pulse, acquire, control: ten years of on-line high ...may 02, 2005 · process nmr associates mra...

Process NMR Associates

Pulse, Acquire, Control: Ten years of On-Line High Resolution NMR in Refining,

Petrochemical, and Food Manufacturing

Presented By

John Edwards, Ph.D.Process NMR Associates, LLC

Danbury, Connecticut

May 2, 2005ACS Meeting: Mid-Hudson Section

Vassar College, Poughkeepsie


Company: Process NMR Associates, LLC

Founded : 1997

Personnel: 2 Ph.D. Chemists

Background: Analytical and Process Spectroscopy in Petroleum and Petrochemical Industry Process NMR Applications and Support Under Contract to Invensys (1997-2003)Process and Analytical NMR Instrumentation Development

Facilities: 2 Invensys 58 MHz Process MRA Units300 MHz NMR (Liquids)200 MHz NMR (Solids)

Business: Application Development for Process NMR TechnologyProcess NMR Instrumentation DevelopmentAnalytical NMR Services for Commercial and Academic CustomersProcess NMR Database DevelopmentLicensing of Copyrighted NMR Databases and Patented Applications


Presentation Overview

• NMR Basics – Briefly

• Advantages/Disadvantages as a Process Spectroscopy

• Applications1. Reformer Unit Control2. Crude Distillation Unit Control and Optimization3. Naphtha Steam Cracking Control and Optimization

• Application Snippets

Aromaticity – FCC, Base Oil ManufactureStyrene-Butadiene RubbersAromaticsFood

• Conclusion


pp m1234567

CH3

CH3

CH3

O

OHA

B

C

D E F

G

H

A

F

B

CG

H

D E

PEG OH

PEG

ppm4060801001201 401 60

CH3

CH3

CH3

O

OHA

B

C

D E F

G

H

I J

HI

J

D E

F

A

B

G

C

PEG

CDCl3

FT-13C FT-1H

300 MHz

A

F

B

C

GH

D E

PEG OH

PEG

58 MHz

TD-NMRLow Field, FID, Curve-Fitting


TD-NMR PAT Applications+ Tablet hardness / density testing+ Contactless weighing of tablets+ Moisture in powders / tablets+ Moisture in lipophilized proteins+ Total oil / solvent content+ Droplet size distribution of emulsions+ Pore-size of encapsulated liquids


Industrial MRI Applications


TD-NMR - One Sided NMR MOUSE


TD-NMRDownhole Drilling Tool


High Resolution FT-NMRhttp://www.liposcience.com/


High Resolution FT-NMR - MetabonomicsMetabolism Analysis by NMR – Toxicological Screening


Superconducting NMR Systems


High Resolution FT-NMR – Online / in Process


NMR Innovations Developed to Bring NMR On-Line

• Permanent Magnet Stability and Design

• Shimming Protocols

• Flow-Through Probe Technology

• Post Processing Developments

Robust auto-phasing routines

Frequency Domain Averaging

Post-processing monitoring of each constituent spectrumfor heavy stream analyses where sediment/rust may be present.


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 Without Impact

Disadvantages:Solids Cannot be Observed in a Liquid StreamIndividual 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 (Exceptions Na, P, F, Al)


H-Types Observed in a Gasoline 1H NMR Spectrum

8 7 6 5 4 3 2 1 0

CH

RR

HH

R

H

R

H

R

H

HR

CH2CH3

CH3

CH3

PPMOxygenate

H-Types Observed in a Gasoline 1H NMR Spectrum

8 7 6 5 4 3 2 1 0

CH

RR

HH

R

H

R

H

R

H

HR

CH2CH3

CH3

CH3

PPMOxygenate

8 7 6 5 4 3 2 1 0

CH

RR

HH

RR

HH

R

H

R

H

R

H

HR

R

H

R

H

R

H

HR

R

H

HR

CH2CH3

CH3CH3

CH3

PPMOxygenate


H2O


Lab and On-Line InstallationsLab Installations

Planned Installations

Equilon, LATosco

BRC

Aramco FPCC

PDVSA Reliance

MotivaFina

EquistarValero Pertamina

BP BASF

Petrochina

AGIP

On-Line Installation - Foods

Invensys Process NMR Installations

Shell

Tnuva

4/29/02

ORLERG

PNAInvensys


Application: Closed Loop Reformer Control

Reformer Capacity: 34,000 Barrels per Day

Control Strategy: Control on MON and Benzene Content

NMR Analysis: 2 Minute Analysis

NMR PLS Outputs: RONMONBenzeneTotal Aromatics

Value Added: Initially - Maximize Benzene Content of Reformate at 1 Wt%Conservatively 4 cents per Barrel (Can Be Much More)

