Innovation in Spectroscopic Sensor Design Enables in-line Large-Scale Hazardous Reaction Analysis Dr. Jim Rutherford 3rd Annual Hazardous Chemistry for Streamlined Large-Scale Synthesis 29 Nov 2017 │ Antwerp, Belgium

Challenge to industry A real-time multi component analyser Instrumentation Performance Process NIR Great, but not got the resolving power Process GC Lengthy, very expensive Process Mid IR To date limited by the technology Raman Good, suffers sensitivity, noise, lifetime www.keit.co.uk 14 November 2018

FTIR Spectrometer www.keit.co.uk www.keit.co.uk 14 November 2018 3

Scale www.keit.co.uk 14 November 2018

Power of Mid-Infrared 800-4000 cm-1 / 12.5-2.5 µm www.keit.co.uk 14 November 2018

Certified for explosion risk areas Class 1 Div 2 to follow by Q4 www.keit.co.uk 14 November 2018

Using mid-infrared light to measure water Detector Infrared (IR) Source Broadband IR light is shone through the sample Some of the light is absorbed by the water. The light pattern is confirmed by the detector. linear relationship between amount of light absorbed and concentration of water. www.keit.co.uk 14 November 2018

Sagnac Interferometer Interferogram Curved mirror Processing Curved mirror Interference image Fourier Transform Beam splitter Detector array How the Sagnac works Sample Spectrum Infrared source (emitter) www.keit.co.uk 14 November 2018

NB: To watch the light path, view slide in presentation mode 14 November 2018

Data Flow Head End Unit DCS Local Configuration via keyboard, video, mouse. Head End Unit OPC over Ethernet Spectra DCS Modbus over RS-485 Chemometrics Profibus Concentrations 4-20mA www.keit.co.uk 14 November 2018

Typical data 14 November 2018 www.keit.co.uk

IRmadillo in situ www.keit.co.uk 14 November 2018

Challenge to industry Producers struggle to safely monitor real-time* reactions The need for in situ monitoring Material hazard: The reaction is exothermic Examples: Production of polyols Water in solvents Water sensitive substances such as NaH, LiAlH4 ‒ processes where it is essential to confirm dryness of solvents www.keit.co.uk 14 November 2018

Challenge to industry Producers struggle to safely monitor real-time reactions 2. Toxicity: The substances are toxic – Limit exposure to humans* 3. Operating conditions* 4. Closed loop feed back control. ROI. www.keit.co.uk 14 November 2018

Current solutions Summary Innovation! Keit in situ spectrometer – ATEX certified safe to use, solid-state instrument using mid-infrared spectral analysis (an information rich area of spectrum) www.keit.co.uk 14 November 2018

Working Examples 14 November 2018

Example – Catalytic reactions Catalytic reaction monitoring Example acetic acid IRmadillo currently developed to monitor process in line NB: Fibre instruments cut off at approx. 2,100-2,200 wave numbers. MCO (metal carbonyl) band is higher than this - approx. 2,400. The IRmadillo is the only in situ FTIR instrument that can see this www.keit.co.uk 14 November 2018

Example 1 – Catalytic reactions Acetic acid 1 plant producing 650,000 tonnes per year Cost of production is $560/tonne Not a nice reaction methyl halides elevated temp and pressure and expensive Rhodium catalyst www.keit.co.uk 14 November 2018

Acetic acid production Exothermic in process plant Elevated temperature Utilises Rh catalyst 180 0C 10 Barr www.keit.co.uk 14 November 2018

Acetic acid production Elevated temperature Utilises catalyst Currently process GC monitoring over 10 minutes and cost of $750 k Process MID IR gives a 15 second analysis of 7 components. www.keit.co.uk 14 November 2018

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Mid-IR vs fibre probe vs Raman www.keit.co.uk 14 November 2018

Enzymatic production of Propanediol Maize (sugars) => Poly ols Use for Polymers PET to Dairy thickener in yoghurt Dextrose concentration is crucial www.keit.co.uk 14 November 2018

Heat control is critical 2 g /l increase in sugar leads to a thermal runaway. Individual batch loss $200k www.keit.co.uk 14 November 2018

Executive Summary Trial has successfully observed production of glycerol and propanediol simultaneously Separate model has been made to observe consumption of dextrose Current detection limits are: Glycerol – 3.99 g L-1 1,3-propanediol – 7.37 g L-1 Dextrose – 1.45 g L-1 www.keit.co.uk 14 November 2018

