JP2006076979A - Method for producing phenol derivative from wood chip as raw material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To finely identify the production conditions of low mol. wt. phenol derivatives and the products obtained by the high pressure hot water treatment of wood chip biomass, thus contributing to the effective utilization of the wood wastes. <P>SOLUTION: This method for producing the phenol derivative from wood chips comprises cooking a mixture of the wood chips with water alone or alkaline water under high pressure to obtain the solid-liquid mixture reaction product, subjecting the solid-liquid mixture reaction product to extraction with an organic solvent, and then separating the phenol derivative from the obtained oil fraction. The phenol derivative oil fraction consists mainly of 3-methylphenol or 4-methylphenol, 4-hydroxyphenol or 4-methylphenol, 3-hydroxy-2-pentanone and 3-methoxy-1-propene, and the like. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a phenol derivative such as phenol, alkoxyphenol, cresol, etc., directly from wood or wood waste, or from wood or wood waste as a raw material (hereinafter referred to as “wood chip”).

  In particular, the present invention relates to a method for efficiently producing a useful phenol derivative from an oil (liquid hydrocarbon) obtained by catalytic hydrothermal treatment of wood chips.

  From forestry or lumber mills, or construction site paper mills, a large amount of thinned lumber or lumber and processed waste (hereinafter referred to as “wood waste”) are generated, and waste disposal has become a problem in terms of environmental conservation. For this reason, technological development for recycling these wood chips as wood resources has become active. Wood resources generally consist of lignocellulose, and many patents have been found on methods for producing lignophenol derivatives therefrom. For example, Patent Document 1 describes the method. Here, the production of lignophenol derivatives is carried out by adding an acid to the lignocellulosic material sorbed with the phenol derivative and mixing it, and then purifying the separated insoluble fraction of the crude lignophenol derivative by adding excess water. Description of a method for separating and purifying by first adding a predetermined concentration of antioxidant to the crude lignophenol derivative, then adding a predetermined concentration of alkali and reacting, followed by solid-liquid separation. There is.

  Patent Document 2 discloses a method for extracting a natural fluid from a woody plant material, wherein a sealed enclosure containing the woody plant material is pressurized to a pressure higher than atmospheric pressure, and saturated water vapor is generated. Alternatively, a method is described which includes the steps of injecting, heating to the core of the woody plant material by electromagnetic waves, and recovering by liquid the liquid exudates from the treated woody plant material. . Through this process, it is possible to extract various natural molecules from wood and use them in various business sectors such as pharmaceutical, cosmetics, food industry and fine chemistry. When these liquids are used, phenol, polyphenol, tannin, terpene, vitamins, acetic acid, salicylic acid, seasonings and the like can be extracted later.

  Patent Document 3 is a method for producing a carboxyalkylated lignin derivative in which lignin is immersed in an alkaline aqueous solution, the immersion product is dispersed in an organic solvent, and then a monohalogenoalkylcarboxylic acid is added to the obtained dispersion. is there. Here, a carboxyalkylated lignin derivative having significantly improved solubility in water can be obtained even when acetic acid digested lignin, steamed crushed lignin or the like is used as a starting material.

  Patent Document 4 aims to provide a means for efficiently reusing a lignocellulosic substance, and the second or sixth position (ortho position) of a phenol derivative having a substituent at the fourth position (para position). And / or the carbon atom at the 6-position (ortho position) of the phenol derivative having a substituent at the 2-position (ortho position) and 4-position (para-position) binds to the carbon atom at the benzyl position of the phenylpropane unit of lignin The resulting lignophenol derivative is reacted with a crosslinkable functional group-forming compound under alkaline conditions to prepare a crosslinkable lignophenol derivative having a crosslinkable functional group at the ortho position of the phenolic hydroxyl group, and heated to form a crosslinked product. A polymer material comprising a lignophenol derivative obtained by preparing the is described.

  Kruse et al. Listed as Non-Patent Document 1 tried steam decomposition of biomass as in the present invention, and reacted in water in an autoclave at 330-410 ° C., 30-50 MPa for 15 minutes. It has been reported to be decomposed into aldehydes. In addition, a mixture obtained by adding alkaline water to wood or a lignocellulosic material that is a component of wood, which is a premise of the present invention, is steamed under high pressure to obtain a solid-liquid mixed reaction product, Non-patent document 2 shows a method for separating a phenol derivative from an oil obtained by extraction with the method described above.

