Cementation of Radioactive Waste

CEMENTATION OF RADIOACTIVE WASTE

Introduction
Cementation is one of the most commonly used methods for conditioning radioactive wastes. It provides a cost-effective solution for encapsulation of various kinds of radioactive waste into a solid, safe form suitable for long term storage. The main advantages of cementation are: Simple, low-temperature process. Well proven technology. The cemented product is not combustible and has good thermal stability. The cemented product is chemically and biochemically stable. All forms of waste can be either incorporated in a cement matrix or encapsulated by grout.

NUKEM offers five different mixing techniques: High Performance In-Drum Mixer, Lost Stirrer In-Drum Mixer, Slant Batch Mixer, High Shear Mixer and High Throughput Continuous Mixer.

Overview on Characteristics of Mixing Techniques High Performance In-Drum Mixer Throughput Rate Suitable for Portable Unit Variable Batch Size Product Quality 1 Suitable for Grout Preparation Easy Decontamination low,
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Lost Stirrer InDrum Mixer

Slant Batch Mixer

High Shear Mixer excellent

High Throughput Continuous Mixer N/A

high,

very high,

Compressive Strength, Leach Rate

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High Performance In-Drum Mixer

The High Performance In-Drum Mixer is a combination of planetary mixer with double helical mixer. The mixing elements are in the form of two counter-rotating cylindrical helices. This design ensures high shear dispersion and compensates all torque forces that might be transmitted to the drum. Intimate mixing is accomplished by having the mixing unit assembly revolving in a planetary motion so that the rotating helical blades sweep the entire circumference of the drum. The mixing elements are raised from the drum by a vertical lift. After separation, the mixing elements drain into the drum. If maintenance is required the blades can be cleaned with a hand held vibrator after curing of the residue. As an alternative, it is possible to decontaminate them in place by rotating them in decontamination solution.

Process Description

Fig. 1

Simplified Flow Sheet of the In-Drum Mixer

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A waste storage drum, prefilled with cement or a mixture of cement and dry additives appropriate to the cementation recipe is placed onto the roller conveyor. The roller conveyor transfers the drum beneath the docking hole of the mixer box/cell. Here, the docking device lifts the drum and seals the rim to the mixer box/cell. After the liquid waste filling tube is directed into the drum the first portion of waste is metered into the drum. This portion constitutes a third of the total waste quantity for one drum for a given cementation recipe. The mass flow is measured by a Coriolis flow meter, integrated and counted electronically. When the point is reached, the waste flow is shut off automatically. Usually, the drum is filled up to 95% of its height after the first portion of waste is added. The first mixing cycle now takes place. The mixer-unit assembly is lowered into the drum, down to approximately one third of its depth. The mixing elements revolve for a few minutes and bring the level of waste/cement down. The drum is then ready to receive the second portion of waste. This portion, as well as the third portion, is treated in the same way as the first. While mixing the third portion of waste, the mixing elements are submersed down within of a few centimeters of the bottom and rotated at a higher speed than before. This ensures the highest achievable homogeneity of the grout. This high degree of homogeneity ensures the product quality is very high. Compressive strength and leach rate will achieve be at their optimum values.

Application NUKEM's High Performance InDrum Mixer has been used successfully in a series of permanent and mobile applications. The flow sheet, shown in Figure 1, is applicable to both applications. For permanent installation the High Performance In-Drum Mixer is arranged in-side a hot/warm cell. Depending on the radiation level, the machinery will be operated by remote manipulators or hands-on through gloves fitted on the cell. An example of such arrangement is given in figure 2 and 3. These figures show a facility, that is owned and operated by the Research Center Karlsruhe, Germany. Auxiliary equipment is arranged in the building around the cell to suite the specific requirements of the client. The mobile unit as described below, is called DEWA. It represents a movable hot/warm cell containing the High Performance In-Drum Mixer.

