JP4448941B2 - Method for producing gasoline alternative fuel, kerosene alternative fuel and diesel oil alternative fuel using animal and vegetable oils and fats as raw materials - Google Patents
Method for producing gasoline alternative fuel, kerosene alternative fuel and diesel oil alternative fuel using animal and vegetable oils and fats as raw materials Download PDFInfo
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- JP4448941B2 JP4448941B2 JP2005336080A JP2005336080A JP4448941B2 JP 4448941 B2 JP4448941 B2 JP 4448941B2 JP 2005336080 A JP2005336080 A JP 2005336080A JP 2005336080 A JP2005336080 A JP 2005336080A JP 4448941 B2 JP4448941 B2 JP 4448941B2
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- 239000003502 gasoline Substances 0.000 title claims description 43
- 239000003350 kerosene Substances 0.000 title claims description 32
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- HNBDRPTVWVGKBR-UHFFFAOYSA-N methyl pentanoate Chemical compound CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 description 2
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- 239000007858 starting material Substances 0.000 description 2
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- XNCNNDVCAUWAIT-UHFFFAOYSA-N Methyl heptanoate Chemical compound CCCCCCC(=O)OC XNCNNDVCAUWAIT-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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Description
本発明はガソリン代替燃料、灯油代替燃料及び軽油代替燃料の製造方法に関する。 The present invention relates to a method for producing gasoline alternative fuel, kerosene alternative fuel, and light oil alternative fuel.
現在の生活を変えることなく、京都議定書の二酸化炭素排出量の目標値を達成するためにはバイオマス燃料のさらなる高度利用が必要である。 In order to achieve the target value of carbon dioxide emissions under the Kyoto Protocol without changing the current life, further advanced use of biomass fuel is necessary.
そのような状況の中で農林水産業等で多く利用されている軽油の代替燃料としては、バイオマス由来のバイオディーゼル燃料が提唱されている。バイオディーゼル燃料は、動植物油脂を低級アルコール（メタノール、エタノール等）でエステル交換して得られる脂肪酸アルキルエステルを主成分とし、欧米では普及している。しかしながらバイオディーゼル燃料は粘度が高いという問題がある。 Under such circumstances, biomass-derived biodiesel fuel has been proposed as an alternative fuel for light oil that is widely used in agriculture, forestry and fisheries. Biodiesel fuel has a fatty acid alkyl ester obtained by transesterifying animal and vegetable oils and fats with lower alcohols (methanol, ethanol, etc.) as a main component, and is widely used in Europe and the United States. However, biodiesel fuel has a problem of high viscosity.
そこでバイオディーゼル燃料の物性を改善するための技術として、油脂等を触媒を用いて分解し、低分子成分を得る熱分解法、接触分解法などの技術が提唱されている。しかしながら、触媒が必要であること、分解生成物以外に残渣としてタール等の液体燃料としては利用が困難な副産物が生成されること等が問題となっている。 Thus, as a technique for improving the physical properties of biodiesel fuel, techniques such as a thermal decomposition method and a catalytic decomposition method for decomposing oils and fats using a catalyst to obtain low molecular components have been proposed. However, there are problems that a catalyst is required and that by-products that are difficult to use as a liquid fuel such as tar are generated as a residue in addition to the decomposition products.
本発明者らは優れた性状を有する新たなバイオディーゼル燃料の製造法としてＳＴＩＮＧ（ｓｉｍｕｌｔａｎｅｏｕｓ ｒｅａｃｔｉｏｎ ｏｆ ｔｒａｎｓｒｅｓｔｅｒｉｆｉｃａｔｉｏｎ ａｎｄ ｃｒａｃｋｉｎｇ）法の開発を行っている（特許文献１参照）。ＳＴＩＮＧ法は、超臨界メタノール中でトリグリセリドを反応させることにより、脂肪酸メチルエステルの生成とともに燃料成分の低分子化を同時に行う方法である。本発明者らはこれまでに、ＳＴＩＮＧ法によりバイオディーゼル燃料の流動点等の物性改善が可能であることを明らかにしてきた。 The present inventors have developed a STING (simultaneous reaction of transcription and cracking) method as a method for producing a new biodiesel fuel having excellent properties (see Patent Document 1). The STING method is a method in which triglyceride is reacted in supercritical methanol to simultaneously produce a fatty acid methyl ester and lower the molecular weight of a fuel component. The present inventors have clarified that physical properties such as the pour point of biodiesel fuel can be improved by the STING method.
