JP2008150241A - System for rendering refuse incineration ash harmless and manufacturing artificial zeolite - Google Patents
System for rendering refuse incineration ash harmless and manufacturing artificial zeolite Download PDFInfo
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- JP2008150241A JP2008150241A JP2006339262A JP2006339262A JP2008150241A JP 2008150241 A JP2008150241 A JP 2008150241A JP 2006339262 A JP2006339262 A JP 2006339262A JP 2006339262 A JP2006339262 A JP 2006339262A JP 2008150241 A JP2008150241 A JP 2008150241A
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- incineration ash
- artificial zeolite
- heavy metal
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 66
- 239000010457 zeolite Substances 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000009877 rendering Methods 0.000 title abstract 3
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 40
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 230000001678 irradiating effect Effects 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims description 26
- 238000004056 waste incineration Methods 0.000 claims description 26
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 238000007885 magnetic separation Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 19
- 239000002956 ash Substances 0.000 description 69
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 65
- 239000000047 product Substances 0.000 description 34
- 238000000605 extraction Methods 0.000 description 31
- 229910052751 metal Inorganic materials 0.000 description 23
- 239000002184 metal Substances 0.000 description 23
- 235000011121 sodium hydroxide Nutrition 0.000 description 21
- 239000007788 liquid Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 238000011021 bench scale process Methods 0.000 description 14
- -1 ferrous metals Chemical class 0.000 description 14
- 239000007790 solid phase Substances 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000010881 fly ash Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 150000004763 sulfides Chemical class 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical class [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052981 lead sulfide Inorganic materials 0.000 description 2
- 229940056932 lead sulfide Drugs 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BFRXZIMAUMUZJH-UHFFFAOYSA-M [OH-].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] Chemical compound [OH-].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] BFRXZIMAUMUZJH-UHFFFAOYSA-M 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001678 gehlenite Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese 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
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
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- Processing Of Solid Wastes (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
本発明は、ゴミ焼却灰の無害化、人工ゼオライトの製造システムに関し、より具体的にはゴミ焼却灰を無害化するとともに、ゴミ焼却灰を主原料として人工ゼオライトを製造するためのシステムに関するものである。 The present invention relates to a garbage incineration ash detoxification and artificial zeolite production system, and more specifically, to a system for detoxifying garbage incineration ash and producing artificial zeolite using garbage incineration ash as a main raw material. is there.
家庭やビル等から排出される都市ゴミは、処分施設や埋立地に集積される。処分施設では焼却等により処理される。都市ゴミを焼却により処理すると、未燃成分はゴミ焼却灰として残るが、ゴミ焼却灰には、鉄類、非鉄金属類等の重金属、酸化珪素、アルミナ、非晶質の珪酸アルミニウム塩などの成分が含まれている。 Municipal waste discharged from homes and buildings is collected in disposal facilities and landfills. It is processed by incineration at the disposal facility. When municipal waste is treated by incineration, unburned components remain as incineration ash, but incineration ash contains heavy metals such as iron and non-ferrous metals, silicon oxide, alumina, amorphous aluminum silicate salts, etc. It is included.
近年、ゴミ焼却灰の有効利用法として、その中の酸化珪素、アルミナ、非晶質の珪酸アルミニウム塩を原料として人工ゼオライトを製造することが考えられており、本発明者ら（一部）は、人工ゼオライトを製造する方法について一連の開発を続けている（特開平１０−３２４５１８号公報、特開平１１−１９９２２５号公報、特開２００１−２２０１３２号公報、特開２００３−２３８１４６号公報）。 In recent years, as an effective utilization method of refuse incineration ash, it has been considered to produce artificial zeolite using silicon oxide, alumina, and amorphous aluminum silicate salt as raw materials, and the present inventors (part) In addition, a series of developments on a method for producing artificial zeolite is continued (Japanese Patent Laid-Open Nos. 10-324518, 11-199225, 2001-220132, and 2003-238146).
例えば、特開２００１−２２０１３２号公報では、珪酸およびアルミニウムを含む物質に０．１〜０．５Ｎのアルカリ水溶液を加え、６０〜８０℃の温度で加熱した後、溶液部分を濃縮し、１００〜３００℃の温度で加熱処理することにより人工ゼオライトを製造し、特開２００３−２３８１４６号公報では、都市ゴミ焼却灰を水およびアルカリの存在下で１２０乃至２３０℃の温度で加熱処理することにより人工ゼオライトを製造するものである。 For example, in Japanese Patent Application Laid-Open No. 2001-220132, a 0.1-0.5N aqueous alkali solution is added to a substance containing silicic acid and aluminum, heated at a temperature of 60-80 ° C., and then the solution portion is concentrated, Artificial zeolite is produced by heat treatment at a temperature of 300 ° C., and Japanese Patent Application Laid-Open No. 2003-238146 discloses artificial ash by heat treatment of municipal waste incineration ash at a temperature of 120 to 230 ° C. in the presence of water and alkali. It produces zeolite.
その際、ゴミ焼却灰に含まれる鉄類、非鉄金属類等の重金属の粗大分は予め分離されるが、分離後のゴミ焼却灰に含まれる非鉄金属類のうち特に鉛は、有害成分であることから予め除去して無害化しておく必要がある。 At that time, the bulk of heavy metals such as iron and non-ferrous metals contained in the garbage incineration ash is separated in advance, but among the non-ferrous metals contained in the garbage incineration ash after separation, lead is a harmful component. Therefore, it is necessary to remove them in advance and make them harmless.