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Fig. 2

In-Drum Mixer arranged inside a Hot-Cell

Fig. 3
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Operator Filling the Drum with Liquid Waste

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Mobile Solidification Unit DEWA The DEWA is an assembly of simple, robust and reliable components. The method of operation is simple. The cementation process takes place in the waste container itself; the cement is filled in beforehand. There is no requirement for the transportation of the binding agent or for its metering in the area where the radioactive material is handled. Tests have shown that the physical properties - such as compressive strength and leach rates - of the products obtained are excellent. The products meet the regulations for final disposal. The dose rates are within the required limits. The final products contain no free water. The DEWA solidification unit does not make high demands regarding the wastes to be solidified. The wastes must merely be pumpable. They may contain up to 25% boric acid, and up to 35% dry matter. As to cementation, it is unimportant whether the wastes to be solidified are high or low activity. However, the level of radioactivity requires a suitable container for shielding. The DEWA cementation unit is shipped to the point of use on a flatbed trailer. The unit unloads by selfaction using its telescopic legs, which are swung in position and than run out. For setting up, a 6 m by 3.3 m foot print with a loading capacity of 0.09 N/mm and total height of 4.53 m is required. The unit consists of a cube-shaped frame in which the steel-shielded hot/warm cell is arranged. There is an operating platform with a control panel and a roller conveyor for the transportation of the drums to be

filled. The drum docking device joins the drum to the cell where the waste is metered in and the content of drum is mixed. The cell accommodates the High Performance In-Drum Mixer, an ultrasonic level sensor, the hand held vibrator for cleaning, a line for ash supply, if required, and the exhauster with HEPA filter system. A swivelling lid covers the docking hole in the bottom of cell. The container, pre-filled with cement, is carried to the roller conveyor by a forklift and is clamped to the docking hole. The liquid waste is then transferred in portions by a Coriolis quantity meter and homogeneously mixed with the cement. The mixing process can be observed through lead glass windows. The closing of the container takes places on the roller conveyor. If the wastes are low activity it is done manually. If the activity is higher, lid closure is performed by remote control. The plant can also deal with solid wastes. In this case the drum, which is about half filled with waste material (e.g. powder, granules etc.), is transported to the cells opening as before. Cement is now added dry or mixed with water. In all other respects, the procedure is similar to that described above. Contaminated parts that cannot be compacted (filter candles, small parts) can also be placed in drums and treated likewise. The DEWA can handle all types of drums licensed by the authorities. The type of drum chosen depends on the level of activity and the particular qualities of the waste to be disposed of. The dimensions of the DEWA unit in working position are shown in Figure 4.

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Operating experience Since the start of operations with the DEWA unit, several campaigns of solidification of radioactive wastes have been carried out at the BWR at Gundremmingen, Germany and at the PWRs at Biblis, Germany and Neckarwestheim, Germany. Including the foreman, a team of three to four operators was needed. Depending on the local conditions, the setting-up times ranged from 1 to 2 days. The availability reached 95% not considering the delays caused by the plant. Filter aid sludge, precipitated slurries, decontamination effluents and evaporator concentrates with activities between 3.7 E +09 Bq/m and 1.85 E +11 Bq/m have been solidified. The performance of the unit depends on the specific activity of the wastes, the resulting

shielding requirements and on the dry substance content. A volume to 1.8 - 2.2 m per day can be solidified in externally shielded 200 l drums and a volume of 3.6 - 4.6 m per day can be solidified if using internally shielded 400 l drums. The massive steel and lead shielding of the unit and the largely remote handling of the containers ensures that the accumulated dose received by the crew remained low. While processing slurries with an activity of about 1.48 E +10 Bq/m with a nuclide distribution of 14% Cs-134, 33%Cs-137, 36% Co-60, and 5% Mn-54, the measured dose rates were < 3 m Rem/hr at the wall surface and < 0.35 m Rem/hr at the operators position. The average dose rate was less than 10 m Rem per day and per person.

