John Edwards and Paul Giammatteo of Process NMR Associates have written a chapter “Process NMR Spectroscopy: Technology and On-Line Applications” to appear in the 2nd Edition of “Process Analytical Technology” published by Wiley and Sons and Edited by Katherine Bakeev. The book will be published in May 2010 and is available for pre-order.
The use of an NMR as a simple flow detector for benchtop reaction monitoring, mixing monitoring, dilution monitoring, or conversion monitoring has been limited by the need to bring the “reaction” to the typical “supercon” NMR lab. We are introducing a continuous flow NMR system that can be on the benchtop. The system uses a high resolution 60 MHz permanent magnet with a simple flow cell and total system volumes of 2 to 5 ml depending on the length and diameter of the transfer tubing. Further, detection limits of analytes in the 200+ ppm range are possible without the use of typical deuterated NMR solvents. Analysis times of 5 to 20 seconds are also possible at flow rates of 5 to 20+ ml/minute.
As an example, we observed the Hydrogen bonding exchange rate between the OH protons on isopropyl alcohol with the hydrogen of water as a function of increasing water concentration. Figure 1 shows the starting spectrum (blue) of “of the shelf” 91 vol % IPA obtained at the local pharmacy flowing through the NMR at 10 ml/min. At this concentration, the IPA OH hydrogen and water hydrogen are spectrally distinct. The red spectrum is the final spectrum after 50 minutes of slowing adding water to the original IPA to bring the IPA concentration to approximately 76 vol %. At the end of the dilution, the OH peaks from IPA and water are in complete exchange as represented by the single peak.
Figure 1: “Off the Shelf” Isopropyl Alcohol at the original concentration of 91 vol % IPA (blue) and diluted to 76 vol % (red).
Figure 2 shows the results of the sequential addition of 20 0.5 ml aliquots of water that take the original 91% IPA to its final concentration of 76%. As shown in Figure 3, one can readily observe the convergence of the OH peaks as the dilution progresses.
Figure 2. Continuous flow NMR dilution monitoring of 91% by volume isopropyl alcohol with water to a final concentration of 76%.
Figure 3. Continuous flow NMR monitoring of OH hydrogen exchange between water and isopropyl alcohol as a function of IPA concentration.
Continuous Flow NMR was also used to monitor solute addition in a non-mixed vessel. In this experiment a concentrated table sugar solution (2.19 molar) was injected every 100 seconds at an injection volume of 0.083 ml each for the first 30 minutes (1 ml total) with two final injections of 0.5 ml each. Starting volume of water was 25 ml. Total volume of sugar solution injected was 2.0 ml representing 1.5 grams of table sugar. Flow rate through the NMR flow cell was 10 ml/min with a total NMR sample volume (tubing + flow cell) was 5 ml. Again, no solvent suppression was applied.
Figure 4 shows the overall spectra through the entire run. Figure 5 shows the expansion of the water/carbohydrate region showing the sensitivity of the 60 MHz flow NMR to sugar concentration.
Figure 4. Overall flow NMR results for concentrated sugar solution addition to water.
Figure 5. Water/carbohydrate region expansion showing table sugar addition to water.
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 Tel: +1 (203) 744-5905
An 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.
If you are interested in finding out more about NMR and diesel production control contact Paul Giammatteo or phone him at +1 (203) 744-5905 – see the Process NMR Associates website for further information
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 refiners 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 hydro-treaters. 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 observesthe 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.
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)
Title:
Process Analytical Technology (PAT) Manager
Description:
Implement Process Analytical Technology (PAT) throughout all the Global Quality Sites to identification of incoming materials and monitor manufacturing processes.
Work directly with the sites and Schering Plough Research Institute to help support / initiate the development, validation, and deployment of PAT at the sites.
Review, evaluate, implement, and manage PAT activities.
Provide guidance / technical help to the sites to conduct evaluation and purchase commercial PAT related analytical equipment (e.g. NIR / FT-NIR, Raman / FT-Raman, IR / FT – IR etc.).
Maintain analytical instruments in the lab to comply with cGMP standards and requirements.
Train and mentor laboratory staff on PAT to generate analytical data for routine experiments.
Generate network and infrastructures with various sites of the corporation.
Take full ownership / responsibility and provide effective, meaningful, result driven and pro-active leadership on all PAT projects.
Responsible to transfer knowledge / technology of PAT related projects and activities to sites. Job is located in New Jersey.
