JP3612543B2 - Method for fractional collection of aluminum and phosphorus - Google Patents
Method for fractional collection of aluminum and phosphorus Download PDFInfo
- Publication number
- JP3612543B2 JP3612543B2 JP37773198A JP37773198A JP3612543B2 JP 3612543 B2 JP3612543 B2 JP 3612543B2 JP 37773198 A JP37773198 A JP 37773198A JP 37773198 A JP37773198 A JP 37773198A JP 3612543 B2 JP3612543 B2 JP 3612543B2
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- Prior art keywords
- aluminum
- phosphorus
- phosphate
- added
- separated
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 36
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 36
- 239000011574 phosphorus Substances 0.000 title claims description 36
- 229910052782 aluminium Inorganic materials 0.000 title claims description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 32
- 238000000034 method Methods 0.000 title claims description 25
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- 229910001385 heavy metal Inorganic materials 0.000 claims description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 description 19
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- HSEYYGFJBLWFGD-UHFFFAOYSA-N 4-methylsulfanyl-2-[(2-methylsulfanylpyridine-3-carbonyl)amino]butanoic acid Chemical compound CSCCC(C(O)=O)NC(=O)C1=CC=CN=C1SC HSEYYGFJBLWFGD-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 235000021317 phosphate Nutrition 0.000 description 7
- 238000010306 acid treatment Methods 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000010440 gypsum Substances 0.000 description 6
- 229910052602 gypsum Inorganic materials 0.000 description 6
- 229910000398 iron phosphate Inorganic materials 0.000 description 6
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 5
- 239000004254 Ammonium phosphate Substances 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 4
- 235000019289 ammonium phosphates Nutrition 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 description 4
- 235000011151 potassium sulphates Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 229940037003 alum Drugs 0.000 description 3
- -1 aluminum ions Chemical class 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 3
