Reformulyzer Operating and Application Manual V 2016 2.5.0 20160511 PDF

AC
REFORMULYZER M4
Operating and Application

Manual
Version 2016 2.5.0
OPERATING AND APPLICATION MANUAL
Copyright
Copyright © 2016 by Petroleum Analyzer Company, L.P.
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Table of Contents
1. Introduction ....................................................................................... 11
1.1. Who should read this manual............................................................. 11
1.2. Manual setup ............................................................................... 11
1.3. Technical information ..................................................................... 12
1.3.1. System pressure test .................................................................. 12
2. Terminology ....................................................................................... 13
2.1. General terms .............................................................................. 13
2.2. ASTM definitions ........................................................................... 13
2.3. EN-ISO definitions .......................................................................... 13
2.4. EN definitions............................................................................... 14
3. Software ........................................................................................... 15
3.1. Software startup ........................................................................... 15
3.1.1. Startup of OpenLAB ................................................................... 15
3.1.2. Startup of Workbench ................................................................. 16
3.2. Reformulyzer Help ......................................................................... 16
3.3. Reformulyzer Main Screen ................................................................ 17
3.3.1. Run Control ............................................................................. 17
3.3.2. Results tab .............................................................................. 19
3.3.3. Diagnostics menu ...................................................................... 22
3.3.4. QC History tab ......................................................................... 25
3.3.5. Online Manager tab ................................................................... 25
4. Running samples and tuning analysis parameters ........................................... 26
4.1. Running sample analysis .................................................................. 26
4.1.1. Step 2A: Select the analysis mode for samples with known composition ..... 27
4.1.2. Step 2B: Select the analysis mode for samples with unknown composition .. 28
4.1.3. Step 3: Set specific parameters ..................................................... 28
4.1.4. Step 4: Add samples to the queue .................................................. 30
4.1.5. Step 6: Viewing Results ............................................................... 30
4.1.6. Step 7: Put GC into standby.......................................................... 30
4.1.7. Approving results ...................................................................... 30
4.2. Tuning analysis parameters............................................................... 31
4.2.1. Tuning the A-time ..................................................................... 31

4.2.2. Tuning the B-time ..................................................................... 32

4.2.3. Tuning the D-time or flow B ......................................................... 32
4.2.4. Tuning the Eth-Alc Trap separation temperature (EthAlcSep) .................. 33
4.2.5. Tuning the Olefin-Trap separation temperature .................................. 33
4.3. Set points standard samples .............................................................. 34
4.3.1. Gasoline ................................................................................. 34
4.3.2. High RVP gasoline...................................................................... 34
4.3.3. Straight naphtha ....................................................................... 34
4.3.4. Reformer feed ......................................................................... 35
4.3.5. Light FCC................................................................................ 35
4.3.6. Heavy FCC .............................................................................. 35
4.3.7. Other samples .......................................................................... 35
5. Theory, background, and historical development ........................................... 36
5.1. Component structure ...................................................................... 36
5.1.1. Paraffins ................................................................................ 36
5.1.2. Naphthenes ............................................................................. 37
5.1.3. Aromatics ............................................................................... 37
5.1.4. Olefins................................................................................... 37
5.1.5. Poly-Naphthene ........................................................................ 38
5.1.6. Ethers ................................................................................... 38
5.1.7. Alcohols ................................................................................. 39
5.2. Response factors ........................................................................... 40
5.3. Calculations ................................................................................. 41
5.3.1. Concentration (mass or volume %) .................................................. 41
5.3.2. RON/MON ............................................................................... 41
5.3.3. Calorific value.......................................................................... 41
5.3.4. C:H:O Ratio ............................................................................. 41
5.3.5. Average Molecular Weight............................................................ 41
5.3.6. Density .................................................................................. 41
5.4. Historical development ................................................................... 42
5.4.1. Evolution of the PNA Method ........................................................ 42
5.4.2. nPiPNA .................................................................................. 42
5.4.3. PIONA.................................................................................... 42
5.4.4. PIONA plus: the AC Reformulyzer™ ................................................. 42

5.4.5. The Reformulyzer® M3 ................................................................ 42

5.4.6. The Reformulyzer® M4 ................................................................ 42
6. Standardization and Specifications ............................................................ 43
6.1. Introduction................................................................................. 43
6.2. EN 228 ....................................................................................... 43
6.3. Obsolete and redrawn methods .......................................................... 44
6.4. EN ISO 22854 ................................................................................ 44
6.4.1. Scope .................................................................................... 45
6.4.2. Precision and bias ..................................................................... 45
6.5. Specifications according to ASTM D6839 (under revision in 2013) .................. 45
6.5.1. Scope .................................................................................... 45
6.5.2. Precision of the method .............................................................. 46
6.6. System performance specifications ..................................................... 46
7. Application range and analysis modes ......................................................... 47
7.1. Application range .......................................................................... 47
7.1.1. Introduction ............................................................................ 47
7.1.2. Separating hydrocarbon classes ..................................................... 47
7.1.3. Dedicated Analysis Modes ............................................................ 47
7.2. Reformulyzer® M4 analysis modes ....................................................... 48
7.3. PNA........................................................................................... 49
7.3.1. PNA: order of elution and typical sample analysis results ....................... 49
7.4. nPIPNA ....................................................................................... 50
7.4.1. nPiPNA: order of elution and typical analysis results ............................ 50
7.5. PONA ......................................................................................... 53
7.5.1. PONA: order of elution ............................................................... 53
7.6. PIONA ........................................................................................ 55
7.6.1. PIONA: Order of elution .............................................................. 55
7.7. PIANO ........................................................................................ 58
7.7.1. PIANO: order of elution ............................................................... 58
7.8. OPNA ......................................................................................... 61
7.8.1. OPNA: order of elution ............................................................... 61
7.9. Gasoline ..................................................................................... 65
7.9.1. Gasoline: order of elution ............................................................ 65
7.10. OPIONA ...................................................................................... 70

7.10.1. OPIONA: order of elution .......................................................... 70

7.11. Gasoline E85 ................................................................................ 74
7.11.1. Gasoline E85: order of elution .................................................... 74
7.12. Fast Group Type (FGT) .................................................................... 75
7.12.1. Fast Group Type (FGT): order of elution ........................................ 75
8. Troubleshooting .................................................................................. 76
8.1. General troubleshooting list .............................................................. 76
8.1.1. Problem indication .................................................................... 76
8.1.2. Low recovery for Benzene and/or poly-naphthene ............................... 76
8.1.3. Sharp C9 Paraffin, bad peak shape 13X Column fraction ........................ 77
8.1.4. Baseline increase on 13X Column fraction, Olefin result too low .............. 78
8.1.5. Extra (small) peaks in Olefin section (for samples that contain Olefins) ...... 78
8.1.6. No Aromatics elution .................................................................. 79
8.1.7. Empty cells in report, misidentification ........................................... 80
8.1.8. General trouble-shooting list ........................................................ 81
8.2. Performance check ........................................................................ 82
8.3. Ghost peaks ................................................................................. 83
8.3.1. Introduction ............................................................................ 83
8.3.2. Eliminating ghost peaks............................................................... 83
8.4. Leak checking .............................................................................. 84
8.4.1. Introduction ............................................................................ 84
8.4.2. Check for leaks using a soap solution ............................................... 84
8.4.3. Flow measurement .................................................................... 85
8.4.4. Check for leaks by pressurizing the system ........................................ 85
8.5. System deviations .......................................................................... 86
8.5.1. Introduction ............................................................................ 86
8.5.2. Checking the system .................................................................. 86
8.5.3. Injection port liner .................................................................... 86
8.6. Column deviations ......................................................................... 87
8.6.1. Introduction ............................................................................ 87
8.6.2. The Polar-Column (OV275) ........................................................... 87
8.6.3. The Boiling Point Column set ........................................................ 87
8.6.4. The Eth-Alc Trap ....................................................................... 87
8.6.5. The Olefin-Trap ........................................................................ 87

8.6.6. The Pt-Catalyst ........................................................................ 88

8.6.7. The 5A-Trap ............................................................................ 88
8.6.8. The 13X Column ....................................................................... 88
8.7. Hardware deviations ....................................................................... 89
8.7.1. Introduction ............................................................................ 89
8.7.2. Check Six-port rotary valves (Valve 1 to 7) ........................................ 89
8.7.3. Check the Reformulyzer® M4 Electronic Control Unit ............................ 89
8.7.4. Log files ................................................................................. 89
8.8. Software deviations........................................................................ 91
9. Index ............................................................................................... 95
10. Contact ......................................................................................... 99

1. Introduction
1.1. Who should read this manual
This manual is intended for people operating the Reformulyzer® M4 and accompanying
software, or any part of it.
1.2. Manual setup

This manual describes the software (overview, structure and administrative actions),
theory, tuning, background and troubleshooting of the Reformulyzer® M4.
Chapter 2: Terminology, describes specific words and terms used in the Reformulyzer®
M4 and in its field of operation.
Chapter 3: Software, explains starting the software and the basic dialogs.
Chapter 4: Running samples and tuning analysis parameters, describes the ‘daily’
Reformulyzer® M4 operations, like running analyses and viewing and
reporting results.
Chapter 5: Theory, background, and historical development, contains detailed

background information regarding component structure and historical
development of the Reformulyzer® M4.
Chapter 6: Standardization and Specifications, describes the specific standardization

methods in terms of gasoline specs and the analysis of these streams.
Chapter 7: Application range and analysis modes, describes the analysis matrix of the
Reformulyzer® M4 and the detailed analysis structure of the Reformulyzer®
M4 analysis modes.
Chapter 8: Troubleshooting, describes various symptoms that can be noticed in the

Reformulyzer® M4, their possible causes, and possible solutions.
Chapter 10: Contact

1.3. Technical information

The Reformulyzer® M4 Application Unit has been designed and tested in accordance with
recognized safety standards and is designed for use indoors. If the instrument is used in a
manner not specified by the manufacturer, the protection provided by the instrument may
be impaired.
Voltage range 120 VAC, 60 Hz, 750 VA

240 VAC, 50 Hz, 750 VA
Fuse ratings 10A T 120 V
6.3A T 240 V
Altitude Up to 2000 m
Operating temperatures 15 to 35 °C
Maximum relative 80 % for temperatures up to 31 degrees centigrade
humidity decreasing linearly to 50 % relative humidity at 40 degrees
centigrade, recommended 50 to 60%, non-condensing
Power connection Grounded outlet within 1.5 meter of the instrument with a
grounded power cable
Ventilation requirements The Reformulyzer M4 is cooled by air flow which enters the
Application Unit at the back side of the right hand side and
exits through left hand side. Do not obstruct the air flow at
the inlet and outlet.
Main switch location
At the back side of the Application Unit

Cleaning To clean the unit, disconnect the power and wipe down
with a damp, lint-free cloth.
1.3.1. System pressure test

A pressure test is performed at a maximum pressure of 500 kPa. The maximum pressure
drop is 10 kPa in 10 minutes @ 500 kPa.
Pressures and flows are regulated by the Agilent GC. Flows going from the Agilent GC into
the Reformulyzer M4 application unit are 2 x 5.0 ml/min Nitrogen and 1 x 4.0 ml/min
Hydrogen. These flows are flow-regulated by the Agilent EPC’s.

