JP2003171670A - Method for producing hydrocarbons and catalyst for producing hydrocarbons - Google Patents
Method for producing hydrocarbons and catalyst for producing hydrocarbonsInfo
- Publication number
- JP2003171670A JP2003171670A JP2001374642A JP2001374642A JP2003171670A JP 2003171670 A JP2003171670 A JP 2003171670A JP 2001374642 A JP2001374642 A JP 2001374642A JP 2001374642 A JP2001374642 A JP 2001374642A JP 2003171670 A JP2003171670 A JP 2003171670A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- oils
- producing hydrocarbons
- hydrocarbons
- natural fats
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は炭化水素の製造方法
に関するものである。より詳細には、植物油脂、動物油
脂、魚脂等の天然油脂類あるいはその誘導体、廃油、廃
液等を主原料に、それらを水素化処理することで、産業
上有益な炭化水素を製造する方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing hydrocarbons. More specifically, a method for producing an industrially useful hydrocarbon by subjecting natural fats and oils such as vegetable fats, animal fats and fish fats or fish fats or derivatives thereof, waste oils, waste liquids, etc. as main raw materials to hydrotreating them It is about.
【０００２】[0002]
【従来の技術】炭化水素類の工業的な製造方法は石油、
石炭等の化石資源が主であり、大規模な火力発電や自動
車燃料から家庭用暖房燃料までエネルギー源として産業
の基盤を成している。2. Description of the Related Art The industrial production method of hydrocarbons is petroleum,
Fossil resources such as coal are the main sources, and they form the basis of industry as an energy source from large-scale thermal power generation and automobile fuels to household heating fuels.
【０００３】しかしながら、その莫大な消費量のため昨
今の環境汚染問題が深刻化し、加えて化石資源の枯欠の
危機に至っている。However, due to the enormous amount of consumption, the recent problems of environmental pollution have become serious, and in addition, fossil resources have run out of danger.
【０００４】従来の炭化水素類の製造方法において、石
油由来の場合は、産油国である中近東各国より大型タン
カー等により輸入し、製油精製工場で含有する硫黄分を
除去するために４５０気圧の水素加圧下、反応温度４０
０℃にて、いわゆる水素化脱硫処理を行い、さらに各成
分に蒸留分画するという複雑な処理を必要とする。In the conventional method for producing hydrocarbons, when the oil is derived from petroleum, it is imported from a country of the Middle East, which is an oil producing country, by a large tanker or the like, and at 450 atm in order to remove the sulfur content contained in the refinery plant. Under hydrogen pressure, reaction temperature 40
A so-called hydrodesulfurization treatment is performed at 0 ° C., and a complicated treatment of fractionating each component by distillation is required.
【０００５】そして、この一段の水素化脱硫処理では、
硫黄分を完全に除去することは困難で、最近の公害規制
法及びマスキー法をクリヤーできず、さらなる高度技術
による深度脱硫が要求されている。In this one-stage hydrodesulfurization treatment,
It is difficult to completely remove the sulfur content, the recent pollution control law and the Musky method cannot be cleared, and deep desulfurization by further advanced technology is required.
【０００６】また、石炭由来の場合は、固体である石炭
を液化する方法の研究は進められているものの、いまだ
実用化の域にはほど遠いのが現状であり、液状化が完成
しても石炭に含まれる硫黄分の除去の問題は石油由来の
炭化水素類製造と同じく依然として存在している。[0006] In the case of coal-derived coal, although research on a method for liquefying solid coal is under way, it is still far from being put to practical use. The problem of removing the sulfur content contained in the oil remains the same as in the production of hydrocarbons derived from petroleum.
【０００７】また、最近になって、化石資源の燃焼に伴
い発生する排ガス中に、喘息や気管支炎の原因となる炭
素系粒子状物質（パーティキュレート）も硫黄を含む芳
香族環系有機物類が原因であることが突き止められてい
る。[0007] Recently, in the exhaust gas generated by the combustion of fossil resources, carbonaceous particulate matter (particulate) that causes asthma and bronchitis are also aromatic ring organic compounds containing sulfur. The cause has been identified.
【０００８】一方、石炭からコークスを製造し、いわゆ
る水性ガス反応で一酸化炭素と水素を合成し、フイッシ
ヤー−トロプッシュ反応で炭化水素類を製造する方法が
有るが、鉄、コバルトあるいはルテニウム等の８族金属
を触媒にして２００〜５００℃の高温と数十気圧の反応
条件で行われている。また同様な反応条件下で銅や酸化
亜鉛を触媒にするとメタノール等のアルコール類が合成
できることが知られており、このメタノールを原料とし
て、ＺＳＭ−５触媒を用いる炭化水素合成も検討されて
いる。しかし、いずれの場合も反応条件が過酷であり、
高価な貴金属触媒やゼオライトを触媒として使用するた
め、実用性の乏しいものとなっている。On the other hand, there is a method of producing coke from coal, synthesizing carbon monoxide and hydrogen by a so-called water gas reaction, and producing hydrocarbons by a Fisher-Tropsch reaction, but iron, cobalt, ruthenium, etc. It is carried out under a reaction condition of a high temperature of 200 to 500 ° C. and several tens of atmospheric pressure using a Group 8 metal as a catalyst. Further, it is known that alcohols such as methanol can be synthesized by using copper or zinc oxide as a catalyst under similar reaction conditions, and hydrocarbon synthesis using this methanol as a raw material and using a ZSM-5 catalyst is also under study. However, in any case, the reaction conditions are severe,
Since expensive precious metal catalysts and zeolites are used as catalysts, they are of poor practicality.
【０００９】しかも、これらの方法では軽質油成分のみ
であり、エネルギー用の燃料油を合成することは、困難
である。Moreover, these methods use only light oil components, and it is difficult to synthesize fuel oil for energy.
【００１０】更に、炭化水素製造原料となる化石資源
は、資源エネルギー庁の統計的な試算では２０２０年に
は枯渇窮乏が始まるとしている。したがって、新たなエ
ネルギー源の開発が緊急な社会的課題である。Furthermore, the fossil resources used as a raw material for producing hydrocarbons will be exhausted by 2020, according to statistical calculations by the Agency for Natural Resources and Energy. Therefore, the development of new energy sources is an urgent social issue.
【００１１】即ち、これまでの化石資源由来の炭化水素
では、その成分中に、人体に有害なベンゼンやベンツピ
レン等の発がん物質を多量に含み、また酸性雨の原因と
なる硫黄を完全に取り除くことは困難な状況にあり、低
コストで、複雑プロセスを経ず、クリーンで燃焼効率の
高い炭化水素類を得ることを特徴とする炭化水素類の製
造方法の開発が強く望まれていた。That is, the hydrocarbons derived from fossil resources so far contain a large amount of carcinogens such as benzene and benzpyrene which are harmful to the human body in their components, and must completely remove sulfur that causes acid rain. In a difficult situation, there has been a strong demand for the development of a method for producing hydrocarbons, which is characterized by obtaining hydrocarbons that are low in cost, do not undergo complicated processes, and are clean and have high combustion efficiency.
