To NeSSI or Not to NeSSI: A Fast and Micro GC … · 27 New School, Ethylene Purity Application CALIDUD CS, Dual Column, TCD & FID Column 1 MXT-U-Bond Column 2 MXT-Molesieve 5A FID

[email protected] Tel: (304) 647-5860Copyright Falcon Analytical 2/24/2016

433 AEI Drive – Lewisburg, WV 24901 1

Falcon Analytical makers of the . . .

To NeSSi or Not to NeSSi:A Fast and Micro GC Experience Review

IFPAC® Annual Meeting January 26, 2016

Grand H

NeSSi

Arlington, VA (Washington DC), U.S.A

mailto:[email protected]



Abstract

• By now there is substantial experience using NeSSi systems with fast and micro gas chromatography. All are successful but some are more successful than others. On the surface, the modular fluid delivery sample systems are a perfect fit for fast and micro gas chromatography. However, just because one can use NeSSi doesn’t necessarily mean one should use NeSSi in every case. Technical issues such as temperature, pressure and especially flow rate and even aesthetic issues must be considered carefully before plowing ahead. This presentation will review the current status of 3 installations and discuss the lessons learned.




What Is A Fast & Micro Gas Chromatograph?

• … a GC having internal dimensions measured in microns not millimeters, retention times in seconds, not minutes and none of the limitations of silicon chip based GCs• One tenth the size of conventional GCs – 30 lbs vs 300

lbs

• One tenth the power of conventional GCs – 300 watts vs 3000 watts

• Analysis times 10 – 50 times faster than conventional GCs – Fixed gases and Hydrocarbons up to C50

• Using resistively heated steel capillary column modules eliminating air bath ovens




… MUST have…all the major attributes of conventional GCs

• Split/splitless injector with a variety of sampling options• Manual syringes as well as

syringe based autosamplers

• Fully automated gas & liquid sample valves

• Range of sample pretreatment options: traps, headspace, pyrolysis and…

• Process sample systems for automated process analysis &

control… even NeSSI





• Programmed temperature and/or isothermal columns• Up to 2 modules, each having 1

and up to 8 meters of stainless steel capillary GC columns

• Independently controlled from 5oC above ambient to the limit of the column type or 400oC whichever is lower

• Can include one column switching valve

NO air bath oven!





• Detectors• Thermal Conductivity

• Flame Ionization

• Flame Photometric

• Dielectric Barrier Discharge• Electron Capture for halogens

• Photo Ionization for aromatics & olefins

• Helium Ionization for everything

• Even… High Pressure Mass Spec Detector




… AND has…modern software and communications technology

• …to match the analytical and automation requirements• Sensor rich GC system &

firmware

• Chromperfect Ethernet/PC based data system

• Application modules to fit• Process analyzer HMI

• TC/PIP communications

• MODBUS via Ethernet

• BTU calculations

• Links to other Windows applications




… AND has…modern software and communications technology

• …to match the analytical and automation requirements• Simulated Distillation

applications

• Infometrix chemometricapplications• LineUp for retention time

alignment

• InStep for runtime chemometricmodels

• PCA

• PLS & other Pirouette apps




Falcon Calidus Intellectual Property

Trans-Configurable Modular Chromatographic

Assembly US Patent 8336366

Fast Micro Gas Chromatograph System

US Patent 8414832




*

* Dielectric Barrier Discharge Detector

Modular Calidus GC Single Injections

• Models are made of modules

• Currently there are 7 Calidus models are available• 101, single column & detector

• 201, dual serial columns, single detector

• 301, dual parallel columns & detectors

• CS, dual columns & detectors

• Heartcut

• Trap/bypass

• Backflush

• GS & GS-T for environmental

• MT for transportable fraud detection




Modules Make InstrumentsInstruments Make Analyzers

Analyzers plus Sample Systems Make Solutions… One Solution




Network

Micro-PROCESS

Photometer

Micro LABMass

Spectometer

Micro LABOptical

Spectrometer

Micro LABPhotometer

Micro-PROCESS

GC

Micro-PROCESS

MassSpectrometer

Micro LABGC

At-LinePackaging

Pro

cess

Co

ntr

ol N

etw

ork

Lab

Inst

rum

en

t N

etw

ork Transportable

Packaging

Network

Micro-PROCESSOpticalSpectrometer

ERP

Copyright Falcon Analytical 2015

Old School

New Thinking…CONVERGENCE!




FalconFAST Analytical Solutions and the Promise of NeSSi

• Easy to use: Sophisticated instrument/analyzer pairs employed with intelligence, agility and transparency to the user - thereby unifying the measurement results from the laboratory, at-line, on-line or in the field

• Ultrafast gas chromatography instrumentation with applications technology designed to perform the job combined with

• NeSSI sampling,

• Advanced data processing and

• Enlightened interpretation

• “Customers need and want the answers…Not the hassles associated with analytical chemistry!”

