GB2445420A

GB2445420A - Hazardous Waste Treatment Process

Info

Publication number: GB2445420A
Application number: GB0700205A
Authority: GB
Inventors: David Deegan; Chris David Chapman; Saeed Ismail
Original assignee: Tetronics Ltd
Current assignee: Tetronics International Ltd
Priority date: 2007-01-05
Filing date: 2007-01-05
Publication date: 2008-07-09
Also published as: CA2674502C; WO2008081155A1; CA2674502A1; GB0700205D0; GB0708452D0; EP2118022A1; EP2118022B1; US8404919B2; GB2448556A; US20100069698A1

Abstract

A method comprises treating hazardous waste with a host slag material containing SiO2, CaO, and Al2O3 in a plasma reactor so as to incorporate the non-combustible waste components into the melted slag. Preferably the slag comprises 43 wt.% SiO2, 29 wt.% CaO, and 28 wt.% Al2O3. An oxidant, such as oxygen, as well as steam may be present in the plasma reactor. The waste to be treated may contain radioactive material and/or hazardous material, such as asbestos. An apparatus for the plasma treatment of waste is also disclosed, which comprises a plasma reactor having a crucible comprising SiO2, CaO, Al2O3, and optionally MgO. The reactor may comprise two plasma torches or one or more alumina-coated electrodes. The apparatus may also comprise inlets for steam and oxygen arranged such that, in use, the oxygen and steam may be mixed before or upon entry into the interior of the reactor.

Description

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2445420

Hazardous Waste Treatment Process

The present invention relates to a method of treating waste, particularly waste containing harmful substances such 5 as radioactive materials and/or hazardous waste components such as asbestos. Hazardous waste includes a material contaminated with radionuclides or hazardous materials at concentrations or activities in excess of the regulator thresholds.

10

Since the operation of the first nuclear power plants there has been a need to safely dispose of waste that contains radioactive materials. Radioactive waste materials which need to be disposed of may also be produced in other 15 industrial environments, such as hospitals, research establishments, decommissioning of nuclear power stations and in industry. The waste materials can arise from operational sources or during decommissioning activities. Such waste may be in the form of metal, soil, building 20 rubble and organic materials such as paper towels, clothing and general laboratory equipment.

Recent developments for disposing of hazardous wastes include in-drum pyrolysis processes, such as that disclosed 25 in the patent publication WO 2004/036117. This document discloses a process that involves pyrolysis and then steam reforming of waste containing organic materials and radionuclides, i.e. radioactive materials. The pyrolysis volatises the organic materials within the drums at a 30 temperature of between 200°C - 800°C. The resulting solid material remaining in the drums after the pyrolysis is a dry, inert inorganic matrix, which contains the

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radionuclides and their compounds. This inert inorganic matrix has a high carbon content, indicating the active form of the residues and ineffectiveness of the thermal treatment. The remaining species in the gaseous phase 5 following pyrolysis are water vapour, volatised organics and acid gases, which then are fed to a steam reformer, which operates at a temperature of 800 °C to 1000 °C. This •process is only of use for waste which is contained in drums and can only be carried out in a batch-wise operation. The 10 drum material provides a barrier between a user handling the waste and the radioactive materials contained within the solid product material in the drum. However, it is not convenient to treat all waste in drums. Additionally, the present inventors have found that the final solid product 15 produced with the in-drum process does not form a satisfactory physical and chemical barrier to radionuclides contained within the solid product as it forms a product that can be described as a clinker (fused at the edges), as opposed to a dense slag. This means that the hazardous 20 components of the waste offer the potential to be mobilised.

US patent publication US 2005/0120754 discloses a method for the plasma treatment of radioactive waste in a stainless steel crucible. The method involves passing an 2 5 electrical arc between two plasma torches in an oxygen containing atmosphere. The arc may pass through the oxygen atmosphere or through the waste being treated. While this process does to an extent achieve its aims of being able to incinerate combustible materials and vitrify certain types 30 of waste (e.g. ion exchange resins contaminated with radioactive materials on a glass in the nepheline family), there are a number of drawbacks. Firstly, it would seem to

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be limited to batch-wise treatment of the waste. It would also appear to be limited to waste that would itself vitrify under plasma conditions (form a stable glassy slag without material addition or the use of a host material repository).

5 Not all hazardous or radioactive waste, of course, will, on its own, vitrify (for example - highly combustible waste, such as paper that has radioactive particles on its surface). The present inventors also found that a plasma process is highly corrosive and will degrade the exposed 10 interior surfaces of a metal crucible during plasma treatment. Here the high chlorine content attributed to the use of PVC would lead to stress corrosion cracking of the plasma devices. The present inventors also believe that the process disclosed in US 2005/0120754 could be adapted so 15 that it operated more efficiently.

In the proceedings of GLOBAL 2 005, held at Tsukuba, Japan, on Oct 9-13 2005, (Paper No. 016) a process for treating low and intermediate level nuclear waste in an 20 incinerator and melting furnace was disclosed. The process involved the incineration of the waste in a plasma furnace that had a centrifuge chamber. When the waste was loaded into the plasma furnace, the centrifuge would force the waste to the sides of the rotating walls of the chamber. On 25 initiating the plasma furnace, the waste melts and runs towards the centre of the furnace floor and exits the chamber through an outlet in the floor into a mould beneath the outlet. The design of the chamber is complex and difficult to service, which presents health and safety 30 risks. The process also results in a large amount of offgas containing many contaminants, which must be treated in a

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separate part of the apparatus. The offgas treatment is an expensive and energy-consuming process.

It is an aim of the present invention to overcome or 5 mitigate the problems associated with the prior art.

The present invention provides a method for treating waste comprising:

providing a plasma reactor and waste to be treated; 10 contacting within the plasma reactor the waste and a host slag material containing Si02, CaO and Al203 (also possibly MgO within limitation due phase stability influences, i.e. <15% w/'w) ; and treating the waste and the host slag material using plasma treatment to melt the host 15 slag material and incorporate non-combustible and subsequently oxidised components of the waste within the slag material. The host slag material may further contain MgO, preferably 15% by weight or less of MgO.

