JP5214843B2 - Heavy metal fixative - Google Patents
Heavy metal fixative Download PDFInfo
- Publication number
- JP5214843B2 JP5214843B2 JP2005074313A JP2005074313A JP5214843B2 JP 5214843 B2 JP5214843 B2 JP 5214843B2 JP 2005074313 A JP2005074313 A JP 2005074313A JP 2005074313 A JP2005074313 A JP 2005074313A JP 5214843 B2 JP5214843 B2 JP 5214843B2
- Authority
- JP
- Japan
- Prior art keywords
- heavy metal
- weight
- fly ash
- parts
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910001385 heavy metal Inorganic materials 0.000 title claims description 140
- 239000000834 fixative Substances 0.000 title claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 93
- 239000010881 fly ash Substances 0.000 claims description 53
- 239000000428 dust Substances 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 230000002265 prevention Effects 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 32
- 150000003839 salts Chemical class 0.000 claims description 25
- 230000003100 immobilizing effect Effects 0.000 claims description 19
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 17
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical group NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 13
- 239000002956 ash Substances 0.000 claims description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 12
- 239000013522 chelant Substances 0.000 claims description 12
- 229920000768 polyamine Polymers 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 description 59
- 239000000047 product Substances 0.000 description 55
- 229920002451 polyvinyl alcohol Polymers 0.000 description 30
- 239000004372 Polyvinyl alcohol Substances 0.000 description 28
- 239000007787 solid Substances 0.000 description 24
- 239000000126 substance Substances 0.000 description 24
- 230000000694 effects Effects 0.000 description 17
- 229920002678 cellulose Polymers 0.000 description 15
- 239000001913 cellulose Substances 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 15
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 14
- 239000000920 calcium hydroxide Substances 0.000 description 14
- 235000011116 calcium hydroxide Nutrition 0.000 description 14
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000004056 waste incineration Methods 0.000 description 14
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 12
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 12
- -1 thiol compounds Chemical class 0.000 description 12
- 229920006184 cellulose methylcellulose Polymers 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- NLZXQOOZQAGNCY-UHFFFAOYSA-L dipotassium;piperazine-1,4-dicarbodithioate Chemical compound [K+].[K+].[S-]C(=S)N1CCN(C([S-])=S)CC1 NLZXQOOZQAGNCY-UHFFFAOYSA-L 0.000 description 10
- 238000010828 elution Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 8
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 8
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 8
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 8
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 6
- IHPYMWDTONKSCO-UHFFFAOYSA-N 2,2'-piperazine-1,4-diylbisethanesulfonic acid Chemical compound OS(=O)(=O)CCN1CCN(CCS(O)(=O)=O)CC1 IHPYMWDTONKSCO-UHFFFAOYSA-N 0.000 description 5
- HSHXDCVZWHOWCS-UHFFFAOYSA-N N'-hexadecylthiophene-2-carbohydrazide Chemical compound CCCCCCCCCCCCCCCCNNC(=O)c1cccs1 HSHXDCVZWHOWCS-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229920000609 methyl cellulose Polymers 0.000 description 5
- 239000001923 methylcellulose Substances 0.000 description 5
- 235000010981 methylcellulose Nutrition 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 229940105329 carboxymethylcellulose Drugs 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 4
- 229940032147 starch Drugs 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 229920000896 Ethulose Polymers 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 3
- 239000004368 Modified starch Substances 0.000 description 3
- 229920000881 Modified starch Polymers 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CWYYYJDYYCIWRK-UHFFFAOYSA-N [K].N1(CCN(CC1)C(=S)S)C(=S)S Chemical compound [K].N1(CCN(CC1)C(=S)S)C(=S)S CWYYYJDYYCIWRK-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 230000003449 preventive effect Effects 0.000 description 3
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 229920001059 synthetic polymer Polymers 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- XPCTZQVDEJYUGT-UHFFFAOYSA-N 3-hydroxy-2-methyl-4-pyrone Chemical compound CC=1OC=CC(=O)C=1O XPCTZQVDEJYUGT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229920003114 HPC-L Polymers 0.000 description 2
- 229920003115 HPC-SL Polymers 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920003112 high viscosity grade hydroxypropyl cellulose Polymers 0.000 description 2
- 125000001183 hydrocarbyl group Chemical class 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229920003117 medium viscosity grade hydroxypropyl cellulose Polymers 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 1
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- ZAXCZCOUDLENMH-UHFFFAOYSA-N 3,3,3-tetramine Chemical compound NCCCNCCCNCCCN ZAXCZCOUDLENMH-UHFFFAOYSA-N 0.000 description 1
- HWZGZWSHHNWSBP-UHFFFAOYSA-N 3-(2,3-diaminophenoxy)benzene-1,2-diamine Chemical compound NC1=CC=CC(OC=2C(=C(N)C=CC=2)N)=C1N HWZGZWSHHNWSBP-UHFFFAOYSA-N 0.000 description 1
- XYUINKARGUCCQJ-UHFFFAOYSA-N 3-imino-n-propylpropan-1-amine Chemical compound CCCNCCC=N XYUINKARGUCCQJ-UHFFFAOYSA-N 0.000 description 1
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- VZNUCJOYPXKLTA-UHFFFAOYSA-N 5-chlorobenzene-1,3-diamine Chemical compound NC1=CC(N)=CC(Cl)=C1 VZNUCJOYPXKLTA-UHFFFAOYSA-N 0.000 description 1
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- 244000205754 Colocasia esculenta Species 0.000 description 1
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
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- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 240000004584 Tamarindus indica Species 0.000 description 1
- 235000004298 Tamarindus indica Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
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- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- WMEKSYHDIDMJMC-UHFFFAOYSA-L [Na+].[Na+].[S-]SSS[S-] Chemical compound [Na+].[Na+].[S-]SSS[S-] WMEKSYHDIDMJMC-UHFFFAOYSA-L 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
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- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
Description
本発明は、飛灰等に含まれる重金属の固定剤に関し、更に詳細には、重金属を固定すると同時に、処理飛灰等から発生する粉塵を抑制することのできる重金属固定剤に関する。 The present invention relates to a fixing agent for heavy metals contained in fly ash and the like, and more particularly to a heavy metal fixing agent capable of fixing heavy metals and at the same time suppressing dust generated from treated fly ash and the like.
飛灰等の粉塵防止方法として、例えば、界面活性剤と多価アルコールとを水溶液にして散布することを特徴とする粉塵防止方法が知られている（例えば、特許文献１参照）。また、生分解性樹脂を水に乳化してなる、生分解性樹脂のエマルジョンよりなることを特徴とする粉塵発生防止剤（例えば、特許文献２参照）や、解膠した繊維及び分散媒を含有することを特徴とする粉塵防止剤（例えば、特許文献３参照）や、石膏及び／又は粘土と高分子ポリマーとを含む高粘性スラリーからなることを特徴とする粉塵発生防止（例えば、特許文献４参照）や、水硬性材料から発生する粉塵を防止する方法であって、あらかじめ添加剤に起泡剤を混合し、泡沫を形成したものを上記水硬性材料に添加することを特徴とする粉塵発生防止法（例えば、特許文献５参照）が知られている。 As a dust prevention method for fly ash and the like, for example, there is known a dust prevention method characterized by spraying a surfactant and a polyhydric alcohol in an aqueous solution (for example, see Patent Document 1). Further, it contains a dust generation inhibitor (e.g., see Patent Document 2) characterized by comprising a biodegradable resin emulsion emulsified in water, and a peptized fiber and dispersion medium A dust prevention agent (see, for example, Patent Document 3), or a high-viscosity slurry containing gypsum and / or clay and a high-molecular polymer (for example, Patent Document 4). Dust generation characterized in that it is a method for preventing dust generated from a hydraulic material, wherein a foaming agent is mixed with an additive in advance and a foam is added to the hydraulic material. The prevention method (for example, refer patent document 5) is known.
一方、低毒防錆粉塵防止用組成物として、オキシ脂肪酸アミドポリオキシアルキレンエーテルと金属石鹸の混合物中に、ポリビニルアルコールを含有させた組成物が知られており、完全ケン化ポリビニルアルコールを用いることが記載されている（例えば、特許文献６参照）。また、イ草の処理方法において、ポリビニルアルコールやセルロース誘導体が染色土の粉塵飛散を抑制できることが知られている（例えば、特許文献７参照）。 On the other hand, a composition containing polyvinyl alcohol in a mixture of an oxyfatty acid amide polyoxyalkylene ether and a metal soap is known as a low-poisoning rust-proof dust-preventing composition, and a completely saponified polyvinyl alcohol should be used. (For example, refer to Patent Document 6). In addition, it is known that polyvinyl alcohol and cellulose derivatives can suppress dust scattering of dyed soil in the grass treatment method (see, for example, Patent Document 7).
また、焼却施設の各種設備や焼却施設の解体時に発生する廃棄物に付着したダイオキシン類や重金属類等を含有する煤塵等の有害付着物の飛散を確実に防止するため、合成樹脂系、水溶性高分子系、吸水性樹脂等の合成高分子材料を含む飛散防止剤を作業前に焼却施設の各種設備又は塊状廃棄物に噴霧して表面に飛散防止膜を形成させることや、この飛散防止剤に重金属固定化剤を含有させても良いことが提案されている（例えば、特許文献８参照）。 In addition, in order to reliably prevent the scattering of harmful deposits such as dust containing dioxins and heavy metals attached to the waste generated at the time of dismantling of the various facilities of the incineration facility, synthetic resin-based, water-soluble Spraying anti-scattering agent containing synthetic polymer material such as polymer and water-absorbing resin on various equipment or lump waste in incinerator before work to form anti-scattering film on the surface, or this anti-scattering agent It has been proposed that a heavy metal immobilizing agent may be contained in the material (for example, see Patent Document 8).
また、廃水や廃ガス、固体状廃棄物中の金属を効率よく捕集するため、金属捕集剤とポリビニルアルコール等の水溶性高分子を併用する金属捕集方法が提案されている（例えば、特許文献９参照）。また、土壌や固体状廃棄物の飛散防止剤として、分子内にエポキシ基を２個以上有する化合物（Ａ）、該エポキシ基と反応する官能基を２個以上有する硬化剤（Ｂ）からなる飛散防止剤に重金属固定剤を含有できることが提案されている（例えば、特許文献１０参照）。 In addition, in order to efficiently collect metal in wastewater, waste gas, and solid waste, a metal collection method using a metal collector and a water-soluble polymer such as polyvinyl alcohol has been proposed (for example, (See Patent Document 9). In addition, as an anti-scattering agent for soil and solid waste, a scattering agent comprising a compound (A) having two or more epoxy groups in the molecule and a curing agent (B) having two or more functional groups that react with the epoxy group. It has been proposed that a heavy metal fixing agent can be contained in the inhibitor (for example, see Patent Document 10).