JP 2003-268116 A Special Table 2002-54294 JP-A-5-294981 JP 2001-261839 A Kruse.A; Gawlik.A: Ind.Eng.Chem.Res.2003,42-2,267-279 Shin-ya YOKOYAMA et al: Journal of Petroleum Society 29, No. 3, 262-266, 1986

  In general, as seen in Non-Patent Document 1 above, steam decomposition of biomass such as wood chips has been performed, and in a high-temperature and high-pressure water reaction in an autoclave, in addition to phenols, furfurals, acids, Degradation to aldehyde has been done conventionally. Moreover, although it is seen also in said patent document that it decomposes | disassembles into various phenol derivatives, the detail of the product by the alkali cooking under high temperature and a high pressure is not exhausted.

  Further, the method of biomass decomposition of wood chips shown in Non-Patent Document 2 is similar to the decomposition method premised on the present invention, but the purpose is to efficiently convert wood chips into heavy oil and use it as an effective energy source. To do. Instead, the present invention aims to contribute to effective utilization of wood waste such as wood chips by finely identifying the production conditions and products of low molecular weight phenol derivatives from this oily oil. .

  The means of the present invention is to make a solid-liquid mixed reaction product obtained by steaming a mixture obtained by adding only water or alkali water as a catalyst to a wood chip under high pressure, and this solid-liquid mixed reaction product with an organic solvent. A method for producing a phenol derivative using wood chips as a raw material, wherein the phenol derivative is separated from an oil (liquid hydrocarbon) obtained by extraction. The raw materials for wood chips are originally various, but even if the type of wood changes, it is essentially lignocellulose. In Japan, it is a collective term for “wood waste”, which is a large amount of thinned wood or lumber discharged from forestry or lumber mills, or construction sites and paper mills. That is, in addition to pine, firewood, cedar, oak, firewood, firewood.

  The alkaline water used here is potassium carbonate, caustic potash, sodium carbonate or caustic soda having a concentration of 0.2 to 3 M / L, preferably 0.5 to 2 M / L, and steamed under pressure in the presence of alkaline water. The reaction yield is greatly increased compared to simple steaming only with water, and the content of the product differs depending on the type of alkali used. Can be manufactured well. When the concentration of alkaline water is 0.2 M / L or less, the catalytic effect is insufficient, and when it is 3 M / L or more, the alkali content becomes excessive, such being undesirable.

  Moreover, steaming under high pressure as a reaction condition for wood chips is high-pressure steam heat treatment (hereinafter referred to as “hot water treatment”) performed in an autoclave at a temperature of 180 to 320 ° C., preferably 230 to 300 ° C. . Although the content of the product varies slightly depending on the reaction temperature, most of what is obtained is a phenol derivative. The reaction temperature greatly affects the yield, the type of product, and also the scale of the pressure production apparatus. It is not preferable because it is difficult to liquefy at 180 ° C. or lower and gasifies at 320 ° C. or higher. Although the range of reaction time is not specifically limited, It is 5 to 30 minutes normally in the said temperature range, Preferably, it is 10 to 20 minutes.

  Organic solvents used for oil extraction from solid-liquid reactants obtained by hydrothermal treatment of wood chips are ethers, acetones or esters. Since the reaction product is extracted in an aqueous solution, these strongly polar organic solvents can be used effectively.

  The phenol derivative oils obtained by ether extraction from the filtrate of the solid-liquid reaction product obtained by this hydrothermal treatment are mainly composed of methoxyphenols such as 2-methoxyphenol and 4-ethyl-2-methoxyphenol. In addition, alkylphenols such as 3-methylphenol and 4-methylphenol are produced. Alkaline water acts as a catalyst for the former methoxyphenol, and the yield increases dramatically.

  The main component of the phenol derivative oil obtained by acetone extraction from the residue of the solid-liquid reaction product is 3-methylphenol or 4-methylphenol.

  Although the component obtained by extraction with ethyl acetate from the ether-unextracted residue of the solid-liquid reaction product filtrate cannot be said to be a phenol derivative oil, its main components are 3-hydroxy-2-pentanone and 3-methoxy-1 as by-products. -Propene.

