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 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
Process NMR Associates
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.”
Process NMR Associates
Quantitative 13C NMR of F-T Wax
p p m1 01 52 02 53 03 54 04 5
Process NMR Associates
Quantitative 13C NMR of F-T Wax - Vertical Expansion
p p m1 01 52 02 53 03 54 04 5
Process NMR Associates
1H-13C DEPT NMR of F-T Wax
All Protonated Carbons
CH Carbons
CH2 Carbons
CH3 Carbons
Process NMR Associates Exxon FT-wax Patent
Process NMR Associates
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
Process NMR Associates
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 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
Process NMR Associates
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
Process NMR Associates
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”
Process NMR Associates
0
50
100
150
200
0 50 100 150 200
Aromatics
Aliphatics
13C NMR Data
Process NMR Associates
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
Carbon Type Parameters (%C Unless Otherwise Listed)Index
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
Carbon Type Parameters (%C Unless Otherwise Listed)Index
Calculated C-Type Parameters
Process NMR Associates
0
20
40
60
80
0 10 20 30 40 50 60 70
C-Type NMR ParametersDepicted as a “Spectrum”
Process NMR Associates
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
Actual Density (g/ml)
Pre
dict
ed D
ensi
ty (g
/
Process NMR Associates
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
Actual Density (g/ml)
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
Actual Density (g/ml)
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
Process NMR Associates
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
Process NMR Associates
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
Process NMR Associates
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.
Process NMR Associates
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