JP2001149884A - Method for treating molten fly ash - Google Patents
Method for treating molten fly ashInfo
- Publication number
- JP2001149884A JP2001149884A JP33778199A JP33778199A JP2001149884A JP 2001149884 A JP2001149884 A JP 2001149884A JP 33778199 A JP33778199 A JP 33778199A JP 33778199 A JP33778199 A JP 33778199A JP 2001149884 A JP2001149884 A JP 2001149884A
- Authority
- JP
- Japan
- Prior art keywords
- fly ash
- metal
- carrier
- component
- molten fly
- 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.)
- Granted
Links
- 239000010881 fly ash Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 185
- 239000002184 metal Substances 0.000 claims abstract description 182
- 238000002844 melting Methods 0.000 claims abstract description 81
- 230000008018 melting Effects 0.000 claims abstract description 80
- 238000011084 recovery Methods 0.000 claims abstract description 57
- 239000007788 liquid Substances 0.000 claims abstract description 55
- 239000007787 solid Substances 0.000 claims abstract description 46
- 239000003480 eluent Substances 0.000 claims abstract description 33
- 238000010828 elution Methods 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 238000011282 treatment Methods 0.000 claims abstract description 25
- 150000002678 macrocyclic compounds Chemical class 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims description 25
- 230000007246 mechanism Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract description 39
- 239000000428 dust Substances 0.000 abstract description 11
- 238000010309 melting process Methods 0.000 abstract description 2
- 239000011133 lead Substances 0.000 description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 38
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 239000011701 zinc Substances 0.000 description 24
- 229910001385 heavy metal Inorganic materials 0.000 description 22
- 229910052725 zinc Inorganic materials 0.000 description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 239000002956 ash Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000010949 copper Substances 0.000 description 15
- 238000004090 dissolution Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000002893 slag Substances 0.000 description 14
- 239000011780 sodium chloride Substances 0.000 description 14
- 239000011550 stock solution Substances 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000007922 dissolution test Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- -1 metal compound ions Chemical class 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000002633 crown compound Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 229910021514 lead(II) hydroxide Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、廃棄物を溶融処理
する際に発生する、複数の金属成分を含有する溶融飛灰
の処理に関し、特に、金属成分を回収すると共に灰を無
害化する溶融飛灰の処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the treatment of molten fly ash containing a plurality of metal components, which is generated during the melting treatment of wastes, and more particularly to a method of recovering metal components and detoxifying the ash. The present invention relates to a method for treating fly ash.
【０００２】[0002]
【従来の技術】廃棄物の溶融処理によって生じる溶融ス
ラグの安全基準は、前記溶融スラグに含まれる夫々の金
属の溶出量や前記溶融スラグの金属含有量を基準とす
る。しかし、前記溶融スラグに含まれる金属の溶融量や
含有量は、廃棄物の金属含有量に左右されるため、何ら
かの処理を施さないと、一定の基準内の量とすることは
困難である。Ｐｂ、Ｃｄ、Ｚｎ、Ｃｕ等の重金属は、溶
融炉内のような高温条件下では揮発するので前記溶融ス
ラグとして回収され難く、溶融飛灰に存在することとな
る。そして、これらの重金属は、溶融設備内を循環しな
がら濃縮されて蓄積し、設備を構成する部材の腐食等を
招く原因となっていた。又、前記重金属は、資源の有効
利用の面からも、回収して再利用することが好ましいと
考えられている。2. Description of the Related Art Safety standards for molten slag generated by the melting treatment of waste are based on the amount of each metal contained in the molten slag and the metal content of the molten slag. However, the amount and content of the metal contained in the molten slag depend on the metal content of the waste, and it is difficult to set the amount within a certain standard unless some treatment is performed. Heavy metals such as Pb, Cd, Zn, and Cu volatilize under high-temperature conditions such as in a melting furnace, so that they are difficult to be recovered as the molten slag, and are present in the molten fly ash. These heavy metals are concentrated and accumulated while circulating in the melting equipment, causing corrosion of members constituting the equipment and the like. It is also considered that the heavy metal is preferably recovered and reused from the viewpoint of effective utilization of resources.
【０００３】このような背景があって、溶融飛灰から重
金属を回収して、灰類を無害化する方法が求められてい
た。そして、従来の技術としては、以下の方法が知られ
ていた。 乾燥式精錬法 焼却灰等を蒸発固化した上で、加熱溶融し、湯状にした
後、比重分離を行い、アルカリ金属、および各種金属を
回収する方法である。この方法を採用するにあたって、
溶融炉の底部に、溶融スラグ出滓口とは別に、溶融メタ
ル出滓口を設けて、ここから溶融した金属を回収するこ
とができる。 湿式精錬法 前記溶融炉の下流に溶融飛灰の回収を目的とする集塵器
（第一バグフィルタ）と、前記集塵器を通過した空気に
含まれる酸等の中和物の回収を目的とする集塵器（第二
バグフィルタ）を設けて、前記第一バグフィルタに捕捉
された前記溶融飛灰の一部を、前記第二バグフィルタに
捕捉された塩と共に回収して、以下の薬剤処理を施す。
即ち、前記溶融飛灰を酸で溶解して、重金属成分を液相
に移行させた上で、その溶液に水酸化ナトリウム、硫化
ナトリウム、アンモニア、酢酸、炭酸ナトリウム等の薬
剤を添加し、溶解度差を利用して、各種金属を硫化物、
水酸化物、アンモニア錯体等の沈澱物のかたちで分離回
収する。尚、残渣は、前記溶融設備の処理系外に搬出す
る。このようにすると、前記溶融設備内に、揮発性の高
い重金属が蓄積するのを、ある程度は抑制することがで
きる。 キレート吸着法 前記の方法と同様に、前記第一バグフィルタで捕捉・
回収した溶融飛灰を酸で溶解して、重金属成分を液相に
移行させた上で、その溶液を配位子に窒素等を有するキ
レート性イオン交換樹脂に通液し、重金属イオンを吸着
回収する方法である。[0003] Against this background, there has been a demand for a method of recovering heavy metals from molten fly ash and detoxifying the ash. The following methods have been known as conventional techniques. Dry refining method This is a method of evaporating and solidifying incineration ash and the like, melting it by heating, making it into a hot water state, and then performing specific gravity separation to recover alkali metals and various metals. In adopting this method,
At the bottom of the melting furnace, a molten metal slag port is provided separately from the molten slag slag port, from which molten metal can be collected. Wet refining method A dust collector (first bag filter) for collecting molten fly ash downstream of the melting furnace, and a neutralized substance such as an acid contained in air passing through the dust collector. A dust collector (second bag filter) is provided to collect a part of the molten fly ash captured by the first bag filter together with the salt captured by the second bag filter. Perform chemical treatment.
That is, after dissolving the molten fly ash with an acid to transfer the heavy metal component to the liquid phase, a solution such as sodium hydroxide, sodium sulfide, ammonia, acetic acid, or sodium carbonate is added to the solution, and the solubility difference is increased. Using various metals to sulfide,
Separated and recovered in the form of precipitates such as hydroxides and ammonia complexes. In addition, the residue is carried out of the processing system of the melting facility. By doing so, the accumulation of highly volatile heavy metals in the melting facility can be suppressed to some extent. Chelate adsorption method In the same manner as the above method,
After dissolving the recovered molten fly ash with acid to transfer the heavy metal component to the liquid phase, the solution is passed through a chelating ion exchange resin having nitrogen or the like as a ligand to adsorb and recover heavy metal ions. How to
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記
〜の方法では、下記のような問題がそれぞれ存在す
る。つまり、上記の方法では、蒸気圧の高い重金属
は、再び蒸発して飛灰側に移行し、飛灰回収・溶融サイ
クルを循環するので、依然として、その回収率は低かっ
た。また、重金属を回収し無害化ができたとしても、加
熱溶融時に多量のエネルギーを使用する点、これらの重
金属が合金化したり、比重分離が困難もしくは不完全で
あるため回収された重金属の純度が低い点などの問題点
を有していた。However, the above-mentioned methods have the following problems. That is, in the above method, the heavy metal having a high vapor pressure evaporates again and moves to the fly ash side, and circulates in the fly ash recovery / melting cycle, so that the recovery rate is still low. Also, even if heavy metals can be recovered and made harmless, a large amount of energy is used during heating and melting.These heavy metals are alloyed or the specific gravity separation is difficult or incomplete. There were problems such as low points.
【０００５】上記の方法では、回収、個別分離は共に
可能であるが、純度がそれほど高くなく、多種の薬剤を
必要とする点で問題があった。又、前記処理を施した残
渣（溶融飛灰）は、溶融設備外へ持ち出されるので、系
外排出飛灰量が増加するという問題があった。[0005] In the above-mentioned method, both recovery and individual separation are possible, but there is a problem in that the purity is not so high and various kinds of drugs are required. In addition, the residue (melted fly ash) subjected to the above treatment is taken out of the melting equipment, so that the amount of fly ash discharged outside the system increases.
【０００６】更に、上記の方法では、キレート性イオ
ン交換樹脂の重金属選択性が低いため、回収は可能であ
るものの高純度に分離することが困難であった。また、
キレート性イオン交換樹脂に捕捉された金属は結合力が
強いため、溶脱が困難であって、キレート性イオン交換
樹脂の再生使用が困難であるという問題点があった。Further, in the above-mentioned method, since the chelating ion exchange resin has low selectivity for heavy metals, it is possible to recover it, but it is difficult to separate it into high purity. Also,
Since the metal captured by the chelating ion exchange resin has a strong binding force, there is a problem that leaching is difficult, and it is difficult to recycle the chelating ion exchange resin.
【０００７】即ち、上記の従来法では、いずれも回収す
る金属の選択性および回収した金属の純度が劣るととも
に、金属の回収操作に各種の困難を伴っていた。That is, in the above conventional methods, the selectivity of the metal to be recovered and the purity of the recovered metal are inferior, and various difficulties are involved in the operation of recovering the metal.
【０００８】本発明は、かかる実情に鑑みてなされたも
のであり、その目的は、回収する金属の選択性および回
収した金属の純度に優れると共に、金属成分の回収操作
が容易で、溶融設備外への飛灰排出量を抑制することが
できる溶融飛灰の処理方法を提供することにある。The present invention has been made in view of such circumstances, and it is an object of the present invention to not only excel in the selectivity of the metal to be recovered and the purity of the recovered metal, but also to facilitate the operation of recovering the metal component, and to provide an external device for the melting equipment. It is an object of the present invention to provide a method for treating molten fly ash which can suppress the amount of fly ash discharged to the ash.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、上記目的
を達成すべく、灰処理分野に限らずより幅広い技術分野
における金属分離技術を検討し、特に大環状化合物を固
定化した担体を用いる分離技術に着目して、適切な前処
理を行った後にかかる担体を用いて金属成分の結合・溶
離を行うことにより、各種灰から高選択性、高純度で種
々の金属成分が回収できることを見出した（特開平１０
−１７４９５０公報参照）。そして、この担体を利用し
た重金属回収方法を、溶融設備に対して効果的に適用す
べく、鋭意研究した結果、本発明を完成するに到った。Means for Solving the Problems In order to achieve the above object, the present inventors have studied metal separation techniques not only in the field of ash treatment but also in a wider range of technical fields. Focusing on the separation technology to be used, after performing appropriate pretreatment and binding and elution of metal components using such a carrier, it is possible to recover various metal components with high selectivity and high purity from various ash. (Japanese Unexamined Patent Application Publication No.
174950 publication). The present inventors have conducted intensive studies to effectively apply the heavy metal recovery method using the carrier to melting equipment, and as a result, have completed the present invention.
