JPH06299169A - Method for gasifying plastics - Google Patents
Method for gasifying plasticsInfo
- Publication number
- JPH06299169A JPH06299169A JP5093014A JP9301493A JPH06299169A JP H06299169 A JPH06299169 A JP H06299169A JP 5093014 A JP5093014 A JP 5093014A JP 9301493 A JP9301493 A JP 9301493A JP H06299169 A JPH06299169 A JP H06299169A
- Authority
- JP
- Japan
- Prior art keywords
- reactor
- reaction
- gas
- gasifying
- water
- 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
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229920003023 plastic Polymers 0.000 title claims abstract description 32
- 239000004033 plastic Substances 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 61
- -1 polyethylene Polymers 0.000 abstract description 27
- 239000004698 Polyethylene Substances 0.000 abstract description 16
- 229920000573 polyethylene Polymers 0.000 abstract description 16
- 230000035484 reaction time Effects 0.000 abstract description 15
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 11
- 239000004793 Polystyrene Substances 0.000 abstract description 9
- 229920002223 polystyrene Polymers 0.000 abstract description 9
- 239000004814 polyurethane Substances 0.000 abstract description 9
- 239000004743 Polypropylene Substances 0.000 abstract description 8
- 229920001155 polypropylene Polymers 0.000 abstract description 8
- 229920002635 polyurethane Polymers 0.000 abstract description 8
- 229920000877 Melamine resin Polymers 0.000 abstract description 7
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 4
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 3
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002309 gasification Methods 0.000 description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、プラスチック、すなわ
ちポリエチレン、ポリプロピレン、ポリスチレン、ポリ
塩化ビニルなどの熱可塑性樹脂、ポリウレタン、メラミ
ン、ＰＥＴなどの熱硬化性樹脂を水素ガス、炭化水素ガ
スなどの有用なガスに転化する方法に関する。The present invention relates to plastics, that is, thermoplastic resins such as polyethylene, polypropylene, polystyrene and polyvinyl chloride, thermosetting resins such as polyurethane, melamine and PET, which are useful in hydrogen gas and hydrocarbon gas. The method of converting to pure gas.
【０００２】[0002]
【従来の技術】従来、プラスチックは生活廃棄物、産業
廃棄物として膨大な量が排出されており、その処分ある
いは再利用が現在急務の課題となっている。そのため、
これら廃棄物としてのプラスチックをガス化し、再利用
する方法が従来、種々提案されている。その方法の一つ
として、８００℃前後の高温で熱分解する方法が知られ
ているが、塩素ガス、炭酸ガスなど多くの有害ガスの発
生を伴うことなどの問題があった。2. Description of the Related Art In the past, enormous amounts of plastics have been discharged as domestic wastes and industrial wastes, and the disposal or reuse thereof has become an urgent issue. for that reason,
Various methods for gasifying and recycling these plastics as waste have been proposed. As one of the methods, a method of thermally decomposing at a high temperature of about 800 ° C. is known, but there is a problem in that many harmful gases such as chlorine gas and carbon dioxide gas are generated.
【０００３】[0003]
【発明が解決しようとする課題】したがって、本発明
は、廃棄されるプラスチックを有効利用するため、簡単
な方法でプラスチックを有用なガス状物質に分解する方
法を提供することを目的とする。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for decomposing plastic into useful gaseous substances in a simple manner in order to make effective use of discarded plastic.
【０００４】[0004]
【課題を解決するための手段】本発明者は、上記課題を
解決するため、プラスチックのガス化に超臨界水を含む
高温熱水を利用するという手段を採用した。すなわち、
本発明は、プラスチックを反応器内で超臨界水を含む高
温熱水と接触、反応せしめ、ガス化することを特徴とす
るプラスチックのガス化方法を提供するものである。In order to solve the above problems, the present inventor has adopted a means of utilizing high temperature hot water containing supercritical water for gasification of plastics. That is,
The present invention provides a method for gasifying plastic, which comprises contacting and reacting plastic with high-temperature hot water containing supercritical water in a reactor to gasify the plastic.
【０００５】この場合、反応器内に予め充填される水の
充填率は反応器内の圧力の大きさに直接影響し、かつ、
得られるガス化率に関係し、目的に応じ適宜選択しうる
が、通常、１容量％以上９０容量％以下、好ましくは５
〜４０容量％の範囲で適宜選択することができる。In this case, the filling rate of the water pre-filled in the reactor directly affects the magnitude of the pressure in the reactor, and
Although it can be appropriately selected depending on the purpose in relation to the obtained gasification rate, it is usually 1% by volume or more and 90% by volume or less, preferably 5% by volume or less.
