JP7408365B2 - How to dispose of smoke ash - Google Patents
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- JP7408365B2 JP7408365B2 JP2019220292A JP2019220292A JP7408365B2 JP 7408365 B2 JP7408365 B2 JP 7408365B2 JP 2019220292 A JP2019220292 A JP 2019220292A JP 2019220292 A JP2019220292 A JP 2019220292A JP 7408365 B2 JP7408365 B2 JP 7408365B2
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- 239000000779 smoke Substances 0.000 title claims description 76
- 239000003960 organic solvent Substances 0.000 claims description 105
- 229910001385 heavy metal Inorganic materials 0.000 claims description 70
- 238000000034 method Methods 0.000 claims description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- 238000000638 solvent extraction Methods 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 26
- 238000000605 extraction Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 239000011133 lead Substances 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000011135 tin Substances 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 150000002923 oximes Chemical class 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000002956 ash Substances 0.000 description 54
- 239000011575 calcium Substances 0.000 description 48
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000012071 phase Substances 0.000 description 17
- 239000008346 aqueous phase Substances 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- 239000010440 gypsum Substances 0.000 description 13
- 229910052602 gypsum Inorganic materials 0.000 description 13
- 238000005191 phase separation Methods 0.000 description 13
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 12
- 238000003723 Smelting Methods 0.000 description 10
- 229910052736 halogen Inorganic materials 0.000 description 10
- 150000002367 halogens Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000010881 fly ash Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 239000010944 silver (metal) Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- -1 ferrous metals Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Processing Of Solid Wastes (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、煙灰の処理方法に関する。 The present invention relates to a method for processing smoke ash.
産業上発生する煙灰（特に金属製錬に伴い発生する煙灰）には、種々の金属が含有される。従来の煙灰の処理方法としては、非特許文献１に記載の技術が知られている。 BACKGROUND ART Industrially generated smoke ash (especially smoke ash generated in metal smelting) contains various metals. As a conventional method for processing smoke ash, the technique described in Non-Patent Document 1 is known.
非特許文献１には、金属製錬に伴い発生した煙灰を消石灰（Ｃａ（ＯＨ）２）にて中和した後、煙灰に含有される金属を酸浸出し、苛性ソーダおよび水硫化ソーダなどにより煙灰を処理する技術が記載されている。 Non-Patent Document 1 states that after the smoke ash generated during metal smelting is neutralized with slaked lime (Ca(OH) 2 ), the metals contained in the smoke ash are leached with acid, and the smoke ash is made with caustic soda, sodium hydrosulfide, etc. Techniques for processing this are described.
本発明者により、以下の課題が見出された。 The inventor discovered the following problem.
煙灰がＣａ（カルシウム）を含有する場合、煙灰に含有される金属（特に、非鉄金属であって亜鉛、銅、鉛、錫、レアメタル、カドミウム、貴金属等の有価金属）を硫酸にて酸浸出しようと試みてしまうと、難溶性である石膏（ＣａＳＯ４）が形成されてしまう。この石膏に、本来酸浸出すべき金属が随伴し、結果として煙灰に含有される金属が回収不能となる。この現象は、特に、消石灰による中和処理が行われた後のアルカリ性の消石灰含有煙灰だと顕著である。 If the smoke ash contains Ca (calcium), the metals contained in the smoke ash (especially valuable metals such as non-ferrous metals such as zinc, copper, lead, tin, rare metals, cadmium, and precious metals) should be leached out with sulfuric acid. If this is attempted, gypsum (CaSO 4 ), which is sparingly soluble, will be formed. This gypsum is accompanied by metals that should originally be leached out with acid, and as a result, the metals contained in the smoke ash cannot be recovered. This phenomenon is particularly noticeable with alkaline slaked lime-containing smoke ash that has been neutralized with slaked lime.
本発明の目的は、石膏の発生を抑制しつつもＣａ含有アルカリ性煙灰から重金属を抽出することにある。
本発明の別の目的は、抽出後の該重金属を回収可能とすることにある。
An object of the present invention is to extract heavy metals from Ca-containing alkaline smoke while suppressing the generation of gypsum.
Another object of the present invention is to make it possible to recover the heavy metals after extraction.
本発明の第１の態様は、
プロトン放出型の有機溶媒によりＣａ含有アルカリ性煙灰から重金属を該有機溶媒へと溶媒抽出する重金属溶媒抽出工程を有する、煙灰の処理方法である。
The first aspect of the present invention is
This is a method for treating smoke ash, which includes a heavy metal solvent extraction step of extracting heavy metals from Ca-containing alkaline smoke ash into the organic solvent using a proton-releasing organic solvent.
本発明の第２の態様は、第１の態様に記載の発明において、
前記Ｃａ含有アルカリ性煙灰は消石灰を含有する。
A second aspect of the present invention is the invention described in the first aspect,
The Ca-containing alkaline smoke ash contains slaked lime.
本発明の第３の態様は、第１または第２の態様において、
前記Ｃａ含有アルカリ性煙灰においてＣａは０．１質量％以上である。
A third aspect of the present invention is, in the first or second aspect,
In the Ca-containing alkaline smoke ash, Ca is 0.1% by mass or more.
本発明の第４の態様は、第１～第３のいずれかの態様に記載の発明において、
前記重金属溶媒抽出工程に際し、ＴＢＰ（リン酸トリブチル）を加える。
A fourth aspect of the present invention is the invention according to any one of the first to third aspects,
TBP (tributyl phosphate) is added during the heavy metal solvent extraction step.
本発明の第５の態様は、第１～第４のいずれかの態様に記載の発明において、
前記重金属溶媒抽出工程の後、前記有機溶媒からＣａを除去し且つ前記有機溶媒のプロトンを再生する有機溶媒洗浄工程を更に有する。
A fifth aspect of the present invention is the invention according to any one of the first to fourth aspects,
After the heavy metal solvent extraction step, the method further includes an organic solvent washing step of removing Ca from the organic solvent and regenerating protons of the organic solvent.
