Quantitative NMR Analysis of Wine - qNMR
Here is an example of a 1H NMR analysis of a 2007 Red Wine submitted for chemical analysis by John W.
If you are interested in wine analysis please contact us.
Contact:
(203) 744-5905
This page contains NMR Method information posted on the PNA Blog Site
Diesel Production Control - Combination of NMR and Simulated Distillation to Yield On-Line Carbon Number Distributions
Process NMR Associates has developed a database of Simulated Distillation database on a large number of diesel fuels on our Shimadzu 2010-GC with SimDis Software. The analysis is being used to develop distillation prediction models for the process NMR systems as well as explore new avenues of control information that can be derived by combining carbon number distributions obtained from the GC data with the predictive capabilities of online NMR.
For a PDF version of this application article download this: Combination of NMR and Simulated Distillation for Diesel Production Control
Simulated distillation allows carbon number distributions to be calculated and in combination with chemistry observed in the NMR analysis the effect of aromatics and olefins on the paraffin distributios can be estimated. Online NMR predictions can be established that yield real-time carbon number distributions for production control and sulfur species monitoring.
Contact: Paul Giammatteo at paul@process-nmr.com or +1 (203) 744-5905
Extensive NMR Diesel Database Enhances NMR Model Performance for Unit Control and Product ManufacturingAn extensive database (10 years) of diesel samples incorporating all refining processes (distillation through product blending) enables development of robust, wide ranging property predictions independent of crude sources and refinery processing. Consistent attention to data integrity enables expanding model ranges well beyond any typical single unit or process operation. The following slides elucidate the consistency in spectra whether obtained 10 years ago or last week, from within a refinery or on a laboratory spectrometer.
For a PDF version of this application article download this: NMR for Diesel Production Control
If you are interested in discussing the applicability of NMR to diesel production control do not hesitate to contact us at (203) 744-5905 or at paul@process-nmr.com.
September 15, 2008
Solid-State 13C NMR Analysis of Carbonaceous Materials
Over the past 20 years we have obtained the solid-state NMR analysis of pretty much every carbonaceous material that exists - including coal/oil shales/bitumen, polymers/catalysts/fibers, cellulose/polysaccharides/foodstuffs/gels, deposits/dried sewage/meteorites/soils/clays, etc. With the increased attention to coal liquifaction and gasification technologies we have developed an interest in creating an NMR database for coals. Coals were obtained from the Penn State Coal Sample Bank at a very reasonable cost. We have performed CP-MAS, DD-MAS, Variable Contact Time, and T1 inversion recovery experiments on all the samples. We are currently developing regression relationships between the NMR data and the physical and chemical testing data that is provided with the samples. At some point we will write this up as a journal article. Here are some snippets of data from the coal analysis along with a few results obtained on the menagerie of samples we look at on any given day including some oil shales, engine deposits, refinery coke, asphaltenes, and pipe tobacco.
Please inquire if you are interested in the details of the above analyses.
September 13, 2008
60 MHz TD-NMR System
Process NMR Associates and Spin Resonance Ltd have recently completed the construction a small 60 MHz (1.4T) 5mm TD-NMR system that can be utilized to study T1 and T2 characteristics of novel contrast agents at typical MRI frequencies. Here are a few pictures of the magnet. It is based on N42 neodymium-iron discs (120mm diameter x 30 mm deep).
February 28, 2008
Process NMR Application: Spectro-Molecular Control for Enhanced Diesel Recovery
NMR Process Systems – Integrated Solution
Application
for Crude Unit and Downstream Processes:
Spectro-Molecular Control for Enhanced Diesel Recovery
NMR Process Systems’ (NPS) on-line NMR based analytical and process control strategy for enhanced diesel recovery at the crude distillation unit maximizes clean diesel recovery by enabling closer cut point control in the mid-section of the CDU.
Clean Fuels regulations in both the European and American markets have had a substantial impact on a refiner’s ability to maximize product draws at the refinery front end. Extremely low sulfur requirements for gasoline and diesel have resulted in refiners now being more constrained at the hydrotreaters. Lack of reliable, focused, measurement and control of critical CDU product draws has forced many refiners to significantly undercut these draws in order to ensure minimum error in the final product blends, especially with respect to total sulfur. Depending on a refinery’s crude supply and CDU capacity, a conservative estimate of 300-500+ barrels per day of loss diesel production is typical. With an average of $25-$35 per barrel margin loss, the economic impact of these Clean Fuels Regulations are substantial.