It can be appropriately selected within the range of ˜40% by volume.
【０００６】また、反応温度としては２００℃以上、好
ましくは２５０ないし４５０℃とする。本発明の方法は
ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩
化ビニルなどの熱可塑性樹脂、ポリエチレンテレフタレ
ート、ポリウレタン、メラミン樹脂などの熱硬化性樹脂
など、ほとんど全てのプラスチックに適用することがで
きる。The reaction temperature is 200 ° C. or higher, preferably 250 to 450 ° C. The method of the present invention can be applied to almost all plastics such as thermoplastic resins such as polyethylene, polypropylene, polystyrene and polyvinyl chloride, and thermosetting resins such as polyethylene terephthalate, polyurethane and melamine resin.
【０００７】本発明の方法は反応器内に予め、反応触媒
（反応助剤）を添加してもよい。この場合の反応触媒の
例としては、ＮａＯＨなどのアルカリ、金属イオン（Ｎ
ｉイオン、Ｆｅイオン）、ＳＤＢＳ（アルキルベンゼン
スルホン酸ナトリウム）などの界面活性剤、メチルアル
コール、エチルアルコールなどアルコール類、その他固
体触媒などを挙げることができる。なお、反応器として
ステンレス鋼製など、反応触媒としての金属イオン源を
含むものを用いてもよい。In the method of the present invention, a reaction catalyst (reaction aid) may be added in advance in the reactor. Examples of the reaction catalyst in this case include alkali such as NaOH and metal ions (N
Examples thereof include surfactants such as i ions, Fe ions), SDBS (sodium alkylbenzene sulfonate), alcohols such as methyl alcohol and ethyl alcohol, and other solid catalysts. The reactor may be made of stainless steel or the like and includes a metal ion source as a reaction catalyst.
【０００８】用いられる水としては、純水のほか、上述
のように必要に応じて添加物、例えば触媒を含むもので
あってもよく、また、一度用いられた水を再度利用する
こともできるし、むしろ水を再度利用することによりガ
ス化に好ましい場合もある。これは一度反応に使用した
水に本発明の方法によるガス化に有用な成分（反応助
剤）が含まれることによるものである。As the water used, in addition to pure water, additives such as catalysts may be added as necessary as described above, and water used once may be reused. However, it may be preferable for gasification by reusing water. This is because the water once used for the reaction contains a component (reaction aid) useful for gasification by the method of the present invention.
【０００９】[0009]
【作用】本発明によれば、反応器内での水の充填率、反
応温度、反応時間に応じて、プラスチックを任意の成分
のガス状物質に短時間で改質することができる。According to the present invention, the plastic can be reformed into a gaseous substance of any component in a short time according to the filling rate of water in the reactor, the reaction temperature and the reaction time.
【００１０】[0010]
【実施例】以下、図示の実施例を参照して本発明をより
具体的に説明する。 （実施例１）図１および図２に示すオートクレーブ装置
を用いて、ポリ塩化ビニルのガス化実験をおこなった。
すなわち、２４０℃ないし２８０℃までは図１のチュー
ブ型反応容器を用い、３００℃ないし４００℃までは図
２のＨＡＳＴＥＬＬＯＹ−Ｃ製オートクレーブ装置を用
いた。図１において、１は反応容器（公称容量１００ｍ
ｌ）、２はキャップ、３はるつぼ、４は熱電対、５は圧
力変換器、６は温度コントローラー、７は記録計、８は
シグナルコンデショナー、９はボールバルブである。ま
た、図２において、１１は反応容器（公称容量１００ｍ
ｌ）、１２は蓋板、１３はヒーター、１４は熱電対、１
５は圧力変換器、１６は温度コントローラー、１７はサ
イリスタレギュレーター、１８はシグナルコンデショナ
ー、１９はバルブ、２０はコネクター、２１は回転コン
トローラー、２２はレコーダーである。The present invention will be described more specifically below with reference to the illustrated embodiments. (Example 1) A gasification experiment of polyvinyl chloride was carried out using the autoclave apparatus shown in FIGS. 1 and 2.
That is, the tube-type reaction container of FIG. 1 was used from 240 ° C. to 280 ° C., and the HASTELLOY-C autoclave device of FIG. 2 was used from 300 ° C. to 400 ° C. In FIG. 1, 1 is a reaction vessel (nominal capacity 100 m
l) 2 is a cap, 3 is a crucible, 4 is a thermocouple, 5 is a pressure transducer, 6 is a temperature controller, 7 is a recorder, 8 is a signal conditioner, and 9 is a ball valve. Further, in FIG. 2, 11 is a reaction vessel (nominal volume 100 m
l), 12 is a cover plate, 13 is a heater, 14 is a thermocouple, 1
5 is a pressure converter, 16 is a temperature controller, 17 is a thyristor regulator, 18 is a signal conditioner, 19 is a valve, 20 is a connector, 21 is a rotation controller, and 22 is a recorder.