上記のように、重金属固定化剤を含有する焼却施設の付着物の飛散防止剤（特許文献８参照）は知られていたが、特許文献８には「［００２８］このような重金属固定化剤の含有量は、少な過ぎると添加による十分な重金属類の溶出防止効果を得ることができず、多いと相対的に飛散防止膜形成のための合成高分子材料の含有量が少なくなり、飛散防止効果が低下することから、飛散防止剤中の全有効成分（合成高分子材料と重金属固定化剤との合計）に対する割合で０．１〜３０重量％、特に０．５〜１０重量％とするのが好ましい。」と記載されているように、焼却施設の付着物の飛散防止に重点がおかれ、飛灰の飛散防止効果を維持すると共に、飛灰中の重金属を確実に固定することができる重金属固定剤は知られていなかった。特許文献９及び１０には、飛灰に対して、飛散防止剤と重金属固定剤を別々に添加した例しか具体的に記載されていない。本発明の課題は、飛灰の飛散を防止することができるとともに、飛灰中の重金属を確実に固定することができる重金属固定剤及び重金属固定化方法を提供することにある。 As described above, an anti-scattering agent for deposits in an incineration facility containing a heavy metal fixing agent (see Patent Document 8) has been known. However, Patent Document 8 discloses “[0028] Such a heavy metal fixing agent. If the content is too small, it will not be possible to obtain a sufficient elution prevention effect for heavy metals by addition, and if it is too large, the content of the synthetic polymer material for forming the anti-scattering film will be relatively small, preventing scattering. Since the effect is lowered, the ratio is 0.1 to 30% by weight, particularly 0.5 to 10% by weight, based on the total active ingredients (total of the synthetic polymer material and the heavy metal fixing agent) in the anti-scattering agent. ”Is preferable.” As described in the document, the emphasis is on the prevention of scattering of deposits in the incineration facility, while maintaining the effect of preventing the scattering of fly ash and securing the heavy metals in the fly ash reliably. No known heavy metal fixative was known. Patent Documents 9 and 10 specifically describe only examples in which a scattering inhibitor and a heavy metal fixing agent are separately added to fly ash. An object of the present invention is to provide a heavy metal fixing agent and a heavy metal immobilization method capable of preventing fly ash from being scattered and capable of reliably fixing heavy metals in the fly ash.
本発明者らは、上記課題を解決すべく、重金属固定化能力のある化合物、及び粉塵防止剤を水に均一に溶解させた重金属固定剤を用いて飛灰を処理することにより、重金属固定化能力のある化合物と、粉塵防止剤を別々に添加して飛灰を処理するよりも、飛灰の飛散防止効果が向上するとともに、飛灰中の重金属をより確実に固定することができることを見い出し、本発明を完成するに至った。 In order to solve the above-mentioned problems, the present inventors fixed heavy metals by treating fly ash with a compound capable of fixing heavy metals and a heavy metal fixing agent in which a dust prevention agent is uniformly dissolved in water. It has been found that the effect of preventing fly ash scattering can be improved and heavy metals in fly ash can be fixed more securely than the treatment of fly ash by separately adding a powerful compound and a dust inhibitor. The present invention has been completed.
すなわち、本発明は、以下の重金属固定剤に関する。
（１）重金属固定化能力のある化合物、粉塵防止剤、及び水を含有する重金属固定剤であって、重金属固定化能力のある化合物、及び粉塵防止剤が水に溶解していることを特徴とする重金属固定剤。
（２）粉塵防止剤が、完全ケン化ポリビニルアルコール及びセルロース誘導体から選ばれる少なくとも１種であることを特徴とする（１）に記載の重金属固定剤。
（３）完全ケン化ポリビニルアルコールが、親水性基を有する完全ケン化ポリビニルアルコールであることを特徴とする（１）又は（２）に記載の重金属固定剤。
（４）セルロース誘導体が、カルボキシメチルセルロース又はその塩、カルボキシメチルエチルセルロース又はその塩、メチルセルロース、エチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、エチルヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、及びヒドロキシプロピルメチルセルロースから選ばれる少なくとも１種であることを特徴とする（１）〜（３）のいずれかに記載の重金属固定剤。
（５）重金属固定化能力のある化合物が、ジチオカルバミン酸又はその塩であることを特徴とする（１）〜（４）のいずれかに記載の重金属固定剤。
（６）ジチオカルバミン酸又はその塩が、ポリアミンポリジチオカルボン酸又はその塩であることを特徴とする（５）に記載の重金属固定剤。
（７）重金属固定剤のｐＨが８以上であることを特徴とする（１）〜（６）のいずれかに記載の重金属固定剤。
（８）重金属が、飛灰中の重金属であることを特徴とする（１）〜（７）のいずれかに記載の重金属固定剤。
That is, this invention relates to the following heavy metal fixing agents.
(1) A heavy metal fixing agent containing a compound capable of fixing heavy metals, a dust prevention agent, and water, wherein the compound capable of fixing heavy metals and the dust prevention agent are dissolved in water. Heavy metal fixative.
(2) The heavy metal fixing agent according to (1), wherein the dust preventing agent is at least one selected from completely saponified polyvinyl alcohol and a cellulose derivative.
(3) The heavy metal fixing agent according to (1) or (2), wherein the completely saponified polyvinyl alcohol is a completely saponified polyvinyl alcohol having a hydrophilic group.
(4) The cellulose derivative is at least one selected from carboxymethylcellulose or a salt thereof, carboxymethylethylcellulose or a salt thereof, methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose. The heavy metal fixing agent according to any one of (1) to (3).
(5) The heavy metal fixing agent according to any one of (1) to (4), wherein the compound capable of fixing a heavy metal is dithiocarbamic acid or a salt thereof.
(6) The heavy metal fixing agent according to (5), wherein the dithiocarbamic acid or a salt thereof is a polyamine polydithiocarboxylic acid or a salt thereof.
(7) The heavy metal fixing agent according to any one of (1) to (6), wherein the pH of the heavy metal fixing agent is 8 or more.
(8) The heavy metal fixing agent according to any one of (1) to (7), wherein the heavy metal is a heavy metal in fly ash.
また本発明は、以下の飛灰中の重金属固定化方法に関する。
（９）飛灰に、水、並びに、重金属固定化能力のある化合物、粉塵防止剤、及び水を含有する重金属固定剤を添加して混練する飛灰中の重金属固定化方法であって、重金属固定化能力のある化合物、及び粉塵防止剤が水に溶解していることを特徴とする飛灰中の重金属固定化方法。
（１０）粉塵防止剤が、完全ケン化ポリビニルアルコール及びセルロース誘導体から選ばれる少なくとも１種であることを特徴とする（９）に記載の飛灰中の重金属固定化方法。
（１１）完全ケン化ポリビニルアルコールが、親水性基を有する完全ケン化ポリビニルアルコールであることを特徴とする（１０）に記載の飛灰中の重金属固定化方法。
（１２）セルロース誘導体が、カルボキシメチルセルロース又はその塩、カルボキシメチルエチルセルロース又はその塩、メチルセルロース、エチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、エチルヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、及びヒドロキシプロピルメチルセルロースから選ばれる少なくとも１種であることを特徴とする（１０）又は（１１）に記載の飛灰中の重金属固定化方法。
（１３）重金属固定化能力のある化合物が、ジチオカルバミン酸又はその塩であることを特徴とする（９）〜（１２）のいずれかに記載の飛灰中の重金属固定化方法。
（１４）ジチオカルバミン酸又はその塩が、ポリアミンポリジチオカルボン酸又はその塩であることを特徴とする（１３）に記載の飛灰中の重金属固定化方法。
（１５）重金属固定剤のｐＨが８以上であることを特徴とする（９）〜（１４）のいずれかに記載の飛灰中の重金属固定化方法。
Moreover, this invention relates to the heavy metal fixation method in the following fly ash.
(9) A method for immobilizing heavy metals in fly ash by adding water and a compound capable of immobilizing heavy metals and dust, a heavy metal fixing agent containing water, and kneading to fly ash, A method for immobilizing heavy metals in fly ash, wherein a compound having an immobilizing ability and a dust inhibitor are dissolved in water.
(10) The method for immobilizing heavy metals in fly ash according to (9), wherein the dust preventing agent is at least one selected from completely saponified polyvinyl alcohol and cellulose derivatives.
(11) The method for immobilizing heavy metals in fly ash according to (10), wherein the completely saponified polyvinyl alcohol is a completely saponified polyvinyl alcohol having a hydrophilic group.
(12) The cellulose derivative is at least one selected from carboxymethylcellulose or a salt thereof, carboxymethylethylcellulose or a salt thereof, methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose. (10) The heavy metal immobilization method in fly ash as described in (11) characterized by the above-mentioned.
(13) The method for immobilizing heavy metal in fly ash according to any one of (9) to (12), wherein the compound capable of immobilizing heavy metal is dithiocarbamic acid or a salt thereof.
(14) The method for immobilizing heavy metals in fly ash according to (13), wherein the dithiocarbamic acid or a salt thereof is polyamine polydithiocarboxylic acid or a salt thereof.
(15) The method for immobilizing heavy metal in fly ash according to any one of (9) to (14), wherein the pH of the heavy metal fixing agent is 8 or more.
以上述べたように、本発明の重金属固定剤を用いれば、飛灰の飛散を防止することができるとともに、飛灰中の重金属を確実に固定することができる。従って、１工程で有害物質の環境への放出を効果的に抑制することができるので、既存の設備をそのまま使用することができ、産業上の利用価値は高いといえる。 As described above, by using the heavy metal fixing agent of the present invention, it is possible to prevent the fly ash from being scattered and to reliably fix the heavy metal in the fly ash. Therefore, since the release of harmful substances into the environment can be effectively suppressed in one step, the existing equipment can be used as it is, and it can be said that the industrial utility value is high.
本発明の重金属固定剤に用いられる重金属固定化能力のある化合物としては、重金属と何らかの相互作用により重金属を水に不溶な形にできる化合物であって、かつ粉塵防止剤と共に水に溶解、好ましくは水に均一に溶解する化合物であれば特に限定されるものでなく、有機化合物であっても、無機化合物であってもかまわない。具体的には、苛性ソーダ等のアルカリ性物質；リン酸化合物；チオフェノール、エチルメルカプタン、メチルメルカプタン、低分子又は高分子有機ポリチオール化合物等の有機チオール化合物；一硫化ナトリウム、二硫化ナトリウム、三硫化ナトリウム、四硫化ナトリウム、五硫化ナトリウム等のポリ硫化ナトリウム、硫化水素ナトリウム等の硫化ナトリウム類；トリメルカプトトリアジン又はその塩類の少なくとも一種等の無機硫黄化合物；金属キレート化合物；などを例示することができ、特に、金属キレート化合物を好ましく例示することができる。 The compound having the ability to immobilize heavy metals used in the heavy metal fixing agent of the present invention is a compound capable of making heavy metals insoluble in water by some interaction with heavy metals, and is soluble in water together with dust prevention agents, preferably The compound is not particularly limited as long as it is a compound that dissolves uniformly in water, and may be an organic compound or an inorganic compound. Specifically, alkaline substances such as caustic soda; phosphoric acid compounds; organic thiol compounds such as thiophenol, ethyl mercaptan, methyl mercaptan, low molecular or high molecular organic polythiol compounds; sodium monosulfide, sodium disulfide, sodium trisulfide, Examples thereof include sodium polysulfides such as sodium tetrasulfide and sodium pentasulfide, sodium sulfides such as sodium hydrogen sulfide, inorganic sulfur compounds such as at least one kind of trimercaptotriazine or salts thereof, metal chelate compounds, and the like. A metal chelate compound can be preferably exemplified.