以上の通りバイオマス由来の軽油代替燃料の開発はこれまでにも行われているが、民間で多く利用されているガソリンのバイオマス由来の代替燃料は未だ提唱されていない。バイオディーゼル燃料は燃料としての性状は重油相当であり、揮発油としての利用は不可能であるという問題がある。また、上述のＳＴＩＮＧ法は軽油代替燃料の製造法であり、特許文献１記載の条件ではガソリン代替燃料は製造できない。また、ＳＴＩＮＧ法では原料として水を用いることはできないという問題がある。 As described above, biomass-derived light oil alternative fuels have been developed so far, but no alternative fuel derived from gasoline, which is widely used in the private sector, has been proposed yet. Biodiesel fuel has the problem that its properties as fuel are equivalent to heavy oil and cannot be used as volatile oil. Further, the above STING method is a method for producing a light oil alternative fuel. Under the conditions described in Patent Document 1, a gasoline alternative fuel cannot be produced. Further, there is a problem that water cannot be used as a raw material in the STING method.
ガソリンの一部をバイオマス由来の代替燃料に置き換えるために、ガソリンにバイオエタノールを添加する試みが行われている。しかしバイオエタノールのガソリン中への添加量は３％程度と少なく、その効果も添加量相応である。また、アルコールは腐食性が高く熱量が低いため、ガソリン代替燃料として１００％利用することは困難であり、日本国内ではガソリンに対して３％程度添加する添加物としての利用が限界である。また、エタノール発酵時の残渣の処理について有効な利用方法が確立されていないこと、エタノールを１００％近くまで濃縮するには多くのエネルギーが必要であることなどから経済的にも問題を残している。 Attempts have been made to add bioethanol to gasoline in order to replace part of the gasoline with alternative fuel derived from biomass. However, the amount of bioethanol added to gasoline is as low as 3%, and the effect is commensurate with the amount added. Moreover, since alcohol is highly corrosive and has a low calorific value, it is difficult to use 100% as an alternative fuel for gasoline, and in Japan, its use as an additive to add about 3% to gasoline is limited. In addition, there is an economic problem because there is no effective method for treating residues during ethanol fermentation, and a lot of energy is required to concentrate ethanol to nearly 100%. .
以上の通り、１００％バイオマス由来のガソリン代替燃料の開発が望まれている。
本発明は動植物油脂からガソリン代替燃料または灯油代替燃料を製造することを目的とする。本発明はまた、動植物油脂からガソリン代替燃料または灯油代替燃料と軽油代替燃料とを同時に製造することを目的とする。 An object of the present invention is to produce gasoline alternative fuel or kerosene alternative fuel from animal and vegetable fats and oils. Another object of the present invention is to produce gasoline alternative fuel or kerosene alternative fuel and light oil alternative fuel from animal and vegetable fats and oils at the same time.
本発明は以下の発明を包含する。
（１）動植物油脂またはその廃食油と、水、低級アルコール、または水および低級アルコールの混合物とを混合し、得られた混合物を高温高圧条件下で処理することにより、ガソリン代替燃料または灯油代替燃料として使用できる成分を生成させることを特徴とする、ガソリン代替燃料または灯油代替燃料を製造する方法。
（２）動植物油脂またはその廃食油と、水、低級アルコール、または水および低級アルコールの混合物とを混合し、得られた混合物を高温高圧条件下で処理することにより、ガソリン代替燃料または灯油代替燃料として使用できる成分と、軽油代替燃料として使用できる成分とを生成させることを特徴とする、ガソリン代替燃料または灯油代替燃料と軽油代替燃料とを製造する方法。
（３）前記混合物を５Ｍｐａ〜１００ＭＰａの圧力条件下で処理することを特徴とする（１）または（２）記載の方法。
（４）前記混合物を３００℃〜８００℃の温度条件下で処理することを特徴とする（１）〜（３）のいずれか記載の方法。
（５）前記混合物を高温高圧条件下で３〜６０分間処理することを特徴とする（１）〜（４）のいずれか記載の方法。
（６）（１）または（２）記載の方法により製造されたガソリン代替燃料。
（７）（１）または（２）記載の方法により製造された灯油代替燃料。
（８）（２）記載の方法により製造された軽油代替燃料。
（９）動植物油脂またはその廃食油と、水、低級アルコール、または水および低級アルコールの混合物とを出発原料として、ガソリン代替燃料または灯油代替燃料と軽油代替燃料とを製造するための装置であって、出発原料の混合物を高温高圧条件下で処理するための反応装置と、処理物を気体成分と液体成分とに分離する気液分離器と、分離された液体成分を、未反応の水、低級アルコール、または水および低級アルコールの混合物と、ガソリン代替燃料または灯油代替燃料として使用できる成分と、軽油代替燃料として使用できる成分とに分離する分離装置と、を備えることを特徴とする前記装置。
The present invention includes the following inventions.
(1) Gasoline substitute fuel or kerosene substitute fuel by mixing animal and vegetable fats and oils or waste cooking oil thereof with water, lower alcohol, or a mixture of water and lower alcohol, and treating the resulting mixture under high temperature and high pressure conditions A method for producing a gasoline alternative fuel or a kerosene alternative fuel, characterized in that a component that can be used as a fuel is produced.
