Life Cycle Assessment of Intensified Flow Chemical Processes - Guidance and Judgement Christin Staffel, Dana Kralisch, Denise Ott, Sabine Kressirer, Ina Sell

CPAC/ATOCHEMIS Rome 2013 March, 25th 2013

Motivation CoPIRIDE – FP7 large scale collaborative EU project with focus on PI of chemical processes

CoPIRIDE`s process development focus  Epoxidation of vegetable oils  Biodiesel production  Ammonia production  Polymer reactions  Sugar hydrogenation

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Motivation Searching for novel approaches in chemical processing…

…Evaluation concerning resulting environmental impacts and costs …

…Supporting decision process during process design. V. Hessel, Chem. Eng. Technol. 2009, 32, 1655-1681

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COPIRIDE´s Priorities Process Intensification Criteria

Assessable, predictable and comparable! © 16.04.2013

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Variables of Chemical Process Design and their link to material and energy flows SYNTHESIS, PROCESS, SERVICE etc.

Method I: LCA INPUT (Elementary flows)

SYNTHESIS Pressure

Temperature

Time

OUTPUT (Elementary flows)

Solvent Work-up

Energy Supply/production* Renewable resources

Emissions into air, water and soil

Chemical reaction Treatment of waste

Equipment, techniques

stoichometry

Waste Energy

Raw materials * Reactants, catalyst, solvents, auxiliaries

PRODUCT

Costs/ Earnings

Method II: LCC © 16.04.2013

Method III: EHS 5

Systematic approach

Industrial & societal needs

Knowledge-based design of sustainable chemical processes

Research

First insights by parameter screening utilizing simplified LCA

Detection of ecological hotspots

Process design

Screening of process alternatives by LCA, risk and cost analyses

Processes with best-trade-off between environmental, economic and risk concerns

Scale-up

Holistic LCA and LCC analysis of the new designed process compared to reference processes

Judgement of significant benefits against state of the art in front of industrial use

Superior chemical process improving today`s chemical production

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Objectives of ecological & economic assessment

 Screening different process parameters:  Comparison between alternatives  Hot-spot and weak point analysis  Effect of potential improvements  Making prognoses  Decision guidance during process design:  Supporting the development of micro reaction processes to come off with economic benefits, less environmental burden as well as lowest risks

Sustainability … often not easy

… but feasible!

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Method I: Life Cycle Assessment

 Methodological framework for estimating and assessing the environmental impact attributable to the life cycle of a product or process − Holistic approach − Avoids problem shiftings − Makes the environmental impacts of alternative synthesis pathways comparable − Standardised: DIN EN ISO 14040, 14044 − Software: Umberto®, Ecoinvent© ISO 14040: 2006, Environmental management - Life cycle assessment – Principles and framework. Brussels, Belgium, European Commitee for Standardization, 2006; ISO 14044: 2006, Environmental management - Life cycle assessment Requirements and guidelines. Brussels, Belgium, European Commitee for Standardization, 2006. Umberto, v. 5.6, ifu Institut für Umweltinformatik, Hamburg, Germany; ifeu Institut für Energie- und Umweltforschung, Heidelberg, Germany, 2010. Ecoinvent Centre, Ecoinvent Data v2.2. Ecoinvent Reports No. 1-25, Swiss Centre for Life Cycle Inventories, Dübendorf, Switzerland, 2010, retrieved from: www.ecoinvent.org. Picture taken from: www.unep.fr 8

Method II: Environmental, Health and Safety Risk Assessment

EHS-Tool G. Koller, U. Fischer and K. Hungerbühler, Industrial & Engineering Chemistry Research, 2000, 39, 960 H. Sugiyama, U. Fischer and K. Hungerbühler, The EHS Tool, ETH Zurich, Safety & Environmental Technology Group, Zurich, 2006, http://sustchem.ethz.ch/tools/EHS

Methodological Approach Ex-ante Analyses

Detailed Analysis

Screening on a superficial level Up-front analysis as prognosis tool

Holistic and detailed analysis of costs and environmental impacts including all life cycle stages

Environmental Impact: Global warming, ozone depletion, human and ecotoxicity, … Risk assessment: Risks concerning environmental, health and safety issues Coupled with

Economic Impact:

Initial costs, supplies, operation, materials, labour, disposal, …

 Multi-criteria decision making! 10

Process Design & Intensification through Continuous Processing - Examples Epoxidation of Soybean Oil

D. Kralisch, I. Streckmann, D. Ott, U. Krtschil, E. Santacesaria, M. Di Serio, V. Russo, L. De Carlo, W. Linhart, E. Christian, B. Cortese, M. H.J.M. de Croon, V. Hessel, ChemSusChem 2012, 5, 300–311 Parameter Screening Screening Parameter 1,0 1.0

EE Effects of yield yield Effects of

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Epoxidized SoyBean Oil (ESBO) -most common oleochemical Used for PVC compounding (additive increasing light and heat stability of PVC, lubricant inside PVC), manufacturing of packaging and capsules for foodstuffs, calendering

