Process NMR Associates

RCC Feedstream Analysis by 1H and 13C NMR: Multivariate Prediction of Chemical and Physical Properties
By John C. Edwards , Ph.D. Process NMR Associates, LLC, 87A Sand Pit Rd, Danbury CT USA Jincheol Kim, SK Energy Co., Ltd, SK Energy Technology Center, 140-1, Wonchon-dong, Yuseong-gu, Daejeon 305-712, Korea

At the 236th ACS National Meeting, Philadelphia PA, August 17-21, 2008

Process NMR Associates

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 Process NMR Project Suppliers

Facilities:

Two Qualion 60 MHz Process MRA Units

300 MHz NMR (Liquids) and 200 MHz NMR (Solids) Oxford Instruments 20 and 2 MHz Bench-top NMR Resonance Systems NMR Spectrometer 20 MHz Bench-top and Surface Analyzer Shimadzu GC-2010 Simulated Distillation Smiths Detection FTIR-ATR

Business:

Application Development for Process NMR Technology Process NMR Instrumentation Development and Implementation Analytical NMR Services for 300+ Commercial and Academic Customers Process and Laboratory NMR Database Development Licensing of Copyrighted NMR Databases and Patented Applications TTC Labs, USA (ttclabs.com) Modcon Systems, Israel (modcon-systems.com) Qualion, Israel (qualion-nmr.com) Smiths Detection, USA (smithsdetection.com) Resonance Systems, Russia (mobilenmr.com) Swagelok, USA (swagelok.com) Triangle Analytical, USA (triangleanalytical.com)

Business Partners:

Process NMR Associates

NMR Analyzers

Process NMR Associates

Application: Steam Cracking Optimization Installed 2000

Cracker Facility Capacity: 600,000 Tonnes per Year Control Strategy: Feed Forward Detailed Hydrocarbon Analysis to SPYRO Optimization NMR Analysis: 3-4 Minute Cycle (Single Stream) NMR PLS Outputs: Naphtha Detailed PIONA C4-C10 n-paraffin, i-paraffin, aromatics, naphthenes

Process NMR Associates

Application: Closed Loop Reformer Control

Installed 1998

Reformer Capacity: 34,000 Barrels per Day Control Strategy: Control on MON and Benzene Content NMR Analysis: 2 Minute Analysis NMR PLS Outputs: RON, MON, Benzene (Wt%), Total Aromatics (Wt%)

Col 2, line 8, These base stocks are premium synthetic lubricating oil base stocks of high purity having a high VI, a low pour point and are iso-paraffinic, in that they comprise at least 95 wt. % of non-cyclic iso-paraffins having a molecular structure in which less than 25% of the total number of carbon atoms are present in the branches, and less than half the branches have two or more carbon atoms.

Col 4, line 5-14, with at least 50% of the oil molecules containing at least one branch, at least half of which are methyl branches. At least half, and more preferably at least 75% of the remaining branches are ethyl, with less than 25% and preferably less than 15% of the total number of branches having three or more carbon atoms. The total number of branch carbon atoms is typically less than 25%, preferably less than 20% and more preferably no more than 15% (e.g., 10-15%) of the total number of carbon atoms comprising the hydrocarbon molecules. Col 4, line 24-29, Thus, the molecular make up of a base stock of the invention comprises at least 95 wt. % isoparaffins having a relatively linear molecular structure, with less than half the branches having two or more carbon atoms and less than 25% of the total number of carbon atoms present in the branches. Col 12, Line 4-21, What is claimed is: 1. A lubricant base stock comprising at least 95 wt. % non-cyclic iso-paraffins having a molecular structure in which less than 25% of the total number of carbon atoms of the isoparaffin structure are contained in the branches and less than half of the total iso-paraffin branches contain two or more carbon atoms. 2. A base stock according to claim 1 wherein at least half of the iso-paraffin branches are methyl branches. 3. A base stock according to claim 2 wherein at least half of the remaining, non-methyl branches are ethyl, with less than 25% of the total number of branches having three or more carbon atoms. 4. A base stock according to claim 3 wherein at least 75% of the non-methyl branches are ethyl. 5. A base stock according to claim 4 wherein of the total number of carbon atoms contained in the iso-paraffin molecule, 1015% of the carbon atoms are located in the branches.