(2) By mixing animal and vegetable fats and oils or waste cooking oil thereof with water, lower alcohol, or a mixture of water and lower alcohol, and treating the resulting mixture under high temperature and high pressure conditions, gasoline alternative fuel or kerosene alternative fuel A method for producing a gasoline alternative fuel or a kerosene alternative fuel and a light oil alternative fuel, characterized by producing a component that can be used as a fuel oil and a component that can be used as a light oil alternative fuel.
(3) The method according to (1) or (2), wherein the mixture is treated under a pressure condition of 5 Mpa to 100 MPa.
(4) The method according to any one of (1) to (3), wherein the mixture is treated under a temperature condition of 300 ° C to 800 ° C.
(5) The method according to any one of (1) to (4), wherein the mixture is treated under high temperature and high pressure conditions for 3 to 60 minutes.
(6) Gasoline substitute fuel produced by the method according to (1) or (2).
(7) A kerosene alternative fuel produced by the method according to (1) or (2).
(8) A light oil alternative fuel produced by the method described in (2).
(9) An apparatus for producing gasoline alternative fuel or kerosene alternative fuel and light oil alternative fuel using, as starting materials, animal and vegetable fats and oils or waste edible oil thereof and water, lower alcohol, or a mixture of water and lower alcohol. A reaction apparatus for treating a mixture of starting materials under high temperature and high pressure conditions, a gas-liquid separator for separating the treated product into a gas component and a liquid component, and separating the separated liquid component into unreacted water, The apparatus comprising: a separation device that separates alcohol or a mixture of water and lower alcohol, a component that can be used as a gasoline alternative fuel or a kerosene alternative fuel, and a component that can be used as a light oil alternative fuel.
本発明において「ガソリン代替燃料または灯油代替燃料として使用できる成分」としては、具体的には、沸点２００℃以下の成分が挙げられる。 In the present invention, “components that can be used as gasoline substitute fuel or kerosene substitute fuel” specifically include components having a boiling point of 200 ° C. or less.
本発明において「軽油代替燃料として使用できる成分」としては、具体的には、沸点２００℃超の成分（沸点２００℃の成分は含まない）が挙げられる。 Specific examples of the “component that can be used as a light oil substitute fuel” in the present invention include components having a boiling point of more than 200 ° C. (components having a boiling point of 200 ° C. are not included).
本発明により、動植物油脂からガソリン代替燃料または灯油代替燃料を製造することが可能となる。本発明により、動植物油脂からガソリン代替燃料または灯油代替燃料と、軽油代替燃料とを同時に製造することが可能となる。 According to the present invention, it is possible to produce gasoline alternative fuel or kerosene alternative fuel from animal and vegetable fats and oils. According to the present invention, it is possible to simultaneously produce gasoline alternative fuel or kerosene alternative fuel and light oil alternative fuel from animal and vegetable fats and oils.
本発明によるガソリン代替燃料の製造方法は、動植物油脂またはその廃食油（以下「原料Ａ」という場合がある）と、水、低級アルコール、または水および低級アルコールの混合物（以下「原料Ｂ」という場合がある）とを混合し、得られた混合物を高温高圧条件下で処理することにより、ガソリン代替燃料または灯油代替燃料として使用できる成分を生成させることを特徴とする。上記工程において、軽油代替燃料として使用できる成分も同時に発生する。すなわち本発明によれば、原料Ａ及び原料Ｂの混合物からガソリン代替燃料または灯油代替燃料と、軽油代替燃料とを同時に製造することができる。 The method for producing a gasoline alternative fuel according to the present invention includes animal and vegetable fats or waste edible oil (hereinafter sometimes referred to as “raw material A”) and water, lower alcohol, or a mixture of water and lower alcohol (hereinafter referred to as “raw material B”). And the resulting mixture is processed under high temperature and high pressure conditions to produce components that can be used as gasoline substitute fuel or kerosene substitute fuel. In the above process, components that can be used as a light oil substitute fuel are also generated. That is, according to the present invention, a gasoline alternative fuel or kerosene alternative fuel and a light oil alternative fuel can be simultaneously produced from a mixture of the raw material A and the raw material B.
原料Ａについて。本発明に使用できる植物油脂としては、例えばナタネ油、キャノーラ油、コーン油、大豆油、ヒマワリ油、または紅花油が挙げられるがこれらに限定されない。本発明に使用できる動物油脂としては、豚脂（ラード）または牛脂が挙げられるがこれらに限定されない。廃食油とは、家庭、レストラン、ファーストフード店、弁当製造工場等において調理に用いた後に劣化のために廃棄されることとなった動植物油脂を意味する。本発明に使用できる動植物油脂の廃食油としては、例えば天ぷら、トンカツ、フライドチキン等の調理に用いた揚げ油の廃棄品が挙げられるがこれらに限定されない。 About raw material A. Examples of vegetable oils and fats that can be used in the present invention include, but are not limited to, rapeseed oil, canola oil, corn oil, soybean oil, sunflower oil, or safflower oil. Animal fats and oils that can be used in the present invention include but are not limited to pork fat (lard) or beef tallow. Waste cooking oil means animal and vegetable oils and fats that have been discarded due to deterioration after being used for cooking at home, restaurants, fast food stores, bento manufacturing factories, and the like. Examples of the waste edible oil of animal and vegetable oils and fats that can be used in the present invention include, but are not limited to, waste products of fried oil used for cooking such as tempura, tonkatsu, and fried chicken.
