WO2010101120A1 - Appareil de production d'hydrocarbures aromatiques ou de composés cétonique, appareil de production d'acide lévulinique, appareil de séparation d'acide lévulinique, et appareil de production d'hydrocarbures à partir d'acide lévulinique - Google Patents

Appareil de production d'hydrocarbures aromatiques ou de composés cétonique, appareil de production d'acide lévulinique, appareil de séparation d'acide lévulinique, et appareil de production d'hydrocarbures à partir d'acide lévulinique Download PDF

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WO2010101120A1
WO2010101120A1 PCT/JP2010/053255 JP2010053255W WO2010101120A1 WO 2010101120 A1 WO2010101120 A1 WO 2010101120A1 JP 2010053255 W JP2010053255 W JP 2010053255W WO 2010101120 A1 WO2010101120 A1 WO 2010101120A1
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Prior art keywords
acid
biomass
levulinic acid
reactor
reaction
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PCT/JP2010/053255
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English (en)
Japanese (ja)
Inventor
俊雄 筒井
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国立大学法人 鹿児島大学
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Priority claimed from JP2009048439A external-priority patent/JP5504494B2/ja
Priority claimed from JP2009048421A external-priority patent/JP5504493B2/ja
Application filed by 国立大学法人 鹿児島大学 filed Critical 国立大学法人 鹿児島大学
Publication of WO2010101120A1 publication Critical patent/WO2010101120A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper

Definitions

  • the aspect of the present invention I relates to an apparatus (method) for producing an aromatic hydrocarbon or a ketone compound.
  • the aspect of the present invention II relates to an apparatus (method) for producing levulinic acid from biomass, an adsorption / separation apparatus (method) for levulinic acid, and an apparatus (method) for producing hydrocarbons from levulinic acid.
  • Biomass conversion techniques such as thermochemical conversion methods such as decomposition with subcritical water (Patent Publication 2008-249207) and methane fermentation and ethanol fermentation (Patent Publication 2008-182925) have been known as biomass conversion techniques. It has been.
  • thermochemical conversion method in the case of gasification, it is generally converted to a gas containing hydrogen or carbon monoxide at a high temperature of 700 ° C. or higher.
  • This gasification product is further separated from CO 2 and purified to be used as a methanol synthesis raw material, and further through dimethyl ether as a chemical raw material for aromatics and olefins.
  • a complicated and multi-step process is required to convert it into a chemical raw material, which is not economical.
  • Supercritical water decomposition can be converted into oxygen-containing hydrocarbon compounds such as hydroxymethylfurfural, furfural, dihydroxyacetone and glyceraldehyde, but its use is limited, and basic chemical substances are not necessarily produced.
  • methane and CO 2 can be obtained in methane fermentation, but since it is a mixture, the calorific value is low.
  • ethanol fermentation ethanol obtained together with CO 2 is expected as a gasoline alternative fuel. It is difficult to say that it is a high value-added product for the energy consumption and production cost required for separation, and more steps are required to make it a high-value-added chemical raw material.
  • a method for producing a high chemical substance in a short process has not been sufficiently established. Therefore, there is still an urgent need to develop a method for directly producing chemical raw materials that are high-value-added basic chemical substances using biomass.
  • decomposition with supercritical water produces various decomposition products such as 5-hydroxymethylfurfural and oxygenated tar, but these products are not necessarily basic chemical substances and have little utility value. Also when the excessive reaction in supercritical water to produce large quantities of CO 2, not achieve the reduction of CO 2.
  • ethanol fermentation is expected as an alternative to gasoline, but there are problems such as low added value to cost and the need for enormous energy input to separate ethanol and water. Accordingly, there is a need to realize a method for producing a basic chemical substance from biomass that suppresses excessive energy consumption and extremely suppresses CO 2 emission.
  • levulinic acid can be obtained by treating the sugar with an acid.
  • a carbonaceous material is easily produced as a by-product, and a method for selectively producing levulinic acid in a high yield has not been clarified.
  • the use of levulinic acid is not known except as a raw material for aminolevulinic acid, an agrochemical, and if levulinic acid can be converted and industrial hydrocarbons can be obtained efficiently, it will be epoch-making. Technology.
  • the present invention is an apparatus for producing an aromatic hydrocarbon or ketone compound,
  • a reactor for reacting an organic acid with a zeolite catalyst (preferably a ZSM-5 type zeolite catalyst) is provided.
  • the present invention also proposes a method for producing an aromatic hydrocarbon or ketone compound, which comprises reacting an organic acid with a zeolite catalyst (preferably a ZSM-5 type zeolite catalyst). To do.
  • an apparatus for producing an aromatic hydrocarbon or a ketone compound from biomass A first feeder for supplying biomass and acid-fermenting bacteria to the first reactor; A first reactor for fermenting the biomass with the acid-fermenting bacteria to produce an organic acid; A second feeder for feeding the produced organic acid and a zeolite catalyst (preferably a ZSM-5 type zeolite catalyst) to the second reactor; It comprises a second reactor for reacting the organic acid with a zeolite catalyst (preferably a ZSM-5 type zeolite catalyst) under heating.
  • a zeolite catalyst preferably a ZSM-5 type zeolite catalyst
  • Another aspect of the present invention is a method for producing an aromatic hydrocarbon or ketone compound from biomass, Prepare biomass and acid-fermenting bacteria, Fermenting the biomass with the acid-fermenting bacteria to produce an organic acid, And reacting the produced organic acid with a zeolite catalyst (preferably a ZSM-5 type zeolite catalyst) under heating.
  • a zeolite catalyst preferably a ZSM-5 type zeolite catalyst
  • the present invention is an essential chemical substance necessary for human society using an organic acid (preferably obtained from biomass), and can produce a high value-added chemical raw material in a high yield. More preferably, in the present invention, each process from biomass as a raw material to a product can be performed with low energy (or without using energy), and the production cost can be significantly reduced, It becomes possible to achieve production efficiency (yield improvement).
  • “levulinic acid” obtained by the method (apparatus) of the embodiment II of the present invention can be used as a raw material. Therefore, in a preferred embodiment of the present invention, it is possible to propose a hydrocarbon production method (manufacturing apparatus) that combines the embodiment of the present invention II and the embodiment of the present invention I.
  • Embodiment of Invention II First Embodiment of Invention II
  • the present inventor carried out a reaction (preferably a hydrothermal reaction) with biomass using an acid catalyst, and thus, the basic chemistry was performed under low energy. It was found that levulinic acid, which is one of the substances, can be selectively obtained in high yield.
