Multinuclear and hypersensitive MRM in heterogeneous catalysis

In many heterogeneous catalytic processes, heat transport is an important factor which, if not properly controlled, can lead to the formation of hot spots in the catalyst bed, degradation of reaction conversion and selectivity, reactor runaway and even explosion. The development of non-invasive thermometry techniques for the studies of operating reactors is necessary to advance our understanding of heat transport processes in the catalyst bed and is essential for the development of efficient and environmentally safe industrial reactors and processes.

NMR analyzer and MRI techniques are known to be able to evaluate local temperatures of liquids. However, for a multiphase gas-liquid-solid reactor the available techniques based on the liquid phase benchtop NMR signal detection are not applicable since the local liquid content in the catalyst pores varies with space and time.

We have demonstrated earlier that the direct 27Al MRI of industrial alumina-supported catalysts (e.g., Pd/Al2O3) is a potential way toward the spatially resolved thermometry of an operating packed bed catalytic reactor. Recently, we were able to implement this approach and to obtain 2D temperature maps of the catalyst directly in the course of an exothermic catalytic reaction. The images obtained clearly demonstrate the temperature changes with the variation of the reactant feed and also the existing temperature gradients within the catalyst at a constant feed.

One of the obstacles in developing novel applications of MRM in porous media is its fairly low sensitivity even if 1H signal detection is used. A number of hyperpolarization techniques are currently being developed that can enhance the NMR signal by 4-5 orders of magnitude even at intermediate (3-7 T) magnetic fields, and even more in low and ultra-low magnetic field applications that are currently gaining popularity. Parahydrogen-induced polarization (PHIP) is the only hyperpolarization technique of relevance to catalysis as PHIP effects are observed in hydrogenation reactions when parahydrogen is involved.

We have shown that PHIP can be generated not only in homogeneous hydrogenation reactions but also in heterogeneous catalytic processes catalyzed by a broad range of different heterogeneous catalysts. Thus, the development of the novel hypersensitive NMR/MRI techniques for heterogeneous catalysis becomes possible.

Also, this approach can provide hyperpolarized gases and catalyst-free hyperpolarized liquids for a wide range of novel applications of NMR and MRI in, e.g., materials science, chemical engineering and in vivo biomedical research. Applications of this hypersensitive approach to the studies of gas flow in microfluidic chips and of the hydrogenation reaction in a packed bed microreactor will be demonstrated.

This work was supported by the following grants: RAS 5.1.1, RFBR 11-03-00248-a and 11-03-93995-CSIC-a, SB RAS integration grants 9, 67 and 88, NSh-7643.2010.3, FASI 02.740.11.0262 and МК-1284.2010.3.

Laplace Inversion for Obtaining Relaxation-Chemical Shift Correlation

Kerogen is the most abundant organic matter that is dispersed in the earth’s formation and is the source of fossil fuels such as oil and gas. Large amounts of kerogen exist in the form of oil shale which is not favorable for extraction.

The largest accumulation of oil shale is located in the Piceance Basin, Colorado. The so called ‘Green River oil shale’ was deposited in a lacustrine environment and contains type-1 kerogen as an organic resource. Even though the depositional environment is known there are details of the molecular structure of type-1 kerogen which still have to be identified.

We used 13C and 15N high resolution solid state benchtop NMR spectroscopy as one of the primary methods to elucidate the structure of kerogen through measurements of chemical shift, spin-lattice relaxation time, variable contact time, and dipolar dephasing rates. Using single or double exponential fitting methods, one can extract structural information from the variation of peak intensity with mixing times used in CP/MAS or dipolar dephasing experiments.

Here we introduce a new data processing method that uses a Laplace inversion algorithm to process a set of CP/MAS NMR analyzer data with different mixing times to generate 2D NMR spectrum that gives a chemical shift in one dimension and relaxation time in the second dimension.

The relaxation-chemical shift 2DNMR can be used to determine 13C (or 15N) chemical shift, proton spin-lattice relaxation time, cross polarization time, and dipolar dephasing time constant as well as their distributions for mixture samples such as oil shale. It also improves the accuracy of deriving structural parameters of macromolecules using both 13C or 15N chemical shift and relaxation cutoffs.