【００１０】即ち、本発明の溶融飛灰の処理方法の特徴
構成は、溶融飛灰を回収する回収部を設けた溶融設備に
おける溶融飛灰の処理方法であって、前記回収部で回収
された前記溶融飛灰を、酸又はアルカリを用いて一部溶
解させて懸濁液を得る溶解工程と、前記懸濁液を、固体
分と分離液に固液分離する分離工程と、分離された前記
固体分を前記溶融炉に戻す飛灰返送工程とを含む再溶融
処理工程及び、前記分離液を、前記分離液中に溶解した
溶解金属成分と選択的に結合し得る大環状化合物を固定
化した担体に接触させて、その溶解金属成分を前記担体
に結合させる結合工程と、その担体に溶離液を接触させ
て、前記担体に結合した金属成分を溶離させる溶離工程
とを含む金属回収処理工程を行う点にあり 更に、前記
金属回収処理工程が、前記溶離工程により溶離液中に溶
離した金属成分を析出させる析出工程を含むことが好ま
しい。又、本発明の溶融設備の特徴構成は、溶融飛灰を
回収する回収部を設けた溶融設備において、前記回収部
で回収された前記溶融飛灰を、酸又はアルカリを用いて
一部溶解させて懸濁液を得る溶解槽と、前記懸濁液を、
固体分と分離液に固液分離する固液分離装置とを設け、
分離された前記固体分を前記溶融炉に返送する固体分返
送機構を設けるとともに、前記分離液中に溶解した溶解
金属成分を、大環状化合物を固定化した担体に接触させ
て結合させた後、溶離回収させる金属回収装置を設けた
点にあり、更に、前記固体分返送機構が、前記固体分を
乾燥させる乾燥装置と、前記乾燥された固体分を粉砕す
る粉砕装置と、粉砕された前記固体分を前記溶融炉に空
気搬送する空気搬送装置とを備えたものであることが好
ましい。そして、これらの作用効果は、以下の通りであ
る。That is, the characteristic structure of the method for treating molten fly ash according to the present invention is a method for treating molten fly ash in a melting facility provided with a recovery section for recovering the molten fly ash. A dissolving step of partially dissolving the molten fly ash using an acid or alkali to obtain a suspension, a separating step of solid-liquid separating the suspension into a solid component and a separated liquid, A remelting treatment step including a fly ash return step of returning a solid content to the melting furnace, and a macrocyclic compound capable of selectively bonding the separated liquid with a dissolved metal component dissolved in the separated liquid was immobilized. A metal recovery treatment step including a binding step of bringing the dissolved metal component into contact with the carrier by contacting the carrier with the carrier, and an elution step of bringing the carrier into contact with an eluent to elute the metal component bound to the carrier. In addition, the metal recovery processing step Preferably, the method further includes a deposition step of depositing the metal component eluted in the eluent by the elution step. Further, the characteristic configuration of the melting facility of the present invention, in a melting facility provided with a recovery unit for recovering the molten fly ash, the molten fly ash recovered in the recovery unit, partially melt using acid or alkali. Dissolving tank to obtain a suspension,
A solid-liquid separation device is provided for solid-liquid separation into a solid component and a separated liquid,
A solid content return mechanism for returning the separated solid content to the melting furnace is provided, and the dissolved metal component dissolved in the separated liquid is brought into contact with the carrier on which the macrocyclic compound is immobilized, and then bonded. In the point that a metal recovery device for eluting and recovering is provided, further, the solids return mechanism is a drying device for drying the solids, a crushing device for crushing the dried solids, and the crushed solids. It is preferable that the apparatus is provided with an air transfer device for transferring the air to the melting furnace. And these effects are as follows.
【００１１】〔作用効果〕本発明の特徴は、金属成分を
除去した溶融飛灰を溶融炉に返送する再溶融処理工程
と、前記金属成分を回収する金属回収処理工程を有する
ものであって、前記再溶融処理工程においては、先ず、
溶解工程において、前記回収部で回収された前記溶融飛
灰を、酸又はアルカリを用いて一部溶解することによっ
て、灰中に存在する金属単体、金属酸化物、金属水酸化
物などの金属成分を、金属イオン、金属化合物イオン等
にして可溶化し、後の結合工程に好適な形態とすること
ができる。また、分離工程において、得られた懸濁液を
固液分離して固体分を除去することにより、後の結合工
程に悪影響を及ぼす不溶性の残渣（固体分）を除去する
ことができる。尚、分離された前記固体分は、飛灰返送
工程において、再び溶融炉に返送されて、再溶融され
る。この際、金属分を除去した固体分が前記溶融炉に返
送されるので、溶融炉に返送される飛灰の量を減らして
負荷を下げることができると共に、腐食等の影響を抑制
することができる。又、これによって、処理系外への前
記溶融飛灰の排出を抑制することができる。そして、前
記金属回収処理工程にあっては、先ず、結合工程におい
て、得られた分離液中に溶解した溶解金属成分と選択的
に結合し得る大環状化合物を固定化した担体に、前記分
離液を接触させることにより、その溶解金属成分を前記
担体に、溶解状態のままの形態で又は何らかの変化を受
けた状態で高選択性で結合させることができる。溶離工
程においては、金属成分が結合した担体に溶離液を接触
させることにより、前記担体に結合した金属成分の選択
性が高いために、高純度で溶離させることができる。そ
の際、特別なエネルギーを要することなく、また前記担
体が溶離工程により再生されるなど、回収操作も容易で
ある。その結果、回収する金属の選択性および回収した
金属の純度に優れると共に、金属成分の回収操作が容易
な溶融飛灰の処理方法を提供することができた。The present invention is characterized in that it has a re-melting process for returning the molten fly ash from which the metal component has been removed to a melting furnace, and a metal recovery process for recovering the metal component. In the re-melting step, first,
In the dissolving step, the molten fly ash recovered in the recovery section is partially dissolved using an acid or an alkali, whereby a metal element such as a simple metal, a metal oxide, or a metal hydroxide present in the ash is provided. Is solubilized into metal ions, metal compound ions, or the like, and can be made into a form suitable for the subsequent binding step. In addition, in the separation step, the obtained suspension is subjected to solid-liquid separation to remove solid components, whereby insoluble residues (solid components) that adversely affect the subsequent bonding step can be removed. The separated solids are returned to the melting furnace again in the fly ash return step and re-melted. At this time, since the solid component from which the metal component has been removed is returned to the melting furnace, the load can be reduced by reducing the amount of fly ash returned to the melting furnace, and the effect of corrosion and the like can be suppressed. it can. This also makes it possible to suppress the discharge of the molten fly ash outside the processing system. Then, in the metal recovery treatment step, first, in the binding step, the separation liquid is immobilized on a carrier on which a macrocyclic compound capable of selectively binding to the dissolved metal component dissolved in the obtained separation liquid is immobilized. By contacting with the carrier, the dissolved metal component can be bound to the carrier with high selectivity in the form of being dissolved or undergoing some change. In the elution step, by bringing the eluent into contact with the carrier to which the metal component has been bound, the metal component bound to the carrier has high selectivity, and thus can be eluted with high purity. At that time, the recovery operation is easy without requiring any special energy and the carrier is regenerated by the elution step. As a result, it was possible to provide a method for treating molten fly ash which is excellent in the selectivity of the metal to be recovered and the purity of the recovered metal and in which the operation of recovering the metal component is easy.
【００１２】上記構成において、前記金属回収処理工程
が、前記溶離工程の後に、溶離液中に溶解した金属成分
を不溶化して析出させる析出工程を更に行う場合、溶離
液中に溶解した金属成分が高純度であるため、高純度の
金属成分を水酸化物、酸化物、硫酸化物等の形で高純度
で得ることができる。In the above structure, when the metal recovery treatment step further includes, after the elution step, a precipitation step of insolubilizing and precipitating a metal component dissolved in the eluent, the metal component dissolved in the eluent is removed. Due to the high purity, a high-purity metal component can be obtained in the form of a hydroxide, oxide, sulfate or the like.
【００１３】前述した溶融飛灰の処理方法を溶融設備に
採用するには、前記溶融炉の下流に配置されて溶融飛灰
を回収する回収部を設けた溶融設備に溶解槽を設けて、
前記回収部の少なくとも一部、例えば、金属成分を多く
含む飛灰を回収することができる減温塔や第一集塵器で
回収された前記溶融飛灰を、酸又はアルカリを用いて一
部溶解させて懸濁液を得て、固液分離装置を設けて、前
記懸濁液を、固体分と分離液に固液分離し、更に、金属
回収装置を設けて、前記分離液中に溶解した溶解金属成
分を、大環状化合物を固定化した担体に接触させて結合
させた後、溶離回収すれば良い。尚、分離された前記固
体分は、固体分返送機構を設けて、前記溶融炉に返送す
れば良い。In order to employ the above-described method for treating molten fly ash in a melting facility, a melting tank is provided in a melting facility provided downstream of the melting furnace and provided with a recovery section for recovering the molten fly ash.
At least a part of the recovery part, for example, the molten fly ash recovered by a cooling tower or a first dust collector capable of recovering fly ash containing a large amount of metal components, partially using an acid or an alkali. The suspension is dissolved to obtain a suspension, a solid-liquid separation device is provided, and the suspension is separated into a solid component and a separated solution by solid-liquid separation. Further, a metal recovery device is provided to dissolve the suspension in the separated solution. The dissolved metal component thus obtained may be brought into contact with a carrier having the macrocyclic compound immobilized thereon to bind thereto, and then eluted and recovered. The separated solids may be returned to the melting furnace by providing a solids return mechanism.
【００１４】更に、前記固体分返送機構が、乾燥装置で
前記固体分を乾燥させて、前記乾燥された固体分を粉砕
装置で粉砕し、粉砕され溶融容易な状態とした前記固体
分を、空気搬送装置で前記溶融炉に空気搬送するもので
あると、金属成分が除去されているので前記固体分全体
としての返送量を減量することができ、かつ、空気を同
時に溶融炉内に供給することとなるので、前記溶融炉の
運転状態を良好に保つことができる。Further, the solid content returning mechanism dries the solid content in a drying device, pulverizes the dried solid content in a pulverizing device, and pulverizes the solid content in an easily meltable state into air. When the air is conveyed to the melting furnace by the transfer device, since the metal component is removed, it is possible to reduce the amount of the solids returned as a whole, and supply air into the melting furnace at the same time. Therefore, the operating state of the melting furnace can be kept good.
【００１５】尚、前記溶解工程に用いる酸として、硝酸
水溶液を用いるか、又は塩素イオンの共存下で塩酸水溶
液を用いる場合、後述の実験例９の結果が示すように、
特に１回の溶解工程で必要な金属成分の十分な溶解が行
える。ここで、硝酸水溶液が有用なのは、灰中に含まれ
る金属成分と特に難溶性の塩類を形成しにくいためと考
えられる。また、塩酸水溶液を塩素イオンの共存下で用
いるのが有用なのは、灰中に含まれる金属成分（特に鉛
成分）と塩酸単独では、例えばＰｂＣｌ2等の難溶性の
塩類を形成し易いが、塩素イオンの共存下では、例えば
ＰｂＣｌ3 - 、ＰｂＣｌ4 2-等を形成して可溶化するため
と考えられる。When an aqueous nitric acid solution is used as the acid used in the dissolving step, or when an aqueous hydrochloric acid solution is used in the presence of chloride ions, as shown in the results of Experimental Example 9 described below,
In particular, sufficient melting of the necessary metal component can be performed in one melting step. Here, it is considered that the nitric acid aqueous solution is useful because it is difficult to form particularly insoluble salts with the metal component contained in the ash. Also, it is useful to use an aqueous hydrochloric acid solution in the presence of chlorine ions because a metal component (particularly a lead component) contained in the ash and hydrochloric acid alone easily form hardly soluble salts such as PbCl 2. It is considered that, in the coexistence of ions, for example, PbCl 3 − , PbCl 4 2− and the like are formed and solubilized.
【００１６】また、前記溶解工程に用いる酸として塩素
イオンの共存下で塩酸水溶液を用い、かつ前記溶離工程
に用いる溶離液として水を用いる場合、後述の実験例１
の結果が示すように、コストや取扱の面で有利な水を用
いて高純度で金属成分を溶離することができる。なお、
溶解工程で上記の物質を用いた場合に水を用いるのが有
効なのは、水により塩素イオン濃度が低下すると、例え
ばＰｂＣｌ3 -、ＰｂＣｌ4 2-等の塩化物錯体の形で大環
状化合物に結合した金属成分から、塩素イオンの配位が
失われて金属イオン化することにより、大環状化合物と
の結合力が低下して溶離するためと考えられる。When an aqueous hydrochloric acid solution is used in the coexistence of chloride ions as the acid used in the dissolving step, and water is used as the eluent used in the eluting step, the following Experimental Example 1 is used.
As shown in the results, the metal component can be eluted with high purity using water which is advantageous in terms of cost and handling. In addition,
When the above substances are used in the dissolving step, it is effective to use water because when the chloride ion concentration is reduced by water, the water binds to the macrocyclic compound in the form of a chloride complex such as PbCl 3 − or PbCl 4 2−. It is considered that the coordination of the chloride ion is lost from the metal component and the metal component is ionized, whereby the binding force with the macrocyclic compound is reduced and the metal component is eluted.
【００１７】前記大環状化合物として、鉛成分を対象と
する結合に、１８−クラウン−６エーテルを用いる場
合、後述の実験例１、３、８の結果が示すように、灰を
溶解、固液分離した分離液から直接に、高選択性、高純
度、高収率で鉛成分を結合することができる。なお、Ｐ
ｂ2+用の担体は、鉛イオンを直接、及びＰｂＣｌ3 -、Ｐ
ｂＣｌ4 2-等から鉛イオンを引き抜いて結合することが
できるためＰｂ2+に限らず塩化物イオンからもＰｂ2+を
結合できると考えられる。また、ＰｂＣｌn-用の担体
は、ＰｂＣｌ3 -、ＰｂＣｌ4 2-等を直接結合することが
できるが、過剰の塩素イオンの存在下ではＰｂ2+はこの
形で結合できると考えられる。When 18-crown-6 ether is used as the macrocyclic compound for bonding to a lead component, as shown in the results of Experimental Examples 1, 3, and 8 below, ash is dissolved, solid-liquid The lead component can be directly bonded with high selectivity, high purity, and high yield from the separated separation liquid. Note that P
The carrier for b 2+ can directly convert lead ions, and PbCl 3 − , P
believed capable of binding Pb 2+ from chloride ions is not limited to the Pb 2+ for the Bcl 4 2-or the like can be attached pull the lead ions. Further, the carrier for PbCl n− can directly bind PbCl 3 − , PbCl 4 2- and the like, but it is considered that Pb 2+ can bind in this form in the presence of excess chloride ions.
