JPH0959519A - Production of resin raw material composition by thermal modification of lignocellulosic substance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply produce a resin raw material composition extremely useful for effective utilization of wastes such as wood in an ultrashort time by carrying out the thermal modification according to the internal heating with steam. SOLUTION: The thermal modification is carried out by the internal heating with steam (preferably under conditions of 120-260 deg.C temperature under 1-40kg/cm<2> steam pressure) in adding (B) a solvent, preferably a phenol compound or the phenol compound and an acid or an alkaline compound, especially a polyhydric alcohol compound to (A) a lignocellulosic substance and thermally modifying and liquefying the component (A). Furthermore, the temperature in a reactional vessel is previously raised by the internal heating with the steam and produced drain is subsequently removed. The components (A) and (B) are then preferably charged into the reactional vessel in thermally modifying the component (A).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the effective use of lignocellulosic materials such as wood such as plants and trees, which are renewable resources. More specifically, the present invention is a method for producing a resin raw material composition by adding a solvent to a lignocellulosic material such as wood, denaturing by heating and liquefying. The resin raw material composition obtained by the present invention has the property of becoming a resin by further treatment with methylolation, epoxidation, urethanization, etc. Therefore, the production method of the present invention is extremely effective for effective utilization of waste materials such as wood. It is useful.

[0002]

2. Description of the Related Art At present, in the wood industry and the like, the treatment of wastes such as bark, sawdust and planks discharged during lumbering has become a serious problem. Forestry managers are also worried about how to use thinned timber (young trees thinned down to make thick standing good trees). Therefore, there is an urgent need to develop effective utilization methods for these wood-based wastes. As a method of effectively utilizing a lignocellulosic substance such as wood, a method is known in which a phenol compound, a polyhydric alcohol compound or the like is added to wood to heat-denature it into a wood solution, and the resulting wood solution is used as a resin raw material. There is.

In these methods, usually, a method is used in which a lignocellulosic substance and a solvent are charged into a reaction vessel, the reaction vessel is externally heated with oil or steam heating medium, and the lignocellulosic substance is heat-denatured to be liquefied. Has been done.
When industrializing such a liquefaction technology, when it is carried out in a large-capacity reactor, it takes a long time to heat the water in the solvent and the lignocellulosic material such as wood, which is the raw material, so that liquefaction is required. The problem is that it takes a long time.
Therefore, it is possible to completely dry the lignocellulosic material that is the raw material in advance, but when the dried lignocellulosic material is used, the viscosity of the resin raw material composition obtained becomes high and the work becomes very difficult. . For this reason, there is a drawback that only a treatment with a large reaction solvent ratio can be performed. Further, even if the stirring device is attached, it takes a long time to uniformly heat the entire raw material in the device.

On the other hand, in the dissolution reaction of the lignocellulosic material and the phenol compound under heating, a method of accelerating the dissolution reaction by treating with saturated steam having a pressure of 20 to 40 kg / cm ² and a temperature of 200 to 250 ° C. Has been reported (JP-A-4-126725). However, this method is an explosive treatment in which the pressure is released all at once immediately after the treatment with saturated steam, and this explosive treatment is carried out in the explosive device and then transferred to a normal reaction vessel to carry out the liquefaction reaction. It is a very complicated method.

[0005]

As described above, the conventional liquefaction techniques for lignocellulosic materials are not efficient and complicated when they are carried out on an industrial scale. Therefore, it is an object of the present invention to provide an industrially advantageous method for producing a resin raw material composition by heat denaturation of a lignocellulosic material, in which the production time is shortened and the production method is simplified.

[0006]

Means for Solving the Problems As a result of earnest research for the purpose of developing a method for producing a resin raw material composition by heat modification of a lignocellulosic material, the present inventor has conducted extensive research and The present invention has been completed by finding that the above object can be achieved by carrying out internal heating with steam instead of conventional external heating with oil or the like for modification liquefaction by heating. That is, the present invention is a method for producing a resin raw material composition by adding a solvent to a lignocellulosic material and denaturing by heating to liquefy the resin raw material composition, wherein the heating denaturation is performed by internal heating with steam. It is a manufacturing method.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The lignocellulosic substance, which is a starting material in the method for producing a resin material composition of the present invention, is a plant such as sawdust, wood flour, wood chips, veneer scraps, plywood scraps and bark. It refers to various kinds of plant-derived materials containing cellulose, lignins, and the like as the main components, such as fibrin and straw, rice husk, coffee bean dregs, bagasse squeezed dregs, and beet pulp. Examples of the solvent added to liquefy and modify such a lignocellulosic material include phenol compounds and polyhydric alcohol compounds. Examples of such phenol compounds include phenol, o-, m
-, P-cresol, 3,5-, 2,3-, 2-6-xylenol, o-, m-, p-propylphenol, o
-, M-, p-secondary butylphenol, o-,
m-, p-tertiary butylphenol, hexylphenol, phenylphenol, octylphenol,
Monohydric phenols such as naphthol; divalent phenols such as catechol, resorcinol, quinol, bisphenol A, bisphenol B, bisphenol F; trivalent phenols such as pyrogallol, phloroglucyl, trihydrobenzane, gallic acid and chlorides thereof. There are things etc.

