membrane-based solvent dehydration to facilitate

1
U.S. Environmental Protection Agency Office of Research and Development Membrane-based Solvent Dehydration to Facilitate Industrial Solvent Reuse and Remanufacturing Leland Vane 1 , Franklin Alvarez 1 , Vasudevan Namboodiri 1 , and Michael Abar 2 1 U.S. EPA, National Risk Management Research Laboratory, 26 W. Martin Luther King Dr., Cincinnati, Ohio 2 NCBA, SEE Program, 26 W. Martin Luther King Dr., Cincinnati, Ohio 45268 USA l [email protected] l 513-569-7799 high Motivation Solvents Targeted Project Approach References/Acknowledgements/Disclaimers The life cycle of industrial solvents presents sources of emissions that potentially impact human health and the environment. The impact of using solvents can be reduced by recovering and reusing the solvents. The Remanufacturing Exclusion in EPA’s Definition of Solid Waste rule 1 intended, in part, to promote reuse of 18 organic solvents in four industrial sectors: paints & coatings basic organic chemicals pharmaceuticals plastics & resins 1) www.regulations.gov/document?D=EPA-HQ-RCRA-2010-0742-0368 2) “Review: Membrane materials for the removal of water from industrial solvents by pervaporation and vapor permeation” by L.M. Vane (in review). This project is carried out under the Sustainable & Healthy Communities national research program. The views expressed herein are those of the authors and do not necessarily represent the views or policies of the EPA. The mention of trade names or commercial products does not constitute an endorsement or recommendation for use. Toluene* Methanol Xylenes* Ethanol* Ethylbenzene* 1-Butanol* 1,2,4-Trimethylbenzene Tetrahydrofuran* Chlorobenzene* N,N-Dimethylformamide n-Hexane* Acetonitrile* Cyclohexane* Methyl isobutyl ketone* Chloroform* Methyl tert-butyl ether* Chloromethane Acetone Dichloromethane* 2-Propanol* * Solvent forms azeotrope with water Solvent to be highlighted in this project Related solvent to be included in study In-house development, evaluation, and review of advanced separation materials & technologies for energy-efficient solvent re-processing. o Focus on separating solvent/water mixtures because most of the 18 targeted solvents form azeotropic aqueous mixtures. o Emphasize the membrane processes pervaporation (PV) and vapor permeation (VP) which have proven effective at efficiently separating azeotropic mixtures. PV/VP separate based on sorption & diffusion differences Developing and Evaluating Membranes Lab- and pilot-scale PV and VP testing. Creating new materials and modifying existing materials. e.g. “Preparation of water-selective polybutadiene membranes and their use in drying alcohols by pervaporation and vapor permeation technologies,” Vane, Namboodiri, Lin, Abar, and Alvarez, ACS Sustainable Chemistry & Engineering, 4, 4442-4450 (2016). e.g. U.S. Patent 9,266,803: “Liquid separation by membrane assisted vapor stripping process” (2016), Vane and Alvarez. Demonstrate Innovative Technologies Cooperative R&D Agreement (CRADA) with Membrane Technology and Research, Inc., “Membrane-based processes for the separation of solvent/water mixtures”. Opportunities for collaboration We seek input and partners from the end-user, separations, and regulatory communities to ensure the project is relevant, practical, and useful. o Also demonstrating desalination brine treatment technologies A robust and varied industry has developed to provide PV/VP membranes and systems for solvent dehydration. Membranes made from at least 7 water-selective materials are commercially available for this application: o Inorganic materials: Zeolites (NaA, T-type, and Chabazite) and Hybrid Silica. o Polymeric materials: Poly(vinyl alcohol), Polyimides, and Amorphous Perfluoropolymers. Reviewed Water-Selective Membranes 2 Design and Demonstrate Efficient Solvent Drying Processes Incorporate PV/VP into existing solvent reclaiming operations. We will leverage prior experience developing efficient processes for the recovery and drying of alcohol-based biofuels. Solvent reclamation requires separation technologies to recover and purify them to meet reuse specifications. Water can be a problematic contaminant when difficult-to- separate “azeotropic” mixtures form with solvents. Conventional solvent separation technologies introduce significant material and energy demands. o separation of azeotropic mixtures further increases complexity and resource usage. To make solvent reclamation/reuse as environmentally beneficial as possible, efficient alternative separation technologies are needed. The Challenge Ethanol/Water Feed Mixture Dried Ethanol Ethanol-Depleted Water Condenser Make-up steam/gas Vapor Compressor Water-selective vapor permeation membrane Water vapor recycle Vapor stripping column .

