TW201038737A - Catalyst for degrading lignin, catalyst for degrading aromatic hydrocarbon, and porphyrin - Google Patents

Abstract

A catalyst for degrading lignin and a catalyst for degrading an aromatic hydrocarbon, each of which contains a porphyrin. A solution containing an alkali compound is added to lignin, a catalyst for degrading lignin is allowed to act on the resulting lignin-alkali compound solution as needed, which is irradiated with light as needed, or a catalyst for degrading lignin is allowed to act on lignin as needed, which is irradiated with light, whereby alcohols and organic acids are separated. A degradation product generated when the alcohols and organic acids are separated is recovered, and also hydrogen ions are released. A porphyrin having a catalytic function of converting lignin into alcohols and organic acids, a porphyrin having a catalytic function of degrading a compound containing an aromatic hydrocarbon in which an oxygen atom is bound to carbon which forms a benzene ring, or a porphyrin obtained by culturing Escherichia coli that cannot express a gene ypjD (b2611) due to mutation.

Description

[Technical Field] The present invention relates to a catalyst for lignin decomposition, a method for producing an alcohol and an organic acid, a method for producing a lignin decomposition product, and a catalyst for decomposing an aromatic hydrocarbon, a method for releasing a hydrogen ion, and a porphyrin, particularly a catalyst for lignin decomposition by porphyrin, a method for producing an alcohol such as methanol from an lignin, an organic acid, or a method for producing a lignin decomposition product, A catalyst for decomposing an aromatic hydrocarbon into which the morpholine is 0, a method of using a catalyst for lignin decomposition by a porphyrin, a method of extracting a hydrogen ion from lignin, and a porphyrin. [Prior Art] After the acceleration of warming on the earth after the 21st century, carbon dioxide and carbon became the control industry and even the key to controlling the world economy. As long as the fossil fuel blocked in the ground or on the sea floor is used as an energy source, it is impossible to reduce carbon dioxide in the atmosphere, and it is difficult to suppress the increase. The person who receives attention here is an alcohol such as bioethanol manufactured by plants, which is expected to be used as an energy source. However, at this time, in the past, technology used almost as a raw material for sugar, which caused a problem of competition between human food sources and energy. Recently, it has finally not competed with food sources, for example, alcohol technology has been advanced to use cellulose as a carbon source. Grasses that cannot be wood or foodstuffs are mainly made up of cellulose and lignin. When the wood which is close to the so-called waste or the cellulose of the grass is used as the carbon source as the waste material or the sheet construction material, the carbon dioxide carbon emission can be suppressed, which contributes to the industrial and economic circles. For the use of cellulose as compared to the above advancement, the effective use of lignin with a rich carbon source of cellulose is still extremely limited. As a practical step, for example, it is simply burned as a heat source, or a preservative, or a structural strengthening agent mixed in cement. Moreover, with the development of science and technology and industry, the accumulation of industrial waste that produces compounds that were originally present in non-high concentrations in nature has become a very large negative asset for human beings. Most of these compounds are compounds containing an aromatic hydrocarbon bonded to an oxygen atom on a carbon atom forming a benzene ring. For example, a dioxin class can be mentioned. Regarding the dioxin class, the high temperature treatment in the stage of the burning of the source has been considerably improved, but there have been many harmful compounds that have spread. Therefore, these harmful compounds are further decomposed by the use of sunlight which is infinitely injected into the earth, using the harmful compound decomposition catalyst originally existing in nature, which contributes to natural purification and human health maintenance. However, this useful decomposition catalyst has not been proposed so far. Further, in recent years, as a source of energy, a fuel cell that receives an electromotive force by movement of hydrogen ions is attracting attention. However, when hydrogen is used as a source of hydrogen ions, hydrogen is almost always produced from fossil fuels. Further, hydrogen gas can be obtained by electrolysis of water, but power must be supplied at this time. Further, when a solar cell obtained from sunlight is used, it is necessary to manufacture a semiconductor device. Therefore, if the current energy demand depends on the solar cell, resources and costs become a great burden. For a dye-sensitized solar cell, a nanometer-sized titanium oxide is necessary, and a synthetic pigment having a certain degree of electromotive force is expensive. In the past, it was known that a lignin-based substance is in contact with functional water under light irradiation to decompose the lignin system. A method of decomposing a substance (for example, refer to Patent Document 1). -6- 201038737 This prior art describes sodium hydroxide as functional water. However, there is no specific description of the decomposition product, and there is no description about the alcohol. Further, it is known that porphyrins containing a large number of C1 and F are active in the reaction of acidification of lignin and conversion of an alkane to an alcohol (for example, see Patent Document 2). However, the use of an alkali compound or a photocatalyst has not been described in the prior art. [Patent Document 1] [Patent Document 1] JP-A-2000- 1 44592 (Patent Document Scope, Paragraph: 0 0 3 0) [Patent Document 2] Japanese Patent Publication No. 2-503086 (No. In the upper left column of the four pages, the present invention provides a lignin decomposition catalyst and lignin which are formed from porphyrins which have not been used in the prior art, and which are used to produce alcohols such as methanol and organic acids. The method, a method for producing a lignin decomposition product, a catalyst for decomposing an aromatic hydrocarbon by a porphyrin, a method for using a lignin as a raw hydrogen ion, and a porphyrin. The catalyst for lignin decomposition of the present invention is characterized by containing a porphyrin which exhibits a catalytic function by light irradiation. The catalyst for lignin decomposition of the present invention is further characterized by a porphyrin which exhibits a catalytic function in an alkali solution. 201038737 The catalyst for lignin decomposition of the present invention is further characterized by a porphyrin containing a catalyst function by irradiation with light in an alkali solution. In the above catalyst system for lignin decomposition, a porphyrin is a tetrapyrrole compound containing a methyl group and an ethyl ester or an acetate group (propionic acid group) in the porphyrin ring. In the above catalyst system for lignin decomposition, a porphyrin is a tetrapyrrole compound containing four methyl groups, four ethyl esters or an acetate group (propionic acid group) in the porphyrin ring. The above-mentioned catalyst system for lignin decomposition is characterized in that porphyrin is a porphyrin having a carboxyl group in a molecule. The above-mentioned catalyst system for lignin decomposition is characterized in that porphyrin is a porphyrin having a total of two, four or eight carboxyl groups in the molecule. The catalyst system for lignin decomposition described above is characterized in that porphyrin is at least one selected from the group consisting of uroporphyrin, protoporphyrin, and coproporphyrin. In the above-mentioned catalyst system for lignin decomposition, a porphyrin is a tetrapyrrole compound having a porphyrin ring structure obtained by culturing a large intestine in a medium. In the above-mentioned catalyst system for lignin decomposition, a medium containing a tetrapyrrole compound having a porphyrin ring structure obtained by culturing a large rod in a ± primordial group is characterized. In the above-mentioned catalyst system for lignin decomposition, Escherichia coli which is characterized by the mutation of Escherichia coli as the gene yPJD (b26n) is characterized, and for the above-mentioned catalyst system for lignin decomposition, Escherichia coli is a gene-8- 201038737 The transposon of ypjD (b2611) is characterized by insertion of a mutant