WO2010143316A1 - Halogen trapping additive - Google Patents
Halogen trapping additive Download PDFInfo
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- WO2010143316A1 WO2010143316A1 PCT/JP2009/064077 JP2009064077W WO2010143316A1 WO 2010143316 A1 WO2010143316 A1 WO 2010143316A1 JP 2009064077 W JP2009064077 W JP 2009064077W WO 2010143316 A1 WO2010143316 A1 WO 2010143316A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
Disclosed is an additive for trapping a halogen conveniently and at low cost in a conventional recycling apparatus without the need of attaching any specialized unit to the recycling apparatus.
Specifically disclosed is a halogen trapping additive which comprises 100 parts by mass of a mixture composed of 49.5 to 75 parts by mass inclusive of urea, 20 to 49.5 parts by mass inclusive of a hydroxide of at least one member selected from calcium, magnesium and barium and 1 to 5 parts by mass inclusive of a stearic acid metal salt. In the halogen trapping additive, the mixture preferably takes the form of powder having a particle size of 0.01 to 5 mm inclusive.
Description
本発明は、ハロゲン捕集添加剤に関し、具体的には、廃プラスッチックを再資源化するためのプロセスにおいて、再資源化装置の腐食原因となるハロゲン物質を捕集して無害化する添加剤に関するものである。
The present invention relates to a halogen collecting additive, and more specifically, to an additive that collects and detoxifies halogen substances that cause corrosion of a recycling apparatus in a process for recycling waste plastics. Is.
化石資源である石油から作られるプラスチック（ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリエチレンテレフタレート、ポリカーボネート等）は大量に生産されており、使用済みの廃プラスチックを焼却すると大量の温暖化ガスである二酸化炭素を大量に発生するため、再資源化（リサイクル）が地球温暖化防止のために重要である。再資源化技術の中でも、廃プラスチックの再生利用（マテリアルリサイクル）や熱分解油化（ケミカルリサイクル）が特に期待されている。
Plastics (polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.) made from petroleum, a fossil resource, are produced in large quantities. When used waste plastic is incinerated, a large amount of greenhouse gas is generated as CO2. Since a large amount of carbon is generated, recycling (recycling) is important to prevent global warming. Among the recycling technologies, recycling of waste plastic (material recycling) and pyrolysis oil (chemical recycling) are particularly expected.
再生利用（マテリアルリサイクル）は、廃プラスチックを種類毎に選別し熱溶融、ペレット化し再生プラスチックとして再び成型品の原料等に使うことである。この再生利用は、プラスチックを循環使用する点で最も環境負荷が小さく好ましいリサイクル法であるが、選別を完全に行うことが出来ないため、不純物としてポリ塩化ビニルや臭素系難燃剤の混入が避けられない。このため熱溶融時に腐食性のハロゲン化水素ガスが発生し再生装置の長期安定運転を困難にしている。
Recycling (material recycling) is to sort waste plastics by type, heat melt, pelletize them, and use them again as raw materials for molded products. This recycling is the preferred recycling method with the least environmental impact in terms of recycling plastics. However, since recycling cannot be performed completely, the inclusion of polyvinyl chloride or brominated flame retardants as impurities is avoided. Absent. For this reason, corrosive hydrogen halide gas is generated at the time of hot melting, making long-term stable operation of the regenerator difficult.
熱分解油化（ケミカルリサイクル）は、廃プラスチックを分解するまで加熱し、発生する分解ガスを冷却して液化し、この液体を燃料とするものでプラスチックを石油に戻すリサイクル法である。この方法は選別をあまり必要とせず、数種の廃プラスチックを処理できるが、やはり混入するポリ塩化ビニルや臭素系難燃剤から発生する腐食性のハロゲン化水素ガスが再生装置の長期安定運転を困難にしている、特にこの方法では処理温度が高いため、ハロゲン対策は必須である。
Pyrolysis oil conversion (chemical recycling) is a recycling method in which waste plastic is heated until it is decomposed, the cracked gas generated is cooled and liquefied, and this liquid is used as fuel to return the plastic to petroleum. This method does not require much sorting and can treat several types of waste plastic, but corrosive hydrogen halide gas generated from mixed polyvinyl chloride and brominated flame retardants makes it difficult to operate the regenerator for a long period of time. In particular, in this method, since the processing temperature is high, a countermeasure against halogen is indispensable.