金属キレート化合物としては、重金属とキレートを形成できる官能基を有する化合物であれば特に限定されず、そのようなキレート形成基としては、グリシン基、β−アラニン基、イミノジ酢酸基等のアミノ酸基；ジチオカルバミン酸基、ジチオカルボン酸基、ポリアミノ基、チオウレイド基、ホスホメチルアミノ基、カルボン酸基などを例示することができ、特にジチオカルバミン酸基を好ましく例示することができる。また、金属キレート化合物が、水溶性であるのが好ましく、その場合、キレート形成基も親水性基であるのが好ましい。 The metal chelate compound is not particularly limited as long as it has a functional group capable of forming a chelate with a heavy metal. Examples of such chelate-forming groups include amino acid groups such as a glycine group, a β-alanine group, and an iminodiacetic acid group; A dithiocarbamic acid group, a dithiocarboxylic acid group, a polyamino group, a thioureido group, a phosphomethylamino group, a carboxylic acid group and the like can be exemplified, and a dithiocarbamic acid group can be particularly preferably exemplified. The metal chelate compound is preferably water-soluble, and in that case, the chelate-forming group is also preferably a hydrophilic group.
ジチオカルバミン酸基を有する金属キレート化合物を形成するアミンは、特に限定されず、低分子アミン化合物、高分子アミン化合物、１級アミン化合物、２級アミン化合物、モノアミン化合物、ポリアミン化合物いずれも使用することができる。そのようなアミン化合物として、具体的には、メチルアミン、ジメチルアミン、エチルアミン、ジエチルアミン、ｎ−ブチルアミン、ジ−（ｎ−ブチル）アミン、ピロリジン、ピペリジン、モルホリン、アニリン、１−ナフチルアミン、エチレンジアミン、プロピレンジアミン、ブチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、ジプロピレントリアミン、ジブチレントリアミン、トリエチレンテトラミン、トリプロピレンテトラミン、トリブチレンテトラミン、テトラエチレンペンタミン、テトラプロピレンペンタミン、テトラブチレンペンタミン、ペンタエチレンヘキサミン等のポリアルキレンポリアミン；フェニレンジアミン、ｏ−、ｍ−、ｐ−キシレンジアミン、イミノビスプロピルアミン、モノメチルアミノプロピルアミン、メチルイミノビスプロピルアミン、１，３−ビス（アミノメチル）シクロヘキサン、１，３−ジアミノプロパン、１，４−ジアミノブタン、３，５−ジアミノクロロベンゼン、メラミン、１−アミノエチルピペラジン、ピペラジン、３，３’−ジクロロベンジジン、ジアミノフェニルエーテル、トリジン、ｍ−トルイレンジアミン、ポリエチレンイミン、ポリプロピレンイミンなどを例示することができ、これらは１種単独で、また２種以上混合して用いることもできる。 The amine that forms the metal chelate compound having a dithiocarbamic acid group is not particularly limited, and any of low molecular amine compounds, high molecular amine compounds, primary amine compounds, secondary amine compounds, monoamine compounds, and polyamine compounds may be used. it can. Specific examples of such amine compounds include methylamine, dimethylamine, ethylamine, diethylamine, n-butylamine, di- (n-butyl) amine, pyrrolidine, piperidine, morpholine, aniline, 1-naphthylamine, ethylenediamine, and propylene. Diamine, Butylenediamine, Hexamethylenediamine, Diethylenetriamine, Dipropylenetriamine, Dibutylenetriamine, Triethylenetetramine, Tripropylenetetramine, Tributylenetetramine, Tetraethylenepentamine, Tetrapropylenepentamine, Tetrabutylenepentamine, Pentaethylenehexamine, etc. Polyalkylene polyamines: phenylenediamine, o-, m-, p-xylenediamine, iminobispropylamine, monomethylaminopropyl Pyramine, methyliminobispropylamine, 1,3-bis (aminomethyl) cyclohexane, 1,3-diaminopropane, 1,4-diaminobutane, 3,5-diaminochlorobenzene, melamine, 1-aminoethylpiperazine, piperazine, 3,3′-dichlorobenzidine, diaminophenyl ether, tolidine, m-toluylenediamine, polyethyleneimine, polypropyleneimine and the like can be exemplified, and these may be used alone or in combination of two or more. it can.
ポリエチレンイミン誘導体等の高分子ポリアミンとしては、平均分子量５０００以上、好ましくは平均分子量１００００〜２０００００、特に好ましくは平均分子量２００００〜１５００００であるのが好ましい。 The polymer polyamine such as a polyethyleneimine derivative preferably has an average molecular weight of 5000 or more, preferably an average molecular weight of 10,000 to 200,000, particularly preferably an average molecular weight of 20,000 to 150,000.
上記ポリアミン、ポリエチレンイミン（以下、ポリアミン、ポリエチレンイミンを総称してポリアミン類と呼ぶ場合がある。）はアルキル基、アシル基あるいはβ−ヒドロキシアルキル基をＮ−置換基として有していてもよい。上記Ｎ−置換アルキル基は炭素数２〜１８のものが好ましく、Ｎ−置換アシル基は炭素数２〜３０のものが好ましい。また、Ｎ−置換したβ−ヒドロキシアルキル基としては、アルキル基の炭素数が２〜３５のものが好ましい。 The polyamine and polyethyleneimine (hereinafter, polyamine and polyethyleneimine may be collectively referred to as polyamines) may have an alkyl group, an acyl group, or a β-hydroxyalkyl group as an N-substituent. The N-substituted alkyl group preferably has 2 to 18 carbon atoms, and the N-substituted acyl group preferably has 2 to 30 carbon atoms. The N-substituted β-hydroxyalkyl group is preferably an alkyl group having 2 to 35 carbon atoms.
上記したジチオカルバミン酸基を有する金属キレート化合物のうち、特に、ポリアミンポリジチオカルボン酸化合物を好ましく例示することができる。また、これらのジチオカルバミン酸化合物等金属キレート化合物は、そのままでも使用することができるが、アルカリ金属、アルカリ土類金属、アンモニア等のアミンとの塩として使用することもできる。 Of the above-described metal chelate compounds having a dithiocarbamic acid group, a polyamine polydithiocarboxylic acid compound can be preferably exemplified. These metal chelate compounds such as dithiocarbamic acid compounds can be used as they are, but can also be used as salts with amines such as alkali metals, alkaline earth metals and ammonia.
また、上記例示した重金属固定化能力のある化合物は、１種単独で、また２種以上混合して用いることができる。 Moreover, the compound which has the ability to fix heavy metals exemplified above can be used singly or in combination of two or more.
ここで、重金属とは、鉛、クロム、カドミウム、砒素、セレン，水銀、銅、亜鉛、アルミニウム等を例示する事ができる。 Here, examples of the heavy metal include lead, chromium, cadmium, arsenic, selenium, mercury, copper, zinc, and aluminum.
本発明に用いられる粉塵防止剤としては、粉塵の発生を抑制する効力のある薬剤であって、かつ重金属固定化能力のある化合物と共に水に溶解、好ましくは水に均一に溶解する化合物であれば特に制限されず、これら条件を満たす公知の粉塵防止剤を用いることができるが、ポリビニルアルコール及びセルロース誘導体から選ばれる少なくとも１種であるのが好ましい。上記ポリビニルアルコールとしては、さらに完全ケン化品のポリビニルアルコールが好ましい。完全ケン化品であれば、特に製造メーカーは限定されない。この場合、完全ケン化品とは、ケン化度が、９６．０％以上のものをいい、特に、ケン化度が９８％以上のものが好ましい。また、ケン化度が所定の値であれば、水酸基の置換基は、アセチル基に限定されず、シリル基、他のアシル基であってもよく、特に親水性基を有するものを好ましく例示することができる。親水性基は、水と親和性の高い官能基であれば特に限定されず、具体的には下記に示す官能基を例示することができる。 The dust preventing agent used in the present invention is a drug that is effective in suppressing the generation of dust and is a compound that dissolves in water together with a compound capable of fixing heavy metals, and preferably dissolves uniformly in water. Although it does not restrict | limit and can use the well-known dust prevention agent which satisfy | fills these conditions, It is preferable that it is at least 1 sort (s) chosen from polyvinyl alcohol and a cellulose derivative. The polyvinyl alcohol is more preferably a completely saponified polyvinyl alcohol. If it is a completely saponified product, the manufacturer is not particularly limited. In this case, the completely saponified product refers to those having a saponification degree of 96.0% or more, and particularly those having a saponification degree of 98% or more. Further, if the degree of saponification is a predetermined value, the substituent of the hydroxyl group is not limited to an acetyl group, and may be a silyl group or another acyl group, and particularly those having a hydrophilic group are preferably exemplified. be able to. A hydrophilic group will not be specifically limited if it is a functional group with high affinity with water, Specifically, the functional group shown below can be illustrated.
上記親水基は、ポリビニルアルコール中に、どのような形で含まれていても構わないが、ポリビニルアルコールのケン化された水酸基の一部に置換基として有するのが好ましい。 The hydrophilic group may be contained in any form in the polyvinyl alcohol, but it is preferable to have a part of the saponified hydroxyl group of the polyvinyl alcohol as a substituent.
また、重合度は特に限定されないが、飛散防止効果の点において、重合度が３００〜６０００のものが好ましく、重合度が４００〜４０００のものがより好ましく、重合度が１０００〜３０００のものが特に好ましい。 Further, the degree of polymerization is not particularly limited, but in terms of the scattering prevention effect, those having a polymerization degree of 300 to 6000 are preferable, those having a polymerization degree of 400 to 4000 are more preferable, and those having a polymerization degree of 1000 to 3000 are particularly preferable. preferable.
また、上記セルロース誘導体としては、水溶性セルロース誘導体であるのが好ましく、カルボキシメチルセルロース又はその塩、カルボキシメチルエチルセルロース又はその塩、メチルセルロース、エチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、エチルヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、及びヒドロキシプロピルメチルセルロース等を好ましく例示することができる。これらは１種単独又は混合物として使用することができる。これらの中でも、飛散防止効果の点で、カルボキシメチルセルロースの塩が好ましく、カルボキシメチルセルロースナトリウムがより好ましい。 The cellulose derivative is preferably a water-soluble cellulose derivative, such as carboxymethyl cellulose or a salt thereof, carboxymethyl ethyl cellulose or a salt thereof, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, and Hydroxypropyl methylcellulose and the like can be preferably exemplified. These can be used alone or as a mixture. Among these, the salt of carboxymethylcellulose is preferable and carboxymethylcellulose sodium is more preferable in terms of the scattering prevention effect.
また、セルロース誘導体の分子量は特に制限されないが、飛散防止効果の点において、分子量が、１×１０３〜１×１０７のものが好ましく、１×１０４〜５×１０６のものがより好ましく、２．５×１０４〜２×１０６のものが特に好ましい。 The molecular weight of the cellulose derivative is not particularly limited, but in terms of the scattering prevention effect, the molecular weight is preferably 1 × 10 3 to 1 × 10 7 , more preferably 1 × 10 4 to 5 × 10 6. 2.5 × 10 4 to 2 × 10 6 are particularly preferable.