本発明は、ゴミ焼却灰からそのような有害成分、特に鉛を除去してゴミ焼却灰を無害化し、且つ、有害成分を除去したゴミ焼却灰を主原料として、超音波の利用、加熱を含む一連の工程により低コスト、高効率で人工ゼオライトを製造するためのシステムを提供することを目的とするものである。 The present invention includes the use of ultrasonic waves and heating, using as a main raw material garbage incineration ash from which such harmful components, especially lead, are removed from the waste incineration ash to detoxify the waste incineration ash and from which harmful components have been removed. An object of the present invention is to provide a system for producing artificial zeolite at low cost and high efficiency by a series of processes.
本発明は、ゴミ焼却灰を無害化し、人工ゼオライトを製造するためのシステムであって、（ａ）ゴミ焼却灰から重金属を抽出分離する工程と、（ｂ）重金属分離後のゴミ焼却灰に水およびアルカリを混合してスラリーを生成する工程と、（ｃ）該スラリーを固形分とろ液とに分離する工程と、（ｄ）該固形分に水およびアルカリを混合して水性スラリーにする工程と、（ｅ）該水性スラリーに対して超音波を照射する工程と、（ｆ）該水性スラリーを加熱する工程を備えてなることを特徴とするゴミ焼却灰からの人工ゼオライトの製造システムである。 The present invention is a system for detoxifying refuse incineration ash and producing artificial zeolite, comprising: (a) a step of extracting and separating heavy metals from waste incineration ash; and (b) water in the incineration ash after separation of heavy metals. And (c) a step of separating the slurry into a solid content and a filtrate, and (d) a step of mixing water and an alkali with the solid content to form an aqueous slurry. And (e) a process for irradiating the aqueous slurry with ultrasonic waves, and (f) a process for heating the aqueous slurry, which is a system for producing artificial zeolite from refuse incineration ash.
本発明によれば、ゴミ焼却灰から重金属類、特に鉛を除去して無害化するとともに、重金属類を除去したゴミ焼却灰を主原料として、低エネルギー、低コストで人工ゼオライトを製造することができる。本発明で製造した人工ゼオライトには有害金属を含まないので各種用途に使用することができる。 According to the present invention, it is possible to detoxify heavy metals, in particular lead, from garbage incineration ash, and to produce artificial zeolite at low energy and low cost using waste incineration ash from which heavy metals have been removed as a main raw material. it can. Since the artificial zeolite produced in the present invention does not contain harmful metals, it can be used for various purposes.
本発明は、ゴミ焼却灰を無害化し、人工ゼオライトを製造するためのシステムである。そして、（ａ）ゴミ焼却灰から重金属を抽出分離する工程と、（ｂ）重金属分離後のゴミ焼却灰に水およびアルカリを混合してスラリーを生成する工程と、（ｃ）該スラリーを固形分とろ液とに分離する工程と、（ｄ）該固形分に水およびアルカリを混合して水性スラリーにする工程と、（ｅ）該水性スラリーに対して超音波を照射する工程と、（ｆ）該水性スラリーを加熱する工程を備えてなることを特徴とする。 The present invention is a system for producing artificial zeolite by detoxifying refuse incineration ash. And (a) a step of extracting and separating heavy metals from the waste incineration ash, (b) a step of mixing the waste incineration ash after heavy metal separation with water and alkali to produce a slurry, and (c) the slurry as a solid content. A step of separating into a filtrate, (d) a step of mixing water and an alkali with the solid content to form an aqueous slurry, (e) a step of irradiating the aqueous slurry with ultrasonic waves, and (f) It comprises a step of heating the aqueous slurry.
また、本発明においては、前記（ａ）ゴミ焼却灰から重金属を抽出分離する工程の前に、ゴミ焼却灰に対して順次、磁力選別、非鉄選別、風力選別を行うことにより、ＳＵＳ等の鉄類や鉛等の非鉄金属類、陶磁器類を分離する。そして、それらを分離したゴミ焼却灰から重金属を抽出分離した後、重金属の抽出分離後のゴミ焼却灰に含まれるシリカ、アルミニウム、非晶質の珪酸アルミニウム塩を主原料とし、これに水およびアルカリを加えて人工ゼオライトを製造する。アルカリとしては特に苛性ソーダが有効である。 In the present invention, before the step (a) of extracting and separating heavy metals from garbage incineration ash, iron, such as SUS, is sequentially performed on the garbage incineration ash by magnetic separation, non-ferrous sorting, and wind sorting. And non-ferrous metals such as lead and ceramics. Then, after extracting and separating heavy metals from the waste incineration ash from which they have been separated, the main raw materials are silica, aluminum, and amorphous aluminum silicate salt contained in the waste incineration ash after the heavy metal extraction and separation. To produce artificial zeolite. Caustic soda is particularly effective as the alkali.
このように、事前に磁力選別、非鉄選別、風力選別により鉄類や非鉄金属類、陶磁器類等を分離した後のゴミ焼却灰について、苛性ソーダにより重金属、特に有害成分である鉛を抽出分離することにより、製品人工ゼオライト中に金属類、特に鉛が混入するのを防止する。抽出分離工程では鉛のほか、亜鉛、マンガン、クロム、銅等の重金属も分離され、分離した重金属は、鉛を含めて資源化し、有効に利用することができる。 In this way, heavy metals, especially lead, which is a harmful component, is extracted and separated from caustic soda from garbage incineration ash after separating iron, non-ferrous metals, ceramics, etc. by magnetic sorting, non-ferrous sorting, wind sorting in advance. This prevents metal, especially lead, from being mixed into the product artificial zeolite. In the extraction and separation process, heavy metals such as zinc, manganese, chromium and copper are separated in addition to lead, and the separated heavy metals including lead can be recycled and used effectively.