20 The present invention will be illustrated with reference to the accompanying drawings, in which:

Figures la-lc show a crucible suitable for use in the method of the present invention, with la showing a plan view, lb showing a cross section of the crucible, with 25 cooling water channels shown between the inner and outer walls, and lc showing a detail of the cross section in operation, i.e. with a cold skull in place;

Figure 2 shows a plasma reactor for use in the method of the present invention, including a crucible, the roof and 30 two plasma device manipulators ("vertical actuators" in diagram) for both vertical and angular manipulation;

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Figure 3 shows a cross section of the crucible and roof along the dotted line shown in Figure 2, with molten final wasteform (oxidised hazardous or radioactive waste and host slag material in a combined glassy form) material inside the 5 crucible flowing out of its exit with an intact host slag skul1;

Figure 4 shows a plenum device having oxygen and steam inlets with a water cooling chamber/jacket. The plenum device permits mixing of the oxidant with the solid waste; 10 Figure 5 shows (i) a three-component phase diagram of a material containing primarily CaO, Al203 and Si02, where the dark irregular shaped area marks a region of preferred compositions and (ii), indicated by an arrow, a two-component phase diagram for the two components Ca0.Si02 and 15 CaO. Al203 . 2Si02 (Anorthite), showing the phases present at different temperatures. Ca0.Si02 and anorthite can be seen on the three-component phase diagram and the oval shape marks compositions containing both of these phase compositions.

2 0 Figure 6 shows an XRD diffractogram for a sample of a product slag material formed from the plasma treatment of a host slag material and an asbestos-containing waste material according to the present invention. The product slag material contains no characteristic peaks for asbestos, 2 5 indicating that no asbestos is present.

Figures 7a and 7b show SEM micrograph at 2000X and 4000X magnification, respectively, of a broken vertical edge of product slag material formed from the plasma treatment of a host slag material and an asbestos-containing waste 30 material according to the present invention. No fibrous material, i.e. asbestos, is present.

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Figures 8a and 8b show SEM micrograph at 2000X and 500X magnification, respectively, of a horizontal and vertical edge of product slag material formed from the plasma treatment of a host slag material and an asbestos-containing 5 waste material according to the present invention. Again, no fibrous material, i.e. asbestos, is present.

Figures 9 and 10 show EDX analysis of product slag material formed from the plasma treatment of a host slag ma-terial and an asbestos-containing waste material according 10 to the present invention. These Figures show that the slag product contained calcium, silicon, iron, aluminium and magnesium, the last of which derived from the asbestos-containing material.

Figure 11 shows a refractory-lined plasma furnace 15 (plasma reactor), for use in the method of the present invention, having a single tap hole for intermittent slag removal from the interior of the furnace.

Figure 12 shows a refractory-lined plasma furnace, for use in the method of the present invention, having a 20 continuous overflow spout and graphite containment crucible.

The present inventors have found that using a host slag material containing Si02, CaO and Al203 allows the plasma treatment process to be used in treating heterogeneous 25 waste. For instance, the waste may contain many different types of components, both combustible and non-combustible and/or components of varying size and density. The method is also suitable for treating waste composed entirely or almost entirely of combustible material (i.e. non-vitrifying 30 material) . The method of the present invention has the advantage that the heat from the plasma gasifies the combustible waste, while non-combustible waste is

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incorporated into the host slag material, which will form a solid vitrified mass (the product material) once the host slag material is allowed to cool. The method may be used to treat waste containing radioactive materials, since these 5 are safely incorporated within the slag material, but the method is not limited to this type of waste; for instance, the method has been found to be successful in the treatment of hazardous wastes such as APC residue and asbestos-containing wastes. No asbestos is detectable in the final 10 solid product of the method of the present invention when used to treat asbestos-containing materials. The waste may comprise various components such as one or more of metals, soil, building rubble and organic materials, such as paper items, clothing, organic liquids and materials such as 15 plastics. The waste may comprise halogenated (e.g.

chlorinated) compounds. The metal may be in the form of metal equipment or parts of equipment. The method of the present invention may be used to treat the above components when they have been contaminated with radioactive 20 substances. Additionally, if the waste material contains non-volatile radionuclides, such as plutonium, and chlorinated compounds, it has been found that very small amounts, if any, of volatile chloride and oxychlorides species of these radionuclides (e.g. PuClO Plutonium(III) 25 chloride oxide & PuCl3(g) Plutonium(III) chloride) result from the method and nearly all, if not all, of the radionuclides reside in the host slag material and the resultant product material

30 The present inventors have found that the method can be optimised by carefully selecting the composition of the slag material. Preferably, the host slag comprises 90% wt or less

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of Si02, more preferably 30 to 60 wt % Si02, more preferably 42 to 44 wt % Si02| most preferably about 43 wt % Si02. Preferably, the host slag comprises 70 wt% or less CaO, more preferably, 4 0 wt% or less CaO, still more preferably 20 to 5 35 wt % CaO, more preferably, 28 to 30 wt % CaO, most preferably about 29 wt % CaO. Preferably, the host slag material comprises 90 wt% or less Al203, more preferably 50 wt% or less Al203, still more preferably 20 to 40 wt % Al203, more preferably 26 to 2 9 wt % Al203, most preferably about 10 28 wt % A1203.

The host slag material preferably comprises a material comprising Si02r CaO and Al203 in the relative proportions shown in the (outer irregular shaped) boundary marked zone 15 on the three-component phase diagram of Figure 5. The zone provides for a fluid that has a low viscosity when molten and a material having a relatively low liquidus temperature such that it can be molten at typical operational temperatures of a plasma reactor.

20

The preferred compositions of the host slag material have been found to form a product material that has few pores or cracks, if any. This is advantageous in treating hazardous and/or radioactive waste, since the hazardous 25 material and/or radionuclides of the radioactive materials are incorporated entirely within the material and they have also been found to be evenly distributed throughout the material. The final product material formed from the preferred host slag material is preferably substantially 30 homogenous. It has been found that large metallic objects, including radionuclide species such as plutonium, will be incorporated into the microstructure of the final product

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material, rather than simply being encapsulated within larger pores of the product material.

