July 17, 2006
Abstracts Available for Magnetic Resonance in Food Science Meeting
The Abstracts for the Posters and Speaker Sessions of the 8th International Conference on The Application of Magnetic Resonance in Food Science (July 16-19, 2006) can be found at the following locations – Poster Abstracts and Speaker Abstracts .
July 13, 2006
Stelar Develops New Benchtop FFC Spectrometer and Forms JV Company Invento
Stelar s.r.l. has announced that it will be producing a new benchtop design for it’s Fast Field Cycling NMR product becoming available in September 2006, and also the availability of a new single board NMR console - available June 2006. the company has also formed a JV company called Invento s.r.l. which is a combination of Stelar and a business incubator at the Univerity of Torino. The mission of Invento is to further the development of FFC NMR techniques as standard methodolgies in testing laboratories and to perhaps replace other TD-NMR spectrometers.
July 11, 2006
NMR Monitoring of Magnetic Field Strength of CERN Large Hadron Collider
A group of physicists at the University of Manchester are developing NMR probe technologies to monitor the magnetic field strength inside the solenoids of the Atlas LHC at CERN. The probe technology and accompanying NMR spectrometers are described on the Manchester website.
July 3, 2006
Process NMR Paper at San Francisco ACS Meeting - September 2006
ENITechnologie will be presenting a paper on the on-line application of NMR in lube plant operation at the upcoming ACS Meeting in San Francisco.
Experiencing Process MRA Industrial Lube Plant Application – Roberto Giardino1, Silvia Guanziroli1, Cinzia Passerini1, and Antonio Farina2. (1) EniTecnologie S.p.A, via Maritano, 26, San Donato M.se (MI), 20097, Italy, (2) Divisione Refining & Marketing – Raffineria di Livorno, Eni S.p.A, via Aurelia, 7, 57017 Stagno (LI), Italy.
In a conventional base oil production plant the operating conditions needed to produce products at a desired specification are very sensitive to feed quality. At Livorno refinery an on-line Process Magnetic Resonance Analyzer (MRA) has been installed to identify the feedstock and product composition and properly set an advanced process control system. By using MRA it is possible to reduce the product quality give-away due to feed quality variation. In this work the industrial experience acquired is reported.
Characterization, On-Line Monitoring, and Sensing of Petroleums and Petrochemicals 8:30 AM-11:30 AM, Thursday, 14 September 2006 Sheraton Palace—Telegraph Hill
Division of Petroleum ChemistryThe 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006
June 19, 2006
Application Overview for Spin Track TD-NMR Spectrometers
Due to it’s broad versatility the Spin Track NMR Hardware supports all standard NMR routines such as AOCS Cd 16b-93, AOCS Cd 16-81, ISO 8292, IUPAC2.150 and creative scientific research. Spin Track has been successfully approved in the food and polymer industries for routine analysis. If your application is not described below please contact John Edwards for discussion.
Solid Fat Content (SFC) AnalysisThe quality of food products containing fats and oils depends on solid fat content (SFC). SFC determination is an essential measurement in the baking, confectionery, and fat industries. NMR has been established as the method for SFC determination by ISO 8292. Measurements of SFC by the Spin Track NMR analyzer can be performed quickly and accurately with great benefit for the manufacturer.
Simultaneous Rapid-Determination of Oil and Water in SeedsSunflower, soybean, groundnut, rape and mustard are appreciated for their oil content, but excess of water content reduces their price. Thus, an accurate and fast determination of oil and water content is important to both manufacturers and customers. The Spin Track NMR analyzer meets ISO 10565 requirements and gives the possibility to simultaneously determine of oil and water content.
Oil/Fat and Moisture analysis in Chocolate, Powdered Milk, Cheese and other Food ProductsTime of storage of food products depends strongly on moisture content. Excess moisture leads to microbiological activity and can make food consumption dangerous. Fat and moisture content also heavily influence taste. Manufacturers are also regulated to disclose the exact information on the fat content of their products. NMR is the most rapid and exact method to determine these essential parameters. The Spin Track NMR analyzer is especially suitable for regular analysis of food quality.
Curing Degree and Elasticity Analysis in Rubber-Type Materials
Over the past years Rheology has become widely accepted as a tool in the investigation of rubber properties. However, rheological testing equipment can be extremely expensive and complicated. NMR is very sensitive to the structure and properties of investigated rubber materials. The Spin Track NMR-analyzer allows investigators to obtain data complementary to rheology and can also prove to be more informative.
Moisture and Crystallinity Analysis in PolysaccharidesPolysaccharides like chitin, chitosan etc. are widely used because of inherent unique properties. Adsorbents and food bio-additions based on them require a regular check of quality. Spin Track NMR-analyzer allows investigators to obtain information about moisture, crystallinity, purity and structure of polysaccharides.
Porosity of Rock Cores/Heterogeneous Catalysts/ZeolitesThe possibility of oil development can be defined more exactly in the initial stages of exploration by using NMR. Rock cores saturated by bitumen or water provide information on degree of saturation, structure of saturating compounds, porosity, and diffusion characteristics. This information allows the prediction of oil production yields. The Spin Track NMR-analyzer with a 35mm probe gives the possibility to obtain such information.
Scientific applicationsThe spectrometer’s Relax software allows construction of many types of NMR pulse sequences, user-defined interfaces, data processing (digital experiments filtering, fitting, Fourier and Laplace transforms) and data manipulations. Thus, customers can directly run automated standard type NMR experiments just by “pressing one button” in the program shell, or create new applications using the powerful pascal-like script language. Widely used experiments like measurements of T1 and T2 (90-tau-90, 180-tau-90, CPMG, FID, Spin Echo, Solid-Echo) are included into the Relax software as default examples. The NMR measurements can be accompanied with the high precision calibration samples and built-in software calibration procedures. Easy automatic tuning of the NMR frequency, pulse-durations, TX power and RX gain is included into the software package.
Process NMR Associates Begins Marketing of Cutting Edge TD-NMR Spectrometer
Resonance Systems Ltd. has granted Process NMR Associates the rights to promote, market, and sell it’s NMR products and custom NMR hardware in the Americas, and Worldwide. The basic product of the company is a portable NMR-analyzer called Spin Track that can be used for many different low and high resolution NMR applications.
Spin Track meets the requirements of many relaxation and diffusion based NMR analyses:
Food industry (Solid Fat Content Analysis, Dairy Products, Oil and Moisture in Chocolate, Powdered Milk, Cheese and other food products; Oil and Moisture in seeds, Emulsion Characteristics)Lipid Analysis – Fatty Acid DistributionCellulose and paper manufacturing (Moisture/Crystallinity Analysis, investigations of ageing effects)Oil industry (rock cores analysis, oil-water, oil-water-gas, viscosity, physical property correlation, )Polymer and rubber industry (Curing degree and elasticity analysis, polymer ageing, glass transition, amorphous/crystalline content)Chemical industry (Density, Melting Points, Copolymer Ratios, Compatibility, Cure, Cross Linking, H or F content,Medicine (NMR Surface Analysis of Patients, Plasma Analysis)Environmental (Water Pollution, Forest Degradation, Soils, Fertilizers)Fibers – Moisture and Finish ContentPharmaceuticals (Tablet Analysis, Coatings/Components/Moisture, Hydrogen/Fluorine/Sodium Content)Relaxation, Diffusion, Particle Size, Pore Size Distribution
Utilization of mobile NMR measurement equipment from Process NMR Associates provides the following advantages:
Reduction of expenses associated with meeting quality requirements of productsSimplicity of use in routine production measurements and in advanced laboratories for complicated analysisMobility of the hardware and low cost for the overall deviceNon-invasive measurements of any sampleHardware solutions for non-standard NMR applicationsPermanent technical support and comprehensive scientific consultingFair price and absolute ease of operation!
Portable Low-Resolution NMR Analyzer
Analyzer is designed to perform:
All standard NMR applicationsDevelopment of new NMR-based techniquesTeaching quantum physics, NMR, analytical chemistry in Universities and Colleges
NMR analyzer Spin Track comprises functional parts (probes, preamplifier and duplexer, TX Power Amplifier, Sequence Generator and PC Interface, Data Acquisition System, NMR Transceiver) which can be purchased separately and used for the specific needs of an advanced customer (see example of connection assembly). Depending on the required magnet system the Spin Track can be used as NMR relaxometer or high resolution NMR spectrometer.
Basic characteristics of Spin Track analyzer:
Frequency range of the NMR spectrometer module: 5..60 MHz
Ringing time for 10 mm NMR probe is 8 ms
Probe tube diameter: up to 35 mm
Changeable preamplifiers and 50 Ohm matched duplexers with self bandwidth of 5 MHz
Customer-defined set of sensors (5, 10 and 30mm test-tube magnet systems, NMR surface sensors)
Adjustable TX output power up to 400 Watts
Adjustable RX channel gain up to 107
RX Sensitivity better than 1 mV (conditions: signal to noise ratio 3)
Adjustable digital filter bandwidth from 100 Hz up to 1 MHz
Pulse sequence length up to 64K events with resolution 100 ns
Quadrature 64Kx10-bit data acquisition system
Complete control of functions via personal computer – USB 2.0 ConnectivityFast sensors replacement
Compatible with all Microsoft® Windows® operating systems
Software
The product software, Relax, is a powerful tool containing many standard NMR relaxation routines and applications, and can also be used to create new pulse-sequences, pulsed field gradients, gains and attenuations, post-processing methodolgies of considerable complexity. The built-in script language is based on a widespread Pascal syntax and is enriched with commands for fitting, Fourier and Laplace transforms, Low-pass filtering, etc. The script supports dialogue windows, static messages, user-defined diagrams, data manipulation procedures. Relax also allows direct processing of data obtained when utilizing Spin Track as a high-resolution NMR spectrometer.
Stationary Low-Resolution TD-NMR Analyzer
Analyzer is designed to perform:
Standard routine NMR applicationsDevelopment of new NMR-based techniquesTeaching quantum physics, NMR, and analytical chemistry in Universities and Colleges
The Spin Track Stationary fulfills all requirements to conduct NMR measurements like portable version of NMR analyzer.In addition it is supplied with the possibility for increased probe volume to facilitate excellent statistical averaging of experimental results or to accomodate large samples.