2. Terminology
2.1. General terms
 Olefin = any unsaturated hydrocarbon containing one or more pairs of carbon atoms
linked by a double bond., having the general formula CnH2n, also known as alkene.
Please refer to chapter 5.1 for a more detailed description.
 Paraffin = any saturated hydrocarbon having the general formula CnH2n+2, also
known as alkane. Please refer to chapter 5.1 for a more detailed description.
 Oxygenate = chemical compounds containing oxygen as a part of their chemical
structure. Please refer to chapter 5.1 for a more detailed description.
 Ether = a class of organic compounds that contain an ether group — an oxygen atom
connected to two alkyl or aryl groups — of general formula R–O–R’. Please refer to
chapter 5.1.6 for a more detailed description.
 Alcohol = an organic compound in which the hydroxyl functional group (-OH) is
bound to a carbon atom. Please refer to chapter 5.1.7 for a more detailed
description.
 Fore flush = position of column of trap in which the flow is directed from the
beginning to the end of the column of trap
 Back flush = position of column of trap in which the flow is reversed from the end
to the beginning. This technique is mainly used to elute higher retained
components faster, mostly in combination with higher temperatures
2.2. ASTM definitions

According to ASTM D6839
Repeatability The difference between successive test results obtained by the same
operator and same apparatus under constant operating conditions on identical test
materials would, in the long run, in the normal and correct operation of the test method,
exceed the repeatability values only in one case in twenty. Repeatability values can be
found in Table 6.
Reproducibility The difference between two single and independent test results obtained
different operators working in different laboratories on identical test materials would, in
the long run, in the correct operation of the test method, exceed the reproducibility
values only in one case in twenty. Reproducibility values can be found in Table 6.
2.3. EN-ISO definitions

According to EN ISO 22854
Repeatability (one operator, one instrument): If two results from one operator are
determined as volume % or mass % under repeatability conditions, then both results are
considered acceptable or authorized for standardization when they do not differ more than
the values given in Table 5.
Reproducibility (more operators, more instruments): If results in two different

laboratories are determined as volume % or mass % under reproducibility conditions, both

results are considered acceptable and authorized for standardization when they do not
differ more than the values given in Table 5.
2.4. EN definitions
EN standards are European standards.
The EN 228 method describes the requirements and test methods for unleaded petrol used
in petrol engine vehicles. Please refer to chapter 6.2 for a detailed overview of this
method.

3. Software
This chapter describes some basic operations of the software. More details can be found in
Reformulyzer help. Accessing Reformulyzer help is also described in this chapter.
3.1. Software startup
3.1.1. Startup of OpenLAB

The software can be started by selecting the ‘OpenLAB icon’ on your desktop (or in the
Windows Start menu). Depending on the configuration, it might be necessary to logon.
Select the Reformulyzer instrument from the list and press the ‘Launch’ button.
Figure 1 - Agilent OpenLAB Control Panel
Agilent OpenLAB Control Panel has the option to create shortcuts for an
instrument on the desktop. This allows starting up an instrument, without
using Agilent OpenLAB Control Panel.
When using Agilent OpenLAB ChemStation edition, the online instrument

must be started before starting IRIS (online).
Please refer to the Agilent OpenLAB manual for more information about this
product.

3.1.2. Startup of Workbench

The software can be started by selecting the ‘Reformulyzer Workbench icon’ on your
desktop. When the software is started the logon screen is shown. Provide your user name
and password. Check the ‘Work offline’ option when you are not planning to do analysis
and press OK.
Figure 2 - IRIS Workbench startup screens
Select the instrument and press the connect (plug) button. When the instruments tab is not
visible, make sure ‘Instruments’ is checked in the ‘View’ menu.
IRIS Enterprise Workbench has the option to create shortcuts for an

instrument on the desktop. This allows starting up an instrument faster.
If you don’t have an account, contact your site administrator.
Passwords are case sensitive.
3.2. Reformulyzer Help

Help about Workbench can be found in the Help menu. Help about Reformulyzer can be
found in the Reformulyzer – Help menu. Pressing ‘F1’ will show help about the part of the
screen having the focus.

3.3. Reformulyzer Main Screen

Reformulyzer software is part of IRIS Enterprise. When opened, it adds the instrument
screen and the Reformulyzer menu to Workbench.
3.3.1. Run Control

The Run Control tab shows information about the current state of the instrument,
including scheduled analysis and recently completed analysis. The user can schedule new
analysis by adding single runs or sequences to the queue.
Figure 3 - Workbench Run Control

Schedule a single run

Add single runs by clicking the button in the Run Control menu. Sample name,
vial, sample type, test and specification (QC reference) have to be filled in. The sample is
added to the queue by pressing the save button. More single runs can be added. Pressing
the ‘Exit’ button will close the dialog.
Figure 4 - Workbench Run Control add single run

Please note that this screen has optional parts, which can be switched on or off
using the Options menu.
Schedule a sequence
Sequences can be managed by the sequence editor by clicking the button. The
sample name, vial, sample type, test and specification have to be entered. New sequences
can be processed and saved with a new (unique) name. By selecting the
button, all sequence lines will be added to the queue.
Figure 5 - Workbench Sequence Editor

3.3.2. Results tab

The results tab is used to view results. When the checkbox is not selected, all
tests will be shown in the table on the left hand side. Selecting one of these tests, results
in a preview in the right window with a preview of the chromatogram and a summary of
the numbers.
A Analyses section
B Analysis results section
Find an analysis
All analyses that are done on the Reformulyzer® M4 are listed in the Analyses section and
sorted on date (newest on top).
 Select an analysis in the list to display basic information about the analysis in the
Analysis Information part of the Analyses section.
 Double-click an analysis (or click the Open chromatogram button) to open the
chromatogram of the selected analysis in the Analysis results section.
Search window - filter the results

The use of filters can shorten the list of analyses and help finding analyses. You can show
for example only the analyses that were analyzed with a certain sample type. Click the set
filter button to set the filter.
Selecting the button opens a window with filter options to narrow your
search.
Figure 6 - Workbench Search filter
Notes about the search window:
 Several filter options can be combined.

 When you enter a phrase in the Name field, all samples that contain the phrase
somewhere in the sample name are included.
 Do not forget to set the appropriate date range in the fields From date and Till
date.

The test will open in the right window by double click on the test name.
Figure 7 - Workbench Result Tab
Figure 8 - Workbench Analysis Results
The Task button can be used for the following actions:

- Restore Identification From Method: grouping times will be copied from the method
- Save Identification To Method: grouping times will be copied to the method
- Sample Type: sample Type can be changed (Sample or QC)

- Sample Information: sample information can be added

- Reintegration: after reintegration, the new integration results can be imported
Comparing chromatograms (overlay)

The chromatograms can be viewed separated or overlaid. For easy comparison, the same
time and response scales are used for both chromatograms.
1 Right-click on an analysis in the Analyses window:

A pop-up menu appears.
2 In the pop-up menu, select Open chromatogram:
The first chromatogram is shown.
3 Right-click on another analysis in the Analyses window:
The pop-up menu re-appears.
4 In the pop-up menu, select Open in the current window:
The first and second chromatograms are shown.
5 Optionally, in the View menu, select References to show or hide the References
window (containing the legend of the opened results).
6 Optionally, in the View menu, select Overlaid to see the chromatograms overlaid
over each other. This is done by default if an overlay is made.
7 Optionally, in the View menu, select Separated to see the chromatograms below
each other.
Figure 9 - Workbench Result overlay in separate windows

You can close each individual analysis included in the overlay separately.
This means that, if you accidentally opened an incorrect analysis, you can
remove that specific result.
When two or more chromatograms are displayed separately, they will retain
their own grouping times. This is useful when comparing against a reference
chromatogram and displaying in separate mode. Small shifts in grouping
times can be corrected while the general picture remains visible.
3.3.3. Diagnostics menu

The diagnostics menu contains five pull down menus:
Hardware state:
Actual temperatures and valve positions are displayed. New settings can be entered by
selecting a heater or valve using the right mouse button.
Figure 10 - Workbench Diagnostic tab, Heater / Valve state

Heater Chart:
Displays the actual temperatures in time.
Figure 11 - Workbench Diagnostic tab, Heater Chart
Valve chart:
Displays the actual valve position in time.
Figure 12 - Workbench Diagnostic tab, Valve Chart

Manual Control:
The most important buttons in this menu are:
 Clear ECU Errors
This option is used when the ECU is in shutdown mode. It will clear all errors of the
ECU.
 PID settings
This option is used when it is needed to set or adjust the PID settings. The PID
settings are stored as in a file on the PC and in the ECU on the internal SD card.
 Tune valve
This option is currently not active.
Figure 13 - Workbench Diagnostic tab, Manual Control
Browser:
This manual interface program communicates directly to the ECU and can be used for
advanced troubleshooting. This is not required for day-to-day operation.
Figure 14 - Workbench Diagnostic tab, Browser for actual settings ECU

3.3.4. QC History tab

This menu is used to view the diagnostic trends of standard QC samples. Again a filter is
used to select specific methods, QC samples or dates. The list can be refreshed by using
the button. To see the history trend, select the button.
Figure 15 - Workbench QC History
Trend lines for different components can be viewed by selecting the desired component in
the right lower table.
3.3.5. Online Manager tab

This menu gives access to the database.
Figure 16 - Workbench Online manager

4. Running samples and tuning analysis parameters

4.1. Running sample analysis
This chapter describes the procedure to analyze samples. It is assumed that the system is
started up, configured and the Reformulyzer® M4 software is started with a user is logged
on.
To start and perform an analysis, a number of actions should be carried out.
Table 1 Stepwise analysis planner

Step Action
1 Select the type of the sample. Sample = unknown composition. QC =
reference with known composition. Execute step 2A or step 2B respectively.
2A Select analysis modes for samples with known composition.
Use Quality Control samples as reference to verify system performance.
2B Configure analysis modes for samples with unknown composition.
3 Set parameters
4 Fill the queue
5 Start the analyses
6 When an analysis is completed, the results can be viewed, reprocessed

and/or reported.
7 When all analyses are done, the GC and ECU will stay in their last loaded
temperature settings. The GC can be put into standby by loading the
standby GC method.

4.1.1. Step 2A: Select the analysis mode for samples with known composition
Default analysis modes

The Reformulyzer® M4 system has a set of pre-defined analysis modes or streams. The next
table gives an overview of refinery streams plus blends and the analysis mode to use for
optimum analysis.
Table 2 Product analysis modes of the Reformulyzer® M4 PNA
(n)PiPNA
Gasoline
Gasoline
OPIONA
PIONA
PIANO
OPNA
PONA
PNA
E85
Light straight run ● ● ●
Heavy straight run ● ● ●
Depentanized bottom ● ● ●
Reformate ● ● ●
FCC-light ● ●
FCC-medium ● ●
FCC-heavy ● ●
Visbreaker ● ●
Alkylate ●
Isomerate ●
Gasoline blend ● ● ●
E85 Gasoline ●
Analysis time (min) 26 32 34 35 59 44 42 61 42
Quality Control sample analysis modes

Besides the default analysis modes, the operator can check whether the sample is
comparable to one of the QC samples listed in the next table. If so, the set conditions and
parameters of the analysis mode for the QC sample can be used for this sample.
After the first analysis, check if the used analysis mode gives proper results.
Table 3 Quality Control sample description

No. Name Composition
1 Reformer Feed paraffins, naphthenes, aromatics, benzene
2 Reformate paraffins, naphthenes, aromatics, benzene, olefins
3 FCC-Naphtha paraffins, naphthenes, aromatics, benzene, olefins
4 Gasoline K reformate, FCC, naphtha, MTBE
5 Gasoline L reformate, isomerate, alkylate, FCC, naphtha,
6 Gasoline M reformate, isomerate, alkylate, FCC, naphtha, ethanol
7 Gasoline N reformate, FCC, naphtha, ETBE, ethanol

4.1.2. Step 2B: Select the analysis mode for samples with unknown composition
Default analysis modes

Samples with an unknown composition and distribution can best be run first in the PNA
mode (or OPNA if oxygenates are to be expected). This will give information about the
distribution and can serve as a reference when you run modes with a higher degree of
group type breakdown.
When you compare analytical modes, the sum of the non-aromatics with the same carbon
number must be equal.
Sample-specific non-oxygenates modes

When you have a number of samples that need to be analyzed regularly and do not differ
much in distribution and concentration levels, a derived method can be created. The
software can derive analytical modes from a main mode.
For the new mode, different cutting times and separation temperatures can be used.
Configuring new modes can best be set up in the simplest mode, which is mostly PNA.
Sample-specific oxygenates modes

As for non-oxygenates modes (see above), also new oxygenates modes with specific cutting
times and separation temperatures can be derived from a main mode.
Configuring new Reformulyzer® M4 modes can best be set up in the simplest mode, which is
OPNA.
4.1.3. Step 3: Set specific parameters
Sample injection volume

A 0.10 µl injection volume is the standard injection volume for most samples. Due to gas-
solid interactions the distribution of the components may change if you use a different
injection volume, which is confusing.
One of the characteristics of gas-solid chromatography is that the front of the peak moves
to an earlier retention time with increasing concentrations.
Another effect is that the peaks are interdependent because the total capacity of the
columns is limited: peaks may push aside other peaks. A low injection volume minimizes
these effects.
If you are looking for low levels of certain components or groups, you may want to use
injection volume of 0.2 µl or 0.3 µl.

