JP2015067800A - Manufacturing method of hydrocarbon - Google Patents
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Abstract
Description
本発明は、セルロース系バイオマスから炭化水素を製造する方法に関し、特に、触媒の存在下でセルロース系バイオマスから糖類を経て炭化水素を得る製造方法に関する。 The present invention relates to a method for producing hydrocarbons from cellulosic biomass, and more particularly to a production method for obtaining hydrocarbons from cellulosic biomass via saccharides in the presence of a catalyst.
セルロース系バイオマスから燃料基材としての炭化水素を製造する方法が提案されている。例えば、セルロース系バイオマスを熱化学反応で一酸化炭素及び水素にガス化し、鉄やコバルトなどの化合物からなる触媒を用いたフィッシャー・トロプシュ（ＦＴ）法で液体炭化水素を合成する方法などが知られている。一般的にセルロース系バイオマスは水に溶解しないことから、上記したようなガス化を利用することが多いが、これを経由しない方法も提案されている。 A method for producing a hydrocarbon as a fuel base material from cellulosic biomass has been proposed. For example, a method is known in which cellulosic biomass is gasified into carbon monoxide and hydrogen by a thermochemical reaction and liquid hydrocarbons are synthesized by a Fischer-Tropsch (FT) method using a catalyst made of a compound such as iron or cobalt. ing. Since cellulosic biomass generally does not dissolve in water, gasification as described above is often used, but methods that do not go through this have also been proposed.
例えば、特許文献１では、セルロースや木粉などのバイオマス原料をアルコールで前処理した後に、触媒の存在下で水素化させて酸素を含まない炭化水素混合物を製造する方法を開示している。詳細には、メタノールなどのモノアルコールやエチレングリコールなどの多価アルコールからなるアルコール中でバイオマス原料を前処理し、周期律表第１０族に属する金属又はこれを含む化合物によって修飾した多孔性固体酸化物を含有する触媒、例えば、白金／Ｈ−ＺＳＭ−５等を用いて水素化し、炭化水素混合物を製造している。かかる方法によれば、炭素数２〜９程度の炭化水素を収率よく製造できるとしている。 For example, Patent Document 1 discloses a method for producing a hydrocarbon mixture containing no oxygen by pretreatment of biomass raw materials such as cellulose and wood flour with alcohol and then hydrogenating them in the presence of a catalyst. Specifically, a porous solid oxide obtained by pretreating a biomass raw material in an alcohol composed of a monoalcohol such as methanol or a polyhydric alcohol such as ethylene glycol and modified with a metal belonging to Group 10 of the periodic table or a compound containing the same. A hydrocarbon mixture is produced by hydrogenation using a catalyst containing a product such as platinum / H-ZSM-5. According to this method, hydrocarbons having about 2 to 9 carbon atoms can be produced with high yield.
ところで、セルロース系バイオマスからガス化を利用せず燃料基材を製造するには、まずセルロースを加水分解して糖化させ単糖類であるグルコースを得る。これを水素化して得た多価アルコールを脱水及び水素化させると炭化水素が得られる。かかる多段階反応では、所定の化合物についての選択率を高めその収率を上げるのに適した触媒がそれぞれ用いられる。 By the way, in order to produce a fuel base material without using gasification from cellulosic biomass, first, cellulose is hydrolyzed and saccharified to obtain glucose which is a monosaccharide. When the polyhydric alcohol obtained by hydrogenating this is dehydrated and hydrogenated, hydrocarbons are obtained. In such a multistage reaction, a catalyst suitable for increasing the selectivity for a given compound and increasing its yield is used.
例えば、特許文献２では、グルコースやキシロースと同様に、エーテル結合を有する環状エーテルを水素化して還元する方法として、Ｒｈ（ロジウム）触媒とともに、Ｒｅ（レニウム）、Ｍｏ、及び、Ｗから選択された１種又は２種以上の金属元素を共存させることを開示している。触媒の必須の活性成分はＲｈである一方で、Ｐｄ、Ｐｔ等のＲｈ以外の貴金属を用いても環状エーテルを開環させることは可能ではあるが、その収率が高くないことを述べている。また、Ｒｅなどの金属元素を共存させることで、環状エーテルの開裂位置の選択性が高まることで、所定の多価アルコールを高い選択率で収率を上げて得られるとしている。 For example, in Patent Document 2, as with glucose and xylose, a method of hydrogenating and reducing a cyclic ether having an ether bond was selected from Re (rhenium), Mo, and W together with an Rh (rhodium) catalyst. It discloses that one or more metal elements coexist. While the essential active component of the catalyst is Rh, it is possible to open the cyclic ether using noble metals other than Rh such as Pd and Pt, but the yield is not high. . In addition, by coexisting a metal element such as Re, the selectivity of the cleavage position of the cyclic ether is increased, so that a predetermined polyhydric alcohol can be obtained with a high selectivity and a high yield.
