Process NMR Associates, LLC NMR Process Systems, LLC 87A ... EAS 2007.pdf · Process NMR Associates, LLC NMR Process Systems, Inc Actual Crude TBP Curves 0 10 20 30 40 50 60 70 80

More From the Barrel

On-Line NMR Increases Diesel Production and Quality (Part I)

Paul J. GiammatteoProcess NMR Associates, LLC NMR Process Systems, LLC

87A Sand Pit Road

Danbury, CT 06810203-744-5905

Paul J. Giammatteo

Process NMR Associates, LLC www.process-nmr.com

NMR Process Systems, Inc www.nmr-automation.com

On-line, high resolution nuclear magnetic resonance spectroscopy (NMR) made its introduction into refinery processes twelve yearsago with installation of two units into Texaco’s Los Angeles area refinery. From then to now, integration of the proper NMR hardware with the properly designed applications have proven economicallyand operationally beneficial. Whether the on-line NMR application serves as a preferred multi-parameter analyzer, or, integrated into advanced process control and optimization, the accuracy, reliability, and performance of on-line NMR delivers true value throughout the refining process.

Paul J. Giammatteo



Refinery Applications

Advantages and Disadvantages of NMR Applied to ProcessAdvantages:Non-Optical SpectroscopyNo Spectral Temperature DependenceMinimal Sampling RequirementsSpectral Response to Sample Chemistry is LinearChemical Regions of NMR Spectra are OrthogonalEntire Volume is Sampled by the RF ExperimentWater is in Distinct Region and can be digitally removedDetailed Hydrocarbon information is readily observed.Fundamental Chemical Information Can be Derived Directly from Spectrum.Colored/Black Samples Readily Observed

Disadvantages:Solids Cannot be ObservedIndividual Molecular Component Sensitivity Not Observed Directly in the Spectrum.Low Sensitivity to Impurities – Quantitative > 1000 ppm.Sensitive to Ferro-magnetics.Sample Viscosity Causes Resolution ChangesNon-Hydrogen Containing Species are Not Observed

Paul J. Giammatteo



Paul J. Giammatteo



NMR - What a difference one letter can make!!

.2

.4

.6

.8

1

10000 9000 8000 7000 6000 5000 4000

NIR

Typical Variability Observed in Gasoline Blending

8 7 6 5 4 3 2 1 0 -1

0

.5

1

1.5

2

2.5

3 CH

RR

HH

RH

RH

R

H

HR

CH2

CH3

CH3

CH3CH-C= and

57 M Hz

Aromatic Olefinic Water OxygenateMethylAromatic

Aliphatic

Hydrocarbon Picture

Paul J. Giammatteo



Paul J. Giammatteo



ASTM ASTM EngineeringMethod Used Reproducibility Units

Gasoline Blending RON D 2699 0.4 Octane Gasoline Blending MON D 2700 0.4 Octane Gasoline Blending T10 D 86 9.50 Degrees FGasoline Blending T50 D 86 13.00 Degrees FGasoline Blending T90 D 86 13.50 Degrees FGasoline Blending EBP D 86 13.50 Degrees FGasoline Blending Aromatics detailed GC 1.1 Volume %Gasoline Blending Benzene D 3606 0.5 Volume %Gasoline Blending RVP - information only

Diesel Blending API D 4052 1 DegreeDiesel Blending IBP D 86 14 Degrees FDiesel Blending T10 D 86 14 Degrees FDiesel Blending T50 D 86 14 Degrees FDiesel Blending T90 D 86 14 Degrees FDiesel Blending EBP D 86 14 Degrees FDiesel Blending Viscosity D 445 - informational data onlyDiesel Blending Cloud Point D 5773 7 Degrees CDiesel Blending Cetane Index D 976 - D 4737 2 Index NumberDiesel Blending Pour Point D 97 6 Deg C