従って、再資源化装置の長期安定運転を可能にするために、熱融解や熱分解時にポリ塩化ビニル（以下「ＰＶＣ」という。）から発生する塩素化合物やプラスチック中に添加されている臭素系難燃剤から発生する臭素化合物を無害化する方法が要望されている。
Therefore, in order to enable long-term stable operation of the recycling equipment, chlorine compounds generated from polyvinyl chloride (hereinafter referred to as “PVC”) during thermal melting and thermal decomposition and bromine-based difficulties added to plastics There is a demand for a method for detoxifying bromine compounds generated from a flame retardant.
ＰＶＣ中のハロゲン（塩素等）を処理する方法として、例えば下記特許文献１乃至３がある。
As a method for treating halogen (chlorine or the like) in PVC, for example, there are Patent Documents 1 to 3 below.
特許文献１には、アルカリ化合物等の無機添加剤を含む水溶液中でハロゲン含有ポリマーを加圧状態で加熱し、ハロゲン化水素として除去する方法が開示されている。しかしながら、圧力容器が必要なため装置が高価となり経済性、利便性に問題がある。
Patent Document 1 discloses a method in which a halogen-containing polymer is heated under pressure in an aqueous solution containing an inorganic additive such as an alkali compound and removed as hydrogen halide. However, since a pressure vessel is required, the apparatus becomes expensive and there is a problem in economy and convenience.
特許文献２には、アルカリ金属の水酸化物等を添加し、２５０~７００℃で熱分解させ、アルカリ金属ハロゲン化合物を生成させる方法が開示されている。しかしながら、この方法は高温で反応させるためエネルギーを要する上に、生成したハロゲン化合物を系外に移送させる不活性キャリアーガスを使用するのでコストが掛かり汎用性に乏しいといった問題がある。
Patent Document 2 discloses a method of adding an alkali metal hydroxide or the like and thermally decomposing at 250 to 700 ° C. to produce an alkali metal halogen compound. However, this method has a problem that it requires energy to react at a high temperature and uses an inert carrier gas for transferring the produced halogen compound to the outside of the system, so that the cost is high and the versatility is poor.
特許文献３には、ＰＶＣに酸化カルシウム（ＣａＯ）を混合し、常温で粉砕（メカノケミカル処理）し、脱塩素化する方法が開示されている。しかしながら、粉砕機が必要であり装置が大規模になるといった問題がある。
Patent Document 3 discloses a method in which calcium oxide (CaO) is mixed with PVC, ground at room temperature (mechanochemical treatment), and dechlorinated. However, there is a problem that a pulverizer is necessary and the apparatus becomes large-scale.
そこで、本発明は上記課題を鑑み、従来の再資源化装置に特別な装置を付加することなく、安価で簡便にハロゲンを捕集することのできるハロゲン捕集添加剤を提供することを目的とする。
Therefore, in view of the above problems, the present invention has an object to provide a halogen-collecting additive that can easily collect halogen at a low cost without adding a special device to a conventional recycling apparatus. To do.
本発明者らは、上記課題について精意研究を重ねた結果、尿素、水酸化物、及びステアリン酸金属塩の組合せからなる混合物を含むハロゲン捕集添加剤を新規に考案し、本発明を完成させるに至った。
As a result of extensive research on the above problems, the present inventors have devised a halogen collecting additive including a mixture comprising a combination of urea, hydroxide, and metal stearate, and completed the present invention. I came to let you.