【００１１】実験条件は図１のチューブ型反応容器の場
合は、試料３．０ｇ、純水２６ｃｃ、反応時間２０時間
とした。図２のＨＡＳＴＥＬＬＯＹ−Ｃ製オートクレー
ブ装置の場合は、試料４．０ｇ（但し、４００℃では
０．５ｇとした）、純水４０ｃｃ、反応時間１時間とし
た。なお、実験は反応容器を脱気したのちに行った。以
下に述べる発生ガス量は、容器に残っているガスの量は
入っていない。従って、実際に発生したガス量は、容器
の気相の体積を加えたものになる。図３にガス発生量と
反応温度との関係を示す。図３から明らかなように、ガ
ス発生量は反応温度の上昇とともに著しく増加した。In the case of the tube type reaction vessel of FIG. 1, the experimental conditions were 3.0 g of sample, 26 cc of pure water, and a reaction time of 20 hours. In the case of the HASTELLOY-C autoclave apparatus of FIG. 2, the sample was 4.0 g (however, it was 0.5 g at 400 ° C.), pure water was 40 cc, and the reaction time was 1 hour. The experiment was conducted after deaeration of the reaction vessel. The amount of generated gas described below does not include the amount of gas remaining in the container. Therefore, the amount of gas actually generated is the sum of the volume of the gas phase of the container. FIG. 3 shows the relationship between the gas generation amount and the reaction temperature. As is clear from FIG. 3, the gas generation amount increased remarkably as the reaction temperature increased.
【００１２】また、図４にガス組成と反応温度との関係
を示す。図４から明らかなように、２８０℃までは各成
分の割合はほぼ等しく、ＣＯ2 は約２０％、Ｈ2 は約８
０％であり、その他のガスはほとんど検出されなかっ
た。また３００℃以上ではＨ2が発生ガスのほとんどを
占め、温度の上昇とともに炭化水素ガスが増加した。FIG. 4 shows the relationship between the gas composition and the reaction temperature. As is apparent from FIG. 4, the proportion of each component is almost equal up to 280 ° C., CO 2 is about 20%, and H 2 is about 8%.
0%, and almost no other gas was detected. At 300 ° C. or higher, H 2 occupies most of the generated gas, and the hydrocarbon gas increases as the temperature rises.
【００１３】（実施例２）図５に示すオートクレーブ装
置を用いて、ポリエチレン、ポリプロピレンおよびポリ
スチレンのガス化実験をおこなった。ただし、試料がポ
リエチレンで２４０℃での実験においては図１に示すチ
ューブ型オートクレーブ装置を用いた。なお図５におい
て、３１は反応容器（公称容量１００ｍｌ）、３２は蓋
体、３３はヒーター、３４は熱電対、３５は圧力変換
器、３６は温度コントローラー、３８はシグナルコンデ
ショナー、３９はバルブ、４０はコネクター、４１は回
転コントローラーである。実験条件はチューブ型オート
クレーブ装置を用いた場合は、試料３．０ｇ、純水２６
ｃｃ、反応時間２０時間とし、図５に示すオートクレー
ブ装置を用いた場合は、試料４．０ｇ、純水４０ｃｃ、
反応時間６時間とした。図６にポリエチレン、ポリプロ
ピレンおよびポリスチレンのそれぞれについてガス発生
量と反応温度との関係を示す。図６から明らかなよう
に、いずれの場合も、ガス発生量は反応温度の上昇とと
もに著しく増加した。特にポリエチレンでは超臨界状態
で著しいガスの発生量が見られた。Example 2 A gasification experiment of polyethylene, polypropylene and polystyrene was carried out using the autoclave apparatus shown in FIG. However, in the experiment at 240 ° C. using polyethylene as the sample, the tube type autoclave apparatus shown in FIG. 1 was used. In FIG. 5, 31 is a reaction vessel (nominal volume 100 ml), 32 is a lid, 33 is a heater, 34 is a thermocouple, 35 is a pressure converter, 36 is a temperature controller, 38 is a signal conditioner, 39 is a valve, 40 Is a connector and 41 is a rotation controller. As for the experimental conditions, when a tube type autoclave was used, a sample of 3.0 g, pure water 26
cc, the reaction time was 20 hours, and when the autoclave apparatus shown in FIG. 5 was used, a sample of 4.0 g, pure water of 40 cc,
The reaction time was 6 hours. FIG. 6 shows the relationship between the gas generation amount and the reaction temperature for each of polyethylene, polypropylene and polystyrene. As is clear from FIG. 6, in any case, the gas generation amount remarkably increased as the reaction temperature increased. Especially in polyethylene, a remarkable amount of gas was observed in the supercritical state.