【００１８】また、前記結合工程と前記溶離工程を、前
記担体の種類を変えて繰り返して行うことにより、複数
の金属成分を順次、回収する場合、本発明では結合工程
により特定の金属成分のみが担体に結合され、他の金属
成分はそのまま分離液に残存するので、引き続き担体の
種類を変えて結合工程を好適に行うことができ、また各
担体から別個に金属成分の溶離を行えば、各担体より複
数の金属成分を高純度で順次、回収することができる。In the present invention, when a plurality of metal components are sequentially recovered by repeatedly performing the binding step and the elution step while changing the type of the carrier, only a specific metal component is removed by the binding step in the present invention. Since the other metal components remain bound to the separated solution as they are bound to the carrier, the binding step can be continuously performed by changing the type of carrier, and if the metal components are separately eluted from each carrier, A plurality of metal components can be sequentially recovered with high purity from the carrier.
【００１９】その時、亜鉛成分以外の金属成分を順次回
収した後、亜鉛成分を回収することが好ましいのは、亜
鉛成分が上述の担体を以てしても亜鉛成分だけを選択性
よく結合するのは難しいが、亜鉛成分以外の金属成分を
順次回収した後、亜鉛成分を回収することにより、高純
度で亜鉛成分を回収できるからである。At this time, it is preferable to recover the zinc component after sequentially recovering the metal components other than the zinc component, because it is difficult to bind only the zinc component with high selectivity even if the zinc component is provided with the above-mentioned carrier. However, by sequentially recovering the metal components other than the zinc component, and then recovering the zinc component, the zinc component can be recovered with high purity.
【００２０】[0020]
【発明の実施の形態】本発明の溶融飛灰を回収する回収
部を設けた溶融設備における溶融飛灰の処理方法は、前
記回収部で回収された前記溶融飛灰を、酸又はアルカリ
を用いて一部溶解させて懸濁液を得る溶解工程と、前記
懸濁液を、固体分と分離液に固液分離する分離工程と、
分離した前記固体分を前記前記溶融炉に戻す飛灰返送工
程とを含む再溶融処理工程及び、前記分離液を、前記分
離液中に溶解した溶解金属成分と選択的に結合し得る大
環状化合物を固定化した担体に接触させて、その溶解金
属成分を前記担体に結合させる結合工程と、その担体に
溶離液を接触させて、前記担体に結合した金属成分を溶
離させる溶離工程とを含む金属回収処理工程を行うもの
である。BEST MODE FOR CARRYING OUT THE INVENTION The method for treating molten fly ash in a melting facility provided with a recovery section for recovering molten fly ash according to the present invention comprises the steps of: A dissolving step of obtaining a suspension by partially dissolving the suspension, the separation step of solid-liquid separation of the suspension into a solid component and a separated solution,
A remelting treatment step including a fly ash return step of returning the separated solid to the melting furnace, and a macrocyclic compound capable of selectively binding the separated liquid to a dissolved metal component dissolved in the separated liquid. A metal step comprising the steps of: bringing a dissolved metal component into contact with the carrier by contacting the carrier with the carrier; and an elution step of contacting the carrier with an eluent to elute the metal component bound to the carrier. A collection process is performed.
【００２１】〔溶融設備〕先ず、本発明に係る溶融飛灰
の処理方法を実施するための溶融設備について説明す
る。かかる溶融設備は、図１に示すように、破砕機７１
を備え、これによって一定の大きさに破砕した廃棄物
を、熱分解ドラム７２に投入して還元雰囲気中で間接加
熱して、熱分解ガスと熱分解残渣とする。前記熱分解残
渣は、熱分解残渣選別設備７３によって鉄・アルミニウ
ム等の有価物を分別回収した後、前記熱分解ガスと共に
溶融炉７４に空気輸送で吹き込まれて、例えば、空気比
１．３以下、灰の融点より高い温度（１３００℃）で旋
回燃焼して、溶融スラグとして回収する。前記溶融炉７
４内で発生する、揮発性の高い金属等を含む溶融飛灰
は、排ガスと共に減温塔７５に移送されて冷却され、更
に第一集塵器７６へと移送される。この過程で、多くの
溶融飛灰は、前記減温塔７５又は第一集塵器７６で回収
され、溶融飛灰返送路６４を通じて、後に詳述する金属
回収装置Ａに移送される。そして、前記金属回収装置Ａ
においては、揮発性が高くて溶融スラグで回収すること
が困難な金属類が回収される。金属回収後の残渣は、固
体分返送機構６によって前記溶融炉７４に輸送されて、
再び溶融される。この固体分返送機構６は、図２に示す
ように前記残渣を乾燥機６１によって乾燥させて重量及
び容積を減少させた後に、破砕機６２によって、溶融し
易いように一定の大きさに破砕し、前記破砕後の残渣
を、空気供給を兼ねてブロア６３が形成する空気流によ
って前記溶融炉７４に移送する。これにより返送される
固体分は粉末状で、搬送用エアと共に、前記溶融炉に供
給されるので、前記溶融炉７４内の溶融効率を高く維持
することができる。[Melting Facility] First, a melting facility for carrying out the method for treating fly ash according to the present invention will be described. As shown in FIG.
The waste crushed to a certain size by this is put into the pyrolysis drum 72 and indirectly heated in a reducing atmosphere to produce pyrolysis gas and pyrolysis residue. The pyrolysis residue is separated into valuable resources such as iron and aluminum by the pyrolysis residue sorting equipment 73, and then blown into the melting furnace 74 together with the pyrolysis gas by pneumatic transport. For example, the air ratio is 1.3 or less. , And is swirled at a temperature higher than the melting point of the ash (1300 ° C.) to be recovered as molten slag. The melting furnace 7
The molten fly ash generated in 4 and containing a highly volatile metal or the like is transferred to the temperature reducing tower 75 together with the exhaust gas, cooled, and further transferred to the first dust collector 76. In this process, a large amount of molten fly ash is collected in the cooling tower 75 or the first dust collector 76, and is transferred to the metal recovery device A described later in detail through the molten fly ash return path 64. And the metal recovery device A
In, metals that are highly volatile and are difficult to recover with molten slag are recovered. The residue after metal recovery is transported to the melting furnace 74 by the solids return mechanism 6,
It is melted again. As shown in FIG. 2, the solids returning mechanism 6 reduces the weight and the volume by drying the residue with a drier 61 and then crushes the residue to a predetermined size with a crusher 62 so as to be easily melted. The crushed residue is transferred to the melting furnace 74 by an air flow formed by the blower 63, also serving as air supply. As a result, the solids returned in the form of powder are supplied to the melting furnace together with the conveying air, so that the melting efficiency in the melting furnace 74 can be kept high.
【００２２】一方、排ガスに含まれる揮発性の酸は、中
和装置７７から供給される消石灰や助剤と反応して塩と
なって析出し、その下流に位置する第二集塵器７８に捕
捉された後に、薬剤処理装置７９に移送され、ここで、
種々の化学的処理を施されて無害化される。このように
して、溶融飛灰や揮発性物質を除去した後の排ガスは、
煙突８０を通じて、前記溶融設備外へと排出される。On the other hand, the volatile acid contained in the exhaust gas reacts with slaked lime and an auxiliary supplied from the neutralizing device 77 to form a salt, which is deposited in the second dust collector 78 located downstream thereof. After being captured, it is transferred to a drug processing device 79, where:
It is rendered harmless by various chemical treatments. In this way, the exhaust gas after removing the molten fly ash and volatile substances,
Through the chimney 80, it is discharged out of the melting facility.
【００２３】更に詳しくは、前記金属回収装置Ａは、図
２に示すような構成であって、溶解工程を行うための溶
融飛灰溶解槽１２は、灰を供給する溶融飛灰供給経路１
０と、酸又はアルカリを供給する薬品供給経路１１と、
モータＭ１を駆動力としてそれらの混合物を攪拌する攪
拌手段１３とを備える。分離工程を行うための濾過手段
１４は、前記溶融飛灰溶解槽１２から排出される懸濁液
から固体分（溶解残渣）を除去して溶解残渣回収手段１
５に取り除くと共に、濾過された分離液は三方弁２１に
送られるように配管されている。三方弁２１はかかる分
離液と、溶離液槽２４からの溶離液とを切換により、カ
ラム２２に供給するものである。結合工程および溶離工
程を行うためのカラム２２は、前述のような大環状化合
物を固定化した担体２３が充填されており、カラム２２
内に分離液を通液することにより結合工程を行い、溶離
液を通液することにより溶離工程を行う。カラム２２か
ら排出される分離液および溶離液は、三方弁２５に送ら
れるように配管されている。三方弁２５はその分離液と
溶離液とを、それぞれ第一析出槽３１と第二析出槽４１
に供給するためのものである。More specifically, the metal recovery apparatus A has a configuration as shown in FIG. 2, and a molten fly ash melting tank 12 for performing a melting step includes a molten fly ash supply path 1 for supplying ash.
0, a chemical supply path 11 for supplying an acid or an alkali,
And a stirring means 13 for stirring the mixture by using the motor M1 as a driving force. The filtration means 14 for performing the separation step removes solid components (dissolved residues) from the suspension discharged from the molten fly ash dissolving tank 12 to remove the dissolved residue
5 and the filtered liquid is sent to a three-way valve 21. The three-way valve 21 switches between the separated liquid and the eluent from the eluent tank 24 to supply the separated liquid to the column 22. The column 22 for performing the binding step and the elution step is packed with the carrier 23 having the macrocyclic compound immobilized thereon as described above.
The binding step is performed by passing the separation solution through the inside, and the elution step is performed by passing the eluent. The separated liquid and the eluent discharged from the column 22 are connected to be sent to the three-way valve 25. The three-way valve 25 transfers the separated liquid and the eluent to the first precipitation tank 31 and the second precipitation tank 41, respectively.
It is for supplying to.
【００２４】第一析出槽３１と第二析出槽４１とには、
不溶化剤槽３３から不溶化剤が供給されるようになって
おり、図２の装置では同一の不溶化剤槽３３から不溶化
剤が供給される構成となっているが、別々に不溶化剤槽
３３を設けてもよい。また、第一析出槽３１と第二析出
槽４１とには、夫々、析出に適当なモータＭ２，Ｍ３を
駆動源とする攪拌手段３２、４２が設けられている。濾
過手段３４、４３は、夫々、第一析出槽３１と第二析出
槽４１から排出される懸濁液から析出物をそれぞれ除去
して、析出物回収手段３５、４４に取り除くと共に、濾
過された濾液はともに中和槽５１に送られるように配管
されている。The first precipitation tank 31 and the second precipitation tank 41 have:
The insolubilizing agent is supplied from the insolubilizing agent tank 33 and the insolubilizing agent is supplied from the same insolubilizing agent tank 33 in the apparatus of FIG. You may. Further, the first precipitation tank 31 and the second precipitation tank 41 are provided with stirring means 32 and 42, respectively, which use motors M2 and M3 suitable for precipitation as driving sources. The filtering means 34 and 43 respectively remove the precipitate from the suspension discharged from the first precipitation tank 31 and the suspension discharged from the second precipitation tank 41, and remove the precipitate by the precipitate collection means 35 and 44, respectively. The filtrate is piped so as to be sent to the neutralization tank 51.
【００２５】濾液中和するための中和槽５１は、モータ
Ｍ４を駆動源とする攪拌手段５２と中和剤供給経路５３
と排出経路５４とを備える。また、中和により塩化ナト
リウム等の塩が生じる場合には、それを溶解工程等で再
利用することができる場合があり、中和液をリサイクル
するための循環経路Ｒを設けるとよい。The neutralization tank 51 for neutralizing the filtrate includes a stirring means 52 driven by a motor M4 and a neutralizing agent supply path 53.
And a discharge path 54. Further, when a salt such as sodium chloride is generated by the neutralization, it may be able to be reused in the dissolving step or the like, and a circulation route R for recycling the neutralized solution may be provided.
【００２６】複数の金属成分を回収する場合、図２に示
す金属回収装置Ａにおいて、各金属成分に応じたカラム
２２と、析出槽３１及び濾過手段３４を増設し、溶離液
が異なる場合にはそれぞれ溶離液槽２４を設ければよ
い。このときカラム２２には、各金属成分に応じた担体
２３が選択される。In the case of recovering a plurality of metal components, in the metal recovery apparatus A shown in FIG. 2, a column 22 corresponding to each metal component, a precipitation tank 31 and a filtering means 34 are added. An eluent tank 24 may be provided for each. At this time, a carrier 23 corresponding to each metal component is selected for the column 22.