- 239000010801 sewage sludge Substances 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910001467 sodium calcium phosphate Inorganic materials 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 235000010210 aluminium Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- KDKJYYNXYAZPIK-UHFFFAOYSA-J aluminum potassium disulfate hydrate Chemical compound O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KDKJYYNXYAZPIK-UHFFFAOYSA-J 0.000 description 1
- 229940103272 aluminum potassium sulfate Drugs 0.000 description 1
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 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
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010800 human waste Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000013067 intermediate product 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 235000014786 phosphorus Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Processing Of Solid Wastes (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、下水汚泥やごみなどの各種焼却灰の処理、有効利用技術に関する。
【０００２】
【従来の技術】
下水汚泥やごみなどの各種焼却灰の処理技術として溶融スラグ法や薬剤を用いた固形化などによる固形物として利用する方法が主に開発されている。近年、酸を用いて焼却灰中の重金属や燐、アルミニウムを回収する方法が研究されている。この一つとして焼却灰から酸を用いて燐、アルミニウムを溶出し、これに各種アルカリを加えてｐＨを調整することにより燐を主に燐酸アルミニウムの形態で回収する方法がある。
【０００３】
【発明が解決しようとする課題】
酸溶出液をアルカリでｐＨ調整する燐の回収方法では焼却灰中の燐は、主に燐酸アルミニウムとして回収される。燐酸アルミニウムついては未だ利用用途が充分に開発されていないことから、実用化にあたっては燐をアルミニウムから分離し、燐酸あるいは燐酸カルシウムあるいは燐酸ナトリウムなどの燐酸アルミニウム以外の各種燐酸塩として回収する方法が要求される。また、廃棄物中に含まれている重金属などの各種有害物の除去が必要である。これらの処理過程において有害な排水、廃棄物など２次的な副製物を生じないことも要求される。
【０００４】
【課題を解決するための手段】
本発明のアルミニウムおよび燐の分別回収方法は、燐酸アルミニウムを主体とする素材に硫酸を加えて燐、アルミニウムを溶出させ、ろ過分離した溶出液に、硫酸アンモニウム又は硫酸カリウムを加えて冷却することによりアルミニウム明礬として結晶化分離するアルミニウム回収工程と、上記アルミニウムをアルミニウム明礬として結晶化分離したろ液にアンモニア水又はアルカリ金属の水酸化物又は炭酸塩、重炭酸塩を加えてＰＨ１０に調節して溶出重金属を沈殿分離したろ液に硫酸を加えてＰＨ８〜９に調節して燐を燐酸塩として回収する燐回収工程とを含むことを特徴とする。
また、上記燐酸アルミニウムを主体とする素材は、焼却灰に硫酸を加えて燐、アルミニウムを溶出させ、ろ過分離した溶出液に、炭酸カルシウム又は水酸化カルシウムを加えてＰＨ４に調節して回収することを特徴とする。
焼却灰からの燐を燐酸アルミニウムを主体とする素材として回収する場合は、まず焼却灰に酸を加えて燐を溶出させる。酸として価格の安価な硫酸を用いる。溶出した燐はアルカリを用いてｐＨ調節することにより回収できる。このアルカリとしては安価な炭酸カルシウム、あるいは水酸化カルシウムを用いる。燐は主に燐酸アルミニウムと硫酸カルシウムの混合物として回収される。
【０００５】
本発明におけるアルミニウム回収工程は、焼却灰などから回収された燐酸アルミニウムからアルミニウムと燐とを分離する方法であるが、燐酸アルミニウムはｐＨ２以下の酸性では燐酸とアルミニウムイオンに解離しているものと考えられる。アルミニウム塩の多くは水に易溶であるが、硫酸アルミニウムカリウム、硫酸アルミニウムアンモニウムなどのアルミニウム明礬類は０℃前後の低温域で水溶解度が低いことからこうした形態にすることによって燐酸アルミニウム中のアルミニウムと燐酸との分離が可能と考えられる。
【０００６】
このためにｐＨ２以下の酸性域において燐酸とアルミニウムイオンに解離した状態で硫酸カリウム又は硫酸アンモニウムを加えた後、結晶化が可能な温度に冷却し、アルミニウム明礬の結晶として分離することが考えられる。このためにはアルミニウム明礬を結晶化させるために必要な濃度にすることが要求され、アルミニウム濃度が低い場合には濃縮をおこなう必要がある。しかし、焼却灰の酸溶出液には酸のほか各種塩類、珪酸質などが含まれているため溶液を濃縮することは技術的に可能ではあるが特殊な設備を要し、またコスト的にも高いものとなる。こうした酸性液体を蒸発などによる濃縮を行なわずにアルミニウム塩を結晶化除去できる濃度にする方法が望まれる。