【００１２】[0012]
【発明が解決しようとする課題】本発明は、天然油脂ま
たはその誘導体や廃油等を主原料にして、それらを水素
化処理することで、複雑プロセスを経ず、クリーンで燃
焼効率の高い炭化水素類を得ることを特徴とする炭化水
素類の製造方法を提供するものである。DISCLOSURE OF THE INVENTION The present invention uses natural fats and oils or their derivatives, waste oils, etc. as a main raw material and hydrotreates them as a main raw material, so that hydrocarbons having a clean and high combustion efficiency can be obtained without complicated processes. The present invention provides a method for producing hydrocarbons, which comprises obtaining the same.
【００１３】[0013]
【課題を解決するための手段】本発明者らは、天然油脂
またはその誘導体や廃油等と水素とを反応させることに
より炭化水素類を製造できれば上記問題を解決し得るこ
とに着目し、触媒の選定、反応条件の検索を行った結
果、触媒を反応に供する前に硫黄化合物で処理した後反
応に使用した場合、硫黄化合物で処理しない触媒に比較
して、より高収率に、より低温度で炭化水素類が製造さ
れることを見出した。Means for Solving the Problems The present inventors have noticed that the above problems can be solved if hydrocarbons can be produced by reacting natural fats and oils or their derivatives, waste oil and the like with hydrogen. As a result of selection and search of reaction conditions, when the catalyst was treated with a sulfur compound before being used in the reaction and then used in the reaction, the yield was higher and the temperature was lower than that of the catalyst not treated with the sulfur compound. It was found that hydrocarbons are produced in.
【００１４】すなわち第１の本発明は、天然油脂、天然
油脂誘導体および廃天然油脂から選ばれる少なくとも１
種と、活性化した水素とを金属触媒、合金触媒、金属担
持触媒および合金担持触媒からなる群より選ばれる触媒
の存在下反応させることを特徴とする炭化水素類の製造
方法に関するものである。That is, the first aspect of the present invention is at least one selected from natural fats and oils, natural fats and oils derivatives, and waste natural fats and oils.
The present invention relates to a method for producing hydrocarbons, which comprises reacting a seed with activated hydrogen in the presence of a catalyst selected from the group consisting of a metal catalyst, an alloy catalyst, a metal-supported catalyst and an alloy-supported catalyst.
【００１５】第２の本発明は、上記第１の発明であっ
て、前記触媒が、硫黄含有化合物で前処理された触媒で
あることを特徴とするものである。The second invention of the present invention is the above-mentioned first invention, characterized in that the catalyst is a catalyst pretreated with a sulfur-containing compound.
【００１６】第３の本発明は、周期律第２Ｂ〜６Ｂに属
する典型金属または典型金属酸化物又は、遷移金属の単
独あるいは複合体、酸化物、酸化物複合体から選択さ
れ、硫化水素で前処理された触媒からなることを特徴と
する天然油脂またはその誘導体から炭化水素類を製造す
るための炭化水素類製造用触媒に関するものである。The third aspect of the present invention is selected from typical metals or typical metal oxides belonging to Periodic Nos. 2B to 6B or single or complex compounds of transition metals, oxides, and oxide complexes, and is selected with hydrogen sulfide. The present invention relates to a catalyst for producing hydrocarbons for producing hydrocarbons from natural fats and oils or their derivatives, which comprises a treated catalyst.
【００１７】第４の本発明は、遷移金属８族に属する金
属と８族を除く遷移金属からなる合金及び金属複合酸化
物からなる事を特徴とする天然油脂またはその誘導体か
ら炭化水素類を製造するための炭化水素類製造用触媒に
関するものである。The fourth aspect of the present invention is to produce hydrocarbons from natural fats and oils or their derivatives, which are characterized by comprising a metal belonging to Group 8 of transition metals and an alloy of transition metals other than Group 8 and a metal complex oxide. The present invention relates to a catalyst for producing hydrocarbons.
【００１８】第５の本発明は、前記第３または第４の発
明の炭化水素類を製造するための炭化水素類製造用触媒
をシリカ、アルミナ、ゼオライト、チタニア、ジルコニ
ア等の担体に担持したことを特徴とする天然油脂または
その誘導体から炭化水素類を製造するための炭化水素類
製造用触媒に関するものである。In a fifth aspect of the present invention, the catalyst for producing hydrocarbons for producing the hydrocarbons of the third or fourth aspect is supported on a carrier such as silica, alumina, zeolite, titania, zirconia. The present invention relates to a catalyst for producing hydrocarbons for producing hydrocarbons from natural fats and oils or their derivatives.
【００１９】[0019]
【発明の実施形態】本発明の炭化水素類の原料は、エス
テル結合を有する物で、融点或いは溶融点を有する物で
あれば使用できるが、これらの条件に最も合致する原料
として天然油脂またはその誘導体を挙げることができ
る。BEST MODE FOR CARRYING OUT THE INVENTION The hydrocarbon raw material of the present invention can be used as long as it has an ester bond and has a melting point or a melting point. Derivatives can be mentioned.
【００２０】天然油脂としては、植物油脂、動物油脂、
魚脂を原料とすることが可能である。植物油脂として
は、ヤシ油、カカオ脂、パーム油、パーム核油等が好適
例としてあげられる。動物油脂としては牛脂、豚脂、羊
脂等が好適例としてあげられる。The natural fats and oils include vegetable fats and oils, animal fats and oils,
It is possible to use fish fat as a raw material. Preferable examples of vegetable oils and fats include palm oil, cacao butter, palm oil, palm kernel oil and the like. Suitable examples of animal fats and oils include beef tallow, lard, sheep fat and the like.
【００２１】また、これらの天然油脂は通常天然原料に
精製工程を経て工業原料とされるが、本発明の原料とし
てこれら精製工程の残留物を使用することも可能であ
る。Further, these natural fats and oils are usually used as an industrial raw material after undergoing a refining step on a natural raw material, but it is also possible to use the residue of the refining step as a raw material of the present invention.
【００２２】天然油脂誘導体としては、上記動植物油脂
を原料として製造された界面活性剤等の工業製品が例示
される。Examples of natural oil and fat derivatives include industrial products such as surfactants produced from the above-mentioned animal and vegetable oils and fats.
【００２３】さらにまた、これらの天然油脂や天然油脂
誘導体を含む廃油や廃液等の廃天然油脂を原料としても
よい。廃油、廃液としては、近年その処理法が問題にな
っている廃食油等が例示され、廃油に１２−ヒドロキシ
ステアリン酸等の固化処理剤を投入した物もそのまま原
料とすることができる。Furthermore, waste natural oils and fats such as waste oils and liquids containing these natural oils and fats and natural oil and fat derivatives may be used as raw materials. Examples of the waste oil and the waste liquid include waste cooking oil whose treatment method has become a problem in recent years, and a waste oil into which a solidifying agent such as 12-hydroxystearic acid is added can also be used as a raw material.
