RCC Feedstream Analysis by 1H and 13C NMR: Multivariate ... · RCC Feedstream Analysis by 1H and 13C NMR: Multivariate Prediction of Chemical and Physical Properties By John C. Edwards

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


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 DevelopmentProcess NMR Project Suppliers

Facilities: Two Qualion 60 MHz Process MRA Units300 MHz NMR (Liquids) and 200 MHz NMR (Solids)Oxford Instruments 20 and 2 MHz Bench-top NMRResonance Systems NMR Spectrometer – 20 MHz Bench-top and Surface AnalyzerShimadzu GC-2010 – Simulated DistillationSmiths Detection – FTIR-ATR

Business: Application Development for Process NMR TechnologyProcess NMR Instrumentation Development and ImplementationAnalytical NMR Services for 300+ Commercial and Academic CustomersProcess and Laboratory NMR Database DevelopmentLicensing of Copyrighted NMR Databases and Patented Applications

Business Partners: 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)

Process NMR Associates NMR Analyzers


Application: Steam Cracking Optimization Installed 2000Cracker Facility Capacity: 600,000 Tonnes per YearControl Strategy: Feed Forward Detailed Hydrocarbon Analysis to SPYRO OptimizationNMR Analysis: 3-4 Minute Cycle (Single Stream)NMR PLS Outputs: Naphtha – Detailed PIONA

C4-C10 n-paraffin, i-paraffin, aromatics, naphthenes

Process NMR AssociatesApplication: Closed Loop Reformer Control Installed 1998Reformer Capacity: 34,000 Barrels per DayControl Strategy: Control on MON and Benzene ContentNMR Analysis: 2 Minute AnalysisNMR PLS Outputs: RON, MON, Benzene (Wt%), Total Aromatics (Wt%)

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. % isoparaffinshaving 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, 10-15% of the carbon atoms are located in the branches.”

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.”


Quantitative 13C NMR of F-T Wax

p p m1 01 52 02 53 03 54 04 5


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

p p m1 01 52 02 53 03 54 04 5


1H-13C DEPT NMR of F-T Wax

All Protonated Carbons

CH Carbons

CH2 Carbons

CH3 Carbons

Process NMR Associates Exxon FT-wax Patent


ppm15202530354045505560

β

γ

δ

ε

α' β'γ'

t-etp-et

p-pr

t-pr

Sub-Me

4-Me

Adj-Me

3-Me

2-Me

t-Bu

p-Bu

Reg1 Reg2 Reg3 Reg4 Reg5 Reg6

α

Peak X

p p m1 21 41 61 82 02 22 42 62 83 0

δ β'γ'

