JPH10310778A - Purification of oil made from waste plastic and purified fraction - Google Patents
Purification of oil made from waste plastic and purified fractionInfo
- Publication number
- JPH10310778A JPH10310778A JP9137898A JP13789897A JPH10310778A JP H10310778 A JPH10310778 A JP H10310778A JP 9137898 A JP9137898 A JP 9137898A JP 13789897 A JP13789897 A JP 13789897A JP H10310778 A JPH10310778 A JP H10310778A
- Authority
- JP
- Japan
- Prior art keywords
- oil
- waste plastic
- catalytic cracking
- fraction
- catalyst
- 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.)
- Pending
Links
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
- Y02P20/584—Recycling of catalysts
-
- 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
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、廃プラスチック油
化生成油中に含まれるジエン類、塩素分、酸素分成分を
流動接触分解装置にて除去し、自動車用燃料としての使
用を可能にする精製処理方法及び精製留分に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention makes it possible to remove diene, chlorine and oxygen components contained in waste plastic oil-forming oil by a fluidized catalytic cracking apparatus, and to use it as an automotive fuel. The present invention relates to a purification method and a purified fraction.
【０００２】[0002]
【従来の技術】廃棄物埋立地の残存量は年々、減少傾向
にあり問題となっている。そのような中、廃棄物中で最
も大きな比率を占めるものとして容器包装品がある。そ
こで、この容器包装品の分別収集及び再生資源化の義務
を定めた「容器包装リサイクル法」が１９９５年に公布
された。この法律では廃プラスチックも対象となってお
り、その再生資源方法として、次のような方法が知られ
ている。 再びペレット材とし、プラスチックとして再利用する
マテリアルリサイクル 焼却してエネルギーとして利用するサーマルリサイク
ル モノマーまたは油、ガスに戻しプラスチック原料また
は燃料として利用するケミカルリサイクル これらのうち、は単一の種類のプラスチックをペレッ
ト化することから廃プラスチックを種類毎に分けること
が必要で、また、プラスチックの洗浄も必要なことか
ら、プラスチック選別の行い易い産業廃棄物中の廃プラ
スチックに限られている。はゴミ焼却炉にて、その他
のゴミと燃やす方法や、廃プラスチックを固形燃料へと
加工し、ボイラー等の燃料とする方法があるが、プラス
チックの発熱量がその他のゴミに比べ高いことによるゴ
ミ焼却炉への負荷問題や、廃プラスチック中に含まれる
成分、各種添加剤による燃焼廃ガス中の有害成分（ダイ
オキシン、重金属含有の灰等）の問題がある。は廃プ
ラスチックを化学的な処理プロセスにより油やガス等の
燃料に変換しており、のようなプラスチック選別は燃
料化では不要であり、また、のような有害成分はプロ
セス中にて処理が可能である。そのため、特に、多種プ
ラスチックが混ざっており、プラスチックの汚れもひど
い一般廃棄物系廃プラスチックの再生資源化方法として
有望視されている。2. Description of the Related Art The amount of waste remaining in landfills has been decreasing year by year and has become a problem. In such a situation, containers and packaging are the largest items in waste. Accordingly, the Containers and Packaging Recycling Law was promulgated in 1995, which stipulates the obligation to separate and collect these containers and packages and recycle them. This law covers waste plastics, and the following methods are known as methods for recycling them. Material recycling to recycle as pellet material and reuse as plastic Thermal recycling to incinerate and use as energy Chemical recycling to return to monomer or oil or gas to use as plastic raw material or fuel Therefore, it is necessary to separate waste plastics for each type, and it is also necessary to wash the plastics. Therefore, waste plastics are limited to waste plastics in industrial wastes which can be easily sorted. There is a method of burning other garbage with a garbage incinerator or a method of processing waste plastic into solid fuel and using it as fuel for boilers, etc., but the garbage due to the higher calorific value of plastic than other garbage There are problems such as load on the incinerator, components contained in the waste plastic, and harmful components (dioxin, heavy metal-containing ash, etc.) in the combustion waste gas due to various additives. Converts waste plastics into fuels such as oil and gas by a chemical treatment process.Plastic sorting such as is not necessary for fuel conversion, and harmful components such as can be treated during the process. It is. Therefore, in particular, various kinds of plastics are mixed, and the dirt of the plastics is considered to be a promising method for recycling waste plastics.