本発明の第６の態様は、第５の態様に記載の発明において、
前記有機溶媒洗浄工程後、硫酸により前記有機溶媒から重金属を逆抽出する逆抽出工程を更に有する。
A sixth aspect of the present invention is the invention described in the fifth aspect,
After the organic solvent washing step, the method further includes a back extraction step of back extracting heavy metals from the organic solvent using sulfuric acid.
本発明の第７の態様は、第１～第６のいずれかの態様に記載の発明において、
前記有機溶媒は、ジチオカルバミン酸、リン酸、カルボン酸、オキシムまたはそれらの誘導体の少なくともいずれかを含有する。
A seventh aspect of the present invention is the invention according to any one of the first to sixth aspects,
The organic solvent contains at least one of dithiocarbamic acid, phosphoric acid, carboxylic acid, oxime, or a derivative thereof.
本発明によれば、石膏の発生を抑制しつつもＣａ含有アルカリ性煙灰から重金属を抽出できる。
また、本発明によれば、抽出後の該重金属を回収できるようになる。
According to the present invention, heavy metals can be extracted from Ca-containing alkaline smoke while suppressing the generation of gypsum.
Further, according to the present invention, the heavy metals can be recovered after extraction.
本明細書における「～」は所定の数値以上かつ所定の数値以下を指す。
以下、本実施形態について説明する。図１は、本実施形態に係る煙灰の処理方法のフローチャートである。
In this specification, "~" refers to a value greater than or equal to a predetermined value and less than or equal to a predetermined value.
This embodiment will be described below. FIG. 1 is a flowchart of the smoke ash processing method according to the present embodiment.
本実施形態における「Ｃａ含有アルカリ性煙灰」は、産業上発生する煙灰であれば限定は無い。本実施形態においては、金属製錬に伴い発生する煙灰（特に溶融飛灰）を例示し、且つ、消石灰による中和処理がなされた後の煙灰すなわち消石灰含有煙灰を例示する。つまり、本実施形態で主に例示するＣａは、水酸化カルシウム（Ｃａ（ＯＨ）２）である。他にも少ないが酸化カルシウム、炭酸カルシウムなどが混合されている可能性はある。 The "Ca-containing alkaline smoke ash" in this embodiment is not limited as long as it is industrially generated smoke ash. In this embodiment, smoke ash (particularly molten fly ash) generated during metal smelting is illustrated, and smoke ash that has been neutralized with slaked lime, that is, smoke ash containing slaked lime, is illustrated. That is, Ca mainly exemplified in this embodiment is calcium hydroxide (Ca(OH) 2 ). It is possible that other substances such as calcium oxide and calcium carbonate are mixed in, although they are rare.
消石灰による中和処理の形式には限定は無く、湿式でも乾式でもよい。また、該煙灰の粒子の大きさには限定は無いが、例えば粒径が１～５０００μｍであってもよい。 The type of neutralization treatment with slaked lime is not limited, and may be wet or dry. Further, the size of the smoke ash particles is not limited, but may be, for example, 1 to 5000 μm.
煙灰に含有されるＣａの量には特に限定は無いが、例えば、Ｃａ含有アルカリ性煙灰においてＣａは０．１質量％以上、好ましくは２質量％以上であっても、本実施形態の処理方法を採用することにより、本発明の課題の欄で述べたような石膏の発生に伴う不具合は生じない点で、本発明の技術的思想には大きな意義がある。 There is no particular limitation on the amount of Ca contained in the smoke ash, but for example, even if the Ca content in the Ca-containing alkaline smoke ash is 0.1% by mass or more, preferably 2% by mass or more, the treatment method of this embodiment can be applied. The technical idea of the present invention has great significance in that by employing this method, the problems associated with the generation of gypsum as described in the section on the problems of the present invention do not occur.
また、Ｃａ含有アルカリ性煙灰そのものに対して本実施形態の処理方法を適用してもよいし、該煙灰を水と混合することによりスラリー化したものに対して本実施形態の処理方法を適用してもよい。いずれにせよ、Ｃａ含有アルカリ性煙灰から重金属を溶媒抽出することに変わりはない。本実施形態においては、スラリー化した煙灰を例示する。 Further, the treatment method of this embodiment may be applied to the Ca-containing alkaline smoke ash itself, or the treatment method of this embodiment may be applied to a slurry made by mixing the smoke ash with water. Good too. In any case, heavy metals are still extracted with a solvent from Ca-containing alkaline smoke. In this embodiment, smoke ash made into a slurry is exemplified.
Ｃａ含有アルカリ性煙灰は、その名のとおり、Ｃａを含有し且つアルカリ性であれば特に限定は無い。Ｃａ含有アルカリ性煙灰を水と混合することによりスラリー化したときのスラリーのｐＨが７を超える状態の煙灰を「Ｃａ含有アルカリ性煙灰」とする。 As the name suggests, the Ca-containing alkaline smoke ash is not particularly limited as long as it contains Ca and is alkaline. The ash in which the pH of the slurry when the Ca-containing alkaline ash is mixed with water to form a slurry is defined as "Ca-containing alkaline ash".
Ｃａ含有アルカリ性煙灰に含有される重金属には特に限定は無く、Ｚｎ（亜鉛）、Ｐｂ（鉛）、Ｃｕ（銅）、Ｓｎ（錫）、Ａｇ（銀）、Ａｕ（金）、ＰＧＭ（白金族元素、すなわちルテニウム（Ｒｕ）、ロジウム（Ｒｈ）、パラジウム（Ｐｄ）、オスミウム（Ｏｓ）、イリジウム（Ｉｒ）、白金（Ｐｔ）からなる群の少なくともいずれか）などが挙げられ、これらの少なくともいずれかを含んでいてもよい。 There are no particular limitations on the heavy metals contained in the Ca-containing alkaline smoke, including Zn (zinc), Pb (lead), Cu (copper), Sn (tin), Ag (silver), Au (gold), and PGM (platinum group metal). elements, such as at least one of the group consisting of ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt), and at least one of these. May contain.