β

t-etp-et

p-pr

t-pr

Sub-Me

4-Me

Adj-Me

3-Me

2-Me

t-Bu

α

p-Bu

Peak X

Reg6Reg5Reg4Reg3





Residual Catalytic Cracking – Feed-stream Analysis

Analysis – Refractive Index, Distillation, Specific Gravity

Calculation – Watson K-Factor

Outcome: aromatic carbon numberaromatic hydrogen numbertotal hydrogen content

Proposition: Detailed hydrocarbon analysis for kinetic model development

0

5

10

15

20

25

20 40 60 80 100 120 140

0

.05

.1

.15

.2

.25

30 35 40 45 50 55 60

0

5

10

15

20

85 90 95 100 105 110 115 120 125

Aliphatic Region

CH3

CH2

Aromatic Region

60 MHz Process – 1H NMR Data

50 Samples


0

20

40

60

80

100

120

0 20 40 60 80 100

300 MHz - 1H NMR – RCC Feeds

0

20

40

60

80

100

120

0 20 40 60 80 100

Aromatic Region

15 20 25 30 35

Mono

Di

Tri

0

50

100

150

200

250

55 60 65 70 75 80 85 90 95 100

Aliphatic Region

CH3

CH2

Alpha-Protons

CH+Nap


0

20

40

60

80

0 5 10 15 20

Saturates (wt %)25

Oxygenates (wt %)24

Olefin functions (wt %)23

Benzene (wt %)22

Di+ aromatics (wt %)21

Mono aromatics (wt %)20

Total aromatics (wt %)19

Bridgehead carbons18

Substituted aromatic carbon17

Paraffinic CH316

Paraffinic CH315

Paraffinic CH14

Saturates13

a-CH3 to aromatics12

a-CH2 to aromatics11

a-CH to aromatics10

Total α protons to aromatics9

Oxygenates protons8

RHC=CH27

RHC=CHR6

RHC=CH25

Total olefinic4

Monoaromatic protons3

Diaromatic+ protons2

Total aromatic1

1H - Type AnalysisParameter

H-Type NMR AnalysisDepicted as a “Spectrum”


0

50

100

150

200

0 50 100 150 200

Aromatics

Aliphatics

13C NMR Data


Aromatic Region

40 50 60 70 80 90

140 150 160 170 180 190

Aliphatic Region

Total aliphatic carbon25

Total olefinic carbon24

Total heteroaromatic carbon23

Peripheral unsubstituted aromatic carbon22

Internal aromatic carbon21

Naphthenic substituted aromatic carbon20

CH2 & CH substituted aromatic carbon19

Methyl-substituted aromatic carbon18

Aliphatic sub aromatic carbon17

Total aromatic carbon16

Total carbonyl carbon15

Methyl carbon14

Methylene carbon13

Methine carbon12

Heteroaromatic other than phenoxy carbon11

Protonated aromatic carbon10

Protonated Internal aromatic C+ 1/2 internal aromatic C9

Half of internal aromatic carbon8

CH3 sub aromatic carbon7

Naphthenic sub aromatic carbon6

CH2 & CH sub aromatic carbon5

Phenoxy carbon4

Carboxylic acids, esters and amides carbonyl carbon3

Aldehyde carbonyl carbon2

Ketone carbonyl carbon %c1

Carbon Type Parameters (%C Unless Otherwise Listed)Index

Peak x50

t-Bu49

p-Bu48

Reg547

b'46

Reg445

d44

e43

g'42

Reg341

g40

Reg239

a'38

Reg137

Naphthenic methyl carbon (CH3)36

Naphthenic methylene carbon (CH2)35

Naphthenic methine carbon (CH)34

Total naphthenic carbon33

Paraffinic methyl carbon (CH3)32

Paraffinic methylene carbon (CH2)31

Paraffinic methine carbon (CH)30

Total paraffinic carbon29

Aliphatic methyl carbon (CH3)28

Aliphatic methylene carbon (CH2)27

Aliphatic methine carbon (CH)26


Total butyl branching content75

Total propyl branching content74

Total ethyl branching content73

Butyl branching Index72

Propyl branching Index71

Ethyl branching Index70

Methyl branching index69

Average Straight Chain Length (C No.)68

C in Branched Environment: % 1-linear paraffin structure67

Total Branching Content: % C Near Branching C/Total C66

Branching Index: %Branching CC/Total Paraffin 65

Waxiness : % Epsilon C/Total Paraffin64

Linear Paraffin Structure: % Linear Paraffin/Total Paraffin63

p-Ethyl62

t-Ethyl61

a60

4-Me59

t-Pr58

p-Pr57

Reg756

3-Me55

All other-Me54

Aromatic a methyl carbon53

2-Me52

b51


Calculated C-Type Parameters


0

20

40

60

80

0 10 20 30 40 50 60 70

C-Type NMR ParametersDepicted as a “Spectrum”