Integrating proven NMR technology with a focused measurement and control strategy enables crude unit operations to cut “chemically” closer to the hydrotreater constraint limit. The strength of NMR is that it quantitatively and accurately “observes” the chemistry of each refinery stream and readily relates that chemistry to chemically dependent parameters such as distillation, cetane, freeze points, etc. The NPS strategy is to cut and control CDU diesel production as closely to the dibenzothiophene distillation limit as possible. Figure 1 illustrates this strategy in terms of both current and proposed NMR based measurements.
Figure 1: Overall NMR measurement and control outline highlighting measurement/control strategies.
Let NMR Process Systems deliver “Spectro-Molecular” Control to your refinery so that you can achieve real economic and production benefits.
January 28, 2008
Process NMR Associates - Archives - Gasoline Analysis by NMR and Chemometrics - ENC 1996
Just came across an old presentation on gasoline analysis by NMR and chemometrics with direct comparisons to Mid-IR and NIR. Presented at the Experimental NMR Conference in March 1996….PDF (3 MB)
Conjugated Diolefins Analysis by COSY NMR
Conjugated diolefins are responsible for fouling of many processes in a refinery. COSY NMR analysis can determine the concentration of these species in many processed petroleum product streams….see PNA webs site.
June 12, 2007
NMR Analysis of Jasmine Absolute - jasmine officinale - Egypt
NMR analysis of Jasmine Absolute.
For
more information on NMR of Essential
Oils visit the PNA website.
May 15, 2007
Omega-3 Dietary Supplements - NMR Analysis
Fish Oils - Flaxseed Oils
NMR is extensively utilized to analyze fish oils and edible oils high in omega-3 fatty acids.
Examples of 1H and 13C data and analysis are provided below:
13C NMR Analysis of Fish Oil Supplement
13C NMR of Flaxseed Oil Supplement
May 14, 2007
Wine Analysis by NMR
Brief Overview of Wine Analysis by 1H and 13C NMR
Wine analysis by 1H or 13C NMR can be used to follow acid content during maturation. Lactic, succininc and acetic acid can be followed readily by both techniques and presence of sugar, glycerol, and methanol can be observed.
Chemometric approaches are starting bear fruit with respect to quantitative analysis:
NMR Without Solvents - Biodiesel Production Process - FAME, Glycerol, FFA, and Methanol
1H and
13C NMR NMR is typically
obtained using deuterated NMR solvents
to lock the field during acquisition. In
some cases the use of these solvents is
problematic as it prevents observation
of solublized phases present in the
sample. As an example we show here the
NMR data obtained on a biodiesel
production process. One of the major
issues with the FAME product is the
presence of glycerol in the product. NMR
analysis is usually performed by
dissolving the FAME in CDCl3
in which glycerol is completely
insoluble. Thus NMR analysis performed
in this way does not allow analysis of
residual glycerol content. However, if
the FAME is run neat this issue does not
arise.
Another
analysis of enormous interest from the
process control standpoint is the
analysis of the glycerol/methanol phase.
This phase contains considerable free
fatty acids as well as the glycerol by
product and excess methanol from the
transesterification process. The three
components are readily observed by 1H
and 13C NMR, and 23Na
can be used to observe NaOH content in
the phase. Finally the shift and shape
of the observed OH resonance can yield
information on the pH of the glycerol
phase. Typically this analysis is done
in DMSO-d6
Below are some examples of NMR obtained without a deuterated solvent:
Difference in aliphatic carbon distribution between FAME phase and Free Fatty Acids (FFA)
found in the glycerol - methanol phase.
1H NMR of aliphatic component found in the FAME phase as well as the FFA in the glycerol phase.
May 10, 2007
NMR PhD Position with Damien Jeannerat at Universite de Geneve
I am posting this on behalf of Damien Jeannerat.
April 16, 2007
Monitoring of a Biodiesel Transesterification Process with a TD-NMR Spectrometer
The 19.5 MHz Spintrack NMR analyzer was utilized to study a FAME biodiesel production reaction. The samples analyzed were:
1) Used vegetable oil
2) Partially transesterified biodiesel product (bad biodiesel)
3) High yield FAME biodiesel product
4) Glycerin by-product from the process
CPMG T2 decays were generated and then that data was processed with a inverse laplace transformation to produce T2 distribution profiles.