strain. The method for producing an alcohol or an organic acid according to the present invention is characterized in that a lignin is added to a solution containing an alkali compound, and an alcohol and an organic acid are separated from the lignin-base compound solution. In the method for producing the above alcohols and organic acids, the alcohol is separated from the lignin-alkali compound solution by light irradiation (preferably, irradiation with q such as ultraviolet rays or sunlight). And the organic acid type is characterized in that the lignin-alkali compound solution is further subjected to the lignin-base compound solution, and then the lignin-base compound solution is separated by the lignin-base compound solution. Alcohols and organic acids are characteristic. In the method for producing the above-mentioned alcohols and organic acids, the lignin-base compound solution is subjected to the above-mentioned lignin decomposition catalyst, and then subjected to light irradiation (preferably by ultraviolet rays or sunlight). It is characterized by separating the alcohol and the organic acid from the lignin-base compound solution. The method for producing an alcohol and an organic acid according to the present invention is characterized in that, after the lignin is decomposed by the lignin, the alcohol and the organic acid are separated from the lignin. The method for producing an alcohol or an organic acid according to the present invention is characterized in that an alcohol and an organic acid are separated from the lignin by light irradiation (preferably, irradiation with ultraviolet rays or sunlight). The method for producing the above-mentioned alcohols and organic acids is carried out by irradiating the above-mentioned lignin decomposition catalyst with wood-9-201038737, and then irradiating with light (preferably by ultraviolet rays or sunlight) to obtain lignin. It is characterized by the separation of alcohols and organic acids. The method for producing the above alcohols and organic acids is characterized in that the alkali compound is at least one of KOH and NaOH. The method for producing the above alcohols and organic acids is characterized in that the alcohol is methanol and the organic acid is formic acid, acetic acid, malic acid, succinic acid or pyruvic acid. The method for producing the above alcohols and organic acids is characterized in that the separation of alcohols is carried out by distillation. The method for producing a lignin decomposition product of the present invention is a method for producing a lignin decomposition product of a low molecular weight carbon-containing compound which is produced by separating an alcohol or an organic acid according to the method for producing an alcohol or an organic acid. Characterized. The aromatic hydrocarbon-decomposing catalyst for binding an oxygen atom to a carbon atom forming a benzene ring of the present invention is characterized by containing a porphyrin. The catalyst system for the decomposition of aromatic hydrocarbons is characterized in that the porphyrin is a tetrapyrrole compound having a porphyrin ring structure obtained by culturing Escherichia coli in a medium. The catalyst system for the decomposition of aromatic hydrocarbons is characterized in that the catalyst is composed of a medium containing a tetrapyrrole compound having a porphyrin ring structure obtained by culturing Escherichia coli in a culture medium. In the above-mentioned catalyst system for aromatization of aromatic hydrocarbons, Escherichia coli which is expressed by mutation of Escherichia coli as a gene ypjD (b261 1 ) is a special -10-201038737. The above-mentioned aromatic hydrocarbon decomposition catalyst system is characterized in that a transposon (Transposon) insertion mutant strain of Escherichia coli is a gene ypjD (b261 1 ). The catalyst system for the decomposition of aromatic hydrocarbons is characterized in that the porphyrin is a tetrapyrrole compound containing a methyl group and an ethyl ester or an acetate group (propionic acid group) in the porphyrin ring. The catalyst system for the decomposition of aromatic hydrocarbons is characterized in that the porphyrin is a tetrapyrrole compound containing four methyl groups, four ethyl esters or an acetate group (propionic acid group) in the porphyrin ring. The catalyzed catalyst for the decomposition of aromatic hydrocarbons is characterized in that porphyrin is at least one selected from the group consisting of urinary sputum, protoplast, sputum, and etioporphyrin. The catalyst system for the decomposition of aromatic hydrocarbons is characterized in that porphyrin is a porphyrin having a carboxyl group in the molecule. Q The catalyst system for the decomposition of aromatic hydrocarbons is characterized in that porphyrin is a porphyrin having a total of two, four or eight carboxyl groups in the molecule. The above-mentioned aromatic hydrocarbon decomposition catalyst system is characterized in that the aromatic hydrocarbon is dioxin. The free ion ion method of the present invention is characterized in that the lignin or lignin-alkali compound solution is used to cause the lignin decomposition to act as a catalyst, and the solution is irradiated with light (preferably by ultraviolet light or sunlight). ), characterized by the release of hydrogen ions. The porphyrin system of the present invention is characterized by having a catalytic function of converting lignin into an alcohol and an organic acid -11 - 201038737. The porphyrin of the present invention is further characterized by a catalyst function having a compound which decomposes an aromatic hydrocarbon having an oxygen atom bonded to a carbon which forms a benzene ring. The porphyrin of the present invention is obtained by culturing the gene ypjD (b2611) by Escherichia coli which cannot be expressed by mutation. The catalyst for lignin decomposition of the present invention is further characterized by comprising a porphyrin obtained by culturing Escherichia coli which is incapable of expressing the gene ypjD (b2 6 11) by mutation. Advantageous Effects of Invention According to the present invention, a porphyrin having a porphyrin structure or a synthetic porphyrin having a porphyrin structure produced by using Escherichia coli can be used as a catalyst for decomposing lignin and a catalyst for decomposing aromatic hydrocarbons. The effect of the media. In the present invention, lignin is caused by a single or a combination of an alkali compound, light irradiation, and a catalyst for lignin decomposition, and an alcohol and an organic acid can be produced from lignin, and a decomposition product of a low molecular weight can be obtained, and The effect of free hydrogen ions can be achieved. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. The embodiment relates to a catalyst for decomposing an aromatic hydrocarbon which binds an oxygen atom to a carbon atom of a lignin decomposition agent and a benzene ring of the present invention, and these catalysts are contained by light irradiation and/or in an alkali solution. The porphyrin is a porphyrin having a catalytic function, and the porphyrin is preferably a tetrapyrrole compound or a synthetic p-porphyrin having a porphyrin ring structure in which Escherichia coli is cultured in a medium of -12-201038737. For example, these catalysts may be those obtained from a medium containing a tetrapyrole compound having a porphyrin ring structure obtained by culturing Escherichia coli in a culture medium, or may be a recovered or purified cell. The extract obtained by culturing the obtained cells may also be obtained. The Escherichia coli in which the above-mentioned Escherichia coli is mutated, such as the gene ypjD (b2611), exhibits a change in the expression of Escherichia coli, and the transposon (Transposon) insertion mutant of the gene ypjD (b2611) is more good. The porphyrin is preferably a tetrapyrrole compound containing a methyl group (e.g., four), an ethyl ester or an acetate group (propionic acid group) (e.g., four) in the porphyrin ring. The catalyst for lignin decomposition and the catalyst for decomposition of aromatic hydrocarbons derived from Escherichia coli according to the present invention can be produced, for example, by the following. The medium for producing the above-mentioned catalyst is only a medium capable of culturing Escherichia coli, and can be used without particular limitation. The Escherichia coli is cultured in a lean Q culture medium or a nutrient-rich medium, and the tetrapyrrole compound is separated and recovered from the medium to produce a porphyrin ring structure having a catalyst for lignin decomposition and a catalyst for