EP0228816B1

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Publication number: EP0228816B1
Application number: EP86309280A
Authority: EP
Inventors: Eric John Ramm
Original assignee: Australian National University; Australian Nuclear Science and Technology Organization
Current assignee: Australian National University; Australian Nuclear Science and Technology Organization
Priority date: 1985-11-29
Filing date: 1986-11-27
Publication date: 1991-04-10
Also published as: EP0228816A1

Description

The present invention relates to vibratory processing arrangements and is particularly concerned with such a processing arrangment applicable to impregnating solid particulate synthetic rock precursor in an active cell with high level radioactive waste. Subsequent hot pressing causes the formation of synthetic rock in which the waste is immobilised.
The present applicant and The Australian National University are the proprietors of a series of inventions in this field. Australian patent application no. AU-B65176/80 (now Patent 531, 250) describes a hot uniaxial pressing process including embodiments in which a canister having a generally cylindrical wall of bellows-like formation is used to contain the supply material to be pressed and while heating is maintained pressure is applied by a hydraulic press. The synthetic rock product is formed as the bellows like canister is axially compressed (see also EP-A-102 246).
A further patent application no. AU-72825/82 (now Patent 524, 883) describes a development of the hot uniaxial pressing in which the pressing is conducted in an upward direction against a fixed top abutment in the press.
The prior art referred to in the above specifications includes prior art of The Australian National University describing the formation of synthetic rock from selected phases and suitable for the immobilisation of radioactive waste.
Typically, syhthetic rock precursor is in the form of a fine powder and high-level radioactive waste is a liquid which must be impregnated into the powder in the active cell and pressing must also take place in an active cell. Extremely reliable mechanical handling methods and equipment are required since it is desired for the equipment to operate for tens of years with servicing and repairs conducted only through remote manipulators.
The present invention is directed to processing arrangements and corresponding apparatus which can facilitate active cell processes which are highly reliable and conducted with equipment which is intrinsically relatively simple so that long working life and maintenance with remote manipulators can be provided.
According to a first aspect of the invention there is provided a method of producing synthetic rock with radioactive waste immobilized therein, comprising the steps of:

feeding particulate synthetic rock precursor into a vibratory conveying means having an elongated path along which the particulate material in the form of a bed is progressively moved under vibration,
spraying the particulate material with a liquid incorporating radioactive waste at each of a series of locations spaced along and above the elongated path such that the liquid is absorbed into the particulate material which continues to advance to the discharge end of the device,
applying heat to the bottom of the bed over an extended region of said elongated path for treating the impregnated synthetic rock precursor for maintaining the synthetic rock precursor in a substantially dry state and causing evaporation of water contained in said liquid, and
pouring the synthetic rock precursor into a canister having a generally cylindrical form with a bellows-like cylindrical wall and flat end walls, closing the canister after pouring the synthetic rock precursor into the canister and effecting a hot pressing operation to form dense synthetic rock with the radioactive waste immobilized therein.