本実施形態の大きな特徴の一つが、プロトン放出型の有機溶媒によりＣａ含有アルカリ性煙灰（本実施形態の一例だと該煙灰のスラリー）から重金属を該有機溶媒へと溶媒抽出する重金属溶媒抽出工程を有することである。 One of the major features of this embodiment is the heavy metal solvent extraction process in which heavy metals are extracted from Ca-containing alkaline smoke ash (slurry of the smoke ash in an example of this embodiment) using a proton-releasing organic solvent. It is to have.
重金属溶媒抽出工程では以下の反応が生じる。Ｈ－Ｒは、プロトン放出型の有機溶媒を指す。Ｍ２＋は重金属イオンを指し、説明の便宜上、２価の重金属イオンを例示する。
２Ｈ－Ｒ＋Ｃａ（ＯＨ）２＝Ｃａ－２Ｒ＋２Ｈ２Ｏ ・・・（１）（主反応）
２Ｈ－Ｒ＋Ｍ２＋＝Ｍ－２Ｒ＋２Ｈ＋ ・・・（２）（副反応その１）
Ｃａ（ＯＨ）２＋２Ｈ＋＝Ｃａ２＋＋２Ｈ２Ｏ ・・・（３）（副反応その２）
溶媒抽出において、プロトン放出型の有機溶媒を採用するため、煙灰中の重金属は有機溶媒（すなわち油相）へと溶媒抽出される（（２）のＭ－２Ｒ）。なお、Ｃａ含有アルカリ性煙灰中のＣａ（ＯＨ）２は、プロトン放出型の有機溶媒により酸溶解され、油相（有機溶媒）に溶媒抽出されたり（（１）のＣａ－２Ｒ）、元スラリーにより構成される水相に移行したりする（（３）のＣａ２＋）。このようにＣａは、石膏のような中和物でないため、他の金属イオンを巻き込む共沈を抑制し、さらにはアルカリ性の反応剤としても利用可能な状態である。
The following reactions occur in the heavy metal solvent extraction step. HR refers to a proton-releasing organic solvent. M 2+ refers to a heavy metal ion, and for convenience of explanation, a divalent heavy metal ion is exemplified.
2H-R+Ca(OH) 2 =Ca-2R+2H 2 O...(1) (main reaction)
2H-R+M 2+ =M-2R+2H + ...(2) (Side reaction 1)
Ca(OH) 2 +2H + =Ca 2+ +2H 2 O...(3) (Side reaction 2)
In the solvent extraction, since a proton-releasing organic solvent is used, the heavy metals in the smoke ash are solvent extracted into the organic solvent (ie, oil phase) (M-2R in (2)). Note that Ca(OH) 2 in the Ca-containing alkaline smoke is acid-dissolved in a proton-releasing organic solvent, extracted into the oil phase (organic solvent) (Ca-2R in (1)), or extracted into the original slurry. (Ca 2+ in (3)). In this way, since Ca is not a neutralized substance like gypsum, it suppresses coprecipitation involving other metal ions, and can also be used as an alkaline reactant.
つまり、重金属溶媒抽出工程により、本発明の課題で述べたような石膏は発生させずにＣａ含有アルカリ性煙灰から重金属を分離することが可能となる。それに加え、以下の顕著な効果も備える。すなわち、上記（１）～（３）が示すように、重金属溶媒抽出工程ならば、Ｃａ（ＯＨ）２の浸出処理と金属Ｍの抽出処理とを同時に行える。これは、石膏形成を回避すべく単に硫酸以外の鉱酸を使用する選択をしただけでは得られない効果である。 In other words, the heavy metal solvent extraction step makes it possible to separate heavy metals from Ca-containing alkaline smoke without generating gypsum as described in the problem of the present invention. In addition, it also has the following notable effects: That is, as shown in (1) to (3) above, in the heavy metal solvent extraction process, the leaching process of Ca(OH) 2 and the extraction process of metal M can be performed simultaneously. This is an effect that cannot be obtained simply by choosing to use mineral acids other than sulfuric acid to avoid gypsum formation.
また、重金属溶媒抽出工程がもたらす効果として、ハロゲン（塩素（Ｃｌ）、臭素（Ｂｒ）、ここではＣｌを例示）が水相中に残置されることがある。ハロゲンは、煙灰に含有されるＮａ、Ｋに付随する形で主に存在しているが、重金属溶媒抽出工程により、Ｎａ、Ｋの大部分が水相中に残置される（後掲の実施例１参照）。これは、ハロゲンも水相中に残置されることを意味し、有機溶媒にはハロゲンがほとんど抽出されないことを意味する。これにより、既存の製錬工程に該有機溶媒を投入した場合において、製錬工程に与える影響を軽減できる。 Further, as an effect brought about by the heavy metal solvent extraction step, halogens (chlorine (Cl), bromine (Br), Cl is exemplified here) may remain in the aqueous phase. Halogens mainly exist in the form associated with Na and K contained in smoke ash, but due to the heavy metal solvent extraction process, most of Na and K remain in the aqueous phase (see Examples below). (see 1). This means that the halogen is also left in the aqueous phase, and that almost no halogen is extracted into the organic solvent. Thereby, when the organic solvent is introduced into an existing smelting process, the influence on the smelting process can be reduced.
しかも、本実施形態に係る重金属溶媒抽出工程後だと、元スラリーである水相中にハロゲンが多量に存在することから、この水相をブライン浸出に利用することも可能となる。 Moreover, after the heavy metal solvent extraction step according to the present embodiment, since a large amount of halogen is present in the aqueous phase that is the original slurry, this aqueous phase can also be used for brine leaching.