Basic characteristics of Stationary Spin Track Analyzer:
Frequency range of the NMR spectrometer module: 5..60 MHz
Ringing time for 10 mm NMR probe is 8 ms
Probe tube diameter: up to 35 mm
Changeable preamplifiers and 50 Ohm matched duplexers with self bandwidth of 5 MHz
Customer-defined set of sensors (5, 10 and 30mm test-tube magnet systems, NMR surface sensors)
Adjustable TX output power up to 400 Watts
Adjustable RX channel gain up to 107RX Sensitivity better than 1 mV (conditions: signal to noise ratio 3)
Adjustable digital filter bandwidth from 100 Hz up to 1 MHz
Pulse sequence length up to 64K events with resolution 100 ns
Quadrature 64Kx10-bit data acquisition system
Complete control of functions via personal computer – USB 2.0 ConnectivityFast sensors replacement
Compatible with all Microsoft® Windows® operating systems
Relax Software
Educational Low-Resolution TD-NMR Spectrometer
Analyzer is designed to demonstrate NMR spin dynamics as well as provide a basic platform for undergraduate level chemistry and physics labs.Standard routine NMR applications (FID, Spin Echo, CPMG, Carr-Purcell, T1-Determination (90-90 or inversion recovery))Development of new NMR-based techniques – software allows development of pulse sequences by students without risk of instrument damage.Teaching quantum physics, NMR, and analytical chemistry in Universities and Colleges
Basic characteristics of Stationary Spin Track Analyzer:
Frequency range of the NMR spectrometer module: 10..20 MHz
NMR Probe tube diameter: 5 mm
10-20 MHz Magnets,
Surface NMR Sensors
Changeable preamplifiers and 50 Ohm matched duplexers with self bandwidth of 5 MHz
Adjustable TX output power up to 100 Watts
Adjustable RX channel gain up to 107
RX Sensitivity better than 1 mV (conditions: signal to noise ratio 3)
Adjustable digital filter bandwidth from 100 Hz up to 1 MHz
Pulse sequence length up to 64K events with resolution 100 ns
Quadrature 64Kx10-bit data acquisition system
Complete control of functions via personal computer – USB 2.0 ConnectivityCompatible with all Microsoft® Windows® operating systems
Relax Software
Custom NMR Components
For NMR engineers and advanced specialists Process NMR Associates offers accessories to upgrade, modernize, or build new NMR related devices (see connection example). All modules can be purchased separately and modules can be developed with unique characteristics to fulfill special requirements of the customer.
Surface NMR Sensors NMR Sequence Generator
Data Acquisition Unit Wide-Band NMR Transceiver
NMR Power Amplifier NMR Pre-Amplifiers and Duplexers
For more information and pricing please contact John Edwards
Back to Process NMR Associates Home Page
June 1, 2006
United States Department of the Interior - Oil Shale and Tar Sands Leasing Programmatic EIS
The public forum site of the department of the interior related to the environmental impact statement is found at the following location. The site contains excellent overviews of the tar sands and oil shales found in Wyoming-Colorado-Utah. Excellent Oil Shale site from the DOE with strategic significance reports and government policy statements.
Bruker BioSciences Corporation Announces Agreement to Acquire Bruker Optics Inc.
An interesting news article from Bruker world – “Bruker BioSciences Corporation Announces Agreement to Acquire Bruker Optics Inc. for $135 Million in Cash and Stock” dated April 17, 2006. Fascinating…. of particular interest from the process analytical and molecular spectroscopy side was Bruker Optics VP Dan Klevisha’s comment – ” For Bruker Optics, becoming part of a larger and public company will also allow us to explore complementary acquisitions.”
Materials Research Society - Symposium on Magnetic Resonance in Material Science
The Materials Research Society announces a call for papers for it’s Symposium (MM) on Magentic Resonance in Material Science to be held at the Fall Meeting in Boston on November 27 – December 1, 2006. Abstracts are due by June 20th.
Alternative Sources of NMR Equipment - Beyond the Big 3
There are a number of alternatives to buying new systems from Bruker-Varian-JEOL. A number of third party suppliers are present in the market selling and supporting refurbished used NMR systems. These companies can install and warranty the systems as well as maintain the cryogens for you if you wish. The companies that specialize in supercon NMR systems are Triangle Analytical, RS2D, NMR Associates, and MR Resources. A great place for used probes and repair is J S Research. Consoles can be obtained from Tecmag and from Anasazi (Anasazi also provides refurbished 60 and 90 MHz electro/permanent magnet systems). Spincore provides NMR spectrometer components for those who want to build their own instruments. Magritek, Minispec, Oxford Instruments, Resonance Systems, Progression, PCT, all sell TD-NMR instruments.
Process NMR Associates can guide you through this maze of choices.
May 31, 2006
Stan’s NMR Blog - Two Articles on Magnetic Field Noise Effects
Stan Sykora continues to expand his excellent NMR blog with two new articles on NMR signal reproducibility. His articles cover how field noise effects the repeatability of NMR signals such as FIDs and spectra and Hahn echoes and CPMG trains. In our experience of online NMR we have worked extensively on this topic with respect to the repeatability of the processed NMR spectrum and it’s effect on the repeatability/reproducibility of the chemometric predictions employed for process control. As Stan notes, if people have done a lot of work in this area it is certainly not being reported … mea culpa.
FAPRI World Agricultural Outlook 2006
The Food and Agricultural Policy Research Institute has published it’s annual U.S and World Agricultural Outlook for 2006.
May 30, 2006
Online TD-NMR Analyzers for 19F and 31P Analysis of Minerals and Phosphates
I guess you learn something everyday… The Harrison R. Cooper Systems Company of Bountiful Utah has been marketing low field Phosphorus-31 and Fluorine-19 NMR analyzers for a phospate mineral benefication process and for fluorine monitoring in mineral slurries. It appears from the site that only a few installations were made and no indication of successful outcomes or benefits are provided in the analyzer and process descriptions. I can’t decipher where the NMR technology originated….perhaps Auburn?
May 26, 2006
21.1 Tesla Quench Video
The University of Colorado Health Science Center installed a pumped 900 MHz system in 2005. They have an awesome video of a deliberate quench of the magnet as part of the ramping protocol. Here is the link to the video and here is a link to the NIH funded facility.
1H and 13C Shifts of Common NMR Solvents - Excel Table
Edward Vawter of QD Information Services has made available two useful excel spreadsheets containing the 1H chemical shifts and 13C chemical shifts of most common deuterated NMR solvents. He also has a few other useful articles available from his download page.
Hilarious NMR Adventures at Stanford
Dylan Stiles at Stanford has an often hilarious blog category dedicated to the NMR aspects of his natural product synthesis projects. He gets a lot of commentary which is great as I think he has the only NMR blog that anyone cares to read. His blog is at http://blog.tenderbutton.com/?cat=9.
NMR Post-Processing Software for Mac Users
Phillip Grandinetti of Ohio State University (Research Group Site) offers an NMR post processing program for mac users called RMN at his website. He has an alpha version that runs under OS X and he is looking for alpha-testers to kick the tires. A more mature version is available that runs under Mac Classic OS.
Mestrec laboratories also offer a cheap (50/100 Euro) software package that is available at iNMR.
May 22, 2006
AMMRL Meeting at 47th ENC - Asilomar, CA, April 2006 - Presentations
The AMMRL (Association of Managers in Magnetic Resonance Laboratories) held an annual meeting at which a number of presentations were given that give an idea of the economics and issues that arise for University NMR Facility Managers and Administrators, the links are below:Charlie Fry—IntroductionKen Visscher—Open-Access Laboratories in Industry Nick Burlinson—Design and Installation of a Departmental NMR FacilityEugene DeRose—Problems and Protections for Pumped Magnets Josh Kurutz—A Survey of Business Models for Academic Facilities David Vander Velde—Cryoprobes and Money (a.k.a. Losing Money) Klaas Hallenga—Practical Tips and Tricks with Cryogenic Probes
The AMMRL has a website with some basic information at http://chemnmr.colorado.edu/ammrl/ and has an invaluable archive of “user group” e-mails that discuss all aspects of running and maintaining an NMR facility (Email – Archives 1993-Present). If you have a question about instrument problems, instrument and cryogen maintenance, user training, user competency, safety issues, etc …. chances are the answers are already included in this database. The database can also be searched by key word to arrive at “on-topic” material.
May 18, 2006
The Anatomy of a Superconducting NMR Magnet
Dr Joseph Vaughn of Florida State University has placed an autopsy of a Varian R2D2 7.05 Tesla NMR magnet on the department website. The innards of the magnet and probe are all exposed in the gory photographs. Check it out at the FSU chemistry site : http://www.chem.fsu.edu/facilities/cutaway_nmr_magnet.asp
This is one of the siblings of the magnets that we operate in our labortory at Process NMR Associates. The site is only for those with a strong stomach.
May 16, 2006
8th International Bologna Conference on Magnetic Resonance in Porous Media
Filed under: PNA, Process NMR, Analytical NMR — Administrator @ 11:58 am
This conference (MRPM8) will be held September 10-14 at the University of Bologna, Italy. It is being held a few days after the 6th Colloquium on Mobile magnetic Resonance in Aachen Germany, (September 6-8, CMMR6) to facilitate the attendance of conferees at both meetings.
May 3, 2006
Symbion Systems Inc
Symbion Systems Inc has developed a family of software products that provide a common interface for communicating with, networking, and controlling many analytical instruments, and sample systems, in a laboratory or process analysis setting. The software can control many individual analyzers from different vendors, process the data and visualize it, store the data in SQL databases, and perform complex chemometric analysis by calling various calibrations from many chemometric software platforms. The predictions obtained from process analytical instrumentation can be plotted, visualized, stored, and outputted under many standard formats for integration with process control and optimization software. A version can be obtained that is GLP/GMP/21 CFR, Part 11 compliant. The software will provide an excellent platform for development and execution of analytical laboratory methods, as well as process analytical applications.
One Moon Scientific Inc.
Bruce Johnson of One Moon Scientific (ex Merck) has produced a series of software tools for visualizing and analyzing spectroscopic data with particular emphasis on NMR data. His NMRViewJ can process and visualize NMR datasets in 1 or multiple dimensions and has built in molecular visualization and statistical data analysis tools. The software is “free” but Bruce asks that if you download and use it you should pay a “support contract fee” in order to support the ongoing development of the NMR software products.
April 26, 2006
16th ISMAR 2007 - Website Posted
Filed under: Analytical NMR — Administrator @ 11:09 am
The International Society of Magnetic Resonance announces the 16th Triennial Conference to be held at Kenting, Taiwan, October 14-19, 2007. Organized by the Taiwan Magnetic Resonance Society, Academia Sinica, Taiwan – Website is found at http://www.ismar2007.sinica.edu.tw/
April 1, 2006
Energy Information
Here are a few excellent links to the energy situation in the 21st Century:
Energy Technologies for the Twenty-First CenturyWEC - Survey of Energy Resources 2001DOE - This Week in PetroleumEnergy Information Administration – Main Site
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March 15, 2006
Modern Drug Discovery - NMR Articles
Filed under: Analytical NMR — Administrator @ 2:00 pm
ACS Publication “Modern Drug Discovery” – Available NMR ArticlesScreening with NMRNMR Spectroscopy Software – Molecular biologists can now use proton NMR data to elucidate protein structure.NMR on TargetUltracool NMR Technology – CryoprobesLooking for Quality
March 14, 2006
NMR of Silicones in Pharmaceutical Developments
Dow Corning have published a small overview paper on manufacturing processes and development of silicones in pharmaceutical formulations. The paper includes characterization details by FT-IR and NMR.
The 6th Colloquium on Mobile Magnetic Resonance - Official Website now Posted
The 6th Colloquium on Mobile Magnetic Resonance has now posted an official website to cover the meeting at http://www.cmmr.de/index.htm
March 13, 2006
PNA Talk - Dr Giammatteo to Present Sigma Xi Seminar at Quinnipiac University
Hamden, Conn. – Dr. Paul J. Giammatteo, co-founder of Process NMR Associates, will present “Pulse, Acquire, Control: Ten Years of Online High-Resolution Nuclear Magnetic Resonance (NMR) in Refining, Petrochemical and Food Manufacturing” at 12 p.m. on Monday, March 27, in the Clarice L. Buckman Theater at Quinnipiac University.
The free lecture is open to the public and is part of Sigma XI Special Seminar Series.
From gasoline manufacturing to butter production, more than 140 online NMRs have been placed in manufacturing plants worldwide. Giammatteo will discuss installation and utilization of this technology, its application in the petroleum and petrochemical industries and the future in pharmaceuticals.
