JP6078882B2 - Process for producing hydrocarbons - Google Patents
Process for producing hydrocarbons Download PDFInfo
- Publication number
- JP6078882B2 JP6078882B2 JP2013161413A JP2013161413A JP6078882B2 JP 6078882 B2 JP6078882 B2 JP 6078882B2 JP 2013161413 A JP2013161413 A JP 2013161413A JP 2013161413 A JP2013161413 A JP 2013161413A JP 6078882 B2 JP6078882 B2 JP 6078882B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- filter
- biomass
- platinum
- reactor
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、炭化水素の製造方法に関し、特に、木質系、草本類、廃棄物系などのバイオマス原料から酸素を含まない炭化水素を効率よく製造する方法に関する。 The present invention relates to a method for producing hydrocarbons, and more particularly, to a method for efficiently producing hydrocarbons free of oxygen from biomass materials such as woody, herbaceous, and waste materials.
ユーカリなどの木質系、雑草などの草本類、パームやジャトロファ廃材などの廃棄物系バイオマスは、セルロース／ヘミセルロース／リグニン等を含むため反応性が低い物質である。このような反応性が低い原料から炭素と水素から成る炭化水素混合物(燃料用途など)を得るためには、（１）ガス化−ＦＴ(フィッシャー・トロプシュ)反応経由、（２）熱分解−水素化脱酸素反応経由、（３）超臨界メタノール中でバイオマスを熱処理及び水素化を行う方法などが想定されている。
しかし、(１)は、900℃程度の高温のスチームでガス化する必要がある、またＦＴ反応後に高級ワックスの水素化分解が必要(非特許文献１)、(２)は、熱分解温度が500〜600℃であるが、得られたバイオオイルには40重量％を超える酸素が含有しているため、石油系の燃料と同品質にするためには、大量の水素による水素化脱酸素工程が必要(特許文献１、２)、(３)は、熱処理温度が300〜400℃とより低いが、得られた液体の脱酸素処理には(２)と同様に大量の水素が必要、またバイオマス処理量に比例して大量のメタノール溶媒が必要かつ、水素化処理前の溶媒除去(蒸留など)では大量のエネルギーが必要(特許文献３、４、非特許文献２)、など、原料は再生可能資源でも、省エネルギー・省資源プロセスの観点からは問題が多い。
Woody materials such as eucalyptus, herbs such as weeds, and waste-based biomass such as palm and jatropha waste are low-reactivity substances because they contain cellulose / hemicellulose / lignin and the like. In order to obtain a hydrocarbon mixture composed of carbon and hydrogen (such as fuel use) from such a low-reactivity raw material, (1) gasification-via FT (Fischer-Tropsch) reaction, (2) pyrolysis-hydrogen A method of performing heat treatment and hydrogenation of biomass in supercritical methanol via a hydrodeoxygenation reaction is assumed.
However, (1) needs to be gasified with steam at a high temperature of about 900 ° C., and hydrocracking of higher wax is necessary after the FT reaction (Non-patent Document 1), (2) has a thermal decomposition temperature of Although it is 500-600 ° C, since the obtained bio-oil contains more than 40% oxygen, hydrodeoxygenation process with a large amount of hydrogen to make it the same quality as petroleum-based fuel (Patent Documents 1 and 2) and (3) have a lower heat treatment temperature of 300 to 400 ° C., but a large amount of hydrogen is required for deoxygenation of the obtained liquid as in (2). Raw materials are regenerated such that a large amount of methanol solvent is required in proportion to the biomass processing amount, and a large amount of energy is required for solvent removal (distillation, etc.) before hydrotreatment (Patent Documents 3 and 4, Non-Patent Document 2). Even with possible resources, there are many problems from the viewpoint of energy and resource saving processes.
これに対して、(２)の熱分解を触媒存在下で行う方法があるが、適切な触媒の選択や触媒とバイオマス原料との適切な接触がなされていないために、脱酸素した燃料化可能な芳香族炭化水素の選択率は24％程度にとどまっていた(非特許文献３)。 On the other hand, there is a method in which the thermal decomposition of (2) is performed in the presence of a catalyst. The selectivity of aromatic hydrocarbons was only about 24% (Non-patent Document 3).
