C180-E062

Shimadzu Simulated Distillation GC Analysis System

Shimadzu Simulated Distillation GC Analysis System

Features of the Simulated Distillation GC Software

Total area method and internal standard method are available. The distillation curve can be displayed as a graph and printed. Baseline correction. Automatic calibration correction. By setting the identification retention time range, the identification table is automatically updated, so long as the retention time is within that range. The fraction at a specific temperature range can be calculated. The fraction ratio for a certain range can be easily obtained since the elution amount (%) at a specific temperature range that has been designated can be calculated. Convert into ASTM D-86, D-1160. D-86 is applied to kerosene and light oil, while D1160 is applied to samples which require reducedpressure distillation, such as lubricating oil. Automatic end-point detection Automatic end-point detection is useful for the samples containing components with high boiling points. Typical batch templates have been prepared. Typical method files have been prepared. Analysis and post run analysis employ the same operations used in the GCsolution. Since the batch table option is used, analysis and post run analysis can be operated using the same operations employed in the GCsolution.

Simulated Distillation GC Analysis System

This is a method of measuring the boiling point distribution of oil fractions using gas chromatography. This technique is commonly called Simulated Distillation Gas Chromatography, as the measurement results obtained are similar to those obtained with the conventional distillation method.

(1) Measurement of Boiling Point Distribution using the Total Area Method
When a linear temperature programming method is applied to the analysis using a gas chromatograph with a non-polar liquid phase column, the hydrocarbons will be eluted in the order of boiling point. Since the elution time is more or less directly proportional to the boiling point, a calibration curve of the retention time and boiling point can be created, as shown in Fig.1.1. In other words, the retention time can be converted into the boiling point. Therefore, by working out the relationship between the retention time and the boiling point beforehand through the analysis of a hydrocarbon mixture with a known boiling point (with the gas chromatograph analysis conditions kept constant), it becomes possible to convert the retention time of an unknown sample into the boiling point. Furthermore, the total area of the gas chromatogram obtained is divided into fixed time intervals, and the smaller areas comprised by each time period are calculated. Since the time interval can be converted into the boiling point interval, this in effect calculates the gas chromatogram area for the fraction of a particular boiling point. In addition, by obtaining the cumulative area through the addition of all the small areas from the start point onwards, and expressing it as a ratio of the area of the entire gas chromatogram, the elution amount up to that time will have been calculated. In Fig.1.2 for example, the cumulative area up to n consists of S1, S2, Sn-1, Sn. By figuring out the ratio with respect to the total area St, the elution amount at tn is obtained. The data in Fig.1.3 is an example of the elution amount (corresponds to the amount of distillate). This method is applied to samples where all the components of the sample are eluted from the column during high temperature analysis using GC, such as the oil fractions of gasoline, kerosene, and light oil.

Boiling point

Overview of Simulated Distillation GC Analysis

Retention time
Fig.1.1 Calibration Curve

Total area

Fig.1.2 Calculating the elution amount

(2) Measurement of Boiling Point Distribution using the Internal Standard Method
When analyzing samples containing components with boiling points higher than 1000F (538C), such as lubricating oil and crude oil, all of the components will not be eluted from the column during high temperature analysis. Therefore, the total amount of components cannot be obtained and the elution amount cannot be calculated. To overcome this, a known quantity of an internal standard substance is added. Using the fact that it will be equivalent to the ratio of this internal standard substance to the sample amount, the area for all components, including those which are not eluted from the column, can be obtained by calculation. From this, the relationship between the amount of sample eluted and the boiling point is sought out in the same way as (1).

Elution temperature

Elution amount
Fig.1.3 Distillation characteristics curve

Simulated Distillation GC Analysis System

Total Area Method

Samples with boiling points below 538C are measured using the total area method. The chromatogram is divided into fixed time intervals, and the distillation characteristics are calculated based on this data. The maximum number of data that can be collected is 5000. The scale on the temperature axis of the graph changes automatically within a range of 0 to 900C. The printing sections (distillate amount %) within the table can be set from 1 to 99. Up to 10 sections of specific temperature range fractions can be calculated.

Internal Standard Method

There are two internal standard methods: the single method and the double method. The single method is used in cases where the standard sample and the unknown sample do not overlap, whereas the double method is used when samples which overlap with the standard sample are analyzed.