Parameter Description

Paul J. Giammatteo



Paul J. Giammatteo



Aramco

BASF

Petrochina

High Resolution Process NMR Installations

ORL

PNA

Aramco

BASF

Petrochina


ORL

PNA

Aramco

BASF

Petrochina


ORL

PNA


PNA

Atm

osph

eric

Tow

er

Vac

uum

Tow

er

Cok

erFCCU*

HydrocrackerDesalter

HTU

HTU

HTU

HTU

Reformer AromaticsExtraction

Gas

Pla

nt Polymerization

Alkylation

LPG

Gasoline

Aromatics

Kerosene

Distillates

Lubricant Oils

Asphalt

Coke

VGO

Gas

Lt Naphtha

Hv Naphtha

Kerosene

AGO

Crude

Residue

Olefins

i-C4

Reformate

FCC Gasoline

Naphtha

Motor Alkylate

Gasoline StreamsKerosene/AvJetDistillate Streams

*or Resid Cracker

HeavyOilUpgradingUnit

Current Commercial NMR Units

BlendHead

Atm

osph

eric

Tow

er

Vac

uum

Tow

er

Cok

erFCCU*


HTU

HTU

HTU

HTU


Gas

Pla

nt Polymerization

Alkylation

LPG

Gasoline

Aromatics

Kerosene

Distillates

Lubricant Oils

Asphalt

Coke

VGO

Gas

Lt Naphtha

Hv Naphtha

Kerosene

AGO

Crude

Residue

Olefins

i-C4

Reformate

FCC Gasoline

Naphtha

Motor Alkylate


*or Resid Cracker



BlendHead

Paul J. Giammatteo



Paul J. Giammatteo



“Effective feedstock management can save up to 70 cents/barrel for refineries….”

“….modern analytical tools contribute significantly to this ….”

Hydrocarbon Processing,September 1998

In 1998 crude was less than $30/barrel.

What about $100+?

Paul J. Giammatteo



NMR NeSSI: Never expect Small Sample Input!

Paul J. Giammatteo



Paul J. Giammatteo



Crude Unit Overview

•Distillation (D86, Sim Dis, TBP)

•Flash Point

•Cloud Point

•Pour Point

•Freeze Point

•Chemistry (Fa, Fn, Fp, Naphthalene)

•PONA/PIONA

•API Gravity/Density

•Octane/Cetane

APC and OptimizationNaphtha

Kero

Diesel

AGO

Crude

Paul J. Giammatteo



0

5

10

15

20

10 8 6 4 2 0

NMR Spectra Showing Spectral Variability of 6 Crudes

ppm

CH

CH2

CH3CH3

CH3

Paul J. Giammatteo



Actual Crude TBP Curves

0

10

20

30

40

50

60

70

80

90

100

30 130 230 330

Temperature (C)

Cum

ulat

ive

Wei

ght L

oss

( Wt%

)

KuwaitMarib LightNembaGOS MixDulangBacho

Actual Crude TBP Curves

0

10

20

30

40

50

60

70

80

90

100

30 130 230 330

Temperature (C)

Cum

ulat

ive

Wei

ght L

oss

( Wt%

)

KuwaitMarib LightNembaGOS MixDulangBacho

NMR Predicted TBP Curves for Crudes

0102030405060708090

100

30 130 230 330Temperature (C)

Cum

ulat

ive

Wei

ght L

oss

(Wt%

)

NMR Predicted TBP Curves for Crudes

0102030405060708090

100

30 130 230 330Temperature (C)

Cum

ulat

ive

Wei

ght L

oss

(Wt%

)

Paul J. Giammatteo



Marib Light Crude TBP Curves(Actual and NMR Predicted)

0

10

20

30

40

50

60

70

80

90

100

30 130 230 330

Temperature (C)

Cum

ulat

ive

Wei

ght L

oss

(Wt%

)

ActualPredicted

Marib Light Crude TBP Curves(Actual and NMR Predicted)

0

10

20

30

40

50

60

70

80

90

100

30 130 230 330

Temperature (C)

Cum

ulat

ive

Wei

ght L

oss

(Wt%

)

ActualPredicted

Dulang Crude TBP Curves

(Actual and NMR Predicted)

0

10

20

30

40

50

60

70

80

90

100

30 80 130 180 230 280 330 380

Temperature (C)

Cum

ulat

ive

Wei

ght L

oss

(Wt%

)

Actual

Predicted

Dulang Crude TBP Curves

(Actual and NMR Predicted)

0

10

20

30

40

50

60

70

80

90

100

30 80 130 180 230 280 330 380

Temperature (C)

Cum

ulat

ive

Wei

ght L

oss

(Wt%

)

