Hydrothermal Technology for recovery of
Molybdenum from spent Hydro-Treating
catalysts.
Wilfred van Wijk
Rob van der Meij
December 3, 2014
1
Rob van der Meij
•
•
•
Serial Entrepreneur in
Clean Tech
> 25 years in catalyst, water and
chemical industry
• Akzo Nobel, Cap Gemini,
Shell Chemicals
• 7 years Start Ups Catalysts,
Biofuels, Water, Separations
• KiOR, fluXXion, BiAqua,
Hermes Catalysts, HyVent
Chemical Engineer TU Delft, NL
December 3, 2014
Wilfred van Wijk
• > 20 years in Organophosphorus,
Specialty monomer, Organics,
Chemical by-and waste streams
and general chemical industry
• CYTEC Industries Phosphine
and derivatives
• 5 years providing chemistry,
chemical and technology
solutions; HyVent,
Gulf Interchem, ICSP.
• Chemist, University of Leiden, NL
2
HyVent Technology
Core Technology
⇨ HydroThermal treatment
Processes in the
sub- or supercritical regime of
water
Testing facilities in The Netherlands
and Germany
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3
HyVent Technology application areas
Synthesis
Heavy Oil Upgrading
Oxides
Bitumen
Ferrites
Vacuum Resid
Removal of metals
Destruction
Toxic wastes
Spent refinery catalysts
Organic/Inorganic mixtures
Mixed oxides
High COD water
December 3, 2014
4
Historical Molybdenum (Mo) pricing
MoO3 price
(USD/lb)
Hydroprocessing Catalyst contain 15-25% MoO3
?
Historical
pricing
2.5 $/lb
December 3, 2014
Year
5
Spent hydrotreating catalysts are both a hassle
and a source of value for refiners
Liability risk
when done
incorrectly
160,000 tpa
Needs to be
removed prior
to processing
Remove S from oil
Legal waste
disposal
obligation
20 % Carbon
and Sulfur
Co-Mo
Ni-Mo
Export
Needs
to be
Documentation
removed
prior
and
transport
to processing
hassle
Metals value
 4000 $/ton
>20% metals
Largely Mo
December 3, 2014
Hazardous
waste
6
High costs in metal recovery value
chain limits return to refiner
Unload spent
catalyst
Special
packaging
> 65% generated in North America,
Europe, Middle East
Roaster for
C,S removal
Metal
reclaim
• Large facilities
> 65% reclaim capacity in Asia
• Roasting and metal reclaim often
not at same site
⇨ Large transport volumes,
Export chemical waste
⇨ Multi-step location, international
processing, documentation hassle
Total costs > $ 2500 /ton
December 3, 2014
7
Current metal recovery technologies for
Mo and V have serious limitations
• Roasting for Carbon and Sulfur removal
– Environmentally unfriendly
– High capital investment, High maintenance
• Pyro metal recovery
– Smelting of material in electronic furnaces
– yielding Ferro-alloys used in steel industry, no re-use for catalysts
– Low recovery value (alloy)
– High capital investment, High energy consumption
• Hydrometallurgical metal recovery
– Chemical leaching with acid or base materials
– Complex processing with many contamination limitations
– Environmentally unfriendly waste waters
December 3, 2014
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HyVent’s Integrated Processing Scheme
Integrated Metal Recovery Process
CO2, N2
Spent Catalysts
Water
Hydrothermal
processing
• Hydrothermal dissolution of
C, S and metals
• Destruction of organic
compounds
December 3, 2014
energy
solids
Metal Recovery
Metal salts
• Combination of proven processes
from catalyst and battery recycle
industry
• Zero Liquid Discharge process
• High recovery value for M and V
9
The HyVent process is environmentally friendly
No waste water or NOX and SOX emissions
Pretreatment
Spent
Catalyst
Reactor
Separation
Recovery
Vanadium salt
Mo recovery
Molybdenum salt
feed
depressurize
Water
V- recovery
grind
mill
HT
Reactor
liquids
Liquids
centrifuge
Water
treatment
Clean water for
re-use
treatment
+ leaching
Salts for disposal
Solids
Additives
mix
HP
Pump
December 3, 2014
Solids
collection
Alumina/Ni/Co cake
10
HyVent uses all commercially proven equipment
Tubular
Hydrothermal
Reactor system
All stackable,
modular container
framed & sized
equipment
Slurry of unregenerated
catalyst
prior to
hydrothermal
treatment
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11
HyVent’s process has strong advantages
Current Processes
Large, fixed units
High CAPEX
Multi-location process:
- Roasting separate from metal recovery
- multi transport, non-local
- export
Metal recovery
pyrometallugy ⇨ ferro-alloy (low value)
hydrometallurgy ⇨ large acqueous
waste volumes
Gas emissions
Sulfuroxides, CO2, NOx and Ccompounds
December 3, 2014
HyVent Hydrothermal Process
Modular, small
Low CAPEX
Local, single location process
⇨ C & S removal in process
⇨ Local single transport
Mo and V compound as salt solutions
⇨ high value
Zero Liquid Discharge
⇨ recycle process water
12
HyVent will build local, customized, modular facilities
to eliminate transport hassle and reduce costs
•
•
•
•
•
•
•
Modular, containerized local facility
NO transport, NO documentation hassle
High return value for Mo and V metal recovery
Modular facility with ‘plug and play’ construction set up
Low CAPEX ⇨ 5-6 million USD per plant
ZLD processing, full water recycle, no emissions
High flexibility to adapt to local market
– Mo or Mo and V recovery
– Chemical catalyst processing with other metals (Cu, Zn, RE etc.) add on
possible
– Noble metal recovery scheme under development
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Several 1000-4000 tpa facilities can be build
around refining centers in the world
10,300
2
Asia
3
40,000
2
3
1
1
60,000
30,000
2
2
2
2
1
1
Americas
Europe
Global hydro-processing spent
catalyst generation (tons/year)
#
Potential number of facilities by region
America’s, Europe, export >65 % of
spent catalyst to Asia Pacific now
(VN, K, CN, TW)
USD / ton
Better return to refiner with HyVent:
⇨ avg >700 $/ton over past 15 years !!
December 3, 2014
Net return difference for
refinery HyVent vs competition
(current pricing)
Year (+2000)
15
Higher value return to Refinery
without hassle
• Recovery of Mo reduces refinery exposure to metal price
fluctuations
• Swap recovered Mo with fresh catalyst Mo
• Better value recovery for refinery
• No documentation and transport hassle for refinery
• No export waste liability risk
• Long term guaranteed off-take agreement
December 3, 2014
16
Closing remarks
The HyVent integrated HydroThermal process
for treatment of spent refinery catalyst and
recovery of Molybdenum offers an
environmentally friendly, economic and flexible
processing technology in answer to changing
market demand and requirements
Thank you for your attention
December 3, 2014
17