【００２４】本発明における炭化水素類の製造方法にお
いて使用する触媒について詳細に説明する。The catalyst used in the method for producing hydrocarbons in the present invention will be described in detail.
【００２５】原油中に含有される硫黄により触媒効果を
削減されぬ様に反応に供する触媒自体にあらかじめ硫黄
化合物で処理した触媒を使用することは、石油化学業界
では知られていた。It has been known in the petrochemical industry to use a catalyst which has been previously treated with a sulfur compound as the catalyst itself to be subjected to the reaction so that the catalytic effect is not reduced by the sulfur contained in the crude oil.
【００２６】しかしながら、今回原料として想定した天
然油脂またはその誘導体や廃油は、硫黄をほとんど含有
しない。にも関わらず天然油脂に対しても、硫黄化合物
で処理した触媒は硫黄処理しない触媒に比較して高い収
率を示した。この反応の仕組みに関しては、解明されて
いないが、従来の知見とは乖離した結果を示している。However, the natural fats and oils or their derivatives and waste oil assumed as the raw materials at this time contain almost no sulfur. Nevertheless, the catalyst treated with sulfur compounds also showed a higher yield than natural fats and oils compared to the catalyst not treated with sulfur. Although the mechanism of this reaction has not been clarified, it shows results that deviate from the conventional findings.
【００２７】例えば、高級脂肪酸或いはエステルを高温
下還元すれば、カルボニル部分は一部脱炭酸を起こすこ
とが予想されるが、本発明触媒による炭化水素製造実験
によると、製造した炭化水素と原料脂肪酸部位を比較す
ると、炭素数の減少が見られず脱炭酸はほとんど起こら
ないことが示された。この事は燃料製造の点から見れ
ば、製造工程に際して、脱炭酸によるカーボン損失がな
く、より効果的な燃料用炭化水素製造触媒であるともい
える。For example, if a higher fatty acid or ester is reduced at a high temperature, it is expected that a part of the carbonyl portion will be decarboxylated. However, according to the hydrocarbon production experiment using the catalyst of the present invention, the produced hydrocarbon and the raw material fatty acid are Comparing the sites showed that carbon number did not decrease and decarboxylation hardly occurred. From the viewpoint of fuel production, this can be said to be a more effective hydrocarbon production catalyst for fuel without carbon loss due to decarboxylation in the production process.
【００２８】本発明の炭化水素類製造方法に使用する触
媒としては、周期律第２Ｂ〜６Ｂに属する典型金属また
は典型金属酸化物を使用することが出来る。周期律第２
Ｂ〜６Ｂに属する典型金属としては、スズ、カドミウ
ム、亜鉛、鉛等が挙げられ、これらの周期律第２Ｂ〜６
Ｂに属する典型金属または典型金属酸化物の単独または
担持触媒として使用される。支持体としてはアルミナ、
シリカ、ゼオライト、チタニア、シリカアルミナ等が、
適宜、担体として使用出来る。遷移金属としては、ニッ
ケル、コバルト、銅、鉄、ルテニウム、ロジウム、白
金、銀、金、クロム、タングステン、モリプデン、バナ
ジウム等であり、それら金属の単独あるいは複合体、酸
化物、酸化物複合体として使用することが好ましい。好
適例を示せば、ニッケル、白金、銅亜鉛合金、銅クロム
合金、コバルト／モリブデン合金、コバルト／タングス
テン合金、コバルト／ニッケル／モリブデン合金、コバ
ルト／ニッケル／タングステン合金、ニッケル／モリブ
デン合金、ニッケル／タングステン合金およびこれらの
複合酸化物等が挙げられ、これら遷移金属の単独あるい
は複合体、酸化物、酸化物複合体を触媒として供しても
良いが、アルミナ、シリカ、ゼオライト、チタニア、シ
リカアルミナ等に担持させて反応に供することも出来
る。更に遷移金属の中でも８族に属するニッケル、コバ
ルト、鉄、ルテニウム、ロジウム、白金、パラジウムの
金属或いは金属酸化物は遷移金属の中でも活性が高くよ
り好ましく、また８族に属する金属と８族以外の遷移金
属例えばクロム、モリブデン、タングステン、バナジウ
ム等で構成される合金及び金属複合酸化物は活性が高く
より好ましい。As the catalyst used in the method for producing hydrocarbons of the present invention, typical metals or typical metal oxides belonging to Periodic Nos. 2B to 6B can be used. Periodic second
Typical metals belonging to B to 6B include tin, cadmium, zinc, lead, and the like.
It is used alone or as a supported catalyst of a typical metal belonging to B or a typical metal oxide. Alumina as the support,
Silica, zeolite, titania, silica-alumina, etc.
It can be appropriately used as a carrier. The transition metal includes nickel, cobalt, copper, iron, ruthenium, rhodium, platinum, silver, gold, chromium, tungsten, molypden, vanadium, etc., and these metals alone or as a complex, oxide, or oxide complex. Preference is given to using. Preferred examples are nickel, platinum, copper-zinc alloy, copper-chromium alloy, cobalt / molybdenum alloy, cobalt / tungsten alloy, cobalt / nickel / molybdenum alloy, cobalt / nickel / tungsten alloy, nickel / molybdenum alloy, nickel / tungsten. Examples thereof include alloys and their composite oxides, and these transition metals may be used alone or in the form of composites, oxides, and oxide composites as catalysts, but they are supported on alumina, silica, zeolite, titania, silica-alumina, etc. It can also be used for the reaction. Further, among the transition metals, nickel, cobalt, iron, ruthenium, rhodium, platinum, and palladium or metal oxides belonging to Group 8 have high activity among the transition metals and are more preferable, and metals belonging to Group 8 and those other than Group 8 are also preferable. Alloys composed of transition metals such as chromium, molybdenum, tungsten, vanadium and the like and metal composite oxides are more preferable because of their high activity.
【００２９】触媒の使用にあたっては、そのまま使用し
ても良いが、本発明に最も適する方法は、予め或いは反
応の直前に反応に供する触媒に硫黄化合物で処理した物
を使うことが好ましい。The catalyst may be used as it is, but the most suitable method of the present invention is to use a catalyst treated with a sulfur compound in advance, or just before the reaction, for the catalyst to be used in the reaction.
【００３０】前処理に使用する硫黄化合物としては硫化
水素、二硫化炭素、チオフェン、チオール、スルフィド
等が上げられるが、前処理の簡便性より硫化水素が特に
好ましい。As the sulfur compound used in the pretreatment, hydrogen sulfide, carbon disulfide, thiophene, thiol, sulfide and the like can be mentioned, but hydrogen sulfide is particularly preferable because of the ease of pretreatment.
