optimizing ultra fast simulated distillation with a low thermal … · 2016-09-04 · basic system...

LTM ULTRA FAST Simulated Distillation

10/29/2014

Optimizing Ultra Fast Simulated Distillation with a Low Thermal Mass (LTM) GC System

Jim McCurry Roger Firor Agilent Technologies Wilmington, DE

http://www.google.com/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&docid=ZWT8tdZnMAB-tM&tbnid=yyGuzjRGFFFE-M:&ved=0CAUQjRw&url=http://ffden-2.phys.uaf.edu/212_spring2011.web.dir/kristine_odom/temp/10956/ftddrops/Downstream.html&ei=Qgd0UouvAcKCyAGZmoDYBQ&bvm=bv.55819444,d.aWc&psig=AFQjCNHwcSSXRLfDhNliZkAkgxtul0P96A&ust=1383422136663800

Scope of the Analyzer

Designed for ASTM D7798

• For the determination of boiling range distribution of petroleum products and biodiesel (B5,B10,B20)

• Applicable to petroleum distillates having a final boiling point not greater than 538 °C

• Difference between initial BP and final BP must be greater than 55 °C

• Not applicable to naphthas, reformates, gasolines or full range crude oils


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Basic System Structure

• G3440B, 7890B

• #211, Capillary FID

• #112 Split/splitless Inlet or #150 MMI with CO2 cooling

• 160-2255-5, 5 meter 0.25 mm fused silica deactivated

Used for connecting column unions to inlet and detector

• G3440-85037, Calibration Mix C5-C44

• 5060-9086, Reference Gas Oil


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LTM Configuration Options

• G6678A/79A/80A: 5-inch format Bundle

• Choose option:

78A 1-channel, 5 inch format, 1 power supply

• G6578-60561: ULM Union kit w/ferrules


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Note: Supported as a single channel system only

Auto Injector Options

Auto Injector required

G4513A: 7693A with 16 sample module

G4514A: 7693A Tray

G4520A: 7693A Tray with heater/mixer and barcode reader

G4520A is highly recommended

5uL syringe required: G4513-80206


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Software

Requires the following:

• OpenLab CDS ChemStation Addition C 1.05 or greater

• Simulated Distillation Software Add on: G2887-64010


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Note: Not supported on any other software platform

Column Investigation

Three columns were considered for D7798:

5 m x 0.32mm x 0.52 um DB-1

4 m x 0.25 mm x 0.50 um DB-1

4m x 0.25 mm x 0.25 um DB-1


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The focus here will be on the two 0.25 um ID columns

New Columns for Ultra Fast Simulated Distillation

• 5 inch LTM Format

• Dimensions: 4 m x 0.25 mm I.D. x 0.50 um DB-1 4 m x 0.25 mm I.D. x 0.25 um DB-1

• Temp limits are: -60ºC to 360ºC

• Part Number: G33900-65003 (0.50 um column)

• Part Number: G33900-65004 (0.25 um column)

• Column should be installed with unions

• Column shipped with unions attached in special packaging


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LTM Column Technology


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LTM Column Heating and Cooling Characteristics


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LTM Ultra Fast Simulated Distillation Configuration for D7798


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7890B with helium carrier gas

MMI or S/S Inlet

FID 5 Inch LTM

Module

0.5 m x 0.25mm deactivated fused silica

Working with Flexible Metal Ferrules


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Sample Preparation: General Guidelines


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Calibration Mix:C5-C44 Reference Gas Oil

Inject 0.1 uL neat

Viscous Oil Samples

Dilute approx. 3:1 with Carbon disulfide

Inject 0.1 uL

Dilute as needed with Carbon disulfide, Typically 5 to 1.

Heat 3 min. in tray at 80 C

if required

Inject from 0.1 to 0.5 uL

Parameters for Split/Splitless/LTM System Inlet: Split/Splitless, 355 °C

Liner: Single taper w/glass wool, #5183-4647 or #5190-2295

Split ratio: 30:1, helium carrier

Column: 4 m x 0.25 mm x 0.25 um DB1

inSeg: 0.5 m x 0.25 mm fused silica

outSeg: 0.5 m x 0.25 mm fused silica

Flow: 8 mL/min, 18.5 psi @ 35 °C, constant flow

LTM Oven Program: 35 °C (0.1 min) to 355 °C (0.8 min) @ 160 °C/min

FID: 355 °C

Data Rate: 10 Hz or 20 Hz

7890B oven temp: 320 °C isothermal


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Parameters for MMI/LTM System Inlet: MMI, 355 °C