本発明は、こうした現状を鑑みてなされたものであって、木質系、草本類、廃棄物系などのバイオマスから酸素を含まない炭化水素混合物を十分な収率で製造することができる新規な触媒と反応方法を提供することを目的とする。 The present invention has been made in view of the present situation, and is a novel catalyst capable of producing a hydrocarbon mixture containing no oxygen from biomass such as woody, herbaceous, and waste-based in a sufficient yield. And to provide a reaction method.
本発明者らは、前記課題を解決すべく、改良触媒及び反応方法について鋭意研究を重ねた結果、バイオマス原料と触媒とが直接接触しない構造を有する反応器を用い、バイオマス原料を熱分解し、発生した熱分解有機物を改質触媒によってその場改質することにより、上記課題を解決しうることを見いだした。 As a result of intensive studies on the improved catalyst and the reaction method in order to solve the above problems, the present inventors thermally decomposed the biomass material using a reactor having a structure in which the biomass material and the catalyst are not in direct contact, It has been found that the above-mentioned problems can be solved by in-situ reforming of the generated pyrolytic organic matter with a reforming catalyst.
本発明は該知見に基づいて完成するに至ったものであり、本発明によれば、以下の発明が提供される。
〈１〉内部に触媒を配した反応器内で、バイオマス原料を該触媒と直接接触しないようにして熱分解し、発生する熱分解有機物を前記触媒により改質することを特徴とする炭化水素の製造方法。
〈２〉前記バイオマス原料として、セルロース、木質系または廃棄物系バイオマスを用いることを特徴とする〈１〉に記載の炭化水素の製造方法。
〈３〉前記触媒として、周期律表第１０族に属する金属もしくはこれを含む化合物一種類以上で修飾された多孔性固体酸化物を含有してなる触媒を用いることを特徴とする〈１〉又は〈２〉に記載の炭化水素の製造方法。
〈４〉前記多孔性固体酸化物がゼオライト化合物であることを特徴とする〈３〉に記載の炭化水素の製造方法。
〈５〉前記反応器が、最下層に設けられた第１のフィルターと、該第１のフィルターの上部に設けられた触媒載置用の第２のフィルターを有し、前記第１のフィルター上に落下した前記バイオマス原料が熱分解し、発生した熱分解有機物が前記第２のフィルター上に載置された触媒を通過するように構成されていることを特徴とする請求項１〜４のいずれか１項に記載の炭化水素の製造方法。
The present invention has been completed based on this finding, and according to the present invention, the following inventions are provided.
<1> In a reactor in which a catalyst is arranged, a biomass raw material is pyrolyzed so as not to be in direct contact with the catalyst, and a generated pyrolytic organic substance is reformed by the catalyst. Production method.
<2> The method for producing hydrocarbons according to <1>, wherein cellulose, woody or waste biomass is used as the biomass raw material.
<3> A catalyst comprising a porous solid oxide modified with at least one metal belonging to Group 10 of the periodic table or a compound containing the metal, as the catalyst <1> or The method for producing a hydrocarbon according to <2>.
<4> The method for producing a hydrocarbon according to <3>, wherein the porous solid oxide is a zeolite compound.
<5> The reactor includes a first filter provided in a lowermost layer and a second filter for placing a catalyst provided on an upper portion of the first filter. The biomass raw material that has fallen to the bottom is pyrolyzed, and the generated pyrolyzed organic matter passes through a catalyst placed on the second filter. A method for producing a hydrocarbon according to claim 1.
本発明の新規な製造方法を用いれば、木質系、草本類、廃棄物系などのバイオマス原料からガソリン等の炭化水素燃料混合物を高められた収率で製造することができる。 If the novel manufacturing method of this invention is used, hydrocarbon fuel mixtures, such as gasoline, can be manufactured with the increased yield from biomass raw materials, such as a wood type, a herb, and a waste type.