  • the first aspect of the present invention II has been made based on such findings.
  • the first aspect of the present invention II proposes a production apparatus for producing levulinic acid from biomass, A feeder for supplying biomass, an acid catalyst and water to the reactor; The biomass, the acid catalyst, and a reactor for reacting the water are provided.
  • a method for producing levulinic acid from biomass is proposed, Prepare biomass, acid catalyst and water, Reacting the biomass, the acid catalyst, and the water.
  • the first aspect of the present invention II is a production apparatus that uses biomass and is a basic chemical substance necessary in the human society and produces high-value-added chemical raw materials in high yield and with low energy consumption in the production process. (Method) is provided.
  • Second aspect of Invention II At the time of the present invention, the present inventor made contact with the composition comprising a significant amount of levulinic acid under heating with an adsorbent under low energy. It was found that one levulinic acid can be efficiently separated from the composition by adsorbing it to the adsorbent. The second aspect of the present invention II has been made based on such findings.
  • the second aspect of the present invention II is an apparatus for separating levulinic acid from a composition comprising levulinic acid, and proposes the apparatus.
  • a feeder for supplying the adsorber with a composition comprising levulinic acid and an adsorbent;
  • An adsorber for bringing the composition into contact with the adsorbent and adsorbing levulinic acid to the adsorbent is provided.
  • a method for separating levulinic acid from a composition comprising levulinic acid is proposed.
  • the composition comprising levulinic acid and an adsorbent are brought into contact under heating, and levulinic acid is adsorbed from the composition onto the adsorbent.
  • the second aspect of the present invention II is adsorbed on the adsorbent, does not evaporate a solvent such as water, and the amount of adsorbed water is very small. It is extremely small, which is good in terms of both production cost reduction and production efficiency.
  • the distillation method used for concentration and separation of levulinic acid requires a very large amount of energy to evaporate a large amount of water. Therefore, it can be said that the second aspect of the present invention II is a very effective production technique as compared with the distillation method.
  • the present inventor made a reaction between levulinic acid and a zeolite catalyst or an adsorbent adsorbing levulinic acid by heating to produce industrial raw materials under low energy. The knowledge that it can produce efficiently (conversion) to a certain hydrocarbon was acquired. The third aspect of the present invention II has been made based on this finding.
  • the third aspect of the present invention II proposes an apparatus for obtaining hydrocarbons from levulinic acid, A feeder for supplying levulinic acid and a zeolite catalyst to the reactor; A reactor for reacting the levulinic acid with the zeolite catalyst is provided.
  • a method for producing a hydrocarbon from levulinic acid is proposed, Prepare levulinic acid and zeolite catalyst, It comprises reacting levulinic acid with the zeolite catalyst.
  • Preferred Embodiment of Invention II According to a preferred embodiment of Invention II, a combination of the first embodiment of Invention II and the second embodiment of Invention II, the second embodiment of Invention II and the invention II A production apparatus or production method according to the combination of the third aspect and the first aspect of the present invention II to the combination of the third aspect of the present invention II (fourth aspect of the present invention II) is proposed.
  • hydrothermal reaction can be fully utilized, so that each process from biomass as a raw material to hydrocarbons generated can be performed with low energy (or without using energy). It is possible to achieve a significant reduction in production cost and excellent production ease and production efficiency (yield improvement).
  • Embodiment I of the Invention (Catalyst) Reaction: Conversion Reaction (Second Reactor)
  • a zeolite catalyst preferably a ZSM-5 type zeolite catalyst
  • the reactor (second reactor) can be suitable for solid catalytic reactions such as a fixed bed, fluidized bed, moving bed, etc., and has sufficient resistance even when heated and pressurized at about 500 ° C. Use things.
  • the reactor may be a multi-stage reactor in which a first stage for supplying raw materials and a second stage in which a zeolite catalyst (preferably a ZSM-5 type zeolite catalyst) is present are arranged in series.
  • a reactor is equipped with a heating apparatus and reaction is performed under heating. Specifically, heating is performed at a temperature of 370 ° C. or higher and 500 ° C. or lower.
  • a reactor provided with a part for supplying a carrier gas and a part for supplying other components. Their presence makes it possible to introduce nitrogen, steam, hydrogen, and a gas containing them, preferably hydrogen or a hydrogen-containing gas, as carrier gases into the reactor in accordance with the target product.
  • a compound capable of generating hydrogen in the reactor such as formic acid
  • the reactor can be set in multiple stages as necessary, and set to different temperatures within the above temperature range for each stage, and introduce different carrier gases for each stage. These combined reactions can be realized. And it becomes possible to select advantageously the chemical raw material produced
  • the present invention uses an organic acid.
  • the organic acid is an organic acid having 2 to 4 carbon atoms, particularly a carboxylic acid having 2 to 4 carbon atoms, and in particular, acetic acid, propionic acid, lactic acid and butyric acid are preferably used. Further, it may be a mixture or solution containing one or more of these acids, for example, an aqueous solution.
  • levulinic acid can be used, and according to a more preferred embodiment, one obtained by the embodiment of the present invention II can be used. Accordingly, the “levulinic acid” used in the aspect of the present invention I naturally includes not only the general description but also those prepared and explained in the aspect of the present invention II.
  • an organic acid obtained by fermenting with an acid-fermenting bacterium is used.
  • the acid-fermenting bacteria any fermenting bacteria capable of generating an organic acid can be used. Examples include methane-fermenting bacteria, acetic acid-fermenting bacteria, lactic acid-fermenting bacteria, butyric acid-fermenting bacteria, mixtures thereof, and fermented sludge containing one or more of them.
  • methane-fermenting bacteria or a mixture or sludge containing it it is necessary to ferment without making it anaerobic.
  • the raw material for obtaining an organic acid by fermenting with an acid-fermenting bacterium may be any material as long as it generates a significant amount of the organic acid, but preferably biomass is used. Any biomass may be used. According to a preferred aspect of the present invention, it is preferable to use saccharide biomass capable of producing a significant amount of organic acid.
  • carbohydrate biomass include monosaccharides (glucose, fructose, etc.), disaccharides (sucrose, maltose, cellobiose, etc.), oligosaccharides and glycosides condensed with 10 or less monosaccharides, starch, alginic acid, etc. Examples include carbohydrates, biomass containing one or more of these, and processed products thereof.
  • Biomass is, for example, all plant biomass such as trees, grasses, cereals, fruits, seaweeds, etc., and includes roots, stems, bulbs, leaves, and the like.
