I will be presenting a poster and two invited talks at three meetings this Summer and Fall. The first meeting is Petrophase XI 2010 (11th International Conference on Petroleum Phase Behaviour and Fouling) in Jersey City, NJ, June 13-17 – my poster is entitled: “Improved Approach to the Calculation of Average Molecular Descriptions of Heavy Petroleum Hydrocarbons by Combined Analysis by Quantitative 13C and DEPT-45 NMR Experiments”. The poster describes a new methodology for 13C NMR analysis of heavy petroleum materials based on quantitative 13C and DEPT experiments which can be used in combination to calculate an average aromatic cluster size that is consistent with other analysis techniques. Published approaches being used currently underestimate the size of the aromatic groups in heavy petroleum materials.

In July I will be presenting an invited talk: “A Self-Employed Application Chemists Odyssey in the World of Analytical Instrument Development The Viability of a $50K High Resolution NMR and $15K ESR Spectrometers”, at the University of South Dakota, Vermillion, SD. The date has yet to be set.

I will be presenting an invited talk in a session on reaction monitoring with NMR at SMASH 2010 in Portland Oregon, September 26-29 – my talk is entitled: “Simple and Continuous Flow Reaction Monitoring by High Resolution Bench-top Permanent Magnet 1H NMR at 60 MHz”, by John C. Edwards, Paul J. Giammatteo, at SMASH 2010, in Portland, Oregon. Other speakers in the session include Søren Balling Engelsen of the UNiversity of Copenhagen speaking on “New chemometric methods for alignment (icoshift), classification (ECVA) and information extraction of NMR data”, and Encarnación Fernández Valle & Dolores Molero of the Universidad Complutense de Madrid – Fast 2D Methods for reaction monitoring of organic reactions.

Finally, I will present an invited talk entitled in a session on, “Bench-top and On-line High Resolution Permanent Magnet 60 MHz NMR for Reaction Monitoring and Process Control” , by John C. Edwards, Paul J. Giammatteo, in a session on Portable NMR and Hyphenation of NMR to Chromatography and Electrophoresis at FACSS 2010, in Raleigh, NC, October 17-21.

I’m available to discuss the NMR details of these presentations at any time – I will provide copies of the talks upon request. JE

We are currently developing a spinner system for the process NMR system in order to improve spectral resolution sufficiently to quantify omega-3 fatty acids in fish oils. The omega-3 fatty acid methyl group can be discerned in the 1H spectra currently produced by the spectrometer but improvement can be made with sample spinning which will improve the quantitation.

It was announced this week that the ACD NMR Processor Academic Edition is freely available for non-commercial use and can be downloaded from the ACD Website. Other Windows based NMR processing software packages are available and here is a listing of where they can be downloaded:

1) SpinWorks – written by Kirk Marat at the University of Manitoba – Download Here

2) GSim – written by Vadim Zorin Download Here

3) RNMR (Requires R Statistical Freeware Package) – Download Here – R Software can be obtained here

4) MatNMR (Requires MATLAB) – Download Here

5) Hires – Download Here

Digital Spectrometers based on field programmable gate arrays will soon change the face of NMR spectroscopy as a routine use analytical instrument. Stan Sykora in his excellent blog (http://www.ebyte.it/stan/blog07.html#07jun14) describes how the transition of NMR spectrometers to digital electronics has drastically reduced the footprint and price of NMR spectrometers and increased the potential complexity of the RF synthesis as well as the NMR post processing on the same chip. In fact single chips can hold multiple spectrometers enabling the building of single spectrometers that can perform experiments on multiple magnet systems.