decomposition of aromatic hydrocarbons. Tetrapyrrole compound. In the process of culturing and proliferating Escherichia coli in a medium, a tetrapyrrole compound is produced in Escherichia coli, and a tetrapyrrole compound is produced by recovering a tetrapyrrole compound secreted in the medium. In order to prevent a component such as a natural substance contained in the medium from becoming a barrier to the separation of the tetrapyrrole compound, it is preferred to use a lean nutrient medium, but the medium is not particularly limited. As the oligotrophic medium, it is preferred to use glucose or lactose, but it is not limited thereto -13-201038737 and the like. It is preferable that the Escherichia coli used for the production of the catalyst for lignin decomposition and the catalyst for decomposing aromatic hydrocarbons is agglomerated by the mutation of the gene ypjD (b261 1 ). For example, Escherichia coli derived from the K12 strain and the BL21 strain can be mentioned. For example, it is preferred to use Escherichia coli which is not expressed by mutation from the gene ypj D (b 2 6 1 1) of the K 1 2 strain. An Escherichia coli strain which is incapable of being expressed by mutation of the gene ypjD (b261 1 ), for example, a transposon insertion mutant of the gene ypjD (b261 1 ). This mutant is a state in which the expression of the gene ypjD (b261 1 ) is partially or completely absent. Further, the K12 strain can be obtained, for example, from National BioResource, and the BL21 strain can be obtained, for example, from Takarabio. Further, as a transposon insert of the gene ypjD (b2611), a mutant strain such as JD23504 available from National BioResource is used. For the embodiment of the present invention, Escherichia coli is first cultured in a oligotrophic medium. In this case, Escherichia coli is precultured in a medium other than a poor nutrient medium, for example, a medium such as LB medium, and it is preferred to inoculate the obtained culture in a poor nutrient medium for the present culture. Further, as the culture medium, a nutrient-rich medium other than the oligotrophic medium or a synthetic culture solution or the like can be used. For example, a synthetic culture solution of an aqueous solution obtained by adding KH2p〇4, k2hpo4, (nh4)2so4, citric acid dihydrate, glucose, and MgS〇4 may be used in the deionized water. It is only a medium which can increase the cells of Escherichia coli, and it is not particularly limited as long as it is any one. The culture conditions of Escherichia coli are 'the general conditions for Escherichia coli. This is, for example, when the medium is cultured in the cultivar -14-201038737 culture medium after pre-cultivation of Escherichia coli, and the culture conditions are the same for any of the culture conditions. For example, using LB medium, after culturing at a temperature of 15 ° C to 40 ° C for 6 hours to 24 hours, 'the resulting cell suspension is placed in a poor nutrient medium for 2 (TC ~ 40 ° C temperature) The culture is carried out for 12 hours to 96 hours. Thereby, the cells can be proliferated in the medium to obtain a culture (product) having a specific color tone of the tetrapyrole compound. Next, the culture is separated as follows. Specifically, the clarified liquid obtained by centrifuging the culture is filtered, and then, for example, an ion exchange resin column or a reverse phase column is used to adsorb the tetrapyrrole compound from the filtrate. For example, the culture is isolated. The cells were precipitated by a centrifugal separator to obtain a clear liquid containing the culture (product). Next, the clear liquid was filtered through a filter having a predetermined pore size (for example, 0.22 #m), and then adsorbed to the ion exchange resin using the above-mentioned column. For example, after the product is eluted from the ion exchange resin by using a 20% acetonitrile-0.1% trifluoroacetic acid solution or the like, Q is freeze-dried, and the dissolution at this time is used for The solvent of the organic solvent contains an acid or a base solution. In the embodiment of the present invention, one or two or more kinds of tetrapyrrole compounds can be obtained, and for example, a milligram to several tens of mg of a tetrapyrrole compound can be obtained from a cell suspension of 500 mL. When the product separated by the above operation was analyzed by NMR (Nuclear Magnetic Resonance) or the like, it was confirmed that the tetrapyrrole compound was contained. Further, when the product was analyzed by absorbance, it was found that the dye had absorption in a specific wavelength region. A compound similar to chlorophyll, protoglobin or ruthenium, which exhibits a bimodal peak, -15-201038737. Such a pigment compound is used as a photocatalyst or electron transporter that causes electrons to be excited by light. In addition, in aqueous solution, or in the cell membrane and redox reaction, it is also possible to consider the function of the battery. As described above, porphyrins such as porphin and porphyrin can be produced by using Escherichia coli. a tetrapyridyl compound, as in the case of chemical synthesis, a device for the compound of the purpose or If the medium is necessary and there is no need to use a solvent, there are fewer concerns about the bad influence on the environment. Moreover, when Escherichia coli is cultured, it is not necessary to add a precursor of a tetrapyrrole compound such as 5-aminolevulinic acid in the culture medium (Special Kaiping 5- U.S. Patent No. 24,493, and the tetrapyrrole compound is recovered and secreted in the culture medium, and it is not required to be taken from the cells (Japanese Patent Laid-Open Publication No. Hei 5-9 1 866). That is, the culture of Escherichia coli or the recovery of tetrapyrrole compounds. The tetrapyrrole compound can be easily produced without a specific compound or device. The tetrapyrrole compound thus obtained can be used in various industrial fields such as medical, food, and electronics. For the above-mentioned separation of tetrapyrrole compounds from culture, Catalyst for decomposition of lignin and a catalyst for decomposition of aromatic hydrocarbons. It is preferred to use a compound recovered from the culture, but the culture or the cells obtained by the culture may contain the tetrapyrrole compound, and the culture may be used as a catalyst for lignin decomposition or a catalyst for decomposition of aromatic hydrocarbons. use. The catalyst for lignin decomposition and the catalyst for decomposing aromatic hydrocarbons which can be used in the present invention, as the other synthetic porphyrin, may, for example, be selected from the group consisting of protoporphyrin, urinary porphyrin, coproporphyrin, and primary purple. At least one kind of quality. However, aeioporphyrin cannot decompose lignin. As the porphyrin, -16-201038737 In the following examples, porphyrin IX (manufactured by ALDRICH) containing two carboxyl groups in the molecule and urinary porphyrin 1 (manufactured by SIGMA) containing 8 carboxyl groups in the molecule were used. The fecal porphyrin 1 (manufactured by ALDRICH Co., Ltd.) having four carboxyl groups and the primary purpurin (manufactured by ALDRICH Co., Ltd.) having no carboxyl group in the molecule. Similarly to the porphyrin obtained by culturing the above Escherichia coli, the porphyrin does not have a transition metal atom coordination at the center of the porphyrin ring. Next, an embodiment of the method for producing the alcohol and the organic acid of the present invention will be described. The alcohol and the organic acid in the present invention can be produced by using lignin alone or in combination with an alkali compound, light irradiation, or the above-mentioned lignin decomposition catalyst. In other words, the alcohol such as methanol is, for example, (1) a solution containing at least one alkali compound selected from the group consisting of KOH and NaOH, and the lignin-base compound solution is separated from the alcohol by distillation or the like, for example. 