JPH10226793A - Process for solidifying waste - Google Patents
Process for solidifying wasteInfo
- Publication number
- JPH10226793A JPH10226793A JP9029921A JP2992197A JPH10226793A JP H10226793 A JPH10226793 A JP H10226793A JP 9029921 A JP9029921 A JP 9029921A JP 2992197 A JP2992197 A JP 2992197A JP H10226793 A JPH10226793 A JP H10226793A
- Authority
- JP
- Japan
- Prior art keywords
- waste
- pellets
- dechlorinating agent
- chloride
- solidified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 239000008188 pellet Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 230000000382 dechlorinating effect Effects 0.000 claims abstract description 30
- 239000004033 plastic Substances 0.000 claims abstract description 17
- 229920003023 plastic Polymers 0.000 claims abstract description 17
- 238000007711 solidification Methods 0.000 claims abstract description 12
- 230000008023 solidification Effects 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000000197 pyrolysis Methods 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 9
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000005539 carbonized material Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 16
- 150000001805 chlorine compounds Chemical group 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004449 solid propellant Substances 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 13
- 239000000460 chlorine Substances 0.000 description 13
- 229910052801 chlorine Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 8
- 239000000378 calcium silicate Substances 0.000 description 6
- 229910052918 calcium silicate Inorganic materials 0.000 description 6
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 239000000920 calcium hydroxide Substances 0.000 description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 5
- 238000006298 dechlorination reaction Methods 0.000 description 5
- 239000010813 municipal solid waste Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000010849 combustible waste Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- NPYIJOKBWMGNEV-UHFFFAOYSA-K O.[OH-].[Ba+2].C([O-])([O-])=O.[Mg+2] Chemical compound O.[OH-].[Ba+2].C([O-])([O-])=O.[Mg+2] NPYIJOKBWMGNEV-UHFFFAOYSA-K 0.000 description 1
- SKZKKFZAGNVIMN-UHFFFAOYSA-N Salicilamide Chemical compound NC(=O)C1=CC=CC=C1O SKZKKFZAGNVIMN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000013361 beverage Nutrition 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
- MIAKRAULTMFNJM-UHFFFAOYSA-K calcium;magnesium;carbonate;hydroxide Chemical compound [OH-].[Mg+2].[Ca+2].[O-]C([O-])=O MIAKRAULTMFNJM-UHFFFAOYSA-K 0.000 description 1
- DGVMNQYBHPSIJS-UHFFFAOYSA-N dimagnesium;2,2,6,6-tetraoxido-1,3,5,7-tetraoxa-2,4,6-trisilaspiro[3.3]heptane;hydrate Chemical compound O.[Mg+2].[Mg+2].O1[Si]([O-])([O-])O[Si]21O[Si]([O-])([O-])O2 DGVMNQYBHPSIJS-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000010806 kitchen waste Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- PEBLYNZJKGNAFS-UHFFFAOYSA-L lithium sodium hydrogen carbonate hydroxide hydrate Chemical compound C([O-])(O)=O.[Na+].O.[OH-].[Li+] PEBLYNZJKGNAFS-UHFFFAOYSA-L 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 plastics Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UFYYBPVKADFYIQ-UHFFFAOYSA-K potassium disodium hydrogen carbonate carbonate hydrate Chemical compound [OH-].[Na+].C([O-])([O-])=O.[K+].C(O)(O)=O.[Na+] UFYYBPVKADFYIQ-UHFFFAOYSA-K 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- LGXRKHRMKTXDSP-UHFFFAOYSA-K strontium barium(2+) carbonate hydroxide Chemical compound [OH-].[Sr+2].C([O-])([O-])=O.[Ba+2] LGXRKHRMKTXDSP-UHFFFAOYSA-K 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Landscapes
- Processing Of Solid Wastes (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、廃棄物を加熱して
固形化処理する方法に関し、特に、プラスチック類を含
有する廃棄物に脱塩素剤を混入して乾留処理し、これを
ペレット状に固形化処理した後、マイクロ波加熱により
炭化処理する廃棄物の処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for solidifying a waste by heating it, and more particularly to a method for mixing a dechlorinating agent into a waste containing plastics, subjecting the waste to dry distillation, and forming the pellet into a pellet. The present invention relates to a method for treating waste which is subjected to carbonization treatment by microwave heating after solidification treatment.
【0002】[0002]
【従来の技術】都市ゴミ等の廃棄物は、年々その量が増
加し、その処理が問題となっている。都市ゴミは一般的
に、一般家庭とかオフィス等から廃棄物として排出さ
れ、可燃性のものが主となっている。この可燃性の廃棄
物を単に焼却処理するのではなく、廃棄物の再資源化の
一環として、これを固形化処理して固形化燃料として再
利用することが行われている。2. Description of the Related Art The amount of waste such as municipal garbage increases year by year, and its disposal is a problem. Generally, municipal waste is discharged as waste from ordinary households and offices, and is mainly combustible. This combustible waste is not simply incinerated but is solidified and reused as solid fuel as part of the recycling of waste.