According to the method for producing a phenol derivative using wood of the present invention as a raw material, the product obtained by subjecting the wood chip biomass to low-temperature liquefaction treatment at 280 ° C. for 15 minutes by high-pressure hydrothermal treatment and hydroxylation of Na and K in the boiling point distribution The effect of the product and carbonate was revealed in detail on the composition and amount of the product by independently analyzing the oil product extracted in various stages. That is, with ether extracted oil 1 obtained from all alkali catalyst treatments (NaOH, Na ₂ CO ₃ , KOH and K ₂ CO ₃ ), the main hydrocarbon is 2-methoxy-phenol in high yield. . On the other hand, only the hydrothermal treatment produces a low yield compared to the catalyst treatment, but 3- or 4-methyl-phenol is produced as the main hydrocarbon. In addition, oil 3 obtained by acetone extraction from the high-pressure pyrolysis residue is also decomposed and produced by the use of these basic solutions, and eugenol is also produced as 4-methyl-2-methoxyphenol. It was generated. Furthermore, the production of other compounds such as benzenediol derivatives was promoted from oil 2 of the ethyl acetate extract of the ether extraction residue.

And basic catalysts, such as an alkali, increased the water-soluble hydrocarbon and decreased the solid residue (biocarbide). As a result of TOC analysis of the aqueous phase, the basic catalyst increases the total organic carbon content. Furan derivatives were observed in the hydrothermal treatment, but not in the catalyst treatment. In oil 2, 3-methoxy-1-propene was found both in the case of heat and catalyst treatment. Oil 3 by the hydrothermal treatment contained both low-boiling compounds and high-boiling compounds. Oil 3 obtained by the hydrothermal treatment mainly contained tar together with a small amount of other hydrocarbons such as hexadecanoic acid and octadecanoic acid. Phenol compounds were mainly produced by liquefying wood chips with alkaline catalyst hot water, and the amount of product distribution varied depending on the type of basic solution, and in particular, high yields were obtained with K ₂ CO ₃ .

  The phenol derivative obtained by the production method of the present invention is promised to be used as a raw material for synthesis of drugs, fragrances and the like. For example, 2-methoxyphenol is also called guaiacol, and is a synthetic raw material such as guaiacol glycerin ether and guaiacol potassium sulfonate. 3- or 4-methylphenol is so-called cresol and has a wide range of uses such as disinfectant, synthetic resin raw material, plasticizer, and varnish. Eugenol is a component of clove oil and can also be used as a fragrance.

  Hereinafter, specific embodiments of the production method of the present invention will be described in detail with reference to the drawings. FIG. 1 is a flowchart showing a method for producing a phenol derivative using wood chips as a raw material. FIG. 2 is a graph showing the influence of the alkali catalyst on the thermal decomposition yield.

  As is apparent from FIG. 1, first, the raw wood chips were subjected to thermal decomposition by steaming only with water and steaming in the presence of various alkalis in a reaction tank composed of a pressure kettle. The thermal decomposition condition is a hot water treatment performed under the conditions of 180 to 320 ° C., here, 280 ° C. and 15 minutes as described above. The obtained reaction product is neutralized with hydrochloric acid, acidified, filtered, and solid-liquid separated.

  Ethyl ether is added to the liquid to separate it into an ether extraction phase and an aqueous phase, and the ether extraction phase is distilled to recover the “oil 1” residue and ether content. Further, ethyl acetate is added to the aqueous phase to separate “oil 2”, and ethyl acetate is recovered and reused by distillation.

  On the other hand, the reactant filtration residue solid on the right side of FIG. 1 is extracted with acetone, and acetone is separated from the soluble matter to separate “oil 3”. By these reactions and separation and separation procedures, a method for producing a phenol derivative using the wood chip of the present invention as a raw material is established. Details thereof will be described in detail in later examples. If the conclusion is described first, the mass balance as shown in FIG. 2 is obtained. That is, although the conversion yield to oil is less than 10% in the case of water alone, it reaches 25 to 35% in the presence of alkali, and is particularly maximized by the addition of potassium carbonate.