All spectra gathered during trial Top: NIST reference spectra for glycerol, 1,3-propanediol and water vapour. Bottom: All the spectra used to build the model (both fermentation references and water spectra were used (as these show natural variation in water vapour in the air as well as “0 g L-1 values” for organic species. Results show good correlation with the NIST reference spectra for the alcohols. Liquid water is present in all samples (not surprising as this is an aqueous fermentation). There is possible evidence of water vapour in the spectra, which could fluctuate with time of day, weather etc…and adds noise into the measurement. Potential evidence of water vapour www.keit.co.uk 14 November 2018

Glycerol summary Top left: Beta coefficients (spectral features used to build model). Top right: Predicted vs actual plot. Bottom: plot of predicted values and HPLC measured value for each sample. Conclusion: The model shows a good correlation with the reference spectra, but there is a little bit of noise in the model (possibly caused by water vapour). The LOD for glycerol is 3.99 g L-1 www.keit.co.uk 14 November 2018

1,3-propanediol summary Top left: Beta coefficients (spectral features used to build model). Top right: Predicted vs actual plot. Bottom: plot of predicted values and HPLC measured value for each sample. Conclusion: The model shows a good correlation with the reference spectra, with very little noise in the model. The LOD for 1,3-propanediol is 7.37 g L-1, which could be decreased further by analysing more samples with a lower alcohol content. www.keit.co.uk 14 November 2018

Dextrose summary Top left: Beta coefficients (spectral features used to build model). Top right: Predicted vs actual plot. Bottom: plot of predicted values and HPLC measured value for each sample. Conclusion: Dextrose required a separate model to be built because of its low concentration and noise in the data (probably caused by water vapour). The correlation is reasonable, especially with the lower concentrations of sugar. The LOD for dextrose is 1.45 g L-1. www.keit.co.uk 14 November 2018

Propanediol production www.keit.co.uk 14 November 2018

Propanediol production Hazard 2g /l increase in dextrose leads to thermal runaway and subsequent loss of 2 – 3 days production with a cost of $200k www.keit.co.uk 14 November 2018

Why does NIR struggle? Glucose/dextrose Fructose Sucrose All sugars are made up of C-C bonds, C-O bonds, C-H bonds and O-H bonds. The arrangement is fairly similar in all cases. Raman and FTIR both look at fundamental vibrations, so can detect these changes. NIR looks at combinations and overtones of fundamentals, so struggles to detect these. www.keit.co.uk 14 November 2018

Hydrogen peroxide Hydrogen peroxide IRmadillo can monitor down to <0.1% 14 November 2018 www.keit.co.uk

14 November 2018 www.keit.co.uk

Water absorption Un agitated solution absorbing water from 100ppm to 2.5% in less than 2 hours. www.keit.co.uk 14 November 2018

Fermentation: Sugars to Ethanol Real-time Concentration Monitoring www.keit.co.uk 14 November 2018

Summary 14 November 2018

Summary Industry need of safe, real-time monitoring of hazardous chemistry Challenges and options Advantages of in situ monitoring Future of technology in process monitoring www.keit.co.uk 14 November 2018

In measuring any reaction hazardous or not. Instrument stability is key and mustn’t contribute variation in data. www.keit.co.uk 14 November 2018

Having static optics means that the spectral signal does not drift over time and therefore does not need re-baselining or re-calibrating. If it doesn’t move, it can’t go out of spec Measuring the absorbance at a given wavenumber over a period of 10 months When did you last recalibrate your bathroom mirror, or your camera lens? Customer measured the same mixture 6 times over the course of 3 months and superimposed the plots

Calibration Transfer www.keit.co.uk 14 November 2018

Hazardous is in the eye of the beholder What's the worst we can analyse www.keit.co.uk 14 November 2018

Hazardous is in the eye of the beholder www.keit.co.uk 14 November 2018

Municipal Solid Waste MSW Keit Fit for Process Environment www.keit.co.uk 14 November 2018

Rugged Solid-state sensor Compact Safe for use in hazardous environments Inert Hastelloy probe Solid-state sensor No moving parts In-line process monitoring of liquids Real-time reaction analysis Compact Probe length 180mm / 7” Body length 310mm / 12.2” Placed at point of generation www.keit.co.uk 14 November 2018

Any questions? jim.rutherford@keit.co.uk www.keit.co.uk Solid-state FTIR sensor for real-time process monitoring Follow Keit Spectrometers www.keit.co.uk 14 November 2018