CEMTREX, INC.
MODCON SYSTEMS LTD
MOD 8000 Process MRS Analyzer 3rd
Generation On-Line MRS Analyzers
November 2012
The NMR Technology Fundamental Background
Proton – Magnetic Moment (M)
Hydrogen Atom
(Proton)
+
M
Proton is spinning Magnetic moment(M) generated
Spins
With no magnetic field,
magnetic moments are random
In Strong Magnetic Field
(Bo), magnetic moments align along Bo
Align and Precess
Magnetic Moments Align and Precess
at a Frequency wo
wo is Proportional to size of Bo
Bo = 1.4 Tesla wo = 60 MHz
Magnetic Moment
Precessing Spins can be described as
a Bulk Magnetic Moment Mo*
*Mo = Summation of Individual Magnetic Moments
Radio Frequency Pulse
RF Pulse turned on for 4-20 microseconds
Generates a Second Magnetic Field B1
Re-Align to Second Magnetic Axis
Magnetic Field B1 Causes Mo to Move
and re-align to second Magnetic axis
Re-Align to Original Magnetic Axis
When RF Pulse ends protons relax and align to
their original equilibrium position along Bo Axis
A decay signal is generated : Free induction Decay Signal (FID)
Fourier Transform
F.F.T.
Free Induction Decay(FID)
Time domain signal
NMR Spectrum
Frequency domain
The Technology :What is NMR?
•
Nuclear Magnetic Resonance - is an effect whereby magnetic nuclei in a magnetic field absorb and re-emit
electromagnetic (EM) energy at a specific resonance frequency. The resonance frequency depends mainly
on the strength of the magnetic field.
•
This physical phenomena can provides picture or spectra of the hydrocarbon structure, which enable to
determine physical and chemical information.
•
A major benefit of this analyzer is the capability to provides continuous flow-through and accurate chemical
and physical analysis of multiple components in dense and opaque materials.
•
Additional key advantage is a linear spectral
response across a broad range which enables
models to be extrapolated accurately. NMR
technology does not have the continual model
maintenance issue which caused by spectral
changes seen with crude composition changes.
Typical Hydrocarbon Spectrum
Evolution of Process NMR Systems
•
First process NMR analyzer was introduced in the late nineties of the last century.
•
This analyzer was characterized by its high sensitivity towards temperature
variations, which is its main drawback.
•
In spite of improvement made in previous generations, the magnets were typify by a
low to medium homogeneity and of high susceptibility towards temperature
fluctuations. The stability of the magnets homogeneity was affected by temperatures
differences between process streams.
•
To achieve stable homogeneity of the magnetic field, temperature fluctuations must
be isolated from influencing the magnet properties.
•
The re-design of the 3rd generation process NMR analyzers (hardware and software),
resulted in a decreased temperature susceptibility. Allowable temperature deviations,
without affecting the accuracy and reliability of the analytical measurements
increased from ± 2C to ± 10C. It enables the NMR analyzer to be applied to any
stream, notwithstanding the temperature differences between them.
•
The overall new design ensure successful application of this unique technology in
refineries and chemical process industries.
1997- 1st Generation of Process NMR System
– Magnet – 18mm bore size (medium homogeneity; high temperature susceptibility;
inadequate repeatability)
– 7 Electronic units (Shim controller; RF unit; PS unit; 19” rack PC; Heater controller;
ADC PCB; Timing PCB)
– Shim coils – manually wrap around coils ( inferior performance; inadequate
repeatability)
– Probe – Low Q (low SNR- Signal to Noise Ratio); defective temperature insulation
– Software – DOS based software (awfully limited; no remote diagnostic; lacking major
process requirements; imperfect signal processing algorithms; imperfect
communication ability)
– Huge overall foot print of the entire enclosure
2000- 2nd Generation of Process NMR System
– Magnet – 24mm bore size (high homogeneity; high temperature susceptibility)
– 6 Electronic units (Shim-Heater controller; RF unit; PS unit; 19” rack PC; ADC PCB;
Timing PCB)
– Shim Coils – manually wrap around coils ( inferior performance; inadequate
repeatability)
– Probe – Low Q (low SNR- Signal to Noise Ratio); imperfect temperature insulation
– Software – Windows NT based software
– Large overall foot print of the entire enclosure
2010- 3rd Generation of Process NMR System
New magnet design – 30mm bore size
• The amount of magnetic pieces that assemble the magnet
reduced from 34 to 10. This contributed to major improvement in
the mechanical structure and enhances the overall magnet
stability.