本発明に用いるバイオマス原料には、木質系および廃棄物系が通常用いられ、木質系としては、杉、米松、ユーカリ、竹、などが例示され、また廃棄物系としては、ジャトロファ、パームなどからの油脂搾油後の廃材、稲わら、バガス、コーンストーバー、廃芝などの農業残渣、下水汚泥、食品残渣などの生活廃材、ボトリオコッカスなどの油産生藻類の搾油後の残渣などが例示される。これらは必要に応じて、天日乾燥、粉砕などの前処理が行われる。また別の原料として、これらバイオマスを構成するセルロース、ヘミセルロース、リグニンなどを個別に反応させることもできる。 Woody materials and waste materials are usually used as biomass raw materials used in the present invention. Examples of woody materials include cedar, rice pine, eucalyptus, bamboo, and the like, and examples of waste materials include jatropha and palm. Examples include waste materials after oil extraction of oil, agricultural residues such as rice straw, bagasse, corn stover and waste turf, domestic waste materials such as sewage sludge and food residues, residues after oil extraction of oil-producing algae such as Botryococcus, etc. . These are subjected to pretreatments such as sun drying and pulverization as necessary. Further, as another raw material, cellulose, hemicellulose, lignin and the like constituting these biomass can be reacted individually.
本発明の製造方法は、改質触媒と固体のバイオマス原料とが直接接触しないように工夫した反応器を用いて熱分解を行うことを特徴とする。
すなわち、本発明に用いられる反応器は、改質触媒とバイオマス原料とが直接接触しないようにされたものであればよく、特に限定されるものではない。
図１は、本発明の方法に用いられる反応器の一例の構造を模式的に示す図である。
図１に示す反応器は、最下層の第１のフィルターの上部に別の第２のフィルターを設置し、触媒はこの第２のフィルター上に配置する。バイオマス原料は、第１のフィルター上に落下し、熱分解により生成した有機物からなるガスが、反応器の下部から導入された窒素ガスと共に触媒層を通過して改質が起こり、改質された生成物がトラップ(氷および液体窒素)にて液体または固体としてトラップされる。トラップされない無機ガス(メタン、CO、CO２、水素など)はガス溜に捕集される。通常の反応管では、図２に示すように、バイオマス原料と触媒が直接接触する構造となっている。
The production method of the present invention is characterized in that pyrolysis is performed using a reactor devised so that the reforming catalyst and the solid biomass raw material do not come into direct contact with each other.
That is, the reactor used in the present invention is not particularly limited as long as the reforming catalyst and the biomass raw material are not in direct contact with each other.
FIG. 1 is a diagram schematically showing the structure of an example of a reactor used in the method of the present invention.
In the reactor shown in FIG. 1, another second filter is installed on top of the first filter in the lowermost layer, and the catalyst is placed on this second filter. The biomass raw material falls on the first filter, and the gas composed of organic matter generated by thermal decomposition passes through the catalyst layer together with the nitrogen gas introduced from the lower part of the reactor, and reformed. The product is trapped as a liquid or solid in a trap (ice and liquid nitrogen). Untrapped inorganic gases (methane, CO, CO 2 , hydrogen, etc.) are collected in the gas reservoir. As shown in FIG. 2, the normal reaction tube has a structure in which the biomass material and the catalyst are in direct contact.
本発明において、熱分解におけるガス雰囲気は任意であるが、通常バイオマス原料の酸化を防ぐために、窒素、アルゴン、ヘリウム、二酸化炭素などの不活性雰囲気または水素中で行われる。
反応温度は、50〜800℃、好ましくは450〜600℃の条件下であり、また反応圧力は通常常圧であるが、加圧で行うこともできる。この場合の圧力は、0.01MPa〜50MPa、好ましくは0.5MPa〜5MPaである。
水素の場合の使用割合は、バイオマス原料１ｇ当たり、0.0001〜1000ｇ、好ましくは0.01〜10ｇの割合である。また、水素は、窒素、ヘリウム、アルゴンガス等の不活性ガスで希釈して用いることができる。
反応管中のガスの滞留時間は、１〜1000秒、好ましくは10〜100秒である。
In the present invention, the gas atmosphere in the pyrolysis is arbitrary, but is usually performed in an inert atmosphere such as nitrogen, argon, helium, carbon dioxide or hydrogen in order to prevent the biomass raw material from being oxidized.
The reaction temperature is 50 to 800 ° C., preferably 450 to 600 ° C., and the reaction pressure is usually normal pressure, but it can also be carried out under pressure. The pressure in this case is 0.01 MPa to 50 MPa, preferably 0.5 MPa to 5 MPa.
The use ratio in the case of hydrogen is 0.0001 to 1000 g, preferably 0.01 to 10 g, per 1 g of biomass raw material. Hydrogen can be diluted with an inert gas such as nitrogen, helium, or argon gas.