【０００７】
濃縮工程を必要としない方法として、あらかじめ焼却灰中の燐分を燐酸アルミニウムを沈澱、回収することによって結晶化に必要な濃度に高める方法が考えられる。また、アルミニウム明礬類は多くの結晶水を有し、結晶化させて分離する際、多くの水分が結晶水として除去される結果、更に溶液の濃縮を図ることできる。
【０００８】
本発明における燐回収工程は、まず、前記の酸溶出液中のアルミニウムをアルミニウム明礬として除去した液にアンモニア水又はアルカリ金属の水酸化物、炭酸塩あるいは重炭酸塩を加えてｐＨ４に調整し、一部残存した燐酸アルミニウムを沈澱分離する。更にアンモニア水又はアルカリ金属の水酸化物又は炭酸塩を加えｐＨ１０として重金属を沈澱分離する。このろ液を濃縮し、結晶化により燐酸アンモニウムあるいはアルカリ金属の燐酸塩として回収する。
【０００９】
燐酸水素２ナトリウムは低温において水溶解度が低いことから燐をこの形態にすることにより、前述の濃縮を行なわずに結晶分離が可能と考えられる。このため、酸溶出液に硫酸アンモニウムを加えてアルミニウムを分離除去した液に水酸化ナトリウム又は炭酸ナトリウム、重炭酸ナトリウムなどを加えｐＨ４にし残存した燐酸アルミニウムを除去し、さらにこれらのアルカリを添加して、燐酸水素２ナトリウムが生成するｐＨ８〜９に調整する。これを結晶分離が可能な温度に冷却することにより燐を燐酸水素２ナトリウムとして結晶化分離する。
【００１０】
焼却灰中に含まれる有害物の除去であるが、焼却灰に硫酸を加えることにより灰中の重金属類の多くを溶出除去できると考えられる。このため酸処理によって重金属を除去した焼却灰はセメント等への有効利用が容易である。次に溶出した重金属と燐を分離することであるが、液ｐＨを４に調整することにより、燐を燐酸アルミニウムとして回収する際、カドミウム、水銀、マンガン、亜鉛、銅など多くの重金属は沈殿せずに液中の残ると考えられるので、回収燐と分離することが可能である。この残液中の重金属は水酸化カルシウムを加えてｐＨ１０とし、沈殿させ分離する。重金属を分離した排液中には一部溶解した硫酸カルシウム、水酸化カルシウムを含むだけで他の塩類は少ないので、排水処理を要せず、再度、焼却灰の酸処理用水に使用できる。
【００１１】
前述のｐＨ４で回収した燐酸アルミニウム中に重金属が一部残ったとしても、本発明のアルミニウムと燐酸塩の分離工程において結晶化などにより再度除去精製が可能である。さらに回収したアルミニウム明礬や燐酸水素２ナトリウムなどは再結晶法により更に精製できる。
【００１２】
また、請求項２の処理を行なわず焼却灰から燐を硫酸処理により溶出させた液の加熱蒸発などにより濃縮し、請求項１の方法により直接的に燐酸塩とアルミニウム分を分離回収することもできる。
【００１３】
【発明の実施の形態】
対象としてはごみ、ＲＤＦ（ごみ発電用燃料）あるいは下水、し尿、上水汚泥などの各種焼却灰が考えられる。必要に応じて前処理を行なう。例ば粗大物を含む場合には酸処理し易いように粉砕を行なう。塩化ナトリウム等の塩分を多量に含む場合には水洗を行なう。
【００１４】
焼却灰に希硫酸を加えてｐＨ２以下の状態で１時間程度撹拌し、燐、アルミニウム、重金属などの溶出を行なう。これを濾過分離する。残渣物は燐や重金属が除去されていることから回収し、セメントの原料等として使用する。
【００１５】
この溶出液に炭酸カルシウム又は水酸化カルシウムの粉末を加え、ｐＨを４に調整し、１時間以上、充分撹拌を行なう。これを濾過し、燐を燐酸アルミニウムと硫酸カルシウムの混合物として回収する。回収物は風乾、または加熱乾燥を行なう。ろ液には更に水酸化カルシウムの粉末を加え、撹拌を行いｐＨ１０に調整し重金属を沈澱分離する。重金属を除去したろ液は少量の一部溶解した硫酸カルシウムを含むだけであり、焼却灰の酸処理液として再度使用する。
【００１６】
上記の燐酸アルミニウムと硫酸カルシウムの混合物に、これら混合物中の燐酸アルミニウム（無水物）と硫酸のモル比を２：３となるように希硫酸を加え、燐酸アルミニウムを溶出し、燐酸アルミニウム濃度を１０％（重量）程度とする。これを濾過して燐酸アルミニウムと硫酸カルシウムを分離させる。溶出液に硫酸アンモニウム又は硫酸カリウム粉末を燐酸アルミニウム２モルに対して１モルの割合で加え撹拌、加温溶解する。これをアルミニウム明礬の結晶化可能な温度に冷却し、種結晶として硫酸アルミニウムアンモニウムまたは硫酸アルミニウムカリウムの結晶を少量加え、撹拌を行なう。生成した硫酸アルミニウムアンモニウムの結晶を分離回収する。
【００１７】
硫酸アルミニウムアンモニウムまたは硫酸アルミニウムカリウムの結晶を分離した残液にアンモニア水またはアルカリ金属の水酸化物、炭酸塩、重炭酸塩の粉末を加えて撹拌溶解し、ｐＨ４に調整する。溶液中に一部残ったアルミニウム分は燐酸アルミニウムとして不純物の燐酸鉄などと共に沈澱するので、これを分離除去する。このものは再度、酸処理の工程に戻し再処理を行なう。燐酸鉄が多く存在する場合には燐酸鉄としての利用を行う。
【００１８】
未反応の燐酸アルミニウムを除去した液に更にアンモニア水またはアルカリ金属の水酸化物、炭酸塩、重炭酸塩を加え、ｐＨ１０とする。液中に残った重金属は水酸化物又は炭酸塩、燐酸塩などとなって沈澱するので、これをろ過分離する。この溶液を濃縮し、燐酸塩を一部副生する硫酸塩とともに結晶化分離する。
【００１９】
