JPS5977396A - Method of solidfying radioactive waste - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention t.1. This invention relates to a method for solidifying and burying radioactive waste using thermosetting resin.

``Technical background of the invention and its problems'' Conventionally, radioactive waste fluid generated from nuclear power plants and other nuclear facilities is treated in various ways, and then finally assimilated by the following method ( ``The environment is prevented from being contaminated by radioactivity in waste.

The most common solidification treatment methods used at the Ikyo Power Plant are the cement solidification method, which solidifies dried and powdered radioactive waste with cement 1- or asphalt, and the asphalt (and assimilation method C), but recently The plastic assimilation method is attracting attention for its excellent ability to contain radioactivity and its ability to reduce the volume of radioactive waste.

In such plastic assimilation methods, a thermoplastic resin such as polyethylene is used as an assimilating agent, but an unsaturated polyester resin consisting of an unsaturated polyester and a polyester is used as a thermosetting resin. In particular, the plastic solidification method using thermosetting resin is #11.
By selecting Qt and catalysts such as polymerization initiators and polymerization promoters, it is possible to proceed with the d3 (III! conversion reaction) at the temperature of the temperature, and if the radioactive waste 1!, resin, and catalysts are uniformly mixed, the solidifying agent This is a preferred method because the polymerization reaction proceeds at room temperature and a plastic assimilate product can be obtained quickly.

However, it has been found that radioactive waste may contain substances that inhibit the polymerization reaction of thermosetting resins. For example, the main component of the concentrated waste liquid from boiling water nuclear photovoltaic power station C/i is sodium sulfate (Na 2 SOn), but in addition to this, trace components and L'(Ca, 3+
, Fe, Go, 'Ni, CI, and other elements are commonly found in the chemical industry.In particular, it has been found that the presence of CI hydroxide significantly impairs the combination reaction of thermosetting resins.

By the way, 1-lium sulfate powder, which is the main component of concentrated waste liquid, and copper hydroxide powder are mixed in a ratio of 59:1, and this powder is heat-cured with unsaturated polyester resin as the main component. The powder mixture was added to the thermosetting resin at a mixing rate of 60% by weight, and further, C methyl ethylene chloride per A key lead was added as a polymerization initiator to the thermosetting resin. %, as a polymerization accelerator (cobalt naphthenate for thermosetting resins)
When 0.5% by weight of U was added and mixed and the condition was examined after being left for day and night, it was found that although progress of the polymerization reaction was observed, it was found that the reaction had stopped and the mixture had hardened.

This is because copper hydroxide has amphoteric properties and dissociates into J of the following formula, C" (OH) 2 ;======Cu
” ” + 2 0 1-l -CU (01
'') 2 = CuQ2-' -+2 El ``The 11+ generated here reacts with the primary radicals generated by the polymerization initiator and the polymerization accelerator, and with the radicals generated in the subsequent chain reaction. This is thought to be to inactivate radicals.

The following experiment confirms that the polymerization and curing of thermosetting resins containing acidic substances is extremely difficult.

That is, 59% by weight of sodium sulfate, 40% of a thermosetting resin whose main component is unsaturated polyester resin, and 1% of hydroxide steel were mixed, and this mixture was irradiated with cobalt-60 gamma rays at 7 megaroentgen. However, the mixture remained liquid, and no progress of the polymerization reaction was observed. On the other hand, when only the thermosetting resin and sodium sulfate were used without mixing copper hydroxide, 11llj was completely converted and a strong plastic assimilated product was obtained.

In this way, thermosetting resins that undergo radical polymerization and harden are difficult to convert into 1-1 ÷ sources that react with radicals, such as copper hydroxide (f7I!J). A mixture of radioactive waste and thermosetting resin will be stored in a storage container without polymerization or with insufficient hardening.If this mixture remains unpolymerized, the radioactivity trapping capacity will decrease. What's more, the unpolymerized assimilation agent [it is classified as a dangerous substance under the Fire Service Act] 1.
JII￥i! The problem was that it would put Tomono in a more dangerous situation.

