DE2363475B2 - PROCESS FOR RECYCLING SOLID WASTE CONTAINING RADIOACTIVE OR TOXIC SUBSTANCES - Google Patents

Description

The invention relates to a method for processing of solid waste containing radioactive or toxic substances for safe handling. Transport and disposal, for the: dt: .s: fall with a polymerizable mixture \ v; i ;; u:.; and through polymerization into a solid block.: ■ listed will.

In the Tedi.iik, especially in the Kerm ^ hi; ^ there are waste ships that are highly toxic or r; inter alia: ■. are heavily contaminated and if they fail .-. ,, r should be transposed, a treatment i>. J. · fen that prevents them from entering the biocycle 1. ,, ·., ·. -

It is known to eject such solid waste as /.ti. Felling sludge, exhausted ion exchangers, .When and combustion residues, metal shavings, etc., to be stored in containers or with cement slurry / u urtic tables and enclosed in cement / ti. From the German Disclosure Document 22 12 57-. ui further provides a process / ui conditioning radio.i-SIiver waste known gernäß which one the Abiälic m the form of dry powder, in an interfering polymcnsierbares at Raumtempuaiur resin and this Ii _1;. / with a monomer such. B. styrene, / u an iesun block polymerized. The German Offenleguiiusschrift 17 69 911 describes a process for concentrating aqueous solutions and suspensions of radioactive waste, according to which these are solidified in thickened form with polymeric alcohols to form a rubber-like homogeneous body. From the German Offenlegungssdinft 22 63 676 it is known to convert aqueous solutions into radiation-absorbing solutions by adding vinyl monomers and catalysts and then polymerizing them. to transfer no longer flowable gels.

However, these known methods have serious disadvantages. So the storage in Containers because of the appearance of corrosion Containers proved problematic. The N'aditeiie of inclusion in cement are the associated large volumes of waste, the poor setting \ enable the waste to be included and poor ^ leaching behavior of the im Cement trapped waste ^. According to the German Offenlegiingsschriften 22 12 574 and 17 (19 91t described processes use polymers obtained, in which the leaching behavior of the radioactive waste dumps polymi'fe so What is bad is that a safe landfill of the polymers is not guaranteed. Furthermore, the thermal stability of the polymers inadequate for safe handling and storage. The same There are also disadvantages when using the

in German Offenlegungsschrift 22 63 676 described Polymers to contain radioactive substances to be expected.

The invention is therefore based on the object

luene, vinyl chloride, vinyl acetate and vinylidene chloride.
Polyethylenically unsaturated ones are also suitable
Monomers such as isoprene, butadiene, and chloroprene.
Furthermore, there are heterocyclic monovinyl compounds

_e in process for processing radioactive or 5 bonds in question such as vinylpyridine, 2-methyl-'S-

to create solid waste containing toxic substances, which avoids the disadvantages of the known processes, and with the help of which radioactive or toxic solid waste, or radioactive or toxic

vinylpyridine, 2-ethyl-5-vinylpyridine, 3-methyl-5-vinylpyridine, 2,3-dimethy! -5-vinylpyridine, 2-methyl-3-ethyl-5-vinylpyridine, 2-methyl-5-vinyiquinoline, 4 -Methyl-4-vinylquinoline, 1-methyl- or 3-methyl-5-vi-substances containing solid waste materials irreversible to io nylisoquinoline and vinylpyrrolidone.
Block can be solidified, which behaves particularly preferably styrene, vinyl toluene,

To the right, moderately high leaching and washing-out Besländig acrylic acid methyl ester.

exhibit ability. The solid waste materials should be used as polyvinyl compounds:

in a dry state, as well as in a mixture with was- divinylbenzene, divinylpyridine, divinyltoluene, di-

