solvent recovery from abe solutions applying ......martin miltner, florian kirchbacher, antonia rom,...

Martin Miltner, Florian Kirchbacher, Antonia ROM, Walter WUKOVITS, Michael HARASEK, Anton FRIEDL

Technische Universität Wien, Vienna, Austria

5th PVVPMD Conference, Torun, 20-23 June 2017

w w w . w a s t e 2 f u e l s . e u

Grant agreement no: 654623

H 2 0 2 0 – L C E - 1 1 - 2 0 1 5

Solvent Recovery From ABE Solutions Applying Pervaporation Under Realistic Process Conditions

www.waste2fuels.eu2

Copyright © Waste2Fuels Consortium

Objectives

WASTE2FUELS aims to:

• Develop next generation biofuels technologies

• Contribute to a decentralized energy production

• Produce bio-butanol as sustainable alternative fuel

• Enlarge the current biomass feedstock basis

• Convert unavoidable agrofood waste streams (AFW)

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Agenda

Butanol and ABE fermentation

Energy demand for separation and dehydration

Composition of typical ABE fermentation broth

Experimental procedure

Analysis of influencing factors on pervaporation

• Temperature

• Glucose content

• Salt content

Comparison of membrane materials

Summary and Outlook

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ABE Fermentation

Pro Butanol Contra Butanol

High energy content Low productivity

Low water absorption Product inhibition at 20g/l

Low vapour pressure

Good blending ability

Low corrosivity

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Solvent recovery from fermentation

1. StageAcetogenic

2. StageSolventogenic Downstream to distillation

In-situ product recovery

Inhibition level

Co

nce

ntr

atio

n

Stages of fermentation and product recovery

Mas

s fr

acti

on

of

Bu

tan

oli

n v

apo

ur

Mass fraction of Butanol in liquid

VLE Butanol/Water:

non-ideal behaviour

Miscibility gap Butanol/Water

High fugacity at low concentrations

Ideal for thermal separation process

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Energy demand

Energy content Butanol: 35 MJ/kg

Energy demand for separation and dehydration (BuOH 2 % 98 %): Conventional Rectification: 79,5 MJ/kg Gas Stripping/Rectification: 14-31 MJ/kg Extraction/Rectification: 4 – 6 MJ/kg Pervaporation/Rectification: 4 – 8 MJ/kg

Source: Rom, Miltner, Wukovits, Friedl; Chemical Engineering and Processing 104 (2016) 201-211

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Composition of fermentation broth

ComponentConcentration

[g/l]

Butanol 8 – 15

Acetone 4 - 8

Ethanol 1 - 2

Residual sugar up to 50 (depending)

Acetic acid 0.85

Propionic acid 1.76

Butyric acid 0.44

Sources:Universita degli studi di Napoli Federico II, Italy; University of Natural Resources and Life Sciences, Austria

ComponentConcentration

[g/l]

NH4Cl 2.0

K2HPO4 0.25

KH2PO4 0.25

MgSO4 0.2

FeSO4 0.01

MnSO4 0.01

Typical composition of real ABE fermentate from model substrates

Organic compounds strongly depending on fermentation design and microbial strain

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Experimental setup

Cross-flow pervaporation cell

Flat sheet membrane (0.0144m²)

POMS membrane from HZG

Hollow fiber modules possible

Feed: 100l/h flowrate, 25 - 70°C temperature

10mbar(a) permeate pressure

Liquid nitrogen condensation

Composition analysis by GC-FID

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Temperature dependence

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Temperature dependence

Transmembrane fluxes significantly higher at elevated temperatures

Enrichment similar at all analysed temperatures (uncertainties)

Permeance of BuOH is decreasing, selectivity stays constant

Product recovery at fermentation temperature is favoured



Glucose dependence



Glucose dependence

No influence of glucose content at reasonable levels (0 – 50g/l)

Slight decrease of permeances at very high glucose content (200g/l):

BuOH: -15% AcO: -23% EtOH: -17% Water: -16%

No fouling detected



Salt dependence



Salt dependence

No influence of NH4Cl content at levels expected in fermentation broth

No fouling and scaling detected



Permeances



Selectivities

BuOH

AcO

EtOH



Performance indicators

Membrane Type

Separation factor i/j[-]

PSIi[kg/m².h]

BuOH/W AcO/W EtOH/W BuOH AcO EtOH

POMS(HZG)

33.0(±5.6)

51.2(±9.3)

9.0(±1.4)

2.83(±1.6)

2.76(±1.3)