また、例えば、特許文献３では、多価アルコールの１種であるグリセリンの還元方法として、触媒としてのＲｕ（ルテニウム）とともに、ＳＯ２濃度を所定範囲にしたイオン交換樹脂を使用することを開示している。ここでも、Ｒｅ、Ｍｏ、及び、Ｗなどから選択された１種又は２種以上の金属元素を共存させることで、所定のグリセリン還元化合物の選択率が高まることを述べている。特に、Ｒｅを共存させた場合、ＲｅとＲｕのモル比（［Ｒｅ］／［Ｒｕ］）に係わらず、グリセリンの転化率が向上し、且つ、１，２−プロパンジオール及び１，３−プロパンジオールの選択率が高まるとしている。 In addition, for example, Patent Document 3 discloses the use of an ion exchange resin having a SO 2 concentration in a predetermined range together with Ru (ruthenium) as a catalyst as a method for reducing glycerin, which is one of polyhydric alcohols. ing. Here too, it is stated that the selectivity of a predetermined glycerin reducing compound is increased by the coexistence of one or more metal elements selected from Re, Mo and W. In particular, when Re coexists, the conversion of glycerin is improved regardless of the molar ratio of Re to Ru ([Re] / [Ru]), and 1,2-propanediol and 1,3-propane are improved. The selectivity of diol is said to increase.
同様に、特許文献４では、グリセリンの還元方法として、触媒としてのＩｒ（イリジウム）とともに、Ｒｅ、Ｍｏ、及び、Ｗなどから選択された１種又は２種以上の金属元素を共存させることを開示している。活性炭などにＩｒを担持させた触媒では特定のグリセリン還元化合物を高い選択率で得ることはできないが、上記したＭｏなどの金属元素を共存させることでこの選択率を向上できるとしている。 Similarly, Patent Document 4 discloses that as a method for reducing glycerin, one or more metal elements selected from Re, Mo, W and the like are coexisted with Ir (iridium) as a catalyst. doing. A catalyst in which Ir is supported on activated carbon or the like cannot obtain a specific glycerin reducing compound with high selectivity, but it is said that this selectivity can be improved by coexisting a metal element such as Mo described above.
セルロース系バイオマスから燃料基材を製造する方法において、燃料基材として炭素数の大きい炭化水素が求められる。例えば、セルロースを加水分解して得られるグルコースはＣ６Ｈ１２Ｏ６の分子式で表されるが、これを脱水及び水素化して得られるもっとも炭素数の大きい炭化水素はヘキサンである。しかしながら、上記したようにセルロース系バイオマスから燃料基材を製造する行程において、従来の加水分解や脱水・水素化触媒を用いると、断片化して有機酸に変化したり、水素化分解して炭素数の小さい炭化水素となったりして、ヘキサンの選択率が上がらずその収率は低くなってしまう。 In a method for producing a fuel base material from cellulosic biomass, a hydrocarbon having a large carbon number is required as the fuel base material. For example, glucose obtained by hydrolyzing cellulose is represented by a molecular formula of C 6 H 12 O 6 , and the hydrocarbon having the largest carbon number obtained by dehydration and hydrogenation thereof is hexane. However, as described above, in the process of producing a fuel base material from cellulosic biomass, if a conventional hydrolysis or dehydration / hydrogenation catalyst is used, it is fragmented to change into an organic acid or hydrocracked to have a carbon number. As a result, the selectivity of hexane does not increase and the yield decreases.
そこで、本発明は、上記したような状況に鑑みてなされたものであって、その目的とするところは、触媒の存在下でセルロース系バイオマスから糖類を経て炭素数のより多い炭化水素を高い収率で得ることのできる炭化水素の製造方法を提供することにある。 Therefore, the present invention has been made in view of the above situation, and the object of the present invention is to obtain a high yield of hydrocarbons having a higher carbon number from cellulosic biomass via sugars in the presence of a catalyst. An object of the present invention is to provide a hydrocarbon production method that can be obtained at a high rate.