Actual

Predicted

Crude Feed API D 4052 1 DegreeCrude Feed Sulfur D 2622 - D 4294 - Weight % information onlyCrude Feed TBP wt% 38 C D 2892 2.2 Weight %Crude Feed TBP wt% 105 C D 2892 2.2 Weight %Crude Feed TBP wt% 165 C D 2892 2.2 Weight %Crude Feed TBP wt% 365 C D 2892 2.2 Weight %Crude Feed TBP wt% 565 C D 2892 2.2 Weight %

FCC Feed API D 4052 1 DegreeFCC Feed Viscosity D 2161 - information onlyFCC Feed IBP D 2887 42 Degrees FFCC Feed T10 D 2887 12 Degrees FFCC Feed T50 D 2887 12 Degrees FFCC Feed T90 D 2887 12 Degrees FFCC Feed EBP D 2887 25 Degrees FFCC Feed Sulfur D 2622 - D 4294 - Weight % information onlyFCC Feed Carbon Aromaticity D 5292 2 mole %FCC Feed Carbon Naphthenicity - mole % internal proprietaryFCC Feed Carbon Parafinicity - mole % internal proprietary

CDU AGO API D 4052 1 DegreeCDU AGO T10 D 2887 12 Degrees FCDU AGO T50 D 2887 12 Degrees FCDU AGO T90 D 2887 12 Degrees FCDU AGO Sulfur D 2622 - D 4294 - Weight % information only

Method UsedReproduc

ibility UnitsParameter Description

Paul J. Giammatteo



Paul J. Giammatteo



Real Time Crude Assays• On-Line Analysis:

– Light to Heavy Crude– Accurately measured both Actual Crudes and

Blends– Database of more than 110 Crudes in the Model– Does not require exact Crude and/or Blend for an accurate

Measurement

• Universal Model– Reproducibility– Yield Curve < 2 %– Broad Range, API Gravity from >9 to 52 deg

Paul J. Giammatteo



Lagomar/Basrah 71/29GP(Lagotreco/DZO/Boscan) 95/4/1GP(Lagotreco/DZO/Boscan/Slops) 90/4/1/5GP(Lagotreco/DZO) 95/5GP(Lagotreco/Oriente/DZO/Slops) 68/23/4/5GP(Lagotreco/Oriente/DZO) 92/3/5GP(Lagotreco/Oriente/mesa/DZO) 74/14/7/5GP(Lagotreco/Oriente/mesa/DZO/slops) 51/11/28/5/5GP(Lagotreco/LagotrcoMediano/Oriente/mesa/DZO/Slops) 37/2/24/28/4/5GP(DZO/MESA/Lagotreco/LagotrcoMediano/Orientae/Slops) 5/27/42/6/12/3

Some Crude Slates and Compositions used in Isla.

GP = General Purpose Crude. Slops = refinery slop re-blends of unknown composition and quality.

Paul J. Giammatteo



Paul J. Giammatteo



Net Benefit of NMR + Optimization - $3 million/yr.

PDVSA-Curacao implemented their own Romeo Optimization project. The NMR feed forward predictions accurately measured the crude blend properties even though no individual crudes, crude blends, or, on-site lab measurements were used in the NMR crude property models.

Crude Adjustment

0

10

20

30

40

50

60

70

80

90

100

-150 50 250 450 650 850 1050CutPoint Deg C

WT%

Yie

ld

LPReconNMR

Crude Adjustment

0

10

20

30

40

50

60

70

80

90

100

-150 50 250 450 650 850 1050CutPoint Deg C

WT%

Yie

ld

LPReconNMR

Blue line represents the predicted yield

curve using only an off-line LP

program based on historical crude

properties of the blend.

Red line is the actual yield curve for the same crude blend obtained using the reconciliation function of the optimizer. The triangles are the feed forward NMR predicted yield curve demonstrating the NMR accuracy compared to the LP.

Crude Adjustment

0

10

20

30

40

50

60

70

80

90

100

-150 50 250 450 650 850 1050CutPoint Deg C

WT%

Yie

ld

LPReconNMR

Crude Adjustment

0

10

20

30

40

50

60

70

80

90

100

-150 50 250 450 650 850 1050CutPoint Deg C

WT%

Yie

ld

LPReconNMR

Blue line represents the predicted yield

curve using only an off-line LP

program based on historical crude

properties of the blend.