【００３１】触媒の前処理に当たっては、公知の方法で
可能であるが、水素及び不活性ガスで希釈された硫化水
素を混合したガスにより前処理する方法が最も簡便で好
ましい。The pretreatment of the catalyst can be carried out by a known method, but the method of pretreatment with a mixed gas of hydrogen and hydrogen sulfide diluted with an inert gas is the most simple and preferable.
【００３２】具体的には、上記触媒を流通式反応器に入
れ、１〜１０ｗｔ％の硫化水素を含有する水素混合ガス
を適度な流速で流しながら１００〜５００℃に昇温した
後、０．５〜１０時間その温度に維持してから室温まで
冷却し取り出すことにより容易に調整できる。Specifically, the above catalyst was placed in a flow reactor and the temperature was raised to 100 to 500 ° C. while flowing a hydrogen mixed gas containing 1 to 10 wt% of hydrogen sulfide at an appropriate flow rate. It can be easily adjusted by maintaining the temperature for 5 to 10 hours, then cooling to room temperature and taking out.
【００３３】本発明炭化水素の製造方法において使用す
る水素は純粋なものである必要はなく、いかなる純度、
濃度の水素ガスも使用できるが、好ましくは工業用水素
ガスである。The hydrogen used in the process for producing hydrocarbons of the present invention does not have to be pure and may be of any purity,
Hydrogen gas having a concentration can be used, but industrial hydrogen gas is preferable.
【００３４】より具体的に炭化水素の製造方法を開示す
ると本発明において用いる炭化水素製造装置は、回分式
反応器または流通式反応器のいずれでも良い。上記装置
による炭化水素製造の際、水素源ガスのガス圧力は常圧
下でも加圧下でも良く、製造する炭化水素の成分及び製
造設備により適宜変えることができる．好ましくは常圧
から４０ＭＰａである．上記装置による炭化水素製造の
際の使用温度は、摂氏２０℃から８００度の高温下でも
良く、好ましくは１００〜４００℃である。更に好まし
くは１５０〜２５０度の領域である。The hydrocarbon producing apparatus used in the present invention will be disclosed as a more specific hydrocarbon producing method. The hydrocarbon producing apparatus may be either a batch reactor or a flow reactor. During the production of hydrocarbons by the above apparatus, the gas pressure of the hydrogen source gas may be under normal pressure or under pressure, and can be appropriately changed depending on the components of the hydrocarbon to be produced and production equipment. It is preferably normal pressure to 40 MPa. The temperature for use in the production of hydrocarbons by the above apparatus may be a high temperature of 20 ° C to 800 ° C, preferably 100 to 400 ° C. More preferably, it is in the range of 150 to 250 degrees.
【００３５】摂氏２０℃を下回ると十分な触媒活性が得
られず、８００℃を上回ると分解反応、触媒の耐久性及
び設備上の点から好ましくない。最適温度である１５０
〜２５０度を含め石油化学で行われる４００〜４５０度
の処理温度に比較して低温で炭化水素が製造されるの
で、炭化水素の切断等の副反応が起こりにくく、製造コ
ストも低く押さえることが可能となる。When the temperature is lower than 20 ° C, sufficient catalytic activity cannot be obtained, and when the temperature is higher than 800 ° C, the decomposition reaction, the durability of the catalyst and the facility are not preferable. The optimum temperature is 150
Since hydrocarbons are produced at a lower temperature than the processing temperature of 400 to 450 degrees, which is performed in petrochemistry including 250 degrees Celsius, side reactions such as cutting of hydrocarbons are less likely to occur and production costs can be kept low. It will be possible.
【００３６】本発明に係る反応は反応原料、触媒及び水
素の系で行われるが、原料により適宜溶媒を使用するこ
とが出来る。溶媒としては脂肪族及び芳香族系炭化水
素、アルコール等の各種有機溶媒、あるいは水等が上げ
られる。また、反応原料の液性は中性溶液、酸性溶液、
アルカリ性溶液とも用いることが出来、特に限定されな
い。The reaction according to the present invention is carried out in the system of reaction raw material, catalyst and hydrogen, but a solvent can be appropriately used depending on the raw material. Examples of the solvent include aliphatic and aromatic hydrocarbons, various organic solvents such as alcohol, and water. The liquid properties of the reaction raw materials are neutral solution, acidic solution,
It can be used with an alkaline solution and is not particularly limited.
【００３７】[0037]
【実施例】本発明を下記実施例によりさらに詳細に説明
するが、本発明はこれらの実施例により限定されるもの
でない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００３８】製造例１ 硫化水素処理Ｎｉ／Ｗ-アルミ
ナ触媒の調整
Ｎｉ／Ｗ-アルミナ触媒６．０ｇを流通式反応器に入
れ、５ｗｔ％の硫化水素を含有する水素混合ガスを適度
な流速で流しながら３００℃に昇温した後、２時間その
温度に維持してから室温まで冷却し取り出した。Preparation Example 1 Preparation of Ni / W-Alumina Catalyst Treated with Hydrogen Sulfide 6.0 g of Ni / W-alumina catalyst was placed in a flow reactor, and a hydrogen mixed gas containing 5 wt% of hydrogen sulfide was added at an appropriate flow rate. After the temperature was raised to 300 ° C. while flowing, the temperature was maintained for 2 hours, then cooled to room temperature and taken out.
【００３９】製造例２ 硫化水素処理Ｃｏ／Ｍｏ触媒の
調整
Ｃｏ／Ｍｏ触媒６．０ｇを流通式反応器に入れ、５ｗｔ
％の硫化水素を含有する水素混合ガスを適度な流速で流
しながら３３０℃に昇温した後、８時間その温度に維持
した後室温まで冷却し取り出した。Production Example 2 Preparation of Co / Mo Catalyst Treated with Hydrogen Sulfide 6.0 g of Co / Mo catalyst was placed in a flow reactor and 5 wt.
The temperature was raised to 330 ° C. while flowing a hydrogen mixed gas containing hydrogen sulfide at an appropriate flow rate, maintained at that temperature for 8 hours, cooled to room temperature, and taken out.
【００４０】製造例３ 硫化水素処理Ｎｉ／Ｗ触媒の調
整
Ｎｉ／Ｗ触媒６．０ｇを流通式反応器に入れ、５ｗｔ％
の硫化水素を含有する水素混合ガスを適度な流速で流し
ながら３００℃に昇温した後、２時間その温度に維持し
てから室温まで冷却し取り出した。Production Example 3 Preparation of Ni / W catalyst treated with hydrogen sulfide 6.0 g of Ni / W catalyst was put into a flow reactor to obtain 5 wt%.
The hydrogen mixed gas containing hydrogen sulfide of was heated to 300 ° C. while flowing at an appropriate flow rate, maintained at that temperature for 2 hours, cooled to room temperature, and taken out.
