JP4568878B2 - Biomass decomposition method and decomposition apparatus - Google Patents

Description

  The present invention relates to a method and apparatus for efficiently decomposing biomass such as woody or herbaceous materials and producing various useful organic materials.

  In woody and herbaceous biomass, cellulose components and hemicellulose are complexed with lignin to form lignocellulose, etc., so if you want to take out useful components contained in them efficiently and use them, It is necessary to separate cellulose and hemicellulose.

  And when utilizing biomass in this way, separating lignin and other components has been carried out so far, for example, a method of treating lignocellulose with steam to convert a part thereof into an organic solvent soluble component (See Patent Document 1), a method of hydrolyzing pulp sludge to decompose and form water-soluble sugars (see Patent Document 2), hydrolyzing cellulose powder with pressurized hot water to produce water-soluble oligosaccharides A method of manufacturing (see Patent Document 3), a method of solubilizing woody biomass by applying subcritical water (see Patent Document 4), and the like have been proposed.

  However, in these methods, the cellulose decomposition reaction is directly performed following the step of pulverizing the biomass without being particularly conscious of separating lignocellulose into lignin and cellulose. Therefore, soluble components are formed in a state in which cellulose and lignin are firmly bound without sufficient separation of lignin and cellulose in the pulverization step, so that the reaction efficiency is low and a long treatment is required. Inevitably, this may cause excessive decomposition as a result of unnecessary processing.

  In addition, cellulose is hydrolyzed using supercritical or subcritical water to produce glucose (see Patent Documents 5 and 6), and wet toner is produced using a grinding medium under heating. Although methods (see Patent Document 7) have also been proposed, no consideration is given to decomposing lignocellulose into lignin and cellulose in advance even in these methods.

  On the other hand, as a method of producing useful materials by mechanochemical treatment of wood-based organic matter, the composite of wood-based waste, polyolefin and maleic acid or maleic anhydride modified polyolefin is substantially completed at 120-190 ° C. Until then, a method of producing a wood-plastic composite material by performing mechanical pulverization has been proposed (see Patent Document 8).

  However, this method requires the use of a special binder called maleic acid or maleic anhydride-modified polyolefin in order to firmly bond the plastic and the wood, which inevitably increases the cost. This was a major reason for impeding its practical application as a method for treating large amounts of wooden waste.

JP-A-2004-243541 (Claims and others) JP 2001-79595 A (Claims and others) JP-A-10-327900 (Claims and others) JP 2003-117526 A (Claims and others) JP-A-5-31000 (Claims and others) JP-A-10-327900 (Claims and others) JP-A-5-333606 (Claims and others) JP 2002-225011 A (Claims and others)

  The present invention uses biomass, such as woody or herbaceous plant material, as a raw material to efficiently react when producing a useful substance by chemical decomposition reaction, enzyme reaction, chemical reaction, intercalation, non-crystallization, etc. The object of the present invention is to provide a method for activating by applying a preliminary treatment for performing the above.

  The present inventors have conducted various studies on pre-activation so that biomass can be decomposed or reacted with high conversion efficiency, and as a result, chemical, physical or microbiological treatment is performed on biomass. When manufacturing various useful substances from now on, mechanical pulverization is performed in advance, and the lignocellulose present as its main component is mechanochemically decomposed to separate into lignin and cellulose. The present inventors have found that the activity for chemical, physical or biological treatment is remarkably improved and based on this finding, the present invention has been made.

  That is, the present invention is a biomass decomposition method characterized by subjecting biomass to a mechanochemical reaction in the presence of a high-temperature and high-pressure fluid, a biomass introduction port and a decomposition product discharge port at positions corresponding to the rotation centers of both side plates. A biomass decomposing apparatus comprising a heat-resistant pressure-resistant rotating drum provided, a driving means for rotating the drum, a grinding medium loaded in the drum, and a heating means arranged around the rotating drum, and a grinding medium The present invention provides a biomass decomposing apparatus comprising a shake-type autoclave that is embedded.

  In the method of the present invention, the biomass used as a raw material is not particularly limited, but is preferably a woody or herbaceous plant material. This woody biomass includes, for example, thinned wood, sawn timber, scraps of demolished house, wood processing waste, furniture waste, etc., and herbaceous plant materials include, for example, bagasse, rice husk, rice straw, straw, bamboo, There are stems, pineapples and banana leaves, coconut coconut shells, sugar cane stems, rice bran and so on.