Although preferably the invention is implemented in a continuous process in which the elongated path extends from spaced upstream and downstream ends, the process can also be operated with paths of different configuration and indeed can be operated in a batch process in which the vibratory conveying means causes the particulate precursor to move around within a suitable vessel as it is being sprayed with radioactive waste liquid. For example, a generally square trough like vessel may be used and the vibratory conveyor means can cause the particulate material to circulate around the trough.
One very important embodiment of the invention is one in which heat is applied to the impregnated synthetic rock precursor thereby maintaining a substantially dry state and causing evaporation of water thereby leaving the radioactive material impregating the waste. The level of heating is preferably relatively low e.g. 300°C whereby the powder can remain in a flowable state and components of the radioactive waste which are volatile at higher temperatures remain substantially in the synthetic rock.
The conveyor may be inclined either upwardly or downwardly or may be horizontal. This in dictated by the physical form of the precursor.
Preferably the invention is implemented in a generally trough like vibratory conveyor and has a vibrating element applied near its upstream end, its downstream end being supported in a flexible mounting and remaining substantially stationary.
Preferably a series of spray heads are spaced along the trough-like conveyor.
In a preferred embodiment, the synthetic rock precursor is formed into granules having an improved pourability and packing density compared with the particles of synthetic rock precursor: it has been found that use of this aspect of the invention permits very effective impregnation of such granules with highly uniform dispersion of radioactive components through the final synthetic rock produced after a hot uniaxial pressing process.
According to a second, preferred aspect of the invention the calcining is effected by passing the impregnated synthetic rock precursor in flowable particulate form and having impregnated therethrough radioactive waste, the method comprising passing the material into an upstream end of an elongated downwardly inclined tubular duct, establishing vibration of the tubular duct whereby the particulate material advances progressively and applying high level heating so as to calcine the particulate material, and discharging the calcined material at the downstream end of the apparatus.
Preferably, the apparatus is orranged to provide an operating temperature of about 750°C.
The calcining apparatus preferably has a variable frequency vibration unit which preferably is directed to actuate vibrations at the downstream end of the tube, the upstream end being mounted in suitable flexible mountings and substantially not moving.
With advantage, induction heating can be used for the furnace which can be surrounded by insulating material.
Furthermore, in this aspect of the invention a most advantageous embodiment is one in which the tubular duct is connected to a gas circulation system whereby a controlled atmosphere can be passed preferably in a counter current arrangement through the tubular duct, whereby volatile radioactive components from the waste can be taken up and removed through suitable filtering arrangements.
This aspect of the invention permits a reliable and very compact capital effective plant to be devised thereby obviating the complexity and very considerable volume required for an apparatus such as a rotary calciner. The capital cost per cubic meter of an active cell is very high and therefore a major impact on the economics of safe disposal of radioactive material may result from use of embodiments of the present invention.
According to a third preferred aspect of the invention, there is provided an arrangement for mixing a titanium powder into a calcined synthetic rock precursor incorporating therein radioactive waste: the arrangement comprises using a tubular vibratory conveyor which is downwardly inclined in the downstream direction and the titanium powder is introduced just downstream of the synthetic rock precursor inlet to the vibratory tube, whereby intimate mixing of the particulate material occurs in a well controlled and continuous manner.
The discharge can be to a receiving hopper and/or to a bellows-like container whereby the poured material is ready for a hot uniaxial pressing process.
An apparatus for producing synthetic rock precursor with radioactive waste immobilized therein is disclosed inclaim 13.
Various embodiments of the invention can contribute substantially to a most effective plant for high level waste immobilisation in synthetic rock by providing a compact and reliable process substantially avoiding the handling of any solids other than dry pourable solids at each stage.
In a most effective and important embodiment all three of the above aspects of the invention are used in combination in sequence and furthermore a further inventive combination is one in which the above three aspects are used in combination with the further inventive step the subject of the present applicant's co-pending application entitled "Formation of Ceramics" and which is directed to an invention consisting in an apparatus for hot uniaxial pressing of heat resistant metal canisters containing synthetic rock components, the canisters having a generally cylindrical wall incorporating bellows-like formations, the apparatus comprising a hydraulic press having an upwardly acting ram with a refractory facing thereon for supporting the bottom of the canister, a fixed top abutment, a heating zone immediately below the abutment and adapted to surround the bellows container during the hot uniaxial pressing process and a retractable platen adapted to be inserted laterally into the press below the heating zone such that a bellows canister can be placed on the refractory facing and partially compressed at ambient temperature by upward displacement of the hydraulic press, the platen being removable to permit the press to be displaced upwardly to a higher level whereby the bellows-like canister is inserted within the heating zone and abuts against the top abutment.
For illustrative purposes only an embodiment will be described with reference to the accompanying drawings of which:

Fig. 1 illustrates schematically the processing steps for impregnating synthetic rock precursor and filling bellows like canisters for use in a hot uniaxial pressing process for the production of synthetic rock;
Figure 2 is a schematic side elevation of a hydraulic press arranged in an active cell and ready for the first stage of cold precompaction; and
Figure 3 is a view corresponding to Figure 2 and showing the precompaction stage.