  Hereinafter, the manufacturing method of the phenol derivative which uses the wood chip | tip of this invention as a raw material is further demonstrated by an Example. First, the used wood chip was obtained by crushing pine (No. 1) sawdust into chips having an average particle diameter of 1 to 3 mm, and the properties are shown in Table 1. As a result of elemental analysis, it was 50.7 wt% carbon, 6.2 wt% hydrogen, and 42.6 wt% oxygen.

Examples 1-5
Using the above-mentioned pine wood chip, hot water treatment was performed in the following apparatus and process. First, for hot water treatment and alkali catalyst treatment, 200 mL of TaS-02-HC was used for 15 minutes at 280 ° C. using a solution of NaOH, Na ₂ CO ₃ , KOH and K ₂ CO ₃ (0.94 M). A hot water liquefaction test was conducted in a mold autoclave. In a typical catalytic hot water liquefaction process, 5 g (dry basis) of wood chips and 30 ml each of water or 0.94M alkaline solution (NaOH, Na ₂ CO ₃ , KOH and K ₂ CO ₃ ) are added to the reactor. It was.

  In the hot water treatment, 5 g (dry basis) of wood chips and 30 ml of ion-exchanged water were added to the reactor. The reactor was then purged 5 times with nitrogen to remove the air inside. The reaction was stirred vertically using a stirrer at 60 rpm / min. Thereafter, the temperature was increased to 280 ° C. at a heating rate of 3 ° C./min, and kept at 280 ° C. for 15 minutes. After the reaction, the reactor was cooled to room temperature with a blower. The procedure for separation and extraction of the reaction product is shown in FIG. The gaseous product was ventilated and collected in a Teflon bag and sealed.

  The solid and liquid products were flushed from the autoclave with ion exchanged water, acidified to pH 1-2 with HCl (1.7 M), capped and stored in the refrigerator overnight (12 h). The solid and liquid products were then separated by filtration under vacuum for 15 minutes. During filtration, the solid product was washed with 100 ml of ion exchange water. The liquid part was extracted with an equal amount of diethyl ether (600 ml). The ether solution thus obtained was dried over anhydrous sodium sulfate, filtered, and concentrated in a rotary evaporator at room temperature. Diethyl ether was removed and the fraction was weighed to give an oil content of 1. The aqueous phase was further extracted with an equal volume of ethyl acetate (200 ml). The ethyl acetate solution thus obtained was dried over anhydrous sodium sulfate. Ethyl acetate was removed under reduced pressure and this fraction was weighed to give an oil content of 2. After extraction, the remaining aqueous phase contained water-soluble hydrocarbons.

  The solid product was extracted with acetone (150 ml) in a Soxhlet extractor until the solvent of the cylindrical filter paper became colorless (about 20 hours). After removing acetone under reduced pressure in the rotary evaporator, this fraction was weighed to give an oil content of 3. The fraction insoluble in acetone was dried at 105 ° C. and weighed to obtain a solid residue (biocarbide). These material balances were calculated by the numerical values obtained by the measurement method described below, and the product distribution amount obtained by decomposing the wood chips was determined and presented in Table 2 collectively.

The liquid product was analyzed as follows. The oil component including oil component 1, oil component 2, and oil component 3 obtained by liquefying the wood chip at low temperature with hot water was analyzed by a gas chromatograph (GC-TCD: Shimazu GC-8A) equipped with a mass selection detector. Measurement conditions are [GC-MS; HP5973; column, HP-1; crosslinked methylsiloxane, 25 × 0.32 mm × 0.17 μm; temperature program, 40 ° C. (10 min hold) to 300 ° C. (rate 5 ° C./min) hold for 10 min; Oil temperature 3 temperature program in catalyst treatment, 40 ° C to 150 ° C (rate 5 ° C / min) to 240 ° C (rate 3 ° C / min) to 300 ° C (rate 10 ° C / min) 30 minutes] Peaks were identified using Wiley Library-HP G1035A, a mass spectral NIST library, a portion of HP G1033A. ¹ H NMR and ¹³ C NMR spectra were obtained using JEOL JNM-LA400. As the solvent, CDCl ₃ (hydrothermal treatment) and C ₃ D ₆ O (catalytic treatment) were used. The amount of cations in the aqueous phase was determined using an ion chromatograph (DIONEX IC25). The total organic carbon content (TOC) in water was measured using TOC analysis (Shimazu TOC-500). The gaseous product was analyzed with a gas chromatograph equipped with a thermal conductivity detector.