2) A solution containing lignin in which the above-mentioned alkali compound is added, and ultraviolet rays are used as the lignin-base compound solution (for example, an ENF type (260c/j, or 2800c/j, etc., manufactured by Q Spectronix) can be used as the ultraviolet ray. ) or ultraviolet light of an ultraviolet lamp such as UVL-56Hand He 1 d manufactured by UVP, or light having a wide wavelength region such as sunlight, after irradiation for a predetermined period of time, after the irradiated lignin-alkali compound solution, for example, by distillation or the like a method for efficiently separating an alcohol, and (3) adding a solution containing the alkali compound to the lignin, and performing the lignin decomposition catalyst on the lignin-base compound solution at a predetermined temperature for a predetermined period of time. After the action, the alcohol can be efficiently separated from the solution by distillation, for example, and (4) the solution containing the above-mentioned alkali compound added to the lignin for the lignin-basic compound-17-2 01038737 The solution of the above-mentioned lignin decomposition catalyst is subjected to a predetermined temperature, and the solution is irradiated with ultraviolet light or light of the solar region for a predetermined hour. 'Secondly, the solution of the compound is irradiated, for example, by distillation, etc.' After the lignin is subjected to the action of the lignin decomposition catalyst for a predetermined period of time, the solution is subjected to vaporization to separate the alcohol, for example, and (6) the lignin is irradiated with light of a broad wavelength region of ultraviolet light for a predetermined period of time. By distillation or the like, the alcohol can be efficiently separated, and the lignin decomposing catalyst can be irradiated with light at a predetermined temperature for 5 hours, and then the solution is irradiated with ultraviolet or solar light for a predetermined period of time. It is efficient to pass through the compound solution, for example, by distillation or the like. When the light irradiation is carried out, it is preferable to contact the gas containing lignin or oxygen, oxygen and/or nitrogen, etc., and to effectively exhibit the catalytic function of the porphyrin in the environment. Degree 2.5mg/mL, Yulin 50//g/mL (mass ratio 5 mg can be used in an amount of 0.2 to 0.5 mL of oxygen. Further, formic acid, acetic acid, malic acid, succinic acid and the like are the same as the above alcohols. The lignin can be used as the lignin used in the present invention, and the purity of the impurities such as reducing sugar or cellulose is not particularly used. Catalog No. 47 1 003 manufactured by SIGMA Co., Ltd., manufactured by ALDRICH, catalog No. 47 1 046, sub-degrees: The wavelength of the light is measured at a wide wavelength [after the lignin-alkali 1 separated alcohol, (5 at a fixed temperature, etc., can be efficient or sunlight, etc., by the solution, for example: 7) When a lignin-alkali separated alcohol having a wide wavelength region, such as a predetermined time, is used to produce an aqueous solution and an air containing gas, for example, when lignin is concentrated: 1), per plant pyruvic acid, etc. Organic acid separation. Do not limit, for example, high-yield products (for example, 60,000; 12,000). -18- 201038737 Products with reduced purity and slightly lower purity (for example, catalogue No. 47 1 03 8 made by SIGMA) , molecular weight 52,000), and insoluble The product (for example, catalog No. 3 70967 manufactured by ALDRICH Co., Ltd.), etc. The present invention is capable of separating almost all alcohols such as methanol and formic acid, acetic acid, malic acid, succinic acid, pyruvic acid, etc. from all of these lignin. The organic acid is produced, that is, the lignin can be produced by separating the alcohol and the organic acid by the present invention, regardless of the presence of the impurity, the average molecular weight, or the solubility in water. The solution of the alkali compound is not particularly limited. For example, KOH and/or NaOH of about 0.0025 M to 0.05 M may be used. The separation efficiency of the alcohol and the organic acid may be high, and the solution of the alkali compound is not limited in the concentration range. In one embodiment of the catalyst for decomposing an aromatic hydrocarbon in which an oxygen atom is bonded to a carbon atom of a benzene ring, the catalyst is the same as the catalyst for lignin decomposition by the porphyrin, and the detailed description is as follows. The aromatic hydrocarbon which acts on the catalyst may, for example, be a dioxin or a dioxin-like compound. The dioxin contains, for example, polychlorinated diphenyl dioxide. PCDD), polychlorinated dibenzofuran (PCDF), etc., such as polychlorinated biphenyl (Dioxin-like PCB), etc., in the dioxin-like compound, etc. The catalyst for decomposing aromatic hydrocarbons of the present invention is obtained by decomposition of these dioxins. Further, in another embodiment of the present invention, the lignin free radical ion is added to the lignin-base compound solution containing the pyrrole compound derived from the above Escherichia coli to form a porphyrin or a synthetic卟- 而成 -19- 201038737 The lignin decomposition catalyst 'free hydrogen ion' can be used for photodegradation of lignin. Further, in another embodiment of the present invention, the method for producing an alcohol and an organic acid can recover a low molecular weight carbon-containing compound which is a lignin decomposition product produced by separating an alcohol or an organic acid. The present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the scope of the invention. The manufacturing examples and examples of the present invention will be described in detail below. (Production Example 1) As described above, the lignin can be produced by adding a porphyrin (pyrrole compound) as a lignin decomposition catalyst to produce an alcohol and an organic acid, and decomposing the lignin to obtain a decomposition product. At the same time 'free hydrogen ions. Further, a tetrapyrrole compound or a synthetic porphyrin having a porphyrin structure is effective as a catalyst for decomposition of an aromatic hydrocarbon such as dioxin. In this case, as the porphyrin, for example, a biological method using Escherichia coli can be used. In the production example, a production example using a pyrrole compound of Escherichia coli will be described. First, a transposon (Transposon) from the E. coli gene ypjD (b2611) was inserted into a mutant strain (National).

BioResource JD23504) cells in 2 mL of LB medium (Bacto-tryptone: 1% 'Bacto-yeast extract: 0. 5%, NaCl: 0. In 5%), pre-culture was carried out for 12 hours at 37t. 1 mL of the obtained cell suspension was added to 1 L of deionized water, KH2P04 was 9 g, Κ2ΗΡ04 was 2 1 g, (NH4)2S04 was 2 g, citric acid dihydrate was 1 g -20-201038737, and glucose was 3. 6 g and MgS04 were obtained in 500 mL of an aqueous solution of 200 mg, and the main culture was carried out at 37 ° C for 24 hours. The color of the obtained culture solution was "colorless" at the time of starting the main culture, but became pink after 24 hours. The culture solution was subjected to centrifugation through a centrifugal separator. The resulting clear liquid was filtered through a filter having a pore size of 〇 2 2 v m . Next, after the filtrate is passed through the anion exchange resin, the culture of the resin is adsorbed as 20% acetonitrile-rhodium.  The 1% trifluoroacetic acid solution was dissolved in 0 rows, and the dissolved product was freeze-dried. Thereby, a product with a pink color is obtained. This product was confirmed to have a tetralide compound having the structure shown in Fig. 1 when subjected to various machine analyses described below. The symbols A to G in Fig. 1 are symbols corresponding to the 13C NMR spectrum shown in Fig. 4, and are the same for the other drawings. Further, when the product was analyzed by NMR, it was confirmed that a tetra-pyrrol compound was contained. Further, potassium (K) was detected by ICP (Inductively Coupled Plasma) mass spectrometry and recovered as a compound which forms K and an ion junction Q or a complex. Further, when the absorbance photometric analysis was carried out, as shown in Fig. 2, the porphyrin-specific bimodal peak containing the Soret band was confirmed. In Fig. 2, there are peaks at wavelengths of 3 95 nm and 549 nm. From this, it was confirmed that the product was a free electron-moving organic pigment. The tetrapyrrole compound obtained above was dissolved in a dissimilar solvent (sample 1 and sample 2), and subjected to secondary NMR measurement (COSY 'NOESY, HSQC ' HMBC ), and the spectrum was analyzed and subjected to structural analysis. With respect to sample 1, the sample was dissolved in CD3OD, and N M R measurement was carried out under the following conditions. 201038737 • Device: INOVA500 (made by Varian) • Resonance frequency: 499. 8MHz (4) • Benchmark: 3. 31ppm (CD2HOD, *H NMR) 49 _42 1 ppm (CD3OD, 13 C NMR) • Cumulative number: ΑΝΜΙΐΟό times), 13CNMR (53428), COSY (16 times), NOESY (8 times), HSQC (32 times), HMBC (128 times) • Other: The mixing time of NOESY is set to 400msec. Further, regarding the sample 2, the sample was dissolved in CD3CN: D20: CD3CO〇d=9〇: 1〇: 0. The solvent of 1 was subjected to Nmr measurement under the following conditions. • Device: INOVA600 (manufactured by Varian) • Resonance frequency: 599. 