DE2363475A1 - PROCEDURE FOR PREPARING RADIOACTIVE OR TOXIC MATERIALS CONTAINING MAJOR SOLID WASTE MATERIALS FOR ENVIRONMENTALLY FRIENDLY AND SAFE HANDLING, TRANSPORTATION AND FINAL STORAGE - Google Patents

Description

Society for Nuclear Research 2363475

Bayer Aktiengesellschaft

B / Hor

Procedure for preparing radioactive or toxic Substances containing essentially solid waste materials for environmentally friendly and safe handling, transport and final storage.

The invention relates to: a method for preparing radioactive or containing toxic substances, in substantial solid waste materials for environmentally friendly and safe Handling, transport and final storage, ■ whereby the solids are brought into contact with hardening materials solid masses are allowed to solidify.

It is already known that in technology, and here particularly in nuclear technology, waste materials are produced which are highly toxic or are radioactively contaminated and which - if they are to be stored or transported, require treatment, which prevents them from entering the biocycle.

It is known, such solid waste materials as e.g. B. felling sludge, to store exhausted ion exchangers, ashes and combustion residues, metal shavings, etc. in containers (management of low and intermediate level radioactive was-tes; Proceedings of a Symposium Aix-en-Provence, 7.-11. Sept 1970; IAEA, Vienna, 1970) or to mix with cement paste and put them in To store cement enclosed. Storage in containers has been linked to corrosion of the containers proved problematic. Disadvantages of entrapment

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in the cement are the associated large volumes of waste, the poor setting ability in relation to the waste materials to be enclosed and poor leaching behavior of the im Cement trapped waste.

The invention is based on the object of creating a method that has the disadvantages of the practices listed so far avoids, and with which radioactive or toxic solid waste or containing radioactive or toxic substances, solid waste materials can be irreversibly solidified into blocks or the like., which have a relatively high leaching and have washout resistance. The solid waste should both in the dry state and mixed with water, aqueous solutions or organic liquids or organic liquids Solutions can be solidified equally well. The method should be easy on devices and Costs carried out by semi-skilled workers only in a short time can be. It is said to lead to environmentally friendly solidification products that are safe to use and have a ensure safe transport to a repository.

The object is achieved according to the invention in that the waste materials with polymerizable, essentially made of monovinyl and polyvinyl compounds and polymerization catalysts are blended and polymerized be converted into solid blocks.

The following can be used as Monoviny! Connections:

Styrene, methyl styrene, acrylic acid, methacrylic acid, acrylonitrile, Acrylic acid esters, methacrylic acid esters, vinyl anisole, vinyl naphthalene, Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, Butyl acrylate, tert-butyl acrylate, ethylhexyl acrylate, Cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate,

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Phenyl, lphenylacrylate ALK3 ^r, Älhoxymethylacrylat, Äthoxyäthylacrylat, Äthoxypropylacrylat, Propoxymethylacrylat, Propoxyäthylacrylat, Propoxypropylacrylat, Äthoxyphenylacrylat, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, tert-butyl methacrylate, X thylhexylmethacrylat, cyclohexyl methacrylate, isobornyl methacrylate, benzyl methacrylate, phenyl methacrylate, Alkylphenylmethacrylat, Äthoxymethacrylat, Äthoxyäthylmethacrylat, Äthoxypropylmethacrylat, Propoxymethyl methacrylate, propoxyethyl methacrylate, propoxypropyl methacrylate, ethoxyphenyl methacrylate, ethoxybenzyl methacrylate, vinyl toluene, vinyl chloride, vinyl acetate and vinylidene chloride. Polyethylenically unsaturated monomers such as isoprene, butadiene and chloroprene are also suitable.

Heterocyclic monoviny compounds are also suitable such as vinylpyridine, 2-methyl-5-vinylpyridine, 2-ethyl-5-vinylpyridine, 3-methyl-5-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, 2-methyl-3-ethyl-5-vinylpyridine, 2-methyl-5-vinylquinoline, 4-methyl-4-vinylquinoline, 1-methyl- or 3-methyl-5-vinylisoquinoline and vinyl pyrrolidone.

Styrene, vinyl toluene, and methyl acrylate are particularly preferred.

