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Valorisation des constitutants de catalyseurs du raffinage des essences (vaccares)

Vaccares - recovery of catalyst components from gas refineries.

The EUROPEAN UNION is involved in a programme aimed at reducing gas emissions for 4 gases (SO2, NOx, NH3 and COV) with specifications to be reached before 2010 (see directive nr 2001/81/CE). In FRANCE, annual SO2 emissions have to decrease from 610 kt in 2001 to 375 kt in 2010 (see French Official Journal, October 30th 2003). The main emitters are oil refining and fixed combustion units. Mobile sources such as cars and trucks also contribute to SO2, NOx and COV emissions. The oil refinery industry has to further purify various fuels, e.g. gasoline and diesel, with a maximum of 50 ppm of sulphur in 2005 and 10 ppm in 2009. This will be achieved by the use of much greater quantities of hydroprocessing catalysts. These catalysts are typically made of Molybdenum, Cobalt or Nickel associated with alumina, the so-called CoMo and NiMo catalysts. After use, they have to be either regenerated or treated as wastes for metal reclaiming. Another trend appearing in the refinery industry is the increase of quantities of spent NiMo catalysts used for treating the heaviest crude fractions, due to tough SO2 specifications for fuel combustion as well as the shrinkage of this market. The corresponding spent catalysts are contaminated mainly by Vanadium. The amount of spent CoMo/NiMo and these so called NiMoV are roughly equivalent worldwide. The EUREKA project VACCARES brings together several industrial partners who have found a mutual, integrated and innovative way to combine compliance with SO2 emission legislation and the recycling of different hazardous wastes coming from the oil industry, e.g. spent refinery catalysts, into raw materials to be sold and used in a variety of business. VALDI LE PALAIS is the main leader of the project and is a 100% subsidiary of VALDI, which was created in 1997 following the successful European EUREKA programme CLEAN foundry which received the Lillehammer Award in 1999. VALDI LE PALAIS operates a pyrometallurgical process for the recovery of metals such as Nickel, Molybdenum and Cobalt contained in spent catalysts. Around 6,000 ton/year of spent catalysts are treated in a 2-step process; the first one is the roasting for hydrocarbon, carbon and sulphur elimination; the second one is the smelting where fluxes are added in an electric furnace for producing ferroalloys. There is a need to treat NiMoV-catalysts as well as other Ni and V containing wastes coming from thermal power stations and the refinery industry (e.g. Partial Oxidation units for heavy fuel upgrading). NiMoV recycling should include a specific V recovery step. Firstly, Mo, Ni and V are collected in the alloy and an aluminia-calcia slag is produced, granulated and sold to the rockwool industry. The V containing alloy is then further treated by oxidising agents to produce a Fe-Mo-Ni alloy, whereby the remaining slag is enriched with vanadium and sodium salts to produce a raw material rich in sodium vanadate and useful for the vanadium chemicals industry. ECORIGEN and its associated company EURECAT are amongst the key actors worldwide for catalyst treatments, and are world leaders for regeneration as well as being recognised companies for spent catalyst recycling. ECORIGEN has a good knowledge of the refinery / petrochemistry / energy markets, can source a variety of products, deal with logistics and regulation, evaluate spent catalysts, and segregate the material for its final destination: recycling or reuse. SOLVAY has developed pioneering expertise in the field of flue gas cleaning with sodium bicarbonate (named NEUTREC (R) process). The catalyst or residue roasting step generates SO2 which has to be eliminated from the stack to an acceptable level of less than 50 mg/Nm3. A specific glue gas dry treatment, without any disposable waste and even with by-products of positive value, is currently being investigated and a patent (nr. 03.15393) was filed by VALDI at the end of 2003. This new process of SO3 scrubbing deserves further study and industrial development. UGITECH annually smelts 200,000 metric tons of stainless steel to produce long products. UGITECH is already a VALDI partner for FeMoNi alloys. All partners are interested in the spin-off from the industrial development brought by the integrated and environmentally friendly project VACCARES: - Providing an improved global set of services to the oil industry. - Developing and marketing a SO2-rich flue gases abatement technology by implementing the technology at VALDI LE PALAIS. - Reinforcing the position taken on Ni, Mo, Co and V-rich spent catalysts. - Enlarging the set of commercial products from VALDI LE PALAIS. - Decreasing production costs by using ferroalloys that are cheaper than standard ferroalloys.
Acronym: 
VACCARES
Project ID: 
3 498
Start date: 
01-01-2005
Project Duration: 
36months
Project costs: 
6 400 000.00€
Technological Area: 
Recycling, Recovery
Market Area: 
Chemical and solid material recycling

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