8MHz (j) • Benchmark: 1 . 92ppm (CD2HCN, H NMR) 1 . 28ppm (CD3CN > 13C NMR) • Cumulative times: *11X1^11 (64 times), 13CNMR (50000), C0SY (16 times), NOESY (16 times), HSQC (32 times), HMBC (128 times) • Other: The mixing time of NOESY is set to 400msec. Structural Analysis of Sample 1 : Fig. 3 shows a 1H NMR spectrum (solvent··CD3OD). The result is at 10·0 〜 l〇. 5ppm near (d), 4. 3ppm near (f), 3. 6ppm with ^ ( , and 3. Nearly 2 ppm (e) was observed to be a signal from the target -22-201038737. The signal strength ratio is approximately 1:2:3:2. The d~g is the same on all other faces. Figure 4 shows the 13C NMR spectrum. It is presumed to be the fragrance of the signals from B and C. Among them, the ifi NMR d signal is generally a characteristic signal that cannot be seen by chemical shift 値, and if it is considered as an aromatic compound, it may be a porphyrin skeleton. As described below, when the binary NMR spectrum (Fig. 0 5 to 9) is analyzed as a porphyrin, it can be analyzed without contradiction. Further, a compound similar to the putative structure of Fig. 1 is given by J.  Org.  Chem.  Vol.  164, No-21, 1999 (7973-7982) It has been reported that the chemical shift 値 of 1H NMR is quite consistent, so it is presumed that the porphyrin structure is appropriate. The analysis of the binary NMR will be described below. Figure 5 shows the HSQC spectrum. The HSQC spectrum is an assay for detecting Wch. The analysis results are shown in the figure. For the proton signal, the number is recorded on the large text of the direct-bonded carbon number. © Figure 6 shows the COSY spectrum. The COSY spectrum is an assay for detecting spin coupling between 1H-4. The analysis results show that f and e are spin couplings, and it is highly probable that the signal intensity ratio and the chemical shift of F and E are -CH2-CH2-X. Wherein X represents an undetermined component of unknown structure. Figure 7 shows the HMBC spectrum. The HMBC spectrum is obtained by measuring the JnCH (η = 2 to 4 degree) to obtain a heterogeneous nuclear distantly bound correlation spectrum. The spectrum is analyzed to obtain (e, A), (e - B), (e - F), (g, B), (g, C), (f, A), (f, B), ( f, C), (f, E), etc. These correlations are not inconsistent with the putative knot -23- 201038737 shown in Figure 1. Figures 8 and 9 show the NOESY spectrum. The NOESY spectrum is a measurement method for detecting magnetization exchange, and the distance between the nuclear spins can be obtained by the magnetization movement of the gradual relaxation. As a result of the analysis of the spectrum, NOE correlation was observed for (g, e), (f, g), (f, e), (d, f), (d, e), (d, g). These NOE correlations are those that support the putative structure shown in Figure 1. Sample 2 related structure analysis: Figure 10 shows the 1H NMR spectrum, and Figure 11 shows the l3C NMR spectrum (solvent: CD3CN: D20: CD3COOD = 90: 10: 0. 1 ). The signal surrounded by the square frame in Fig. ίο indicates the impurity. As a result of comparison with the spectrum of the above sample 1, it was estimated that the structures of the main components were the same. This can also be supported by the analysis results of the respective spectra of COSY, NOESY, HSQC, and HMBC. 〇 Figure 12 shows the NOESY spectrum of the expanded sample 2. Since the d protons are separated into four kinds, the numbers from dl to d4 are given from the low magnetic field (the smaller number). Inductive NOE related as follows. • dl and d4 are simultaneously associated with methyl and -CH2-CH2-X for NOE. . D2 is only related to -CH2-CH2-X is NOE. • d3 is only related to methylation as NOE. This is related to the fact that the methyl groups are not specifically observed or the -CH^CHa-X is related to each other, and the side chain configuration of Fig. 1 is obtained. The number of the 13C signal and signal is observed in almost the same area. -24- 201038737 The signal is assigned a number. The reason for this is that the skeleton of the porphyrin is a repeating structure, so it is difficult to classify it in detail. Regarding the number of repetitions, four methyl groups were observed, so it is estimated that there are four. As described above, from the analysis results of Samples 1 and 2, the structure of Fig. i can be obtained. However, the total of the methyl group of the side chain and the -CHz-CHz-X may be four, and the additional portion as shown in FIG. 1 does not contradict the data, and is not limited to the one shown in FIG. Additional location. Secondly, a review is made for the X portion corresponding to -C Η2 - C Η2 - X. The following analysis was carried out for the product obtained above. (1) Qualitative analysis by thermal decomposition GC/MS······························································································· The gas chromatogram/mass analyzer (hereinafter referred to as "GC/MS") described is subjected to separation analysis. Device name: HP5973 model manufactured by Agilent Technologies with a selective selection detector HP6890 gas color layer FRONTIER LAB P Y-202 0i D Heating furnace type thermal decomposition device measurement sample: 2mg of sample added AcCN lmL solution was injected In the sample cup. 5 mL, and then flushed with nitrogen to remove AcCN. -25- 201038737 (2) Analysis by electric spray-mass analyzer: To investigate the molecular weight of the components in the solution, analyze it by the electric spray-mass analyzer (hereinafter referred to as "ESI-MS") described below. . Device name: Applied Biosystems Qstar introduction solvent · AcCN / 0. 05% formic acid aqueous solution (50/50) Introduction method: Directly guide the measurement solution using a loop wire of 30 // L. Measurement mode: P 〇sitivemode Determination solution: 2 mg of AcCN 1 mL solution in a small glass bottle will be added to the sample. After a small amount, it was diluted with the introduction solvent to about 100 ppm. Carbon dioxide carbon was detected from the sample by the analysis of the above GC/MS. Further, as a result of the analysis by the above ESI-MS (Fig. 14), fragment ions having a molecular weight of 59 (four peaks) were detected, and it was confirmed that the fragment contained an ethyl ester or an acetate group (propionic acid group). Further, the product was analyzed by thermal decomposition GC-MS, as shown in Fig. 15, and the main component was a pyrrole compound. This can be confirmed by comparing the mass spectrum of each component with the data base, and the structure containing the pyrrole ring in the molecule can be confirmed. Further, for the detailed molecular weight, as shown in Fig. 13, an ion of an additional hydrogen ion is detected to obtain a molecular weight of 655·2760-1. 0078 = 654. 2682. From the above, it was confirmed that the side chain contained four ethyl esters or an acetate group (propionic acid group), the molecular weight of four methyl groups was 654, and the porphyrin compound of the formula C36H3808N4 was confirmed to have no transition metal at the center of the porphyrin ring. [Embodiment] -26-201038737 [Example 1] As a lignin, a product having a high purity such as a reducing sugar or cellulose and having a high purity (manufactured by Sigmal Co., Ltd., catalogue ν〇.471003, molecular weight: 60,000) was used. Will contain this lignin: 2. 5mg/mL, 0. Μ ΚΟΗ 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及The test tube was irradiated with ultraviolet light for 1 hour using an ENF 0 type ultraviolet lamp manufactured by Spectronix. Thereafter, the mixture was heated at 80 ° C for 60 minutes, and the volatile gas was analyzed using Shimadzu GC/MS QP-2010, column D B - W A X , and methanol of 170 μg / m L was measured. At this time, the formic acid was obtained as 140 // g/mL, the malic acid was 25 // g/mL, and the acetic acid was 19 #吕/»1[, and the acid was 5. 4//§/1111^, pyruvic acid is 6. 2#£/1111^. At this time, based on the weight of dry lignin, a methanol equivalent of 6.8 wt% is obtained. 