$ er, aqueous solutions or organic liquids 15 vinylnaphthalenes, diallylphti.alat, ethylene glycolites or organic solutions can be solidified equally well acrylate, ethylene glycol dimethacrylate, divinylxylene. The process should only pass through semi-skilled workers in a short time without divinyl ethylbenzene, divinyl sulfone, polyvinyl or large expenditure on devices and costs of polyallyl ally of glycol, glycerine and pentaery, divinyl ketone, divinyl sulfide, allyl acetate. Can be diguided. It is said to solidify pro-allyl maleate. Diallyl fumarate. Diallyl succinate, dialducts that are safe to handle and ei- carbonate, diallyl malonate, diallyl oxalate. Diallyl-γκίι safe transport to a final storage facility ge adipat, Diallylsebacau divinylsebacat, DialKI-guarantee. tartrate, dialylsilicate, triallyl tricarballylate Λ ri-

According to the invention, this object is achieved by using gellylaconitate, triallylcitral. Triallylphosplionate. N.V-Ii) St, that the mixture of Monovinyl- and Polyvin) 1- 25 Meth \ lendiacr \ lamid, N, N'-Methylendinielhacnlverhindungen and polymerization catalysts amide, Ν, Ν'-ethylenediacrylaniid, l, 2-di («- methylmetest. ethylene sulfonamido) ethylene, trivinylbenzene, trivinyl

Those with the aid of the naphthalene and polyvinyl anthracenes to be used according to the invention.
The mixtures of mono- and polyvinyl compounds are particularly preferred divinylbenzene and

produced poly-trivinylbenzene containing solid waste.

Merisates are distinguished from those according to the. For inclusion in the polymers, all are suitable

known processes available, waste material containing waste materials, in particular those waste materials that tending polymers due to their physical and chemical properties Resistance to leaching and washing out and a risk to the environment. That significantly improved thermal resistance 35 method according to the invention is suitable for Veraus. More radioactively contaminated or toxic than in the German disclosure consolidation Scripture 22 12 574 described procedure 'uieten the waste materials, as they are z. B. in nuclear technology at the Use according to the invention of the mixtures from the preparation or separation of radioactive substances Mono- and polyvinyl compounds also soften or clean the equipment used term advantage that both solid waste in dry 40 arise.

nem state, as well as water, aqueous solutions, as radioactively contaminated waste ^ are

Organic liquids or organic solutions named for example:

Containing solid waste is equally effective. Activated charcoal. z. B. from Abluflfilteranlagcn, from the

to be consolidated. In addition, the inven- post-cleaning of evaporator condensals or the like. appropriately to be used mixtures of mono- 45 ash, z. B. from incinerators for combustible radioactive waste,

Metal chips, e.g. B. from the fuel assembly production and the mechanical processing of contaminated Devices and systems, precipitation sludge, such as 50 z. B. from the chemical treatment of radioactive Sewage,

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

Precipitation such as B. in the storage of

tert-butyl acrylate, ethylhexyl acrylate, cyclohexyl acrylate 55 radioactive waste solutions are formed,
lat, isobornyl acrylate, benzyl acrylate, phenyl acrylate, deposits such as those found, for. B. in storage containers,

Alkylphenyl acrylate, ethoxymethyl acrylate, ethoxy pipelines or pumps for radioactive solution ethyl acrylate, ethoxypropyl acrylate, propoxymethyl gen, used ion exchangers, e.g. B. acrylate, propoxyethyl acrylate, propoxypropyl acrylate, from the purification of radioactively contaminated ethoxyphenyl acrylate, propyl ^{methacrylate, isopropyl water circuits} in nuclear reactors and fuel element methacrylate, butyl methacrylate, tert-butyl methacrylate storage basins.
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and polyvinyl compounds compared to the other polymerization processes due to a shorter polymerization time at room temperature.