Flow and Diffusion Measurement with MR

Nuclear magnetic resonance (NMR) non-invasively accesses many parameters in contrast with other commonly used measurement methods, whether they are non-invasive or not.
These parameters can be divided roughly into three classes of information: chemical, physical, and spatial.Chemical includes benchtop NMR spectroscopy, the workhorse in analytical chemistry and in structural biochemistry but, to date, there has been relatively little overlap between this class and this conference.
Physical information accessible with NMR analyzer includes molecular structure, phase transition, diffusion, and flow.Both chemical and physical information can be combined with spatial information to produce maps of such information.In addition, flow and diffusion, by their nature, involve spatial information.
Such spatially resolved information is the main emphasis of this meeting.In this lecture, I shall review NMR flow and diffusion measurements.What is needed for such measurements is the presence of a known gradient of the static magnetic field strength in which the experiments are conducted.
When a nuclear spin moves in the field gradient, its precession rate changes and this can be detected to yield the displacement of the spin in the time required to do the experiment–times measured in milliseconds.The dependence of such displacements as a function of measurement time results in identification of the nature of sample motion, i. e., whether it is flow or diffusion.
We will start with basic principles and go on to examples with emphasis on gaining physical background knowledge that may aid in understanding flow and diffusion presentations during this meeting.Some references to this subject are listed below.The last three are based on previous ICMRM conferences, specifically in 1991, 1997, and 2009.

Mobile Desktop NMR

Mobile NMR started in the well logging industry. Early on, benchtop NMRdevices were developed to be deployed inside the borehole to characterize the fluids of the well downhole [1]. The successful NMR analyzer well-logging devices measure distributions of relaxation and diffusion parameters in the stray field of permanent magnets .

The same principle is followed with the much smaller NMR-MOUSE , which has a higher field, a stronger gradient, and a smaller sensitive volume. It is used for nondestructive materials testing of large objects such as rubber tires, polymer pipes, and objects of art . Today, the NMR force microscope is the smallest stray-field NMR device .

While the sensitive volume of stray-field NMR devices can be shaped with proper magnet design , the sensitivity can significantly be improved only by enlarging the sensitive volume and the field strength, a strategy which returns mobile NMR to the roots of NMR spectroscopy and imaging with closed magnets.

In fact, a variety of desktop MRI magnets has been pioneered by Kose , and the first miniature spectroscopy magnet has been developed by McDowell . Today miniature NMR gadgets are targeted for specific detection of biomarkers , and the first desktop NMR spectrometers for chemical analysis by high-resolution NMR appear on the market .

The advances in mobile NMR are expected to benefit from the progress in developing widely applicable and miniaturized hyperpolarization methodologies, alternative detection schemes, microfluidic components for sample preparation and handling, the use of high-TC superconducting magnets, and the development of user-friendly apps for different types of information-driven measurements by untrained NMR consumers.

Time Domain Analysis Numerical Simulation and Influence Factors of NMR Logging

Time Domain Analysis (TDA) of NMR analyzer logging data has been successfully used to identify and evaluate quantitatively the oil and gas layers. The successfulness of TDA method, however, can be affected by the complex pore structure of rock and the changing properties of reservoir fluids. This paper uses numerical simulation to study the performance of TDA method in the identification and quantitative evaluation of fluids from different kinds of reservoirs.

A number of factors are analyzed, including the type of fluids, different pore sizes, signal-to-noise ratios (SNR) and NMR logging acquisition parameters. The results show that TDA method can accurately identify light oil layer (viscosity < 5mPa.s). In oil-bearing water layer with small-pore movable water, TDA method can accurately determine the oil porosity of formation; in oil-bearing water layer with big-pore movable water, however, TDA method could over-estimate the actual oil porosity of formation.

In a macroporous water layer, a short waiting time of 1s is not sufficient for the water to fully recover in the measurement; consequently, the presence of strong water signal in the differential spectrum of TDA could produce a result that is the opposite of the test result.