The catalytic low temperature hydrothermal treatment of wood chips was carried out at 280 ° C. for 15 minutes in the presence of various basic solutions (NaOH, Na ₂ CO ₃ , KOH and K ₂ CO ₃ ). The reaction conditions were standardized at 280 ° C. for 15 minutes based on preliminary experiments and results. In Table 2, the product distribution amount which decomposed | disassembled the wood chip | tip is shown. In the degradation of wood chips, basic solutions have been shown to have an important effect in terms of oil yield and conversion. Table 2 shows the effect of various bases on the oil yield.

The yield of oil 1 of only the high-pressure hot water treatment of the present invention was 1.3 wt%, and when an alkaline catalyst using various basic solutions was added, the yield increased approximately 6 to 12 times. Oil 1 and oil 2 were viscous liquids, but oil 3 was solid. The yield of oil product ranged from 10.0-16.7 wt%. As described above, the fractions soluble in ether and ethyl acetate are Oil 1 and Oil 2. Among the various basic catalysts, K ₂ CO ₃ gave the highest yielded oil product (total of oil 1 and oil 2 was 16.7 wt%). Considering the yield and conversion of the oil product, the order of catalytic activity is as follows: K ₂ CO ₃ >KOH> Na ₂ CO ₃ > NaOH. Thus, it can be said that the alkali salt is more effective than the corresponding hydroxide. This is one of the possible reasons that an alkali salt reacts with water to produce its base and bicarbonate. That is, bicarbonate may act as a secondary catalyst.

When the wood chip was hydrothermally treated at a low temperature (280 ° C. for 15 minutes) using K ₂ CO ₃ , the conversion rate was 96%. K ₂ CO ₃ can be said to be an effective basic catalyst not only for gasification but also for decomposition of biomass by liquefaction. In the catalyst treatment, the yield of oil 2 was 1.5-2.3 w%. Oil 3 was the acetone extract from the solid, but the highest when using K ₂ CO ₃ (17%). The use of a basic catalyst also increased the gas yield slightly. The various basic catalysts used in the present invention showed little change in the yield of gaseous products. The composition of the gaseous _{products, CO 2, CH 4, C} 2 H 4, a _{C 2 H 6, C 3 H} 6, the main component in all treatment was CO _2.

In Table 2, as components other than the total oil contained in solid residues and liquid components, there are water-soluble hydrocarbons and extracts. Wood is mainly composed of lignin, cellulose, hemicellulose and extracts. Water-soluble products are produced by degradation of hemicellulose and cellulose. The dry weight of the plant usually contains 50-80 wt% of high molecular carbohydrates together with the constituent substances. Cellulose is rapidly decomposed into water-soluble components (WS). FIG. 3 shows the total organic carbon (TOC) content in the aqueous phase. FIG. 3 clearly shows that the catalyst treatment has a higher TOC content than the hot water treatment. The TOC content was the highest when K ₂ CO ₃ was used (16% based on the raw material carbon), and the lowest value was obtained when NaOH was used. Similarly, in the oil product, the TOC content was higher when the carbonate was used than when the corresponding hydroxide was used.

  Here, the main difference between the alkaline catalyst water observed in the examples and the simple hydrothermal treatment will be described. In the case of the hot water treatment, the solid product needs to adhere to the surface of the autoclave and scrape the solid. However, in the catalyst treatment, all is recovered from the autoclave as a dark liquid. In the case of alkaline catalyst treatment, it is clear that solid residue (biocarbide) is less than that of hydrothermal treatment, and it is advantageous to increase the yield of phenol derivatives (Table 2).

  The other is the solid-liquid separation operation after the reaction in the alkali catalyst treatment. Even if HCl was added after the filtration step after the reaction, it was difficult to sufficiently separate the liquid and the solid part. However, by adding HCl after the reaction and storing it in the refrigerator, liquid and solid were produced. Things could be completely separated. Tables 3, 4 and 5 show the compounds in the oils identified by GC-MS analysis of oil 1, oil 2 and oil 3 and increasing the retention time. The chromatographic area results (% from total area) are attributed to the identified compound. The difference from 100% of the total peak area represents the area of the unidentified compound, and the peak area less than 1.5% is shown by skipping the number.