• Bore size of the magnet was increased to 30 mm, to allow better
temperature insulation between the magnet and the process
probe which improve temperature susceptibility.
New concept of Process Probe
• To minimize heat transfer between samples and the magnet, an
entire ceramic pipe passes contactless throughout the entire
system.
• Temperature insulation increased to a large extent. It prevents
temperature fluctuations in the sample stream to affect magnet
stability.
• Additionally, any welding between ceramic and stainless steel
tubes is omitted.
• Much better temperature insulation
• Higher Q (better SNR)
2010- 3rd Generation of Process NMR System
Shim Cassette
•Previous applied manually wrapped shim coils were replaced
by two single PCB boards assembled in the SHIM cassette. This
serves four major functions:
 Standardize the actual location and shape of the shim
coils.
 Additional thermal insulation between the magnet and
the probe (replacing the Aluminum plate in the previous
generations).
 Easy replacement of the SHIM cassette in case of
malfunction.
 Elimination of cables and soldering of the shim coils
which caused many failures in previous generations.
State of the Art electronics (Only 3 units)
• Magnet Unit includes integrated PCB for Shim & Heater
Control along with Low Noise receiver pre-amplifier
• Spectrometer Unit includes Digital RF & Acquisition
Boards along with Power Supply
• Panel mount touch screen PC ( ATEX certified)
• Overall small foot-print
2010- 3rd Generation of Process NMR System
Windows XP or 7 based Software
• Includes new algorithm for standard and global Models
• Fully automated process capacity
• Extensive remote diagnostic capabilities
Enclosure
• The newly designed MOD 8000 - NMR process analyzer
allowed to reduce the entire enclosure of the analyzer itself
and the surrounding equipment, such as the sampling
systems, air-conditioners etc.
Summary- Old Generation Vs. New Generation
Features
Magnet
Weight & Size
Field strength
Bore size
Mechanical
2nd Generation
3rd Generation
Advantages & Benefits
Improvement in the mechanical structure
and enhances the overall magnet
stability.
Better temperature insulation between
magnet and the process probe.
170Kg; 35 x 45 x 40 cm
1.47 Tesla (60Mhz for H+)
24mm
34 pieces
170Kg; 40 x 40 x 45 cm
1.47 Tesla (60Mhz for H+)
30mm to 34mm
10 pieces
Process Probe
Dewar, Stainless steel
brazed to Ceramic tube
Plain Ceramic pipe
Minimize heat transfer between samples
and magnet. Better temperature
insulation.
Increased reliability and robustness.
Higher Q (better SNR)
Shim Coils
40 copper coils, manually
warped and glued onto
Aluminum plate.
2 PC boards contain
40 copper coils, fit together
as a SHIM cassette
Standardize location of the shim coils.
Additional thermal insulation.
Easy replacement of the SHIM cassette.
Elimination of cables & soldering.
Hardware
6 Electronic units
Plenty of wiring & cables
3 Electronic units
Minimal wiring
Increased reliability.
Overall small foot-print.
Software
Windows NT
Windows XP or 7;
New algorithm for standard Models.
Fully automated process capacity.
Extensive remote diagnostic capabilities.
Temperature Susceptibility
Environment
Fluctuations between streams
Must be within : ±1.5°C
Should not exceed : ±2.5°C
Must be within : ±3°C
Should not exceed : ±10°C
Enables the analyzer to be applied to any
stream, notwithstanding the temperature
differences between them.
Simpler Sampling System.
Why On Line Analyzer?
• Enables real time adjustment of processing conditions
• Increases product quality
• Prevents the need for reprocessing
• Reduces off-spec or borderline product
• Reduces expensive laboratory analyses
On-Line Analyzers Categories
• Discrete Analyzers
– Direct analyses of a physical property according to standardized methods, i.e.