  • processed product of biomass means that a part or all of biomass is subjected to physical treatment such as heating, pressurization, explosion, dissolution, extraction, grinding and mechanical separation; biological treatment such as fermentation and enzyme treatment. Examples of treatments: those subjected to one or more chemical treatments such as hydrolysis, thermal decomposition, solvent decomposition, hydrothermal treatment, cooking, alkali treatment, acid treatment, and catalyst treatment.
  • bagasse which is a pomace of sugarcane
  • cooked foods such as edible grains, wastes and processed products thereof Wood sawn waste, acid digests such as alkaline digestion and concentrated sulfuric acid.
  • Zeolite catalyst As the zeolite catalyst, zeolites such as crystalline aluminosilicate, silicate, metallosilicate are used.
  • crystalline aluminosilicate examples include ZSM-5, ZSM-11, beta, mordenite, X-type and Y-type faujasite, MCM-22, and MCM-68.
  • crystalline silicate examples include silicalite.
  • crystalline metallosilicate examples include metallosilicates in which metal elements other than Si are Fe, Ga, B, Ti and the like.
  • the zeolite catalyst may contain, as a cation, one or more of protons, ammonium ions, alkaline earths such as Ca, Ba, and Mg, and rare earth metal cations such as La and Ce.
  • Preferable specific examples of the zeolite catalyst include ZSM-5 type zeolites having pores having a 10-membered oxygen ring.
  • Examples of the ZSM-5 type zeolite catalyst include ZSM-5, ZSM-11, silicalite, metallosilicates in which metal elements other than Si are Fe, Ga, B, Ti and the like.
  • ZSM-5 having an Si / Al atomic ratio of 50 or more
  • ZSM-11 having an Si / Al atomic ratio of 50 or more
  • M is Fe, Ga, B, Ti
  • these ZSM-5 type zeolites may contain, as cations, one or more of protons, ammonium ions, alkaline earths such as Ca, Ba and Mg and rare earth metal cations such as La and Ce.
  • these ZSM-5 type zeolites may carry transition metals such as Ni, Fe, W, Pt, Rh, Re, Pd, and metals such as Mo in the form of elements or compounds such as oxides. .
  • the apparatus of the present invention is preferably provided with a fermentation reactor (first reactor) before the catalytic reaction (reactor) (second reactor). .
  • the fermentation reaction (equipment) is provided with a first supply device for supplying biomass and the like.
  • the fermentation reaction is performed in the first reactor while preferably stirring the biomass supplied from the first supplier and the acid-fermenting bacteria. Fermentation using acid-fermenting bacteria is preferably performed at a temperature of 30 ° C. or higher and 60 ° C. or lower.
  • organic acids in particular, acetic acid, propionic acid, lactic acid and butyric acid are obtained.
  • As the reactor one capable of using either batch or continuous operation is used.
  • the manufacturing apparatus (manufacturing method) according to the present invention preferably supplies biomass and acid-fermenting bacteria to the first reactor via the first feeder and performs a fermentation reaction at 30 ° C. or higher and 60 ° C. or lower.
  • the organic acid obtained by the fermentation reaction and the ZSM-5 type zeolite catalyst are supplied to the second reactor via the second feeder, at a temperature (350 ° C. or higher and 550 ° C. or lower) at which the desired compound is obtained. React.
  • the products are hydrocarbons, and by using the reaction according to the present invention, water and products by-produced by the entrainment or reaction are separated into two phases which hardly mix, Separation with high energy consumption such as distillation is basically unnecessary, and as a result, it can be said to be an economical and highly efficient production method.
  • aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene; lower olefin hydrocarbons such as propylene, butene, isobutene and ethylene; acetone and ethyl methyl ketone
  • a ketone compound such as dimethyl ketone can be obtained as a product.
  • Embodiment of Invention II First Embodiment of Invention II according to the first embodiment of Invention II, an apparatus and method for producing levulinic acid from biomass is proposed.
  • the raw material may be any biomass as long as it can produce levulinic acid.
  • saccharide biomass capable of producing a significant amount of levulinic acid.
  • carbohydrate biomass include monosaccharides (glucose, fructose, etc.), disaccharides (sucrose, maltose, cellobiose, etc.), oligosaccharides and glycosides condensed with 10 or less monosaccharides, starch, alginic acid, etc.
  • Examples include carbohydrates, biomass containing one or more of these, and processed products thereof.
  • Biomass is, for example, all plant biomass such as trees, grasses, cereals, fruits, seaweeds, etc., and includes roots, stems, bulbs, leaves, and the like.
  • processed product of biomass means that a part or all of biomass is subjected to physical treatment such as heating, pressurization, explosion, dissolution, extraction, grinding and mechanical separation; biological treatment such as fermentation and enzyme treatment. Examples of treatments: those subjected to one or more chemical treatments such as hydrolysis, thermal decomposition, solvent decomposition, hydrothermal treatment, cooking, alkali treatment, acid treatment, and catalyst treatment.
  • bagasse which is a pomace of sugarcane
  • cooked foods such as edible grains and wastes and their processed products
  • wood Sawmill wastes acid digests such as alkaline cooking and concentrated sulfuric acid.
  • the acid catalyst acid catalyst examples include inorganic and organic liquid acids such as hydrochloric acid, sulfuric acid, nitric acid, and acetic acid; and zeolites such as ZSM-5, faujasite, and beta; and amorphous composite oxides such as silica alumina.
  • hydrochloric acid, sulfuric acid, and ZSM-5 zeolite are preferably used.
  • the reactor can use either batch or continuous operation, and a reactor having sufficient resistance even in a heated and pressurized state of about 400 ° C is used.
  • the pressure in the reaction vessel is about 0.49 to 11.5 MPa, and therefore it is preferable that it can withstand such a reaction environment.
  • the “hydrothermal reaction” is a reaction in high-temperature water held in a liquid under pressure. For example, at 2 MPa, 200 ° C. water can be kept in a liquid, and in such water, 100 ° C. It is said that a higher ion product can be obtained than the following water and water under supercritical conditions.
  • Manufacturing equipment Water and acid catalyst are introduced from the feeder into the closed hydrothermal reactor, and saccharide biomass is also introduced from the feeder.
  • Carbohydrate biomass is reacted in water containing an acid catalyst.
  • the reaction is carried out under heating, preferably at a temperature of 150 ° C. or higher and 320 ° C. or lower according to the time corresponding to the temperature.
  • a temperature of 150 ° C. or higher and 320 ° C. or lower By making it react at the temperature of 320 degrees C or less, it becomes possible to suppress effectively that the inside of a reactor approaches the critical temperature vicinity of water, and it becomes possible to prevent material corrosion of a reactor effectively.
