olefin analyzer solutions for polymer grade …...olefin analyzer solutions for polymer grade...

Olefin Analyzer Solutions for Polymer Grade Ethylene and Propylene

Angela Smith Henry

Kelly Beard

George Gonzalez

6/21/2017

ASTS 2017 Houston, TX

1

Impurity Monitoring in Olefin Production

Analysis of contaminants in ethylene and propylene

• Trace impurities can foul the process units and product quality

• Frequently used metallocene catalysts

are susceptible to impurities

- Contaminants can degrade a

polymerization catalyst and can

potentially shut down the production

process for catalyst replacement

• Impurities need to be monitored

at lowest possible detection limits


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Outline

• Arsine Phosphine GC/MS Analyzer

• ASTM Work Item #56896 – Arsine and Phosphine in Ethylene

• GC-FID

• D6159 – Trace Level Hydrocarbons in Ethylene

• D7212 – Trace Level Hydrocarbons in Propylene

• D7423 – Oxygenates in Ethylene

• GC-PDHID

• ASTM Work Item #55889 – Fixed gases in Ethylene with PD-HID

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Arsine Phosphine Analyzer:Detect low level contaminants in ethylene and propylene

Applications Chemists

Angela Smith Henry, Ph.D.

Bruce Quimby, Ph.D.


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Arsine/Phosphine GC/MS Analyzer - Overview

Excellent analytical performance

• Single digit ppb detection limits, RSDs of ~5% or less

• Inert Flow Path for robust operation

• High Efficiency Source for highest sensitivity and JetClean Self

Cleaning Ion Source for long-term precision

• Hands-free multi-level Calibration – Automated calibration sequence

Provides ability of in-house routine monitoring for contaminants

• Detection at this level previously only achievable with GC/ICP-MS

- GC/ICP-MS is still more sensitive than GC/SQ


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Arsine Phosphine GC/MS Analyzer


Novel column:

Resolution of

contaminants in

olefin matrix

Use a GC-controlled back

pressure regulator on

valve system:

High precision

HE Source:

Improved IDL for

single ppb

detection

Agilent

deactivation for

inert flow path

JetClean:

Low maintenance,

high precision

Agilent designed and

manufactured inert

dilution system for built-in

calibration

Fully automated multi-

level calibration system

with PCM modules and

pre-made methods

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Schematic of Arsine Phosphine GC/MS Analyzer


7

7890B

GC5977B

MSD120 m x 0.32 mm x 8 µm Select Olefins

Source

H2

Transfer

Line

JetClean

High Efficiency Source

2 Valve system

3

42

1

6

5

1

4 3

2

Customer

Sample in

He carrier gas

AsH3

PH3

H2S

COS

Permeation tube

dilution device

(for automated

calibration)

Blue lines (or outline) indicate deactivated stainless steel tubing

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GC-Integrated Calibration with G-Cal Permeation Tubes

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• Dilution controlled with GC flow modules

• Performs automated, multi-level calibration runs in same sequence as samples

• User sets up sequence with calibration and sample runs

• Press OK and let the GC/MS do the work

Permeation Tube Dilution System: GC-controlled 2-stage dilution

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Section in gray is incorporated into permeation tube fixture design

GSV 1: 4 port valve to select calibrants or customer sample

GSV 2: 6 port valve to send selected gases (from GSV 1) onto column for analysis (or vent)

GSV 15977B

MSD

PCM

1A 100 mL/min

N2 (or He)

AsH3

PH3

H2S

COS

PCM

2A

BPRPCM 1B*

Column

Regulate P to 2 psi through sample loop

Flow 1 (100 mL/min)

Flow 3 (16-200 mL/min)

Flow 2 (1.2 mL/min)

vent

vent

Restricted vent

Customer sample

GSV 2

*PCM 1B is modified with a split vent valve to handle higher flows.

DG1

DG2BPR

TSV

VT

Restricted vent

ANALYTICAL PERFORMANCE

Ethylene and propylene matrices with permeation tube dilution

system


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Analytes in Ethylene Matrix: Below 1ppb Detection limits


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Analyte R2

Linearity

5-50 ppb

% RSD

50 runs,

~5ppb

IDL

in ppb, 99%

CI

IDL

in fg, 99% CI

Ethylene Matrix

PH3 0.9996 4.40 0.671 38.6

H2S 0.9997 2.66 0.256 14.9

AsH3 0.9999 1.33 0.128 16.9

COS 0.9999 0.77 0.097 9.83

6/21/2017

* IDL = (t* RSD* concentration)/100

(t for 99% confidence level, n-1 degree of freedom)

Propylene Matrix: Below 1ppb Detection Limits


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Analyte R2

Linearity

5-50 ppb

% RSD

50 runs,

~5ppb

IDL

in ppb, 99%

CI

IDL

in fg, 99% CI

Propylene Matrix

PH3 0.9998 3.16 0.541 31.2

H2S 0.9996 3.92 0.431 24.7

AsH3 0.9998 1.39 0.153 20.0

6/21/2017

* IDL = (t* RSD* concentration)/100

(t for 99% confidence level, n-1 degree of freedom)