The residence time of the gas in the reaction tube is 1-1000 seconds, preferably 10-100 seconds.
本発明において、前記熱分解後の生成物を改質して炭化水素混合物を製造する際に用いられる触媒として、周期律表第１０族に属する金属もしくはこれを含む化合物で修飾された多孔性固体酸化物を含有するものが用いられる。
多孔性固体酸化物としては、周期律表第１０族金属もしくはこれを含む化合物と共存、または、その表面に金属等の化合物を担持できるものであれば、いかなる酸化物も含まれるが、一般に触媒担体として知られている金属酸化物や多孔性酸化物を用いることが好ましい。
In the present invention, a porous solid modified with a metal belonging to Group 10 of the periodic table or a compound containing the same as a catalyst used for producing a hydrocarbon mixture by reforming the product after pyrolysis Those containing oxides are used.
The porous solid oxide includes any oxide as long as it can coexist with a group 10 metal of the periodic table or a compound containing the same, or can support a compound such as a metal on the surface thereof. It is preferable to use a metal oxide or porous oxide known as a carrier.
このような多孔性固体酸化物としては、ゼオライト化合物などが挙げられる。ゼオライト化合物としては、Y-型、L-型、モルデナイト、フェリエライト、ベータ型、H-ZSM-5などを挙げることができる。
また、ゼオライト化合物以外の多孔性酸化物としては、TS-1、MCM-22、MCM-48、ガロシリケート、などの結晶性メタロシリケート、MCM-41などのメソポーラスシリカ化合物などを挙げることができる。また、これらの多孔性酸化物にはチタン、アルミニウム、バナジウム、ニオブ、タンタル、ホウ素、ジルコニウムなどの元素を含有するものや非晶質多孔性シリカ化合物も含まれる。
他の多孔性固体酸化物としては、たとえば、シリカ、アルミナ、ジルコニア、チタニア、セリアなどの通常用いられる金属酸化物を用いることもできる。
Examples of such porous solid oxides include zeolite compounds. Examples of the zeolite compound include Y-type, L-type, mordenite, ferrierite, beta-type, and H-ZSM-5.
Examples of the porous oxide other than the zeolite compound include crystalline metallosilicates such as TS-1, MCM-22, MCM-48, and gallosilicate, and mesoporous silica compounds such as MCM-41. In addition, these porous oxides include those containing elements such as titanium, aluminum, vanadium, niobium, tantalum, boron, zirconium, and amorphous porous silica compounds.
As other porous solid oxides, for example, commonly used metal oxides such as silica, alumina, zirconia, titania and ceria can be used.
他の多孔性固体酸化物としては、たとえば、シリカ、アルミナ、ジルコニア、チタニア、セリアなどの通常用いられる金属酸化物を硫酸根やタングステン酸等で表面修飾した酸化物が挙げられる。また、シリカ−アルミナなどの複合酸化物を硫酸根やタングステン酸で修飾した酸化物を用いることも可能である。この場合、通常のジルコニアなどの金属酸化物に硫酸根や水溶性のタングステン化合物を含浸法にて担持し、100℃で乾燥、さらに焼成することにより得ることができる。この時の焼成温度は300〜1500℃、好ましくは500〜900℃である。 Examples of other porous solid oxides include oxides obtained by surface modification of commonly used metal oxides such as silica, alumina, zirconia, titania and ceria with sulfate radicals, tungstic acid and the like. It is also possible to use an oxide obtained by modifying a composite oxide such as silica-alumina with sulfate radical or tungstic acid. In this case, it can be obtained by supporting a sulfate group or a water-soluble tungsten compound on an ordinary metal oxide such as zirconia by an impregnation method, drying at 100 ° C., and further firing. The baking temperature at this time is 300-1500 degreeC, Preferably it is 500-900 degreeC.
