Patent Number: 047327057
Section: description

(a) Cement Solidification of Untreated Resin Particles 60 parts by weight of the untreated resin particle mixture with 50% water content, i.e. fully swelled, were mixed with 100 parts by weight of synthetic Portland cement with high silicate content, designation CPA 55 HTS, produced by Ciments Lafarge France, F-92214 St. Cloud (corresponding to the French norm NF P 15301, December 1978, and the American norm ASTM as type V, quality "low alkali cement"), PA1 40 parts by weight of hydraulic Nettetal trass according to DIN 51043, produced by Trass-Werke Meurin, Andernach/Rhine, FRG, Kruft plant, PA1 10 parts by weight of calcium hydroxide, Ca(OH).sub.2 PA1 4.2 parts by weight of super liquified (naphthaline-formaldehyde condensate), designation Sikament, produced by Sika AG, CH-8048 Zurich, and PA1 30.8 parts by weight of water. PA1 36.0 parts by weight of BaS.sub.4 solution with 72.4% by weight water content (solid matter dry 27.6% by weight) and PA1 43.35 parts by weight of Ba(OH).sub.2.8H.sub.2 O. PA1 100 parts by weight of synthetic Portland cement of the same quality as described in section (a), and PA1 40 parts by weight of hydraulic Nettetal trass of the same quality as described in section (a) PA1 2.5 parts by weight of cement additive for improving the cement density and solidity, designation Sperrbarra Plus OL, supplied by Meynadier & Cie AG, CH-8048 Zurich. The mixture according to the above prescription was left to harden with a water coating. The thus resulting solid matrix provided the values as shown in table II. (b) Pretreatment of the Resin Particles 63.65 parts by weight of the resin particle mixture with 16.4% by weight water content (solid matter dry 83.6% by weight) were mixed to a thin gruel with the following additives: Thereby the cation resin was charged with Ba.sup.++ and the anion resin with S.sub.4.sup.--. The borate which was split off from the anion resin was precipitated with more Ba.sup.++ as insoluble barium-metaborate. This reaction, resulting from the mixing, caused heat to be released, which had the effect that the mixture heated itself from room temperature to about 50.degree. C. Then, the mixture was kept for several hours at 50.degree. C. The cement solidification took place about 24 hours after the described pretreatment. In the meantime, the mixture was stirred further, in order to prevent a settling of the solid matter and the formation of larger crystals. A water loss by evaporation during this time was compensated for by more water. The thus pretreated resin particles provided the values cited in table I under no. 89. (c) Cement Solidification of the Pretreated Resin Particles A previously prepared mixture, consisting of was added to the mixture described in section (b) with the pretreated ion exchange resin particles. At the beginning, only enough of the above mixture was added and homogenically stirred in until there was a thick gruel which ran together by itself. Then followed the addition of With the addition of this cement additive, the gruel became obviously more liquid. It was then possible to add the remaining Portland cement/trass mixture with constant stirring. The final gruel had a just pumpable consistency and was homogenically mixed for another 10 minutes. The mixed in air bubbles were removed by vibration. After about 2 hours, the mixture was gelled sufficiently thixotrope so that it could be coated with water for hardening. The hardening by setting of the cement started after 5 to 6 hours, which could be recognized by a rise in temperature. The finally resulting matrix showed the values as listed in table II. (d) Comparison of the Properties of the Hardened Matrix with Untreated or Treated Ion Exchange Resin Particles Compared in table II are the corresponding values of the hardened matrix produced according to section (a) (state of the art) and the matrix produced according to sections (b) and (c). It can be clearly seen from table II that by the described pretreatment of the ion exchange resin particles, according to the invention, for reduction of the swelling factor has two essential advantages as compared to the state of the art. The main advantage can be seen in the fact that the water resistance of the hardened matrix is