Giammatteo Online NMR EAS 2007

8/14/2019 Giammatteo Online NMR EAS 2007

1/45

More From the Barrel

On-Line NMR Increases Diesel Production

and Quality (Part I)

Paul J. Giammatteo

Process NMR Associates, LLCNMR Process Systems, LLC

87A Sand Pit Road

Danbury, CT 06810

203-744-5905

Paul J. Giammatteo

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

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


2/45

On-line, high resolution nuclear magnetic resonance spectroscopy

(NMR) made its introduction into refinery processes twelve yearsago with installation of two units into Texacos Los Angeles arearefinery. From then to now, integration of the proper NMR hardwarewith the properly designed applications have proven economicallyand operationally beneficial. Whether the on-line NMR application

serves as a preferred multi-parameter analyzer, or, integrated intoadvanced process control and optimization, the accuracy, reliability,and performance of on-line NMR delivers true value throughout therefining process.

Paul J. Giammatteo



Refinery Applications


3/45

Advantages and Disadvantages of NMR Applied to Process

Advantages:Non-Optical Spectroscopy

No Spectral Temperature Dependence

Minimal Sampling Requirements

Spectral Response to Sample Chemistry is Linear

Chemical Regions of NMR Spectra are Orthogonal

Entire Volume is Sampled by the RF Experiment

Water is in Distinct Region and can be digitally removed

Detailed Hydrocarbon information is readily observed.

Fundamental Chemical Information Can be Derived Directly from Spectrum.

Colored/Black Samples Readily Observed

Disadvantages:

Solids Cannot be Observed

Individual 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




4/45

Paul J. Giammatteo



NMR - What a differenceone letter can make!!

.2

.4

.6

.8

1

10000 9000 8000 7000 6000 5000 4000

NIRTypical Variability Observed in

Gasoline Blending


5/45

8 7 6 5 4 3 2 1 0 -10

.5

1

1.5

2

2.5

3 CH

RR

HH

R

H

R

H

R

H

H

R

CH2

CH3

CH3

CH3CH-C= and

57 M Hz

Aromatic Olefinic Water OxygenateMethyl

AromaticAliphatic

Hydrocarbon Picture

Paul J. Giammatteo




6/45

Paul J. Giammatteo




7/45

ASTM ASTM Engineering

Method Used Reproducibility UnitsGasoline Blending RON D 2699 0.4 Octane

Gasoline Blending MON D 2700 0.4 Octane

Gasoline Blending T10 D 86 9.50 Degrees F



Gasoline 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 Degree

Diesel Blending IBP D 86 14 Degrees FDiesel Blending T10 D 86 14 Degrees F

Diesel Blending T50 D 86 14 Degrees F

Diesel Blending T90 D 86 14 Degrees F

Diesel Blending EBP D 86 14 Degrees F

Diesel Blending Viscosity D 445 - informational data only

Diesel Blending Cloud Point D 5773 7 Degrees CDiesel Blending Cetane Index D 976 - D 4737 2 Index Number

Diesel Blending Pour Point D 97 6 Deg C

Parameter Description

Paul J. Giammatteo




8/45

Paul J. Giammatteo



Aramco

BASF

Petrochina

High Resolution Process NMR Installations

ORL

PNA

Aramco

BASF

Petrochina


ORL

PNA

Aramco

BASF

Petrochina


ORL

PNA


PNA


9/45

AtmosphericTower

VacuumTower

Coker

FCCU*

Hydrocracker

Desalter

HTU

HTU

HTU

HTU

ReformerAromatics

Extraction

GasPlant

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/AvJet

Distillate Streams

*or Resid Cracker

HeavyOil

Upgrading

Unit

Current Commercial

NMR Units

Blend

Head

AtmosphericTower

VacuumTower

Coker

FCCU*

Hydrocracker

Desalter

HTU

HTU

HTU

HTU

ReformerAromatics

Extraction

GasPlant

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/AvJet

Distillate Streams

*or Resid Cracker

HeavyOil

Upgrading

Unit

Current Commercial

NMR Units

Blend

Head

Paul J. Giammatteo




10/45

Paul J. Giammatteo



Effective feedstock management can save up to70 cents/barrel for refineries.

.modern analytical tools contribute significantlyto this .

Hydrocarbon Processing,

September 1998

In 1998 crude was less than $30/barrel.

What about $100+?


11/45

Paul J. Giammatteo



NMR NeSSI: Never expect Small Sample Input!