One of the best journal articles on the topic is by Kazuyuki Takeda “OPENCORE NMR: Open-source core modules for implementing an integrated FPGA-based NMR spectrometer”, Journal of Magnetic Resonance, 192(2), 218-229, 2008. This gentleman also included all the core modules, console software, pulse programs and board designs required to build your own spectrometer (see Opencore Website). The availability of superconducting NMR magnets are still the barrier to entry for cheaper high field NMR systems but in the lower field NMR area these spectrometers will enable a drastic reduction in instrumentation cost and perhaps lead to a larger NMR market. In the near future I feel that NMR systems in the 200/300 MHz range will be quite affordable especially if the consoles are married to older magnets that are currently gathering dust in rear storage areas.

The appearance of Bruker’s Fourier 300 NMR spectrometer bears witness to the market that is there for a company that can deliver a well priced NMR instrument in combination with strong application software. In fact I think that these cheaper spectrometers will facilitate the development of a market where NMR instrumentation will be sold to address individual analytical problems in routine testing laboratories. Perhaps NMR standard methods will become as prevalent as GC and MS methods currently are. Imagine an NMR spectrometer sold to a laboratory not as a general research tool but as a dedicated instrument performing authentification testing on olive oils sold in the EU. This is a new concept for NMR chemists to wrap their heads around….smaller, cheaper NMR instruments driven by applications rather than magnetic field strength.

A two FPGA spectrometer design is illustrated in the two figures.

Presented here are several simple reactions monitored by 60 MHz process NMR performed in a 5 mm NMR tube.

Reaction #1: Acetic Anhydride in Water – Reacts to form Acetic Acid

NMR Monitored Reaction Profile

Reaction #2: Acetic Anhydride + Excess of Methanol + Acid – Yields Acetic Acid and Acetic Methyl Ester

First Reaction was Performed without Shaking the Sample before Observation

NMR Monitored Reaction Profile

Second Reaction was Performed with a vigorous shake of the NMR tube before observation.

NMR Monitored Reaction Profile

For More Information Contact John Edwards

These are non-spinning spectra obtained on a Qualion process NMR spectrometer operating at 58 MHz. The spec on water at this shim level is 1.5/5/20 Hz at 50%/10%/0.5% peak height. The first spectrum is of 91% isopropyl alcohol in water – store bought pharmacy product. The second spectrum shows the comparison of a 300 MHz 1H NMR spectrum of Advil compared to a non-spinning 58 MHz spectrum.

Presented on June 18, 2009
Philadelphia, PA

“Spectroscopy Based Crude Assays for Laboratory, At-Line, and On-Line Applications”

This Presentation can be found at the Crude Oil Quality Group Website (http://www.coqa-inc.org/061809Giammatteo.pdf)

Presented at Marist College, Poughkeepsie
September 23, 2009

A Self-Employed Application Chemists Odyssey in the World of Analytical Instrument Development The Viability of a $50K High Resolution NMR and $15K ESR Spectrometers

By John C. Edwards, Ph.D.
Process NMR Associates, LLC, Danbury CT

The availability of cheap commodity electronics developed for the cellular phone industry is revolutionizing the design of NMR and ESR spectrometers. Rather than instruments that fill half a room, cost $200-3,000K+, and intimidate users, it is possible to produce spectrometers that are an order of magnitude cheaper to produce. Examples of NMR and ESR spectrometer development projects will be described as well as the wide-ranging applications that these spectrometers can deliver to the areas or process control, food authentification and automated laboratory analysis.

John Edwards was born and raised in Bolton, UK. He graduated from the University of Durham, UK with a B.Sc. in Chemistry in 1986. He obtained his Ph.D. in Physical Chemistry from the University of South Carolina in 1990, working on solid-state NMR applied to heterogeneous catalysts under the guidance of Professor Paul Ellis. From 1990-1997 he worked as a research chemist at the Texaco R&D facilityin Beacon, NY where he was responsible for global NMR support of upstream, downstream, and petrochemical Texaco ventures. In 1997 he formed Process NMR Associates which operates as a commercial analytical NMR spectroscopy service and consultancy. Process NMR Associates along with its engineering company partners, develops, markets, and supports on-line process NMR spectrometers utilized for control and optimization of refinery, petrochemical, pharmaceutical and food manufacturing operations. The company also acts as an application development company for several analytical instrument companies and supports the chemometric development of several process analytical products. He currently resides in Poughkeepsie, NY, with his wife and 3 sons. He is an affiliate professor of Chemistry at Marist College, a Research Associate at SUNY New Paltz, and an active member of the American Chemical Society.

