NMR Testing Laboratory

Industrial NMR Spectroscopy Applications

You are here: Home / Archives for NMR

Talks to be Presented at IFPAC 2012 – Baltimore, MD January 22-25

by NMR Tagged: , ,

Talk 1 by John Edwards

Mutivariate Analysis of 1H and 13C NMR Data of Residual Catalytic Cracker Feed-Streams: NMR Pre-Processing Strategies that Allow the Development of Predictive Models of Physical and Chemical Properties that are Independent of NMR Instrument Magnetic Field Strength

John C. Edwards*# and Jincheol Kim†
*Process NMR Associates, LLC, 87A Sand Pit Rd, Danbury, CT 06810 USA
† SK Innovation Co., Ltd, SK Innovation Technology Center, 140-1, Wonchon-dong, Yuseong-gu, Daejeon 305-712, Korea
# Speaker

Historically refinery control engineers are familiar with GC derived chemical properties such as aromatics, benzene, PONA, olefins in wt% or vol%, as well as physical properties such as distillation, viscosity, conradson carbon, sulfur, density, etc. We have developed generally applicable multivariate regression methods that allow many of these familiar chemical and physical properties to be derived from quantitative 1H or 13C NMR data. We have also developed magnetic field independent data manipulation methods that allow 1H or 13C NMR derived parameters to be utilized as the X matrix “spectral” data rather than the spectra themselves. This allows field independent models to be developed as these parameters are calculated from the spectrum and are the same regardless of the magnetic field strength at which the NMR data was collected. This has implications with respect to calibration transfer between laboratories and analyzers. In this work we describe the application of these methods to feed-streams to a residual catalytic cracker (RCC), which represents the core gasoline and diesel production facility in many refineries.

Talk 2 by Paul Giammatteo

Practical Applications of Compact High-Resolution 60 MHz Permanent Magnet NMR Systems for Reaction Monitoring and Online Process Control

John Edwards*, Paul Giammatteo*#, Mark Zell†, and David Foley†
* Process NMR Associates, 87A Sand Pit Rd, Danbury, CT, 06810 USA
† Pfizer Global Research and Development, Groton Laboratories, Eastern Point Road, Groton, CT 06340 USA
# Speaker

Process NMR Associates will be exhibiting the Spin Pulse range of TD-NMR spectrometers as well as the Aspect Italia 60 MHz high resolution NMR system – See us at the Cosa-Xentaur booth in the exhibition.

For more details on IFPAC visit http://www.ifpac.com/

New Conference Being Planned for Practical Applications of NMR in Industry

by NMR Tagged: , , ,

CASSS announces the first Practical Applications of NMR Conference 2012. Save the Date: October 15-17, 2012. The conference will be held at the Hyatt Regency Schaumberg, Schaumberg, IL USA. John Edwards has volunteered to serve on the organizing committee and will be developing a session of talks on on-line/at-line NMR and TD-NMR technologies. Other exciting sessions will revolve around other practical NMR applications in industry – more details will be posted when the program has been developed further.

1H NMR – 60 MHz Permanent Magnet System – Reaction Monitoring

by NMR, PAT, Process NMR

Below are a few further examples of acetylation reactions of acetic anhydride with an excess of alcohol. The alcohols include tert-butanol and isopropanol.

Reaction 1: Acetylation of t-butyl alcohol with acetic anhydride in the presence of acid.

Acetylation of t-butanol with acetic anhydride - 1H NMR Reaction Monitoring

Reaction 2: Acetylation of Isopropanol with acetic anhydride in the presence of acid.

Acetylation of isopropanol with acetic anhydride - 1H NMR Reaction Monitoring

Reaction 3: Methoxyacetone and hydroxylamine reaction in methanol to form an Oxime

Oxime Production from Ketone and Hydroxylamine - 1H NMR Reaction Monitoring

Oxime Production from Ketone and Hydroxylamine - Zoomed spectrum - 1H NMR Reaction Monitoring

Resolution of the methylenes in the methoxyacetone and the reaction product is readily observed.