本発明によるセルロース系バイオマスから炭化水素を製造する方法は、セルロース系バイオマスを加水分解し糖化させて糖類を得る第１の反応行程と、前記糖類を水素化して得た糖アルコールを水素化分解して炭化水素を得る第２の反応行程と、を含み、前記第１の反応行程及び前記第２の反応行程を同一のＩｒ−Ｒｅ（イリジウム−レニウム）系触媒の存在下で進行させ、主として前記第１の反応行程で得た糖類の炭素数を維持した炭化水素を得ることを特徴とする。 The method for producing hydrocarbons from cellulosic biomass according to the present invention includes a first reaction step of hydrolyzing cellulosic biomass and saccharifying it to obtain a saccharide, and hydrocracking a sugar alcohol obtained by hydrogenating the saccharide. A second reaction step for obtaining hydrocarbons, and the first reaction step and the second reaction step are allowed to proceed in the presence of the same Ir-Re (iridium-rhenium) -based catalyst, The hydrocarbon obtained by maintaining the carbon number of the saccharide obtained in the first reaction step is characterized.
また、上記した発明において、前記炭化水素の収率は２０％以上であることを特徴としてもよい。 In the above invention, the yield of the hydrocarbon may be 20% or more.
かかる発明によれば、多段階反応を同一の触媒の存在下で進行させて個々の反応間での反応効率を高めることができ、より高い収率で特定の炭化水素が得られる。特に、Ｉｒ−Ｒｅ系触媒を用いることで、セルロース系バイオマスから主として前記第１の反応行程で得た糖類の炭素数を維持した炭化水素を高い収率で得られるのである。 According to this invention, the multistage reaction can proceed in the presence of the same catalyst to increase the reaction efficiency between individual reactions, and a specific hydrocarbon can be obtained with a higher yield. In particular, by using an Ir-Re catalyst, a hydrocarbon maintaining the carbon number of the saccharide obtained mainly from the cellulosic biomass in the first reaction step can be obtained in a high yield.
上記した発明において、前記Ｉｒ−Ｒｅ系触媒はＩｒ−ＲｅＯｘ／ＳｉＯ２であることを特徴としてもよい。かかる発明によれば、より高い収率でセルロース系バイオマスから主として前記第１の反応行程で得た糖類の炭素数を維持した炭化水素を得られるのである。 In the above-described invention, the Ir—Re catalyst may be Ir—ReOx / SiO 2 . According to this invention, it is possible to obtain a hydrocarbon maintaining the carbon number of the saccharide obtained mainly from the cellulosic biomass in the first reaction step with a higher yield.
また、上記した発明において、前記第１の反応行程はグルコースを主とする炭素数６の単糖を得る行程であって、前記第２の反応行程はソルビトールを主とする炭素数６の糖アルコールから主としてヘキサンを得ることを特徴としてもよい。かかる発明によれば、より高い収率でセルロース系バイオマス中のセルロースから主としてヘキサンを得られるのである。 In the above-described invention, the first reaction step is a step of obtaining a monosaccharide having 6 carbons mainly including glucose, and the second reaction step is a sugar alcohol having 6 carbons mainly including sorbitol. It is good also as obtaining hexane mainly from. According to this invention, hexane can be mainly obtained from cellulose in cellulosic biomass with higher yield.
さらに、上記した発明において、前記第１の反応行程はキシロースを主とする炭素数５の単糖を得る行程であって、前記第２の反応行程はキシリトールを主とする炭素数５の糖アルコールから主としてペンタンを得ることを特徴としてもよい。かかる発明によれば、より高い収率でセルロース系バイオマス中のヘミセルロースから主としてペンタンを得られるのである。 Furthermore, in the above-described invention, the first reaction step is a step of obtaining a monosaccharide having 5 carbon atoms mainly including xylose, and the second reaction step is a sugar alcohol having 5 carbon atoms mainly including xylitol. Mainly, pentane may be obtained from According to this invention, pentane can be mainly obtained from hemicellulose in cellulosic biomass with a higher yield.
さらにまた、上記した発明において、前記第１の反応行程及び第２の反応行程を同一の反応容器内で進行させることを特徴としてもよい。かかる発明によれば、多段階反応の個々の反応間でのロスを減じて反応効率を高めることができ、より高い収率でセルロース系バイオマスから主として前記第１の反応行程で得た糖類の炭素数を維持した炭化水素を得られるのである。 Furthermore, in the above-described invention, the first reaction step and the second reaction step may be advanced in the same reaction vessel. According to this invention, it is possible to increase the reaction efficiency by reducing the loss between the individual reactions of the multistage reaction, and the carbon of the saccharide obtained mainly from the cellulosic biomass in the first reaction step with a higher yield. The number of hydrocarbons can be obtained.
以下に、本発明の炭化水素の製造方法について詳細に説明する。
本発明の炭化水素の製造方法は、セルロース系バイオマスから炭化水素を製造する方法である。ここで、セルロース系バイオマスとしては、セルロースやヘミセルロース等を主として含むものであれば特に限定されないが、例えば、稲藁や麦藁等の藁類、籾殻、草本類などの農業系バイオマス、または、林地残材、製材所廃材、剪定枝、果樹剪定枝、建築解体廃材、新増築廃材などの木質系バイオマス等が好ましい。
Below, the manufacturing method of the hydrocarbon of this invention is demonstrated in detail.
