Harrison_Simbol_Presentation Peer Review 2012

1 | US DOE Geothermal Program eere.energy.gov

Public Service of Colorado Ponnequin Wind Farm

Geothermal Technologies Program 2012 Peer Review

Technologies for extracting valuable metals and compounds from geothermal fluids

Principal Investigator Dr. Stephen Harrison Simbol Materials Track Name: Working Fluids

May 9, 2012

This presentation does not contain any proprietary confidential, or otherwise restricted information.


Introduction

•  Simbol Materials (Simbol) will produce lithium, manganese and zinc battery chemicals from the Salton Sea hypersaline geothermal reservoir, Imperial Valley, CA

mg/kg mg/kg

Na 53,000 Li 200

K 29,000 Mn 1,500

Ca 33,000 Zn 500

SiO2 200 Cs 20

Fe 1,500 Rb 100

TDS 31 wt% Cl 180,000

pH 5

Product Tonnes per year

Lithium carbonate 16,000

Manganese sulfate 42,000

Zinc sulfate 20,000

Potash (KCl) 410,000

Brine composition

Annual production from 50 MW plant


•  CalEnergy - site access agreement for demonstration plant testing •  EnergySource - resource agreement and bench testing at Hudson

Ranch 1 geothermal power plant (site of Simbol’s first commercial plant) –  49.9 MW plant in operation; 3+ others planned

•  Argonne National Laboratory - Work-for-Others agreement (testing geothermal compounds as components of lithium-ion battery cathodes; $450,000)

•  Jobs –  16 jobs created (operators, engineers, technicians, scientists)

•  75% in Imperial Valley, CA; 25% at R&D headquarters in Pleasanton, CA

Collaborations


•  Mineral extraction from geothermal brines has not been successfully commercialized despite its economic potential

•  Geothermal development of the hypersaline Salton Sea resource has been hampered by high development and O&M costs

•  Mineral extraction will improve project economics by creating new revenue streams for the geothermal operator through royalties from the sale of geothermal by-products –  Decrease levelized cost of electricity by up to 0.5¢/kWh per mineral –  Provide mineral royalties of over $3MM annually per 1% royalty to the

geothermal operator –  Annual revenues will be multiples larger than those from electricity sales –  Simbol’s process removes potential fouling agents from geothermal

brine, reducing operation and maintenance costs of injection wells –  Accelerate development of 1400+ MW in Salton Sea Geothermal Field

Relevance/Impact of Research


•  Project goals –  Demonstrate the technical and economic feasibility of

geothermal mineral extraction –  Produce products for market development –  Validate geothermal battery chemicals by independent testing –  Generate operational and scale up data so commercial plants

can be designed, built and financed

Relevance/Impact of Research


Schematic of R&D tasks

To injection well

Brine

Silica mgmt. Lithium adsorption

By-‐products:Colloidal silicaIron compounds

Mn / Zn precipitation

Manganesesulfate

Zinc sulfate Product

conversion

Lithium carbonate(Li2CO3)

Lithium hydroxide(LiOH)

Lithium chloride

Silica removal Improved Li sorbentsZn and MnO2 lab tests

Manufacture of cathode materials

K recovery

Lab tests and field demonstration


•  Project start: January 29, 2010 (pre-award activities since Oct. 22, 2009)

•  Project end: Sept. 28, 2012 •  70% complete

•  $ 8,573,399 spent as of Dec. 31, 2011 •  Contract will be modified to increase Simbol share

Overview

DOE share Simbol share Total

Project Funding $3,000,000 (31%)

$6,633,543 (69%)

$9,633,543


Scientific/Technical Approach

Liquid-liquid extraction

Precipitation

Sorbents

Lab pilot

Ion exchange

Optimization, purification, product generation

Select best technology

Proceed to lab pilot?

Test potential extraction technologies in the lab, e.g.

Proceed to field demonstration?