  • by reacting at a temperature of about 320 ° C. or less it is possible to effectively suppress the reaction pressure from becoming high, and reduce the cost of the entire apparatus without using a large amount of expensive corrosion-resistant material. It is preferable because it can reduce the ion product of water effectively and can improve the reactivity.
  • the reactivity can be improved, the yield of levulinic acid as a product can be improved, and the reaction time can be shortened.
  • the reaction can be carried out at a temperature of 150 ° C. or higher and 240 ° C. or lower which is a low temperature region.
  • the reaction time is slightly longer, but it becomes possible to suppress the by-product of the carbonaceous material to a very small amount and to improve the yield of levulinic acid.
  • it can react at the temperature of 240 degreeC or more and 320 degrees C or less which is a high temperature range.
  • a side reaction may produce a little carbonaceous material.
  • the reaction rate is high and the reaction can be carried out in a short time. It becomes possible to manufacture in a yield. Therefore, in the present invention, it is possible to suitably perform both the reaction in the low temperature region and the high temperature region.
  • the reaction is preferably performed by stirring the mixed solution in the reactor.
  • it can be carried out by either batch operation or continuous operation.
  • the batch operation can be performed, for example, by introducing the raw sugar biomass into the hydrothermal reactor at a time and reacting for a predetermined time.
  • the reaction time can be appropriately determined according to the reaction temperature.
  • the continuous operation for example, the raw material sugar biomass is continuously supplied to the hydrothermal reactor that holds the water maintained at the reaction temperature and the acid catalyst, and the reaction solution is allowed to react continuously or intermittently. Also good.
  • the energy required is only the energy to replenish the supplemented water, the acid catalyst, and the raw material biomass up to the reaction temperature.
  • regenerate suitably the water and acid catalyst of a hydrothermal reactor as needed.
  • Second aspect of Invention II According to the second aspect of Invention II, a production apparatus and method for separating levulinic acid from a composition comprising (significant amount) levulinic acid is proposed.
  • the raw material is a composition (preferably a liquid composition) comprising levulinic acid.
  • the product solution comprising a significant amount of levulinic acid obtained in the first embodiment of the present invention II can be preferably used.
  • the adsorbent adsorbent may be any as long as it can adsorb levulinic acid from the above composition, and examples thereof include zeolite such as ZSM-5, faujasite, beta, and activated carbon. Zeolite such as ZSM-5 is preferable.
  • the adsorber adsorber can be used for either batch or continuous operation, and an adsorber having sufficient resistance even in a heated and pressurized state of about 300 ° C. is used.
  • Manufacturing equipment (manufacturing method) Separation in the present invention is performed by reacting a composition comprising levulinic acid with an adsorbent.
  • This adsorption operation can be performed at any temperature from room temperature to the hydrothermal reaction temperature (first aspect of the present invention II), preferably 30 ° C. or higher and 320 ° C. or lower, more preferably the lower limit is 80 ° C. or higher.
  • the upper limit can be set to 240 ° C. or lower.
  • This step is important for separating levulinic acid at low cost from a composition comprising levulinic acid.
  • Levulinic acid is obtained, for example, in the form of an aqueous solution as in the first embodiment of the present invention II.
  • water having a boiling point lower than that of levulinic acid is used.
  • adsorptive separation is performed under conditions where water is not substantially evaporated.
  • Desorption of levulinic acid from the adsorbent can be performed in various ways. For example, a method of desorbing the adsorbent at a high temperature (for example, 240 ° C. or higher), a method of desorbing at a reduced pressure, a method of desorbing through water, steam, carrier gas, solvent or vapor thereof.
  • the first aspect (generation) of the present invention II can be carried out by either a batch operation or a continuous operation.
  • the batch operation for example, after the raw material biomass is introduced into the hydrothermal reactor at a time and reacted for a predetermined time, the second aspect (separation) of the present invention II is repeated.
  • the reactor of the first aspect of the present invention II is also used as the adsorber of the second aspect of the present invention II.
  • the raw material biomass is continuously supplied to a hydrothermal reactor having water and an acid catalyst maintained at the reaction temperature, and the reaction liquid is continuously or intermittently used. Send to the second operation for separation. A semi-batch operation combining both of these may be used.
  • the hydrothermal reaction raw material can be supplied to the previous residual liquid and the reaction can be repeated again.
  • the acid catalyst used in the hydrothermal reaction is not adsorbed by the adsorption operation, and most of it returns with the remaining liquid, so that it is possible to reduce the acid catalyst added when repeating the hydrothermal reaction. Further, since the high-temperature liquid is returned to the hydrothermal reactor, the heating energy input to the hydrothermal reactor is extremely small.
  • separation can be reduced significantly.
  • the purpose of the regeneration is to separate and remove the substance produced in the first aspect (production) of the present invention II and remaining without being adsorbed by the adsorbent in the first aspect (separation) of the present invention II.
  • By exchanging heat between the extracted liquid and the regenerated liquid it is preferable because energy loss can be extremely small.
  • the adsorption of levulinic acid by the adsorbent in the second embodiment (separation) of the present invention II is the product of the hydrothermal reactor of the first embodiment (production) of the present invention II.
  • a method of separating the adsorbent adsorbed with levulinic acid from the product liquid, or after completion of the hydrothermal reaction in the first aspect (production) of the present invention II or during the reaction Any of the methods may be used in which the product liquid containing is sent to an adsorption tank filled with an adsorbent and the residual liquid after adsorption is returned to the reactor.
  • the former method is suitable when the first embodiment (production) of the present invention II is carried out by batch operation, and the latter method is suitable for the first embodiment (production) of the present invention II by batch operation or continuous operation. Suitable for performing.
  • a production apparatus for producing and separating levulinic acid from biomass can be proposed,
  • the biomass, the acid catalyst, and water are reacted under heating, and after the reaction, a composition comprising levulinic acid and an adsorber that contacts the adsorbent under heating are provided. It will be.
  • This aspect is suitable for a batch operation method.
  • a method for producing and separating levulinic acid from biomass can be proposed, Prepare biomass, acid catalyst, water and adsorbent, Supplying the biomass, the acid catalyst, the water, and the adsorbent; Reacting the biomass, the acid catalyst, and the water in the presence of the adsorbent; Contacting the adsorbent with a composition comprising the produced levulinic acid, Adsorbing and separating the levulinic acid from the composition.
