JPH0476024A - Method for producing lignocellulose-phenolic compound composite - Google Patents

Abstract

PURPOSE:To obtain the title composite at good efficiency by decreasing a lignocellulose material in the obtained reaction system by heating a solvent containing a lignocellulose material and a phenolic compound as the principal components and accelerating their dissolution and reaction under specified conditions. CONSTITUTION:A process for producing the title material by heating a solvent containing a lignocellulose material (e.g. undeinked waste newspapers) and at least one phenolic compound (e.g. phenol) as the principal components and dissolving and reacting them, wherein their dissolution and reaction are accelerated by raising the temperature in the reaction system by removing the formed water from the system.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a lignocellulose-phenol compound composite. More specifically, by removing water generated by the dissolution reaction of lignocellulose material into a phenol compound to the outside of the reaction system, it was possible to increase the temperature within the reaction system and promote the dissolution reaction. It is something.

[Conventional technology]

Resources produced from forests are renewable, and their effective cyclical use is currently strongly desired. For example, in industries that use wood as raw material, such as the pulp industry and the timber industry, there is an urgent need to establish ways to effectively utilize the wood waste generated. There is also a need for urgent development of methods for effectively utilizing agricultural waste containing lignocellulosic materials.

In particular, recently, the development of effective ways to use waste paper has become an urgent issue.

The existence of lignocellulose materials including wood etc. 1) Effective usage methods include, for example, Japanese Patent Application Laid-Open No. 57-2360,
and Japanese Patent Publication No. 63-1992, etc., a chemically modified lignocellulose material obtained by introducing at least one substituent group into a portion of the water storage group in the lignocellulose molecule is dissolved in an organic solvent, and this solution is mixed into various A method of using the compound as a raw material for a resin material is disclosed.

Also, JP-A Nos. 60-206883 and 60-104
Publication No. 5.13 discloses a method of using a lignocellulose material as a phenol compound-formaldehyde resin adhesive, and a method of making it into fibers.

Furthermore, JP-A-61-215676 and JP-A-61-21
No. 5675 discloses that a lignocellulose material is dissolved in a solvent consisting of a polyhydric alcohol or a bisphenol compound, and this solution is used together with a polyurethane-based, epoxy-based, or other resin material to form a molded product, foam, or adhesive. A method for manufacturing the agent is disclosed.

Furthermore, JP-A No. 61-261358 discloses a method of directly dissolving wood without pretreatment in a solvent consisting of a phenol compound or a bisphenol compound without using a catalyst. 6279230 discloses a method of directly dissolving wood without pretreatment in a solvent consisting of an alcohol compound, a polyhydric alcohol compound, an oxyether compound, a cyclic ether compound, or a ketone compound without using a catalyst. .

Further, Japanese Patent Publication No. 61-2697 discloses a technique in which wood flour is dissolved and reacted in phenol in the presence of a mineral acid, and a similar technique is also disclosed in Japanese Patent Publication No. 1-217070.

In addition, the need for effective use of waste paper has recently increased,
The value-added use of waste paper as a lignocellulose material, especially the technology for turning it into a resin raw material, is still undeveloped.

[Problem to be solved by the invention]

In the conventional technology for dissolving lignocellulose materials in phenolic compounds, the technology for promoting the dissolution reaction has not yet been clarified. However, the development of this dissolution promotion technology is an essential and extremely important issue in order to realize the industrial use of lignocellulose material-phenol compound composites.

Furthermore, in recent years, the issue of how to use waste paper has become important, and the development of its various uses is eagerly awaited. In particular, it is expected that waste paper will be turned into a resin raw material.

[Means and actions to solve the problem]

The method for producing the lignocellulose-phenol compound composite of the present invention comprises a lignocellulose material and at least one
When performing a dissolution reaction with a solvent containing a phenol compound as a main component under heating, at that time, water generated by the reaction of both components is removed from the reaction system to promote the temperature rise of the reaction system, This is characterized by promoting the above-mentioned dissolution reaction.

In the method of the present invention, the reaction system includes an inorganic acid, an organic acid,
A catalyst containing at least one selected from Lewis acids and Lewis acids may be added in portions before and after the reaction product water removal operation, thereby further promoting the dissolution reaction of both components.