NMR Experiment explanation is given below:
The CPMG data obtained on the four samples is shown below:
The T2 distribution profiles obtained by inverse Laplace transformation of the CPMG data are shown below:
Plainly TD-NMR can play a role in monitoring the biodiesel production process.
TD-NMR Analysis of Catalytic Cracker Feedstocks
The 19.5 MHz Spintrack NMR analyzer was utilized to study a large series of vacuum gas oils and FCC feeds for which PNA also has laboratory test data.
The analysis was performed on a SpinTrack 19.5 MHz TD-NMR spectrometer - CPMG T2 decays were generated and then that data was processed with a inverse laplace transformation to produce T2 distribution profiles. These T2 distribution profiles are currently being correlated to physical and chemical property data.
NMR Experiment explanation is given below:
The CPMG data obtained on the four samples is shown below:
The T2 distribution profiles obtained by inverse Laplace transformation of the CPMG data are shown below:
The correlation between T2 distribution and the metal content, viscosity, distillation range, density, asphaltene content are all being investigated at the current time.
April 15, 2007
13C NMR of FAME Biodiesel
Below are examples of 13C NMR data obtained on biodiesel (FAME) and the vegetable oil precursor that it was made from by transesterification process involving microwave activation of the reaction between triglycerides and methanol in the presence of a caustic catalyst. Process NMR Associates is developing correlations between 13C NMR data and biodiesel properties stipulated in ASTM 6751.
Detailed 13C NMR Analysis of Hydrocarbons - Patent Applications
Today one often finds hydrocarbon mixtures described by the detailed carbon type analysis that is possible from 13C NMR.
Many petroleum related products are being described in this way in patents leading to a novel way of describing a material and restricting others from using those same materials in products of their own. See Exxon, Mobil, and Chevron patents such as:
6,090,989 ; 6,210,559 ; 6,059,955 ; 6,846,778 ; 20050077208 ; and 20050077209
In this PDF file we have shown some of the details present in a 13C NMR spectrum on petroleum products such a base oils, gas oils, diesels, etc.
There are some issues with the assignements of many of these patents … for more details on how NMR might be of use in the patent process contact John Edwards
April 14, 2007
Naphtha Chemistry Analysis by 1H NMR
1H NMR has been used extensively by Process NMR Associates to determine PIONA analysis of Naphthas and to determine detailed aromatics breakdown in aromatics unit feeds, products, and intermediate products. Below are a few examples of naphtha chemistries that are observed and quantified by 1H NMR.
Conjugated Olefin analysis is performed by a combination of HH-COSY and 1D 1H NMR.
For more details contact John Edwards
NMR Job Opportunity - Saudi Aramco
Saudi Aramco Research and Development are searching for an experienced NMR spectroscopist - see details
Anyone who has NMR employment opportunities should contact Process NMR Associates. We would be happy to post you job listing to our blog and website.
If interested please e-mail a job description, requirements, and contact information to John Edwards
April 13, 2007
Quantifying Adulteration of Licorice With Maltodextrin by Liquid and Solid-State NMR
Three samples were analyzed to determine if liquid or solid-state NMR techniques could be utilized to quantify adulteration of licorice powders by maltodextrin. Samples analyzed were:
Maltodextrin, Licorice #1, Licorice #2
Licorice #1 and Licorice #2 were analyzed by a combination of liquid-state 1H and 13C NMR on a Varian Unity-300 spectrometer, and solid-state 13C NMR on a Varian UnityPlus 200 spectrometer. The resulting spectra are shown in the attached plots.
One of the Licorice samples is adulterated by maltodextrin to an unknown concentration, the other licorice sample is pure licorice. Which sample was which was not known during the analysis. Initially it was hoped that the addition of maltodextrin to the licorice would be readily observed as new peaks appearing in the spectrum of the licorice sample. However, it can be seen that in both the 1H and 13C NMR there is considerable overlap of the peaks in the spectra of pure licorice and maltodextrin.
