calibrated Mixtures (in UK)

Goals:• Evaluate accuracy and linearity

• Evaluate calibration robustness

Methods: • Use certified bottled gases & MFC

Mix 1. 100% ethane

Mix 2. 50% ethylene bal N2

Mix 3 . Mix 1 and 2 and N2

Mix 4. Methane 29.88% ,Ethane 6.987%,

Propene 14.92%,Ethylene 32.663 %

Balance (approx. 15% ) H2

Mix 5. Mix 1 and Mix 4 and N2

Mix 6 .Methane 30%,Ethane 10.04%,Ethene 29.88%,Propane 10.05% n Butane 4.93%

Mix 7. iso Butane 2.2% in N2

Mix 8 .Mix 7 and Mix 6 and N2

Mix 9 . n Butane 1.98 % in N2

Channel Compound Range

1 Methane 0 – 100%

2 Ethane 0 – 25%

3 Propane 0 – 25%

4 iso-Butane 0 – 10%

5 n-Butane 0 – 10%

6 Propylene 0 – 10%

7 Ethylene 0 – 10%

Analyzer Configuration

Accuracy – C1 to C4 alkanes &

ethylene (cont…)

Linearity

Out-of-range

ethylene

CV Measurement Linearity

Measured CV (BTU/SCF)

Th

eore

tica

l C

V (

BT

U/S

CF

)

Error (RSMEP): 1.8 BTU/SCF

(0.067 MJ/NM3)

%

40-hour Pipeline Natural Gas: side-by-

side test with a GC-TCD (CH4

values)

CH4 discrepancies: 0 – 0.3%

Due to calibration gas differences

TFS can be re-spanned as other instruments do in the field

TFS could be calibrated with the same standard as the GC

%

40-hour Pipeline Natural Gas: side-by-

side test with a GC-TCD (C2H

6values)

• C2H6 discrepancies: 0.1 – 0.25%

• Due to calibration gas differences

28 days LNG composition (GC vs TFS)

GC – daily update

(daily calibration)

TFS – 5 second updates

(no calibration, no re-zero)

As can be seen, the TFS based infrared measurements track the daily GC reading

very well, quite noticeably the low methane readings on around 8/2 and 8/15,

higher C4 readings around 8/15 and high C3 reading around 8/2.

More importantly, the infrared reading captures the fluctuations that

otherwise would be missed by the daily GC measurements.

TFS-ASU-Trace Gas Monitor (M3)

Advantages• Replacing different gas sensors in a rack

with a single multi-component monitor.

• Reducing the interference in the

measurement

• Lower ownership cost and low

maintenance

• Real time response (up to 1 Hz reporting

rate)

Packaging and interfaces:• 4U box compatible to standard 19” rack mount

• ¼” VCR fittings for gas sampling

• 110/220 V power input

• LCD touchscreen

• Modbus on TCP/IP and RS485

• 4 4-20mA Analog output

• 4 configurable actuator outputs

Measurement range 10 ppb to 1000 ppm

Multi-component monitoring; CH4, C2+ Alkanes, CO, CO2, N2O, H2O

TFS M3 System Overview

TFS Analyzer Engine:

a. Configurable filter bands

(up to 4 different bands)

b. Broadband transfer optics

(Visible to MIR)

c. Multiple detector options(

InGaAs, MCT, DTGS)

10 meter Multi-pass Gas

Cell:

a. Specially designed high

throughput cell

b. Oxygen compatible

c. Temperature up to 190 C

Electronics:

a. Algorithm fully

embedded

b. Programmable

system

settings/Analog

IOs/Interfaces

ASU Measured Results

Linearity test results (measured with CH4, CO and CO2, mixture, 5 second

measurement)

Sensitivities (5σ) in 5 second measurement (ppbv):

CH4 CO CO2 C2+ N2O

5.9 19.6 88.5 57.9 7.6

Sensitivity of Other Gases

All assume 30 second measurement time and

sensitivity is estimated by 5X RMS noise

Gases Sensitivity(ppb)

NO 100

NO2 15

SO2 20

C2H5OH 80

HCl 140

AsH3 12

SiH4 5

H2O 125

SiF4 8

Summary

Industry-first, All-optical Gas Analyzer Platform (MIR, NIR, UV)

– GC-like multi-component speciation (ie alkanes, alkynes, alkenes, dipoles)

– Fast update rate (down to 1 second)

– No carrier gas required & no instrument gas required (no purge)

– Permanently calibrated

– Accuracy & repeatability equivalent or better than a gas chromatograph

Proven Technology & Platform

– 2700+ units deployed (upstream, downstream, HPI, power)

– 350+ years of cumulative run time

– OEM, CE, or CSA/ATEX hazardous area certified

Versatile Spectroscopic Hardware Platform

– UV – midIR analysis

– Process-mounted or portable-field (24VDC)

– An attractive alternative to GC, residual oxygen and refraction based

analyzers in hydrocarbon/fuel gas analysis

– Replace multi/single component analyzers (CLD, UV,FID, NDIR, CRDS)