Possible monovinyl compounds in the process according to the invention are:

Styrene, methyl styrene, acrylic acid, methacrylic acid, acrylonitrile, acrylic acid ester, methacrylic acid ester, vinyl anisole, Vinyl naphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, bulyl acrylate,

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lat, ethylhexyl methacrylate, cyclohexylmeihacrylate, isobornyl methacrylate, benzyl methacrylate, phenyl methacrylate, Alkylphenyl methacrylate, ethoxymethyl methacrylate, ethoxyethyl methacrylate, ethoxypropyl methacrylate, Propoxymethyl methacrylate, propoxyethyl methacrylate, propoxypropyl methacrylate, ethoxyphenyl methacrylate, Ethoxybenzyl methacrylate, vinylto-

The following toxic waste materials should be mentioned: Cadmiuni- and arsenic compounds, cyanides. Connections of chromium, mercury and its salts, tin and antimony compounds, thallium compounds, Solid waste with pesticides, insecticides. Fungicides, food poisons and the like dry waste materials as well as waste materials in the

mix with water or aqueous solutions as well as with organic liquids or organic solutions are solidified.

Dry waste materials are in a range between 2 and 75 percent by weight, preferably «Between 30 and 70 percent by weight, based on the mixture (waste materials and polymerisation mixture), the monovinyl compounds in a range between 60 and 99 percent by weight, preferably between 80 and 98 percent by weight, based on the polymerisation mixture, of the polyvinyl compounds in a range between 0.5 and 30 percent by weight, preferably between 1 and 15 Percentage by weight, based on the polymerization mixture, and the polymerization catalysts in one in the range between 0.1 and 10 percent by weight, preferably between 0.5 and 5 percent by weight, based on the polymerization mixture used.

Solid waste materials that contain water or aqueous solutions are emulsified with and / or swellable or absorbent solids are added before they are mixed with the polymerization mixture (monomer mixture) in the weight ratio range of solids to polymerization mixture between 2: 1 and 1: 1 be mixed up.

In this case, it is advantageous to for better mixing of the monomer with the contained in ■ Δετή solid water emulsifiers to. Particularly suitable as such are:

Anionic surfactants, especially alkyl sulfonates, alkyl and aryl benzene sulfonates, and non-ionic ones Surfactants, especially ethoxylated and propoxylated Fatty alcohols, fatty acids and fatty amines.

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

As swellable or absorbent solids, carrier substances are to be mentioned, which due to their physical Structure can absorb liquids. Organic adsorbents, mainly macroporous crosslinked copolymers, and in particular ion exchangers. Inorganic GeIo, such as, for. B, silica gel, silica gel, clay gel or kieselguhr, zeolites and especially vermiculite are used.

Solid waste materials mixed with organic liquids or organic solutions are present the mixing with the polymerization mixture with sorbents in the weight ratio range of solid content added to monomer mixture between 2: 1 and 1: 1. Vermiculite or macroporous are used as sorbents Styrene-divinylbenzene copolymers are used.

The process according to the invention is generally carried out in such a way that the solid is removed in portions, preferably without stirring, at room temperature to form a reaction mixture from the monovinyl compound and the polyvinyl compound gives.

The ratio of monomer mixture to solids can vary between 50: 1 and 1: 3, expediently between 2: 1 and 1: 2. In the use of moist solids, it is advantageous to slightly increase the partial Monomerenan- ⁶ S, so that the ratio of monomer mixture to solids between 1: is set to 2: 1 and the first

The polymerization is carried out in a manner known per se with the aid of polymerization catalysts before. The polymerization catalysts used are also known; for example: Acetyl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, Cumene peroxide, lauroyl peroxide, azodiisobutyric acid dinitrile, Methyl ethyl ketone peroxide, tetraun peroxide and persulfates. Preferably recommended the use of catalysts with a low light-off temperature, e.g. B. Azodiisobutyric acid dinitrile. When using azodiisobutyric acid dinitrile, one works with an amount of catalyst between 0.1 and 10 percent by weight, preferably between 0.5 and 5 percent by weight. To The material is the fading of the heat tint! cured and the radioactively contaminated or toxic solids enclosed by the polymer. The mixtures to be polymerized solidify in the generally after 2 to 20 days to a solid block and can then advantageously in the polymerization vessel remain.