  • a production apparatus for producing and separating levulinic acid from biomass can be proposed, A first feeder for supplying biomass, an acid catalyst, and water to the reactor; A reactor for reacting the biomass, the acid catalyst, and water; A second feeder for feeding a composition comprising levulinic acid produced in the reactor to the adsorber along with an adsorbent; It comprises an adsorber formed by bringing the composition into contact with the adsorbent (suitable for batch operation method / continuous operation method).
  • a method for producing and separating levulinic acid from biomass can be proposed, Prepare biomass, acid catalyst, water and adsorbent, Reacting the biomass, the acid catalyst, and water; Contacting the adsorbent with a composition comprising the produced levulinic acid, Adsorbing and separating the levulinic acid from the composition.
  • aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene
  • lower olefin hydrocarbons such as propylene, butene, isobutene, and ethylene
  • propane, butane, isobutane, and ethane It is possible to obtain lower paraffin hydrocarbons such as oxygen-containing hydrocarbons such as ethyl methyl ketone, acetone, vinyl methyl ketone, and acetic acid as products.
  • the raw material is levulinic acid, whether it is itself (including levulinic acid desorbed from the adsorbent), levulinic acid adsorbed on the adsorbent, or previously contacted with a zeolite catalyst Good.
  • the one obtained by the second aspect of the present invention II or the one obtained by the apparatus or method combining the first aspect of the present invention II and the second aspect of the present invention II is preferably used. Can do.
  • Zeolite catalyst As the zeolite catalyst, zeolites such as crystalline aluminosilicate, silicate, metallosilicate are used. Examples of the crystalline aluminosilicate include ZSM-5, ZSM-11, beta, mordenite, X-type and Y-type faujasite, MCM-22, and MCM-68. Examples of the crystalline silicate include silicalite. Examples of the crystalline metallosilicate include metallosilicates in which metal elements other than Si are Fe, Ga, B, Ti and the like. Preferred zeolite catalysts include zeolites having 10-membered oxygen pores such as ZSM-5, ZSM-11, silicalite, and metallosilicate.
  • the zeolite catalyst may contain, as a cation, one or more of protons, ammonium ions, alkaline earths such as Ca, Ba, and Mg, and rare earth metal cations such as La and Ce.
  • Zeolite catalysts carry transition metals such as Ni, Fe, W, Pt, Rh, Re, Pd, etc., and metals having hydrogenation activity such as Mo in elements or compounds (for example, in the form of oxides). Those are more preferably used. Examples of such preferred examples include ZSM-5, ZSM-11, silicalite, and metallosilicate supporting the above metals, and in particular, ZSM-5, ZSM-11, silica supporting Ni or Pt. Light and metallosilicate are preferably exemplified.
  • the reactor reactor can be one that is suitable for solid catalytic reactions, such as a fixed bed, fluidized bed, moving bed, etc., and uses a reactor that has sufficient resistance even when heated and pressurized at about 600 ° C. .
  • the reactor may be a multistage reactor in which a first stage for supplying a raw material and a second stage in which a zeolite catalyst is present are arranged in series.
  • the reactor is equipped with a warming device, and the reaction is carried out under warming. Specifically, heating is performed at a temperature of 300 ° C. or higher and 550 ° C. or lower. Further, it is preferable to use a reactor provided with a part for supplying a carrier gas and a part for supplying other components.
  • the reactor can be set in multiple stages as necessary, and set to different temperatures within the above temperature range for each stage, and introduce different carrier gases for each stage. These combined reactions can be realized. And it becomes possible to select advantageously the chemical raw material produced
  • the production apparatus (production method) supplies, as a raw material, levulinic acid desorbed from an adsorbent, an adsorbent adsorbed with levulinic acid, or a zeolite catalyst adsorbed with levulinic acid to a (catalyst) reactor.
  • the zeolite catalyst (used in this reaction) is reacted at a temperature of 300 ° C. or higher and 550 ° C. or lower, preferably a lower limit of 350 ° C. or higher and an upper limit of 500 ° C. or lower.
  • the product is a hydrocarbon
  • the water-insoluble hydrocarbon the water and the product by-produced by entrainment or reaction are separated into two phases that hardly mix, Separation with high energy consumption such as distillation is basically unnecessary, and as a result, it can be said to be an economical and highly efficient production method.
  • an apparatus or combined method that combines the second embodiment of Invention II and the third embodiment of Invention II.
  • the adsorbent adsorbed with levulinic acid is introduced into the third embodiment (desorption / conversion) of the present invention II, and desorption is performed in the reactor.
  • a method for carrying out the reactions simultaneously is proposed.
  • the zeolite catalyst used in the third aspect of the present invention II is also used as the adsorbent used in the second aspect of the present invention II, so that the zeolite catalyst adsorbed with levulinic acid is converted into the second aspect of the present invention II.
  • desorption and reaction can be carried out simultaneously.
  • the production process is omitted, and beneficial hydrocarbons can be obtained by adsorption separation of levulinic acid and desorption / conversion of levulinic acid, which is effective.
  • an adsorbent adsorbing levulinic acid or a zeolite catalyst adsorbing levulinic acid is used as a reactor.
  • the adsorbent is introduced into the first stage with two reactors in series, and the adsorbent is recovered after the reaction.
  • the adsorbent or the zeolite catalyst used for the adsorption is replaced with another zeolite catalyst.
  • An apparatus (method) that can be easily separated from (used in this reaction) and can be recovered after the reaction can be employed. In that case, for example, it is preferable to separate the adsorbent from another zeolite catalyst (used in this reaction) with a different particle size.
  • a production apparatus for obtaining hydrocarbons from a composition comprising levulinic acid can be proposed.
  • the reactor comprises a reactor for reacting the composition with the adsorbent and reacting the levulinic acid adsorbed on the adsorbent with the zeolite catalyst under heating.
  • a production method for obtaining hydrocarbons from a composition comprising levulinic acid can be proposed.
  • the method comprises reacting levulinic acid adsorbed on the adsorbent (zeolite catalyst) under heating.
  • acetone, acetic acid, and hydroxyethyl methyl ketone were obtained.
  • the conversion from levulinic acid was 80% or more, and the selectivities of acetone, acetic acid and hydroxyethyl methyl ketone were each about 15 to 20%.
  • hydroxyethyl methyl ketone was converted to vinyl methyl ketone, but when reacted with Ni / ZSM-5 in a hydrogen atmosphere, in addition to ethyl methyl ketone, benzene, toluene, xylene, Converted to propylene.
  • Acetic acid and acetone were converted to benzene, toluene, xylene, propylene, and the like. It can be said that the conversion from acetic acid and the like to aromatics was a surprising technical achievement.