Giammatteo co-founded Process NMR Associates, based in Danbury, in 1997. He previously worked for Texaco for 17 years. Giammatteo received his doctorate in chemistry from Wesleyan University and has published and presented more than 30 papers.
For more information, contact James Kirby, associate professor of chemistry at Quinnipiac, at (203) 582-8275 or James.Kirby@quinnipiac.edu
March 10, 2006
NMR Applications in Food Quality
Overview document on Belgian Science Policy as it pertains to the use of low and high field NMR in the quality control of food.
Quantification by 1H NMR of Fatty Acids and Their Derivatives – by G. Knothe – USDA
An incredible repository of NMR information related to 1H and 13C NMR of Fatty Acids and their derivatives is found at the Lipid Library.
What is Your Carbon Footprint?
A handy calculator from BP allows you to calculate your impact on global warming – Carbon Calculator.
Heavy Oil and Bitumen Upgrading
“Bitumen from Canadian Oil Sands – The Worlds New Marginal Supply of Oil” – January 2006
“Oil Sands: Alberta’s Opportunity to Become a Significant Oil Exporter” – by Fluor, February 2004.
National Center for Upgrading Technology – Conference on “Upgrading and Refining of Heavy Oil, Bitumen and Synthetic Crude Oil” – September 2006 – Details
“Bitumen and Very Heavy Crude Upgrading Technology – A Review of Long Term R&D Opportunities” March 2004
Genoil demonstration of an upgraded bitumen – effects on TBP and other physical properties.
“Fueling an Integrated Energy Future” – Energy Innovation Network, December 2004
Kearl Lake Bitumen Extraction Project
“Historical Perspective of the Heavy Oil Resources of Utah”
USGS - “Heavy Oil and Natural Bitumen-Strategic Petroleum Resources”
“Non-Conventional Hydrocarbons – Where and How Much”
Energy Independence for North America Through Heavy Oil Upgrading – Presentation – same material but presented as a Paper
Alberta Energy Research Institute – Strategic Research Plan
Shell – Gasification in Heavy Oil Upgrading in Alberta
“The Impact of Emerging Research Techniques on Exploitation and Refining Technology Development” John Shaw – University of Alberta
“Alberta’s Oils Sands Opportunity”
Jacobs Engineering – Oils Sands Production Presentation
Total – Tar Sands Production Presentation
Effect of Tar Sands on World Oil Supply – Imperial Oil
Association for the Study of Peak Oil & Gas
Alternative Fuels – An Energy technology Perspective – March 2005
“Integration Opportunities for Coal/Oil Coprocessing With Existing Refineries”
Oil Sands Supply Outlook – March 2004
March 9, 2006
Spatial Encoding Produces 2D-NMR in a Single Scan
Ultrafast 2D NMR spectroscopy obtained in a single scan is described by Lucio Frydman of the Weizman Institutein his paper entitled “Single Scan 2D NMR”
Metabonomics Overview - High Field 1H NMR in Metabolite Profiling
Professor John Lindon (Metabometrix Ltd) provides an Overview of Metabonomics relating the role of high field 1H NMR in metabolite profiling in biofluids.
March 1, 2006
Polymer Chemistry Resource
Beautiful site that gives overviews of most polymer chemistry systems.
Wednesday, March 01, 2006
DECRA-FID Processing to Obtain Quantitative NMR Data???? March 1st, 2006
A strange CPACT NMR project development – DECRA processing of FID data - this involves quantitative analysis of FID signals in order to avoid automated phasing routines – in our process NMR experience phasing is a critical issue in the reproducibility of online NMR data, however, it is not an unsurmountable problem that leads to the development of new processing techniques such as those described here. Robust, repeatable phasing algorithms can be developed and implemented.
The Oil Drum - Peak Oil Blog March 1st, 2006
The Oil Drum is a blog dealing with the impending global problem of Peak Oil Production also called “Hubbert’s Peak” – or should we say Peak “Easy” Oil Production.Other sites that cover this topic are: Peak Oil News, Peak Energy, Past Peak (A little bit anti-Bush), and Peak Oil.Org.
Fossil fuel developments in Oil Shale, Tar Sands, and Coal Liquifaction will have to replace the “Easy Oil”. At $70 per barrel these are all plausible but research and development dollars have to be allocated. Running the world on Corn production is not the way to go technologically even though it satisfies the farming lobby.
European Commision Report on Food Quality Sensors March 1st, 2006
A short European Commision Report on “Food Quality Sensors” – includes spectroscopy (NMR, UV/Vis, NIR-Vis, Vis-Fluorescence, thermoraphy, acoustic impulse, electronic noses).
Cheddar Cheese Flavour - Chemistry and Sensory Perceptions March 1st, 2006
An excellent review on the chemistry of cheddar cheese and the sensory perceptions that arise from that chemistry. Comprehensive Reviews in Food Science and Food Safety, Vol 2 (2003).
Time-Domain NMR of Lipid Mobility in Bread March 1st, 2006
Low resolution 1H TD-NMR was utilized to determine the mobility and translational diffusion coefficients of lipids in a low moisture (glassy) bread. The mobility of the lipids was found to be independent of moisture content. Journal of Cereal Science (28) 1998, 147-155.
Solid-State 13C NMR of Meteors March 1st, 2006
Solid-state 1H and 13C Nuclear Magnetic Resonance (NMR) Spectroscopic experiments on isolated meteoritic Insoluble Organic Matter (IOM) obtained from four different carbonaceous chondrite meteorites; a CR2 (EET92042), a CI1 (Orgueil), a CM2 (Murchison), and an undesignated rank 2 meteorite, Tagish Lake. Short overview web page of NMR investigations into the carbon chemistry of meteorites. Journal article on this subject in PDF can be found here.
If you are interested in having your meteor materials analyzed by solid-state 13C NMR contact John Edwards at Process NMR Associates.
NMR in Industry - Review Papers Available February 26th, 2006
Industrial Applications of Nuclear Magnetic Resonance
NMR in Process Control
Applications of NMR to Food and Model Systems in Process Engineering
Process NMR Spectrometry
Practical Applications of NMR in Civil Engineering February 26th, 2006
Practical Applications of NMR in Civil Engineering.
NMR of Hydrocarbons - Online Papers Available February 26th, 2006
Though we have been performing NMR analysis to accurately correlate 1H NMR spectra with physical and chemical properties of gasoline (distillation, octane numbers, benzene, aromatics, olefins, oxygenates, RVP, density) for over a decade, papers still appear in the literature to vindicate that NMR is a powerful tool in the gasoline testing arena.
In a Fuel paper (Vol 83, 2004, 187-193) the Swiss Federal Laboratories for Materials Testing and Research demonstrate a integral ratio method was demonstrated to yield excellent results for many gasoline parameters of interest to the engineer.
Another strong proponent of NMR utilization in the study of petroleum hydrocarbons is G.S. Kapur of the Indian Oil Corporation. Here are a few of his papers:
1) “Analysis of Hydrocarbon mixtures by Diffusion Ordered Spectroscopy”, Fuel 79, 1347-51 (2000).
2)”The qualitative probing of hydrogen bond strength by diffusion-ordered NMR spectroscopy”, Tetrahedron Letters 41, 7181-7185 (2000).
3)“Unambigous Resolution of a-Methyl and a- Methylene Protons in 1H-NMR Spectra of Heavy Petroleum Fractions”, Energy Fuels 2005, 19, 508-511
4)”Simplification an assignment of proton and 2-dimensional hetero-correlated NMR spectra of petroleum fractions using gradient selected editing pulse sequences” Fuel 81 (2002) 883-892
A practical guide to PFG spin echo NMR for mixture analysis has been written by Brian Antelek of Eastman Kodak.
Characterization of Coke - Analytical Approach February 25th, 2006
An RSC review paper (Catalysis Volume 17) on the Characterization of Coke (on catalyst surfaces) is presented at the RSC site. The review covers use of AES, IR, Raman, UV, NMR, XRD, SIMS, etc.
NMR and Porometry February 25th, 2006
An overview of NMR applied to porosity of technology materials is presented in the dissertation of Roland Valckenborg entitled “NMR of Porous Technology Materials” (Eindhoven University of Technology 2001).
Another site covering a peculiar NMR application to porosity is the site for NMR Cryoporometry. In this one measures pore size distribution by freezing liquids in the pores and then monitoring melting temperatures by NMR - as the melting point is depressed for crystals of small size the melting point depression gives a measurement of the pore simension that the frozen liquid was in. This is a speciality of Dr. J.B.W. Webber at the University of Kent, UK.
High Resolution Flow NMR for Reaction and Process Monitoring February 23rd, 2006
Where NMR will make an impact in the process monitroing arena is in reaction monitoring where it has huge advantages over optical spectrocopy due to the chemical resolution inherent in the spectrum. An excellent poster by Mailwald et al. presents flow NMR applied to reaction monitoring utilizing a superconducting NMR spectrometer.
Bayesian Analysis of NMR Data - Software Available February 23rd, 2006
Professor Larry Bretthorst (Washington University at St Louis) has made available a Varian VNMR based software package for Bayesian analysis of NMR data. He also maintains a site on Bayesian probability theory.
A strange CPACT NMR project development – DECRA processing of FID data - this involves quantitative analysis of FID signals in order to avoid automated phasing routines – in our process NMR experience phasing is a critical issue in the reproducibility of online NMR data, however, it is not an unsurmountable problem that leads to the development of new processing techniques such as those described here. Robust, repeatable phasing algorithms can be developed and implemented.
The Oil Drum - Peak Oil Blog March 1st, 2006
The Oil Drum is a blog dealing with the impending global problem of Peak Oil Production also called “Hubbert’s Peak” – or should we say Peak “Easy” Oil Production.Other sites that cover this topic are: Peak Oil News, Peak Energy, Past Peak (A little bit anti-Bush), and Peak Oil.Org.
Fossil fuel developments in Oil Shale, Tar Sands, and Coal Liquifaction will have to replace the “Easy Oil”. At $70 per barrel these are all plausible but research and development dollars have to be allocated. Running the world on Corn production is not the way to go technologically even though it satisfies the farming lobby.
European Commision Report on Food Quality Sensors March 1st, 2006
A short European Commision Report on “Food Quality Sensors” – includes spectroscopy (NMR, UV/Vis, NIR-Vis, Vis-Fluorescence, thermoraphy, acoustic impulse, electronic noses).
Cheddar Cheese Flavour - Chemistry and Sensory Perceptions March 1st, 2006
An excellent review on the chemistry of cheddar cheese and the sensory perceptions that arise from that chemistry. Comprehensive Reviews in Food Science and Food Safety, Vol 2 (2003).
Time-Domain NMR of Lipid Mobility in Bread March 1st, 2006
Low resolution 1H TD-NMR was utilized to determine the mobility and translational diffusion coefficients of lipids in a low moisture (glassy) bread. The mobility of the lipids was found to be independent of moisture content. Journal of Cereal Science (28) 1998, 147-155.
Solid-State 13C NMR of Meteors March 1st, 2006
Solid-state 1H and 13C Nuclear Magnetic Resonance (NMR) Spectroscopic experiments on isolated meteoritic Insoluble Organic Matter (IOM) obtained from four different carbonaceous chondrite meteorites; a CR2 (EET92042), a CI1 (Orgueil), a CM2 (Murchison), and an undesignated rank 2 meteorite, Tagish Lake. Short overview web page of NMR investigations into the carbon chemistry of meteorites. Journal article on this subject in PDF can be found here.