Oxime from ketone and hydroxylamine - assignment - 1H NMR Reaction Monitoring

All the above experiments were performed in an NMR tube. We are currently looking at the same reactions under flow conditions utilizing a HPLC pump and PEEK tubing to transport sample to the NMR probe at 5 ml/min.

Selective Observation of High Resolution 19F Spectrum by 1.4 Tesla Process NMR System

by NMR

Below is an example of a 19F NMR Spectrum obtained at 54.6 MHz on a 1.4 Tesla permanent magnet-based NMR System.

This is a 2 minute spectrum obtained by co-averaging 16 FIDs after zero-fill, autophase, referencing of each individual FID. The NMR system is not locked. No apodization of the NMR FID data was performed.

19F NMR Analysis by Process NMR Spectrometer

For more details on potential applications of 19F NMR please contact John Edwards (Tel: +1 203-744-5905)

Chevron Installs Low Field NMR Application: 31P NMR Analysis of Phosphoric Acid Strength in Alkylation Process

by NMR, PAT, Process NMR

New Flash: Chevron purchases high resolution 31P NMR system for at-line analysis of a phosphoric acid catalyzed alkylation process.

The Chevron Richmond Refinery needed a simple and quick measurement of phosphoric acid strength and quality. Prior analysis procedures included transporting samples several miles from the refinery process to the technical center in order to perform the 31P NMR analysis on a high field superconducting NMR system. This process was also complicated by the fact that the process operators were not able to perform the analyses on the conventional high field NMR systems (400 MHz for 1H, 161 MHz for 31P) themselves, but had to wait for NMR technician and instrument availability. If sample analyses was required after research facility working hours the NMR lab technicians were required to come in and run the NMR for the process operators.

A simple permanent magnet bench-top NMR system has now been placed in the existing process lab adjacent to the process unit control room. The NMR samples are placed in specially designed 9 mm (diameter) x 50 mm (length) sample tubes in order to accommodate sample handling issues (high viscosity sample with no solvents being added) and are place easily into the NMR probe. Sample preparation is essentially non-existent and sample waste is minimal. The 31P NMR analysis itself takes around 3 minutes to perform.

The “at-line” NMR system is a high resolution Qualion permanent magnet system operating at 58.3 MHz for 1H and 24.2 MHz for 31P. The system is located on a lab bench in the process lab building. Some examples of the system performance are shown along with the comparison with high field NMR results. It can be seen that the lower field instrument provides more than adequate resolution to perform the acid strength analysis.

31P NMR - Orthophosphoric Acid

Figure 1: 31P NMR of 85% Phosphoric Acid

Figures 1 and 2 show quantitative 31P NMR spectra of different phosphoric acid concentrations dissolved in water. The NMR analysis is found to be fully quantitative.

31P NMR of Different Concentrations of H3PO4 in Water - At-Line NMR

Figure 2: 31P NMR signal acquired at 24.2 MHz on several concentrations of phosphoric acid in water.

Figure 3 shows the 31P NMR data obtained at 7 Tesla (121 MHz) and 1.4 Tesla (24.2 MHz) of actual process samples. The peak at 0 ppm corresponds to orthophosphoric acid, the peak at -15 ppm corresponds to the terminal P atoms of a polyphosphoric acid chain, and the peak at -30 ppm corresponds to internal P atoms in the middle of polyphosphoric acid chains. Relative areas of these peaks are used to calculate the acid strength.

31P NMR - Phosphoric Acid Strength - At-Line Assay

Figure 3: High field and low field 31P NMR spectra of Used Phosphoric Acid from Alkylation Process

Used Phosphoric Acid - At-Line 31P NMR Analysis

Figure 4: 31P NMR spectra and calculated acid strengths obtained on 3 different used phosphoric acid samples

Used Phosphoric Acid - At-Line 31P NMR - Acid Strength Assay

Figure 5: Another comparison of 7 Tesla laboratory acquired NMR data compared to rapid at-line 1.4 Tesla NMR assay of phosphoric acid strength.

The NMR system being utilized at the Chevron Richmond refinery is a Qualion 60 MHz NMR system utilizing a 31P probe.

For further details or to discuss your own NMR applications please contact Paul Giammatteo (Tel: +1 203-744-5905)