When no observable maltodextrin peaks could be assigned it was decided to simply use the quantitative integral data from the regions of the spectrum where the maltodextrin overlaps with the licorice spectrum compared to the integrals obtained from regions solely assignable to licorice. In Tables 1-3 are the quantitative results for each of the experiments performed.
Table 1: 1H NMR Integral Regions
|
Normalized on Reg 4
|
|
|
|
|
Regions 1 and 2 contain maltodextrin/licorice peaks.
Regions 3 and 4 contain only licorice peaks …. Data was norma lized to region 4. The norma lization norma lizes the licorice signal intensity. Thus the increased intensity of regions 1 and 2 in sample #1 is indicative that this sample contains maltodextrin. Samples #1+ and #2+ were made by adding more maltodextrin to the samples. Sample #1+ contains a further 10.9 wt % maltodextrin, while sample #2+ contains 11.4 wt% maltodextrin. The values were used to calculate the maltodextrin content in sample #1.
The 1H analysis indicates that there is 3.3 wt% maltodextrin in sample #1
Table 2: 13C NMR Integral Regions
|
Normalize on Region 7
|
|
|
|
|
|
|
|
Regions 1-3 were common to licorice and maltodextrin signals, while regions 4-7 were exclusive to licorice signals. Normalization on region 7 sets the licorice at a norma lized intensity. Again the intensty of regions 1-3 increases from sample #2 to sample #1 indicating the presence of maltodextrin in sample #1.
Calculation indicates that there is 6.1 wt% maltodextrin in the sample.
Table 3: Solid-State 13C Integral Regions
|
Solids 13C CPMAS
|
Normalized to Reg 3
|
|
|
Region 1 contains maltodextrin and licorice signals, while regions 2 and 3 contain only licorice signals.
Again, the intensity of region 1 increases from sample #2 to 31 upon norma lization of the licorice only region 3. This confirms the presence of maltodextrin in sample #1. Samples #2+ and #1+ were not analyzed by solid-state NMR. This 13C analysis is much faster than the liquid-state NMR and would be a plausible short cut to quantify maltodextrin content.
Upon completion of the analysis it was revealed that the adulteration value was 5% maltodextrin.
March 30, 2007
Process NMR Symposia to be held at EAS 2007
John Edwards of Process NMR Associates has organized and sponsored two symposium sessions at the Eastern Analytical Symposium in Somerset New Jersey, November 12-15, 2007. One session will focus on high-resolution process NMR and the other on applications of TD-NMR in process control. The speakers and talk titles are listed below. Check the EAS site for exact details on the date and time of the sessions (EAS website). If you are interested in attending and would like to submit a paper for presentation visit the EAS Abstract submission site.
Session Title: Process NMR Technology - High Resolution NMR
John Edwards, Process NMR Associates, “Introduction to NMR in Process Control”
Miko DeLevy, Qualion NMR Analyzers, “Standardizing and Stabilizing NMR Calibration Transfer”
Paul Giammatteo, NMR Process Systems, “More from the Barrel - On-line NMR Increases Diesel Production and Quality”
Marcus Trygstad, Invensys Process Systems, “Taking NMR into the Refining Process: Best Practices and Benefits”
Andreas Kaerner , Eli Lilly, “Get Your Head Out of the Sand: Use of Reaction-NMR to Better Understand Reactions in Process Development”
Veena Bansal, Indian Oil Corporation, “Direct Prediction of Gasoline Properties for Monitoring Refinery Processes by 1H NMR Spectroscopy”
Session Title: Process NMR Technology - TD-NMR
Harry Xie, Bruker Optics, “Recent Developments in Time-domain NMR and its Applications in Polymer Industry”
Vaughn Davis, Progression Inc, “Time Domain NMR: Uses and Contributions to Process Control”
YiQiao Song, Schlumberger-Doll, “Recent Progress of NMR and MRI in Petroleum Exploration”
Maziar Sardashti, ConocoPhillips, “Applications of TD NMR to Laboratory and On-line Polymer Analysis”
Sergey Kryuchkov, University of Calgary, “Challenges in Online Water Cut Monitoring of Heavy Oil Thermal Operations Using Low Field NMR”
Chris Borgia, Colgate Palmolive, “Benchtop Fluoride NMR: A Rapid QC/QA Method”
March 25, 2007
Trans Fat Analysis by NMR
A series of Trans Fat standards was purchased from AOCS. The ability of 1H and 13C NMR to predict Trans Fat Content as well as
Saturated, Poly-unsaturated, and Mono-unsaturated Fat Content
The data of the samples is presented in the table below:
PLS regression techniques were used to correlate 1H and 13C NMR spectral variation to the unsaturation level and type of unsaturation of the samples.