Liquid propylene sampling: Micro Gasifier

• Can be connected to the

Arsine Phosphine Analyzer

• < 1% sample carryover

• Max inlet pressure of 1000 psi

• Pre-set to 100°C and outlet

pressure of 10 psi

• Sample and vent flows are

user controlled

• Excellent repeatability: < 5%

RSD for 50 runs at 5ppb

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Agilent Technologies Micro Gasifier

5ppb Standards through Gasifier:

14 Selected Runs of 50 Runs

Unmatched Long Term Precision

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Compound % RSD (5ppb)

Phosphine 4.23

H2S 2.76

Arsine 2.30

COS 1.42

Overlays of Total Ion Chromatograms (TIC) for every 50th run out of 300 runs

completed over 4.5 days. Runs 2, 50, 100, 150, 200, 250, and 300 are shown

for 5ppb compounds in helium

Using Scan mode to identify other impurities in ethylene

Gulf Coast Conference 2016

15

TIC: JC200uL_ethylene_Scan3.D\data.ms

Average of 15.165 to 15.662 min.: JC200uL_ethylene_Scan3.D\ data.ms EthaneHead to Tail MF=932 RMF=933

10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50

0

50

100

50

100

12

13

13

14

14

15

15 16

24

24

25

25

26

26

27

27

28

28

29

29

30

30

31

31

42 43 44

Component at scan 862 (20.378 min) [Model = +37u] in D:\ MASSHUNTER\ GCMS\ 1\ DATA\ JETCLEAN\ ETHYL\ JC200UL_ETHYLENE_SCAN3.D\ DATA.MS PropeneHead to Tail MF=972 RMF=972

20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50

0

50

100

50

100

20 21 24 2526

27

27

28

36

36

37

37

38

38

39

39

40

40

41

41

42

42

43 44

11 12 13 14 15 16 17 18 19 20 21 22

MSD offMSD on

Propylene

Ethane

min

6/21/2017

• Compared spectra of

peaks to NIST library

• Identified ethane and

propylene impurities in

ethylene

• Let’s take a closer look

around the propylene

peak….

Impurities in ethylene matrix near propylene peak: Scan mode

RTs: Propylene (20.383 min), water (20.465 min) and COS (20.697 min)

Closely eluting compounds can be separated and identified with Scan mode

39 m/z

41 m/z

18 m/z

60 m/z

MSD off

MSD on

COSH2O

Propylene ions

11 12 13 14 15 16 17 18 19 20 21 22 min

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Gulf Coast Conference 2016

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Early eluting compounds in propylene: Extracted Ion Chromatograms from Scan


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Ion 16Ion 44Ion 26Ion 15Ion 25Ion 27

11 12 13 14 15 16 17 18

Ethane

CO2

Methane

N2O2

Ethylene

min

Identify low level hydrocarbon impurities with Scan Mode

14.1 14.5 15.0

Ethylene

6/21/2017

Arsine/Phosphine GC/MS Analyzer - Summary

• Robust solution for routine monitoring of olefin impurities

• Single digit ppb detection limits for AsH3 & PH3 in monomer

grade ethylene and propylene

• High efficiency source and JetClean for highest sensitivity

and long-term precision

• Gas or liquid sampling possible

• Applicable to other low-boiling point matrices (e.g. H2, N2,

O2)

In-house routine monitoring allows fast mitigation

and cost savings


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FID and PDHID Olefin Solutions

6/21/2017


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Ethylene Monomer Purity with GC-FID – D6159

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Contaminant detection in ethylene matrix

• Trace level hydrocarbon detection

• IDL less 1 ppm

• Repeatability, less than 4 % RSD

• Excellent linearity in matrix

Propylene Monomer Purity with GC-FID – D2712

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Oxygenates in Ethylene with GC-FID – D7423

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Contaminant detection in matrix

• IDL less 1 ppm

• Repeatability, less than 5 % RSD

• Excellent linearity in matrix

Non-condensable Gases with GC-PDHID ASTM Work Item #55889

6/21/2017


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Plumbing diagram

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Linear calibration curve in ethylene

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371.1

7829.6

17006.6

32031.0

R² = 0.9929

0

5000

10000

15000

20000

25000

30000

35000

0 10 20 30 40 50

Are

a

Concentration (ppm)

CO2

170.8

1797.0

4335.6

8597.2

R² = 0.9875

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

0.0 10.0 20.0 30.0 40.0 50.0

Are

aConcentration (ppm)

Hydrogen

675.2

3934.8

10010.0

18670.9

R² = 0.9835

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

0.0 20.0 40.0 60.0

Are

a

Concentration (ppm)

Oxygen

1100.8

10347.3

23389.2

44190.2

R² = 0.9936

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

0.0 10.0 20.0 30.0 40.0 50.0

Are

a

Concentration (ppm)

Methane

504.4

4889.8

11204.0

21964.4

R² = 0.9899

0

5000

10000

15000

20000

25000

0.0 10.0 20.0 30.0 40.0 50.0

Are

a

Concentration (ppm)

CO

2792.0

4419.2

9705.8

15165.5

R² = 0.9981

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

0.0 20.0 40.0 60.0 80.0

Are

a

Concentration (ppm)

Nirtorgen

Summary

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Agilent Olefin Analyzer Suite provide a complete polymer grade ethylene and propylene contaminant testing capability.