Respectfully, Vincent L. Graziano
Recruiting Manager / Global Staffing
Schering-Plough Corporation
556 Morris Avenue, S1-1
Summit, N.J. 07901
Ph: 908-473-2745
Fx: 908-473-2793
Ph: 908-298-5232 (Kenilworth)
Careers: Employment Opportunities
email: vincent.graziano@spcorp.comÂ
Press Release – NMR Process Systems – Swagelok Technology Conference, Teaneck NJ - October 23, 2007
NMR Process Systems, LLC Announces : NPS-IS© – NPS Integrated Solutions
NMR Process Systems (NPS) announces a new era in advanced analyzer and process control solutions for on-line and at-line process applications. NPS’s Integrated Solutions (NPS-IS©) approach is designed to take advanced on-line analysis to the next level in delivering real engineering and economic benefit to the user.
NPS-IS©: the first and original source for any and all on-line NMR applications regardless of NMR vendor.
NPS-IS©: the first to offer integrated advanced analytical solutions using multiple technologies in one box.
NPS-IS©: the first to offer a fully integrated Swagelok sampling solution for improved sample switching and reliable measurement.
Too many spectroscopic based on-line analyzer projects (FTIR, NIR, NMR) have failed to meet expectations and/or objectives due to:
·Overselling the measurement
·Underestimating the sampling requirements
·Trying to replace all traditional analyzers with one technique.
NMR Process Systems is positioned to deliver the real benefits of advanced analytical systems in petroleum, petrochemical, chemical, food and beverage and pharmaceutical applications. Moving beyond the traditional replacement analyzer philosophy, NPS-IS© integrating analyzers and advanced controls to deliver real process improvement and economic benefit. Such integration leverages the strength of any individual spectroscopy, shortens per stream analysis time, and builds in internal cross-checking to ensure accuracy.
For more information contact Paul Giammatteo Principal, NMR Process Systems
87A Sand Pit Rd, Danbury, CT 06810 U.S.A. Tel: (203) 744-5905
Press Release – NMR Process Systems – Gulf Coast Conference, Galveston Island, Texas - October 17, 2007
NMR Process Systems, LLC and Smith’s Detection Launch RefinIRTM – The New Refinery Products Analyzer
In a joint development effort NMR Process Systems and Smith’s Detection have developed a range of petroleum analyzer products based on a mid-infrared spectrometer which utilizes an attenuated total reflection (ATR) sample interface. The ATR allows wipe and swipe sample introduction that is ideal for heavy petroleum analysis. Chemometric approaches to chemical and physical property prediction have been developed as well as analysis by spectral database matching. The FTIR-ATR spectrometer is called the RefinIR which can be utilized in the laboratory for rountine, multi-parameter prediction of petroleum product properties or to aid in process troubleshooting on unusual samples or solid foulants.
For more information contact Paul Giammatteo Principal, NMR Process Systems
87A Sand Pit Rd, Danbury, CT 06810 U.S.A. Tel: (203) 744-5905
In a joint development effort Process NMR Associates and Resonance Systems Ltd have developed a replacement NMR spectrometer for the Oxford QP-20 TD-NMR analyzer. In many cases the excellent magnet and probe of the QP-20 continue to work effectively long after the NMR spectrometer has died. The Spin Track-20 spectrometer enables the user to completely replace the QP-20 NMR system while retaining the use of the original magnet and probe configuration. The product represents state-of-the-art digital NMR technology allowing newly developed TD-NMR methodologies to be applied to complex systems with all the advantages of a windows computer system (replacing the paper cartridge of the original system). Customers who have malfunctioning QP-20 NMR systems can obtain a modern digital NMR system within 8 weeks of order and for less than $16,000. The modular design of the Spin Track TD-NMR systems allows our engineers to develop replacement systems for all benchtop NMR systems such as those marketed by Oxford Instruments, Bruker Minispec, and Resonance Systems. Contact us if you have a non-functioning system that might be a candidate for the Spin Track upgrade.
For more information contact John Edwards Principal, Process NMR Associates – Spin Track Division
87A Sand Pit Rd, Danbury, CT 06810 U.S.A. Tel: (203) 744-5905
State University of New York
College of Environmental Science and Forestry (SUNY-ESF)
Syracuse, NY, 13210
Alumni Lounge– Marshall Hall
October 12, 2007
| SUNY-ESF | Syracuse University | SUNY Upstate Medical University | Bristol-Myers Squibb |
| Art Stipanovic | Phil Borer | Stewart Loh | Doug Weaver |
| Dave Kiemle | Stephan Wilkens |
The 9th annual Upstate NY NMR Symposium will be held at SUNY-ESF on Friday, October 12th featuring keynote speaker Professor Ruth E. Stark, Director Institute for Macromolecular Assemblies, CUNY. Others from around the region will also highlight their work in short presentations and posters.