Process NMR Associates

Quantitative 13C NMR of F-T Wax

Process NMR Associates

45

40

35

30

25

20

15

10

ppm

Quantitative 13C NMR of F-T Wax - Vertical Expansion

Process NMR Associates

1H-13C

DEPT NMR of F-T Wax

CH3 Carbons

CH2 Carbons

CH Carbons

All Protonated Carbons

45 40 35 30 25 20 15 10 ppm

Process NMR Associates

Exxon FT-wax Patent

Process NMR Associates

' '

'

Sub-Me 2-Me t-Bu 3-Me p-Bu 4-Me

t-pr p-pr
Adj-Me

t-et p-et

60

55

50

45

40

35

30

25

20

15

ppm

Reg1

Reg2

Reg3

Reg4

Reg5

Reg6

Peak X

Process NMR Associates

' '
Peak X 2-Me t-Bu p-Bu Adj-Me 3-Me 4-Me Sub-Me

t-pr p-pr t-et p-et

30

28

26

24

22

20

18

16

14

12

ppm

Reg3

Reg4

Reg5

Reg6

Process NMR Associates

Process NMR Associates

Process NMR Associates

Residual Catalytic Cracking Feed-stream Analysis

Analysis Refractive Index, Distillation, Specific Gravity Calculation Watson K-Factor Outcome: aromatic carbon number aromatic hydrogen number total hydrogen content

Proposition: Detailed hydrocarbon analysis for kinetic model development

25

20

60 MHz Process 1H NMR Data

50 Samples

15

10

0 20 .25 .2 .15 .1 .05 0 30 35 40 45 50 55 60 10 15 40 60 80 100 120 140

CH2

Aromatic Region
20

Aliphatic Region

CH3

0 85 90 95 100 105 110 115 120 125

Process NMR Associates

300 MHz - 1H NMR RCC Feeds
120

100

80

60

40

20

20

40

60

80

100

Aromatic Region Mono Di Tri

15
250

20

25

30

35

Aliphatic Region
200

CH2

150

100

CH+Nap
50

CH3

Alpha-Protons

0 55 60 65 70 75 80 85 90 95 100

Parameter 1

1H - Type Analysis
Total aromatic Diaromatic+ protons Monoaromatic protons Total olefinic RHC=CH2 RHC=CHR RHC=CH2 Oxygenates protons Total protons to aromatics a-CH to aromatics a-CH2 to aromatics a-CH3 to aromatics Saturates Paraffinic CH Paraffinic CH3 Paraffinic CH3 Substituted aromatic carbon Bridgehead carbons Total aromatics (wt %) Mono aromatics (wt %) Di+ aromatics (wt %) Benzene (wt %) Olefin functions (wt %) Oxygenates (wt %) Saturates (wt %)

Process NMR Associates H-Type NMR Analysis Depicted as a Spectrum

80

2 3 4 5 6 7 8 9 10

60

11 12 13

40

14 15 16 17

20

18 19 20 21

22 23

10

15

20

24 25

Process NMR Associates Aliphatics

200

13C NMR Data

150

100

50

Aromatics
0

50

100

150

200

Process NMR Associates Aromatic Region

40

50

60

70

80

90

Aliphatic Region

140

150

160

170

180

190

Calculated C-Type Parameters

Index 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Carbon Type Parameters (%C Unless Otherwise Listed) Ketone carbonyl carbon %c Aldehyde carbonyl carbon Carboxylic acids, esters and amides carbonyl carbon Phenoxy carbon CH2 & CH sub aromatic carbon Naphthenic sub aromatic carbon CH3 sub aromatic carbon Half of internal aromatic carbon Index 26 27 28 29 30 31 32 33 Carbon Type Parameters (%C Unless Otherwise Listed) Aliphatic methine carbon (CH) Aliphatic methylene carbon (CH2) Aliphatic methyl carbon (CH3) Total paraffinic carbon Paraffinic methine carbon (CH) Paraffinic methylene carbon (CH2) Paraffinic methyl carbon (CH3) Total naphthenic carbon Naphthenic methine carbon (CH) Naphthenic methylene carbon (CH2) Naphthenic methyl carbon (CH3)
Reg1 a'

Index 51 52 53 54 55 56 57 58 59 60 61 62 63

Carbon Type Parameters (%C Unless Otherwise Listed) b 2-Me Aromatic a methyl carbon All other-Me 3-Me Reg7 p-Pr t-Pr 4-Me a t-Ethyl p-Ethyl Linear Paraffin Structure: % Linear Paraffin/Total Paraffin Waxiness : % Epsilon C/Total Paraffin Branching Index: %Branching CC/Total Paraffin Total Branching Content: % C Near Branching C/Total C C in Branched Environment: % 1-linear paraffin structure Average Straight Chain Length (C No.) Methyl branching index Ethyl branching Index Propyl branching Index Butyl branching Index Total ethyl branching content Total propyl branching content Total butyl branching content