また、セルロース誘導体のエーテル化度は特に制限されないが、飛散防止効果及び品質の安定性の面において、０．５〜２．６のものが好ましく、０．８〜２．３のものがより好ましく、１．０〜２．０のものが特に好ましい。ここでエーテル化度とは、セルロースのグルコース環単位当たり、アルコキシル基で置換された水酸基の平均個数を表す。 In addition, the degree of etherification of the cellulose derivative is not particularly limited, but in terms of scattering prevention effect and quality stability, 0.5 to 2.6 is preferable, and 0.8 to 2.3 is more preferable. 1.0 to 2.0 are particularly preferable. Here, the degree of etherification represents the average number of hydroxyl groups substituted with an alkoxyl group per glucose ring unit of cellulose.
その他の粉塵防止剤としては、特に限定されるわけではないが、アクリル酸、メタクリル酸、それらのエステル又はアクリルアミドを構成単位とするアクリル系重合体又はその加水分解物、並びにそれらの塩、キシリトール、ソルビトール、マルトール、マンニット、マルチトール、イノシトール、フィチン酸、等の糖アルコール、グリセリン、ジグリセリン、ジエチレングリコール、トリエチレングリコール、トリメチロールプロパン、プロピレングリコール、ジプロピレングリコール、グリセリン、ペンタエリスリトール、ソルビトール、ソルビタン、ポリエチレングリコール、ポリプロピレングリコール、ポルグリセリン等の多価アルコール、トウモロコシ、小麦、馬鈴薯、タピオカ、タロイモ、サツマイモ、米等の生デンプンや、これらのα化デンプン、デキストリン、酸化デンプン、アルデヒド化デンプン、エステル化デンプン、エーテル化デンプン、カチオン化デンプン、架橋デンプン等の変性デンプン、ノニオン界面活性剤、アニオン界面活性剤、カチオン界面活性剤、等の界面活性剤、セルソルブ、ブチルセルソルブ、ブチルセルソルブアセテート、ブチルカルビトール、ブチルテレフタレート、プルラン、アラビアガム、デキストラン、キサンタンガム、ポリビニルピロリドン、タマリンドガム、ファーセルラン、デンプングリコール酸ナトリウム、カラギーナン、ポリεカプロラクトン、ポリアミド、ポリアミン、ポリイミン、カゼイン、ガラクトマンナン、アルギン酸及びその塩、等を挙げることができる。 Other dust prevention agents are not particularly limited, but acrylic polymers having acrylic acid, methacrylic acid, esters or acrylamides thereof or hydrolysates thereof, and salts thereof, xylitol, Sugar alcohol such as sorbitol, maltol, mannitol, maltitol, inositol, phytic acid, glycerin, diglycerin, diethylene glycol, triethylene glycol, trimethylolpropane, propylene glycol, dipropylene glycol, glycerin, pentaerythritol, sorbitol, sorbitan , Polyalcohols such as polyethylene glycol, polypropylene glycol and porglycerin, raw starch such as corn, wheat, potato, tapioca, taro, sweet potato, rice, etc. Α-modified starch, dextrin, oxidized starch, aldehyde-modified starch, esterified starch, etherified starch, cationized starch, modified starch such as crosslinked starch, nonionic surfactant, anionic surfactant, cationic surfactant, etc. Surfactant, Cellsolve, Butylcellosolve, Butylcellosolve acetate, Butylcarbitol, Butylterephthalate, Pullulan, Gum arabic, Dextran, Xanthan gum, Polyvinylpyrrolidone, Tamarind gum, Farcellulan, Sodium starch glycolate, Carrageenan, Poly Examples include ε-caprolactone, polyamide, polyamine, polyimine, casein, galactomannan, alginic acid, and salts thereof.
本発明の重金属固定剤は、上記した重金属固定化能力のある化合物、粉塵防止剤、及び水を含有する重金属固定剤であって、重金属固定化能力のある化合物、及び粉塵防止剤が水に溶解していることを特徴とする。水に溶解しているとは、例えば、室温や使用時に有効成分である重金属固定化能力のある化合物、及び粉塵防止剤が水溶液中で溶解していることを意味し、完全に溶解しておらず、若干の析出物が存在する場合も本発明に含まれるが、使用時において、目詰まり等の問題の発生防止や、重金属固定能及び飛散防止効果の低下防止の点で均一に溶解していることが好ましい。 The heavy metal fixing agent of the present invention is a heavy metal fixing agent containing the above-mentioned compound capable of fixing a heavy metal, a dust prevention agent, and water, and the compound capable of fixing a heavy metal and the dust prevention agent are dissolved in water. It is characterized by that. The term "dissolved in water" means, for example, that a compound capable of immobilizing heavy metals, which is an active ingredient at room temperature or in use, and a dust prevention agent are dissolved in an aqueous solution. The present invention also includes a case where some precipitates are present, but in use, the precipitate is uniformly dissolved in terms of prevention of problems such as clogging and prevention of reduction of heavy metal fixing ability and scattering prevention effect. Preferably it is.
重金属固定化能力のある化合物と、粉塵防止剤の混合比は、重金属固定効果及び飛散防止効果が十分に得られれば特に限定されないが、飛灰の飛散を防止するとともに、飛灰中の重金属を確実に固定するため、重金属固定化能力のある化合物１００重量部に対して、粉塵防止剤が０．０１〜１００重量部、好ましくは０．０２〜５０重量部、より好ましくは０．０３〜２０重量部、特に好ましくは０．５〜１５重量部の範囲である。 The mixing ratio of the compound capable of immobilizing heavy metal and the dust prevention agent is not particularly limited as long as the effect of immobilizing heavy metal and the effect of preventing scattering are sufficiently obtained, while preventing the scattering of fly ash and reducing the heavy metal in the fly ash. In order to reliably fix the compound, the dust inhibitor is 0.01 to 100 parts by weight, preferably 0.02 to 50 parts by weight, more preferably 0.03 to 20 parts by weight based on 100 parts by weight of the compound capable of fixing heavy metals. Part by weight, particularly preferably in the range of 0.5 to 15 parts by weight.
また、本発明の重金属固定剤は、ｐＨ８以上、さらにはｐＨ１０以上、中でもｐＨ１２以上で用いるのが好ましい。ｐＨ８以上では、重金属固定能力及び保存安定性が向上する。このｐＨ領域で粉塵防止剤を用いる場合、粉塵防止剤として、完全ケン化ポリビニルアルコール又はセルロース誘導体を用いると、水溶液中で均一に溶解しやすく、飛散防止効果に優れる点で好ましい。また、飛散防止効果も、重金属固定剤と共に水溶液として併用することにより向上する場合がある。 The heavy metal fixing agent of the present invention is preferably used at a pH of 8 or more, more preferably a pH of 10 or more, especially a pH of 12 or more. Above pH 8, the heavy metal fixing ability and storage stability are improved. When using a dust preventive agent in this pH range, it is preferable to use completely saponified polyvinyl alcohol or a cellulose derivative as the dust preventive agent in that it easily dissolves uniformly in an aqueous solution and has an excellent scattering prevention effect. Further, the scattering prevention effect may be improved by using it together with the heavy metal fixing agent as an aqueous solution.
また、本発明の重金属固定剤の粘度は、２０℃で１０〜１０００ＣＰＳであることが好ましく、２０〜６００ＣＰＳであることがより好ましく、２５〜３００ＣＰＳであることが特に好ましい。 Moreover, the viscosity of the heavy metal fixing agent of the present invention is preferably 10 to 1000 CPS, more preferably 20 to 600 CPS, and particularly preferably 25 to 300 CPS at 20 ° C.
本発明の重金属固定剤の水溶液中の重金属固定化能力のある化合物、及び粉塵防止剤の固形分濃度は特に限定されないが、１０〜８０重量％の範囲が好ましく、２０〜７０％の範囲がより好ましく、３０〜６０％の範囲が特に好ましい。 The solid metal concentration in the aqueous solution of the heavy metal fixing agent of the present invention and the solid content concentration of the dust prevention agent is not particularly limited, but is preferably in the range of 10 to 80% by weight, more preferably in the range of 20 to 70%. A range of 30 to 60% is particularly preferable.
本発明の重金属固定剤は、重金属を含有する固体状物質に対して使用することで重金属を固定するとともに、飛散防止効果をも有する。かかる重金属を含有する固体状物質としては、具体的には、焼却灰、鉱滓、土壌、汚泥等を好ましく例示することができる。焼却灰とは、飛灰と残灰とがあり、飛灰はゴミや産業廃棄物等の焼却に伴って発生する粉状の煤塵や、残灰処理における熔融炉から発生する煤塵を集塵したものであり、集塵方法により以下のように分類される。最も広く利用されている電気集塵法（ＥＰ法ともいう。）により集塵された飛灰をＥＰ灰という。次に多い集塵法は遠心集塵法（サイクロン法）で、特にサイクロンを並列にして用いるマルチサイクロン法（ＭＣ法ともいう。）により集塵された飛灰をＭＣ灰という。また洗浄集塵法（スクラバー法）による集塵灰、バッグフィルターを用いて集塵した集塵灰等である。これらの集塵法は単独の場合もあるが、２つの方法を併用することもあり（例えばＭＣ法とＥＰ法等）、本発明の重金属固定剤は、このようにして得られた飛灰も対象とすることができる。一方、残灰は、ゴミ焼却場及び産業廃棄物の焼却場等で、焼却後、焼却炉の残る灰であり、有害な重金属を含むものが対象となる。これらのなかでも、本発明の重金属固定剤は、焼却灰に対して好ましく用いることができる。 The heavy metal fixing agent of the present invention is used for a solid substance containing a heavy metal to fix the heavy metal and also has a scattering prevention effect. Specific examples of such solid substances containing heavy metals include incinerated ash, slag, soil, and sludge. Incinerated ash includes fly ash and residual ash. Fly ash collects powdered dust generated from incineration of garbage and industrial waste, and dust generated from melting furnaces in residual ash treatment. It is classified as follows according to the dust collection method. Fly ash collected by the most widely used electric dust collection method (also called EP method) is called EP ash. The next most dust collection method is centrifugal dust collection method (cyclone method). In particular, fly ash collected by multi-cyclone method (also called MC method) using cyclones in parallel is called MC ash. Also, dust collection ash obtained by a cleaning dust collection method (scrubber method), dust collection ash collected using a bag filter, and the like. These dust collection methods may be used alone, or two methods may be used in combination (for example, the MC method and the EP method), and the heavy metal fixing agent of the present invention is not limited to the fly ash thus obtained. Can be targeted. On the other hand, residual ash is ash that remains in an incinerator after incineration at garbage incinerators and industrial waste incinerators, and includes toxic heavy metals. Among these, the heavy metal fixing agent of the present invention can be preferably used for incineration ash.