Lost Stirrer In-Drum Mixer

The lost stirrer technique was employed by NUKEM to develop a very highly sophisticated, portable unit that provides a high throughput as well as ease of operability. This unit is called MOWA. Although designed to be portable, NUKEM also used the MOWA-baseline to build a permanent Lost Stirrer InDrum Mixer facility. Mobile Waste Conditioning Plant MOWA The MOWA system (Fig. 5 and 6) features all the advantages of a compact plant, as it can be shipped and stored in a 20 ft-ISO-container. It has a high waste throughput, deals with drums of several sizes (< 100-400 litre) and different shielding. The MOWA is able to process concentrates and sludge as well as granular resin with a high specific activity.
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Facility Description The MOWA, as depicted in Figure 5 and Figure 6, consists basically of two dosing and mixing positions for waste disposal drums, an accessible sealed cell with the dosing devices for sludge, concentrates and granular resins and the two hydraulic units for the drives of the in-drum-stirrers. All parts are skid-mounted. The MOWA is equipped with a PLC for automatic operations and a mobile control panel. Heavy lead shielding on the equipment containing radioactive materials and steel shielding at the mixing positions reduce the radiation exposure of the staff to a minimum (less than 10 m Rem/h at the surface of the plant while treating granular resin with 3.7 E +13 Bq/m). The disposal drums can be equipped with additional shielding, if necessary.
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Figure 4: Mobile Cementation Unit DEWA

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Fig. 5

Layout of the Mobile Waste Conditioning Plant

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Fig. 6

Mobile Waste Conditioning Plant MOWA

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Process Description The waste is drawn into MOWA metering system by vacuum or fed by an external pump. From here the waste is transferred into the cement pre-filled drums by means of a pump. Mixing of the binding agent with the waste takes place in these drums during feeding. They are equipped with the lost-stirrer. The displaced air is released through HEPA-filters. The waste disposal drums are fitted with a second cover, located below the upper rim. The connections for waste feeding, air outlet and the lost stirrer are grouped on this intermediate cover. Thus, the entire mixing process takes place within an enclosed system, avoiding the spread of contamination. The two dosing and mixing locations are stocked alternately with drums. While one drum is mixing, the other one is changed. This improves the throughput of MOWA significantly. Ion exchange resin is prepared for cementation by adjusting the stipulated water to resin ratio. This is done in the resin metering pot. The resin metering pot is equipped with a

slot sieve base to drain the excess water. The resin is then pumped with exactly the excess water required for cementation into the drum in the same manner as sludge. After being sealed remotely, the waste drum is replaced by a new one. Technical Data Overall Dimensions: Length Width Height Weight approx.

5700 mm 2220 mm 2180 mm 22,000 kg

Throughput: - Sludge/Concentrate: up to 10 m per shift - Bead Resin: up to 2 m per shift Controls: PLC, with mobile control panel Electrical Power Load: Utilities: 2 x 63 A, 380 V Water, 6 bar (for potential flush of radioactive system) 1 Foreman and 2 Operators

Staff Required:

Slant Batch Mixer

The Slant Batch Mixer (Fig. 7) is successfully installed at several Waste Treatment Centers (WTC). NUKEM set up these mixers with extensive auxiliary systems to facilitate all the cementation tasks of a WTC. Auxiliary systems such as a resin dewatering unit, ash transfer . and metering system are also available with NUKEM's other mixers. The description of the Slant Batch Mixer along with its auxiliary systems of a WTC is intended to be an example of NUKEM's system design capability

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Fig. 7

Slant Batch Mixer

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Pre-treatment of Liquid Radioactive Waste Pre-treatment of liquid, inorganic waste is carried out in NUKEM's enhanced evaporator facility (see NUKEM Brochure: Concentration of Evaporator Concentrates). The salt content in evaporator concentrates is usually in the range of 20% by weight. Direct cementation of this waste would result in a final product with a salt content of approx. 10% by weight. The enhanced concentration process generates a highly concentrated product, a so-called Super-Concentrate. Its salt content is between 500 and 700 g/l. In order to obtain a high quality cemented product, chemical addition will occasionally be required prior to cementation, e.g. in cases of high borate content. Process Description A simplified flow diagram is shown in Fig. 8. The radioactive waste enters the cementation facility in various ways: Waste, which can be forwarded by pump (like waste solutions or radioactive sludge), is received in a liquid waste receiving tank. Super-concentrates from the concentration facility are received directly by gravity flow in a metering tank for solutions. Ion exchange resin with water are transferred hydraulically and

received under pressure in the resin receiver tank. There, excess carrier water is separated by means of built-in slot sieve filters. This water is returned to the transport vessel. Ashes entering the cementation facility, are held in adequate containers. These containers are emptied into the metering pot for ashes within the transfer box. The solids to be encapsulated (for example compacted solid waste) are put in the long-term storage container before entering the cementation facility. The remaining free space is usually more than 50% of the container volume.

