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Advancing New Research in Water Innovation for the Future at INL

Aaron D. Wilson, Christopher J. Orme, Michael G. Jones, Catherine M. Hrbac, Birendra Adhikari, Daniel S. Wendt, and Gregory L. Mines

November 17h, 2015

Water Efficiency in Downstream Refinery, Petrochemical and Chemical processing Workshop

AIChE

INL/MIS-xxxxxxx

INL Water Technology and Science

• Translational technology research

– 30 year history in chemical (membrane) separations

– Emergent and disruptive new technology

– Bridging the gap between TRL 2 and TRL 6

• Aquifer level modeling

– Surface water, ground water, and energy

– History in CCS, geothermal energy, and hydraulic fracturing

2

• National security research Water Security Test Bed

– Simulating a municipal water system at scale with real materials

– Developed with the EPA

DOE’s Interest in the Energy Water-Nexus

Summary of meeting

• Meeting report was promised.

• DOE is currently seeking feedback and input from industry; Formal RFI expected.

• Large Hub or multiple large projects are anticipated

• Call(s) to be funded 2/3 out of EERE (AMO and Solar) and 1/3 FE

• Desalination not limited to seawater, includes

– Brackish water

– Municipal reuse

– Industrial reuse

– Oil and Gas water

• Push to move away from looking at core desalination energy cost to include total process cost:

– Pretreatment

– Brine Disposal

• Pipe parity mentioned multiple times as the target.

Impact of Water on Energy Generation

5 Water-Smart Power (2013) Union of Concerned Scientists. Select events 2006-2012

State of the Art Publications in FO/PRO

*Topic “forward osmosis” or “pressure retarded osmosis”

in Web of Science

0

40

80

120

160

200

Nu

mb

er

of

Pu

bli

ca

tio

ns

*

Year

State of the Art: Forward Osmosis Introduction

• Forward osmosis membrane flux spontaneous (No energy input)

• Primary process energy requirements delivered during draw solute recovery,

which can include:

• Reverse Osmosis,

• Various Distillation including Membrane Distillation, and

• Thermal solute separation such as thermolytic solutes (Switchable

Polarity Solvents).

Brine

Saline

Water

Membrane

Dilute

draw

solution

Draw

solute

recovery

Product

Water

Concentrated

draw solution

Energy input

(deus ex machina)

Tertiary Amine Switchable Polarity Solvents

• High concentration in polar form.

• Can be mechanically separated once switched to non-polar form.

1-cyclohexylpiperidine

• 2nd Generation SPS Draw Solute.

• Identified with Quantitative Structural Activity Relationship (QSAR) model.

• Material balances non-orthogonal (interdependent) draw solute properties.

1-cyclohexylpiperidenium bicarbonate

• Maximum concentrations over 70 wt%.

• Has an osmotic pressure over 500 atm which should extract water from a fully saturated brine solution (6.14 mol/Kg ~370 atm), precipitating NaCl solid.

8

Orme, Wilson, 1-Cyclohexylpiperidine as a Thermolytic Draw Solute for Engineered Osmosis. Desalination 2015. 371, 126-133

McNally, Wilson Density Functional Theory Analysis of Steric Impacts on Switchable Polarity Solvent (SPS) Journal of Chemical Physics B 2015, 119, 6766-6775.

Wilson, Orme Concentration Dependent Speciation and Mass Transport Properties of Switchable Polarity Solvents RCS Advances 2015, 5, 7740-7751

Wilson, A. D.*; Stewart, F. F. Structure-Function Study of Tertiary Amines as Switchable Polarity Solvents RCS Advances 2014, 4, 11039-11049.

Tertiary Amine Switchable Polarity Solvents

• High concentration in polar form.

• Can be mechanically separated once switched to non-polar form.

9

Organic DMCHA

+ H2O + CO2

Aqueous DMCHAH-HCO3

- H2O - CO2

CO2

Sparging

CO2

Stripping

HCO3-

Proposed Switchable Polarity Solvents Forward Osmosis System

10

Thermally driven process with the majority of energy

input at the CO2 degasser

Stone; Rae; Stewart; Wilson

Switchable Polarity Solvents as

Draw Solutes for Forward Osmosis

Desalination 2013, 312,124-129.

Wilson; Stewart; Stone Methods and Systems for Treating

Liquids Using Switchable Solvents. US20130048561 A1.

Wilson; Stewart; Stone Methods and Systems for Treating

Liquids Using Switchable Solvents. WO2013032742 A1.

High Salinity, High Fouling, High Recovery

• Pre-treatment can be the bulk of the water treatment cost.

