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Page 1 C2, C3, C4 Monomer Analysis Malgorzata Sierocinska Agilent Technologies Waldbronn
Page 1
C2, C3, C4 Monomer Analysis
Malgorzata Sierocinska
Agilent Technologies Waldbronn
Page 2
Why Analyze Monomers ?
To Insure Consistent Production of High Quality Polymer
• Protect against food contamination in food packaging
Protect Catalysts from Irreversible Poisoning
Increase Time between Catalyst Changes
Better Market Position for Product Sales
• Higher product quality = higher price
Page 3
Compounds to be Analyzed in HP Olefin
Monomers
Oxygenates Sulfurs
Ammonia
Arsine
PhosphineChlorides
A Solution for Monomer Impurities
Page 4
Pressurized Liquids InjectorSimple, No transfer line, High pressure, Automatic operation and long service life
Syringe Body
replaced by Liquid Valve
Removable Needle
installed on one
Port of valve
4-Port LS Valve
Page 5
FLOW DIAGRAM Of The Injection Device
C
W
PS
FID
Sample In
Sample Out
(6) Restrictor
Column
Carrier GasSplit Vent
(3) EPC
(5) Fused silica
tubing
(2) Needle
Figure 1, Flow Diagram of HPID
(1) Valve
(4) Filter
Page 6
Hydrocarbon Impurities in Propylene by FID
0 2.5 5 7.5 10 12.5 15
1 2 3 4 5
6
7
8 9
10
1112
1314
15
1. methane
2. ethane
3. ethylene
4. propane
5. Propylene
6. Acetylene
7. i-butane
8. Propadiene
9. n-butane
10. t-2-butene
11. 1-butene
12. Isobutylene
13. c-2-butene
14. Methyl acetylene
15. 1,3-butadiene
Page 7
Hydrocarbon Impurities in of Ethylene
5 10 15 20 25
1
2 3
4
5
7 9
8 6
10 11 12 13 15
14
1 methane 6 acetylene 11 1-butene
2 ethane 7 isobutane 12 isobutylene
3 ethylene 8 propadiene 13 c-2-butene
4 propane 9 n-butane 14 methylacetylene
5 propylene 10 t-2-butene 15 1,3-butadiene
“M” Deactivated Alumina PLOT Column
50 m x 530 mm
Excess resolution will allow shorter
columns
Page 8
14X Faster Than Original Method
Faster analysis and shorter cycle time achieved by
Shorter column - 10 meter
Increasing the temperature programming rate
Higher starting temperature and lower end temperature
0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
2.5 5 7.5 10 12.5 15 17.5 20 22.5
Page 9
Impurities in Pressurized 1, 3-Butadiene 1, Methane; 2, Ethane; 3, Ethylene; 4, Propane; 5, Propylene; 6, i-Butane; 7, n-Butane; 8, t-2-Butene; 9, 1-Butene;
10, i-Butene; 11, c-2-Butene; 12, i-Pentane; 13, n-Pentane; 14, n-Hexane; 15 , 1,3-Butadiene; 16, 1-Pentene;
17, c-2-Pentene; 18, Hexane; 19, Toluene; 20, Dimer
5 10 15 20 25
1 2 3
4
5 20
19
6
7
9
10
8
11
12
1314
15
1617
18
Oven: 35 C, 2 min. 10C/min to 195 C, 16 min.
Column: PLOT AL2O3/ KCL (PN:3352), 30m,
0.53mm,15ul
Flow 10 ml/min, Split flow: 150
Sampling Valve:05W-0056V, 0.5ul (180 psi)
Page 10
Impurities in Liquified Propylene1, Methan; 2, Ethane; 3, Ethylene; 4, Propane; 5, Propylene; 6, i-Butane; 7, n-Butane
8, t-2-Butene; 9, 1-Butene; 10, i-Butene; 11,c-2-Butene; 12, i-Pentane; 13, n-Petane; 14, n-Hexane
1
2
4 5
6
7
8910
11
12 13 143
2 4 6 8 10 12 14 16 18
Oven: 35 C, 10 min. 10C/min 190 C 3 min.
Column: PLOT AL2O3/ KCL PN:3352,
30m, 0.53mm,15ul
Flow 10 ml/min , 11.782 psi
Split flow: 150.3; Total 163
Split ratio: 15:1
EPC: 50 psi (246 ml/min), Room Temp.