即ち、本発明の一観点に係るハロゲン捕集添加剤は、４９．５重量部以上７５重量部以下の尿素、２０重量部以上４９．５重量部以下のカルシウム、マグネシウム、バリウムの１種または２種以上からなる水酸化物、及び、１重量部以上５重量部以下のステアリン酸金属塩からなる混合物１００重量部を含むことを特徴とする。
That is, the halogen-collecting additive according to one aspect of the present invention includes 49.5 parts by weight or more and 75 parts by weight or less of urea, 20 parts by weight or more and 49.5 parts by weight or less of calcium, magnesium, or barium. It is characterized by containing 100 parts by weight of a mixture comprising a hydroxide comprising at least a seed and 1 to 5 parts by weight of a metal stearate.
なおこの観点において、限定されるわけではないが、ハロゲン捕集添加剤は、粒径が０．０１ｍｍ以上５ｍｍ以下の範囲にある粉状であることが好ましい。
Although not limited in this respect, it is preferable that the halogen-collecting additive is in the form of a powder having a particle size in the range of 0.01 mm to 5 mm.
以上、本発明により、従来の再資源化装置に特別な装置を付加することなく、安価で簡便にハロゲンを捕集する添加剤が提供でき、塩素、臭素、等のハロゲン物質による装置腐食が防止でき再資源化装置の長期安定運転が達成される。
As described above, according to the present invention, it is possible to provide an additive for easily collecting halogen at a low cost without adding a special device to the conventional recycling apparatus, and preventing corrosion of the device due to halogen substances such as chlorine and bromine. Long-term stable operation of the recycling system is achieved.
以下、本発明の実施の形態について詳細に説明するが、本発明は多くの異なる形態が実施可能であり、以下に示す実施形態、実施例の記載のみに限定されるものではない。
Hereinafter, embodiments of the present invention will be described in detail. However, the present invention can be implemented in many different forms, and is not limited to the description of the following embodiments and examples.
本実施形態は、廃プラスチック再資源化におけるハロゲン捕集添加剤に関するものである。
This embodiment relates to a halogen collection additive in waste plastic recycling.
本発明形態に係るハロゲン捕集添加剤は、４９．５重量部以上８０重量部以下の尿素、２０重量部以上４９．５重量部以下のカルシウム、マグネシウム、バリウムの１種または２種以上からなる水酸化物、及び、１重量部以上５重量部以下のステアリン酸金属塩からなる混合物１００重量部を含むことを特徴とする。この混合物をポリ塩化ビニル（ＰＶＣ）や臭素系難燃剤含有プラスチックを含む廃プラスチックに均一に塗して（散布して）加熱させると、効率的にハロゲンを捕集することができ再資源化装置の長期安定操業が可能になる。
The halogen scavenging additive according to the present invention is composed of one or more of 49.5 parts by weight to 80 parts by weight of urea, 20 parts by weight to 49.5 parts by weight of calcium, magnesium and barium. It contains 100 parts by weight of a mixture comprising a hydroxide and a metal stearate of 1 to 5 parts by weight. When this mixture is evenly applied (sprayed) to waste plastics including polyvinyl chloride (PVC) and brominated flame retardant-containing plastics and heated, the halogen can be efficiently collected and recycled. Long-term stable operation.
ここで尿素（ＣＨ４Ｎ２Ｏ）は、加熱すると約１３３℃で分解してアンモニア（ＮＨ３）を生成することができる。生成したアンモニアは、ポリ塩化ビニル〔（ＣＨ２＝ＣＨＣｌ）ｎ〕を加熱することにより発生する塩化水素（ＨＣｌ）と結合して塩化アンモニウム（ＮＨ４Ｃｌ）となるため、塩素捕集剤として用いることができる。また、尿素から生成したアンモニアは、廃プラスチック中に含まれている臭素系難燃化剤から発生する臭化水素（ＨＢｒ）と結合して臭化アンモニウム（ＮＨ４Ｂｒ）となるため、臭素捕集剤としても用いることができる。
Here, urea (CH 4 N 2 O) can be decomposed at about 133 ° C. when heated to produce ammonia (NH 3 ). The produced ammonia is combined with hydrogen chloride (HCl) generated by heating polyvinyl chloride [(CH 2 ═CHCl) n ] to become ammonium chloride (NH 4 Cl), and is therefore used as a chlorine scavenger. be able to. In addition, ammonia produced from urea binds to hydrogen bromide (HBr) generated from brominated flame retardant contained in the waste plastic and becomes ammonium bromide (NH 4 Br). It can also be used as a collecting agent.