Human Toxicity Potential

www.eatsmarter.de

Human Toxicity Potential

EffectsofofNPW NPW Effects

M M

0,9 0.9

0,8

Effectofofheat heat Effect recovery recovery

0.8

Effect of

Effect of micromicroprocessing processing

K K I

DD

L

L

H

H

A

B B A

G

G

C

0,7

0.7

I

FF

Effect Effectofof feedstock feedstock

Effect of catalyst change Effect of catalyst change

C N N

Effect of green chemistry

Effect of green chemistry

0,6

0.6 0,6 0.6

0,7

0.7

0,8

0.8

Global Warming Potential

0,9

1,0

0.9

1.0

Global Warming Potential

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Mythens expectations: - Switch from a batch to continuous process - More economic and shorter process - Safer and smaller equipments - Less reactant consumption - More constant product quality

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Process Design & Intensification through Continuous Processing - Examples Gasification of Biomass for Syngas and Ammonia Production

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Low/no cost feedstock No fossil CO2 emissions

SLCA study: scaled life cycle impact categories for the production of 1 ton syngas using different feedstock

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Production of polybutadiene based synthetic rubber

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Evonik

Living Anionic Polymerisation + Hydrogenation

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www.thecleanenergyleader.com

Case Example: Biodiesel Production -

Competitiveness depends on efficiency of production pathway, also due to high feedstock price (vegetable oil) Search for novel, intensified production pathways for green and cost efficient biodiesel generation

CATALYST

TRIGLYCERIDE

METHANOL

METHYL ESTERS

GLYCEROL

Selected CoPIRIDE references (see also references therein): D. Kralisch, C. Staffel, D. Ott, S. Bensaid, G. Saracco, P. Bellantoni, P. Loeb, Green Chemistry 2013, 15, 463-477 M. Di Serio, S. Mallardo, G. Carotenuto, R. Tesser, E. Santacesaria, Catalysis Today 2012, 195, 54-58 P. Campanelli, M. Banchero, L. Manna, Fuel 2010, 89, 3675–3682 M. Di Serio, R. Tesser, L. Casale, A. D'Angelo, M. Trifuoggi, E. Santacesaria, Topics in Catalysis 2010, 53, 811-819 © 16.04.2013

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Status Quo and Expectations Current Biodiesel Production • • • • •

Reaction conditions: T ~ 60-80 °C, t > 1 h, p = 1-4 bar, CSTR Feedstock: fresh vegetable oil (FFA, water content low!) FAME yield: about 98 % Catalysts: Alkali based, acid based, heterogeneous (e.g., SnO) Excess of solvents, material and energy demanding pre-/post-treatment steps

Expectations  Switch from a batch to continuous process  Methyl acetate supercritical processing  Use of waste vegetable oil (WVO) as feedstock without catalyst  Reduced reaction time, high conversion  simplifying down-stream purification  Reduce biodiesel production costs and environmental impacts  Competitiveness hindered by price of vegetable oils  Avoidance of material and energy demanding pre- and post-treatment steps

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Open Questions Conventional vs. supercritical Batch vs. continuous at high p, T

Oil bath, microwave, ultrasound, electrically heated

Efficient heating strategy

Processing

Biodiesel Optimal process conditions

Media Methanol, ethanol, methyl acetate

Influence of reaction temperature, molar ratio of reagents and solvent

Waste oil vs. fresh oil Influence / share of work-up Homogeneous vs. heterogeneous catalyst

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1. Screening during Process Design: Selected Results

Data basis for screening: P. Campanelli, M. Banchero, L. Manna, Fuel 2010, 89, 3675-3682 CoPIRIDE, internal communication, 2012 A. H. West, D. Posarac and N. Ellis, Bioresource Technology 2008, 99, 6587-6601 T. M. Barnard, N. E. Leadbeater, M. B. Boucher, L. M. Stencel and B. A. Wilhite, Energy & Fuels 2007, 21, 1777-1781 P. Wu, Y. Yang, J. A. Colucci and E. A. Grulke, Journal of the American Oil Chemists` Society 2007, 84, 877-884 L. F. Bautista, G. Vicente, R. Rodriguez and M. Pacheco, Biomass and Bioenergy 2009, 33, 862-872 © 16.04.2013

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Selected Results: SLCA via GWP Molar ratio