燐酸分を燐酸水素２ナトリウムの形態で回収する場合には燐酸アルミニウムからアルミニウム明礬としてアルミニウムを除去した液に水酸化ナトリウム又は炭酸ナトリウム、重炭酸ナトリウムなどの粉末を加えて撹拌溶解し、ｐＨ４に調整する。残存した燐酸アルミニウム等を分離除去し、更に水酸化ナトリウム又は炭酸ナトリウムなどの粉末を加えてｐＨ１０に調整し、同様に重金属の除去を行なう。燐酸ナトリウムの結晶が生じる恐れがある場合には加温、溶解してからろ過により重金属を分離する。また、硫酸ナトリウム濃度が多量に存在し、結晶化、混入する恐れがある場合にはナトリウム量を過剰とならないように水酸化ナトリウム又は炭酸ナトリウム等の代わりとしてアンモニア水を混合して使用する。
【００２０】
ｐＨ１０で重金属を分離したろ液に希硫酸を少量加えてｐＨ８−９に調節したのち燐酸水素２ナトリウムの結晶化に必要な温度に冷却し、燐酸水素２ナトリウムの結晶種を少量加えて撹拌を継続する。結晶化した燐酸水素２ナトリウムを分離回収する。残液中には一部硫酸アンモニウム、燐酸水素２ナトリウムなどがあるので濃縮して硫酸アンモニウム等と共に回収する。あるいは再度、燐酸アルミニウムの酸溶解工程で再使用する。
【００２１】
請求項４の方法は請求項１の方法と同様に焼却灰に希硫酸を加えてｐＨ２以下の状態で１時間程度撹拌し、燐、アルミニウム、重金属などの溶出を行なう。これをろ過分離する。これを加熱、蒸発により燐酸アルミニウム濃度１０％程度に濃縮する。沈澱が生じた場合は必要に応じて沈澱物を除去したのち、同様に請求項２及び３の方法によりアルミニウムと燐酸塩の分離を行なう。
【００２２】
【発明の実施例】
５００ｇの下水汚泥焼却灰に水５０００ｍｌと硫酸１５０ｇを加えｐＨ２以下で１時間、撹拌を行った。これをろ過し、ろ液に炭酸カルシウム微粉末８０ｇを加え１時間撹拌を行い、最終的なｐＨを４に調整した。沈澱した燐酸アルミニウム、石膏等の混合物をろ過回収し、１０５℃で乾燥を行なった。燐酸アルミニウム、硫酸カルシウムを含む回収物は２５０ｇであった。ろ液には水酸化カルシウム粉末を加え１時間撹拌を行いｐＨ１０に調整して重金属類を沈殿により回収分離した。燐酸アルミニウム、石膏等の回収物の組成を表１に示す。
【００２３】
表１
【００２４】
前記の燐酸アルミニウム、石膏等の回収物２５０ｇに硫酸１５０ｇと水１０００ｍｌを加え燐酸アルミニウムを溶解した。ろ過分離により石膏を除去し、さらに硫酸アンモニウム粉末６０ｇを加え加温溶解後、３℃に冷却した。種結晶として硫酸アルミニウムアンモニウム結晶を少量加え、１昼夜放置した。生成した硫酸アルミニウムアンモニウムの結晶を分離回収し、１０５℃で乾燥を行なった。
【００２５】
硫酸アルミニウムアンモニウムを除去した液に炭酸水素ナトリウム粉末１６０ｇを加え撹拌、ｐＨ４とし、残存した燐酸アルミニウム等の沈澱をろ過分離した。このろ液に水酸化ナトリウム２０ｇを加え、撹拌、加温溶解しｐＨ１０に調整した。生成した重金属を含む沈澱物をろ過分離した。少量の希硫酸を用いてｐＨ８〜９に調整した後、３℃に冷却した。種結晶として燐酸水素２ナトリウム結晶を少量加えて１昼夜放置し燐酸水素２ナトリウムの結晶を分離した。このものを１０５℃で乾燥した。これら回収物等の収量を表２に示す。
【００２６】
燐酸分を燐酸アンモニウムとして回収する方法としては、同様に燐酸アルミニウム、石膏等の回収物２５０ｇに硫酸１５０ｇと水１０００ｍｌを加え燐酸アルミニウムを溶解した。これをろ過し、石膏分を除去しさらに硫酸アンモニウム粉末６０ｇを加え加温溶解後、３℃に冷却した。種結晶として硫酸アルミニウムアンモニウム結晶を少量加え、１昼夜放置した。生成した硫酸アルミニウムアンモニウムの結晶を分離回収し、１０５℃で乾燥を行なった。この残液にアンモニア水を１５０ｍｌ加え、ｐＨ４．５にして残存した燐酸アルミニウムあるいは不純物として存在する燐酸鉄の沈澱をろ過分離した。ろ液を加熱濃縮し２００ｍｌとし、３℃に冷却し、燐酸アンモニウムの結晶を回収した。これらの結果を表２に示す。
【００２７】
表２
【００２８】
【本発明の効果】
各種焼却灰中に含まれるアルミニウムを硫酸アルミニウムアンモニウムとして回収される。硫酸アルミニウムアンモニウムあるいは硫酸アルミニウムカリウムはアルミニウム製造の中間製品でもあり、再結晶法により容易に精製し、各種の用途に使用できる。燐は燐酸アンモニウム、燐酸ナトリウム、燐酸カルシウムなど各種燐酸塩の形で回収されるので多くの用途に使用できる。
【００２９】
硫酸、炭酸カルシウム、硫酸アンモニウム、炭酸ナトリウムなど安価な材料を使用しており経済的な方法である。蒸発その他の物理的手段による溶液の濃縮を行なわず、あるいは必要最小限の濃縮操作により処理ができる。また、この工程における未反応の燐酸アルミニウム、硫酸アンモニウム、硫酸カリウムなどの試薬は再度工程に使用可能である。また一部不純物の燐酸鉄は燐酸鉄としての利用が考えられるなど資源の有効利用が図られる。燐酸アルミニウムの回収処理を終えた排水中には重金属や各種塩類が少ないため排水処理を行なわずに再度使用できるため排水や廃棄物の発生が極めて少ない。
【図面の簡単な説明】
【図１】この工程の概要を示したものである。
【表１】
BACKGROUND OF THE INVENTION
The present invention relates to a technique for treating and effectively using various incineration ash such as sewage sludge and garbage.