また、本発明においては、上記（ａ）ゴミ焼却灰から重金属を抽出分離する工程の前に、ゴミ焼却灰を乾式微粉砕機を用いて微粉砕することによりゼオライト化反応を促進することができる。すなわち、上記磁力選別、非鉄選別、風力選別を行い、鉄類や非鉄金属類、陶磁器類等を分離した後のゴミ焼却灰を乾式微粉砕機を用いて微粉砕することによりゼオライト化反応を促進することができる。 In the present invention, the zeolitization reaction can be promoted by pulverizing the waste incineration ash using a dry pulverizer before the step (a) extracting and separating heavy metals from the waste incineration ash. . That is, the zeolitization reaction is promoted by finely pulverizing the waste incineration ash after separating the iron, non-ferrous metals, ceramics, etc. using a dry pulverizer after performing the above-mentioned magnetic sorting, non-ferrous sorting, and wind sorting. can do.
そして、有害成分を分離した固形分にアルカリを加えて人工ゼオライトを製造する。その際必要に応じて、ゼオライト生成成分としてアルカリのほか、水ガラス、アルミニウム等を添加してもよい。アルカリとしては特に苛性ソーダが有効である。 Then, an artificial zeolite is produced by adding alkali to the solid content from which harmful components have been separated. At that time, if necessary, water glass, aluminum or the like may be added in addition to alkali as a zeolite-forming component. Caustic soda is particularly effective as the alkali.
本発明においては、フィリップサイト、ホージャサイト、ゼオライトＡ、ヒドロキシソーダライトなどの形で人工ゼオライトが得られる。本発明によれば、予め重金属類、特に鉛を予め分離していることから、製品人工ゼオライトには、それら有害成分が含まれていないので、肥料、土壌改良剤、脱臭剤その他の用途に利用できる。 In the present invention, artificial zeolite is obtained in the form of Philipsite, faujasite, zeolite A, hydroxysodalite and the like. According to the present invention, since heavy metals, in particular lead, are separated in advance, since the product artificial zeolite does not contain these harmful components, it is used for fertilizers, soil improvers, deodorizers and other uses. it can.
本発明において照射する超音波の周波数には特に限定はないが、好ましくは２０〜２００ｋＨｚの範囲の低周波域超音波を使用する。また、本発明におけるゼオライト合成反応は９５℃以上の常圧状態で実施することができる。圧力が常圧であることから、温度は９５〜１００℃の範囲となる。反応条件を常圧、低温度で行えるので低エネルギー、低コストで人工ゼオライトを製造することができる。 Although there is no limitation in particular in the frequency of the ultrasonic wave irradiated in this invention, Preferably the low frequency range ultrasonic wave of the range of 20-200 kHz is used. Moreover, the zeolite synthesis reaction in the present invention can be carried out at a normal pressure of 95 ° C. or higher. Since the pressure is normal pressure, the temperature is in the range of 95-100 ° C. Since the reaction conditions are normal pressure and low temperature, artificial zeolite can be produced with low energy and low cost.
都市ゴミはストーカー（stoker）炉、その他の焼却炉で焼却される。ストーカー炉の場合、主灰は炉下から排出され、飛灰は焼却炉の燃焼ガス流路から捕集される。本発明は、ゴミ焼却灰からの人工ゼオライトの製造システムとして、焼却炉の炉下から排出される主灰を対象とする。ただし、本発明は焼却炉の燃焼ガス流路から捕集される飛灰、流動床炉、直接溶融炉、灰溶融炉等からの排ガスから捕集される飛灰についも適用することができる。 Municipal waste is incinerated in stoker furnaces and other incinerators. In the case of a stalker furnace, main ash is discharged from the bottom of the furnace, and fly ash is collected from the combustion gas flow path of the incinerator. The present invention is directed to main ash discharged from the bottom of an incinerator as a system for producing artificial zeolite from refuse incineration ash. However, the present invention can be applied to fly ash collected from the combustion gas flow path of the incinerator, fly ash collected from exhaust gas from a fluidized bed furnace, a direct melting furnace, an ash melting furnace, and the like.
ここで一例として、都市ゴミを焼却したストーカー炉の炉下から排出される主灰は全体の約４/５を占め、飛灰は約１/５である。その主灰について分析した化学組成を表１、表２に示している（平成１７年度における７箇月）。表１は主成分、表２は重金属類（表１に記載のＺｎ、Ｃｕを除く）である。 Here, as an example, the main ash discharged from the bottom of a stalker furnace that incinerated municipal waste accounts for about 4/5 of the total, and fly ash is about 1/5. The chemical compositions analyzed for the main ash are shown in Tables 1 and 2 (7 months in 2005). Table 1 shows main components, and Table 2 shows heavy metals (excluding Zn and Cu described in Table 1).
表１のとおり、主灰の主要成分はＳｉＯ2、ＣａＯ、Ａｌ2Ｏ3であり、このうちＳｉＯ2、Ａｌ2Ｏ3はゼオライトの原料となる成分である。表２（Ｚｎ、Ｃｕは表１に記載）のとおり、主灰には各種重金属が含まれており、特にＰｂについては平均２６８１ｍｇ/ｋｇ含まれている。 As shown in Table 1, main components of the main ash are SiO 2 , CaO, and Al 2 O 3 , and among these, SiO 2 and Al 2 O 3 are components that serve as raw materials for zeolite. As shown in Table 2 (Zn and Cu are listed in Table 1), the main ash contains various heavy metals, and in particular, Pb contains an average of 2681 mg / kg.
本発明においては、そのような主灰、また飛灰を無害化し且つ有用物を製造することにより、それらを資源化し且つリサイクル化を図ることができる。またこれにより、埋立地の確保難の問題を解決し、施設の延命化を図ることができる。以下において、主灰を例にして説明するが、飛灰についても同様である。 In the present invention, by making such main ash and fly ash harmless and producing useful products, they can be turned into resources and recycled. This also solves the problem of difficulty in securing landfills and extends the life of the facilities. In the following, the main ash will be described as an example, but the same applies to fly ash.