【0003】[0003]
【発明が解決しようとする課題】廃棄物を加熱処理する
際に問題となるのは、廃棄物中に含まれる塩素及び塩素
化合物等の塩化物の処理であり、加熱過程で発生する塩
素ガス,塩化水素ガス等の塩素系ガスは、フィルタ等で
吸着処理し、塩素系ガスが大気中に排出されないように
している。A problem in the heat treatment of waste is the treatment of chlorides such as chlorine and chlorine compounds contained in the waste. A chlorine-based gas such as a hydrogen chloride gas is subjected to an adsorption treatment with a filter or the like so that the chlorine-based gas is not discharged into the atmosphere.
【0004】一方、加熱過程でガス化しなかった塩化物
は処理灰と結合してしまい、高濃度の塩化物を含有した
処理灰となる。On the other hand, chlorides that have not been gasified during the heating process are combined with the treated ash, resulting in treated ash containing a high concentration of chloride.
【0005】このように処理灰に塩化物が含有している
と、処理灰を資源として再利用することは困難であり、
もっぱら地中に埋設することで処理されている。[0005] When chloride is contained in the treated ash, it is difficult to reuse the treated ash as a resource.
It is treated by burying it exclusively in the ground.
【0006】そのため、処理灰を再利用しようとする場
合には、事前に廃棄物を分別して塩素系ガスの発生の少
ない廃棄物のみ選別して加熱処理し、その処理灰(残
渣)を燃料として又はブロック等に固形化して再利用す
ることが行われている。Therefore, when attempting to reuse the treated ash, the waste is separated in advance, and only the waste that generates less chlorine gas is selected and heated, and the treated ash (residue) is used as fuel. Or, they are solidified into blocks or the like and reused.
【0007】しかし、廃棄物の分別を行うことは効率が
悪く、しかも、資源回収率も低いことから、塩化物を効
果的に除去するか、塩素系ガスの発生を抑制する技術の
確立が望まれている。However, since the separation of waste is inefficient and the resource recovery rate is low, it is desired to establish a technology for effectively removing chlorides or suppressing generation of chlorine-based gas. It is rare.
【0008】また、廃棄物を固形化して燃料として利用
することも行われているが、現状では、単に可燃性の廃
棄物を圧縮固形化する程度のものであり、ある程度の減
量化は達成できるが、燃料として使用する場合は、前記
と同様に、有害なガスを発生し、その対策が必要とな
る。[0008] Further, solidification of waste is also used as fuel, but at present, it is only to compress and solidify combustible waste, and a certain amount of weight reduction can be achieved. However, when used as a fuel, harmful gas is generated in the same manner as described above, and countermeasures are required.
【0009】本発明は、このような課題に鑑みなされた
もので、その目的とするところは、廃棄物を固形化処理
して燃料としての再利用を可能にし、且つ、固形化処
理,炭化処理および燃料としての使用時に、塩素系ガス
が発生しない廃棄物の固形化処理方法を提供しようとす
るものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to solidify waste to enable reuse as fuel, and to solidify and carbonize the waste. Another object of the present invention is to provide a method for solidifying waste which does not generate chlorine gas when used as a fuel.
【0010】[0010]
【課題を解決するための手段】本願の発明者らは、数々
の実験調査の結果、廃棄物に含まれる塩化物と反応しや
すいアルカリ系の物質を脱塩素剤として廃棄物に適量混
入し、所定の温度で加熱処理すると、塩化物が確実に残
渣に固形化され、加熱処理中に発生するガスには塩素系
ガスが含まれないことを見い出した。また、この残渣を
水洗浄することで残渣から効果的に塩化物を除去できる
こともわかった。As a result of numerous experimental investigations, the inventors of the present application have mixed an appropriate amount of an alkaline substance which is liable to react with chloride contained in the waste as a dechlorinating agent, It has been found that when heat treatment is performed at a predetermined temperature, chlorides are surely solidified into a residue, and the gas generated during the heat treatment does not contain chlorine-based gas. Further, it was also found that the chloride can be effectively removed from the residue by washing the residue with water.