As can be seen from Table 3, the main component in the hydrothermal treatment was 3- or 4-methylphenol, 2-furancarboxaldehyde, and 2-methoxyphenol. However, in the catalyst treatment, 2-furancarboxaldehyde was not observed, and 3-methyl or 4-methylphenol was observed as a minor component when NaOH and Na ₂ CO ₃ were used. FIG. 4 shows the total ion chromatogram (retention time up to 25 minutes) of oil 1 obtained from only hot water and alkali catalyst treatment (K ₂ CO ₃ ). The peak numbers in FIG. 4 correspond to the numbers in Table 3. As seen in FIG. 4, a peak belonging to the 2-furan carboxaldehyde (peak No.3) and 3-methyl phenol (peak No.11) was observed in hydrothermal treatment, these compounds are _K 2 CO It was not observed in ₃ . From both Table 3 and FIG. 4, in hydrothermal treatment, 2-furancarboxaldehyde, 2-methyl-2-cyclopenten-1-one, 1- (2-furanyl) -ethanone, 2,5-hexanedione, 5 It is clear that -methyl-2-furancarboxaldehyde, phenol, 2-hydroxy-3-methyl-2-cyclopenten-1-one and 4-hydroxy-3-methoxybenzeneacetic acid were observed. However, these compounds were not observed when using K ₂ CO ₃ or other catalyst treatments. Acetic acid and propionic acid were observed in the catalyst treatment, but only propionic acid was observed in the hydrothermal treatment. The acetic acid peak overlaps the solvent peak (ether). The main difference between hydrothermal treatment and catalyst treatment is that 4-methyl-1,2-benzenediol, 4,5-dimethyl-1,3-benzenediol and 4-ethyl-1,3-benzenediol are used for catalyst treatment. There are benzenediol derivatives such as However, in the case of hydrothermal treatment, only 1,2-benzenediol was observed.

In oil 1, it is considered that 2-methoxyphenol is first produced and decomposed to produce 1,2-benzenediol. Compared to hydrothermal treatment, the use of a basic solution increased the amount of 2-methoxyphenol (Table 4). The percentage of 2-methoxyphenol was higher in the presence of NaOH and Na ₂ CO ₃ than in the presence of KOH and K ₂ CO ₃ . In contrast to hydrothermal treatment, 3- or 4-methoxyphenol was low in the case of NaOH or Na ₂ CO ₃ and was not observed in KOH or K ₂ CO ₃ . Lignin in wood binds to polysaccharide components (cellulose, hemicellulose, etc.) both physically and chemically and is complex, including acetals, α-phenyl-β-ether, phenyl-β-glucosidic and hydrogen bonds A three-dimensional network is formed.

  In the catalyst treatment, the main components of the hydrocarbon of oil 1 are a phenol derivative and a benzenediol derivative. The β-allyl and benzoyl ether bond in lignin was cleaved to produce a phenol compound, which was further decomposed to produce a benzenediol derivative. The thermochemical conversion of wood produces three types of products: liquid (consisting of oil and water), solid (biocarbide) and gas. The yield of these products containing phenolic compounds depends on experimental conditions including lignin configuration in wood, solvent, reaction temperature, reaction time, solvent / biomass ratio, reactor type, and the like. Except in the case of using NaOH in the catalyst treatment, 2,3-dimethylhydroquinone and 1- (4-hydroxy-3-methoxyphenyl) -ethanone were observed in oil 1 in addition to phenol and benzenediol derivatives.