原料Ｂについて。本発明において低級アルコールとは、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、ｔ−ブタノール、イソブタノール等の炭素数１〜４のアルコールを意味する。複数種の低級アルコールが混合されたものも用いることができる。なかでもメタノールが好ましい。原料Ｂとしては水、低級アルコール、または水および低級アルコールの混合物を使用できる。水および低級アルコールの混合物の混合率は特に限定されない。原料Ｂとしては水、または水および低級アルコールの混合物が好ましい。 About raw material B. In the present invention, the lower alcohol means an alcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, and isobutanol. What mixed multiple types of lower alcohol can also be used. Of these, methanol is preferable. As the raw material B, water, lower alcohol, or a mixture of water and lower alcohol can be used. The mixing ratio of the mixture of water and lower alcohol is not particularly limited. The raw material B is preferably water or a mixture of water and a lower alcohol.
原料Ａと原料Ｂの混合比率は特に限定されないが、原料Ａの炭化等に起因した製造装置の閉塞を防止できる比率であることが好ましい。より具体的には、原料Ａと原料Ｂの混合比率は原料Ａ：原料Ｂ＝４：１〜１：４（ｖ／ｖ）程度の範囲が好ましい。 Although the mixing ratio of the raw material A and the raw material B is not specifically limited, It is preferable that it is a ratio which can prevent the obstruction | occlusion of the manufacturing apparatus resulting from the carbonization etc. of the raw material A. More specifically, the mixing ratio of the raw material A and the raw material B is preferably in the range of the raw material A: the raw material B = 4: 1 to 1: 4 (v / v).
次に、原料Ａと原料Ｂの混合物を高温高圧下で処理する条件について説明する。圧力条件は、原料Ｂが亜臨界または超臨界状態となり、原料Ａを十分に混和できる圧力であれば特に限定されないが、好ましくは５ＭＰａ〜１００ＭＰａ、より好ましくは２０ＭＰａ〜５０ＭＰａである。温度条件は原料Ａが分解され低分子化される条件であれば特に限定されないが、好ましくは３００℃〜８００℃、より好ましくは４５０℃〜６００℃、更に好ましくは４５０℃〜５５０℃、最も好ましくは５００℃〜５５０℃（ただし５００℃は含まない）である。処理時間は反応が十分進行しうる時間であれば特に限定されないが、好ましくは３分〜６０分、より好ましくは３分〜３０分、更に好ましくは４分〜１６分である。 Next, conditions for treating the mixture of the raw material A and the raw material B under high temperature and high pressure will be described. The pressure condition is not particularly limited as long as the raw material B is in a subcritical or supercritical state and can sufficiently mix the raw material A, but is preferably 5 MPa to 100 MPa, more preferably 20 MPa to 50 MPa. The temperature condition is not particularly limited as long as the raw material A is decomposed and reduced in molecular weight, but is preferably 300 ° C to 800 ° C, more preferably 450 ° C to 600 ° C, still more preferably 450 ° C to 550 ° C, and most preferably. Is 500 ° C. to 550 ° C. (however, 500 ° C. is not included). The treatment time is not particularly limited as long as the reaction can proceed sufficiently, but is preferably 3 minutes to 60 minutes, more preferably 3 minutes to 30 minutes, and further preferably 4 minutes to 16 minutes.