There is no cost to attend this symposium due to the generosity of the sponsors listed above but pre-registration is required
Lodging arrangements have not been made for this symposium but a variety of options are available:
The conference will be held in the Alumni Lounge (a.k.a. Nifkin Lounge), Marshall Hall on the SUNY-ESF campus located adjacent to Syracuse University.
Parking has been arranged in the Irving Garage just a short walk from Marshall Hall (campus map).
| Time | Place | Speaker | Title |
| 8:00-9:10 AM | Alumni Lounge Marshall Hall |
Check-In Coffee + Bagels Poster Setup |
Posters on Display |
| 9:15 | Alumni Lounge | Phil Borer Syracuse University |
Welcome |
| 9:30 | “ | Thomas Szyperski SUNY-Buffalo |
Where do we stand on GFT projection NMR spectroscopy? |
| 9:55 | “ | Yibing Wu SUNY-Buffalo |
GFT-NMR based high throughput structure determination exemplified for NESG targets NeT4 and SR500A |
| 10:10 | “ | Arindam Ghosh SUNY-Buffalo |
NMR structure of NESG target MR32, a member of the family of Trm112p-like proteins |
| 10:25 | “ | Bio-Break | |
| 10:35 | “ | David LeMaster Wadsworth Center – NYS Dept. of Health | Electrostatic stabilization and general base catalysis in the active site of the human protein disulfide isomerasea domain monitored by hydrogen exchange |
| 11:00 | “ | Joseph Hornack RIT |
The relaxivity of Gd-(DTPA-BMA) / Cu+2 mixtures and evidence for a Gd-(DTPA-BMA)-Cu complex. |
| 11:25 | “ | Nelly Aranibar Bristol-Myers Squibb |
Metabolomics in Drug Discovery and development |
| 11:50 | “ | Lunch Poster Session |
|
| 1:30 PM | 140 Baker Lab | Nikolaos Sgourakis Rensselaer Polytechnic Institute |
Pressure Effects on the Ensemble Dynamics of ubiquitin at the Picosecond-to-Nanosecond timescale investigated with isotropic reorientational eigenmode dynamics |
| 1:55 | “ | Paul Giammatteo or John Edwards Process NMR Associates, LLC |
New Developments in Non-traditional NMR Applications |
| 2:25 | “ | George Crull Bristol-Myers Squibb |
Extending Solid State NMR to Address Process Development Issues |
| 2:50 | “ | Gwen Lubey P+G Pharmaceuticals |
Solid State NMR Characterization of Risedronate Hydrate Forms and Dehydrated Risedronate |
| 3:15 | “ | - | Break |
| 3:30 | Keynote Lecture | Prof. Ruth Stark CUNY |
NMR Structural Studies of Protective Plant Biopolymers |
The Mid-Hudson Section of the American Chemical Society and Vassar College Announce
The Wood-Based Biorefinery in a Petroleum Depleted World
Dr. Arthur J. Stipanovic,
Professor and Chair, Department of Chemistry
State University of New York, College of Environmental Science and Forestry (SUNY-ESF)
Wednesday, November 7th, 2007
Time: 7:00 pm
Location: Mudd Chemistry Building, Third Floor
Refreshments will be served at 6:30 pm
Vassar College, Poughkeepsie, New York
Contact: Dr Joseph Tanski (jotanski@vassar.edu, 845-437-7503)
Abstract: The 21st century is envisioned to become the age of biology as renewable biomass resources replace petroleum in energy and industrial product applications. Motivated by concerns over national energy security, global CO2 reduction, a need for biodegradable products, and enhanced rural economic development, the engineering and construction of biorefineries for the manufacture of fuels, chemicals, polymeric materials and power from renewable resources is now a critical national priority. The context and intent of a biorefinery must be much more than simply replacing crude oil with renewable raw materials. A successful biorefinery must: 1) efficiently separate its raw material source into individual components, and, 2) be able to convert these components into marketplace products. The biorefinery must mirror the efficiency of today’s modern petrochemical refinery in using all components of its raw material source for the production of chemicals, fuels, and power.
Woody lignocellulosic biomass is a complex, composite material consisting of three polymers in close association: hemicellulose, cellulose, and lignin plus small amounts of low molecular weight extractives and inorganics. In this presentation, a group of synergistic biomass feedstock and biorefining technologies under development at SUNY-ESF, in collaboration with many industrial and academic partners, will be discussed including: short-rotation fast growing willow production, biodelignification, hemicellulose extraction, polymer conversion to fermentable sugars, biodegradable thermoplastics and hemicellulose-based composites.