Set separation temperatures

In the various modes several separation temperatures need to be optimized. These
separation temperatures are used for columns with gas-solid interaction chromatography.
Table 4 Overview Reformulyzer® M4 Electronic Control Unit

Backplane Board type Heater connection Valve Fan
position connection connection
Position 10 Safety board n.a. n.a. n.a.

Position 9 Not connected
Position 8 Not connected
Position 7 Heater/Valve 13X Column Valve 5 13X Column
Position 6 Heater/Valve EA trap Valve 2 EA trap
Position 5 Heater/Valve Olefin-Trap heater Valve 1 Olefin-Trap
Position 4 Heater/Valve 5A-Trap heater Valve 3A 5A-Trap
Position 3 Heater/Valve Pre-Column Valve 1A Pre column
Position 2 Heater/Valve Pt-Catalyst Valve 3
Position 1 Heater/Valve Valve Box heater Valve 4
Main Main CPU Controls all
Heater/Valve boards
General guidelines to optimize separation temperatures are given below.
Guidelines to set separation temperatures

1. Determine the component (group) that needs to elute completely from the trap and
check this component in your results.
2. Determine the component that will break through first and check this component in
your results.
Check how break through will be visible in your system.
3. If possible, find a secondary reference with similar distribution as your sample has and
analyze and check the results.
4. Lower the separation temperature of that trap if breakthrough is seen and analyze
again.
5. Increase the separation temperature if you see that heavier components that should
not be retained do not elute correctly.
6. Use the specific tuning instructions per separation temperature.

4.1.4. Step 4: Add samples to the queue

Please refer to chapter 3.3.1. Samples added to the queue are automatically started. The
queue can be paused by selecting the run / pause button in the RunControl
menu.
4.1.5. Step 6: Viewing Results

When an analysis is completed, the results can be viewed in the results menu.
4.1.6. Step 7: Put GC into standby

It is not recommended to turn off the GC and/or ECU. Standby settings for all heaters and
valves prevent the system to collect impurities. These settings will be loaded
automatically when the system is not used for more than 10 minutes.
4.1.7. Approving results

Select Tasks - Approve Analyses to lock an analysis.
When an analysis is approved, the grouping time cannot be changed any more, unless it is
made editable again by a user with sufficient rights.
An approved analysis can be made editable again by a user with appropriate user rights.

4.2. Tuning analysis parameters
4.2.1. Tuning the A-time
Once determined, the A-time generally does not need modification.
When problems are suspected this is often due to:
 a first injection where moisture is collected, or

 a leaking septum
The A-time can best be determined in a simple mode like PNA with a well-known sample
like the AC Quantitative Reference sample 50.16.512 (box 20001.157).
Benzene and Poly-Naphthene must elute completely in the first aromatic fraction, best
verified with the weight percent results. Most of the Dodecane must elute in the 13X
Column fraction (verify visually or through Agilent integration report).
Checks
Benzene sample target  0.1 weight %
Poly Naphthene sample target  0.1 weight %
Dodecane peak in 13X Column fraction more than half the height of Undecane
when using 20001.157
Operating range
Generally the A-time is found between 1.5 and 2.0 minute
The lower limit for the A-time is 1.1 minute.
The upper limit for the A-time is 2.2 minute
Adjusting
Make small adjustments of 0.01 to 0.05 minutes and reanalyze.
When reaching one of the operating limits, there is the possibility to change
the flow A.
A-time tuning check parameters are also influenced by pre-column

temperature settings and pre-column condition.

4.2.2. Tuning the B-time

Once determined, the B-time generally does not need modification. When
problems are suspected this is often due to a first injection where moisture is
collected, a leaking septum or incorrect pressure applied to the valves
The B-time can best be determined in a simple mode like PNA with a well-known sample
like the AC Quantitative Reference sample 50.16.512 (box 20001.157).
Checks
Toluene second aromatic fraction less than 0.2%
Poly Naphthene second aromatic fraction less than 0.1%
C8 aromatic the second C8 aromatic is not allowed in the first aromatic fraction
Operating range
Generally the B-time is found between 1.6 and 2.1 minute
The lower limit for the B-time is 1.2 minute.
The upper limit for the B-time is 2.3 minute
Adjusting
Make small adjustments of 0.01 to 0.05 minutes and reanalyze.
The OPNA mode requires a longer B-time than other modes to be sure to elute all
oxygenates in the first aromatic fraction. Tune this mode separately.
4.2.3. Tuning the D-time or flow B

Due to resolution and time limitations, not the D-time is changed but the B-flow.
Flow B is set by the column flow of the Boiling Point Column set (column 2). This
parameter must be changed in the GC method. The flow must be optimized in different
modes with a well-known sample like the AC Quantitative Reference sample 50.16.512
(box 20001.157).
Checks
1. PNA mode
Poly Napthene retention time of 16.0 ± 0.1 min
Use this flow for all modes.
2. OPNA mode
Poly Napthene retention time of 19.6 ± 0.1 min
Use the found flow for OPNA and Gasoline mode.
Operating range
B-flow is set to 5  1.0 ml/min
D-time is set to 3.15 min

Adjusting
Make adjustments to column 2 flow of 0.1 mL/min and reanalyze.
4.2.4. Tuning the Eth-Alc Trap separation temperature (EthAlcSep)

The Eth-Alc Trap separation temperature can best be set in OPNA mode with a well-known
sample like the AC Quantitative Reference sample 50.16.512 (box 20001.157) and a well-
known sample containing the oxygenate you need to analyze.
Most commercial gasolines (over 80%) contain MTBE or ETBE as the oxygenated component.
Concentrations are generally 11 weight percent or lower. Sample 00.02.045 (box
20001.542) Gasoline K with MTBE can be used for fine tuning of the Eth-Alc Trap separation
temperature in the Gasoline mode.
Checks
MTBE target value  0.5%
Decane target value  0.2% (when running 50.16.512 sample)
Operating range
EthAlcSep 95 - 130°C
Adjusting
Make adjustments of 5°C min and reanalyze. If MTBE is low, decrease the temperature. If
decane is low, increase the temperature.
When MTBE breaks through the trap to the 13X Column it will most likely elute at the
position of the C4 hydrocarbons. When running the Gasoline mode, it will elute at the C4
olefin location resulting in a higher olefin concentration.
MTBE and other ethers may partly be catalytically converted into methanol
and a C4 olefin on the trap. It will then show up as a peak at around 20
minute (OPNA mode) or just before 14 minute (Gasoline mode). These
peaks can be calculated as MTBE (or the ether present in your sample) since
they actually represent material. This catalytic activity decreases over time
but may increase when moisture is introduced in the carrier gas.
4.2.5. Tuning the Olefin-Trap separation temperature

Since this temperature depends on the sample, target values based on compositions as
routinely found in practice are given.

4.3. Set points standard samples
4.3.1. Gasoline
Analysis mode: PONA, Gasoline
OlefinSep 130 - 150°C
Generally an olefin separation temperature of 150°C can be used initially for gasoline
analysis on a new Olefin-Trap. During the life time of the trap the temperature can be
decreased in order to retain all of the olefins.
Concentrations are generally 11 weight percent or lower. Sample 00.02.045 (box
20001.542) Gasoline K with MTBE can be used for fine tuning of the Eth-Alc and Olefin trap
separation temperatures and as a check for the analysis mode.
4.3.2. High RVP gasoline

Analysis mode: Gasoline
Concentrations are generally 11 weight percent or lower. The 26516.510 sample or another
reference with a known value can be used to check the correct analysis and the Eth-Alc
Trap separation temperature.
Start with an OlefinSep temperature of 150°C. Use a reference gasoline to check if the
settings are correct. When C4 olefins are lost, reduce the temperature by 5°C.
4.3.3. Straight naphtha

Analysis mode: PNA or PIANO
OlefinSep 165°C
5A 140°C
The straight naphtha generally contains less than 0.5% olefins. A high Olefin-Trap
separation temperature can be used to avoid that traces of paraffins are counted as
olefins.
The straight naphtha usually does not contain butane but has pentane as lowest n-paraffin.
Therefore an intermediate 5A-Trap temperature can be used. If butane is present, a 5A-
Trap temperature of 120°C needs to be used.

4.3.4. Reformer feed

Analysis mode: PNA or PIANO
OlefinSep 165°C
5A 140°C
Generally contains less than 0.5% olefins. A high Olefin-Trap separation temperature can
be used to avoid that traces of paraffins are counted as olefins.
The reformer feed usually does not contain butane but has pentane as lowest n-paraffin.
Therefore an intermediate 5A-Trap temperature can be used. If butane is present, a 5A-
Trap temperature of 120°C needs to be used.
4.3.5. Light FCC

Analysis mode: PONA, PIANO
OlefinSep 110 - 130°C PONA
5A 120 PIANO
This sample is most easily analyzed using the PONA mode (no normal paraffin separation).
Research labs often need to determine the normal paraffins.
4.3.6. Heavy FCC

Analysis mode: PONA, PIANO, PIONA streams
5A 140 - 160°C
These samples contain high levels of olefins (range 20 - 40%) but since the olefins have
higher boiling points a relatively high Olefin-Trap separation temperature can be used.
Because there is generally no butane present in the sample, a 5A-Trap separation

temperature of 140°C can be used. If there is very little pentane as well, the temperature
can be increased up to 160°C in order to get a better separation of Decane and Undecane.
4.3.7. Other samples

If the sample you need to analyze is not discussed, please try to match the sample to one
of the listed samples. A platformate can be analyzed more or less like a reformate (in
PIANO mode). However, components may have been formed in concentrations that require
verification across methods in order to be sure. A check between the results of PNA and
the required analysis mode of the sample assists in judging if the results are correct.

5. Theory, background, and historical development

5.1. Component structure
The objective of hydrocarbon type analysis is to provide a breakdown analysis of naphtha
into component classes by carbon number. When the molecules consist solely of the
elements carbon (C) and hydrogen (H), they are termed hydrocarbons. Refinery streams
can contain up to a few thousand different hydrocarbon components of the following
types:
-Straight alkanes = normal paraffins-
Branched alkanes = iso-paraffins
-Straight alkenes = normal olefins
-Branched alkenes = iso-olefins
-Cyclo-alkanes = naphthenes
-Cyclo-alkenes = cyclic olefins
-Polycyclo-alkanes = poly-naphthenes
-Aromatics
5.1.1. Paraffins
Paraffins can be divided into normal paraffins (straight chain or linear) and iso-paraffins
(branched). To the oil refiners, gasolines with normal paraffins are undesirable because
they have much lower octane numbers than the highly branched paraffins, naphthenes and
aromatics
Examples:
n-pentane (normal paraffin) C C

C C C
iso-pentane (iso-paraffin) C
C C
C C

5.1.2. Naphthenes
By removing two hydrogen atoms from the end carbon atoms of a paraffin chain and
joining the ends together we get a cyclo-alkane (naphthenes).
Examples:
cyclohexane
methyl-cyclopentane
5.1.3. Aromatics
Aromatics are compounds containing the benzene ring structure. They are desirable in
gasoline because of their high octane numbers. However, concentrations are often
restricted in finished gasolines due to legal constraints.
Examples:
benzene
toluene (methyl-benzene)
naphthalene
5.1.4. Olefins
Olefins are the unsaturated counterpart of the paraffins and naphthenes. They are not
found in crude oils but are made during processing. Straight-run naphtha normally contains
only minor amounts (0.2 %), reformate around 0.5 % while FCC naphtha can contain up to
60% normal, cyclic and iso-olefins.
Examples:
n-butene
or or

iso-butene
cyclohexene
5.1.5. Poly-Naphthene
By joining two or more naphthene rings together, or by joining naphthenes and aromatic
rings, a vast array of complex molecules results. It is believed that much of the higher
boiling portions of crude petroleum consist of mixed molecules.
Examples:
Poly-Naphthene
5.1.6. Ethers
Ethers are hydrocarbon molecules with an oxygen atom in their carbon chain. The four
ethers which may be present in fuels are the following:
MTBE C C
O C
(Methyl-Tertiary-Butyl-Ether)
C C
ETBE C C C
O C
(Ethyl-Tertiary-Butyl-Ether)
C C
DIPE C C
(Di Iso-Propyl-Ether) C C
C O C
TAME C C
O C
(Tertiair-Amyl-Methyl-Ether)
C C C