また、硫酸はもとより、それ以外の酸をわざわざ使用する必要もない。プロトン放出型の有機溶媒を利用すれば、溶媒抽出を利用してＣａ含有アルカリ性煙灰から重金属を回収できるようになるという効果もある。 Moreover, there is no need to take the trouble to use not only sulfuric acid but also other acids. The use of a proton-releasing organic solvent also has the effect of making it possible to recover heavy metals from Ca-containing alkaline smoke using solvent extraction.
本実施形態における「プロトン放出型の有機溶媒」は、上記（１）（２）のようにプロトン（Ｈ＋）を放出可能な有機溶媒であれば限定は無い。具体例を挙げると、ジチオカルバミン酸、リン酸、カルボン酸、オキシムに代表されるキレート型抽出剤またはそれらの誘導体の少なくともいずれかを含有するものであってもよい。なお、リン酸またはその誘導体を含有する市販の試薬としてはＤ２ＥＨＰＡ（ジ－（２－エチルヘキシル）リン酸）、ＰＣ－８８Ａ（大八化学工業株式会社製：化合物名は２－エチルヘキシルホスホン酸２－エチルヘキシル）、ＣＹＡＮＥＸ２７２（ＳＯＬＶＡＹ製：化合物名はジ（２，４，４－トリメチルペンチル）ホスフィン酸）が挙げられる。 The "proton-releasing organic solvent" in this embodiment is not limited as long as it is an organic solvent that can release protons (H + ) as described in (1) and (2) above. To give a specific example, it may contain at least one of a chelate extractant represented by dithiocarbamic acid, phosphoric acid, carboxylic acid, and oxime, or a derivative thereof. Commercially available reagents containing phosphoric acid or its derivatives include D2EHPA (di-(2-ethylhexyl) phosphoric acid), PC-88A (manufactured by Daihachi Kagaku Kogyo Co., Ltd.; the compound name is 2-ethylhexylphosphonic acid 2- ethylhexyl) and CYANEX272 (manufactured by SOLVAY; compound name is di(2,4,4-trimethylpentyl)phosphinic acid).
なお、プロトン放出型の有機溶媒以外の有機溶媒と混合して本実施形態に使用してもよい（例えば後掲の実施例１におけるケロシン）。その際の混合物を総有機溶媒とも称する。 Note that it may be used in this embodiment by mixing with an organic solvent other than a proton-releasing type organic solvent (for example, kerosene in Example 1 described below). The mixture at that time is also referred to as total organic solvent.
具体的な重金属溶媒抽出工程の作業内容としては限定は無いが、例えば、プロトン放出型の有機溶媒を収めた容器に煙灰を投入した後、撹拌、振とう等を行うことが挙げられる。もちろん、煙灰を収めた容器に有機溶媒を添加しても構わない。また、その際に、本実施形態で例示するようにスラリー化した煙灰を使用しても構わない。 Although there are no specific limitations on the specific work contents of the heavy metal solvent extraction step, for example, stirring, shaking, etc. may be performed after pouring smoke ash into a container containing a proton-releasing organic solvent. Of course, an organic solvent may be added to the container containing the smoke ash. Further, at that time, smoke ashes made into a slurry may be used as exemplified in this embodiment.
重金属溶媒抽出工程によりもたらされる分相状態をＴＢＰ（リン酸トリブチル）により改善する分相改善工程を更に有するのが好ましい。分相改善工程により、煙灰の残渣成分（固体成分）が油相（有機溶媒）中に残置されるのを抑制できる。それに加え、油相の下方の水相中においても、水相下方に固体成分が沈降し、水相中でも液体と固体とに好適に分相する。別の言い方をすると、上方から順に油相、水相、固相（すなわち固体成分）とに良好に分相する。これは、油相（有機溶媒）の分離回収が容易化する（例えばろ過が不要になる）ことにもつながるし、水相に対する残渣除去処理の手間が相当省ける（例えばろ過が不要になる）ことにもつながる。これは、ハロゲンが多量に存在する水相をブライン浸出に利用可能であることを考慮すると、有利な効果である。 It is preferable to further include a phase separation improvement step of improving the phase separation state brought about by the heavy metal solvent extraction step using TBP (tributyl phosphate). The phase separation improvement step can suppress residual components (solid components) of smoke ash from remaining in the oil phase (organic solvent). In addition, even in the aqueous phase below the oil phase, a solid component precipitates below the aqueous phase, and the aqueous phase is suitably separated into a liquid and a solid. In other words, the phase is favorably separated into an oil phase, an aqueous phase, and a solid phase (that is, a solid component) in order from the top. This also makes it easier to separate and recover the oil phase (organic solvent) (e.g., no filtration is required), and it also significantly reduces the effort required to remove residue from the aqueous phase (e.g., no filtration is required). It also leads to This is an advantageous effect considering that a halogen-rich aqueous phase is available for brine leaching.
また、分相を改善するということは、Ｃａ含有アルカリ性煙灰の固体成分が該溶媒中に残置されることを抑制できることにつながる。該固体成分が該溶媒中にてクラッド化（一具体例としては油相（有機溶媒）と水相との間にて固体成分が凝集）してしまうと、処理装置の操業に影響を及ぼすおそれがある。このおそれは、煙灰が、ＳｉＯ２の品位が比較的低く（例えば煙灰中でＳｉＯ２が１０質量％以下）、油相（有機溶媒）中にて沈降しづらい溶融飛灰である場合、より顕著になる。その一方、分相改善工程を採用することにより、そのようなおそれを排することができる。 Moreover, improving phase separation leads to being able to suppress the solid components of the Ca-containing alkaline smoke from remaining in the solvent. If the solid component becomes clad in the solvent (for example, the solid component aggregates between the oil phase (organic solvent) and the aqueous phase), it may affect the operation of the treatment equipment. There is. This fear is more pronounced when the smoke ash is molten fly ash that has a relatively low SiO 2 quality (for example, SiO 2 in the smoke ash is 10% by mass or less) and is difficult to settle in the oil phase (organic solvent). become. On the other hand, such a fear can be eliminated by employing a phase separation improvement process.