〈（１）ゴミ焼却灰の前処理工程〉
本発明においてはゴミ焼却灰を前処理する。図１はそのフローを示す図である。図１に従い順次説明する。ゴミ焼却灰すなわち主灰を分級する。先ず粗分級により、一例として３０ｍｍアンダー、つまりその篩下分と粗大分に分ける。篩下分をさらに分級し、一例として５ｍｍアンダー、つまりその篩下分を取得する。これら両分級で分離した粗大分はＳＵＳ等の鉄類や鉛等の非鉄金属類、陶磁器類等である。
<(1) Pretreatment process of garbage incineration ash>
In the present invention, waste incineration ash is pretreated. FIG. 1 is a diagram showing the flow. A description will be made sequentially with reference to FIG. Classify waste incineration ash, ie main ash. First, by coarse classification, as an example, it is divided into 30 mm under, that is, its under-sieving part and coarse part. The under-sieving portion is further classified, and as an example, 5 mm under, that is, the under-sieving portion is obtained. Coarse portions separated by these two classifications are ferrous metals such as SUS, non-ferrous metals such as lead, and ceramics.
そして、上記篩下分を粗粉砕する。粗粉砕にはハンマーシュレッダー等を使用する。粗粉砕後、ＳＵＳ等の鉄類を磁力選別により分離した後、鉛等の非鉄金属分を非鉄選別により分離し、さらに風力選別により比重の大きいものを分離する。磁力選別にはマグネットを利用し、非鉄選別には渦電流を利用し、風力選別には比重差を利用する。磁力選別、非鉄選別では分離されなかった鉄類、非鉄金属類、あるいは陶磁器類の砕粉等が風力選別により分離される。 Then, the portion under the sieve is coarsely pulverized. A hammer shredder or the like is used for coarse grinding. After coarse pulverization, irons such as SUS are separated by magnetic sorting, non-ferrous metals such as lead are separated by non-ferrous sorting, and those having a large specific gravity are further separated by wind sorting. Magnets are used for magnetic sorting, eddy currents are used for non-ferrous sorting, and specific gravity differences are used for wind sorting. Iron, non-ferrous metals, or ceramics crushed powder, etc. that were not separated by magnetic sorting and non-ferrous sorting are separated by wind sorting.
ここで、篩下分の粗粉砕物以降の各選別工程毎の鉛の含有量の実測例を示すと、粗粉砕物＝2110ｍｇ/ｋｇ、磁力選別後＝1490ｍｇ/ｋｇ、非鉄選別後＝1090ｍｇ/ｋｇ、風力選別後＝700ｍｇ/ｋｇであった。このように鉛分は磁力選別によっても除去されるが、これは鉄との合金等の形で含まれた鉛が鉄と一緒に除去されたことによるものと推定される。 Here, when the actual measurement example of the content of lead for each sorting step after the coarsely pulverized product under the sieve is shown, the coarsely pulverized product = 2110 mg / kg, after magnetic sorting = 1490 mg / kg, after non-ferrous sorting = 1090 mg / kg, after wind sorting = 700 mg / kg. Thus, the lead content is also removed by magnetic separation, but this is presumably due to the removal of lead contained in the form of an alloy with iron together with iron.
これらの分離工程を経たものをさらに微粉砕する。微粉砕は、鉛の抽出、ゼオライト化反応を促進するための工程であり、好ましくは乱流、衝突形式の乾式粉砕機を使用する。こうして得た微粉砕物をサイクロン、バッグフィルターにかけ、微粉部分を取得する。本発明においては、こうして得た微粉砕物を人工ゼオライト製造用の主原料とするものである。 What passed through these separation steps is further pulverized. The fine pulverization is a process for accelerating the lead extraction and zeolitic reaction, and preferably uses a turbulent, collision type dry pulverizer. The finely pulverized product thus obtained is subjected to a cyclone and a bag filter to obtain a fine powder portion. In the present invention, the finely pulverized product thus obtained is used as a main raw material for producing artificial zeolite.
〈本発明を実施する基本的システムのフロー〉
微粉砕物から重金属類、特に鉛を分離した後、重金属類分離済みの微粉砕物を利用して人工ゼオライトを製造する。図２はそのシステムのフローを示す図である。図２に従い順次説明する。
<Flow of basic system for carrying out the present invention>
After separating heavy metals, particularly lead, from the finely pulverized product, an artificial zeolite is produced using the finely pulverized product from which the heavy metals have been separated. FIG. 2 is a diagram showing a flow of the system. Description will be made sequentially with reference to FIG.
〈（２）主原料から金属類、特に鉛の分離工程〉
非鉄金属の一種である鉛は電極やパイプの材料として使用され、鉛合金は活字、はんだ、軸受、ケーブル被覆用など各種用途に使用され、鉛酸化物は上絵付用ガラスや光学ガラスなどの成分としても使用されている。これらの広範な用途に起因して、ゴミ焼却灰中には鉛が、鉛そのもののほか、合金や化合物の形で含まれ、これらは微粉砕物中にも含まれている。鉛は有害物で環境汚染物質である。
<(2) Separation process of metals, especially lead from main raw materials>
Lead, a kind of non-ferrous metal, is used as a material for electrodes and pipes, lead alloys are used for various applications such as printing, soldering, bearings, and cable coating, and lead oxide is a component such as glass for painting and optical glass. It is also used as. Due to these wide uses, lead is contained in the garbage incineration ash in the form of alloys and compounds in addition to lead itself, and these are also contained in finely pulverized products. Lead is a hazardous substance and an environmental pollutant.