The method for producing hydrocarbons of the present invention is a method for producing hydrocarbons from cellulosic biomass. Here, the cellulosic biomass is not particularly limited as long as it mainly contains cellulose, hemicellulose, and the like. Woody biomass such as lumber, sawmill waste, pruned branches, fruit tree pruned branches, building demolition waste, new extension waste, and the like are preferable.
図１は、本発明における反応の一例を示す図である。第１の反応行程では、セルロース系バイオマス中のセルロースを加水分解し糖化させることで、炭素数が６のグルコースを得ている。さらに、第２の反応行程では、グルコースを水素化して炭素数が６の糖アルコールであるソルビトールを生成させ、さらに水素化分解反応によって炭素数が６のヘキサンを得ている。 FIG. 1 is a diagram showing an example of the reaction in the present invention. In the first reaction step, glucose having 6 carbon atoms is obtained by hydrolyzing and saccharifying cellulose in cellulosic biomass. Further, in the second reaction step, glucose is hydrogenated to generate sorbitol, which is a sugar alcohol having 6 carbon atoms, and hexane having 6 carbon atoms is obtained by a hydrogenolysis reaction.
図２は、本発明における反応の他の一例を示す図である。第１の反応行程では、セルロース系バイオマス中のヘミセルロースを加水分解し糖化させることで、炭素数が５のキシロースを得ている。さらに、第２の反応行程では、キシロースを水素化して炭素数が５の糖アルコールであるキシリトールを生成させ、さらに水素化分解反応によって炭素数が５のペンタンを得ている。 FIG. 2 is a diagram showing another example of the reaction in the present invention. In the first reaction step, xylose having 5 carbon atoms is obtained by hydrolyzing and saccharifying hemicellulose in cellulosic biomass. Furthermore, in the second reaction step, xylose is hydrogenated to produce xylitol, which is a sugar alcohol having 5 carbon atoms, and pentane having 5 carbon atoms is obtained by a hydrogenolysis reaction.
また、本発明では、かかる第１の反応行程及び第２の反応行程を同一のＩｒ−Ｒｅ系触媒の存在下で進行させている。これにより、主として第１の反応行程で得た糖類の炭素数を維持した炭化水素を得ることができる。 In the present invention, the first reaction step and the second reaction step are allowed to proceed in the presence of the same Ir-Re catalyst. Thereby, the hydrocarbon which maintained the carbon number of the saccharide mainly obtained in the 1st reaction process can be obtained.
さらに、本発明では、得られた炭化水素のうち、第１の反応行程で得られた糖類と同じ炭素数である炭化水素の収率が多いことが好ましく、第１の反応行程で得られた糖類より少ない炭素数である炭化水素の生成を抑制するものである。具体的には、図１の例では炭素数が５以下の炭化水素の生成を抑制して炭素数が６のヘキサンの収率が最も多く、図２の例では炭素数が４以下の炭化水素の生成を抑制して炭素数が５のペンタンの収率が最も多くなる。 Furthermore, in the present invention, among the obtained hydrocarbons, it is preferable that the yield of hydrocarbons having the same carbon number as the saccharide obtained in the first reaction step is high, and the hydrocarbon obtained in the first reaction step is obtained. It suppresses the production of hydrocarbons with fewer carbons than sugars. Specifically, in the example of FIG. 1, the production of hydrocarbons having 5 or less carbon atoms is suppressed and the yield of hexane having 6 carbon atoms is the highest, and in the example of FIG. 2, hydrocarbons having 4 or less carbon atoms. The yield of pentane having 5 carbon atoms is maximized.
ここで、収率はセルロースまたはヘミセルロースから変換された着目する生成物の収率であり、次式で与えられる。
収率（％）＝（着目する生成物の総炭素モル数）／（セルロースまたはヘミセルロースの総炭素モル数）×１００
例えば、「着目する生成物の総炭素モル数」は、ガスクロマトグラフ及び高速液体クロマトグラフにより分析された着目する生成物のモル数にその生成物の炭素数をかけて算出できる。また、「セルロースまたはヘミセルロースの総炭素モル数」は、反応容器に仕込んだセルロースまたはヘミセルロースの単糖単位のモル数にそれぞれの単糖単位の炭素数をかけて算出できる。
Here, the yield is the yield of the product of interest converted from cellulose or hemicellulose and is given by:
Yield (%) = (Total number of moles of carbon of product of interest) / (Total number of moles of carbon in cellulose or hemicellulose) × 100
For example, the “total number of carbon moles of the product of interest” can be calculated by multiplying the number of moles of the product of interest analyzed by the gas chromatograph and the high performance liquid chromatograph by the number of carbons of the product. The “total number of moles of carbon of cellulose or hemicellulose” can be calculated by multiplying the number of moles of monosaccharide units of cellulose or hemicellulose charged in the reaction vessel by the number of carbons of each monosaccharide unit.