【００４１】実施例１
予め、製造例１で製造した触媒３．０ｇと、羊脂１００
ｍｌを回分式反応器に仕込んだ後、回分式反応器中の空
気を窒素続いて水素と置換し、所定の水素圧力（４ＭＰ
ａ）に設定し、さらに所定の温度（３２０℃）まで上昇
させた後に、激しく撹拌して（２０時間）反応を行っ
た。その後、容器より内容物を取り出し固形物をロ過に
より分離したところ、無色透明な液状物質が仕込み量の
７８wt％回収された。この液状物質をＧＣ−ＭＳ装置で
分析したところ、主成分はＣ１４〜Ｃ１８の脂肪族系炭
化水素であった。
トータルイオンクロマトグラムの面積百分率
Ｃ14Ｈ30 ： ２．３８％ Tetradecane
Ｃ15Ｈ32 ： ２．２６％ Penntadecane
Ｃ16Ｈ34 ： ２１．８４％ Hexadecane
Ｃ17Ｈ36 ： ６．２０％ Heputadecane
Ｃ18Ｈ36 ： ７．５４％ 9-Octadecene
Ｃ18Ｈ38 ： ４９．８１％ Octadecane。Example 1 3.0 g of the catalyst previously produced in Production Example 1 and 100% sheep's fat
After charging ml to the batch type reactor, the air in the batch type reactor was replaced with nitrogen and then with hydrogen to obtain a predetermined hydrogen pressure (4MP).
After the temperature was set to a) and the temperature was further raised to a predetermined temperature (320 ° C.), the reaction was vigorously stirred (20 hours). Then, the contents were taken out of the container and the solid substance was separated by filtration. As a result, a colorless and transparent liquid substance was recovered in an amount of 78 wt% of the charged amount. When this liquid substance was analyzed by a GC-MS apparatus, the main component was C14 to C18 aliphatic hydrocarbon. Area percentage of total ion chromatogram C 14 H 30 : 2.38% Tetradecane C 15 H 32 : 2.26% Penntadecane C 16 H 34 : 21.84% Hexadecane C 17 H 36 : 6.20% Heputadecane C 18 H 36: 7.54% 9-octadecene C 18 H 38: 49.81% Octadecane.
【００４２】実施例２
予め、製造例２で製造した触媒３．０ｇと、牛脂１００
ｍｌを回分式反応器に仕込んだ後、回分式反応器中の空
気を窒素続いて水素と置換し、所定の水素圧力（４ＭＰ
ａ）に設定し、さらに所定の温度（２５０℃）まで上昇
させた後に、激しく撹拌して（２０時間）反応を行っ
た。その後、容器より内容物を取り出し固形物をロ過に
より分離したところ、無色透明な液状物質が仕込み量の
８２wt％回収された。この液状物質をＧＣ−ＭＳ装置で
分析したところ、主成分はＣ１４〜Ｃ１８の脂肪族系炭
化水素であった。Example 2 3.0 g of the catalyst prepared in Preparation Example 2 and 100 parts of beef tallow were prepared in advance.
After charging ml to the batch type reactor, the air in the batch type reactor was replaced with nitrogen and then with hydrogen to obtain a predetermined hydrogen pressure (4MP).
After the temperature was set to a) and the temperature was further raised to a predetermined temperature (250 ° C.), the reaction was vigorously stirred (20 hours). Then, the contents were taken out of the container and the solid substance was separated by filtration. As a result, a colorless and transparent liquid substance was recovered in an amount of 82 wt% of the charged amount. When this liquid substance was analyzed by a GC-MS apparatus, the main component was C14 to C18 aliphatic hydrocarbon.
【００４３】実施例３
反応物を植物油脂の粗バーム油に変えた以外は実施例２
と同様な条件で反応を行った。その後、容器より内容物
を取り出し固形物をロ過により分離したところ、少し黄
色がかった透明な液状物質が仕込み量の８０wt％回収さ
れた。この液状物質をＧＣ−ＭＳ装置で分析したとこ
ろ、主成分はＣ８〜Ｃ１８の脂肪族系炭化水素であっ
た。Example 3 Example 2 except that the reaction product was changed to crude balm oil of vegetable oil.
The reaction was carried out under the same conditions as in. Then, the contents were taken out of the container and the solid substance was separated by filtration. As a result, a slightly yellowish transparent liquid substance was recovered in an amount of 80 wt% of the charged amount. When this liquid substance was analyzed by a GC-MS apparatus, the main component was C8 to C18 aliphatic hydrocarbon.
【００４４】実施例４
触媒を製造例３の触媒に変えた以外は実施例２と同様な
条件で反応を行った。その後、容器より内容物を取り出
し固形物をロ過により分離したところ、少し黄色がかっ
た透明な液状物質が仕込み量の６０wt％回収された。こ
の液状物質をＧＣ−ＭＳ装置で分析したところ、主成分
はＣ１４〜Ｃ１８の脂肪族系炭化水素であった。Example 4 The reaction was carried out under the same conditions as in Example 2 except that the catalyst of Production Example 3 was used in place of the catalyst. Then, the contents were taken out of the container and the solid substance was separated by filtration. As a result, a slightly yellowish transparent liquid substance was recovered in an amount of 60 wt% of the charged amount. When this liquid substance was analyzed by a GC-MS apparatus, the main component was C14 to C18 aliphatic hydrocarbon.
【００４５】実施例５
反応物を植物油脂の粗バーム油に変え、さらに触媒を製
造例３の触媒に変えた以外は実施例２と同様な条件で反
応を行った。その後、容器より内容物を取り出し固形物
をロ過により分離したところ、少し黄色がかった透明な
液状物質が仕込み量の６３wt％回収された。この液状物
質をＧＣ−ＭＳ装置で分析したところ、主成分はＣ８〜
Ｃ１８の脂肪族系炭化水素であった。Example 5 A reaction was carried out under the same conditions as in Example 2 except that the reaction product was changed to crude balm oil of vegetable oil and fat, and the catalyst was changed to the catalyst of Production Example 3. Then, when the contents were taken out from the container and the solid was separated by filtration, a slightly yellowish transparent liquid substance was recovered in an amount of 63 wt% of the charged amount. When this liquid substance was analyzed by a GC-MS apparatus, the main component was C8-
It was a C18 aliphatic hydrocarbon.
【００４６】実施例６
触媒を製造例３の触媒に変え、反応温度を２００℃にし
た以外は実施例２と同様な条件で反応を行った。その
後、容器より内容物を取り出し固形物をロ過により分離
したところ、無色透明な液状物質が仕込み量の７５wt％
回収された。この液状物質をＧＣ−ＭＳ装置で分析した
ところ、主成分はＣ１４〜Ｃ１８の脂肪族系炭化水素で
あった。Example 6 The reaction was carried out under the same conditions as in Example 2 except that the catalyst of Production Example 3 was used as the catalyst and the reaction temperature was 200 ° C. After that, the contents were taken out of the container and the solid was separated by filtration. As a result, a colorless and transparent liquid substance was 75 wt% of the charged amount.