Valve:05W-0056V, 0.5ul, The biger size
Page 11
Impurities in Liquified Ethylene1, Methane; 2,Ethane; 3, Ethylene; 4, Propane; 5, i-Butane; 6, n-Butane; 7 n-Pentane; 8, n-Hexane
5 10 15 20 25 30
1
22 3
4
56 7
8
Oven: 35 C, 0 min. 4C/min 120 C 8.75 min.
Column: PLOT AL2O3+KCL + DB-1, 30m,
0.53mm,5ul
flow 1.399 ml/min, (7ml/min) , 12 psi
Split flow: 250.8(154ml/min)
Split ratio: 178:1
EPC: 50 psi (170 ml/min), Room Temp.
Valve:05W-0056V, 0.5ul The biger one
Page 12
Traces of Oxygenates in Gas and LPG Type
Matrices with Purged Tee Backflush
Page 13
2 ppm of Oxygenates Standard
Page 14
Enhanced ASTM D6584 with Traces of Oxygenates-
ASTM D6584 measures trace
hydrocarbons
• uses alumina PLOT column
Oxygenates best separated
on HP-Innowax column
Use Deans switch to combine
two methods into one
• primary column separates
oxygenates
• Deans switch selectively
transfers only the hydrocarbons
to alumina PLOT
• HP-Innowax column protects
alumina PLOT from damage…Capillary Flow Technology
Deans Switch
PCM
FID 1
Inlet
FID 2
Restrictor
Primary ColumnHP-Innowax
(30m x 0.32mm ID x 0.5 um)
Secondary ColumnHP-Alumina PLOT “M”
(30 m x 0.53mm ID x 15um)
Page 15
Complete Separation of Oxygenates and
Hydrocarbons
20
40
60
80
100
120
140pA
0 5 10 15 20 25 Min.
1
2
3
4
67 8
910
1112 13
1415
16
PLOT Alumina “M”
(19095P-M23)
20
25
30
35
pA
0 5 10 15 20 25 Min.
Cut time: 2.3 – 4.3 min.
5 (methanol)
HP-Innowax
(19091N-213)
C1 to C4 Hydrocarbons Separated
on Secondary Column
Heart-Cutting 100 ppmV Impurities in Ethylene
… Complete separation in one run
Page 16
Excellent Precision for Trace Compounds in
Ethylene
Peak # Name Avg. (ppmV)* % RSD*
1 methane 2.1 0.5%
2 ethane 21.5 0.2%
3 ethylene Balance Balance
4 propane 2.1 3.0%
5 methanol 2.1 3.8%
6 propylene 2.1 1.1%
7 isobutane 2.1 0.7%
8 n-butane 2.0 0.5%
9 propadiene 2.1 1.2%
10 acetylene 1.9 1.9%
11 tran-2-butene 2.1 0.5%
12 1-butene 2.0 0.7%
13 isobutylene 2.1 0.8%
14 cis-2-butene 2.1 0.8%
15 1,3-butadiene 2.1 0.9%
16 methylacetylene 2.0 0.7%
20 Runs of Ethylene Spiked with 2 ppmV
… Most RSD’s< 2%
Page 17
2-D GC Analysis of Olefin Feedstocks
0 5 10 15 20 25
0 5 10 15 20 25 5 10 15 20 25
5 10 15 20 25 30
2 ppm methanol in Ethylene 2 ppm methanol in PropyleneHP-Innowax
Alumina M PLOT
Page 18
Traces of Permanent Gases in Monomers
Uses the 10 port low leakage valve
The matrix is cut on the packed precolumn
Inerts including H2,O2,N2,CO,CH4 are separated on
packed column
Detection PHID in helium mode
Page 19
Trace of Permanent Gases in Monomers
Page 20
PDHID Description and Operating Principle
• Source for ionization:
Low power pulsed DC discharge in
helium which generates high energy
photons
• Non-destructive process
(0.01 – 0.1% ionization)
• Detector response is universal
except for Neon
• Linear Dynamic Range ~ 105
MDL in low picogram range
• The PDHID has numerous applications
across HPI and environmental industries
due to its universal and sensitive response
PDHID.02
INTERCONNECT
Analyzer for Traces of Permanent Gases
in CO2, Ethylene , Propylene
Page 21
Page 22
CO ,CO2 Traces in Monomers and Process Gases
Uses methanizer and FID detection for high sensitivity .
May include 4 port venting valve for venting high CH4
amounts.
C2+ fraction backflushed from the precolumn to vent
Page 23
CO ,CO2 Traces in Process Gases and Monomers
with Venting Valve
.