すると、本発明では、「第１の反応行程で得られた糖類と同じ炭素数である炭化水素」の割合として、上記した収率を用いると、２０％以上を得ることが出来て、３０％以上であることが好ましく、６０％以上であることがさらに好ましく、８０％以上であることがさらにより好ましい。 Then, in the present invention, when the above-mentioned yield is used as the ratio of “hydrocarbon having the same carbon number as the saccharide obtained in the first reaction step”, 20% or more can be obtained, and 30% Preferably, it is 60% or more, more preferably 80% or more.
さらに、本発明において、Ｉｒ−Ｒｅ系触媒としては、ＩｒとＲｅを含むものであれば特に限定されないが、Ｉｒ−ＲｅＯｘ／ＳｉＯ２であることが好ましい。ここで、ＲｅＯｘにおけるｘは酸化数を示し、任意の実数である。 Furthermore, in the present invention, the Ir—Re catalyst is not particularly limited as long as it contains Ir and Re, but Ir—ReOx / SiO 2 is preferable. Here, x in ReOx represents an oxidation number and is an arbitrary real number.
さらにまた、本発明の炭化水素の製造方法は、前記第１の反応行程及び前記第２の反応行程を同一の反応容器内で進行させることが好ましい。かかる反応容器としては、炭化水素の製造方法に使用でき、加圧及び加熱に耐久性があれば特に限定されない。 Furthermore, in the hydrocarbon production method of the present invention, it is preferable that the first reaction step and the second reaction step are carried out in the same reaction vessel. Such a reaction vessel is not particularly limited as long as it can be used in a hydrocarbon production method and has durability in pressurization and heating.
上記した触媒のうち代表としてＩｒ／Ｒｅ／ＳｉＯ２触媒（Ｒｅ／Ｉｒ＝２（ｍｏｌ比））を調製してセルロース系バイオマスから炭化水素を得る試験を行った。以下にその詳細について説明する。 As a representative of the above catalysts, an Ir / Re / SiO 2 catalyst (Re / Ir = 2 (mol ratio)) was prepared and a test for obtaining hydrocarbons from cellulosic biomass was conducted. The details will be described below.
［触媒の調製］
二酸化ケイ素（ＳｉＯ２）（富士シリシア化学株式会社製「ＣＡＲｉＡＣＴ Ｇ−６」）を担体とし、塩化イリジウム酸（Ｈ２ＩｒＣｌ６）水溶液を滴下して、担体全体を湿潤させ、９０℃程度で乾燥させる。かかる湿潤及び乾燥を繰り返して、Ｉｒが二酸化ケイ素に対して４質量％になるように担持させた後、１１０℃で終夜乾燥させた。次に、過レニウム酸アンモニウム（ＮＨ４ＲｅＯ４）水溶液により、同様に湿潤及び乾燥を繰り返して、ＲｅがＩｒに対してＲｅ／Ｉｒ＝２になるように担持させた。その後、空気雰囲気下で、５００℃、３時間焼成して、触媒としてＩｒ／Ｒｅ／ＳｉＯ２、Ｒｅ／Ｉｒ＝２を得た。
[Preparation of catalyst]
Silicon dioxide (SiO 2 ) (“CariACT G-6” manufactured by Fuji Silysia Chemical Co., Ltd.) is used as a carrier, an aqueous solution of chloroiridium acid (H 2 IrCl 6 ) is added dropwise to wet the whole carrier, and dried at about 90 ° C. Let Such wetting and drying were repeated so that Ir was supported at 4% by mass with respect to silicon dioxide, and then dried at 110 ° C. overnight. Next, wetting and drying were repeated in the same manner with an aqueous ammonium perrhenate (NH 4 ReO 4 ) solution so that Re was Re / Ir = 2 with respect to Ir. Thereafter, it was calcined in an air atmosphere at 500 ° C. for 3 hours to obtain Ir / Re / SiO 2 and Re / Ir = 2 as catalysts.
