JP2991466B2 - Method for producing lignocellulose-phenol compound composite using explosive method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a lignocellulose-phenol compound composite using an explosion method.

More specifically, when the lignocellulose material and a solvent containing at least one phenol compound as a main component are dissolved and reacted under heating, the lignocellulose material is subjected to a special pretreatment in advance, thereby shortening the reaction time. And a method for producing a lignocellulose-phenol compound composite therein.

[Conventional technology]

The resources produced from forests are renewable, and their effective recycling is currently strongly desired. For example, in the wood-based industries such as the pulp industry and the wood industry, it is urgent to establish effective ways to use the wood-based waste generated from the wood-based waste. Immediate development of a method for effectively utilizing agricultural waste containing lignocellulosic substances is also awaited.

Examples of the effective use of lignocellulose materials including wood and the like include, for example, JP-A-57-2360 and
No. 63-1992 or the like, a chemically modified lignocellulose material obtained by introducing at least one substituent into a part of hydroxyl groups in lignocellulose molecules is dissolved in an organic solvent, and this solution is used as a raw material for various resin materials. Methods of use are disclosed.

JP-A-60-206883 and JP-A-60-104513 disclose a method of using a lignocellulose material as a phenol compound-formaldehyde resin-based adhesive and a method of fiberizing the same.

Further, JP-A-61-215676 and JP-A-61-215675 disclose a lignocellulose material in a solvent composed of a polyhydric alcohol or a bisphenol compound, and dissolve this solution with a polyurethane-based, epoxy-based, or other A method for producing a molded article, a foam, or an adhesive by using the resin material together with the resin material is disclosed.

Further, JP-A-61-261358 discloses a method of directly dissolving wood without pretreatment in a solvent comprising a phenol compound or a bisphenol compound without using a catalyst. JP-79230 discloses a method of directly dissolving wood without pretreatment in a solvent composed of an alcohol compound, a polyhydric alcohol compound, an oxyether compound, a cyclic ether compound, or a ketone compound without using a catalyst. I have.

Japanese Patent Publication No. 61-2697 discloses a technique of dissolving wood powder in phenol in the presence of a mineral acid, and Japanese Patent Application Laid-Open No. 1-217070 discloses a similar technique. .

[Problems to be solved by the invention]

In the conventional technique of dissolving a lignocellulose material in a phenol compound, the mechanism of promoting the dissolution reaction has not yet been sufficiently elucidated. However, the development of this dissolution promoting technology is an essential and extremely important issue for realizing the industrial use of a lignocellulose material-phenol compound composite.

An object of the present invention is to provide a novel method for producing a lignocellulose-phenol compound composite that can dissolve a lignocellulose material in a phenol compound in a short time.

[Means and actions to solve the problem]

The method for producing a lignocellulose-phenol compound composite using the explosion method of the present invention is used as a pretreatment when a lignocellulose material and a solvent containing at least one phenol compound as a main component are dissolved and reacted under heating. And subjecting the lignocellulose material to an explosion treatment in the presence of the phenol compound.

In the method of the present invention, the explosion treatment for the lignocellulose material is performed by reducing the lignocellulose material by 20 to 40 kg.
After treating with saturated steam having a pressure of / cm ² and a temperature of 200-250 ° C for several minutes, the internal structure of the lignocellulosic material is destroyed by releasing this pressure at a stretch, and this is defibrated or pulverized. Processing. The explosion method was developed by Masson in the 1920's on wood for hardboard.
It is based on the te process.

In the explosion treatment, a part of the lignocellulose material undergoes decomposition due to high-temperature and high-pressure steam treatment, and becomes solvent-soluble. Therefore, the explosion treatment has the effect of accelerating the solubilization of the lignocellulose material.

This is because in the blasting treatment, the lignocellulosic material, for example, wood is chemically and physically decomposed by the steaming treatment with high-temperature and high-pressure saturated steam. In particular, during steaming, the hemicellulose in the lignocellulose material elutes and undergoes hydrolysis, and due to autohydrosis and homolytic decomposition by the acid generated at this time, the hemicellulose and lignin are further reduced in molecular weight. Solvent solubility is improved.

In the method of the present invention, in the presence of a phenol compound,
By subjecting the lignocellulose material to pre-explosion treatment,
It has been found that the phenolic compound reacts with the lignocellulosic material component and becomes more soluble.

