Process NMR Associates – http://process-nmr.com

NMR Technology and Applications

Archive for category Energy

Solid-State 13C NMR Analysis of Carbonaceous Materials

Sep 15

Posted by processn in Energy, NMR | 1 Comment

Over the past 20 years we have obtained the solid-state NMR analysis of pretty much every carbonaceous material that exists – including coal/oil shales/bitumen, polymers/catalysts/fibers, cellulose/polysaccharides/foodstuffs/gels, deposits/dried sewage/meteorites/soils/clays, etc. With the increased attention to coal liquifaction and gasification technologies we have developed an interest in creating an NMR database for coals. Coals were obtained from the Penn State Coal Sample Bank at a very reasonable cost. We have performed CP-MAS, DD-MAS, Variable Contact Time, and T1 inversion recovery experiments on all the samples. We are currently developing regression relationships between the NMR data and the physical and chemical testing data that is provided with the samples. At some point we will write this up as a journal article. Here are some snippets of data from the coal analysis along with a few results obtained on the menagerie of samples we look at on any given day including some oil shales, engine deposits, refinery coke, asphaltenes, and pipe tobacco.

Solid-State 13C NMR - Illinois #6 Coal

Solid-State 13C NMR - Hiawatha Coal

Solid-State 13C NMR - Coals: Rosebud and Dietz

Solid-State 13C NMR - Engine Deposits: CCD and IVD

Solid-State 13C NMR - Refinery Coke

Solid-State 13C NMR - Arab Medium Heavy Asphaltene

Solid-State 13C NMR - Pipe Tobacco

Please inquire if you are interested in the details of the above analyses.

Process NMR Application: Spectro-Molecular Control for Enhanced Diesel Recovery

Feb 28

Posted by processn in Energy, NMR, Process NMR | 3 Comments

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.

Enhanced Diesel Recovery

Let NMR Process Systems deliver Spectro-Molecular Control to your refinery so that you can achieve real economic and production benefits.

NPS – IS : A New Approach to Process Analytical

Oct 29

Posted by processn in Chemistry, Energy, IR-ATR, NIR, NMR, Process NMR, TD-NMR | 4 Comments

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

The Wood-Based Biorefinery in a Petroleum Depleted World

Oct 5

Posted by processn in Chemistry, Energy, IR-ATR, NIR, NMR, PAT, Process NMR, TD-NMR | 2 Comments

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.

NMR Without Solvents – Biodiesel Production Process – FAME, Glycerol, FFA, and Methanol

May 14

Posted by processn in Chemistry, Energy, NMR, Process NMR | 4 Comments

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.

Monitoring of a Biodiesel Transesterification Process with a TD-NMR Spectrometer

Apr 16

Posted by processn in Chemistry, Energy, NMR, Process NMR | 4 Comments

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.

 

TD-NMR Analysis of Catalytic Cracker Feedstocks

Apr 16

Posted by processn in Chemistry, Energy, NMR, Process NMR | 4 Comments


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.

13C NMR of FAME Biodiesel

Apr 15

Posted by processn in Chemistry, Energy, NMR, Process NMR | 31 Comments

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.

Detailed 13C NMR Analysis of Hydrocarbons – Patent Applications

Apr 15

Posted by processn in Chemistry, Energy, NMR, Process NMR | 2 Comments

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

NMR Analysis of Hydrocarbonic Solvents

Apr 14

Posted by processn in Chemistry, Energy, NMR, Process NMR | 5 Comments

pdf version


Naphtha Chemistry Analysis by 1H NMR

Apr 14

Posted by processn in Chemistry, Energy, NMR, Process NMR | 1 Comment

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

Process NMR for Transesterification Monitoring and Certification of Biodiesel

Mar 24

Posted by processn in Chemistry, Energy, NMR, Process NMR | 2 Comments

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).