6 wt% of formic acid. In addition, as a lignin, a product having a high degree of purity without containing impurities such as reducing sugar or cellulose (made by Aldrich Co., Ltd., Catalog No.) is used. 471046, molecular weight 12 > ° 〇〇), a product containing a reducing sugar and having a slightly lower purity (manufactured by Sigmal Corporation) Catalog No. 471038, molecular weight 52,000), and products that are insoluble in water (made by Aldrich, catalog No.) 3 70967 ), repeating the above process @ ' gives the same degree of the amount of methanol and the amount of the above organic acid. That is, irrespective of the presence of impurities in the lignin used, the average molecular weight of lignin, and the solubility of lignin in water, it was found that alcohols and organic acids can be separated from lignin. Further, when sunlight is used instead of ultraviolet light, the above process is repeated, and -27-201038737 is obtained as the same result as the amount of methanol and the amount of organic acid. A sample of the reaction liquid obtained by irradiation with ultraviolet light as described above was subjected to HPLC (High Speed Liquid Chromatography) and analyzed using a colloidal filter column. As a reference, the solution before ultraviolet irradiation was also analyzed. The results of the analysis showed that the lignin was detected in the absorption of 3 1 Onm before irradiation, and the peak of dissolution at 7-9 min was detected. However, when porphyrin was added to lignin and converted into methanol or organic acid by ultraviolet light, as described above, In the absorption of 310 nm, the peak area of the dissolved lignin at 7-9 min was reduced to 20%. That is, when it is known that porphyrin is added to lignin and irradiated with ultraviolet light, 80% of lignin is decomposed. The decomposition product is filtered by colloid to elute a lower molecular weight fraction. Therefore, methanol equivalent to about 8.5 wt% of methanol and about 7 wt% of formic acid can be obtained on the basis of the decomposed lignin. [Example 2] As a lignin, a product having high purity without containing impurities such as reducing sugar or cellulose (made by Si gmal, catalog No.) was used. 471003, molecular weight 60, 〇〇〇). Will contain this lignin·· 2. 5mg/mL, 0. 05M KOH, and porphyrin IX (manufactured by ALDRICH Co., Ltd.) containing two carboxyl groups in the molecule of the synthetic porphyrin, urinary porphyrin I (manufactured by SIGMA) having eight carboxyl groups in the molecule, and four carboxyl groups in the molecule 1 mL of each of 5 〇//g/mL of the coproporphyrin I (manufactured by ALDRICH Co., Ltd.) was placed in a light-transmissive cylindrical test tube having a degree of Eppendorf tube made of polypropylene, and an ENF type manufactured by Spectronix Co., Ltd. was used. The ultraviolet lamp was irradiated with ultraviolet light for 12 hours. The resulting reaction solution was heated at 80 ° C for 60 minutes, and the volatilized -28-201038737 gas was analyzed using Shimadzu GC/MS QP-2010' column DB-WAX. After repeating the above operation several times, methanol and formic acid which were almost the same amount as in the case of Example 1 were obtained on the basis of the weight of dry lignin based on the conditions of the original porphyrin ι, urinary porphyrin 1, and porphyrin I. Namely, about 6 to 9 wt% is converted to methanol 'about 2 to 4 wt% based on the weight of dry lignin to be converted into formic acid. A sample of each reaction liquid obtained as described above was analyzed by HPLC (High Speed ◎ Liquid Chromatography) using a colloidal filter column. As a control, the solution before ultraviolet irradiation was also analyzed. As a result of the analysis, before the irradiation, the lignin was detected to absorb the peak at 7-9 min in the light absorption at 310 nm, but the lignin was added to the above-mentioned porphyrins to convert ultraviolet light into alcohol and organic acid (formic acid, etc.). In the reaction solution, 'pro-porphyrin IX was reduced to about 60%, urinary porphyrin I was reduced to about 15%, and coproporphyrin I was reduced to about 20%. That is, it is known that when porphyrin is added to lignin and irradiated with ultraviolet light, the protoporphyrin IX is decomposed by about Q 40%, and the case of urinary porphyrin I is decomposed by about 85 %, and the case of coproporphyrin I is To decompose about 80% of lignin. The decomposition product is soluble in the lower molecular weight fraction by colloidal filtration. Further, as a lignin, a product having no purity such as reducing sugar or cellulose and having high purity (Aldrich, catalog No.) is used. 47〗 046, molecular weight 1 2,0 00 ), a product containing a reducing sugar and a slightly lower purity (Sigmal, catalog No. 471038, molecular weight 52,000), and products that are insoluble in water (made by Aldrich, catalog No.) 3 70967), after repeating the above process, the use of synthetic porphyrins also results in the same process -29 - 201038737 degrees for the decomposition of lignin. That is, regardless of the presence of impurities in the lignin used, the average molecular weight of lignin, or the solubility of lignin in water, the same degree of lignin can be decomposed. And when the sunlight is used instead of ultraviolet light, the same result as the decomposition of lignin can be obtained after repeating the above process. [Example 3] As a lignin, a product having high purity without containing impurities such as reducing sugar or cellulose (made by Si gmal, catalog No.) was used. 471003, molecular weight 60,000). Will contain this lignin: 1 . 8mg/mL, 0. 05M KOH, and 31 1111^1 company of the original porphyrin 1 乂 (catalog >} 〇. 258385-10) : 50 mL of a solution of 50 #g/mL, placed in a light-transmissive cylindrical test tube of a degree of Eppendorf tube made of polypropylene, irradiated with ultraviolet light by an ENF-type ultraviolet lamp manufactured by Spectronix. hour. Thereafter, the mixture was heated at 80 ° C for 60 minutes, and when volatilized gas was analyzed using Shimadzu GC/MS QP-2010 and column DB-WAX, 54 #g/mL of methanol was measured. That is, on the basis of the weight of dry lignin, 3. 0% by weight of methanol 〇 Further, as a lignin, a product having high purity, such as reducing sugar or cellulose, is used (Aldrich, catalog No.). 471046, a molecular weight of 12,000), a product containing a reducing sugar and a slightly lower purity (manufactured by Sigmal, catalog No.). 471038, molecular weight 52,000), and products that are insoluble in water (made by Aldrich, catalog No.) 370967), after repeating the above process, the same degree of methanol was obtained. Namely, it was found that the alcohol was separated from the lignin by the presence of impurities, the average molecular weight of the lignin, or the solubility in water of the lignin used in the use of -30-201038737. And when the sunlight is used instead of ultraviolet light, the above process is repeated until the same result as the amount of methanol. [Example 4] As a lignin, a product containing no impurities such as reducing sugar or cellulose, 0 (manufactured by Sigmal Co., Ltd., Catalog No.) was used. 47 1 003, molecular weight). Will contain this lignin: 7. 5mg/mL and 0. 05M KOH lmL 'Cylindrical tube placed in a light with a degree of Eppendorf tube made of polypropylene' is heated at 8 〇t for 60 minutes, and volatilized using Shimadzu GC/MS QP-2010, column DB-WAX 93 #g/mL of methanol was determined. Namely, 1·24% by weight of methanol can be obtained by drying the weight of lignin. Also, as a lignin, a product having a high degree of impurities such as reducing sugar or cellulose (made by Aldrich Co., Ltd., catalogue N〇. 471 046, 12, 〇〇0), and products that are insoluble in water (Aldrich Company No. 3 70967 ) ' After repeating the above process, the result as a degree of methanol was obtained. That is, it is known that the average molecular weight of the impurities present in the lignin used or the solubility of the lignin in water is irrelevant, and the same quality of methanol is produced. [Example 5] As a lignin, an impurity such as reducing sugar or cellulose was not used, and after lignin, a gas having a purity of 60,000 was obtained, and the gas was precipitated, and the standard was pure, and the molecular weight was the same. It can be made of wood with high purity -31 - 201038737 (made by Sigmal, catalog No. 471003, molecular weight 60,000). Will contain the lignin· 7. 5mg/mL and 0. A 10 mL solution of 05 M KOH was placed in a light-transmissive cylindrical test tube having a degree of Eppendorf tube, and irradiated with ultraviolet light for 24 hours using an ENF type ultraviolet lamp manufactured by Spectronix. Thereafter, the mixture was heated at 80 ° C for 60 minutes, and when the volatile gas was analyzed using Shimadzu GC/MS QP-2010 and column DB-WAX, 1 50 /i g/mL of methanol was measured. Namely, 2% by weight of methanol based on the weight of dry lignin can be obtained. Further, as a lignin, a product having no purity such as reducing sugar or cellulose and having high purity (Aldrich, catalog No.) is used. 47 1 046, molecular weight 1 2,0 00 ), and products not dissolved in water (made by Aldrich, catalogue NO.) 3 70967 ), after repeating the above process, the result is the same as the amount of methanol. Namely, it was found that the same degree of methanol was produced from lignin regardless of the presence of impurities in the lignin used, the average molecular weight of the lignin, or the solubility of lignin in water. And when the sunlight is used instead of ultraviolet light, the same result as the amount of methanol is obtained after repeating the above process. [Example 6] As a lignin, a product containing no impurities such as reducing sugar or cellulose and having high purity (manufactured by Sigmal Co., Ltd., Catalog No.) was used. 471003, molecular weight 60,000). Will contain this lignin: 2. 