Recovered. When this liquid substance was analyzed by a GC-MS apparatus, the main component was C14 to C18 aliphatic hydrocarbon.
【００４７】実施例７
触媒を製造例３の触媒に変え、反応温度を２００℃に
し、原料を植物油脂の粗パーム油に変えた以外は実施例
１と同様な条件で反応を行った。その後、容器より内容
物を取り出し固形物をロ過により分離したところ、無色
透明な液状物質が仕込み量の７４wt％回収された。この
液状物質をＧＣ−ＭＳ装置で分析したところ、主成分は
Ｃ８〜Ｃ１８の脂肪族系炭化水素であった。Example 7 The reaction was carried out under the same conditions as in Example 1 except that the catalyst of Production Example 3 was used as the catalyst, the reaction temperature was 200 ° C., and the raw material was crude palm oil. Then, the contents were taken out of the container and the solid substance was separated by filtration. As a result, a colorless and transparent liquid substance was recovered in an amount of 74 wt% of the charged amount. When this liquid substance was analyzed by a GC-MS apparatus, the main component was C8 to C18 aliphatic hydrocarbon.
【００４８】[0048]
【発明の効果】本発明により、純粋な液状炭化水素類が
容易に且つ安全にしかも連続的に製造でき、製造場所を
選ばず、安価で高純度に得ることができる。Industrial Applicability According to the present invention, pure liquid hydrocarbons can be easily, safely and continuously produced continuously, inexpensively and highly purely at any production site.
【００４９】本発明により製造した炭化水素類は、大気
汚染の原因となる硫黄、窒素、あるいはベンゼンやベン
ツピレンの様なアロマチックスを含有しないので極めて
無公害でクリーンである。The hydrocarbons produced by the present invention are extremely pollution-free and clean because they do not contain sulfur, nitrogen, or aromatics such as benzene and benzpyrene, which cause air pollution.
【００５０】さらに本発明により生成する炭化水素類は
水素／炭素比が高く、燃焼に際して高エネルギーを発生
する。Further, the hydrocarbons produced according to the present invention have a high hydrogen / carbon ratio and generate high energy upon combustion.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０７Ｃ 9/14 Ｃ０７Ｃ 9/14 9/22 9/22 11/02 11/02 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (72)発明者 スティーブ バグショー ニュージーランド国，ウェリントン，カン ダラー，118 ホームブッシュロード (72)発明者 佐藤孝美 埼玉県川越市今福2835 川研ファインケミ カル株式会社内 (72)発明者 伊藤和久 埼玉県川越市今福2835 川研ファインケミ カル株式会社内 Ｆターム(参考） 4G069 AA02 AA03 BA01A BA01B BA02A BA04A BA05A BA07A BB02A BB06A BB09A BB09B BC30A BC34A BC53A BC57A BC59B BC60B BC65A BC67B BC68B BC69A CC05 CC40 4H006 AA02 AC11 BA09 BA11 BA13 BA14 BA15 BA17 BA20 BA21 BA30 BA55 BC10 BC11 BE20 4H039 CA19 CA29 CB10 CB20 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C07C 9/14 C07C 9/14 9/22 9/22 11/02 11/02 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Steve Bagshaw, New Zealand, Wellington, Kanderer, 118 Home Bush Road (72) Inventor Takami Sato 2835 Imafuku, Kawagoe City, Saitama Prefecture (72) Inventor Kazuhisa Ito 2835 Imafuku, Kawagoe City, Saitama Prefecture F-term within Kawaken Fine Chemicals Co., Ltd. (reference) 4G069 AA02 AA03 BA01A BA01B BA02A BA04A BA05A BA07A BB02A BB06A BB09A BB09B BC30A BC34A BC53A BC57A BC59A BC59A BC59A BC59A BC59A BC59A BA11 BA13 BA14 BA15 BA17 BA20 BA21 BA30 BA55 BC10 BC11 BE20 4H039 CA19 CA29 CB10 CB20
Claims (5)
油脂から選ばれる少なくとも１種と、活性化した水素と
を金属触媒、合金触媒、金属担持触媒および合金担持触
媒からなる群より選ばれる触媒の存在下反応させること
を特徴とする炭化水素類の製造方法。1. A catalyst selected from the group consisting of metal catalysts, alloy catalysts, metal-supported catalysts and alloy-supported catalysts, wherein at least one selected from natural fats and oils, natural fats and oils derivatives and waste natural fats and oils, and activated hydrogen. A method for producing hydrocarbons, which comprises reacting in the presence of a hydrocarbon.
れた触媒であることを特徴とする請求項１に記載の炭化
水素類の製造方法。2. The method for producing hydrocarbons according to claim 1, wherein the catalyst is a catalyst pretreated with a sulfur-containing compound.
たは典型金属酸化物又は、遷移金属の単独あるいは複合
体、酸化物、酸化物複合体から選択され、硫化水素で前
処理された触媒からなることを特徴とする天然油脂また
はその誘導体から炭化水素類を製造するための炭化水素
類製造用触媒。3. A catalyst selected from a typical metal or a typical metal oxide belonging to Periodic Nos. 2B to 6B, a transition metal alone or a complex, an oxide or an oxide complex, which is pretreated with hydrogen sulfide. A catalyst for producing hydrocarbons for producing hydrocarbons from natural fats and oils or their derivatives.
遷移金属からなる合金及び金属複合酸化物からなる事を
特徴とする天然油脂またはその誘導体から炭化水素類を
製造するための炭化水素類製造用触媒。4. A hydrocarbon for producing hydrocarbons from natural fats and oils or their derivatives, which comprises an alloy of a metal belonging to Group 8 of transition metals and a transition metal other than Group 8 and a metal complex oxide. Catalysts for manufacturing products.