The method of the present invention was found to have 5 advantages over the in-drum pyrolysis method mentioned above, since lower levels of residue carbon were achieved in the final waste product. If the method resulted in a solid material having a high carbon content (such as in the in-drum pyrolysis) this solid material would adversely alter 10 the oxidation state of the melt and would also be environmentally mobile (result in high leaching characteristics) and would be mechanically disadvantageous for long term storage. Additionally, che solid product material of the present invention has a higher density than 15 the in-drum product, and higher levels of oxidation of metals were achieved compared to the in-drum process, resulting in reduced metallic phase occurrence in the solid product material and higher levels of radioactive material retention in the solid product material when used to process 20 radioactive waste.

Preferably, the host slag material comprises, in the solid phase, material within one or more of the compositional phase fields of gehlenite, pseudowolastonite 25 and anorthite. Similar metastable phases are also to be expected, the ultimate microstructure being a function of composition processing regime and cooling regime.

The host slag material may comprise one or more 30 magnesium-containing compounds, such as magnesium oxide.

Preferably, the magnesium-containing material is present in an amount of 15 wt% or less.

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The waste may constitute 80 wt% or less of the total amount of solid material in the plasma reactor, preferably 60 wt% or less, more preferably 50 wt % or less. Although 5 it is possible to carry out the method of the present invention with a surprisingly high proportion of waste relative to the host slag material, it has been found that the resultant product material incorporates more of the original metallic species as oxides and is more uniform when 10 the waste constitutes 50% or less of the solid material in the reactor.

Preferably, an oxidant is present within the plasma reactor. The oxidant may comprise oxygen gas and/or a component that 15 is able to act as an oxidant such as water, saturated steam, superheated steam, air or mixtures thereof. Oxygen gas is preferred. Preferably, steam is also present in the plasma reactor to active any residue pyrolytic carbon through the formation of intermediate hydrocarbons and combustion gas 20 species (ie CO and H2) . Typical oxidant flow rates are : gaseous 02 at 4.5 to nv'hr"1 and 0.5 barg dry steam @ 7 -8 kg/hr, which may be used for treating a waste at 7.5 kg/hr at 1600 °C. The waste used in this example is 30 - 40 %w/w organic, i.e. materials containing hydrocarbons, including 2 5 hydrocarbonates, carbohydrates and halogenated hydrocarbons.

The present inventors have found that steam also reacts with the chlorinated organic species to form, inter alia, HCl.

30

The oxidant may be introduced into the plasma reactor either above the level of the host slag material and the

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waste or directly into the host slag material and the waste (the latter process sometimes being termed 'sparging' in the art). The oxygen, and optionally the steam, may be introduced directly into the host slag material by use of a 5 porous refractory plug, or inlet components made from comprising clay-graphite or a refractory metal .

An advantage of using oxygen, and particularly an oxygen and steam combination, is that this has been found to

10 more readily oxidise all elemental and metallic components present in the waste, thus improving its incorporation into the microstructure of the product material, i.e. the final wasteform.

15 Preferably, the waste and the host slag material are mechanically agitated during the plasma treatment. This will improve heat penetration and melt stirring due to buoyancy effects and produce uniform joule heating. In addition, the penetration of current into the melt and its

20 subsequent divergence in favour of lower current densities has lead to the generation of Lorentz forces that will also improve stirring, this being a 'plasma effect'. Here the ability to reconfigure the plasma arc circuitry dynamically during the active processing period is preferably employed.

25 Alternatively, a similar effect may be achieved by stirring the host slag material or by vibrational or other movement of the crucible that will promote mixing of the host slag material and the waste.

30 Preferably, the temperature of the host slag material during the plasma treatment is sufficiently high such that the host slag material is fluid, preferably sufficiently

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fluid to allow mixing of the host slag material with the waste and also sufficiently fluid to allow the host slag material to flow to the exterior of the chamber when required. Preferably, the temperature of the host slag 5 material and the waste during the plasma treatment is higher than the liquidus temperature of the host slag material. Preferably, the temperature within the plasma reactor during the plasma treatment is 1500°C or more, more preferably 1600°C or more.

10

As is known to one skilled in the art, a plasma reactor comprises a crucible for holding the material to be treated, in this case the waste and the host slag material.

Preferably, the crucible has a cooled internal wall. 15 Preferably, the crucible has a cooling system for maintaining the internal wall of the crucible at a temperature below 10 0 °C, irrespective of pressure, to avoid film boiling and maintain good heat transfer. Preferably, the cooling system is a water-cooling system, wherein 20 preferably water is passed between an outer wall and an inner wall of the crucible in order to cool the inner wall. The crucible containment device can also be refractory lined with indirect water-cooling, i.e. remote water-cooling to the process with conductive heat transfer into the working 25 environment to provide for the desired temperature profile. Alternatively, the plasma reactor may comprise a shell for holding the waste and the host slag material, the shell having a refractory-lined internal surface. For instance, the surface may have an internal covering of a refractory 3 0 material such as alumina to improve energy efficiency.

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Preferably, during the method of the present invention, the inner wall of the crucible is maintained below the liquidus, more preferably the solidus, temperature of the host slag material. (The liquidus and solidus temperatures 5 of the host slag material are readily measured by one skilled in the art by routine experimentation.) This has been found to have a number of advantages. Firstly, the host slag material forms a solid coating on the interior surface of the crucible, protecting the material of the 10 crucible from corrosion and hazardous or radiological contamination from the plasma environment. Additionally, it has been found that high temperatures can be reached, with high energy fluxes, within the plasma reactor because of the solid coating layer of host slag material, which has 15 relatively low heat transfer properties or high thermal resistance. Preferably, the method involves first plasma treating the host slag material in the absence of waste, and with the internal surface of the crucible maintained at a temperature below the liquidus, more preferably solidus, 20 temperature of the host slag material in order to form the solid interfacial coating of the material for containment, and subsequently adding the waste to the host slag material. This avoids incorporation of any hazardous materials present in the waste into the solid coating layer as the low 25 temperature inhibits diffusional processes.