The present inventors have repeatedly conducted research on dissolving lignocellulosic materials, such as waste paper, into a phenolic compound liquid together with an acid catalyst. As a result, the phenolic compound and the constituent components of the lignocellulosic material become composites due to chemical bonds. It became clear that the reaction was mainly a dehydration reaction.

Therefore, in order to promote this reaction, an attempt was made to distill the water produced by the reaction out of the system. Furthermore, this operation was able to raise the temperature within the system by distilling out water, which has a lower boiling point than that of the phenol compound, and was also found to be effective in accelerating the reaction.

Furthermore, by adding a new acid catalyst after distilling the reaction product water out of the system, it becomes possible to shorten the reaction time by a quarter, thereby further promoting the industrialization of the method of the present invention. It has come to be expected.

In one example of the method of the invention, lignocellulosic material, such as waste paper, is mixed with 10 phenolic compounds in a reaction vessel charged with a solvent containing at least one phenolic compound.
Add in an amount not exceeding 35 parts by weight to 0 parts by weight, raise the temperature of this reaction system to a predetermined temperature, start stirring when the whole becomes fluid, and continue for a certain dissolution reaction time. The end point is the point in time when .

At this time, there is no particular limitation on the order in which the raw materials are charged, and the order described above may be used, or the phenol compound and, if necessary, the dissolved catalyst may be charged after charging the refried cellulose material into the reaction apparatus. good. Alternatively, the catalyst may be added at the same time as charging the lignocellulosic material.

In the dissolution reaction step, reaction product water is removed from the reaction system. The reaction product water may be removed by using a conventional distillation device, that is, by condensing the product water using a cooler and taking it out of the reaction system.

The amount of distillation is determined based on the amount required for the temperature in the system to reach the desired temperature. Usually, when the reaction product water corresponding to 10% by weight of the charged lignocellulose material is distilled off, the temperature in the system increases. will rise by several tens of degrees.

For example, if the heating medium temperature for the reaction vessel is 185°C, the system temperature at the start of the reaction is about 125°C.
When reaction product water in an amount corresponding to 10% by weight of the charged lignocellulose material is distilled off, the temperature inside the system rises to 160°C.

As described above, when the temperature inside the system becomes several tens of degrees higher than the temperature before distilling the reaction product water, the distillation operation may be terminated.

As mentioned above, in the dissolution reaction process of the lignocellulosic material and the phenolic compound, the reaction product removal operation is generally carried out at 80 to 130 °C under normal pressure, or at 2 to 1
It is preferable to start at 120 to 180°C under an applied pressure of 0 kg/c-G.

Immediately after dissolving the reaction system and starting the reaction, the reaction system has not yet reached a state where it can be stirred uniformly, and therefore, the reaction product water removal operation cannot be performed on it.

In general, it is possible to start distilling and removing the water produced by the reaction within 15 to 30 minutes after the start of the dissolution reaction, and the desired distillation amount is reached in about 30 minutes.

In the method of the present invention, a dissolved catalyst may be added to the reaction system before the start of the reaction, but it may not be added, or the dissolved catalyst may be added in portions before and after the removal of reaction water. good. In other words, in the single-stage catalyst addition method, all the catalyst is added to the reaction system at the beginning of the dissolution reaction, but in the split-addition method, the first stage addition is performed at the beginning of the dissolution reaction, and the second stage addition is carried out at the beginning of the dissolution reaction. After removing water, the temperature of the reaction system is -L
It is done after rising.

In the split addition method, the first stage charging operation is performed at the start of the dissolution reaction, and the second stage charging operation is performed by directly adding the catalyst into the stirred reactor, or by adding the catalyst to a small amount of fresh phenol compound. Add the solution prepared by dissolving it into the inside of the device.

If the amount added in the pre-addition operation is small, the dissolution reaction may not proceed sufficiently and uniform stirring may not be achieved, so in this case, it is necessary to add an amount that ensures uniform stirring even in the pre-addition operation. For example, when titanium tetrachloride is used as the dissolved catalyst, it is necessary to charge the catalyst in an amount of at least 1% (by weight) of the total amount of raw materials charged in the first stage.

In the case of divided addition, there are no other particular restrictions as long as the above-mentioned minimum addition amount is ensured in the first stage addition operation.