See the Stipanovic Website at SUNY_ESF for further details…..http://www.esf.edu/chemistry/faculty/stipanov.htm
Bio: Dr. Arthur J. Stipanovic is currently Professor and Chair of the Department of Chemistry at the SUNY College of Environmental Science and Forestry (SUNY-ESF) in Syracuse , NY , and also serves as Director, Analytical and Technical Services. His research interests include biodegradable polymers from renewable resources, high-throughput analytical techniques for determining the composition of woody biomass and new processes for the wood-based biorefinery. Dr. Stipanovic received both his B.S. and Ph.D. degrees from SUNY-ESF in polymer chemistry and much of his career was spent at the Texaco R&D labs in Beacon, NY, in new technology and lubricants research. He is a past Councilor and Executive Board member of the Mid-Hudson ACS section and, more recently, has served as Chair of the Syracuse section.
Directions: Vassar College is located off Raymond Avenue in Poughkeepsie , NY. Refer to the following link for driving directions and campus map: http://www.vassar.edu/directions/. Enter the Main Entrance of the campus on Raymond Avenue and go right towards the Mudd Chemistry Building. The Security Guard at the Main Entrance will direct you to parking.
May 14
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:
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.
The 19.5 MHz Spintrack NMR analyzer was utilized to study a FAME biodiesel production reaction. The samples analyzed were:Â
1) Used vegetable oil
2) Partially transesterified biodiesel product (bad biodiesel)Â
3) High yield FAME biodiesel productÂ
4) Glycerin by-product from the process
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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:
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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:
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Plainly TD-NMR can play a role in monitoring the biodiesel production process.
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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:
Â
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The CPMG data obtained on the four samples is shown below:
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The T2 distribution profiles obtained by inverse Laplace transformation of the CPMG data are shown below:
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The correlation between T2 distribution and the metal content, viscosity, distillation range, density, asphaltene content are all being investigated at the current time.
Apr 15
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.
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
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.
Â
For more details contact John Edwards
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:Â 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:Â A Rapid QC/QA Method”
Mar 25
A series of Trans Fat standards was purchased from AOCS. The ability of 1H and 13C NMR to predict Trans Fat Content as well asÂ
Saturated, Poly-unsaturated, and Mono-unsaturated Fat Content
The data of the samples is presented in the table below:
Â
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PLS regression techniques were used to correlate 1H and 13C NMR spectral variation to the unsaturation level and type of unsaturation of the samples.
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Processed 13C data is shown below:
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1H NMR data is shown below:
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The following correlations were obtained from the 13C NMR data.
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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
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).
Press Release – NMR Process Systems – Danbury CT - February 14, 2007 Â
Hello to all,
I have been asked by Cecil Dybowski to chair a session on Process NMR Technology at the 2007 Eastern Analytical Symposium to be held November 12-15 at the New Jersey Garden State Exhibit Center in Somerset New Jersey. At this point I am putting out some feelers to gauge the level of interest that is out there amongst NMR practitioners in this field. I would like the session(s) to encompass both high resolution and time-domain applications of NMR in process control applications and at-line in manufacturing facilities in all industry sectors. The work can be actual on-line examples or laboratory based analysis being used to justify or prove applications before they are spun out to the plant. Developments in hardware, software and chemometrics would also be of general interest and to this end hardware talks on magnet and NMR-sensor development and their potential application would be encouraged. Fully automated NMR analysis in the laboratory that simply requires a technician to load the samples would also be considered as a valid topic.
The abstract deadline for EAS is April 15th. If you are interested in presenting a paper I would appreciate hearing from you by e-mail. Once I know how much interest is out there I will begin pulling the details together and have the speakers submit abstracts through the EAS website. For your information the EAS is the premier analytical meeting for the U.S. East coast and it has a website at http://www.eas.org. Also, as an introduction to the symposium itself, I am providing a link to the program chairs letter – http://www.eas.org/symposium/symposium.html
The distribution I have included in this e-mail are of persons and organizations that I know are working in this field. If you have any colleagues, customers, or acquaintances who you feel could provide a good presentation on their research or applications please feel free to forward this e-mail on to them, or inform me of their e-mail address and I will contact them.
I look forward to hearing from you and hope that you will join us in New Jersey,
Best Regards,
John
Contact : John Edwards, (203) 744-5905Â E-Mail: john@process-nmr.com