本発明では、上記重金属固定剤を重金属を含有する固体状物質の表面に散布するだけでもよいが、重金属を含有する固体状物質に添加して混合及び／又は混練することが好ましい。この際、混合及び／又は混練作業を容易とするために、更に水を添加しても良い。 In the present invention, the heavy metal fixing agent may be merely sprayed on the surface of the solid substance containing heavy metal, but it is preferable to add and mix and / or knead the solid metal containing heavy metal. At this time, water may be further added to facilitate mixing and / or kneading.
以下、本発明を、実施例を用いて詳細に説明するが、本発明の範囲は、実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, the scope of the present invention is not limited to an Example.
（１）重金属固定剤の調製−１
ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０％、ｐＨ＝１２以上）と、完全ケン化ポリビニルアルコール（ＨＰ−Ｈ１０５、重合度５００、分子量２万２千、ケン化度９７．５〜９９．０％、クラレ（株）社製）をそれぞれ７．５重量％、１０．０重量％、１２．５重量％、１５．０重量％に調整した水溶液とを、重量比で１：１となるように混合して、重金属固定剤（Ｎｏ１〜４）を調製した。その外観をまとめて表１に示す。
（２）重金属固定剤の調製−２
ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０％、ｐＨ＝１２以上）と、完全ケン化ポリビニルアルコール（ＡＦ−１７、重合度１７００、ケン化度９８．０％、日本酢ビ・ポバール（株）社製）を７．５重量％に調整した水溶液とを重量比で１：１となるように混合して、重金属固定剤（Ｎｏ５）を調製し３日間放置したのち、その外観を観察した。その結果をまとめて表１に示す。
(1) Preparation of heavy metal fixing agent-1
Piperazine-N, N′-biscarbodithioic acid potassium salt aqueous solution (solid content 40%, pH = 12 or more) and completely saponified polyvinyl alcohol (HP-H105, polymerization degree 500, molecular weight 22,000, Ken An aqueous solution with a degree of conversion of 97.5 to 99.0%, manufactured by Kuraray Co., Ltd.) adjusted to 7.5% by weight, 10.0% by weight, 12.5% by weight, and 15.0% by weight, It mixed so that it might become 1: 1 by weight ratio, and the heavy metal fixing agent (No1-4) was prepared. The appearance is summarized in Table 1.
(2) Preparation of heavy metal fixing agent-2
Piperazine-N, N′-biscarbodithioic acid potassium salt aqueous solution (solid content 40%, pH = 12 or more) and completely saponified polyvinyl alcohol (AF-17, polymerization degree 1700, saponification degree 98.0%) , Manufactured by Nippon Vinegar Poval Co., Ltd.) to an aqueous solution adjusted to 7.5% by weight so as to have a weight ratio of 1: 1 to prepare a heavy metal fixing agent (No. 5) and leave it for 3 days After that, the appearance was observed. The results are summarized in Table 1.
ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０％、ｐＨ＝１２以上）と、完全ケン化ポリビニルアルコール（ＡＦ−１７、重合度１７００、ケン化度９８．０％、日本酢ビ・ポバール（株）社製）を７．５重量％含有する水溶液とを重量比３：１で混合して重金属固定剤Ｎｏ６を調製した。消石灰により前処理されｐＨが１２以上であるアルカリ性鉛含有ごみ焼却飛灰（Ｐｂ含有量：５６００ｍｇ／ｋｇ）１００重量部に対して、室温にて、水４４重量部、重金属固定剤Ｎｏ６：４重量部を添加し、ポバートミキサーで十分に混練し、２５℃で１日放置した。その後、環境庁告示第１３号により、鉛の溶出試験を行った。その結果、鉛の溶出量は、０．０２ｍｇ／Ｌであった。また、完全ケン化ポリビニルアルコールを用いない重金属固定剤３重量部を用いる以外、同様に行い、鉛の溶出試験を行った。その結果、０．０４ｍｇ／Ｌであった。この結果、完全ケン化ポリビニルアルコールを用いることにより、重金属固定能力に影響がないことがわかった。 Piperazine-N, N′-biscarbodithioic acid potassium salt aqueous solution (solid content 40%, pH = 12 or more) and completely saponified polyvinyl alcohol (AF-17, polymerization degree 1700, saponification degree 98.0%) A heavy metal fixing agent No6 was prepared by mixing an aqueous solution containing 7.5% by weight of Nihon Vinegar & Poval Co., Ltd. in a weight ratio of 3: 1. Alkaline lead-containing waste incineration fly ash (Pb content: 5600 mg / kg) pretreated with slaked lime and having a pH of 12 or more, 100 parts by weight of water at room temperature, 44 parts by weight, heavy metal fixing agent No 6: 4 weights Part was added, kneaded thoroughly with a Pobert mixer, and allowed to stand at 25 ° C. for 1 day. Thereafter, a lead elution test was conducted according to Notification No. 13 of the Environment Agency. As a result, the elution amount of lead was 0.02 mg / L. Further, a lead elution test was conducted in the same manner except that 3 parts by weight of a heavy metal fixing agent not using completely saponified polyvinyl alcohol was used. As a result, it was 0.04 mg / L. As a result, it was found that the use of completely saponified polyvinyl alcohol has no effect on the ability to fix heavy metals.
消石灰により前処理されｐＨが１２以上であるアルカリ性鉛含有ごみ焼却飛灰（Ｐｂ含有量：５６００ｍｇ／ｋｇ）１００重量部に対して、室温にて、水３０重量部、及びピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０％、ｐＨ１２以上）と、表２に示す濃度及び種類の完全ケン化ポリビニルアルコールとを重量比３：１で混合して調製した重金属固定剤４重量部を添加し、ポバートミキサーで十分に混練した。その後、６０℃で２４時間加熱乾燥した。乾燥したものを粉砕し、メッシュ径が２ｍｍの篩で分級し、粒径が２ｍｍ以下のものを試験試料とした。 100 parts by weight of alkaline lead-containing waste incineration fly ash (Pb content: 5600 mg / kg) pretreated with slaked lime and having a pH of 12 or more, at room temperature, 30 parts by weight of water and piperazine-N, N ′ -Heavy metal fixing agent prepared by mixing aqueous solution of potassium biscarbodithioate (solid content 40%, pH 12 or more) and fully saponified polyvinyl alcohol of the concentration and type shown in Table 2 at a weight ratio of 3: 1. 4 parts by weight were added and kneaded thoroughly with a Pobert mixer. Then, it heat-dried at 60 degreeC for 24 hours. The dried product was pulverized, classified with a sieve having a mesh diameter of 2 mm, and a test sample having a particle size of 2 mm or less was used.
図１に示す分散度測定装置（ホソカワミクロン株式会社製：パウダテスタ）を用い、分散度を測定した。測定装置は、上下方向に同軸上に配置された上部ホッパー部１（内径５０ｍｍ）、ガラス円筒部２（内径１００ｍｍ、長さ３４０ｍｍ）及び円盤状ガラス板３（直径１００ｍｍ）からなる。 The dispersity was measured using the dispersity measuring apparatus (Hosokawa Micron Corporation: Powder Tester) shown in FIG. The measuring device is composed of an upper hopper portion 1 (inner diameter 50 mm), a glass cylindrical portion 2 (inner diameter 100 mm, length 340 mm) and a disk-shaped glass plate 3 (diameter 100 mm) arranged coaxially in the vertical direction.
上記調製した試験試料１０ｇを上部ホッパー部１からガラス円筒部２の頂部開口に自然落下させ、ガラス円筒部２の底部開口部から円盤状ガラス板３の上に落下した試料の重量を未飛散試料重量として測定し、下記計算式により分散度をもとめた。同一の試料につき５回測定を行い、最大と最小の値を除いた３回の値の平均値を分散度とした。その結果を表２にまとめて示す。尚、分散度の値が小さいほど、粉塵防止効果が大きいことを示す。 10 g of the prepared test sample is naturally dropped from the upper hopper portion 1 to the top opening of the glass cylindrical portion 2, and the weight of the sample dropped on the disk-shaped glass plate 3 from the bottom opening portion of the glass cylindrical portion 2 is unscattered sample. It measured as a weight and calculated | required dispersion degree with the following formula. The same sample was measured 5 times, and the average of 3 values excluding the maximum and minimum values was defined as the degree of dispersion. The results are summarized in Table 2. In addition, it shows that a dust prevention effect is so large that the value of dispersion degree is small.
完全ケン化ポリビニルアルコールを用いない以外は、実施例４と同様に試験試料を調製し、同様の方法で分散度を求めた。その結果を表２に示す。
A test sample was prepared in the same manner as in Example 4 except that completely saponified polyvinyl alcohol was not used, and the degree of dispersion was determined in the same manner. The results are shown in Table 2.
（３）重金属固定剤の調製−３
ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０％、ｐＨ＝１２以上）に、ヒドロキシプロピルセルロースの１％水溶液（品名：ＨＰＣ−Ｈ、日本曹達（株）社製）、２％水溶液（品名：ＨＰＣ−Ｍ、日本曹達（株）社製）、５％水溶液（品名：ＨＰＣ−Ｌ、日本曹達（株）社製）又は１０％水溶液（品名：ＨＰＣ−ＳＬ、日本曹達（株）社製）のいずれかを、重量比で１：１となるように混合して重金属固定剤（Ｎｏ７〜１０）を調製した。その外観をまとめて表３に示す。
(3) Preparation of heavy metal fixing agent-3
Piperazine-N, N′-biscarbodithioic acid potassium salt aqueous solution (solid content: 40%, pH = 12 or more) and 1% aqueous solution of hydroxypropyl cellulose (product name: HPC-H, manufactured by Nippon Soda Co., Ltd.) ) 2% aqueous solution (product name: HPC-M, manufactured by Nippon Soda Co., Ltd.), 5% aqueous solution (product name: HPC-L, manufactured by Nippon Soda Co., Ltd.) or 10% aqueous solution (product name: HPC-SL, A heavy metal fixing agent (No. 7 to 10) was prepared by mixing any one of Nippon Soda Co., Ltd.) at a weight ratio of 1: 1. The appearance is summarized in Table 3.
消石灰により前処理されｐＨが１２以上であるアルカリ性鉛含有ごみ焼却飛灰（Ｐｂ含有量：５６００ｍｇ／ｋｇ）１００重量部に対して、室温にて、水４４重量部、実施例５で調製した重金属固定剤（Ｎｏ７〜１０）４重量部を添加し、ポバートミキサーで十分に混練し、２５℃で１日放置した。その後、環境庁告示第１３号により、鉛の溶出試験を行った。その結果、鉛の溶出量は、それぞれ、Ｎｏ９添加：２２ｍｇ／Ｌ、Ｎｏ１０添加：２０ｍｇ／Ｌ、Ｎｏ１１添加：２１ｍｇ／Ｌ、Ｎｏ１２添加：２０ｍｇ／Ｌであった。また、ヒドロキシプロピルセルロースを用いない重金属固定剤２重量部を用いる以外、同様に行い、鉛の溶出試験を行った。その結果、２０ｍｇ／Ｌであった。この結果、ヒドロキシプロピルセルロースを用いることにより、重金属固定能力に影響がないことがわかった。 Heavy metal prepared in Example 5, 44 parts by weight of water at room temperature with respect to 100 parts by weight of alkaline lead-containing waste incineration fly ash (Pb content: 5600 mg / kg) pretreated with slaked lime and having a pH of 12 or more 4 parts by weight of a fixing agent (No. 7 to 10) was added, kneaded sufficiently with a Pobart mixer, and allowed to stand at 25 ° C. for 1 day. Thereafter, a lead elution test was conducted according to Notification No. 13 of the Environment Agency. As a result, the elution amounts of lead were No9 addition: 22 mg / L, No10 addition: 20 mg / L, No11 addition: 21 mg / L, and No12 addition: 20 mg / L, respectively. Further, a lead elution test was conducted in the same manner except that 2 parts by weight of a heavy metal fixing agent not using hydroxypropylcellulose was used. As a result, it was 20 mg / L. As a result, it was found that the use of hydroxypropylcellulose has no influence on the ability to fix heavy metals.