The lignocellulosic material used in the present invention includes wood chips,
Wood flour, wood fibers, wood chips, veneer scraps, plywood scraps, waste paper, pulp, rice straw, rice husk, kolyang, bagasse,
Although plant fiber materials can be selected from, including bamboo, wheat straw, etc., the success of combining waste paper with phenolic compounds to produce an entirely new composite material is remarkable.
This can be called groundbreaking.

In addition, the lignocellulose material referred to in the present invention includes raw materials consisting only of cellulose, cellulose, and hemicellulose.

In the present invention, the phenolic compound forming the dissolved composite with the lignocellulosic material can be selected from the following metal compound group.

(1) -valent phenol compound: for example, phenol, 0
-1m-1 and p-cresol, 3°5-12,3-
1 and 2,6-xylenol, 0-1m-1 and p
- dihydric phenols such as propylphenol, 0, m-1 and p-butylphenol, 0m-1 and p-5ec-butylphenol, Om- and p-tert-butylphenol, hexylphenol, phenylphenol, octylphenol, and naphthol; Compounds: such as cateconoperesorcinonopequinol, bisphenol A1 bisphenol B and bisphenol F. (3) Trihydric phenolic compounds: such as pyrogallol, chloroglycine, trihydrobenzene, and erosic acids.

In the method of the present invention, a lignocellulose material is mixed with a solvent containing at least one phenol compound as a main component, and the mixture is heated to homogeneously compound and dissolve the lignocellulose material to form a lignocellulose-phenol compound composite. Prepare the solution. The solvent used in the method of the present invention preferably contains at least one phenolic compound in a content of at least 50% by weight, and the compound that can be mixed with the phenolic compound is compatible with the phenolic compound, It is easy to remove and can be selected from aromatic hydrocarbon solvents such as xylene and toluene.

In the above solution preparation, in order to uniformly dissolve the lignocellulose material, the weight ratio of the lignocellulose material to the phenolic compound is preferably 0.1:1 to 0.35:1, and preferably 0.2:1 to 0. More preferably, the ratio is .25:1. At this time, if the content weight ratio of the lignocellulose material is lower than 0.1 = 1, it may take a lot of energy and time to remove the phenolic compound afterwards, and the content weight ratio of the lignocellulose material (
If L is higher than 35:1, it may be difficult to obtain a homogeneous solution.

The dissolved catalyst used in the method of the present invention preferably consists of at least one member selected from the following compound group.

(1) Inorganic (mineral) acids: such as hydrochloric acid, sulfuric acid, phosphoric acid, and hydrogen bromide (2) Organic acids (a) Carboxylic acids: formic acid, acetic acid, oxalic acid, tartaric acid, and benzoic acid, etc. (b) Organic sulfones Acids: For example, phenolsulfonic acid and p-)luenesulfonic acid, etc. (iii) Sulfinic acids: For example, phenolsulfinic acid, etc. (d) Others: For example, uric acid, etc. (3) Lewis acids: For example, titanium tetrachloride, aluminum chloride, etc. It is generally preferred that the dissolved catalyst is used in a proportion of 0.1 to 20% based on the weight of the lignocellulosic material.

The temperature and pressure of the dissolution reaction in the method of the present invention can be appropriately set depending on the type of phenol compound.

Generally, in the case of normal pressure melting, the melting temperature is 100 to 200°C.
In the case of pressurized dissolution, it is preferably 10 to 40k.
The melting temperature is preferably 200 to 300°C under a pressure of g/cut.

Dissolution generally takes from 1 to IO hours, preferably 2 hours, under stirring.
It will last for ~5 hours.

〔Example〕

The invention will be further illustrated by the following examples.

Example 1 (distillation of produced water, partial addition of catalyst)
0 kg and 1.3 kg of titanium tetrachloride were placed in a reaction vessel equipped with a reflux device, and dissolved in an oil bath at 185°C for 1 hour (internal temperature of the reaction vessel was 125°C), and then a cooling pipe was attached to the reaction vessel. 2.5 kg of produced water was distilled off.

At this time, the internal temperature of the reaction vessel rose from 125°C to 160°C. Furthermore, 1.3 kg of titanium tetrachloride was added to the reaction system.
was added and the reaction was continued for 2 hours for a total of 3 hours.

The percentage of undissolved waste paper in the reaction product liquid was 134% (based on the weight of waste paper).