本発明では、３つの処理条件（温度、圧力、時間）を例えば上記範囲内から選択して適宜組合せることにより、反応混合物中の原料Ａを分解して低分子化してガソリンまたは灯油代替燃料の成分を得ることができる。処理温度が高いほど、処理圧力が高いほど、処理時間が長いほど、原料Ａの分解は進む傾向があるため、処理温度が顕著に高い場合、処理圧力が顕著に高い場合、あるいは処理時間が顕著に長い場合には、残りの条件は上記範囲内で比較的自由に選択することができる。例えば、処理温度が５００℃を超える場合には、処理圧力および処理時間は上記の範囲で任意に選択することができる（ただし、処理圧力は高いほど、処理時間は長いほど原料Ａの分解は更に進む傾向がある）。処理圧力が４０ＭＰａ（好ましくは５０ＭＰａ、より好ましくは６０ＭＰａ）を超える場合、処理温度および処理時間は上記の範囲で任意に選択することができる（ただし、処理温度は高いほど、処理時間は長いほど原料Ａの分解は更に進む傾向がある）。処理時間が１２分を超える場合、処理温度および処理圧力は上記の範囲で任意に選択することができる（ただし、処理温度および処理圧力は高いほど原料Ａの分解は更に進む傾向がある）。なお上記の通り、処理温度が高いほど、処理圧力が高いほど、処理時間が長いほど、原料Ａの分解は進む傾向があるが、同時に脂肪酸の重合なども進み易くなるため、所望の生成物を効率的に得るには各条件は前段落に示す上限の範囲内であることが好ましい。 In the present invention, the raw material A in the reaction mixture is decomposed and reduced in molecular weight by appropriately selecting and combining the three processing conditions (temperature, pressure, time) from the above range, for example, for gasoline or kerosene alternative fuel. Ingredients can be obtained. The higher the processing temperature, the higher the processing pressure, the longer the processing time, the more the raw material A decomposes. Therefore, when the processing temperature is significantly higher, the processing pressure is significantly higher, or the processing time is remarkable. In the case of a long time, the remaining conditions can be selected relatively freely within the above range. For example, when the processing temperature exceeds 500 ° C., the processing pressure and the processing time can be arbitrarily selected within the above range (however, the higher the processing pressure, the longer the processing time, the further decomposition of the raw material A). Tend to go forward). When the processing pressure exceeds 40 MPa (preferably 50 MPa, more preferably 60 MPa), the processing temperature and processing time can be arbitrarily selected within the above ranges (however, the higher the processing temperature, the longer the processing time, the raw material The decomposition of A tends to proceed further). When the treatment time exceeds 12 minutes, the treatment temperature and the treatment pressure can be arbitrarily selected within the above ranges (however, the higher the treatment temperature and the treatment pressure, the more the decomposition of the raw material A tends to proceed). As described above, the higher the processing temperature, the higher the processing pressure, and the longer the processing time, the more likely the decomposition of the raw material A tends to proceed, but at the same time, the polymerization of fatty acids and the like easily proceed. In order to obtain efficiently, each condition is preferably within the upper limit range shown in the preceding paragraph.
上記高温高圧処理を経た処理物は気体成分と液体成分とからなる。気体成分にはメタン等が含まれる。この気体成分は好ましくは気体燃料として利用できる。 The processed material that has undergone the high-temperature and high-pressure treatment is composed of a gas component and a liquid component. Gas components include methane and the like. This gaseous component can preferably be used as gaseous fuel.
液体成分は、未反応の原料Ｂ（以下「生成物ａ」という場合がある）、ガソリン代替燃料または灯油代替燃料として使用できる成分（以下「生成物ｂ」という場合がある）、および、軽油代替燃料として使用できる成分（以下「生成物ｃ」という場合がある）を含む。生成物ａ〜ｃは通常の方法（分留、比重選、膜分離、各種クロマトグラフィなど）で分離することができる。 The liquid component includes unreacted raw material B (hereinafter sometimes referred to as “product a”), a component that can be used as a gasoline substitute fuel or kerosene substitute fuel (hereinafter also referred to as “product b”), and a light oil substitute. It contains components that can be used as fuel (hereinafter sometimes referred to as “product c”). The products a to c can be separated by a usual method (fractional distillation, specific gravity selection, membrane separation, various chromatography, etc.).
生成物ａは再び原料Ｂとして利用できる。
生成物ｂの成分は主として分子量８０〜１６０の炭化水素、すなわち直鎖アルカン、アルキル側鎖アルカン、シクロアルカン等である。より具体的には、シクロアルカン類(メチルシクロヘキサン、メチルシクロプロパン、ブチルシクロペンタンなど)、アルカン類(ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカンなど)、脂肪酸メチルエステル類(ペンタン酸メチルエステル、ヘプタン酸メチルエステルなど)、ベンゼン類（ベンゼン、トルエンなど）などである。これらには現在利用されているガソリンとほぼ同じ成分も含まれる。また、反応混合物から生成物ｂへの反応が促進される条件下（温度５１０℃以上、圧力は任意、時間４分以上、特に灯油に相当する成分の収率を向上させたい場合は温度５１０〜５５０℃、圧力４０ＭＰａ以上、時間５〜１０分）では、生成物ｂとしてガソリンに相当する成分と、灯油に相当とする成分が含まれることがある。この場合は、任意の方法でガソリンに相当する成分と、灯油に相当する成分とを分離することが可能である。分離方法の一例を挙げれば、生成物ｂを４０℃、２５０ｈＰａで減圧蒸留することにより、蒸留物としてガソリン相当画分を、残留物として灯油相当画分を得ることができる。生成物ｂは、バイオエタノールと異なり、ガソリン又は灯油とほぼ同様に利用できる。また、任意の割合（例えば１０％（ｖ／ｖ）程度）でガソリン、灯油、軽油、重油等に添加できる添加剤としても利用できる。
Product a can be used again as raw material B.