With the inclusion of aqueous swollen solids. z. B. of vermiculite or dried ion exchangers, It has proven advantageous to use small amounts of the corresponding dry swellable Add solid to bind the condensation water caused by the temperature rise during the Polymerization process arises.

Since the inclusion of radioactively contaminated and toxic solids is advantageous without further Mixing is carried out in the containers in which the final disposal takes place, is due to the low A high level of operational reliability is given in terms of equipment expense. The method according to the invention can be used for all solids, which can even have a high liquid content.

example 1

In a container of 200 l, Ki 25 ^c C are in a solution of

21.55 kg styrene,
0.75 kg divinylbenzene

(60 percent by weight) and
0.70 kg of azodiisobutyric acid nitrile.

60 kg of a radioactively contaminated vessel. which one from an incinerator for combustible radioactive waste received, entered in portions. At 45 ° C the mixture solidifies after 2 days and hardened after 5 days.

Example 2

In a container from 2001 the contents are added 20 'C in a solution of

56.2 kg styrene,
2.0 kg divinylbenzene

(60 percent by weight) and
1.8 kg of azodiisobutyric acid nitrile

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

8 J »

using a dosing device, portion-

Example 3 entered wisely. The mixture solidifies at 45 ° C In a container with a capacity of 200 liters, after 3 days and after approx. 4 weeks, the

12 ° C in a solution of tet.

93.7 kg styrene, ⁵ bis ρ ie 1 6

3.3 kg divinylbenzene _A ) Swelling of a radioactively contaminated

(60 per cent by weight) and solution in vermiculite
3.0 kg of azodiisobutyric acid nitrile

In a jar with a capacity of 200 liters at 24 ° C

80 kg of a damp, radioactively contaminated heavily io .... .

basic anion exchanger based on a radioactively contaminated 30 kg with 50 kg

40/0 divinylbenzene cross-linked polyvinylbenzyl trim- weight percent sodium nitrate solution

thylammonium hydroxide entered. Presented at 30 ° C and added

the mixture stiffens after 3 days and is given after 6 days ⁹ kS vermiculite,

cured genes. 15 Let it swell for at least 1 hour, suck it up

Example 4 swollen material and sets the moist product

,. for polymerization.
In a container from 2001 the contents are added

25 ° C in succession B) Block polymerization

58 kg of styrene, "In a container from 2001, the contents are at

2 kg divinylbenzene (00 percent by weight), 20 ° C in succession

3 kg azodiisobutyric acid dinitrile and 53g _k g styrene,

6 of a 18 kg moles of ethylene oxide umgesetz- _2, 0 kg divinylbenzene

ten oleyl alcohol _a5 '(OO weight percent) and

given. By stirring by hand, a ho- °> ^{3 k} S azodiisobutyric acid nitrile

homogeneous solution produced. In this solution are given. Stirring by hand creates a

A water-swollen, radioactive con- _m Ogene solution 100 kg produced. Be in this solution

-contaminated strongly acidic cation exchanger from the 39 _{kg of the under g A)} e _Wonnenen product simultaneously

Type of a polystyrene crosslinked with 8% divinylbenzene _{with 2 kg} vermiculite, possibly using

rolsulfonic acid entered. At 50 C, the manure from a dosing device solidifies and is added in portions.