本発明でとりわけ好ましく使用される多孔性固体酸化物は、熱分解により得られた有機物などを表面に吸着でき、周期律表第１０族の金属との協調効果によりフェノール誘導体、カルボン酸誘導体などを水素化／脱酸素し、飽和炭化水素に変換することができる。シリカ／アルミナ比が小さなゼオライト化合物(特にH-ZSM5)や、固体超強酸性を有する硫酸根またはタングステン酸ジルコニアなどを挙げることができる。この場合のシリカ／アルミナ比は5〜500、好ましくは20〜80である。 The porous solid oxide particularly preferably used in the present invention can adsorb organic substances and the like obtained by thermal decomposition on the surface, and can produce phenol derivatives, carboxylic acid derivatives, etc. by the cooperative effect with metals of Group 10 of the periodic table. It can be hydrogenated / deoxygenated and converted to saturated hydrocarbons. Examples thereof include zeolite compounds having a small silica / alumina ratio (particularly H-ZSM5), sulfate radicals having solid superacidity, and zirconia tungstate. In this case, the silica / alumina ratio is 5 to 500, preferably 20 to 80.
本発明で用いる多孔性固体酸化物はその使用にあたって、周期律表第１０族に属する金属を含む化合物少なくとも一種類以上で修飾しておくことが必須である。
周期律表第１０族に属する金属を含む化合物としては、白金化合物、パラジウム化合物などが挙げられ、白金化合物としては、塩化白金酸、塩化第一白金アンモニウム、塩化第２白金ナトリウム、シアン化第一白金カリウム、ジクロロテトラアンミン白金、テトラミン硝酸白金、ビス−アセチルアセトナト白金、テトラキストリフェニルフォスフィン白金等が挙げられる。パラジウム化合物としては、酢酸パラジウム、ビス−アセチルアセトナトパラジウム、塩化パラジウム、四塩化パラジウムアンモニウム、六塩化パラジウムナトリウム、ジアミノ亜硝酸パラジウム、テトラキストリフェニルフォスフィンパラジウム、硝酸パラジウム、硫酸パラジウム等が挙げられる。
The porous solid oxide used in the present invention must be modified with at least one compound containing a metal belonging to Group 10 of the periodic table.
Examples of the compound containing a metal belonging to Group 10 of the periodic table include a platinum compound and a palladium compound. Examples of the platinum compound include chloroplatinic acid, ammonium platinum chloride, sodium chloroplatinum chloride, and cyanide first. Examples include platinum potassium, dichlorotetraammine platinum, tetramine platinum nitrate, bis-acetylacetonato platinum, tetrakistriphenylphosphine platinum, and the like. Examples of the palladium compound include palladium acetate, bis-acetylacetonato palladium, palladium chloride, ammonium ammonium tetrachloride, sodium palladium hexachloride, palladium diaminonitrite, tetrakistriphenylphosphine palladium, palladium nitrate, palladium sulfate and the like.
多孔性固体酸化物に白金等の化合物を含有させる方法としては、物理混合法や，含浸法、沈殿法、混練法、インシピエントウェットネス法等の従来公知の方法を採用することが出来る。
たとえば、白金等の化合物は、通常、水溶液として固体酸化物に担持される。またアセトン、イソプロパノール、ベンゼンなどの有機溶媒も用いられる。白金等の化合物を含有させたゼオライト酸化物等の焼成温度は、300〜900℃，好ましくは500〜700℃程度である。白金等の担持量は、任意であるが、白金金属として、担体酸化物100ｇ当たり、0.001〜10ｇ、好ましくは0.1〜10ｇである。これらの添加物は、単独もしくは２種以上の混合物として用いることができる。焼成温度は300〜1000℃、好ましくは400〜700℃、その後の水素還元は100〜500℃、好ましくは200〜400℃、水素圧は常圧〜20MPa、好ましくは1〜5MPaである。
As a method for incorporating a compound such as platinum into the porous solid oxide, a conventionally known method such as a physical mixing method, an impregnation method, a precipitation method, a kneading method, or an incipient wetness method can be employed.
For example, a compound such as platinum is usually supported on a solid oxide as an aqueous solution. Organic solvents such as acetone, isopropanol, and benzene are also used. The firing temperature of the zeolite oxide or the like containing a compound such as platinum is about 300 to 900 ° C, preferably about 500 to 700 ° C. The supported amount of platinum or the like is arbitrary, but it is 0.001 to 10 g, preferably 0.1 to 10 g as platinum metal per 100 g of the carrier oxide. These additives can be used alone or as a mixture of two or more. The calcination temperature is 300 to 1000 ° C., preferably 400 to 700 ° C., and the subsequent hydrogen reduction is 100 to 500 ° C., preferably 200 to 400 ° C., and the hydrogen pressure is normal pressure to 20 MPa, preferably 1 to 5 MPa.