化水素類を製造するための炭化水素類製造用触媒をシリ
カ、アルミナ、ゼオライト、チタニア、ジルコニア等の
担体に担持したことを特徴とする天然油脂またはその誘
導体から炭化水素類を製造するための炭化水素類製造用
触媒。5. The hydrocarbon-producing catalyst for producing the hydrocarbons according to claim 3 or 4 is carried on a carrier such as silica, alumina, zeolite, titania, zirconia or the like. A catalyst for producing hydrocarbons for producing hydrocarbons from natural fats and oils or its derivatives.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001374642A JP2003171670A (en) | 2001-12-07 | 2001-12-07 | Method for producing hydrocarbons and catalyst for producing hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001374642A JP2003171670A (en) | 2001-12-07 | 2001-12-07 | Method for producing hydrocarbons and catalyst for producing hydrocarbons |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003171670A true JP2003171670A (en) | 2003-06-20 |
Family
ID=19183176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001374642A Pending JP2003171670A (en) | 2001-12-07 | 2001-12-07 | Method for producing hydrocarbons and catalyst for producing hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003171670A (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006192380A (en) * | 2005-01-14 | 2006-07-27 | Matsushita Electric Ind Co Ltd | Gas adsorption alloy |
| WO2007063872A1 (en) * | 2005-11-30 | 2007-06-07 | Nippon Oil Corporation | Method for production of hydrogen, method for production of re-formulated gasoline, and method for production of aromatic hydrocarbon |
| WO2007132857A1 (en) * | 2006-05-17 | 2007-11-22 | Nippon Oil Corporation | Hydrorefining process |
| JP2007308563A (en) * | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | Hydrofining method |
| JP2007308565A (en) * | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | Hydrogenation purification method |
| JP2007308574A (en) * | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | Gasoline composition |
| JP2007308564A (en) * | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | Hydrogenation purification method |
| JP2007308566A (en) * | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | Hydrogenation purification method and environmental low load type gasoline base material |
| JP2007332360A (en) * | 2006-05-17 | 2007-12-27 | Nippon Oil Corp | Gasoline composition |
| WO2008117856A1 (en) | 2007-03-28 | 2008-10-02 | Nippon Oil Corporation | Gas oil composition |
| JP2008239876A (en) * | 2007-03-28 | 2008-10-09 | Nippon Oil Corp | Gas oil composition |
| JP2008239875A (en) * | 2007-03-28 | 2008-10-09 | Nippon Oil Corp | Gas oil composition |
| JP2008545034A (en) * | 2005-07-04 | 2008-12-11 | ネステ オイル オサケ ユキチュア ユルキネン | Method for producing diesel range hydrocarbons |
| WO2008157465A2 (en) * | 2007-06-15 | 2008-12-24 | E. I. Du Pont De Nemours And Company | Catalytic process for converting renewable resources into paraffins for use as diesel blending stocks |
| WO2009011160A1 (en) * | 2007-07-13 | 2009-01-22 | Nippon Oil Corporation | Process for producing hydrocarbon oil |
| JP2009518533A (en) * | 2005-12-12 | 2009-05-07 | ネステ オイル オサケ ユキチュア ユルキネン | Process for producing hydrocarbons |
| JP2009275113A (en) * | 2008-05-14 | 2009-11-26 | Nippon Oil Corp | Gas oil base and gas oil composition |
| WO2010032752A1 (en) | 2008-09-18 | 2010-03-25 | 新日本石油株式会社 | Process for producing hydrocarbon oil |
| KR20100102050A (en) * | 2009-03-10 | 2010-09-20 | 아이에프피 | Process for hydrodeoxygenation of feeds derived from renewable sources with limited decarboxylation conversion using a catalyst based on nickel and molybdenum |
| WO2010068904A3 (en) * | 2008-12-12 | 2011-01-06 | E. I. Du Pont De Nemours And Company | Process for making linear dicarboxylic acids from renewable resources |
| JP2011148909A (en) * | 2010-01-21 | 2011-08-04 | Tokyo Univ Of Agriculture & Technology | Biohydrocarbon, method for manufacturing biohydrocarbon and apparatus for manufacturing biohydrocarbon |
| JP2012077131A (en) * | 2010-09-30 | 2012-04-19 | Hidenori Kanetsuna | Method for producing biopetroleum fuel, catalyst used therein and production system |
| US8212094B2 (en) | 2005-07-05 | 2012-07-03 | Neste Oil Oyj | Process for the manufacture of diesel range hydrocarbons |
| US8278492B2 (en) | 2005-07-05 | 2012-10-02 | Neste Oil Oyj | Process for the manufacture of diesel range hydrocarbons |
| CN110845290A (en) * | 2019-11-02 | 2020-02-28 | 华东师范大学 | Preparation method of biomass-based T-type low-viscosity fully-synthetic lubricating oil |
-
2001
- 2001-12-07 JP JP2001374642A patent/JP2003171670A/en active Pending
Cited By (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006192380A (en) * | 2005-01-14 | 2006-07-27 | Matsushita Electric Ind Co Ltd | Gas adsorption alloy |
| JP4741661B2 (en) * | 2005-07-04 | 2011-08-03 | ネステ オイル オサケ ユキチュア ユルキネン | Method for producing diesel range hydrocarbons |
| JP2008545034A (en) * | 2005-07-04 | 2008-12-11 | ネステ オイル オサケ ユキチュア ユルキネン | Method for producing diesel range hydrocarbons |
| US10059887B2 (en) | 2005-07-05 | 2018-08-28 | Neste Oyj | Process for the manufacture of diesel range hydrocarbons |
| US9598327B2 (en) | 2005-07-05 | 2017-03-21 | Neste Oil Oyj | Process for the manufacture of diesel range hydrocarbons |
| US8212094B2 (en) | 2005-07-05 | 2012-07-03 | Neste Oil Oyj | Process for the manufacture of diesel range hydrocarbons |
| US8278492B2 (en) | 2005-07-05 | 2012-10-02 | Neste Oil Oyj | Process for the manufacture of diesel range hydrocarbons |
| US8859832B2 (en) | 2005-07-05 | 2014-10-14 | Neste Oil Oyj | Process for the manufacture of diesel range hydrocarbons |
| US10550332B2 (en) | 2005-07-05 | 2020-02-04 | Neste Oyj | Process for the manufacture of diesel range hydrocarbons |
| US10800976B2 (en) | 2005-07-05 | 2020-10-13 | Neste Oyj | Process for the manufacture of diesel range hydrocarbons |
| US11473018B2 (en) | 2005-07-05 | 2022-10-18 | Neste Oyj | Process for the manufacture of diesel range hydrocarbons |
| JP2007153931A (en) * | 2005-11-30 | 2007-06-21 | Nippon Oil Corp | Method for producing hydrogen, method for producing reformed gasoline and method for producing aromatic hydrocarbon |
| WO2007063872A1 (en) * | 2005-11-30 | 2007-06-07 | Nippon Oil Corporation | Method for production of hydrogen, method for production of re-formulated gasoline, and method for production of aromatic hydrocarbon |
| JP2009518533A (en) * | 2005-12-12 | 2009-05-07 | ネステ オイル オサケ ユキチュア ユルキネン | Process for producing hydrocarbons |
| WO2007132857A1 (en) * | 2006-05-17 | 2007-11-22 | Nippon Oil Corporation | Hydrorefining process |
| JP2007332360A (en) * | 2006-05-17 | 2007-12-27 | Nippon Oil Corp | Gasoline composition |
| JP2007308566A (en) * | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | Hydrogenation purification method and environmental low load type gasoline base material |
| JP2007308563A (en) * | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | Hydrofining method |