5mg/mL, 0. 05M KOH, and the solution obtained according to the above-mentioned preparation example 1 : 2 m yg / m L of solution 1 m L, placed in a light-transmissive cylindrical test tube-32- with a polypropylene Eppendorf tube 201038737, using an ENF-type ultraviolet lamp manufactured by Spectr〇nix, irradiated with ultraviolet light for 12 hours. Thereafter, the mixture was heated at 80 ° C for 60 minutes, and the volatilized gas was analyzed using Shimadzu GC/MS QP-2010, column DB-WAX, and 16 ng/mL of methanol was measured. That is, on the basis of the weight of dry lignin, 6. 4% by weight of methanol. It was found that by further adding a porphyrin as a photocatalyst to the lignin-alkali compound solution, the amount of methanol produced from lignin can be dramatically promoted. 0. As a lignin, a product containing no impurities such as reducing sugar or cellulose and having high purity (made by Aldrich Co., Ltd., Catalog No.) 471046, molecular weight 1 2,000 ), and products that are insoluble in water (made by Aldrich, catalog No.) 37〇967), after repeating the above process, the results were obtained as the same amount of methanol. That is, it was found that the same degree of methanol can be produced from lignin regardless of the presence of impurities in the lignin used, the average molecular weight of the lignin, or the solubility of lignin in water. And when the sunlight is used instead of ultraviolet light, the same result is obtained by repeating the above process and making Q the amount of methanol. [Example 7] As a lignin, a product having high purity without containing impurities such as reducing sugar or cellulose (made by Si gmal, catalog No.) was used. 471003, molecular weight 60,000). Will have 3 of this lignin: 2. 1 mL of a 5 mg/mL solution was placed in a light-transmissive cylindrical tube holding a polypropylene-like EPpend〇rf tube, and ultraviolet light was irradiated for 24 hours using an enf type ultraviolet lamp manufactured by Spectronix. Thereafter, the mixture was heated at 8 Torr for 60 minutes, and the volatilized gas was analyzed for -33-201038737 using Shimadzu GC/MS QP-2010, column DB-WAX, and methanol of 21 // g/mL was determined. That is, it can be obtained by the weight of dry lignin. 8 4% by weight of methanol. Further, as a lignin, a product having no purity such as reducing sugar or cellulose and having high purity (made by Aldrich Co., Ltd., Catalog No.) is used. 47 1 046, molecular 毚 1 2,0 0 0 ), and a product which is insoluble in water (manufactured by A1 dri ch Co., Ltd., catalogue 33 70967), and after repeating the above process, the same amount of methanol was obtained. Namely, it was found that the same degree of methanol was obtained from lignin regardless of the presence of impurities in the lignin used, the average molecular weight of the lignin, and the solubility of lignin to water. Further, when sunlight is used instead of ultraviolet light, the same result is obtained for the amount of methanol after repeating the above process. [Example 8] In the present embodiment, the decomposition treatment method of the aromatic hydrocarbon decomposition catalyst of the present invention will be described with respect to the aromatic hydrocarbon to which an oxygen atom is bonded to the benzene ring. The photodecomposition was carried out using Remazol Brilliant Blue (RBBR; manufactured by SIGMA Co., Ltd.) containing a compound having an aromatic hydrocarbon bonded to an oxygen atom in a benzene ring. The RBBR is a similar test drug used as an indicator for decomposing dioxin. Will contain RBBR: 250pg/mL, 0. 05 M KOH, and each of 25 MPa/mL of the porphyrin, protoporphyrin IX (manufactured by ALDRICH), urinary porphyrin I (manufactured by SIGMA), and manure porphyrin ICALDRICH) obtained in the above Production Example 1. Solution (using 30% acetonitrile as solvent, -34- 201038737 0. 1 mL of 1% trifluoroacetic acid, 60% methanol) was placed in a light-transmissive cylindrical test tube of a polypropylene-made Eppendorf tube, and irradiated with ultraviolet light for 2 hours using an ENF-type ultraviolet lamp manufactured by Spectronix. As a result, in the case of using any porphyrin and a solvent, it was found that the blue tone of the RBBR disappeared and the RBBR was decomposed. Further, when sunlight is used instead of ultraviolet light, the decomposition of RBBR can be confirmed by repeating the above process. [Example 9] In the present example, the photodecomposition was carried out using cyanoxylene (manufactured by Takara Co., Ltd.) and bromophenol blue (manufactured by Takara Co., Ltd.) containing a compound having an aromatic hydrocarbon bonded to an oxygen atom on a benzene ring. . Will contain cyanoxylene: 5mg/mL and bromoindigo: 5mg/mL, 0. 05M KOH, and porphyrin, protoporphyrin IX (manufactured by ALDRICH Co., Ltd.), urinary porphyrin I (manufactured by SIGMA Co., Ltd.), Q coproporphyrin I (manufactured by ALDRICH Co., Ltd.), and primrose (ALDRICH) obtained according to the above Production Example 1. Each company's 40) g/mL solution (using 30% acetonitrile as solvent, 0. 1 mL of 1% difluoroacetic acid was placed in a light-transmissive cylindrical tube holding a polypropylene Eppendorf tube, and irradiated with ultraviolet light for 2 hours using an ENF type ultraviolet lamp manufactured by Spectronix. As a result, when any of the porphyrins and the solvent were used, the blue and yellow hue of cyanoxylene and bromophenol blue disappeared, and it was found that cyanoxylene and bromophenol blue were decomposed. Further, when solar light is used instead of ultraviolet light, the decomposition of cyanoxylene and bromophenol blue can be confirmed by repeating the above process. -35-201038737 [Example ι〇] In the present embodiment, the lignin decomposition catalyst of the present invention is used as a lignin in the method of lignin free hydrogen ions, and does not contain impurities such as reducing sugar cellulose. High product (made by sigmal company, catalog No. 471003, molecular weight 60,000). Will contain the lignin 2. 5 mg/mL, and the porphyrin obtained according to the above Production Example 1 : 50 mL of a solution of 50 // g/mL, placed in a light-transmissive cylindrical test tube having a degree of Eppendorf tube made of polypropylene, and manufactured by Spectronix Co., Ltd. The ENF type ultraviolet lamp was irradiated with ultraviolet light for 12 hours. As a result, the pH of the lignin reaction solution decreased from 9.2 to 6. 4. Therefore, it is known that lignin can free hydrogen ions. Further, as a lignin, a product having high purity, such as a reducing sugar or cellulose, is used (made by Aldrich Co., Ltd., catalogue Νο. 47 1 046, molecular weight 1 2,000 ), a product containing a reducing sugar and a slightly lower purity (manufactured by Sigmai, catalog No.) 471038, molecular weight 52,000), and products that are insoluble in water (made by Aldrich, catalog No. 3 70967), repeating the above process, the same free hydrogen ion. Namely, it is known that there is no impurity in the lignin to be used, the average molecular weight of lignin, or the solubility of lignin in water, and hydrogen ions which are freely liberated by lignin. And when the sunlight is used instead of ultraviolet light, the same result is obtained after repeating the above process. [Example 1 1 1 -36- 201038737 As a lignin, a product having high purity without impurities such as reducing sugar or cellulose (manufactured by Sigmal Co., Ltd., Catalog No.) was used. 471003, molecular weight 60,000). Will contain this lignin: 2. 5mg/mL, 2. 