The apparatus shown in Fig. 1 comprises three main stages:

A. High level waste vibratory impregnator
B. Vibratory calciner and
C. Vibratory powder mixer

The waste impregnator A. comprises a downwardly inclined trough 1 havingflexible mountings 2 and avibrator 3 at its upstream end, a hood structure 4 and a series of liquid sprays 5 connected to a high levelwaste supply tube 6.
The hood structure 4 has, at its upstream end, an inlet hopper 7 through which synthetic rock precursor material in powder or preferably in granulated form is poured. This powder is formed outside the active cell and is not radioactive. By operation of thevibrator 3, the powder continuously and steadily moves down the trough ready for discharge at the open downstream end into adischarge hopper 8.
As the precursor moves down the trough it is impregnated through the sprays 5 with a solution of high level waste, the spray rate being controlled so that the powder remains sufficiently dry to remain in a fluidised and pourable state. Aradiant heating unit 9 is located beneath the trough, as schemically shown, and causes evaporation of the aqueous solvent from the radioactive waste at a steady rate.
The impregnated precursor discharges through thehopper 8 into adischarge tube 10 and into the upstream end of the closedtube 12 of the vibratory calciner B.
Thetube 12 is downwardly inclined and is connected through a downstreamflexible coupling 13 to adischarge tube 14.Discharge tube 14 has aninlet pipe 15 for reducing gas (typically N₂/3 Volume % H₂ or H₂ alone). The reducing gas passes upwardly through the tube to a gas discharge take offtube 16 near the upstream end. In this way volatile radioactive components produced during the calcining can be taken up and filtered out.
Afurnace 13 surrounds the central region of the tube for causing the synthetic rock precursor to undergo partial mineral transformations and the nitrates associated with the high level waste are decomposed. Minor amounts of volatile radioactive components may be evolved. The furnace raises the temperature of the particulate material to about 750°C.
At its upstream end, aflexible mounting 17 supports thetube 12 and at its downstream end a variable frequency vibrator unit 18 is provided together with aflexible mounting 19.
The vibratory actuator 18 is tuned to provide the desired flow rate by varying frequency and amplitude.
The calcined discharged powder falls downwardly into a vibratory mixer C. having avibratory actuator 20 andflexible mountings 21. Asecondary inlet 23 is provided for titanium powder which is intimately mixed as the powders pass downwardly through the inclined tube to be discharged to adischarge hopper 24 from whichbellows canisters 25 may be filled.
Reference will now be made to Figures 2 and 3 which illustrate how the filled canisters can be uniaxially pressed.
Referring to the drawings a hydraulic press comprises a fixedbase 31, an open, upwardly extendingframework 32, a fixedtop press frame 33, a refractorytop pad 34 and just below the top pad a heating unit comprising anelectrical induction coil 35 with acylindrical metal sleeve 36 functioning as a susceptor sleeve. Furthermore, the press has an upwardly actinghydraulic ram 17 with apiston 38 on the top of which a refractorytop pad 39 is mounted.
For the purpose of cold pre compaction of thecanisters 25, the hydraulic press incorporates a retractable plate-like platen 40 which is horizontaly slidably displacable in guides (not shown) by actuation of asecondary ram 41.
Figure 2 shows the first stage in which a bellowscanister 25 has been placed on the refractorybottom pad 39. The canister is of a heat resistant alloy or steel such as INCONEL 601. As filled through hopper 24 (Fig 1), the calcined impregnated synthetic rock will have a typical density of 19% of the maximum theoretical density of the final synthetic rock. A cold precompaction is applied by first actuating theram 41 to displace horizontally theplaten 40 to adopt the position shown in Figure 3 and then thehydraulic ram 37 is actuated to place thebellows canister 25 into abutment with theplaten 40. Pressure is maintained until the density of the synthetic rock powder approaches the maximum which can be achieved at ambient temperatures, e.g. about 35% theoretical maximum density. Typically, the press will be operating at the order of 20 MPa and the time for this pressing step will be the order of 3 minutes.
Theram 37 is then lowered slightly, theram 41 actuated to retract theplaten 40, and (unless an optional separate pre-heating furnace is used) theram 37 is raised to place the bellows container within the heating zone and to occupy the position shown in dotted lines and referenced 42′. It is necessary to heat the bellows container and its contents to a typical temperature in the range 1050° to 1260°C and this will take typically 510 minutes for a 40 cm diameter bellows canister.
Subsequently, pressure can be applied through the ram so that the bellows canister is in abutment with thetop pad 34 and pressures of about 14 MPa or higher are applied for several hours until full compression of the bellows canister occures and a density of about 99% theoretical density is achieved.
It will be appreciated that during normal operations the induction coil is continuously operated and appropriate insulation material surrounds the upper part of the press to reduce heat losses. However, thebottom pad 39 is itself raised to very high temperatures and as soon as thecanister 25 is placed on top of the pad there will be a heat flow into the metal forming the walls of the canister. It has, interestingly, been found that nevertheless, an effective precompaction can occur in the manner described above and the shape of the bellows container achieved during the final hot uniaxial pressing stage is highly predictable and repeatable.