【００２７】以下、前記金属回収装置Ａにおいてなされ
る各処理工程について説明する。 〔溶解工程〕本発明の溶解工程は、複数の金属成分を含
有する溶融飛灰を、酸又はアルカリを用いて一部溶解さ
せて懸濁液を得るものである。かかる溶融飛灰は、複数
の金属成分を含有するものであるが、金属成分を構成す
る金属元素としては、例えば鉛、カリウム、カルシウ
ム、銅、鉄、マンガン、珪素、カドミウム、アルミニウ
ム、マグネシウム、ナトリウム、亜鉛等が挙げられる。
また、かかる金属元素を有する金属成分としては、これ
ら金属元素単体に加え、その酸化物、水酸化物、硫化
物、塩化物等の種々のものが挙げられる。Hereinafter, each processing step performed in the metal recovery apparatus A will be described. [Dissolution Step] In the dissolution step of the present invention, a molten fly ash containing a plurality of metal components is partially dissolved using an acid or an alkali to obtain a suspension. Such molten fly ash contains a plurality of metal components, and examples of metal elements constituting the metal components include lead, potassium, calcium, copper, iron, manganese, silicon, cadmium, aluminum, magnesium, and sodium. , Zinc and the like.
Examples of the metal component having such a metal element include various metal oxides, hydroxides, sulfides, chlorides, and the like in addition to these metal elements alone.
【００２８】溶解に用いられる酸としては、上記の金属
成分を可溶化して液側に移行できるものであればいずれ
でもよいが、典型的なものとして硝酸、硫酸、塩酸、リ
ン酸、シュウ酸等が挙げられる。また、溶解に用いられ
るアルカリとしては、上記の金属成分を可溶化して液側
に移行できるものであればいずれでもよいが、典型的な
ものとして、水酸化ナトリウム、水酸化カリウム等の水
酸化アルカリ金属、水酸化カルシウム等の水酸化アルカ
リ土類金属、アルカリ金属炭酸塩、リン酸塩、アンモニ
ア等が挙げられる。As the acid used for dissolution, any acid can be used as long as it can solubilize the above-mentioned metal component and transfer to the liquid side, and typical examples include nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid and oxalic acid. And the like. As the alkali used for dissolution, any alkali can be used as long as it can solubilize the above metal component and move to the liquid side, and typical examples thereof include hydroxides such as sodium hydroxide and potassium hydroxide. Examples thereof include alkali metals, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates, phosphates, and ammonia.
【００２９】また、上記の酸又はアルカリに加えて、金
属成分の溶解性を高めるために、各種塩類や溶解促進剤
を添加してもよい。特に、塩酸を用いる場合、鉛成分が
過剰の塩素イオンの存在下で高い溶解性が得られるの
で、塩化ナトリウム、塩化カルシウム等が適量添加され
る。具体的には、塩酸に対して塩素イオン濃度で、好ま
しくは０．５〜１０モル倍、より好ましくは１〜３モル
倍となるように用いられる。In addition to the above-mentioned acids or alkalis, various salts and dissolution promoters may be added to enhance the solubility of the metal component. In particular, when hydrochloric acid is used, a high solubility is obtained in the presence of an excessive amount of chloride ions in the lead component. Therefore, an appropriate amount of sodium chloride, calcium chloride or the like is added. Specifically, it is used so that the chloride ion concentration is preferably 0.5 to 10 times, more preferably 1 to 3 times the molar concentration of hydrochloric acid.
【００３０】上記のうち、本発明では硝酸水溶液を用い
るか、又は塩素イオンの共存下で塩酸水溶液を用いるこ
とが前述の作用効果の点から好ましい。Among the above, in the present invention, it is preferable to use an aqueous nitric acid solution or to use an aqueous hydrochloric acid solution in the presence of chloride ions from the viewpoint of the above-mentioned effects.
【００３１】なお、金属成分の溶解を容易にするため、
適宜、水溶液の濃度を調整したり、加熱や攪拌を行うこ
とができる。そして、使用する酸の好ましい濃度は、灰
の濃度によって異なるが、最終ｐＨが１以下となる濃度
が特に有効である。得られた懸濁液には、金属成分が金
属イオン、金属化合物イオン（錯イオンを含む）等の形
で溶解した液体成分と、不溶性の残渣が存在することに
なる。In order to facilitate dissolution of the metal component,
The concentration of the aqueous solution can be adjusted as appropriate, and heating and stirring can be performed. The preferred concentration of the acid used depends on the concentration of the ash, but a concentration at which the final pH is 1 or less is particularly effective. The resulting suspension contains a liquid component in which the metal component is dissolved in the form of metal ions, metal compound ions (including complex ions), and the like, and an insoluble residue.
【００３２】〔分離工程〕本発明の分離工程は、得られ
た懸濁液を固液分離して、固体分を除去した分離液を得
るものである。つまり、不溶性の残渣を固体分として除
去し、金属成分が溶解した分離液を得るものである。固
液分離の方法としては、懸濁液から固体分が除去できる
ものであればいずれの方法も採用できるが、濾過、遠心
分離、沈降分離などが挙げられる。なお、金属成分の回
収率を高めるには、除去した固体分に液体成分の付着量
が少ない方法をとることが好ましい。[Separation Step] In the separation step of the present invention, the obtained suspension is subjected to solid-liquid separation to obtain a separated liquid from which solid components have been removed. That is, the insoluble residue is removed as a solid component to obtain a separated solution in which the metal component is dissolved. As a method of solid-liquid separation, any method can be adopted as long as solids can be removed from the suspension, and examples thereof include filtration, centrifugation, and sedimentation. In order to increase the recovery rate of the metal component, it is preferable to adopt a method in which the amount of the liquid component attached to the removed solid component is small.
【００３３】〔飛灰返送工程〕前記不溶性残渣（固体
分）には、珪素化合物、塩素化合物、ナトリウム化合物
等が含まれており、これらは、乾燥装置で乾燥させた後
に破砕装置で破砕される。このようにして、溶融炉で溶
融するのに適した状態とした前記固体分は、空気搬送装
置（ブロア）が形成する空気流によって、前記溶融炉に
空気輸送され、再び溶融される。従って、本発明に係る
溶融飛灰の処理方法にあっては、従来の様に、不溶性残
渣を前記溶融設備外に持ち出さず、溶融スラグとして系
外へ排出することとなる。[Fly Ash Return Step] The insoluble residue (solid content) contains a silicon compound, a chlorine compound, a sodium compound, etc., which are dried by a drying device and then crushed by a crushing device. . In this way, the solid component which is in a state suitable for melting in the melting furnace is pneumatically transported to the melting furnace by the air flow formed by the pneumatic conveying device (blower) and melted again. Therefore, in the method for treating molten fly ash according to the present invention, the insoluble residue is discharged to the outside as molten slag without being taken out of the melting facility as in the related art.
【００３４】〔結合工程〕本発明の結合工程は、前記分
離液中に溶解した溶解金属成分と選択的に結合し得る大
環状化合物を固定化した担体に、前記分離液を接触させ
て、その溶解金属成分を前記担体に結合させるものであ
る。大環状化合物を固定化した担体が、特定の溶解金属
成分と選択的に結合し得ることは従来より金属分離の分
野で知られていた（特開平１−１３９１４２号公報、特
表平６−５０８３３８号公報等）。しかしながら、本発
明の分離液のように、灰から抽出されたもので複数の金
属を含有し、かつｐＨも中性と大きく異なるものから、
金属を選択的に結合・溶離して回収する技術はこれまで
提案されておらず、当業者が容易に想到できるものでは
なかった。本発明は多くの実験を重ねた上で得られた、
前述の知見に基づいて完成されたものである。つまり、
本発明に用いられる大環状化合物を固定化した担体は、
クラウン化合物等の大環状化合物をスペーサーを介し
て、シリカ等の担体に共有結合させたものであり、その
環径と結合対象物の径との関係や両者の化学的親和性等
に基づき、溶解金属成分と選択的に結合し得る性質を発
現する。[Binding Step] In the binding step of the present invention, the separation solution is brought into contact with a carrier on which a macrocyclic compound capable of selectively binding to the dissolved metal component dissolved in the separation solution is immobilized. The molten metal component is bonded to the carrier. It has been known in the field of metal separation that a carrier having a macrocyclic compound immobilized thereon can selectively bind to a specific dissolved metal component (JP-A-1-139142, JP-T-6-508338). No.). However, as in the case of the separation liquid of the present invention, which is extracted from ash and contains a plurality of metals, and whose pH is significantly different from neutral,
Techniques for selectively binding and eluting and recovering metals have not been proposed so far, and could not be easily conceived by those skilled in the art. The present invention was obtained after many experiments.
It has been completed based on the above findings. That is,
The carrier on which the macrocyclic compound used in the present invention is immobilized,
A macrocyclic compound such as a crown compound is covalently bonded to a carrier such as silica via a spacer, and is dissolved based on the relationship between the ring diameter and the diameter of the binding object and the chemical affinity of both. It develops properties that can selectively bind to metal components.
【００３５】従って、本発明に用いられる大環状化合物
を固定化した担体としては、特開平１−１３９１４２号
公報、特表平６−５０８３３８号公報等に開示されたも
のを用いることができ、その製造もかかる開示に基づい
て行うことが可能である。また、かかる担体は既に商品
化されており、各種のものが、対象金属成分に応じて市
販されており、容易に入手することができる。Accordingly, as the carrier on which the macrocyclic compound used in the present invention is immobilized, those disclosed in JP-A-1-139142, JP-T-6-508338 and the like can be used. Manufacturing can also be performed based on such disclosure. Such carriers have already been commercialized, and various carriers are commercially available depending on the target metal component and can be easily obtained.
【００３６】特に後述の実験例で使用したものを例示す
ると次のようになる。 Ｐｂ2+用担体、ＰｂＣｌn-用担体、Ｃｕ用担体、
Ｆｅ用担体、Ａｌ用担体、Ｚｎ用担体。Particularly, the ones used in the experimental examples described below are as follows. Pb 2+ carrier, PbCl n- carrier, Cu carrier,
Carrier for Fe, carrier for Al, carrier for Zn.
【００３７】用いられる担体の形態としては、微粒子
状、ビーズ状（多孔質、無孔質）、膜状（多孔質、無孔
質）のものが挙げられるが、多孔質ビーズが接触効率や
取扱のし易さから好ましい。また、膜状のものを用い
て、その膜に固液分離機能を持たせることで、前述の分
離工程を結合工程と同時に行うようにしてもよい。な
お、担体の材料としては、シリカゲルの他、ガラス、
砂、アルミナ、チタニア、ジルコニア等が挙げられる。
また、前記分離液を担体に接触させる方法としては、接
触面積と接触時間を考慮しつつ、適当な方法で行えばよ
いが、例えばビーズ状担体をカラムに充填して分離液を
通液する方法、ビーズ状担体を流動状態で分離液と接触
させる方法、膜状担体に分離液を通液等する方法などが
挙げられる。The carrier may be in the form of fine particles, beads (porous or non-porous), or membrane (porous or non-porous). It is preferable from the viewpoint of ease of operation. Alternatively, the above-described separation step may be performed at the same time as the bonding step by using a film-like material and giving the film a solid-liquid separation function. In addition, as a material of the carrier, in addition to silica gel, glass,
Sand, alumina, titania, zirconia and the like can be mentioned.
Further, as a method of bringing the separation liquid into contact with the carrier, an appropriate method may be used while considering the contact area and the contact time, for example, a method of filling the column with bead-like carriers and passing the separation liquid. And a method in which the bead-shaped carrier is brought into contact with the separation liquid in a fluidized state, a method in which the separation liquid is passed through a membrane-like carrier, and the like.
【００３８】上記の結合工程で結合されなかった溶解金
属成分は、担体と接触後の分離液にそのまま存在するこ
とになるが、アルカリ等を用いて全てを析出・回収して
もよく、また更に個別に金属成分を回収する操作を行っ
てもよい。つまり、前記結合工程と前記溶離工程を、前
記担体の種類を変えて繰り返して行うことにより、複数
の金属成分を順次、回収することができる。その時、前
述の作用効果より、亜鉛成分以外の金属成分を順次回収
した後、亜鉛成分を回収することが好ましい。つまり、
選択性の高い金属成分から順に回収することが、回収さ
れる各金属成分の純度を高める上で好ましい。The dissolved metal component not bound in the above-mentioned binding step is present in the separated liquid after contact with the carrier, but may be entirely precipitated and recovered using an alkali or the like. An operation of individually collecting metal components may be performed. That is, by repeatedly performing the binding step and the elution step while changing the type of the carrier, a plurality of metal components can be sequentially recovered. At this time, it is preferable to recover the zinc component after sequentially recovering the metal components other than the zinc component from the above-mentioned effects. That is,
It is preferable to sequentially recover the metal components with high selectivity in order to increase the purity of each metal component to be recovered.