  • the fourth aspect of the present invention II proposes a combination of all the manufacturing apparatuses (manufacturing methods) in the first to third aspects of the present invention II.
  • An apparatus and method for producing the above beneficial hydrocarbons is proposed. Therefore, the fourth aspect of the present invention II is an apparatus for producing hydrocarbons from biomass, Biomass, an acid catalyst, water, an adsorbent, and a feeder for supplying a zeolite catalyst to the reactor as required;
  • the biomass, the acid catalyst and water are reacted, the composition comprising levulinic acid is brought into contact with the adsorbent, and the levulinic acid adsorbed on the adsorbent, and if necessary, the zeolite catalyst Is provided with a reactor that reacts with.
  • an apparatus for producing hydrocarbons from biomass A first feeder for supplying biomass as raw materials, an acid catalyst, and water to the reactor; A reactor for reacting the biomass with an acid catalyst under heating; A second feeder for feeding a composition comprising levulinic acid produced in the reactor to the adsorber with an adsorbent and optionally a zeolite catalyst; The composition, the adsorbent, and an adsorber for obtaining hydrocarbons by reacting the zeolite catalyst as necessary.
  • another preferable aspect of the present invention II is a method for producing hydrocarbons from biomass, Prepare the biomass as raw materials, acid catalyst, water, adsorbent, and zeolite catalyst if necessary, Reacting the biomass with an acid catalyst and water to obtain a composition comprising levulinic acid; Contacting the composition with the adsorbent, adsorbing levulinic acid to the adsorbent; The adsorbent adsorbed with levulinic acid is reacted with the zeolite catalyst, if necessary, under heating to obtain hydrocarbons.
  • Aspect 1 of the present invention 1) After storing raw sludge collected from a methane fermentation tank of acid fermented garbage of sugar solution at about 5 ° C in a refrigerator, separating the amount used for the experiment and leaving it at room temperature for 24 hours The acid-fermenting bacteria sludge was used in the experiment. A 200 mL aqueous solution containing a predetermined amount of acid-fermenting bacteria sludge and a raw sugar at a predetermined concentration was placed in a 300 mL Erlenmeyer flask, and a rubber stopper with a gas outflow tube and a liquid sampling tube was attached. A Tedlar bag was attached to the outlet of the gas sampling tube, and a rubber cap was attached to the outlet of the liquid sampling tube.
  • This conical flask was placed in a shaking water tank whose water temperature was controlled at 35 ° C. or 55 ° C., and the experiment was started. After elapse of a predetermined number of days, the Erlenmeyer flask was taken out from the water tank, the fermentation broth was filtered and separated from sludge, and the components in the fermentation broth were analyzed. Analysis was performed using a high-performance liquid chromatograph (Shimadzu LC-06) equipped with Shimpack SCR-102H as the separation column and differential refractive index detector RID-6A as the detector, and 5 mmol / L perchloric acid water as the moving bed. And the column temperature was 50 ° C.
  • Examples F-1 to 2 The results when using 20-40 g / L of acid-fermenting bacterial sludge using 2% glucose and sucrose aqueous solutions as raw materials are shown below.
  • the product yield is expressed in terms of C yield (carbon number of product / carbon number of raw material ⁇ 100). After 9-14 days, the sugar was converted to organic acid in high yield and the total organic acid yield was about 63%. Acetic acid, lactic acid and butyric acid were mainly produced as organic acids. The results were as described in Table I-1 below.
  • Examples F3-6 The results when using glucose and fructose aqueous solutions with a concentration of 1 to 3.33% as raw materials and using 20 to 200 g / L of acid-fermenting bacteria sludge are shown below. The total organic acid yield after 6-14 days was about 12 to about 61%. As produced organic acids, butyric acid was mainly produced in Example F-3, butyric acid and acetic acid were produced in F-4, lactic acid and butyric acid were produced in F-5, and acetic acid was produced in F-6. The results were as described in Table I-2 below.
  • Example F7 A fermentation experiment was conducted using a glucose aqueous solution with a concentration of 1% as a raw material and 50 g / L of acid-fermenting bacterial sludge.
  • F-7a had a total organic acid yield of about 60% after 14 days in the first fermentation, and the main products were butyric acid and acetic acid.
  • an aqueous glucose solution was again added thereto, and the second fermentation was performed.
  • F-7b is the second result. After 12 days, the total organic acid yield was about 51%, and butyric acid and acetic acid were obtained as the main products as in the first time. This shows that it is possible to perform repeated fermentation.
  • the results were as described in Table I-3 below.
  • Examples F8-9 A fermentation experiment was conducted using a glucose aqueous solution having a concentration of 10% as a raw material and 75-100 g / L of acid-fermenting bacteria sludge. After 12 days, the total organic acid yield was about 20% and the main products were lactic acid and butyric acid. From this, it can be seen that even an extremely high concentration sugar solution can be converted into an organic acid as compared with ordinary fermentation. The results were as described in Table I-4 below.
  • a predetermined amount of zeolite catalyst was packed in a SUS-316 reaction tube with an inner diameter of 6 mm and a length of 600 mm, and the tube was placed in an electric furnace equipped with a temperature controller.
  • a raw material liquid was introduced into the upper inlet of the reaction tube using a plunger pump, and a carrier gas was introduced from a cylinder.
  • a condenser cooled with ice water was connected to the outlet at the bottom of the reaction tube, and the product liquid was recovered.
  • a Tedlar bag was attached to the outlet of the condenser to collect the generated gas.
  • the composition of the product solution was analyzed using a gas chromatograph with an FID detector (6890 manufactured by Agilent) equipped with a capillary column and a gas chromatograph mass spectrometer (JEOL JMS9000GC) equipped with the same kind of capillary column.
  • the composition of the product gas was analyzed using a gas chromatograph equipped with Cimalite / SM-6, Molecular Sieve 13X, and Porapak-Q as packed columns.
  • Example ZA-1 Using the organic acid mixture produced in Example F-2 as a raw material liquid and using ZSM-5 pellets (containing 20% alumina as a binder) having a Si / Al ratio of 27 as a catalyst, the conversion reaction was carried out for 1 hour. went. Reaction conditions and product yields are shown in Table I-5. As a result, an aromatic compound mainly composed of benzene, toluene and xylene and a hydrocarbon gas mainly composed of ethylene, propylene and butene are obtained from a mixture of acetic acid, lactic acid and butyric acid obtained by acid fermentation of the sugar solution. A high yield could be obtained.