The phenol compound may be used alone or in combination with an acid or alkali compound. Examples of the acid include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid; formic acid,
Examples thereof include organic acids such as acetic acid and p-toluenesulfonic acid. Examples of the alkaline compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkali metal carbonates such as calcium carbonate; ammonia; or monoethanolamine. There are amines. Examples of the polyhydric alcohol compound used as the solvent include polyethylene glycol, polypropylene glycol, glycerin, ethylene glycol, 1,4-butanediol, 1,6-hexanediol and the like. The polyhydric alcohol compound may be used in combination with the above-mentioned acid.

In the present invention, the above solvent is usually added to the lignocellulosic material such as wood in an amount of 10-1,0.
00% by weight is added. In the present invention, a lignocellulosic material such as sawdust and bark, a phenol compound, a solvent such as a polyhydric alcohol are added, and usually in the initial stage of the reaction, a runaway reaction due to heat generation is prevented by heating at a temperature not higher than the boiling point of the solvent. In the latter stage, the reaction temperature is raised and kept constant to allow the liquefaction reaction to proceed to obtain a resin raw material composition.

In the present invention, the heating when the denaturation of the lignocellulosic material is carried out is carried out by the internal heating with steam instead of the external heating with oil or the like which has been conventionally adopted. That is, a pressure resistant reaction vessel is charged with a lignocellulosic material such as wood and a solvent, and then steam is blown in a sealed state to raise the temperature in the reaction vessel. Usually, in this case, the steam temperature is 1 to 40 kg / cm ² and the system temperature is 120 to
Raise to about 260 ° C. It is possible to raise the target temperature in an extremely short time, for example, in about 5 minutes by internal heating with steam. After raising the temperature in the system, the temperature is kept constant and the liquefaction reaction proceeds. In this way, the reaction material is charged in a pressure-resistant reaction vessel, then heated in a sealed state to raise the temperature, and then kept at a constant temperature, in which the water content of the lignocellulosic material such as wood as a raw material is It is suitable for carrying out the reaction by using the raw material having a high water content as it is.

In the present invention, internal heating with steam may be used together with external heating with a heating medium such as oil that has been conventionally used. For example, after charging the reaction material in a pressure-resistant reaction vessel and sealing it, after external heating with a heating medium, steam is blown into the reaction vessel to raise the temperature inside the system, and after reaching a certain temperature, the temperature is increased by external heating with a heating medium. Can be kept constant to allow the liquefaction reaction to proceed.

Further, in the present invention, when a lignocellulosic material such as wood as a raw material having a low water content is used and the reaction is carried out while keeping the water content low in the liquefaction reaction, first, the pressure resistance reaction is carried out. Only steam is blown into the vessel to raise the temperature inside the system, after which the drain generated in the system is removed, then the lignocellulosic substance and solvent are charged into the pressure resistant reaction vessel to raise the reaction temperature and then keep it constant. It is also possible to employ a method of advancing the liquefaction reaction by using the In the case of such a method, the first steam is usually blown with a steam pressure of 1 to 40 kg / cm ² and a temperature of 120.
It can be performed at ˜260 ° C.

In the production method of the present invention, water, acetone, at the beginning of the reaction or in the middle of the reaction for the purpose of lowering the solution viscosity of the lignocellulosic material or promoting dissolution thereof,
It is also possible to add and coexist an organic solvent such as ethyl acetate. In addition, in order to mitigate the runaway reaction due to heat generation in the initial stage of the reaction and to remove a large amount of water in the lignocellulosic material such as wood, which is the starting material, to the outside of the system, an organic solvent that is azeotropic with water or a resin produced It is also possible to add a solvent or the like which dissolves the raw material composition in the initial stage of the reaction or during the reaction. The apparatus used in the production method of the present invention is preferably equipped with a stirring device to which a large torque can be applied in order to make the reaction uniform in the pressure resistant reactor. The resin raw material composition produced by the method of the present invention has high reactivity with aldehydes, epoxies, isocyanates and the like regardless of whether unreacted phenols are contained or not. Therefore, the obtained resin raw material composition has a property of becoming a polymer resin substance by an acid, an alkali catalyst, or heating. Therefore, the resin raw material composition obtained by the present invention is a raw material for adhesives, molded products and the like.

[0014]

EFFECTS OF THE INVENTION When a solvent such as a phenol compound or a polyhydric alcohol compound is added to a lignocellulosic material such as wood and densified by heating and liquefaction, a method of internal heating with water vapor is used. The desired resin raw material composition can be easily produced in a short time. Further, internal heating with steam, that is, by blowing steam into the lignocellulosic material charged in the reaction vessel, liquefaction of the lignocellulosic material is promoted.

