FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

LIQUID SOLAR FUEL FROM CARBON DIOXIDE(with a strong bias towards element nine)

Egmont Rohwer*, Emil Roduner*, Philip Crouse** & Salmon Lubbe**

University of Pretoria*Department of Chemistry, NAS

**Department of Chemical Engineering, EBIT

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

Element nine

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

Fluorspar – CaF2

CaF2 (sol) + H2SO4 (liq) → CaSO4 (sol) + 2HF (gas)

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

Fluorspar sources in SA

Witkop mine

Vergenoeg mine

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

RESERVESPRODUCTION

SA’s Fluorspar Position

8041South Africa

Reserve Base

Reserve

180110Other countries

00USA

32Kenya

1410France

480230TOTAL

86Spain

53Namibia

NANAMorocco

18-Russia

1612Mongolia

4032Mexico

11021China

World Reserves (million tons)

8041South Africa

Reserve Base

Reserve

180110Other countries

00USA

32Kenya

1410France

480230TOTAL

86Spain

53Namibia

NANAMorocco

18-Russia

1612Mongolia

4032Mexico

11021China

World Reserves (million tons)20032002

320310Other countries

00United States

10098Kenya

110105France

45404550TOTAL

135130Spain

8581Namibia

9595Morocco

200200Russia

190200Mongolia

240227South Africa

650630Mexico

24502450China

World Mine Production (1000 t/yr)

20032002

320310Other countries

00United States

10098Kenya

110105France

45404550TOTAL

135130Spain

8581Namibia

9595Morocco

200200Russia

190200Mongolia

240227South Africa

650630Mexico

24502450China

World Mine Production (1000 t/yr)

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

Henri Moissan – 1906 Nobel Prize winner for chemistry

“Professor Henri Moissan, the whole world has admired the great experimental skill with which you have isolated and studied

fluorine – the savage beast amongst the elements.”

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

Background to fluorochemicalsq Fluorochemicals are any organic or inorganic

compound containing one or more fluorine atoms,

q Fluorochemicals are generally industrial chemicals as opposed to consumer chemicals,

q Fluorochemicals are used in the production of a range of consumer goods,

q The global market for fluorochemicals was 12 billion USD in 2006,

q The growth rate is approximately 5 % per year.

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

World market for fluorochemicals

q $12 billion USDq 5% growth rate

Global Fluorochemical Market

3.4 3.4

6.5 6.5 6.5

5.4 5.4 5.4 5.4

9.1 9.410

11.6 11.9 12.112.9

13.5

15.1

0

2

4

6

8

10

12

14

16

2001 2002 2003 2004 2005 2006 2007 2008 2009

Year

Bill

ion

USD

Growth (value %)Size (USD billion)

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

Global demand by type

0%

20%

40%

60%

80%

100%

1999 2004 2009 2014

Fluorocarbons Inorganics & Specialities Fluoropolymers

Source: THE FREEDONIA GROUP, INC. , September 2005

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

Global demand by markets

0%

20%

40%

60%

80%

100%

1994 1999 2004 2009 2014

Refrigerants Aluminium production Blowing agents Components other

Source: THE FREEDONIA GROUP, INC. , September 2005

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

Fluorsparbeneficiation process

Calcium FluorideSouth Africanmineral<10 US cents/kg

Hydrogen Fluoride

~1 USD/kg

Fluorine

>15 USD/kg

Fluorochemicalproducts>30 USD/kg

Local & export Industrial/ Consumer

goods

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

To establish world class fluorochemical facilities in South Africa for producing and exporting high value fluorochemical products in support of the country’s key imperatives:

q mineral beneficiation (fluorspar),

q reduce chemical trade deficit through exports,

q increased high tech R&D,

q attracting foreign direct investments,

q chemical sector development strategy.

Fluorochemical Expansion Initiative (FEI)

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

Background to current fluorochemicals manufacturingNuclear conversion process at Necsa – ‘60s

Need hydrogen fluoride (AHF) and fluorine

(F2) for uranium hexafluoride (UF6) production

AECI stopped as AHF Producer in ‘84

Necsa commissioned HF plant in ‘85

Industrialization and commercialization – ‘92

FEI adopted as a national initiative – ‘06

Pelchem mandated to champion FEI by Necsa BOD –’07

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

Fluorochemical manufacturing status q 4,500 ton HF plant

q Fluorine production + on-tap supply

q Organic fluoride facilities

q NF3 plant

q XeF2 plant

q Multipurpose Fluorination Pilot Plant (MFPP)

q WF6 plant

q ClF3 production capability

q SF6 plant – decommissioned

q Naproxen precursor - mothballed

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

Nuclear fuel cycle

Fluorspar beneficiation(FEI)

Fluorsparmining

Hydrogen fluoride

Fluorine

Higher valueproducts

Etc.

Uraniummining

Conversion

Enrichment

Etc.

Linkage between uranium, fluorspar and new metals

New metals(AMI)

Zr, Ti, Nb

Chemical synthesis

Purification

Etc.

DME DSTThe dti

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

The $%^& nuclear industry ruined my life!!!!!

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

25

Schematic of SOEC with oxygen ion conducting Yttria stabilized ZrO2 electrolyte (left)and cathode flow field with H2O/CO2 inlet and CO/H2 outlet. (Siemens)

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

The SA share of world minerals

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

Zircon Processing

• Plasma dissociation• MW ammonium acid

fluoride• Caustic fusion &

precipitation as ZOC

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

ELEKTROCHEMICAL Li-ION BATTERY

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

FFF Hybrid Energy Conference – Melrose JHB 2014-08-20/21 Crouse et al. – University of Pretoria

FINIS