  These biomasses are preferably preliminarily pulverized to a size of 30 mm or less in order to facilitate mechanochemical reaction. This rough pulverization can be performed by using a pulverizer commonly used for normal coarse pulverization such as a hammer mill, a rotary mill, or a crusher.

  The method of the present invention is carried out using a pulverizer that can perform pulverization under sealed conditions and is provided with a heating means such as a heating heater. As the pulverizer, a rotary shaker having a mill shaking speed of a maximum rotation speed of 300 rpm, a heat-resistant pressure-resistant drum filled with a pulverizing medium, and the like are preferable, but other pulverizers such as mechanochemical reactions are often used. A planetary ball mill or the like can be used.

  The method of the present invention is carried out in an atmosphere in which at least one gaseous or liquid fluid selected from water, carbon dioxide and an organic solvent is maintained at a high temperature and a high pressure. The temperature in this case is 100 to 330 ° C., preferably 100 to 230 ° C., the pressure is 0.1 to 15 MPa, preferably 0.1 to 5 MPa, and is used when a gaseous fluid is used. Saturated vapor pressure at temperature is preferred.

  Examples of the organic solvent include inert solvents such as aliphatic, alicyclic or aromatic hydrocarbons, alcohols such as methanol, ethanol, propanol, ethylene glycol and diethylene glycol, or alkyl ethers thereof.

  In the method of the present invention, when a mechanochemical reaction is performed, an acidic substance such as oxalic acid or formic acid, an alkali metal, an alkaline earth metal or a compound thereof, an alkaline substance such as an organic amine, Oxidizing substances such as oxygen, hydrogen peroxides and ozone can also be present.

  Thus, by carrying out the method of the present invention, each component of biomass, particularly lignocellulose, is solubilized, swelled, intercalated, non-crystallized, etc., separated from each other, and bound within the separated component molecules. Can be cleaved and activated at the molecular level.

  If desired, the method of the present invention can be carried out while sequentially separating and recovering the product at that stage from the reaction system according to the progress stage of the mechanochemical reaction. For example, when lignocellulose in biomass is separated into lignin and cellulose, lignin or cellulose is separated and recovered, then saccharides are separated and recovered when cellulose is decomposed to produce saccharides, saccharides are decomposed, and aldehydes By separating and recovering carboxylic acids, furfural, etc., various products can be obtained.

Next, an apparatus suitable for carrying out the method of the present invention will be described with reference to the accompanying drawings.
FIG. 1 is a cross-sectional explanatory view of an example of a rotary biomass decomposition apparatus in which a pulverizing medium is loaded. This apparatus is formed mainly of a heat-resistant pressure-resistant rotating drum 1 whose both ends are closed by side plates 2 and 3. One side plate 2 is provided with a biomass inlet 4, and the other side plate 3 is provided with a decomposition product outlet 5 at a position corresponding to the respective rotation centers.

  Biomass A is supplied into the rotary drum 1 through the inlet 4 and heated to a predetermined temperature by heating means 9 such as a heater outside the drum in a state where the opening and closing valves 6 and 7 are closed. Inside the rotating drum 1 is loaded with grinding media 8,..., For example, balls or rods made of a heat-resistant and corrosion-resistant material. When the drum rotates, the biomass is crushed and a mechanochemical reaction proceeds.

  When the reaction is sufficiently performed, the take-off valve 7 is opened and the product is taken out. In this way, a biomass decomposition product is obtained. As the pulverizing medium 8 to be loaded in the rotating drum at this time, a ball or a rod can be used, but it is advantageous to use a cutter rod capable of performing pulverization and cutting simultaneously. As the grinding media 8,..., Different types may be mixed and used as desired.

  In this type of biomass decomposition apparatus, the opening and closing of the valves 6 and 7 are controlled by a computer to continuously introduce the raw material and fluid from the inlet 2 and take out the product from the outlet 3. Automatic operation becomes possible.