【０００３】このような中、ケミカルリサイクルの一つ
として廃プラスチックを液体燃料へと変換する、廃プラ
スチック油化技術がある。廃プラスチック油化技術に適
したプラスチック種は熱可塑性プラスチックであり、一
般廃棄物中に多く含まれるポリエチレン、ポリプロピレ
ン、ポリスチレン等が特に適している。一般廃棄物系廃
プラスチックに含まれるポリ塩化ビニルは油化プロセス
中で腐食性の強い塩化水素を発生するので、廃プラスチ
ック油化技術では原料廃プラスチック中より極力取り除
くことが好ましいが、完全に取り除くのは難しく、油化
技術では脱塩素装置が必要となっている。廃プラスチッ
ク油化技術としては、次のような方法が知られている。 Ａ．熱分解による方法 Ｂ．熱分解の後、ゼオライト触媒等により更に軽質化す
る方法 Ｃ．水素雰囲気中、高温高圧下で接触液化する方法 Ｄ．高温高圧下で超臨界水と反応する方法 これらのうち、プロセス構成、運転操作性、コストの面
等によりＡもしくはＢの方法による実証プラントの稼働
実績が多い。[0003] Under such circumstances, as one of the chemical recycling, there is a technology of converting waste plastic into liquid fuel, and converting the waste plastic into oil. Plastics suitable for waste plastic oiling technology are thermoplastics, and polyethylene, polypropylene, polystyrene and the like, which are often contained in general waste, are particularly suitable. Since polyvinyl chloride contained in general waste plastics generates strongly corrosive hydrogen chloride during the oiling process, it is preferable to remove as much as possible from the raw material waste plastics in the waste plastic oiling technology, but completely remove it. It is difficult, and oil technology requires a dechlorination unit. The following methods are known as waste plastic oil conversion technology. A. Method by thermal decomposition B. A method of further reducing the weight after pyrolysis with a zeolite catalyst or the like. Method of contact liquefaction under high temperature and high pressure in a hydrogen atmosphere D. Method of reacting with supercritical water under high temperature and high pressure Among these, the demonstration plant using method A or B has a large track record in terms of process configuration, operation operability, cost, etc.
【０００４】ＡもしくはＢより得られる油化生成油は沸
点範囲が約５０〜４００℃と、ガソリン留分から軽油留
分であり、自動車燃料としての利用が期待できる。[0004] The oily product oil obtained from A or B has a boiling point range of about 50 to 400 ° C and is a gasoline fraction to a light oil fraction, and can be expected to be used as an automobile fuel.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、廃プラ
スチック油化生成油は燃料油としての貯蔵安定性、腐食
性が一般の石油製品と比較して著しく悪く、そのままで
は自動車用燃料として使用するのは難しい。この原因成
分としては次のものが考えられる。 Ａ．熱分解反応により生成されるジエン類。However, the waste plastic oil-forming oil is remarkably poor in storage stability and corrosiveness as a fuel oil as compared with general petroleum products. difficult. The following can be considered as the cause component. A. Dienes generated by the thermal decomposition reaction.
【０００６】一般の自動車ガソリン材源中にジエン類が
含まれる代表的な油として接触分解ガソリンがある。接
触分解ガソリン中のジエン類はジエン価で約１ｇＩ2／
１００ｇ前後であり、自動車ガソリン中では約０．５ｇ
Ｉ2／１００ｇ以下である。一方、廃プラスチック油化
生成油中には原料廃プラスチック種にもよるが、約２〜
４ｇＩ2／１００ｇで一般石油製品に比べかなり多くの
ジエン類が含まれている。このジエン類は反応性に富
み、重合物であるガム分を生成しやすく、貯蔵安定性を
悪くする成分として知られている。 Ｂ．廃プラスチック中に含まれるポリ塩化ビニルに由来
する塩素分。[0006] Catalytic cracking gasoline is a typical oil containing a diene in a general automobile gasoline material source. The diene in the catalytic cracking gasoline has a diene value of about 1 g I 2 /
About 100g, about 0.5g in car gasoline
I is 2 / 100g or less. On the other hand, depending on the type of raw material waste plastic, the waste plastic oil
It contains quite a lot of dienes than ordinary petroleum products in 4gI 2 / 100g. These dienes are known to be highly reactive, tend to form a polymer as a gum component, and deteriorate storage stability. B. Chlorine content derived from polyvinyl chloride contained in waste plastic.