5.1.7. Alcohols
Alcohols are hydrocarbons with a hydroxyl (OH) group at the hydrocarbon molecule. The
most common alcohols are the C1 up to C4.alcohols.
Methanol C OH
Ethanol C
C OH
n-Propanol C C
C OH
i-Propanol C
C OH
C
n-Butanol C C
C C OH
s-Butanol OH
C C
C C
i-Butanol C OH
C C
C
t-Butanol C
C C OH
C

5.2. Response factors

Flame ionization detector response factors used in the Reformulyzer® M4 software are
based on percentage by mass of carbon. Methane is considered to have a unity (1) response
factor. Response factor calculations are based on an atomic weight of carbon of 12.011
and hydrogen of 1.0080, as specified in ASTM publication DS 4A, Physical Constants of
Hydrocarbons C1 to C10.
The following formula is used to calculate the flame ionization detector response factors:
0.7487 x
C aw xC n    H aw xH n 
Cn
RRf 
C aw
Where:
Caw is the atomic weight of carbon
Cn is the number of carbon molecules in the molecule
Haw is the atomic weight of hydrogen
Hn is the number of hydrogen molecules in the group
0.7487 corrects the response of methane to unity
This formula is only valid for hydrocarbons and not for molecules containing oxygen such as
ethers and alcohols. The C-O bond influences the FID response so the theoretical
calculation based on carbon content cannot be used. The relative response factors for
oxygenates have been determined experimentally.

5.3. Calculations
5.3.1. Concentration (mass or volume %)

After integration and identification of the peaks, the found normalized areas are converted
into to mass concentration by using FID response factor for each component or component
group. Using the density of each component, this mass is converted into volume. The
software supports 2 density values, at 15 °C (59 °F) and 20 °C (68 °F) respectively.
5.3.2. RON/MON
RON/MON can be calculated for FCC samples. A correlation has been developed to
calculate RON and MON for FCC samples in PIONA mode.
RON can be calculated for Reformate samples. A correlation has been developed to
calculate RON in PNA, PIPNA and PIANO modes.
RON/MON calculations are based on proprietary correlations on FCC- and Reformate-
samples. The results can be used for trend monitoring.
Calculation availability:
Method Calculation
PIONA FCC RON/MON
PNA Reformate RON
PIANO Reformate RON
PIPNA Reformate RON
5.3.3. Calorific value

The calorific value of a fuel sample is estimated from hydrocarbon properties using a
proprietary algorithm based on the percentages of Carbon, Hydrogen and Oxygen in the
sample.
5.3.4. C:H:O Ratio

The C:H:O ratio is the mass ratio of Carbon, Hydrogen and Oxygen. The calculation uses
the number of Carbon, Hydrogen and Oxygen atoms as specified in the Components table
to calculate the mass ratios.
5.3.5. Average Molecular Weight

The average molecular mass of a sample can be calculated. This calculation uses the
molecular mass of the component or component group calculated from the number of
Carbon, Hydrogen and Oxygen atoms in the Components table.
5.3.6. Density
The density of the sample can be calculated and is reported at the selected temperature
either at 15 °C (59 °F) or 20 °C (68 °F) respectively. This calculation uses the component
or component group densities. This should be used for trend monitoring.

5.4. Historical development
5.4.1. Evolution of the PNA Method

Multi-dimensional technology is the basis for the Reformulyzer® M4 analyzer. First
introduced as the PNA analyzer developed in the 1960’s, refiners used the PNA analyzer to
determine the composition of reformer feed and other straight Naphtha samples. The
process engineer used the amounts of naphthenes and aromatics from the reformer feed to
predict the final octane number of reformate, which was the basis for gasoline production.
5.4.2. nPiPNA
In the seventies, the price of naphtha increased drastically. This made the analyses for
process control more essential. The n-paraffin amount in the naphtha feed for the stream
cracker is an important parameter in determining the yields of ethylene, propylene and
butadiene, which are the bases for PVC and other plastics. To accommodate this shift, AC
upgraded the PNA analyzer into the nPiPNA analyzer to determine n-Paraffins, Isoparaffins,
Naphthenes and Aromatics.
5.4.3. PIONA
The increased use of the cracking process to reduce the bottom of the barrel gave refiners
sufficient amount of FCC naphtha. Environmental concerns led to the requirement for
unleaded gasoline. To produce unleaded gasoline without reducing the octane number,
refiners blended FCC naphtha directly into the gasoline. It became essential to
characterize olefin content because the amount of olefins influences the octane number.
This led to the development of the PIONA analyzer.
5.4.4. PIONA plus: the AC Reformulyzer™

Additional environmental regulations required the reduction of aromatics, olefins and Reid
vapor pressure as well as elimination of tetra-ethyl lead (TEL) . To keep the octane
number at an acceptable level, refiners blended isomerate, alkylate and oxygenates into
the gasoline. To accommodate the addition of oxygenates, AC Analytical Controls upgraded
the PIONA analyzer to the PIONA plus Oxygenates analyzer system known as the
Reformulyzer.
5.4.5. The Reformulyzer® M3

The need for upgrading the AC Reformulyzer™ to the AC Reformulyzer® M3 model became
important due to the higher number of samples. The analysis time of the various analysis
modes is now reduced to 75 minutes. A new Winterspec mode analyzes winter gasoline
blended with (bio) ethanol in 75 minutes and also provides a complete separation of the
alcohols.
5.4.6. The Reformulyzer® M4

The need for upgrading the AC Reformulyzer™ to the Reformulyzer® M4 model became
important due to the higher number of samples and competition in alternative methods
with shorter analysis times. Also improved performance of the Olefin-Trap (lifetime and
higher concentrations) is implemented in the M4. The analysis time of the various analysis
modes is reduced to approximately 50%. The Winterspec mode is replace by a conventional

Gasoline mode with a total analysis time of 41 and also a PIONA mode for oxygenates is
developed.
6. Standardization and Specifications

6.1. Introduction
The Reformulyzer® M4 system is specified according to the following Standard Methods
 Gasoline specs according to EN 228

 EN ISO 22854
 ASTM D6839
The following section describes the scope and specifications of these methods in detail.
6.2. EN 228
Requirements and test methods for premium grade unleaded petrol.

Property Units Limits Test Method a

Min. Max. (See 2. Normative references)
Research octane number, RON 95,0 -- EN ISO 5164 b
Motor octane number, MON 85,0 -- EN ISO 5163 b
Lead content mg/l -- 5,0 EN 237
Density (at 15 °C) c kg/m3 720,0 775,0 EN ISO 3675
EN ISO 12185
Sulfur content c mg/kg -- 10,00 EN ISO 13032
EN ISO 20846
EN ISO 20884
Manganese content d mg/kg
until 2013-12-31 -- 6,0 EN 16135
from 2014-01-01 -- 2,0 EN 16136
Oxidation stability minutes 360 -- EN ISO 7536
Existent gum content mg/100 ml -- 5 EN ISO 6246
(solvent washed)
Copper strip corrosion rating class 1 EN ISO 2160
(3 h at 50 °C)
Appearance clear and bright visual inspection
Hydrocarbon type content c, % (V/V) EN 1553
EN ISO 22854
- olefins -- 18,0
- aromatics -- 35,0
Benzene content c % (V/V) -- 1,00 EN 238
EN 12177
EN ISO 22854
Oxygen content c % (m/m) 3,7 EN 1601
-- EN 13132
EN ISO 22854
Oxygenates content c % (V/V) EN 1601
EN 13132
- Methanol g -- 3,0 EN ISO 22854
- Ethanol h -- 10,0
- iso-propyl alcohol -- 10,0
- iso-butyl alcohol -- 10,0
- tert-butyl alcohol -- 7,0
- ethers (5 or more C atoms) -- 15,0
- other oxygenates i -- 10,0
NOTE Requirements in bold refer to the European Fuels Directive 98/70/EC [1], including Amendment 2003/17/EC [2]
a See also 5.7.1
b A correction factor of 0,2 for MON and RON shall be subtracted for the calculation of the final result, before reporting according to
the requirements of the European Directive 98/70/EC [1], including Amendment 2003/17/EC [2]
c See also 5.7.2
d The content of oxygenate compounds shall be determined as prescribed in Table 1 in order to make the corrections when necessary
according to clause 13.2 of ASTM D 1319.
e When Ethyl-tert-butyl ether (ETBE) is present in the sample, the aromatic zone shall be determined from the pink brown ring
downstream of the red ring normally used in the absence of ETBE. The presence or absence of ETBE can be concluded from the analysis
as required in footnote d.
f For the purpose of this standard ASTM D 1319 shall be applied without the optional depentanisation step. Therefore clauses 6.1, 10.1
and 14.1.1 shall not be applied.
g Stabilising agents shall be added.
h Stabilising agents may be necessary.
i Other mono-alcohols and ethers with a final boiling point no higher than prescribed in Table 3.
6.3. Obsolete and redrawn methods

With the development of the new EN 228 method, some old standardization methods are
redrawn, replaced or made obsolete.
 ASTM D6839 is the successor of the D6293 method.

 The DIN 51448-2 method has been withdrawn with the development of the EN14517
method.
 EN ISO 22854 supersedes the EN 14517 method.
 EN 14517 is withdrawn in 2008
6.4. EN ISO 22854

Liquid petroleum products -- Determination of hydrocarbon types and oxygenates in
automotive-motor gasoline -- Multidimensional gas chromatography method.

EN ISO 22854 supersedes the EN14517 method which was redrawn in 2008.
6.4.1. Scope
This European Standard specifies two types of unleaded petrol; one type with a maximum
oxygen content of 3.7 % (m/m) and a maximum ethanol content of 10.0 % (V/V) and one
type intended for older vehicles that are not warranted to use unleaded petrol with a high
biofuel content with a maximum oxygen content of 2.7 % (m/m) and a maximum ethanol
content of 5.0 % (V/V).
6.4.2. Precision and bias

Table 5 Repeatability and reproducibility numbers according to EN ISO 22854 for the
Reformulyzer® M4 in Gasoline mode.
Component or group Repeatability Reproducibility
% (V/V)a % (V/V)a
Saturates 0.5 1.6
Aromatics r = 0.0095 X + 0.1952 R = 0.0450 X + 0.1384
Olefins r = 0.0185 X + 0.1415 R = 0.1176 X + 0.5118
Benzene r = 0.0147 X + 0.0031 R = 0.0777 X - 0.0250
For contents > 0.8 % (V/V)
For contents < 0.8 % (V/V) r = 0.02 R = 0.04
Oxygenate compounds r = 0.0193 X + 0.0024 R = 0.0251 X + 0.3515
Total Oxygen content 0.04 % (m/m) 0.31 % (m/m)

a X is the mean of the two results being compared in % (V/V) unless otherwise stated
6.5. Specifications according to ASTM D6839 (under revision in 2013)

The ASTM-method D6839 is titled “Standard Test Method for Hydrocarbon Types,
Oxygenated Compounds and Benzene in Spark Ignition Engine Fuels by Gas
Chromatography”.
6.5.1. Scope
This test method provides for the quantitative determination of saturates, olefins,
aromatics and oxygenates in spark-ignition engine fuels by multidimensional gas
chromatography. Each hydrocarbon type can be reported either by carbon number or as a
total.
This test method is applicable to spark-ignition engine fuel with total aromatic content up
to 50 % (V/V), total olefinic content up to 30 % (V/V) and oxygen compounds up to 15 %
(V/V).