The component of the product b is mainly a hydrocarbon having a molecular weight of 80 to 160, that is, a linear alkane, an alkyl side chain alkane, a cycloalkane and the like. More specifically, cycloalkanes (such as methylcyclohexane, methylcyclopropane, butylcyclopentane), alkanes (such as hexane, heptane, octane, nonane, decane, undecane), fatty acid methyl esters (pentanoic acid methyl ester, Heptanoic acid methyl ester) and benzenes (benzene, toluene, etc.). These include almost the same components as gasoline currently used. In addition, under conditions where the reaction from the reaction mixture to the product b is promoted (temperature: 510 ° C. or higher, pressure is arbitrary, time is 4 minutes or longer, particularly when the yield of components corresponding to kerosene is to be improved, the temperature is from 510 (550 ° C., pressure 40 MPa or more, time 5 to 10 minutes), the product b may include a component corresponding to gasoline and a component corresponding to kerosene. In this case, the component corresponding to gasoline and the component corresponding to kerosene can be separated by any method. For example, the product b is distilled under reduced pressure at 40 ° C. and 250 hPa to obtain a gasoline-equivalent fraction as a distillate and a kerosene-equivalent fraction as a residue. The product b can be used almost the same as gasoline or kerosene, unlike bioethanol. Moreover, it can utilize also as an additive which can be added to gasoline, kerosene, light oil, heavy oil, etc. in arbitrary ratios (for example, about 10% (v / v)).
生成物cとして、重油あるいは軽油に相当する成分が得られる。生成物bの収率が低い生成条件下では脂肪酸メチルエステルを中心とした軽油に近い燃料が得られ、生成物bの収率を増加させる条件下では脂肪酸等の重合などによる生成物を多く含んだより重油に近い性状の燃料が得られる。これらはディーゼルエンジン、ボイラー、バーナーなどの燃料として利用可能である。 A component corresponding to heavy oil or light oil is obtained as the product c. Under production conditions where the yield of product b is low, a fuel close to light oil centered on fatty acid methyl ester can be obtained, and under conditions where the yield of product b is increased, a lot of products such as fatty acid polymerization are contained. On the other hand, fuel with properties close to heavy oil can be obtained. These can be used as fuel for diesel engines, boilers, and burners.
本発明はまた上記方法を実施するための反応装置に関する。図１には、本発明の装置の最も好ましいと考えられる形態を示す。すなわち、原料Ａと原料Ｂを混合し、混合物を任意の条件で反応装置にて処理する。反応後の処理物は気体成分と液体成分とからなり、両者は気液分離器により分離される。得られた気体成分でガスタービンまたはガスディーゼル発電機等を稼動し電力を得、反応装置に供給する。また、得られた液体成分は分離装置により生成物ａ、ｂ、ｃに分離される。生成物ａは原料Ｂとして再利用できる。生成物ｂは、ガソリン代替燃料及び灯油代替燃料として利用することができる。生成物ｃは軽油代替燃料として利用することができる。生成物ｂおよびｃはまた、重油、軽油、灯油、ガソリン、ジェット燃料等への添加剤として利用することができる。生成物ｃの一部は、反応装置を稼動するためのディーゼル発電機またはボイラーの燃料として用いることができる。それによって、外部からの電力供給を必要とせずに電力を反応装置に供給して反応装置を稼動することができる。 The invention also relates to a reactor for carrying out the above process. FIG. 1 shows the most preferred form of the apparatus of the present invention. That is, the raw material A and the raw material B are mixed, and the mixture is processed in a reactor under arbitrary conditions. The processed product after the reaction consists of a gas component and a liquid component, and both are separated by a gas-liquid separator. A gas turbine or a gas diesel generator or the like is operated with the obtained gas component to obtain electric power, which is supplied to the reactor. Further, the obtained liquid component is separated into products a, b, and c by a separation device. Product a can be reused as raw material B. The product b can be used as a gasoline alternative fuel and a kerosene alternative fuel. The product c can be used as a light oil alternative fuel. Products b and c can also be utilized as additives to heavy oil, light oil, kerosene, gasoline, jet fuel, and the like. Part of the product c can be used as fuel for a diesel generator or boiler for operating the reactor. As a result, the reaction apparatus can be operated by supplying electric power to the reaction apparatus without requiring an external power supply.
本発明により、動植物油脂から、田植え機、管理機、畦畔管理作業などに用いられるガソリン代替燃料の製造が可能となる。 According to the present invention, it is possible to produce a gasoline alternative fuel to be used for planting machines, management machines, shore management work and the like from animal and vegetable fats and oils.
本発明により製造されるガソリン代替燃料または軽油代替燃料は、食品加工工場、廃棄物処理場等、廃油脂が発生する個所において各事業所内の車両および発電機等に利用する軽油代替燃料、ガソリン代替燃料あるいはガソリン用添加剤としての利用が可能であり、二酸化炭素排出量抑制が期待できる。 Gasoline alternative fuel or light oil alternative fuel produced by the present invention is a gas oil alternative fuel, gasoline alternative used in vehicles and generators in each office in places where waste oil and fats are generated, such as food processing factories and waste treatment plants. It can be used as an additive for fuel or gasoline and can be expected to suppress carbon dioxide emissions.
以下に実施例を参照して本発明を具体的に説明するが、本発明はこれらの範囲には限定されない。 The present invention will be specifically described below with reference to examples, but the present invention is not limited to these ranges.