If you are interested in having your meteor materials analyzed by solid-state 13C NMR contact John Edwards at Process NMR Associates.
NMR in Industry - Review Papers Available February 26th, 2006
Industrial Applications of Nuclear Magnetic Resonance
NMR in Process Control
Applications of NMR to Food and Model Systems in Process Engineering
Process NMR Spectrometry
Practical Applications of NMR in Civil Engineering February 26th, 2006
Practical Applications of NMR in Civil Engineering.
NMR of Hydrocarbons - Online Papers Available February 26th, 2006
Though we have been performing NMR analysis to accurately correlate 1H NMR spectra with physical and chemical properties of gasoline (distillation, octane numbers, benzene, aromatics, olefins, oxygenates, RVP, density) for over a decade, papers still appear in the literature to vindicate that NMR is a powerful tool in the gasoline testing arena.
In a Fuel paper (Vol 83, 2004, 187-193) the Swiss Federal Laboratories for Materials Testing and Research demonstrate a integral ratio method was demonstrated to yield excellent results for many gasoline parameters of interest to the engineer.
Another strong proponent of NMR utilization in the study of petroleum hydrocarbons is G.S. Kapur of the Indian Oil Corporation. Here are a few of his papers:
1) “Analysis of Hydrocarbon mixtures by Diffusion Ordered Spectroscopy”, Fuel 79, 1347-51 (2000).
2)”The qualitative probing of hydrogen bond strength by diffusion-ordered NMR spectroscopy”, Tetrahedron Letters 41, 7181-7185 (2000).
3)“Unambigous Resolution of a-Methyl and a- Methylene Protons in 1H-NMR Spectra of Heavy Petroleum Fractions”, Energy Fuels 2005, 19, 508-511
4)”Simplification an assignment of proton and 2-dimensional hetero-correlated NMR spectra of petroleum fractions using gradient selected editing pulse sequences” Fuel 81 (2002) 883-892
A practical guide to PFG spin echo NMR for mixture analysis has been written by Brian Antelek of Eastman Kodak.
Characterization of Coke - Analytical Approach February 25th, 2006
An RSC review paper (Catalysis Volume 17) on the Characterization of Coke (on catalyst surfaces) is presented at the RSC site. The review covers use of AES, IR, Raman, UV, NMR, XRD, SIMS, etc.
NMR and Porometry February 25th, 2006
An overview of NMR applied to porosity of technology materials is presented in the dissertation of Roland Valckenborg entitled “NMR of Porous Technology Materials” (Eindhoven University of Technology 2001).
Another site covering a peculiar NMR application to porosity is the site for NMR Cryoporometry. In this one measures pore size distribution by freezing liquids in the pores and then monitoring melting temperatures by NMR - as the melting point is depressed for crystals of small size the melting point depression gives a measurement of the pore simension that the frozen liquid was in. This is a speciality of Dr. J.B.W. Webber at the University of Kent, UK.
High Resolution Flow NMR for Reaction and Process Monitoring February 23rd, 2006
Where NMR will make an impact in the process monitroing arena is in reaction monitoring where it has huge advantages over optical spectrocopy due to the chemical resolution inherent in the spectrum. An excellent poster by Mailwald et al. presents flow NMR applied to reaction monitoring utilizing a superconducting NMR spectrometer.
Bayesian Analysis of NMR Data - Software Available February 23rd, 2006
Professor Larry Bretthorst (Washington University at St Louis) has made available a Varian VNMR based software package for Bayesian analysis of NMR data. He also maintains a site on Bayesian probability theory.
Monday, February 20, 2006
Overview of Solid-State 29Si NMR Studies of Silicone Gasket Materials
Silicon-29 NMR has a unique ability to probe the detailed solid state chemistry of silicone rubber materials. The chemical shift range of the various silicone chemistry groups spans 120 ppm (at 4.9T this equates to 4800 Hz). This is a large dispersion which allows all chemistry types to be readily observed. In these, studies, however, we have not attempted to identify every chemical type present. We have identified general chemical types and followed their relative concentration from one sample to the next. Both cross polarization and single pulse experiments were performed on magic angle spinning samples (a full explanation of these two complimentary experiments is given below). Optimal experimental conditions were initially obtained and all subsequent samples have been analyzed under identical conditions to facilitate an understanding of the spectral changes from a chemistry as well as molecular mobility standpoint. Set NMR experiment conditions were used because of the time consuming nature of these experiments which typically take around 12 hours for each of the cross polarization and single pulse experiments.
Experimental
At the present time samples are being run on a Varian UnityPlus-200 spectrometer operating at a 29Si frequency of 39.74 MHz. The probe was a Doty Scientific 7 mm Supersonic CP/MAS probe using zirconia and Kel-F end caps. For the single pulse NMR experiments a pi/6 pulse of 2 microseconds was used with a relaxation delay of 4 seconds to facilitate quicker acquisition.The 4 second relaxation delay was obatined from full T1-inversion recovery experiments. Gated proton decoupling was used during FID acquisition. For the cross polarization experiments full contact time array experiments were obtained on the initial samples submitted. Due to the mobility of the polymer backbone the optimum cross polarization contact time for the polymer backbone was around 15 ms with signal lasting until 50+ ms. However, the more rigid structures in the polymer – such as the silicates, had optimum contact times around 3-5 ms. As a compromise we chose a 6.4 ms contact time which yielded good signal sensitivity for both the polymer and silicate components. Cross polarization inversion recovery experiments yielded a short relaxation delay of 2 seconds. A 1H pi/2 pulse of 4.6 ms was used along with gated proton decouplind during FID acquisition. For all samples the same experimental conditions have been maintained. MAS spinning speeds were around 7 kHz to avoid spinning side band coincidence on real signals. Also, to avoid MAS induced modulation of the contact-time, the variable amplitude cross-polarization contact pulse was used.
Silicone Chemistry Observed by NMR
The notation in use for silicone chemistry is M,D,T,Q (mono, di, tri and quaternary) denoting the oxygen substitution on the silicon atom. The polymer backbone itself is predominantly D i.e. [(SiO2(CH3)2]n which has a typical resonance frequency around –21 ppm. The termination of the polymer would be an M group (SiO(CH3)3) (found at +4 to +10 ppm) or MOH (SiO(CH3)2OH) (-10 to –15 ppm). Another area of interest in the spectrum is the –20 to –10 ppm region which is partially due to MOH but also due to D type silicon centers that are within 5 monomer units of a termination. Thus, if hydrolysis of the silicone backbone is occuring, this region will increase in intensity as one will now have more silicon centers close to termination points as well as more MOH terminations.
In some gaskets one observes small signals in the –60 to –70 ppm region which is due to T type silicone centers (SiO3(CH3))n, however this is usually not observed. The only other region where one observes signal is in the –80 to –120 ppm region of the spectrum. These silicon centers can only be Q1 (SiO(OH)3), Q2 (SiO2(OH)2), Q3 (Si(OSi)3(OH)) or Q4 (SiO4)types, as only silicons with 4 attached oxygens can appear in this region, any methyl substitution would cause these silicons to appear in the +10 to –70 ppm range of the spectrum. Of relevance to any discussions on silicone polymers it should be noted that Q1 is equivalent to M(OH)3 , Q2 is equivalent to D(OH)2 , Q3 is equivalent to TOH.
When one looks at the NMR experiments for the certain silicones one does not observe a resonance at +10 to +4 ppm. This indicates that the predominant polymer termination is MOH. Silicate is observed, however, it is not clear if this silicate is a filler for hydrogen bonding crosslinking or actual polymer Q4/Q3/Q2 sites of directly condensed silicates acting as bonded crosslinking agents.
SP-MAS NMR Experiments
In this experiment one quantitatively observes all silicon species in the system allowing a “bulk” silicon type distribution to be calculated. One observes a narrow resonance at –21 ppm which is due to the silicone polymer backbone (-O-Si(CH3)2-O-)n. Very little signal is observed in the –20 to –10 ppm region indicating that the polymer chains are quite long. In the –80 to –120 ppm region of the spectrum one observes silicon present in silicate that has been added as a cross-linking agent. The hydrogen bonding between the silicone polymer and the Si-OH groups of the silicate add structural integrity to the gasket. It is differences in the silicate silanol (Si-OH) chemistry that may account for changes in compressibility of the gasket during service. Thus, one will observe relative changes in the amount of 29Si signal observed in the –80 to –103 ppm and –10 to –23 ppm regions of the spectrum. This region is where Q3 (Si(OSi)3(OH)), Q2 (Si(OSi)2(OH)2), and Q1 (Si(OSi)(OH)3) groups are found.
Parameters Calculated:
Silicate Content – %Si in silicate filler
Q4 - %Si atoms in Q4 silicate – Si(OSi)4
Qn – %Si atoms in Qn silicate (Q1, Q2, Q3)Q4/Qn Ratio – Silanol (Si-OH) distribution
% Polymer – %Si in D & MOH polymer units
Relative changes in these parameters can be utilized to interpret changes in silicon chemistry caused by coolant exposure and service.
CP-MAS NMR Experiments
This experiment warrants a detailed explanation as the results are not quantitative from a “bulk” silicon chemistry standpoint. The CPMAS experiment utilizes the strong NMR signal that can be generated from protons (H) in the sample. The experiment preferentially observes silicons that are in close proximity to H. However, mobility is also a “problem” in this experiment. The way the experiment works is that the protons in the sample are polarized initially and magnetization is transferred from the protons to the silicons via their dipole-dipole interaction (similar to the interaction between 2 bar magnets). This interaction weakens the further the H and Si are from each other, and also weakens if there is considerable molecular motion. In the case of these samples this means that in the silicate region of the spectrum one observes an enhancement of the signal due to Si-OH containing species. In the case of the silicone polymer, however, one observes an overall decrease in the signal at –21 ppm due to the –(O-Si(CH3)2-O-)n backbone due to its rapid segmental (rubbery) molecular motions. One observes a large signal (that is hardly observable in the SPMAS spectra) in the –5 to –20 ppm region. This is due to silicone silicons that are at or directly adjacent to crosslinking sites (where there could be a D-silicate bond, or polymer termination sites such as MOH. The fact that they are enhanced by the CP technique indicates that these termination proximate silicons are motionally restricted compared to the rest of the silicone backbone. They represent either strongly hydrogen-bonded regions or chemical crosslinks of the type (O2(CH3)2Si–O–Si-O–Silicate) where a defect in the silicone backbone has reacted with a silanol of the silicate filler to form a Si-O-Si bond. This experiment is very powerful when used to observe relative changes in Si-OH chemistry in the silicate region and relative mobility changes in the polymer backbone.
Parameters Calculated:
% polymer backbone – %Si in mobile silicone backbone
% restricted polymer backbone – %Si in motionally restricted regions of the silicone backbone (D units in close proximity to cross-linking sites, termination sites (MOH) or adjacent to termination sites).
Silicate Content – %Si in silicate filler.
Q4 - %Si in Q4 silicate – Si(OSi)4
Qn – %Si in Qn silicate (Q1, Q2, Q3)
Q4/Qn Ratio – relative change in silanol (Si-OH) distribution
As with the SP-MAS calculated parameters one can utilize these parameters to determine changes in silicon chemistry resulting from coolant exposure and service.