0.9340.9120.6560.9210.913Tetra+ aromatics

0.8630.9390.8620.9110.941TriAromatics

0.8970.9510.8660.9450.927Diaromatics

0.8970.9540.9120.9410.930Monoaromatics

0.9410.9650.9040.9460.936Total Aromatics

0.8620.9220.8190.9140.925HYDROGEN

0.9970.9980.9260.9510.958Carbon Aromaticity

0.9620.9790.8550.9640.931SULPHUR

0.8750.9310.7270.9520.940MCRT

‐0.935‐0.951‐Viscosity Index

0.9740.9820.9240.9830.961Density at 15oC

C‐Type Spectrum13C NMR‐ 1 ppm BinH‐Type Spectrum1H NMR ‐ 0.1 ppm Bin1H NMR 0.1 ppm BinParameter

75 MHz Carbon‐13300 MHz Proton60 MHz ProtonResonance Frequency

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

Density by 13C NMR

0.84

0.86

0.88

0.9

0.92

0.94

0.96

0.98

1

0.84 0.86 0.88 0.9 0.92 0.94 0.96 0.98 1

Actual Density (g/ml)

Pre

dict

ed D

ensi

ty (g

/

density.tdf,3density.tdf,3

-.0025

-.001

0 30 60 90 120 150 180

.0005

0 30 60 90 120 150 180

13C NMR Correlation to Density

1H NMR Correlation to Density

1H NMR - Density Correlation

0.84

0.86

0.88

0.9

0.92

0.94

0.96

0.98

1

0.84 0.86 0.88 0.9 0.92 0.94 0.96 0.98 1


Pre

dict

ed D

ensi

ty (g

/


density_1h.tdf,7density_1h.tdf,7

-.005

-.002

.001

.004

0 30 60 90-.005

-.002

.001

.004

0 30 60 90

Density - H-Type Parameters

0.84

0.86

0.88

0.9

0.92

0.94

0.96

0.98

1

0.84 0.86 0.88 0.9 0.92 0.94 0.96 0.98 1


Pred

icte

d D

ensi

ty (g

/

-.04

-.01

.02

.05

.08

0 6 12 18 24 -.04

-.01

.02

.05

.08

0 6 12 18 24

Density Correlation withProton Type Parameters

Density - C-Type Parameters

0.84

0.86

0.88

0.9

0.92

0.94

0.96

0.98

1

0.84 0.86 0.88 0.9 0.92 0.94 0.96 0.98 1


Pred

icte

d De

nsity

(g/

-.002

-.0005

.001

.0025

0 15 30 45 60 -.002

-.0005

.001

.0025

0 15 30 45 60

Density Correlation withCarbon Type Parameters

density_13c_calculated.tdf,5 (R² = 0.980019145)density_13c_calculated.tdf,5 (R² = 0.980019145)

Actual Concentration ( C1 )Actual Concentration ( C1 )

Pre

dict

ed C

once

ntra

tion

( F6

C1

)P

redi

cted

Con

cent

ratio

n ( F

6 C

1 )

.85

.88

.91

.94

.97

.86 .89 .92 .95 .98

.85

.88

.91

.94

.97

.86 .89 .92 .95 .98

1

2

3

4

5

6

7

8

9

10

12

1415

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

37

38

39

4041

42

43

44

46

4748

49

5051

52

54

55

56

.85

.88

.91

.94

.97

.86 .89 .92 .95 .98

Variable Selection Process

Reduces Number of Variables

Linear Equations that DescribeDensity in terms of 13 CarbonType Parameters

0.8950.697Aromatic carbons per aromatic group

0.8990.448Mole fraction of bridgehead aromatic carbon

0.8780.085N methine/N methylene ratio

0.9660.809N methyl carbon (CH3)

0.9870.957N methylene carbon (CH2)

0.9960.927N methine carbon (CH)

0.9890.964Total naphthenic carbon

0.9600.810P methyl carbon (CH3)

0.9980.987P methylene carbon (CH2)

0.9400.876P methine carbon (CH)

0.9950.984Total paraffinic carbon

0.9960.610Aliphatic methyl carbon (CH3)