【0011】本発明は、これらの知見に基づいてなされ
たもので、廃棄物に脱塩素剤を混入して固形化するとと
もに、この固形化に際して、廃棄物中に含まれているプ
ラスチックの物性に着目し、プラスチックをバインダと
して利用して強固に接着した固形化物を得、更に、この
固形化物をマイクロ波加熱により紙,布などの物質を炭
化処理して、燃料効率の良い固形燃料とし、しかも、燃
焼させたとき、塩素系ガスを発生しない固形化燃料を形
成するものである。The present invention has been made on the basis of these findings, and a dechlorinating agent is mixed into waste to solidify it. At the time of this solidification, the physical properties of the plastic contained in the waste are reduced. Focusing on the use of plastic as a binder to obtain a solidified product that is firmly bonded, and furthermore, the solidified product is carbonized by microwave heating to a material such as paper or cloth to produce a solid fuel with high fuel efficiency. It forms a solidified fuel that does not generate chlorine-based gas when burned.
【0012】本発明における廃棄物の炭化処理方法は、
まず、廃棄物を固形化処理する。この処理方法は、プラ
スチックを含有する廃棄物と塩化物と反応する脱塩素剤
とを混合して乾留処理し、乾留処理によって生成された
生成物(残渣)をペレット状に加圧成形して固形化す
る。The method for carbonizing waste according to the present invention comprises:
First, the waste is solidified. In this treatment method, a waste containing plastic and a dechlorinating agent that reacts with chloride are mixed and carbonized, and the product (residue) produced by the carbonization is pressed into a pellet and solidified. Become
【0013】また、他の施設で処理され、脱塩素剤を含
有しない固形化された処理物と、脱塩素剤とを混合す
る。Further, the dechlorinating agent is mixed with a solidified processed material which is treated in another facility and does not contain a dechlorinating agent.
【0014】次いで、この固形化処理物を加熱して炭化
処理する。Next, the solidified product is heated and carbonized.
【0015】前記の乾留処理の加熱温度は、塩化物の析
出が始まる温度(200℃)以下、またはプラスチック
の溶解が始まる温度(100℃〜150℃)以下とす
る。The heating temperature for the above-mentioned dry distillation treatment is set to a temperature at which chloride precipitation starts (200 ° C.) or lower, or a temperature at which plastic dissolution starts (100 ° C. to 150 ° C.).
【0016】また、塩化物と反応する脱塩素剤は、アル
カリ土類金属,アルカリ土類金属化合物,アルカリ金
属,アルカリ金属化合物のいずれかの単体又はこれらの
混合物から成り、添加量は、処理される廃棄物の5〜3
0重量%を好適とする。The dechlorinating agent which reacts with the chloride is composed of any one of alkaline earth metals, alkaline earth metal compounds, alkali metals and alkali metal compounds, or a mixture thereof. 5 to 3 of waste
0% by weight is preferred.
【0017】また、炭化処理は、内部を含めた全体を均
一に加熱できるマイクロ波加熱による。The carbonization is performed by microwave heating that can uniformly heat the entire structure including the inside.
【0018】以上のように、乾留処理時の加熱温度は、
廃棄物に含まれている塩化物が析出する温度以下である
ので、乾留処理中には塩素系ガスの発生はなく、また、
プラスチック類が軟化してバインダの役目を果し、取り
扱いの安定した形状の脱塩素剤を混合した固形化処理物
(ペレット)が得られ、しかも、炭化処理しているの
で、燃焼効率の良い固形化燃料が得られる。As described above, the heating temperature during the carbonization treatment is as follows:
Since the temperature is lower than the temperature at which the chloride contained in the waste precipitates, no chlorine-based gas is generated during the dry distillation, and
The plastics soften and serve as a binder, and a solidified product (pellet) mixed with a dechlorinating agent in a stable shape can be obtained. In addition, since the carbonized material is used, a solid material with good combustion efficiency is obtained. Fuel is obtained.
【0019】また、固形化処理物を炭化処理する場合、
固形化処理物には脱塩素剤が混合されているので、塩化
物は固形化処理物に固定化され、発生ガス中には塩素系
ガスは含まれなくなる。When the solidified product is carbonized,
Since the solidified material contains a dechlorinating agent, the chloride is fixed to the solidified material, and the generated gas does not contain chlorine-based gas.
【0020】従って、ダイオキシンの発生のない、安全
な固形化燃料として有効再利用が可能となる。Therefore, it is possible to effectively reuse as a safe solidified fuel without generating dioxin.
【0021】[0021]
【発明の実施の形態】以下、本発明の実施の形態を図面
によって説明する。図1は本発明の実施の形態の概念図
で、1は廃棄物供給部、2は混合機、3は脱塩素剤供給
部を示す。4は加熱手段で、混合機2内の処理物を加熱
する。この加熱手段4は、ガス加熱,電気加熱又は燃焼
加熱,マイクロ波加熱,誘導加熱等のいずれかの加熱手
段でもよいが、図示の例は誘導加熱を使用した場合を示
し、誘導加熱コイルに交流電力を供給して誘導加熱す
る。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a conceptual diagram of an embodiment of the present invention, wherein 1 is a waste supply unit, 2 is a mixer, and 3 is a dechlorinating agent supply unit. Reference numeral 4 denotes a heating means for heating the processed material in the mixer 2. The heating means 4 may be any heating means such as gas heating, electric heating or combustion heating, microwave heating, induction heating, etc., but the illustrated example shows a case where induction heating is used. Electric power is supplied for induction heating.