In gas layer, TDA method can accurately determine the gas porosity of formation. However, in gas-bearing water layer with small-pore movable water,benchtop NMR results are usually inconsistent with test results. Differential spectra of TDA between gas layer bearing water with big-pore movable water and small-pore oil gas layer can have similar features, which is often difficult to differentiate.

It is suggested to combine the dual-echo-spacing logging data to distinguish the gas layer bearing water with big-pore movable water. When the SNR is lower than a certain threshold, the right hand of the differential spectrum signal diverges, which reduces the accuracy in the determination of the hydrocarbon porosity of formation.

It is also found that high hydrogen index of gas is useful to distinguish the gas layer. A well-designed pre-logging plan can ensure that all logging parameters are optimized, which will improve the results of TDA method for the identification of hydrocarbon fluids.

Nuclear Magnetic Resonance Hardware

This educational session lecture introduces the elements of the generic MR system hardware required to obtain images or spectra. The design criteria and function of the magnets, gradients, radiofrequency spectrometer and RF coils are examined. Examples of each, how they are designed and optimized is given (with examples) in the lecture. As far as possible examples related to the topics covered by ICMRM 11 will be given. 

Magnets It is most usual for high field, homogeneity and stability magnets to be based on superconductive technology with axially symmetric coil windings. These magnets deliver the highest performance but require cryogenic cooling and are generally not portable (a 7T whole body system is 35 tons). In microscopy and materials applications the desirable parameters may be compromised in order to give portability, light weight or to fit with other constraints. These magnetic fields are then generated by a combination of electromagnet, permanent magnets and other magnetic materials. Magnetic fields may be optimized to give the best homo-geneity or gradient at a particular sweet-spot (which could be outside the magnet itself). 

Gradients In order to spatially resolve the benchtop NMR signal then electromagnets are employed to give a (usually) linear profile in Bz with all three (or fewer) spatial axes. Gradient design techniques based on target field and boundary element methods are discussed. Examples of conventional cylindrical gradient design are shown. These design methods can be further exploited to give gradient designs on non-cylindrical geometries or arbitrary former shapes. Gradient design methods can be used to design both shim and pure electromagnet based field profiles. 

RF Systems: Spectrometer The radiofrequency (RF) spectrometer is the central control component for the NMR analyzer system and provides system master clock and timings of gradient and RF pulses. The phase and timing stability in a high resolution system is critical and should exceed the magnet in its performance. This level of performance can be achieved if certain design specifications and criteria are followed. The modern spectrometer system is predominantly digital, with analogue components only making up the final parts nearest to the RF coils (i.e. power amplifiers, low-noise pre-amplifiers and transmit-receive switching et el). For example, in the most recent Ingenia body systems from Philips the entire acquisition system is placed on the receive coil itself within the magnet. 

RF Systems: Coils After the main field strength, it is the quality and ability of the coil to faithfully pick up the NMR signal from the sample which defines the overall quality of our information. Signals and noise in an NMR experiment is discussed and the importance of optimum noise matching is introduced. Examples of coils which satisfy a range of demands in various geometries are discussed. The role of finite element RF simulation in coil design is demonstrated. This educational session lecture introduces the elements of the generic MR system hardware required to obtain images or spectra. The design criteria and function of the magnets, gradients, radiofrequency spectrometer and RF coils are examined. Examples of each, how they are designed and optimized is given (with examples) in the lecture. As far as possible examples related to the topics covered by ICMRM 11 will be given. 

Magnets It is most usual for high field, homogeneity and stability magnets to be based on superconductive technology with axially symmetric coil windings. These magnets deliver the highest performance but require cryogenic cooling and are generally not portable (a 7T whole body system is 35 tons). In microscopy and materials applications the desirable parameters may be compromised in order to give portability, light weight or to fit with other constraints. These magnetic fields are then generated by a combination of electromagnet, permanent magnets and other magnetic materials. Magnetic fields may be optimized to give the best homo-geneity or gradient at a particular sweet-spot (which could be outside the magnet itself). 