ところでポリ塩化ビニル（ＰＶＣ）は、プラスチックの中でも最も低温から熱分解するものであり、３００℃までに第一段階の分解を起こし、ＨＣｌを脱離させる。離脱したＨＣｌは強い腐食作用を有するため、再資源化装置の長期運転を妨げることとなる。しかしながら、尿素が分解する温度は低温（１３３℃）であるため、ポリ塩化ビニルと尿素とを混ぜて加熱すれば、ポリ塩化ビニルが熱分解温度領域（約３００℃）に至ったときには既に尿素からアンモニアを十分に発生させておくことができる。この結果、ＰＶＣから離脱するＨＣｌを捕集し、塩化アンモニウム（ＮＨ４Ｃｌ）として無害化することができる。即ち、尿素は廃プラスチックの再資源化過程の初期から作用させることができ、極めて優位である。
By the way, polyvinyl chloride (PVC) is thermally decomposed from the lowest temperature among plastics, and causes the first stage decomposition up to 300 ° C. to desorb HCl. Since the separated HCl has a strong corrosive action, it prevents the long-term operation of the recycling apparatus. However, since the temperature at which urea decomposes is low (133 ° C.), when polyvinyl chloride and urea are mixed and heated, when the polyvinyl chloride reaches the thermal decomposition temperature range (about 300 ° C.), it is already from urea. Ammonia can be sufficiently generated. As a result, HCl released from PVC can be collected and detoxified as ammonium chloride (NH 4 Cl). That is, urea can be made to act from the early stage of the waste plastic recycling process, which is extremely advantageous.
ところで、尿素のみでもハロゲン捕集効果は大きいが、低温から作用するため、加熱初期に生成したハロゲン化アンモニウムが加熱時間とともに再び廃プラスチックに混入してしまう場合がある。そこで、カルシウム、マグネシウム、バリウムの１種または２種以上からなる水酸化物を同時添加しておくことで、一旦生成したハロゲン化アンモニウムを安定化させ、かつハロゲン化物を生成させることによりハロゲン捕集効果が向上することができる。なお限定されるわけではないが、経済性の観点及び取扱容易の観点から、水酸化カルシウムがより好ましい。
By the way, although urea alone has a large halogen trapping effect, it acts from a low temperature, so that the ammonium halide generated in the initial stage of heating may be mixed into the waste plastic again with the heating time. Therefore, by simultaneously adding one or more hydroxides of calcium, magnesium, and barium, the ammonium halide once generated is stabilized, and the halide is collected by generating a halide. The effect can be improved. Although not limited, calcium hydroxide is more preferable from the viewpoint of economy and easy handling.
ところで、尿素が低温の状態から作用するといった利点を生かすためには、この尿素と水酸化物の混合物を加熱前に廃プラスチックと混ぜておくことが有用である。廃プラスチックは形状・大きさが一定していないため、尿素を均一に塗すには細かい粉体状で混合することが極めて有用である。しかしながら、尿素には吸湿性があるため粒状化し易く、細かい粉体状態を維持するのが困難である。そこで本発明者らは、尿素のハロゲン捕集効果を損なうことなく細かい粉体状態を維持する薬剤を検討した結果、ステアリン酸金属塩を適量混合することで細かい粉体状態を維持できることを見出した。
Incidentally, in order to take advantage of the fact that urea acts from a low temperature state, it is useful to mix this urea and hydroxide mixture with waste plastic before heating. Since waste plastics are not uniform in shape and size, it is extremely useful to mix them in a fine powder form in order to uniformly apply urea. However, since urea is hygroscopic, it is easy to granulate and it is difficult to maintain a fine powder state. Therefore, the present inventors have studied a drug that maintains a fine powder state without impairing the halogen trapping effect of urea, and as a result, found that a fine powder state can be maintained by mixing an appropriate amount of a metal stearate. .