Table I Summary of 29Si NMR Chemical Shift Regions
Chemical Shift
Region (ppm) Species
+10 to +4 Polymer termination sites (SiO(CH3)3) M
-5 to –15 Polymer Termination Sites (SiO(CH3)2OH) MOH
-10 to -20 Motionally restricted silicone polymer. Cross-linked and H-bonded –(O-Si(CH3)2-O-)n D units within five monomer units of polymer termination(-21) D Units – motionally unrestricted silicone –(O-Si(CH3)2-O-)n
-75 to -85 Q1 Si(OSi)(OH)3 Silicate Center (M(OH)3)
-85 to -94 Q2 Si(OSi)2(OH)2 Silicate Center (D(OH)2)
-94 to -104 Q3 Si(OSi)3(OH) Silicate Center (TOH)
-104 to -120 Q4 Si(OSi)4 Silicate Center (Q)
Discussion
In use one observes that the gasket silicon chemistry changes dependent on additive chemistry and temperature/pressure conditions. When the polymers degrade one observes a general loss of D type signal intensity in the 29Si SP/MAS experiment as well as a corresponding increase in silicate content. One does not typically see changes in Q4 type but instead large changes in Q3 and Q2 content. These changes occur regardless of the presence of silicate in the coolant. This leads one to deduce that the Q3 and Q2 types are being generated by degradation of the polymer itself rather than a change in the chemistry of the silicate that was present in the sample initially. The author is not privy to additives and experimental conditions so he cannot speculate on the effect of silicate and other additives on the speed of the degradation that occurs. At the same time that Q3 and Q2 types are increasing in intensity the CP/MAS experiment clearly shows that there is a large increase in the relative amount MOH types and D types close to terminations (-5 to –20 ppm region). This proves that the exposure to coolants causes a hydrolysis of the Si-O-Si bond. However, it should also be notes that for the Q3 and Q2 types to appear one must also be hydrolyzing the Si-CH3 bonds.
The complimentary nature of the SP/MAS and CP/MAS experiments along with the use of only on set of experimental CP/MAS conditions means that relative changes in the various silicon chemistries can be analyzed to quantify the degree of degradation that a polymer has gone through.
Excellent Silicone Chemistry Link – Silicones in Pharmacutical Applications
For more information on this topic please contact:
John EdwardsManager, Process and Analytical NMR Services
Process NMR Associates LLC,
87A Sand Pit Rd
Danbury, CT 06810, USA
Tel: (203) 744-5905
Experimental
At the present time samples are being run on a Varian UnityPlus-200 spectrometer operating at a 29Si frequency of 39.74 MHz. The probe was a Doty Scientific 7 mm Supersonic CP/MAS probe using zirconia and Kel-F end caps. For the single pulse NMR experiments a pi/6 pulse of 2 microseconds was used with a relaxation delay of 4 seconds to facilitate quicker acquisition.The 4 second relaxation delay was obatined from full T1-inversion recovery experiments. Gated proton decoupling was used during FID acquisition. For the cross polarization experiments full contact time array experiments were obtained on the initial samples submitted. Due to the mobility of the polymer backbone the optimum cross polarization contact time for the polymer backbone was around 15 ms with signal lasting until 50+ ms. However, the more rigid structures in the polymer – such as the silicates, had optimum contact times around 3-5 ms. As a compromise we chose a 6.4 ms contact time which yielded good signal sensitivity for both the polymer and silicate components. Cross polarization inversion recovery experiments yielded a short relaxation delay of 2 seconds. A 1H pi/2 pulse of 4.6 ms was used along with gated proton decouplind during FID acquisition. For all samples the same experimental conditions have been maintained. MAS spinning speeds were around 7 kHz to avoid spinning side band coincidence on real signals. Also, to avoid MAS induced modulation of the contact-time, the variable amplitude cross-polarization contact pulse was used.
Silicone Chemistry Observed by NMR
The notation in use for silicone chemistry is M,D,T,Q (mono, di, tri and quaternary) denoting the oxygen substitution on the silicon atom. The polymer backbone itself is predominantly D i.e. [(SiO2(CH3)2]n which has a typical resonance frequency around –21 ppm. The termination of the polymer would be an M group (SiO(CH3)3) (found at +4 to +10 ppm) or MOH (SiO(CH3)2OH) (-10 to –15 ppm). Another area of interest in the spectrum is the –20 to –10 ppm region which is partially due to MOH but also due to D type silicon centers that are within 5 monomer units of a termination. Thus, if hydrolysis of the silicone backbone is occuring, this region will increase in intensity as one will now have more silicon centers close to termination points as well as more MOH terminations.
In some gaskets one observes small signals in the –60 to –70 ppm region which is due to T type silicone centers (SiO3(CH3))n, however this is usually not observed. The only other region where one observes signal is in the –80 to –120 ppm region of the spectrum. These silicon centers can only be Q1 (SiO(OH)3), Q2 (SiO2(OH)2), Q3 (Si(OSi)3(OH)) or Q4 (SiO4)types, as only silicons with 4 attached oxygens can appear in this region, any methyl substitution would cause these silicons to appear in the +10 to –70 ppm range of the spectrum. Of relevance to any discussions on silicone polymers it should be noted that Q1 is equivalent to M(OH)3 , Q2 is equivalent to D(OH)2 , Q3 is equivalent to TOH.
When one looks at the NMR experiments for the certain silicones one does not observe a resonance at +10 to +4 ppm. This indicates that the predominant polymer termination is MOH. Silicate is observed, however, it is not clear if this silicate is a filler for hydrogen bonding crosslinking or actual polymer Q4/Q3/Q2 sites of directly condensed silicates acting as bonded crosslinking agents.
SP-MAS NMR Experiments
In this experiment one quantitatively observes all silicon species in the system allowing a “bulk” silicon type distribution to be calculated. One observes a narrow resonance at –21 ppm which is due to the silicone polymer backbone (-O-Si(CH3)2-O-)n. Very little signal is observed in the –20 to –10 ppm region indicating that the polymer chains are quite long. In the –80 to –120 ppm region of the spectrum one observes silicon present in silicate that has been added as a cross-linking agent. The hydrogen bonding between the silicone polymer and the Si-OH groups of the silicate add structural integrity to the gasket. It is differences in the silicate silanol (Si-OH) chemistry that may account for changes in compressibility of the gasket during service. Thus, one will observe relative changes in the amount of 29Si signal observed in the –80 to –103 ppm and –10 to –23 ppm regions of the spectrum. This region is where Q3 (Si(OSi)3(OH)), Q2 (Si(OSi)2(OH)2), and Q1 (Si(OSi)(OH)3) groups are found.
Parameters Calculated:
Silicate Content – %Si in silicate filler
Q4 - %Si atoms in Q4 silicate – Si(OSi)4
Qn – %Si atoms in Qn silicate (Q1, Q2, Q3)Q4/Qn Ratio – Silanol (Si-OH) distribution
% Polymer – %Si in D & MOH polymer units
Relative changes in these parameters can be utilized to interpret changes in silicon chemistry caused by coolant exposure and service.
CP-MAS NMR Experiments
This experiment warrants a detailed explanation as the results are not quantitative from a “bulk” silicon chemistry standpoint. The CPMAS experiment utilizes the strong NMR signal that can be generated from protons (H) in the sample. The experiment preferentially observes silicons that are in close proximity to H. However, mobility is also a “problem” in this experiment. The way the experiment works is that the protons in the sample are polarized initially and magnetization is transferred from the protons to the silicons via their dipole-dipole interaction (similar to the interaction between 2 bar magnets). This interaction weakens the further the H and Si are from each other, and also weakens if there is considerable molecular motion. In the case of these samples this means that in the silicate region of the spectrum one observes an enhancement of the signal due to Si-OH containing species. In the case of the silicone polymer, however, one observes an overall decrease in the signal at –21 ppm due to the –(O-Si(CH3)2-O-)n backbone due to its rapid segmental (rubbery) molecular motions. One observes a large signal (that is hardly observable in the SPMAS spectra) in the –5 to –20 ppm region. This is due to silicone silicons that are at or directly adjacent to crosslinking sites (where there could be a D-silicate bond, or polymer termination sites such as MOH. The fact that they are enhanced by the CP technique indicates that these termination proximate silicons are motionally restricted compared to the rest of the silicone backbone. They represent either strongly hydrogen-bonded regions or chemical crosslinks of the type (O2(CH3)2Si–O–Si-O–Silicate) where a defect in the silicone backbone has reacted with a silanol of the silicate filler to form a Si-O-Si bond. This experiment is very powerful when used to observe relative changes in Si-OH chemistry in the silicate region and relative mobility changes in the polymer backbone.
Parameters Calculated:
% polymer backbone – %Si in mobile silicone backbone
% restricted polymer backbone – %Si in motionally restricted regions of the silicone backbone (D units in close proximity to cross-linking sites, termination sites (MOH) or adjacent to termination sites).
Silicate Content – %Si in silicate filler.
Q4 - %Si in Q4 silicate – Si(OSi)4
Qn – %Si in Qn silicate (Q1, Q2, Q3)
Q4/Qn Ratio – relative change in silanol (Si-OH) distribution
As with the SP-MAS calculated parameters one can utilize these parameters to determine changes in silicon chemistry resulting from coolant exposure and service.
Table I Summary of 29Si NMR Chemical Shift Regions
Chemical Shift
Region (ppm) Species
+10 to +4 Polymer termination sites (SiO(CH3)3) M
-5 to –15 Polymer Termination Sites (SiO(CH3)2OH) MOH
-10 to -20 Motionally restricted silicone polymer. Cross-linked and H-bonded –(O-Si(CH3)2-O-)n D units within five monomer units of polymer termination(-21) D Units – motionally unrestricted silicone –(O-Si(CH3)2-O-)n
-75 to -85 Q1 Si(OSi)(OH)3 Silicate Center (M(OH)3)
-85 to -94 Q2 Si(OSi)2(OH)2 Silicate Center (D(OH)2)
-94 to -104 Q3 Si(OSi)3(OH) Silicate Center (TOH)
-104 to -120 Q4 Si(OSi)4 Silicate Center (Q)
Discussion
In use one observes that the gasket silicon chemistry changes dependent on additive chemistry and temperature/pressure conditions. When the polymers degrade one observes a general loss of D type signal intensity in the 29Si SP/MAS experiment as well as a corresponding increase in silicate content. One does not typically see changes in Q4 type but instead large changes in Q3 and Q2 content. These changes occur regardless of the presence of silicate in the coolant. This leads one to deduce that the Q3 and Q2 types are being generated by degradation of the polymer itself rather than a change in the chemistry of the silicate that was present in the sample initially. The author is not privy to additives and experimental conditions so he cannot speculate on the effect of silicate and other additives on the speed of the degradation that occurs. At the same time that Q3 and Q2 types are increasing in intensity the CP/MAS experiment clearly shows that there is a large increase in the relative amount MOH types and D types close to terminations (-5 to –20 ppm region). This proves that the exposure to coolants causes a hydrolysis of the Si-O-Si bond. However, it should also be notes that for the Q3 and Q2 types to appear one must also be hydrolyzing the Si-CH3 bonds.
The complimentary nature of the SP/MAS and CP/MAS experiments along with the use of only on set of experimental CP/MAS conditions means that relative changes in the various silicon chemistries can be analyzed to quantify the degree of degradation that a polymer has gone through.