The following are possible as polyvinyl compounds:

Divinylbenzene, divinylpyridine, divinyltoluenes, divinylnaphthalenes, Diallyl phthalate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, Diviny! Xylene, divinylethylbenzene, divinyl sulfone, Polyvinyl or polyallyl ethers of glycol, glycerine and pentaerythritol, Divinyl ketone, divinyl sulfide, allyl acrylate, diallyl maleate, Diallyl fumarate, diallyl succinate, diallyl carbonate, diallyl malonate, Diallyl oxalate, diallyl adipate, diallyl sebacate, divinyl sebacate, diallyl tartrate, diallyl silicate, triallyl tricarballylate, Triallylaconitate, triallyl citrate, triallyl

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phosphonate, Ν, Ν'-methylenediacrylamide, Ν, Ν'-methylenedimethacrylamide, Ν, Ν'-ethylene diacrylamide, l, 2-di (tiC-methylmethylene sulfonamido) -ethylene, Trivinylbenzene, Triviny! Naphthalene and Polyvinyl anthracenes.

Divinylbenzene and trivinylbenzene are particularly preferred.

All waste materials are suitable for inclusion in the polymers, advantageously those waste materials which, by their physical and chemical properties pose a threat to the environment. After the method according to the invention come radioactively contaminated or toxic waste materials in question, the z. B. in nuclear technology through their use the processing or separation of radioactive substances or the cleaning of the equipment used is radioactively contaminated will.

Examples of radioactively contaminated waste are:

Activated carbon, such as B. from exhaust air filter systems, from post-cleaning from evaporator condensates or the like, ashes, such as. B. from incinerators for combustible radioactive Waste,

Metal chips, such as B. from the fuel assembly production and the mechanical processing of contaminated devices and systems, felled sludge, such as B. from chemical treatment of radioactive waste water.

Apparatus parts such. B. from the maintenance of contaminated systems and devices,

Precipitation, such as B. arising from the storage of radioactive waste solutions,
Deposits such as B. in storage tanks, pipelines,

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Pumps or the like arising for radioactive solutions, spent ion exchangers, such as. B. from the purification of radioactively contaminated water cycles in nuclear reactors and fuel element storage pools.

The following toxic waste materials should be mentioned: cadmium and arsenic compounds, Cyanides, compounds of chromium, mercury and its salts, tin and antimony compounds, thallium compounds, Solid waste with pesticides, insecticides, fungicides, food poisons and the like. It can do both dry waste materials as well as waste materials mixed with water or aqueous solutions and with organic liquids or organic solutions are solidified.

Dry waste materials are in a range between 2 wt .-% and 75 wt .-%, preferably between 30 wt -.% And 70 wt .-%, based on the mixture (waste materials and polymerization), the mono-vinyl compounds in a range between 60% and 99% by weight, preferably between 80% and 98% by weight, based on the polymerization mixture, of the polyvinyl compounds in a range between 0.5% and 30% by weight wt .-%, preferably between 1 wt -.% and 15 wt .-%, based on the polymerization mixture and the polymerization in a range between 0.1 wt .-% and 10 wt .-%, preferably between 0.5 % And 5% by weight, based on the polymerization mixture, are used.

Solid waste materials that contain water or aqueous solutions are treated with emulsifiers and / or swellable or ' absorbent Solids are added before they are added to the polymerization mixture (Monomer mixture) in the weight ratio range of solids Polymerization mixture between 2: 1 and 1: 1 are mixed.

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In this case, it is advantageous to use for better mixing of the monomer mixture with that contained in the solid Water emulsifiers too. Particularly suitable as such are:. .

Anion-active surfactants, especially alkyl sulfonates, alkyl and Arylbenzenesulfonate, and non-ionic surfactants, especially ethoxylated and propoxylated fatty alcohols, fatty acids and Fatty amines.

For the process according to the invention, swellable or absorbent solids' in question, which are soaked with radioactively contaminated or toxic liquids.

Carriers are to be used as swellable or absorbent solids which can absorb liquids due to their physical structure. The swellable solids are organic Adsorbents, mainly macroporous cross-linked copolymers, as described e.g. in DT-AS 1.274.128 and especially ion exchangers. As absorbent Substances are also inorganic gels, such as. B. kieselgei, silica gel, alumina gel or kieselguhr, zeolites and in particular Vermiculite used.

Solid waste materials mixed with organic liquids or organic solutions are mixed with sorbents before they are mixed with the polymerization mixture in the weight ratio range of solids to monomer mixture between 2: 1 and 1: 1. Vermiculite or macroporous styrene-divinylbenzene copolymers are used as sorbents used. As radioactively contaminated liquids come z. B. in question:

1.) Radioactive aqueous solutions and sludges, such as. B. evaporator concentrates from the evaporation of radioactive waste

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solutions, felled sludge from chemical precipitation treatment of radioactive waste solutions, precipitation and debris from the storage of radioactive liquids and the like.

2.) Waste alkalis, such as those used in the processing of fuel element residues incurred, such as B. highly concentrated neutral nitrate solutions.