[0002]
[Prior art]
As a treatment technique for various incineration ash such as sewage sludge and garbage, a method of using as a solid material by a molten slag method or solidification using a chemical has been mainly developed. In recent years, methods for recovering heavy metals, phosphorus, and aluminum in incinerated ash using acid have been studied. As one of them, there is a method of recovering phosphorus mainly in the form of aluminum phosphate by eluting phosphorus and aluminum from the incinerated ash using acid and adjusting the pH by adding various alkalis thereto.
[0003]
[Problems to be solved by the invention]
In the phosphorus recovery method in which the pH of the acid eluate is adjusted with an alkali, phosphorus in the incinerated ash is recovered mainly as aluminum phosphate. Since aluminum phosphate has not yet been fully developed for use, phosphorous is separated from aluminum for practical use, and a method for recovering it as various phosphates other than aluminum phosphate such as phosphoric acid, calcium phosphate or sodium phosphate is required. The In addition, it is necessary to remove various harmful substances such as heavy metals contained in the waste. It is also required that secondary by-products such as harmful drainage and waste are not generated in these treatment processes.
[0004]
[Means for Solving the Problems]
In the method for separating and recovering aluminum and phosphorus according to the present invention, sulfuric acid is added to a material mainly composed of aluminum phosphate to elute phosphorus and aluminum, and ammonium sulfate or potassium sulfate is added to the eluate after filtration to cool the aluminum. Aluminum recovery step for crystallizing and separating as alum, and ammonia water or alkali metal hydroxide or carbonate or bicarbonate to the filtrate obtained by crystallizing and separating the aluminum as alum and adjusting to PH10 to elute heavy metals And a phosphorus recovery step of adding phosphorus to the filtrate obtained by precipitation and adjusting the pH to pH 8-9 to recover phosphorus as a phosphate.
In addition, the material mainly composed of aluminum phosphate should be recovered by adding sulfuric acid to incineration ash to elute phosphorus and aluminum, and adjusting the pH to PH4 by adding calcium carbonate or calcium hydroxide to the effluent separated by filtration. It is characterized by.
When recovering phosphorus from incineration ash as a material mainly composed of aluminum phosphate, first, acid is added to the incineration ash to elute phosphorus. An inexpensive sulfuric acid is used as the acid. The eluted phosphorus can be recovered by adjusting the pH with an alkali. As this alkali, inexpensive calcium carbonate or calcium hydroxide is used. Phosphorus is recovered primarily as a mixture of aluminum phosphate and calcium sulfate.
[0005]
The aluminum recovery step in the present invention is a method of separating aluminum and phosphorus from aluminum phosphate recovered from incineration ash or the like, but aluminum phosphate is considered to be dissociated into phosphoric acid and aluminum ions when the pH is 2 or lower. It is done. Most aluminum salts are readily soluble in water, but aluminum alums such as aluminum potassium sulfate and ammonium ammonium sulfate have low water solubility in the low temperature range of about 0 ° C., so this form allows aluminum in aluminum phosphate to be dissolved. And phosphoric acid can be separated.
[0006]
For this purpose, it is conceivable that potassium sulfate or ammonium sulfate is added in a state dissociated into phosphoric acid and aluminum ions in an acidic range of pH 2 or lower, and then cooled to a temperature at which crystallization is possible, and separated as aluminum alum crystals. For this purpose, it is required to have a concentration necessary for crystallizing aluminum alum, and when the aluminum concentration is low, it is necessary to perform concentration. However, the acid eluate of incineration ash contains various salts, silicic acid, etc. in addition to acid, so it is technically possible to concentrate the solution, but it requires special equipment and is also costly. It will be expensive. There is a demand for a method of adjusting the concentration of such an acidic liquid so that the aluminum salt can be crystallized and removed without concentrating by evaporation or the like.
[0007]
As a method that does not require the concentration step, a method is conceivable in which the phosphorus content in the incinerated ash is increased to a concentration necessary for crystallization by precipitating and recovering aluminum phosphate. Aluminum alum has a lot of water of crystallization, and when it is crystallized and separated, a lot of water is removed as water of crystallization, so that the solution can be further concentrated.
[0008]
The phosphorus recovery step in the present invention is first adjusted to pH 4 by adding ammonia water or alkali metal hydroxide, carbonate or bicarbonate to the solution obtained by removing aluminum in the acid eluate as aluminum alum, A part of the remaining aluminum phosphate is precipitated and separated. Further, aqueous ammonia or alkali metal hydroxide or carbonate is added to adjust the pH to 10 to precipitate and separate heavy metals. The filtrate is concentrated and recovered by crystallization as ammonium phosphate or alkali metal phosphate.