【0022】5は造粒機で外部に加熱手段6を有し、内
部には加圧ローラ等から成るプレス手段を備えている。
7は造粒機5で成形された固形化処理物(以下、ペレッ
トと称す)を示す。このペレットを炭化処理するのであ
るが、炭化処理手段は、造粒機5の加熱手段6をマイク
ロ波加熱器で形成し、造粒機内で炭化処理するか、又は
鎖線で示すように炭化処理手段8を別に設け、マイクロ
波加熱器9で加熱して炭化処理してもよい。Reference numeral 5 denotes a granulator having a heating means 6 on the outside and a press means comprising a pressure roller and the like inside.
Reference numeral 7 denotes a solidified product (hereinafter, referred to as a pellet) formed by the granulator 5. The pellets are carbonized, and the carbonizing means is formed by forming the heating means 6 of the granulator 5 with a microwave heater and carbonizing in the granulator, or as shown by a dashed line. 8 may be provided separately and carbonized by heating with a microwave heater 9.
【0023】ペレットを製造する手順は、まず、廃棄物
を廃棄物供給部1に投入し、脱塩素剤供給部3に脱塩素
剤を収容して、これらを所定の割合で混合機2に供給す
る。混合機2では、廃棄物と脱塩素剤と混合しながら、
加熱処理手段4で200℃以下、好ましくは100℃〜
150℃の温度で外気を遮断した状態で10分間加熱処
理(乾留)する。The procedure for producing pellets is as follows. First, waste is put into a waste supply unit 1, a dechlorinating agent is stored in a dechlorinating agent supply unit 3, and these are supplied to the mixer 2 at a predetermined ratio. I do. In the mixer 2, while mixing the waste and the dechlorinating agent,
200 ° C. or less, preferably 100 ° C.
A heat treatment (dry distillation) is performed for 10 minutes at a temperature of 150 ° C. with the outside air shut off.
【0024】次に、混合機2の開閉扉2bを開き、混合
物を造粒機5に供給し、この造粒機5で混合物を前記と
同様の温度条件で加熱しながらプレス手段で圧縮成形
し、ペレット7を形成する。なお、混合機2に破砕機能
を付加してもよい。Next, the opening / closing door 2b of the mixer 2 is opened, the mixture is supplied to the granulator 5, and the mixture is compression-molded by press means while heating the mixture under the same temperature conditions as described above. Then, a pellet 7 is formed. The crushing function may be added to the mixer 2.
【0025】上記の工程において廃棄物内にプラスチッ
ク類が混入していると、(混入していないか又は少ない
ときは、別途廃棄物供給部1から供給する)プラスチッ
ク類は軟化した状態で廃棄物と混合され、そして成形さ
れるので、廃棄物間の接着剤(バインダ)としての役目
を果し、製造されたペレットは安定した固体形状を維持
する。In the above process, if plastics are mixed in the waste, the plastics are supplied in a softened state (if they are not mixed or small, they are separately supplied from the waste supply unit 1). As it is mixed and molded, it acts as an adhesive (binder) between the wastes, and the pellets produced maintain a stable solid form.
【0026】プレス手段としては、例えば、混合物を送
り出す送り回転ローラと圧縮成形する絞り回転ローラ
(加熱ローラとしてもよい)とを備え、送り回転ローラ
間の間隔を調整して加圧力を100〜1000kg/c
m2に調整する。この加圧力が小さいと固形化が困難と
なり、また大き過ぎると設備が大がかりとなる。The pressing means includes, for example, a feed rotary roller for feeding the mixture and a squeezing rotary roller (which may be a heating roller) for compression molding. / C
to adjust to the m 2. If the pressure is small, solidification becomes difficult, and if it is too large, the equipment becomes large.
【0027】このように圧縮成形することにより、ペレ
ットの体積比は、表1に示すように減量化される。By performing compression molding in this manner, the volume ratio of the pellets is reduced as shown in Table 1.
【0028】[0028]
【表1】 [Table 1]
【0029】次に、このペレット7を造粒機5内又は別
置の炭化処理手段8で炭化処理する。炭化処理は、マイ
クロ波加熱器を使用し300℃〜600℃で加熱してペ
レット内の紙や布などの有機物を炭化させる。このとき
排気ガスが発生するが、ペレット内の塩化物は後述する
ように脱塩素剤によってペレット内に固定され、排気ガ
ス中には塩素系ガスは含まれない。Next, the pellets 7 are carbonized by the carbonizing means 8 in the granulator 5 or separately. In the carbonization treatment, a microwave heater is used to heat at 300 ° C. to 600 ° C. to carbonize organic substances such as paper and cloth in the pellets. At this time, exhaust gas is generated, but chloride in the pellet is fixed in the pellet by a dechlorinating agent as described later, and the exhaust gas does not include chlorine-based gas.