12/45

Paul J. Giammatteo




13/45

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


14/45

Paul J. Giammatteo



0

5

10

15

20

10 8 6 4 2 0

NMR Spectra ShowingSpectral Variability of 6 Crudes

ppm

CH

CH2

CH3CH3

CH3


15/45

Paul J. Giammatteo



Actual Crude TBP Curves

0

10

20

30

40

50

60

70

80

90

100

30 130 230 330

Temperature (C)

C

um

ulative

W

eightLoss

(W

t%

)

KuwaitMarib Light

Nemba

GOS Mix

DulangBacho

Actual Crude TBP Curves

0

10

20

30

40

50

60

70

80

90

100

30 130 230 330

Temperature (C)

C

um

ulative

W

eightLoss

(W

t%

)

KuwaitMarib Light

Nemba

GOS Mix

DulangBacho

NMR Predicted TBP Curves for Crudes

0

10

20

30

40

50

60

70

80

90

100

30 130 230 330

Temperature (C)

C

um

ulativ

e

W

eightLoss(W

t%

)

NMR Predicted TBP Curves for Crudes

0

10

20

30

40

50

60

70

80

90

100

30 130 230 330

Temperature (C)

C

um

ulativ

e

W

eightLoss(W

t%

)


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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

ulative

W

eightLoss

(W

t%

)

Actual

Predicted

Marib Light Crude TBP Curves


0

10

20

30

40

50

60

70

80

90

100

30 130 230 330

Temperature (C)

Cum

ulative

W

eightLoss

(W

t%

)

Actual

Predicted

Dulang Crude TBP Curves


0

10

20

30

40

50

60

70

80

90

100

30 80 130 180 230 280 330 380

Temperature (C)

Cum

ulative

W

eightLoss

(W

t%

)

Actual

Predicted

Dulang Crude TBP Curves


0

10

20

30

40

50

60

70

80

90

100

30 80 130 180 230 280 330 380

Temperature (C)

Cum

ulative

W

eightLoss

(W

t%

)

Actual

Predicted


17/45

Crude Feed API D 4052 1 DegreeCrude Feed Sulfur D 2622 - D 4294 - Weight % information only

Crude Feed TBP wt% 38 C D 2892 2.2 Weight %





FCC Feed API D 4052 1 Degree

FCC Feed Viscosity D 2161 - information only

FCC Feed IBP D 2887 42 Degrees F

FCC Feed T10 D 2887 12 Degrees F



FCC Feed EBP D 2887 25 Degrees FFCC Feed Sulfur D 2622 - D 4294 - Weight % information only

FCC Feed Carbon Aromaticity D 5292 2 mole %

FCC Feed Carbon Naphthenicity - mole % internal proprietary

FCC Feed Carbon Parafinicity - mole % internal proprietary

CDU AGO API D 4052 1 Degree

CDU AGO T10 D 2887 12 Degrees FCDU AGO T50 D 2887 12 Degrees F

CDU AGO T90 D 2887 12 Degrees F

CDU AGO Sulfur D 2622 - D 4294 - Weight % information only

Method Used

Reproduc

ibility UnitsParameter Description

Paul J. Giammatteo




18/45

Paul J. Giammatteo




19/45

Real Time Crude Assays On-Line Analysis:

Light to Heavy Crude

Accurately measured both Actual Crudes andBlends

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




20/45

Lagomar/Basrah 71/29

GP(Lagotreco/DZO/Boscan) 95/4/1

GP(Lagotreco/DZO/Boscan/Slops) 90/4/1/5

GP(Lagotreco/DZO) 95/5GP(Lagotreco/Oriente/DZO/Slops) 68/23/4/5

GP(Lagotreco/Oriente/DZO) 92/3/5

GP(Lagotreco/Oriente/mesa/DZO) 74/14/7/5GP(Lagotreco/Oriente/mesa/DZO/slops) 51/11/28/5/5

GP(Lagotreco/LagotrcoMediano/Oriente/mesa/DZO/Slops) 37/2/24/28/4/5

GP(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 unknowncomposition and quality.

Paul J. Giammatteo




21/45


22/45

Crude API 8/25-9/6/01

25

2627

28

29

30

31

32

33

34

35

0:03:38

15:16:27

6:29:22

21:42:25

12:55:32

4:08:17

19:21:02

10:33:52

1:46:49

18:49:43

10:10:13

1:30:48

16:51:30

8:12:22

23:32:13

14:53:09

6:14:16

5:48:57

21:07:14

12:25:33

Crude Switch

Tank Switch

Feed change

causing CDU

upset.