Processed 13C data is shown below:
1H NMR data is shown below:
The following correlations were obtained from the 13C NMR data.
NMR Analysis of Essential Oils - Example of Sri Lankan Citronella
The data below shows the ability of 13C NMR to assign the natural product distribution found in essential oils. Once assignment of the oil hgas been obtained by 13C NMR the 1H NMR can also be assigned. For QA/QC a benchtop 60 MHz system has enough resolution that authenticity of essential oils can be performed either visually of by PCA type analysis.
Ger - Geraniol GerAc - Geranyl Acetate iEugMe - Methylisoeugenol Bor - Borneol
aPin - alpha-pinene Lim - Limonene tOci - trans-beta-Ocimene Cen - Camphene
Cllo - Citronellol Clla - Citronellal GenD - Germacrene D aCal - Citral A (Geranial)
aTol - alpha-Terpiniol cOci - cis-beta-Ocimene Myr - Myrcene
March 24, 2007
Process NMR for Transesterification Monitoring and Certification of Biodiesel
1H NMR has been used extensively to analyze biodiesel the vegetable oil feeds, reaction intermediates, and final products of the biodiesel transesterification process.
See Oliviera et al, Talanta 69 (2006) 1278-1284 and Gnothe, J. Am. Oil Chem. Soc 78, 1025-1028 (2001)
The final biodiesel product is a B5 (5% Biodiesel) or B20 (20% Biodiesel) blend of biodiesel in refinery produced diesel fuel. Researchers have performed method developments to analyze the biodiesel content in diesel fuels by NIR using 1H NMR as the primary method to quantify the biodiesel content. (See Jin et al, Fuel 86(7-8), 1201-1207 (2007) and Knothe J. Am. Oil Chem. Soc. 77 489-493 (2001). Process NMR at 60 MHz can be used to quantify the biodiesel directly. Below is an example slide of a biodiesel 1H NMR spectrum compared to two different diesel fuel spectra.
The chemistry that is directly observed in the NMR spectrum as well as the distinct chemical regions that are present in the diesel and biodiesel make this analysis relatively straightforward. Chemometrics can be used or quantitation can be obtained directly from a simple spectral calibration.
Biodiesel Production Monitoring
NMR can be used to follow the reaction of biodiesel directly, the following slides show the steps in the transesterification process.
Glycerol content in the biodiesel or unconverted vegetable oil content can be determined easily directly from the spectrum.
Expansion of Incomplete Reaction Series
Work is currently underway to develop NMR calibration models that can predict the various quality parameters specified in ASTM D6751 for biodiesel.
These calibrations, based on either 1H or 13C NMR, when validated would allow rapid testing of biodiesel production batches and would make complete analysis of small production batches economically feasible (there is no point making 300 gallons of biodiesel if you have to perform $1300 of testing on the batch).
July 28, 2006
New CAPP NMR Method - Olefin Content of Crude Oils, Condensates, and Diluents by 1H NMR
The Canadian Association of Petroleum Producers has produced a test method to quantify olefins in crude oils, condenates and diluents. The method is particularly aimed at heavy oils and bitumens and their products that are not amenable to traditional olefin analysis. The method is published at the following link. We have developed many methods similar to this and have the ability to quantify and speciate the olefins present in the sample. The current CAPP method developed by the Canadian Crude Quality Technical Association (CCQTP) can be used to obtain total olefin content. Further NMR analysis and a few other experiments would allow some more detailed olefin chemistry distributions to be determined as well as observe the presence of conjugated diolefins that would be particularly troublesome in the processing of these materials. 1H NMR spectroscopy can be used very effectively to obtain many chemical and physical properties of crudes, heavy crudes, bitumen, and the distillate products that are produced by these materials. 1H NMR spectral correlation with these properties by PLS or non-linear PLS regression can yield extremely robust models, and for the chemical properties much more detailed chemical structure information can be obtained fro combining 13C NMR data with 1H NMR results.