[0009]
Since disodium hydrogen phosphate has low water solubility at a low temperature, it is considered that crystal separation can be performed without performing the above-described concentration by using phosphorus in this form. For this reason, ammonium hydroxide is added to the acid eluate to separate and remove aluminum, and sodium hydroxide, sodium carbonate, sodium bicarbonate, etc. are added to remove the remaining aluminum phosphate to pH 4, and these alkalis are added. The pH is adjusted to 8 to 9 where disodium hydrogen phosphate is produced. This is cooled to a temperature at which crystal separation is possible, so that phosphorus is crystallized and separated as disodium hydrogen phosphate.
[0010]
Although it is removal of harmful substances contained in incineration ash, it is thought that many heavy metals in ash can be eluted and removed by adding sulfuric acid to incineration ash. For this reason, incineration ash from which heavy metals have been removed by acid treatment is easy to use effectively for cement and the like. The next step is to separate the eluted heavy metal and phosphorus. By adjusting the pH of the solution to 4, when recovering phosphorus as aluminum phosphate, many heavy metals such as cadmium, mercury, manganese, zinc and copper precipitate. Therefore, it can be separated from the recovered phosphorus. The heavy metal in this residual liquid is precipitated by adding calcium hydroxide to pH 10 and separated. The waste liquid from which heavy metals are separated contains only partially dissolved calcium sulfate and calcium hydroxide, and there are few other salts. Therefore, wastewater treatment is not required, and it can be used again for the acid treatment water of incineration ash.
[0011]
Even if a part of heavy metal remains in the aluminum phosphate recovered at pH 4 described above, it can be removed and purified again by crystallization or the like in the separation step of aluminum and phosphate of the present invention. Further, the recovered aluminum alum, disodium hydrogen phosphate and the like can be further purified by a recrystallization method.
[0012]
Further, the phosphorous and aluminum components may be directly separated and recovered by the method of claim 1 by concentrating by heating and evaporating a liquid obtained by eluting phosphorus from incinerated ash by sulfuric acid treatment without performing the treatment of claim 2. it can.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the target include waste, RDF (waste power generation fuel), or various incineration ash such as sewage, human waste, and water sludge. Pre-processing is performed as necessary. For example, when a coarse product is included, it is pulverized to facilitate acid treatment. If it contains a large amount of salt such as sodium chloride, wash it with water.
[0014]
Dilute sulfuric acid is added to the incinerated ash, and the mixture is stirred for about 1 hour at a pH of 2 or less to elute phosphorus, aluminum, heavy metals and the like. This is separated by filtration. Residues are recovered from the removal of phosphorus and heavy metals and used as raw materials for cement.
[0015]
Calcium carbonate or calcium hydroxide powder is added to the eluate, the pH is adjusted to 4, and the mixture is sufficiently stirred for 1 hour or longer. This is filtered and the phosphorus is recovered as a mixture of aluminum phosphate and calcium sulfate. The collected material is air-dried or heat-dried. Calcium hydroxide powder is further added to the filtrate, and the pH is adjusted to 10 by stirring to precipitate and separate heavy metals. The filtrate from which heavy metals have been removed only contains a small amount of partially dissolved calcium sulfate and is used again as an acid treatment solution for incineration ash.
[0016]
To the above mixture of aluminum phosphate and calcium sulfate, dilute sulfuric acid is added so that the molar ratio of aluminum phosphate (anhydride) to sulfuric acid in the mixture is 2: 3, and the aluminum phosphate is eluted, so that the aluminum phosphate concentration is 10 % (Weight). This is filtered to separate aluminum phosphate and calcium sulfate. Ammonium sulfate or potassium sulfate powder is added to the eluate at a ratio of 1 mol per 2 mol of aluminum phosphate, and the mixture is stirred and dissolved by heating. This is cooled to a temperature at which aluminum alum can be crystallized, and a small amount of aluminum ammonium sulfate or potassium potassium sulfate crystal is added as a seed crystal, followed by stirring. The produced crystals of ammonium aluminum sulfate are separated and recovered.
[0017]
Ammonia water or alkali metal hydroxide, carbonate, bicarbonate powder is added to the residual liquid from which the crystals of aluminum ammonium sulfate or potassium aluminum sulfate have been separated, dissolved by stirring, and adjusted to pH 4. A part of the aluminum remaining in the solution is precipitated together with impurities such as iron phosphate as aluminum phosphate, and this is separated and removed. This is again returned to the acid treatment step and reprocessed. When there is a lot of iron phosphate, it is used as iron phosphate.
[0018]
Ammonia water or alkali metal hydroxide, carbonate and bicarbonate are further added to the solution from which the unreacted aluminum phosphate has been removed to adjust the pH to 10. The heavy metal remaining in the liquid precipitates as hydroxide, carbonate, phosphate, etc., and is separated by filtration. The solution is concentrated and crystallized and separated together with sulfate, which is a by-product of some phosphates.