【０００７】ポリ塩化ビニルを分解した場合、発生する
塩素分の大部分はプロセス中の発生ガス成分として除去
されるが、一部は油化生成油中に含まれる。各社プロセ
スにおいて、油化生成油中の塩素分が極力含まれないよ
うに脱塩素工程を取り入れているが、油化生成油中に
は、原料廃プラスチック中のポリ塩化ビニル含有量、脱
塩素工程内容にもよるが、約数百ｐｐｍ程度の塩素分が
含まれている。一般の石油製品中の塩素分はほとんど含
まれず１ｐｐｍ以下であり、高塩素分含有の廃プラスチ
ック油化生成油による燃料機関等への腐食が考えられ
る。 Ｃ．廃プラスチック中に含まれるエステル系可塑剤に由
来する酸素分。[0007] When polyvinyl chloride is decomposed, most of the generated chlorine is removed as a generated gas component during the process, but a part is contained in the oily product oil. In each company's process, a dechlorination process is introduced to minimize the chlorine content in the petroleum product oil, but the petroleum product oil contains the polyvinyl chloride content in the raw material waste plastic and the dechlorination process. Although it depends on the contents, it contains about several hundred ppm of chlorine. The chlorine content in general petroleum products is hardly contained, and is 1 ppm or less. Corrosion to a fuel engine or the like by waste plastic petrochemical oil containing high chlorine content is considered. C. Oxygen content derived from ester plasticizer contained in waste plastic.
【０００８】プラスチックに含まれるエステル系可塑剤
としてはフタル酸エステル系があり、これは油化プロセ
スによりフタル酸、安息香酸等になることが知られてい
る。廃プラスチック油化生成油中の酸素分は、ほとんど
がフタル酸、安息香酸等によるものと考えられる。フタ
ル酸の融点は約２１０℃、安息香酸の融点は約１２５℃
であり、廃プラスチック油化生成油中のフタル酸、安息
香酸濃度及び油温によってこれらの結晶化により燃料機
関系配管等での閉塞が考えられる。As an ester plasticizer contained in plastics, there is a phthalate ester, which is known to be converted to phthalic acid, benzoic acid and the like by an oiling process. It is considered that most of the oxygen content in the waste plastic oil-forming oil is due to phthalic acid, benzoic acid and the like. The melting point of phthalic acid is about 210 ° C, and the melting point of benzoic acid is about 125 ° C
According to the concentration of phthalic acid and benzoic acid in the waste plastic oil-forming oil and the oil temperature, the crystallization of these oils may cause blockage in fuel engine piping and the like.
【０００９】これらの成分により油化生成油の用途は現
在、ボイラー燃料の混合材源等に使用されているのみ
で、その使用範囲が制限されるという問題がある。Due to these components, the oil-forming oil is used only as a mixture source of a boiler fuel at present, and there is a problem that its use range is limited.
【００１０】廃プラスチック油化生成油の軽質であると
いう長所を生かし、これらの成分を除去して自動車用燃
料として使用する精製方法として水素化処理が考えられ
る。しかし、この方法を実施した場合、特にジエン類を
除去するためには廃プラスチック油化生成油に富みに含
まれるオレフィン分の水素化が同時に進行するため、多
量の水素が必要となり、精製コストが高くなる上、ジエ
ン類の重合化により、触媒層が閉塞してしまう危険もあ
る。[0010] Taking advantage of the lightness of the waste plastic oil-forming oil, hydrogenation treatment can be considered as a refining method for removing these components and using it as an automotive fuel. However, when this method is carried out, particularly in order to remove dienes, hydrogenation of olefins contained in the waste plastic oil-producing oil proceeds at the same time, so that a large amount of hydrogen is required, and purification cost is reduced. In addition, there is a danger that the catalyst layer will be clogged by the polymerization of dienes.
【００１１】また、水素化精製に用いられる触媒は表面
にコークが堆積することで活性が失われていくことが知
られているが、ジエン類、酸素分成分を含む廃プラスチ
ック油化生成油を水素化精製触媒にて処理を行うとコー
ク発生量は著しく多くなり、触媒寿命期間が大きく短く
なり、触媒交換頻度が増加し、安定的な廃プラスチック
油化生成油の精製処理が難しくなる。It is known that the catalyst used in hydrorefining loses its activity by depositing coke on the surface. However, waste plastic oil produced from dienes and oxygen components is produced. When the treatment is carried out using a hydrorefining catalyst, the amount of coke generated is remarkably increased, the life of the catalyst is greatly shortened, the frequency of catalyst replacement is increased, and it is difficult to stably purify the waste plastic oil-forming oil.
【００１２】本発明の目的は、前記従来技術の問題点を
解決し、低コストにて廃プラスチック油化生成油を高品
質な自動車用燃料油へ精製する方法及び精製留分を提供
することにある。An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a method and a refined fraction for refining waste plastic oil-forming oil into high-quality automotive fuel oil at low cost. is there.