［還元処理］
反応容器として、ガラス製内管を有するＳＵＳ３１６製オートクレーブ（容量：１９０ｍＬ）を用意した。オートクレーブは内部を加熱できるよう周囲に電気炉を配置させる。また、内部を攪拌できるように、マグネチックスターラーを下方に配置させて、内管の内側にテフロン（登録商標）コーティングを施されたマグネチックスターラーチップ（攪拌子）を収容させる。上記した触媒の調製で得られた触媒を０．１５ｇ、Ｈ−ＺＳＭ−５（シリカ／アルミナ比の小さなゼオライト化合物）０．０６ｇ、水９．５ｇを反応容器に入れ、水素置換作業を三回以上繰り返した後、反応容器内が２００℃になった時に、全圧を８ＭＰａとするように水素を導入し、２００℃で１時間保持して触媒を還元させた。還元処理後の触媒を収容する反応容器は複数用意され、後述する複数の実施例のそれぞれにおいて使用される。
[Reduction treatment]
A SUS316 autoclave (capacity: 190 mL) having a glass inner tube was prepared as a reaction vessel. The autoclave has an electric furnace around it so that the inside can be heated. Further, a magnetic stirrer chip (stirring bar) having a Teflon (registered trademark) coating on the inner side of the inner tube is accommodated by arranging a magnetic stirrer downward so that the inside can be stirred. 0.15 g of the catalyst obtained by the above catalyst preparation, 0.06 g of H-ZSM-5 (zeolite compound having a small silica / alumina ratio), and 9.5 g of water were put in a reaction vessel, and the hydrogen replacement operation was performed three times. After repeating the above, when the inside of the reaction vessel reached 200 ° C., hydrogen was introduced so that the total pressure was 8 MPa, and the catalyst was reduced by maintaining at 200 ° C. for 1 hour. A plurality of reaction vessels for storing the catalyst after the reduction treatment are prepared and used in each of a plurality of examples described later.
［ミル処理］
反応に用いるセルロースには予めミル処理を施しておく。後述する実施例１〜７におけるミル処理では、ＺｒＯ２球を１００個投入したドラムの回転数を３００ｒｐｍとした上で、「１．５時間順回転、１時間静止、１．５時間逆回転、１時間静止」の工程を４回繰り返した。後述する実施例７におけるミル処理では、「１．５時間順回転」の工程を１回のみとした。
[Mill processing]
The cellulose used for the reaction is previously milled. In the mill processing in Examples 1 to 7 to be described later, after the rotation speed of the drum into which 100 ZrO 2 balls were thrown 100 was set to 300 rpm, “1.5 hour forward rotation, 1 hour stationary, 1.5 hour reverse rotation, The process of “1 hour rest” was repeated 4 times. In the milling process in Example 7 to be described later, the “1.5 hour forward rotation” step was performed only once.
上記した還元処理後の触媒を有する反応容器内に、ミル処理を施したセルロース０．５ｇを添加した。反応容器内には、さらに、分析用としてｎ−ドデカン４ｍＬを加え、室温で水素を５ＭＰａにて導入した上で、１９０℃で２時間保持して反応させた。反応後の生成物をガスクロマトグラフ及び高速液体クロマトグラフにより分析し、その結果を下記表１に示す。 In the reaction vessel having the catalyst after the reduction treatment described above, 0.5 g of milled cellulose was added. In the reaction vessel, 4 mL of n-dodecane was further added for analysis, hydrogen was introduced at room temperature at 5 MPa, and the reaction was continued at 190 ° C. for 2 hours. The product after the reaction was analyzed by gas chromatography and high performance liquid chromatography, and the results are shown in Table 1 below.
上記した還元処理後の触媒を有する反応容器内に、ミル処理を施したセルロース０．５ｇを添加した。反応容器内には、さらに、分析用としてｎ−ドデカン４ｍＬを加え、室温で水素を５ＭＰａにて導入した上で、１９０℃で５時間保持して反応させた。反応後の生成物をガスクロマトグラフ及び高速液体クロマトグラフにより分析し、その結果を下記表１に示す。 In the reaction vessel having the catalyst after the reduction treatment described above, 0.5 g of milled cellulose was added. Further, 4 mL of n-dodecane was added for analysis in the reaction vessel, hydrogen was introduced at room temperature at 5 MPa, and the reaction was carried out by maintaining at 190 ° C. for 5 hours. The product after the reaction was analyzed by gas chromatography and high performance liquid chromatography, and the results are shown in Table 1 below.