The cement powder is delivered in a conventional silo-truck and unloaded into a cement-silo. From there it is transferred into the cement-metering tank. Any additives required, such as concrete super-plastifier, concrete retarder, filling material or lime are weighed on a scale and put into the additive tank. Processing is preferable in a campaign featuring similar types of waste. For example, liquid waste is mixed with cement and the mixture is poured into a storage container. The filled container is transported to a buffer store where curing takes place and the container is further prepared for long-term storage.

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Legend
(Please refer to Fig. 8 Cementation Facility Flow Sheet) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 Resin mixture receiving tank Agitator Resin mixture transfer pump Liquid waste receiving tank Agitator Liquid waste transfer pump Metering tank for solutions or resin mixtures Agitator Heating Slant mixer Storage container Roller conveyor Vibrating equipment Pump Filter Ash transfer box Drum tilting device Elevator Filter Filter Ash metering tank Cellular wheel Vibrating conveyor Additive weighing equipment Additive tank Cement metering tank Cellular wheel Vibrating conveyor Filter Cement-silo

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Fig. 8 Cementation Facility Flow Sheet

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Example 1: Cementation of SuperConcentrate An empty storage container is placed under the mixer discharge tube on a vibrator that is a part of the roller conveyer. The Super-concentrate is delivered by gravity to the solutions metering tank. The sole function of the metering tank is for weight control of the liquid part of a mixer-load. The weighed solution is then transferred by gravity into the slant mixer and the mixer is started. An alternative to this technique is the metering of all by a Coriolis flow meter with electronic integrator. This is the state of the art method. The required quantity of cement is delivered to the rotating slant mixer by means of a rotary valve and a vibrating conveyor. The metering of the cement is automatically controlled by weight reduction in the cementmetering tank. After a predetermined mixing time (approx. 30 min.), the cemented product is discharged into the storage container. During filling of the storage container with the cemented product, the vessel can be vibrated in order to improve the cement distribution in the container. The storage container will usually be filled up to 95% of its volumetric capacity. The filled storage container lid is then remotely installed and the container transported to buffer storage for curing. After curing, the lid is remotely sealed behind shielding. Example 2: Cementation of Waste Solutions The quantity of waste solution needed, as stipulated by the cementation recipe, is transferred from the liquid waste receiving tank to the so-

lutions metering tank by a pump. The rest of the procedure including feed of possible additives is identical to the cementation of SuperConcentrates. Example 3: Cementation of Ion-Exchange Resin along with SuperConcentrate The ion-exchange resins are embedded in cement together with Super-concentrate. This combined cementation provides a homogeneous final product. The resin is mixed with the residual water by an agitator in the resin receiving tank. It is then transferred by a pump into the solutions or resin metering tank. The transfer is stopped when the stipulated weight of resin is achieved. In the metering tank the batch is stirred by an agitator in order to maintain the fluidity of the resin mixture. The requisite amount of Superconcentrate is now added to the resin in the same manner as described in Example 1. The metered mixture of resin and Super Concentrate is transferred by gravity into the slant mixer and the mixer is turned on. The additives, stipulated by cementation recipe, are delivered via the additive tank and the vibrating conveyor to the rotating slant mixer. The cement feed, the mixing procedure and the filling of the storage container are as described in Example 1. Example 4: Cementation of Ashes Ashes from an incinerator facility are usually cemented with the scrubber solution. The quantity of solution re-

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quired by cementation recipe is fed by gravity from the solutions metering tank into the slant mixer. Ashes are forwarded by means of a rotary valve and the ash vibrating conveyor. The rest of procedure is identical to the cementation of waste solutions. Cementation Recipes In order to ensure and optimize the properties of product, each form of waste has to be cemented with its own recipe. To achieve this, it is necessary to know the composition of waste to be cemented. Depending on the waste composition, the best matching recipe will be chosen from NUKEM's cementation database. If the waste form deviates significantly from waste form in the Cementation Database, laboratory tests will clarify or confirm missing or uncertain recipe data. The recipes given below are examples only, and will be confirmed by laboratory tests with actual waste material. Example of Recipes for Reference: Cementation of Super-Concentrates Total salt content: 600 100 g / l Density: approx. 1450 kg/m Salt content in the cement matrix: 25% wt Water/cement ratio: 0.55 Common cementation of ion exchange resin and Super-Concentrate Composition of the cemented product Content of salt: 14% Content of dry resin: 3% Water/cement ratio: 0.7