【００１４】また、図７にポリエチレンからの発生ガス
組成と反応温度との関係、図８にポリプロピレンからの
発生ガス組成と反応温度との関係、図９にポリスチレン
からの発生ガス組成と反応温度との関係を示す。図７か
ら明らかなように、３００℃まではＨ2 ガスが殆どであ
り、残りはＣＯ2 であった。しかし反応温度が３００℃
以上では炭化水素ガスが増加しＣＯ2 は減少した。ま
た、図８から明らかなように、ポリプロピレンからの発
生ガスは３６５℃から４１５℃にかけてＨ2 ガスが増加
し、ＣＯ2 は減少した。炭化水素ガスは常に５０％以上
存在し、殆ど変化しなかった。また、図９から明らかな
ように、ポリスチレンからの発生ガスは３６５℃から４
１５℃の範囲では、炭化水素ガス以外の全てのガスの割
合が温度の上昇とともに減少しており、４１５℃では炭
化水素ガスがほぼ１００％となり、ポリエチレン、ポリ
プロピレンと比較してＣＨ4 の割合が大きく、Ｈ2 の割
合は小さかった。Further, FIG. 7 shows the relationship between the gas composition from polyethylene and the reaction temperature, FIG. 8 shows the relationship between the gas composition from polypropylene and the reaction temperature, and FIG. 9 shows the gas composition from polystyrene and the reaction temperature. Shows the relationship. As is apparent from FIG. 7, most of the H 2 gas was up to 300 ° C., and the rest was CO 2 . However, the reaction temperature is 300 ℃
With the above, the hydrocarbon gas increased and CO 2 decreased. Further, as is clear from FIG. 8, in the gas generated from polypropylene, H 2 gas increased and CO 2 decreased from 365 ° C. to 415 ° C. The hydrocarbon gas was always present at 50% or more and hardly changed. Further, as is clear from FIG. 9, the gas generated from polystyrene is 4 ° C from 365 ° C.
In the range of 15 ° C, the proportions of all gases other than the hydrocarbon gas decrease with increasing temperature, and at 415 ° C, the hydrocarbon gas becomes almost 100%, and the proportion of CH 4 is much higher than that of polyethylene and polypropylene. It was large and the proportion of H 2 was small.
【００１５】（実施例３）図５に示すオートクレーブ装
置を用い、触媒（反応助剤）としてＳＤＢＳおよびＮａ
ＯＨ等を添加し、ポリエチレンのガス化実験をおこなっ
た。実験条件は試料４．０ｇ、純水４０ｃｃ、反応温度
４１５℃、反応時間２時間、攪拌回転数３００ｒｐｍと
した。下記表１にその結果を示す。Example 3 Using the autoclave apparatus shown in FIG. 5, SDBS and Na as catalysts (reaction aids) were used.
A gasification experiment of polyethylene was carried out by adding OH and the like. The experimental conditions were 4.0 g of a sample, 40 cc of pure water, a reaction temperature of 415 ° C., a reaction time of 2 hours, and a stirring rotation speed of 300 rpm. The results are shown in Table 1 below.
【００１６】[0016]
【表１】 [Table 1]
【００１７】この結果からＳＤＢＳおよびＮａＯＨがポ
リエチレンのガス化に有効であることが確認された。Ｎ
ａＯＨを添加した場合と触媒無添加の場合を比較する
と、ガス発生量は３倍以上に増加した。From these results, it was confirmed that SDBS and NaOH are effective for the gasification of polyethylene. N
Comparing the case where aOH was added and the case where no catalyst was added, the gas generation amount increased three times or more.
【００１８】（実施例４）図５に示すオートクレーブ装
置を用い、触媒（反応助剤）としてＣＨ3 ＯＨ、ＳＤＢ
ＳおよびＮａＯＨを添加し、ポリスチレンのガス化実験
をおこなった。実験条件は試料４．０ｇ、純水４０ｃ
ｃ、反応温度４１５℃、反応時間２時間、攪拌回転数３
００ｒｐｍとした。下記表２にその結果を示す。Example 4 Using the autoclave apparatus shown in FIG. 5, CH 3 OH and SDB were used as catalysts (reaction aids).