A copy of the presentation can be provided on request… contact John Edwards if interested.

Topnir Systems is proud to announce the signature in October 2009 of a Partnership Agreement with Process NMR Associates, LLC.

This partnership enables Process NMR to utilize our field proven software in complementary fields NMR and MIR combining forces to deliver total solutions with increased added value to customers.

Topnir Systems is a French company leader in the field of online Near InfraRed (NIR) analyzers. Topnir enables measuring and monitoring multiple hydrocarbon streams in less than one minute using a single online system. The company has a long history in the refining and petrochemicals business, being the first world wide to implement an online application designed to measure and control octane number for gasoline production, first NIR on-line application worldwide on Ethylene Plant Naphtha feed (1986), Gasoline (1989) and Crude (1991). The business started in the late 80s within BP Oil, with applications development around gasoline and diesel blending, as well as FCC, CDU, Reformer and Ethylene plant feed andproducts characterization. Major oil companies such as Shell, BP, Repsol, Aramco… have adopted Topnir solutions.

Topnir has recently expanded its activities to provide platform independent software for NIR systems already installed in the field. Topnirs modeling technology offers a full set of properties from a single model which offers the advantage of a robust, reliable system requiring very light maintenance. In addition Topnir is field proven to have ASTM and better results.

Process NMR Associates, LLC is an American company and leader in the field of online Nuclear Magnetic Resonance (NMR) process applications. The company also has a long history in the refining and petrochemicals business, being the first world wide to implement online NMR applications for gasoline and diesel blending, FCC, CDU, Reformer and Ethylene plant feed and products characterization.

Topnir Systems
425, rue RenéDescartes
Espace Descartes, Bat C
Parc de la Duranne
13857 Aix-en-Provence, France
Tel +3350 73 47 / Fax+3350 73 50
Web: www.topnir..com
USA Contact: Julie Williams Tel: +1-508-736-2696

Process NMR Associates, LLC
87A Sand Pit Road
Danbury, Connecticut 06810 USA
Tel +203-744-5905
Fax +203-743-9297
Web: www.process-nmr.com
Contact: Dr. Paul Giammatteo

Paul Giammatteo recently presented two papers at the Gulf Coast conference that was held in Galveston, Texas on January 20-21.

His first paper was entitled “Counting Carbons for Tighter Control: Combining GC and NMR to Improve Distillate Manufacturing” and centers on the topics of Simulated distillation correlated to 1H NMR.

The second paper was entitled “Analytical Data For Engineering Support: Improving the Lab/Process Interface”. This paper details the development of a series of heavy petroleum applications on a Smiths Detection FTIR-ATR spectrometer.

PDFs of the presentations can be obtained from the following links: 1) NMR Talk 2) FTIR-ATR Talk

Alginate is a linear polysaccharide composed of mannuronate (M) and a-L-guluronate (G). The polysaccharide is characterized by the relative ratio of M/G, G-Content, and average length of blocks of G in the polymer. M and G are:

ASTM F2259 recounts the standard sample preparation and 1H NMR analysis that allows the following parameters to be calculated:

The 1H Spectra obtained on a typical alginate sample are show below:

Finally the peaks representing the individual M and G components and sequences are deconvoluted from the spectrum.
The intensities obtained from the deconvolution are input into the excel spreadsheet shown above and the various ratios, M and G content and a series of diads and triads are calculated along with some G block lkength information. It is the block length information that often reveals telling differences between samples.