その結果、重金属溶媒抽出工程により、石膏の発生を抑制しつつもＣａ含有アルカリ性煙灰から重金属を抽出できた後、抽出後の該重金属が回収可能となる。 As a result, after heavy metals can be extracted from Ca-containing alkaline smoke while suppressing the generation of gypsum through the heavy metal solvent extraction step, the extracted heavy metals can be recovered.
なお、重金属溶媒抽出工程と分相改善工程とを同時に行うのが手間が省けて好ましい。具体的には、プロトン放出型の有機溶媒とＴＢＰとを予め混合した混合溶媒を用意しておき、この混合溶媒を用いて煙灰に対して溶媒抽出を行ってもよい。もちろん、重金属溶媒抽出工程を行った後の有機溶媒に対してＴＢＰを添加し、重金属溶媒抽出工程と分相改善工程とを別々に行うことに妨げは無い。これらの作業をまとめて「重金属溶媒抽出工程に際し、ＴＢＰ（リン酸トリブチル）を加える」と称する。 Note that it is preferable to perform the heavy metal solvent extraction step and the phase separation improvement step at the same time because it saves time and effort. Specifically, a mixed solvent in which a proton-releasing organic solvent and TBP are mixed in advance may be prepared, and the smoke ash may be subjected to solvent extraction using this mixed solvent. Of course, there is no hindrance to adding TBP to the organic solvent after performing the heavy metal solvent extraction step and performing the heavy metal solvent extraction step and the phase separation improvement step separately. These operations are collectively referred to as "adding TBP (tributyl phosphate) during the heavy metal solvent extraction step."
分相改善工程のその他の好適な条件は後掲の実施例２にて述べる。 Other suitable conditions for the phase separation improvement step will be described in Example 2 below.
重金属溶媒抽出工程および分相改善工程の後、有機溶媒からＣａを除去する有機溶媒洗浄工程を更に有するのが好ましい。なお、分相改善の必要がなければ、重金属溶媒抽出工程後、分相改善工程を行わず、有機溶媒洗浄工程を行ってもよい。これにより、有機溶媒から重金属を逆抽出する際に硫酸を使用しても、石膏の発生を抑制できる。 After the heavy metal solvent extraction step and the phase separation improvement step, it is preferable to further include an organic solvent washing step for removing Ca from the organic solvent. Note that if there is no need to improve phase separation, an organic solvent washing step may be performed after the heavy metal solvent extraction step without performing the phase separation improvement step. Thereby, even if sulfuric acid is used when back-extracting heavy metals from an organic solvent, the generation of gypsum can be suppressed.
有機溶媒洗浄工程の具体的な手法には限定は無く、硫酸以外の酸（例えば塩酸）（好適にはｐＨ４～５程度）と有機溶媒とを接触させることにより洗浄を行ってもよい。また、有機溶媒洗浄工程は複数回行うのが、Ｃａ除去の度合いを高めるという点で好ましい（後掲の実施例３では３回行っている）。 There are no specific limitations on the specific method of the organic solvent cleaning step, and cleaning may be performed by bringing an acid other than sulfuric acid (eg, hydrochloric acid) (preferably pH 4 to 5) into contact with the organic solvent. Furthermore, it is preferable to perform the organic solvent washing step multiple times in order to increase the degree of Ca removal (in Example 3, which will be described later, the step is performed three times).
また、有機溶媒洗浄工程がもたらす効果として、Ｃａと同様、有機溶媒に含まれるハロゲンも除去できることがある。これにより、有機溶媒中にハロゲンを残置させずに済み、既存の製錬工程に該有機溶媒を投入した場合において、製錬工程に与える影響を軽減できる。 Further, as an effect brought about by the organic solvent cleaning step, halogen contained in the organic solvent can be removed as well as Ca. This eliminates the need for halogen to remain in the organic solvent, and when the organic solvent is introduced into an existing smelting process, the influence on the smelting process can be reduced.
更に、有機溶媒洗浄工程により、有機溶媒はプロトン放出前の状態へと再生させるのがよい。別の言い方だと、有機溶媒洗浄工程によりプロトン付着させる、いわゆるプロトン再生工程を行うのがよい。塩酸により有機溶媒を洗浄する場合、以下の反応が生じる。
Ｃａ－２Ｒ＋２Ｈ＋＝Ｃａ２＋＋２Ｈ－Ｒ ・・・（４）
Furthermore, the organic solvent is preferably regenerated to the state before proton release through an organic solvent washing step. In other words, it is preferable to carry out a so-called proton regeneration process in which protons are attached through an organic solvent washing process. When washing an organic solvent with hydrochloric acid, the following reaction occurs.
Ca-2R+2H + =Ca 2+ +2H-R...(4)
プロトン再生工程を経た後の有機溶媒は、別サイクルの煙灰処理において使用可能である。なお、この有機溶媒洗浄工程を経た後でも重金属は有機溶媒中に残置される（後掲の実施例３参照）。洗浄後液に移行するのは、ここではＮａ、Ｋ、Ｃａのような軽金属（非重金属）である。 The organic solvent after the proton regeneration step can be used in another cycle of smoke ash treatment. Note that even after this organic solvent washing step, heavy metals remain in the organic solvent (see Example 3 below). Here, it is light metals (non-heavy metals) such as Na, K, and Ca that migrate to the post-washing solution.