ここでステアリン酸金属塩としては、限定されるわけではないがステアリン酸亜鉛及びステアリン酸カルシウムの少なくともいずれかであることが好ましく、ステアリン酸亜鉛には再生プラスチックが再生装置の金属に付着することを防止する効果があるためより好ましく、更にはこれらの併用添加も好ましい。
Here, the metal stearate salt is not limited, but is preferably at least one of zinc stearate and calcium stearate. Zinc stearate prevents the recycled plastic from adhering to the metal of the regenerator. Therefore, it is more preferable, and further, the combined use of these is also preferable.
本実施形態に係るハロゲン捕集添加剤は、含まれる尿素、水酸化物及びステアリン酸金属塩の重量を１００重量部とした場合、尿素が４９．５重量部以上７５重量部以下、カルシウム、マグネシウム、バリウムの１種または２種以上からなる水酸化物が２０重量部以上４９．５重量部以下、ステアリン酸金属塩が１重量部以上５重量部以下含まれ、好ましくは尿素５５重量部以上７５重量部以下、水酸化物２４重量部以上４４重量部以下、ステアリン酸金属塩が１重量部以上５重量部以下である。
In the halogen collecting additive according to the present embodiment, when the weight of urea, hydroxide, and metal stearate contained is 100 parts by weight, urea is 49.5 parts by weight to 75 parts by weight, calcium, magnesium 20 to 49.5 parts by weight of a hydroxide composed of one or more kinds of barium, 1 to 5 parts by weight of a metal stearate, preferably 55 to 75 parts by weight of urea. Not more than parts by weight, not less than 24 parts by weight and not more than 44 parts by weight of hydroxide, and 1 to 5 parts by weight of metal stearate.
尿素を４９．５重量部以上とすることでハロゲン捕集効果を十分発揮することが可能となり、５５重量部以上とすることでこの効果がより顕著となる。一方、尿素を７５重量部以下とすることでハロゲン化アンモニウムの再混入を防止することができるといった効果がある。また、水酸化物を２０重量部以上とすることで、ハロゲン化アンモニウムの再混入防止を十分図ることができ、２４重量部以上とすることでこの効果がより顕著となる。一方水酸化物を４９．５重量部以下とすることで尿素の効果を十分に発揮させることができ、４４重量部以下とすることでこの効果がより顕著となる。また、ステアリン酸金属塩の添加量を１部以上とすることで粉体状態の維持を図ることが可能であり、５重量部以上とすることで尿素のハロゲン捕集効果を妨げないようにすることができる。なお、上記混合物には、不可避の不純物又は効果を妨げない程度の少量の添加剤を含んでも良い。
When the urea content is 49.5 parts by weight or more, the halogen trapping effect can be sufficiently exerted, and when the urea content is 55 parts by weight or more, this effect becomes more remarkable. On the other hand, by setting urea to 75 parts by weight or less, there is an effect that ammonium halide re-mixing can be prevented. Further, by making the hydroxide 20 parts by weight or more, it is possible to sufficiently prevent remixing of the ammonium halide, and by making it 24 parts by weight or more, this effect becomes more remarkable. On the other hand, if the hydroxide is 49.5 parts by weight or less, the effect of urea can be sufficiently exerted, and if it is 44 parts by weight or less, this effect becomes more remarkable. In addition, it is possible to maintain the powder state by setting the amount of the stearic acid metal salt to 1 part or more, and to prevent the halogen collecting effect of urea from being disturbed by setting it to 5 parts by weight or more. be able to. The mixture may contain an inevitable impurity or a small amount of an additive that does not interfere with the effect.