Single Method
When a sample containing components which do not elute are analyzed using the gas chromatograph, a known component is added to correct for the area of the component which is not eluted. By multiplying the area/ component amount ratio with the sample amount, the total area of the sample is calculated. The difference between this value and the area that was actually obtained is taken to be the area of the components which did not elute. In the single method, the unknown area is calculated by adding the standard sample (known sample) to the unknown sample. The boiling point range of the internal standard component can be set freely.

Double Method
Unlike the single method described on the left, a sample to which the known component (internal standard) is added and a sample without the known component is analyzed in succession. The area of the components of this difference between the two is calculated. The boiling point range of the internal standard component can be set freely.
Chromatogram for a sample to which the internal standard has been added AIS 1000F(538C) S A A'

Chromatogram of the sample only BIS 1000F(538C) S B I - IBP I - FBP B'

MAX - BP

T = B + B' = (AIS X T A

B BIS S BIS) X I A AIS

: Theoretical total area : Area of the part below 538C for the sample to which the internal standard has been added B : Area of the part below 538C for the sample without the internal standard AIS : Area of the internal standard substance distillate section for the sample to which the internal standard has been added BIS : Area of the section corresponding to the internal standard substance distillate for the sample without the internal standard S : Sample amount I : Amount of internal standard added A, B : Area corresponding to the components which are not distilled from within the sample

Estimation of the surface area using the internal standard method

Simulated Distillation GC Software

Simulated Distillation GC Software

Initial Settings
Since the screens have been made to match the GCsolution, settings can be made using the same operations. The initial settings are comprised of settings for calibration, parameters, and reports.

Distillation Characteristics Calculation Results

After analysis/ Post run analysis, a report on the distillation characteristics calculation results is printed out automatically. The results can be checked on the screen as well.

Analysis/Post run analysis

As it uses the batch processing of GCsolution, the operation is the same as the GCsolution.

Printout Example
Refer to the application examples on the next page.

Simulated Distillation GC Software

Application Examples
Initial Settings
Analysis Date & Time User Name Vial# Sample Name Sample ID Sample Type Injection Volume ISTD Amount Data Name Method Name Intensity : 3/8/2001 6:31:38 PM : wada :1 : Unknown Sample : : Unknown : 0.3 : : F:\E_DGC\DemoFile\TotalArea\Diesel\Diesel1.gcd : F:\E_DGC\DemoFile\TotalArea\Diesel\Diesel1.gcm

15000000

/7.341

10000000

**** BOILING RANGE DISTRIBUTION ****

5000000

10 Peak# Ret.Time Area Height Conc. Unit Mark ID# Cmpd Name 1 7.341 5440496082 8429712 100.000 Total 5440496082 8429712

min

SAMPLE NAME SAMPLE ID SAMPLE TYPE ANALYSIS TIME TOTAL AREA OUTPUT FILE CALIBRATION FILE PARAMETER DATA FILE REPORT DATA FILE

: : : : : : : : :

Unknown Sample UNKNOWN 2001/03/08 18:31:38 TOTAL AREA F:\GCsolution\dgc1\data\Diesel1.dat F:\GCsolution\dgc1\Calib\Diesel1.clb F:\GCsolution\dgc1\PARM\Diesel1.par F:\GCsolution\dgc1\PARM\Diesel1.rep

ASTM D-86 %OFF (%) IBP 10 20 30 50 70 80 90 FBP VABP BP (C) 176.0 209.2 238.3 258.9 293.0 315.1 329.4 346.2 369.8 ----BP (F) 348.8 408.6 460.9 498.0 559.4 599.2 624.9 655.1 697.6 544.051(F)

Engine oil sample

Analysis Date & Time User Name Vial# Sample Name Sample ID Sample Type Injection Volume ISTD Amount Data Name Method Name

: 3/15/2001 11:41:01 PM : Admin :1 : Sample+IS : Ultra ALLOY-SIM : Unknown : 1.0 : : F:\E_DGC\DemoFile\IS\Sgl\EngineOil+IS.gcd : F:\E_DGC\DemoFile\IS\Sgl\EngineOil.gcm