原料Ａとしてキャノーラ油、大豆油、コーン油等とそれらの廃食油の混合物を用いた。原料Ｂとしてメタノールを用いた。原料Ａと原料Ｂの混合比を２：１（ｖ／ｖ）とした。得られた混合物を圧力２０ＭＰａ、反応管出口温度５２２℃、時間５分で処理した。処理後、ロータリーエバポレーターにて減圧蒸留を行ない、生成物ｃと生成物ａおよびｂの混合物とに分離した。分離の際、温度は５０℃、圧力は１００ｈＰａ以下とした。その後、生成物ａおよびｂの混合物を数時間静置し、上層を生成物ｂ、下層を生成物ａとした。さらに生成物ｂを４０℃、２５０ｈＰａで減圧蒸留し、蒸留物である生成物ｂ’（ガソリン相当）と残留物である生成物ｂ’’（灯油相当と推測）を得た。この時、生成物ｂ’、ｂ’’ともに凝固点は−２０℃以下であった。生成物ｂ’をＧＣ／ＭＳを用いて定性分析を行った結果、推測された成分の代表的なものの一部を表１に、生成物ｂ’’の成分と推測された代表的なものの一部を表２に示す。分析にはＡｇｉｌｅｎｔＴｅｃｈｎｏｌｏｇｙ製ガスクロマトグラフィ６８９０Ｎと日本電子データム製質量分析計ＧＣ−ｍａｔｅ ＩＩを用い、カラムにはＡｇｉｌｅｎｔ製ＨＰ−５ＴＡ（１５ｍ ｘ ０．３２ｍ ｘ ０．１μｍ）を用いた。キャリアガスにヘリウム（流量１．５ｍｌ／ｍｉｎ）、オーブン温度は測定開始時に５０℃で１分間保持し、その後２５０℃までは１０℃／ｍｉｎ、３６５℃までは１５℃／ｍｉｎで昇温し３６５℃で８分間保持するよう設定した。また、注入口温度２２０℃、スプリット比４００：１、注入量１μｌとし、試料の希釈は行わなかった。 As the raw material A, a mixture of canola oil, soybean oil, corn oil and the like and waste cooking oils thereof was used. Methanol was used as the raw material B. The mixing ratio of the raw material A and the raw material B was 2: 1 (v / v). The obtained mixture was treated at a pressure of 20 MPa, a reaction tube outlet temperature of 522 ° C., and a time of 5 minutes. After the treatment, vacuum distillation was performed on a rotary evaporator to separate into product c and a mixture of products a and b. During the separation, the temperature was 50 ° C. and the pressure was 100 hPa or less. Thereafter, the mixture of the products a and b was allowed to stand for several hours, and the upper layer was the product b and the lower layer was the product a. Further, the product b was distilled under reduced pressure at 40 ° C. and 250 hPa to obtain a product b ′ (equivalent to gasoline) as a distillate and a product b ″ (estimated as equivalent to kerosene) as a residue. At this time, the freezing points of the products b ′ and b ″ were −20 ° C. or lower. As a result of qualitative analysis of the product b ′ using GC / MS, some of the typical components estimated are shown in Table 1, and one of the typical components estimated as the component of the product b ″ is shown in Table 1. The parts are shown in Table 2. Agilent Technologies gas chromatography 6890N and JEOL Datum mass spectrometer GC-mate II were used for analysis, and Agilent HP-5TA (15 m × 0.32 m × 0.1 μm) was used for the column. The carrier gas is helium (flow rate 1.5 ml / min), the oven temperature is maintained at 50 ° C. for 1 minute at the start of measurement, and then the temperature is increased to 10 ° C./min up to 250 ° C. and 15 ° C./min up to 365 ° C. 365 It was set to hold at 8 ° C for 8 minutes. The inlet temperature was 220 ° C., the split ratio was 400: 1, the injection volume was 1 μl, and the sample was not diluted.
また、生成物ｂ’の性状をガソリンの品質要求規格に従い測定したところ、表３のようになった。一部を除いてガソリンの要求品質規格を満たしていた。 Further, the properties of the product b 'were measured in accordance with gasoline quality requirement standards, and as shown in Table 3. Except for some, it met the required quality standards for gasoline.
この生成物ｂ’をさらに３０℃、１５０ｈＰａで減圧蒸留し、得られた蒸留物の蒸留性状および実在ガムを測定したところ、表４のようにそれぞれ低下させることができ、よりガソリン規格に合致するものとなった。これらの結果から、この時点で規格外の項目についても添加剤等の使用、あるいはガソリンとの混合によって規格を満たすことが可能であると考えられた。 This product b ′ was further distilled under reduced pressure at 30 ° C. and 150 hPa, and the distillation properties and the actual gum of the obtained distillate were measured. As a result, they could be reduced as shown in Table 4, and more conform to gasoline standards. It became a thing. From these results, it was considered that it was possible to satisfy the standard by using an additive or the like or mixing with gasoline for items outside the standard at this point.