Process NMR Associates performs this analysis at a cost of $225 per sample. The samples, however, must be prepared by the customer using the methodologt set forth in the test method.

Over the past few years balsamic vinegars have been the subject of a number or NMR studies to determine authenticity, degree of aduleration, and age. 1H NMR has been used to quantify the relative concentrations of a series of organic components (ethanol, fructose, glucose, acetic acid, succinic acid, lactic acid, butandiol, etc (ref 1). 13C NMR has been used to determine the aunthenticity and degree of adulteration (ref 2) as well as the length of the ageing process that a given sample has undergone. Also the formation of glucose and fructose acetates during maturation and ageing has been studied by 1H and 13C NMR.

Refs.
1) Caligiani et al., Anal. Chim. Acta, 585 (2007) 110-119
2) Consonni et al., Talanta, 75 (2008) 765-769
3) Consonni et al., Anal. Chim. Acta, 611 (2008) 31-40
4) Consonni and Caligiani, Talanta, 73 (2007) 332-339
5) Cirlini et al, Food Chemistry, 112 (2009) 51-56

The concentration and distribution of the organic components has been found to correlate well with ageing process analysis, identification of adulteration, and determination of authenticity of traditional balsamic vinegars and balsamic vinegars of Modena.
Below are a series of spectra showing what can chemistry can be quantified in the balsamic vinegars as well as a few comparative spectra of apple cider vinegar and malt vinegar.

For comparison with the home made ciders analyzed in the previous posting I am including the NMR of analysis of a commercial pear cider. The previous ciders were very dry while the pear cider was decidedly sweet. The carbohydrate content is a notable difference. The 1H spectrum is shown with chemical components identified.

There have been quite a lot of NMR studies centered around apple cider (non-alcoholic) and apple cider vinegar. However a search of the literature turns up no reference for NMR analysis of hard apple cider. This effort was undertaken to analyse the alcohol content of the ciders and to determine the malic and acetic acid content. Ciders were produced by Dr Tim McMahon of Orange Community College, NY….for his own consumption.

Below are the NMR spectra obtained by regular 1H acquisition and with BINOM solvent suppression.

Data was obtained on our Varian 300 MHz spectrometer. Samples were prepared by degassing followed by addition of 1 drop of D2O as lock solvent.

Process NMR Associates, LLC (Danbury CT) and Active Spectrum, Inc (San Carlos CA) are collaborating in the application of micro-ESR technology to petroleum applications. The initial work has focussed on crude oils but will soon be expanded to residues and cracker feedstocks.

Five samples of crude oil were tested by Micro-ESR spectrometry. The samples were:

1. Vasconia, Magdalena Basin, Columbia (V=39 ppm)
2. Merey, Eastern Venezuela Basin, Venezuela (V=303 ppm)
3. Oriente, Oriente Basin, Ecuador (V=65 ppm)
4. Qua Iboe, Agbada Formation, Niger Delta (V=2 ppm)
5. Basrah Light, Zubair Zone, Iraq (V=29 ppm)

The following spectra were observed:

Figure 1: Micro-ESR Spectra of Crude Oil

The central peak is a combination of a persistent carbon-centered organic radical (g = 2.003) found in asphaltenes, and a vanadyl (VO2+) peak. The additional smaller peaks are associated with vanadyl only.

For producers, the technique could be used to rapidly measure asphaltene concentration on-line. The spin density of the organic radical is a function of the maturity of the oil and will of course vary between deposits. Notwithstanding, rapid electronic measurement of asphaltenes remains a topic of great interest. Similar techniques have also been used to assess the quality of coals. For refiners, vanadium is a contaminant that poisons the refinery catalyst. ESR has been used by refiners since 1962 to rapidly measure vanadium content in crude oil feedstocks both on-line and in laboratories. Active Spectrum Inc.’s Micro-ESR is shown below. It is 2.25″ in diameter by 2.5″ high. Power input is 12-30VDC, and the data interface is USB. The device is available as either an on-line sensor or as a benchtop unit.