] Purpose of the Invention The present invention has been made to solve these problems.
The object of the present invention is to provide a method for assimilating radioactive waste that can be sufficiently cured even if it contains J and C.

[Summary of the invention] That is, the method of the present invention is a method for producing radioactive FJ containing copper hydroxide.
The method is characterized in that the assimilation treatment of waste with a thermosetting resin is carried out in the presence of a halogen substance.

The thermosetting resin used in the present invention is an unsaturated polyester resin.
It is an unsaturated poly-1-sprue resin consisting of aluminum and a polymerizable monomer, and refers to a J-stellated polycondensate of an unsaturated polyester, a dibasic acid component, and a glycol component. Typical basic acid components include α,β-unsaturated dibases such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, laconic acid, mesaconic acid, and chlorinated maleic acid. Acid list: Phthalic anhydride, isophthalic anhydride, terephthalic acid, monochlorophthalic acid, dichlorophthalic acid, trichlorophthalic acid, tetrachlorophthalic anhydride, atrabromophthalic anhydride, endomethylenethiF・Ujidrophthalic anhydride, Tel-Rahydride 1] 1
It is a saturated dibasic acid such as phthalic anhydride, adipic acid, sebacic acid, and succinic acid, and of course also includes combinations with saturated dibasic acids such as the above-mentioned α, β-unsaturated dichlorosulfonic acid. .

On the other hand, C7, which is typical as the above-mentioned Green: TJ-le component.
L, e.g. tamethylene glycol, propylene glycol J-
J'JI non-glycol, 1 pyrene glycol on the jib, 1 pyrene glycol on the edge, 1.4 pylene glycol, 1.4-butyl
Renglilin], neobenbul glycol-1silene glycol, octyl glycol, bisphenol Δ
・Di-A: V-chill l-chill (j+additive, hydrogenated bisphenol A, bisphenol A ・Gio: 1: schizo 1-1 pyru-r-delui 1-additive J: bi-dilene A-1 Lid, /1-1 Pyrene A Kizaide, Butylene Oxide'Al, Run A Kiriido, Still Jishi 9th Pentaji J
-N, Deck 1'' Pentadiene polymer etc. C・ Yes, as required (' 1 ~ Rimethi 1] - Shiv 11 Pan, Grit!
A desired amount of polyhydric alcohol of phosphorus can also be added.

The unsaturated poly 1 sprue resin binding C used in the present invention is
Those having an acid value of 80 or less are preferred.

fF-combined Nakagawa Yodoshiku (-unsaturated poly-[stell and co-combined with Nazube C) can be used. Typical examples include styrene, α-methylstyrene, and vinyl styrene. Soil, Ri:l IN Styrene, acrylic acid, methacrylic acid alkyl costyl 1-lylyl cyanurate-1, triallyl isocyanurate, acrylamide, Q!i is preferably suburene enomer, methyl methacrylate .These l) 1 hanging body)
The amount used ranges from 20% to 80% when combined with unsaturated polyester.

This unsaturated polyester resin can be used with C-hyde [
Polymerization inhibitors such as 1-quinone, benzoquinone, and butylene quinone are included.

To the obtained composition of the present invention (J, calcium carbonate, resin, gypsum, alumina hydroxide 11, fillers such as sulfur salt, etc., and as a resin modifier, C dibutylnotare-1-
, dizotyl male earth-1-, diocvulphthalate I, etc.;

-1-, trisph [''loethyl phosphene 1-, etc. 11]
Flame retardants such as Nisdel lyphosphate, chlorinated paraffin, antimony trioxide, decanolomodiphenyl ether, right 11
Natural or inorganic pigments, low shrinkage agents such as thermoplastic resins, etc. can be added.

Polymerization of the above-mentioned unsaturated polyester resin (1, 1) 1 (metal salt and 1 - amber oxide (31, 2) and somemenalaniline or diethylaniline (
According to the method, also benzoyl per'A-1-lead,
Examples include high-temperature decomposition with t-butylperΔxybenzo-I-'l-.