Laboratories

Process

Field

LoadingDock

InfometrixChemo-metrics

ParkerNeSSI

Sampling

FalconFast GC

ChromperfectData System




Modularity… Modularity… Modularity

• Modularity from the analytical elements to the entirety of the system• Calidus

• Process Enclosure

• NeSSI Modular Fluid Delivery Systems

• Even software

• Calidus firmware

• Chromperfect Engine

• Chromperfect Apps

• Pirouette Engine

• LineUp

• InStep

• Pirouette models

• From sample probe to the DCS connection… modularity makes jobs easier




Just because one can use NeSSi doesn’t necessarily mean one should use NeSSi.

• Sample systems STILL need the right fundamental engineering design must be done• Temperature, pressure and flow rate

• Preconditioning for particulate or condensate or, or, or must be properly done

• Transport distance and mechanism

• Sample stability and materials in contact

• And all the others

•What follows are some examples in FalconFast experience.




The Right Stuff – full scale plant system

• 3 Calidus Process Analyzers

• 3 Single Stream Parker Intraflow systems with autocal

• Chromperfect operational controls and data system & communications

• Infometrix retention time alignment for rock solid stability

• 3 process streams: dimer, trimer & tetramers of propylene




What about Stability? Single System Exampleat the End of the 1st Quarter

Q 1 Visit: part of last run showing 60 to 140 seconds

101 seconds




Single System Exampleat the End of the 1st and 2nd Quarter Overlaid

Q 1 & 2 Visits Overlaid: part of last run showing 60 to 140 seconds

101 seconds




Single System Exampleat the End of the 1st,2nd and 3rd Quarter Overlaid

Q 1, 2 & 3 Visits Overlaid: part of last run showing 60 to 140 seconds

101 seconds




Single System Example after a Whole Year!End of the 1st,2nd,3rd and 4th Quarter Visits Overlaid

Q 1, 2, 3 & 4 Visits Overlaid: part of last run showing 60 to 140 seconds

Of course operating processes show compositional variance. However, theretention times don’t!

4th chromatogram is after > 175,000 runs with ZERO downtime, no sample valve rotor nor column change nor detector maintenance…

ZIP

One year RT drift using

Infometrix LineUP… ZERO

Peak to peak RAW (without LineUP) drift 0.6 seconds for a WHOLE YEAR!!!




Works OK… after rework

• Pilot plant operations• The measurement goal: help find

optimum processing conditions• Somewhat reactive samples

• Analysis is for ppm level impurities in product

• Process development campaigns mean different compositions at different times

• The issues: • Very small process volume

• Sample system rework to return analyzer loop to the process WITHOUT contamination (disturbing the process)




Works Just Fine… but should it have been done?

• 8 Small Bioreactors• Off gas analysis for the

product concentration

• Indicates performance of the microbes and nutrient and air feed rate requirements

• Heat tracing absolutely required to get the C10

product through the tubing to the sample system & GC sample valve




Why the Second Guessing? LOST ORDERS!

• Small reactors• Probably should have used a

rotary selector valve

• Small diameter tubing would have fit in a single heated bundle

• Biological culture not really in tune with our industrial culture

• It all works great BUT… it isn’t really a good fit in this lab…• Well… they said they would

ultimately put it on very large fermentors




The Next Big Thing… not NeSSI

• Highly reactive monomer production

• Sample must be kept above 200 C… or polymer fills the tubing and sets like concrete!

• Sample system components become “a disposable item”

• We will see how this works out soon




IFPAC 2016, NeSSi

Have you been listening?

No one asks Falcon to do C1/C2 ratios.


26

Old SchoolPropylene Purity Application Single Oven

• Ethylene purity would be very similar to this application.

SBFV SBFV SEL

SBFV SBFV

FID

TCD

methanizer

Ref. Low ppm H2

Mea. %

C3H8

ppm C0,

C02

ppm

MeOH

27

New School, Ethylene Purity Application CALIDUD CS, Dual Column, TCD & FID

Column 1

MXT-U-BondColumn 2

MXT-Molesieve 5A

FID TCD



All Leads to…

Data

Equivalency




Industrial Implications (leaving you with food for thought)

Analytical Results Enable

• Lab to Process equivalency

• Using same instrument, same method eliminates the variables with the exception of sampling

• Possibilities for online product certificates of analysis

• Plant to plant equivalency

• Improves corporate product consistency, quality and tighter process control

• Inter plant process trouble shooting

• Work can now be focused on process variances by elimination of analytical variances

System Modularity Enables• Significant maintenance reductions

• Substitute whole instruments as a module, eliminating field repairs and costs

• Repairs/refurbishment in the lab or return to factory… like a premium car

• Packaging appropriate for the installation site

• Purpose built for the application

• Deploy only what is needed for the job

• Potential for shelterless installations

• Lower costs

• Capital costs

• Operational costs

• Long term maintenance costs


Documents

To NeSSI or Not to NeSSI: A Fast and Micro GC … · 27 New School, Ethylene Purity Application CALIDUD CS, Dual Column, TCD & FID Column 1 MXT-U-Bond Column 2 MXT-Molesieve 5A FID