6.5.2. Precision of the method

The repeatability and reproducibility of the test method are determined for a number of
various concentration levels. The reported values in Table are based on 95% confidence
limits.
Table 6 Repeatability and Reproducibility for ASTM D6839

Range (% V/V)
Category Repeatability Reproducibility
Conc. Low Conc. High
Aromatics 0.012 (10 + X) 0.036· (10 + X) 20 45
Olefins 0.13 · X0.46 0.72 · X0.46 0 28
Saturates 0.5 1.6 25 80
Oxygen 0.02 0.10 0.25 1.8
Benzene 0.019 · X1.6 0.053 · X1.6 0.5 1.6
MTBE 0.14 0.37 10
Ethanol 0.06 0.37 0.5 4
ETBE 0.09 0.67 10
TAME 0.07 0.71 4.5
6.6. System performance specifications

The system performance specifications for the Reformulyzer® M4 on the AC Quantitative
Reference sample (50.16.512, box 20001.157) and quality control samples are described in
the software and sample documents in the database supplied with each set of samples.

7. Application range and analysis modes

7.1. Application range
7.1.1. Introduction
The Reformulyzer® M4 is suitable for GC analysis of the following gasoline components and
blends:
 FCC naphtha’s
 Hydrocracked naphtha’s
 Straight run naphtha’s
 Reformates
 Alkylates
 Isomerate
 Finished gasolines
 All oxygenated blends
 E85 samples
7.1.2. Separating hydrocarbon classes

A breakdown of this naphtha's into component class carbon number is important for
process control and product specifications, especially for feed stocks and final products.
The Reformulyzer® M4 separates and reports hydrocarbons and oxygen containing
components.
Hydrocarbon classes that can be separated are Paraffins, (Iso- and normal), olefins, (iso-
and normal) Naphthenes and Aromatics by carbon number.
Oxygen containing components that are separated individually by the Reformulyzer® M4

are four ethers (MTBE, ETBE, DIPE and TAME) and nine alcohols (Methanol, Ethanol, n-
Propanol, i-Propanol, n-Butanol, i-Butanol, t-Butanol, s-Butanol and tert-Amyl alcohol).
7.1.3. Dedicated Analysis Modes

The Reformulyzer® M4 software includes dedicated analysis modes. All modes have pre-
programmed GC parameters, temperatures and integration parameters. Selecting a mode
enables analysts to save time and automatically dedicate the analysis to their sample.
AC offers you the following modes:
 The PIPNA or PIANO modes determine Normal Paraffin, Iso-Paraffin, Naphthene and
Aromatic content within 34 or 44 minutes and are dedicated to Naphtha, Reformer
Feed and Reformate samples. The PIANO mode also tests for olefins.
 The PONA mode is tuned to the analysis of samples having olefin contents up to 75%
such as FCC naphtha and require 35 minutes.
 The Gasoline mode determines Aromatics, olefins and Benzene in Motor Gasoline
according the EN 228 specifications in 42 minutes. It is also suitable for blended
with bio-ethanol and separates the traces of higher alcohols.
The software also offers the option to create additional references to analysis modes,
which allows you to use names that apply to your routine samples. This helps analysts to
ensure that the appropriate analysis is performed.

7.2. Reformulyzer® M4 analysis modes

The AC software offers multiple modes for the Reformulyzer® M4 analysis. You select a
mode depending on sample type and data required. For each mode all settings are
preprogrammed to enable automatic column switching and temperature control.
Table 7 Product analysis modes of the Reformulyzer® M4 PNA
(n)PiPNA
Gasoline
Gasoline
OPIONA
PIONA
PIANO
OPNA
PONA
PNA
E85
Light straight run ● ● ●
Heavy straight run ● ● ●
Depentanized bottom ● ● ●
Reformate ● ● ●
FCC-light ● ●
FCC-medium ● ●
FCC-heavy ● ●
Visbreaker ● ●
Alkylate ●
Isomerate ●
Gasoline blend ● ● ●
E85 Gasoline ●
Analysis time (min) 26 32 34 35 59 44 42 61 42

7.3. PNA
7.3.1. PNA: order of elution and typical sample analysis results
Start End Description

0.00 13.00 C1-C12 paraffins and naphthenes by carbon number from 13X Column
13.00 16.15 C6-C8 aromatics and Poly-naphthenes from Boiling Point Column set
16.20 19.00 Higher boiling saturates (> 200°C) back flush from Boiling Point
Column set
20.00 24.00 C8-C10 aromatics from Boiling Point Column set
23.20 26.00 Higher boiling aromatics (> 200°C) back flush from the Boiling Point
Column set
Figure 17 - PNA M4 analysis of the AC Quantitative Reference Standard 50.16.512 (box

20001.157).

7.4. nPIPNA
7.4.1. nPiPNA: order of elution and typical analysis results

0.00 13.00 C4-C12 iso-paraffins and naphthenes by carbon number from 13X
Column
13.00 16.15 C6-C8 aromatics and Poly-naphthenes from the Boiling Point Column
set
16.15 17.50 Higher boiling saturates (> 200°C) back flush from the Boiling Point
Column set
17.50 26.50 C3-C12 normal paraffins by carbon number from 5A-Trap and 13X
Column
27.50 31.55 C8-C10 aromatics from the Boiling Point Column set
31.55 34.00 Higher boiling aromatics (> 200°C) back flush from the Boiling
Point Column set
Figure 18 - nPiPNA M4 analysis of AC Quantitative Reference standard 50.16.512 (box

20001.157).

Sample Reformer feed (00.02.040)

Mode nPIPNA
Injection volume 0.10 µl
5A-Trap 150°C
Remarks The first n-alkane is hexane (dehexanized sample, small
hexane peak is present). Therefore a 5A-Trap temperature of
150°C can be used. If the sample contains butane, a 5A-Trap
separation temperature of 120°C is required. On a
depentanized sample a 5A-Trap temperature of 140°C can be
used.
Figure 19 - nPiPNA M4 analysis of the AC Reformer feed QC (00.02.040).
Please refer to the sample documents in the database supplied with each set of samples.
Sample Reformate (00.02.041)

Mode nPIPNA
5A-Trap 150°C
Remarks The first n-alkane in this sample is pentane but Reformate
can contain butane as well. Because the carbon distribution is
relatively narrow a 5A-Trap temperature of 120°C is generally
a good choice. If the sample is known to have no or a very
low butane content, a 5A-Trap separation temperature of
140°C can be used as well.

Figure 20 - nPiPNA M4 analysis of the AC Reformate QC (00.02.041).

7.5. PONA
7.5.1. PONA: order of elution

0.00 13.00 C1-C12 paraffins and naphthenes by carbon number from 13X
Column
13.00 16.15 C6-C8 aromatics and poly naphthenes from the Boiling Point Column
set
Column set
17.50 27.50 C3-C12 olefins and cyclic olefins by carbon number from Olefin-Trap
and 13X Column
32.55 35.00 Higher boiling aromatics (> 200°C) back flush from the Boiling
Point Column set
Figure 21 - PONA M4 analysis of the AC Quantitative Reference standard 50.16.512 (box

20001.157).

Sample Medium FCC (00.02.042)

Mode PONA
Olefin-Trap 150°C (range 135 - 155°C)
Remarks
Figure 22 - PONA M4 analysis of the AC medium FCC QC (00.02.042).

7.6. PIONA
7.6.1. PIONA: Order of elution

Column
13.00 16.15 C6-C8 aromatics and Poly-naphthenes from the Boiling Point
Column set
16.15 17.50 higher boiling saturates (> 200°C) back flush from the Boiling
Point Column set
17.50 32.00 C3-C12 normal paraffins by carbon number from 13X Column
32.00 42.00 C3-C12 iso-olefins and cyclic olefins by carbon number from
Olefin-Trap and 13X Column
47.05 48.50 higher boiling saturates (> 200°C) back flush from the Boiling
Point Column set
48.50 59.00 C3-C12 normal olefins by carbon number from 13X Column
Figure 23 - PIONA M4 analysis of the AC Quantitative Reference standard 50.16.512 (box

20001.157).


Mode PIONA
Olefin-Trap 150°C
5A-Trap 175°C
Remarks
Figure 24 - PIONA M4 analysis of the AC Reformer feed QC (00.02.040).


Mode PIONA
Olefin-Trap 150°C
5A-Trap 175°C
Remarks
Figure 25 - PIONA M4 analysis of the AC Reformate QC (00.02.041).

7.7. PIANO
7.7.1. PIANO: order of elution

Column
13.00 16.15 C6-C8 aromatics and Poly-naphthenes from the Boiling Point Column
set
Column set
17.50 26.50 C3-C12 normal paraffins by carbon number from 5A-Trap and 13X
Column
Column set
33.00 44.00 C3-C12 olefins and cyclic olefins by carbon number from Olefin-Trap
and 13X Column
Figure 26 - PIANO M4 analysis of the AC Quantitative Reference standard 50.16.512 (box

20001.157).


Mode PIANO
Olefin-Trap 150°C
5A-Trap 175°C
Remarks
Figure 27 - Figure 27 PIANO M4 analysis of the AC Reformer feed QC (00.02.040).


Mode PIANO
Olefin-Trap 150°C
5A-Trap 175°C
Remarks
Figure 28 - PIANO M4 analysis of the AC Reformate QC (00.02.041).

7.8. OPNA
7.8.1. OPNA: order of elution

0.00 11.00 C1-C10 paraffins and naphthenes by carbon number from 13X
Column
11.00 14.45 Ethers from the Boiling Point Column set
14.45 16.50 High boiling non-aromatics back flush from the Boiling Point
Column set
Column set
19.65 22.50 Higher boiling saturates (>200°C) back flush from the Boiling Point
Column set
23.50 29.85 Alcohols and C8-C10 aromatics from the Boiling Point Column set
29.85 32.00 Higher boiling aromatics (>200°C) back flush from the Boiling Point
Column set
Figure 29 - OPNA M4 analysis of AC Quantitative Reference standard 50.16.512 (box

20001.157).

Sample Gasoline K (00.02.045)

Mode OPNA
EthAlcSep 110°C
Remarks
Figure 30 - OPNA M4 analysis of the AC Gasoline K QC (00.02.045).

Sample Gasoline L (00.02.046)

Mode OPNA
EthAlcSep 120°C
Remarks
Figure 31 - OPNA M4 analysis of the AC Gasoline L QC (00.02.046).

Sample Gasoline N (00.02.048)

Mode OPNA
EthAlcSep 120°C
Remarks
Figure 32 - OPNA M4 analysis of the AC Gasoline N QC (00.02.048).

7.9. Gasoline
7.9.1. Gasoline: order of elution

0.00 11.50 Saturated C1 - C11 paraffins and naphthenes by carbon number
from 13X Column
Column set
16.50 26.50 C3-C10 olefins and cyclic olefins by carbon number from Olefin-
Trap and 13X Column
Column set
29.65 32.50 Higher boiling saturates (>200°C) back flush from the Boiling
Point Column set
39.85 42.00 Higher boiling aromatics (>200°C) back flush from the Boiling
Point Column set
Figure 33 - Gasoline analysis of AC Quantitative Reference standard 50.16.512 (box 20001.157).


Mode Gasoline
OlefinSep 150
EthAlcSep 110°C
Remarks
Figure 34 - Gasoline analysis of the AC Gasoline K QC (00.02.045).


Mode Gasoline
OlefinSep 150°C
EthAlcSep 110°C
Remarks
Figure 35 - Gasoline analysis of the AC Gasoline L QC (00.02.046).

Sample Gasoline M (00.02.047)

Mode Gasoline
OlefinSep 150°C
EthAlcSep 110°C
Remarks
Figure 36 - Gasoline analysis of the AC Gasoline M QC (00.02.047).


Mode Gasoline
Remark
OlefinSep 150°C
EthAlcSep 110°C
Figure 37 - Gasoline analysis of the AC Gasoline N QC (00.02.048).

7.10. OPIONA
7.10.1. OPIONA: order of elution

from 13X Column
Column set
16.50 26.50 C3-C12 normal paraffins by carbon number from 13X Column
Column set
Point Column set
31.00 42.00 C3-C10 olefins and cyclic olefins by carbon number from Olefin
trap and 13X Column
Point Column set
50.00 61.00 C3-C11 n-olefins by carbon number from Olefin-Trap and 13X
Column
Figure 38 - OPIONA analysis of AC Quantitative Reference standard 50.16.512 (box 20001.157


Mode OPIONA
OlefinSep 150
EthAlcSep 120°C
Remarks
Figure 39 - OPIONA analysis of the AC Gasoline K QC (00.02.045).


