CERAMIC OXIDES INTERNATIONAL B.V.

EXPERTS in MATERIALS SCIENCE and ENVIRONMENTAL SOLUTIONS

COMPANY HISTORY Ceramic Oxides International B.V. has been established in 1971 by the founder and became a limited liability company in 1978. C.O.I.’s main activities are focussed on the synthetisation of minerals under hydrothermal conditions.

Although still active in the field of materials design (smart materials, magnetic materials, rheological fluids, conductive polymers), C.O.I. has been focussing since 1994 on hazardous waste streams produced by oil, pharmaceutical, chemical and associated companies. By means of both hydrothermal and electrochemical processes, C.O.I. proved to be capable of processing these waste streams in an environmentally sound manner. Applying the C.O.I. technologies has economical, technological and ecological advantages.

THE HYDROTHERMAL PROCESS The hydrothermal process facilitates the complete destruction, separation and/ or immobilization of stable (in)organic compounds in industrial waste streams. Hydrothermal processes are a little younger than the universe. Minerals and metals were created under high temperature and high pressure using water as a solvent and taking billions of years. To obtain the same results within a period of a few years, months, weeks or even hours, open-air processes have to be imitated. Approximately two decades ago C.O.I. started to focus on the behaviour of water in the supercritical domain, a domain that, up to then, was not extensively explored. In this domain no distinction can be made between the liquid and the gas phase, thus enabling the disintegration of stable organic and harmful compounds. The basic principle of this technology is already proven in production processes and is in operation in three plants in the USA, Belgium and The Netherlands. For large industrial waste quantities a patented continuous plug flow reactor system is available.

The hydrothermal process works at near critical, critical and supercritical conditions and is patented worldwide.

THE ELECTROCHEMICAL PROCESS The Electrochemical process facilitates the recuperation of noble and other valuable metals out of inorganic waste streams. Electrochemistry, such as the gold plating of small silver boxes, goes back some 3,000 years and was later developed for more extensive use in industry in the early 19th century by the Italian scientist Galvano. It is now possible, as a result of further inventions, to use the same technology to extract precious and valuable materials from waste streams. The acquired electrochemical process is unique in the sense that proven technologies such as bi-polar electrodialysis, reverse osmosis and concentrated sulphuric acid production, are combined in a closed-loop system. All noble and other valuable elements will, after being brought into solution, be recuperated by means of selective ion-exchangers and electrolysis. The basic principle of the technology is in operation in plants in Switzerland, Germany and France.

Since 1998 C.O.I. has acquired the “Batenus Process”, initially developed as a process for the recovery of raw materials from presorted collected waste, especially electrochemical batteries and accumulators. After ample consideration, C.O.I. has adapted this process in such a way wherby its aim has become the recovery of precious and other valuable materials (metals).

C.O.I. offers both the hydrothermal and electrochemical technologies on a license basis to those companies dealing with said streams.

The Batenus Process Waste catalysts (powder) and wash water from mechanical part

sulfuric acid

leaching in sulfuric acid

chlorine absorption in NaOH

filterpress

aluminium oxide carrier

Hg ion exchanger

loaded resin

Selective ion exchanger Pt,Pd,Au,Ag Selective electrolysis

Pt,Pd,Au,Ag

Cu ion exchanger Cu electrolysis

copper

Ni ion exchanger Ni electrolysis

nickel

evaporator

Aluminium Oxide precipitation

reverse osmosis

bipolar electrodialysis

demineralized water

evaporator

Aluminium Oxide

conc. sulfuric acid

Na-hypochlorite

Na-,K-,Li-hydroxide for pH-adjustion

APPLICATION OF THE TECHNOLOGIES Based on economically sound and ecological sustainable principles, the patented C.O.I. technologies are capable of: • Recuperate noble and other valuable materials such as platinum, gold, silver palladium, rhodium, vanadium, tungsten, chrome, nickel, cobalt, copper and molybdenum out of spent industrial catalysts; • Destroy and/or separate ozone layer depleting CFC’s such as freon in refrigerators and halon in fire extinguishers; • Destruct and/or separate chemical additives such as tetra ethyl led; • Immobilize mercury from chloralkaline processes; • Destruct pesticides and insecticides completely; • Transform the carcinogenic needle structure from asbestos into a harmless spheral one; • Destroy biological warfare substances such as mustard gas, Sarin and Tabun; • Harmless disintegration of DDT; • Disintegration of explosives and rocket propellants. Conventional technologies such as washing and filtering do not prevent vast amounts of heavily contaminated waste streams remaining in the incineration furnaces post treatment. These organisations must make heavy investments in new washing and filter technologies and improved incineration methods such as smoke gas cleaning in order to preserve their waste disposal license. Incineration is one of the major methodologies used for the sanitation of waste streams containing harmful compounds. These techniques do not separate polluted waste disposal streams, but simply expel all the hazardous compounds into the atmosphere. The two most common methodologies are:

a) Plasma Furnace treatment (France and Australia), operating at temperatures in excess of 1,800 degr. C, with quenching facilities (rapid cooling) to reduce the liberation of dioxins, but producing large quantities of ozone depleting substances; b) Incineration treatment (AVR, Rotterdam), operating at temperatures in excess of 1,200 degr. C, with hardly any equipment to avoid emissions such as dioxins and metals in vapour form. This process still emits substantial quantities of ozone depleting substances and produces chemical fly ash containing large amounts of heavy elements. Comparing these two technologies with the hydrothermal process, it is apparent that the energy consumption of the incineration treatment methods is many times larger than that of the hydrothermal process. The elegance of the hydrothermal technology in a confined vessel or a continuous plug flow reactor is that the majority of the organic matter is destroyed. At refineries and chemical plants, pre-treatment of waste streams containing organic matter is executed to reduce the Chemical Oxygen Demand (COD). Treatment by means of the C.O.I. technology reduces the COD amount by more than 91%. The residual flow may or can be treated subsequently by aerobic or anaerobic microbes. The intellectual property for the hydrothermal technology is vested in patent US 6,241,953 B1 granted June 5, 2001. An application for a second patent in the field of hydrothermal technology will be filled shortly to strengthen coverage in the USA, Europe and Japan. The electrochemical technology is vested in three patents: • EP 0 652 811 B1 (Europe, granted December 27, 1996); • 5,575,907 (United States, granted November 19, 1996); • 3014452 (Japan, granted December 17, 1999). The patents are kept up to date by regularly filing applications on new insights and/or additions to above exisiting patents (continuation in application).

Environmentally benign waste disposal is becoming a more and more acute problem. A newly-developed process, supercritical water oxidation is demonstrating extremely efficient organic waste destruction (> 96 %) plus excellent environmental characteristics (none of the emissions associated with incineration). L’élimination des déchets bénins pour l’environnement pose un problème de plus en plus sérieux. Un procédé récemment mis au point, l’oxydation supercritique de l’eau s’est avéré extrêmement efficace pour détruire les déchets organiques (> 96 %), tout en offrant d’excellentes propriétés environnementales (sans entraîner d’émissions comme dans le cas de l’incinération). (source: Steve Minett and Keld Fenwick – in ‘Process Technology’)

P.O. Box 8, 8190 AA Wapenveld, The Netherlands Phone: (+31) (0) 38 – 44 70 268, Facsimile: (+31) (0) 38 – 44 70 264 e-mail: [email protected] Chamber of Commerce: No. 08041300 – Zwolle, The Netherlands