Molybdenum production:
9-10 March, 2017
the state of the art
Guozhu Ye, Xianfeng Hu and Lena Sundqvist Ökvist
Swerea MEFOS
Based on contribution from REFRAM partners
1 Mo production from primary resources
What are the primary resources?
Mo ore: Mo exists in the ore as molybdenite (MoS2).
o Primary Mo ore: only Mo in the ore is considered; account for
around 40-45% of the world’s Mo production.
o Cu-Mo ore: both Cu and Mo are considered; account for around
50% of world’s Mo production;
o Other ores: such as W-Mo ore.
The concentrate of Mo in the ore is quite low: ~ 0.01-0.25 wt.%.
Mineral processing is needed.
Mineral processing
o Primary Mo ores:
Crushing Grinding Flotation
Product: molybdenite with 48-56% Mo.
By-product: tailing, sludge, etc. → Secondary Mo resources.
o Cu-Mo ore:
Crushing Grinding Bulk flotation
Selective flotation to separate molybdenite from copper sulphide
Product: Copper ore concentrate with 30% Cu;
Molybdenite with > 55% Mo.
By-product: tailing, sludge, etc. → Secondary Mo resources.
Extraction and application
Primary use of Mo, which determines the Mo production
• Roasting molybdenite concentrate in air
Molybdenite Further Lubricant
Floatation
concentrate grinding grade MoS2
Roasting
in air o A small part of molybdenite concentrate
is directly used to produce lubricant
grade MoS2.
Tech-grade o A large part of molybdenite concentrate is
MoO3 used to produce technical grade MoO3 by
roasting molybdenite concentrate in air.
Downstream
processing
The roasting furnace:Multiple hearth furnace
Roasting temperature: 500 and 650°C
The chemical reactions:
Roasting product: MoO3 with Mo > 57% and S < 0.1%.
By-product: Dust → Secondary resources
Sulfurous gas
Challenge of the roasting process: emission
of sulfurous gas and dust to the environment.
The multiple hearth furnace
• Direct alloying steel with tech-grade MoO3
Account for the major use of MoO3;
MoO3 is charged into the molten steel in the EAF, AOD converter,
BOF, etc. to directly alloy steel with Mo.
Challenge of the process:
Volatilization of MoO3 and therefore loss of Mo in the dust → secondary resource
• Ferromolybdenum production
30-40% of tech-grade MoO3 is processed into FeMo alloy
The process: commonly by silico-/alumino- thermic reduction;
The product: FeMo alloy with 60 and 75% Molybdenum;
Byproduct: slag with very low Mo content → secondary resource
Advantage of the process: high Mo recovery
Challenges of the process:
Relatively high cost of silicon and aluminum compared with the carbonaceous.
• Mo Powder production
Two step process:
1. Reduction of MoO3 to MoO2
at 450-650 oC to prevent the
caking and volatilization of
MoO3;
2. Reduction of MoO2 to Mo at
around 1050 oC.
Product: Mo powder with desired particle
size and high specific surface area.
Challenges:
Use of high quality MoO3;
Use of H2 with two reduction steps.
• Use MoO3 concentrate to produce Mo-containing
chemicals: miscellaneous
Dominantly used to produce catalysts.
2 Mo production from second resources
What are the secondary resources?
o Waste rock and tailings from the mining and mineral processing;
o Mo-containing mill scale and dust from the steelmaking industries;
o Mo-containing fly ash from certain type of power stations
o Copper slag of certain type
o Mo-containing spent acid from incandescent lamp making industries
o Aqueous waste water
o Radioactive wastes from Mo/Tc generators production
Mo extraction from secondary resources
• Waste rock and tailings
Waste Flotation Extraction
Concentrate Mo
rock/tailings
Step 1 Flotation to get the concentrate
o Mo tailings from molybdenum mine
Flotation or jet flotation to concentrate Mo.
o Flotation tailings from Cu-Mo mine
Processes including one or several processes of desliming, bulk
flotation (recleaner flotation) of Cu and Mo in the coarse
fractions, separation of Cu-Mo, washing, separating S from
bulk flotation tailings and low-intensity magnetic separation of
Fe from S flotation tailings were used to recover Cu, Mo, S and Fe
minerals.
Step 2 Hydro extraction
o Hydrometallurgical process is preferable:
Attractive especially for low-grade Mo sources.
o Existing industrial hydrometallurgical routes to recover
molybdenum from mineral wastes consists of:
i) Pressure oxidative leaching (POX) or acidic/alkaline
leaching;
ii) Precipitation/crystallization, ion-exchange and solvent
extraction.
• Mo-containing mill scale
o Crushing/grinding, for oily mill scale also de-oiling, then
briquetting/pelletizing;
o Smelting reduction of the briquettes in the EAF or other reactors.
• Mo-containing steelmaking dust
o Briquetting or pelletizing.
o Reduction in different processes:
• The rotary hearth kiln pre-reduction of pellets followed by
submerged arc furnace smelting (Inmetco USA, other plants in
Japan Nippon Steel and Taiwan);
• The non-transferred plasma arc heated coke-filled shaft kiln with
dust injection via tuyeres (Scandust Sweden);
• The smelting of briquetted dust in a conventional submerged arc
furnace (Metal Europe France);
• The reduction in DC transferred open arc furnace (Heckett
Multiserv Italy and Mogale Alloys South Africa);
• DC arc process for the reduction of selected metal oxides at high
temperatures by means of carbonaceous reducing agents (Mintek).
• Mo-containing fly ash from heavy oil-fired power station
Two-stage leaching process: (i) alkaline
leaching to dissolve V and Mo and (ii) sulfuric
acid leaching to recover Ni.
For Mo recovery:
o Leaching with NaOH to dissolve V and Mo;
o Filtration to get the leaching solution;
o Alkali-precipitation to precipitate V;
o Filtration to get the V compounds and Mo-
containing filtrate;
o Acidification of the filtrate to facilitate the
transformation and precipitation of molybdic
acid;
o Filtration to get the molybdic acid.
Mo and V recovery from fly ash
• Copper slag
• Carbothermic reduction of the slag;
• Mo is recovered as Fe-Mo alloy.
Proposed Mo recovery process from Chilean copper slag
• Spent acid
o Exothermic neutralization by NH3;
o Precipitation of Mo compound as ammonium
molybdate;
o Filtration to collect ammonium molybdate;
o Roasting of ammonium molybdate to obtain
MoO3 powder;
o Two stage H2 reduction to get Mo powder.
Mo recovery from spent acid
3 Mo production from urban mine
What are the dominant urban mine (EoL
products) for Mo?
+
Mo-containing steel Spent Mo-containing
scrap catalyst
Mo extraction from urban mine
• Mo-containing steel scrap
o Re-melting in the Electric Arc Furnace
Challenge: Mo is downgraded in the steel without using its Mo content.
• Spent Mo-containing catalysts
o Process: roasting; leaching; smelting
reduction
o Product: Mo metal and/or ferroalloys
(depending on the process)
o By-product: slag
Challenge: Less cost-efficient, especially when
considering the low price of Mo at the moment
Typical process for Mo recovery from spent catalyst
4 Mo production: the present value chain
Thank you!