消石灰により前処理されｐＨが１２以上であるアルカリ性鉛含有ごみ焼却飛灰（Ｐｂ含有量：５６００ｍｇ／ｋｇ）１００重量部に対して、室温にて、水３０重量部；ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０％、ｐＨ１２以上）を３重量部と、ヒドロキシプロピルセルロースの１％水溶液（品名：ＨＰＣ−Ｈ、日本曹達（株）社製）、２％水溶液（品名：ＨＰＣ−Ｍ、日本曹達（株）社製）、５％水溶液（品名：ＨＰＣ−Ｌ、日本曹達（株）社製）又は１０％水溶液（品名：ＨＰＣ−ＳＬ、日本曹達（株）社製）のいずれか１重量部を、あらかじめ均一に混合した重金属固定剤（Ｎｏ１１〜Ｎｏ１４）４重量部；を添加し、ポバートミキサーで十分に混練した。その後、６０℃で２４時間加熱乾燥した。乾燥したものを粉砕し、メッシュ径が２ｍｍの篩で分級し、粒径が２ｍｍ以下のものを試験試料とした。 100 parts by weight of alkaline lead-containing waste incineration fly ash (Pb content: 5600 mg / kg) pretreated with slaked lime and having a pH of 12 or more, at room temperature, 30 parts by weight of water; piperazine-N, N′- 3 parts by weight of a biscarbodithioic acid potassium salt aqueous solution (solid content 40%, pH 12 or more) and a 1% aqueous solution of hydroxypropylcellulose (product name: HPC-H, Nippon Soda Co., Ltd.), 2% aqueous solution (Product name: HPC-M, manufactured by Nippon Soda Co., Ltd.), 5% aqueous solution (Product name: HPC-L, manufactured by Nippon Soda Co., Ltd.) or 10% aqueous solution (Product name: HPC-SL, Nippon Soda Co., Ltd.) 4 parts by weight of a heavy metal fixing agent (No. 11 to No. 14), which was uniformly mixed beforehand, was added and kneaded sufficiently with a Pobert mixer. Then, it heat-dried at 60 degreeC for 24 hours. The dried product was pulverized, classified with a sieve having a mesh diameter of 2 mm, and a test sample having a particle size of 2 mm or less was used.
実施例３と同様にして分散度を測定した。その結果を表４に示す。
比較例２
ヒドロキシプロピルセルロースを用いない以外は、実施例６と同様に試験試料を調製し、同様の方法で分散度を求めた。その結果を表４に示す。
The dispersity was measured in the same manner as in Example 3. The results are shown in Table 4.
Comparative Example 2
A test sample was prepared in the same manner as in Example 6 except that hydroxypropylcellulose was not used, and the degree of dispersion was determined in the same manner. The results are shown in Table 4.
（４）重金属固定剤の調製−４
ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０％、ｐＨ＝１２以上）に、カルボキシメチルセルロースナトリウムの２％水溶液（品名：ＣＭＣ＜１３３０＞、ダイセル化学工業（株）社製）、１％水溶液（品名：ＣＭＣ＜１３５０＞、分子量７６万、ダイセル化学工業（株）社製）、０．５％水溶液（品名：ＣＭＣ＜１３８０＞、分子量１１０万、ダイセル化学工業（株）社製）又は１．５％水溶液（品名：ＣＭＣ＜アーネストガム＞、ダイセル化学工業（株）社製）のいずれかを、重量比で１：１となるように混合して重金属固定剤（Ｎｏ１５〜１８）を調製した。その外観をまとめて表５に示す。
(4) Preparation of heavy metal fixing agent-4
Piperazine-N, N′-biscarbodithioic acid potassium salt aqueous solution (solid content 40%, pH = 12 or more), 2% aqueous solution of sodium carboxymethylcellulose (product name: CMC <1330>, Daicel Chemical Industries, Ltd.) 1% aqueous solution (product name: CMC <1350>, molecular weight 760,000, manufactured by Daicel Chemical Industries, Ltd.), 0.5% aqueous solution (product name: CMC <1380>, molecular weight 1.1 million, Daicel Chemical Industries ( Co., Ltd.) or 1.5% aqueous solution (product name: CMC <Ernest Gum>, manufactured by Daicel Chemical Industries, Ltd.) is mixed so as to have a weight ratio of 1: 1 to a heavy metal fixing agent. (No. 15 to 18) were prepared. The appearance is summarized in Table 5.
消石灰により前処理されｐＨが１２以上であるアルカリ性鉛含有ごみ焼却飛灰（Ｐｂ含有量：５６００ｍｇ／ｋｇ）１００重量部に対して、室温にて、水３０重量部；ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０％、ｐＨ１２以上）を３重量部と、カルボキシメチルセルロースナトリウムの２％水溶液（品名：ＣＭＣ＜１３３０＞、ダイセル化学工業（株）社製）、１％水溶液（品名：ＣＭＣ＜１３５０＞、分子量７６万、ダイセル化学工業（株）社製）、０．５％水溶液（品名：ＣＭＣ＜１３８０＞、分子量１１０万、ダイセル化学工業（株）社製）又は１．５％水溶液（品名：ＣＭＣ＜アーネストガム＞、ダイセル化学工業（株）社製）のいずれか１重量部を、あらかじめ均一に混合した重金属固定剤（Ｎｏ１９〜Ｎｏ２２）４重量部；を添加し、ポバートミキサーで十分に混練した。その後、６０℃で２４時間加熱乾燥した。乾燥したものを粉砕し、メッシュ径が２ｍｍの篩で分級し、粒径が２ｍｍ以下のものを試験試料とした。 100 parts by weight of alkaline lead-containing waste incineration fly ash (Pb content: 5600 mg / kg) pretreated with slaked lime and having a pH of 12 or more, at room temperature, 30 parts by weight of water; piperazine-N, N′- 3 parts by weight of an aqueous solution of potassium biscarbodithioate (solid content 40%, pH 12 or more) and a 2% aqueous solution of sodium carboxymethylcellulose (product name: CMC <1330>, manufactured by Daicel Chemical Industries, Ltd.), 1 % Aqueous solution (product name: CMC <1350>, molecular weight 760,000, manufactured by Daicel Chemical Industries, Ltd.), 0.5% aqueous solution (product name: CMC <1380>, molecular weight 1.1 million, manufactured by Daicel Chemical Industries, Ltd.) Alternatively, heavy metal fixing in which any one part by weight of a 1.5% aqueous solution (product name: CMC <Ernest Gum>, manufactured by Daicel Chemical Industries, Ltd.) is uniformly mixed in advance. (No19~No22) 4 parts by weight; was added and sufficiently kneaded in Po Bad mixer. Then, it heat-dried at 60 degreeC for 24 hours. The dried product was pulverized, classified with a sieve having a mesh diameter of 2 mm, and a test sample having a particle size of 2 mm or less was used.
実施例３と同様にして分散度を測定した。その結果を表６に示す。
比較例３
カルボキシメチルセルロースナトリウムを用いない以外は、実施例８と同様に試験試料を調製し、同様の方法で分散度を求めた。その結果を表６に示す。
The dispersity was measured in the same manner as in Example 3. The results are shown in Table 6.
Comparative Example 3
A test sample was prepared in the same manner as in Example 8 except that sodium carboxymethylcellulose was not used, and the degree of dispersion was determined in the same manner. The results are shown in Table 6.
（５）重金属固定剤の調製−５
ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０％、ｐＨ＝１２以上）に、ヒドロキシエチルセルロースの３％水溶液（品名：ＨＥＣ（ＳＰ−４００）、ダイセル化学工業（株）社製）、１％水溶液（品名：ＨＥＣ（ＳＰ−６００）、ダイセル化学工業（株）社製）、０．５％水溶液（品名：ＨＥＣ（ＳＰ−９００）、ダイセル化学工業（株）社製）又はカチオン化ヒドロキシエチルセルロースの２％水溶液（品名：ジェルナー（ＱＨ３００）、ダイセル化学工業（株）社製）のいずれかを、重量比で１：１となるように混合して重金属固定剤（Ｎｏ２３〜２６）を調製した。その外観をまとめて表７に示す。
(5) Preparation of heavy metal fixing agent-5
Piperazine-N, N′-biscarbodithioic acid potassium salt aqueous solution (solid content 40%, pH = 12 or more), hydroxyethylcellulose 3% aqueous solution (product name: HEC (SP-400), Daicel Chemical Industries, Ltd. 1% aqueous solution (product name: HEC (SP-600), manufactured by Daicel Chemical Industries, Ltd.), 0.5% aqueous solution (product name: HEC (SP-900), Daicel Chemical Industries, Ltd.) Or a 2% aqueous solution of cationized hydroxyethyl cellulose (product name: Gerner (QH300), manufactured by Daicel Chemical Industries, Ltd.) is mixed to a weight ratio of 1: 1 to obtain a heavy metal fixing agent ( No. 23-26) were prepared. The appearance is summarized in Table 7.
消石灰により前処理されｐＨが１２以上であるアルカリ性鉛含有ごみ焼却飛灰（Ｐｂ含有量：５６００ｍｇ／ｋｇ）１００重量部に対して、室温にて、水３０重量部；ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０％、ｐＨ１２以上）を３重量部と、ヒドロキシエチルセルロースの３％水溶液（品名：ＨＥＣ（ＳＰ−４００）、ダイセル化学工業（株）社製）、１％水溶液（品名：ＨＥＣ（ＳＰ−６００）、ダイセル化学工業（株）社製）、０．５％水溶液（品名：ＨＥＣ（ＳＰ−９００）、ダイセル化学工業（株）社製）又はカチオン化ヒドロキシエチルセルロースの２％水溶液（品名：ジェルナー（ＱＨ３００）、ダイセル化学工業（株）社製）のいずれか１重量部を、あらかじめ均一に混合した重金属固定剤（Ｎｏ２７〜Ｎｏ３０）４重量部；を添加し、ポバートミキサーで十分に混練した。その後、６０℃で２４時間加熱乾燥した。乾燥したものを粉砕し、メッシュ径が２ｍｍの篩で分級し、粒径が２ｍｍ以下のものを試験試料とした。 100 parts by weight of alkaline lead-containing waste incineration fly ash (Pb content: 5600 mg / kg) pretreated with slaked lime and having a pH of 12 or more, at room temperature, 30 parts by weight of water; piperazine-N, N′- 3 parts by weight of a biscarbodithioic acid potassium salt aqueous solution (solid content 40%, pH 12 or more), a 3% aqueous solution of hydroxyethyl cellulose (product name: HEC (SP-400), manufactured by Daicel Chemical Industries, Ltd.), 1% aqueous solution (product name: HEC (SP-600), manufactured by Daicel Chemical Industries, Ltd.), 0.5% aqueous solution (product name: HEC (SP-900), manufactured by Daicel Chemical Industries, Ltd.) or cationization Heavy metal in which one part by weight of a 2% aqueous solution of hydroxyethyl cellulose (product name: Gerner (QH300), manufactured by Daicel Chemical Industries, Ltd.) is uniformly mixed in advance. Fixative (No27~No30) 4 parts by weight; was added and sufficiently kneaded in Po Bad mixer. Then, it heat-dried at 60 degreeC for 24 hours. The dried product was pulverized, classified with a sieve having a mesh diameter of 2 mm, and a test sample having a particle size of 2 mm or less was used.