Excellent Silicone Chemistry Link – Silicones in Pharmacutical Applications
For more information on this topic please contact:
John EdwardsManager, Process and Analytical NMR Services
Process NMR Associates LLC,
87A Sand Pit Rd
Danbury, CT 06810, USA
Tel: (203) 744-5905
Thursday, February 16, 2006
High Temperature Simulated Distillation in Petroleum Characterization February 16th, 2006
“High Temperature Simulated Distillation” by Dan Villalanti et al. in Encyclopedia of Analytical Chemistry, “Yield Correlations between Crude Assay Distillation and High Temperature Simulated Distillation” by Villalanti et al., and “Refinery Analytical Techniques Optimize Unit Performance” . All discuss the panacea of developing rapid HTSD as a suitable replacement for the very lengthy crude assay distillation.
Exxon Technology Reviews - February 15th, 2006
Residue Upgrading Technologies are discussed in severla papers including one presented in India, and another at ERTC 2004 in Prague In Moscow at the 1st Bottom of the Barrel Technology Conference a paper was presented on “Delivering Value for Resid and Heavy Feed“.
Trends in NMR Logging - Schlumberger Review Article - February 15th, 2006
Oil exploration companies are using NMR measurements in a number of downhole applications, such as characterizing formation fluids during reservoir evaluation and assessing formation producibility. In their article “Trends in NMR Logging” Schlumberger describe how NMR technology is changing the way reservoirs are designed, developed and managed. A similar paper, “Advances in NMR Logging” is presented by Robert freedman of Schlumberger.Another review was produced in 1995, and “How to Use Borehole Nuclear Magnetic Resonance” was produced in 1997.
NMR Petrophysics offers NMR logging courses and provide NMR log analysis services.
A paper on the effect of sorbed oil on 1H NMR response was published byStanford University researchers.
A book is available on the subject entitled, “NMR Logging – Principles and Applications”
“Oil-Viscosity Predictions From Low-Field NMR Measurements” by J. Bryan and A. Kantzas, U. of Calgary/Tomographic Imaging and Porous Media Laboratory, and C. Bellehumeur, U. of Calgary
Application of TD-NMR in Civil Engineering - February 15th, 2006
Practical Applications of NMR in Civil Engineering by Bernd Wolter, Frédéric Kohl, Nina Surkowa, Gerd DobmannFraunhofer-Institut fuer zerstoerungsfreie Pruefverfahren (IZFP), Saarbruecken, Germany
Book Chapter - Monitoring Thermal Processes by NMR Technology - February 15th, 2006
A neew book on Emerging Technologies for Food Processing has been published by Elsevier, edited by professor Da-Wen Sun ( National University of Ireland, Dublin) and has contribution from KVL Quality & Technology: Monitoring Thermal Processes by NMR Technology by Nanna Viereck, Marianne Dyrby and Søren B. Engelsen. (Oct 2005)
MathNMR - NYU Software for Spin and Spatial Tensor Manipulations - February 15th, 2006
Professor Alexej Jerschow has made available a Mathematica package that allows calculation of spin and spatial tensors – it is available at the following link : MathNMR.
Also available at this site are a very handy palm utility that lists frequencies, gyromagnetic ratios, natural abundances, receptivities, magnetic and quadrupolar moments, and reference compounds of most NMR active nuclei – download PalmNMR. He also provides a nicely designed interactive NMR frequency map.
Italian patent - New Pre-Saturation Methodology - PERFIDI - February 15th, 2006
Stanislav Sykora, in his NMR blog describes a recent patent applied for by himself and Paola Fantazzini, under the auspices of the University of Bologna. The patent surrounds a new pulse sequence that will allow selective excitation of components of a complex mixture based on the T1 relaxation differences between the NMR active nuclei in the components. The pulse sequence pre-amble is called PERFIDI. The Italian patent (#BO2005A000445 of July 01, 2005) is currently confidential but the invcentors have set up a website for potential licensors of the technology. The website includes a brief overview of the patent.
Thursday, February 09, 2006
NMR Processing Freeware - SpinWorks
Dr. Kirk Marat at University of Manitoba has developed (and continues to develop) and excellent NMR processing freeware package that works very intuitively and well.
The FTP link to download the software is ftp://davinci.chem.umanitoba.ca/pub/marat/SpinWorks/.
The current version is 2.5.3. There is also an excellent documentation PDF file to help users work through the program functionality.
“What is SpinWorks:
SpinWorks has two functions: The first is to provide easy basic off-line processing of 1D NMR and 2D data on personal computers. SpinWorks other function is the simulation and iterative analysis of complex second order spectra including dynamic NMR problems and certain solid-state NMR problems, in a manner similar to our UNIX Xsim program. SpinWorks 2.4 is the forth release of SpinWorks version to contain 2D processing. Full support is included for Bruker (XwinNMR/UXNMR) and Varian (Unix VNMR) data formats. Included F1 detection modes include States, TPPI, States-TPPI, Single Detection (QF), and echo-antiecho. There have also been some improvements and bug fixes in the 1D and simulation routines, and these should be at least as stable as those in version 1.3. While the program is to the point where it should (I hope) be useful, there will, no doubt, be bugs and there are things that don’t yet work. The aim of the program is to make a program easy enough for undergrads to process magnitude COSY spectra (for example) with a single mouse click, and yet still be flexible enough for research use. SpinWorks currently handles only one data set at a time. However, most new computers have sufficient memory to run two or three copies of SpinWorks simultaneously. This can be very useful when examining the rows and columns of a 2D data set.
Computer Requirements:
SpinWorks requires a 486 or higher processor (Pentium recommended) running Windows 95, 98, NT 4.0, Windows 2000 Pro, or XP (NT 4.0, XP or Win 2000 recommended). Windows ME is probably O.K., but is untested. Installation currently requires about 5 Mbytes of disk space exclusive of NMR data. 32 Mbytes or more of RAM are recommended, depending on NMR data set and simulation sizes. SVGA 800 x 600 or better display required (1024×768 or better recommended). For 2D processing a Pentium class processor with 64 Mbytes of memory is the practical minimum. For 2D you should also have your display set to at least 16 bit colour, otherwise the image and contour level colours will be strange. I have received reports (but have not confirmed) that SpinWorks will run under Linux with the WINE package and on a Mac with SoftWindows. A three-button mouse is ideal, but SpinWorks will work just fine with a two-button mouse. Note that on “Wheel Mice” the mouse wheel also serves as the middle mouse button. The mouse wheel can also be used for vertical scaling of 1D spectra.”
Some NMR Technology Patents
Process NMR Technology Patents
Qualion NMR Patents
4998976 5063934 5072732 5162734 5184078 5320103 5371464 5462054 5978694 6281775 6310480 6670877 200400114236 20050040827
Other In-Line NMR Patents
Mobility Detected NMR - 6479994 6549007 6744251 6828892
Blending Control by NMR - 5796251
Ex-Situ NMR - 20030052677
Oil-Water Emulsion Compositions by NMR - 6794864
Bitumen Content by NMR - 6630357
Mobile NMR Analyzer - 5994903
Detection of Spoilage - 5270650
Microcoil Benchtop NMR - 5654636 6097188
Control of Process by NMR Gas Analyzer - 5265635
To search and get adobe acrobat pdf versions of patents go to Freepatentsonline.com
http://www.freepatentsonline.com/#.pdf
where # is patent number without commas patent 5,265,635 is 5265635.pdf
Qualion NMR Patents
4998976 5063934 5072732 5162734 5184078 5320103 5371464 5462054 5978694 6281775 6310480 6670877 200400114236 20050040827
Other In-Line NMR Patents
Mobility Detected NMR - 6479994 6549007 6744251 6828892
Blending Control by NMR - 5796251
Ex-Situ NMR - 20030052677
Oil-Water Emulsion Compositions by NMR - 6794864
Bitumen Content by NMR - 6630357
Mobile NMR Analyzer - 5994903
Detection of Spoilage - 5270650
Microcoil Benchtop NMR - 5654636 6097188
Control of Process by NMR Gas Analyzer - 5265635
To search and get adobe acrobat pdf versions of patents go to Freepatentsonline.com
http://www.freepatentsonline.com/#.pdf
where # is patent number without commas patent 5,265,635 is 5265635.pdf
Time-Domain NMR Spectrometers - Benchtop and Online Relaxometers
Time Domain Process NMR Spectrometers - Bench Top and On-Line Relaxometers
There are several NMR analyzers on the market that use an entirely different approach to some of the more simplistic on-line NMR applications. These spectrometers are very different from the Invensys MRA system in that they do not produce an chemical information. The Invensys MRA is a fully shimmed 60 MHz high resolution FT-NMR spectrometer that yields high resolution 1H NMR spectra which contain detailed chemical information that can be correlated with changes in chemical and physical properties. The other type of process NMR equipment is a low resolution time domain spectrometer that consists of a 1-30 MHz NMR system tied to an un-shimmed magnet. Only time domain data is acquired and relaxation time constants are calculated or correlated to physical properties or mixed phase content of mixtures.
For an overall view of NMR applied to process control or quality testing we are providing several links to papers or sites which adequately describe this "flip-side" of process NMR spectrometry.
On-Line Process NMR Relaxometry - Based on Auburn International/Oxford Instruments/Progression Technology - Polymer Qualities
The Analyst - Review Paper on Process NMR Spectrometry Covering Mainly Relaxometry Applications
Magritek - Low Field Portable and Specialty NMR Equipment
Minispec Analyzer from Bruker - Application Note Web Page
Maran NMR Analyzer from Universal Systems Inc - Applications Page
On-Line TD-NMR - Progression Inc
Applications of NMR Relaxometry - Process Control Technologies Inc
Time Domain Process NMR Spectrometers - NMR MOUSE
A handheld NMR surface analyzer is now available from Bruker or the collaborative research group that developed the technology.
NMR Mouse - Aachen Group Bruker Minispec MOUSE
Applications of NMR Mouse More Applications
Time Domain Process NMR Spectrometers - NMR Logging Tool
NMR logging tools have been developed for down-hole profiling of oil well pore structure and fluid reservoir structure and composition. This is NMR 1 mile down a hole.
Schlumberger NMR Logging Tool Description
Overview Paper - Trends in NMR Logging
Overview Paper - How to Use Down-Hole NMR
Lecture on Down-Hole NMR Logging
There are several NMR analyzers on the market that use an entirely different approach to some of the more simplistic on-line NMR applications. These spectrometers are very different from the Invensys MRA system in that they do not produce an chemical information. The Invensys MRA is a fully shimmed 60 MHz high resolution FT-NMR spectrometer that yields high resolution 1H NMR spectra which contain detailed chemical information that can be correlated with changes in chemical and physical properties. The other type of process NMR equipment is a low resolution time domain spectrometer that consists of a 1-30 MHz NMR system tied to an un-shimmed magnet. Only time domain data is acquired and relaxation time constants are calculated or correlated to physical properties or mixed phase content of mixtures.
For an overall view of NMR applied to process control or quality testing we are providing several links to papers or sites which adequately describe this "flip-side" of process NMR spectrometry.
On-Line Process NMR Relaxometry - Based on Auburn International/Oxford Instruments/Progression Technology - Polymer Qualities
The Analyst - Review Paper on Process NMR Spectrometry Covering Mainly Relaxometry Applications
Magritek - Low Field Portable and Specialty NMR Equipment
Minispec Analyzer from Bruker - Application Note Web Page
Maran NMR Analyzer from Universal Systems Inc - Applications Page
On-Line TD-NMR - Progression Inc
Applications of NMR Relaxometry - Process Control Technologies Inc
Time Domain Process NMR Spectrometers - NMR MOUSE
A handheld NMR surface analyzer is now available from Bruker or the collaborative research group that developed the technology.