  • aromatics mainly consisted of benzene, toluene and xylene, which are important as chemical raw materials, and the production of heavy aromatics could be suppressed.
  • Trimethylbenzene is characterized by a high yield of 1,2,4-trimethylbenzene, which is an important starting material for polyimide
  • methylnaphthalene is characterized by a high yield of 2-methylnaphthalene, which is used for many purposes.
  • the high selectivity of these useful products is considered to be due to the fact that the shape selectivity of the ZSM-5 used was exhibited in this reaction. The results were as described in Table I-5 below.
  • Examples ZA-2 to 4 A conversion reaction was carried out for 1 hour using a 50% aqueous solution of lactic acid as a raw material solution, commercially available butyric acid and acetic acid, and ZSM-5 as a catalyst. Reaction conditions and product yields are shown in Table I-6. As a result, similar to Example ZA-1, an aromatic compound mainly composed of benzene, toluene and xylene and a hydrocarbon gas mainly composed of ethylene, propylene and butene could be obtained in high yield. The results were as described in Table I-6 below.
  • Examples ZA-5 to 11 The conversion reaction was carried out for 1 hour using commercially available acetic acid as a raw material liquid, various zeolites as catalysts and ZSM-5 having a different Si / Al ratio. Y is a Y-type fauger site. A non-catalytic reaction was also carried out. The results were as described in Table I-7 below.
  • Examples ZA-12 to 14 The reactions of Examples ZA-5 to 7 are continued, and the reaction results after about 7 hours are shown as Examples ZA-12 to 14. As can be seen from Table I-8, when ZSM-5 having a Si / Al ratio of 80 or more is used, the reactivity is maintained even after a long period of time, and a high activity and aromatic yield are obtained in a long-time reaction. I understood it. The results were as described in Table I-8 below.
  • Embodiment II of Invention II First Embodiment of Invention II A hydrothermal reaction tube made of SUS316 having an inner diameter of 7.5 mm, a length of 20 mm, and an internal volume of 8.8 mL was prepared. The reaction tube was charged with 7 mL of an aqueous raw material solution and an acid catalyst, and a reaction tube cap was attached and sealed. The reaction was performed by immersing the reactor in a sand bath heated to a predetermined temperature. Since the temperature of the raw material liquid in the reaction tube reached the temperature of the sand bath 50 seconds after the reaction tube was immersed, this time was taken as the reaction start time.
  • the reaction tube was taken out of the sand bath and quenched, and the product was filtered to separate the product liquid and the carbonaceous material.
  • the components in the product liquid were analyzed by a high performance liquid chromatograph.
  • the amount of organic carbon in the product liquid and the raw material liquid was measured using an organic carbon analyzer, and the difference was defined as the amount of by-product carbonaceous material.
  • Product yields are expressed on a carbon basis.
  • Example H-1 to Comparative Example H-4-R (Effect of acid catalyst and influence of reaction temperature) The reaction was carried out at various temperatures using hydrochloric acid as the acid catalyst. In order to investigate the effect of the acid catalyst, an experiment was also conducted in the case where no acid catalyst was added. The results were as described in Table II-1 below. When an acid catalyst is used, a high conversion rate and a high levulinic acid yield can be obtained in a short time of several minutes to 10 minutes at a high temperature of 250 ° C. or 300 ° C. and a reaction time of 30 min or more at a low temperature of 180 ° C. It was.
  • levulinic acid and formic acid are obtained in a C yield of 5: 1.
  • the levulinic acid in the product is less than 5 times that of formic acid, and most of it is retained in the zeolite catalyst. it is conceivable that. Therefore, the levulinic acid actually produced is estimated to be larger than the values in the table.
  • the adsorbing tube was immersed in a sand bath heated to a predetermined temperature and adsorbed for a predetermined time, and then the adsorbing tube was taken out to recover the liquid.
  • the concentration of levulinic acid in this solution was measured with a high performance liquid chromatograph and an organic carbon analyzer, and the adsorption rate of levulinic acid was determined.
  • the results were as described in Table II-5 below. Examples A-1 to A-3 show the results at various adsorption temperatures. In Example A-1, adsorption was performed at room temperature, and levulinic acid could be adsorbed and separated at a high adsorption rate.
  • Examples A-2 and A-3 when adsorption was performed in a heated state, adsorption could be performed in a shorter adsorption time than at normal temperature. In the case of 180 ° C, the pressure in the adsorber was about 1 MPa.
  • Example A-4 Using the same adsorber as in Example A-1, two sand baths were prepared, and the first step was performed at 180 ° C., and the second step was performed at 30 ° C.
  • Example A-5 The hydrothermal reaction tube in the first aspect of the present invention II, the adsorption tube filled with the adsorbent, and the hydrothermal reaction product liquid from the hydrothermal reaction tube to the adsorption tube, and if necessary, from the adsorption tube to hydrothermal
  • the adsorption operation was performed following the hydrothermal reaction in the first aspect of the present invention II using an apparatus comprising a pipe that can be sent to the reaction tube.
  • the product solution is sent from the reaction tube to the adsorption tube, and is adsorbed by contacting the adsorbent with the adsorption tube for a predetermined time.
  • the reaction in the first aspect of the present invention II was carried out under the same conditions as in Example H-7, that is, 7 mL of reaction solution, 1.8 wt% glucose concentration, 0.5 mol / L hydrochloric acid concentration of acid catalyst, reaction temperature 300 ° C., reaction time It took 3 minutes.
  • the adsorption tube was filled with 2 g of the same ZSM-5 pellets as in Example A-4 as an adsorbent. The adsorption rate was calculated by measuring the amount of levulinic acid in the product solution after adsorbed on the adsorbent and comparing it with the amount of levulinic acid in the product solution of Example H-7.
  • the adsorption rate of levulinic acid was 51% when adsorption was performed at an adsorption temperature of 180 ° C. and an adsorption time of 5 minutes.
  • the first step is adsorption temperature 180 ° C, adsorption time 31 minutes
  • the second step is adsorption temperature 90 ° C, adsorption time 30 minutes
  • the adsorption rate of levulinic acid is 87% Met. In this way, levulinic acid was adsorbed and separated at a high temperature without distilling the reaction solution, and the reaction solution could be used again for the hydrothermal reaction.
  • a fixed bed reactor comprising a reaction tube made of SUS-306 having an inner diameter of 6 mm, an outer diameter of 10 mm, and a length of 600 mm installed in an electric furnace was used, and this was filled with a catalyst.
  • a preheating tube is connected upstream of the fixed bed reactor.