また、本実施形態に係るハロゲン捕集添加剤は粉体状であることが好ましく、数として８０％以上の粒径が０．０１ｍｍ以上５ｍｍ以下の範囲にあることが好ましい。粉体の粒径が０．０１ｍｍ以上とすることで粉体製造コストを抑えることができるといった効果があり、５ｍｍ以下とすることで廃プラスッチックに十分均一に塗すことができるといった効果がある。
Further, the halogen collecting additive according to the present embodiment is preferably in the form of powder, and as a number, it is preferable that the particle size of 80% or more is in the range of 0.01 mm or more and 5 mm or less. When the particle size of the powder is 0.01 mm or more, there is an effect that the production cost of the powder can be suppressed, and when it is 5 mm or less, there is an effect that it can be applied uniformly to the waste plastic.
以上、本実施形態により、従来の再資源化装置に特別な装置を付加することなく、安価で簡便にハロゲンを捕集する添加剤が提供でき、塩素、臭素、等のハロゲン物質による装置腐食が防止でき再資源化装置の長期安定運転が達成される。
As described above, according to the present embodiment, it is possible to provide an additive for collecting halogen easily and inexpensively without adding a special apparatus to the conventional recycling apparatus, and corrosion of the apparatus due to halogen substances such as chlorine, bromine and the like can be provided. Long-term stable operation of the recycling device can be achieved.
以下、上記実施形態において説明したハロゲン捕集添加剤について、以下に実施例として詳しく説明するが、本発明はこれらの範囲に限定されるものではない。
Hereinafter, the halogen collection additive described in the above embodiment will be described in detail as examples below, but the present invention is not limited to these ranges.
１~５ｍｍ程度に破砕した、４９．１２ｇのポリエチレン（ＰＥ）と０．８８ｇのポリ塩化ビニル（ＰＶＣ）を混合した総量５０ｇを原料とし、これに尿素、水酸化カルシウム、ステアリン酸亜鉛、ステアリン酸カルシウムからなる混合物（粒度：０．０５ｍｍ~２ｍｍ）を、混合比を変えて１ｇ均一に塗した物を２２０℃に加熱した。発生した熱分解ガスを水相に捕集し塩素量を定量した。ここで実施例と比較例における熱分解発生ガス中の塩素量を表１に示す。
A total amount of 50 g of 49.12 g of polyethylene (PE) and 0.88 g of polyvinyl chloride (PVC), crushed to about 1 to 5 mm, is used as raw material, and urea, calcium hydroxide, zinc stearate, calcium stearate A mixture of 1 g (particle size: 0.05 mm to 2 mm) coated uniformly with varying mixing ratios was heated to 220 ° C. The generated pyrolysis gas was collected in the aqueous phase and the amount of chlorine was quantified. Here, the amount of chlorine in the pyrolysis gas in Examples and Comparative Examples is shown in Table 1.
塩素量測定結果を示した表１から分かるように、実施例では発生ガス中の塩素濃度が小さく、塩素の固定無害化効果が大きいことが分かる。特に、上記の結果によると、尿素５５重量部以上７５重量部以下、水酸化物２４重量部以上４４重量部以下、ステアリン酸金属塩１重量部以上５重量部以下の範囲に抑えておくことで、補修添加剤を何ら加えていない状態（比較例１）に対し、最大３％程度まで塩素量を抑えることができている。
As can be seen from Table 1 showing the results of measuring the amount of chlorine, it can be seen that in the examples, the chlorine concentration in the generated gas is small and the effect of fixing and detoxifying chlorine is large. In particular, according to the above results, it is possible to keep urea in a range of 55 parts by weight or more and 75 parts by weight or less, a hydroxide of 24 parts by weight or more and 44 parts by weight or less, and a metal stearate salt of 1 part by weight or more and 5 parts by weight or less. The amount of chlorine can be suppressed to about 3% at maximum with respect to a state where no repair additive is added (Comparative Example 1).
本発明は、廃プラスチックの再資源化において、特に再生利用（マテリアルリサイクル）や熱分解油化（ケミカルリサイクル）の産業上用途において広く利用でき、再資源化装置の長期安定運転を可能にする。このことは地球温暖化防止に大きな寄与をもたらすものである。
The present invention can be widely used in the recycling of waste plastics, especially in industrial applications such as recycling (material recycling) and pyrolysis oil (chemical recycling), and enables long-term stable operation of the recycling apparatus. This greatly contributes to the prevention of global warming.