Performance : NMR Available 98%+ For Past 4 YearsModels Updated Once in Past 4 YearsValue Gained From Control $10,000 - $35,000 / Week


RON Validation - April 2001 - April 2002

100

101

102

103

104

105

106

107

108

1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39

NMRCFR

SEP = 0.33 Octane


Application: Crude Distillation Unit Optimization and Control

Crude Unit Capacity: 180,000 Barrels per Day

Control Strategy: Control on Kero Freeze PointCrude Tower Optimization

NMR Analysis: 15 Minute CycleNMR Results into ROMEO CDU Optimization Package

NMR PLS Outputs: Naphtha – T10, T50, T90, EP Kero – Freeze, FlashCrude – API, Sulfur, TBP (38, 105, 165, 365, 565C)

Value Added: Kero - Approach Freeze Point Limit – Worth $600K/YearCDU Optimization- Conservatively 4 cents per Barrel

Performance : NMR Available 98% 2000-2004


SSC &

MRA


Crude Fast Loop Crude Fast Loop HeaterHeater


MRA Sample System

Crude Brought into NMR at 70C (Crude Fast Loop Heater)

Kerosene and Naphtha Also Brought to NMR at 70C(Sample Heater With PID Control at NMR SSC

All Samples are routed to crude sample return and Pass Through CDU Again

Double Block-and-Bleed and Flushing Protocol to Prevent Cross Contamination of Light Ends With Crude.


-60

-55

-50

-45

-40

-35

-30

2002

/05/

01

2002

/05/

0220

02/0

5/03

2002

/05/

04

2002

/05/

0520

02/0

5/06

2002

/05/

07

2002

/05/

0820

02/0

5/09

2002

/05/

10

2002

/05/

11

2002

/05/

1220

02/0

5/13

2002

/05/

14

2002

/05/

1520

02/0

5/16

2002

/05/

17

2002

/05/

1820

02/0

5/19

2002

/05/

20

Freeze NfreezeKero Lab v. NMR


Crude Analysis


Crude Adjustment

0

10

20

30

40

50

60

70

80

90

100

-150 50 250 450 650 850 1050

CutPoint Deg C

WT%

Yie

ld

BeforeAfterNMR

Crude Crude ReconciliationReconciliation


Application: Steam Cracking Optimization

Cracker Facility Capacity: 600,000 Tonnes per Year

Control Strategy: Feed Forward Detailed Hydrocarbon Analysis to SPYROOptimization Package

NMR Analysis: 3-4 Minute Cycle (Single Stream)16 Minute Cycle (4 Feed Streams)

NMR PLS Outputs: Naphtha – Detailed PIONAC4-C10 n-paraffin, i-paraffin, aromatics, naphthenes

Value Added: Unit Optimization - $150K /year 4 Units Now Being Optimized ($600K/year)

Performance : NMR Available 98%+ Since August 2000Models Updated in a Limited Manner


Steam Cracker Optimization - Project Timeline Feasibility Performed (30 Samples) – December 1999

Further Model Expansion (90 Samples) – December 1999-March 2000

Online System Installed – April 2000

On-Line Localization and Further Model Expansion (65 Sampes)– May to July 2000

Validation Period – 1 Month 100% Availability Within Specified Accuracy Limit - Aug 2000

System Validated and Accepted – September 2000

Add Validation Period Samples to Models – (Models now contain 215 Samples)

NMR Put on Control (Detailed PIONA into SPYRO Model for Unit Optimization) Oct 2000

Models have been performing relatively untouched (6 parameters updated on 4 occasions) since end of validation period.