Cementation of ashes Composition of the cemented product Content of ashes: 30% Water/cement ratio: 0.7 Technical Data Batch Size:

200 to 500 litre cemented product 3,400 kg to 8,500 kg/8 h shift up to 30% wt up to 10% wt

Throughput:

Salt Load: Resin Load:

The waste load depends on the chemical composition of the liquid waste and on quality related requirements for the cemented product and its packaging. Product Quality: Leach rate for Cs: 10 -2 g/cm day (calculated as average per year) Compression Strength: 10 N/mm Homogeneous distribution of activity

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High Shear Mixer

The High Shear Mixer is a batch mixer, operated to obtain a colloidal cement slurry. NUKEM uses this slurry to grout packed solid waste items. Another field of application is the preparation of cap grout, to seal the surface of cemented liquid waste in drums or boxes. The design of the High Shear Mixer ensures that the highest possible quality of grout is achieved. Usually, the mixer and its auxiliary facilities are arranged outside of the area where radioactive materials are handled. There the inactive grout is prepared and transferred by pump into the hot/warm cell where the drums or boxes are waiting to be grouted. The High Shear Mixer can also be used for homogeneous cementation of radioactive waste.

High Throughput Continuous Mixer

The continuously operating screw mixer (Figure 9) provides a high throughput. One or more dry components are continuously fed to the mixer where liquid waste or water is added. After a relatively short residence time in the mixing zone, the mixture is poured in drums or other containers for final disposal. Throughput: 3 m/h Space envelope required: 3 x 3.6 x 1.5 m

Fig. 9

High Throughput Continuous Mixer

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References
Scope of supply Client Putting in operation in 2006

Planning and delivery of 2 liquid radioactive waste solidification systems (1000 litre drums) In-drum cementation facility (200 litre drums) In-drum cementation facility (200 litre drums) Cementation plant with slant mixer for Waste Treatment Centre Cementation plant with slant mixer for Waste Treatment Centre In-drum cementation Facility (200 litre drums) In-drum cementation facility (200 litre drums)

Jiangsu Nuclear Power Corporation, PR China NAVY, PR China CIAE, PR China Sarubeshatomenergostroi, Russia (Atomenergoexport) / Balakovo NPP SE a. s./ Bohunice NPP, Slovakia Nuclear Power Institute of China, PR China Qin Shan NPP, PR China

2 3 4

2003 2002 2002

1999

6 7 8

1999 1998 1996

Design of cementation plant with Chmelnitzki NPP, Ukraine slant mixer for Waste Treatment Centre at Chmelnitzki NPP Upgrade of the existing mobile waste cementation plant Paks NPP, Hungary Kola NPP, Russia

1996 1994

10 Design of cementation plant as part of the treatment facility for liquid radioactive waste and resins 11 Upgrade of the existing mobile waste cementation plant 12 Basic engineering of a cementation plant for radioactive waste and resins in the frame of the TACIS-91/93 program, project 1.6 Radioactive Waste Treatment 13 Mobile waste cementation plant (MOWA) for Paks NPP
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Nucleco, Italy Novovoronezh NPP, Russia

1994 1993

NIKEX, Hungary

1991

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14 Stationary cementation plant 15 Mobile waste cementation plant (MOWA) 16 Mobile waste cementation plant (MOWA) 17 Stationary cementation plant 18 Mobile cementation unit MOWA 19 Mobile waste cementation plant (MOWA) 20 Mobile waste cementation plant (DEWA)

Uranium enrichment plant Gronau, Germany Nucleco, Italy Studsvik, Sweden Fairy Engineering, UK KFA, Germany Transnuklear, Germany Transnuklear, Germany

1986 1985 1985 1984 1980 1978 1977

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NUKEM Technologies GmbH Industriestr. 13 63755 Alzenau Germany T +49 (0) 6023 9104 F +49 (0) 6023 911188 E info@nukem.de

www.nukemgroup.com