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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

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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

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Halotechnics, Inc.

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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
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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

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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

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Halotechnics, Inc.

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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

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Halotechnics, Inc.

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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

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Quaternary mixture

High order mixtures

Ternary + Ca = 90 C

Quaternary +++ = 75 C

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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

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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

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FEEDBACK

Halotechnics, Inc.

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Baseline Li-Na-K-NO3 system

All values in mol%


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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

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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

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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

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Halotechnics, Inc.

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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

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Halotechnics, Inc.

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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

Halotechnics, Inc.

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