3.) Radioactively contaminated extraction agents, such as those used in e.g. B. incurred in the processing of radioactive residues by liquid-liquid extraction, such. B. tributyl phosphate and acidic di-ethylhexyl phosphoric acid esters.

4.) Organic auxiliary liquids used in nuclear facilities such as B. machine oils, pump oils, vacuum oils, fats, waxes and soaps.

As toxic liquids come z. B. in question: Solutions of cadmium and arsenic compounds, cyanide solutions, chromate solutions, mercury and its salt solutions, solutions of tin, antimony and thallium compounds, solutions in which * pesticides, insecticides, fungicides and food poisons are contained.

The process according to the invention is generally carried out so that the solid is added in portions, preferably without stirring, at room temperature to a reaction mixture of the monovinyl compound and the polyvinyl compound gives.

The ratio of monomer mixture to solids can be between 50: 1 and 1: 3, expediently between 2: 1 and 1! ^, Vary. When using moist solids, it is advantageous to to slightly increase the monomer content, so that the ratio

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Mixture of monomers to solid between 1: 1 and 1: 2 to be added is.

The polymerization is carried out in a manner known per se with the aid of polymerization catalysts. The used Polymerization catalysts are also known; for example acetyl peroxide, benzoyl peroxide, tert-Buty! hydroperoxide, cumene peroxide, lauroyl peroxide, azodiisobutyric acid dinitrile, methyl ethyl ketone peroxide, tetralin peroxide and persulfates. The use of catalysts with a low light-off temperature is preferably recommended, see above z. B. Azodiisobutyric acid dinitrile. When using azodiisobutyric acid dinitrile one works with an amount of catalyst between 0.1 and 10 wt .-%, preferably between 0.5 and 5% by weight. After the heat tint has subsided, the material is cured and the radioactively contaminated or toxic solid enclosed by the polymer. The ones to be polymerized Mixtures generally solidify to a solid block after 2 to 20 days and can then advantageously remain in the polymerization vessel.

When including aqueous swollen solids, e.g. B. of vermiculite or dried ion exchangers, see it Proven to be advantageous, small amounts of the corresponding dry swellable solid to bind the condensation s to add, which is caused by the rise in temperature during the polymerization process.

Because the inclusion of radioactively contaminated and toxic solids is advantageously carried out without further mixing in the containers in which the final storage takes place, is a high level of operational reliability due to the low expenditure on equipment given. The inventive method can be used for all solids, which even have a high liquid content have to apply.

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example 1

In a 200 liter container, immerse in a solution of at 25 ° C

21.55 "kg of styrene, ■ .- ■

0.75 kg divinylbenzene (60% by weight) and 0.7 kg of azodiisobutyric acid nitrile

60 kg of a radioactively contaminated boiler ash is obtained from a "combustion system for combustible radioactive waste introduced in portions. At 45 ⁰ C, the mixture solidified after 2 days and is cured after 5 days.

Example 2 In a B «a solution of

A 200-liter container is placed at 20 C in

56.2 kg of styrene, ■ 2.0 kg of divinylbenzene (60% by weight) and ' 1.8 kg of azodiisobutyronitrile

50 kg of a moist, radioactively contaminated mixed-bed exchanger which is composed in the equivalent ratio of an anion exchanger based on a polyvinyl trimethylammonium hydroxide crosslinked with 4% divinylbenzene and a cation exchanger based on a polystyrene sulfonic acid crosslinked with 8% divinylbenzene. At 35 ° C the mixture solidifies after 2 days and is hardened after 6 days.

Example 3 In a B (solution of

In a container with a capacity of 200 liters at 22 ⁰ C in a

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93.7 kg of styrene,.

3.3 kg divinylbenzene (60% by weight) and 3.0 kg of azodiisobutyric acid nitrile

80 kg of a moist, radioactively contaminated, strongly basic anion exchanger based on a polyvinylbenzyltrimethylammonium hydroxide crosslinked with 4% divinylbenzene. At 30 ^° C., the mixture solidifies after 3 days and is hardened after 6 days.

Example 4
In a
each other

In a container with a capacity of 200 liters at 25 ° C -after-

58 kg styrene,

2 kg divinylbenzene (60 %),

3 kg of azodiisobutyric acid dinitrile and

6 kg of an oleyl alcohol reacted with 18 mol of ethylene oxide

given. A homogeneous solution is produced by stirring by hand. 100 kg of a radioactively contaminated strongly acidic cation exchanger of the type of a polystyrene sulfonic acid crosslinked with 8% divinylbenzene are introduced into this solution. At 50 ^° C., the mixture solidifies after 4 days and is hardened after 14 days.