実施例３と同様にして分散度を測定した。その結果を表８に示す。
比較例４
ヒドロキシエチルセルロースを用いない以外は、実施例１０と同様に試験試料を調製し、同様の方法で分散度を求めた。その結果を表８に示す。
The dispersity was measured in the same manner as in Example 3. The results are shown in Table 8.
Comparative Example 4
A test sample was prepared in the same manner as in Example 10 except that hydroxyethyl cellulose was not used, and the degree of dispersion was determined in the same manner. The results are shown in Table 8.
（６）重金属固定剤の調製−６
ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０％、ｐＨ＝１２以上）に、メチルセルロースの２％水溶液（品名：ＭＣ（ＳＭ−４００）、信越化学工業（株）社製）、ヒドロキシプロピルメチルセルロースの４％水溶液（品名：ＨＰＭＣ（６５ＳＨ−５０）、信越化学工業（株）社製）、２％水溶液（品名：ＨＰＭＣ（６５ＳＨ−４００）、信越化学工業（株）社製）、１％水溶液（品名：ＨＰＭＣ（６５ＳＨ−４０００）、信越化学工業（株）社製）又は１％水溶液（品名：ＨＰＭＣ（６０ＳＨ−４０００）、信越化学工業（株）社製）のいずれかを、重量比で１：１となるように混合して重金属固定剤（Ｎｏ３１〜３５）を調製した。その外観をまとめて表９に示す。
(6) Preparation of heavy metal fixing agent-6
Piperazine-N, N′-biscarbodithioic acid potassium salt aqueous solution (solid content 40%, pH = 12 or more), methylcellulose 2% aqueous solution (product name: MC (SM-400), Shin-Etsu Chemical Co., Ltd.) 4% aqueous solution (product name: HPMC (65SH-50), manufactured by Shin-Etsu Chemical Co., Ltd.), 2% aqueous solution (product name: HPMC (65SH-400), Shin-Etsu Chemical Co., Ltd.) 1% aqueous solution (product name: HPMC (65SH-4000), manufactured by Shin-Etsu Chemical Co., Ltd.) or 1% aqueous solution (product name: HPMC (60SH-4000), manufactured by Shin-Etsu Chemical Co., Ltd.) Any of these were mixed so as to have a weight ratio of 1: 1 to prepare a heavy metal fixing agent (No. 31 to 35). The appearance is summarized in Table 9.
消石灰により前処理されｐＨが１２以上であるアルカリ性鉛含有ごみ焼却飛灰（Ｐｂ含有量：５６００ｍｇ／ｋｇ）１００重量部に対して、室温にて、水３０重量部；ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０％、ｐＨ１２以上）を３重量部と、メチルセルロースの２％水溶液（品名：ＭＣ（ＳＭ−４００）、信越化学工業（株）社製）、ヒドロキシプロピルメチルセルロース４％水溶液（品名：ＨＰＭＣ（６５ＳＨ−５０）、信越化学工業（株）社製）、２％水溶液（品名：ＨＰＭＣ（６５ＳＨ−４００）、信越化学工業（株）社製）、１％水溶液（品名：ＨＰＭＣ（６５ＳＨ−４０００）、信越化学工業（株）社製）又は１％水溶液（品名：ＨＰＭＣ（６０ＳＨ−４０００）、信越化学工業（株）社製）のいずれか１重量部を、あらかじめ均一に混合した重金属固定剤（Ｎｏ３６〜Ｎｏ４０）４重量部；を添加し、ポバートミキサーで十分に混練した。その後、６０℃で２４時間加熱乾燥した。乾燥したものを粉砕し、メッシュ径が２ｍｍの篩で分級し、粒径が２ｍｍ以下のものを試験試料とした。 100 parts by weight of alkaline lead-containing waste incineration fly ash (Pb content: 5600 mg / kg) pretreated with slaked lime and having a pH of 12 or more, at room temperature, 30 parts by weight of water; piperazine-N, N′- 3 parts by weight of an aqueous solution of potassium biscarbodithioate (solid content 40%, pH 12 or more), a 2% aqueous solution of methylcellulose (product name: MC (SM-400), manufactured by Shin-Etsu Chemical Co., Ltd.), hydroxy Propylmethylcellulose 4% aqueous solution (product name: HPMC (65SH-50), manufactured by Shin-Etsu Chemical Co., Ltd.), 2% aqueous solution (product name: HPMC (65SH-400), manufactured by Shin-Etsu Chemical Co., Ltd.), 1% Aqueous solution (product name: HPMC (65SH-4000), manufactured by Shin-Etsu Chemical Co., Ltd.) or 1% aqueous solution (product name: HPMC (60SH-4000), Shin-Etsu Chemical Co., Ltd.) Any 1 part by weight of Ltd.), previously homogeneously mixed heavy metal fixatives (No36~No40) 4 parts by weight; was added and sufficiently kneaded in Po Bad mixer. Then, it heat-dried at 60 degreeC for 24 hours. The dried product was pulverized, classified with a sieve having a mesh diameter of 2 mm, and a test sample having a particle size of 2 mm or less was used.
実施例３と同様にして分散度を測定した。その結果を表１０に示す。
比較例５
セルロース誘導体を用いない以外は、実施例１２と同様に試験試料を調製し、同様の方法で分散度を求めた。その結果を表１０に示す。
The dispersity was measured in the same manner as in Example 3. The results are shown in Table 10.
Comparative Example 5
A test sample was prepared in the same manner as in Example 12 except that the cellulose derivative was not used, and the degree of dispersion was determined in the same manner. The results are shown in Table 10.
消石灰により前処理されｐＨが１２以上であるアルカリ性鉛含有ごみ焼却飛灰（Ｐｂ含有量：５６００ｍｇ／ｋｇ）１００重量部に対して、室温にて、水４４重量部、実施例７、９、１１で調製した重金属固定剤（Ｎｏ１６、Ｎｏ１８、Ｎｏ２５、Ｎｏ２６、Ｎｏ３１、Ｎｏ３３、Ｎｏ３５）４重量部を添加し、ポバートミキサーで十分に混練し、２５℃で１日放置した。その後、環境庁告示第１３号により、鉛の溶出試験を行った。その結果、鉛の溶出量は、それぞれＮｏ１６添加：１８ｍｇ／Ｌ、Ｎｏ１８添加：１８ｍｇ／Ｌ、Ｎｏ２５添加：１７ｍｇ／Ｌ、Ｎｏ２６添加：１９ｍｇ／Ｌ、Ｎｏ３１添加：１８ｍｇ／Ｌ、Ｎｏ３３添加：１８ｍｇ／Ｌ、Ｎｏ３５添加：１８ｍｇ／Ｌであった。また、セルロース誘導体を用いない重金属固定剤２重量部を用いる以外、同様に行い、鉛の溶出試験を行った。その結果、１８ｍｇ／Ｌであった。この結果、セルロース誘導体を用いることにより、重金属固定能力に影響がないことがわかった。 44 parts by weight of water, Examples 7, 9, and 11 at room temperature with respect to 100 parts by weight of alkaline lead-containing waste incineration fly ash (Pb content: 5600 mg / kg) pretreated with slaked lime and having a pH of 12 or more 4 parts by weight of the heavy metal fixing agent (No. 16, No. 18, No. 25, No. 26, No. 31, No. 33, No. 35) prepared in (1) was added, kneaded sufficiently with a Pobert mixer, and left at 25 ° C. for 1 day. Thereafter, a lead elution test was conducted according to Notification No. 13 of the Environment Agency. As a result, the lead elution amounts were No16 addition: 18 mg / L, No18 addition: 18 mg / L, No25 addition: 17 mg / L, No26 addition: 19 mg / L, No31 addition: 18 mg / L, No33 addition: 18 mg / L, No35 addition: 18 mg / L. Moreover, it carried out similarly except having used 2 weight part of heavy metal fixing agents which do not use a cellulose derivative, and performed the elution test of lead. As a result, it was 18 mg / L. As a result, it was found that the heavy metal fixing ability was not affected by using the cellulose derivative.
（７）重金属固定剤の調製−７
ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０．５％、ｐＨ１２以上）８７．５重量部に、カルボキシメチルセルロースナトリウム（品名：ＣＭＣ（１３５０）ダイセル化学工業（株）社製）１重量部、蒸留水９．５重量部を混合し、均一透明の重金属固定剤（Ｎｏ．４１）を調製した。このＮｏ．４１の２０℃粘度は３１０ｃｐｓであった。
(7) Preparation of heavy metal fixing agent-7
Piperazine-N, N′-biscarbodithioic acid potassium salt aqueous solution (solid content 40.5%, pH 12 or more) 87.5 parts by weight, sodium carboxymethylcellulose (product name: CMC (1350) Daicel Chemical Industries, Ltd.) 1 part by weight) and 9.5 parts by weight of distilled water were mixed to prepare a uniform transparent heavy metal fixing agent (No. 41). This No. 41 had a 20 ° C. viscosity of 310 cps.
消石灰により前処理されｐＨが１２以上であるアルカリ性鉛含有ごみ焼却飛灰（Ｐｂ含有量：８７０ｍｇ／ｋｇ）１００重量部に対して、室温にて、重金属固定剤（Ｎｏ．４１）を１重量部、水２５重量部を添加し、ポバートミキサーで３分３０秒間混練りした。その後、６０℃で１５時間加熱乾燥した。乾燥したものを粉砕し、メッシュ径が２ｍｍの篩で分級し、粒径が２ｍｍ以下のものを試験試料とした。実施例３と同様にして分散度を測定した。この結果を表１１に示す。 1 part by weight of heavy metal fixing agent (No. 41) at room temperature with respect to 100 parts by weight of alkaline lead-containing waste incineration fly ash (Pb content: 870 mg / kg) pretreated with slaked lime and having a pH of 12 or more Then, 25 parts by weight of water was added and kneaded for 3 minutes and 30 seconds with a Pobert mixer. Then, it heat-dried at 60 degreeC for 15 hours. The dried product was pulverized, classified with a sieve having a mesh diameter of 2 mm, and a test sample having a particle size of 2 mm or less was used. The dispersity was measured in the same manner as in Example 3. The results are shown in Table 11.