In the method of the present invention, the saturated steam treatment in the pre-explosion treatment is carried out at 200 to 250 ° C. (pressure 20 to 40 kg / cm ² ).
It is preferably applied for 1 to 30 minutes, after which the pressure is released at once.

As an apparatus for performing the explosion treatment in the method of the present invention, a continuous explosion apparatus such as Iotech or Stake technology may be used, or a batch-type explosion apparatus may be used.

The lignocellulosic material used in the method of the present invention includes wood chips, wood flour, wood fibers, wood chips, veneer chips, plywood chips, waste paper, pulp, rice straw, fir grass, kolyan, bagasse, bamboo, straw, and the like. It can be selected from plant fiber materials.

In the present invention, the phenol compound forming a dissolved complex with the lignocellulose material can be selected from the following compound group.

(1) Monohydric phenol compound: for example, phenol, o
-, M-, and p-cresol, 3,5-, 2,3-, and 2,6-xylenol, o-, m-, and p-propylphenol, o-, m-, and p-butylphenol, o-, m-, and p-sec-butylphenol,
o-, m-, and p-tert-butylphenol, hexylphenol, phenylphenol, octylphenol, and naphthol (2) dihydric phenol compounds: for example, catechol, resorcinol, quinol, bisphenol A, bisphenol B and bisphenol F (3 ) Trihydric phenolic compounds: for example pyrogallol, chloroglycine, trihydrobenzene, and gallic acid.

The present invention is characterized in that, when a lignocellulose material is dissolved and reacted with a phenol compound, in the presence of the phenol compound, solubilization is promoted even without a dissolving catalyst by performing explosion pretreatment. . However, it is also possible to further promote dissolution by using a catalyst. In that case, it is preferable to use a catalyst comprising at least one member selected from the following compound group as the dissolution catalyst.

(1) Inorganic (mineral) acid: for example, hydrochloric acid, sulfuric acid, phosphoric acid, hydrogen bromide, etc. (2) Organic acid (a) Carboxylic acid: formic acid, acetic acid, oxalic acid, tartaric acid,
And benzoic acid, etc. (b) Organic sulfonic acid: for example, phenolsulfonic acid and p-toluenesulfonic acid, etc. (c) Organic sulfinic acid: for example, phenolsulfinic acid, etc. (d) Others: for example, uric acid, etc. (3) Lewis acid: for example In general, it is preferable that the dissolving catalyst such as titanium tetrachloride or aluminum chloride is used in a ratio of 0.1 to 20% based on the weight of the lignocellulose material.

In the method of the present invention, a mixture of the phenolic compound and the explosion-treated product of the lignocellulosic material is subjected to a heat dissolution treatment. The temperature and pressure of this heat dissolution reaction can be appropriately set according to the type of the phenol compound and the like.

For general always lysis, dissolution temperature is preferably 100 to 200 ° C., if the pressure dissolution, under a pressure of 10~40kg / cm ^2, it is preferred that the dissolution temperature is 200 to 300 [° C. .

The dissolution generally takes place under stirring for 1 to 10 hours, preferably 2 hours.
５5 hours.

〔Example〕

 The present invention is further described by the following examples.

Comparative Examples 1 to 5 In each of Comparative Examples 1 to 5, 250 g of birch chips and 250 g of phenol were charged into a two-batch type explosive crusher, and the mixture was subjected to ² , 4, 8, or 230 ° C. and a pressure of 28 kg / cm ² , or
Steaming was performed for 16 minutes, after which the pressure was released and explosion was performed. The amount of free phenol and water in the obtained explosive product was determined and the composition of the explosive product was examined.
The results in the table were obtained.

The wood component in the explosion product was dissolved in dioxane at room temperature, the undissolved residue was collected using a glass filter paper, and the residue ratio was determined. The results in Table 2 were obtained. . Table 2 shows that the amount of wood dissolved was only about half the amount of the explosion alone, and that the solubilization of the wood was insufficient by the explosion treatment alone.

Comparative Examples 6 to 9 The same operation as in Comparative Examples 1 to 5 was performed. However, the amount of phenol charged was doubled to 500 g. When the composition of the obtained explosive product was examined, the results shown in Table 3 were obtained.

The solubility of each of these explosive compositions in dioxane at room temperature was examined. That is, when the insoluble residue ratio was determined, the results shown in Table 4 were obtained. Even when a large amount of phenol was added during the explosion, the amount of wood dissolved by the explosion alone was less than 50%.