Mode OPIONA
OlefinSep 150°C
EthAlcSep 120°C
Remarks
Figure 40 - OPIONA analysis of the AC Gasoline L QC (00.02.046).


Mode OPIONA
OlefinSep 150°C
EthAlcSep 120°C
Remarks
Figure 41 - OPIONA analysis of the AC Gasoline N QC (00.02.048).

7.11. Gasoline E85
7.11.1. Gasoline E85: order of elution

from 13X Column
Column set
16.50 26.50 C3-C10 olefins and cyclic olefins by carbon number from Olefin-
Trap and 13X Column
Column set
Point Column set
Point Column set
Figure 42 - Gasoline E85 analysis of the AC Ethanol Fuel Blend E85 QC (00.02.697).

7.12. Fast Group Type (FGT)
7.12.1. Fast Group Type (FGT): order of elution

0.00 6.00 C4-C12 paraffins and naphthenes
6.00 7.30 Benzene
9.00 12.00 C4-C12 Olefins
Figure 43 - Fast Group Type (FGT) analysis of AC Quantitative Reference standard 50.16.512
(box 20001.157).

8. Troubleshooting
8.1. General troubleshooting list
The following sub-sections describe various symptoms that can be noticed in the
Reformulyzer® M4, their possible causes, and possible solutions.
8.1.1. Problem indication

Normally a problem in the system can be noticed from the analysis chromatograms. These
indications include:
 Poor peak profiles

 Bad separation
 Missing peaks or component fractions
 Any other deviation from the normal chromatographic performance
 Unexpected results
Whenever a problem occurs, first check the readable parameters of the system. This can
be performed by running the AC Quantitative Reference sample or an AC QC sample in the
mode in which the problem occurs.
8.1.2. Low recovery for Benzene and/or poly-naphthene
Chromatogram examples:
A6 PolyN
Figure 44 - Example analysis long A-time
Possible causes Solution

- C12 / Poly naphtene / Benzene separation on - Reduce the A-time.
Polar column is not OK

8.1.3. Sharp C9 Paraffin, bad peak shape 13X Column fraction

Regular
Moisture
Figure 45 - Example analysis moisture on 13X column

- Moisture introduction - Use purified gasses (nitrogen carrier gas and hydrogen
Pt-Catalyst flow).
- Check for leaks.
- Replace septum.
- Check (and renew) filters.
- Condition the 13X Column.
Columns will be affected by moisture:
 Shortened lifetime: Olefin-Trap

 Insufficient hydrogenation: Pt-Catalyst
 Catalytic breakdown: Eth-Alc Trap
 C12 / Benzene separation: Polar-Column set

8.1.4. Baseline increase on 13X Column fraction, Olefin result too low
Figure 46 - Example analysis bad Olefin trap

- Break-through on olefin-Trap - Reduce Olefin-Trap separation temperature.
- Replace trap.
8.1.5. Extra (small) peaks in Olefin section (for samples that contain Olefins)
Regular
Incomplete
Figure 47 - Example analysis bad Pt-Column


- Pollution, Moisture - Condition the Pt-Catalyst at 350.
introduction
- Incomplete hydrogenation - Check H2 flow and/or condition the Pt-Catalyst
8.1.6. No Aromatics elution

Figure 48 - Example analysis no Aromatic fractions

- Non-switching valve 2 - Manually switch valve 2 to check (tune
- Septum leak valves if necessary)
- Leak at valve 1 - Replace septum.
- Leaking of the Polar-Column set - Check (and replace) valve 1.
- Leak at valve 5 - Check connections.
- Leak at valve 2 - Check (and replace) valve 5.
- Leaking of the Boiling Point Column set - Check (and replace) valve 2.

8.1.7. Empty cells in report, misidentification

- Shift in retention time due to moisture - Check filters, search for leaks.
- Misidentification by peak grouping - Correct the identification.
Figure 49 - Example analysis wrong identification

8.1.8. General trouble-shooting list
Symptom Possible causes Solution

Broad or sharp C9 P+N - Moisture introduction - Use purified gas.
- Check for leaks.
- Check (and renew) carrier gas
filters.
- Condition the 13X Column.
Elution of aromatics or Poly- - A-time is too long - Shorten the A-time.

Naphthene during the P+N
elution of the 13X Column.
Ghost peaks at the end of - Glass wool inside the - Replace the liner.
the 13X Column elution liner moved
and/or in the beginning of
the first aromatic fraction
No peaks at all in the - FID flame out - Check the FID signal.
chromatogram - Electronic Control - Check the start signal of the GC
Unit does not start and the cable connections.
- Blockage of syringe - Clean or replace the syringe.
- Large septum leak - Replace the septum.
Elution of ethers during the - Separation - Reduce the Eth-Alc Trap

first 13X Column fraction. temperature of Eth-Alc separation temperature.
Trap too high
- Bad working Eth-Alc - Replace the Eth-Alc Trap.
Trap
Elution of C11 and/or C12 - Separation - Increase the Separation

saturates in the olefin 13X temperature of the temperature of the Olefin-Trap.
Column run. Olefin-Trap too low
Poly-Naphthene elutes in - Flow B too low - Increase flow B until Poly-

the back flush fraction. Naphthene elutes at 3.0 min after
the injection from the Eth-Alc Trap
on the Boiling Point Column set
No elution during an olefin - Leak at the Olefin- - Check the connections.

run. Trap
No elution during a 5A run. - Leak at the 5A-Trap - Check the connections.
No complete elution of - Flow B too low - Increase flow B until TAME elutes
TAME in the ether fraction. at 3.5 min after the injection from
the Eth-Alc Trap on the Boiling
Point Column set.

8.2. Performance check

Before you check for a leak or replace parts, the following should be checked (if possible,
compare them with the normal operating values):
1. Check inlet pressures.

Hydrogen 5 bar / 75 psi
Nitrogen 6 bar / 90 psi
Air 5 bar / 75 psi
If one of these pressures is lower than normal, check the inlet or bottle pressures.
2. Read the head pressure of flow A and flow B. The normal stand-by pressures are listed
in the test results. Also, compare them with the normal operating values, if possible.
If the pressure of flow A is too low, then check the septum.
If the septum is OK, then check the system flows.
3. Switch valves 1 through 7 sequentially, and read the head pressure of flows A and B.
When valve 2 is switched to the on position, the pressure of flow B may drop a little. In
all other cases, the pressure readings should be equal or a little bit higher.
If the pressure decreases, the corresponding valve and columns connections should be
checked for leaks.
4. Use the Communication Control program and verify proper performance of all heated
zones. Heat up each heated zone and read the status of the heaters.
Activate Valve 3 before heating up heater 4.
Activate Valve 4, before heating up heater 5.
 Heater 1 (valve box) must heat up to 110°C in about 15-30 minutes.

 Heater 2 (Pt-Catalyst) must heat up to 180 °C in about 30 seconds.
 Heater 3 (Pre-Column (Alc Trap)) must heat up to 230°C in about 30 seconds.
 Heater 4 (5A-Trap) must heat up from 150°C to 450°C in about 45 seconds.
 Heater 5 (Olefin-Trap) must heat up from 70°C to 250°C in about 30 seconds.
 Heater 6 (Eth-Alc Trap) must heat up from 70°C to 280°C in about 30 seconds.
 Heater 7 (13X Column) must heat up to 300°C in about 1 minute.
If one or more heaters do not respond in this way, check the following items:
1. Check the error status and clear all errors

2. Turn the Reformulyzer® M4 Electronic Control Unit off and on and heat up each
heated zone and read the status of the heaters.
3. Check all thermocouple sensor connections.
4. Check the thermocouple sensor connection on the traps.

8.3. Ghost peaks
8.3.1. Introduction
Ghost peaks can come from several sources, for example:
 Impure hydrogen or nitrogen carrier gas

 Inefficient carrier gas molecular sieves
 Inefficient chemical filters
 Bleed of the septum
 A contaminated injector (with pieces of septa or sample residue)
Ghost peaks cannot be completely eliminated, but much can be done to reduce their
concentration to acceptable levels.
8.3.2. Eliminating ghost peaks

Steps which could be followed to minimize ghost peaks:
1. Use high-purity hydrogen and nitrogen carrier gas.

2. Regenerate or condition the 13X Column and Pt-Catalyst periodically.
3. Use high-grade septa in the injector (11 mm Teflon lined septa 21040.005).
4. Clean the injector every 3-4 months.
5. Replace the liner (21032.015).

8.4. Leak checking
8.4.1. Introduction
This section contains information on detecting and/or localizing leaks in the Reformulyzer®
M4.
The Reformulyzer® M4 uses flow-controlled carrier gases. This means that any flow going
into the system, must also leave the system. In a leak-tight system the set combined flows
A, B and Pt-Catalyst must equal the flow at the FID. To measure the total carrier gas flow
at the FID, the detector gases should be turned off. When the combined flows at the FID
differ from the combined ingoing flows, a leak might be present in the system.
Execute the following procedure only when a leak is suspected. Before

starting extensive procedures, make sure that the septum is leak tight.
Only a qualified service engineer should carry out this procedure.
There are three ways to detect and/or localize leaks in the system:
 Using a soap solution: see section 8.4.2.

 Flow measurement in different parts of the system: see section Flow measurement.
 Pressurizing the system: see section Check for leaks by pressurizing the system.
8.4.2. Check for leaks using a soap solution

This method only works if a reasonable pressure is present at the point in the system that
is tested. Be aware that soap might be introduced into the system in case of a leak. It is
advisable to use a pressure test instead. It is recommended to use i-Propanol instead of a
soap solution on the capillary column connections.
1. Cool down the oven temperature, injector, detector, valve box, and all heated zones
from the Reformulyzer® M4 Electronic Control Unit.
If the tested parts are not cooled down, a soap solution will boil on the surface. This
also results in bubbles but this is not necessarily a leak.
Turn the Reformulyzer® M4 Electronic Control Unit off and disconnect the
main power cord to avoid a potential shock hazard.
2. Apply a soap solution on the connections in the system.

When a leak is present small or large bubbles will appear.
Be careful with soap solutions. Do not spill any soap solution on any
electrical part.
3. Repeat the previous step for all connections.

8.4.3. Flow measurement

1. Cool down the oven temperature, injector, detector, valve box, and all heated
zones from the Reformulyzer® M4 Electronic Control Unit
2. Measure the flows in the various parts of the instrument with use of the flow
scheme.
Start at the beginning of the flow scheme.
3. Measure the flow at a certain point.
4. Connect a restriction to the point of interest that point, for example a needle
valve.
Make sure that the restriction it is not so high that the flow controller is
unable to reach the desired flow. As a guideline the pressure at the flow
controller gauge should be at least 1 bar less than the pressure at the
pressure regulator of the gas flow tuning module.
5. Measure the flow again.

6. Check if the flow with or without the restriction is the same.
If not, then a leak exists between the flow controller and that point.
7. Repeat the previous step for all connections and for all valve positions.
8.4.4. Check for leaks by pressurizing the system

1. Cool down the oven temperature, injector, detector, valve box, and all heated
zones from the Reformulyzer® M4 Electronic Control Unit.
2. Set the PCM B flow off, to turn off the hydrogen flow to the Pt-Catalyst by (Aux
EPC# button on the GC).
3. Wait several minutes to let the hydrogen leave the system.
4. Disconnect the detector connection and block the flow exit. Block the split injector
as well.
5. Turn off the flow when the pressure of the Reformulyzer® M4 reaches the maximum
value of 500 kPa.
Alternatively you can switch the PCM to pressure mode and set the pressure to 500
kPa. Switch it off when this maximum pressure is reached.
6. The pressure drop should be less than 10 kPa in 10 minutes.
If the pressure drops more there is a leak between the pressure regulator and the
position where the flow channels are blocked.
The pressure may increase slightly, due to small internal PCM leaks.
7. Repeat the previous steps for all parts of the system and for all valve positions.