A gasification experiment of polystyrene was conducted by adding S and NaOH. The experimental conditions are 4.0 g of sample and 40 c of pure water.
c, reaction temperature 415 ° C., reaction time 2 hours, stirring rotation number 3
It was set to 00 rpm. The results are shown in Table 2 below.
【００１９】[0019]
【表２】 [Table 2]
【００２０】この結果からＣＨ3 ＯＨ、ＳＤＢＳおよび
ＮａＯＨがポリスチレンのガス化に有効であることが確
認され、触媒無添加の場合を比較すると、ガス発生量は
約３倍以上に増加した。From these results, it was confirmed that CH 3 OH, SDBS and NaOH are effective for the gasification of polystyrene, and the gas generation amount increased about three times or more when comparing the case where no catalyst was added.
【００２１】（実施例５）図５に示すオートクレーブ装
置を用いて、ＰＥＴ（ポリエチレンテレフタレート）、
ポリウレタン、ウレタンフォームおよびメラミンのガス
化実験をおこなった。実験条件は、試料４．０ｇ、純水
４０ｃｃ、反応時間６時間とした。図１０にＰＥＴ、ポ
リウレタン、ウレタンフォームおよびメラミンのそれぞ
れについてガス発生量と反応温度との関係を示す。図１
０から明らかなように、温度３６５℃ではＰＥＴとポリ
ウレタンはほぼ等しいガス発生量を示したが、温度４１
５℃ではＰＥＴのガス発生量が著しく増加した。Example 5 PET (polyethylene terephthalate), using the autoclave apparatus shown in FIG.
Gasification experiments of polyurethane, urethane foam and melamine were conducted. The experimental conditions were a sample of 4.0 g, pure water of 40 cc, and a reaction time of 6 hours. FIG. 10 shows the relationship between the gas generation amount and the reaction temperature for each of PET, polyurethane, urethane foam and melamine. Figure 1
As is clear from 0, PET and polyurethane showed almost the same gas generation amount at a temperature of 365 ° C.
At 5 ° C., the amount of PET gas generation increased remarkably.
【００２２】また、図１１にＰＥＴからの発生ガス組成
と反応温度との関係、図１２にポリウレタンからの発生
ガス組成と反応温度との関係、表３に４００℃でのウレ
タンフォームおよびメラミンからの発生ガス組成を示
す。FIG. 11 shows the relationship between the gas composition from PET and the reaction temperature, FIG. 12 shows the relationship between the gas composition from polyurethane and the reaction temperature, and Table 3 shows the relationship between the urethane foam and melamine at 400 ° C. The generated gas composition is shown.
【００２３】[0023]
【表３】 [Table 3]
【００２４】図１１から明らかなように、実験の温度範
囲ではＣＯ2 が全体の７０〜８０％を占めていたが、こ
れはＰＥＴに多量の酸素原子が含まれているためと考え
られ、このことは脱炭酸反応が比較的容易に起こり得る
ことを示唆している。また、３６５℃から４１５℃にか
けてＣＯ2 、ＣＯが減少し、Ｈ2 ガスおよび炭化水素ガ
スが増加した。As is clear from FIG. 11, CO 2 occupies 70 to 80% of the whole in the temperature range of the experiment, which is considered to be because PET contains a large amount of oxygen atoms. This suggests that the decarboxylation reaction can occur relatively easily. Further, CO 2 and CO decreased from 365 ° C. to 415 ° C., and H 2 gas and hydrocarbon gas increased.
【００２５】ポリウレタンについては、図１２から明ら
かなように、ＣＯ2 の占める割合が大きく、３６５℃か
ら４１５℃にかけてＣＯ2 が減少し、ＣＨ4 を含む炭化
水素ガスの割合が増加した。As for the polyurethane, as is clear from FIG. 12, the proportion of CO 2 was large, the CO 2 decreased from 365 ° C. to 415 ° C., and the proportion of hydrocarbon gas containing CH 4 increased.
【００２６】ウレタンフォームおよびメラミンについて
は、表３から明らかなように、ＰＥＴ、ポリウレタンに
比較してＣＯ2 が少なく、Ｈ2 ガスおよび炭化水素ガス
が多い。As is clear from Table 3, urethane foam and melamine contain less CO 2 and more H 2 gas and hydrocarbon gas than PET and polyurethane.