そこで本発明においては、主原料つまり微粉砕物から先ず残留金属、特に鉛を分離する。この処理には好ましくはアルカリ抽出法を適用するが、特に苛性ソーダによる抽出法が有効である。この抽出法では微粉砕物に水とＮａＯＨを加えて攪拌・混合する。得られたスラリーをろ過して固形分とろ液に分離する。抽出された鉛は、ろ液中に移行し、液中に含まれている。 Therefore, in the present invention, the residual metal, particularly lead, is first separated from the main raw material, that is, the finely pulverized product. An alkaline extraction method is preferably applied to this treatment, but an extraction method using caustic soda is particularly effective. In this extraction method, water and NaOH are added to a finely pulverized product and stirred and mixed. The resulting slurry is filtered to separate the solid and filtrate. The extracted lead moves into the filtrate and is contained in the liquid.
そこで、ろ液に硫化ソーダを加える。この処理により残留金属、特に鉛の硫化物を生成する。金属類は、前述〈（１）都市ゴミ焼却灰の前処理工程〉により分離しているが、さらに、抽出処理のろ液中に残存する金属類を硫化物に変えて分離するものである。硫化物は固体として生成しているので、この工程で得られたスラリーをろ過し、固形分とろ液に分離する。固形分は金属硫化物、特に鉛硫化物である。一方、ろ液には抽出に用いた苛性ソーダが含まれているので、循環して鉛、その他の金属の抽出用に利用する。 Therefore, sodium sulfide is added to the filtrate. This treatment produces residual metals, especially lead sulfide. The metals are separated by the above-mentioned <(1) Pretreatment process of municipal waste incineration ash>, but further, the metals remaining in the filtrate of the extraction treatment are separated into sulfides and separated. Since sulfide is generated as a solid, the slurry obtained in this step is filtered and separated into a solid and a filtrate. The solids are metal sulfides, especially lead sulfide. On the other hand, since the filtrate contains caustic soda used for extraction, it is circulated and used for extraction of lead and other metals.
なお、当該〈（２）主原料から金属類、特に鉛の分離工程〉との関連で、特開２００６−２５５５０１号公報において、廃棄物処理装置から排出される飛灰にアルカリ水溶液を混合し、混合物をろ過し、ろ液に水溶性硫化物を加え、混合物をろ過して、飛灰から重金属類を除去するに際し、飛灰にアルカリ水溶液を混合する工程を加熱して行う飛灰の重金属類除去方法が開示されている。これに対して、本発明においては、ゴミ焼却灰からの人工ゼオライトの製造システムの一環として主灰に対して適用するものである。 In addition, in relation to the <(2) Separation process of metals, particularly lead from main raw materials>, in JP-A-2006-255501, an alkaline aqueous solution is mixed with fly ash discharged from a waste treatment apparatus, Filter the mixture, add water-soluble sulfides to the filtrate, filter the mixture, and remove heavy metals from the fly ash. A removal method is disclosed. On the other hand, in this invention, it applies with respect to main ash as a part of the manufacturing system of the artificial zeolite from refuse incineration ash.
〈（３）固形分からのゼオライト合成工程〉
主灰から鉛の分離工程を経て得られた固形分の主成分は珪酸アルミニウム塩（アルミノ珪酸塩）であるので、これを人工ゼオライトの主原料として利用する。
<(3) Zeolite synthesis process from solid content>
Since the main component of the solid content obtained through the lead separation step from the main ash is aluminum silicate (aluminosilicate), this is used as the main raw material for artificial zeolite.
その固形分に水およびＮａＯＨを加え、必要に応じて、原料成分調整のため水ガラス、アルミニウム等を加えて攪拌・混合する。その際、混合物に超音波を照射し、さらに加熱してゼオライト合成反応を行う。超音波の照射と加熱は同時に行ってもよいが、先ず超音波を照射して超音波処理をした後、加熱処理をするのが好ましい。 Water and NaOH are added to the solid content, and water glass, aluminum, etc. are added as necessary to adjust the raw material components and stirred and mixed. At that time, the mixture is irradiated with ultrasonic waves and further heated to perform a zeolite synthesis reaction. Ultrasonic irradiation and heating may be performed at the same time, but it is preferable to first perform ultrasonic treatment by irradiating ultrasonic waves and then heat treatment.
〈（４）生成人工ゼオライトの分離〉
反応完了後ろ過して、固形分とろ液に分離する。そして固形分を中和、水洗する。中和、水洗済みの固形分が人工ゼオライトであるが、これを乾燥することで製品人工ゼオライトが得られる。製品人工ゼオライトには鉛等の有害成分が含まれていないので各種種用途に利用することができる。中和、水洗に使用した洗浄水は水処理施設に送られる。
<(4) Separation of produced artificial zeolite>
After completion of the reaction, the mixture is filtered to separate into solid and filtrate. The solid content is neutralized and washed with water. The solid content after neutralization and washing with water is artificial zeolite, but product artificial zeolite can be obtained by drying it. Since product artificial zeolite does not contain harmful components such as lead, it can be used for various types of applications. Wash water used for neutralization and washing is sent to water treatment facilities.
以下、本発明を実験例を基に発明をさらに詳しく説明する。本発明においては、まず主要工程についてビーカースケールでの実験を行い、その結果を踏まえ、さらに実用化に向けて仮設プラント、すなわちベンチスケールでの一連の実験を行った。 Hereinafter, the present invention will be described in more detail based on experimental examples. In the present invention, first, experiments on the beaker scale were performed for the main processes, and based on the results, a series of experiments on a temporary plant, that is, a bench scale, was conducted for practical use.
ここではベンチスケールでの実験を基に説明するが、適宜、ビーカースケールでの実験結果についても記載している。図３は本試験のフローである。以下、図３に従い順次説明する。 Here, the description is based on an experiment on a bench scale, but an experimental result on a beaker scale is also described as appropriate. FIG. 3 shows the flow of this test. In the following, description will be made sequentially with reference to FIG.