Claims

1. A method of producing synthetic rock with radioactive waste immobilized therein, comprising the steps of:
feeding particulate synthetic rock precursor into a vibratory conveying means (A) having an elongated path along which the particulate material in the form of a bed is progressively moved under vibration,
spraying the particulate material with a liquid incorporating radioactive waste at each of a series of locations spaced along and above the elongated path such that the liquid is absorbed into the particulate material which continues to advance to the discharge end of the device,
applying heat to the bottom of the bed over an extended region of said elongated path for treating the impregnated synthetic rock precursor for maintaining the synthetic rock precursor in a substantially dry state and causing evaporation of water contained in said liquid,
calcining the impregnated synthetic rock precursor,
pouring the synthetic rock precursor into a canister (25) having a generally cylindrical form with a bellows-like cylindrical wall and flat end walls, closing the canister after pouring the synthetic rock precursor into the canister and effecting a hot pressing operation to form dense synthetic rock with the radioactive waste immobilized therein.

2. A method as claimed in claim 1 characterised by a temperature of the order of 300°C being established in the synthetic rock precursor passing along said elongated path.

3. A method as claimed in claim 1 or 2, characterised in that the conveying means (A) has an inclined trough (1) and a vibrating element (3) connected thereto near the upstream end of the trough, the downstream end of the vibratory conveying means being mounted and supported in flexible mountings (2) and remaining substantially stationary.

4. A method as claimed in any one of the preceding claims characterised by the conveyor means using a multiplicity of spray heads (5) spaced along and above said elongated path for spraying said liquid.

5. A method as claimed in any one of the preceding claims and characterised by including taking synthetic rock precursor in powder form and forming the precursor into a granulated form and supplying the granulated form of the precursor to be fed into said vibratory conveying means (1).

6. A method as claimed in any one of the preceding claims and further characterised in that the calcining of the impregnated synthetic rock precursor is effected by advancing said impregnated synthetic rock precursor in flowable particulate form into an elongated downwardly inclined tubular duct (10, 12), establishing vibration of the tubular duct (10, 12) and applying high level heating so as to calcine the synthetic rock precursor during its passage along said duct, and discharging the calcined synthetic rock precursor at the downstream end of the duct.

7. A method as claimed in claim 6 and characterised in that said applied high level heating establishes a temperature of the order of 750°C in the synthetic rock precursor passing down the duct.