• Disposal of the waste brine can be the bulk of the water treatment cost.

• State of the art methods are reaching thermodynamic limits but the cost is still too high.

• FO requires little to no pre-treatment.

• High recover even from high salinity feeds.

• Thermally driven processes uses lower cost energy than electrically driven processes.

11

Technical Target: Selecting an amine SPS for osmotically driven membrane processes

• Desired properties for SPS draw solute

–Effective polar to non-polar phase transition

• Rapid transition kinetics

• Low temperature/energy requirements

• Completeness of transition

–Low SPS water solubility of the non-polar form

–Low SPS membrane permeability

–High osmotic pressure in the polar form

–Effective mass transport (High flux, Low viscosity)

–Compatibility with a wide range of materials

Proof of concept SPS Draw Solute

13

Jw

(Water Flux)

Js

(Reverse Solute Flux)

, c

(Osmotic density

and cost)

V/VHI or KV

(Carrying Capacity)

HI

(Maximum Available

Osmotic Pressure)

Π/T

(Entropic Sensitivity)

SPO

(Minimum Stimuli-Driven

Osmotic Concentration)

Molecular Mass Low High

Material/Membrane

Compatibility

Orme; Wilson 1-Cyclohexylpiperidine as a Thermolytic Draw Solute for

Osmotically Driven Membrane Processes. Desalination 2015, 371, 126–133.

???

Equilibrium “Maximum” Concentration of the SPS Polar Form

• SPS Function can be defined as the ratio between the ammine/ammonium solution concentration in the presence and absence of CO2.

• The physical/molecular drivers for high concentrations is what is in most need of elucidation.

Ambient pressure

and temperature

SPS Active

SPS Inactive

Amines Tested in SPS Function Study

• No simple correlation between structure and function.

15

Wilson; Stewart Structure–function Study of

Tertiary Amines as Switchable Polarity

Solvents. RSC Adv. 2014, 4 (22), 11039–11049.

y = -0.618 x + 7.865 R² = 0.999

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5 6 7 8 9 10 11 12 13 14

mola

r

Carbon:Nitrogen Ratio

NR3 molar

H2CO3 molar

Equilibrium Concentration of SPS Polar Form

dimethyl-n-alkylamines


0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5 6 7 8 9 10 11 12 13 14

mola

r


NR3 molar

H2CO3 molar

amines with ancillary

carbon functionality


amines with ring systems

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5 6 7 8 9 10 11 12 13 14

mo

lar


NR3 molar

H2CO3 molar

y = 0.987x - 0.056 R² = 0.961

0.0

1.0

2.0

3.0

4.0

5.0

0.0 1.0 2.0 3.0 4.0 5.0C

alc

ula

ted

(M

) Observed (M)

The correlation between the observed

maximum molarity of SPS and those

calculated from equation.

Predicating the Equilibrium Concentration of SPS Polar Form with QSAR

• Our QSAR model predicts the SPS performance of tertiary amines.

𝑆𝑃𝑆 𝐻2𝐶𝑂3 (𝑀) = 7.87 − 0.62( Carbon) − 0.55𝛽 − 1.1𝛾 − 0.5𝛿 + 1.2(𝛼 𝑟𝑖𝑛𝑔)

Wilson*; Stewart Structure-Function Study of Tertiary Amines as

Switchable Polarity Solvents RSC Advances 2014, 4, 11039-11049.

19

0

100

200

300

400

500

600

700

800

900

5 6 7 8 9 10 11 12

Os

mo

tic

Pre

ss

ure


Gen 1

Projected Osmotic Pressures of Equilibrium Concentrations

Osmotic Pressure of

Saturated NaCl Brine

Gen 2

20 Wilson; Stewart Structure–function Study of

Tertiary Amines as Switchable Polarity Solvents.

RSC Adv. 2014, 4 (22), 11039–11049.

Advantages of 2nd Generation SPS Draw

21

Jw

(Water Flux)

Js

(Reverse Solute Flux)

, c

(Osmotic density

and cost)

V/VHI or KV

(Carrying Capacity)

HI

(Maximum Available

Osmotic Pressure)

Π/T

(Entropic Sensitivity)

SPO

(Minimum Stimuli-Driven

Osmotic Concentration)

Molecular Mass Low High

Material/Membrane

Compatibility


Osmotically Driven Membrane Processes. Desalination 2015, 371, 126–133.

Degassing Experiments

• Un-optimized conditions intended for rough temperature sensitivity comparison between amines.

• N,N-Dimethylcyclohexylamines (DMCA) requires 95 C to achieve a good degassing and phase separation at ambient atmospheric pressures.