98+% Availability September 2000 – September 2004

March 2002 – Three Further Feed-Streams Added to NMR


Cyclopentane

5/17

5/24

5/31 6/7 6/14

6/21

6/28 7/5 7/12

7/19

7/26 8/2 8/9 8/16

8/23

8/30 9/6

Date

Wt% GC

NMR


Parameter R Std Dev Mean Devn-c4 0.9340 0.52 0.067n-c5 0.9761 0.73 -0.004n-c6 0.9616 0.73 -0.093n-c7 0.9840 0.33 -0.032n-c8 0.9882 0.29 -0.008n-c9 0.9918 0.18 -0.003n-c10 0.9716 0.13 0.022Total n-paraffin 0.9840 0.81 0.013I-c4 0.8765 0.07 0.001I-c5 0.9834 0.76 0.043i-C6 0.9865 0.59 -0.050i-C7 0.9119 0.46 -0.015i-C8 0.9800 0.42 -0.035i-C9 0.9905 0.26 0.010i-C10 0.9866 0.24 0.013i-C11 0.9613 0.08 -0.007Total I-paraffin 0.9617 0.81 -0.011cyclopentane 0.9821 0.14 -0.004me-cyclopentane 0.9937 0.23 -0.018Cyclohexane 0.9940 0.26 0.034Methylcyclohexane 0.9872 0.29 0.001Other C7-Nap 0.9025 0.32 -0.052c8-Nap 0.9713 0.36 0.002c9-Nap 0.9892 0.28 0.026c10-Nap 0.8950 0.06 -0.001Total Naphthenes 0.9794 0.83 0.019Benzene 0.9950 0.10 0.006Toluene 0.9920 0.17 0.007Ethylbenzene 0.9902 0.04 0.002Xylenes 0.9951 0.14 0.003C9 - Arom 0.9875 0.16 0.006C10-arom 0.9586 0.07 0.001Total Aromatics 0.9967 0.31 0.022

Single PLS Model for Each GC Component

Low Model Maintenance

SPYRO Optimization and APC Utilize Real Time Analysis

4 Crackers Now Covered by 1 NMR

Multiple GC Analyzers Replaced Reduced Maintenance

Reduced Laboratory Participation

Other Installations:Expanding Model Base to Cover Gas Oils andMixed Naphtha/Gas Oil Blend Operation


0

5

10

15

20

25

20 40 60 80 100 120 140

Arbitrary Y / Arbitrary X Overlay Z-Zoom CURSOR

File #16 = RFYOG33 9/7/00 2:40 PM Res=None

Foxboro NMR SPC File.

Milk

Half and Half

Light Cream

Sour Cream

Reduced Fat Yogurt

Strawberry Yogurt

Block Cream Cheese

Tub Cream Cheese

Light Cream Cheese

Fat Free Cream Cheese

Margarine

Butter

Water and Fat Content models were built using all products listed. All products

were purchased from a local supermarket.

Water and fat contents (weight percent) were estimated using food label

information only.

Initial model results: R2 > 0.96

error <1 wt%

Process NMR – Dairy


010 8 6 4 2 0 -2

Butter - before phase separation

Cis/trans olefins

CH and alpha

to olefins

Water

CH2

CH3

10 8 6 4 2 0 -2

Cis/trans olefins

CH and alpha

to olefins

CH2

CH3

Butter - after phase separation

Process NMR

Butter


0

5

10

15

20 40 60 80 100 120 140

0

5

10

15

20 40 60 80 100 120 140

Water

Unsaturated fat regionCarbohydrates

and sugars

Saturated fat and protein

Overlay of 4 Cream Cheese Products

Regular BlockRegular TubLightFat-Free


Process NMR – 23Na Monitoring of Sodium Content in Food

0

20000

40000

60000

80000

6600 6800 7000 7200 7400 7600 7800 8000 8200

0

20000

40000

60000

80000

6600 6800 7000 7200 7400 7600 7800 8000 8200

7750 7800 7850 7900 7950 8000 8050 8100 7750 7800 7850 7900 7950 8000 8050 8100

Whiskeys, Vodkas, Gin, Rum

Lower Alcohol Liquors

Non Alcoholic Beer

BeersWine

Port


Process NMR – Alcoholic Beverages

0

20000

40000

60000

80000

100000

7000 7200 7400 7600 7800 8000

0

20000

40000

60000

80000

100000

7000 7200 7400 7600 7800 8000

Exchangable carbohydrate hydroxylsand H2O (Peak moves depending oncarbohydrate concentration).

Carbohydrates


Process NMR – “Fruit” Juices


ConclusionHigh Resolution FT-NMR has

Left the Research Laboratory…. and is Arriving in a Process

Near You!

See Further Information at http://www.process-nmr.com


Acknowledgements

Paul Giammatteo – PNA

Tony Van Poyenbroeck – Cardoen Technology, Belgium

Our NMR Customers

pulse, acquire, control: ten years of on-line high ...may 02, 2005 · process nmr associates mra...

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