Liner: Single taper w/glass wool, #5183-4647 or #5190-2295

Split ratio: 30:1, helium carrier

Column: 4 m x 0.25 mm x 0.25 um DB1

inSeg: 0.5 m x 0.25 mm fused silica

outSeg: 0.5 m x 0.25 mm fused silica

Flow: 8 mL/min, 18.5 psi @ 35 °C, constant flow

LTM Oven Program: 35 °C (0.1 min) to 355 °C (0.8 min) @ 160 °C/min

FID: 355 °C

Data Rate: 10 Hz or 20 Hz

7890B oven temp: 320 °C isothermal


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C5-C40 Calibration Mix: 160 °C/min, MMI


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4 m x 0.25 mm x 0.50 um DB-1

C40

C44 Elution on the Thicker Film Column


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C44 elutes on final isothermal section

4 m x 0.25 mm x 0.50 um DB-1 160 °C/min, MMI

Parameters not optimized: All calibration hydrocarbons should elute during the temperature program ramp

C5-C44 Calibration: 150 °C/min


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Column: 4 m x 0.25 mm x 0.25 um DB-1

C44 elutes during oven ramp

Comparison of Thin and Thick Film Columns for C5-C6 Separation


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C5 C6

C5

C6

4 m x 0.25 mm x 0.50 um DB-1

4 m x 0.25 mm x 0.25 um DB-1

Both provide adequate separation

The MMI Shows Minimal Discrimination Over a Wide Boiling Point Range


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The S/S Discrimination Test


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Hydrocarbon Conc. (ppm) Area nC12/nCx nC10/nCx

100 ppm HC's 200 ppm HC's

C10 200 130 1

C12 100 65.9 1 C14 200 133 0.98

C16 100 66.6 1 C18 100 66.5 1 C20 100 65.4 1.02 C22 100 67 1.02 C23 200 133 1

C24 100 65.7 1.03 C26 100 66.4 1.03 C28 100 66 1.04 C30 100 66.5 1.05 C32 100 65.3 1.08 C38 100 64.8 1.12 C40 100 65 1.14 C44 100 63.8 1.16

RGO: 150 °C/min


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Column Flow vs. LTM Oven Program Rate


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0

5

10

15

20

25

0 50 100 150 200 250 300 350Program rate °C/min

Col

umn

flow

mL/

min

As the column ramp rate increases, flow rates must increase to maintain separation, speed and elution

Starting with a flow of 8 mL/min @ 150 °C/min

Method Translation for 2X Speed Gain


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Programmed at 300 °C/min: C5 - C44


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Column Flow Rate: 21.7 mL/min Column: 4 m x 0.25 mm x 0.25 um DB-1

C44 elutes at less than 1.10 min.- Faster rates not recommended

RGO: MMI, 160 °C/min


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RGO Setup in the Software


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RGO Engineering Report 160 °C/min S/S Inlet


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n-butanol

n-butanol

Yield table meets method specifications for RGO No. 1 Batch 2

RGO Overlay of 5 runs: S/S Inlet 160 °C/min


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RGO Overlay of 5 Runs: 160 °C/min, MMI


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Repeatability: RGO with MMI @ 160 °C/min


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% OFF 1 2 3 4 5 6 7 8 9 10 AVG RSD %RSD ASTM DIFF °F

0.5 239 238 239 238 240 239 239 238 239 238 239 0.67 0.0028 13.7 240 5 303 302 303 303 303 303 303 302 303 302 303 0.48 0.0016 6.8 304 10 352 352 352 352 352 352 352 351 352 352 352 0.32 0.0009 7.4 348 15 398 397 398 398 398 398 398 397 398 398 398 0.42 0.0011 8.1 393 20 440 440 440 440 440 440 440 440 440 440 440 0.00 0.0000 8.7 435 25 474 473 475 474 474 473 474 473 474 474 474 0.63 0.0013 470 30 503 502 504 502 503 502 503 502 503 503 503 0.67 0.0013 8.4 499 35 530 530 531 530 531 530 531 530 531 530 530 0.52 0.0010 527 40 556 555 556 556 556 556 556 556 556 556 556 0.32 0.0006 7.7 552 45 577 576 577 577 577 577 577 577 577 577 577 0.32 0.0005 576 50 597 597 597 597 597 596 597 597 597 597 597 0.32 0.0005 7.7 594 55 612 612 613 612 613 612 613 612 613 612 612 0.52 0.0008 7.7 611 60 629 629 629 629 630 629 629 629 629 629 629 0.32 0.0005 7.7 629 65 650 650 651 649 651 650 651 649 650 649 650 0.82 0.0013 7.7 649 70 670 670 670 670 671 670 671 670 670 670 670 0.42 0.0006 7.7 668 75 692 691 692 691 692 692 692 691 692 691 692 0.52 0.0007 7.7 690 80 714 714 714 714 714 714 714 714 714 714 714 0.00 0.0000 7.7 712 85 737 737 738 737 738 737 738 737 737 737 737 0.48 0.0007 7.7 736 90 767 766 767 766 767 766 767 766 767 766 767 0.53 0.0007 7.7 764 95 807 806 807 807 807 806 807 806 807 807 807 0.48 0.0006 9 803