8. A method as claimed in claim 6 or claim 7 and characterised in that said step of establishing vibration of the tubular duct (10, 12) is effected by a vibrator unit (18) connected to the downstream region of the tubular duct, the upstream end of the tubular duct being mounted in flexible mountings (17) and the method further comprising adjusting the frequency of vibrations to control the flow rate of the synthetic rock precursor.

9. A method as claimed in any one of claims 6 to 8 and characterised by further comprising using a gas circulation system through said tubular duct and controlling the atmosphere within the tubular duct, gas extracted from the tubular duct being filtered to remove volatile radioactive components taken up from the radioactive waste content of the synthetic rock precursor.

10. A method as claimed in any one of claims 6 to 9 and characterised by further comprising mixing titanium powder into the discharged calcined synthetic rock precursor by using a vibratory conveyor (20) which is downwardly inclined in the downstream direction, the titanium powder being mixed into the synthetic rock precursor near the upstream end of said vibratory conveyor.

11. A method as claimed in any one of the preceding claims, characterised by effecting a cold precompaction of the synthetic rock precursor by uniaxial pressing along the axis of the canister after the synthetic rock precursor has been poured into the canister and the canister has been closed.

12. A method as claimed in claim 11 and characterised in that the cold precompaction of each bellows canister is effected using an apparatus comprising a hydraulic press having an upwardly acting ram (37) with a refractory facing abutment and adapted to surround the bellows container during the hot uniaxial pressing process and a retractable platen (40) adapted to be inserted laterally into the press below the heating zone such that a bellows canister (25) can be placed on the refractory facing and partially compressed at ambient temperature by upward displacement of the hydraulic press, the platen being removable to permit the press to be displaced upwrdly to a higher level whereby the bellows like canister is inserted within the heating zone and abuts against the top abutment.

13. Apparatus for producing synthetic rock precursor with radioactive waste immobilized therein comprising:
vibratory conveying means (1) having an elongated path, an inlet for receiving in particulate form synthetic rock precursor and means for discharging impregnated synthetic rock precursor, the vibratory conveying means being operable to move the synthetic rock precursor in the form of a bed along an elongated path,
means (5) for spraying the synthetic rock precursor at each of a series of locations spaced along and above the elongated path with a liquid incorporating the radioactive waste such that the liquid is absorbed into the synthetic rock precursor as it advances along the elongated path,
means (9) for applying heat to the bottom of the bed of the synthetic rock precursor over an extended region of said elongated path for maintaining the synthetic rock precursor in a substantially dry state and causing evaporation of water contained in said liquid,
means (B) for calcining the impregnated synthetic rock precursor,
means for discharging the impregnated synthetic rock precursor, and
means (24) for pouring the synthetic rock precursor into canisters (25) having a generally cylindrical form with a bellows-like cylindrical wall and flat end walls, means for closing each canister after the synthetic rock precursor has been poured into the canister, and means for effecting a hot pressing operation to form dense synthetic rock with the radioactive waste immobilized therein.

14. Apparatus as claimed in claim 13 characterised in that the vibrating conveying means incorporates a vibrating element (3) located near its upstream end, the conveying means (1) being of trough like form and being mounted in a flexible mount (2) near its downstream end.

15. Apparatus as claimed in either of claims 13 or 14 and characterised by the calcining means comprising an elongated downwardly inclined tubular duct (10, 12) having an upstream inlet (8) arranged to receive synthetic rock precursor discharged from said vibratory conveying means, the tubular duct having vibration means for advancing the synthetic rock precursor therealong and heating means for calcining the synthetic rock precursor as it is advanced along the duct and before it is discharged from the downstream end.

16. Apparatus as claimed in claim 15 and characterised by incorporating a gas circulation system for controlling the atmosphere within the tubular duct and removing and filtering of radioactive particles and absorbing any volatile products.

17. Apparatus as claimed in claim 16 and characterised by further comprising a further vibratory conveyor (C) for mixing titanium powder in to the calcined synthetic rock precursor prior to its being poured into the canisters.