JP4673255B2 - Monosaccharide and furfural production method - Google Patents

Description

  The present invention belongs to a technical field relating to a method for producing monosaccharides and furfural, and in particular, monosaccharides that produce monosaccharides such as glucose and furfural with high production rate from woody biomass (wood chips, sawdust, building waste, etc.). And it belongs to the technical field regarding the production method of furfural.

  Industrial and household waste contains large amounts of biopolymers and synthetic polymers, but most of them are discarded without being reused. These polymers can be valuable chemical raw materials and energy resources, and it is desired to develop a technology capable of processing them in large quantities and effectively using them.

  One of the most promising polymer resources is the large amount of cellulose contained in agricultural, forestry products such as paper, wood and straw. There are various techniques for obtaining useful components such as sugars such as glucose from cellulose, such as (1) thermal decomposition, (2) high-temperature hydrolysis using acid catalyst, and (3) enzymatic hydrolysis. However, the above method (1) has the disadvantages that the reaction control is impossible and the rate of saccharide formation is low. There is a problem such as acid removal from the water, and there is a disadvantage that the rate of sugar production is reduced if the acid concentration is suppressed to avoid such problems. The method (3) has a slow reaction rate and cannot be used as an industrial production technique.

Thus, a technique for performing hydrolysis without using an acid or an enzyme has been proposed (disclosed). For example, Japanese Patent Laid-Open No. 10-327900 discloses that a saccharide can be obtained by contacting cellulose powder with 200 to 300 ° C. hot pressurized water to perform hydrolysis. JP-A-2002-85100 discloses that a cellulose or cellulose-containing substance powder is hydrolyzed by contacting it with pressurized hot water at 220 to 270 ° C. in the presence of a lanthanoid ion as a catalyst. It is disclosed that it can be obtained.
JP-A-10-327900 JP 2002-85100 A

  However, the techniques disclosed in the above-mentioned JP-A-10-327900 and JP-A-2002-85100 (hereinafter referred to as conventional techniques) are still inadequate due to the poor decomposition rate, and the sugar yield is inevitably high. Since most of the useful component cellulose is recovered as an oligosaccharide which is difficult to use as it is, the enzyme treatment for monosaccharide conversion is required to utilize this.

  By the way, until now, since the main purpose was to obtain monosaccharides such as glucose, furfurals, which are decomposition products of monosaccharides, were used as by-products, but these furfurals were used as plastic materials, It is now a more expensive and useful material than most monosaccharides. Therefore, it is desirable to actively produce monosaccharides and furfurals.

  The present invention has been made in view of such circumstances, and the object thereof is to produce monosaccharides and furfural that can produce monosaccharides and furfural from woody biomass at a higher production rate than in the case of the prior art. Is to provide a method.

  As a result of intensive studies to achieve the above object, the present inventors have completed the present invention. According to the present invention, the above object can be achieved.

The present invention, which has been completed in this way and has achieved the above object, relates to a method for producing monosaccharides and furfural. The method for producing monosaccharides and furfurals according to claim 1 or 2 (inventions 1 to 2) . A method for producing such monosaccharides and furfural), which has the following constitution.

That is, according to the method for producing monosaccharides and furfural according to claim 1, the woody biomass is decomposed by contacting it with high-temperature and high-pressure water of more than 300 ° C. and not more than 350 ° C. and 13 to 30 MPa for 5 minutes or more, and is produced by this decomposition treatment. A method for producing monosaccharides and furfural by adsorbing and separating furfural from monosaccharides and furfural on an adsorbent, wherein the adsorbent is obtained by carbonizing a residue generated by the decomposition treatment. A method for producing monosaccharides and furfural [first invention].

Method for producing a monosaccharide and furfural as claimed in claim 2, wherein, as the adsorbent, after carbonizing the residue, a method for producing a monosaccharide and furfural as claimed in claim 1, wherein the use of those activation treatment Second invention〕.

  According to the method for producing monosaccharides and furfural according to the present invention, monosaccharides and furfural from woody biomass are obtained from the conventional techniques (the techniques disclosed in JP-A-10-327900 and JP-A-2002-85100). Can be produced at a high production rate.