有機溶媒洗浄工程後、硫酸により有機溶媒から重金属を逆抽出する逆抽出工程を更に有するのが好ましい。逆抽出においては以下の反応が生じる。
Ｍ－２Ｒ＋２Ｈ＋＝Ｍ２＋＋２Ｈ－Ｒ ・・・（５）
After the organic solvent washing step, it is preferable to further include a back extraction step of back extracting heavy metals from the organic solvent using sulfuric acid. The following reactions occur during back extraction.
M-2R+2H + =M 2+ +2H-R...(5)
（５）に示すように、逆抽出工程においてもプロトン再生工程が行われる。この有機溶媒も、別サイクルの煙灰処理において使用可能である。 As shown in (5), a proton regeneration step is also performed in the back extraction step. This organic solvent can also be used in a separate cycle of smoke ash treatment.
このとき、硫酸の濃度は１００～２５０ｇ／Ｌとしてもよい。なお、逆抽出の手法としては公知のものを採用しても構わない。もちろん、硫酸以外を採用しても構わない。その場合、ｐＨは４以下にするのがよい。 At this time, the concentration of sulfuric acid may be 100 to 250 g/L. Note that a known back-extraction method may be used. Of course, a substance other than sulfuric acid may be used. In that case, the pH is preferably 4 or less.
ただ、本発明の課題にて述べたように硫酸を使用することに伴う課題が、本発明の技術的思想を適用することにより解決され、硫酸を使用可能となるという点でも本発明の技術的意義がある。 However, as mentioned in the problem of the present invention, the problems associated with using sulfuric acid can be solved by applying the technical idea of the present invention, and the technical aspect of the present invention is also that sulfuric acid can be used. it makes sense.
逆抽出された重金属は、硫酸ごと既存の金属製錬工程へと移すことにより回収工程を行ってもよい。そのため本実施形態に係る煙灰の処理方法は、重金属の回収方法としての側面もある。なお、逆抽出工程後の有機溶媒はプロトンが再生されていることから、別サイクルの煙灰の処理工程にて再利用してもよい。
また、元スラリーであった水相は、ハロゲンを多量に含有しているためブライン浸出に利用してもよい。
固体成分（固相）は、ろ過後、Ｐｂ、Ａｇなどの重金属を公知の手法で回収してもよい。その後、残りの部分は、金属製錬の原料として既存の金属製錬工程へ移してもよい。
有機溶媒洗浄工程後の洗浄液はＣａを多量に含んでおり、これを再利用してもよいし、重金属がほとんど含まれていない状態なのでｐＨ調整等の処理を行ったうえで排水としても構わない。
The back-extracted heavy metals may be subjected to a recovery process by being transferred together with sulfuric acid to an existing metal smelting process. Therefore, the method for treating smoke ash according to the present embodiment also serves as a method for recovering heavy metals. In addition, since the protons of the organic solvent after the back extraction process have been regenerated, it may be reused in another cycle of the smoke ash treatment process.
Furthermore, the aqueous phase, which was originally a slurry, contains a large amount of halogen and may therefore be used for brine leaching.
After filtering the solid component (solid phase), heavy metals such as Pb and Ag may be recovered by a known method. The remaining portion may then be transferred to an existing metal smelting process as raw material for metal smelting.
The cleaning solution after the organic solvent cleaning process contains a large amount of Ca, so it can be reused, or it can be treated as wastewater after adjusting the pH since it contains almost no heavy metals. .
本発明の技術的範囲は上述した実施の形態に限定されるものではなく、発明の構成要件やその組み合わせによって得られる特定の効果を導き出せる範囲において、種々の変更や改良を加えた形態も含む。 The technical scope of the present invention is not limited to the embodiments described above, but also includes various modifications and improvements within the scope of deriving specific effects obtained by the constituent elements of the invention and their combinations.
次に実施例を示し、本発明について具体的に説明する。本発明は、以下の実施例に限定されるものではない。なお、以下に記載のない内容は、本実施形態で述べた内容と同様とする。 Next, the present invention will be specifically explained with reference to Examples. The present invention is not limited to the following examples. Note that contents not described below are the same as those described in this embodiment.
なお、実施例１では重金属溶媒抽出工程に係る結果を示し、実施例２では分相改善工程に係る結果を示し、実施例３では有機溶媒洗浄工程に係る結果を示し、実施例４では逆抽出工程に係る結果を示す。 In addition, Example 1 shows the results related to the heavy metal solvent extraction process, Example 2 shows the results related to the phase separation improvement process, Example 3 shows the results related to the organic solvent washing process, and Example 4 shows the results related to the back extraction process. The results related to the process are shown.
＜実施例、比較例にて使用した煙灰＞
以下の組成を有する溶融飛灰を用意した。以下の組成は、ＩＣＰ－ＭＳを使用して得た。その結果を示すのが以下の表１である。
Molten fly ash having the following composition was prepared. The following compositions were obtained using ICP-MS. Table 1 below shows the results.
＜比較例１＞
上記溶融飛灰５０ｇと蒸留水１００ｍｌとを混合したものを封入した容器を、室温（２５℃程度）にて、振とう機（ＴＡＩＴＥＣ製のダブルシェーカーＮＲ－３０）を使用し、２００ｒｐｍで３０分間振とうした。その後、内容物をＩＣＰ分析装置（Ｔｈｅｒｍｏ Ｓｃｉｅｎｔｉｆｉｃ製のｉＣＡＰ６０００）にて分析した。その結果を示すのが以下の表２である。
A container containing a mixture of 50 g of the above molten fly ash and 100 ml of distilled water was heated at room temperature (approximately 25°C) using a shaker (TAITEC double shaker NR-30) at 200 rpm for 30 minutes. I shook it. Thereafter, the contents were analyzed using an ICP analyzer (iCAP6000 manufactured by Thermo Scientific). Table 2 below shows the results.