[0019]
When recovering the phosphoric acid content in the form of disodium hydrogen phosphate, add aluminum hydroxide, aluminum carbonate, sodium bicarbonate powder, etc. to the solution from which aluminum was removed from aluminum phosphate as an alum and adjust to pH 4. To do. The remaining aluminum phosphate or the like is separated and removed, and a powder such as sodium hydroxide or sodium carbonate is added to adjust the pH to 10, and heavy metals are similarly removed. If there is a possibility that crystals of sodium phosphate may be formed, the heavy metal is separated by filtration after heating and dissolution. Also, when there is a large amount of sodium sulfate and there is a risk of crystallization and contamination, ammonia water is mixed and used instead of sodium hydroxide or sodium carbonate so that the amount of sodium does not become excessive.
[0020]
Adjust the pH to 8-9 by adding a small amount of dilute sulfuric acid to the filtrate from which heavy metals have been separated at pH 10, cool to the temperature required for crystallization of disodium hydrogen phosphate, add a small amount of disodium hydrogen phosphate crystal seeds, and stir. continue. The crystallized disodium hydrogen phosphate is separated and recovered. In the residual liquid, there are some ammonium sulfate, disodium hydrogen phosphate, etc., so they are concentrated and recovered together with ammonium sulfate. Alternatively, it is reused again in the acid dissolution step of aluminum phosphate.
[0021]
In the method of claim 4, as in the method of claim 1, dilute sulfuric acid is added to the incinerated ash, and the mixture is stirred for about 1 hour at a pH of 2 or less to elute phosphorus, aluminum, heavy metals and the like. This is separated by filtration. This is concentrated by heating and evaporation to an aluminum phosphate concentration of about 10%. If precipitation occurs, the precipitate is removed if necessary, and then the aluminum and phosphate are separated by the methods of claims 2 and 3 in the same manner.
[0022]
DETAILED DESCRIPTION OF THE INVENTION
To 500 g of sewage sludge incineration ash, 5000 ml of water and 150 g of sulfuric acid were added and stirred at pH 2 or lower for 1 hour. This was filtered, 80 g of calcium carbonate fine powder was added to the filtrate and stirred for 1 hour, and the final pH was adjusted to 4. A mixture of precipitated aluminum phosphate, gypsum and the like was collected by filtration and dried at 105 ° C. The recovered material containing aluminum phosphate and calcium sulfate was 250 g. Calcium hydroxide powder was added to the filtrate, and the mixture was stirred for 1 hour, adjusted to pH 10 and heavy metals were recovered and separated by precipitation. Table 1 shows the composition of recovered materials such as aluminum phosphate and gypsum.
[0023]
Table 1
[0024]
150 g of sulfuric acid and 1000 ml of water were added to 250 g of the recovered material such as aluminum phosphate and gypsum to dissolve the aluminum phosphate. The gypsum was removed by filtration separation, and 60 g of ammonium sulfate powder was further added and dissolved by heating, followed by cooling to 3 ° C. A small amount of aluminum ammonium sulfate crystal was added as a seed crystal and allowed to stand for one day. The produced aluminum ammonium sulfate crystals were separated and recovered and dried at 105 ° C.
[0025]
160 g of sodium hydrogen carbonate powder was added to the solution from which the aluminum ammonium sulfate had been removed and stirred to adjust the pH to 4, and the remaining precipitates such as aluminum phosphate were separated by filtration. To this filtrate was added 20 g of sodium hydroxide, and the mixture was stirred and dissolved by heating to adjust the pH to 10. The precipitate containing the heavy metal produced was separated by filtration. After adjusting to pH 8-9 using a small amount of dilute sulfuric acid, it cooled to 3 degreeC. A small amount of disodium hydrogen phosphate crystal was added as a seed crystal and allowed to stand overnight for separation of disodium hydrogen phosphate crystal. This was dried at 105 ° C. Table 2 shows the yield of these recovered materials.
[0026]
As a method for recovering the phosphoric acid content as ammonium phosphate, 150 g of sulfuric acid and 1000 ml of water were similarly added to 250 g of recovered material such as aluminum phosphate and gypsum to dissolve the aluminum phosphate. This was filtered, the gypsum content was removed, 60 g of ammonium sulfate powder was further added and dissolved by heating, and then cooled to 3 ° C. A small amount of aluminum ammonium sulfate crystal was added as a seed crystal and allowed to stand for one day. The produced aluminum ammonium sulfate crystals were separated and recovered and dried at 105 ° C. 150 ml of aqueous ammonia was added to the remaining liquid to adjust the pH to 4.5, and the remaining aluminum phosphate or the precipitate of iron phosphate present as an impurity was separated by filtration. The filtrate was concentrated by heating to 200 ml and cooled to 3 ° C. to recover ammonium phosphate crystals. These results are shown in Table 2.