【００３９】なお、本発明では、前述のように鉛成分を
鉛イオン又は含鉛塩化物イオンとして結合することがで
き、鉛成分を対象とする結合に、１８−クラウン−６エ
ーテル、又はこれに類する化合物からなる群より選ばれ
る１種以上を用いることが好ましい。In the present invention, as described above, the lead component can be bonded as a lead ion or a lead-containing chloride ion, and the bond targeting the lead component can be bonded to 18-crown-6 ether or to this. It is preferable to use one or more selected from the group consisting of similar compounds.
【００４０】〔溶離工程〕本発明の溶離工程は、金属成
分が結合した担体に溶離液を接触させて、前記担体に結
合した金属成分を溶離させるものである。用いられる溶
離液は、結合した各種金属成分や溶解工程で用いた酸等
に応じて適宜選択することができるが、担体に結合した
金属イオンを脱離させるキレート化剤又は錯形成剤や、
金属イオンを再び可溶化させる酸や、溶解工程で用いた
酸等の濃度を低下させることにより金属イオンを脱離さ
せる水等の溶媒などを用いることができる。具体的に
は、キレート化剤としては、クエン酸塩、エチレンジア
ミンテトラアセテート（ＥＤＴＡ）、アセチルアセトン
等の各種のものが挙げられ、錯形成剤としては、各種金
属と配位結合により錯形成する配位子を有する化合物、
例えば結合したＰｂ2+に対する過剰の塩化ナトリウム等
の添加が挙げられる。金属イオンを再び可溶化させる酸
としては、硫酸等が挙げられる。上記において、前述の
作用効果より、溶離工程の一部又は全部において、水
（特に蒸留水）を用いることが好ましい。[Elution Step] In the elution step of the present invention, the metal component bound to the carrier is eluted by bringing the eluent into contact with the carrier to which the metal component has been bound. The eluent to be used can be appropriately selected depending on various kinds of bound metal components and the acid used in the dissolving step, and a chelating agent or a complex forming agent for desorbing metal ions bound to the carrier,
It is possible to use a solvent such as an acid for solubilizing a metal ion again or water for removing a metal ion by reducing the concentration of an acid or the like used in the dissolving step. Specifically, various chelating agents such as citrate, ethylenediaminetetraacetate (EDTA), acetylacetone and the like can be mentioned, and examples of complexing agents include a coordination complex which forms a coordination bond with various metals. Compounds having a child,
For example, addition of excess sodium chloride or the like to the bound Pb 2+ can be mentioned. As an acid for solubilizing metal ions again, sulfuric acid and the like can be mentioned. In the above, it is preferable to use water (particularly distilled water) in part or all of the elution step from the above-mentioned effects.
【００４１】なお、担体に溶離液を接触させ方法は、上
記の結合工程と同様である。上記で得られた溶離液に
は、高い選択性で結合された金属成分が、金属イオン、
キレート、錯体等の形で溶解している。この溶離液によ
って、灰中に含有される金属成分が高純度で回収された
ことになるが、次のような析出工程により、固体として
金属成分を回収してもよい。The method for bringing the eluent into contact with the carrier is the same as in the binding step described above. The eluent obtained above contains a metal component bound with high selectivity, a metal ion,
It is dissolved in the form of chelates and complexes. Although the metal component contained in the ash has been recovered with high purity by this eluent, the metal component may be recovered as a solid by the following precipitation step.
【００４２】〔析出工程〕任意の工程である析出工程
は、前記溶離工程の後に、溶離液中に溶解した金属成分
を不溶化して析出させるものである。かかる析出工程
は、従来の湿式精錬法と同様にして行うことができる
が、不溶化の方法としては、溶解した金属成分に応じて
適宜不溶化剤が選択されるが、一般的には水酸化アルカ
リ金属、水酸化アルカリ土類金属等が用いられ、水酸化
物として金属成分を回収することができる。また、鉛等
については硫酸等が用いられ、硫酸鉛等として回収する
ことができる。また、電気化学的手法により金属を析出
させることも可能である。[Precipitation Step] In the optional precipitation step, the metal component dissolved in the eluent is insolubilized and precipitated after the elution step. Such a precipitation step can be performed in the same manner as in a conventional wet refining method. As an insolubilization method, an insolubilizing agent is appropriately selected according to a dissolved metal component. , An alkaline earth metal hydroxide or the like is used, and a metal component can be recovered as a hydroxide. Sulfuric acid or the like is used for lead and the like, and can be recovered as lead sulfate and the like. It is also possible to deposit a metal by an electrochemical method.
【００４３】〔その他の工程〕析出工程で析出した沈澱
物は、固液分離により回収することができる。また、分
離後の分離液は、通常、アルカリ性又は酸性であるた
め、通常公知の方法により中和することができる。更
に、中和により生じた塩化ナトリウム等の塩は、それを
溶解工程、結合工程、溶離工程で再利用できる場合があ
るため、得られた中和液又は塩を単離して、再利用する
ことができる。つまり、例えば溶解工程で塩酸と塩化ナ
トリウムを用い、中和剤として水酸化ナトリウム等を用
いることにより、中和工程で塩化ナトリウムが生成する
ため、これを溶解工程で使用する塩化ナトリウムとして
再利用することができる。その時、溶解中の塩化ナトリ
ウム濃度をモニターしつつ、再利用のための中和液の供
給量を制御するようにしてもよい。これにより、原料費
を低減できる。[Other Steps] The precipitate deposited in the precipitation step can be recovered by solid-liquid separation. Moreover, since the separated liquid after separation is generally alkaline or acidic, it can be neutralized by a generally known method. Furthermore, salts such as sodium chloride generated by neutralization may be reused in the dissolving step, the binding step, and the elution step, so the neutralized solution or salt obtained should be isolated and reused. Can be. That is, for example, hydrochloric acid and sodium chloride are used in the dissolving step, and sodium hydroxide or the like is used as the neutralizing agent, so that sodium chloride is generated in the neutralizing step. This is reused as sodium chloride used in the dissolving step. be able to. At this time, the supply amount of the neutralizing solution for reuse may be controlled while monitoring the concentration of sodium chloride during dissolution. Thereby, the raw material cost can be reduced.
【００４４】また、各工程に先立って原液を希釈するた
めの希釈工程を採用したり、結合工程と溶離工程の間に
洗浄工程を採用するなど、任意の工程を付加することも
できる。Further, an arbitrary step can be added, such as adopting a dilution step for diluting the stock solution prior to each step, or adopting a washing step between the binding step and the elution step.
【００４５】このようにして、本発明に係る溶融方法に
あっては、廃棄物に含まれている金属成分を、高収率、
高純度で回収することができる。As described above, in the melting method according to the present invention, the metal component contained in the waste can be removed with a high yield.
It can be recovered with high purity.
【００４６】[0046]
【実験例】以下、前記金属回収装置Ａの重金属回収特性
を実証するための試験と、前記金属回収装置Ａを組み込
んだ溶融設備の運転実績について説明する。[Experimental Examples] Tests for demonstrating the heavy metal recovery characteristics of the metal recovery apparatus A and the operation results of the melting equipment incorporating the metal recovery apparatus A will be described below.
【００４７】実験例１ 都市ゴミ焼却炉から発生する飛灰と焼却灰をプラズマ溶
融炉にて溶融処理した時に発生する溶融飛灰を採取し、
その組成分析を行った。組成分析は、ＩＣＰ発光分光分
析法および原子吸光分析法で行った。その結果を表１に
示す。なお、以下の実験例における組成分析結果もすべ
て同様の方法で測定を行ったものである。EXPERIMENTAL EXAMPLE 1 Fly ash generated from a municipal garbage incinerator and molten fly ash generated when melting the incinerated ash in a plasma melting furnace were collected.
Its composition was analyzed. The composition analysis was performed by ICP emission spectroscopy and atomic absorption spectrometry. Table 1 shows the results. The results of composition analysis in the following experimental examples were all measured by the same method.
【００４８】[0048]
【表１】 [Table 1]
【００４９】表１の結果が示すように、溶融飛灰は原料
飛灰と比較して鉛や亜鉛のような蒸気圧の高い金属元素
が濃縮されていることが分かった。以下の実験例はかか
る溶融飛灰を用いて行ったものであるが、他の方法で得
られる溶融飛灰も同様の組成を示し、また、焼却灰や焼
却飛灰ではやや組成が異なるものの、その組成からする
と本発明の処理方法が溶融飛灰の場合と同様に適用でき
る。As shown in the results of Table 1, the molten fly ash was found to be enriched with metal elements having a high vapor pressure, such as lead and zinc, as compared with the raw fly ash. The following experimental examples were performed using such molten fly ash, but the molten fly ash obtained by other methods also shows the same composition, and although the composition is slightly different in incinerated ash and incinerated fly ash, Based on the composition, the treatment method of the present invention can be applied in the same manner as in the case of fly ash.
【００５０】上記の飛灰３００ｇを０．７Ｎ塩酸と１Ｎ
塩化ナトリウムの水溶液３リットルに攪拌しつつ約３０
分かけて溶解し（溶解工程）、濾過した時（分離工程）
の濾液中の溶解金属の濃度分析を行った。その結果を表
２に示す。なお、溶解後のｐＨは１．１であった。300 g of the above fly ash is mixed with 0.7N hydrochloric acid and 1N
Approximately 30
Dissolve over a minute (dissolution step) and filter (separation step)
Was analyzed for the concentration of dissolved metals in the filtrate. Table 2 shows the results. The pH after dissolution was 1.1.
【００５１】[0051]
【表２】 [Table 2]
【００５２】表２の結果が示すように、かかる濾液中に
は、多種の金属成分と共に、鉛成分がかなり多く溶解し
ていることが分かった。As shown in the results of Table 2, it was found that the filtrate contained a considerable amount of lead components together with various metal components.
【００５３】直径２．５ｃｍ×高さ１０ｃｍのガラス製
の円筒カラム内に、前述のＰｂＣｌ n-用担体を２５ｇ充
填し、上記濾液をその上部より通液し、その下部より排
出させた（結合工程）。その時の排出液を表３に示す時
点で採取し、それぞれの溶解金属の濃度分析を行った。
その結果を表３に示す。Made of glass 2.5 cm in diameter x 10 cm in height
Of the above PbCl n-25g of carrier
The filtrate is passed through the upper part and drained from the lower part.
(Bonding step). The effluent at that time is shown in Table 3.
The samples were collected at points, and the concentration of each dissolved metal was analyzed.
Table 3 shows the results.
【００５４】[0054]
【表３】 [Table 3]
【００５５】表３の結果が示すように、２０００ｍｌま
での排出液には鉛成分が全く含まれておらず、一方、他
の金属成分は殆ど濃度低下せずに排出されているため、
鉛成分のみが高い選択性および高い回収率（ほぼ１００
％）で担体に結合されたことが分かった。As shown in the results in Table 3, the effluent up to 2000 ml contains no lead component, while the other metal components are discharged with almost no decrease in concentration.
Only the lead component has high selectivity and high recovery (almost 100
%) Was found to be bound to the carrier.
【００５６】次いて、水（好ましくは蒸留水）を溶離液
として上記の円筒カラムの上部より通液し、その下部よ
り排出させた（溶離工程）。その時の排出液を表４に示
す時点で採取し、それぞれの溶解金属の濃度分析を行っ
た。その結果を表４に示す。Subsequently, water (preferably distilled water) was passed through the upper part of the above-mentioned cylindrical column as an eluent, and was discharged from the lower part (elution step). The effluent at that time was collected at the time shown in Table 4, and the concentration of each dissolved metal was analyzed. Table 4 shows the results.
【００５７】[0057]
【表４】 [Table 4]
【００５８】表４の結果が示すように、１２００ｍｌま
での排出液に鉛成分が多く含まれており、一方、他の金
属成分（亜鉛成分を除く）は全く含まれていないため、
鉛成分のみが高い純度で溶離・回収できることが分かっ
た。なお、亜鉛成分のみは上記担体で一部捕捉され、溶
離液中に溶離するが（表３、表４参照）、溶離が初期に
完了するため、その後の溶離液のみを利用することによ
り、鉛成分のみをより高い純度で溶離・回収できる。な
お、後述の実験例８の結果が示すように、担体としてＰ
ｂ2+用担体を用いると、亜鉛成分の結合・溶離が起こら
ず、鉛成分のみをより高い純度で溶離・回収できる。As can be seen from the results in Table 4, the effluent up to 1200 ml contains a large amount of lead components, while no other metal components (excluding zinc components) are contained.
It was found that only the lead component could be eluted and recovered with high purity. Although only the zinc component is partially captured by the above carrier and eluted in the eluent (see Tables 3 and 4), since the elution is completed in the initial stage, the use of only the subsequent eluent results in the use of lead. Only components can be eluted and recovered with higher purity. As shown in the results of Experimental Example 8 described later, P
When the carrier for b 2+ is used, binding and elution of the zinc component do not occur, and only the lead component can be eluted and recovered with higher purity.