ビーカースケール（主灰５０ｇ）からベンチスケール（主灰５ｋｇ）への１００倍スケールアップによる差異の確認として、（６）苛性ソーダによる主灰からの鉛の抽出、（７）鉛抽出液からの鉛の回収率、（８）ゼオライトの合成効率を指標として評価を行った。 As confirmation of the difference by 100 times scale-up from beaker scale (main ash 50g) to bench scale (main ash 5kg), (6) lead extraction from caustic soda, (7) lead extraction from lead extract Evaluation was performed using the recovery rate and (8) the synthesis efficiency of zeolite as an index.
〈（５）苛性ソーダによる主灰からの鉛の抽出試験〉
ビーカースケールによって設定した諸条件を基に、仮設粉砕プラントにおいて、順次、磁力選別、非鉄選別、風力選別、および微粉砕処理を行った。こうして得た主灰５ｋｇに対して、２Ｎ苛性ソーダ水溶液を５０Ｌ（固液比１：１０）を加え、抽出法による脱鉛処理を行った。脱鉛処理を２時間行った後、遠心分離器を用いて固液分離を行い、再度２Ｎ苛性ソーダ水溶液を５０Ｌ（固液比１：１０）を用いて抽出法による脱鉛処理・固液分離を行った。図３中（１）〜（５）の工程である。このうち（４）固液分離で分離した固相を人工ゼオライト製造の主原料とする。
<(5) Extraction test of lead from main ash with caustic soda>
Based on the conditions set by the beaker scale, magnetic sorting, non-ferrous sorting, wind sorting, and fine grinding were sequentially performed in a temporary grinding plant. To 5 kg of the main ash thus obtained, 50 L (solid-liquid ratio 1:10) of 2N sodium hydroxide aqueous solution was added, and deleading treatment was performed by an extraction method. After lead-free treatment for 2 hours, solid-liquid separation is performed using a centrifuge, and again 2N caustic soda aqueous solution is used 50 L (solid-liquid ratio 1:10) for lead removal treatment and solid-liquid separation by extraction method. went. It is the process of (1)-(5) in FIG. Of these, (4) the solid phase separated by solid-liquid separation is used as the main raw material for the production of artificial zeolite.
遠心分離器による固液分離で得られたそれぞれの液相を混合し、混合液に１０％（ｗｔ％）硫化ソーダ水溶液を加えて鉛イオンを硫化物とした後、凝集剤を用いてこの硫化物を沈殿させた。これを一晩静置した後、遠心分離器を用いて、固相である凝集した硫化物と液相を分離し、固相である硫化物を乾燥した。図３中（６）〜（９）の工程である。液相は廃水処理する。図３中（15）の工程である。 Each liquid phase obtained by solid-liquid separation using a centrifuge is mixed, and 10% (wt%) sodium sulfide aqueous solution is added to the mixture to make lead ions sulfide, and this sulfide is then added using a flocculant. The product was precipitated. After allowing this to stand overnight, the solid phase aggregated sulfide and the liquid phase were separated using a centrifuge, and the solid phase sulfide was dried. It is the process of (6)-(9) in FIG. The liquid phase is treated with waste water. This is step (15) in FIG.
〈（６）人工ゼオライト合成試験〉
図３中（４）の固液分離で分離した固相を人工ゼオライト製造の主原料とした。３．１２５Ｎ苛性ソーダ水溶液２０Ｌに対して水ガラスを３．５ｋｇ加えて十分攪拌した後、前記２回の脱鉛処理を行った主原料を加えて攪拌・混合した後、底面から超音波処理を行い、続いてペンタゴン方式で側面から超音波処理を行った。超音波の照射時間は合わせて１５分である。超音波処理後、加熱容器に内容物を移し替え、９８℃で２時間加熱し、人工ゼオライトの製造を行った。図３中（10）〜（11）の工程である。
<(6) Artificial zeolite synthesis test>
The solid phase separated by solid-liquid separation in (4) in FIG. 3 was used as the main raw material for artificial zeolite production. 3. After adding 3.5 kg of water glass to 20 L of 125N sodium hydroxide aqueous solution and stirring well, add the main raw material that has been subjected to the above-mentioned deleading treatment twice, stir and mix, and then perform ultrasonic treatment from the bottom. Subsequently, ultrasonic treatment was performed from the side by the Pentagon method. The total irradiation time of ultrasonic waves is 15 minutes. After the ultrasonic treatment, the contents were transferred to a heating container and heated at 98 ° C. for 2 hours to produce an artificial zeolite. This is the steps (10) to (11) in FIG.
こうして得られたスラリーを遠心分離器により固液分離し、回収した固相について余剰の苛性ソーダを水道水で２回洗浄した。引き続き、ろ過により固液分離し、固相を乾燥した。こうして最終的に主灰から合成したゼオライトを得た。図３中（12）〜（14）の工程である。液相は廃水処理する。図３中（15）の工程である。 The slurry thus obtained was subjected to solid-liquid separation using a centrifugal separator, and excess caustic soda was washed twice with tap water for the recovered solid phase. Subsequently, solid-liquid separation was performed by filtration, and the solid phase was dried. Thus, the zeolite synthesized from the main ash was finally obtained. It is the process of (12)-(14) in FIG. The liquid phase is treated with waste water. This is step (15) in FIG.