上記した還元処理後の触媒を有する反応容器内に、ミル処理を施したセルロース０．５ｇを添加した。反応容器内には、さらに、分析用としてｎ−ドデカン４ｍＬを加え、室温で水素を５ＭＰａにて導入した上で、１９０℃で１０．５時間保持して反応させた。反応後の生成物をガスクロマトグラフ及び高速液体クロマトグラフにより分析し、その結果を下記表１に示す。 In the reaction vessel having the catalyst after the reduction treatment described above, 0.5 g of milled cellulose was added. In the reaction vessel, 4 mL of n-dodecane was further added for analysis, hydrogen was introduced at room temperature at 5 MPa, and the reaction was continued at 190 ° C. for 10.5 hours. The product after the reaction was analyzed by gas chromatography and high performance liquid chromatography, and the results are shown in Table 1 below.
上記した還元処理後の触媒を有する反応容器内に、ミル処理を施したセルロース０．５ｇを添加した。反応容器内には、さらに、分析用としてｎ−ドデカン４ｍＬを加え、室温で水素を５ＭＰａにて導入した上で、１９０℃で２４時間保持して反応させた。反応後の生成物をガスクロマトグラフ及び高速液体クロマトグラフにより分析し、その結果を下記表１に示す。 In the reaction vessel having the catalyst after the reduction treatment described above, 0.5 g of milled cellulose was added. Further, 4 mL of n-dodecane was added for analysis in the reaction vessel, hydrogen was introduced at room temperature at 5 MPa, and the reaction was carried out by maintaining at 190 ° C. for 24 hours. The product after the reaction was analyzed by gas chromatography and high performance liquid chromatography, and the results are shown in Table 1 below.
上記した還元処理後の触媒を有する反応容器内に、ミル処理を施したセルロース０．５ｇを添加した。反応容器内には、さらに、分析用としてｎ−ドデカン４ｍＬを加え、室温で水素を５ＭＰａにて導入した上で、１５０℃で２４時間保持して反応させた。反応後の生成物をガスクロマトグラフ及び高速液体クロマトグラフにより分析し、その結果を下記表１に示す。 In the reaction vessel having the catalyst after the reduction treatment described above, 0.5 g of milled cellulose was added. In the reaction vessel, 4 mL of n-dodecane was further added for analysis, hydrogen was introduced at room temperature at 5 MPa, and the reaction was carried out by maintaining at 150 ° C. for 24 hours. The product after the reaction was analyzed by gas chromatography and high performance liquid chromatography, and the results are shown in Table 1 below.
上記した還元処理後の触媒を有する反応容器内に、ミル処理を施したセルロース０．５ｇを添加した。反応容器内には、さらに、分析用としてｎ−ドデカン４ｍＬを加え、室温で水素を５ＭＰａにて導入した上で、１７０℃で２４時間保持して反応させた。反応後の生成物をガスクロマトグラフ及び高速液体クロマトグラフにより分析し、その結果を下記表１に示す。 In the reaction vessel having the catalyst after the reduction treatment described above, 0.5 g of milled cellulose was added. In the reaction vessel, 4 mL of n-dodecane was further added for analysis, hydrogen was introduced at room temperature at 5 MPa, and the reaction was continued at 170 ° C. for 24 hours. The product after the reaction was analyzed by gas chromatography and high performance liquid chromatography, and the results are shown in Table 1 below.
上記した還元処理後の触媒を有する反応容器内に、ミル処理を施したセルロース０．５ｇを添加した。なお、上記したようにミル処理では「１．５時間順回転」の工程を１回のみ施している。反応容器内には、さらに、分析用としてｎ−ドデカン４ｍＬを加え、室温で水素を５ＭＰａにて導入した上で、１９０℃で１８時間保持して反応させた。反応後の生成物をガスクロマトグラフ及び高速液体クロマトグラフにより分析し、その結果を下記表１に示す。 In the reaction vessel having the catalyst after the reduction treatment described above, 0.5 g of milled cellulose was added. As described above, in the milling process, the “1.5 hour forward rotation” step is performed only once. Further, 4 mL of n-dodecane was added for analysis in the reaction vessel, hydrogen was introduced at room temperature at 5 MPa, and the reaction was carried out by maintaining at 190 ° C. for 18 hours. The product after the reaction was analyzed by gas chromatography and high performance liquid chromatography, and the results are shown in Table 1 below.
表１中、他のヘキサン類は２−メチルペンタン、３−メチルペンタンおよびシクロヘキサンを示す。表１から、実施例１〜７は、いずれもｎ−ヘキサンが良好な収率で得られていることがわかる。 In Table 1, other hexanes indicate 2-methylpentane, 3-methylpentane and cyclohexane. From Table 1, it can be seen that in Examples 1 to 7, n-hexane was obtained in a good yield.