【００５９】実験例２ 実験例１で得られた、鉛成分を結合・除去した分離液
（組成は表５を参照）約２５００ｍｌに対して、ＮａＨ
ＣＯ3を添加してｐＨを約２．０に調整し、原液を得
た。直径１．０ｃｍ×高さ３４ｃｍのガラス製の円筒カ
ラム内に前述のＣｕ用担体を１５ｇ充填し、上記原液を
その上部より通液し、その下部より排出させた（結合工
程）。その時の排出液を表５に示す時点で採取し、それ
ぞれの溶解金属の濃度分析を行った。その結果を表５に
示す。Experimental Example 2 NaH was added to about 2500 ml of the separated liquid (composition shown in Table 5) obtained by binding and removing the lead component obtained in Experimental Example 1.
The pH was adjusted to about 2.0 by adding CO 3 to obtain a stock solution. A glass column having a diameter of 1.0 cm and a height of 34 cm was filled with 15 g of the above-mentioned carrier for Cu, and the stock solution was passed through the upper portion and discharged from the lower portion (combining step). The effluent at that time was collected at the time shown in Table 5, and the concentration of each dissolved metal was analyzed. Table 5 shows the results.
【００６０】[0060]
【表５】 [Table 5]
【００６１】表５の結果が示すように、２０００ｍｌま
での排出液には銅成分が全く含まれておらず、一方、他
の金属成分は全く濃度低下せずに排出されているため、
銅成分のみが高い選択性および高い回収率（ほぼ１００
％）で担体に結合されたことが分かった。As shown in the results of Table 5, the effluent up to 2000 ml does not contain any copper component, while the other metal components are discharged without any reduction in concentration.
Only the copper component has high selectivity and high recovery (almost 100
%) Was found to be bound to the carrier.
【００６２】次いて、１Ｎ硫酸を溶離液として上記の円
筒カラムの上部より通液し、その下部より排出させた
（溶離工程）。その時の排出液を表６に示す時点で採取
し、それぞれの溶解金属の濃度分析を行った。その結果
を表６に示す。Then, 1N sulfuric acid was passed through the upper part of the cylindrical column as an eluent, and was discharged from the lower part (elution step). The effluent at that time was collected at the time shown in Table 6, and the concentration of each dissolved metal was analyzed. Table 6 shows the results.
【００６３】[0063]
【表６】 [Table 6]
【００６４】表６の結果が示すように、１２００ｍｌま
での排出液に銅成分が多く含まれており、一方、他の金
属成分は全く含まれていないため、銅成分のみが高い純
度（ほぼ１００％）で溶離・回収できることが分かっ
た。As can be seen from the results in Table 6, the effluent up to 1200 ml contains a large amount of copper component, while no other metal component is contained at all. Therefore, only the copper component has high purity (almost 100%). %) Can be eluted and recovered.
【００６５】実験例３ 実験例１と同じ溶融飛灰を用いて、飛灰３０ｇを０．１
Ｍ硝酸水溶液３リットルに攪拌しつつ約３０分かけて溶
解した（溶解工程）。溶解後のｐＨは１．５〜１．７で
あった。これを濾過して（分離工程）以下の工程の原液
とした。かかる原液中には、多種の金属成分と共に、鉛
成分がかなり多く溶解していることが分かった（表７参
照）。EXPERIMENTAL EXAMPLE 3 Using the same molten fly ash as in Experimental Example 1, 30 g of fly ash was added in 0.1 g.
The solution was dissolved in 3 liters of an aqueous solution of M nitric acid over about 30 minutes while stirring (dissolution step). The pH after dissolution was 1.5 to 1.7. This was filtered (separation step) to give a stock solution for the following steps. In this stock solution, it was found that the lead component was considerably dissolved together with various metal components (see Table 7).
【００６６】直径０．８ｃｍ×高さ１９．３ｃｍのガラ
ス製の円筒カラム内に、前述のＰｂ 2+用担体を１０ｇ充
填したものを２本上下に配置し、上記濾液をその上部よ
り通液し、その下部より排出させた（結合工程）。その
時の排出液を表７に示す量ごとに分取し、それぞれの溶
解金属の濃度分析を行った。その結果を表７に示す。A glass having a diameter of 0.8 cm and a height of 19.3 cm
In the cylindrical column made of stainless steel, 2+10 g of carrier
Place the two bottles one above the other and place the above filtrate on top of it.
The liquid was passed through and drained from the lower part (a binding step). That
The effluent at the time is separated by the amount shown in Table 7 and
The analysis of the concentration of the peptized metal was performed. Table 7 shows the results.
【００６７】[0067]
【表７】 [Table 7]
【００６８】表７の結果が示すように、約２０００ｍｌ
までの排出液には鉛成分が全く含まれておらず、一方、
他の金属成分は殆ど濃度低下せずに（最初の分取液を除
く）排出されているため、鉛成分のみが高い選択性およ
び高い回収率（ほぼ１００％）で担体に結合されたこと
が分かった。As shown by the results in Table 7, about 2000 ml
Does not contain any lead components,
Since the other metal components are discharged with almost no decrease in concentration (excluding the first fraction), only the lead component was bound to the carrier with high selectivity and high recovery (almost 100%). Do you get it.
【００６９】次いて、水３０ｍｌで上記カラムを洗浄し
た後、０．３Ｍクエン酸カリウムを溶離液として上記の
円筒カラムの上部より通液し、その下部より排出させた
（溶離工程）。その時の排出液を表８に示す量ごとに分
取し、それぞれの溶解金属の濃度分析を行った。その結
果を表８に示す。Next, after washing the column with 30 ml of water, the column was passed through the upper part of the cylindrical column using 0.3 M potassium citrate as an eluent and discharged from the lower part (elution step). The effluent at that time was collected for each amount shown in Table 8, and the concentration of each dissolved metal was analyzed. Table 8 shows the results.
【００７０】[0070]
【表８】 [Table 8]
【００７１】表８の結果が示すように、１１０ｍｌまで
の排出液に鉛成分が多く含まれており、一方、他の金属
成分は全く含まれていないため、鉛成分のみが高い純度
で溶離・回収できることが分かった。As can be seen from the results in Table 8, the effluent up to 110 ml contains a large amount of lead component, while other metal components are not contained at all. Therefore, only the lead component is eluted with high purity. It turns out that it can be recovered.
【００７２】実験例４ 実験例３で得られた、鉛成分を結合・除去した分離液
（組成は表９を参照）約２５００ｍｌに対して、ＮａＨ
ＣＯ3を添加してｐＨを約２．０に調整し、原液を得
た。直径０．８ｃｍ×高さ１３．４ｃｍのガラス製の円
筒カラム内に前述のＣｕ用担体を３ｇ充填したものを２
本上下に配置し、上記原液をその上部より通液し、その
下部より排出させた（結合工程）。その時の排出液を表
９に示す量ごとに分取し、それぞれの溶解金属の濃度分
析を行った。その結果を表９に示す。Experimental Example 4 NaH was added to about 2500 ml of the separated liquid (composition shown in Table 9) obtained by binding and removing the lead component obtained in Experimental Example 3.
The pH was adjusted to about 2.0 by adding CO 3 to obtain a stock solution. A glass cylindrical column having a diameter of 0.8 cm × a height of 13.4 cm and filled with 3 g of the aforementioned carrier for Cu was filled with 2 pieces.
The stock solution was placed above and below the book, and the stock solution was passed from above and discharged from below (combining step). The effluent at that time was separated for each amount shown in Table 9, and the concentration of each dissolved metal was analyzed. Table 9 shows the results.
【００７３】[0073]
【表９】 [Table 9]
【００７４】表９の結果が示すように、約２０００ｍｌ
までの排出液には銅成分が全く含まれておらず、一方、
他の金属成分は全く濃度低下せずに排出されているた
め、銅成分のみが高い選択性および高い回収率（ほぼ１
００％）で担体に結合されたことが分かった。As shown by the results in Table 9, about 2000 ml
The effluent does not contain any copper components, while
Since other metal components are discharged without any reduction in concentration, only the copper component has high selectivity and high recovery (almost 1%).
00%) was found to be bound to the carrier.
【００７５】次いて、水１０ｍｌで上記カラムを洗浄し
た後、１Ｍ硫酸を溶離液として上記の円筒カラムの上部
より通液し、その下部より排出させた（溶離工程）。そ
の時の排出液を表１０に示す量ごとに分取し、それぞれ
の溶解金属の濃度分析を行った。その結果を表１０に示
す。Next, the column was washed with 10 ml of water, and then passed through the upper part of the cylindrical column using 1M sulfuric acid as an eluent, and discharged from the lower part (elution step). The effluent at that time was separated for each amount shown in Table 10, and the concentration of each dissolved metal was analyzed. Table 10 shows the results.
【００７６】[0076]
【表１０】 [Table 10]
【００７７】表１０の結果が示すように、３５ｍｌまで
の排出液に銅成分が多く含まれており、一方、他の金属
成分は全く含まれていないため、銅成分のみが高い純度
（ほぼ１００％）で溶離・回収できることが分かった。As can be seen from the results in Table 10, the effluent up to 35 ml contains a large amount of copper component, while no other metal components are contained at all. Therefore, only the copper component has a high purity (almost 100%). %) Can be eluted and recovered.
【００７８】実験例５ 実験例４で得られた、銅成分を結合・除去した分離液
（組成は表１１を参照）約２５００ｍｌをそのまま原液
とし、直径０．８ｃｍ×高さ６．７ｃｍのガラス製の円
筒カラム内に前述のＦｅ用担体を１．５ｇ充填したもの
を２本上下に配置し、上記原液をその上部より通液し、
その下部より排出させた（結合工程）。その時の排出液
を表１１に示す量ごとに分取し、それぞれの溶解金属の
濃度分析を行った。その結果を表１１に示す。Experimental Example 5 Approximately 2500 ml of the separated liquid (composition shown in Table 11) obtained by binding and removing the copper component obtained in Experimental Example 4 was used as a stock solution as it was, and the glass having a diameter of 0.8 cm and a height of 6.7 cm was used. The above-mentioned Fe column was filled with 1.5 g of the above-described carrier for Fe in a cylindrical column, and two of them were arranged one above the other.
It was discharged from the lower part (combining step). The effluent at that time was separated for each amount shown in Table 11, and the concentration of each dissolved metal was analyzed. Table 11 shows the results.
【００７９】[0079]
【表１１】 [Table 11]
【００８０】表１１の結果が示すように、約２０００ｍ
ｌまでの排出液には鉄成分が全く含まれておらず、一
方、他の金属成分は全く濃度低下せずに排出されている
ため、鉄成分のみが高い選択性および高い回収率（ほぼ
１００％）で担体に結合されたことが分かった。As shown in the results of Table 11, about 2000 m
The effluent up to 1 contains no iron component, while the other metal components are discharged without any reduction in concentration, so that only the iron component has high selectivity and high recovery (almost 100%). %) Was found to be bound to the carrier.
【００８１】次いて、水５ｍｌで上記カラムを洗浄した
後、１Ｍ硫酸を溶離液として上記の円筒カラムの上部よ
り通液し、その下部より排出させた（溶離工程）。その
時の排出液を表１２に示す量ごとに分取し、それぞれの
溶解金属の濃度分析を行った。その結果を表１２に示
す。Subsequently, the column was washed with 5 ml of water, and then passed through the upper part of the cylindrical column using 1M sulfuric acid as an eluent, and discharged from the lower part (elution step). The effluent at that time was collected for each amount shown in Table 12, and the concentration of each dissolved metal was analyzed. Table 12 shows the results.
【００８２】[0082]
【表１２】 [Table 12]
【００８３】表１２の結果が示すように、１７ｍｌまで
の排出液に鉄成分が多く含まれており、一方、他の金属
成分は全く含まれていないため、鉄成分のみが高い純度
（ほぼ１００％）で溶離・回収できることが分かった。As can be seen from the results in Table 12, the effluent up to 17 ml contains a large amount of iron component, while no other metal components are contained at all. Therefore, only the iron component has high purity (almost 100%). %) Can be eluted and recovered.
【００８４】実験例６ 実験例５で得られた、鉄成分を結合・除去した分離液
（組成は表１３を参照）約２５００ｍｌをそのまま原液
とし、直径０．８ｃｍ×高さ１９．３ｃｍのガラス製の
円筒カラム内に前述のＡｌ用担体を５ｇ充填したものを
２本上下に配置し、上記原液をその上部より通液し、そ
の下部より排出させた（結合工程）。その時の排出液を
表１３に示す量ごとに分取し、それぞれの溶解金属の濃
度分析を行った。その結果を表１３に示す。Experimental Example 6 Approximately 2,500 ml of the separated liquid (composition shown in Table 13) obtained by binding and removing the iron component obtained in Experimental Example 5 was used as a stock solution as it was, and the glass having a diameter of 0.8 cm and a height of 19.3 cm was used. Two columns each having 5 g of the above-mentioned Al carrier were placed in a cylindrical column made of aluminum and placed above and below, and the stock solution was passed through the upper part and discharged from the lower part (combining step). The effluent at that time was separated for each amount shown in Table 13, and the concentration of each dissolved metal was analyzed. Table 13 shows the results.