The amount of phenol combined with the waste paper component was 100 parts by weight (per 100 parts by bone dry weight of the waste paper).

Comparative Example 1° (no distillation of produced water, addition of catalyst stage) The same operation as in Example 1 was carried out. However, 2.6 kg of titanium tetrachloride was added to the reaction system by the one-stage addition method, and the dissolution reaction was carried out for 3 hours without distilling off the reaction product water. The percentage of undissolved waste paper in the resulting reaction system was determined to be 219.
% (based on waste paper).

This result shows that when compared with Example 1, the undissolved waste paper rate is
This was an increase of about 40%.

Comparative Example 2° (no distillation of produced water, partial addition of catalyst) The same operation as in Example 1 was performed. However, after adding 1.3 kg of titanium tetrachloride to the reaction system and reacting for 1 hour, 1.3 kg of titanium tetrachloride was further added without distilling off the water produced by the reaction, and the reaction was continued for 2 hours. The percentage of undissolved waste paper in the resulting reaction system was 18.8% (based on the weight of waste paper). This result shows that when compared to Example 1, the undissolved waste paper rate was approximately 3.
It was an increase of 0%.

Example 2 (Example of extension of reaction time in Example 1) The same operation as in Example 1 was performed. However, the dissolution reaction time was extended to a total of 6 hours. When the percentage of undissolved waste paper in the resulting reaction system was measured, it was 8.1% (based on waste paper weight), which was further decreased from the percentage of undissolved waste paper in Example 1 (13.4%). .

Comparative Example 3 (time extension example of Comparative Example 2) The same operation as in Comparative Example 2 was performed. However, although the dissolution reaction time was extended to a total of 6 hours, that is, the reaction was carried out for the same time as in Example 2, the proportion of undissolved waste paper in the resulting reaction mixture was 15.5%.
However, it was unsatisfactory.

Comparative Example 4 The same operation as in Comparative Example 2 was performed. However, when the dissolution reaction time was extended and the time required to reach the same undissolved waste paper rate as in Example 2 was determined, it was 24 hours, which could not be practically adopted.

Example 3 (change of raw materials in Example 1) The same operation as in Example 1 was performed. However, instead of the waste paper raw material, cellulose powder (Avicel manufactured by Fuikasei Co., Ltd.) was used. The undissolved cellulose content in the resulting reaction mixture is
It was 15.2% (based on cellulose weight).

Comparative Example 5 (Example of changing raw materials in Comparative Example 1) The same operation as in Example 1 was performed. However, cellulose powder (Avicel) was used instead of waste paper raw material. The undissolved cellulose content in the resulting reaction mixture was 26.9
% (based on cellulose weight).

Example 4 (distilled produced water and no post-catalyst added) The same operation as in Example 1 was carried out. However, the post-stage catalyst was not added after the reaction product water was removed by distillation.

Percentage of undissolved waste paper in the obtained reaction mixture (based on waste paper weight)
was 25.3%.

Comparative Example 6° (no distillation of produced water, no addition of post-stage catalyst) The same operation as in Example 1 was carried out. However, the reaction product water was not removed by distillation and the post-stage catalyst was not added. The percentage of undissolved waste paper in the resulting reaction mixture was 304% (based on the weight of waste paper).

〔Effect of the invention〕

The method of the present invention significantly accelerates the dissolution reaction, making it possible to practically produce a lignocellulose-phenol compound composite. In particular, when a dissolved catalyst is added in portions before and after the reaction product removal operation, for example, when used newspaper is used as a lignocellulose material, the content of undissolved waste paper in the resulting reaction mixture (based on waste paper weight?!S) ), and the time required for the dissolution reaction can be shortened to about 174 times compared to that in the conventional method.

Claims (1)

[Claims] 1. When dissolving and reacting a lignocellulose material and a solvent containing at least one phenolic compound as a main component under heating, water produced by the reaction of both components is removed from the reaction system. removing it to promote a temperature increase in the reaction system, thereby promoting the dissolution reaction,
A method for producing a lignocellulose-phenol compound composite. 2.Claim 1, wherein a catalyst containing at least one selected from inorganic acids, organic acids, and Lewis acids is added to the reaction system in portions before and after the reaction product water removal operation. The method described in.