Paul J. Giammatteo




23/45

Kero Freeze 8/25-9/6/01

-56

-54

-52

-50

-48

-46

-44

-42

-40

0:0

9:21

14:4

7:44

5:2

6:11

20:0

4:47

10:4

3:26

1:2

1:49

16:0

0:06

6:3

8:27

21:1

6:55

12:5

2:00

3:5

3:51

18:3

9:41

9:2

5:36

0:1

1:36

14:5

7:45

5:4

2:54

20:2

9:08

19:3

1:01

10:1

4:35

0:5

8:13

15:5

9:14

Tower Upset

Paul J. Giammatteo




24/45

Kero Flash 8/25-9/6/01

30

35

40

45

50

55

60

0:0

9:21

14:4

7:44

5:2

6:11

20:0

4:47

10:4

3:26

1:2

1:49

16:0

0:06

6:3

8:27

21:1

6:55

12:5

2:00

3:5

3:51

18:3

9:41

9:2

5:36

0:1

1:36

14:5

7:45

5:4

2:54

20:2

9:08

19:3

1:01

10:1

4:35

0:5

8:13

15:5

9:14

Tower Upset

Paul J. Giammatteo




25/45

Naphtha 8/25-9/6/01

90

110

130

150

170

190

0:15

:07

14:53

:30

5:31

:57

20:10

:32

10:49

:12

1:27

:34

16:05

:52

6:44

:13

21:22

:41

13:15

:08

4:34

:24

19:20

:13

10:06

:09

0:52

:12

15:37

:18

6:23

:28

21:09

:43

19:36

:48

10:20

:22

1:04

:00

15:47

:42

T10 T50 T90 EP

Tower Upset

Paul J. Giammatteo




26/45

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 only

Naphtha (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 only

Kerosene 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 only

Diesel 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 C

Light Cycle Gas Oil T90 D 8614

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 only

Light 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 F

FCC Gasoline T90 D 86 14 Degrees FFCC Gasoline Aromatics detailed GC 1.1 Volume %FCC Gasoline Benzene 0.5 Volume %

Parameter Description


27/45

24 Hour NMR Data on 5 Crude Unit Rundown Streams

T10, T50, T90

300

350

400

450

500

550

600

650

700

750

800

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

E. Kero Product (Hydrotreater)

DegF

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




28/45

Paul J. Giammatteo



SHS

CU diesel

Coker diesel

Hydrocracker feed

DensityD-86 distillationFlash point

Cetane NumberCloud PointPour Point

Clean Fuels

Clean Fuels Project Bakersfield, CA


29/45

Typical NMR Diesel Measurements

deg C7.63.8D86 T5

deg C52.5D86 T10

deg C5.42.7D86 T30deg C63D86 T50

deg C8.64.3D86 T70

deg C8.24.1D86 T90

deg C84D86 T95deg C7.43.7D86 FBP

deg C4.42.2Flash

g/mL0.00280.0014Density

%0.170.085Viscositydeg C31.5Cloud

UnitsLab MethodReproducibility

NMR ModelAccuracyParameter


30/45

Advancements in Advanced ProcessAnalyzer Technology

Who, What, When, Where, Why and How?

Or, dj vu All Over Again!

(Part II)

Paul J. GiammatteoProcess NMR Associates, LLC

NMR Process Systems, LLC

87A Sand Pit Road

Danbury, CT 06810

203-744-5905

Paul J. Giammatteo




31/45

Paul J. Giammatteo



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

Overselling the measurements

Underestimating the sampling requirementsTrying to replace all traditional analyzers with one technique.Dj vu!!

3500 3000 2500 2000 1500 100010000 9000 8000 7000 6000 5000 4000


32/45


33/45

Paul J. Giammatteo



Who? Whos selling it?

Who wants it?

Who needs it?

Who is responsible it? Who should be responsible?


34/45

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?


35/45

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?


36/45

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?

Engineers desk?

Management/accounting?

Nowhere?


37/45

Paul J. Giammatteo



Why? Why are we doing this?

Replacement and/or update?

New measurement/control strategy?

Because!!!!!!


38/45

Paul J. Giammatteo

Process NMR Associates, LLC www.process-nmr.comNMR Process Systems, Inc www.nmr-automation.com

How? How will the project be:

Budgeted?

Implemented?

Supported?

Integrated?

How complicated is this?

How beneficial is it?

How will my performance review beaffected?


39/45

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 limitingproperty (end point, smoke point, cloud point &freeze point).

Maybe we need better tools in the control room.

Paul J. Giammatteo



40/45

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 dieselworth an average daily loss of 400 500 barrels ofdiesel production?

Can 200 to 500+ BPD of diesel and gasoline be found?

Paul J. Giammatteo



41/45


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Paul J. Giammatteo


SHS

CU diesel

Coker diesel

Hydrocracker feed

DensityD-86 distillationFlash point

Cetane NumberCloud PointPour Point

Clean FuelsSHS


43/45

Typical NMR Diesel Measurements

deg C7.63.8D86 T5

deg C52.5D86 T10

deg C5.42.7D86 T30

deg C63D86 T50

deg C8.64.3D86 T70

deg C8.24.1D86 T90

deg C84D86 T95

deg C7.43.7D86 FBP

deg C4.42.2Flash

g/mL0.00280.0014Density%0.170.085Viscosity

deg C31.5Cloud

UnitsLab MethodReproducibility

NMR ModelAccuracyParameter


44/45

Paul J. Giammatteo

Process NMR Associates, LLCwww.process-nmr.com


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

$$$$$$$$$$$


45/45

NPS ISNPS ISNPS ISNPS IS

NMR Process Systems, LLC87A 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 analyticalsolutions 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

Process NMR Associates, LLCwww.process-nmr.com


Giammatteo Online NMR EAS 2007

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