Field demonstration

Develop end-to-end processes for product production

Acquire data to design demo plant

Acquire data and product samples required for commercialization

Commercial plant operation

Design, construct, build commercial plant


Project Management/Coordination


•  5 gpm geothermal brine feed (1/1000th scale) at CalEnergy’s Elmore plant

•  Previous accomplishments –  Demonstrated silica management and

lithium extraction •  Reduced silica to targeted levels •  Produced 2% LiCl solution •  Tested two Li extraction media •  1500 hours of operation

•  2011-2012 goals –  Upgrade equipment and optimize

equipment performance –  Purify and concentrate LiCl solution –  Convert LiCl to Li2CO3 and LiOH products –  Test third Li extraction media

Accomplishments, Results and Progress: Lithium extraction demonstration plant


Accomplishments, Results and Progress: Equipment upgrades to lithium demo plant

Newly designed silica reactors increase reaction rates, decrease residence time

New clarifier design and flocculant speed up silica removal and improve feed to Li extraction


Accomplishments, Results and Progress: Added LiCl purification and concentration

Purification Columns

Evaporation System

Chiller

Filters for impurity removal, NaCl separation

•  Validated processes for LiCl purification through demo and pilot scale tests

•  Example of results

Analyte Initial conc. (mg/kg)

After Pur I (mg/kg)

After Pur II,III (mg/kg)

B 33. 32 <0.4

Ba 5 1.5 <0.1

Ca 315 5 <0.9

Mg 0 0.8 <0.1

Mn 305 0 <0.04

Sr 3 0.4 <0.01

Zn 0.6 0 <0.1


Accomplishments, Results and Progress: LiCl conversion to lithium carbonate

Lithium carbonate pilot •  Converts LiCl solution to Li2CO3 by addition of

soda ash (Na2CO3) •  Added drier •  24 hour continuous operations •  Built and operated at Pleasanton R&D lab •  Moved to Brawley facility, recommissioned and

resumed operations •  Optimized processes •  Demonstrated battery grade

99.9 % pure lithium carbonate •  Demonstrated chemical yield and purity

Lithium carbonate pilot at Brawley, CA facility


Accomplishments, Results and Progress: LiCl conversion to lithium hydroxide

Lithium hydroxide lab pilot at Pleasanton, CA R&D facility •  Designed, built and commissioned pilot •  Operated 24 hours/day, 5 days/week •  Yields are 20% greater than expected


Accomplishments, Results and Progress: LiCl conversion to lithium hydroxide

Lithium hydroxide pilot at Brawley, CA •  Designed

•  Under construction

Construction- 3/28/2012


Accomplishments, Results and Progress: Geothermal products as cathode materials

•  Argonne National Laboratory (Dr. Khalil Amine) characterized Simbol’s high purity plant lithium carbonate (Li2CO3) and used it to synthesize cathode material (lithium manganese spinel, LiMn2O4) for lithium ion batteries –  Compared to four reference materials –  Li2CO3 and spinels have same purity, structure

•  Simbol’s LiMn2O4 had higher tap density, resulting in desirable higher electrode loading

–  Simbol’s spinel had similar or better performance •  High capacity after 50 cycles •  Exceptional cycling performance

0 20 40 60 80 100 120 1403.0

3.2

3.4

3.6

3.8

4.0

4.2

4.4

Volta

ge (V

)

Capacity (mAh/g)

Simbol

3.0 3.5 4.0 4.5-0.003

-0.002

-0.001

0.000

0.001

0.002

0.003

0.004

Cur

rent

(mA

)

Voltage (V)

Simbol

Initial charge and discharge curve and cyclic voltammetry of LiMn2O4 Cycle performance of LiMn2O4

A B C D Simbol

A B C D Simbol

Simbol- best cycling performance


Accomplishments, Results and Progress: Limiting toxic elements in filter cake

•  Goal: Develop viable method for control of toxic elements (e.g. arsenic, lead, NORM) in silica management filter cake