Gradients In order to spatially resolve the NMR signal then electromagnets are employed to give a (usually) linear profile in Bz with all three (or fewer) spatial axes. Gradient design techniques based on target field and boundary element methods are discussed. Examples of conventional cylindrical gradient design are shown. These design methods can be further exploited to give gradient designs on non-cylindrical geometries or arbitrary former shapes. Gradient design methods can be used to design both shim and pure electromagnet based field profiles. 

RF Systems: Spectrometer The radiofrequency (RF) spectrometer is the central control component for the NMR system and provides system master clock and timings of gradient and RF pulses. The phase and timing stability in a high resolution system is critical and should exceed the magnet in its performance. This level of performance can be achieved if certain design specifications and criteria are followed. The modern spectrometer system is predominantly digital, with analogue components only making up the final parts nearest to the RF coils (i.e. power amplifiers, low-noise pre-amplifiers and transmit-receive switching et el). For example, in the most recent Ingenia body systems from Philips the entire acquisition system is placed on the receive coil itself within the magnet. 

RF Systems: Coils After the main field strength, it is the quality and ability of the coil to faithfully pick up the NMR signal from the sample which defines the overall quality of our information. Signals and noise in an NMR experiment is discussed and the importance of optimum noise matching is introduced. Examples of coils which satisfy a range of demands in various geometries are discussed. The role of finite element RF simulation in coil design is demonstrated. 

2016-2021 NMR Spectrometer Overall Market Research Report

This report studies Nuclear Magnetic Resonance Spectrometer (NMR) in Global and China market, focuses on top manufacturers in global and China market, involving Nuclear Magnetic Resonance Spectrometer (NMR analyzer) price of each type, production, revenue and market share for each manufacturer. This report also displays the production, revenue and market share of Nuclear Magnetic Resonance Spectrometer (NMR) in USA, EU, China, Japan, India and Southeast Asia, forecast to 2020, from 2011.

The market intelligence report on the Global and China Nuclear Magnetic Resonance Spectrometer NMR market offers a detailed analysis of the market, emphasizing on the key growth drivers and challenges. The study intends to provide a clear understanding of the market along with the prominent factors that are estimated to impact the Global and China Nuclear Magnetic Resonance Spectrometer NMR market in the next few years. The comprehensive summary presented in the research study analyzes the market and the major segments.

The research study presents the past performance of the Global and China Nuclear Magnetic Resonance Spectrometer benchtop NMR market along with the estimated figures with the help of tables, graphs, info-graphics, and charts to give a clear picture of the market. In addition, several tools are used to determine the growth rate of the overall market from 2016 to 2021. These statistics have been given on the basis of value as well as on volume.

The research report has answered to some queries concerning the Global and China Nuclear Magnetic Resonance Spectrometer NMR market. Some of the questions are given below:
- What are the prominent factors driving the Global and China Nuclear Magnetic Resonance Spectrometer NMR market?
- What is the estimated size of the Global and China Nuclear Magnetic Resonance Spectrometer NMR market in the coming few years?
- What are the major sustainability strategies and policies adopted by the leading players?
- Which application segment is estimated to lead the Global and China Nuclear Magnetic Resonance Spectrometer NMR market?
- Which region is anticipated to remain dominant in the Nuclear Magnetic Resonance Spectrometer NMR market?
- How is the competitive scenario of the Global and China Nuclear Magnetic Resonance Spectrometer NMR market?
- What are the major market trends influencing the growth of the Global and China Nuclear Magnetic Resonance Spectrometer NMR market?

Furthermore, the research study covers the competitive scenario of the Global and China Nuclear Magnetic Resonance Spectrometer NMR market and offers detailed profiles, including the product portfolio, business policies, and financial status of the leading players in the market. In addition, a SWOT analysis of the prominent players has also been discussed in the research report.

Table of Contents

1 Industry Overview of Constant Nuclear Magnetic Resonance Spectrometer NMR
1.1 Definition and Specifications of Constant Nuclear Magnetic Resonance Spectrometer NMR
1.1.1 Definition of Constant Nuclear Magnetic Resonance Spectrometer NMR