The composition of the biomass from which oil 1 has been extracted is a very complex mixture. In this study, we used GC-MS analysis data to show the boiling point distribution of biomass from which oil 1 was extracted. FIG. 5 is a so-called C-NP (standard paraffin) gram, in which the area fraction of each component is plotted against the number of carbons to which the standard paraffin corresponds. The number of carbons on the horizontal axis represents the range of the corresponding boiling point (BP) of standard paraffin. Details about the C-NPgram can be found at any point. Both the oxidized hydrocarbons obtained from the hydrothermal treatment and the catalyst treatment are also distributed in the C ₇ to C ₁₆ boiling range. In all processes, including a hydrothermal treatment, the main component of hydrocarbon oil 1 clearly corresponds to C _11. Of the catalysts evaluated, Na ₂ CO ₃ produced the most C ₁₁ hydrocarbons, 56%. When Na ₂ CO ₃ is used, 2-methoxyphenol is the main component in oil 1, but 2-methoxy-phenol mainly increases C ₁₁ hydrocarbons. For C ₁₁ (174.0-195.8 ° C.), the hydrocarbon was 50% with NaOH, 42% with hydrothermal treatment, 36% with KOH, and 28% with K ₂ CO ₃ . It is clear that the use of K ₂ CO ₃ produces other oxidized hydrocarbons such as benzenediol and 4-ethyl-2-methoxyphenol. _The boiling point of the hydrocarbons from the K 2 CO ₃ was distributed _{C 11} is _{28% C 12} is _{15% C 13 23%,} and _{C 14} 20%. It is interesting that C ₁₃ hydrocarbons are 23% for K ₂ CO ₃ and KOH, compared to 11% for NaOH and Na ₂ CO ₃ . Distribution of hydrocarbons obtained from the hydrothermal treatment shows a sharp peak at C _8, it is clear that mainly 2-furan carboxaldehyde.

  Table 4 shows the identified compounds in Oil 2. As can be seen in Table 4, 3-methoxy-1-propene was observed in all treatments. In the hydrothermal treatment, 4-oxo-pentanoic acid and 5-ethyldihydroxy-2 (3H) -furanone were observed, while in the catalyst treatment, 3-hydroxy-2-pentanone was observed. In all catalyst treatments, 3-hydroxy-2-pentanone was the main component. However, the oil content 2 is a small amount of only 0.1 to 1.5% in view of the product distribution amount in Table 2.

Thirty-two compounds were identified in Oil 3 obtained by the hydrothermal treatment and are shown in Table 5. However, in the alkali catalyst treatment, 2-methoxyphenol (RT, 5.884), 1,2-dimethoxybenzene (RT, 7.246 minutes, not observed with NaOH), 4-methyl- Compounds of 2-methoxy-phenol (RT, 8.398 minutes), hexadecanoic acid (RT, 26.659 minutes), octadecanoic acid (RT, 31.525 minutes) were observed. . In the hydrothermal treatment, the compounds observed in oil 1 (peak Nos. 1 to 11 and No. 16 in Table 5) were also observed in oil 3. This is because these compounds remain in the solid part, which can pass into the liquid part. The compound remaining in the solid part could be extracted with acetone in a Soxhlet extractor. The compounds (peak Nos. 17 to 32) observed in the hydrothermal treatment were compounds having a higher boiling point. By using the basic solution, the compound having a higher boiling point cracked, and the compound could pass through the solution part. The ¹ H NMR spectrum of oil 3 of hot water and catalyst treatment (KOH) is shown in FIG. In the figure, (a) shows hot water treatment, and (b) shows KOH catalyst treatment.

  As can be seen from FIG. 6, the spectrum of oil 3 is significantly different between the hydrothermal treatment and the catalyst treatment. In the case of hydrothermal treatment, a sharp peak was observed, but in the catalyst treatment, a broad peak with low intensity was observed particularly in the aromatic region. This indicates that the oil component 3 by the catalyst treatment is composed of a tar-like compound. In the hydrothermal treatment, peaks observed at 9.5377 ppm and 9.7588 ppm were assigned to the protons of aldehydes of 2-furancarboxaldehyde and 5-methyl-2-furancarboxaldehyde. Aromatic protons ranged from 6-8 ppm. The sharp peak at 7.117 ppm is mainly due to the aromatic proton at the meta position of 3-methylphenol. The hydroxyl moiety of the phenolic compound is less shielded than that of the alcohol derivative. The exact location of the OH signal depends on the degree of hydrogen bonding and whether the hydrogen bonding is intramolecular or intermolecular. The degree of intermolecular hydrogen bonding depends on the concentration of the phenolic compound and greatly affects the position of the OH signal. A peak in the range of 4-6 ppm shows an OH signal. The peak at 4.6607 ppm is mainly due to the —OH protons of 4-methylphenol and 2-methoxyphenol. The peak at 3.8076 is due to the -OCH3 signal of 2-methoxyphenol, 4-ethyl-2-methoxyphenol and 4-methyl-2-methoxyphenol. The alkyl proton is in the range of 0.5-3.5 ppm.