[Used conveniently in the present invention] Examples of alkaline substances include hydroxides of sodium chloride, sodium chloride, calcium hydroxide (1)
Examples include powders or aqueous solutions of blue (3) goiif compounds. J, t, (- The mixture of alkaline substances is preliminarily mixed with 11-contained 1j ``U t> J, ku,
Alternatively, thermosetting ↑ (1 resin and 64 t! I- It is also good to add 1 alkaline substance when mixing and covering the waste. Furthermore, it is also possible to add an alkaline substance to the polymerization 1je promoter. It is better to add Ct). The amount added is almost the same as that of copper hydroxide.

In the present invention, a thermosetting resin is added to and mixed with dried and powdered radiation fL waste, and an alkaline substance is evenly mixed therein. Mix and let stand at normal humidity.

[Embodiments of the invention] Next, examples of the present invention will be explained.

Example 1 1IllI acid Pr 1 ~ LiP 1 ~ Lium 59 Thermal sanding tree IIiLi'IO for producing and separating unsaturated polynisder resin
In a mixture of 1% by weight of copper hydroxide, 2% by weight of the thermosetting f1-resin, 2% by weight of the intermediate initiator methyl ethylene chloride peroxide, and 1% by weight of the intermediate accelerator nanodenic acid Pal 1- (added at 0.5% by weight each to the thermosetting resin). Add 5 alkaline substances to this mixture! A 20% solution of sourium to hydroxide (i) was added to the thermosetting resin in an amount of 5% by weight and further mixed. -Day and night tJ! A strong Shirasudek assimilate was obtained after iHvi. Gelation time and surface of the obtained Shirasdek assimilate) I! I! The degree is shown in the table T0 Example t 5 Toto% of sodium hydroxide 20%'? One part of liquid B!
Example 1 was repeated except that magnesium oxide of v% was used.
A 1-thin snack solidified body was obtained. Gel time is J, surface hardness is 1'! 14 Similarly shown in the table -0 Example 5 Hydroxide (wt%) I. Lium 20% solution was added to magnesium hydroxide 1 wt ω% C
When the mixture was mixed and left for day and night, a strong 41 plastic assimilation period was obtained. The gluing time and surface hardness are shown in the table.

Example 1 The mixture was mixed in the same manner as in Example 1 except that the IJ hydroxide 1-silium 0% solution was replaced with 1% calcium oxide, and the mixture was exposed day and night, resulting in strong plus book assimilation. It was done.

Example 5 The same IJ was hydrated: The mixture was mixed in the same manner as in Example 1, except that the 20% solution of -lium was replaced with 1% calcium hydroxide. r-glass book assimilation holiday was obtained. The gelation time d3 and surface hardness are shown in the table.

Note that the reference examples in the table are examples in which hydroxide 'Mn3 and alkaline substances are not present.

(Hereinafter in the margin); To JIS K7215 (Hereinafter in the margin) "Effects of the Invention" As explained above, according to the method of the present invention, even if there is a substance such as copper hydroxide that harms the polymerization curing reaction, curing is not possible. Sufficient (-j), a strong plus 1- ivy assimilate is obtained.

Representative Patent Attorney Su 111 Sa - Continued from page 1 ■Submitted by: Mitsui Toatsu Chemical Co., Ltd. 3-2 Kasumigaseki, Chiyoda-ku, Tokyo number 5 ■Submitted by: Tokyo Shibaura Electric Co., Ltd. 72 Horikawa-cho, Saiwai-ku, Kawasaki City

Claims (1)

[Claims] (1) Thermosetting resin of radioactive waste containing copper hydroxide [I iff waste characterized in that the solidification treatment is carried out in the presence of an alkaline substance] anabolic processing power method. (2〉Mature) Enamel resin is unsaturated polyester and f11
It is an unsaturated polyester resin consisting of a synthetic neutral medium.
R1i'l Claim 1] The method for assimilating radioactive waste according to i'i. (3) Alkaline substances are heated to almost the same level as copper hydroxide! h9 according to claim 1 or 2, which is added to any mixture of resin and radioactive waste.
Assimilation treatment method for scraping waste.