99.5 895 895 896 895 897 895 896 895 896 895 896 0.71 0.0008 21.2 888

ASTM DIFF = Allowable difference (+ or -) from last column

Temperatures in °F

Repeatability: RGO with Split/Splitless @ 160 °C/min


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Temperatures in °F

% OFF 1 2 3 4 5 6 7 8 9 10 AVG RSD %RSD ASTM DIFF °F

0.5 238 239 238 238 239 238 238 239 239 239 239 0.53 0.0022 13.7 240 5 302 302 302 302 302 301 302 302 303 302 302 0.47 0.0016 6.8 304

10 346 345 346 346 346 345 345 346 348 348 346 1.10 0.0032 7.4 348 15 394 391 394 393 393 392 393 394 395 395 393 1.26 0.0032 8.1 393 20 436 432 436 435 435 434 434 436 437 437 435 1.55 0.0036 8.7 435 25 470 467 470 470 470 469 469 471 471 471 470 1.23 0.0026 470 30 499 496 499 499 499 497 498 500 500 500 499 1.34 0.0027 8.4 499 35 527 525 527 527 527 526 526 528 528 528 527 0.99 0.0019 527 40 552 550 552 551 552 551 551 553 553 553 552 1.03 0.0019 7.7 552 45 575 575 575 575 576 575 575 576 576 576 575 0.52 0.0009 576 50 595 594 594 594 595 594 594 596 595 595 595 0.70 0.0012 7.7 594 55 611 610 611 610 611 610 610 612 611 611 611 0.67 0.0011 7.7 611 60 628 628 628 628 628 628 628 629 628 628 628 0.32 0.0005 7.7 629 65 649 649 649 649 649 649 649 649 649 649 649 0.00 0.0000 7.7 649 70 668 668 668 668 668 668 668 670 669 669 668 0.70 0.0010 7.7 668 75 690 690 690 690 690 689 690 691 690 690 690 0.47 0.0007 7.7 690 80 712 712 712 712 712 712 712 713 712 712 712 0.32 0.0004 7.7 712 85 736 736 736 736 736 736 736 736 736 736 736 0.00 0.0000 7.7 736 90 764 764 764 764 764 763 764 765 765 765 764 0.63 0.0008 7.7 764 95 803 803 803 803 803 803 803 804 804 804 803 0.48 0.0006 9 803

99.5 881 881 881 881 882 881 881 882 882 882 881 0.52 0.0006 21.2 888

ASTM DIFF = Allowable difference (+ or -) from last column

Cracked Gas Oil Setup Pane: Split/Splitless Inlet


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Cracked Gas Oil Engineering Report

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Blanks Following 10 runs of a Gas Oil Showing Absence of Carryover


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blanks

runs


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Summary: Simulated Distillation Solutions

• Two Configurations are available

7890B/FID

7890B/LTM II/FID

• Auto Injector with Tray provides sample heating to reduce viscosity prior to injection

• Simulated Distillation Software is partially integrated into the OpenLab ChemStation for calculation and report automation

Summary • A 4 m x 0.25 mm x 0.25 um column proved optimal for elution

of C44 while maintaining C5/C6 separation

• An LTM program rate of 150 °C/min offers speed while eluting C44 easily during the temperature ramp

• LTM program rates above 300 °C/min are not recommended as higher boiling hydrocarbons may will not elute during the temperature program ramp and little speed advantage is obtained

• Discrimination is nearly absent with the Multimode Inlet (MMI) and Split/Splitless over a C10 to C44 range

• Rapid cool down of the LTM oven greatly reduces cycle time


10/29/2014

optimizing ultra fast simulated distillation with a low thermal … · 2016-09-04 · basic system...

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