1.0000.976Aliphatic methylene carbon (CH2)

0.9990.932Aliphatic methine carbon (CH)

0.9970.952Total aliphatic carbon

0.9760.275Total heteroaromatic carbon

0.9960.950Peripheral unsubstituted aromatic carbon

0.9940.949Internal aromatic carbon

0.9960.973Naphthenic substituted aromatic carbon

0.9960.935CH2 & CH substituted aromatic carbon

0.9940.970Methyl-substituted aromatic carbon

0.9990.962Aliphatic substituted aromatic carbon

0.9960.980Total aromatic carbon

13C NMR

1H NMR13C Parameter

0.9500.917Total butyl branching content

0.9330.919Total propyl branching content

0.9460.946Total ethyl branching content

0.9510.919Butyl branching Index

0.9320.919Propyl branching Index

0.9450.945Ethyl branching Index

0.9620.972Methyl branching index

0.9860.967Average straight chain length

0.9760.972Carbons in branched environment

0.9720.964Total branching content

0.9720.973Branching index

0.9830.977Waxiness : e/total paraffin

0.9760.972Linear paraffin structure

0.9320.913Average chain length of paraffinic substitutions

0.9340.892# of paraffinic carbons per cluster

0.9390.317Naphthenic rings per cluster

0.9240.524# of naphthenic ring carbons per cluster

0.9060.449Naphthenic CH3 per cluster

0.9260.032Heteroatoms per cluster

0.9100.227Naphthenic substitutions per cluster

0.8990.063CH2 & CH substitutions per cluster

0.9090.379Methyl-substitutions per cluster

0.9060.087Aliphatic substitutions per cluster

13C NMR0.995

1H NMR0.941

13C Parameter

Cluster number (=aromatic group number)

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


Carbon Aromaticity Corrletaed by 1H NMR

5

10

15

20

25

30

5 10 15 20 25 30

Actual Fa (%C)

Pre

dict

ed F

a (%

Carbon Aromaticity Correlated to 13C Spectra

5

10

15

20

25

30

5 10 15 20 25 30

Actual Fa (%C)

Pred

icte

d Fa

(%

1H and 13C NMR Correlation to Carbon Aromaticity


13C NMR Branching Index - 1H NMR

3

4

5

6

7

8

9

10

11

12

3 4 5 6 7 8 9 10 11 12

Actual Branching Index

Pred

icte

d Br

anch

ing

Ind

13C NMR Branching Index - 13C NMR

3

4

5

6

7

8

9

10

11

12

3 4 5 6 7 8 9 10 11 12

Actual Branching Index

Pred

icte

d Br

anch

ing

Ind

1H and 13C NMR Correlation to Branching Index

Branching Carbons/Total Paraffinic Carbons


Summary

Chemical and Physical Properties of RCC Feedstreams can be determinedby 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 observedby 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 carbontype analysis for RCC Feeds

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


Parallel Work

Similar analysis has been performed on:

Crude Oil - TBP, Density, WaterCanadian Syncrude - Olefins, Density, DistillationVacuum Residues – Distillation, Density, 13C ParametersNaphtha – Density, PIONA, DistillationGasoline – Octane, Benzene, Oxygenates, Distillation, AromaticsKerosene – Distillation, Smoke PointJet Fuel – Cloud Point, Freeze Point, Distillation, DensityDiesel – Density, Cloud point, Flash, Distillation, Cetane IndexReformate – Octanes, Benzene, AromaticsAlkylate – Octane, DistillationLubricant Oil – Pour, VI, Distillation, 13C ParametersFT-Waxes – 13C ParametersVGO – FCC Feeds (Same as RCC Feeds)Biodiesel

Documents

RCC Feedstream Analysis by 1H and 13C NMR: Multivariate ... · RCC Feedstream Analysis by 1H and 13C NMR: Multivariate Prediction of Chemical and Physical Properties By John C. Edwards