0.04(±0.02)

PDMS(Sulzer)

29.0(±4.3)

53.3(±8.5)

9.2(±1.1)

3.31(±1.3)

4.59(±1.9)

0.06(±0.02)

Membrane Type

Permeancei[kmol/m².h.bar]

Selectivity P i/j[-]

BuOH AcO EtOH W BuOH/W AcO/W EtOH/W

POMS(HZG)

0.67(±0.19)

0.26(±0.05)

0.21(±0.03)

0.27(±0.06)

2.46(±0.50)

0.99(±0.21)

0.79(±0.15)

PDMS(Sulzer)

1.04(±0.29)

0.51(±0.15)

0.40(±0.07)

0.46(±0.07)

2.37(±1.17)

1.16(±0.65)

0.89(±0.31)

PDMS analysis has been performed under the Austrian research project KASAV, grant No 838708



Summary

Solvent enrichment in the permeate:

Taking advantage of phase separation behavior (organic phase with 80% BuOH, aqueous phase with 8%)

Reduction of energy demand for extraction & dehydration

Influence of secondary components in fermentation broth

Feed:BuOH 1.5wt%AcO 0.75wt%EtOH 0.25wt%Water 97.5wt%

Permeate:BuOH 31.5wt%AcO 24.0wt%EtOH 1.5wt%Water 43.0wt%



Outlook

Resistance to acidic fermentation broth conditions

Influence of organic acids (acetic, propionic, butyric)

Performance with real fermentation broth

Further comparison to other membrane materials:

• Flat sheet PDMS and POMS from different vendors

• Hollow fiber module (interesting for upscaling)

Process simulation:

• Development and parameterization of rigorous model

• Validation of model (chemometrics)

• Simulation of different downstream process options

beyond the advanced precision agriculture/farming systems.

Partners

www.waste2fuels.euThis project has received funding from the European Union’s Horizon 2020 researchand innovation programme under grant agreement No 654623

Contact: [email protected], [email protected]

Thanks for your attention!

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Formula & Definitions

Driving force - Partial pressure difference

Selectivity

Transmembrane component flux

Separation factor

Pervaporation separation index

𝑁𝑖 = Π𝑖 ∗ 𝑝𝑖𝑠𝑎𝑡𝛾𝑖𝑥𝑖 − 𝑝𝑝𝑒𝑟𝑚𝑦𝑖

𝛼𝑖𝑗 =Π𝑖Π𝑗

𝐽𝑖 =𝑚𝑖𝐴𝑡

𝛽 =𝑤𝑓𝑖𝑤𝑝𝑗

𝑤𝑓𝑗𝑤𝑝𝑖

𝐴 𝑚𝑒𝑚𝑏𝑟𝑎𝑛𝑒 𝑎𝑟𝑒𝑎 [𝑚²]

𝑡 𝑡𝑖𝑚𝑒 [ℎ]

𝑤𝑓 , 𝑤𝑝 𝑤𝑒𝑖𝑔ℎ𝑡 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑖𝑛 𝑓𝑒𝑒𝑑 𝑎𝑛𝑑 𝑝𝑒𝑟𝑚𝑒𝑎𝑡 [−]

𝐽𝑖 𝑡𝑟𝑎𝑛𝑠𝑚𝑒𝑚𝑏𝑟𝑎𝑛𝑒 𝑓𝑙𝑢𝑥 𝑘𝑔 𝑚2ℎ

𝑚𝑖 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑖 [𝑘𝑔]

𝑝𝑖𝑠𝑎𝑡 𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑖𝑜𝑛 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 [𝑏𝑎𝑟]

𝛾𝑖 𝑎𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 [−]

𝑥𝑖 , 𝑦𝑖 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑖𝑛 𝑙/𝑣 𝑝ℎ𝑎𝑠𝑒 [−]

𝑁𝑖 𝑡𝑟𝑎𝑛𝑠𝑚𝑒𝑚𝑏𝑟𝑎𝑛𝑒 𝑓𝑙𝑢𝑥 𝑘𝑚𝑜𝑙 𝑚2ℎ

Π𝑖 𝑃𝑒𝑟𝑚𝑒𝑎𝑛𝑐𝑒 [𝑘𝑚𝑜𝑙/𝑚2ℎ𝑏𝑎𝑟]

𝑃𝑆𝐼𝑖 = 𝐽𝑖 ∗ 𝛼𝑖𝑗 − 1

solvent recovery from abe solutions applying ......martin miltner, florian kirchbacher, antonia rom,...

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