【００８５】[0085]
【表１３】 [Table 13]
【００８６】表１３の結果が示すように、約２０００ｍ
ｌまでの排出液にはＡｌ成分が全く含まれておらず、一
方、他の金属成分は全く濃度低下せずに排出されている
ため、Ａｌ成分のみが高い選択性および高い回収率（ほ
ぼ１００％）で担体に結合されたことが分かった。As shown in the results of Table 13, about 2000 m
1 does not contain any Al component, while the other metal components are discharged without any reduction in concentration, so that only the Al component has high selectivity and high recovery (almost 100%). %) Was found to be bound to the carrier.
【００８７】次いて、水１５ｍｌで上記カラムを洗浄し
た後、１Ｍ硫酸を溶離液として上記の円筒カラムの上部
より通液し、その下部より排出させた（溶離工程）。そ
の時の排出液を表１４に示す量ごとに分取し、それぞれ
の溶解金属の濃度分析を行った。その結果を表１４に示
す。Subsequently, the column was washed with 15 ml of water, and then passed through the upper portion of the cylindrical column using 1M sulfuric acid as an eluent, and discharged from the lower portion (elution step). The effluent at that time was separated for each amount shown in Table 14, and the concentration of each dissolved metal was analyzed. Table 14 shows the results.
【００８８】[0088]
【表１４】 [Table 14]
【００８９】表１４の結果が示すように、３７ｍｌまで
の排出液にＡｌ成分が多く含まれており、一方、他の金
属成分は全く含まれていないため、Ａｌ成分のみが高い
純度（ほぼ１００％）で溶離・回収できることが分かっ
た。As shown in the results of Table 14, the effluent up to 37 ml contains a large amount of Al component, while no other metal component is contained at all. Therefore, only the Al component has high purity (almost 100%). %) Can be eluted and recovered.
【００９０】実験例７ 実験例６で得られた、Ａｌ成分を結合・除去した分離液
（組成は表１５を参照）約２５００ｍｌをそのまま原液
とし、直径３．９ｃｍ×高さ１４．６ｃｍのガラス製の
円筒カラム内に前述のＺｎ用担体を７５ｇ充填したもの
を２本上下に配置し、上記原液をその上部より通液し、
その下部より排出させた（結合工程）。その時の排出液
を表１５に示す量ごとに分取し、それぞれの溶解金属の
濃度分析を行った。その結果を表１５に示す。Experimental Example 7 Approximately 2500 ml of the separated liquid obtained in Experimental Example 6 in which the Al component was bound and removed (see Table 15 for the composition) was used as a stock solution as it was, and the glass was 3.9 cm in diameter × 14.6 cm in height. A column filled with 75 g of the above-mentioned Zn carrier is placed in a cylindrical column made of aluminum, and two of them are arranged above and below, and the stock solution is passed through the upper part thereof,
It was discharged from the lower part (combining step). The effluent at that time was separated for each amount shown in Table 15, and the concentration of each dissolved metal was analyzed. Table 15 shows the results.
【００９１】[0091]
【表１５】 [Table 15]
【００９２】表１５の結果が示すように、約２０００ｍ
ｌまでの排出液には亜鉛成分が全く含まれておらず、一
方、他の金属成分は殆ど濃度低下せずに（初期を除く）
排出されているため、亜鉛成分のみが高い選択性および
高い回収率（ほぼ１００％）で担体に結合されたことが
分かった。As shown in the results of Table 15, it was found that about 2000 m
The effluent up to 1 contains no zinc component, while the other metal components hardly decrease in concentration (except in the initial stage)
As a result, it was found that only the zinc component was bound to the carrier with high selectivity and high recovery (almost 100%).
【００９３】次いて、水１５０ｍｌで上記カラムを洗浄
した後、１Ｍ硫酸を溶離液として上記の円筒カラムの上
部より通液し、その下部より排出させた（溶離工程）。
その時の排出液を表１６に示す量ごとに分取し、それぞ
れの溶解金属の濃度分析を行った。その結果を表１６に
示す。Next, the column was washed with 150 ml of water, and then passed through the upper portion of the cylindrical column using 1M sulfuric acid as an eluent, and discharged from the lower portion (elution step).
The effluent at that time was collected for each amount shown in Table 16, and the concentration of each dissolved metal was analyzed. Table 16 shows the results.
【００９４】[0094]
【表１６】 [Table 16]
【００９５】表１６の結果が示すように、２６０ｍｌま
での排出液に亜鉛成分が多く含まれており、一方、他の
金属成分は全く含まれていないため、亜鉛成分のみが高
い純度（ほぼ１００％）で溶離・回収できることが分か
った。As can be seen from the results in Table 16, the effluent up to 260 ml contains a large amount of the zinc component, while no other metal components are contained. Therefore, only the zinc component has a high purity (almost 100%). %) Can be eluted and recovered.
【００９６】実験例８ 実験例１において、結合工程でＰｂ2+用担体を１０ｇ×
２本分用い、溶離工程で０．１Ｍ塩酸と５Ｍ塩化ナトリ
ウムの水溶液を用いる以外は、実験例１と同様の操作を
行った。その時、結合工程で分取された排出液と、結合
工程で分取された排出液の濃度分析のの結果を表１７と
表１８に示す。Experimental Example 8 In the experimental example 1, the carrier for Pb 2+ was 10 g ×
The same operation as in Experimental Example 1 was performed except that two tubes were used and an aqueous solution of 0.1 M hydrochloric acid and 5 M sodium chloride was used in the elution step. At this time, Table 17 and Table 18 show the results of the concentration analysis of the effluent fractionated in the binding step and the effluent fractionated in the binding step.
【００９７】[0097]
【表１７】 [Table 17]
【００９８】表１７の結果が示すように、約２０００ｍ
ｌまでの排出液には鉛成分が全く含まれておらず、一
方、他の金属成分は殆ど濃度低下せずに（初期を除く）
排出されているため、亜鉛成分のみが高い選択性および
高い回収率（ほぼ１００％）で担体に結合されたことが
分かった。As shown in the results of Table 17, about 2000 m
The effluent up to 1 contains no lead components, while the other metal components have almost no decrease in concentration (except for the initial stage)
As a result, it was found that only the zinc component was bound to the carrier with high selectivity and high recovery (almost 100%).
【００９９】[0099]
【表１８】 [Table 18]
【０１００】表１８の結果が示すように、２６５ｍｌま
での排出液に鉛成分が多く含まれており、一方、他の金
属成分は全く含まれていないため、鉛成分のみが高い純
度（ほぼ１００％）で溶離・回収できることが分かっ
た。As shown in the results in Table 18, the effluent up to 265 ml contains a large amount of lead component, while no other metal components are contained at all. Therefore, only the lead component has high purity (almost 100%). %) Can be eluted and recovered.
【０１０１】実験例９（溶解試験） 前記表１に示す組成の溶融飛灰を用いて、表１９に示
す、酸又はアルカリ、灰濃度、薬剤濃度にて溶解試験を
行った。溶解はマグネチックスターラーで攪拌しつつ約
３０分間行った（溶解工程）。得られた懸濁液を濾過し
（分離工程）、その濾液中の溶解金属の濃度分析を行っ
た。その結果を表１９に示す。Experimental Example 9 (Dissolution test) Using a melt fly ash having the composition shown in Table 1 above, a dissolution test was conducted at the acid or alkali, ash concentration and drug concentration shown in Table 19. The dissolution was performed for about 30 minutes while stirring with a magnetic stirrer (dissolution step). The obtained suspension was filtered (separation step), and the concentration of dissolved metal in the filtrate was analyzed. Table 19 shows the results.
【０１０２】[0102]
【表１９】 [Table 19]
【０１０３】表１９の結果が示すように、硝酸又は塩酸
と塩化ナトリウムの併用が、鉛、亜鉛、銅、アルミニウ
ム等の成分を良く溶解していることが分かった。一方、
硫酸は、鉛と不溶性塩を形成するためその溶解性に劣
り、水酸化ナトリウムは鉛と亜鉛には溶解性を示すもの
の、他の金属成分の溶解性に劣っていた。また、使用す
る酸等の好ましい濃度は、灰の濃度によって異なるが、
最終ｐＨが１以下となる濃度が特に有効である。As shown in the results of Table 19, it was found that the combined use of nitric acid or hydrochloric acid and sodium chloride dissolved components such as lead, zinc, copper, and aluminum well. on the other hand,
Sulfuric acid was inferior in solubility because it formed an insoluble salt with lead, and sodium hydroxide was soluble in lead and zinc, but poor in solubility of other metal components. In addition, the preferred concentration of the acid or the like used depends on the concentration of the ash,
A concentration at which the final pH is 1 or less is particularly effective.
【０１０４】上記の溶解試験では、塩酸と塩化ナトリウ
ムを併用する場合を示したが、０．７５Ｎ塩酸を用い
て、塩化ナトリウム濃度を変えた時の鉛成分の溶解性を
示したのが図３のグラフである。このグラフより、塩酸
濃度の１．０モル倍（即ち０．７５Ｍ）の濃度以上で特
に鉛成分の溶解効果が高いことが分かった。In the above-mentioned dissolution test, the case where hydrochloric acid and sodium chloride were used in combination was shown. FIG. 3 shows the solubility of the lead component when the concentration of sodium chloride was changed using 0.75N hydrochloric acid. It is a graph of. From this graph, it was found that the effect of dissolving the lead component was particularly high at a concentration of 1.0 mol times the hydrochloric acid concentration (that is, 0.75 M) or more.
【０１０５】実験例１０（溶解試験） 前記表１に示す組成の溶融飛灰を用いて、１Ｍ硫酸によ
り鉛以外の金属成分をまず溶解し、その溶解残渣に対し
て更に表２０に示す酸にて溶解試験を行った。溶解はマ
グネチックスターラーで攪拌しつつ約３０分間行った
（以上溶解工程）。得られた懸濁液を濾過し（分離工
程）、その濾液中の溶解金属の濃度分析を行った。その
結果を表２０に示す。Experimental Example 10 (Dissolution test) Using molten fly ash having the composition shown in Table 1 above, metal components other than lead were first dissolved with 1M sulfuric acid, and the dissolved residue was further dissolved in an acid shown in Table 20. To perform a dissolution test. The dissolution was performed for about 30 minutes while stirring with a magnetic stirrer (the above dissolution step). The obtained suspension was filtered (separation step), and the concentration of dissolved metal in the filtrate was analyzed. Table 20 shows the results.
【０１０６】[0106]
【表２０】 [Table 20]
【０１０７】表２０の結果が示すように、硫酸で十分溶
解されなかった鉛成分を、硝酸、塩酸、塩酸＋塩化カル
シウムにより溶解できることが分かった。つまり、酸を
併用することによって、より多種の金属成分を溶解する
ことができ、それぞれに対して後の結合工程〜溶離工程
を適用することができる。ただし、表１に示す組成の溶
融飛灰に対しては、最初から硝酸を使用又は塩酸と塩化
ナトリウムを併用することにより、本発明の目的に合っ
た溶解工程を好適に行うことができる。As shown in the results of Table 20, it was found that the lead component which was not sufficiently dissolved by sulfuric acid could be dissolved by nitric acid, hydrochloric acid, hydrochloric acid + calcium chloride. That is, by using an acid in combination, more kinds of metal components can be dissolved, and the subsequent binding step to elution step can be applied to each of them. However, for the molten fly ash having the composition shown in Table 1, by using nitric acid or a combination of hydrochloric acid and sodium chloride from the beginning, a dissolving step suitable for the purpose of the present invention can be suitably performed.
【０１０８】実験例１１（析出工程） 実験例３で得られた鉛成分を溶離した溶離液に対し、硫
酸を不溶化剤として鉛成分の析出を行った。析出前の溶
離液と析出後に濾過した濾液の鉛濃度を表２１に示す。Experimental Example 11 (Precipitation Step) The eluate eluted from the lead component obtained in Experimental Example 3 was used to precipitate the lead component using sulfuric acid as an insolubilizing agent. Table 21 shows the lead concentrations of the eluent before the precipitation and the filtrate filtered after the precipitation.
【０１０９】[0109]
【表２１】 [Table 21]
【０１１０】表２１の結果が示すように、略１００％の
鉛成分が析出により回収できることが分かった。As shown in the results of Table 21, it was found that approximately 100% of the lead component can be recovered by precipitation.
【０１１１】実験例１２（析出工程） 実験例４〜７で得られた各金属成分を溶離した溶離液に
対し、水酸化ナトリウムを不溶化剤として各金属成分の
析出を行った。析出前の溶離液と析出後に濾過した濾液
の金属濃度をそれぞれ表２２に示す。EXPERIMENTAL EXAMPLE 12 (Precipitation Step) Each of the metal components obtained in Experimental Examples 4 to 7 was precipitated using sodium hydroxide as an insolubilizing agent. Table 22 shows the metal concentrations of the eluent before the precipitation and the filtrate filtered after the precipitation.