〈（７）評価試験１：脱鉛処理による主灰からの鉛の抽出率〉
図３における（１）脱Ｐｂ処理工程において、処理開始から３０分毎にサンプリングを行い、液中の鉛の濃度をＩＣＰ（ＩＣＰ分光分析）によって測定し、処理の時間依存性を調べた。図４はその結果である。なお、初期の主灰中に含まれる鉛は、６７０ｍｇ/ｋｇであり、抽出率（ｗｔ％）は下記式により求めた。また、ビーカースケールにおいて行った結果を図５に示している（主灰１０ｇ、２Ｎ-ＮａＯＨ １００ｍＬ)。
<(7) Evaluation test 1: Extraction rate of lead from main ash by deleading treatment>
In (1) De-Pb treatment step in FIG. 3, sampling was performed every 30 minutes from the start of treatment, and the lead concentration in the liquid was measured by ICP (ICP spectroscopic analysis) to examine the time dependency of the treatment. FIG. 4 shows the result. In addition, the lead contained in the initial main ash was 670 mg / kg, and the extraction rate (wt%) was obtained by the following formula. Moreover, the result performed in the beaker scale is shown in FIG. 5 (
図４、図５を比較して、両者とも２時間の処理によって、最終的に含有量の約６０ｗｔ％の鉛の抽出がなされ、ベンチスケールでも、ビーカースケールと同等の効果が確認された。ただし、図４のとおり、抽出速度の観点では、ベンチスケールでは反応時間１時間、１.５時間、２時間の３者で大きな違いがなく、時間効率を考慮すると反応時間は１時間程度で十分と言える。この理由は、ビーカースケールで用いた主灰は、磁力選別、非鉄選別、風力選別の処理をしていないため、鉛の初期含有量は３０７０ｍｇ／ｋｇであったことから、これに起因して、鉛の苛性ソーダ溶液への溶解に時間を要した可能性がある。 4 and 5, in both cases, the lead of about 60 wt% of the content was finally extracted by the treatment for 2 hours, and the same effect as the beaker scale was confirmed even on the bench scale. However, as shown in FIG. 4, in terms of extraction speed, there is no significant difference between the three reaction times of 1 hour, 1.5 hours, and 2 hours on the bench scale, and considering the time efficiency, a reaction time of about 1 hour is sufficient. It can be said. This is because the main ash used in the beaker scale is not subjected to magnetic sorting, non-ferrous sorting, or wind sorting, so the initial content of lead was 3070 mg / kg. It may have taken time to dissolve lead in caustic soda solution.
〈（８）評価試験２：苛性ソーダの濃度とＰｂ抽出率の関係〉
ゴミ焼却灰（主灰）に各種溶媒を加えて抽出操作を行った後、０．８μｍのフィルターでろ過して検液を調製した。得られた検液について、ＩＣＰによりＰｂの濃度を測定した。抽出率は上記式により求めた。図６はその結果である。図６りとおり、焼却灰からのＰｂ抽出には苛性ソーダが有効であり、それが３Ｎの濃度のとき抽出率が最も高い。
<(8) Evaluation Test 2: Relationship between Caustic Soda Concentration and Pb Extraction Rate>
Extraction operation was performed by adding various solvents to waste incineration ash (main ash), followed by filtration with a 0.8 μm filter to prepare a test solution. About the obtained test solution, the density | concentration of Pb was measured by ICP. The extraction rate was determined by the above formula. FIG. 6 shows the result. As shown in FIG. 6, caustic soda is effective for extracting Pb from incinerated ash, and the extraction rate is the highest when the concentration is 3N.
〈（９）評価試験３：反応時間とＰｂ抽出率の関係〉
苛性ソーダ濃度１Ｎ、２Ｎ、３．１２５Ｎ、４Ｎ、５Ｎの各種溶媒を用いて反応時間を変えて、上記〈（８）評価試験２：苛性ソーダの濃度とＰｂ抽出率の関係〉と同様にして反応時間の如何によるＰｂ抽出率を求めた。図７はその結果である。図７のとおり、いずれの濃度の溶媒についても、反応時間２時間までは経時的に抽出率が向上するが、２時間を超えると抽出率は一定乃至ほぼ一定になる。このことから苛性ソーダによる鉛抽出時間は２時間で十分と言える。
<(9) Evaluation Test 3: Relationship between Reaction Time and Pb Extraction Rate>
The reaction time was changed using various solvents having caustic soda concentrations of 1N, 2N, 3.125N, 4N, and 5N, and the reaction time was the same as in the above <(8) Evaluation Test 2: Relationship between Caustic Soda Concentration and Pb Extraction Rate>. The Pb extraction rate was determined by any of the above. FIG. 7 shows the result. As shown in FIG. 7, for any concentration of solvent, the extraction rate improves with time until the reaction time is 2 hours, but when it exceeds 2 hours, the extraction rate is constant or almost constant. From this, it can be said that 2 hours is sufficient for lead extraction with caustic soda.
〈（10）評価試験４：脱鉛処理による主灰の鉛の濃度〉
主灰（原料）と、図３における（２）の固液分離後の固相の乾燥物と、（４）の固液分離後の固相の乾燥物と、（14）の乾燥物と、（９）の乾燥物の５種類について重金属の含有量を測定した。表３はその結果である。
<(10) Evaluation test 4: Lead concentration of main ash by deleading treatment>
Main ash (raw material), solid phase dried product after solid-liquid separation in (2) in FIG. 3, solid phase dried product after solid-liquid separation in (4), dried product in (14), The heavy metal content was measured for the five types of dry matter of (9). Table 3 shows the results.
表３のとおり、原料から生成物（13）までは各処理において鉛の含有量が有効に減少していることが認められる。すなわち、原料（主灰）の鉛含有量は６７０ｍｇ/ｋｇであったのに対して、（２）の固液分離後の固相の乾燥物の鉛含有量は３８０ｍｇ/ｋｇ、（４）の固液分離後の固相の乾燥物の鉛含有量は３３０ｍｇ/ｋｇ、生成物（13）の鉛含有量は３００ｍｇ/ｋｇである。 As shown in Table 3, from the raw material to the product (13), it is recognized that the lead content is effectively reduced in each treatment. That is, while the lead content of the raw material (main ash) was 670 mg / kg, the lead content of the solid phase dried product after the solid-liquid separation of (2) was 380 mg / kg, (4) The lead content of the dried solid phase after solid-liquid separation is 330 mg / kg, and the lead content of the product (13) is 300 mg / kg.