The plasma reactor may comprise one or two plasma torches and/or electrodes. If the plasma reactor comprises a single plasma torch, the crucible may act as a live 30 component of system.

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Preferably the plasma reactor comprises two plasma torches, which are preferably operable in one or both of the following modes: a first mode in which an electric arc is passed above the level of the host slag material (i.e.

5 remotely coupled between the electrodes but remote from the host slag) and a second mode in which an electric arc is passed through the host slag material (i.e. directly coupled to the host slag material, i.e. transferred mode). The fi-rst mode allows the plasma process to be initiated while 10 processing a ceramic material system, avoiding the need for a conductive hearth. The second mode allows ohmic heating of the host slag material. This means that the electrical current passes through the material undergoing treatment and therefore provides for a higher power input per unit current 15 that is spatially distributed, i.e. two arc attachment points, with a high coupling efficiency.

Preferably, the one or more plasma torches comprise graphite electrodes, which have been surprisingly found to 20 be particularly durable when used in the method of the present invention and resistant to corrosive chemicals such as halogens. Preferably the electrodes are coated with alumina, which will give more consistent wear characteristics and minimise lateral electrode carbon losses 25 due to the high temperature oxidising environment.

The present invention further provides an apparatus for the plasma treatment of waste comprising a plasma reactor having a crucible containing a host slag material, as 30 defined herein, comprising Si02, CaO and Al203 and,

optionally, magnesium oxide.

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The plasma reactor may comprise an inlet for oxygen gas and optionally an inlet for steam. The inlet for oxygen and the inlet for steam may be adapted such that the oxygen and steam are mixed before or upon entry into the plasma 5 reactor.

The inlet for oxygen and optionally the inlet for steam may be arranged such that the oxygen and optionally the st-eam enter the plasma reactor chamber through the host slag 10 material.

Preferably, the apparatus is adapted such that the plasma power input and/or oxygen supply are controlled using automated control loops, rather than being set at 15 predetermined levels throughout the treatment process. Here experimentation has indicated that a free oxygen concentration during the method of 15.7 % v/v (or within the range of 14 - 17% v/v) has minimised the formation of soot and heavy hydrocarbon molecules and stabilised plasma 20 operation. This was observed using Flame Ionisation

Detection (FID). This value was measured after the point of secondary air injection, i.e. air to cool the gas stream after post combustion. The metered oxidant level therefore needs to modulate in response to the demands of the organic

2 5 waste fraction. The reactor was assumed to operate at a temperature of 1600°C with a material feed rate of waste of <10 kg hr'1. The net or theoretical energy requirements (TER) were determined from specific heat and latent heats of transformation data. The gross energy requirement (GER)

3 0 took into account the thermal losses of the reactor's structure, i.e. the energy conducted to the water-cooled elements and that retained in the off-gas stream. During

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operation the plasma power was maintained between 150 - 350 kW.

Preferably, the oxygen gas concentration in the gas 5 within the plasma reactor is preferably 17 % v/v or less, most preferably from 14 to 17% v/v. At the start of the plasma treatment of the waste, the oxygen concentration in the plasma reactor may be higher than 17% v/v, but during the process, the oxygen concentration is preferably brought 10 within and then maintained within 14 to 17 % v/v. The plasma reactor will include a plasma gas, such as argon. Other gases that may be present in the plasma reactor include nitrogen, steam, and gases produced from the treatment of the waste, such as carbon monoxide and/or 15 carbon dioxide. Nitrogen may be present from the inlet of air, which may be used to cool the gas stream, if required.

Preferably, the plasma reactor is maintained at a power consumption rate of from 150 to 350kW.

20

Preferably, the reactor comprises monitoring equipment, including, but not limited to equipment selected from: CCTV monitoring equipment for viewing the molten material within the plasma reactor, equipment for monitoring the amount of 25 waste material and/or host slag material being fed to the reactor, equipment for monitoring the internal temperature of the plasma reactor and equipment for monitoring the internal pressure of the plasma reactor.

30 The apparatus may be operable using a sealed gravity feed mechanism. The apparatus may comprise a working upper chamber and a lower receptor chamber, wherein the upper

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chamber is adapted such that the molten slag material in the upper chamber can flow by gravity into the lower chamber. This is particularly advantageous in a continuous process, in which host slag material and waste are fed into the 5 chamber continuously or periodically and avoids the requirement to run the process in a batch-wise manner. The upper and lower chambers are preferably sealed to prevent ingress of diatomic species into the plasma reactor from its exterior and egress of hazardous species. The host slag 10 material and/or the waste may be fed to the reactor through an airlock device, which ensure positive displacement of the waste into the reactor, and prevents ingress or egress of gases and heat to/from the interior of the plasma reactor. Feed ports containing airlock devices are known to the 15 skilled person. The product material in the lower chamber can be removed after solidification through an air-lock device.

The present invention will now be illustrated with the 20 following non-limiting Example.

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Example

A plasma reactor was provided as shown in Figure 2 having a crucible 1 as shown in Figures lb, lc and 3. The 5 crucible 1 had an inner wall 2 and an outer wall 3, both formed from cast copper. The external flange diameter A of the crucible was 780 mm. The internal cold crucible diameter B was 600 mm. The melt volume of the crucible was 36- litres and 108 kg of material at a melt density of 3000 10 kgm"3. Between the inner and outer walls 2,3 were water cooling channels 3A for cooling the inner surface of the crucible. The channels ensured positive plug flow of water.

The reactor further comprised one or more plasma torches/electrodes and more preferably two plasma torches/electrode, their longditual axis of location are shown at 4 and 5. The electrodes are manipulated using vertical and horizontal electromechanical actuation. The vertical manipulators alter the vertical height of the electrode within the chamber and the angular manipulators allow for alteration of the included angle between the electrodes. All the manipulation allow for arc length adjustment due to electrode wear and melt height as well as for altering the spatial distribution of the arc during different operational stages.

The roof 6 comprised copper.