【００２７】（実施例６）図５に示すオートクレーブ装
置を用い、ポリエチレンのガス化実験をおこなった。こ
の場合、水の充填率、反応温度、反応時間が発生ガス量
に及ぼす影響について調べた。その結果を図１３〜１５
に示す。図１３は水の充填率を変え、反応温度４１５
℃、反応時間３時間、ポリエチレン試料１０．０ｇとし
た場合、図１４は反応時間を変え、水の充填率を４０
％、反応温度４１５℃、ポリエチレン試料１０．０ｇと
した場合、図１５は反応温度を変え、水の充填率を４０
％、反応時間３時間、ポリエチレン試料１０．０ｇとし
た場合をそれぞれ示すものである。Example 6 A polyethylene gasification experiment was conducted using the autoclave apparatus shown in FIG. In this case, the effects of the filling rate of water, the reaction temperature, and the reaction time on the amount of generated gas were investigated. The results are shown in FIGS.
Shown in. FIG. 13 shows the reaction temperature 415 when the filling rate of water is changed.
14 ° C., reaction time 3 hours, polyethylene sample 10.0 g, the reaction time was changed and the filling rate of water was 40%.
%, The reaction temperature was 415 ° C., and the polyethylene sample was 10.0 g, FIG. 15 shows that the reaction temperature was changed and the filling rate of water was 40%.
%, A reaction time of 3 hours, and a polyethylene sample of 10.0 g are shown.
【００２８】ポリエチレン試料量等の実験条件の相違に
よりガスの発生量と組成は若干変化は見られるが、これ
らの結果から明らかなように、水の充填率が低いほど、
反応時間が長いほど、反応温度が高いほど発生ガス量が
多いことが確認された。Although the amount and composition of gas slightly changed due to the difference in experimental conditions such as the amount of polyethylene sample, as is clear from these results, the lower the filling rate of water,
It was confirmed that the longer the reaction time and the higher the reaction temperature, the larger the amount of generated gas.
【００２９】なお、上記のいずれの実施例においても、
反応温度が３７５℃以下の場合は、固体残渣は油状には
なっておらず、反応温度が３７５℃以上のときはプラス
チックの残渣物は非水溶性の油状物質となっている。さ
らに反応温度が高いほどより軽質な油状物質が得られ
る。In any of the above embodiments,
When the reaction temperature is 375 ° C or lower, the solid residue is not oily, and when the reaction temperature is 375 ° C or higher, the plastic residue is a water-insoluble oily substance. Further, the higher the reaction temperature, the lighter the oily substance is obtained.
【００３０】[0030]
【発明の効果】以上詳述したように、本発明によれば、
プラスチックを反応器内で超臨界水を含む高温熱水と接
触、反応せしめることにより、プラスチックを効率良く
短時間でガス化することができる。As described in detail above, according to the present invention,
By contacting and reacting the plastic with high-temperature hot water containing supercritical water in the reactor, the plastic can be efficiently gasified in a short time.
【図１】本発明の方法を実施するために用いられるオー
トクレーブの模式図。FIG. 1 is a schematic diagram of an autoclave used to carry out the method of the present invention.
【図２】本発明の方法を実施するために用いられるオー
トクレーブの模式図。FIG. 2 is a schematic diagram of an autoclave used to carry out the method of the present invention.
【図３】本発明の方法における反応温度と発生ガス量と
の関係を示す図。FIG. 3 is a diagram showing a relationship between a reaction temperature and a generated gas amount in the method of the present invention.
【図４】本発明の方法における反応温度と発生ガス濃度
との関係を示す図。FIG. 4 is a diagram showing a relationship between reaction temperature and generated gas concentration in the method of the present invention.
【図５】本発明の方法を実施するために用いられるオー
トクレーブの模式図。FIG. 5 is a schematic diagram of an autoclave used to carry out the method of the present invention.
【図６】本発明の方法における反応温度と発生ガス量と
の関係を示す図。FIG. 6 is a graph showing the relationship between the reaction temperature and the amount of generated gas in the method of the present invention.
【図７】本発明の方法における反応温度と発生ガス濃度
との関係を示す図。FIG. 7 is a graph showing the relationship between reaction temperature and generated gas concentration in the method of the present invention.
【図８】本発明の方法における反応温度と発生ガス濃度
との関係を示す図。FIG. 8 is a graph showing the relationship between reaction temperature and generated gas concentration in the method of the present invention.
【図９】本発明の方法における反応温度と発生ガス濃度
との関係を示す図。FIG. 9 is a graph showing the relationship between reaction temperature and generated gas concentration in the method of the present invention.
【図１０】本発明の方法における反応温度と発生ガス量
との関係を示す図。FIG. 10 is a graph showing the relationship between the reaction temperature and the amount of generated gas in the method of the present invention.
【図１１】本発明の方法における反応温度と発生ガス濃
度との関係を示す図。FIG. 11 is a graph showing the relationship between reaction temperature and generated gas concentration in the method of the present invention.
【図１２】本発明の方法における反応温度と発生ガス濃
度との関係を示す図。FIG. 12 is a graph showing the relationship between reaction temperature and generated gas concentration in the method of the present invention.
【図１３】本発明の方法における水充填率と発生ガス量
との関係を示す図。FIG. 13 is a diagram showing the relationship between the water filling rate and the amount of generated gas in the method of the present invention.
【図１４】本発明の方法における反応時間と発生ガス量
との関係を示す図。FIG. 14 is a diagram showing the relationship between the reaction time and the amount of generated gas in the method of the present invention.
【図１５】本発明の方法における反応温度と発生ガス量
との関係を示す図。FIG. 15 is a graph showing the relationship between the reaction temperature and the amount of generated gas in the method of the present invention.
１、１１、３１…反応容器 ２…キャップ ３…るつぼ ４、１４、３４…熱電対 ５、１５、３５…圧力変換器 ６、１６、３６…温度コントローラー １２、３２…蓋体 １３、３３…ヒーター 1, 11, 31 ... Reaction container 2 ... Cap 3 ... Crucible 4, 14, 34 ... Thermocouple 5, 15, 35 ... Pressure converter 6, 16, 36 ... Temperature controller 12, 32 ... Lid 13, 33 ... Heater
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山崎 仲道 高知県高岡郡佐川町甲107 (72)発明者 牧野 久昭 宮城県仙台市青葉区中山７丁目２番１号 東北電力株式会社応用技術研究所内 (72)発明者 守谷 武彦 宮城県仙台市青葉区中山７丁目２番１号 東北電力株式会社応用技術研究所内 (72)発明者 石井 四郎 千葉県佐倉市大作２丁目４番２号 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yamazaki Nakamichi Ko Sagawa, Takaoka-gun, Kochi 107 Ko (72) Inventor Hisaki Makino 7-2-1, Nakayama, Aoba-ku, Sendai-shi, Miyagi Tohoku Electric Power Co., Inc. (72) Inventor Takehiko Moriya 72-1 Nakayama, Aoba-ku, Sendai City, Miyagi Prefecture, Tohoku Electric Power Co., Inc. Applied Technology Laboratory (72) Inventor Shiro Ishii 2-4-2 Daisaku Sakura City, Chiba Prefecture
Claims (8)
む高温熱水と接触、反応せしめ、ガス化することを特徴
とするプラスチックのガス化方法。1. A method of gasifying a plastic, which comprises contacting and reacting plastic with high-temperature hot water containing supercritical water in a reactor to gasify the plastic.
上とすることを特徴とする請求項１記載のプラスチック
のガス化方法。2. The method for gasifying plastic according to claim 1, wherein the filling rate of water in the reactor is 1% by volume or more.
０容量％とすることを特徴とする請求項２記載のプラス
チックのガス化方法。3. The filling rate of water in the reactor is 5 to 4
3. The method for gasifying plastic according to claim 2, wherein the content is 0% by volume.
徴とする請求項１記載のプラスチックのガス化方法。4. The method for gasifying plastic according to claim 1, wherein the reaction temperature is 200 ° C. or higher.
ことを特徴とする請求項４記載のプラスチックのガス化
方法。5. The method for gasifying plastic according to claim 4, wherein the reaction temperature is 250 to 450 ° C.
とを特徴とする請求項１記載のプラスチックのガス化方
法。6. The method for gasifying a plastic according to claim 1, wherein a reaction catalyst is added to the inside of the reactor in advance.
面活性剤、アルコール類、固体触媒等から選ばれるもの
であることを特徴とする請求項６記載のプラスチックの
ガス化方法。7. The method of gasifying a plastic according to claim 6, wherein the reaction catalyst is selected from alkali, metal ions, surfactants, alcohols, solid catalysts and the like.
オン源を含むものを用いることを特徴とする請求項１記
載のプラスチックのガス化方法。8. The method for gasifying plastic according to claim 1, wherein a reactor containing a metal ion source as a reaction catalyst is used as the reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09301493A JP3469604B2 (en) | 1993-04-20 | 1993-04-20 | Gasification method of plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09301493A JP3469604B2 (en) | 1993-04-20 | 1993-04-20 | Gasification method of plastic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06299169A true JPH06299169A (en) | 1994-10-25 |
| JP3469604B2 JP3469604B2 (en) | 2003-11-25 |
Family
ID=14070598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09301493A Expired - Fee Related JP3469604B2 (en) | 1993-04-20 | 1993-04-20 | Gasification method of plastic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3469604B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0770664A1 (en) * | 1995-10-23 | 1997-05-02 | Mitsubishi Jukogyo Kabushiki Kaisha | Oil-forming method of chlorine-containing plastic refuse |
| JPH11253786A (en) * | 1998-01-16 | 1999-09-21 | General Atomics Inc | Pressure reaction vessel |
| JP2009030071A (en) * | 2001-09-21 | 2009-02-12 | National Univ Corp Shizuoka Univ | Method for gasifying organic substance |
| WO2009048312A1 (en) * | 2008-04-08 | 2009-04-16 | Young-Mok Kim | A method for treating waste plastic |
| KR101218661B1 (en) * | 2012-06-19 | 2013-01-09 | 김영목 | Clean substitute energy of Hydrogen and apparatus thereof |
| WO2017115019A1 (en) | 2015-12-30 | 2017-07-06 | Forestgas Oy | Arrangement and method for preparing a gas |
-
1993
- 1993-04-20 JP JP09301493A patent/JP3469604B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0770664A1 (en) * | 1995-10-23 | 1997-05-02 | Mitsubishi Jukogyo Kabushiki Kaisha | Oil-forming method of chlorine-containing plastic refuse |
| US5728910A (en) * | 1995-10-23 | 1998-03-17 | Mitsubishi Jukogyo Kabushiki Kaisha | Oil-forming method of chlorine-containing plastic refuse |
| JPH11253786A (en) * | 1998-01-16 | 1999-09-21 | General Atomics Inc | Pressure reaction vessel |
| JP2009030071A (en) * | 2001-09-21 | 2009-02-12 | National Univ Corp Shizuoka Univ | Method for gasifying organic substance |
| WO2009048312A1 (en) * | 2008-04-08 | 2009-04-16 | Young-Mok Kim | A method for treating waste plastic |
| KR101218661B1 (en) * | 2012-06-19 | 2013-01-09 | 김영목 | Clean substitute energy of Hydrogen and apparatus thereof |
| WO2017115019A1 (en) | 2015-12-30 | 2017-07-06 | Forestgas Oy | Arrangement and method for preparing a gas |
| US10752851B2 (en) | 2015-12-30 | 2020-08-25 | Forestgas Oy | Arrangement and method for preparing a gas |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3469604B2 (en) | 2003-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1446354B1 (en) | Production of hydrogen from hydrocarbons and oxygenated hydrocarbons | |
| EP0890388B1 (en) | Carbon dioxide fixation system | |
| US5630854A (en) | Method for catalytic destruction of organic materials | |
| Glória et al. | Stripping and dissipation techniques for the removal of dissolved gases from anaerobic effluents | |
| JP2003034794A (en) | Method of simultaneous removal of chlorine and nitrogen present in oil | |
| JPH06299169A (en) | Method for gasifying plastics | |
| EP1509926B1 (en) | New recovery process | |
| TW580507B (en) | Oil-forming method of chlorine-containing plastic refuse | |
| KR19980702096A (en) | Method and apparatus for treating oil and solvent contaminated with radioactive material | |
| JP4304237B2 (en) | Gasification method of organic matter | |
| WO2007037813A2 (en) | Production of hydrogen from non-cyclic organic substances having multiple alcohol functionality | |
| US7700071B2 (en) | Production of hydrogen via a base-facilitated reaction of carbon monoxide | |
| JP2009030071A (en) | Method for gasifying organic substance | |
| JP2001288480A (en) | Method and apparatus for plastic waste gasification | |
| CN209343793U (en) | Decomposition device of organic waste | |
| JPH1180745A (en) | Waste plastic recycling system | |
| JP2004131358A (en) | Method and apparatus for producing hydrogen by using mixed molten salt | |
| US5817288A (en) | Process for treating a non-distillable halogenated organic feed stream | |
| JPH11140460A (en) | Thermal decomposition of plastics, and device and dechlorinating agent used therefor | |
| JP3478324B2 (en) | Gasification method of plastic | |
| Bjerre et al. | Thermal and oxidative decomposition of lower fatty acids with special attention to formic acid | |
| Boock | A quantitative analysis of reactions in supercritical water: experimental kinetics and mechanistic modelling | |
| Kemmler et al. | Pilot-scale testing of pyrolysis for the volume reduction of organic waste | |
| Rosen | State-of-the-art of ozonation for commercial applications in the US | |
| GB1602647A (en) | Separation of tritium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080905 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080905 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090905 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090905 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100905 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100905 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110905 Year of fee payment: 8 |
|
| LAPS | Cancellation because of no payment of annual fees |