• Gen 2 can be degassed at 70 C under ambient atmospheric pressures or less with limited amount of vacuum.

0

0.5

1

1.5

2

2.5

3

0 500 1,000 1,500 2,000

Osm

ola

lity

(O

sm

/Kg

)

Time (min)

70 °C DMCHA

80 °C DMCHA

95 °C DMCHA

70 °C CHP

80 °C CHP


Osmotically Driven Membrane Processes. Desalination 2015, 371, 126–133. CHP = 1-Cyclohexylpiperidine

0

2

4

6

8

10

12

0 1 2 3 4 5 6

Wat

er

Flu

x (k

g/m

2h

r)

CHP Concentration ( mol/kg )

DI Water 0.5 mol/Kg NaCl

1 mol/Kg NaCl

Porifera (2014)

FO mode

Feed: DI water

~25 ⁰C

CHP flux over a range of concentration feeds

• FO flux tests against DI water can have limited implications on FO performance against a feed with real world osmotic pressures. Thus tests against 0.5 and 1.0 mol/Kg NaCl feed solutions.

• There is a modest flux attenuation for CHP vs DMCHA attributed to a shift is rheological properties associated with moving from a 8 to an 11 carbon amine.

Christopher Orme

Long term membrane performance with CHP

• Demonstrates compatibility between amine and membrane.

• Results are consistent with previous initial flux study with DMCHA and CTA membranes once membrane orientation/specifications and draw solution concentrations influences are considered.

24

2

2.5

3

3.5

4

4.5

5

5.5

6

6.5

7

0 1 2 3 4 5

Wate

r F

lux (

kg

/m2h

r)

Run Time (hr)

1st 4 hrs

(hrs : 1 to 4)

last 4 hrs

(hrs : 28 to 32 )

(~2 mol/Kg SPS )

(~3 mol/Kg SPS) Porifera (2014)

FO mode

Feed: DI water

Draw: Initial 3 mol/Kg CHP

~25 ⁰C

0.0

1.0

2.0

3.0

4.0

5.0

6.0

0 40 80 120 160 200 240 280 320 360

Rela

tive E

nerg

y (

kcal)

Relative Dihedral Angle (degrees)

DFT Potential Energy Surface (PES) Scan

• A potential energy surface scan of the C1-N1-C7-H dihedral angle allowed for a ‘conformational analysis’ associated with the complete rotation along the N1-C7 bond.

0

2

4

6

8

10

12

0 100 200 300

Re

lati

ve E

ne

rgy

(kca

l)

Degrees

2a

3a

4a

2b

3b

3ad

4ad

3bd

DFT Potential Energy Surface (PES) Scan with R-group rotation for model compounds

• Work conducted by post doc Josh McNally now a full time employee.

• -bond barrier of rotation for interactions with amine substituent.

• -bond barrier of rotation direct interactions with the bicarbonate ion through a pseudo-six membered interaction.

2a

3a

4a

2b

3b

3aβ

4aβ

3bβ

α-bond rotation

Interaction with N-Me α-bond rotation

Limited interaction

with bicarbonate

β-bond rotation

Interaction with

bicarbonate

McNally; Noll; Orme; Wilson Density

Functional Theory Analysis of the Impact

of Steric Interaction on the Function of

Switchable Polarity Solvents. J. Phys.

Chem. B 2015, 119 (22), 6766–6775.

System Design and Testing

27

Initial scale

(2011)

Lab scale (2014)

10 gallon per hour pilot system

(2015)

ASPEN Evidence for SPS FO cost competitiveness

• Rough ASPEN techno-economic analysis estimated small scale (480 m3/day) SPS FO cost between 1.7 to 2.6 USD/m3 which is competitive with injection which ranges from 1.9 to 63 USD/m3.

28

Wendt, D. S.; Orme, C. J.; Mines, G. L.; Wilson, A. D.* Energy requirements of the switchable polarity solvent forward osmosis (SPS-FO) water

purification process. Desalination 2015, 374, 81-91, DOI:10.1016/j.desal.2015.07.012

High Salinity, High Fouling, High Recovery

• Pre-treatment can be the bulk of the water treatment cost.

• Disposal of the waste brine can be the bulk of the water treatment cost.

• State of the art methods are reaching thermodynamic limits but the cost is still too high.

• FO requires little to no pre-treatment.

• High recover even from high salinity feeds.

• Thermally driven processes uses lower cost energy than electrically driven processes.