Protonated Internal aromatic C+ 1/2 internal aromatic C 34 Protonated aromatic carbon Heteroaromatic other than phenoxy carbon Methine carbon Methylene carbon Methyl carbon Total carbonyl carbon Total aromatic carbon Aliphatic sub aromatic carbon Methyl-substituted aromatic carbon CH2 & CH substituted aromatic carbon Naphthenic substituted aromatic carbon Internal aromatic carbon Peripheral unsubstituted aromatic carbon Total heteroaromatic carbon Total olefinic carbon Total aliphatic carbon 35 36

37 38 39 40 41 42 43 44 45 46 47 48 49 50

Reg2

64
g Reg3 g' e d Reg4 b' Reg5 p-Bu t-Bu Peak x

65 66 67 68 69 70 71 72 73 74 75

Process NMR Associates

80

60

C-Type NMR Parameters Depicted as a Spectrum

40

20

10

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50

60

70

Process NMR Associates

Summary of RCC Feed NMR Analysis Correlations to Physical/Chemical Properties

Resonance Frequency Parameter Densityat15oC ViscosityIndex MCRT SULPHUR CarbonAromaticity HYDROGEN TotalAromatics Monoaromatics Diaromatics TriAromatics Tetra+aromatics 60MHzProton 1HNMR0.1ppm Bin 0.961 0.940 0.931 0.958 0.925 0.936 0.930 0.927 0.941 0.913 300MHzProton 1HNMR 0.1ppm Bin 0.983 0.951 0.952 0.964 0.951 0.914 0.946 0.941 0.945 0.911 0.921 HTypeSpectrum 0.924 0.727 0.855 0.926 0.819 0.904 0.912 0.866 0.862 0.656 75MHzCarbon13 13CNMR 1ppm Bin 0.982 0.935 0.931 0.979 0.998 0.922 0.965 0.954 0.951 0.939 0.912 CTypeSpectrum 0.974 0.875 0.962 0.997 0.862 0.941 0.897 0.897 0.863 0.934

Density by 13C NMR 1

0.98

0.96 Predicted Density (g/

0.94

0.92

0.9

13C

NMR Correlation to Density

0.88

0.86
density.tdf,3

0.84 0.84

0.86

0.88

0.9

0.92

0.94

0.96

0.98

Actual Density (g/ml)

.0005

-.001

-.0025 0 30 60 90 120 150 180

1H NMR - Density Correlation

1

0.98

0.96 Predicted Density (g/ 0.94

1H NMR Correlation to Density

0.92

0.9

0.88 0.86

density_1h.tdf,7
0.84 0.84 0.86 0.88 0.9 0.92 0.94 .004 0.96 0.98 1

Actual Dens (g/ml) ity

Process NMR Associates

.001

-.002

-.005 0

30

60

90

Density - H-Type Parameters

1

0.98

0.96 Predicted Density (g/

0.94

0.92

0.9

0.88

.08
0.86

0.84 0.84

.05
0.86 0.88 0.9 0.92 0.94 0.96 0.98 1 Actual Dens (g/ml) ity

.02

Density Correlation with Proton Type Parameters

-.01

-.04 0

12

18

24

Density - C-Type Parameters

1

0.98

0.96

Predicted Density (g/

0.94

Density Correlation with Carbon Type Parameters

0.92

0.9

0.88

0.86

.0025
0.84 0.84

0.86

0.88

0.9

0.92

0.94

0.96

0.98

Actual Dens (g/ml) .001 ity

-.0005

-.002 0

15

30

45

60

density_13c_calculated.tdf,5 (R = 0.980019145)

.97

Variable Selection Process

Predicted Concentration ( F6 C1 )

38

.94

1 28 43 16 1926 4 10 52 842 44 56 35 4830 23 47 21

29

Reduces Number of Variables Linear Equations that Describe Density in terms of 13 Carbon Type Parameters

.91
34 46 37 50 41 40 49 25 54 7 55 18 39

27

12 24 20 17

31

.88
9 32 15 14 22

6 51

33

.85

.86

.89

.92

.95

.98

Actual Concentration ( C1 )

