Eastern Analytical Symposium – November 12-15, 2007
Garden State Convention Center, Somerset, New Jersey

Process NMR Technology Sessions
Wednesday, November 14, 2007
Chair: John Edwards, Process NMR Associates
Sponsored by Process NMR Associates

Process NMR Technology I: High-Resolution Studies

9:00 “Introduction to NMR in Process Control”
John Edwards, Process NMR Associates

9:25 “Standardizing and Stabilizing NMR Calibration Transfer”
Miko DeLevy, Qualion NMR Analyzers

9:50 “More from the Barrel – On-line NMR Increases Diesel Production and Quality”
Paul Giammatteo, Process NMR Associates

10:15 Break

10:35 “Taking NMR into the Refining Process: Best Practices and Benefits”
Marcus Trygstad, Invensys Process Systems

11:00 “Get Your Head Out of the Sand: Use of Reaction NMR to Better Understand Reactions in Process Development”
Andreas Kaerner, Eli Lilly

11:25 “Direct Prediction of Gasoline Properties for Monitoring Refinery Processes by H-1 NMR Spectroscopy”
Veena Bansal, Indian Oil Company

Process NMR Technology II: Time-Domain Studies
Chair: John Edwards, Process NMR Associates
Sponsored by Process NMR Associates

2:00 “Recent Developments in Time-domain NMR and Its Applications in Polymer Industry”
Harry Xie, Bruker Optics

2:25 “Time-domain NMR: Uses and Contributions to Process Control”
Vaughn Davis, Progression

2:50 “Recent Progress of NMR and MRI in Petroleum Exploration”
YiQiao Song, Schlumberger-Doll

3:15 Break

3:35 “Applications of Time-domain NMR to Laboratory and On-line Polymer Analysis”
Maziar Sardashti,ConocoPhillips

4:00 “Challenges in On-line Water Cut Monitoring of Heavy Oil Thermal Operations Using Low Field NMR”
Sergey Kryuchkov, University of Calgary

4:25 “Benchtop Fluoride NMR: A Rapid QC/QA Method”
Chris Borgia, Colgate-Palmolive

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 21^st 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.

NMR analysis of Jasmine Absolute.

For more information on NMR of Essential Oils visit the PNA website.

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

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.

I am posting this on behalf of Damien Jeannerat.

PhD Position Available Starting in September 2007

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.

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.

pdf version

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.

Details of NMR Analysis

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

pdf version

PDF Version

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

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

 PDF Version