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Page 1: Membrane-based Solvent Dehydration to Facilitate

U.S. Environmental Protection AgencyOffice of Research and Development

Membrane-based Solvent Dehydration to Facilitate Industrial Solvent

Reuse and Remanufacturing

Leland Vane1, Franklin Alvarez1, Vasudevan Namboodiri1, and Michael Abar2

1U.S. EPA, National Risk Management Research Laboratory, 26 W. Martin Luther King Dr., Cincinnati, Ohio2NCBA, SEE Program, 26 W. Martin Luther King Dr., Cincinnati, Ohio 45268 USA

l [email protected] l 513-569-7799

high

Motivation Solvents Targeted

Project Approach

References/Acknowledgements/Disclaimers

The life cycle of industrial solvents presents sources of emissions that potentially impact human health and the environment. The impact of using solvents can be reduced by recovering and reusing the solvents.

The Remanufacturing Exclusion in EPA’s Definition of Solid Waste rule1 intended, in part, to promote reuse of 18 organic solvents in four industrial sectors:

paints & coatings basic organic chemicals

pharmaceuticals plastics & resins

1) www.regulations.gov/document?D=EPA-HQ-RCRA-2010-0742-0368

2) “Review: Membrane materials for the removal of water from industrial

solvents by pervaporation and vapor permeation” by L.M. Vane (in review).

• This project is carried out under the Sustainable & Healthy Communities

national research program.

The views expressed herein are those of the authors and do not necessarily represent

the views or policies of the EPA. The mention of trade names or commercial products

does not constitute an endorsement or recommendation for use.

Toluene* Methanol

Xylenes* Ethanol*

Ethylbenzene* 1-Butanol*

1,2,4-Trimethylbenzene Tetrahydrofuran*

Chlorobenzene* N,N-Dimethylformamide

n-Hexane* Acetonitrile*

Cyclohexane* Methyl isobutyl ketone*

Chloroform* Methyl tert-butyl ether*

Chloromethane Acetone

Dichloromethane* 2-Propanol*

* Solvent forms azeotrope with water Solvent to be highlighted in this project Related solvent to be included in study

In-house development, evaluation, and review of advanced separation materials & technologies for energy-efficient solvent re-processing.

o Focus on separating solvent/water mixtures because most of the 18 targeted solvents form azeotropic aqueous mixtures.

o Emphasize the membrane processes pervaporation (PV) and vapor permeation (VP) which have proven effective at efficiently separating azeotropic mixtures.

• PV/VP separate based on sorption & diffusion differences

Developing and Evaluating Membranes

• Lab- and pilot-scale PV and VP testing.

• Creating new materials and modifying existing materials.e.g. “Preparation of water-selective polybutadiene membranes and their use in drying alcohols by pervaporation and vapor permeation technologies,” Vane, Namboodiri, Lin, Abar, and Alvarez, ACS Sustainable Chemistry & Engineering, 4, 4442-4450 (2016).

e.g. U.S. Patent 9,266,803: “Liquid separation by membrane assisted vapor stripping process” (2016), Vane and Alvarez.

• Demonstrate Innovative TechnologiesCooperative R&D Agreement (CRADA) with Membrane Technology and Research, Inc., “Membrane-based processes for the separation of solvent/water mixtures”.

Opportunities for collaboration

We seek input and partners from the end-user, separations, and regulatory communities to ensure the project is relevant, practical, and useful.

o Also demonstrating desalination brine treatment technologies

A robust and varied industry has developed to provide PV/VP membranes and systems for solvent dehydration.

Membranes made from at least 7 water-selective materials are commercially available for this application:

o Inorganic materials: Zeolites (NaA, T-type, and Chabazite) and Hybrid Silica.

o Polymeric materials: Poly(vinyl alcohol), Polyimides, and Amorphous Perfluoropolymers.

Reviewed Water-Selective Membranes2

Design and Demonstrate Efficient Solvent Drying Processes

• Incorporate PV/VP into existing solvent reclaiming operations.

• We will leverage prior experience developing efficient processes for the recovery and drying of alcohol-based biofuels.

Solvent reclamation requires separation technologies to recover and purify them to meet reuse specifications.

Water can be a problematic contaminant when difficult-to-separate “azeotropic” mixtures form with solvents.

Conventional solvent separation technologies introduce significant material and energy demands.

o separation of azeotropic mixtures further increases complexity and resource usage.

To make solvent reclamation/reuse as environmentally beneficial as possible, efficient alternative separation technologies are needed.

The Challenge

Ethanol/Water Feed Mixture

DriedEthanol

Ethanol-Depleted Water

Condenser

Make-up steam/gas

VaporCompressor

Water-selective vapor permeation membrane

Water vapor recycle

Vapor stripping column

.