8.5. System deviations
8.5.1. Introduction
System deviations can be caused by all individual parts of the system. Leaks at connections
or soldering of the different parts might introduce system deviations but these can also be
caused by column deterioration. Minor faults in the system might only affect the
quantitative behavior of the system.
Therefore, it is strongly recommended to check the system regularly with the AC

Quantitative Reference sample 50.16.512 (box 20001.157) or the AC QC samples.
8.5.2. Checking the system

Please refer to chapter 8, for calibrating and validating the Reformulyzer® M4.
8.5.3. Injection port liner

The liner can cause disturbance peaks and memory peaks to next runs when not properly
packed.
This results in small contamination peaks in the aromatic fractions. It can show Poly-
Naphthene peaks in the aromatic fractions as memory peaks after a reformate sample
analysis.

8.6. Column deviations
8.6.1. Introduction
The columns in the system will generally loose performance. Some columns may perform
well over the lifetime of the instrument; others have to be replaced at some interval.
Decreasing performance generally shows in the chromatography. AC engineers are
experienced to locate the source of a problem based on the chromatographic analysis
results of the AC Quantitative Reference sample or AC QC samples.
8.6.2. The Polar-Column (OV275)

Generally, the Polar-Column has a lifetime comparable to that of the instrument. It may
gradually loose its selectivity to separate benzene from dodecane (drop in the column’s
polarity). The Polar-Column is affected by oxygen and moisture in carrier gas or by system
leaks.
8.6.3. The Boiling Point Column set

Generally, the Boiling Point column has a lifetime comparable to that of the instrument. It
may gradually loose its selectivity due to drop in the column’s polarity. The boiling point
column is affected by oxygen and moisture in carrier gas or by systems leaks.
8.6.4. The Eth-Alc Trap

Deterioration of the Ether/alcohol trap will cause an extra broad peak in the back flush
fractions of the aromatic elution. Furthermore, a deteriorated trap might not adsorb the
low-boiling aromatics or ethers completely. This is indicated by extra peaks during the
naphthene and paraffin elution.
Leaking trap connections will cause a loss of aromatics and oxygenates in the final analysis
results.
The Eth-Alc Trap is affected by moisture in the carrier gas or by system leaks. Moisture
introduces catalytic breakdown and accelerates loss of capacity to retain ethers. The trap
may suffer from capacity limitations and catalytic breakdown of ethers.
8.6.5. The Olefin-Trap

Deterioration of the olefin trap is shown as olefin break-through.
Not all olefins are adsorbed in the adsorption phase of the analysis and the olefins
(especially those with low boiling points) will elute during the first 6 minutes of the
analysis as a broad "hump". This effect can also be caused by an injection volume that is
too high.
The Olefin-Trap is affected by moisture in the carrier gas. Its lifetime is also affected by
the number of olefin analyses and by the concentration and distribution of olefins in the
sample.
Possibly the Olefin-Trap can be affected by some sulfur components in the sample.

8.6.6. The Pt-Catalyst

The Pt-Catalyst may lose its power to hydrogenate olefins. This is shown as an irregular
pattern of peaks in the olefin 13X Column fraction, particularly at higher carbon numbers
(C7 and above).
Hydrogenation capacity is affected by moisture in the carrier gas as well as in the Pt-
Catalyst. A leak at the connections of the Pt-Catalyst will lower the contents of
naphthenes and paraffins throughout the analysis. Furthermore, a leak will introduce
moisture in the system which can be recognized by poor separation or peak shape of C9
naphthenes and paraffins on the 13X Column.
A poor performing Pt-Catalyst will not hydrogenate all olefins into saturates. These
incompletely hydrogenated olefins can be recognized as extra "ghost" peaks between the
paraffins of one carbon number and the naphthenes of the next carbon number. Compare
the suspected chromatogram with previous chromatograms to find the "ghost" peaks.
Condition the Pt- Catalyst.
1. Check for leaks.

2. Set the 13X Column at a high temperature (like 450 C) to let the impurities (coming out
of the Pt-Catalyst) pass the 13X Column to the detector.
3. Set the Pt-Catalyst to 350 °C for 30 minutes.
4. Check the results by analyzing an AC QC standard.
8.6.7. The 5A-Trap

Deterioration of the 5A-Trap is indicated by tailing n-paraffins, small peaks at the start of
the n-paraffin fraction or small peaks at the end of the n-paraffin fraction.
Peak tailing means that the material in the 5A-Trap is damaged and can cause a lower n-
paraffin value if the peaks are not integrated properly. A small peak at the start of the n-
paraffin fraction can often be removed by conditioning the trap for 10 minutes at 450
degrees Celsius. Set the 13X Column at a 450 °C as well to let the impurities pass the 13X
Column to the detector.
Also the selectivity of the trap (5 carbon numbers) might be affected, which is indicated by
adsorption of branched paraffins with higher carbon numbers and breakthrough of light
normal paraffins.
A leak at the connections of the trap will cause a loss of n-paraffins in the analysis result.
A leak will probably also introduce moisture in the system.
8.6.8. The 13X Column

The start of deterioration of the 13X Column is indicated by tailing peaks in the
chromatogram (especially the n-paraffins) and loss of resolution.
A poor separation of C9 paraffins and naphthenes indicates the presence of moisture in the
system. This can be caused by a leak or contaminated carrier gases. A leak at the
connections of the 13X Column will cause the paraffins and naphthenes to be reported low.

The automated feature of the software keeps the 13X Column at 300 °C or 330 °C when
the instrument is idle: this prevents the column from collecting moisture.
8.7. Hardware deviations
8.7.1. Introduction
Malfunctioning hardware is often more difficult to locate. Problems with heated zones can
be found relatively easy by a manual check. Problems with valves are more difficult to
troubleshoot. Some general checks and performance problems are described below.
8.7.2. Check Six-port rotary valves (Valve 1 to 7)

A restriction from one of the rotary valves will cause an increased column-head pressure
for flow A (V1 to V4) or flow B (V2 or V5).
Valve leaks will cause the following problems:
V1 & V1A Missing aromatics.

V2 Missing aromatics.
V3 & V3A Missing olefins, paraffins and naphthenes.
V4 Missing n-paraffins, paraffins and naphthenes.
V5 Missing aromatics or back flush fractions from the Boiling Point Column
set
8.7.3. Check the Reformulyzer® M4 Electronic Control Unit

Problems related to the Reformulyzer® M4 Electronic Control Unit can be identified by
using the Communication Control program. A status report is produced which shows
whether the heater is enabled or not. Always inspect the connections of the thermocouple
leads, heater leads and thermocouple sensor to the trap.
8.7.4. Log files

The Reformulyzer® M4 maintains log files in the following directory:
C:\Users\Admin\AppData\Roaming\PAC-PDS
The exact location depends on the Windows version used.
Depending on your folder settings, some folders might not be visible.
(Tools – Folder Options , Show hidden files and folders and Show Operating
System files)

Figure 50 - Workbench Diagnostic tab, Error messages
Information about the sequencing process in the control engine is stored in the file:
ReformulyzerLog.txt
Events in the module that handles the sequencing are stored in the file:
ReformulyzerServiceLog.txt
The instrument log contains events from ChemStation but also from the Reformulyzer® M4
macros.

8.8. Software deviations

Cannot log in Username password Default administrator account:
forgotten / changed Username = admin
Password = admin
Some functions are Function has been Use Function Access in the
not available in the disabled for a Maintenance – Access control menu to
menu or task bars particular user level. select which user levels can perform
which functions.
I want to operate As a restricted user you There are several known issues when
using a ‘restricted do not have unlimited operating as a restricted user. These
user’ windows account access to all folders. issues are described in the software
operation chapter.
Analysis does not start Different names in Change names such that they are
Reformulyzer® M4 equal. Mind space characters and
configuration and capitals.
ChemStation.
Incorrect Verify the communication in the
communication to M4 control engine. Modify the
electronics selected. communication configuration in the
Reformulyzer® M4 instrument
maintenance.
Verify the RS-232 port and the baud
rate for the RS-232 communication.
Verify the IP address and the remote
port for LAN communication.
Incorrect vial selected. The instrument maintenance dialog
has configuration fields for the allowed
vial range. If this changed (tray /
turret) then the configuration must be
updated.
GC method not Check if ChemStation asks to resolve
resolved. the method. If so, resolve the method.
Too long wait time If the GC does not inject within 10
before instrument is minutes after the instruction is given
ready. to start the run then the control
engine stops. This can happen if a slow
temperature zone such as the valve
box needs to heat up or cool down.


Analysis does not use If the sample type is Use the Modify option near the end of
changed conditions changed after the the sequencing process to modify
analysis is created in conditions (cutting times,
the sequence then the temperatures) of scheduled runs. This
conditions are already is also an option to run with different
stored for the analysis. conditions without having to create
different sample types.
Sequence line with The control engine has Walk through the sequencing process.
bold text cannot be the flag set that this If the run was aborted then control
removed run is in progress. If it engine will notice this and remove the
is not (ChemStation line.
was stopped or control
engine terminated)
then sequence wizard
cannot change this.
I aborted a run before Analysis is manually This analysis will show blue in the
it started. How do I terminated with the completed sequence list and sequence
start it anyway? abort button or on the will be paused. Use right mouse click
GC. on blue sample line to schedule a
retest.
How do I find a The list of analyses can Use the filtering options in the search
specific analysis? become very long after window. Note that filtering options
some time of use. can be combined. For example, you
can search for samples with a name
that contains aaa somewhere in the
name and that is analyzed using
sample group bbb in the period from
xxx to yyy.
I do not see my The filter is set and Change the filtering options or
analysis in the list excludes the analysis. deselect the filter.
I cannot find my Reports are by default You can change the folder for storing
reports stored in the All reports for one specific report or for
Users\Shared all reports generated in the Reports –
Documents folder. Preview option in the taskbar of an
analysis.
If I change the group Grouping times are If you want to use the grouping times
times then the next stored for each of an analysis as standard, use the
analysis does not use analysis individually. Tasks – Copy Group times option to
them copy the group times to the sample
type.


I want to change the In this screen you first You can also change the conditions in
standard conditions of need to select the the Tasks menu of an analysis. If you
a method but I am right method. open an analysis and decide the
confused to find the conditions are incorrect, look up the
right type in the conditions in the Tasks – Analysis
Runtable Parameters Parameters screen and then modify
editor screen the conditions for the sample type in
the Tasks – method – Runtable
Parameters screen.
The specifications for The gravimetric blend By default the volume percent data is
the gravimetric blend is a blend prepared by shown in the Components tab. Change
sample do not match weight so you need to to weight data by selecting View –
with my results in the look at the weight Weight.
components table percent results.
Where can I find the The diagnostics links Select the Diagnostic tab and click on
diagnostics are displayed in the the links of the diagnostics when
Diagnostic tab. present to get more information.
There are many Incorrect sample In the list of reference samples, the
results off-spec for my selected. new reference samples are preceded
reference sample AC introduced new with the numbers 040 through 048.
reference samples. The sample name is in some cases the
same (Reformer feed Reformate, FCC).
Select the correct sample in the Tasks
– Analysis type dialog.
How can I review Integration is not From Print Preview retrieve the
integration of my data stored in the database ChemStation data file and load the file
file? so the marked areas in ChemStation. Make sure to also load
for peaks in the correct GC method.
Reformulyzer® M4 do
not represent how the
peak is integrated.
I changed integration Integration data is Import the ChemStation data file to
but my results are not stored in the database, get the new integration data using the
changed when changed in File – Import function.
ChemStation it has no
effect on
Reformulyzer® M4.
ChemStation appears There is an issue This issue has been solved in
to hang when I open between ChemStation Reformulyzer® M4 software version
or close an instrument and the control engine. 1.0.7.16.