Example 5

A. Swelling of a radioactively contaminated solution into a dried one Ion exchanger

In a 200 liter container

120 kg of a radioactively contaminated approx. 30 wt. Follow. Sodium nitrate solution presented and to it

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45 kg of a dried, with 2 % divinylbenzene

cross-linked strongly acidic cation exchanger
given on the basis of polystyrene sulfonic acid.

The resin is allowed to swell in a solution for 8 hours, which sucks The swollen resin is removed and the moist product is used for block polymerization.

B. bulk polymerization

In a container of 200 liters content are at 20 ⁰ C one after the other

58 kg styrene,

2 kg Diviny! Benzene (60% by weight),

3 kg of azodiisobutyric acid dinitrile and

6 kg of one reacted with 18 moles of ethylene oxide
Given oleyl alcohol.

A homogeneous solution is produced by stirring by hand. Be in this solution

135 kg of the sodium nitrate substance produced under A

term resin and

9 kg of a dried, strongly acidic cation exchanger based on polystyrene sulfonic acid, crosslinked with 2% divinylbenzene

using a metering device, entered in portions. At 45 ° C the mixture solidifies after 3 days and is
hardened after approx. 4 weeks.

Example 6

A. Soaking a radioactively contaminated solution in vermiculite

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In a 200-liter vessel are kept at 24 ° C

50 kg of a radioactively contaminated 30%

Submitted sodium nitrate solution and added 9 kg of vermiculite.

It is left to soak for at least an hour, and what is swollen is sucked off Material and uses the moist product for polymerization.

B-. Bulk polymerization
In a BehJ
after another

In a container with a capacity of 200 liters, the temperature is ^{20 ° C}

53 kg of styrene

2 kg divinylbenzene (60% strength by weight) 0.3 kg azodiisobutyronitrile

given. A homogeneous solution is produced by stirring by hand. 39 kg of the product obtained under A are added in portions to this solution at the same time as 2 kg of vermiculite, if necessary using a metering device. At 60 ° C the mixture solidifies after 4 days and is hardened after approx. 4 weeks. After several days, the heat of reaction causes a temporary temperature increase of 30 to 40 ^° C.

Example 7

Put in a 200 liter container at 20 ° C

30 kg of a radioactively contaminated pump oil are intimately mixed with 50 kg of a pearl-shaped polystyrene crosslinked with 18 % divinylbenzene and made porous with 65% isododecane (based on the monomer mixture).

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The mixture is left to swell for an hour and is added at 22 ° C Solution of

140.5 kg styrene,

5.0 kg Diviny! Benzene (60% by weight) and 4.5 kg of azodiisobutyric acid dinitrile.

At 35 ^° C., the mixture solidifies after 2 days and is hardened after 12 days.

Example 8

In a container with a capacity of 200 liters, the temperature is ^{20 ° C}

.37.5 kg of radioactively contaminated pump oil with 25.0 kg of vermiculite

Mix well for 10 minutes. Then you give one at 24 ° C Solution of

107.7 kg styrene,

3.8 kg div.inylbenzene (60 wt .- ^ - ig) and 3.5 kg of azodiisobutyric acid dinitrile.

At 35 ° C the mixture solidifies after 3 days and is after 8 days hardened.

Example 9

Put in a 200 liter container at 25 ° C

50 kg of a 10% by volume radioactively contaminated Tributyl phosphate solution in isodecane with

50 kg of a pearl-shaped crosslinked with 18% diviny! Benzene and 65 % isododecane (calculated on the monomer mixture)

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made porous polystyrene

good (mixed. The mixture is allowed one hour long and sources are at 25 ⁰ C, a solution of

93.7 kg styrene,

3.3 kg Diviny! Benzene (60% by weight) and 3.0 kg of azodiisobutyric acid dinitrile.

At 40 ^° C., the mixture has solidified after 3 days and hardened after 12 days.

Example 10
In one case
a solution of

In a container of 200 liters are at 25 ⁰ C in

43.0 kg styrene,
1.5 kg divinylbenzene (60% by weight),

1.4 kg of azodiisobutyric acid dinitrile and 120.0 kg of one before the polymerization reaction

crushed, radioactively contaminated broken glass entered.

At 40 C the mixture solidifies to a solid after 2 days Block. When leached with distilled water, no radioactivity was found after 14 days.