Density, Boiling Points, RVP, RON, MON…
• Correlative Analyzers
– Correlative analyzers are based on the correlation between spectral data and
physical properties, i.e. NIR, RAMAN, IR and NMR spectrometry based process
analyzers
– Physical properties are calculated by means of chemo-metrics
– Multi properties for each samples
Principles of Chemo-metrics
Calibration Phase
Reference Spectra
Reference Measurements
mix#
0.25
0.2
0.15
0.25
0.1
0.2
0.05
0.15
0
0.1
0.2
-0.05
810 0.05
0.15
860
0.1
0.2
-0.1
0
-0.05
810 0.05
0.15
860
-0.15
0.25
0.25
910
-0.1
0
0.1
-0.15
-0.05
810 0.05
-0.1
0
-0.15
-0.05
960
1010
910
860
810
960
910
860
+
1060
1010
960
910
1060
1010
960
1060
1010
1060
HCl
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
0
1.178964
0.790395
1.090314
1.06258
0.852719
0.99566
0.873404
0.988138
0.849897
1.000474
1.102819
1.135659
0.799425
0.950737
Calibration Model
HF
0
0.39912
0.442637
0.496751
0.543865
0.593886
0.634382
0.669103
0.721126
0.778561
0.81478
0.853354
0.893109
1.009638
0.958367
-0.1
-0.15
Measurement Phase
Unknown Spectra
Calibration Model
0.25
0.2
+
0.15
0.1
0.05
A1(t)
A2(t)
tote changeover
new lot changeover
0.04
0.03
0.02
0.01
0.05
0
0
-0.05
-0.01
-0.1
-0.02
-0.15
-0.03
-0.04
-0.2
-0.05
-0.25
Wed
07/7
Fri
09/7
Sun
11/7
Tue
13/7
Thu
15/7
Sat
17/7
Mon
19/7
Wed
21/7
Fri
23/7
Sun
25/7
Tue
27/7
Thu
29/7
Sat
31/7
Mon
02/8
Wed
04/8
Fri
06/8
The Linear Modelling - Advantage
• Fewer Data Points required to build model
• Extrapolation for “out-of-range” feeds benefits :
• Faster start up
• Low maintenance
165
145
125
Predicted Flash
(C)
of model
Distillates Flash Point
105
Global Model
Unknown
Sample
85
65
45
25
25
75
125
Actual Flash (C)
Fields of Application for NMR Analyzers
•
•
•
•
•
•
•
•
•
Refineries
Olefins plants
Biotech
Bio-Chemical
Ag/Food
R&D - Both Academia and Industrial
Polymer
Chemical Industries
Pharmaceuticals
Case Study - Crude Oil Distillation
Properties Measurements by NMR
•
•
•
•
•
•
•
•
•
Cetane Index
API Gravity
Distillation
Flash Point
Cloud Point
Sulfur Content
Freeze point
Octane (RON, MON)
Specific gravity
•
•
•
•
•
Density
Boiling Point / Range
Naphthalene Content
PIONA
Pour Point
• Applicable to all refinery streams (transparent dense, opaque)
• Not influenced by hetero-atomic substances – not influenced by crude switching
Case Study – Liquors Analysis
•
Case Study – Dairy Products
Overlay of 4 Cream Cheese Products
Water
•15
•10
Saturated fat and protein
Unsaturated fat region
Carbohydrates
and sugars
•5
•0
• 20
• 40
• 60
• 80
• 100
• 120
• 140
Case Study – Food Oil Analysis
Oils and fats are key elements in the taste, melting
properties, shelf life, and appearance of foods
15
10
5
0
20
40
60
80
100
120
140
Arbitrary Y / Arbitrary X
Overlay X-Zoom CURSOR
File # 4 = OILINT0001
6/27/00 6:30 AM Res=None
Foxboro NMR SPC File.
Composite Spectra of 4 Oils (Olive, Sesame, Canola and Caesar Salad
Dressing) Showing Differences Observed by NMR
Thank You for Your Attention