Claims (2)
- ４９．５重量部以上７５重量部以下の尿素、２０重量部以上４９．５重量部以下のカルシウム、マグネシウム、バリウムの１種または２種以上からなる水酸化物、及び、１重量部以上５重量部以下のステアリン酸金属塩からなる混合物１００重量部を含むハロゲン捕集添加剤。 49.5 parts by weight or more and 75 parts by weight or less of urea, 20 parts by weight or more and 49.5 parts by weight or less of a hydroxide composed of one or more of calcium, magnesium and barium, and 1 part by weight or more and 5 parts by weight Halogen-collecting additive comprising 100 parts by weight of a mixture comprising less than or equal to parts of metal stearate.
- 前記混合物は、粒径が０．０１ｍｍ以上５ｍｍ以下の粉体状である請求項１記載のハロゲン捕集添加剤。 The halogen-collecting additive according to claim 1, wherein the mixture is in the form of a powder having a particle size of 0.01 mm to 5 mm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009138727A JP4381475B1 (en) | 2009-06-09 | 2009-06-09 | Halogen collection additive |
| JP2009-138727 | 2009-06-09 |
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| WO2010143316A1 true WO2010143316A1 (en) | 2010-12-16 |
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| PCT/JP2009/064077 WO2010143316A1 (en) | 2009-06-09 | 2009-08-03 | Halogen trapping additive |
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| WO (1) | WO2010143316A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7219904B1 (en) | 2022-09-22 | 2023-02-09 | 株式会社セレン | Plastic recycling processing modifier and method for producing recycled plastic |
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| JPH07188674A (en) * | 1993-12-27 | 1995-07-25 | Mitsubishi Chem Corp | Method for heat decomposition of synthetic halogenated resin |
| JPH0892412A (en) * | 1994-09-22 | 1996-04-09 | Toshiba Corp | Process for recycling plastic waste |
| JP2000169858A (en) * | 1998-12-07 | 2000-06-20 | Hitachi Ltd | Convertion of waste plastic material into oil and device therefor |
| JP2000290424A (en) * | 1999-04-07 | 2000-10-17 | Matsushita Electric Ind Co Ltd | Recycling treatment of thermoplastic resin composition containing bromine-based flame retardant |
| JP2001145862A (en) * | 1999-11-22 | 2001-05-29 | Miyoshi Oil & Fat Co Ltd | Method for detoxifying incineration ash |
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2009
- 2009-06-09 JP JP2009138727A patent/JP4381475B1/en not_active Expired - Fee Related
- 2009-08-03 WO PCT/JP2009/064077 patent/WO2010143316A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49112979A (en) * | 1973-03-01 | 1974-10-28 | ||
| JPH07188674A (en) * | 1993-12-27 | 1995-07-25 | Mitsubishi Chem Corp | Method for heat decomposition of synthetic halogenated resin |
| JPH0892412A (en) * | 1994-09-22 | 1996-04-09 | Toshiba Corp | Process for recycling plastic waste |
| JP2000169858A (en) * | 1998-12-07 | 2000-06-20 | Hitachi Ltd | Convertion of waste plastic material into oil and device therefor |
| JP2000290424A (en) * | 1999-04-07 | 2000-10-17 | Matsushita Electric Ind Co Ltd | Recycling treatment of thermoplastic resin composition containing bromine-based flame retardant |
| JP2001145862A (en) * | 1999-11-22 | 2001-05-29 | Miyoshi Oil & Fat Co Ltd | Method for detoxifying incineration ash |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7219904B1 (en) | 2022-09-22 | 2023-02-09 | 株式会社セレン | Plastic recycling processing modifier and method for producing recycled plastic |
| JP2024045914A (en) * | 2022-09-22 | 2024-04-03 | 株式会社セレン | Plastic recycling modifier and manufacturing method for recycled plastics |
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| JP4381475B1 (en) | 2009-12-09 |
| JP2010285487A (en) | 2010-12-24 |
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