6:1 NaOH 4h WVO

50:1 H2SO4 4h WVO

4.5:1 SnO 3h WVO 42:1 0.33 WVO

conventional © 16.04.2013

42:1, 0.33 h, fresh oil, EtOH vs. MeOH vs. methyl acetate

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A, B, C: conventional processes, 6:1, KOH, 1 h, homogeneous/ heterogeneous fresh oil, EtOH cat. vs. MeOH vs. 42:1 methyl acetate 0.33 h Use of WVO, connected with a fresh oil pre-treatment 42:1  Additional 0.33 h energy and material WVO demand (30 %) High molar ratio alcohol/oil: 42:1 0.08 dominant impact on GWP: WVO  Higher energy demand for synthesis, work-up - Use of heterogeneous catalyst preferable

supercritical

processing 17

Selected Results: SLCA via GWP

6:1 NaOH 4h WVO

50:1 H2SO4 4h WVO

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42:1 0.33 h fresh oil

4.5:1 SnO 3h WVO 42:1 0.33 h 42:1 WVO 0.08 h WVO

conventional © 16.04.2013

42:1, 0.33 h, fresh oil, EtOH vs. MeOH vs. methyl acetate

Use of WVO, no pre6:1, KOH,(D, 1 h, E) treatment fresh oil, EtOH - Highvs.molar ratio MeOH vs. methyl acetate alcohol/oil (42:1): but less energy demand for 42:1 synthesis, work-up 0.33 h WVO Process F: fresh oil (30 %)

supercritical

processing 18

Selected Results: SLCA via GWP -

Investigations concerning 50:1 choice solvent H2SO4 - Methanol (N, Q): good 4h WVO 42:1 6:1 alternative, esp. concerning 0.33 h NaOH fresh oil 4 h supercritical processing 4.5:1 WVO - Using (O, R): SnOmethyl acetate42:1 h 3h formation of triacetin0.33 WVO WVO (30 %) can decrease ecological 42:1 0.33 42:1 backpack WVO

6:1, KOH, 1 h, fresh oil, EtOH vs. MeOH vs. methyl acetate

42:1, 0.33 h, fresh oil, EtOH vs. MeOH vs. methyl acetate

0.08 WVO

conventional © 16.04.2013

supercritical

processing 19

„Best case“ options © Partner

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Selected Results: EHS of Solvents Used

 Key parameters: substance`s mass, inherent (eco)toxicity and biodegradability properties, boiling point, reaction conditions (mobility!)  Ethanol and methyl acetate: less beneficial against most EHS categories  Harsher reaction conditions  increasing effects  specific technology precautions become necessary reducing the remaining potential of danger © 16.04.2013

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2. Prognosis for Future Mini Plant

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Theoretical assessment based on industrial scale production: 8,000 t/a scScenarios DD, EE: high ratio alcohol:oil, high T, p BUT: counterbalanced by lower residence time, high conversion rates, avoidance of WVO pre-treatment

 Continuously running mini-plant (6 L/h)  sc. conditions, methanol, WVO  Shell and tube reactor  µR, coated with heterogeneous catalyst Outranking of „best case“ results © 16.04.2013

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Conclusion

 Performance of cost and environmental impact evaluation (LCA, EHS): suitable tool for decision support during process design  Importance of different process parameters can be quantified and compared already based on labscale results

 knowledge-based decisions for successfull implementation of new, more sustainable concepts

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Green Intensified Flow Processes?

YES, we found good results in case of: − Strongly exothermic reactions  e.g. organometallic syntheses or polymerisations − Syntheses with short-living intermediates − Phase transfer catalysis − Syntheses with strikingly increased yield and / or selectivity compared to batch by adaptation of chemistry  combination of „green chemistry & engineering“  use of harsh process conditions (NPW) − Integration of efficient work-up, separation, recycling and heat management strategies into process design

Partners Thanks to all partners and to you for your attention! Questions?

The research leading to these results has received funding from the European Community's Seventh Framework Programme [FP7/2007-2013] under grant agreement no. CP-IP 228853-2 © 16.04.2013

Process Design & Intensification through Continuous Processing - Examples Catalyst Removal and Renewal

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S. Kressirer, L. N. Protasova, M. H. J. M. de Croon, V. Hessel, D. Kralisch, Green Chem. 2012, 14, 3034-3046

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Framework

Goal and scope definition

Inventory analysis (LCI)

Interpretation

Impact assessment (LCIA)

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Dana Kralisch

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LC Impact Assessment

Goal and scope definition

Inventory analysis (LCI)

Interpretation

Classification – Qualitative step

Impact assessment (LCIA)

– Grouping of material and energy flows – Relating to impact categories

Characterisation Ziele: – Within each impact category Beurteilung der Bedeutung potenzieller – Quantitative step Umweltauswirkungen – Transfer of mass and energy flows in specific environmental impact potentials by means of impact Komprimieren der aus der Sachbilanz factors erhaltenen Daten Erhöhen der Vergleichbarkeit

Normalisation, grouping, weighting – Optional steps

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Dana Kralisch

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Selected Impact Categories Global Warming Potential (GWP)  Green house gases, climate change, carbon footprint Ozone Depletion Potenial (ODP)  Thinning of the stratospheric ozone layer, increase of UV-B radiation Photochemical Ozone Creation Potential (POCP)  Summer smog, photo-oxidant formation in the troposphere Acidification Potential (AP)  Acid rain, forrest decline, crumbling of building materials Eutrophication Potential (EP)  Nutrient enrichement in aquatic and terrestrial ecosystems 30