Mixture after 4 days and is _{exhausted after 14 days At 6Q} o _{c the} mixture solidifies after 4 days

hardened. _{and 5} ^ _{hardened after about} 4 weeks. By Re-

Example 5 action heat occurs after several days

³⁵ transient temperature increase by 30 to 40 ° C

A) Swelling of a radioactively contaminated _em

Solution in dried ion exchanger

In a container with a capacity of 200 l

,. . . In a container from 2001 the contents are added

120 kg of a radioactively contaminated about 40 20 ° C

30 weight percent sodium nitrate solution and add 30 kg of a radioactively contaminated pump

45 kg of a dried, with 2% divinylben- ° ^ ^s ™ ^l

zol cross-linked strongly acidic ^{cations- 50 k semes pearl-} shaped with 18% divinylben-

Exchanger based on Polysty- 45 ^zo1 cross-linked and with 65% isododecane

given rolsulfonic acid. (calculated on the monomer mixture)

made porous polystyrene intimately

The resin is allowed to swell in a solution for 8 hours, mixed,
sucks off the swollen resin and sets the moist

Product for block polymerization. . The mixture is left to quench for 1 hour and is added at 22 ° C

⁵⁰ erne solution of

B) Bulk polymerization k 140.5 _{g of} styrene, A 2001 container contains 5.0 kg of divinylbenzene

20 ° C in succession (60 percent by weight) and

58 kg styrene, 55 ⁴ > ⁵ * Ι azodiisobutyric acid dinitrile.

2 kg divinylbenzene (OO weight percent), At 35 ° C the mixture solidifies after 2 days and

3 kg azodiisobutyric acid dinitrile and is hardened after 12 days

6kg of one reacted with 18 moles of ethylene oxide- example 8

ten oleyl alcohol given. ^

60 In a container from 2001, the contents are at

By stirring by hand is a homogeneous 2O ⁰ C Solution made. In this solution, _ _. . .

^{ö ö} 37.5 kg radioactively contaminated pump oil

135 kg of the sodium nitrate produced under A) with

containing resin and 25.0 kg vermiculite

^9ks irjssr ^ J ^ Ä ⁶⁵

exchanger based on Polysty- ^{24 C eme} ^^ ^of rolsulfonic acid 107.7 kg of styrene,

9 ^u ίο

3.8 kg divinylbenzene 43.0 kg styrene,

(60 percent by weight) and 1.5 kg divinylbenzene

3.5 kg of azodisobutyric acid dinitrile. (ÖO weight percent) and

1.4 kg of azodiisobutyric acid dinitrile

At 35 ° C the gemisdi solidifies after 3 days and 5 days _of calcium orthoarsenate (Ca ₃ (As ₃ O ^

, st hardened after 8 days. registered. At 35 ° C the mixture continues to solidify

3 days and is hardened after 8 days.
Example 9

In a Retainer :: from 2001 contents are in _io example 12

25 ° C In a container with a capacity of 200 liters, be

50 kg of a 10 percent by volume radioactive concentration of 20 ° C in a solution of
taminated tributyl phosphate solution in ^ ß kg styrene,

Isodecane with ^ _{5 kg} divinylbenzene

50 kg of an arrow-shaped with 18% Divmylben- 15 (60 percent by weight) and

zol crosslinked and with 65% _isododecane 14kg azodiisobutyric acid dinitrile

(calculated on the monomer mixture)

made porous polystyrene 100.0 kg cadmium sulfate (CdSOi) entered. Be:

35 ° C the mixture solidifies after 4 days and isi

well mixed. It is allowed to swell for 1 hour and after 8 days it is hardened to a solid block,
at 25 ° C to add a solution of ' _B ·. . .,

JO C 1 j L / 1 C 1 X J)

⁹ M } ^& 5! - ^Ol 'iu 1 ^{In a} container of 200 l, be

3.3 kg divinylbenzene ₂₅ o _{c in a Lö of}

(60 percent by weight) and ⁶

3.0 kg of azodiisobutyric acid dinitrile. * ⁵ 43.0 kg styrene,

1.5 kg divinylbenzene (60 percent by weight) At 40 ° C there is :; After 3 days, the mixture solidifies and 1.4 kg of azodiisobutyric acid dinitrile

and hardened after 12 days. 100.0 kg of a radioactively contaminated Kie

selgels (grain size from 0.1 to 0.3 mm)

3 °

Example 10, which occurs during kerosene cleaning, entered and

In a 2001 container, the contents are mixed ^{at 8 ut.} At 40 ° C the mixture is after

25 ° C solidified in a solution of 2 days and after 8 days to a solid

_, 'Block hardened.