Correlation of 1H and 13C NMR Spectra to 13C Derived Parameters

13C Parameter Total aromatic carbon Aliphatic substituted aromatic carbon Methyl-substituted aromatic carbon CH2 & CH substituted aromatic carbon Naphthenic substituted aromatic carbon Internal aromatic carbon Peripheral unsubstituted aromatic carbon Total heteroaromatic carbon Total aliphatic carbon Aliphatic methine carbon (CH) Aliphatic methylene carbon (CH2) Aliphatic methyl carbon (CH3) Total paraffinic carbon P methine carbon (CH) P methylene carbon (CH2) P methyl carbon (CH3) Total naphthenic carbon N methine carbon (CH) N methylene carbon (CH2) N methyl carbon (CH3) N methine/N methylene ratio Mole fraction of bridgehead aromatic carbon Aromatic carbons per aromatic group 1H NMR 0.980 0.962 0.970 0.935 0.973 0.949 0.950 0.275 0.952 0.932 0.976 0.610 0.984 0.876 0.987 0.810 0.964 0.927 0.957 0.809 0.085 0.448 0.697 13C NMR 0.996 0.999 0.994 0.996 0.996 0.994 0.996 0.976 0.997 0.999 1.000 0.996 0.995 0.940 0.998 0.960 0.989 0.996 0.987 0.966 0.878 0.899 0.895 13C Parameter Cluster number (=aromatic group number) Aliphatic substitutions per cluster Methyl-substitutions per cluster CH2 & CH substitutions per cluster Naphthenic substitutions per cluster Heteroatoms per cluster Naphthenic CH3 per cluster # of naphthenic ring carbons per cluster Naphthenic rings per cluster # of paraffinic carbons per cluster Average chain length of paraffinic substitutions Linear paraffin structure Waxiness : e/total paraffin Branching index Total branching content Carbons in branched environment Average straight chain length Methyl branching index Ethyl branching Index Propyl branching Index Butyl branching Index Total ethyl branching content Total propyl branching content Total butyl branching content

1H NMR 0.941 0.087 0.379 0.063 0.227 0.032 0.449 0.524 0.317 0.892 0.913 0.972 0.977 0.973 0.964 0.972 0.967 0.972 0.945 0.919 0.919 0.946 0.919 0.917

13C NMR 0.995 0.906 0.909 0.899 0.910 0.926 0.906 0.924 0.939 0.934 0.932 0.976 0.983 0.972 0.972 0.976 0.986 0.962 0.945 0.932 0.951 0.946 0.933 0.950

Process NMR Associates

1H

and 13C NMR Correlation to Carbon Aromaticity

Carbon Aromaticity Correlated to 13C Spectra
30

Carbon A aticity Corrletaed by 1H NMR rom

30

25

25

Predicted Fa (%

Predicted Fa (%

20

20

15

15

10
10

5 5 10 15 Actual Fa (% C) 20 25 30
5 5 10 15 Actual Fa (% C) 20 25 30

Process NMR Associates 1H and 13C NMR Correlation to Branching Index

13C NMR Branching Index - 1H NMR
12 11 Predicted Branching Ind
Predicted Branching Ind 12 11 10 9 8 7 6 5 4 3

13C NMR Branching Index - 13C NMR

10 9 8 7 6 5 4 3 3 4 5 6 7 8 9 10 11 12 Actual Branching Index

10

11

12

Actual Branching Index

Branching Carbons/Total Paraffinic Carbons

Process NMR Associates

Summary
Chemical and Physical Properties of RCC Feedstreams can be determined by 1H NMR (at 60 and 300 MHz) and by 13C NMR H-Type and C-Type Parameters do not provide as good a correlation as is observed by full spectrum regression. This is due to loss of resolved chemical shift information when the spectrum is reduced to larger integral areas.
1H

NMR can be combined with PLS regression modeling to provide detailed carbon type analysis for RCC Feeds

Regression analysis of 13C NMR data can be utilized to fully automate the prediction of 13C NMR type analysis : reducing the necessity for considerable knowledge and analysis time on the part of the analyst.

Process NMR Associates

Parallel Work
Similar analysis has been performed on: Crude Oil - TBP, Density, Water Canadian Syncrude - Olefins, Density, Distillation Vacuum Residues Distillation, Density, 13C Parameters Naphtha Density, PIONA, Distillation Gasoline Octane, Benzene, Oxygenates, Distillation, Aromatics Kerosene Distillation, Smoke Point Jet Fuel Cloud Point, Freeze Point, Distillation, Density Diesel Density, Cloud point, Flash, Distillation, Cetane Index Reformate Octanes, Benzene, Aromatics Alkylate Octane, Distillation Lubricant Oil Pour, VI, Distillation, 13C Parameters FT-Waxes 13C Parameters VGO FCC Feeds (Same as RCC Feeds) Biodiesel