[0015]

【Example】

Example 1 100 g of cedar sawdust (water content 71.4%) and 100 g of phenol (wood flour / phenol = 5/5) were weighed in a 2 L pressure resistant reaction vessel equipped with a stirrer and steam piping, and the system temperature was 250. The inside of the container was treated with steam (gauge pressure of about 35 kg / cm ² ) for 5 minutes until the temperature reached ℃. After that, the mixture was kept at 250 ° C. for 1 hour with steam to obtain a black substance. The liquid was filtered through a G3 glass filter. The residue after filtration was washed with dioxane to obtain about 3% of a black substance as a residue on the glass filter. Example 2 120 g of cedar sawdust (water content 71.4%), 30 g of phenol (wood flour / phenol = 7/3) and 3 g of sodium hydroxide were weighed in a 2 L pressure resistant reaction vessel equipped with a stirrer and a steam pipe, The inside of the container was treated with steam (gauge pressure of about 35 kg / cm ² ) for 5 minutes until the temperature in the system reached 250 ° C. After that, the mixture was kept at 250 ° C. for 1 hour with steam to obtain a black substance. The liquid was filtered through a G3 glass filter. The residue after filtration was washed with dioxane to obtain about 0.6% of a black substance as a residue on the glass filter. Example 3 Sugi sawdust 120 g (water content 71.4%), phenol 30 g (wood flour / phenol = 7/3) and sodium hydroxide 3 g were weighed in a 2 L pressure resistant reaction vessel equipped with a stirrer and a steam pipe. While warming the reaction vessel with a heating medium, a treatment with steam (gauge pressure of about 10 kg / cm ² ) was performed for 5 minutes together until the temperature in the system reached 180 ° C. After that, the temperature was gradually raised to 250 ° C. with an oil heating medium and kept at 250 ° C. for 1 hour, and then a black substance was obtained. The liquid was filtered through a G3 glass filter. The residue after filtration was washed with dioxane to obtain about 0.6% of a black substance as a residue on the glass filter.

Example 4 A 2 L pressure resistant reaction vessel equipped with a stirrer and a steam pipe was treated with steam (gauge pressure of about 4 kg / cm ² ) for 2 minutes until the temperature in the system reached 150 ° C. After draining, cedar sawdust 30g (water content 0%), phenol 70g (wood flour / phenol = 3/7) and sulfuric acid 2.1.
g, and kept at 150 ° C for 30 minutes with steam,
A black substance was obtained. The liquid was filtered through a G3 glass filter. The residue after filtration was washed with dioxane to obtain about 5% black substance as a residue on the glass filter. Example 5 A 2 L pressure resistant reaction vessel equipped with a stirrer and a steam pipe was treated with steam (gauge pressure of about 4 kg / cm ² ) for 2 minutes until the system temperature reached 150 ° C. After removing the drain, 30 g of cedar sawdust (water content 0%) and PEG
400 60 g, glycerin 30 g (wood flour / solvent = 1 /
3) and 2.7 g of sulfuric acid were added, and the mixture was kept at 150 ° C. for 30 minutes with steam to obtain a black substance. The liquid was filtered through a G3 glass filter. The residue after filtration was washed with dioxane to obtain about 5% black substance as a residue on the glass filter.

Comparative Example 1 120 g of cedar sawdust (water content 71.4%), 30 g of phenol (wood flour / phenol = 7/3) and 3 g of sodium hydroxide were weighed in a 2 L pressure resistant reaction vessel equipped with a stirrer. , Weaken the heating in the oil bath at 180 ℃ ± 5 ℃,
The temperature was gradually raised to 250 ° C over about 1 hour from the start of heating, and the temperature was further maintained at 250 ° C for 1 hour, after which a black substance was obtained. The liquid was filtered through a G3 glass filter. The residue after filtration was washed with dioxane to obtain about 0.6% of a black substance as a residue on the glass filter. Next, the filtrate was distilled under reduced pressure to remove water, and the viscosity was measured using an ICI cone plate viscometer (motor speed 750 rpm, plate temperature 25 ° C.).
It was 7.6 poise. In this way, when the reaction is carried out without internal heating with steam, the total reaction is 2
It took more than time.

Claims (7)

[Claims] 1. A method for producing a resin raw material composition by adding a solvent to a lignocellulosic substance, denaturing by heating and liquefying, wherein the denaturation by heating is carried out by internal heating with steam. Law. 2. The manufacturing method according to claim 1, wherein internal heating with steam is performed and external heating with a heating medium is performed. 3. The production method according to claim 1, wherein the reaction temperature is raised by internal heating with steam, and then the temperature is maintained at a constant temperature for denaturation by heating. 4. Internal heating with steam is performed by steam pressure 1
The production method according to claim 3, which is carried out under the conditions of -40 kg / cm ² and a temperature of 120-260 ° C. 5. The method according to claim 1, wherein the temperature inside the reaction vessel is raised in advance by internal heating with steam, the generated drain is removed, and then the lignocellulose substance and the solvent are charged into the reaction vessel to heat-denature. Manufacturing method. 6. The production method according to claim 1, wherein a phenol compound or a phenol compound and an acid or alkali compound is used as the solvent. 7. The production method according to claim 1, wherein a polyhydric alcohol compound is used as the solvent.