NMR Mouse - Aachen Group Bruker Minispec MOUSE
Applications of NMR Mouse More Applications
Time Domain Process NMR Spectrometers - NMR Logging Tool
NMR logging tools have been developed for down-hole profiling of oil well pore structure and fluid reservoir structure and composition. This is NMR 1 mile down a hole.
Schlumberger NMR Logging Tool Description
Overview Paper - Trends in NMR Logging
Overview Paper - How to Use Down-Hole NMR
Lecture on Down-Hole NMR Logging
Compendium of Alternative Fuels Links
Alternative Fuels - General Links
Alternative Fuel Vehicle Directory
AlternativeFuels.Com
Alternate Energy Store
EPA - Alternative Fuels and Additives
Canadian Renewable Fuels Association
Scenarios for a Clean Energy Future
Center for Renewable Energy
Fuel Economy . GOV
How Does a Fuel cell Work?
Fuel Cell Information Center
Renewable Energy Magazine
A Clean Energy Future - Alberta Energy Research Institute
Federal Tax Treatment of Alternative Fuels
Alternative Fuels from Renewable Resources
Renewable biological systems for alternative sustainable energy production (FAO Agricultural Services Bulletin - 128)
Technologies for Clean Energy
Fuel Cells
US DOE Fuel Cells Program 2002 Review Meeting Reports
DOE Technical Publications
DOE General Information
DOE - Fuel Cell Related Links
Fuel Cell Today
The Business of Fuel Cells
SAE - Fuel Cell Technology Showcase
The Hydrogen and Fuel Cell Investor
Hydrogen
US DOE Hydrogen Program 2002 Review Meeting Reports
National Hydrogen Energy Roadmap
DOE Technical Publications
DOE General Information Fact Sheets
DOE Links to Organizations and Associations
DOE - Hydrogen Program Glossary
National Vision of America's Transition to a Hydrogen Economy
Hydrogen Now!
The Hydrogen Economy - Jeremy Rifkin
Hydrogen Economy Again
How Stuff Works - The Hydrogen Economy
The Coming Hydrogen Economy - Fortune
UK Parliament - Prospects for a Hydrogen Economy
Australia - State Sustainability Report - H Economy
The Hydrogen Economy in the 21st Century
Hydrogen and Fuel Cells
The Future of the Hydrogen Economy - Bright or Bleak?
European Perspectives on Facilitating the Hydrogen Economy
Shell Hydrogen Perspectives
Hydromax
Biodiesel
Biodiesel FAQ's
Biodiesel - AFDC
Biodiesel.Org
Canadian Renewable Fuels Association
Marine Biodiesel Handbook
Biodiesel Overview
Biodiesel Legislation - Final Rule
Resources on the Web
Biomass Conversion
BioFuels - DOE
Biofuels - Links
Regional Biomass Energy Program
Biomass Links from ORNL
Energy Crops
American Bioenergy Association
Biomass Conversion Technologies
Biomass Resources
Biomass Applications and Links
Biomass Sources for Industry
Advanced Processes for Biomass Conversion
Advanced Processes for Biomass Conversion to Energy
Biomass Fact Sheet
Biogas and Liquid Fuels from Biomass
Ethanol
Renewable Fuels Association - Ethanol Industry
Ethanol Marketplace
EPA Fact Sheet
Water-Diesel Mixtures
Lubrizol PuriNOx
Diesel Fuel and Gasoline Legislation
Diesel Fuel Regulations - EPA
Gasoline Regulations - EPA
Coal
Coal - Bridge to the Hydrogen Economy
Wood
Liquid Fuels from Wood
Biomass Feedstocks
Wood to Alcohol Fuels - Technology Status
Synthetic Liquid Fuels from Wood and Coal
Wood to Oil Process
Wood and Biomass to Fuel
Heavy Oil and Bitumen
Heavy Oil - Energy Source of the 21st Century
Canada's Heavy Oil and Tar Sands - Overview
Gas to Liquids
DOE - Natural Gas to Liquid Fuels
Rentech Inc - Gas to Liquids Technology
Steam Reforming
Steam Reforming Process - Synetix
Syn GasSynergy Technologies SynGas Process
SynGas Generation Technologies
Refining Overviews
Kittiwake : Fuel and Lube Oil Training Manual
Alternative Fuel Vehicle Directory
AlternativeFuels.Com
Alternate Energy Store
EPA - Alternative Fuels and Additives
Canadian Renewable Fuels Association
Scenarios for a Clean Energy Future
Center for Renewable Energy
Fuel Economy . GOV
How Does a Fuel cell Work?
Fuel Cell Information Center
Renewable Energy Magazine
A Clean Energy Future - Alberta Energy Research Institute
Federal Tax Treatment of Alternative Fuels
Alternative Fuels from Renewable Resources
Renewable biological systems for alternative sustainable energy production (FAO Agricultural Services Bulletin - 128)
Technologies for Clean Energy
Fuel Cells
US DOE Fuel Cells Program 2002 Review Meeting Reports
DOE Technical Publications
DOE General Information
DOE - Fuel Cell Related Links
Fuel Cell Today
The Business of Fuel Cells
SAE - Fuel Cell Technology Showcase
The Hydrogen and Fuel Cell Investor
Hydrogen
US DOE Hydrogen Program 2002 Review Meeting Reports
National Hydrogen Energy Roadmap
DOE Technical Publications
DOE General Information Fact Sheets
DOE Links to Organizations and Associations
DOE - Hydrogen Program Glossary
National Vision of America's Transition to a Hydrogen Economy
Hydrogen Now!
The Hydrogen Economy - Jeremy Rifkin
Hydrogen Economy Again
How Stuff Works - The Hydrogen Economy
The Coming Hydrogen Economy - Fortune
UK Parliament - Prospects for a Hydrogen Economy
Australia - State Sustainability Report - H Economy
The Hydrogen Economy in the 21st Century
Hydrogen and Fuel Cells
The Future of the Hydrogen Economy - Bright or Bleak?
European Perspectives on Facilitating the Hydrogen Economy
Shell Hydrogen Perspectives
Hydromax
Biodiesel
Biodiesel FAQ's
Biodiesel - AFDC
Biodiesel.Org
Canadian Renewable Fuels Association
Marine Biodiesel Handbook
Biodiesel Overview
Biodiesel Legislation - Final Rule
Resources on the Web
Biomass Conversion
BioFuels - DOE
Biofuels - Links
Regional Biomass Energy Program
Biomass Links from ORNL
Energy Crops
American Bioenergy Association
Biomass Conversion Technologies
Biomass Resources
Biomass Applications and Links
Biomass Sources for Industry
Advanced Processes for Biomass Conversion
Advanced Processes for Biomass Conversion to Energy
Biomass Fact Sheet
Biogas and Liquid Fuels from Biomass
Ethanol
Renewable Fuels Association - Ethanol Industry
Ethanol Marketplace
EPA Fact Sheet
Water-Diesel Mixtures
Lubrizol PuriNOx
Diesel Fuel and Gasoline Legislation
Diesel Fuel Regulations - EPA
Gasoline Regulations - EPA
Coal
Coal - Bridge to the Hydrogen Economy
Wood
Liquid Fuels from Wood
Biomass Feedstocks
Wood to Alcohol Fuels - Technology Status
Synthetic Liquid Fuels from Wood and Coal
Wood to Oil Process
Wood and Biomass to Fuel
Heavy Oil and Bitumen
Heavy Oil - Energy Source of the 21st Century
Canada's Heavy Oil and Tar Sands - Overview
Gas to Liquids
DOE - Natural Gas to Liquid Fuels
Rentech Inc - Gas to Liquids Technology
Steam Reforming
Steam Reforming Process - Synetix
Syn GasSynergy Technologies SynGas Process
SynGas Generation Technologies
Refining Overviews
Kittiwake : Fuel and Lube Oil Training Manual
Working Definitions of Use When Comparing Online Analyzer Results with Laboratory Test Data
Working Definitions
Accuracy – the ability of any test method, lab analysis, or analyzer, to yield the true value of the sample as a result of the measurement. That is, the result of the measurement gives the true value within the error of the measurement. The accuracy of any method is best determined by round-robin testing of that method.
Reproducibility – the determination of the spread around the true value. Determined by multiple measurements of the same samples at multiple sites (round-robin testing). It is the true error of the method.
Repeatability – the measurement of the spread around a test result from a single analyst and/or single analyzer at the same site on the same sample. However, this does not mean that the result is accurate (produces the true value).
Precision - the level to which any measurement can be accurate. That is, 46 or 46.259.
Bias – a definite offset from the true value. Consecutive single point measurements can be biased.
Model Definitions
Global Model: Any chemometric based prediction that incorporates lab analyses and samples from multiple locations on multiple streams, multiple processes, and multiple stream sources (i.e. crudes). By definition then, the prediction is accurate (predicting the true value) to within reproducibility. In order to compare a global model prediction to any single point lab measurement, the lab must first validate that the lab can meet the reproducibility requirements of the method, or ascertain it’s actual reproducibility by as described in ASTM D3764. Once the lab measurements are validated, single point lab measurement comparisons to the chemometric prediction should be within reproducibility limits. Global models are less prone to bias errors and drift.
Model Training: The process of enabling a global model to statistically recognize (i.e. f-test, mahalanobis distance, etc) the spectral results of a specific analyzer at a specific location. Requires no extensive lab sampling and analyses or exorbitant input of local unit and process specific spectral files to the model.
Local Models and Localization: Local models are built on data from a specific process unit, in a specific location, usually incorporating only lab analyses from the on-site laboratory. This effectively makes the model an on-line duplicate of the on-site laboratory and therefore subject to bias. Further, if a model is localized too much, it can be prone to drift (moving away from the true value) and/or fail to predict outside of the model space when the process changes or experiences an upset.
NMR Reproducibility: The limits of the differences between a valid, single point lab measurement and an NMR predicted result. This value is determined by the primary method and range of samples that the model is built on.
NMR Repeatability: The limits of the differences between successive predictions on a blocked in sample in the NMR under defined conditions. This value is determined bythe primary method and range of samples that the model is built on.
NMR Model and Application Strategies
NMR models based predictions are based on two types of applications: Process Control or Product Certification.
Process Control: Feed Forward and/or Feedback
Accuracy – the ability of any test method, lab analysis, or analyzer, to yield the true value of the sample as a result of the measurement. That is, the result of the measurement gives the true value within the error of the measurement. The accuracy of any method is best determined by round-robin testing of that method.
Reproducibility – the determination of the spread around the true value. Determined by multiple measurements of the same samples at multiple sites (round-robin testing). It is the true error of the method.
Repeatability – the measurement of the spread around a test result from a single analyst and/or single analyzer at the same site on the same sample. However, this does not mean that the result is accurate (produces the true value).
Precision - the level to which any measurement can be accurate. That is, 46 or 46.259.
Bias – a definite offset from the true value. Consecutive single point measurements can be biased.