guaranteed, even when the matrix is dried to a weight constant at 20% relative humidity and is then stored again in water, whereby the water resistance in the matrix according to the state of the art is only guaranteed as long as there is no intermediate drying. The other advantage is that at a given matrix volume, e.g. 100 liter, a considerably greater amount of resin particles, 35.1 kg as compared to 22 kg dry substance of the original resin particles can be enclosed. This can effectively ease the disposal and final storage for radioactive waste ion exchange resins. It has to be stated as another advantage of the new process that the other properties of the solid matrix, especially the compressive strength and sulfate resistance, are not impaired by the pretreatment of the ion exchange resin particles according to the invention. It is clear that for the pretreatment of the ion exchange resin particles to be solidified it is possible to use a large number of other substances besides those listed in table I and that the prescription stated as example for the cement solidification can be modified. The ion exchange resin particles with reduced swelling factor, pretreated according to the invention, are not only suitable for cement solidification, but can be solidified also, with equally good results, using bitumen or plastics. TABLE I __________________________________________________________________________ Lewatit (%) S M comp. vol. swell No. 100 500 treated with: wet dry factor __________________________________________________________________________ (l/kg) 1 100 -- none 2.50 1.19 2.10 2 -- 100 none 3.23 1.44 2.24 3 50 50 none 2.86 1.28 2.23 4 100 -- cocosamine acetate 2.61 1.89 1.38 5 100 -- dibutylamine 2.59 2.28 1.14 6 100 -- tributylamine 2.67 2.28 1.17 7 100 -- dibutylamine nitrate 2.42 1.94 1.25 8 100 -- tributylamine nitrate 2.51 2.04 1.23 9 100 -- vinyl imidazole 2.56 1.79 1.43 10 100 -- vinyl imidazole nitrate 2.44 1.51 1.62 11 100 -- benzylcocodimethyl- 2.60 1.45 1.79 ammonium chloride 12 100 -- suetalkyltrimethyl- 2.73 1.56 1.75 ammonium chloride 13 100 -- disuetalkyldimethyl- 2.68 1.45 1.85 ammonium chloride 14 100 -- dioctyldimethylammonium 2.57 1.79 1.44 chloride 15 100 -- didecyldimethylammonium 2.61 1.66 1.57 chloride 16 100 -- tetraethylammonium 3.08 2.32 1.33 hydroxide 17 100 -- tetrapropylammonium 3.01 2.43 1.24 hydroxide 18 100 -- tetrabutylammonium 2.85 2.48 1.15 hydroxide 19 100 -- tributylmethylammonium 3.08 2.75 1.12 hydroxide 20 100 -- benzyltrimethylammonium 2.73 2.23 1.22 hydroxide 21 100 -- trimethylammoniumethyl- 2.53 1.59 1.59 methacrylate metho- sulfate 22 100 -- as in 21 then polymerized 2.40 1.84 1.30 with ammonium peroxi- disulfate 23 100 -- ethylenediamine 2.35 1.42 1.65 24 100 -- ethylenediamine carbonate 2.30 1.37 1.68 25 100 -- 1,2 propylenediamine 2.46 1.57 1.57 26 100 -- 1,2 propylenediamine 2.54 1.58 1.61 carbonate 27 100 -- 1,4 phenylenediamine 2.34 1.94 1.21 28 100 -- 1,4 phenylenediamine 2.43 1.86 1.31 carbonate 29 100 -- piperazine 2.52 1.59 1.58 30 100 -- piperazinecarbonate 2.70 1.70 1.59 31 100 -- semicarbazide hydro- 2.19 1.27 1.72 chloride 32 100 -- guanidine carbonate 2.28 1.65 1.38 33 100 -- aminoguanidine carbonate 2.25 1.57 1.43 34 100 -- S--methylisothiourea 2.11 1.66 1.27 hydroxide 35 100 -- S--benzylisothiourea 2.20 1.88 1.17 hydroxide 36 100 -- acethydrazide-trimethyl 2.24 1.37 1.64 ammonium chloride 37 100 -- pentane-1,5-bi-trimethyl 1.81 1.21 1.50 ammonium iodite 38 100 -- decane-1,10-bi-trimethyl 2.01 1.43 1.41 ammonium iodite 39 100 -- hydrazine hydrate 2.26 1.27 1.78 40 100 -- heptamethylguanidine 2.50 1.78 1.40 hydroxide 41 100 -- propane-1,3-bi-trimethyl 2.10 1.45 1.45 ammonium hydroxide 42 100 -- tetrabutylphosphonium 2.58 2.20 1.17 hydroxide 43 100 -- methyltriphenylphospho- 2.32 1.76 1.32 nium hydroxide 44 100 -- trimethylsulphonium 2.51 1.60 1.57 hydroxide 45 100 -- thallium nitrate 2.09 1.19 1.76 46 100 -- magnesium chloride 2.40 1.19 2.02 47 100 -- calcium chloride 2.36 1.20 1.97 48 100 -- barium chloride 2.06 1.21 1.70 49 100 -- barium hydroxide 2.05 1.31 1.56 50 100 -- cadmium chloride 2.45 1.27 1.93 51 100 -- copper chloride 2.47 1.20 2.06 52 100 -- manganese-2-chloride 2.40 1.30 1.85 53 100 -- cobalt chloride 2.48 1.23 2.02 54 100 -- nickel chloride 2.49 1.27 