また、生成物ｂ’をホンダ製歩行型耕耘機に１００％で供試したところ、始動、走行および耕耘作業に問題は生じなかった。 Further, when the product b 'was tested at 100% on a Honda walking type tiller, no problems occurred in starting, running, and tilling work.
原料Ａとしてキャノーラ油、大豆油、コーン油等とそれらの廃食油の混合物を用いた。原料Ｂとしてメタノールを用いた。原料Ａと原料Ｂの混合比を２：１（ｖ／ｖ）とした。得られた混合物を圧力２０ＭＰａ、反応管出口温度４００〜５４０℃、時間５分で処理した。処理後、ロータリーエバポレーターにて減圧蒸留を行ない、生成物ｃと生成物ａおよびｂの混合物に分離した。分離の際、温度は４０℃、圧力の下限を１００ｈＰａとした。その後、生成物ａおよびｂの混合物を遠心分離機で３０００ｒｐｍ、１５分、０℃で処理し、上層を生成物ｂ、下層を生成物ａとした。
各反応温度条件における生成物ｂの原料Ａの重量に対する生成率を図２に示す。
As the raw material A, a mixture of canola oil, soybean oil, corn oil and the like and waste cooking oils thereof was used. Methanol was used as the raw material B. The mixing ratio of the raw material A and the raw material B was 2: 1 (v / v). The resulting mixture was treated at a pressure of 20 MPa, a reaction tube outlet temperature of 400 to 540 ° C., and a time of 5 minutes. After the treatment, vacuum distillation was performed on a rotary evaporator to separate into a mixture of product c and products a and b. During the separation, the temperature was 40 ° C., and the lower limit of the pressure was 100 hPa. Thereafter, the mixture of products a and b was treated with a centrifuge at 3000 rpm for 15 minutes at 0 ° C., and the upper layer was product b and the lower layer was product a.
The production rate of the product b with respect to the weight of the raw material A under each reaction temperature condition is shown in FIG.
原料Ａとしてキャノーラ油、大豆油、コーン油等とそれらの廃食油の混合物を用いた。原料Ｂとして水を用いた。原料Ａに対して原料Ｂを容積比で５０％の割合で混入した（原料Ａと原料Ｂの混合比を２：１（ｖ／ｖ）とした）。得られた混合物を、圧力２０ＭＰａ、反応管出口温度５１４℃、時間５分で処理した。 As the raw material A, a mixture of canola oil, soybean oil, corn oil and the like and waste cooking oils thereof was used. Water was used as the raw material B. The raw material B was mixed in a volume ratio of 50% with respect to the raw material A (the mixing ratio of the raw material A and the raw material B was 2: 1 (v / v)). The obtained mixture was treated at a pressure of 20 MPa, a reaction tube outlet temperature of 514 ° C., and a time of 5 minutes.
処理終了後、原料Ａ＋原料Ｂの総重量に対して約９０重量％の液体成分が回収された。得られた液体成分のうち、約２０重量％が生成物ａに相当する水、約４重量％が生成物ｂに相当するガソリン代替成分、約７５重量％が生成物ｃに相当する軽油代替成分であった。 After the treatment, about 90% by weight of the liquid component was recovered with respect to the total weight of the raw material A + the raw material B. Of the obtained liquid component, about 20% by weight of water corresponding to product a, about 4% by weight of gasoline substitute component corresponding to product b, and about 75% by weight of light oil substitute component corresponding to product c Met.
原料Ａとしてそば屋から排出された廃食油（キャノーラ油および大豆油が中心と推測される）を用いた。原料Ｂとして水を用いた。原料Ａと原料Ｂの混合比を１：１（ｖ／ｖ）とした。得られた混合物を、圧力３０ＭＰａ、反応管出口温度５３２℃、時間５分で処理した。 Waste edible oil discharged from buckwheat noodles (presumed to be canola oil and soybean oil) was used as raw material A. Water was used as the raw material B. The mixing ratio of the raw material A and the raw material B was 1: 1 (v / v). The obtained mixture was treated at a pressure of 30 MPa, a reaction tube outlet temperature of 532 ° C., and a time of 5 minutes.
処理終了後、原料Ａ＋原料Ｂの総重量に対して約９０重量％の液体成分が回収された。得られた液体成分のうち、約４０重量％が生成物ａに相当する水、約７重量％が生成物ｂ’に相当するガソリン代替成分、約３重量％が生成物ｂ’’に相当する灯油代替成分、約４０重量％が生成物ｃに相当する軽油代替成分であった。 After the treatment, about 90% by weight of the liquid component was recovered with respect to the total weight of the raw material A + the raw material B. About 40% by weight of the obtained liquid component corresponds to water corresponding to the product a, about 7% by weight corresponds to the gasoline substitute component corresponding to the product b ′, and about 3% by weight corresponds to the product b ″. About 40% by weight of the kerosene substitute component was a light oil substitute component corresponding to the product c.
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