【００１３】[0013]
【課題を解決するための手段】本発明者らは前記の課題
を解決するため、鋭意研究した結果、水素を使用しない
流動接触分解装置を用い、廃プラスチック油化生成油中
のジエン類、塩素分、酸素分を除去する精製方法を完成
するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the present invention has been applied to the use of a fluid catalytic cracking apparatus that does not use hydrogen to obtain diene, chlorine, etc. And a purification method for removing oxygen.
【００１４】即ち、本発明の上記課題は、 １．ジエン類、塩素分、酸素分を含有する廃プラスチッ
ク油化生成油を流動接触分解装置にて処理することを特
徴とする廃プラスチック油化生成油の精製方法、 ２．流動接触分解装置の原料油として、廃プラスチック
油化生成油１〜１００容量％を、沸点２５０℃以上の石
油留分に混合したものを用い、これを流動接触分解装置
にて処理することを特徴とする前記１記載の廃プラスチ
ック油化生成油の精製方法、 ３．廃プラスチック油化生成油中のジエン類含有量がジ
エン価にて約０．１〜５．０ｇＩ2／１００ｇ、塩素分
含有量が約０．０００１〜１重量％、酸素分含有量が約
０．０００１〜１重量％である廃プラスチック油化生成
油を流動接触分解装置にて処理することを特徴とする前
記１又は２記載の廃プラスチック油化生成油の精製方
法、 ４．流動接触分解装置が、ライザー型反応器、触媒／生
成油分離器、触媒再生塔を有する構成であることを特徴
とする前記１、２又は３記載の廃プラスチック油化生成
油の精製方法、 ５．前記１〜４のいずれかの精製方法で得られた生成油
を分留したガソリン留分、軽油留分又は塔底油留分、 ６．請求項５記載のガソリン留分又は軽油留分を主成分
とする自動車用燃料、の各々によって達成される。That is, the objects of the present invention are: 1. A method for purifying waste plastic oil-forming oil, which comprises treating a waste plastic oil-forming oil containing a diene, chlorine content and oxygen content with a fluid catalytic cracking device. As a feed oil for a fluid catalytic cracking unit, a mixture of 1 to 100% by volume of waste plastic oil-forming oil mixed with a petroleum fraction having a boiling point of 250 ° C. or higher is used, and this is treated by a fluid catalytic cracking unit. 2. The method for purifying waste plastic oil-forming oil according to the above item 1, The diene content in the waste plastic oil-forming oil is about 0.1 to 5.0 g I2 / 100 g in terms of diene value, the chlorine content is about 0.0001 to 1 % by weight, and the oxygen content is about 0. 3. The method for purifying waste plastic oil-forming product oil according to the above 1 or 2, wherein the waste plastic oil-forming oil having a concentration of 0.0001 to 1% by weight is treated by a fluid catalytic cracking device. 4. The method for purifying waste plastic oil-forming product oil according to the above 1, 2, or 3, wherein the fluid catalytic cracking device has a riser type reactor, a catalyst / product oil separator, and a catalyst regeneration tower. . 5. a gasoline fraction, a gas oil fraction or a bottom oil fraction obtained by fractionating the product oil obtained by any of the refining methods of the above 1 to 4, This is achieved by each of the fuels for automobiles mainly comprising a gasoline fraction or a gas oil fraction according to claim 5.
【００１５】本発明は、廃プラスチック油化生成油を固
体酸触媒にて接触分解反応させることで、廃プラスチッ
ク油化生成油中のジエン類、塩素分、酸素分を除去し、
高品質な自動車用燃料へと精製し、しかも、水素を使用
しないことから運転コストが低くできる点で特に有用で
ある。According to the present invention, a waste plastic oil-forming oil is subjected to a catalytic cracking reaction with a solid acid catalyst to remove diene, chlorine and oxygen from the waste plastic oil-forming oil.
It is particularly useful in that it can be refined into a high-quality automotive fuel and can be operated at low cost because it does not use hydrogen.
【００１６】また、本発明での流動接触分解装置は触媒
再生塔を有しており、触媒活性低下の主原因である触媒
表面上に付着したコークはこの再生塔にてほぼ燃焼除去
され、それでも触媒活性が低下してきた際には装置内触
媒を一定量抜き出し、新触媒を一定量補給することで触
媒の活性をほぼ一定に保つことができ、廃プラスチック
油化生成油を安定的に精製できる点においても有用であ
る。Further, the fluidized catalytic cracking apparatus according to the present invention has a catalyst regeneration tower, and coke adhering to the catalyst surface, which is a main cause of a decrease in catalyst activity, is substantially burned and removed in this regeneration tower. When the catalyst activity decreases, a certain amount of catalyst in the device is extracted and a certain amount of new catalyst is replenished, so that the activity of the catalyst can be kept almost constant, and the waste plastic oil produced oil can be stably refined. It is also useful in that respect.