Within the reactor was located a single plenum device 7 3 0 having an oxygen inlet 8 and steam inlet 9 (shown in Figure 4, not shown in Figures la to 3). The plenum device was mounted on the roof of the reactor in a position

15

20

25

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diametrically opposed to the off-gas exhaust point. The device 7 further comprised a jacket having an inlet and an outlet for water for cooling the device 7. The inlet and outlets were both connected to the inner water cooling 3A 5 circuit. The plenum device allows mixing of oxygen and steam before they are introduced to the reactor and also allows good oxidant-feed contact, i.e. contact of the waste with the oxidant (oxygen and steam).

10 The crucible had an exit 11 at one side with a lip 12

extending downwards therefrom. A lower chamber (not shown) is positioned below the exit 11, such that molten host slag material 13 (containing the non-combustible waste) during the reaction can flow by gravity out of the exit 11, down 15 the lip 12 and into the lower chamber.

Figures 11 and 12 illustrate possible constructions of a plasma reactor having a reaction chamber, which may be an upper chamber as defined above. In these embodiments, the 20 lower chamber (not shown) for collection of the slag material may be displaced below the pouring/tapping spout.

Figure 11 shows a refractory-lined plasma furnace having a downwardly-extending pouring spout allowing the 25 slag material to be intermittently removed on opening of a valve (not shown) at or near the connection of the spout with the interior of the furnace. The roof contains ports for insertion of the waste and/or host slag material.

Plasma torches may also be inserted through the top of the 30 chamber. Further features shown are a cooling finger, an anode, and water-cooled roof, all of which are known to the skilled person. A number of cooling fingers may be

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displaced at regular intervals around the interior of the reaction chamber and their purpose is to transmit heat from the refractory material to the exterior of the chamber to aid in keeping the refractory material relatively cool, 5 hence solid. The cooling finger may comprise copper.

Figure 12 shows a refractory-lined plasma furnace having a continuous overflow spout and graphite containment crucible. The refractory or graphite spout can be seen in 10 the copper spout containment chamber extending upwards at a low incline and then (at the end distal from the crucible) extending vertically downwards. In use, the level of the molten host slag material would typically be in line with (or lower than) the highest point of the spout. If more 15 waste and/or slag is added to the chamber to raise the level of the liquid above the highest point of the spout, this displaces some of the molten slag material through the spout, which can exit the spout to the lower chamber below. Because, in use, the portion of the spout extending from the 20 chamber (below the surface of the host slag material) to the highest point of the spout will be filled with molten host slag material, this prevent air ingress into the chamber, but allows the host slag material to exit the chamber, and obviates the need for a seal (e.g. a valve) on the spout. 2 5 Other features of the furnace shown in the diagram include feed ports in the roof of the chamber (for waste and/or slag material), a view port with a small keyhole-sized viewing hole, a copper crucible, graphite anodes, all of which are known to the skilled person.

30

3.2 to 50 kg of a host slag material comprising 43.1 wt% Si02, 29.2 wt% CaO and 27.7 wt% A1203 was placed in the

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crucible 1. (On a molar basis, the host slag material contained 47.5 mol% Si02, 34.5 mol% CaO and 18.0 mol% AI2O3. )

Then waste was added upto a level of 85%w/w waste 5 loading after the plasma had been initiated and the vessel brought upto temperature, e.g. for the 3.2 kg of host slag 15.97 kg of waste was added, the waste comprising up to 50% w/w organic matter was also placed in the plasma reactor.

10 The plasma reactor was initiated in a remote-coupled mode, i.e. where the arc is passed between the two torches 4 and 5 above the level C of the waste material.

Once the plasma process had been initiated, at 60 to 15 120 minutes from the initiation, the plasma torches were lowered such that they were in direct contact with the host slag material and waste feeding was initiated after the gaseous reactant supplies had been started, bringing the process into a direct-coupled mode. The preheat time is a 20 function of the applied power, vessel size and material loading.

Typical supply levels of gaseous reactant for this experiment were: oxidant [02 (g)] flow rate was 4.5 25 - 6 Nm3hr_1 and 0.5 barg dry steam was 7-8 kg/hr while treating waste at 7.5 kg/hr at 1600 °C.

The process was allowed to continue for a period of 5 -7 hours in total, i.e. including wasteform condition phases, 30 until the combustible material had been gasified and the non-combustible material and the host slag material had formed a homogenous material that was degassed and uniform.

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This was allowed to flow into the lower chamber and solidify. The following tests were carried out in the manner described above under the same conditions unless indicated otherwise.

5

The present inventors found in a first test that when only oxygen was used as the oxidant, a homogeneous ceramic product material formed in the apparatus, with the majority of- the hazardous waste components incorporated into the 10 product material. However, it was noticed that some of the metallic components of the waste were not fully oxidised.

In a second test, where the waste further comprised 20 wt % PVC (the slag material being the same as in the first test), and the oxidant was a combination of steam and oxygen as defined previously, it was found that substantially all of the metallic components of the waste susceptible to oxidation were oxidised (due to the oxygen and steam) and incorporated into the ceramic product material. Further, very low concentrations of volatile hazardous components, if any, were detected in the gas phase. The final ceramic product was a non-porous, dense product with relatively few cracks that contained very low levels of residue carbon. Anorthite (CaAl2Si208) was detected as the predominant major crystalline phase in the product.

In a third test, in which the waste material to be treated contained, inter alia, as.bestos, no asbestos was found in the resultant solid product. The resultant solid 3 0 product was examined using a range of techniques that assess the topographic and bulk crystalline character of the material.

15

20

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Various quantitative Material Product analyses were undertaken to validate the effectiveness of the plasma process for asbestos vitrification as described below.

5

The aim of the third test was to establish whether any asbestos minerals were present in the plasma vitrified materials. In all cases a certificate indicating the results was produced in accordance with UKAS accredited 10 procedures.