**** BOILING RANGE DISTRIBUTION **** SAMPLE NAME SAMPLE ID SAMPLE TYPE ANALYSIS TIME TOTAL AREA SAMPLE WEIGHT IS WEIGHT OUTPUT FILE CALIBRATION FILE PARAMETER DATA FILE REPORT DATA FILE : : : : : : : : : : : Sample+IS Ultra ALLOY-SIM UNKNOWN 0200/03/15 1 11:41:01 PM INTERNAL STANDARD (SINGLE) 10 1 F:\GCsolution\dgc1\data\EngineOil+IS.dat f:\GCsolution\dgc1\Calib\EngineOil.CLB f:\GCsolution\dgc1\PARM\EngineOil_S.PAR f:\GCsolution\dgc1\PARM\EngineOil.REP

Intensity 1950000 1900000 1850000 1800000 1750000 1700000 1650000 1600000 1550000 1500000 1450000 1400000 1350000 1300000 1250000 1200000 1150000 1100000 1050000 1000000 950000 900000 850000 800000 750000 700000 650000 600000 550000 500000 450000 400000 350000 300000 250000 200000 150000 100000 50000

Distillation Data in Specified Temperature Range IBP (C) 200.0 300.0 350.0 400.0 FBP (C) 300.0 350.0 400.0 480.0 % 0.0 1.8 17.8 65.4

10

/15.000

20

30

min

Simulated Distillation GC Analysis System

Specifications
No. of input channels Data collection interval No. of data collected Baseline correction Retention time boiling point conversion Area volume % conversion Internal standard method Specific temperature range fraction 2 Depends on each GC Max. 5000 Uses the function of the GCsolution Multi-linear calibration Available The boiling point range can be set as desired 10 sections

Automatic modification of the retention time boiling point calibration curve through standard sample analysis. Re-calculation upon changing the boiling point calibration curve is possible. 5 graphs of the distillation characteristics curve and the boiling point calibration curve can be created. Conversion into ASTM D-86, D-1160 Automatic end-point detection (for the total area method only)

System Configuration Example (for 1ch)

Initial Settings
Gas chromatograph Shimadzu GC-14BPF Gas Chromatograph CRG-15 Cryogenic option (required when an initial column temperature is10C less than room temperature as) Solenoid valve unit for the L-CO2 (required when using the CRG)P/N 221-25347-94 CBM-102 Optical link transmission unit for the GC-14B GCsolution workstation GCsolution reference manual (GCsolution Ver2.0 or higher) Simulated Distillation GC software 0V-1 5% Chromosorb W60/80 1m (2 columns 1 set) P/N 221-41674-** P/N 221-25347-94 P/N 221-43846-** P/N 223-04860-** P/N 221-42171-91 P/N 223-05430-92 P/N 223-00568 P/N 221-57807-92

Data processor

Software Column

For the Capillary Column

Gas chromatograph GC-2010AF Gas Chromatograph P/N 221-47700-** Wide bore injection unit WBI-2010 or P/N 221-47726-** OCI/PTV-2010 P/N 221-49213-** CRG-2010 CO2 100V Cryogenic option P/N 221-48703-** (required when an initial column temperature is less than room temperature +10C) Solenoid valve unit for the L-CO2 (required when using the CRG) P/N 221-43846-** GCsolution workstation P/N 223-05430-92 GCsolution reference manual P/N 223-00568 (GCsolution Ver2.0 or higher) Simulated Distillation GC software P/N 221-57807-92 For kerosene: CBP1-W12-500 (Non polar, 0.53mmI.D., 12m, 5mm) For light oil: CBP1-W12-100 (Non polar, 0.53mmI.D., 12m, 5mm) Note 1) The column type, size and film thickness are important performance factors. Note 2) When the separation characteristics etc. of the capillary column and packed column differ, different measurement results may be obtained. For kerosene: n-C6, 7, 8, 9, 10, 12, 14, 16, 18 in CS2 P/N 221-44247-17 For light oil: n-C6, 7, 8, 10, 12, 14, 16, 18, 20, 22, 24 in CS2 P/N 221-44247-18 Mixed samples: n-C8, 10, 12, 16, 20, 24, 28, 30, 32, 36, 40, 44 in C6 P/N 221-44247-19

Data processor Software Example of columns

Standard sample

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