O/N :
DATE :
6890 Options REM :
FLOWSOURCE
INJECTIONPORT
VALVE COMPARTMENTBLOCK 2 BLOCK 1
DETECTOR
7890 valve system
Valve 1
A
210
Valve 2
File
ITEM
Valve 4
Valve 3
= #87X
301
301
301
Aux 3
Aux 4
Aux 5
12
3
4
567
8
9
10Sample
In
Out
Loop
Vent
1
2
3
4
vent
H2
7890-0282
Page 24
.
O/N :
DATE :
7890 Options REM :
FLOWSOURCE
INJECTIONPORT
VALVE COMPARTMENTBLOCK 2 BLOCK 1
DETECTOR
7890 valve system
Valve 1
A
210
Valve 2
File
ITEM
Valve 4
Valve 3
= #87X
301
301
301
Aux 3
Aux 4
Aux 5
12
3
4
567
8
9
10Sample
In
Out
Loop
Vent
H2
7890-0304
Traces of CO, CO2 ,CH4 in Monomers
Page 25
CO,CO2 at 4.5 ppm and CH4 at 10x higher
Concentration
Page 26
CO,CO2 at 0.45 ppm and CH4 at 10x higher
Concentration
Page 27
CO,CO2,CH4 Determinations Repeatibility
MSD in High Purity Monomer Analysis
Page 28
10000
1.3 ppm per component in helium
Scan 33 – 100 amu
4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00
COS
CS2
H2S
THT
CS2
CH3SH
tBSH
DMS
EtSH
Full Scan!
Improved Response for Sulfur Compounds
Page 29
10000
1.3 ppm per component in helium
Scan 33 – 100 amu
4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00
COS
CS2
H2S
THT
CS2
CH3SH
tBSH
DMS
EtSH
Full Scan!
Improved Response for Sulfur Compounds
Page 30
4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00
Time-->
COS
Sim Mode: 46 ppb per Component In Helium
5ppb level of sulfur possible in SIM
MeSH
THT
CS2
H2S
tBSH
DMS
EtSH
Excellent peak
shape/response
Improved Response for Sulfur Compounds
Page 31
Sulfur in bulk Propylene (COS fully
coeluting with propylene
3.60 3.80 4.00 4.20 4.40 4.60 4.80 5.00 5.20 5.40
100
150
200
250
300
350
400
450
500
550
600
650
700
750
800
850
Abundance
Sim mode: 50 to 1 split
180 ppb each component
H2S COS
Improved Response for Sulfur compounds
Page 32
Sulfur Impurities by GCMS in SIM
Hydrogen Sulfide
Carbonyl Sulfide
Methyl Mercaptan
Ethyl Mercaptan
Conc. (ppb) 101.7 42.0 79.3 60.1
Std. Dev. 7.4 3.9 1.6 2.1
% RSD 7.3% 9.3% 2.0% 3.5%
Component LQL
Hydrogen Sulfide 10 ppb
Carbonyl Sulfide 10 ppb
Methyl Mercaptan 50 ppb
Ethyl Mercaptan 50 ppb
Hydrogen
Sulfide
Carbonyl
Sulfide
Methyl
Mercaptan
Ethyl
Mercaptan
Conc.
Range
25 – 575
ppb
15 – 310
ppb
25 – 410
ppb
15 – 315
ppb
# of Points 4 5 5 5
Corr. Coeff. 0.992 1.000 0.999 1.000
Page 33
Trace Ethanol in Propylene by GC-MS
3 ppm EtOH
Component LQL
Methanol 50 ppb
Ethanol 50 ppb
Isopropanol 50 ppb
t-Butanol 50 ppb
1-Propanol 50 ppb
1-Butanol 50 ppb
MTBE 50 ppb
Page 34
Other Impurities by GC-MS
Component LQL
Arsine 50 ppb
Phosphine 50 ppb
Ammonia 2 ppm
Organic Chlorides ~ 20 ppb each
Page 35
Trace Phosphine in Propylene
3.3 ppm PH3
Page 36
Trace Phosphine in Propylene
3.3 ppm PH3
Page 37
Trace Arsine in Propylene
3.2 ppm AsH3
Page 38
Trace Methylchloride in Propylene
9 ppm MeCl
Page 39
Summary
-GCMSD is a very sensitive and potentially selective GC
detector
- May be used both in process control and quality control of raw
materials and products
- Allows positive identification of unknown compounds and
confirmation of targets
Page 40