Red line is the actual yield curve for the same crude blend obtained using the reconciliation function of the optimizer. The triangles are the feed forward NMR predicted yield curve demonstrating the NMR accuracy compared to the LP.

Crude API 8/25-9/6/01

2526272829303132333435

0:03

:38

15:1

6:27

6:29

:22

21:4

2:25

12:5

5:32

4:08

:17

19:2

1:02

10:3

3:52

1:46

:49

18:4

9:43

10:1

0:13

1:30

:48

16:5

1:30

8:12

:22

23:3

2:13

14:5

3:09

6:14

:16

5:48

:57

21:0

7:14

12:2

5:33

Crude Switch

Tank Switch

Feed change

causing CDU

upset.

Paul J. Giammatteo



Kero Freeze 8/25-9/6/01

-56

-54

-52

-50

-48

-46

-44

-42

-400:

09:2

1

14:4

7:44

5:26

:11

20:0

4:47

10:4

3:26

1:21

:49

16:0

0:06

6:38

:27

21:1

6:55

12:5

2:00

3:53

:51

18:3

9:41

9:25

:36

0:11

:36

14:5

7:45

5:42

:54

20:2

9:08

19:3

1:01

10:1

4:35

0:58

:13

15:5

9:14

Tower Upset

Paul J. Giammatteo



Kero Flash 8/25-9/6/01

30

35

40

45

50

55

600:

09:2

1

14:4

7:44

5:26

:11

20:0

4:47

10:4

3:26

1:21

:49

16:0

0:06

6:38

:27

21:1

6:55

12:5

2:00

3:53

:51

18:3

9:41

9:25

:36

0:11

:36

14:5

7:45

5:42

:54

20:2

9:08

19:3

1:01

10:1

4:35

0:58

:13

15:5

9:14

Tower Upset

Paul J. Giammatteo



Naphtha 8/25-9/6/01

90

110

130

150

170

1900:

15:0

714

:53:

30

5:31

:57

20:1

0:32

10:4

9:12

1:27

:34

16:0

5:52

6:44

:13

21:2

2:41

13:1

5:08

4:34

:24

19:2

0:13

10:0

6:09

0:52

:12

15:3

7:18

6:23

:28

21:0

9:43

19:3

6:48

10:2

0:22

1:04

:00

15:4

7:42

T10 T50 T90 EP

Tower Upset

Paul J. Giammatteo



ASTMASTM Engineering

Method UsedReproducibility Units

Naphtha (med & Hvy) API D 4052 1Degrees F

Naphtha (med & Hvy) IBP D 86 14 Degrees FNaphtha (med & Hvy) T10 D 86 14 Degrees FNaphtha (med & Hvy) T50 D 86 14 Degrees FNaphtha (med & Hvy) T90 D 86 14 Degrees FNaphtha (med & Hvy) EBP D 86 14 Degrees FNaphtha (med & Hvy) Viscosity D 445 - % informational data onlyNaphtha (med & Hvy) Flash Point D 93 5 Degrees C

Kerosene API D 4052 1 DegreeKerosene IBP D 86 14 Degrees FKerosene T10 D 86 14 Degrees FKerosene T50 D 86 14 Degrees FKerosene T90 D 86 14 Degrees FKerosene EBP D 86 14 Degrees FKerosene Viscosity D 445 - % informational data onlyKerosene Flash Point D 56 5 Degrees CKerosene Freeze Point D 2836 3 Degrees CKerosene Cloud Point D 5773 7 Degrees CKerosene Cetane Index D 976 - D 4737 2 Index Number

Diesel API D 4052 1 DegreeDiesel IBP D 86 14 Degrees FDiesel T10 D 86 14 Degrees FDiesel T50 D 86 14 Degrees FDiesel T90 D 86 14 Degrees FDiesel EBP D 86 14 Degrees FDiesel Cloud Point D 5773 7 Degrees CDiesel Freeze Point D 2836 3 Degrees CDiesel Viscosity D 445 - % informational data onlyDiesel Cetane Index D 976 - D 4737 2 Index NumberDiesel Flash Point D 93 5 Degrees C