Temperatures greater than 500-600 °C affect the physical properties of asbestos. Consequently, as the extreme temperatures involved in the plasma vitrification 15 process were likely to render polarised light microscopy

(PLM) characterisation techniques such as birefringence and sign of elongation ineffective. X-Ray Diffraction (XRD) was used for bulk crystallographic characterisation and Scanning Electron Microscopy (SEM) for topographic characterisation 20 both analyses carried out at the Institute of Occupational Medicine (IOM) based in Edinburgh

Five samples were examined in line with HSG 248 Asbestos (The Analysts' Guide for Sampling, Analysis and 25 Clearance Procedures) which forms the current basis of the UKAS accreditation mentioned above.

Full experimental details of the third test are described below. The resulting homogeneous slag material 3 0 samples were handled and bagged by a licensed asbestos contractor. All samples were identified for COSHH purposes as plasma vitrified material (EWC 190401).

- 24 -

The third test was carried out as follows:

A Tetronics Plasma Furnace was operated on two separate 5 days. On the first day, the furnace was heated up to 1600 °C from cold, to reach thermal equilibrium, at close to atmospheric pressure, over a period of 1.5 hours. A host slag material, of similar constitution to that used in the subsequent vitrification of Asbestos Containing Material 10 (ACM), was fed continuously into the plasma furnace to flush out residuals from the reactor in order to minimise cross contamination. The host slag material employed, was prepared from virgin reagent materials and designed to have a liquidus temperature of between 1400 and 1450 "C. It had 15 the following composition:

Chemical Formula

Common

Name

Weight Percentage

Si02

Silica

Sand

33 . 7

CaO

Burnt

Lime

58. 8

A1203

Bauxite

3.2

The furnace was emptied / tapped via a tap hole using a 20 thermic lance and the tap hole was sealed. A further mass of the host slag material was charged to the furnace to act as a receptor for the ACM waste. A total of 70 kg of host slag material was charged to the furnace and approximately half of it was retained to act as a receptor for the ACM 25 waste and as a return path for the DC plasma circuit. The

- 25 -

above operation took place over a period of approximately 5 hours.

The second stage of the third test involved the 5 processing of ACM waste. The material prepared for the trial was certified by a licensed asbestos contractor as being asbestos - containing material. The types of ACM, the amounts and times when they were charged to the plasma furnace are detailed below:

10

Time

Mass

(kg)

ACM Waste type

Comment

13 :00

6.5

Amosite from vessel insulation.

Material saturated with water

13:40

8.0

Amosite from vessel insulation.

Material saturated with water

14 :25

7.0

Amosite from vessel insulation.

Material saturated with water

14 : 30

5 . 0

Amosite from pipe work insulation.

Slightly drier material than above

14 :50

6 . 0

Amosite / hrysotile sbestis Insulating Board (AIB).

Dry material, approximately 50 mm square

15:20

10 .0

Chrysotile ceiling board debris.

Dry material, approximately 50 mm square

Total

42 . 5

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The furnace was heated to 1600 °C from cold; at close to atmospheric pressure, over a period of 3.0 hours. Once steady state conditions had been achieved ACM was fed from 5 within a negative pressure tented enclosure in to the furnace.

The working volume of the furnace was 0.075 m3, so with an- assumed slag density of 3000 kg/m3, 225 kg of slag was 10 required to fill it. Only 130 kg of host slag material was in fact used in this experiment. The ACM waste was charged to the furnace over a period of approximately 2 to 3 hours, then thermally soaked for 50 minutes and finally tapped down in 10 minutes. Five slag samples were taken from the molten 15 slag stream as it exited the furnace.

The plasma furnace performed predictably and accepted all of the different classes of ACM with minimal impact on operational characteristics. The ACM was successfully 20 assimilated into the slag phase to form a final wasteform with an ACM loading of 55% w/w. No plasma outages occurred and the reactor and off-gas system were certified for re-occupation as being asbestos free without cleaning. This indicated that the plasma system was effective in destroying 2 5 the asbestos polymorphs and that fibre carry-over into the off-gas train did not occur during the process. In combination these observations demonstrates minimal environmental impact.

- 27 -

Optical Microscopy Analysis Methodology

Analysis is initially by xlO Low Power Stereo Microscopy (LPSM), then detailed examination by PLM to a 5 minimum x 80 magnification. The samples were initially visually assessed to evaluate for consistency of the sample matrix and identify any strata or layers. Each layer within the sample was analysed separately as a sub sample. If the sample appeared homogeneous then sub samples were taken to 10 give a representative analysis.

X-ray diffraction (XRD) Analysis Methodology

Five product slag samples were taken for non-asbestos certification by mineralogical analysis. Portions of each sample were finely ground to create samples of uniform particle size for X-ray diffraction phase analysis. The resultant diffraction patterns were then compared with standard reference materials and search-match indices.

Scanning Electron Microscopy (SEM) Analysis Methodology

Two random product slag samples (numbers 02 and 05)

were taken for non-asbestos certification by microstructural 25 analysis. Portions of the two samples were mounted on 25 mm SEM sample stubs, coated with a thin layer of conductive gold and examined by SEM. Energy dispersive X-ray (EDX) analysis was used to indicate the elemental composition of the samples and electronic images of their structure were 3 0 recorded.

15

20

- 28 -

It was found that the product material contained melilite materials, which are silicate materials comprising calcium, aluminium and magnesium due to the treatment of asbestos. Among the melilite materials found were gehlenite, 5 an alumina rich melilite, and akermanite, a magnesium rich melilite. The experiment was repeated 5 times with material from different height locations within the furnace. All product materials from the five tests were found to have the same composition. The Asbestos content was analysed using 10 X-ray diffraction, polarized light microscopy and scanning electron microscopy. No asbestos was detected in any of the five product materials.

Analytical Results

The analysis', conducted in accordance with HSG 248 'Asbestos: The Analysts' Guide for Sampling, Analysis and 20 Clearance Procedures', all indicated the presence of no asbestos.

The XRD traces for all five samples were the same.

Most of the material appeared to be crystalline and the 25 diffraction pattern was identified as Akermanite. No peaks were detected in the sample diffraction patterns which corresponded with any of the primary peaks of the original asbestos minerals. An example diffractogram is given in Fig 6.