【0030】上記の固形化処理は、脱塩素処理を施した
一連の廃棄物処理システムの場合であるが、しかし、現
状では、脱塩素処理されることなく、単に廃棄物を圧縮
固形化して燃料として利用することが行われている。The above-mentioned solidification treatment is a case of a series of waste treatment systems which have been subjected to dechlorination treatment. However, at present, the solidification treatment is carried out by simply compressing and solidifying the waste without dechlorination treatment. It has been used as a service.
【0031】このような固形化燃料を燃焼させると塩素
系ガスが発生する。この固形化燃料を本発明において
は、図1の廃棄物供給部1に、プラスチック含有廃棄物
と一緒に投入することで脱塩素剤の入った固形化物とな
すことができる。When such solidified fuel is burned, chlorine-based gas is generated. In the present invention, the solidified fuel containing the dechlorinating agent can be formed by charging the solidified fuel into the waste supply unit 1 in FIG. 1 together with the plastic-containing waste.
【0032】以上の処理方法で固形化処理した廃棄物を
燃料として使用し、燃焼させると廃棄物に含有する塩化
物は次に示す実験の結果、燃焼による処理灰に固定化さ
れ、排気ガスには含まれていないことが判明した。When the waste solidified by the above treatment method is used as a fuel and burned, chloride contained in the waste is fixed to treated ash by combustion as a result of the following experiment, and is converted into exhaust gas. Turned out not to be included.
【0033】実験は、まず、標準的な都市ゴミを模擬し
た次のような模擬ゴミを作成する。In the experiment, first, the following simulated garbage which simulates standard city garbage is prepared.
【0034】 20重量% ・プラスチック(PE,PP,PS,P
VDC) 50重量% ・紙(ティッシュ,新聞,包装紙,箱,
飲料パック) 20重量% ・布(ウエスなど) 10重量% ・厨芥 この模擬ゴミを破砕し、破砕した模擬ゴミ10kgと、
粉末状の添加物を(Ca(OH)2)1kgとを混合機
に投入して密閉し、150℃の温度で10分間加熱しな
がら混合する。20% by weight ・ Plastic (PE, PP, PS, P
VDC) 50% by weight ・ Paper (tissue, newspaper, wrapping paper, box,
Beverage pack) 20% by weight-Cloth (such as waste cloth) 10% by weight-Kitchen waste This simulated garbage is crushed and crushed simulated garbage 10kg.
1 kg of the powdery additive (Ca (OH) 2 ) is charged into a mixer, sealed, and mixed while heating at a temperature of 150 ° C. for 10 minutes.
【0035】次に、同条件で造粒機で固形化物(ペレッ
ト)を作る。このペレットは、添加物の種類を変えて複
数種類のペレットを製造した。Next, a solidified product (pellet) is produced by a granulator under the same conditions. This pellet produced a plurality of types of pellets by changing the type of additive.
【0036】製造したペレットは、 径 :約1cm 長さ :約3cm 体積比:ゴミ+添加物 100 固形化後 20 次に、この製造したペレットを数個排気管付きの密閉容
器に入れ、電気炉にて加熱し、発生ガスを抽出してその
ガス濃度(塩化水素ガス)ppmを測定する試験を行っ
た。The produced pellets are as follows: Diameter: about 1 cm Length: about 3 cm Volume ratio: dust + additive 100 After solidification 20 Next, several of the produced pellets are placed in an airtight container with an exhaust pipe, and placed in an electric furnace. A test was conducted to extract the generated gas and measure the gas concentration (hydrogen chloride gas) ppm.
【0037】加熱温度は、200℃,250℃,300
℃,350℃,400℃,500℃,600℃の7段階
に分け、各温度にて5分間保持し、全体で1時間加熱し
て、各温度におけるガス濃度を測定した。The heating temperature is 200 ° C., 250 ° C., 300 ° C.
C., 350.degree. C., 400.degree. C., 500.degree. C., and 600.degree. C. were divided into seven stages, each temperature was maintained for 5 minutes, the whole was heated for 1 hour, and the gas concentration at each temperature was measured.
【0038】ガス濃度の測定は、JIS−K0804に
規定されている検知管によって測定した。The gas concentration was measured using a detector tube specified in JIS-K0804.
【0039】この測定結果を表2に示す。表2に示す測
定値は実験10回における測定値の平均値である。Table 2 shows the measurement results. The measured values shown in Table 2 are average values of the measured values in 10 experiments.