Agilent’s GC-MS provides lowest detection for arsine and phosphine in the industry.

Description ASTM MethodAgilent Agilent

Instrument Capability Analyzer Product Number

Arsine / Phosphine ASTM Work Item #56896 GC-MS M7474AA / M7484AA

Ethylene monomer purity D6159 GC-FID 7890-0138 (D6159)

Propylene monomer purity D2712 GC-FID 7890-0138 (D2712)

Oxygenates D7423 GC-FID 7890-341

Non-condensable Gases ASTM Work Item #55121 GC-PDHID 7890-0237

Arsine Phosphine Appendix

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Linear working range calibration curve in ethylene - AsP

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R² = 0.9996

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

0 10 20 30 40 50 60 70

Are

a

Concentration (ppb)

PH3 Linearity

60.0

24.8

13.55.7

R² = 0.9997

0

5000

10000

15000

20000

25000

30000

0 10 20 30 40 50

Are

a

Concentration (ppb)

H2S Linearity

38.3

15.8

8.63.6

R² = 0.9999

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

0 5 10 15 20 25 30 35 40

Are

a

Concentration (ppb)

AsH3 Linearity

38.0

15.7

8.53.6

R² = 0.9999

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

100000

0 10 20 30 40 50 60

Are

a

Concentration (ppb)

COS Linearity

49.3

20.4

11.14.7

Deactivation is key: Testing untreated stainless steel with hydrogen sulfide

16.80 16.90 17.00 17.10 17.20 17.30 17.40 17.50 17.60

700

800

900

1000

1100

1200

1300

1400

1500

1600

1700

1800

1900

2000

2100

2200

2300

2400

2500

Time-->

AbundanceIon 34.00 (33.70 to 34.70): CP120_150uLH2_16mL_50ppb_block_1.D\data.msIon 34.00 (33.70 to 34.70): CP120_150uLH2_16mL_50ppb_block_10.D\data.ms (*)Ion 34.00 (33.70 to 34.70): CP120_150uLH2_16mL_50ppb_block_100.D\data.ms (*)Ion 34.00 (33.70 to 34.70): CP120_150uLH2_16mL_50ppb_block_120.D\data.ms (*)Ion 34.00 (33.70 to 34.70): CP120_150uLH2_16mL_50ppb_block_20.D\data.ms (*)Ion 34.00 (33.70 to 34.70): CP120_150uLH2_16mL_50ppb_block_40.D\data.ms (*)Ion 34.00 (33.70 to 34.70): CP120_150uLH2_16mL_50ppb_block_60.D\data.ms (*)Ion 34.00 (33.70 to 34.70): CP120_150uLH2_16mL_50ppb_block_80.D\data.ms (*)

H2S

Stainless steel permeation tube dilution block WITHOUT deactivation:

Takes ~1 day for “in situ” deactivation with hydrogen sulfide samples

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Deactivation is key: Testing deactivated stainless steel dilution block

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Stainless steel permeation tube dilution block WITH deactivation:

Takes ~3 runs to reach a stabilized response

15.00 15.50 16.00 16.50 17.00 17.50 18.00 18.50 19.00 19.50 20.00 20.50

20000

21000

22000

23000

24000

25000

26000

27000

Time-->

Abundance

TIC: 26April_2valves_150uLH2_50ppb_1.D\data.msTIC: 26April_2valves_150uLH2_50ppb_2.D\data.ms (*)TIC: 26April_2valves_150uLH2_50ppb_3.D\data.ms (*)TIC: 26April_2valves_150uLH2_50ppb_a1.D\data.ms (*)

PH3

H2S

AsH3 COS

Conditions

GC conditions

Column Select Olefins (CP8580)

Sample introduction 2 valve system

Carrier gas Helium, constant flow at 1.1 mL/min

Oven program 35 °C for 23 min

MS conditions

Transfer line temperature 60 °C

Source temperature 120 °C

Quadrupole temperatures 100 °C

Solvent delay 8.00 min

SIM ions 33, 34, 60, 75, 76

Tune HES_atune.u

EM gain 1

Hydrogen Cleaning

JetClean H2 0.20 mL/min

Data acquired on prototype equipped with fully automated calibration system


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Detection limits and S/N ratio (5ppb, 50 runs)

6/21/2017

Agilent Restricted

32

ASTM S/N ratio calculated in MassHunter Quantitative Analysis.

Analyte Concentration

(ppb)

ASTM S/N

(average)

S/N Detection

Limit (ppb)

% RSD IDL (ppb,

99% CI)

PH3 6.4 33.5 0.510 1.75 0.300

H2S 4.1 25.1 0.431 2.62 0.287

AsH3 4.1 120.9 0.089 1.07 0.118

COS 5.3 281.7 0.050 0.75 0.106

Overlays of 50 runs

olefin analyzer solutions for polymer grade …...olefin analyzer solutions for polymer grade...

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