Examples 1 to 3 and Comparative Example 10 In each of Examples 1 to 3 and Comparative Example 10, birch chips were steamed for 0.5 minutes in the presence of phenol under the same conditions as Comparative Examples 1 to 5, and then blasted. After the explosion, put the okara-shaped sample in a 30-ml stainless steel pressure-resistant container so that the wood content becomes 10 g.After sealing, leave it at 230 ° C, the same as the explosion temperature, for 0, 30, 60, or 90 minutes. A heat dissolution reaction was performed. This reaction product is dissolved in dioxane at room temperature,
Insoluble residues were collected by filtration using a glass filter paper, and the residue ratio was determined. Table 5 shows the obtained values.

As apparent from Table 5, after the pre-explosion treatment, the explosion product is subjected to a heat dissolution reaction treatment at 230 ° C., whereby the amount of dissolution can be significantly improved. In addition, it was also found that a long steaming time of more than 90 minutes was required before the explosion when attempting to obtain a melt only by explosion in the presence of phenol.

Examples 4 to 8 In each of Examples 4 to 8, after steaming treatment at 230 ° C. was performed for the time shown in Table 6, the mixture was blasted, and the blasted sample was heated and dissolved in a pressure tube. The heating and dissolving treatment time is fixed at 30 minutes, and the treatment temperature is set to the sixth.
The temperature was increased from 230 ° C to 240 or 250 ° C as shown in the table. All other processing conditions were the same as Comparative Examples 1 to 5. The results are shown in Table 6. Table 6 also shows the results of Example 1.

From the results shown in Table 6, it is known that the amount of the reaction product at 250 ° C. is much larger than that in the case where the heating and dissolving temperature is 240 ° C. or lower. It is known that only cellulose has a high molecular weight as a normal explosion effect.
Heat dissolution treatment at a high temperature of 250 ° C. for solubility is extremely effective.

Examples 9 to 14 In each of Examples 9 to 14, 250 g of birch chips and 250 g of phenol were charged into a two-batch explosion apparatus, and the mixture was steamed at 230 ° C for 4 minutes, and then explosion was performed.

After adjusting the composition of the explosion-treated product so that the wood content: phenol: water = 1: 1: 2, the wood content is 1
The mixture containing 0 g was charged into a 30-ml stainless steel pressure-resistant container, and the mixture was subjected to a static heat-dissolution reaction treatment at 250 ° C. for 15, 30, 45, 60, 75, or 90 minutes under a sealed stopper. The obtained reaction product was dissolved in dioxane, and the insoluble residue was collected by filtration using a glass filter paper, and the residue ratio was determined. Table 7 shows the obtained values. Table 7 also shows the results of Comparative Example 3 in which the solubilization reaction time was zero.

As is evident from Table 7, the residue ratio decreases rapidly by the short-time heat-dissolution treatment, and particularly when the treatment is performed for 45 minutes or more, the residue ratio reaches 1-2%, and the dissolution reaction is almost completed. It is known. In the conventional heat dissolution treatment (250 ° C, heat dissolution without catalyst), a heat dissolution reaction time of 90 minutes was required to achieve a residue ratio of about 6%. Thus, it was possible to achieve a residue ratio of about 6% in about 30 minutes by a short-time heat dissolution treatment.

Comparative Example 11 10 g of the present powder prepared from hippo chips was mixed with an equal weight of phenol, and the heat dissolution reaction time required to reach the same residue ratio under the same apparatus and the same temperature conditions as in Example 2 was determined. It took a long time. This time (120 minutes)
This is four times the required heat dissolution treatment time (30 minutes) of Example 10.

〔The invention's effect〕

The method of the present invention enhances the solubility of a lignocellulose material by using a pre-explosion treatment in producing a lignocellulose-phenol compound composite, and enables the production of the composite in a short time. It is useful for realizing the industrial use of the lignocellulose-phenol compound composite.

Continuation of the front page (72) Inventor Nobuo Shiraishi Kita-Shirakawa Oiwakecho, Sakyo-ku, Kyoto-shi, Kyoto Inside the forestry engineering department of the Faculty of Agriculture, Kyoto University (56) References JP-A 1-217070 (JP, A) JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C08H 5/00-5/04 C08B 1/00

Claims (1)

(57) [Claims] When a lignocellulose material and a solvent containing at least one phenol compound as a main component are dissolved and reacted under heating, as a pretreatment, the lignocellulose material is added to the lignocellulose material in the presence of the phenol compound. A method for producing a lignocellulose-phenol compound composite using an explosion method in combination with an explosion treatment.