【0040】なお、表中、※印は10回の実験において
いずれも塩化水素が検出されなかったことを表してい
る。In the tables, the asterisks indicate that no hydrogen chloride was detected in any of the ten experiments.
【0041】[0041]
【表2】 [Table 2]
【0042】以上のことからペレットを炭化処理手段で
300℃〜600℃で炭化処理しても、塩化水素は発生
しないことがわかる。From the above, it can be seen that even if the pellets are carbonized at 300 ° C. to 600 ° C. by the carbonizing means, no hydrogen chloride is generated.
【0043】上記の実験結果から、脱塩素剤としては、
低温域では珪酸カルシウムが、高温域では水酸化カルシ
ウムが塩化物と反応して塩化物の固定化が確実に行われ
ていることが判明した。From the above experimental results, as the dechlorinating agent,
It has been found that calcium silicate reacts with chloride in the low temperature range and calcium hydroxide in the high temperature range, and the chloride is reliably immobilized.
【0044】もちろん、試験では、プラスチックを多く
混入させて試験しており、実用上は、珪酸カルシウム,
水酸化カルシウムの単体の混合でも十分効果がある。Of course, in the test, a large amount of plastic was mixed in the test, and in practice, calcium silicate,
Even a simple mixture of calcium hydroxide is sufficiently effective.
【0045】以上のことから、塩化物を含有する廃棄物
を固形化処理する場合に、脱塩素剤を混入して固形化処
理することで、その固形化物を燃焼させても、塩化水素
が排気ガス中に混入することが防止できることが明らか
となった。From the above, when solidification treatment is performed on waste containing chloride, hydrogen chloride is exhausted even if the solidified matter is burned by mixing with a dechlorinating agent. It became clear that mixing in the gas can be prevented.
【0046】燃焼後の処理灰には塩化物が固定されてい
るので、そのまま廃棄することはできないので脱塩素処
理をする必要がある。Since chloride is fixed in the treated ash after combustion, it cannot be discarded as it is, so it is necessary to perform a dechlorination treatment.
【0047】この脱塩素処理は、図2に示すように、ま
ず、処理灰を水槽に入れて所定時間(約30分間)撹拌
して塩化物を水に溶解する。次に、これを脱水分離し、
処理灰から塩化物を除去し、これを乾燥・固形化する。
分離した排水の方は、別途排水処理手段により脱塩素処
理する。In this dechlorination treatment, as shown in FIG. 2, first, the treated ash is put into a water tank and stirred for a predetermined time (about 30 minutes) to dissolve chlorides in water. Next, this is dehydrated and separated,
The chloride is removed from the treated ash, which is dried and solidified.
Separated wastewater is dechlorinated separately by wastewater treatment means.
【0048】固形化した処理灰中の残留塩化物をイオン
クロマトグラフィで測定した結果、従来1,000pp
mあったものが、5ppm以下でほとんど皆無に等しか
った。The residual chloride in the solidified treated ash was measured by ion chromatography.
However, almost none at 5 ppm or less.
【0049】上記の実験調査により高温域では水酸化カ
ルシウムが良い結果が得られた理由は、廃棄物が熱分解
時に発生する塩化水素ガス(HCl)と気固反応して、
塩化アルカリ{Ca(ClO)2・4HC2O・CaCl
2・4H20}を生成し、処理灰に塩化物を固定化するか
らであり、同様に作用するものであれば、同様の作用効
果が期待できる。The reason why calcium hydroxide obtained good results in the high temperature range from the above experimental investigation is that the waste gas-solid reacts with hydrogen chloride gas (HCl) generated during thermal decomposition.
Alkali chloride {Ca (ClO) 2 · 4HC 2 O · CaCl
This is because 2.4H 2 0} is generated and the chloride is immobilized on the treated ash, and the same action and effect can be expected as long as the action is the same.
【0050】従って、水酸化カルシウム以外のアルカリ
系物資であっても、同様の結果が得られることは明白で
ある。Therefore, it is clear that similar results can be obtained with alkaline substances other than calcium hydroxide.
【0051】アルカリ系物資としては、次のものが使用
できる。The following can be used as the alkaline material.