＜実施例１－１＞
上記溶融飛灰５０ｇと蒸留水１００ｍｌと、更にプロトン放出型の有機溶媒とを混合したものを封入した容器を、比較例１と同様の手法にて振とうし、同様の手法にて内容物を分析した。なお、プロトン放出型の有機溶媒としては、リン酸（ＳＯＬＶＡＹ製のＣＹＡＮＥＸ２７２）を使用した。その他の有機溶媒としてケロシン（三愛石油製のＥｘｘｓｏｌ ＴＭ Ｄ８０）を使用し、総有機溶媒においてＣＹＡＮＥＸ２７２が４０ｖｏｌ％となるように両者を混合した。内容物の分析結果を示すのが以下の表３である。なお、本作業の終点ｐＨは５．４６であった。
A container containing a mixture of 50 g of the above molten fly ash, 100 ml of distilled water, and a proton-releasing organic solvent was shaken in the same manner as in Comparative Example 1, and the contents were emptied in the same manner. analyzed. Note that phosphoric acid (CYANEX272 manufactured by SOLVAY) was used as a proton-releasing organic solvent. Kerosene (Exxsol TM D80 manufactured by San-Ai Oil Co., Ltd.) was used as another organic solvent, and both were mixed so that CYANEX272 was 40 vol % in the total organic solvent. Table 3 below shows the analysis results of the contents. Note that the end point pH of this work was 5.46.
＜実施例１－２＞
プロトン放出型の有機溶媒としてＣＹＡＮＥＸ２７２の代わりにＰＣ－８８Ａを使用した以外は、実施例１－１と同様の手法で試験を行った。内容物の分析結果を示すのが以下の表４である。なお、本作業の終点ｐＨは４．０５であった。
A test was conducted in the same manner as in Example 1-1, except that PC-88A was used instead of CYANEX272 as the proton-releasing organic solvent. Table 4 below shows the analysis results of the contents. Note that the end point pH of this work was 4.05.
＜実施例１－３＞
プロトン放出型の有機溶媒としてＣＹＡＮＥＸ２７２の代わりにＤ２ＥＨＰＡを使用した以外は、実施例１－１と同様の手法で試験を行った。内容物の分析結果を示すのが以下の表５である。なお、本作業の終点ｐＨは３．５４であった。
A test was conducted in the same manner as in Example 1-1, except that D2EHPA was used instead of CYANEX272 as the proton-releasing organic solvent. Table 5 below shows the analysis results of the contents. Note that the end point pH of this work was 3.54.
＜実施例１－４＞
本例は、Ｃａ含有アルカリ性煙灰を水と混合することによりスラリー化する前に、該煙灰を一度洗浄した場合の例である。それ以外は実施例１－１と同様の手法にて試験および分析を行った。
<Example 1-4>
This example is an example in which the Ca-containing alkaline smoke ash was washed once before being made into a slurry by mixing it with water. Other than that, the test and analysis were conducted in the same manner as in Example 1-1.
洗浄を行う本例の結果と、洗浄を行わない実施例１－１の結果とを対比して、実施例１－１の結果の方が良好すなわち重金属が油相（有機溶媒）中により分配していれば、本発明により、該煙灰を洗浄する必要が無くなるという効果が更にもたらされることを意味する。 Comparing the results of this example with washing and the results of Example 1-1 without washing, the results of Example 1-1 are better, that is, the heavy metals are more distributed in the oil phase (organic solvent). If it is, it means that the present invention further brings about the effect that there is no need to wash the smoke ashes.
本例における該煙灰の洗浄の具体的手法は以下の通りである。
まず、比較例１と同様の手法で該煙灰のスラリーを作製した。その後、該スラリーを全量ろ過した。ここまでの内容が、事前の水洗に該当する。その後、ろ物を１００ｍＬの蒸留水に混ぜ、再びスラリー化した。このスラリーに対し、実施例１に記載の総有機溶媒を混合し、実施例１－１に記載の手法にて重金属溶媒抽出工程を行った。内容物の分析結果を示すのが以下の表６である。なお、水洗時のｐＨは１２．０５、再スラリー化の時点でのｐＨは７．２７、重金属溶媒抽出工程の終点ｐＨは実施例１－１と同様の５．４６であった。
First, a slurry of the smoke ash was prepared in the same manner as in Comparative Example 1. Thereafter, the entire slurry was filtered. The content up to this point corresponds to pre-washing. Thereafter, the filtered material was mixed with 100 mL of distilled water to form a slurry again. The total organic solvent described in Example 1 was mixed with this slurry, and a heavy metal solvent extraction step was performed using the method described in Example 1-1. Table 6 below shows the analysis results of the contents. The pH at the time of washing with water was 12.05, the pH at the time of reslurry was 7.27, and the end point pH of the heavy metal solvent extraction step was 5.46, the same as in Example 1-1.
＜実施例２－１＞
上記溶融飛灰５０ｇと蒸留水１００ｍｌと、更に実施例１のプロトン放出型の有機溶媒とを混合したものを封入した容器を、比較例１と同様の手法にて振とうした。なお、振とう時間、振とう後の静置時間は以下の表７に記載のとおりとした。なお、表中のスラリー濃度の単位は（ｇ／Ｌ）であり、ＴＢＰ濃度とＣＹＡＮＥＸ２７２濃度の単位は総有機溶媒中のｖｏｌ％である。
A container containing a mixture of 50 g of the molten fly ash, 100 ml of distilled water, and the proton-releasing organic solvent of Example 1 was shaken in the same manner as in Comparative Example 1. The shaking time and the standing time after shaking were as shown in Table 7 below. Note that the unit of slurry concentration in the table is (g/L), and the unit of TBP concentration and CYANEX272 concentration is vol% in the total organic solvent.
＜実施例２－２～２－６＞
実施例２－１と同様の手法にて、表７に記載の条件で試験を行った。
<Examples 2-2 to 2-6>
A test was conducted using the same method as in Example 2-1 under the conditions listed in Table 7.