Figure 2: Micro-ESR Sensor

Figure 3: Higher Homogeneity Spectrum of Merey Crude

Micro-ESR is complimentary to NMR in that it observes paramagnetic metals and organic radicals which are unobservable by NMR. The stable free radical signal is indicative and quantitative to the amount of asphaltenes in the crude oil sample and vanadium metal content is an important processing parameter for cracking processes as it is active in the passivation of catalysts. NMR on the other hand observed the detailed hydrocarbon chemistry of the sample and yields chemico-physical parameters such as aromaticity, paraffinicity, naphthenicity, distillation, density, PAH distribution. In combination these two technologies yield a detailed picture of the petroleum materials before and during the refining process.

Samples provided by John Edwards of Process NMR Associates, LLC. Micro-ESR analysis provided by James White of Active Spectrum, Inc,

Active Spectrum, Inc. 110 Glenn Way #15, San Carlos, CA 94070 650-610-0720 | 626-628-1970 f | activespectrum.com

Process NMR Associates, LLC. 87A Sand Pit Rd, Danbury, CT 06810 203-744-5905 | 203-743-9297 f | process-nmr.com

PDF Version of Application Note

For more information contact John Edwards (203) 744-5905

Current Technique for Feedstream Analysis:
Analysis Performed – Refractive Index, Distillation, Specific Gravity
Calculation Obtained – Watson K-Factor
Outcome: aromatic carbon number, aromatic hydrogen number, total hydrogen content
Proposition: Detailed hydrocarbon analysis for kinetic model development.

Our experience is that an improved and useful analysis can be obtained from NMR
analysis. There are several ways to approach the NMR analysis and the
chemometric approach to correlating NMR data to physico-chemical parameters of
use to process control.

RCC Feedstream Analysis by 1H and 13C NMR: Multivariate Prediction of Chemical and Physical Properties

Presented at the 236th ACS National Meeting, Philadelphia PA, August 17-21, 2008

John C. Edwards Ph.D.
Process NMR Associates LLC
87A Sand Pit Rd, Danbury, CT 06810

Jincheol Kim,
SK Energy Co., Ltd, SK Energy Technology Center,
140-1, Wonchon-dong, Yuseong-gu, Daejeon 305-712, Korea

Summary of Slides

1) 60 MHz process NMR data available from online NMR unit.

2) 300 MHz 1H NMR data available from standard NMR experiments on laboratory NMR system at Process NMR Associates

3) Expansions of 1H NMR data on RCC Feeds

4) Calculated 1H NMR Parameters Represented as an alternative “spectrum” for use in chemometric modeling and linear regression.

5) 13C NMR Data obtained on RCC Feeds

6) Expansions of 13C NMR Data

7) 13C NMR and Average Molecule Parameters Calculated from 13C Spectrum

Calculated 13C NMR Parameters Represented as an alternative “spectrum” for use in chemometric modeling and linear regression.

9) Correlations of Spectra and Calculated Parameters to Physico-Chemical properties of RCC Feeds

10) Correlation of Spectra and Calculated Parameters to Density

11) Variable Selection for Linear Correlation of Calculated NMR Parameters to Physico-Chemical Properties of RCC Feeds.

12) Correlation of Calculated 13C NMR Parameters (C-Type and Average Molecule) with both high resolution 1H and 13C NMR spectra. Models created can be utilized by personnel with no NMR experience to calculate NMR parameters directly from the spectrum without any prior knowledge of integrations or calculations to be performed.

Summary
Chemical and Physical Properties of RCC Feedstreams can be determined
by 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 observed
by 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 carbon
type analysis for RCC Feeds
Regression analysis of 13C NMR data can be utilized to fully automate the prediction
of 13C NMR type analysis : reducing the necessity for considerable knowledge and
analysis time on the part of the analyst.

For further Detail Contact John Edwards

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.