以上、本発明による実施例及びこれに基づく変形例を説明したが、本発明は必ずしもこれに限定されるものではなく、当業者であれば、本発明の主旨又は添付した特許請求の範囲を逸脱することなく、様々な代替実施例及び改変例を見出すことができるであろう。
As mentioned above, although the Example by this invention and the modification based on this were demonstrated, this invention is not necessarily limited to this, A person skilled in the art will deviate from the main point of this invention, or the attached claim. Various alternative embodiments and modifications could be found without doing so.
Claims (6)
前記セルロース系バイオマスを加水分解し糖化させて糖類を得る第１の反応行程と、
前記糖類を水素化して得た糖アルコールを水素化分解して炭化水素を得る第２の反応行程と、を含み、
前記第１の反応行程及び前記第２の反応行程を同一のＩｒ−Ｒｅ（イリジウム−レニウム）系触媒の存在下で進行させ、主として前記第１の反応行程で得た糖類の炭素数を維持した炭化水素を得ることを特徴とする炭化水素の製造方法。 A method for producing hydrocarbons from cellulosic biomass,
A first reaction step of hydrolyzing and saccharifying the cellulosic biomass to obtain a saccharide;
A second reaction step of hydrocracking a sugar alcohol obtained by hydrogenating the saccharide to obtain a hydrocarbon,
The first reaction step and the second reaction step were allowed to proceed in the presence of the same Ir-Re (iridium-rhenium) -based catalyst, and mainly the carbon number of the saccharide obtained in the first reaction step was maintained. A method for producing hydrocarbons, comprising obtaining hydrocarbons.
前記第２の反応行程はソルビトールを主とする炭素数６の糖アルコールから主としてヘキサンを得ることを特徴とする請求項１〜３のうちいずれか１つに記載の炭化水素の製造方法。 The first reaction step is a step of obtaining a monosaccharide having 6 carbon atoms mainly composed of glucose,
The method for producing hydrocarbons according to any one of claims 1 to 3, wherein in the second reaction step, hexane is mainly obtained from a sugar alcohol having 6 carbon atoms mainly including sorbitol.
前記第２の反応行程はキシリトールを主とする炭素数５の糖アルコールから主としてペンタンを得ることを特徴とする請求項１〜３のうちいずれか１つに記載の炭化水素の製造方法。 The first reaction step is a step of obtaining a monosaccharide having 5 carbon atoms mainly including xylose,
The method for producing a hydrocarbon according to any one of claims 1 to 3, wherein in the second reaction step, pentane is mainly obtained from a sugar alcohol having 5 carbon atoms mainly containing xylitol.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016033129A (en) * | 2014-07-30 | 2016-03-10 | 昭和シェル石油株式会社 | Method for producing hexanol/pentanol |
| JP2017007950A (en) * | 2015-06-17 | 2017-01-12 | 昭和シェル石油株式会社 | Manufacturing method of c5+ compound |
| JP2020172455A (en) * | 2019-04-09 | 2020-10-22 | 出光興産株式会社 | Method for producing c5+ compounds and c5+ compounds |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010505034A (en) * | 2006-09-26 | 2010-02-18 | ユーオーピー エルエルシー | Production of gasoline, diesel, naphthenes and aromatics from lignin and cellulose waste by one-step hydrocracking |
| JP2013017922A (en) * | 2011-07-08 | 2013-01-31 | Daicel Corp | Iridium-rhenium solid catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010505034A (en) * | 2006-09-26 | 2010-02-18 | ユーオーピー エルエルシー | Production of gasoline, diesel, naphthenes and aromatics from lignin and cellulose waste by one-step hydrocracking |
| JP2013017922A (en) * | 2011-07-08 | 2013-01-31 | Daicel Corp | Iridium-rhenium solid catalyst |
Non-Patent Citations (1)
| Title |
|---|
| "One-Pot Conversion of Sugar and Sugar Polyols to n-Alkanes without C[BOND]C Dissociation over the Ir", CHEMSUSCHEM, vol. Volume 6, JPN6017032724, 5 March 2013 (2013-03-05), pages pages 613-621 * |
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|---|---|---|---|---|
| JP2016033129A (en) * | 2014-07-30 | 2016-03-10 | 昭和シェル石油株式会社 | Method for producing hexanol/pentanol |
| JP2020073476A (en) * | 2014-07-30 | 2020-05-14 | 出光興産株式会社 | Process for producing hexanol |
| JP2017007950A (en) * | 2015-06-17 | 2017-01-12 | 昭和シェル石油株式会社 | Manufacturing method of c5+ compound |
| JP2020172455A (en) * | 2019-04-09 | 2020-10-22 | 出光興産株式会社 | Method for producing c5+ compounds and c5+ compounds |
| JP7253960B2 (en) | 2019-04-09 | 2023-04-07 | 出光興産株式会社 | Method for producing C5+ compounds |
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