[0027]
Table 2
[0028]
[Effect of the present invention]
Aluminum contained in various incineration ash is recovered as ammonium ammonium sulfate. Aluminum ammonium sulfate or potassium aluminum sulfate is also an intermediate product of aluminum production, and can be easily purified by a recrystallization method and used for various applications. Since phosphorus is recovered in the form of various phosphates such as ammonium phosphate, sodium phosphate and calcium phosphate, it can be used in many applications.
[0029]
It is an economical method using inexpensive materials such as sulfuric acid, calcium carbonate, ammonium sulfate, and sodium carbonate. The solution can be processed by evaporation or other physical means without concentrating the solution or by a minimum concentration operation. In addition, unreacted reagents such as aluminum phosphate, ammonium sulfate, and potassium sulfate in this step can be used again in the step. Also, some impurities such as iron phosphate can be used as iron phosphate, so that resources can be used effectively. Since the wastewater after the recovery treatment of aluminum phosphate has few heavy metals and various salts, it can be reused without wastewater treatment, so that wastewater and waste are hardly generated.
[Brief description of the drawings]
FIG. 1 shows an outline of this process.
[Table 1]
Claims (2)
前記アルミニウムをアルミニウム明礬として結晶化分離したろ液にアンモニア水又はアルカリ金属の水酸化物又は炭酸塩、重炭酸塩を加えてＰＨ１０に調節して溶出重金属を沈殿分離したろ液に硫酸を加えてＰＨ８〜９に調節して燐を燐酸塩として回収する燐回収工程とを含むことを特徴とするアルミニウムおよび燐の分別回収方法。An aluminum recovery step in which sulfuric acid is added to a material mainly composed of aluminum phosphate to elute phosphorus and aluminum, and ammonium sulfate is added to the eluate that has been filtered and cooled to crystallize and separate as aluminum alum; and
To the filtrate obtained by crystallization and separation of aluminum as aluminum alum, ammonia water or alkali metal hydroxide or carbonate or bicarbonate was added to adjust the pH to 10 and sulfuric acid was added to the filtrate obtained by precipitation separation of the eluted heavy metal. And a phosphorus recovery step of recovering phosphorus as a phosphate by adjusting the pH to 8 to 9, and separating and recovering aluminum and phosphorus.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37773198A JP3612543B2 (en) | 1998-12-28 | 1998-12-28 | Method for fractional collection of aluminum and phosphorus |
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| Application Number | Priority Date | Filing Date | Title |
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| JP37773198A JP3612543B2 (en) | 1998-12-28 | 1998-12-28 | Method for fractional collection of aluminum and phosphorus |
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| JP2000189927A JP2000189927A (en) | 2000-07-11 |
| JP3612543B2 true JP3612543B2 (en) | 2005-01-19 |
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| JP37773198A Expired - Fee Related JP3612543B2 (en) | 1998-12-28 | 1998-12-28 | Method for fractional collection of aluminum and phosphorus |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4002044B2 (en) * | 2000-01-18 | 2007-10-31 | 川崎市 | Treatment method of sludge incineration ash |
| US8673046B1 (en) * | 2008-02-05 | 2014-03-18 | The United States Of America, As Represented By The Secretary Of Agriculture | Process for removing and recovering phosphorus from animal waste |
| CN103539184B (en) * | 2013-10-31 | 2015-05-20 | 洛阳氟钾科技股份公司 | Industrial alumen preparation method |
| CN105772484B (en) * | 2016-03-23 | 2017-12-19 | 武汉纺织大学 | A kind of recovery method of municipal sludge incineration residue innoxious process for treating and phosphorus compound |
| CN108033434B (en) * | 2017-11-03 | 2020-05-08 | 云南中正化学工业有限公司 | Method for producing high-quality industrial diammonium phosphate by triple purification method |
| CN111252792A (en) * | 2020-01-21 | 2020-06-09 | 曲靖市德方纳米科技有限公司 | Recovery method of phosphorus-aluminum slag |
| CN115385312B (en) * | 2021-05-09 | 2024-04-19 | 深圳市环保科技集团股份有限公司 | Recovery method of aluminum or aluminum alloy chemical polishing waste liquid |
| CN114477121A (en) * | 2022-02-25 | 2022-05-13 | 湖南长宏新能源材料有限责任公司 | Production of battery-grade iron phosphate from iron-containing waste residues |
| CN115385535B (en) * | 2022-09-02 | 2023-12-29 | 爱沃特智能水务(安徽)有限公司 | Method for synchronously recycling aluminum and phosphorus from chemical sludge |
| CN117619866B (en) * | 2023-10-26 | 2024-09-20 | 上海市政工程设计研究总院（集团）有限公司 | Phosphorus resource recovery method for sludge incineration fly ash |
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