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)
Archive for category Chemistry
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.
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
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.
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
Wine Analysis by NMR
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:
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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.
13C NMR of FAME Biodiesel
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.
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For more details contact John Edwards
Aloe Vera Analysis by NMR
Apr 13
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
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Normalized on Reg 4 |
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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
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Normalize on Region 7 |
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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
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Solids 13C CPMAS |
Normalized to Reg 3 |
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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.
 
Trans Fat Analysis by NMR
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:
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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).
John Edwards of Process NMR Associates has agreed to chair a session at the Eastern Analytical Symposium in Somerset, New Jersey in November, 2007. The session is entitled “Process NMR Spectroscopy”. If you are interested in presenting a technical paper at this session please contact John directly at john@process-nmr.com
Also listed here is the 2007 Call for Papers for the upcoming meeting.
Dr Edwards of Process NMR Associates recently joined the American Chemical Society (ACS) speaker service which provides a clearing house for speakers who lecture on chemistry topics at local ACS Section Meetings that are typically held once a month during the academic year. Dr Edwards’ talk abstract and bio are provided below. Feel free to contact Dr Edwards if you are interested in hosting his talk at your meeting.
Biographical Sketch
Dr. John C. Edwards
Dr Edwards is currently a partner in Process NMR Associates, LLC where he is responsible for commercial analytical NMR services as well as development of on-line and at-line applications of NMR technology. He received his B.Sc. in Chemistry from Durham University in the UK (1986), and then received his Ph.D. in Physical Chemistry from the University of South Carolina in 1990. His doctoral studies involved solid-state NMR of catalyst materials. He was responsible for all NMR services with Texaco Inc from 1990-97 where he developed his particular expertise in petroleum and petrochemical NMR. In 1997 began Process NMR Associates which is involved in application of high resolution NMR spectroscopy for on-line process control as well as providing commercial analytical NMR service to over 250 industrial and academic customers around the world. Over the past 20 years Dr Edwards has developed an expertise in many types of non-traditional NMR equipment and applications.
Abstract
The Wonderful World of Non-Traditional NMR Spectroscopy
Over the past 60 years NMR has developed into a premier spectroscopic tool in the academic and industrial world. Superconducting spectrometers with fields ranging from 7 to 23 Tesla are considered as typical NMR equipment and NMR “cold probesâ€, operating at near liquid Helium temperatures, are now hot items to improve sensitivity and throughput. NMR technology has also found other application areas to exploit and these areas are a far cry from a laboratory environment. Permanent magnet based NMR systems are currently used to map the underground hydrocarbon-water makeup of oil drilling wells and to control huge production units in refineries and chemical plants based on observed proton chemistry. Portable NMR systems are taken into the field for on the spot analysis of agricultural products, antarctic ice, elastomer performance, concrete and wood moisture analysis. Single-sided NMR probe/magnet sensors are being used to study degradation of antique books, frescoes, and paintings. The non-traditional NMR technology and applications will be described and the economic benefits of the applications will be discussed. The future of NMR will include small, affordable, automated systems that will make NMR a much less exotic technique reserved only for large budget industrial or academic facilities.
Contact : John Edwards, (203) 744-5905 E-Mail: john@process-nmr.com
A new website has been introduced that focusses on the applications of Magnetic Resonance (NMR, MRI, Relaxometry) to the chemistry and physics of foods. The website can be found at magres.foodsciences.org
This organization also arranges the biannual conference on Application of Magnetic Resonance in Food Science – they have an excellent poster session with PDF versions of the poster presentations published to the web – Poster PDFs