29

Funding

30

• DOE Energy Efficiency and Renewable Energy (EERE) Geothermal Technology Office (GTO)

• DOE Office of Science - Small Business Innovation Research (SBIR) Program

• DOE Office of Fossil Energy (FE) -National Energy Technology Laboratory (NETL) Novel Crosscutting Research and Development to Support Advanced Energy Systems

• Battelle Energy Alliance (INL)

• LDRD

• Royalty Fund

Acknowledgements

• Frederick F. Stewart

• Mark L. Stone

• Christopher J. Orme

• Michael G. Jones

• Joshua S. McNally

• Catherine M. Hrbac

• Birendra Adhikari

• Daniel S. Wendt

• Gregory L. Mines

• Jeffrey R. McCutcheon

• Kevin K. Reimund

INL Team

UConn Team

0

2

4

6

8

10

12

14

16

18

20

0 50 100 150 200 250

Wa

ter

Flu

x (

kg

/m2h

r )

Time min

1st Run, Sample HB 14-16, 2 m NaCl

2nd Run, Sample HB 14-16, 2 m NaCl

3rd Run, Sample HB 14-16, 2 m NaCl

Sample LS, 2 m NaCl

Cattle Waste, 2 m NaCl

Cattle Waste, SPS CHP

Scoping Study for FO Treatment of Dairy Waters

• HB ~1,070 mOsm/Kg similar to seawater

• LS ~303 mOsm/Kg similar to mid-range brackish water or plasma

– Contained biofilms when delivered.

– HB may have avoided biological activity due to its salinity

• Manure Water ~68 mOsm/Kg

– ~50% of the water removed in both tests.

32

Porifera (2014)

FO mode

~21 ⁰C

SPS draw vs. Cattle Waste Water

• The redline indicates equilibrated flux for an SPS draw against a DI water feed.

• The high concentration cattle waste water data likely represents pre-equilibration flux conditions.

• The parallel trend suggests that cattle water sample isn’t fouling but approaching an equilibrated polarized flux.

33

0.0

5.0

10.0

15.0

20.0

25.0

3.03.54.04.55.05.5

Wate

r F

lux (

kg

/m2h

r)

CHP (mol/Kg)

Cattle Waste

DI waterPorifera (2014)

FO mode

~21 ⁰C

Proposed Switchable Polarity Solvents Forward Osmosis System

34

Thermally driven process with the majority of energy

input at the CO2 degasser

Stone; Rae.; Stewart.; Wilson* Switchable Polarity

Solvents as Draw Solutes for Forward Osmosis

Desalination 2013, 312,124-129.

0.5

1.0

1.5

2.0

2.5

3.0

5 6 7 8 9 10 11 12 13 14

NR

3:

H2C

O3


What determines an SPS’s “osmotic” character? Osmotic vs. Non-osmotic SPS

Blue diamonds “osmotic” SPS,

Red Cross “nonosmotic” SPS.

• “Osmotic” SPS function with ~1:1 NR3:H2CO3 ratios which vary little with concentration and behave as salty aqueous solutions.

• “Non-osmotic” SPS with >> 1:1 NR3:H2CO3 ratios which vary with concentration and behave similar to polar organic solvents.

quantitative 13C NMR

spectroscopy

Osmotic vs. Non-osmotic SPS

• The osmotic SPS data appears to contain divergent trends

0.5

1.0

1.5

2.0

2.5

3.0

5 6 7 8 9 10 11 12 13 14

NR

3:

H2C

O3

Carbon:Nitrogen Ratio 0.95

1.00

1.05

1.10

1.15

1.20

1.25

1.30

5 6 7 8 9 10 11 12 13 14

NR

3:

H2C

O3



spectroscopy

Molecular surface charge and the “osmotic” character of SPS

• Hypothesis : The molecular structure of an “osmotic” SPS is predominantly contained within an ionic domain.

• Currently being explored via DFT and MD. 37

Ionic Domain

Organic Domain

Ionic Domain

Osmotic SPS Non-osmotic SPS

0.5

1.0

1.5

2.0

2.5

3.0

0 1 2 3 4 5 6 7

NR

3:

H2C

O3

Carbons > 4 Bonds From Nitrogen

The influence of organic domains on the “osmotic” character of SPS

38

Organic regions likely allows the formation of

micelle and/or organic nanostructures.


spectroscopy

Carbon Chain Length vs. Hydrophilicity

• The surface charge of four carbons chains (ionic domain) may define the boarder between water soluble and water insoluble liquid ions.

39 Kohno; Ohno; Temperature-Responsive Ionic Liquid/water Interfaces:

Relation between Hydrophilicity of Ions and Dynamic Phase Change.

Physical Chemistry Chemical Physics 2012, 14 (15), 5063.

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