It seems that I cannot Due to referential If you want to delete a sample type
delete anything, no integrity rules you you must first delete all analyses
peaks from the cannot delete records performed using that sample type. You
identification list, no that refer to each can also hide a sample type from the
sample type other from a database. list in sequence wizard.
ChemStation reports The power settings of Set power options so that the system
that there is an the computer set the never goes to standby.
instrument power system to standby
off/on detected after some time.
How do I report to Report to LIMS is a You need to analyze a sample and
LIMS manual action. specify the LIMS ID number in the
sequencing wizard. After you reviewed
the analysis you can use the option
Tasks – Approve to LIMS to send the
report to the LIMS system.
How do I make a There was no backup Backup option is added in version
backup? option in the 1.0.7.15. This option is available for
Reformulyzer® M4 site-administrators (e.g. admin)
application.
My list of analysis All results are stored in You can remove analyses before a
results grows very long the database. specific date by using the clean-up
function. You can export the data to a
backup XML file with this function too.
I cannot restore the The database may be Close down the Reformulyzer® M4
Reformulyzer® M4 in use. application and terminate the Control
database engine in the task window.

Index
9. Index
AC Reformulyzer™ ......................... 42 oxygenated ............................. 46

adjusting blends ....................................... 27
A-time ................................... 31 board type .................................. 29
B-flow ................................... 32 B-time
D-time................................... 32 checks ................................... 32
Eth-Alc Trap ............................ 33 calculations
Alcohols ..................................... 39 RON/MON ............................... 41
Alkanes checks
Branched................................ 36 A-time ................................... 31
Cyclo .................................... 36 B-flow ................................... 32
Polycyclo ............................... 36 B-time ................................... 32
Straight ................................. 36 D-time................................... 32
Alkanes Eth-Alc Trap ............................ 33
Cyclo .................................... 37 chromatograms
Alkenes comparing .............................. 21
Branched................................ 36 overlay .................................. 21
Cyclo .................................... 36 Column
Straight ................................. 36 13X ...................................... 29
alkylate...................................... 46 column capacity ........................... 28
Alkylate ................................ 27, 47 column deviations ......................... 87
analysis commercial gasolines ..................... 33
finding .................................. 19 Component structure...................... 36
analysis mode components distribution .................. 28
selection ................................ 28 cutting times
analysis mode selection ................... 27 tuning ................................... 26
analysis modes ............................. 46 cyclohexane ................................ 37
default .................................. 28 cyclohexene ................................ 38
analysis planner ............................ 26 dedicated analysis modes ................ 46
analysis section ............................ 19 default analysis modes .................... 27
analysis sequence .......................... 30 definitions
analyzer ASTM .................................... 13
nPIPNA .................................. 42 EN-ISO ................................... 13
PIONA ................................... 42 Depentanized bottom ................ 27, 47
PNA ...................................... 42 development
application range .......................... 46 historical................................ 42
aromatics ................................... 36 deviations
Aromatics ................................... 37 13X Column............................. 88
ASTM D6839 ............................ 43, 45 hardware .......................... 89, 91
A-time Reformulyzer® M4 Electronic Control
adjusting ................................ 31 Unit ...................................... 89
checks ................................... 31 six-port rotary valves ................. 89
operating range ........................ 31 DIPE ..................................... 38, 46
background ................................. 36 D-time
benzene ..................................... 37 adjusting ................................ 32
B-flow check .................................... 32
adjusting ................................ 32 operating range ........................ 32
check .................................... 32 E85
operating range ........................ 32 analysis result .......................... 73
bias .......................................... 44 order of elution ........................ 73
blend E85 gasoline ........................... 27, 47
Index
E85 Gasoline ........................... 27, 47 valve box ............................... 29
E85 sample.................................. 46 heavy FCC ................................... 35
EN 228 ....................................... 43 Heavy straight run Naphtha ......... 27, 47
EN 228 method ............................. 43 historical development .............. 36, 42
EN ISO 22854 ............................... 13 hydrocarbon classes ....................... 46
EN ISO 22854 ............................... 43 hydrocracked naphtha’s .................. 46
EN ISO 22854 ............................... 44 i-Butanol .................................... 39
EN ISO 22854 reproducibility ............. 44 i-Propanol ................................... 39
ETBE .................................... 38, 46 iso-butene .................................. 38
Eth-Alc Trap isomerate ................................... 46
adjusting ................................ 33 Isomerate .............................. 27, 47
checks ................................... 33 leak checking ............................... 84
operating range ........................ 33 flow measurement ............... 84, 85
Eth-Alc Trap pressurizing the system .............. 85
EthAlcSep ............................... 33 soap solution ........................... 84
Ethanol ...................................... 39 light FCC .................................... 35
Ethers........................................ 38 Light straight run Naphtha .......... 27, 47
evolution main CPU.................................... 29
PNA method ............................ 42 main screen
Fast Group Type analysis results section ............... 19
analysis result .......................... 74 analysis section ........................ 19
order of elution ........................ 74 medium FCC ................................ 53
FCC Methanol .................................... 39
heavy .................................... 35 method
light ..................................... 35 derived .................................. 28
medium ................................. 53 EN 228................................... 43
FCC naphtha's .............................. 46 EN ISO 22854 ........................... 44
FCC-heavy.............................. 27, 47 methyl-cyclohexane ....................... 37
FCC-light ............................... 27, 47 modes
FCC-medium ........................... 27, 47 non-oxygenates ........................ 28
FCC-Naphtha ............................... 27 -oxygenates ............................ 28
FGT sample-specific ........................ 28
analysis result .......................... 74 MTBE .................................... 38, 46
order of elution ........................ 74 naphtha’s
finished gasoline ........................... 46 FCC ...................................... 46
gas solid interactions ...................... 28 hydrocracked .......................... 46
gasoline straight run ............................. 46
analysis result .......................... 64 naphthalene ................................ 37
finished ................................. 46 Naphthenes ................................. 36
high RVP ................................ 34 Poly ...................................... 36
order of elution ........................ 64 Naphthenes ................................. 37
regular setpoints ...................... 34 Naphthenes
Gasoline ................................ 27, 47 Poly ...................................... 38
Gasoline blend ........................ 27, 47 n-Butanol ................................... 39
gasolines n-butene .................................... 37
commercial ............................. 33 nPIPNA ....................................... 50
General terms .............................. 13 nPIPNA analyzer............................ 42
General trouble-shooting list ............ 80 n-Propanol .................................. 39
Ghost peaks ................................. 83 olefins ....................................... 37
heater cyclic .................................... 36
5A-Trap ................................. 29 iso- ...................................... 36
EA trap .................................. 29 normal .................................. 36
Olefin-Trap ............................. 29 operating range

Index
A-time ................................... 31 Reformulyzer®M4 .......................... 42
B-flow ................................... 32 repeatability
Eth-Alc Trap ............................ 33 ASTM D6839 ............................ 45
operation range Repeatability
D-time................................... 32 ASTM .................................... 13
OPIONA ................................. 27, 47 EN ISO 22854 ........................... 44
analysis result .......................... 69 reproducibility
order of elution ........................ 69 ASTM D6839 ............................ 45
OPNA.................................... 27, 47 Reproducibility
analysis result .......................... 60 ASTM .................................... 13
order of elution ........................ 60 EN ISO ................................... 13
oxygenated blend .......................... 46 Response factors ........................... 40
paraffins .................................... 36 results
iso- ...................................... 36 approving ............................... 30
Paraffins results filtering............................. 19
Iso- ...................................... 36 running samples ............................ 26
Normal .................................. 36 safety precautions ...........................2
parameters sample
setting .................................. 28 dehexanized............................ 50
PIANO ................................... 27, 47 depentanized .......................... 50
analysis result .......................... 57 E85 ...................................... 46
order of elution ........................ 57 sample modes
PIONA ................................... 27, 47 quality control ......................... 27
analysis result .......................... 54 sample volume ............................. 28
order of elution ........................ 54 samples
PIONA analyzer ............................. 42 unknown composition ................. 28
PIONA plus .................................. 42 sample-specific non-oxygenates modes
PIPNA ................................... 27, 47 ............................................... 28
analysis result .......................... 49 sample-specific oxygenates modes...... 28
order of elution ........................ 49 s-Butanol .................................... 39
PNA ..................................... 27, 47 separation temperature
analysis result .......................... 48 Olefin-Trap ............................. 33
order of elution ........................ 48 separation temperatures ................. 29
PNA analyzer ............................... 42 tuning ................................... 26
PNA method Set points
evolution ............................... 42 standard samples ...................... 34
Poly-Naphthene ............................ 38 specifications ............................... 43
PONA.................................... 27, 47 standardization ............................ 43
analysis result .......................... 52 standby ...................................... 30
order of elution ........................ 52 straight naphtha ........................... 34
PPE .............................................2 straight run naphtha’s .................... 46
precision .................................... 44 streams ...................................... 27
product analysis modes .............. 27, 47 symbol
Pt-Catalyst .................................. 29 accompanying instructions .............2
quality control ............................. 27 compressed gas cylinder ...............2
refinery streams ........................... 27 dangerous voltage .......................2
reformate .............................. 46, 51 electrostatic sensitive device .........2
Reformate ............................. 27, 47 hot surface ...............................2
reformer feed ................ 35, 50, 55, 58 symbols
Reformer Feed ............................. 27 warning and safety ......................2
Reformulyzer® M3 .......................... 42 system deviations .......................... 86
Reformulyzer® M4 TAME .................................... 38, 46
Electronic Control Unit ............... 29 t-Butanol .................................... 39

Index
temperature A-time ................................... 31
Eth-Alc Trap ............................ 33 B-time ................................... 32
Terminology ................................ 13 cutting times ........................... 26
tert-Amyl alcohol .......................... 46 D-time................................... 32
tetra-ethyl lead ............................ 42 olefin separation temperature ...... 33
theory ....................................... 36 separation temperatures ............. 26
time viewing results ............................. 30
A ......................................... 31 Visbreaker ............................. 27, 47
B ......................................... 32 Warning and safety sybols ..................2
D ......................................... 32 Warranty ......................................2
toluene ...................................... 37 window
tuning analysis ................................. 21

Contact
10. Contact
If you have any questions about your PAC products, please contact your nearest PAC office
or PAC Authorized Representative. We are located in most countries worldwide. Use our
website www.paclp.com (Contact Us in the top menu) to find your contact.
The contact details of our Global Headquarters are:
PAC, LP phone: +1 800.444.TEST

8824 Fallbrook Drive office: +1 281.940.1803
Houston, Texas 77064 fax: +1 281.580.0719
e- sales.usa@paclp.com
mail: service.usa@paclp.com
Keep up with the latest and greatest from PAC on www.paclp.com.

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Operating and Application

Copyright © 2016 by Petroleum Analyzer Company, L.P.

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Test certificate acc. to IEC

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4.2.2. Tuning the B-time ..................................................................... 32

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5.4.5. The Reformulyzer® M3 ................................................................ 42

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7.10.1. OPIONA: order of elution .......................................................... 70

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8.6.6. The Pt-Catalyst ........................................................................ 88

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1.2. Manual setup

Chapter 5: Theory, background, and historical development, contains detailed

Chapter 6: Standardization and Specifications, describes the specific standardization

Chapter 8: Troubleshooting, describes various symptoms that can be noticed in the

Chapter 10: Contact

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1.3. Technical information

Voltage range 120 VAC, 60 Hz, 750 VA

At the back side of the Application Unit

1.3.1. System pressure test

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2.2. ASTM definitions

2.3. EN-ISO definitions

Reproducibility (more operators, more instruments): If results in two different

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3.1. Software startup

3.1.1. Startup of OpenLAB

Figure 1 - Agilent OpenLAB Control Panel

When using Agilent OpenLAB ChemStation edition, the online instrument

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3.1.2. Startup of Workbench

Figure 2 - IRIS Workbench startup screens

IRIS Enterprise Workbench has the option to create shortcuts for an

If you don’t have an account, contact your site administrator.

Passwords are case sensitive.

3.2. Reformulyzer Help

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3.3. Reformulyzer Main Screen

3.3.1. Run Control

Figure 3 - Workbench Run Control

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Schedule a single run

Figure 4 - Workbench Run Control add single run

Figure 5 - Workbench Sequence Editor

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3.3.2. Results tab

Search window - filter the results

Figure 6 - Workbench Search filter

Notes about the search window:

 Several filter options can be combined.

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Figure 7 - Workbench Result Tab

Figure 8 - Workbench Analysis Results

The Task button can be used for the following actions:

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