【0052】(a)アルカリ土類金属化合物: 水酸化カルシウム,酸化カルシウム,炭酸カルシウム 水酸化マグネシウム,酸化マグネシウム,炭酸マグネシ
ウム 水酸化バリウム水和物,酸化バリウム,炭酸バリウム 水酸化ストロンチウム,炭酸ストロンチウム ドロマイド(CaCO3・MgCO3),石灰 (b)アルカリ金属化合物: 水酸化ナトリウム,水酸化カリウム,水酸化リチウム水
和物 炭酸ナトリウム,炭酸カリウム,炭酸カリウムナトリウ
ム 炭酸ナトリウム水和物,炭酸リチウム また、珪酸カルシウムが低温領域で塩素成分と反応して
固定化する理由は、珪酸カルシウム水和物は、多孔体で
あり、比表面積が大きく含水しており、処理物が熱分解
時に発生する塩化水素ガスを接触,吸着することにより
処理灰に塩素成分を固定化することができるからであ
り、同様に作用するものであれば、同様の作用効果が期
待できる。(A) Alkaline earth metal compounds: calcium hydroxide, calcium oxide, calcium carbonate magnesium hydroxide, magnesium oxide, magnesium carbonate barium hydroxide hydrate, barium oxide, barium carbonate strontium hydroxide, strontium carbonate dolomide ( (CaCO 3 .MgCO 3 ), lime (b) Alkali metal compounds: sodium hydroxide, potassium hydroxide, lithium hydroxide hydrate sodium carbonate, potassium carbonate, potassium sodium carbonate sodium carbonate hydrate, lithium carbonate and calcium silicate The reason is that calcium silicate hydrate is porous, has a large specific surface area and contains water, and the treated product comes in contact with hydrogen chloride gas generated during thermal decomposition. , Fix the chlorine component in the treated ash by adsorption It is because it is possible to reduction, as long as it functions in the same manner, the same effect can be expected.
【0053】従って、珪酸カルシウム以外の珪酸塩であ
っても、同様な結果が得られることは明白である。Therefore, it is clear that similar results can be obtained with silicates other than calcium silicate.
【0054】珪酸塩としては、次のものが使用できる。The following can be used as the silicate.
【0055】(a)珪酸塩水和物:珪酸カルシウム水和
物,珪酸マグネシウム水和物,ドバモナイド(5CaO
・6Sio2・5H20) (b)珪酸塩化物:珪酸アルミニウム,珪酸ナトリウム そして、実験調査の結果、脱塩素剤の添加量は、処理さ
れる廃棄物の5〜30重量%添加することが好ましく、
また、2種類の脱塩素剤を混合するときは、その混合比
は、低温領域で反応するものをAとし、高温領域で反応
するものをBとしたとき、A≧Bとするのが好ましく、
特に、A:Bの比率を(1.5〜4.0):1とするこ
とが好ましいことがわかった。(A) Silicate hydrate: calcium silicate hydrate, magnesium silicate hydrate, dobamonide (5CaO
· 6Sio 2 · 5H 2 0) (b) silicic acid chlorides: aluminum silicate, sodium silicate and the results of experimental investigations, the amount of dechlorination agent, be added 5 to 30 wt% of the waste to be treated Preferably
When two types of dechlorinating agents are mixed, the mixing ratio is preferably A ≧ B when A reacts in a low-temperature region and B reacts in a high-temperature region.
In particular, it was found that the ratio of A: B was preferably set to (1.5 to 4.0): 1.
【0056】また、脱塩素剤を混合しても、プラスチッ
ク類がバインダの役目をして効果的に結合することもわ
かった。It was also found that even if a dechlorinating agent was mixed, the plastics functioned as a binder and were effectively bonded.
【0057】[0057]
【発明の効果】以上のように本発明は、プラスチック等
の塩化物を含んだ処理物に脱塩素剤を混合して、塩化物
が析出する温度以下で乾留処理し、これを加圧して固形
化物(ペレット)を形成し、更に、これを炭化処理する
ようにしたので、 (1)固形化物を成形するとき、塩素系ガスの発生がな
く、且つ、プラスチック類が軟化して混合物の結合剤の
役目を果し、更に、炭化処理しているので取り扱い易い
安定した形状のペレット、即ち、軽量で持ち運びや運搬
に適したペレットが得られる。As described above, according to the present invention, a dechlorinating agent is mixed with a processed material containing chlorides such as plastics, and the resulting product is subjected to dry distillation at a temperature lower than a temperature at which chlorides are precipitated. (1) When molding a solidified product, there is no generation of chlorine-based gas, and plastics are softened and a binder of the mixture is formed. Further, pellets having a stable shape that are easy to handle since carbonization treatment is performed, that is, pellets that are lightweight and suitable for carrying or transporting can be obtained.
【0058】(2)ペレットおよび炭化後のペレットを
燃料として燃焼させても、脱塩素剤の存在により、塩化
物は残渣に固定され、排気ガス中には塩素系ガスは混入
しないので、そのまま大気中に放出してもダイオキシン
の発生は防止される。(2) Even when the pellets and the pellets after carbonization are burned as fuel, the chloride is fixed to the residue due to the presence of the dechlorinating agent, and no chlorine-based gas is mixed in the exhaust gas. Release of dioxin is prevented even if it is released.