比較例６
消石灰により前処理されｐＨが１２以上であるアルカリ性鉛含有ごみ焼却飛灰（Ｐｂ含有量：８７０ｍｇ／ｋｇ）１００重量部に対して、室温にて、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０．５％、ｐＨ１２以上）２．６２５重量部、カルボキシメチルセルロースナトリウム（品名：ＣＭＣ（１３５０）ダイセル化学工業（株）社製）０．０３重量部、水２５．３４５重量部を添加し、ポバートミキサーで３分３０秒間混練りした。その後、６０℃で１５時間加熱乾燥した。乾燥したものを粉砕し、メッシュ径が２ｍｍの篩で分級し、粒径が２ｍｍ以下のものを試験試料とした。実施例３と同様に分散度を測定した。この結果を表１１に示す。
Comparative Example 6
Piperazine-N, N'-biscarbodithioic acid potassium at room temperature with respect to 100 parts by weight of alkaline lead-containing waste incineration fly ash (Pb content: 870 mg / kg) pretreated with slaked lime and having a pH of 12 or more 2.625 parts by weight of an aqueous salt solution (solid content 40.5%, pH 12 or more), 0.03 parts by weight of sodium carboxymethylcellulose (product name: CMC (1350) manufactured by Daicel Chemical Industries, Ltd.), 25.345 water A part by weight was added and the mixture was kneaded for 3 minutes and 30 seconds with a Pobert mixer. Then, it heat-dried at 60 degreeC for 15 hours. The dried product was pulverized, classified with a sieve having a mesh diameter of 2 mm, and a test sample having a particle size of 2 mm or less was used. The degree of dispersion was measured in the same manner as in Example 3. The results are shown in Table 11.
比較例７
比較例６でカルボキシメチルセルロースナトリウム（品名：ＣＭＣ（１３５０）ダイセル化学工業（株）社製）０．０３重量部を用いない以外は、比較例６と同様に試験試料を調製し、実施例３と同様に分散度を測定した。この結果を表１１に示す。
Comparative Example 7
In Comparative Example 6, a test sample was prepared in the same manner as in Comparative Example 6 except that 0.03 part by weight of sodium carboxymethylcellulose (product name: CMC (1350) manufactured by Daicel Chemical Industries, Ltd.) was not used. Similarly, the degree of dispersion was measured. The results are shown in Table 11.
（８）重金属固定剤の調製−８
ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０．５％、ｐＨ１２以上）８４．０重量部に、完全ケン化ポリビニルアルコール（品名：ＨＰ−Ｆ１１７、重合度１７００、分子量７万６千、クラレ（株）社製）の２０重量％水溶液１６．０重量部を混合し、均一透明の重金属固定剤（Ｎｏ．４２）を調製した。このＮｏ．４２の２０℃粘度は５０ｃｐｓであった。
(8) Preparation of heavy metal fixing agent-8
Piperazine-N, N′-biscarbodithioic acid potassium salt aqueous solution (solid content 40.5%, pH 12 or more) 84.0 parts by weight, completely saponified polyvinyl alcohol (product name: HP-F117, polymerization degree 1700, A uniform transparent heavy metal fixing agent (No. 42) was prepared by mixing 16.0 parts by weight of a 20 wt% aqueous solution having a molecular weight of 76,000 (manufactured by Kuraray Co., Ltd.). This No. The 20 ° C. viscosity of 42 was 50 cps.
消石灰により前処理されｐＨが１２以上であるアルカリ性鉛含有ごみ焼却飛灰（Ｐｂ含有量：８７０ｍｇ／ｋｇ）１００重量部に対して、室温にて、重金属固定剤（Ｎｏ．４２）を３重量部、水２５重量部を添加し、ポバートミキサーで３分３０秒間混練りした。その後、６０℃で１５時間加熱乾燥した。乾燥したものを粉砕し、メッシュ径が２ｍｍの篩で分級し、粒径が２ｍｍ以下のものを試験試料とした。実施例３と同様に分散度を測定した。この結果を表１２に示す。
比較例８
消石灰により前処理されｐＨが１２以上であるアルカリ性鉛含有ごみ焼却飛灰（Ｐｂ含有量：８７０ｍｇ／ｋｇ）１００重量部に対して、室温にて、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０．５％、ｐＨ１２以上）２．５２重量部、完全ケン化ポリビニルアルコール（品名：ＨＰ−Ｆ１１７、クラレ（株）社製）０．１０重量部、水２５．３８重量部を添加し、ポバートミキサーで３分３０秒間混練りした。その後、６０℃で１５時間加熱乾燥した。乾燥したものを粉砕し、メッシュ径が２ｍｍの篩で分級し、粒径が２ｍｍ以下のものを試験試料とした。実施例３と同様に分散度を測定した。この結果を表１２に示す。
比較例９
比較例８で完全ケン化ポリビニルアルコール（品名：ＨＰ−Ｆ１１７、クラレ（株）社製）０．１０重量部を用いない以外は、比較例８と同様に試験試料を調製し、実施例３と同様に分散度を測定した。この結果を表１２に示す。
3 parts by weight of heavy metal fixing agent (No. 42) at room temperature with respect to 100 parts by weight of alkaline lead-containing waste incineration fly ash (Pb content: 870 mg / kg) pretreated with slaked lime and having a pH of 12 or more Then, 25 parts by weight of water was added and kneaded for 3 minutes and 30 seconds with a Pobert mixer. Then, it heat-dried at 60 degreeC for 15 hours. The dried product was pulverized, classified with a sieve having a mesh diameter of 2 mm, and a test sample having a particle size of 2 mm or less was used. The degree of dispersion was measured in the same manner as in Example 3. The results are shown in Table 12.
Comparative Example 8
Piperazine-N, N'-biscarbodithioic acid potassium at room temperature with respect to 100 parts by weight of alkaline lead-containing waste incineration fly ash (Pb content: 870 mg / kg) pretreated with slaked lime and having a pH of 12 or more Aqueous salt solution (solid content 40.5%, pH 12 or more) 2.52 parts by weight, fully saponified polyvinyl alcohol (product name: HP-F117, manufactured by Kuraray Co., Ltd.) 0.10 parts by weight, water 25.38 A part by weight was added and the mixture was kneaded for 3 minutes and 30 seconds with a Pobert mixer. Then, it heat-dried at 60 degreeC for 15 hours. The dried product was pulverized, classified with a sieve having a mesh diameter of 2 mm, and a test sample having a particle size of 2 mm or less was used. The degree of dispersion was measured in the same manner as in Example 3. The results are shown in Table 12.
Comparative Example 9
In Comparative Example 8, a test sample was prepared in the same manner as in Comparative Example 8 except that 0.10 parts by weight of completely saponified polyvinyl alcohol (product name: HP-F117, manufactured by Kuraray Co., Ltd.) was not used. Similarly, the degree of dispersion was measured. The results are shown in Table 12.
（９）重金属固定剤の調製−９
ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０．５％、ｐＨ１２以上）８４．０重量部に、完全ケン化ポリビニルアルコール（品名：ＰＶＡ−１１０、重合度１０００、クラレ（株）社製）の３１重量％水溶液１６．０重量部を混合し、均一透明の重金属固定剤（Ｎｏ．４３）を調製した。このＮｏ．４３の２０℃粘度は５５ｃｐｓであった。
(9) Preparation of heavy metal fixing agent-9
Piperazine-N, N′-biscarbodithioic acid potassium salt aqueous solution (solid content 40.5%, pH 12 or more) 84.0 parts by weight, completely saponified polyvinyl alcohol (product name: PVA-110, polymerization degree 1000, 16.0 parts by weight of a 31 wt% aqueous solution of Kuraray Co., Ltd. was mixed to prepare a uniform transparent heavy metal fixing agent (No. 43). This No. The 20 ° C. viscosity of 43 was 55 cps.
消石灰により前処理されｐＨが１２以上であるアルカリ性鉛含有ごみ焼却飛灰（Ｐｂ含有量：８７０ｍｇ／ｋｇ）１００重量部に対して、室温にて、重金属固定剤（Ｎｏ．４３）を３重量部、水２５重量部を添加し、ポバートミキサーで３分３０秒間混練りした。その後、６０℃で１５時間加熱乾燥した。乾燥したものを粉砕し、メッシュ径が２ｍｍの篩で分級し、粒径が２ｍｍ以下のものを試験試料とした。実施例３と同様に分散度を測定した。この結果を表１３に示す。
比較例１０
消石灰により前処理されｐＨが１２以上であるアルカリ性鉛含有ごみ焼却飛灰（Ｐｂ含有量：８７０ｍｇ／ｋｇ）１００重量部に対して、室温にて、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム塩水溶液（固形分含有量４０．５％、ｐＨ１２以上）２．５２重量部、完全ケン化ポリビニルアルコール（品名：ＰＶＡ−１１０、クラレ（株）社製）０．１５重量部、水２５．３３重量部を添加し、ポバートミキサーで３分３０秒間混練りした。その後、６０℃で１５時間加熱乾燥した。乾燥したものを粉砕し、メッシュ径が２ｍｍの篩で分級し、粒径が２ｍｍ以下のものを試験試料とした。実施例３と同様に分散度を測定した。この結果を表１３に示す。
3 parts by weight of heavy metal fixing agent (No. 43) at room temperature with respect to 100 parts by weight of alkaline lead-containing waste incineration fly ash (Pb content: 870 mg / kg) pretreated with slaked lime and having a pH of 12 or more Then, 25 parts by weight of water was added and kneaded for 3 minutes and 30 seconds with a Pobert mixer. Then, it heat-dried at 60 degreeC for 15 hours. The dried product was pulverized, classified with a sieve having a mesh diameter of 2 mm, and a test sample having a particle size of 2 mm or less was used. The degree of dispersion was measured in the same manner as in Example 3. The results are shown in Table 13.
Comparative Example 10
Piperazine-N, N'-biscarbodithioic acid potassium at room temperature with respect to 100 parts by weight of alkaline lead-containing waste incineration fly ash (Pb content: 870 mg / kg) pretreated with slaked lime and having a pH of 12 or more Aqueous salt solution (solid content 40.5%, pH 12 or more) 2.52 parts by weight, fully saponified polyvinyl alcohol (product name: PVA-110, manufactured by Kuraray Co., Ltd.) 0.15 parts by weight, water 25.33 A part by weight was added and the mixture was kneaded for 3 minutes and 30 seconds with a Pobert mixer. Then, it heat-dried at 60 degreeC for 15 hours. The dried product was pulverized, classified with a sieve having a mesh diameter of 2 mm, and a test sample having a particle size of 2 mm or less was used. The degree of dispersion was measured in the same manner as in Example 3. The results are shown in Table 13.
表１１〜１３の結果から重金属固定化能力のある化合物と粉塵防止剤を別々に飛灰に添加するよりも、重金属固定化能力のある化合物と粉塵防止剤とをあらかじめ水に均一に溶解させた重金属固定剤を使用したほうが明らかに飛散防止効果に優れることがわかる。 From the results of Tables 11 to 13, the compound capable of fixing heavy metals and the dust preventive agent were uniformly dissolved in water in advance rather than separately adding to the fly ash the compound capable of fixing heavy metals and the dust preventing agent. It can be seen that the heavy metal fixing agent is clearly superior in the scattering prevention effect.
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