•  Methods and inhibitors tested in lab and in field using geothermal brine at demo plant ‒  One technique reduced toxic elements to

non-detect levels; identified optimal pH; will be used in commercial plant design

‒  Several viable NORM inhibitors identified •  Obtained new continuous flow apparatus

for testing at EnergySource’s Hudson Ranch 1 geothermal plant ‒  Operations began 3/27/2012

•  Demonstrated that filter cake from silica management passed TCLP and STLC tests

Continuous flow bench scale tests using geothermal brine at Elmore demo plant

Continuous flow testing apparatus installed at Hudson Ranch 1 geothermal power plant


Accomplishments, Results and Progress: Second generation silica management

•  Past batch and column tests showed that silica sorbents are highly effective at removing silica, but there is no economical method for stripping the silica from the sorbent for reuse during silica management –  Sorbents could be used for brine polishing but not for

bulk removal of silica •  Batch tests with two new chemicals removed a majority of the

dissolved silica with limited lithium loss –  Significant caustic was needed to maintain pH for one chemical –  Results indicate chemicals best suited for polishing but not for

bulk removal of silica •  Final report in preparation


Accomplishments, Results and Progress: New materials for lithium extraction

•  Successfully developed a third commercially viable lithium sorbent and scaled up to demo plant (two developed last year) ‒  Capacity 5 g Li/L; lifetime in excess of 3,000 cycles

•  One of the sorbents is loaded for testing in the 5 gpm demonstration plant on geothermal brine

•  Developed route to synthesis of large quantities (300 – 2,000 kg) of sorbents needed for demonstration and commercial plant operations ‒  Identified and tested scale-up equipment ‒  Tested alternate, cheaper sources of starting materials ‒  Developed methods to recycle/regenerate chemicals used in manufacturing process ‒  Created PFDs for manufacturing sorbent ‒  Designed and developed cost estimate for manufacturing facility

capable of producing commercial quantities of sorbent

•  Final report in preparation


Accomplishments, Results and Progress: Potassium extraction

•  Goal: Identify ion exchange material to extract potassium from geothermal brines and produce potassium compounds such as potash ‒  𝑍𝑍𝑍𝑍𝑍𝑍𝑍𝑍+𝑍+ 𝐾𝐾𝑍+𝑍 ←𝑍𝑍 𝑍𝑍𝑍𝐾𝐾𝑍+𝑍+ 𝑍𝑍𝑍𝑍𝑍+𝑍 sodium form of exchanger ;regeneration with NaCl solution

•  14 materials screened in lab at 75, 85, 95⁰C using synthetic geothermal brine ‒  Natural zeolites, modified natural zeolites, synthetic clinoptilolite, synthetic zeolite W,

synthetic crystalline silicotitanate, niobium-substituted silicotitanate, synthetic tin antimonates, commercial CST product, synthetic micas

‒  Batch uptake tests to determine capacity, selectivity, kinetics, affinity for K ‒  Batch strip tests at room temperature to determine rate, completeness, selectivity of K removal ‒  Bench scale column testing of most promising materials to load and strip K

•  Results ‒  Extraction capacities as high as 40 mg/kg; selectivities vs. Na and Ca as high as 12 and 20 ‒  Stripping selectivities vs. Na and Ca as high as 6 and 4; efficiencies as high as 98%

•  Conclusion: K extraction using these materials is uneconomical ‒  Concentration and purity of K in stripping solution inadequate, requiring further treatment;

required volumes of stripping solution too high; need large quantities of IX media