表７に示すように、ＴＢＰを総有機溶媒に対して１ｖｏｌ％以上とし、且つ、（油相体積すなわち総有機溶媒体積）／（水相体積）≧２．５とし、且つ、（プロトン放出型の有機溶媒の質量％）／（全Ｃａ質量％）を１．２～５とする、という好適条件を満たすことにより、固体成分が有機溶媒からほとんど存在しなくなることがわかった。 As shown in Table 7, TBP is 1 vol% or more based on the total organic solvent, (oil phase volume, that is, total organic solvent volume)/(aqueous phase volume)≧2.5, and (proton-releasing type It has been found that by satisfying the preferred condition of 1.2 to 5 (% by mass of organic solvent)/(% by mass of total Ca), almost no solid component is present in the organic solvent.
なお、実施例２－１は実施例２－２～２－６に比べて分相状態は良好ではないが、本発明の課題である「石膏の発生を抑制しつつもＣａ含有アルカリ性煙灰から重金属を抽出する」ことができているため、実施例の扱いとしている。 Although the phase separation state of Example 2-1 is not as good as that of Examples 2-2 to 2-6, the problem of the present invention is to remove heavy metals from Ca-containing alkaline smoke while suppressing the generation of gypsum. This is treated as an example because it was possible to extract the following.
＜実施例３＞
実施例１で使用した総有機溶媒（ＣＹＡＮＥＸ２７２が４０ｖｏｌ％）に対し、蒸留水５０ｍｌと所定量の塩酸とを混合し、総有機溶媒が以下の表８に記載のｐＨとなるよう、有機溶媒洗浄工程を３回行った。各有機溶媒洗浄工程後、総有機溶媒中の各組成を上記ＩＣＰ分析装置にて分析した。その結果を、総有機溶媒からの除去率として示すのが表８である。
The total organic solvent used in Example 1 (40 vol% of CYANEX272) was mixed with 50 ml of distilled water and a predetermined amount of hydrochloric acid, and the total organic solvent was washed with organic solvent so that the pH was as shown in Table 8 below. The process was performed three times. After each organic solvent washing step, each composition in the total organic solvent was analyzed using the above-mentioned ICP analyzer. Table 8 shows the results as the removal rate from the total organic solvent.
＜実施例４＞
実施例３の後の総有機溶媒に対して逆抽出工程を行った。硫酸濃度は２００ｇ／Ｌとした。逆抽出工程後、水相（硫酸）中の各組成を上記ＩＣＰ分析装置にて分析した。その結果を示すのが表９である。
A back extraction step was performed on the total organic solvent after Example 3. The sulfuric acid concentration was 200 g/L. After the back extraction step, each composition in the aqueous phase (sulfuric acid) was analyzed using the above-mentioned ICP analyzer. Table 9 shows the results.
以上のとおり、本実施例ならば、石膏の発生を抑制しつつもＣａ含有アルカリ性煙灰から重金属を抽出できることが明らかとなった。更に、抽出後の該重金属が回収可能となることが明らかとなった。 As described above, it has become clear that in this example, heavy metals can be extracted from Ca-containing alkaline smoke ash while suppressing the generation of gypsum. Furthermore, it has become clear that the heavy metals can be recovered after extraction.
Claims (8)
前記重金属は、Ｚｎ（亜鉛）、Ｐｂ（鉛）、Ｃｕ（銅）、Ｓｎ（錫）、Ａｇ（銀）、Ａｕ（金）、ルテニウム（Ｒｕ）、ロジウム（Ｒｈ）、パラジウム（Ｐｄ）、オスミウム（Ｏｓ）、イリジウム（Ｉｒ）、白金（Ｐｔ）の少なくともいずれかであり、
前記重金属溶媒抽出工程後の前記有機溶媒と硫酸以外の酸とを接触させることにより、前記重金属溶媒抽出工程後の前記有機溶媒からＣａを除去し且つ該有機溶媒のプロトンを再生する有機溶媒洗浄工程を更に有し、
硫酸により前記有機溶媒洗浄工程後の前記有機溶媒から重金属を逆抽出する逆抽出工程を更に有する、煙灰の処理方法。 A heavy metal solvent extraction step in which heavy metals are extracted from the Ca-containing alkaline smoke into the organic solvent by reacting a proton- releasing organic solvent with the Ca-containing alkaline smoke ,
The heavy metals include Zn (zinc), Pb (lead), Cu (copper), Sn (tin), Ag (silver), Au (gold), ruthenium (Ru), rhodium (Rh), palladium (Pd), and osmium. (Os), iridium (Ir), and platinum (Pt),
An organic solvent washing step of removing Ca from the organic solvent after the heavy metal solvent extraction step and regenerating protons of the organic solvent by bringing the organic solvent after the heavy metal solvent extraction step into contact with an acid other than sulfuric acid. It further has
A method for treating smoke ash, further comprising a back-extraction step of back-extracting heavy metals from the organic solvent after the organic solvent washing step with sulfuric acid.
前記重金属溶媒抽出工程後の前記有機溶媒と硫酸以外の酸とを接触させることにより、前記重金属溶媒抽出工程後の前記有機溶媒からＣａを除去し且つ該有機溶媒のプロトンを再生する有機溶媒洗浄工程を更に有し、An organic solvent washing step of removing Ca from the organic solvent after the heavy metal solvent extraction step and regenerating protons of the organic solvent by bringing the organic solvent after the heavy metal solvent extraction step into contact with an acid other than sulfuric acid. It further has
硫酸により前記有機溶媒洗浄工程後の前記有機溶媒から重金属を逆抽出する逆抽出工程を更に有する、煙灰の処理方法。A method for treating smoke ash, further comprising a back-extraction step of back-extracting heavy metals from the organic solvent after the organic solvent washing step with sulfuric acid.
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