  When woody biomass is contacted with high-temperature pressurized hot water (high-temperature and high-pressure water) and hydrolyzed, the high-temperature and high-pressure water after this treatment includes not only monosaccharides but also furfurals, lignin degradation products, lower organic acids, etc. There are several useful components. Since furfurals are attracting attention as plastic materials and the like, it is desirable to actively increase not only monosaccharides but also the amount of furfurals produced. Therefore, the present inventors have conducted extensive studies to increase the production amounts of monosaccharides and furfurals. As a result, when wood biomass is decomposed by contacting it with high-temperature and high-pressure water of more than 300 ° C and less than 350 ° C and 13-30MPa for 5 minutes or more, monosaccharides and furfural are produced from woody biomass at a higher rate than in the case of the prior art. I found out that

The present invention has been completed based on such knowledge, and it relates to a method for producing monosaccharides and furfural. Monosaccharides and manufacturing method of furfural according to the present invention thus has been completed, a woody biomass 300 ° C. Ultra 350 ° C. or less, you decomposed by contacting more than 5 minutes in high-temperature and high-pressure water 13~30MPa [the 1 invention]. According to the method for producing monosaccharides and furfural according to the present invention, monosaccharides and furfural from woody biomass are obtained from the conventional techniques (the techniques disclosed in JP-A-10-327900 and JP-A-2002-85100). Can be produced at a high production rate.

  Here, when the temperature of the high-temperature and high-pressure water is set to 300 ° C. or lower instead of the above temperature (over 300 ° C. to 350 ° C. or lower), the decomposition rate of cellulose (cellulose, hemicellulose) in the woody biomass is low, and most of the cellulose Is recovered as an oligosaccharide, and the amount of monosaccharide and furfural produced is reduced. Since oligosaccharides are difficult to use as they are, enzyme treatment for saccharification is required to use them. If the temperature of the high-temperature and high-pressure water is changed to above 350 ° C instead of the above temperature (over 300 ° C and below 350 ° C), the decomposition of the cellulose will progress too much, and gases such as formic acid, acetic acid, butyric acid, methane, carbon dioxide, etc. The amount of decomposition into components increases, and the amount of monosaccharides and furfural produced decreases. On the other hand, when the temperature of the high-temperature and high-pressure water is set to the above temperature (over 300 ° C to 350 ° C or less), the decomposition of cellulose progresses moderately, and the amount of oligosaccharide produced and the amount of decomposition into acid and gas components are small. Therefore, the production amount of monosaccharide and furfural increases. The amount of monosaccharide and furfural produced is, for example, 30% or more of the total amount of cellulose and hemicellulose. That is, 30% or more of the total amount of cellulose and hemicellulose is recovered as furfural and monosaccharide.

  From this point, in the present invention, the temperature of the high-temperature high-pressure water is set to more than 300 ° C. and not more than 350 ° C. In the present invention, a woody biomass is brought into contact with a high-pressure (13-30 MPa) high-temperature and high-pressure water having such a temperature (over 300 ° C and below 350 ° C) for 5 minutes or longer to decompose the woody biomass from monosaccharides and Furfural can be produced at a higher production rate than in the prior art. In order to make the production rate of monosaccharide and furfural at a higher level, the temperature of the high-temperature high-pressure water is preferably 310 to 340 ° C, and more preferably 315 to 330 ° C. In order to achieve a higher level of furfural even if the production rate of monosaccharides is reduced, the temperature of the high-temperature high-pressure water is preferably 330 to 350 ° C, and more preferably 340 to 350 ° C. It is more desirable. Even if the production rate of furfural is reduced, if the production rate of monosaccharides is desired to be higher, it is desirable to set the temperature of the high-temperature high-pressure water to more than 300 ° C and not more than 330 ° C, and more than 300 ° C to 315 ° C. It is more desirable that the temperature be not higher than ° C.

In the method for producing monosaccharide and furfural according to the present invention, the monosaccharide and furfural produced by the decomposition treatment are present in the high-temperature and high-pressure water (high-temperature and high-pressure water after the decomposition treatment) used for the decomposition treatment. As a method for separating furfural from this high-temperature and high-pressure water, a method for separating the furfural in this high-temperature and high-pressure water by adsorbing it on an adsorbent can be mentioned [ first invention]. More specifically, in this method, the high-temperature and high-pressure water after the decomposition treatment is cooled and depressurized, for example, cooled to normal temperature (room temperature) and normal pressure (atmospheric pressure), depressurized, and then brought into contact with the adsorbent. This is a method of adsorbing furfural in water on an adsorbent. When this adsorbent is washed with an organic solvent such as ethanol, furfural is easily desorbed from the adsorbent, and an organic solvent containing furfural is obtained.

At this time, as the adsorbent, it is more effective and effective in adsorbing furfural if the carbonized residue produced by the decomposition process in the monosaccharide and furfural production method according to the present invention is used. 1 invention]. Furthermore, it is more effective and excellent in the furfural adsorption performance to use the activated carbon after the carbonization of the residue produced by the decomposition treatment [ second invention].