  • the adsorbent that adsorbs the raw material liquid or the raw material liquid and hydrogen or nitrogen as the carrier gas are fed into this, and the raw material liquid is heated to about 300 ° C. Vaporized.
  • a product recovery unit was connected downstream of the reactor, cooled to 0 ° C. with ice water, and the liquid component in the product was condensed and recovered.
  • a gas bag was attached downstream of the product collector to collect the generated gas.
  • the liquid product was analyzed with a gas chromatograph with FID detector (using capillary column DB-1) and a gas chromatograph mass spectrometer (using capillary columns DB-1 and DB-FFAP).
  • the product gas was analyzed with a gas chromatograph equipped with a TCD detector (using Polapack Q and molecular sieve 13X in the packed column).
  • Example C-1 The product obtained from the hydrothermal reaction of Example H-12 (glucose concentration 36%, hydrochloric acid 0.1 mol / L, reaction temperature 300 ° C., reaction time 3 minutes) was adsorbed on ZSM-5 at 90 ° C. Desorption was carried out at 0 ° C. to obtain an aqueous solution containing 50% levulinic acid. This was supplied to the preheating tube of the fixed bed reactor of the previous period packed with ZSM-5 pellets. Nitrogen was used as a carrier gas and reacted at 450 ° C. As shown in Table II-7, as a result of this reaction, oxygen-containing hydrocarbons such as hydroxyethyl methyl ketone, acetone, and acetic acid were obtained in high yield as the hydrocarbon products.
  • Example C-1 The product obtained from the hydrothermal reaction of Example H-12 (glucose concentration 36%, hydrochloric acid 0.1 mol / L, reaction temperature 300 ° C., reaction time 3 minutes) was adsorbed on Z
  • Example C-2 Examples C-2 to C-6 Using hydroxyethyl methyl ketone, acetone, and acetic acid obtained in Example C-1, the previous catalyst reaction apparatus was used, and the reaction was further performed with the zeolite catalysts and reaction conditions shown in Table II-7. The results were as described in Table II-7 below.
  • oxygen-containing hydrocarbons such as ethyl methyl ketone, ethyl vinyl ketone, acetone, and acetic acid are obtained in high yield from hydroxyethyl methyl ketone under low hydrogen pressure, and benzene, toluene, Monocyclic aromatic hydrocarbons such as xylene and bicyclic aromatic hydrocarbons such as methylnaphthalene and dimethylnaphthalene were obtained in high yield.
  • monocyclic aromatic hydrocarbons such as benzene, toluene and xylene, bicyclic aromatic hydrocarbons such as methylnaphthalene and dimethylnaphthalene, lower olefin hydrocarbons such as ethylene, propylene and butene, propane, etc.
  • lower paraffin hydrocarbon was obtained in high yield. When this reaction was continued for a longer time, the lower olefin hydrocarbon / lower paraffin hydrocarbon ratio increased.
  • hydrocarbon compounds obtained by these reactions are basic chemical substances used in the chemical industry. That is, monocyclic aromatic hydrocarbons such as benzene, toluene and xylene and lower olefin hydrocarbons such as ethylene, propylene and butene are the most important compounds as starting materials necessary for the petrochemical industry. Bicyclic aromatic compounds such as methylnaphthalene and dimethylnaphthalene are extremely important compounds as dyes, pharmaceuticals, and functional polymer raw materials.
  • oxygen-containing hydrocarbons such as acetone, ethyl methyl ketone, and acetic acid are important intermediate compounds in the chemical industry
  • vinyl methyl ketone is an important compound as an insecticide, a polymerization agent, and a steroid synthesis intermediate.

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Abstract

La présente invention concerne un appareil et un procédé de production d'hydrocarbures aromatiques ou de composés cétoniques, et un appareil et un procédé de production de produits chimiques clés à partir de la biomasse à faible coût et à rendement élevé. La présente invention concerne un appareil de production doté d'un réacteur pour mettre à réagir un acide organique avec un catalyseur à zéolite. En variante, la présente invention concerne un appareil de production d'acide lévulinique à partir de la biomasse doté d'un dispositif d'alimentation pour introduire une biomasse, d'un catalyseur acide, et d'eau dans un réacteur, et un réacteur pour mettre à réagir la biomasse avec le catalyseur acide et l'eau tout en chauffant.
PCT/JP2010/053255 2009-03-02 2010-03-01 Appareil de production d'hydrocarbures aromatiques ou de composés cétonique, appareil de production d'acide lévulinique, appareil de séparation d'acide lévulinique, et appareil de production d'hydrocarbures à partir d'acide lévulinique WO2010101120A1 (fr)

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JP2009048439A JP5504494B2 (ja) 2009-03-02 2009-03-02 芳香族炭化水素又はケトン化合物を製造する装置
JP2009-048439 2009-03-02
JP2009048421A JP5504493B2 (ja) 2009-03-02 2009-03-02 レブリン酸の製造装置、レブリン酸の分離装置及びレブリン酸から炭化水素を製造する装置

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WO2013159322A1 (fr) * 2012-04-27 2013-10-31 中国科学技术大学 Procédé pour la préparation d'acide acétique
CN106431882A (zh) * 2016-09-06 2017-02-22 安徽理工大学 一种由蔗糖高效分解制备乙酰丙酸的方法

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WO1998019986A1 (fr) * 1996-11-08 1998-05-14 Arkenol, Inc. Technique de production d'acide levulinique et de ses derives
CN1680257A (zh) * 2005-01-07 2005-10-12 浙江大学 用分子筛催化水解葡萄糖制取乙酰丙酸的方法
JP2007153925A (ja) * 2005-11-30 2007-06-21 Nippon Oil Corp 流動接触分解を用いたバイオマスの処理方法
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WO1998019986A1 (fr) * 1996-11-08 1998-05-14 Arkenol, Inc. Technique de production d'acide levulinique et de ses derives
CN1680257A (zh) * 2005-01-07 2005-10-12 浙江大学 用分子筛催化水解葡萄糖制取乙酰丙酸的方法
JP2007153925A (ja) * 2005-11-30 2007-06-21 Nippon Oil Corp 流動接触分解を用いたバイオマスの処理方法
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WO2013159322A1 (fr) * 2012-04-27 2013-10-31 中国科学技术大学 Procédé pour la préparation d'acide acétique
CN106431882A (zh) * 2016-09-06 2017-02-22 安徽理工大学 一种由蔗糖高效分解制备乙酰丙酸的方法
CN106431882B (zh) * 2016-09-06 2019-04-09 安徽理工大学 一种由蔗糖高效分解制备乙酰丙酸的方法

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