Solar Energy Technologies Program Peer Review

Deep Eutectic Salt Formulations Suitable as

Advanced Heat Transfer Fluids
Award No. DE-FG36-08GO18144
CSP
1 | Program
Name
or Ancillary Text
This
presentation
does

Justin W. Raade, PhD

Halotechnics, Inc.
jraade@halotechnics.com
May 26, 2010

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not contain any proprietary, confidential, or otherwise restricted information

Overview
Timeline

Barriers

Project start date: January 1,

2009
Project end date: December
31, 2011
Percent complete: 34%

Budget

Total project funding

DOE share: $1.5 million
Contractor share: $564,000

This project will enable the cost of

CSP electricity to be reduced by
15%. We are developing a heat
transfer fluid that will allow high
temperature operation of CSP
plants.

Partners

Halotechnics, Inc.
Sandia National Laboratories will
partner in Phase 3 for field testing.

Funding received in FY09:

$500,000
Funding for FY10: $500,000

2 | Solar Energy Technologies Program

Halotechnics, Inc.

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Background and objective

Concentrating Solar Power (CSP)

is lowest cost solar electricity
13-17 /kWh

Must reduce cost of CSP to

compete with fossil fuels
Novel materials needed for heat
transfer fluid (HTF) and thermal
energy storage (TES)
Project Objective: Conduct
an R&D program focusing on
deep eutectic (low-melting)
salt formulations suitable as
advanced heat transfer fluids

HTF

TES
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Project milestones

Milestone 1: Approximately 250 (100 minimum) primary candidate formulations

Candidates must meet the following criteria:

Milestone 2: Approximately 10 (5 minimum) secondary candidate formulations.

Candidates must meet the following criteria:

freezing point less than 80C (100C maximum)

thermal stability as a liquid to about 500C (450C minimum)

viscosity of about 1 centipoise (10 centipoise maximum) to about 500C

vapor pressure of about 5 atmospheres (10 atmospheres maximum) to about 500C
specific gravity in the range of 0.7-1.7 (0.5 minimum, no maximum) to about 500C
heat capacity in the range of 2-5 J/g/K (1 J/g/K minimum, no maximum) to about 500C

Milestone 3: At least 1 commercial production candidate. Candidate(s) must meet

the following criteria (as determined by field testing at Sandia):

sufficient pumpability
thermal cycling tolerance
sufficient long-term thermal stability
chemical compatibility with common stainless steels

4 | Solar Energy Technologies Program

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Project timeline

Status May 2010

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Materials discovery workflow

Automation Studio to
create experiments and
manage data

Powdernium powder
dispensing robot

Symyx software and R&D tools enable automated

workflow
Maximum throughput of 500 blends/week
High throughput workflow can be leveraged to
develop advanced materials similar to HTF such
as thermal energy storage materials
6 | Solar Energy Technologies Program

Halotechnics, Inc.

High temperature
furnace for
melting/mixing
Parallel Melting Point
Workstation (PMP) with
96 channel capability
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Thermal properties characterization

Thermal stability

High temperature thermogravimetric

analysis (TGA)
TA Instruments Q500 with 16
position autosampler

Heat capacity

Differential scanning calorimeter

(DSC)
TA Instruments Q200 with 50
position autosampler

TGA with 16 position

autosampler

DSC with 50 position

autosampler

7 | Solar Energy Technologies Program

Viscosity
Brookfield viscometer (to be
acquired)
Capable of testing up to 300 C,
may modify for higher temperature

Molten salt chemistry

Symyx Low Thermal Mass Reactor
for testing salts up to 500 C

High temperature
viscometer
Halotechnics, Inc.