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこの実施例に限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to this Example.
（実施例１）
触媒調製として、日揮触媒化成社製H-ZSM-5(Si/Al2比=30)ペレットにジクロロテトラアンミン白金(白金換算で0.5wt％)およびジアミノ亜硝酸パラジウム(パラジウム換算で0.5wt％)を含浸させ、60℃で一晩乾燥、さらに100℃で3時間乾燥後、500℃で6時間空気焼成した。こうして得られたPtPd/H-ZSM-5(10ｇ)を、水素5MPa、250℃で5時間還元後、室温に冷却し、石英砂20ｇと共に速やかに熱分解用の反応器(図１)に導入し、窒素気流中、滞留時間33秒で、600℃まで昇温した。その後ジャトロファ廃材10ｇを反応管の最下部に導入し、触媒層を通過した有機生成物を、氷および液体窒素トラップにより補足し、液体生成物全体をGC/MSにより分析したところ、オイル収率は38.9％ながら、芳香族炭化水素選択率は73.7％であった。
Example 1
For catalyst preparation, H-ZSM-5 (Si / Al2 ratio = 30) pellets made by JGC Catalysts & Chemicals Co., Ltd. were impregnated with dichlorotetraammine platinum (0.5 wt% in terms of platinum) and palladium diaminonitrite (0.5 wt% in terms of palladium). The mixture was dried at 60 ° C. overnight, further dried at 100 ° C. for 3 hours, and then calcined at 500 ° C. for 6 hours. The PtPd / H-ZSM-5 (10 g) thus obtained was reduced to 5 MPa at 250 ° C for 5 hours, cooled to room temperature, and immediately introduced into the reactor for thermal decomposition (Fig. 1) together with 20 g of quartz sand. The temperature was raised to 600 ° C. in a nitrogen stream with a residence time of 33 seconds. After that, 10 g of Jatropha waste was introduced at the bottom of the reaction tube, the organic product that passed through the catalyst layer was captured by ice and a liquid nitrogen trap, and the entire liquid product was analyzed by GC / MS. The aromatic hydrocarbon selectivity was 73.7%, while 38.9%.
オイル収率、選択率(GC/MS利用)は、便宜的に以下のように計算した。
（１）オイル収率＝
[(トラップに捕集された液体生成物の重量)／(ジャトロファ廃材の導入量)]×100
（２）芳香族炭化水素選択率＝
[(芳香族炭化水素の合計面積)／(全生成物の合計面積)]×100
他の生成物選択率も同様に計算した。
The oil yield and selectivity (GC / MS utilization) were calculated as follows for convenience.
(1) Oil yield =
[(Weight of liquid product collected in trap) / (Amount of introduced Jatropha waste)] × 100
(2) Aromatic hydrocarbon selectivity =
[(Total area of aromatic hydrocarbons) / (total area of all products)] × 100
Other product selectivity was calculated similarly.
（比較例１）
触媒を用いない以外は実施例１と同様にして、ジャトロファ廃材の熱分解を行って、液状生成物を得た。その結果、オイル収率は48.8％であったが、芳香族炭化水素選択率は10.8％と触媒を使用した場合の1／7に減少し、代わりに酸／エステルが38.9％と約8倍に増加した。
(Comparative Example 1)
Except not using a catalyst, it carried out similarly to Example 1, and thermally decomposed the Jatropha waste material, and obtained the liquid product. As a result, the oil yield was 48.8%, but the aromatic hydrocarbon selectivity was reduced to 10.8%, 1/7 of the catalyst, and instead the acid / ester was 38.9%, approximately 8 times. Increased.
（比較例２）
触媒と原料が直接接触する従来の反応器(図２)を用いた以外は実施例１と同様にして、ジャトロファ廃材の熱分解を行って、液状生成物を得たところ、オイル収率は39.7％と同程度であったが、芳香族炭化水素選択率が34.9％と半分以下となり、反応管の形状が選択率に著しく影響していた。
(Comparative Example 2)
A jatropha waste was pyrolyzed in the same manner as in Example 1 except that a conventional reactor (Fig. 2) in which the catalyst and the raw material were in direct contact was used, and a liquid product was obtained. The oil yield was 39.7. However, the aromatic hydrocarbon selectivity was less than half, 34.9%, and the shape of the reaction tube had a significant effect on the selectivity.