Model Definitions
Global Model: Any chemometric based prediction that incorporates lab analyses and samples from multiple locations on multiple streams, multiple processes, and multiple stream sources (i.e. crudes). By definition then, the prediction is accurate (predicting the true value) to within reproducibility. In order to compare a global model prediction to any single point lab measurement, the lab must first validate that the lab can meet the reproducibility requirements of the method, or ascertain it’s actual reproducibility by as described in ASTM D3764. Once the lab measurements are validated, single point lab measurement comparisons to the chemometric prediction should be within reproducibility limits. Global models are less prone to bias errors and drift.
Model Training: The process of enabling a global model to statistically recognize (i.e. f-test, mahalanobis distance, etc) the spectral results of a specific analyzer at a specific location. Requires no extensive lab sampling and analyses or exorbitant input of local unit and process specific spectral files to the model.
Local Models and Localization: Local models are built on data from a specific process unit, in a specific location, usually incorporating only lab analyses from the on-site laboratory. This effectively makes the model an on-line duplicate of the on-site laboratory and therefore subject to bias. Further, if a model is localized too much, it can be prone to drift (moving away from the true value) and/or fail to predict outside of the model space when the process changes or experiences an upset.
NMR Reproducibility: The limits of the differences between a valid, single point lab measurement and an NMR predicted result. This value is determined by the primary method and range of samples that the model is built on.
NMR Repeatability: The limits of the differences between successive predictions on a blocked in sample in the NMR under defined conditions. This value is determined bythe primary method and range of samples that the model is built on.
NMR Model and Application Strategies
NMR models based predictions are based on two types of applications: Process Control or Product Certification.
Process Control: Feed Forward and/or Feedback
- NMR models cover a wider sample range.
- Very Robust: continue to accurately predict over wide process ranges.
- Reproducibility differences between the NMR prediction and any single point lab measurement will be slightly higher.
Product Certification: i.e. Blending
- NMR model ranges are narrowed and confined with respect to the product (i.e. gasoline and blend components only)
- NMR validation set at product certification levels.
- Models are not as robust. That is, a gasoline blending model will not predict a diesel fuel as accurately as a more broad based model.
For more information on this topic please contact:
John Edwards
Manager, Process and Analytical NMR Services
Process NMR Associates LLC,
87A Sand Pit Rd
Danbury, CT 06810, USA
Tel: (203) 744-5905
Online Process NMR Unit Description
Example of a Process NMR Unit
This analyzer, manufactured by Qualion Ltd, is marketed by Donahue Process Systems Inc.
1. Rack Mounted Computer
The rack-mounted computer provides supervisory control for all other units in the analyzer cabinet. This unit is a PC supplied with standard peripherals and I/O functions, such as an analog-to-digital converter for Channels I and Q, a system control board, control for the sample switching system, and a direct digital synthesizer (DDS). It also provides a communication link to a remote computer or modem link.
2. Switching Control Unit (RF Box)
The Switching Control Unit contains the following major components:
36 MHz crystal oscillator RF Sources Module Lock Transmitter Module
Lock Receiver Module Main Transmitter Module Main Receiver Module 36 MHz RF Filter
3. Shim Control Unit
The Shim control unit converts the digital shim signals from the computer and generates the current for the 50-shim coil pairs. It contains a communication board for coms to the computer, 50 ADC’s and 50 current generators.
4. Power Supply I/O Unit
The Power Supply I/O unit contains digital output modules for sample stop and sample switching valve control, digital input modules for enclosure alarms. A RS-485 Field Point connection for analog outputs and a RS-485 Modbus connection for digital connection to a DCS. It also provides all dc operating voltages for the system.
5. Magnet
The magnet is permanent and built from multiple segments of neodymium- boron-iron. This material is used because its very high field strength-to-mass ratio achieves the desired flux density in a small, compact package. Because the flux must be extremely uniform over the entire air gap, construction of the magnet is complex. The magnet is fabricated from several segments bonded together to form the basic assembly. In addition to the bonded segments of magnetic material, each magnet also contains 50 coils of wire arranged about a Shimming Unit mounted in the center of the magnet between the pole pieces. These coils are used as small electromagnets; the strength and polarity of which can be controlled by varying the current through them so as to improve uniformity of the overall field of the magnet assembly.
Prior to assembly in the manufacturing plant, each magnet segment is “cured” at a high temperature to stabilize its field strength. In the fabrication process, the absolute field strength of each individual segment of the magnet is measured. A computer analysis of this data then determines the best placement of each segment in the final assembly to achieve a consistent, uniform field for the assembled magnet. The segments are then bonded together to form the final magnet assembly. The assembly is placed inside a soft iron cylinder, the ‘envelope’, which constrains the magnetic flux and prevents the magnetic field outside the magnet housing from exceeding a value of as little as 5 gauss. More importantly, the iron cylinder raises field strength in the center of the magnet by pushing the flux toward the center; a process called “condensing the field”. There are electric heater strips and thermistors on the magnet and envelope to heat the assembly to the desired temperature.
6.Probe
The sample probe is mounted inside the permanent magnet in the air gap between the magnet poles. The probe contains two coils; the first, the ‘Main Coil’ is wound around a ceramic or molybdenum tube that is inserted in a hole through the shimming unit in the center of the gap between pole pieces of the magnet. The second coil, the ‘Lock Coil’ is wound on a sealed capsule of lithium chloride beside the main coil in the sample probe inside the permanent magnet. This is provided as a reference standard for setting the frequency of the main transmitter.
The constant magnetic field of the permanent magnet is perpendicular to the axis of the transmitter coil in the sample probe. Since the pulsed ac field introduced by the coil around the sample tube coincides with the vertical axis of the probe, the pulsed magnetic field is therefore perpendicular to the constant magnet field of the permanent magnet.
7. Heater Control Unit
The Magnet Heater Control Unit controls the temperature of the magnet and the envelope. The temperature of the magnet is set at 41°C and the temperature of the envelope is maintained at 37°C. The Heater Control Unit is mounted on the interior wall of the Magnet Enclosure Cabinet and has two PID loops that accept measurement input signals from the thermistors mounted on the magnet itself and the envelope. The outputs of these two PID loops control the currents to electric heater strips.
8. Enclosure
The NMR analyzer is housed in a two-door NEMA Type 4 enclosure approximately 48 inches high, 44 inches wide and 30 inches deep. Floor stands are approximately 12 inches high and are welded to the body to make it a freestanding enclosure.
The enclosure with equipment installed weighs approximately 1500 pounds and is equipped with transportation eyebolts. It is fabricated from 304 stainless steel, with all seams continuously welded and ground smooth. A center partition divides the enclosure into Magnet (left) and Electronics (right) compartments.
The magnet side is home to the gas leak detector and the ambient temperature is maintained at 72°F ±1°F. This is accomplished by means of an air conditioner on the outside left wall of the enclosure working in conjunction with a bank of five 500-watt strip heaters and a PID Controller. The ambient temperature in the Electronics side is controlled by an air conditioner on the outside right wall with an internal thermostat set at approximately 70°F.
Principle of Operation
The Qualion Process NMR System
The signal is then digitally processed passed though the prediction models to obtain a prediction, the prediction is then transmitted to a DCS or receiver via analog or modbus outputs. After this has happened the sample stop valve is opened and the cycle is repeated. The lock circuit is constantly performing a NMR experiment on the Lithium Chloride, this is done as a reference. The frequency of Lithium in the NMR magnet is around 22 MHz and therefore does not interfere with observing hydrogen at 60 MHz. Because the magnet is highly dependent on temperature it is impossible to maintain a constant temperature and there for, as we know where the Lithium Chloride peak should be we can reference the main circuit to the same as the Lithium Chloride peak is away from where is should be.
Main Circuit
The crystal oscillator outputs a 36 MHz signal, which is sent to the DDS card. The DDS unit multiplies, divides, and/or phase shifts the signal and outputs a 51 MHz signal that is used as the main transmitter and receiver local oscillators (MAIN_TX_LO and MAIN_RX_LO). A 9 MHz signal from the DDS unit is added to the MAIN_TX_LO signal to produce the main transmitter frequency of 60 MHz, which is transmitted to the diplexer and then switched to the main transmitter coil in the probe. After the main transmitter pulse is removed, the nuclei relax and generate a 60 MHz signal in the coil, which flows to the diplexer, where it is automatically switched to the receiver input. The received signal is amplified and then mixed with the MAIN _RX_LO signal (51 MHz) to produce an Intermediate Frequency (IF) of 9 MHz. This signal is then mixed with 9 MHz from the DDS card to produce an audio frequency of approximately 1 kHz. The audio signal is then split into two equal channels, I and Q, phase separated by 90°. The I and Q signals are then input to the ADC, where they are converted to digital form for input to the PC.
The purpose of the lock system is to provide control of the frequency of the main transmitter pulse, automatically compensating for any minor variations in magnet field strength and temperature. The lock system continuously detects the resonant frequency of the nuclei in a known sample fluid, lithium chloride, and then sets the frequency of the main transmitter to be a fixed ratio to this reference. Since the reference fluid capsule is located inside the main probe, it is subjected to the same magnetic field and temperature as the main transmitter/receiver. Therefore, a change in one affects the other. The lock system functions in the same general way as the main transmitter system, except that the basic transmitter frequency is approximately 22 MHz, the resonance frequency of lithium in a magnetic field of 1.5 tesla. The frequency of the lock transmitter is swept over a range of about 1 MHz (22-23 MHz) as it searches for the resonance frequency of lithium. When it first detects a resonant response (significant increase in signal level) as it increases frequency during the search, it stores this value and then jumps to a higher frequency and approaches resonance from the other direction. When it detects a resonance response as it approaches from the other direction, it stores this frequency and then jumps to a frequency at the mid point between the two stored values and then “locks” on this frequency as the resonance frequency of lithium. The output of the lock system is used as the set point of the main transmitter circuit, which maintains the main transmitter frequency in a fixed ratio to this “lock” frequency.
To obtain a rough magnetic field, the field homogeneity of the permanent magnet is adjusted by mechanical alignment of the magnet pole faces. The more parallel the pole faces, the more homogeneous the magnetic field. The first step in the process of adjusting magnetic homogeneity is to adjust the position of the magnet's pole faces by turning adjustment bolts which hold the pole faces in position. Adjusting these bolts tilts the pole faces relative to each other with the aim of making the pole faces more parallel. In old electromagnetic magnets, if the bolts ran out of range, thin pieces of brass were placed between the magnet yoke and the pole pieces to move the pole pieces as parallel as possible. These thin pieces of brass were also placed in other strategic locations to make the pole faces parallel in a manner not addressed by the adjustment bolts. The metal pieces were called shim stock and the seemingly endless process of placing and removing pieces of shim stock acquired the name "shimming". This is, however, a simple mechanical adjustment that only gets the NMR to a symmetric half height of 700 Hz. To increase performance, reduce the difficulty of adjusting magnetic homogeneity, and reduce the manufacturing difficulty of the magnets, an electronic "shimming" process is used, which uses a series of small electromagnets (essentially shaped coils) having very specific magnetic field contours. These small coils are placed around the sample area in different orientations. Each small coil can be used to adjust the shape of the magnetic field gradients by simply passing different currents through the coil. A complete series of these coils can be used to adjust the magnetic field homogeneity to a given level of “purity”. The process of adjusting the magnetic field homogeneity by adjusting the current in each of the coils has retained the name “shimming” and the small coils assumed the name "shims".
Systems are marketed through Donahue Process Systems Inc
Contact John Edwards for details and visit the Process NMR Associates web page for application examples.
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