  The carbonization is preferably performed at a temperature of 900 ° C. or higher. What is necessary is just to activate the said activation process after the carbonization process by the high temperature steam, and it is desirable to implement at the temperature of 800 degreeC or more.

  In the method for producing monosaccharides and furfural according to the present invention, the amount of the residue generated by the decomposition treatment is, for example, about 20% by mass (% by weight) with respect to the used woody biomass. Since carbonized residue is as low as 1% by mass or less in ash and has the same calorific value as coal, effective heat recovery is possible.

  After separating furfural from the high-temperature and high-pressure water after the decomposition treatment, by removing monosaccharides and the like from the water, this water can be reused as a water source for the high-temperature and high-pressure water for the decomposition treatment. Reusing water in this way eliminates the need for water treatment for drainage, reduces the environmental burden, and improves economic efficiency.

  In the present invention, woody biomass is woody or woody biomass. Examples of the woody biomass include forest land residual materials, residual materials from lumber mills, construction waste materials, building demolition materials, wood chips, wood sawdust, and the like.

  Examples of the present invention and comparative examples will be described below. The present invention is not limited to this embodiment, and can be implemented with appropriate modifications within a range that can be adapted to the gist of the present invention, all of which are within the technical scope of the present invention. include.

[ Reference Example 1]
After filling 30 g of cedar wood flour into the semi-flow reactor (reaction tube) shown in Fig. 1, high temperature and high pressure water at a temperature of 305 ° C and a pressure of 25 MPa at a flow rate of 30 g / min for 60 minutes. Circulated. After the circulation, the high-temperature and high-pressure water (the high-temperature and high-pressure water after the decomposition treatment) is cooled and then put into a reaction liquid receiver through a solid-liquid separation filter and a pressure holding valve.

  With respect to the water (water after decomposition treatment) put in the reaction liquid receiver, the amounts of monosaccharides (glucose and other monosaccharides) and furfural in the water were determined by quantitative analysis. This quantitative analysis was performed at a column temperature of 65 ° C. by liquid chromatography (LC-10A manufactured by Shimadzu Corporation).

  Then, the ratio of each amount of glucose, other monosaccharides, and furfural to the total amount of cellulose and hemicellulose in 30 g of the cedar wood flour [mass% (wt%)]] was determined, and this was determined as the production rate [ Wt% (wt%)]. The production rate of glucose (wt%) where the amounts of glucose, other monosaccharides, and furfural are Ag, Bg, and Cg, and the total amount of cellulose and hemicellulose in 30 g of the cedar wood flour is Tg. = 100 A / T, production rate of other monosaccharides (other than glucose) (wt%) = 100 B / T, production rate of furfural (wt%) = 100 C / T.

  The results are shown in Table 1. The furfural produced from the cedar wood flour is 5-hydroxymethylfurfural (hereinafter also referred to as 5-HMF). Table 1 shows 5-HMF. As can be seen from Table 1, the monosaccharide production rate (glucose production rate + other monosaccharide production rate) (a) and furfural (5-HMF) production rate (b) are both described later. The total generation rate (a + b) is higher than that of Comparative Examples 1 and 2, and is higher than that of Comparative Examples 1 and 2 described later. The amount of the black residue remaining in the reaction tube was 20% by mass (% by weight) based on 30 g of the cedar wood flour.

[ Reference Example 2]
After filling 30 g of cedar wood flour into the semi-flow reactor (reaction tube) shown in Fig. 1, high-temperature high-pressure water at a temperature of 325 ° C and a pressure of 25 MPa is put into this reactor at a flow rate of 30 g / min for 60 minutes. Circulated. Thereafter, in the same manner as in Example 1, the amounts of glucose, other monosaccharides, and furfural in the water after the decomposition treatment were measured, and cellulose and hemicellulose in 30 g of the cedar wood flour in each amount. The ratio (wt%) to the total amount, that is, the production rate (wt%) was determined.

  The results are shown in Table 1. The furfural produced from the cedar wood flour is 5-HMF. As can be seen from Table 1, the monosaccharide production rate (glucose production rate + other monosaccharide production rate) (a) and furfural (5-HMF) production rate (b) are both described later. The total generation rate (a + b) is higher than that of Comparative Examples 1 and 2, and is higher than that of Comparative Examples 1 and 2 described later. The amount of black residue remaining in the reaction tube was 22% by mass with respect to 30 g of the cedar wood flour.