•  Final report in preparation


•  Four patents filed •  Data generated by the project is being synthesized, analyzed and

summarized in technical reports with related data sets, graphs and images •  Simbol participated in a DOE-GDR Introduction to Data Submission Webinar

and had a follow-up one-on-one meeting with GDR personnel

Data Sharing


•  Operate demonstration plant at new site –  Run end-to-end process –  Incorporate toxic element and NORM controls –  Test third new Li extraction media in demo plant –  Test alternate Li2CO3 production techniques –  Produce LiOH from geothermal brine –  Produce Li2CO3 and LiOH products for market qualification –  Finalize design of commercial plant for lithium carbonate and lithium hydroxide

production

•  Operate LiOH pilot in Pleasanton –  Complete process optimization –  Generate samples for grease production

•  Develop products such as iron sulfate and chloride •  Test battery components made with geothermal products

Future Directions


•  Simbol successfully optimized operations and demonstrated –  Production of lithium carbonate and lithium hydroxide with better than

expected yields and purities –  Production of cathodes that meet or exceed performance standards

Summary

Previous year Current year

Target/Milestone Lithium demo plant operating at geothermal power plant

•  Purification of LiCl •  Production of lithium product •  Production of cathodes •  Production of non-hazardous filter cake •  Route to large scale sorbent production

Results Silica mgmt operational 11/2010; LiCl produced 1/2011

-  Validated process for LiCl purification -  Lithium carbonate produced with 99.9% purity -  Cathodes have exceptional performance -  Filter cake passes TCLP, STLC -  Designed commercial plant for sorbent production


Supplemental Slides


BBaatttteerriieess2277%%

GGrreeaasseess 1122%%

FFrriittss99%%

GGllaassss88%%

CCoonnttiinnuuoouuss ccaassttiinngg 33%%

CChheemmiiccaall pprroocceessssiinngg

11%%

PPooyyllmmeerrss 44%%

OOtthheerr2233%%

Lithium used in diverse applications: batteries largest and fastest growing

Source: SQM

113,000 tonnes of lithium carbonate equivalent production (2008)


0

20,000

40,000

60,000

80,000

100,000

120,000

2008

t LC

E

Volume by compound (t LCE)

Other

LiCl

Li metal

Butyl-lithium

LiBr

LiOH

Li minerals

Li2CO3

Lithium sold as various compounds; value varies widely in $800+MM market

$0

$100

$200

$300

$400

$500

$600

$700

$800

$900

2008 $$MM

Value by compound ($M)

Other

LiCl

Li metal

Butyl-lithium

LiBr

LiOH

Li minerals

Li2CO3

Source: Roskill; Frost and Sullivan; Simbol analysis


Manganese and zinc compounds are large markets

Manganese compounds: $30.9 B market

0

35

$ B

Manganese sulfate (Agriculture, Li-ion batteries)

Manganese dioxide "EMD" (Alkaline, Li-ion batteries) Manganese metal "EMM" (Aluminum, steel)

Silico-manganese alloys

Zinc compounds: $26.1 B market

0

35

$ B

Zinc sulfate (Agricultural, industrial) Zinc chloride (Textiles, fluxes)

Zinc oxide (Rubber, glass/ceramics) Zinc metal (Galvanizing)

Source: Roskill; SRI Consulting; Ullmann's Encyclopedia of Industrial Chemistry; Kirk-Othmer Encyclopedia of Chemical Technology; USGS; Simbol analysis

Average price of $1,000 - $4,000 per tonne Average price of $1,500 - $3,000 per tonne


Potassium is mostly used to make potash (KCl) for fertilizer

U.S. production and imports of potash (KCl) from 2002 through 2008

MMaarrkkeett ooppppoorrttuunniittyy ffoorr ggeeootthheerrmmaall ppoottaasshh

0

2

4

6

8

U.S. imports 327 MW 50 MWMillions of ton

nes

Potential geothermal capacity

Existing markets are more than adequate to absorb geothermal potash production

Harrison_Simbol_Presentation Peer Review 2012

Documents

geothermal compounds

sale of geothermal

geothermal brines

us doe geothermal program

geothermal battery chemicals

components of lithium

mw plant

mineral royalties