  Next, FIG. 2 is a cross-sectional explanatory diagram of an example of a batch type biomass analyzer composed of a shaking type autoclave. In this figure, the biomass decomposing apparatus is composed of a container body 11 and a lid 12, and pulverizing media 13,. As this grinding medium, the same one as in the case of the above-described rotary biomass decomposition apparatus can be used.

In order to decompose the biomass using this apparatus, a predetermined amount of the raw material biomass A is charged into the container together with a fluid such as water, the lid 12 is hermetically sealed, and shaken while being heated from the outside. As a result, while the biomass A is crushed by frictional collision with the grinding media 13,..., It generates a high-temperature and high-pressure state, is activated mechanochemically, and promotes decomposition, thereby efficiently forming a decomposition product.
When the reaction is sufficiently performed, the cover 12 is removed after cooling, and the contents are taken out.

  According to the present invention, biomass can be efficiently decomposed by a simple method, and various useful substances can be produced.

  Next, the best mode for carrying out the present invention will be described by way of examples, but the present invention is not limited to these examples.

A stainless steel mechanochemical treatment apparatus having an outer diameter of 300 mm and a length of 350 mm having the structure shown in FIG. 1 is charged with 200 g of eucalyptus granule roughly pulverized to a size of about 30 mm and 100 g of hot water, and further at a high temperature of 120 ° C. Steam was introduced, heated to a high temperature of 220 ± 2 ° C. in a sealed state, and reacted for 10 minutes while rotating at 300 rpm. After the completion of the reaction, the mixture was allowed to cool at room temperature for 1 hour, and the produced eucalyptus powder and aqueous solution were taken out. When the contained components were analyzed for the aqueous solution thus obtained, about 30% by mass of lignin and a small amount of ash were recognized in addition to the hemicellulose degradation product.
Further, in the eucalyptus ground product excluding the aqueous solution, about 40% by mass of lignin and a small amount of ash were observed in addition to cellulose.
According to the conventional method of performing hydrothermal treatment after performing normal pulverization treatment, to obtain the same result, the pulverization treatment required to obtain an aqueous solution having the same solubilizing component content for 30 minutes, and subsequent hydrothermal treatment It takes about 50 minutes, about 20 minutes, so that it can be seen that the method of the present invention is very efficient.

  The method of the present invention is useful for producing various useful substances using biomass as a raw material.

Cross-sectional explanatory drawing of an example of the rotating drum type | mold decomposition device for implementing this invention method. Cross-sectional explanatory drawing of one example of the shaking autoclave type | mold decomposition device for implementing this invention method.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Heat-resistant pressure-resistant rotation drum 2, 3 Side plate 4 Biomass inlet 5 Decomposition product outlet 6, 7 On-off valve 8 Grinding medium 9 Heating means 11 Container main body 12 Cover part 13 Grinding medium A Biomass

Claims (7)

Biomass is one kind of gaseous or liquid fluid selected from the group consisting of water, carbon dioxide, and organic solvent, wherein the temperature is 100 to 330 ° C. and the pressure is 0.1 to 15 MPa . Biomass decomposition method characterized by subjecting to a mechanochemical reaction in the presence.   The biomass decomposition method according to claim 1, wherein the biomass is a woody or herbaceous plant material. The biomass decomposition | disassembly method of Claim 1 or 2 performed by adding an acid, an alkali, or an oxidizing agent. The biomass decomposition | disassembly method of Claim 1 or 2 which isolate | separates and collects a product sequentially from a reaction system according to the progress stage of a mechanochemical reaction. It is a biomass decomposition | disassembly apparatus for implementing the biomass decomposition | disassembly method as described in any one of Claims 1-4, Comprising: The biomass introduction port and the decomposition product discharge port were provided in the position which corresponds to the rotation center of a both-sides board. A biomass decomposing apparatus comprising a heat-resistant pressure-resistant rotating drum, a driving means for rotating the drum, a grinding medium loaded in the drum, and a heating means arranged around the rotating drum. A biomass decomposing apparatus for carrying out the biomass decomposing method according to claim 1, wherein the biomass decomposing apparatus comprises a shaking type autoclave in which a pulverizing medium is embedded. The biomass decomposing apparatus according to claim 5 or 6 , wherein the grinding medium is at least one selected from a ball, a rod and a cutter rod.