【０１１２】[0112]
【表２２】 [Table 22]
【０１１３】表２２の結果が示すように、略１００％の
金属成分が析出によりそれぞれ回収できることが分かっ
た。As shown in the results of Table 22, it was found that approximately 100% of the metal components could be respectively recovered by precipitation.
【０１１４】このように、重金属の選択性及び回収率が
非常に高い金属回収装置Ａを、溶融設備の溶融飛灰返送
路６４に設けることによって、重要な資源である重金属
を効率良く回収することができる。As described above, by providing the metal recovery apparatus A having extremely high selectivity and recovery rate of heavy metals in the molten fly ash return path 64 of the melting equipment, it is possible to efficiently recover heavy metals, which are important resources. Can be.
【０１１５】図１に示すように、前記金属回収装置Ａを
溶融飛灰返送路６４に組み込んで、溶融飛灰中の重金属
を回収すると共に、処理残渣を前記溶融炉７４に返送可
能に構成した溶融設備を、テスト稼動した。前記減温塔
７５及び前記第一集塵器７６から回収されて前記溶融飛
灰返送路６４に搬送された溶融飛灰に含まれる金属の濃
度は、その処理の前後で以下の様に変化した。溶融飛灰
１ｔ当たり、従来の飛灰を返送しない方法では、０．８
〜０．９ｔのスラグと、０．０６〜０．０８ｔの溶融飛
灰が発生していたが、本発明に係る溶融設備で処理した
場合は、溶融飛灰はすべて溶融炉７４に返送されるの
で、系外への持ち出しはなく、溶融スラグが０．８８〜
０．９４ｔ発生した。このように、本発明に係る溶融設
備は、重金属を効率よく系外に除去することができるの
で、前記溶融設備内における重金属の蓄積を防止するこ
とによって腐食等を防止して、設備の保守を容易とする
と共に、設備寿命を改善することができる。更に、処理
後の残渣を、再び前記溶融炉７４に返送して溶融するこ
とができるので、溶融飛灰の系外への持ち出しを抑制す
ることによって、後処理にかかる手間やコストを削減す
ることができる。As shown in FIG. 1, the metal recovery apparatus A was incorporated in the molten fly ash return path 64 to recover heavy metals in the molten fly ash and to return the processing residue to the melting furnace 74. The melting facility was put into test operation. The concentration of metal contained in the molten fly ash collected from the cooling tower 75 and the first dust collector 76 and conveyed to the molten fly ash return path 64 changed before and after the treatment as follows. . The conventional method of not returning fly ash per ton of molten fly ash is 0.8
Although slag of ０．９0.9 t and molten fly ash of 0.06 to 0.08 t were generated, all the molten fly ash is returned to the melting furnace 74 when treated with the melting equipment according to the present invention. Therefore, no slag is taken out of the system and the molten slag is 0.88 ~
0.94t occurred. As described above, the melting equipment according to the present invention can efficiently remove heavy metals from the outside of the system, so that corrosion and the like are prevented by preventing accumulation of heavy metals in the melting equipment, thereby maintaining equipment. In addition to being easy, the equipment life can be improved. Furthermore, since the residue after the treatment can be returned to the melting furnace 74 and melted again, it is possible to reduce the labor and cost for the post-treatment by suppressing the carry-out of the molten fly ash outside the system. Can be.
【０１１６】又、この処理に使用した薬剤は、溶融飛灰
１ｔに対して、塩酸（３５重量％）が１．２ｔ、苛性ソ
ーダ（２５重量％）が２．４ｋｇ、塩化ナトリウムが１
６０（循環利用）ｋｇであり、従来のの方法を用いた
場合と同等程度の薬剤で十分なことが判った。The chemicals used in this treatment were as follows: 1 ton of molten fly ash was 1.2 tons of hydrochloric acid (35% by weight), 2.4 kg of caustic soda (25% by weight), and 1 kg of sodium chloride.
It was 60 (circulation use) kg, and it was found that a drug equivalent to that in the case of using the conventional method was sufficient.
【０１１７】〔別実施形態〕以下に別実施形態を説明す
る。本発明に係る溶融設備にあっては、減温塔７５、第
一集塵器７６で捕捉された溶融飛灰のすべてを、金属回
収装置Ａに移送し、重金属回収処理を施す構成となって
いるが、例えば、これらの溶融飛灰の一部を前記金属回
収装置Ａに移送し、残りを直接溶融炉７４に返送する構
成をとっても良い。又は、前記減温塔７５或いは第一集
塵器７６の何れかで捕捉される溶融飛灰を前記金属回収
装置Ａで処理しても良い。このように、一部のみを前記
金属回収装置Ａに移送して、重金属回収処理を施すこと
によっても、前記溶融設備内を循環する揮発性の高い重
金属を回収して、蓄積を防ぐことができる。[Another Embodiment] Another embodiment will be described below. In the melting facility according to the present invention, all of the molten fly ash captured by the cooling tower 75 and the first dust collector 76 is transferred to the metal recovery device A, and the heavy metal recovery process is performed. However, for example, a configuration may be adopted in which a part of the molten fly ash is transferred to the metal recovery device A, and the rest is directly returned to the melting furnace 74. Alternatively, the molten fly ash captured by either the cooling tower 75 or the first dust collector 76 may be treated by the metal recovery device A. In this way, by transferring only a part to the metal recovery apparatus A and performing the heavy metal recovery processing, the highly volatile heavy metal circulating in the melting facility can be recovered and the accumulation can be prevented. .
【図１】本発明に係る溶融設備を表わすチャート図FIG. 1 is a chart showing a melting facility according to the present invention.
【図２】金属回収装置を表わす概略構成図FIG. 2 is a schematic configuration diagram showing a metal recovery device.
【図３】実験例９で得られた結果を示すグラフFIG. 3 is a graph showing the results obtained in Experimental Example 9.
６ 固体分返送機構 １２ 溶融飛灰溶解槽 １４ 濾過手段 ２３ 担体 Ａ 金属回収装置 6 Solid content return mechanism 12 Melted fly ash melting tank 14 Filtration means 23 Carrier A Metal recovery device
───────────────────────────────────────────────────── フロントページの続き (72)発明者 片岡 静夫 兵庫県尼崎市金楽寺町２丁目２番33号 株 式会社タクマ内 Ｆターム(参考） 4D004 AA37 AB03 AC05 BA05 CA04 CA13 CA35 CA41 CA47 CB44 CB47 CC06 CC12 CC15 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Shizuo Kataoka 2-33 Kingara-cho, Amagasaki-shi, Hyogo F-term in Takuma Co., Ltd. (Reference) 4D004 AA37 AB03 AC05 BA05 CA04 CA13 CA35 CA41 CA47 CB44 CB47 CC06 CC12 CC15
Claims (4)
設備における溶融飛灰の処理方法であって、 前記回収部で回収された前記溶融飛灰を、酸又はアルカ
リを用いて一部溶解させて懸濁液を得る溶解工程と、 前記懸濁液を、固体分と分離液に固液分離する分離工程
と、 分離された前記固体分を前記溶融炉に戻す飛灰返送工程
とを含む再溶融処理工程及び、 前記分離液を、前記分離液中に溶解した溶解金属成分と
選択的に結合し得る大環状化合物を固定化した担体に接
触させて、その溶解金属成分を前記担体に結合させる結
合工程と、 その担体に溶離液を接触させて、前記担体に結合した金
属成分を溶離させる溶離工程とを含む金属回収処理工程
を行う溶融飛灰の処理方法。1. A method for treating molten fly ash in a melting facility provided with a recovery section for recovering the molten fly ash, wherein the molten fly ash recovered in the recovery section is partially treated with an acid or an alkali. A dissolving step of dissolving to obtain a suspension, a separating step of solid-liquid separating the suspension into a solid component and a separated liquid, and a fly ash returning process of returning the separated solid component to the melting furnace. A remelting treatment step comprising: contacting the separated liquid with a carrier on which a macrocyclic compound capable of selectively binding to a dissolved metal component dissolved in the separated solution is immobilized; A method for treating molten fly ash, comprising performing a metal recovery treatment step including a binding step of binding and an elution step of bringing a carrier into contact with an eluent to elute metal components bound to the carrier.
により溶離液中に溶離した金属成分を析出させる析出工
程を含む請求項１に記載の溶融飛灰の処理方法。2. The method for treating molten fly ash according to claim 1, wherein the metal recovery treatment step includes a precipitation step of depositing a metal component eluted in an eluent by the elution step.
設備において、 前記回収部で回収された前記溶融飛灰を、酸又はアルカ
リを用いて一部溶解させて懸濁液を得る溶解槽と、 前記懸濁液を、固体分と分離液に固液分離する固液分離
装置とを設け、 分離された前記固体分を前記溶融炉に返送する固体分返
送機構を設けるとともに、 前記分離液中に溶解した溶解金属成分を、大環状化合物
を固定化した担体に接触させて結合させた後、溶離回収
させる金属回収装置を設けた溶融設備。3. A melting facility provided with a recovery section for recovering molten fly ash, wherein the molten fly ash recovered in the recovery section is partially dissolved using an acid or an alkali to obtain a suspension. A tank, a solid-liquid separator for solid-liquid separating the suspension into a solid component and a separated liquid, a solid component returning mechanism for returning the separated solid component to the melting furnace, A melting facility provided with a metal recovery device for contacting and binding a dissolved metal component dissolved in a liquid to a carrier having a macrocyclic compound immobilized thereon, and then eluting and recovering the metal component.
燥させる乾燥装置と、前記乾燥された固体分を粉砕する
粉砕装置と、粉砕された前記固体分を前記溶融炉に空気
搬送する空気搬送装置とを備えたものである請求項３に
記載の溶融設備。4. The solid content returning mechanism includes a drying device for drying the solid content, a crushing device for crushing the dried solid content, and an air for conveying the crushed solid content to the melting furnace. The melting facility according to claim 3, further comprising a transport device.
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|---|---|---|---|
| JP33778199A JP3633840B2 (en) | 1999-11-29 | 1999-11-29 | Processing method of molten fly ash |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33778199A JP3633840B2 (en) | 1999-11-29 | 1999-11-29 | Processing method of molten fly ash |
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|---|---|
| JP2001149884A true JP2001149884A (en) | 2001-06-05 |
| JP3633840B2 JP3633840B2 (en) | 2005-03-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33778199A Expired - Fee Related JP3633840B2 (en) | 1999-11-29 | 1999-11-29 | Processing method of molten fly ash |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005246226A (en) * | 2004-03-03 | 2005-09-15 | Dowa Mining Co Ltd | Treating method for fly ash |
| US8038969B2 (en) | 2007-05-07 | 2011-10-18 | National University Corporation Akita University | Rare metal/platinum-group metal extractant and method for extracting rare metals and platinum-group metals |
| CN112642842A (en) * | 2021-01-01 | 2021-04-13 | 天津壹鸣环境科技股份有限公司 | Method and system for recycling household garbage incineration fly ash through high-temperature melting and full resource classification |
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| JPH08309313A (en) * | 1995-05-12 | 1996-11-26 | Dowa Mining Co Ltd | Wet treatment method for fly ash containing heavy metal from high temperature treatment furnace |
| JPH10174950A (en) * | 1996-12-19 | 1998-06-30 | Takuma Co Ltd | Treatment of ash |
| JPH10192820A (en) * | 1997-01-13 | 1998-07-28 | Ebara Corp | Treatment of ash in waste disposal by gasification fusion |
| JPH1111999A (en) * | 1997-06-16 | 1999-01-19 | Chichibu Onoda Cement Corp | Performing of fly ash |
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1999
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08309313A (en) * | 1995-05-12 | 1996-11-26 | Dowa Mining Co Ltd | Wet treatment method for fly ash containing heavy metal from high temperature treatment furnace |
| JPH10174950A (en) * | 1996-12-19 | 1998-06-30 | Takuma Co Ltd | Treatment of ash |
| JPH10192820A (en) * | 1997-01-13 | 1998-07-28 | Ebara Corp | Treatment of ash in waste disposal by gasification fusion |
| JPH1111999A (en) * | 1997-06-16 | 1999-01-19 | Chichibu Onoda Cement Corp | Performing of fly ash |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005246226A (en) * | 2004-03-03 | 2005-09-15 | Dowa Mining Co Ltd | Treating method for fly ash |
| US8038969B2 (en) | 2007-05-07 | 2011-10-18 | National University Corporation Akita University | Rare metal/platinum-group metal extractant and method for extracting rare metals and platinum-group metals |
| CN112642842A (en) * | 2021-01-01 | 2021-04-13 | 天津壹鸣环境科技股份有限公司 | Method and system for recycling household garbage incineration fly ash through high-temperature melting and full resource classification |
| CN112642842B (en) * | 2021-01-01 | 2023-12-05 | 天津壹鸣环境科技股份有限公司 | Method and system for high-temperature melting and full-resource classification recycling treatment of household garbage incineration fly ash |
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| Publication number | Publication date |
|---|---|
| JP3633840B2 (en) | 2005-03-30 |
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