（実施例２、３）
H-ZSM-5ゼオライトの代わりに、Beta(22.5)、又はUSY(20)を担体とした以外は実施例１と同様にして、ジャトロファ廃材の熱分解を行って、液状生成物を得たところ、オイル収率はそれぞれ43.9％及び40.5％、また芳香族炭化水素選択率は68.6％及び48.7％となり、H-ZSM-5ゼオライトと遜色ない十分な効果が認められた。
(Examples 2 and 3)
A jatropha waste was pyrolyzed in the same manner as in Example 1 except that Beta (22.5) or USY (20) was used instead of H-ZSM-5 zeolite, and a liquid product was obtained. The oil yields were 43.9% and 40.5%, respectively, and the aromatic hydrocarbon selectivity was 68.6% and 48.7%, respectively, and a sufficient effect comparable to H-ZSM-5 zeolite was observed.
本発明の方法によれば、ジャトロファ廃材などから、熱分解と触媒によるその場改質により、効率よく芳香族炭化水素混合物が得られ、これらはガソリンへの添加や、化学品中間体として極めて有用であり、化学工業や自動車産業への適用が期待される。 According to the method of the present invention, an aromatic hydrocarbon mixture can be efficiently obtained from jatropha waste material, etc. by pyrolysis and in-situ reforming with a catalyst, and these are extremely useful as additions to gasoline and chemical intermediates Therefore, it is expected to be applied to the chemical industry and the automobile industry.
Claims (2)
前記触媒として、白金もしくは白金を含む化合物及び／又はパラジウムもしくはパラジウムを含む化合物で修飾されたゼオライト化合物を含有してなる触媒を用い、
前記反応器が、最下層に設けられた第１のフィルターと、該第１のフィルターの上部に設けられた触媒載置用の第２のフィルターを有し、前記第１のフィルター上に落下した前記バイオマス原料が熱分解し、発生した熱分解有機物ガスが前記第２のフィルター上に載置された触媒を通過するように構成されていることを特徴とする、
炭化水素の製造方法。 In a reactor which arranged catalyst therein, the biomass feedstock so as not to contact directly with the catalyst by thermal decomposition, thermal decomposition organic matter generated in the manufacturing process of hydrocarbons, which comprises modified by the catalyst There,
As the catalyst, a catalyst comprising platinum or a compound containing platinum and / or a zeolite compound modified with palladium or a compound containing palladium,
The reactor has a first filter provided in the lowermost layer and a second filter for placing a catalyst provided on the upper part of the first filter, and dropped on the first filter. The biomass raw material is pyrolyzed, and the generated pyrolyzed organic gas is configured to pass through a catalyst placed on the second filter,
A method for producing hydrocarbons .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013161413A JP6078882B2 (en) | 2013-08-02 | 2013-08-02 | Process for producing hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013161413A JP6078882B2 (en) | 2013-08-02 | 2013-08-02 | Process for producing hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015030794A JP2015030794A (en) | 2015-02-16 |
| JP6078882B2 true JP6078882B2 (en) | 2017-02-15 |
Family
ID=52516404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013161413A Expired - Fee Related JP6078882B2 (en) | 2013-08-02 | 2013-08-02 | Process for producing hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6078882B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016046163A2 (en) * | 2014-09-22 | 2016-03-31 | Huntsman International Llc | Process for the preparation of aromatic compounds |
| CN111268884B (en) * | 2020-03-31 | 2024-04-09 | 浙江科茂环境科技有限公司 | Oil sludge treatment system and method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU760143B2 (en) * | 1998-09-24 | 2003-05-08 | Dingli Zhou | Process and apparatus for producing hydrocarbons from city garbage and/or organic waste material |
| JP2003238973A (en) * | 2001-09-28 | 2003-08-27 | Ebara Corp | Method for reforming combustible gas, apparatus for reforming combustible gas and apparatus for gasification |
| CN102015969B (en) * | 2008-03-04 | 2015-05-27 | 马萨诸塞大学 | Catalytic pyrolysis of solid biomass and related biofuels, aromatic, and olefin compounds |
| WO2011031320A2 (en) * | 2009-09-09 | 2011-03-17 | University Of Massachusetts | Systems and processes for catalytic pyrolysis of biomass and hydrocarbonaceous materials for production of aromatics with optional olefin recycle, and catalysts having selected particle size for catalytic pyrolysis |
| JP5819607B2 (en) * | 2010-12-28 | 2015-11-24 | 活水プラント株式会社 | Low pressure pyrolysis equipment and continuous oil carbonization equipment |