また、表３のとおり、図３における（２）の固液分離後の固相の乾燥物〔表３中“ＮａＯＨ（２）”の処理物〕から生成物（13）までの各処理物においては、Ｚｎ、Ｍｎ、Ｃｒ、Ｃｕについても有意に減少している。表３中硫化処理物（９）は、Ｐｂの硫化物を含むそれらの金属の硫化物の総量である。このように、それらの金属は硫化処理物（９）として分離されることから、環境汚染を回避し、別途資源化することもできる。 In addition, as shown in Table 3, in each processed product from the solid phase dried product (processed product of “NaOH (2)” in Table 3) to the product (13) after solid-liquid separation in FIG. Is significantly decreased for Zn, Mn, Cr, and Cu. In Table 3, the sulfurized product (9) is the total amount of sulfides of these metals including sulfides of Pb. As described above, since these metals are separated as the sulfided product (9), environmental pollution can be avoided and resources can be separately obtained.
図８はベンチスケールでの硫化ソーダ添加量と残存鉛濃度の関係を調べたものである。鉛濃度はＯＲＰ法（電位差測定方法）より測定した。図８のとおり、主灰中のＰｂ濃度は１８.９ｍｇ/Ｌである。その鉛濃度は、硫化ソーダ添加量９．０ｇ程度までは殆ど変化しないが、硫化ソーダ添加量をそれ以上増加すると急激に減少し、硫化ソーダ添加量１２．６ｇで０．４ｍｇ/Ｌにまで減少している。 FIG. 8 shows the relationship between the amount of sodium sulfide added and the residual lead concentration on a bench scale. The lead concentration was measured by the ORP method (potential difference measuring method). As shown in FIG. 8, the Pb concentration in the main ash is 18.9 mg / L. The lead concentration hardly changes until the sodium sulfide addition amount is about 9.0 g, but decreases rapidly when the sodium sulfide addition amount is further increased, and decreases to 0.4 mg / L when the sodium sulfide addition amount is 12.6 g. is doing.
〈（11）評価試験５：ゼオライトの生成〉
前記〈（６）人工ゼオライト合成試験〉で製造した生成物、すなわち図３における（２）の固液分離後の固相の乾燥物についてＸ線回析を行った。図９にそのＸ線回析パターンを示している。図９のとおり、Ｐ型ゼオライトに特有のピーク（５箇所）が観察される。このほか、ゲーレナイト（長石）に特有のピーク（４箇所）が観察され、カルサイト、クオーツのピークも観察される。こうして得られた生成物には、鉛を実質上含有せず、Ｐ型ゼオライトが主成分であることから、そのままゼオライトとしての用途に使用することができる。
<(11) Evaluation test 5: Formation of zeolite>
X-ray diffraction was performed on the product produced in <(6) Artificial zeolite synthesis test>, that is, the solid phase dried product after solid-liquid separation in (2) in FIG. FIG. 9 shows the X-ray diffraction pattern. As shown in FIG. 9, peaks (five places) peculiar to P-type zeolite are observed. In addition, peaks (4 places) peculiar to gelenite (feldspar) are observed, and peaks of calcite and quartz are also observed. The product thus obtained contains substantially no lead and is mainly composed of P-type zeolite, so that it can be used as it is as a zeolite.
図１０はベンチスケールと同様にして、ビーカースケールで製造した生成物についてのＸ線回析パターンである。図１０のとおり、Ｐ型ゼオライトに特有のピークと、ゲーレナイト（長石）に特有のピークが観察される。なお、図１０中“（US30min-2hr）”は超音波照射時間３０分、加熱時間２時間の意味である。 FIG. 10 is an X-ray diffraction pattern for a product produced on a beaker scale in the same way as on a bench scale. As shown in FIG. 10, a peak peculiar to P-type zeolite and a peak peculiar to gehlenite (feldspar) are observed. In FIG. 10, “(US30min-2hr)” means an ultrasonic irradiation time of 30 minutes and a heating time of 2 hours.
〈（12）評価試験６：ゼオライトの溶出試験〉
前記〈（６）人工ゼオライト合成試験〉で製造した生成物を乾燥後、環境庁告示第４６号に基づく溶出試験を行った。表４はその結果である。表４のとおり、鉛を含む６種類の金属のいずれも基準値をクリアする結果が得られた。
<(12) Evaluation test 6: Zeolite dissolution test>
The product produced in <(6) Artificial zeolite synthesis test> was dried and then subjected to an elution test based on Environment Agency Notification No. 46. Table 4 shows the results. As shown in Table 4, the results of clearing the reference value were obtained for all six types of metals including lead.
以上のとおり、ベンチスケールでの実験結果はビーカースケールでの実験結果と一致乃至ほぼ一致しており、実機プラントにおいて必要な、人口ゼオライト生成反応時間、主灰中の重金属、特に鉛濃度に対応する硫化ソーダ添加量、その他の条件についても確認することができた。 As described above, the bench scale experimental results are consistent with or almost consistent with the beaker scale experimental results, corresponding to the artificial zeolite production reaction time, heavy metals in the main ash, especially the lead concentration, which are required in the actual plant. The amount of sodium sulfide added and other conditions could also be confirmed.
Claims (11)
From the refuse incineration ash according to claim 10, wherein the filtrate obtained by filtering the solid content is circulated to the step (b) of mixing the waste incineration ash after heavy metal separation with water and alkali to produce a slurry. Man-made zeolite production system.
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| KR20210007618A (en) * | 2019-07-12 | 2021-01-20 | 건국대학교 산학협력단 | Sequential preparation method of silicon and zeolite by using coal fly ash |
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