Low Thermal Mass Reactor

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Milestone and results

Milestone 1: Approximately 250 (100

minimum) primary candidate formulations
Candidates must meet the following criteria:
freezing point less than 80C (100C
maximum)
thermal stability as a liquid to about 500C
(450C minimum)

Primary screen
Melting
point

5030

Thermal
stability

189

Primary candidate
formulations

138

Phase 1 results
5030 blends screened for melting point
189 blends met melting target <80 C
138 blends met thermal stability target >500 C

8 | Solar Energy Technologies Program

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Heat transfer fluid for trough plants

Recent breakthrough: Discovered formulations with melting
point less than 75 C and thermal stability to 500 C
Halotechnics Solar Salt

Patent Application No. 61325725

traditional salt
synthetic oil
0

100

200

300

400

500

600 C

Must increase plant operating temperature to 500 C to increase thermal

efficiency and reduce levelized cost of electricity would enable
$0.02/kWh reduction according to Sandia study
Current plants limited to 390 C by synthetic oil heat transfer fluid (VP-1)
Existing salt-based heat transfer fluids have unacceptably high melting
point, typically 142 C (Hitec), preventing any CSP applications
Can combine best attributes of both with deep eutectic salt formulations
high thermal stability of salt with low melting point of synthetic oil

9 | Solar Energy Technologies Program

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Deep eutectic salt formulations

Eutectic salt formulations exhibit low melting points

Screened over 5000 unique blends of nitrates, nitrites, and other salts
Discovered many eutectic blends with melting points below 75 C
Large number of possible salt formulations is a combinatorial problem and
significant barrier to entry

Ternary mixture

Binary mixture

Na + K = 220 C

Binary + Li = 120 C

10 | Solar Energy Technologies Program

Quaternary mixture

High order mixtures

Ternary + Ca = 90 C

Quaternary +++ = 75 C

Halotechnics, Inc.

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Thermal stability

TGA thermal stability behavior of Hitec nitrate-only

blend in air and nitrogen.

TGA thermal stability behavior of Hitec nitrate/nitrite

blend in air and nitrogen.

Blends containing nitrite are susceptible to oxidation in air

TGA screening method produces relative ranking of thermal stability
of blends, not absolute measurement
Long term field testing is planned for Phase 3

11 | Solar Energy Technologies Program

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Data flow

Library Studio

Screening workflow

Data

DATA ANALYSIS

EXPERIMENT DESIGN

<<data_mine>>
<<phaseplot>>

<<salt_mine>>

CONSTRAINTS
Cost
Safety
Stability
Previous results

12 | Solar Energy Technologies Program

FEEDBACK

Halotechnics, Inc.

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Baseline Li-Na-K-NO3 system

All values in mol%

13 | Solar Energy Technologies Program

Typical PMP data

Halotechnics, Inc.

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Visualization of quaternary phase

space

Na

Each end face of triangular prism is ternary

system (Li-Na-K-NO3 and Li-Na-K-NO2 in
this example)
Plot series of cross sections at constant NO2
level to visualize melting point data

40%
K
Li

14 | Solar Energy Technologies Program

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Visualization of quinary phase space

ion 6

ion 5

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Visualization of 7 ion phase space

ion 6

Ion 5
ion 7

Ion 5
ion 5

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Phase 2 plans

Viscosity screening
Seek to find good compromise with material properties and cost

Thermodynamic modeling with the FactSage software and databases

Can model eutectic behavior and high temperature reactions

Thermal stability enhancement

Wide net search for any missed eutectic compositions

17 | Solar Energy Technologies Program

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From lab to plant

Next phases will build upon success

of Phase 1 (2009) to transfer
technology from the lab to field testing
Phase 2 (2010) focus on secondary
screening for other desirable
properties
Phase 3 (2011) focus on blend
optimization and field testing with
Sandia National Laboratories
Will work closely with customers to
test HTF in pilot plants before full
scale deployment

18 | Solar Energy Technologies Program

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From lab to plant

Component
testing

R&D

1-10 g

System
testing

10 kg

1000 kg

Pilot plant

100 tons

Commercial
plant

10,000 tons

Must work with leading

CSP technology
developers to bring
HTF from lab to plant

19 | Solar Energy Technologies Program

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Summary

Halotechnics has developed a novel salt mixture suitable for use as a heat
transfer fluid in CSP plants, increasing their efficiency and reducing their
cost
The heat transfer fluid has a broad operating range (75 C to 500 C)
Halotechnics will continue to optimize and field test the heat transfer fluid
with industry partners in order to bring the material to market

20 | Solar Energy Technologies Program

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