1.96 55 100 -- iron-3-chloride 2.44 1.16 2.10 (1 kg) 56 100 -- iron-2-sulfate 2.21 1.37 1.61 57 100 -- chromium chloride 2.59 1.28 2.02 58 100 -- aluminum chloride 2.45 1.24 1.98 59 100 -- titanium-3-chloride 2.57 1.28 2.01 60 100 -- zinc acetate 2.55 1.18 2.16 61 100 -- tin chloride 2.38 1.17 2.03 62 -- 100 ammonium stearate 3.23 2.53 1.28 63 -- 100 acrylic acid 2.89 1.73 1.67 64 -- 100 dimethylacrylic acid 2.86 1.73 1.65 65 -- 100 diammonium sebacate 2.80 1.69 1.66 66 -- 100 sylvatac 140, dimerized 1.98 1.44 1.38 liquid rosin, SZ 134, (Sylvachem Corp., USA) H.sub.2 O soluble w/10% NaOH 67 -- 100 resin B 106, colophonium 2.68 1.80 1.49 pentester SZ 204 (Hercules Inc. USA) H.sub.2 O soluble w/ 6.25% NH.sub.3 68 -- 100 Vinsol resin, pine root 2.72 1.80 1.51 resin SZ 95 (Hercules Inc. USA) H.sub.2 O soluble w/7% NaOH 69 -- 100 ammonium lauryl sulfate 2.84 1.74 1.63 70 -- 100 vinylpentasulphonate-Na 2.83 1.78 1.59 71 -- 100 monobutylphosphoric acid 2.88 1.83 1.57 ester (l/kg) 72 -- 100 mono and dibutylphosphoric 2.98 2.08 1.43 acid ester, 50% each 73 -- 100 monostearylphosphoric 4.09 3.25 1.26 acid ester 74 -- 100 mono + di-nonyletraethoxi- 3.30 2.57 1.28 phenolphosphoric acid ester 75 -- 100 potassium polysulfide 2.61 1.57 1.66 at 20.degree. C. 76 -- 100 potassium polysulfide 2.49 1.51 1.65 at 50.degree. C. 77 -- 100 calcium polysulfide 2.14 1.53 1.40 at 20.degree. C. 78 -- 100 calcium polysulfide 1.55 1.51 1.03 at 50.degree. C. 79 -- 100 as 77 + 10% potassium 1.75 1.70 1.03 ethylxanthogenate (rel. to resin dry) 80 -- 100 barium polysulfide 2.11 1.69 1.25 at 20.degree. C. 81 -- 100 barium polysulfide 1.77 1.71 1.04 at 50.degree. C. 82 -- 100 as 80 + 10% potassium 2.11 1.83 1.15 ethylxanthogenate (rel. to resin dry) 83 -- 100 complete thermolysis at 1.01 1.01 1.00 150.degree. C. in air stream 84 50 50 as 83 1.80 1.10 1.64 85 50 50 tetrabutylammonium hydroxide 1.94 1.86 1.04 then thermolysis at 160.degree. C. in air stream 86 50 50 guanidine carbonate, 1.57 1.28 1.23 then thermolysis at 160.degree. C. in air stream 87 50 50 aminoguanidinehydrogen 1.57 1.31 1.20 carbonate, then thermo- lysis at 160.degree. C. in air stream 88 50 50 tetrabutylammonium hydrox- 2.14 1.89 1.13 ide, then calcium poly- sulfide 89 50 50 barium polysulfide a/50.degree. C. 1.91 1.51 1.26 90 50 50 as 89 + 10% K--ethyl- 2.08 1.57 1.32 xanthogenate a/20.degree. C. 91 50 50 ethylenediamine polysulfide 1.90 1.44 1.32 92 50 50 as 91 + heat treatment at 1.62 1.38 1.17 160.degree. C. 93 50 50 propylenediamine poly- 1.80 1.38 1.30 sulfide 94 50 50 as 93 + heat treatment at 1.57 1.36 1.15 160.degree. C. 95 50 50 piperazine polysulfide 1.96 1.39 1.41 96 50 50 as 95 + heat treatment 1.62 1.37 1.18 160.degree. C. 97 50 50 guanidine polysulfide 1.93 1.51 1.28 98 50 50 as 97 + heat treatment 1.57 1.33 1.18 160.degree. C. 99 50 50 aminoguanidine poly- 1.98 1.57 1.26 sulfide 100 50 50 as 99 + heat treatment 1.75 1.45 1.21 160.degree. C. 101 50 50 tetramethylguanidine 1.97 1.47 1.34 polysulfide 102 50 50 as 101 + heat treatment 1.67 1.59 1.05 160.degree. C. 103 50 50 dicyandiamide + heat 1.89 1.55 1.22 treatment 160.degree. C. __________________________________________________________________________ TABLE II ______________________________________ Cement solidification of Cement solidification of Properties untreated ion exchange pretreated ion exchange of matrix resin particles resin particles ______________________________________ volume 1.8 t/m.sup.3 (water content 1.8 t/m.sup.3 (water content weight acc.to recipe) acc.to recipe) resin 22 kg dry substance 35.1 kg dry substance content in 100 liter matrix without treatment, in 100 liter matrix compressive 22 N/mm.sup.2 after more 21 N/mm.sup.2 after more strength than 20 weeks of than 20 weeks of (acc. SIA hardening hardening 215) sulfate is assured is assured resist. water is assured as long as is assured even when resistance the matrix has not the matrix has been been dried before dried before wetting wetting leach rates in distilled water: values not yet obtained RL 730 10.sup.-4 to 10.sup.-5 for Based on recipe Cs-137 about the same results 10.sup.-6 to 10.sup.-7 for are expected. Co-60 10.sup.-3 to 10.sup.-4 for Sr-90 (in water saturated with gypsum, smaller by 1 or 2 orders of magnitude) ______________________________________