In the alkali catalyst treatment, the peak intensity of GC-MS is small. This is because a large amount of tar extracted from the solid part using acetone is produced by using a basic catalyst. Information on the molecular structure of the tar obtained can only be obtained by analysis in the GC-MS range. This range has an upper limit of approximately 300u, and aromatics with masses greater than 300u usually do not elute from the hot GC column. In order to confirm the presence of hydrocarbons in oil 3, ¹³ C NMR was performed. FIG. 7 shows the ¹³ C NMR spectrum of oil 3 obtained from KOH. The characteristics of a wide range of functional groups are as follows. Signal range 160-185ppm represents the carbon of a carboxylic acid (-COOH), a signal in the range of 120-160ppm aromatic carbon (Ar -), C signal 100-160ppm is attached to -OCH ₃ An atom (—C—OCH ₃ ) and a C atom (—C—OH) bonded to OH are shown. A signal in the range of 0-60 ppm indicates an alkyl carbon (—CH ₃ , —CH ₂ ).

As described above, in the present invention, the product obtained by subjecting the wood chip biomass to low-temperature liquefaction treatment (high-pressure hot water heating treatment) at 280 ° C. for 15 minutes and the boiling point distribution of Na and K hydroxides and carbonates. The effect was examined in detail. In oil 1 obtained from all catalyst treatments (NaOH, Na ₂ CO ₃ , KOH and K ₂ CO ₃ ), the main hydrocarbon was 2-methoxy-phenol. On the other hand, in the hydrothermal treatment, the main hydrocarbon was 3- or 4-methylphenol. The use of a basic solution facilitated the production of other compounds such as 4-methyl-2-methoxyphenol, 4-ethyl-2-methoxyphenol and benzenediol derivatives. The basic catalyst increased water-soluble hydrocarbons and decreased solid residues (biocarbides) to increase the yield of these aromatic hydrocarbons. In oil 2, 3-methoxy-1-propene was found in both hot water and catalyst treatment. Oil 3 from the hydrothermal treatment contained both low and high boiling compounds. Oil 3 obtained by the hydrothermal treatment mainly contained tar together with a small amount of other hydrocarbons such as hexadecanoic acid and octadecanoic acid. The product distribution amount varies depending on the type of basic solution by liquefying wood chips with catalytic hot water, but mainly phenol compounds are produced, and fine identification reveals the types of compounds. High value-added raw materials such as fragrances can be obtained from wood chips.

It is a flowchart which shows the manufacturing method of the phenol derivative which uses a wood chip as a raw material. It is a graph which shows the influence of the alkali catalyst with respect to a thermal decomposition yield. It is a graph which shows total organic carbon (TOC) content (%) in a hydrothermal process and each alkali catalyst process water phase. (A) hydrothermal treatment is a comparison chart of total ion chromatogram for oil 1 from _(b) K 2 CO ₃ catalyst treatment. It is a C-NP gram of the hydrothermal treatment for 15 minutes at 280 ° C. and each alkali catalyst treatment product. (A) Hydrothermal treatment, (b) ¹ H NMR spectrum of oil 3 from KOH catalyst treatment. 3 is a ¹³ C NMR spectrum of oil 3 from KOH catalyst treatment.

Claims (4)

A mixture of wood or a lignocellulosic material, which is a component of wood, added with alkaline water is steamed under high pressure to form a solid-liquid mixed reaction product, and phenol is extracted from the oil obtained by extracting the solid-liquid mixed reaction product with an organic solvent. A method for producing a phenol derivative using wood chips as a raw material, wherein ethers, acetones or esters are used as an organic solvent when separating the derivative. 2. The method for producing a phenol derivative using wood chips as a raw material, wherein the phenol derivative oil obtained by ether extraction from the filtrate of the solid-liquid reaction product is 2-methoxyphenol as a main component. The method for producing a phenol derivative using wood chips as a raw material, wherein the phenol derivative oil obtained by acetone extraction from the residue of the solid-liquid reactant is 3-methylphenol or 4-methylphenol. The oil obtained as a phenol derivative byproduct obtained by extraction with ethyl acetate from the ether-unextracted residue of the solid-liquid reaction product filtrate is mainly composed of 3-hydroxy-2-pentanone and 3-methoxy-1-propene. A method for producing a phenol derivative using the wood chip as described in 1.

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