Light Cycle Gas Oil API D 4052 1 Degrees CLight Cycle Gas Oil IBP D 86 14 Degrees CLight Cycle Gas Oil T10 D 86 14 Degrees CLight Cycle Gas Oil T50 D 86 14 Degrees CLight Cycle Gas Oil T90 D 86 14 Degrees CLight Cycle Gas Oil EBP D 86 14 Degrees CLight Cycle Gas Oil Cloud Point D 5773 7 Degrees CLight Cycle Gas Oil Freeze Point D 2836 3 Degrees CLight Cycle Gas Oil Viscosity D 445 - % informational data onlyLight Cycle Gas Oil Cetane Index D 976 - D 4737 2 Index NumberLight Cycle Gas Oil Flash Point D 93 5 Degrees C

FCC Gasoline RON D 2699 1.7 Octane NumberFCC Gasoline MON D 2700 1.7 Octane NumberFCC Gasoline T10 D 86 14 Degrees FFCC Gasoline T50 D 86 14 Degrees FFCC Gasoline T90 D 86 14 Degrees FFCC Gasoline Aromatics detailed GC 1.1 Volume %FCC Gasoline Benzene 0.5 Volume %

Parameter Description

24 Hour NMR Data on 5 Crude Unit Rundown Streams T10, T50, T90

300350400450500550600650700750800

A. Kero (CDU1), B. Kero (CDU2), C. Diesel (CDU2), D. AGO (CDU2), E. Kero Product (Hydrotreater)

Deg

F

A.

D.

E.C.

B.

There are a total of 3 models for all 5 streams: One each for T10, T50, and T90.

Paul J. Giammatteo



Paul J. Giammatteo



SHS

CU diesel

Coker diesel

Hydrocracker feed

DensityD-86 distillation Flash pointCetane NumberCloud PointPour Point

Clean Fuels

Clean Fuels Project – Bakersfield, CA

Typical NMR Diesel Measurements

deg C7.63.8D86 T5deg C52.5D86 T10deg C5.42.7D86 T30deg C63D86 T50deg C8.64.3D86 T70deg C8.24.1D86 T90deg C84D86 T95deg C7.43.7D86 FBPdeg C4.42.2Flashg/mL0.00280.0014Density

%0.170.085Viscositydeg C31.5CloudUnits

Lab Method Reproducibility

NMR Model AccuracyParameter

Advancements in Advanced Process Analyzer Technology

Who, What, When, Where, Why and How? Or, déjà vu All Over Again!

(Part II)

Paul J. GiammatteoProcess NMR Associates, LLC NMR Process Systems, LLC

87A Sand Pit Road

Danbury, CT 06810203-744-5905

Paul J. Giammatteo



Paul J. Giammatteo



Too many spectroscopic based on-line analyzer projects (FTIR, NIR, NMR, and Raman too) have failed to meet expectations and/or

objectives due to:

•Overselling the measurements•Underestimating the sampling requirements•Trying to replace all traditional analyzers with one technique.•Déjà vu!!

3500 3000 2500 2000 1500 1000 10000 9000 8000 7000 6000 5000 4000

Atm

osph

eric

Tow

er

Vac

uum

Tow

er

Cok

erFCCU*


HTU

HTU

HTU

HTU


Gas

Pla

nt Polymerization

Alkylation

LPG

Gasoline

Aromatics

Kerosene

Distillates

Lubricant Oils

Asphalt

Coke

VGO

Gas

Lt Naphtha

Hv Naphtha

Kerosene

AGO

Crude

Residue

Olefins

i-C4

Reformate

FCC Gasoline

Naphtha

Motor Alkylate


*or Resid Cracker



BlendHead

Atm

osph

eric

Tow

er

Vac

uum

Tow

er

Cok

erFCCU*


HTU

HTU

HTU

HTU


Gas

Pla

nt Polymerization

Alkylation

LPG

Gasoline

Aromatics

Kerosene

Distillates

Lubricant Oils

Asphalt

Coke

VGO

Gas

Lt Naphtha

Hv Naphtha

Kerosene

AGO

Crude

Residue

Olefins

i-C4

Reformate

FCC Gasoline

Naphtha

Motor Alkylate


*or Resid Cracker



BlendHead

Paul J. Giammatteo



Paul J. Giammatteo



Who?• Who’s selling it?• Who wants it?• Who needs it?• Who is responsible it?• Who should be responsible?

Paul J. Giammatteo



What?• What is being sold/promised?• What is the value of the project?• What is the value of each measurement?• What will be done with the information?