30

SEM analysis found no fibrous components in the samples (see Fig 7a to Fig 8b). EDX analysis indicated that the samples comprised calcium, silicon, iron, aluminium and magnesium. The relative proportions of these elements varied

- 29 -

depending on the portion of the sample analysed, see Fig 9 and Fig 10.

It was noted that the different types of ACM wastes 5 presented to the plasma furnace were visually observed to retain their form for a matter of minutes at 1600 °C, as they floated on the molten slag due to density differences. This occurrence was unpredicted as the internal environment of the plasma furnace is extremely demanding and hostile for 10 the majority of materials. This phenomenon was primarily accounted for by the form of the asbestos products, as they are designed to inhibit heat transfer. A secondary reason can be attributed to the ACM waste materials being saturated with water. It is therefore extremely important that 15 control of both residence time and operating temperature are achieved. These conditions must be achieved homogeneously within the treatment vessel and be controlled independently of both process chemistry and ACM product form. In combination these requirements are identified as the unique 2 0 advantage that the method of the present invention can offer.

The experimentation has demonstrated the thorough way in which ACM can be treated using plasma technology and also 25 the potential for the development of secondary products of 'inert' status which will effectively close the recycling loop.

The resultant slag product has been examined in detail 30 using a range of techniques that assess the topographic and bulk crystalline character of the material. The product has been observed to contain melilite minerals, which are a

- 30 -

series of silicate minerals consisting of calcium, aluminium and magnesium; gehlenite is the alumina rich member and akermanite the magnesium rich member. These minerals crystallize from calcium rich, alkaline magmas and from many 5 artificial melts and blast-furnace slags. All five samples appeared to be the same. The crystalline component of the samples was identified by XRD as a melilite mineral and the elemental composition of the samples, as established by EDX analysis, confirmed the elements to be present in the 10 correct proportions to confirm the XRD results. No evidence of asbestos minerals was detected in the samples by PLM, XRD and SEM. No asbestos mineral peaks were detected by XRD and no asbestos fibres were detected by SEM. Therefore the samples are confirmed to contain no Asbestos Minerals.

15

The above tests show that the method of the present invention is an effective means of converting hazardous waste, including ACM, into a harmless slag product, with the potential for re-use. The technology is robust and 20 unaffected by the different types of ACM used. It is compatible with the working practice defined within the regulations for the removal and packaging of ACM waste for disposal.

25 The present invention further provides a method for the treatment of radioactive waste using plasma to form a vitrified solid material. The radioactive waste may be in the form of a sludge. A "sludge" is a well known term in the art of processing radioactive material and generally 30 refers to a liquid containing solid particles, at least some of which are radioactive. The sludge can generally flow and the particles may be present as a suspension in the liquid.

- 31 -

The sludge may contain one or more materials selected from magnesium hydroxide, silicon dioxide, uranium oxide, magnesium carbonate, aluminium oxide, sodium oxide and 5 magnesium oxide. The sludge may contain one or more materials selected from forsterite, cordierite, albite and clinoptilolite and other zeolites.

The plasma treatment of the sludge is preferably

10 carried out in a cooled crucible within a plasma reaction chamber, i.e. a crucible having an internal surface that can be maintained at a temperature cooler than that of the plasma in the chamber. Preferably the crucible is a wacer-cooled crucible as herein described.

15

The plasma treatment of the sludge is preferably carried out in a chamber having two graphite electrodes, which generate the plasma.

20 The plasma treatment is preferably carried out at a temperature of 1000 °C or above, preferably 1500 °C or above, up to a preferable maximum temperature of 1800 °C, more preferably a maximum of 1600 °C. Preferably, the plasma treatment is carried out at a temperature of around

25 1350 °C.

The plasma treatment should be carried out at a temperature at or above the liquidus temperature of the particles in the sludge.

30

Additional material may be added to the sludge as required. Preferably, at least some of the particles within

the sludge have a liquidus temperature of 1600 °C or below, more preferably 1500 °C or below, most preferably 1400 °C or below, and additional material may be added to ensure that the liquidus temperature of the particles is in the preferred range. For example, if the sludge contains one or more of Na20, Al203 and Si02, further amounts of one or more of these materials may be added to the sludge before or during plasma treatment to ensure that the relative ratios of- the material are such that the material can form an albite material (Na20-Al203-6Si02) , preferably a material in which the relative amounts of Na20, A1203 and Si02 are as shown in the triangle-shaped boundary region in Figure 7 of the Annex. An albite material has been found to have a liquidus temperature within the preferred range and also have a suitable viscosity when molten under plasma conditions.

Alternatively, if the sludge contains magnesium species (for example magnesium oxides or hydroxides), Al203 and/or Si02, then further amounts of one or more of these materials may be added to the sludge before or during plasma treatment to ensure that the relative ratios of the material are such that the material can form a forsterite and/or cordierite material (Mg0-2Al203-5Si02 / 2Mg0-Si02) , preferably a material in which the relative amounts of Mg20, Al203 and Si02 are as shown in the triangle-shaped boundary region in either Figure 11 or Figure 16 of the Annex. Forsterite / cordierite materials have been found to have a liquidus temperature within the preferred range and also have a suitable viscosity when molten under plasma conditions.

- 33 -

The method may further comprise carrying out the plasma treatment of the radioactive waste material in a receptacle removable from the plasma chamber and that can be sealed following the plasma treatment, allowing the waste to be 5 disposed of within the receptacle. A new receptacle can then be placed in the plasma treatment chamber and the process repeated. This avoids the need to transfer the molten and/or vitrified radioactive material following plasma treatment from the plasma chamber (e.g. from a 10 crucible) to a separate receptacle (e.g. a drum for the disposal of radioactive waste). The receptacle may, for example, be a receptacle having an inner surface lined with refractory material suitable for withstanding the conditions to which it would be exposed during plasma treatment. The 15 receptacle may be in the form of a drum for the disposal of radioactive waste.