Example 11

In a 200 liter container, in a solution of

43.0 kg styrene,

1.5 kg Diviny lbenzene (60 wt .-? 6 ig) and 1.4 kg of azodiisobutyric acid dinitrile

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100.0 kg of caleium orthoarsenate (Ca ^ (As ₁₅ O /) ,,) entered. At 35 C the mixture solidifies after 3 days and is hardened after days *

Example 12 In a case a solution of

In a container of 200 liters are grown at 20 ⁰ C in

43.0 kg styrene,

1.5 kg Diviny! Benzene (60 wt .- ^ - Ig) and. 1.4 kg of azodiisobutyric acid dinitrile

100.0 kg cadmium sulfate (CdSO ^) entered. Solidified at 35 ° C the mixture after 4 days and becomes a solid after 8 days Block hardened.

Example 13 In a case a solution of

In a 200 liter container, in

43.Ό kg styrene,

1.5 kg divinylbenzene (60% strength by weight), 1.4 kg azodiisobutyric acid dinitrile and 100.0 kg of a radioactively contaminated silica gel (grain size from 0.1 to 0.3 mm),

that accrues with the kerosene cleaning, registered and good mixed. At 40 ° C the mixture has solidified after 2 days and hardened to a solid block after 8 days.

Example 14

In a 200 liter container, in a solution of

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120 kg styrene,

4 kg divinylbenzene,
4 kg azodixsobutyric acid dinitrile, 12 kg sodium salt of dodecylbenzenesulfonic acid

and

100 kg of diatomaceous earth with 15% by weight radioactively contaminated Water

given and mixed well. At 30 ^° C., the mixture solidifies after 4 days and is hardened after 8 days.

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Claims (13)

Claims ι IJ "Vorfalircn to prepare radioactive or toxic Substances containing essentially testing waste materials for environmentally friendly and safe handling, transportation and final disposal, the solids with hardening materials brought into contact .and solidified to solid masses, characterized in that the waste materials with polymerizable, consisting essentially of monovinyl and polyvinyl compounds and polymerization catalysts Mixtures mixed and solidified by polymerization Blocks are transferred. 2. The method according to claim 1, characterized in that one Styrene or methyl acrylate as monoviny compounds and diviny / benzene or triviny / benzene as polyvinyl compounds begins. 3. The method according to claim 1 and 2, characterized in that solid waste, such as that generated in nuclear engineering, is included. 4. The method according to claim 1 and 2, characterized in that one includes toxic waste materials. 5. The method according to claim 1, characterized in that dry waste materials in a range between 2 wt .-% and 75% by weight based on the batch (waste materials and polymerization mixture) who have favourited Monoviny! compounds in one area between 60% by weight and 99% by weight, based on the polymerization mixture, the polyvinyl compounds in a range between 0.5% by weight and 30% by weight, based on the polymerization mixture, and the polymerization catalysts in a range Le A 15 272 - 17 - PLA 73/37 5098 2 6/0500 between 0.1% by weight and 10% by weight, based on the polymerization mixture, can be used. 6. The method according to claim 5, characterized in that dry waste materials in a range between 30 wt .-% and 70 wt .-%, based on the mixture, the monovinyl compounds in a range between 80 wt .-% and 98 wt .-%, based on the polymerization mixture, the polyviny compounds in a range between 1 wt .-% and 15 wt .-%, based on the polymerization mixture and the polymerization in a range between 0.5 wt -.%, and 5% by weight, based on the polymerization mixture, can be used. 7. The method according to claim 1, characterized in that solid waste materials which contain water or aqueous solutions, with emulsifiers and / or swellable or absorbent solids added before they with the polymerization mixture (monomer mixture) in the weight ratio range solids be mixed to a polymerisation mixture between 2: 1 and 1: 1. 8. The method according to claim 7, characterized in that the emulsifiers used are anionic or nonionic surfactants will. 9. The method according to claim 8, characterized in that as anion-active surfactants alkyl sulfonates, alkyl or arylbenzene sulfonates and ethoxylated or propoxylated fatty alcohols, fatty acids or fatty amines are used as nonionic surfactants will. 10. The method according to claim 7, characterized in that as Absorbent substances, dried ion exchangers, inorganic gels, diatomite or vermiculite can be used. Le A 15 272 - 18 - PLA 73/37 509826/0500 11. The method according to claim 1, characterized in that silica gel or alumina gel can be used as inorganic gels. 12. ■ The method according to claim 1, characterized in that solid waste mixed with organic liquids or organic solutions with sorbents before they are mixed with the polymerization mixture in the weight ratio range of solids between 2: 1 and 1: 1 are added to the polymerization mixture. 13. The method according to claim 12, characterized in that as sorbents, vermiculite or macroporous styrene-divinylbenzene copolymers be used. Le A 15 272 - 19 - PLA 73/37 509826/0500