Paul J. Giammatteo



When?

• When will the analyzer be delivered?• When is the project completed?

– When the site is prepared?– When the analyzer completes site acceptance?– When the analyzer is connected to the DCS?– When the analyzer is retired from service?

• When will I get the benefit?

Paul J. Giammatteo



Where?

• Where is the money coming from?• Where is the manpower coming from?• Where are we going to put it?• Where are the samples coming from?• Where is the information going?

– Control room?– Engineer’s “desk”?– Management/accounting?– Nowhere?

Paul J. Giammatteo



Why?

• Why are we doing this?– Replacement and/or update?– New measurement/control strategy?– Because!!!!!!

Paul J. Giammatteo



How?• How will the project be:

– Budgeted?– Implemented?– Supported?– Integrated?

• How complicated is this?• How beneficial is it?• How will my performance review be

affected?

Economic DriversUsually:1. Naphtha is worth more than jet.2. Jet is worth more than diesel.3. Diesel is worth more than gas oil.

The problem is pulling product to some limiting property (end point, smoke point, cloud point & freeze point).

Maybe we need better tools in the control room.

Paul J. Giammatteo



The Real WorldDiesel lost to gas oil

– Loss of diesel product– Tough product properties (cloud)– Diesel worth more than gasoline– Poor feed to FCC

– Loss of diesel product– Not much gasoline– More coke make

– New Clean Fuels Initiatives – Is 10 ppm sulfur diesel worth an average daily loss of 400 – 500 barrels of diesel production?

Can 200 to 500+ BPD of diesel and gasoline be “found”?Paul J. Giammatteo



Current Margin Differentials: Diesel v. Gas Oil

$10 - $30+ / BBL

Big West Refining, Bakersfield, CA

Installation Scheduled for 1st Quarter 2008

• 65,000 Bbl per day

• Conservative estimate leaves 2-300 bbl/day diesel from crude unit and delayed coker.

• $3,000 to $9,000+ in lost profitability

• At 350+ days !!!!!!!!!!!!

Paul J. Giammatteo



Paul J. Giammatteo



SHS

CU diesel

Coker diesel

Hydrocracker feed

DensityD-86 distillation Flash pointCetane NumberCloud PointPour Point

Clean Fuels SHS

Typical NMR Diesel Measurements

deg C7.63.8D86 T5deg C52.5D86 T10deg C5.42.7D86 T30deg C63D86 T50deg C8.64.3D86 T70deg C8.24.1D86 T90deg C84D86 T95deg C7.43.7D86 FBPdeg C4.42.2Flashg/mL0.00280.0014Density

%0.170.085Viscositydeg C31.5CloudUnits

Lab Method Reproducibility

NMR Model AccuracyParameter

Paul J. Giammatteo



Crude Unit Integrated Solution

•Distillation (D86, Sim Dis, TBP)

•Flash Point

•Cloud Point

•Pour Point

•Freeze Point

•Chemistry (Fa, Fn, Fp, Naphthalene)

•PONA/PIONA

•API Gravity/Density

•Octane/Cetane

APC and Optimization

IR

NMR

Two

Parameters

Per

Stream

$$$$$$$$$$$

NPS ISNPS IS©©NPS ISNPS IS©©

NMR Process Systems, LLC 87A Sand Pit Road

Danbury, Connecticut 06810 +203-744-5905 (ph) +203-743-9297 (fax)

www.nmr-automation.com

What the Meaning of IS© Is!

NMR Process Systems, Inc.NMR Process Systems, Inc. is a joint venture company between Process NMR Associates, LLC

(Danbury CT), and TTC Labs Inc. (Fond du Lac WI). NPS markets, installs and supports process NMR and other technology solutions for control and optimization in the refining,

petrochemical, pharmaceutical and food industries.

NPS is now advancing new concepts in process analysis by offering integrated analytical solutions into its product slate. Integrated NMR, NIR and other analyzer solutions offer

strategic reliability, sampling, and control benefits to the end user.

Paul J. Giammatteo



Documents

Process NMR Associates, LLC NMR Process Systems, LLC 87A ... EAS 2007.pdf · Process NMR Associates, LLC NMR Process Systems, Inc Actual Crude TBP Curves 0 10 20 30 40 50 60 70 80