The advantage of this method of treating radioactive sludge is that it does not require the presence of a host 20 slag material, i.e. the radioactive sludge is converted to a solid form in the plasma chamber without the need of much, if any, additional, uncontaminated solid material. The resultant conditioned solid waste product is particularly suitable for disposal, since it is (compared to the original 25 sludge) of relatively low volume and of high density.

Radionuclides are physically and chemically immobilised in the resultant solid waste material. This method is further described in the Annex to this description. All aspects of the methods described in the Annex may be combined together 30 unless otherwise stated. Any aspect of the methods described in the Annex may be combined and with any aspect of the methods described elsewhere in the description unless

otherwise stated.

- 35 -

Claims

CLAIMS:

1. A method for treating hazardous waste comprising: 5 providing a plasma reactor, waste to be treated and a host slag material containing Si02, CaO and Al203;

contacting within the plasma reactor the waste and the host slag material; and treating the waste and the host slag material to a 10 plasma treatment to melt the host slag material and incorporate non-combustible components of the waste within the host slag material.

2. A method as claimed in claim 1, wherein the host 15 slag material comprises 90 wt % or less Si02.

3. A method as claimed in claim 2, wherein the host slag material comprises 42 to 44 wt % Si02.

20 4. A method as claimed in claim 3, wherein the host slag material comprises about 43 wt % Si02.

5. A method as claimed in any one of the preceding claims, wherein the host slag material comprises 40 wt % or

25 less CaO.

6. A method as claimed in claim 5, wherein the host slag material comprises 28 to 30 wt % CaO.

30

7. A method as claimed in claim 6, wherein the host slag material comprises about 29 wt % CaO.

- 36 -

8. A method as claimed in any one of the preceding claims, wherein the host slag material comprises 90 wt % or less Al203.

5 9. A method as claimed in claim 8, wherein the host slag material comprises 26 to 2 9 wt % Al203.

10. A method as claimed in claim 9, wherein the host sl-ag material comprises about 28 wt % Al203.

11. A method as claimed in any one of the preceding claims, wherein the host slag material comprises a material comprising Si02, CaO and Ai203 in the relative proportions shown in the (outer irregular shaped) boundary marked zone on the three-component phase diagram of Figure 5.

12. A method as claimed in any one of the previous claims, wherein an oxidant is present within the plasma reactor.

13. A method as claimed in claim 12, wherein the oxidant comprises oxygen.

14. A method as claimed in any one of claims 12 or 13, 25 wherein the oxidant is introduced directly into the waste and host slag material.

15. A method as claimed in any one of the preceding claims, wherein steam is present in the plasma reactor.

30

16. A method as claimed in any one of the preceding claims, wherein the plasma reactor comprises a crucible for

10

15

- 37 -

holding the waste and the host slag material, the crucible having a cooled internal surface.

17. A method as claimed in any one of the preceding 5 claims, wherein during the plasma treatment the internal wall of the crucible is maintained at a temperature below the solidus temperature of the components of the host slag material.

10 18. A method as claimed in any one of the preceding claims, wherein the internal wall of the crucible is maintained at a temperature below 100DC.

19. A method as claimed in any one of the preceding

15 claims, wherein the internal wall of the crucible comprises copper.

20. A method as claimed in any one of the preceding claims, wherein the internal wall of the crucible is

2 0 refractory lined.

21. A method as claimed in any one of the preceding claims, wherein the plasma reactor comprises one or more torches, preferably two plasma torches.

25

22. A method as claimed in claim 21, wherein the plasma torches are operated in a first mode in which an electric arc is passed between the torches above the level of the waste and host slag material.

30

23. A method as claimed in claim 21, wherein the plasma torches are operated in a second mode in which an electric

- 38 -

arc is passed between the torches through the waste and host slag material.

24. A method as claimed in any one of claims 21 to 23, 5 wherein the plasma torches comprise graphite electrodes.

25. A method as claimed in any one of the preceding claims, wherein the waste and the host slag material are mechanically agitated during the plasma treatment.

10

26. A method as claimed in any one of the preceding claims, wherein the waste to be treated contains radioactive material and or hazardous waste materials such as APC residue or asbestos.

15

27. An apparatus for the plasma treatment of waste comprising a plasma reactor having a crucible containing a host slag material comprising Si02, CaO and Al203 and, optionally, MgO.

20

28. An apparatus as claimed in claim 27, wherein the plasma reactor comprises two plasma torches operable in one or both of the following modes: a first mode in which an electric arc is passed above the level of the host slag

2 5 material (remotely coupled) and a second mode in which an electric arc is passed through the host slag material (transferred).

30

29. An apparatus as claimed in claim 27 or claim 28, wherein the apparatus comprises a water-cooling system for cooling one or more interior walls of the plasma reactor.

- 39 -

30. An apparatus as claimed in claim 29, wherein water can be passed between an outer wall and an inner wall of the crucible in order to cool the inner wall.

5 31. An apparatus as claimed in any one of claims 27 to

30, wherein the apparatus comprises an inlet for steam and an inlet for oxygen.

32. An apparatus as claimed in claim 31, wherein the 10 inlet for oxygen and the inlet for steam are adapted such that the oxygen and steam are mixed before or upon entry into the interior of the plasma reactor.

33. An apparatus as claimed in claim 31 or claim 32, 15 wherein the inlet for oxygen and inlet for steam are arranged such that the oxygen and steam enter the plasma reactor chamber through the host slag material.

34. An apparatus as claimed in any one of claims 27 to 20 33, wherein the crucible is adapted to allow the host slag material to be mechanically agitated.

35. An apparatus as claimed in any one of claims 27 to 34, wherein the apparatus comprises an upper chamber and a

25 lower chamber, the upper chamber being adapted to allow molten slag material in the upper chamber to flow by gravity into the lower chamber.

36. An apparatus as claimed in claim 35, wherein the 3 0 upper and lower chambers are together sealed to prevent ingress of gaseous species from the surrounding environment into the chambers or egress of hazardous components.

- 40 -

37. An apparatus as claimed in any one of claims 27 to 36, wherein the apparatus comprises one or more electrodes having a coating comprising alumina.

5 38. A slag material formable by the method of any one of claims 1 to 26.

10