43.0 kg styrene, ₃₅

1.5 kg divinylbenzene (60 percent by weight), example 14
1.4 kg of azociisobutyric dinitrile and _{In a container of 2} () 0 1 content, 120.0 kg of a solution before the polymerization reaction 2 ^ ~ q j _ne j _{nc solution VO} n
crushed, radioactively contaminated broken glass entered. _Λ0 120 kg of styrene.

⁴ 4 kg divinylbenzene,

At 40 ° C., the mixture solidifies after 2 days to give ⁴ kg of azodiisobutyric acid dinitrile.

a solid block. When leaching by destil- ^{12 k} S Natnumsalz the Dodecylben: olsulfon

Lated water did not become radioacid after 14 days

fixed activity. "100 kg of diatomite with 15 percent by weight radio

⁴⁵ actively contaminated water

Example 11 given and mixed well. It solidifies at 30 ° C

In a Beha! : he of 200 1 content will be exhausted after 4 days with a mixture and after 8 days

25 ° C in a solution of hardens.

Claims (11)

Patent claims: 1. Process for the treatment of solid waste containing radioactive or toxic steiffe for safe handling, transport and disposal, in which the waste with a polymerisierharen mixture mixed and through Polymerization is converted into a solid block, dadurci characterized that the mixture of monovinyl and polyvinyl compounds and polymerization analyzers. 2. procedure; according to claim 1, characterized in that that as monovinyl compounds J5 styrene or methyl acrylate and as polyvinyl compounds Divinylbenzene or trivinylbenzo! be used. 3. The method according to claim 1, characterized in that daC 'based on the mixture of: to waste and polymerisation mixture the waste in solid form in a range between 2 and 75 percent by weight, and based on the polymerization degree ^ h the monovinyl compounds in a range between 60 and 99 percent by weight, the poly vinyl compounds in a range between 0.5 and 30 percent by weight, and the polymerization catalysts are used in a range between 0.1 and 10 percent by weight will. 4. The method according to claim 3, characterized in that daCi based on the mixture Waste and polymerization mixture the waste in solid form in a range between 30 and 70 percent by weight and based on the polymerization mixture the monovinyl compounds in a range between 80 and 98 percent by weight, the poly vinyl compounds in a range between 1 and 15 percent by weight and the Polymerization catalysts are used in a range between 0.5 and 5 percent by weight will. 5. The method according to claim 1, characterized in that dad the solid waste, the wa * - sc or aqueous solutions containing emulsifiers and / or swellable b / w. Absorbent substances is added before it is mixed with an egg polymerization mixture in the weight ratio range waste / u polymerisation mixture between 2.! and is mixed 1: 1. 6. The method according to claim 5, characterized in that that as emulsifiers anion-active or nichlionischi; Surfactants are used. 7. The method according to claim 6, characterized in that the anionic surfactants are alkyl sulfonates, Alkyl or Arylbenzolsulfonaie and as nonionic surfactants ethoxylated or propoxyücrtc Fatty alcohols, fatty acids or Κ-η-amines be used. 8. The method according to claim 5, characterized in that da3 as .absorbent substances dried Ion exchangers, inorganic (icle. Diatomaceous earth or vermiculite used willow. 9. The method according to claim S, characterized in that the inorganic gels are silica gel or clay gel can be used. 10. The method according to claim 1, characterized in that: 3 the solid waste, the organic Liquids or organic solutions are contained. is mixed with sorbents before it is mixed with d, m Polymerization mixture in weight reduction., - schi-n rich waste is mixed to a polymerization mixture between 2: 1 and 1: 1. 11 The method according to claim 10, characterized in that that as sorbents vermiculite ixJ-.r macroporous styrene-divinylbenzene copohmcnsate be used.