| JP2014529663A (en) * | 2011-09-01 | 2014-11-13 | ユニバーシティ オブ マサチューセッツ | Method for producing fluid hydrocarbons |
| JP5831220B2 (en) * | 2011-12-28 | 2015-12-09 | 株式会社Ihi | Circulating fluidized bed gasifier |
-
2013
- 2013-08-02 JP JP2013161413A patent/JP6078882B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015030794A (en) | 2015-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Iliopoulou et al. | Overview of catalytic upgrading of biomass pyrolysis vapors toward the production of fuels and high‐value chemicals | |
| Hernando et al. | Engineering the acidity and accessibility of the zeolite ZSM-5 for efficient bio-oil upgrading in catalytic pyrolysis of lignocellulose | |
| Yung et al. | Biomass catalytic pyrolysis on Ni/ZSM-5: effects of nickel pretreatment and loading | |
| Asadieraghi et al. | Heterogeneous catalysts for advanced bio-fuel production through catalytic biomass pyrolysis vapor upgrading: a review | |
| Wang et al. | Co-cracking of bio-oil model compound mixtures and ethanol over different metal oxide-modified HZSM-5 catalysts | |
| KR102356149B1 (en) | Catalyst for pyrolysis of feedstock | |
| Ma et al. | Controlling the selectivity to chemicals from lignin via catalytic fast pyrolysis | |
| Kubička et al. | Application of molecular sieves in transformations of biomass and biomass-derived feedstocks | |
| Wong et al. | Catalytic cracking of LDPE dissolved in benzene using nickel-impregnated zeolites | |
| Stefanidis et al. | Mesopore-modified mordenites as catalysts for catalytic pyrolysis of biomass and cracking of vacuum gasoil processes | |
| Selvaraj et al. | Hydrodeoxygenation of guaiacol over MoO3-NiO/mesoporous silicates: Effect of incorporated heteroatom | |
| Karnjanakom et al. | Catalytic upgrading of bio-oil over Cu/MCM-41 and Cu/KIT-6 prepared by β-cyclodextrin-assisted coimpregnation method | |
| Zerva et al. | Hydrodeoxygenation of phenol and biomass fast pyrolysis oil (bio-oil) over Ni/WO3-ZrO2 catalyst | |
| Wang et al. | In situ upgrading of cellulose pyrolysis volatiles using hydrofluorinated and platinum-loaded HZSM-5 for high selectivity production of light aromatics | |
| Huang et al. | Clean synthesis of 5-hydroxymethylfurfural and levulinic acid by aqueous phase conversion of levoglucosenone over solid acid catalysts | |
| KR20150045995A (en) | Method for Converting a Hydrocarbonaceous Material to a Fluid Hydrocarbon Product Comprising P-Xylene | |
| Xue et al. | Contribution of different NbOx species in the hydrodeoxygenation of 2, 5-dimethyltetrahydrofuran to hexane | |
| Ma et al. | Chemicals from lignin by catalytic fast pyrolysis, from product control to reaction mechanism | |
| Shang et al. | Regulating light olefins or aromatics production in ex-situ catalytic pyrolysis of biomass by engineering the structure of tin modified ZSM-5 catalyst | |
| Chen et al. | Arene production by W2C/MCM-41-catalyzed upgrading of vapors from fast pyrolysis of lignin | |
| CN105712817A (en) | Method for selective preparation of p-xylene and toluene from p-methylcyclohexene carboxaldehyde | |
| Soongprasit et al. | Pyrolysis of Millettia (Pongamia) pinnata waste for bio-oil production using a fly ash derived ZSM-5 catalyst | |
| Yang et al. | Hydrodeoxygenation (HDO) of biomass derived ketones using supported transition metals in a continuous reactor | |
| Zhang et al. | Selective transformation of methanol to ethanol in the presence of syngas over composite catalysts | |
| JP6078882B2 (en) | Process for producing hydrocarbons |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160328 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20161011 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161208 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20161227 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20161227 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6078882 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |