JP6407215B2 - Method for producing lignophenol - Google Patents

Description

  The present invention relates to a method for producing lignophenol.

Conventionally, as a method for producing lignophenol from a lignocellulosic material (wood flour, etc.) containing lignin and cellulose, lignocellulosic material sorbed a phenol derivative and then lignocellulose sorbed with the phenol derivative. There is known a method of producing lignophenol by mixing a system material and an acid to react lignin with a phenol derivative under an acid catalyst.
In addition, lignocellulosic materials usually contain fat, but since fat inhibits the above sorption and reaction, conventionally, lignocellulosic materials are acetone or hexane before or during sorption. (For example, Patent Documents 1 to 3).

Japanese Patent No. 5458430 Japanese Patent No. 4593706 International Publication No. 2005/042585

  By the way, generally, when manufacturing a product, it is required to reduce the number of types of materials used from the viewpoint of cost reduction or the like.

  Then, in view of such a demand point, this invention makes it a subject to provide the manufacturing method of lignophenol which can reduce the kind number of the material to be used.

The method for producing lignophenol according to the present invention comprises:
By mixing a lignocellulosic material containing fat and a phenol derivative, the lignocellulosic material is defatted with the phenol derivative while sorbing the phenol derivative on the lignocellulosic material, and the phenol derivative A sorption step to obtain a mixture;
A separation step of separating the phenol derivative mixture into a solid containing the lignocellulosic material sorbed by the phenol derivative and a separation liquid containing the phenol derivative and the fat;
An acid mixing step of obtaining an acid mixture containing lignophenol by mixing the solid and the acid.

Since the phenol derivative has a phenol structure in the molecule, it has an affinity for fat. Thus, the phenol derivative can be used to degrease the lignocellulosic material. Therefore, according to such a method for producing lignophenol, the lignocellulosic material can be defatted with a phenol derivative necessary for producing lignophenol in the sorption step. However, the number of types of materials used can be suppressed.
Moreover, according to the method for producing lignophenol, since the solid used in the acid mixing step is separated from the separation liquid containing fat in the separation step, the lignophenol is produced in the acid mixing step. It is possible to suppress the reaction from being inhibited by fat.

  Here, one mode of the method for producing lignophenol according to the present invention is to obtain the solid and the separated liquid by filtering the phenol derivative mixture in the separation step.

  According to the present invention, since the lignocellulosic material can be degreased with a phenol derivative necessary for producing lignophenol, the number of types of materials used can be reduced.

The schematic of the manufacturing apparatus of lignophenol which concerns on this embodiment, and the flowchart of the manufacturing method of lignophenol which concerns on this embodiment. Schematic of the lignophenol production apparatus according to this embodiment. The figure which shows the example of the production | generation reaction of lignophenol.

  Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings.

The method for producing lignophenol according to this embodiment is a method for producing lignophenol from a lignocellulosic material.
Moreover, the manufacturing method of lignophenol which concerns on this embodiment is equipped with the 1st mixing process of obtaining the 1st mixture containing lignophenol by mixing the said lignocellulosic material, the said phenol derivative, and the said acid. .
Further, in the method for producing lignophenol according to the present embodiment, the lignophenol is agglomerated by mixing the first mixture and an organic solvent which is a poor solvent for the lignophenol, A second mixing step of obtaining a second mixture containing aggregates is further provided.
The method for producing lignophenol according to the present embodiment further includes a purification step for obtaining the lignophenol from the second mixture.

  In the first mixing step, the lignocellulosic material containing fat and the phenol derivative are mixed to degrease the lignocellulosic material with the phenol derivative while the phenol derivative is added to the lignocellulosic material. It comprises a sorption step of sorption to obtain a phenol derivative mixture.

The first mixing step is a separation step of separating the phenol derivative mixture into a solid containing the lignocellulosic material sorbed by the phenol derivative and a separation liquid containing the phenol derivative and the fat. Is further provided.
Examples of the method for separating the phenol derivative mixture into a solid and a separation liquid include filtration, stationary separation, and centrifugation. Examples of the filtration include vacuum filtration and pressure filtration. Examples of the filter medium used for filtration include a membrane.
In the separation step, it is preferable to obtain the solid and the separation liquid by filtering the phenol derivative mixture.

  Furthermore, the first mixing step further includes an acid mixing step of obtaining an acid mixture as the first mixture containing lignophenol by mixing the solid and the acid. In the acid mixing step, the acid mixture contains water by mixing the solid, acid and water. Specifically, in the acid mixing step, a solid and an acid aqueous solution are mixed.

In the second mixing step, the acid mixture as the first mixture is added to the organic solvent that is a poor solvent for the lignophenol, thereby aggregating the lignophenol and including the lignophenol aggregate. This is an organic solvent mixing step for obtaining a mixture of organic solvents.
In the organic solvent mixing step, it is preferable that the acid mixture is added to the organic solvent by allowing the acid mixture to flow down into a tank containing the organic solvent. Moreover, it is more preferable to add the acid mixture to the organic solvent by dropping the acid mixture into a tank containing the organic solvent.

  In the purification step, a solid is obtained by filtering the second mixture, and lignophenol is obtained from the solid.

The lignocellulosic material contains lignin and cellulose.
Examples of the lignocellulosic material include woody materials and herbaceous materials. Examples of the woody material include conifers (for example, pine, cedar cypress, etc.), hardwoods (for example, shii, oak, cherry, etc.), and tropical trees. Herbaceous materials include kenaf, ramie (linen), linen (flax), abaca (manila hemp), heneken (sisal hemp), jute (hemp), hemp (palm), palm, palm, mulberry, straw (rice straw, straw) Etc.), bagasse and corn. Lignocellulosic materials are used in various states such as powders and chips (for example, waste wood scraps).

  The lignin is a polymer compound having a phenylpropane unit (C6-C3 unit) as a basic skeleton, and the phenylpropane unit is randomly oxidatively polymerized by an enzyme. Lignin is a component constituting a plant cell wall, and is bound to cellulose or hemicellulose in the plant cell wall.

  The phenol derivative is a compound having a phenol structure in the molecule. Examples of the phenol derivative include phenol, p (para) -cresol, m (meth) -cresol, o (ortho) -cresol, anisole, 2,4-dimethoxyphenol, 2,6-dimethoxyphenol, and 2,4-dimethyl. Group consisting of phenol, 2,6-dimethylphenol, propylphenol, i-propylphenol, tert-butylphenol, catechol, resorcinol, pyrogallol, phloroglucinol, bisphenol, vanillin, syringol, guaiagol, ferulic acid, and coumaric acid At least one selected from the above is preferred. As the phenol derivative, cresol is preferable, and p-cresol is more preferable.

  Examples of the acid include inorganic acids and organic acids. Examples of the inorganic acid include sulfuric acid, phosphoric acid, hydrochloric acid and the like. Examples of the organic acid include p-toluenesulfonic acid, trifluoroacetic acid, trichloroacetic acid, formic acid and the like.

The organic solvent that is a poor solvent for the lignophenol has hydrophobicity.
Examples of the organic solvent include ethers, esters, hydrocarbons and the like. Examples of ethers include asymmetric ethers and symmetric ethers, and more specifically, diisopropyl ether and diethyl ether. Examples of the ester include ethyl acetate. Examples of the hydrocarbon include cyclic hydrocarbons and linear hydrocarbons. More specifically, hexane (n-hexane and the like), toluene, pentane (n-pentane and the like), heptane, octane, cyclohexane, decalin, Examples include benzene.
As the organic solvent, hydrocarbon is preferable, hexane is more preferable, and n-hexane is particularly preferable.

  The method for producing lignophenol according to this embodiment is a method for producing lignophenol from a lignocellulosic material using the apparatus for producing lignophenol according to this embodiment.

The lignophenol production apparatus according to the present embodiment is a lignophenol production apparatus for producing lignophenol from a lignocellulosic material.
The lignophenol production apparatus according to the present embodiment includes a mixing unit that generates lignophenol by mixing the lignocellulosic material, the phenol derivative, and the acid.
The mixing unit obtains a first mixture by mixing the lignocellulosic material, a phenol derivative, and an acid, and mixes the first mixture with an organic solvent that is a poor solvent for the lignophenol. This is a mixing part for obtaining the second mixture.
The lignophenol production apparatus according to this embodiment further includes a purification unit that obtains lignophenol from the second mixture. The purification unit is a purification unit that obtains the lignophenol from the solid by obtaining a solid by filtering the second mixture.

As shown in FIGS. 1 and 2, the lignophenol production apparatus 1 according to the present embodiment includes a pretreatment unit 2 that sorbs a phenol derivative C to a lignocellulose-based material A, and lignocellulose in which the phenol derivative C is sorbed. The first material is obtained by mixing the system material A and the acid aqueous solution D, and the second mixture is obtained by mixing the first mixture and the organic solvent F that is a poor solvent for the lignophenol. And a mixing unit 3.
The lignophenol production apparatus 1 according to this embodiment further includes a purification unit 4 that obtains a solid matter by filtering the second mixture and obtains lignophenol O from the solid matter.

<First mixing step>
In the first mixing step, the pretreatment unit 2 and the mixing unit 3 are used.

The pretreatment unit 2 is the first filtration unit 2, and includes a tank 21, a stirring unit 22 that stirs the contents in the tank 21, and a heating unit 23 that heats the tank 21. At least a part of the bottom 21a is formed of a filter medium so that the contents in the tank 21 can be filtered. The tank 21 is formed in a tapered shape so as to taper downward. Examples of the first filtration unit 2 include “PV mixer with filtration function” manufactured by Shinko Environmental Solution Co., Ltd.
In addition, although the pre-processing part 2 in this embodiment is the 1st filtration part 2, the pre-processing part 2 is not limited to a 1st filtration part, The solid-liquid mixture containing a solid substance and a liquid substance is solid-stated. Any separation unit that separates a product into a liquid product may be used.

In the first mixing step, the lignocellulosic material A and the phenol derivative C containing fat are mixed in the first filtration unit 2 so that the lignocellulosic material A is degreased while being degreased with the phenol derivative C. The phenol derivative C is sorbed on the lignocellulosic material A to obtain a phenol derivative mixture (sorption step a1).
By the sorption step a1, the lignocellulosic material A can be degreased without using an organic solvent (acetone, hexane, etc.) other than the phenol derivative.
About the mixing ratio of lignocellulosic material A containing fat and phenol derivative C, from the viewpoint of degreasing lignocellulosic material A with phenol derivative C and sorbing phenol derivative C onto lignocellulosic material A The phenol derivative is preferably 300 to 1000 parts by mass, more preferably 500 to 700 parts by mass with respect to 100 parts by mass of lignocellulosic material (wet mass) containing fat.
The moisture content of the lignocellulosic material on a wet basis is preferably 15% by mass or less, more preferably 8% by mass or less. The moisture content on a wet basis means a value obtained by dividing the mass of moisture by the sum of the mass of moisture and solid content.

Then, by filtering the phenol derivative mixture through the first filtration unit 2, the solid containing the lignocellulosic material A sorbed with the phenol derivative C, and the separation liquid containing the phenol derivative C and the fat. A first filtrate is obtained (first filtration step a2 as the separation step). In the separation step, phenol derivative K is recovered from the separated liquid. The recovered phenol derivative K can be reused as the phenol derivative C used in the sorption step a1.
In the first mixing step, after the separation step, the tank 21 is heated by the heating unit 23 to volatilize the phenol derivative adhering to the lignocellulosic material A, so that the lignocellulose-based material is volatilized. Excess phenol derivative can be removed from material A.
The lignocellulosic material A from which the excess phenol derivative C has been removed is transferred to the mixing unit 3 for further processing.

  The mixing unit 3 includes a tank 31 and a stirring unit 32 that stirs the contents in the tank 31. The tank 31 and the stirring unit 32 are preferably subjected to glass lining treatment from the viewpoint of excellent acid resistance.

Furthermore, at the said 1st mixing process, the solid substance containing the lignocellulosic material A by which the phenol derivative C was sorbed, and the said acid aqueous solution D are mixed in the said mixing part 3, and lignophenol is produced | generated. Then, an acid mixture which is a first mixture containing lignophenol is obtained (generation step a3 which is the acid mixing step).
In the production step a3, cellulose contained in the lignocellulosic material A is hydrolyzed under an acid catalyst to produce saccharides. Further, the lignin contained in the lignocellulosic material A is hydrolyzed under an acid catalyst to lower the molecular weight. Furthermore, lignin reacts with a phenol derivative under an acid catalyst to produce lignophenol. FIG. 3 shows an example of a reaction for producing lignophenol using sulfuric acid as the acid and p-cresol as the phenol derivative. Moreover, the produced lignophenol is hydrolyzed under an acid catalyst to reduce the molecular weight. And the acid mixture which is the 1st mixture containing lignophenol is obtained.

  The acid aqueous solution usually contains 65 to 98% by mass, preferably 72 to 98% by mass of acid.

  In the first mixing step, the first mixture containing lignophenol and water E are mixed in the mixing unit 3 to dilute the first mixture and reduce the acid concentration in the first mixture. The hydrolysis reaction is suppressed (dilution step a4).

<Second mixing step>
In the second mixing step, an acid mixture that is a first mixture diluted with water E and an organic solvent F that is a poor solvent for the lignophenol are mixed in the mixing unit 3, whereby the first mixture is mixed. The lignophenol dispersed in (1) is agglomerated and solidified to obtain an organic solvent mixture which is a second mixture containing solid lignophenol (second mixing step b which is an organic solvent mixing step).
In the organic solvent mixing step, the acid mixture is mixed with the organic solvent F in a mixed state (without separation).
Further, in the organic solvent mixing step, the lignophenol is aggregated by adding the acid mixture as the first mixture to the organic solvent F to obtain an organic solvent mixture as the second mixture containing the aggregate of lignophenol. .
In the organic solvent mixing step, the acid mixture is added to the organic solvent F by causing the acid mixture to flow down into a tank 31 that contains the organic solvent. In other words, in the organic solvent mixing step, the acid mixture is added to the organic solvent F by causing the acid mixture to flow down onto the liquid surface of the organic solvent accommodated in the tank 31.

<Purification process>
In the said refinement | purification process, using the said refinement | purification part 4, a solid substance is obtained by filtering the oil-water mixture which is the said 2nd mixture, and lignophenol is obtained from this solid substance. In other words, by using the purification unit 4 to simultaneously filter the oil (organic solvent F) and water contained in the second mixture, a solid is obtained, and lignophenol is obtained from the solid.
Moreover, at the said refinement | purification process, Preferably, using the said refinement | purification part 4, a solid substance is obtained by filtering said 2nd mixture, stirring, and lignophenol is obtained from this solid substance.

  The refining unit 4 obtains a solid material containing lignophenol by filtering the second mixture, and by mixing the solid material and the alcohol G, the lignophenol is dissolved in the alcohol G to obtain lignophenol. And a second filtration unit 4a for obtaining an LP alcohol solution containing alcohol G, a pH adjusting unit 4b for adjusting pH by mixing an alkaline agent H with the LP alcohol solution, and removing the alcohol G from the LP alcohol solution. Concentration part 4c for concentrating lignophenol by crystallization, crystallization part 4d for precipitating lignophenol by crystallization by mixing sodium chloride aqueous solution I into the concentrated LP alcohol liquid, and LP alcohol containing the precipitated lignophenol A third lignophenol is obtained by filtering the liquid. Includes an over section 4e, and a drying section 4f for drying the lignophenol obtained in said third filtration unit 4e.

  The second filtration unit 4a includes a tank 4a1 and a stirring unit 4a2 for stirring the contents in the tank 4a1, and at least a part of the bottom 4a1a of the tank 4a1 filters the contents in the tank 4a1. It is formed with a filter medium so that it can. Examples of the filter medium include filter cloth and wire mesh. An example of the wire mesh is a sintered wire mesh. As said 2nd filtration part 4a, the "filter dryer" by a Shinko environment solution company etc. are mentioned, for example.

  In the purification step, the second mixture is filtered by the second filtration unit 4a to obtain a solid containing lignophenol (second filtration step c1). The liquid separated in the second filtration step c1 contains an acid and an organic solvent. The liquid separated in the second filtration step c1 can be separated and recovered into the acid aqueous solution L and the organic solvent M by stationary separation or the like.

As a material of the filter medium used in the filtration of the second filtration step c1, from the viewpoint of excellent corrosion resistance, polypropylene, polytetrafluoroethylene (for example, Teflon (registered trademark)), an alloy containing nickel and molybdenum (for example, Hastelloy (registered trademark)) is preferable, and an alloy containing polypropylene, nickel and molybdenum is particularly preferable.
The pore size of the filter medium is preferably 10 to 30 μm, particularly preferably 20 μm from the viewpoint of suppressing the filtration time while suppressing discharge of lignophenol together with the filtrate.

And in the said refinement | purification process, by mixing this solid substance and alcohol G by the said 2nd filtration part 4a, lignophenol is dissolved in alcohol G and LP alcohol liquid containing lignophenol and alcohol G is obtained ( Dissolution step c2). As the alcohol G, methanol, ethanol or the like can be used.
Next, the LP alcohol liquid is filtered to remove solids (residues) from the LP alcohol liquid (third filtration step c3).

  The pH adjusting unit 4b includes a tank 4b1 and a stirring unit 4b2 for stirring the contents in the tank 4b1. From the viewpoint of excellent acid resistance, the tank 4b1 and the stirring unit 4b2 are preferably glass-lined.

Moreover, in the said refinement | purification process, pH is adjusted by mixing the LP alcohol liquid which removed the solid substance, and the alkaline agent H by the pH adjustment part 4b (pH adjustment process c4).
In the LP alcohol liquid from which the solid matter has been removed, the acid used in the generation step a3 remains without being sufficiently removed, and the pH is usually 0 or more and less than 2.
In the pH adjusting step c4, it is preferable to neutralize this acid to make the pH 2 or more and 4 or less.
Examples of the alkali agent include magnesium hydroxide and sodium hydroxide.

  The said concentration part 4c is equipped with the tank 4c1, the stirring part 4c2 which stirs the content in this tank 4c1, and the heating part 4c3 which heats the inside of this tank 4c1.

  In the purification step, the LP alcohol liquid whose pH is adjusted is heated in the heating unit 4c3 while being stirred in the tank 4c1 by the stirring unit 4c2 (concentration step c5). Thereby, the alcohol in the LP alcohol liquid can be evaporated by the concentration unit 4c. As a result, the lignophenol concentration of the LP alcohol liquid can be increased, and the amount of the LP alcohol liquid to be processed can be reduced. Moreover, lignophenol can be crystallized.

  The crystallization part 4d includes a tank 4d1 and a stirring part 4d2 for stirring the contents in the tank 4d1.

In the purification step, lignophenol is precipitated by crystallization by mixing sodium chloride aqueous solution I in the crystallization part 4d with the LP alcohol solution in which lignophenol is concentrated in the concentration step c5 (crystallization step c6).
Lignophenol is highly protic due to the OH group contained in the phenol skeleton, and as a result, lignophenol is easily soluble in water. However, lignophenol hardly dissolves in water when it coexists with sodium chloride. Therefore, when the sodium chloride aqueous solution I is mixed with the LP alcohol solution, lignophenol is precipitated.
The sodium chloride aqueous solution I preferably has a sodium chloride concentration of 0.1 to 5% by mass.

Moreover, in the said refinement | purification process, solid lignophenol is obtained by filtering the LP alcohol liquid containing the precipitated lignophenol by the said 3rd filtration part 4e (4th filtration process c7). The filtrate obtained in the fourth filtration step c7 can be recovered as alcohol N.
Furthermore, in the said refinement | purification process, the lignophenol O refine | purified is obtained by drying the lignophenol obtained by this 3rd filtration part 4e by the said drying part 4f (drying process c8).

The purified lignophenol O has a weight average molecular weight of preferably 2000 to 6000, more preferably 3500 to 6000, and even more preferably 4000 to 6000. A weight average molecular weight can be measured by the method as described in an Example.
Further, the purified lignophenol O has an acid concentration in terms of dry mass, preferably 7000 mg / kg or less, more preferably 6000 mg / kg or less, and further preferably 1000 mg / kg or less. The acid concentration can be determined by measuring the ion concentration by an electrocapillary method. The acid concentration can also be determined by neutralization titration.

  The lignophenol O obtained by the method for producing lignophenol according to the present embodiment, that is, the purified lignophenol O can be used in applications such as a flame retardant for plastics, a plywood adhesive, and an impregnating material.

  Since the method for producing lignophenol according to the present embodiment is configured as described above, it has the following advantages.

  The method for producing lignophenol according to the present embodiment includes a first mixing step of obtaining a first mixture containing lignophenol by mixing the lignocellulosic material A, the phenol derivative C, and the acid. . Further, in the method for producing lignophenol according to the present embodiment, the lignophenol is agglomerated by mixing the first mixture and the organic solvent F that is a poor solvent for the lignophenol. A second mixing step of obtaining a second mixture containing the agglomerates. The method for producing lignophenol according to the present embodiment further includes a purification step for obtaining the lignophenol from the second mixture.

The reason why lignophenol aggregates and becomes solid in the second mixture containing water, an organic solvent that is a poor solvent for lignophenol, and lignophenol is as follows.
Phenols have a hydroxyl group, which acts as a proton donor and can cause a dissociation reaction in water. In addition, when phenols are dissociated, phenoxide ions are stabilized by resonance. From this, phenols have a certain degree of hydrophilicity.
Therefore, the structural part of phenols in lignophenol has a certain degree of hydrophilicity.
Furthermore, among the lignophenols, the hydroxyl groups other than the phenol structural parts also have a certain degree of hydrophilicity.
On the other hand, lignophenol has a structural part having an affinity for an organic solvent (such as a part composed of a hydrocarbon such as a benzene ring).
That is, lignophenol has a structural portion having a certain degree of hydrophilicity and a structural portion having an affinity for an organic solvent.
Moreover, the organic solvent which becomes a poor solvent with respect to the said lignophenol has hydrophobicity.
From this, when lignophenol and water are mixed with an organic solvent that is a poor solvent for the lignophenol, the water and the organic solvent are repelled, and the repelled water and the organic solvent are repelled. Lignophenol molecules are oriented by water and the organic solvent, and as a result, lignophenol aggregates between water and the organic solvent.

Further, in the method for producing lignophenol according to the present embodiment, the first mixing step mixes the lignocellulosic material A containing fat and the phenol derivative C, whereby the lignocellulosic material A is mixed with the lignocellulosic material A. While defatting with the phenol derivative C, the derivatized lignocellulosic material A is sorbed with the phenol derivative C to obtain a phenol derivative mixture, and the phenol derivative mixture is absorbed into the phenol derivative mixture. The lignophenol is contained by mixing the solid substance containing the worn lignocellulosic material, the separation step containing the phenol derivative and the fat-containing separation liquid, and mixing the solid substance and the acid. A production step a3 which is an acid mixing step for obtaining a first mixture which is an acid mixture.
Since the phenol derivative C has a phenol structure in the molecule, it has an affinity for fat. Therefore, the phenol derivative C can be used to degrease the lignocellulosic material A. Therefore, according to the method for producing lignophenol, since the lignocellulosic material A can be degreased with the phenol derivative C necessary for producing lignophenol in the sorption step a1, the material to be used The number of types can be suppressed.
In addition, according to the method for producing lignophenol, since the solid used in the production step a3 which is the acid mixing step is separated from the separation liquid containing fat in the separation step, the production is the acid mixing step. It can suppress that the production | generation reaction of lignophenol in process a3 is inhibited with fat.
Furthermore, according to such a method for producing lignophenol, degreasing and sorption can be performed simultaneously in the sorption step. As a result, workability is improved compared to the conventional method in which lignocellulosic material and acetone or hexane are mixed and the lignocellulosic material and acetone or hexane are separated separately before the sorption step. .
Further, according to such a method for producing lignophenol, it is possible to degrease the lignocellulosic material with a phenol derivative and sorb the phenol derivative onto the lignocellulosic material. As a result, compared to the conventional method of degreasing using acetone or hexane during the sorption step, that is, the conventional method of sorbing a phenol derivative in the presence of acetone or hexane, the lignocellulosic material is phenolic. The opportunity for the derivative to come into contact increases, and the phenol derivative can be efficiently sorbed to the lignocellulosic material.
Furthermore, according to such a method for producing lignophenol, the lignocellulosic material can be defatted with a phenol derivative, and the phenol derivative can be sorbed on the defatted portion of the lignocellulosic material. As a result, the opportunity for the phenol derivative to come into contact with the site increases, and the phenol derivative can be more efficiently sorbed by the lignocellulosic material.

Furthermore, in the method for producing lignophenol according to the present embodiment, in the separation step, the solid product and the separation liquid are obtained by filtering the phenol derivative mixture.
According to such a method for producing lignophenol, there is an advantage that the phenol derivative mixture can be separated in a short time as compared with the case where the phenol derivative mixture is separated into a solid and a separated liquid by stationary separation.

In addition to the sorption step a1, the separation step, and the generation step a3, the method for producing lignophenol according to this embodiment includes the acid mixture in an organic solvent that is a poor solvent for the lignophenol. Is further provided with an organic solvent mixing step as a second mixing step in which the lignophenol is aggregated to obtain an organic solvent mixture as a second mixture containing the lignophenol aggregate.
The organic solvent which is a poor solvent for lignophenol has hydrophobicity, but in an acid mixture containing water, an organic solvent having hydrophobicity and lignophenol, lignophenol is water and an organic solvent. Aggregate between and.
In addition, the concentration of the phenol derivative in the object to be mixed with the acid in the acid mixing step can be reduced by the separation step, and as a result, the concentration of the phenol derivative in the acid mixture added to the organic solvent in the organic solvent mixing step. Can be reduced. Moreover, since a phenol derivative and lignophenol have a phenol structure, a phenol derivative becomes a good solvent with respect to lignophenol. Therefore, since the concentration of the phenol derivative that is a good solvent for lignophenol in the acid mixture can be reduced by the separation step, lignophenol is easily aggregated in the organic solvent mixing step.
Furthermore, when the acid mixture is added to the organic solvent, the possibility that an acid is present around the lignophenol is reduced when the lignophenol aggregates, compared to the case where the organic solvent is added to the acid mixture. As a result, it becomes difficult for the acid to be taken into the aggregate of lignophenol.
As described above, according to such a method for producing lignophenol, the lignophenol is aggregated so that the lignophenol can be easily separated from other substances and the lignophenol aggregate is less likely to be taken up.
That is, according to such a method for producing lignophenol, the concentration of the acid contained in lignophenol can be lowered.

Furthermore, in the method for producing lignophenol according to this embodiment, in the organic solvent mixing step, the acid mixture is added to the organic solvent by causing the acid mixture to flow down into a tank containing the organic solvent.
In the organic solvent mixture, the acid-containing water has a higher specific gravity than the oil containing the organic solvent and the aggregate of lignophenol.
Thus, when the acid mixture is allowed to flow down into a tank containing the organic solvent, lignophenol aggregates above the tank while the acid moves down the tank. Therefore, the possibility that an acid is present around lignophenol is further reduced, and as a result, the acid is more hardly incorporated into the lignophenol aggregate.
That is, according to the method for producing lignophenol, the concentration of the acid contained in lignophenol can be further reduced.

  In addition, the manufacturing method of lignophenol which concerns on this invention is not limited to the said embodiment. Moreover, the manufacturing method of lignophenol which concerns on this invention is not limited to an above-described effect. The lignophenol production method according to the present invention can be variously modified without departing from the gist of the present invention.

  Next, the present invention will be described more specifically with reference to reference examples and reference comparative examples.

<Test Example 1: Investigation of separation method of second mixture>
(Reference Example 1-1: Filtration separation, using hexane)
After degreasing the wood flour with acetone, cresol was sorbed onto the wood flour degreased with acetone.
Then, 80 g of an aqueous sulfuric acid solution (sulfuric acid: 72% by mass) was added to 20 g of wood powder sorbed with cresol, and vigorously stirred for 1 hour to obtain a first mixture.
Next, the hydrolysis reaction with sulfuric acid was stopped by stirring the first mixture and 120 g of water in a stirring tank for 15 minutes.
Thereafter, 80 g of hexane was added to the first mixture in which the hydrolysis reaction was stopped, and the mixture was vigorously stirred for about 10 minutes to obtain a second mixture.
And this 2nd mixture was transferred to the filter (filter which has a scraper) from a stirring tank with a screw type liquid supply machine, and solid matter was obtained by filtering this 2nd mixture with this filter. Filtration took about 30 minutes.
Next, 60 g of methanol was mixed with the solid, so that lignophenol contained in the solid was dissolved in methanol to obtain an LP methanol solution containing lignophenol and methanol.
Thereafter, the LP methanol solution was suction filtered to remove solids (unreacted wood powder) from the LP methanol solution to obtain 55 g of LP methanol solution from which the unreacted product was removed.
The LP methanol solution (pH: 1) was mixed with powdered magnesium hydroxide to adjust the pH of the LP methanol solution to 3.0.
Next, the pH-adjusted LP methanol solution was suction filtered to remove sulfate and excess magnesium hydroxide from the LP methanol solution.
Thereafter, 100 parts by mass of LP methanol solution from which sulfates and excess magnesium hydroxide were removed and 500 parts by mass of saline (salt concentration: 5.0% by mass) were mixed to crystallize lignophenol.
The LP methanol solution in which lignophenol was precipitated by crystallization was subjected to suction filtration with 5C filter paper to obtain solid lignophenol.
Next, the lignophenol on the filter paper was dried by heating to 50 ° C. overnight to obtain purified lignophenol.
The sulfate ion concentration and weight average molecular weight of the purified lignophenol were measured.
The sulfate ion concentration was measured by the electrocapillary method.
The weight average molecular weight was measured by GPC (gel permeation chromatography).
The sulfate ion concentration was 6000 mg / kg. Moreover, the weight average molecular weight was about 4000.

(Reference Example 1-2: Filtration separation, using toluene)
Purified in the same manner as in Reference Example 1-1 except that phenol was used instead of cresol, toluene was used instead of hexane, and the stirring time of the first mixture and toluene was about 1 hour. Lignophenol was obtained.
Then, the sulfate ion concentration and the weight average molecular weight of the purified lignophenol were measured.
The weight average molecular weight was measured by GPC (gel permeation chromatography).
The sulfate ion concentration was 6500 mg / kg. The weight average molecular weight was about 4100.

(Reference Example 1-3: static separation, hexane use)
A second mixture was obtained in the same manner as in Reference Example 1-1.
Then, the second mixture was allowed to stand and separate in the tank. By this stationary separation, the second mixture was separated into three layers, a hexane layer, a lignophenol layer, and a sulfuric acid layer. This static separation took overnight.
Next, the hexane layer and the sulfuric acid layer were removed from the tank.
And by mixing methanol with the lignophenol layer which remained in the tank, lignophenol was dissolved in methanol and the LP methanol liquid containing lignophenol and methanol was obtained.
Next, purified lignophenol was obtained by treating the LP methanol solution in the same manner as in Reference Example 1-1.
Then, the sulfate ion concentration and the weight average molecular weight of the purified lignophenol were measured.
The sulfate ion concentration was 8000 mg / kg. The weight average molecular weight was about 3000.

(Reference Example 1-4: Static separation)
In the same manner as in Reference Example 1-1, a first mixture in which the hydrolysis reaction was stopped was obtained.
And phenol was added to the 1st mixture which stopped the hydrolysis reaction, and the 2nd mixture was obtained by stirring vigorously for about 1 hour.
Next, the second mixture was allowed to stand and separate in the tank. By this stationary separation, the second mixture was separated into two layers, a phenol layer and a sulfuric acid layer. This static separation took overnight.
And the sodium hydroxide aqueous solution was mixed with the phenol liquid of a phenol layer, and it adjusted to pH 5, filtered, and removed the sulfate.
100 parts by mass of a phenol solution and 500 parts by mass of ethyl ether were mixed to crystallize lignophenol.
The sulfate ion concentration and weight average molecular weight of the crystallized lignophenol were measured.
The sulfate ion concentration was 10,000 mg / kg. The weight average molecular weight was about 2000.

From the above results, it can be seen that the method of Reference Example 1-1 can obtain lignophenol in a shorter time than the methods of Reference Examples 1-3 and 1-4.
Further, the purified lignophenol of Reference Example 1-1 had a higher weight average molecular weight and a lower sulfate ion concentration than those of Reference Examples 1-3 and 1-4.

<Test Example 2: Examination of mixing method of second mixed solution and poor solvent>
(Reference Example 2-1: The second mixed solution was added to the poor solvent.)
By mixing 30 g of wood powder containing fat and 210 g of p-cresol which is a phenol derivative, a phenol derivative mixture was obtained.
Next, the phenol derivative mixture was filtered to obtain a solid containing wood flour sorbed with p-cresol.
Then, 120 g of an aqueous sulfuric acid solution (sulfuric acid: 72% by mass) was added to 30 g of the solid, and the mixture was vigorously stirred at 32 ° C. for 1 hour to obtain a first mixture as an acid mixture.
Next, the hydrolysis reaction with sulfuric acid was stopped by stirring the first mixture and 180 g of water in a stirring tank for 15 minutes.
Then, the 1st mixture which stopped the hydrolysis reaction was added to 120 g of hexane which is a poor solvent, and the 2nd mixture was obtained by stirring vigorously for about 10 minutes.
And this 2nd mixture was transferred to the filter (filter which has a scraper) from a stirring tank with a screw type liquid supply machine, and solid matter was obtained by filtering this 2nd mixture with this filter.
Next, as in Reference Example 1-1, purified lignophenol was obtained using methanol, magnesium hydroxide, and brine (salt concentration: 5.0% by mass).
The sulfate ion concentration of the purified lignophenol was measured.
The sulfate ion concentration was 650 mg / kg.
The yield of lignophenol was 107%. The yield of lignophenol is the ratio of the mass of the obtained lignophenol (purified lignophenol) to the mass of lignin contained in the wood flour used, expressed as a percentage. The amount of lignin contained in the wood flour was quantified using the Klarson method.
The pH of the LP methanol solution adjusted with magnesium hydroxide was 3.68.

(Reference Example 2-2: A poor solvent was added to the second mixed solution.)
Purified lignophenol was obtained in the same manner as in Reference Example 2-1, except that the poor solvent was added to the second mixture without adding the second mixture to the poor solvent.
The sulfate ion concentration of the purified lignophenol was measured.
The sulfate ion concentration was 6600 mg / kg.
The yield of lignophenol was 113%.
The pH of the LP methanol solution adjusted with magnesium hydroxide was 3.08.

  From the above results, it can be seen that the method of Reference Example 2-1 can lower the sulfate ion concentration of lignophenol as compared to the method of Reference Example 2-2.

1: production apparatus, 2: pretreatment unit (first filtration unit), 3: mixing unit, 4: purification unit,
4a: 2nd filtration part, 4a1: tank, 4a1a: bottom part, 4a2: stirring part, 4b: pH adjusting part, 4b1: tank, 4b2: stirring part, 4c: concentrating part, 4c1: tank, 4c2: stirring part, 4c3 : Heating section, 4d: crystallization section, 4d1: tank, 4d2: stirring section, 4e: third filtration section, 4f: drying section,
21: tank, 21a: bottom, 22: stirring section, 23: heating section, 31: tank, 32 stirring section,
A: Lignocellulosic material, C: Phenol derivative, D: Acid aqueous solution, E: Water, F: Organic solvent, G: Alcohol, H: Alkaline agent, I: Sodium chloride aqueous solution, K: Phenol derivative, L: Acid aqueous solution , M: organic solvent, N: alcohol, O: lignophenol,
a1: sorption step, a2: first filtration step (separation step), a3: production step (acid mixing step), a4: dilution step, b: second mixing step, c1: second filtration step, c2: dissolution step C3: third filtration step, c4: pH adjustment step, c5: concentration step, c6: crystallization step, c7: fourth filtration step :, c8: drying step

Claims (2)

By mixing a lignocellulosic material containing fat and a phenol derivative, the lignocellulosic material is defatted with the phenol derivative while sorbing the phenol derivative on the lignocellulosic material, and the phenol derivative A sorption step to obtain a mixture;
A separation step of separating the phenol derivative mixture into a solid containing the lignocellulosic material sorbed by the phenol derivative and a separation liquid containing the phenol derivative and the fat;
A method for producing lignophenol, comprising: mixing the solid and an acid to obtain an acid mixture containing lignophenol.   The method for producing lignophenol according to claim 1, wherein in the separation step, the solid product and the separation liquid are obtained by filtering the phenol derivative mixture.

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