| JP2007308564A (en) * | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | Hydrogenation purification method |
| KR101362950B1 (en) * | 2006-05-17 | 2014-02-12 | 제이엑스 닛코닛세키에너지주식회사 | Hydrorefining process |
| JP2007308574A (en) * | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | Gasoline composition |
| JP2007308565A (en) * | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | Hydrogenation purification method |
| JP2008239876A (en) * | 2007-03-28 | 2008-10-09 | Nippon Oil Corp | Gas oil composition |
| WO2008117856A1 (en) | 2007-03-28 | 2008-10-02 | Nippon Oil Corporation | Gas oil composition |
| JP2008239875A (en) * | 2007-03-28 | 2008-10-09 | Nippon Oil Corp | Gas oil composition |
| WO2008157465A2 (en) * | 2007-06-15 | 2008-12-24 | E. I. Du Pont De Nemours And Company | Catalytic process for converting renewable resources into paraffins for use as diesel blending stocks |
| WO2008157465A3 (en) * | 2007-06-15 | 2009-11-19 | E. I. Du Pont De Nemours And Company | Catalytic process for converting renewable resources into paraffins for use as diesel blending stocks |
| CN101743291B (en) * | 2007-07-13 | 2012-12-26 | 新日本石油株式会社 | Process for producing hydrocarbon oil |
| WO2009011160A1 (en) * | 2007-07-13 | 2009-01-22 | Nippon Oil Corporation | Process for producing hydrocarbon oil |
| JP2009019175A (en) * | 2007-07-13 | 2009-01-29 | Nippon Oil Corp | Hydrocarbon oil production method |
| KR101451604B1 (en) | 2007-07-13 | 2014-10-16 | 제이엑스 닛코닛세키에너지주식회사 | Process for producing hydrocarbon oil |
| JP2009275113A (en) * | 2008-05-14 | 2009-11-26 | Nippon Oil Corp | Gas oil base and gas oil composition |
| US8784645B2 (en) | 2008-09-18 | 2014-07-22 | Jx Nippon Oil & Energy Corporation | Process for producing hydrocarbon oil |
| WO2010032752A1 (en) | 2008-09-18 | 2010-03-25 | 新日本石油株式会社 | Process for producing hydrocarbon oil |
| CN102439118A (en) * | 2008-12-12 | 2012-05-02 | 纳幕尔杜邦公司 | Process for making linear dicarboxylic acids from renewable resources |
| US8753853B2 (en) * | 2008-12-12 | 2014-06-17 | E I Du Pont De Nemours And Company | Process for making linear dicarboxylic acids from renewable resources |
| WO2010068904A3 (en) * | 2008-12-12 | 2011-01-06 | E. I. Du Pont De Nemours And Company | Process for making linear dicarboxylic acids from renewable resources |
| JP2012511907A (en) * | 2008-12-12 | 2012-05-31 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Method for producing linear dicarboxylic acid from renewable resources |
| CN102439118B (en) * | 2008-12-12 | 2015-04-01 | 纳幕尔杜邦公司 | Process for making linear dicarboxylic acids from renewable resources |
| US20110300594A1 (en) * | 2008-12-12 | 2011-12-08 | E.I. Du Pont De Nemours And Company | Process for making linear dicarboxylic acids from renewable resources |
| KR20100102050A (en) * | 2009-03-10 | 2010-09-20 | 아이에프피 | Process for hydrodeoxygenation of feeds derived from renewable sources with limited decarboxylation conversion using a catalyst based on nickel and molybdenum |
| KR101673597B1 (en) | 2009-03-10 | 2016-11-07 | 아이에프피 에너지 누벨르 | Process for hydrodeoxygenation of feeds derived from renewable sources with limited decarboxylation conversion using a catalyst based on nickel and molybdenum |
| JP2010209330A (en) * | 2009-03-10 | 2010-09-24 | Ifp | Method for hydrodeoxygenation of charged material from renewable source with limited conversion to decarboxylation implementing nickel and molybdenum based catalyst |
| JP2011148909A (en) * | 2010-01-21 | 2011-08-04 | Tokyo Univ Of Agriculture & Technology | Biohydrocarbon, method for manufacturing biohydrocarbon and apparatus for manufacturing biohydrocarbon |
| JP2012077131A (en) * | 2010-09-30 | 2012-04-19 | Hidenori Kanetsuna | Method for producing biopetroleum fuel, catalyst used therein and production system |
| CN110845290A (en) * | 2019-11-02 | 2020-02-28 | 华东师范大学 | Preparation method of biomass-based T-type low-viscosity fully-synthetic lubricating oil |
| CN110845290B (en) * | 2019-11-02 | 2022-07-15 | 华东师范大学 | Preparation method of biomass-based T-type low-viscosity fully-synthesized lubricating oil |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2003171670A (en) | Method for producing hydrocarbons and catalyst for producing hydrocarbons | |
| JP5281410B2 (en) | Process for producing branched hydrocarbon components | |
| EP2177587B1 (en) | Deoxygenation of materials of biological origin | |
| Thakur et al. | Catalysts for fatty alcohol production from renewable resources | |
| ES2258472T3 (en) | PROCEDURE FOR THE REACTIVATION OF TITANIA COBALTO CATALYSTS DEACTIVATED BY SULFUR. | |
| CN108465462A (en) | Catalyst, the preparation method of catalyst, the method for deoxidation and the system for fuel making | |
| JP2009518532A (en) | Process for producing branched hydrocarbon components | |
| US20110087058A1 (en) | Deoxygenation of materials of biological origin | |
| CN105237319B (en) | Method for preparation of long-chain alkane from unsaturated fatty acid at zero hydrogen consumption | |
| BRPI0811661A2 (en) | process of hydrotreating a liquid food and process for hydrodeoxygenation of a renewable resource | |
| WO2007063879A1 (en) | Hydrorefining process and hydrorefined oil | |
| CN1189147A (en) | Process for producing oxygenated products | |
| CN102239233A (en) | Hydrocarbon composition useful as fuel and combustible obtained from oil components and a biological component | |
| US3766054A (en) | Demetalation of hydrocarbon charge stocks | |
| JP2003522819A (en) | Integrated manufacturing method for converting natural gas and gas field condensates into high value liquid products | |
| CN115244156A (en) | Cost effective deoxygenation process with gas recycle | |
| JP4143411B2 (en) | Desulfurization of hydrotreated Fischer-Tropsch products | |
| RU2603967C1 (en) | Method for selective production of fraction alkanes, suitable for petrol and diesel fuel | |
| Loe et al. | Upgrading of Lipids to Fuel‐like Hydrocarbons and Terminal Olefins via Decarbonylation/Decarboxylation | |
| JPS6041113B2 (en) | Hydrocarbon conversion methods | |
| CN1233797C (en) | Hydrogenating modifying process for direct liquefying diesel oil of coal | |
| CN108315051B (en) | Method for producing hydrocarbon by using biological material and hydrocarbon and fuel thereof | |
| JP2003160515A (en) | Method for producing decalin from naphthalene by two stage hydrogeneration reaction | |
| JP2617214B2 (en) | Production of high quality isoparaffin | |
| JP2003212800A (en) | Method for producing decalin by hydrogenating naphthalene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20041112 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20061031 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20061107 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20070306 |