【0059】(3)ペレットは炭化されているので燃焼
する際、廃棄物の燃焼力(火力)強め、燃焼効率が向上
する。(3) Since the pellets are carbonized, the burning power (thermal power) of the waste is increased when burning, and the combustion efficiency is improved.
【0060】(4)燃焼の処理灰には塩化物が固定され
るが、水洗浄することで、ほとんど無くなり、処理灰の
有効利用も可能となる。(4) Chloride is fixed to the treated ash of combustion, but it is almost eliminated by washing with water, and the treated ash can be effectively used.
【0061】等の効果を奏する。The following effects are obtained.
【図1】本発明の実施の形態の概念図。FIG. 1 is a conceptual diagram of an embodiment of the present invention.
【図2】処理灰の処理説明図。FIG. 2 is an explanatory diagram of the processing of the processing ash.
1,11…処理物供給部 2…混合機 3,13…脱塩素剤供給部 4,6…加熱手段 5…造粒機 7…ペレット 8…炭化処理手段 9…マイクロ波加熱器 Reference numerals 1, 11: treated material supply unit 2: mixer 3, 13: dechlorinating agent supply unit 4, 6, heating means 5, granulator 7, pellet 8, carbonization treatment means 9, microwave heater
Claims (7)
物と反応する脱塩素剤とを混合して乾留処理し、乾留処
理により生成した生成物をペレット状に固形化処理し、
次に、この固形化処理物を加熱して炭化処理することを
特徴とする廃棄物の固形化処理方法。1. A waste containing plastic and a dechlorinating agent that reacts with chloride are mixed and subjected to dry distillation, and the product produced by dry distillation is solidified into pellets.
Next, the solidification treatment method is characterized by heating and carbonizing the solidified material.
反応する脱塩素剤とを混合して乾留処理し、乾留処理に
より生成した生成物を固形化処理し、次に、この固形化
処理物を炭化処理することを特徴とする廃棄物の固形化
処理方法。2. A treated product having no dechlorinating agent and a dechlorinating agent which reacts with chloride are mixed and subjected to dry distillation, and the product produced by dry distillation is solidified. A method for solidifying waste, comprising subjecting a carbonized material to carbonization.
とを特徴とする請求項1又は2記載の廃棄物の固形化処
理方法。3. The method for solidifying waste according to claim 1, wherein the carbonization is performed by microwave heating.
リ土類金属化合物,アルカリ金属,アルカリ金属化合物
のいずれか単体又はこれらの混合物からなることを特徴
とする請求項1又は2記載の廃棄物の固形化処理方法。4. The waste according to claim 1, wherein the dechlorinating agent is composed of any one of an alkaline earth metal, an alkaline earth metal compound, an alkali metal, and an alkali metal compound, or a mixture thereof. Solidification method of the product.
の5〜30重量%であることを特徴とする請求項1又は
2記載の廃棄物の固形化処理方法。5. The method for solidifying waste according to claim 1, wherein the amount of the dechlorinating agent added is 5 to 30% by weight of the waste to be treated.
析出が始まる温度以下であることを特徴とする請求項1
記載の廃棄物の固形化処理方法。6. The method according to claim 1, wherein the heating temperature at the time of forming the pellets is lower than the temperature at which the precipitation of chloride starts.
The solidification treatment method of the waste described in the above.
下であることを特徴とする請求項1又は6記載の廃棄物
の固形化処理方法。7. The method for solidifying waste according to claim 1, wherein the heating temperature at the time of forming the pellets is 200 ° C. or less.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9029921A JP2985819B2 (en) | 1997-02-14 | 1997-02-14 | Solidification of waste |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9029921A JP2985819B2 (en) | 1997-02-14 | 1997-02-14 | Solidification of waste |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH10226793A true JPH10226793A (en) | 1998-08-25 |
JP2985819B2 JP2985819B2 (en) | 1999-12-06 |
Family
ID=12289467
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9029921A Expired - Fee Related JP2985819B2 (en) | 1997-02-14 | 1997-02-14 | Solidification of waste |
Country Status (1)
Country | Link |
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JP (1) | JP2985819B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101160205B1 (en) * | 2009-07-09 | 2012-06-27 | 정인환 | A Pollutant Disposal System and A Disposal Method |
JP2012179560A (en) * | 2011-03-02 | 2012-09-20 | Taiheiyo Cement Corp | Method for processing waste material |
-
1997
- 1997-02-14 JP JP9029921A patent/JP2985819B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101160205B1 (en) * | 2009-07-09 | 2012-06-27 | 정인환 | A Pollutant Disposal System and A Disposal Method |
JP2012179560A (en) * | 2011-03-02 | 2012-09-20 | Taiheiyo Cement Corp | Method for processing waste material |
Also Published As
Publication number | Publication date |
---|---|
JP2985819B2 (en) | 1999-12-06 |
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