【００１７】本発明で用いる廃プラスチック油化生成油
は、どのような油化技術を用いて得られた廃プラスチッ
ク油化生成油でも構わないが、特にオレフィン分ひいて
はジエン類を生成油中に多く含みやすい熱分解技術を用
いた廃プラスチック油化生成油に有用である。The waste plastic oil-forming oil used in the present invention may be a waste plastic oil-forming oil obtained by using any oiling technology, and particularly, a large amount of olefins and, hence, diene are contained in the oil. It is useful for waste plastic oils produced using pyrolysis technology that is easy to contain.
【００１８】[0018]
【発明の実施の形態】本発明に用いることのできる廃プ
ラスチック油化生成油の性状としては、特に限定はない
が、通常、沸点範囲が約５０〜４００℃、オレフィン分
が約２０〜７０容量％、ジエン類がジエン価にて約０．
１〜５．０ｇＩ2／１００ｇ、塩素分が約０．０００１
〜１重量％、酸素分が約０．０００１〜１重量％であ
る。DESCRIPTION OF THE PREFERRED EMBODIMENTS The properties of the waste plastic oil-forming oil which can be used in the present invention are not particularly limited, but usually the boiling point range is about 50 to 400 ° C. and the olefin content is about 20 to 70 volumes. %, The diene is about 0.
1~5.0gI 2 / 100g, chlorine content of about 0.0001
１1% by weight, oxygen content is about 0.0001 to 1% by weight.
【００１９】かかる性状の廃プラスチック油化生成油を
本発明によって精製して得られる生成油の分留別性状の
代表例は、下記表１の如くなる。The following Table 1 shows typical examples of the fractionation properties of the product oil obtained by purifying the waste plastic oil product oil having such properties according to the present invention.
【００２０】[0020]
【表１】 [Table 1]
【００２１】上記ガソリン留分又は軽油留分を自動車用
燃料油として用いる場合、これのみを主成分としてもよ
いし、通常のガソリン留分又は軽油留分と混合使用して
もよい。また、一般的な添加剤を含有してもよい。When the gasoline fraction or gas oil fraction is used as fuel oil for automobiles, it may be used alone as a main component, or may be mixed with a normal gasoline fraction or gas oil fraction. Further, general additives may be contained.
【００２２】以下、本発明について更に詳述する。流動
接触分解装置の原料油は、廃プラスチック油化生成油単
独でも構わないが、石油精製の分野にて流動接触分解装
置の原料油として通常用いられている減圧軽油や常圧残
油と廃プラスチック油化生成油を混合して使用すること
ができる。流動接触分解装置での反応熱源は再生塔にて
コークを燃焼除去された高温の再生触媒が反応塔に循環
した際の触媒の顕熱であり、この熱量は原料油中の残留
炭素分と関係がある。廃プラスチック油化生成油中の残
留炭素分は反応温度条件にもよるが装置の熱バランスを
保つには不十分の場合もあり、減圧軽油や常圧残油を廃
プラスチック油化生成油に混合し、原料油中残留炭素分
を調整することで順調に装置を運転できる利点がある。Hereinafter, the present invention will be described in more detail. The feedstock oil for the fluid catalytic cracking unit may be a waste plastic oil product oil alone, but the vacuum gas oil or the atmospheric residual oil, which is usually used as the feedstock for the fluid catalytic cracking unit in the field of petroleum refining, and waste plastics The oily product oil can be used as a mixture. The reaction heat source in the fluid catalytic cracking unit is the sensible heat of the catalyst when the high-temperature regenerated catalyst whose coke has been burned off in the regeneration tower circulates through the reaction tower, and this calorific value is related to the residual carbon content in the feed oil. There is. The residual carbon content in the waste plastic petroleum product oil depends on the reaction temperature conditions but may not be enough to maintain the heat balance of the equipment. However, there is an advantage that the apparatus can be smoothly operated by adjusting the residual carbon content in the feedstock oil.
【００２３】本発明に用いられる流動接触分解装置は、
石油精製の分野にて通常用いられている装置を使用する
ことができる。基本的には、反応塔、触媒／生成油分離
器、触媒表面上油分の除去部、触媒再生塔を一つの構成
とし、触媒はこの系内を流動循環する。プロセスとして
は、ＵＯＰ社のＵＯＰ式、Ｍ．Ｗ．Ｋｅｌｌｏｇｇ社の
ウルトラオルソフロー式、ＩＦＰ社のＲ２Ｒ式など各
社、特徴があるが、いずれのプロセスでも構わない。The fluidized catalytic cracking apparatus used in the present invention comprises:
Apparatus usually used in the field of petroleum refining can be used. Basically, a reaction tower, a catalyst / product oil separator, an oil removing unit on the catalyst surface, and a catalyst regeneration tower are configured as one unit, and the catalyst flows and circulates in this system. As the process, UOP's UOP type, M.P. W. Each company has features such as Kellogg's ultra-ortho-flow type and IFP's R2R type, but any process may be used.
【００２４】精製処理条件は、反応器温度約４００〜６
００℃、反応器圧力約０．１〜３．０ｋｇ／ｃｍ２Ｇ、
触媒／原料油比約４〜８ｗｔ／ｗｔ、触媒再生塔温度約
５００〜８００℃、触媒再生塔圧力約０．１〜３．０ｋ
ｇ／ｃｍ２Ｇと石油の流動接触分解で通常使用される範
囲が適応される。The conditions for the purification treatment are as follows:
00 ° C., reactor pressure about 0.1-3.0 kg / cm 2 G,
Catalyst / feed oil ratio about 4-8 wt / wt, catalyst regeneration tower temperature about 500-800 ° C, catalyst regeneration tower pressure about 0.1-3.0 k
The ranges normally used in fluid catalytic cracking of g / cm 2 G and petroleum apply.
【００２５】本発明に使用する触媒としては、石油の流
動接触分解で通常使用される固体酸触媒で、成分として
はシリカ−アルミナ多孔体、合成ゼオライト等で、形状
としては平均粒径（ふるい分け法による）が約６０μｍ
程度の粉状のものを使用することができる。廃プラスチ
ック油化技術において、廃プラスチックを熱分解した
後、その生成ガスを固体触媒酸を用いて改質するプロセ
スがある。この廃プラスチック油化技術で用いられる固
体酸触媒は、成分としては本発明に使用する触媒の成分
とほぼ同じであるが、使用目的は、廃プラスチック油化
技術では熱分解生成油を軽質化することを目的としてい
るが、本発明では廃プラスチック油化生成油中のジエン
類、塩素分、酸素分の除去を目的としており、大きく異
なる。さらに、触媒形状において、廃プラスチック油化
技術では特に指定したものはないが、本発明では触媒の
装置系内での流動循環及び再生を考慮し、粉状触媒を用
いる点が特徴である。The catalyst used in the present invention is a solid acid catalyst usually used in fluid catalytic cracking of petroleum. The component is a porous silica-alumina, synthetic zeolite, etc., and the shape is an average particle size (sieving method). Is about 60 μm
A powdery substance of a degree can be used. BACKGROUND ART In waste plastic oiling technology, there is a process in which waste plastic is thermally decomposed and then the produced gas is reformed using a solid catalytic acid. The solid acid catalyst used in this waste plastic oiling technology is almost the same as the component of the catalyst used in the present invention as a component, but the purpose of use is to lighten the pyrolysis product oil in the waste plastic oiling technology. However, in the present invention, the purpose is to remove diene, chlorine, and oxygen from waste plastic oil-forming oil, which is very different. Further, in the catalyst shape, although there is no particular designation in the waste plastic oiling technology, the present invention is characterized in that a powdery catalyst is used in consideration of fluid circulation and regeneration in the catalyst system.
【００２６】[0026]
【実施例】本発明の実施形態を実施例によりさらに詳細
に説明する。流動接触分解装置の供給原料としては、廃
プラスチックを熱分解反応により油化して得られた廃プ
ラスチック油化生成油５０容量％と脱硫減圧軽油５０容
量％を混合したものを原料油として用いた。触媒は市販
の合成ゼオライト系接触分解触媒を使用した。装置はベ
ンチパイロットプラントの流動接触分解装置を使用し、
その反応条件としては反応器温度５１０℃、反応器圧力
０．１ｋｇ／ｃｍ２Ｇ、触媒／原料油比６．０ｗｔ／ｗ
ｔ、触媒再生塔温度７２０℃、触媒再生塔圧力０．３ｋ
ｇ／ｃｍ２Ｇとした。石油精製においては、流動接触分
解装置より得られた生成油はすぐに分留塔へ入り、ガス
留分、ガソリン留分、軽油留分、塔底油留分に分けられ
る。そこで、この実施例においても接触分解により得ら
れた生成油及び原料である廃プラスチック油化生成油に
ついてガス留分、ガソリン留分、軽油留分、塔底油留分
に分けて、性状を比較した。また、廃プラスチック油化
生成油の精製結果を石油精製での流動接触分解装置にて
得られる一般的な生成油と比較するため、原料油を脱硫
減圧軽油のみとし、同条件にて反応を行った。その結
果、ジエン類についてはガソリン、軽油留分で、約４０
〜６０％減少し、その値は石油精製での流動接触分解装
置より得られるものとほぼ同じ値であった。塩素分につ
いては、各留分ともに約９７〜９９％減少し、ほぼ除去
された。酸素分については、各留分ともに０．００とな
り、ほぼ除去された。この結果を表２に示す。EXAMPLES The embodiments of the present invention will be described in more detail with reference to Examples. As a feedstock for the fluidized catalytic cracking apparatus, a mixture of 50% by volume of waste plastic oilified product oil obtained by turning waste plastic into oil by a thermal decomposition reaction and 50% by volume of desulfurized vacuum gas oil was used as a feedstock. As the catalyst, a commercially available synthetic zeolite-based catalytic cracking catalyst was used. The equipment uses the fluid catalytic cracking unit of the bench pilot plant,
The reaction conditions include a reactor temperature of 510 ° C., a reactor pressure of 0.1 kg / cm 2 G, and a catalyst / feedstock ratio of 6.0 wt / w.
t, catalyst regeneration tower temperature 720 ° C, catalyst regeneration tower pressure 0.3k
g / cm 2 G. In petroleum refining, product oil obtained from a fluid catalytic cracking unit immediately enters a fractionation tower, and is divided into a gas fraction, a gasoline fraction, a gas oil fraction, and a bottom oil fraction. Therefore, also in this example, the properties of the product oil obtained by the catalytic cracking and the waste plastic oil product oil as the raw material are divided into a gas fraction, a gasoline fraction, a light oil fraction, and a bottom oil fraction, and the properties are compared. did. In addition, in order to compare the refining result of waste plastic oil product oil with a general oil produced by a fluid catalytic cracking unit in petroleum refining, the reaction was carried out under the same conditions using only the desulfurized vacuum gas oil as the raw oil. Was. As a result, about 40% of diene in gasoline and gas oil fractions.
-60%, about the same value as obtained from a fluid catalytic cracking unit in petroleum refining. The chlorine content of each fraction was reduced by about 97 to 99%, and was almost removed. The oxygen content of each fraction was 0.00, and was almost removed. Table 2 shows the results.
【００２７】[0027]
【発明の効果】廃プラスチック油化生成油の精製方法と
して石油精製で用いられている流動接触分解装置を使用
して精製処理する本発明により、廃プラスチック油化生
成油中のジエン類、塩素分、酸素分は除去され、腐食性
の低下及び、貯蔵安定性を大きく向上することができ
る。しかも、水素を必要とせず、また、触媒活性を一定
に保つことが触媒の抜き出し及び補給により可能である
流動接触分解装置を使用することで、低コストで、安定
した高品質な自動車用燃料油を製造することができる。According to the present invention, a refining treatment is performed using a fluid catalytic cracking apparatus used in petroleum refining as a method for purifying waste plastic oil-forming product oil. In addition, the oxygen content is removed, and the corrosiveness can be reduced and the storage stability can be greatly improved. In addition, the use of a fluid catalytic cracking device that does not require hydrogen and that can maintain a constant catalytic activity by extracting and replenishing the catalyst enables low-cost, stable and high-quality automotive fuel oil. Can be manufactured.
【００２８】[0028]
【表２】 [Table 2]
Claims (6)
ラスチック油化生成油を流動接触分解装置にて処理する
ことを特徴とする廃プラスチック油化生成油の精製方
法。1. A process for purifying a waste plastic oil-forming oil, comprising treating a waste plastic oil-forming oil containing a diene, chlorine content and oxygen content with a fluidized catalytic cracking device.
スチック油化生成油１〜１００容量％を、沸点２５０℃
以上の石油留分に混合したものを用い、これを流動接触
分解装置にて処理することを特徴とする請求項１記載の
廃プラスチック油化生成油の精製方法。2. A feed oil for a fluidized catalytic cracking apparatus, wherein 1 to 100% by volume of a waste plastic oil-forming oil is used at a boiling point of 250 ° C.
2. The method for purifying a waste plastic oil-forming oil according to claim 1, wherein the oil mixed with the above-mentioned petroleum fraction is used and treated with a fluid catalytic cracking device.
有量がジエン価にて約０．１〜５．０ｇＩ2／１００
ｇ、塩素分含有量が約０．０００１〜１重量％、酸素分
含有量が約０．０００１〜１重量％である廃プラスチッ
ク油化生成油を流動接触分解装置にて処理することを特
徴とする請求項１又は２記載の廃プラスチック油化生成
油の精製方法。Wherein about dienes content of the waste plastics Yuka produced oil is in diene value 0.1~5.0gI 2/100
g, a waste plastic oil-forming oil having a chlorine content of about 0.0001 to 1% by weight and an oxygen content of about 0.0001 to 1% by weight is treated by a fluid catalytic cracking device. The method for purifying waste plastic oil-forming oil according to claim 1 or 2.
触媒／生成油分離器、触媒再生塔を有する構成であるこ
とを特徴とする請求項１、２又は３記載の廃プラスチッ
ク油化生成油の精製方法。4. The fluidized catalytic cracking device is a riser type reactor,
The method for purifying waste plastic oil-forming oil according to claim 1, 2, or 3, wherein the method comprises a catalyst / oil separator and a catalyst regeneration tower.
れた生成油を分留したガソリン留分、軽油留分又は塔底
油留分。5. A gasoline fraction, a gas oil fraction or a bottom oil fraction obtained by fractionating the product oil obtained by the refining method according to claim 1.
を主成分とする自動車用燃料。6. An automotive fuel comprising the gasoline fraction or the gas oil fraction according to claim 5 as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9137898A JPH10310778A (en) | 1997-05-12 | 1997-05-12 | Purification of oil made from waste plastic and purified fraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9137898A JPH10310778A (en) | 1997-05-12 | 1997-05-12 | Purification of oil made from waste plastic and purified fraction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10310778A true JPH10310778A (en) | 1998-11-24 |
Family
ID=15209263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9137898A Pending JPH10310778A (en) | 1997-05-12 | 1997-05-12 | Purification of oil made from waste plastic and purified fraction |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10310778A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003528206A (en) * | 2000-03-20 | 2003-09-24 | クァク、ホ−ジュン | Method and system for continuously producing gasoline, kerosene and diesel oil using waste plastic |
| JP2006206876A (en) * | 2004-12-28 | 2006-08-10 | Japan Energy Corp | Gasoline composition |
| JP2007077324A (en) * | 2005-09-15 | 2007-03-29 | Japan Energy Corp | Method for treating plastic cracked oil |
| JP2007119648A (en) * | 2005-10-31 | 2007-05-17 | Japan Energy Corp | Method for treating plastic cracked oil |
| KR100782381B1 (en) | 2006-08-03 | 2007-12-07 | 한국에너지기술연구원 | Method and apparatus for improving fuel quality of pyrolysis reclaimed fuel from wasted plastic and reclaimed fuel manufactured thereof |
| JP2008024754A (en) * | 2006-07-18 | 2008-02-07 | Nippon Steel Corp | Method for producing thermal decomposition oil from rubber-based waste and production apparatus therefor |
| CN105419840A (en) * | 2015-12-03 | 2016-03-23 | 南京绿帝环保能源科技有限公司 | Waste plastic cracking catalytic device |
| WO2021204818A1 (en) | 2020-04-07 | 2021-10-14 | Total Research & Technology Feluy | Waste plastic based oil upgrading into high value chemicals via direct catalytic cracking |
-
1997
- 1997-05-12 JP JP9137898A patent/JPH10310778A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003528206A (en) * | 2000-03-20 | 2003-09-24 | クァク、ホ−ジュン | Method and system for continuously producing gasoline, kerosene and diesel oil using waste plastic |
| JP2006206876A (en) * | 2004-12-28 | 2006-08-10 | Japan Energy Corp | Gasoline composition |
| JP2007077324A (en) * | 2005-09-15 | 2007-03-29 | Japan Energy Corp | Method for treating plastic cracked oil |
| JP2007119648A (en) * | 2005-10-31 | 2007-05-17 | Japan Energy Corp | Method for treating plastic cracked oil |
| JP2008024754A (en) * | 2006-07-18 | 2008-02-07 | Nippon Steel Corp | Method for producing thermal decomposition oil from rubber-based waste and production apparatus therefor |
| KR100782381B1 (en) | 2006-08-03 | 2007-12-07 | 한국에너지기술연구원 | Method and apparatus for improving fuel quality of pyrolysis reclaimed fuel from wasted plastic and reclaimed fuel manufactured thereof |
| CN105419840A (en) * | 2015-12-03 | 2016-03-23 | 南京绿帝环保能源科技有限公司 | Waste plastic cracking catalytic device |
| WO2021204818A1 (en) | 2020-04-07 | 2021-10-14 | Total Research & Technology Feluy | Waste plastic based oil upgrading into high value chemicals via direct catalytic cracking |
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