[Comparative Example 1]
After filling 30g of cedar wood flour into the semi-flow reactor (reaction tube) shown in Fig. 1, high temperature and high pressure water at a temperature of 370 ° C and a pressure of 25MPa at a flow rate of 30g / min for 60 minutes. Circulated. Thereafter, in the same manner as in Example 1, the amounts of glucose, other monosaccharides, and furfural in the water after the decomposition treatment were measured, and cellulose and hemicellulose in 30 g of the cedar wood flour in each amount. The ratio (wt%) to the total amount, that is, the production rate (wt%) was determined.

  The results are shown in Table 1. The furfural produced from the cedar wood flour is 5-HMF. As can be seen from Table 1, the monosaccharide production rate (glucose production rate + other monosaccharide production rate) (a) and the furfural (5-HMF) production rate (b) are both described above. The total generation rate (a + b) is lower than that in the first and second embodiments, and is lower than that in the first and second embodiments. The amount of black residue remaining in the reaction tube was 25% by mass with respect to 30 g of the cedar wood flour.

[Comparative Example 2]
After filling 30 g of cedar wood flour into the semi-flow reactor (reaction tube) shown in Fig. 1, high-temperature and high-pressure water at a temperature of 270 ° C and a pressure of 25 MPa is put into this reactor for 60 minutes at a flow rate of 30 g / min. Circulated. Thereafter, in the same manner as in Example 1, the amounts of glucose, other monosaccharides, and furfural in the water after the decomposition treatment were measured, and cellulose and hemicellulose in 30 g of the cedar wood flour in each amount. The ratio (wt%) to the total amount, that is, the production rate (wt%) was determined.

  The results are shown in Table 1. The furfural produced from the cedar wood flour is 5-HMF. As can be seen from Table 1, the monosaccharide production rate (glucose production rate + other monosaccharide production rate) (a) and the furfural (5-HMF) production rate (b) are both described above. The total generation rate (a + b) is lower than that in the first and second embodiments, and is lower than that in the first and second embodiments. The amount of black residue remaining in the reaction tube was 18% by mass with respect to 30 g of the cedar wood flour.

Example 3
The black residue remaining in the reaction tube in Reference Example 1 was carbonized by heating at 950 ° C. for 1 hour in a nitrogen atmosphere, and further activated by heating at 950 ° C. for 20 minutes in a steam atmosphere to prepare activated carbon. .

  After the activated carbon is filled in the adsorption tube, an aqueous solution with a glucose concentration of the reagent: 2000 mg / liter (hereinafter, l) and a 5-HMF (5-hydroxymethylfurfural) concentration: 100 mg / l is added to the adsorption tube at 10 ml / min. Adsorption separation was conducted by circulating at a flow rate, and the relationship between the accumulated flow rate at this time and the glucose concentration and 5-HMF concentration in the circulating aqueous solution was determined. The glucose concentration in this aqueous solution was obtained by quantitative analysis by the refractive index method (RI-8011 manufactured by Tosoh Corporation). The concentration of 5-HMF in this aqueous solution was determined by quantitative analysis by an absorptiometric method (Shimadzu SPD-6AV, HITACHI U-2001).

  The result is shown in FIG. As can be seen from FIG. 2, 5-HMF was adsorbed on the activated carbon and separated from the aqueous solution, and it was confirmed that the activated carbon was excellent in the adsorption separation performance of 5-HMF.

  Ethanol was circulated in the adsorption tube after the aqueous solution was circulated. As a result, 5-HMF adsorbed on the activated carbon could be recovered.

  The method for producing monosaccharides and furfural according to the present invention can be preferably used when monosaccharides and furfural are to be obtained from woody biomass because monosaccharides and furfural can be produced from woody biomass at a high production rate. It is useful because it improves the recovery rate of monosaccharides and furfural.

It is a schematic diagram which shows the apparatus used for the decomposition process by the high temperature / high pressure water which concerns on the Example of this invention. It is a figure which shows the relationship between the integrating | accumulating flow volume and density | concentration (glucose concentration, 5-HMF density | concentration) when distribute | circulating the aqueous solution containing glucose and 5-HMF to the activated carbon which concerns on the Example of this invention.

Claims (2)

The woody biomass is decomposed by contacting it with high-temperature and high-pressure water of more than 300 ° C and 350 ° C or less and 13-30MPa for 5 minutes or more, and the furfural is adsorbed and separated from the monosaccharide and furfural produced by this decomposition treatment. A method for producing a sugar and furfural, wherein the adsorbent is obtained by carbonizing a residue produced by the decomposition treatment . The method for producing monosaccharides and furfural according to claim 1 , wherein the adsorbent is obtained by carbonizing the residue and then performing an activation treatment .

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