5 mM KOH, and 1 ml of a solution of 50 yg / m L obtained in the above-mentioned Production Example 1 and placed in a light-transmissive cylindrical test tube of a degree of Eppendorf tube made of polypropylene 'made by Spectronix Co., Ltd. The ENF type ultraviolet lamp is irradiated with ultraviolet light for 12 hours. The sample was analyzed by HP LC (High Speed Liquid Chromatography), 0 using a colloidal filter column. As a control, the solution before ultraviolet irradiation was also analyzed. The analysis results show that the peak dissolved in 7-9 min is detected in the absorption of light at a wavelength of 10 10 nm before irradiation, but the porphyrin is added to the lignin, and when irradiated with ultraviolet light, in the absorption at 310 nm, at 7- The peak area of the lignin dissolved in 9 min was reduced to 78%. That is, it is known that porphyrin is added to lignin, and when irradiated with ultraviolet light, 22% of the mass can be decomposed. Moreover, the pH of the lignin reaction solution is from 10. 7 dropped to 6. 2. Therefore, free hydrogen ions from lignin are known. In addition, as a lignin, a product having a high purity, such as a reducing sugar or cellulose, is used (Aldrich's catalogue No. 471 046, molecular weight 1 2,000 ), a product containing a reducing sugar and a slightly lower purity (manufactured by Sigmal, catalog No.) 471 0 38, molecular weight 52,000), and products that are insoluble in water (made by Aldrich, catalog No.) 3 70967 ), after repeating the above process, the same result is obtained. That is, it is known that, regardless of the presence of impurities in the lignin used, the average molecular weight of lignin, or the solubility of lignin in water, 'the lignin can be decomposed to the same extent, and the hydrogen ions can be treated to the same extent. free. -37- 201038737 And the same result was achieved when UV light was used instead of ultraviolet light. [Example 12] In the method of using the catalyst for lignin decomposition of the present invention, the product used as lignin contains a product (manufactured by Sigmal Co., Ltd., Catalog No. 47 1 038 The ENF-type ultraviolet lamp manufactured by Spectronix Co., Ltd., which contains the above-mentioned lignin 5 mg/mL and yttrium porphyrin compound 50 " g/mL solution, 1 mL Eppendorf tube. As a result, the pH of the lignin reaction solution is from 6. 2 Know the lignin free hydrogen ion. Further, as a lignin, a product having a high degree of reducing sugar (manufactured by Sigmal Co., Ltd., catalogue 〇〇〇' and Aldrich, catalogue 12,000), and a product not dissolved in water (record No.) were used. 370967), after repeating the above process, it is known that hydrogen ions are derived from wood irrespective of the presence of impurities in the lignin used, or the solubility of lignin in water. Moreover, when sunlight is used instead of ultraviolet light, the same result is obtained. After the above process, it is obtained that the lignin free hydrogen is separated from the rat sugar and the purity is slightly lower, and the molecular weight is 52,000. I obtained in the above Production Example 1 and placed in a cylindrical test tube made of polypropylene, and was irradiated with ultraviolet light to a temperature of 12. 8. Therefore, or impurities such as cellulose, pure No. 471003 > Molecular Weight No. 47 1 046, molecular weight, manufactured by Aldrich, with the same results. That is, the average molecular weight of the lignin can be liberated to the same extent and the above process is repeated, and -38-201038737 is obtained. [Example 1 3] The lignin decomposition catalyst is used as a lignin in the method of lignin free hydrogen ion. It does not contain impurities such as reducing sugar cellulose, and the product with high purity (manufactured by Sigmal Co., Ltd., catalog No. 471003, molecular weight 60,000) ° will contain the above lignin: 2. 5mg/mL, 2. 5 mM KOH, and porphyrin (original porphyrin IV manufactured by Sigmal Co., Ltd., catalog number 25 83 8 5- 1 G) · · 50 / / g / mL solution lmL, placed in the light of the degree of polypropylene suspected Eppendorf tube The transmissive cylindrical test tube was irradiated with ultraviolet light for 12 hours using an ENF type ultraviolet lamp manufactured by Spectronix. As a result, it was found that the pH of the lignin reaction solution was 10. 7 dropped to 7. 4. Therefore, it is known that free hydrogen ions are derived from lignin. Also, instead of using ultraviolet light, the same result was obtained after repeating the above process. Q [Example 14] As a lignin, a product having high purity without containing impurities such as reducing sugar or cellulose (manufactured by Sigmal Co., Ltd., Catalog No.) was used. 471003, molecular weight 60,000). Will contain this lignin: 2. 5mg/mL, 0. 05 M KOH, and 1 mL of a porphyrin: 50 yg/mL solution obtained in the above Production Example 1, placed in a light-transmissive cylindrical test tube having a degree of Eppendorf tube made of polypropylene, and an ENF type manufactured by Spectronix Co., Ltd. The UV lamp was irradiated with ultraviolet light for 12 hours. The resulting sample was analyzed using η P L C using a colloidal filter column. As a control, the solution before ultraviolet irradiation was also analyzed -39- 201038737. As a result of the analysis, it was found that, in the light absorption of 3 1 Onm, the sample after the irradiation was decomposed by 72% of the peak area of the lignin dissolved in 7 minutes. The decomposition product is colloidally filtered to dissolve a lower molecular weight fraction. Since the absorbance of the decomposition product of lignin in the present invention is low, the absorbance at 310 nm cannot be drawn, and as a non-volatile decomposition product, the eluted sample is freeze-dried, and the same fraction is collected to obtain a precipitate of the decomposition product. . As a lignin, a product containing no impurities such as reducing sugar or cellulose and having high purity (made by Aldrich, catalog No.) 47 1 046, molecular weight 12,000), and products insoluble in water (made by Aldrich, catalog No.) 3 70967), after the implementation of the above process, the same degree of results were obtained. That is, it is known that there is no impurity in the lignin used, the average molecular weight of lignin, or the solubility of lignin in water. When the lignin-base compound solution is further added as a photocatalyst porphyrin, it can be obtained with wood. The same degree of results associated with the decomposition of light. In addition, the use of sunlight instead of ultraviolet light, after repeating the above process, gave the same result. [Example 1 5] As a lignin, a product having a high purity, such as a reducing sugar or cellulose, and having a high purity (made by Si Gmai Co., Ltd.) is used. 471003, molecular weight 60, 〇〇〇). Will contain 205mg/mL for the lignin, 0. 05M KOH, and a solution of 5 〇//g/mL of manure porphyrin i (manufactured by ALDRICH Co., Ltd.) containing 4 sulfhydryl groups in the synthesis of 卟琳. 5mL, leaving it in the air space -40- 201038737 'Place 2mL of capacity in a light-transmissive cylindrical tube holding a polypropylene Eppendorf tube, irradiated with UV light using an ENF-type UV lamp made by Spectronix 48 hours. The reaction solution thus obtained was treated in the same manner as in Example 2. As a result, it was confirmed that 8 % or more of lignin was decomposed. Further, the space of the air was filled with oxygen, and after irradiation with ultraviolet light as described above, it was confirmed that 80% or more of the lignin was decomposed. Further, the space of the air was filled with oxygen, and after irradiation with ultraviolet light as described above, it was confirmed that 10% of the lignin was decomposed. Further, the above porphyrin-containing lignin solution was further filled in an Eppendorf tube without an air space, and almost no decomposition of lignin was observed after irradiation with ultraviolet light as described above. Further, as a lignin, a product having no purity such as reducing sugar or cellulose and having high purity (Aldrich, catalog No.) is used. 471 046, a molecular weight of 12,000), a product containing a reducing sugar and a slightly lower purity (made by Sigmal's catalogue No. 471038, molecular weight 52,000), and products that are insoluble in water (made by Aldrich, catalog No.) 370967), after repeating the above process, the same degree of results for the decomposition of lignin are obtained. Namely, lignin can be decomposed to the same extent regardless of the presence of impurities in the lignin used, the average molecular weight of lignin, or the solubility of lignin in water. Further, when sunlight is used instead of ultraviolet light, the same result is obtained for the decomposition of lignin after repeating the above process. [Industrial Applicability] -41 - 201038737 The catalyst for lignin decomposition of the present invention is not an enzyme such as white decay fungus, which is a catalyst made of non-protein. By using the catalyst, the lignin is mainly used to decompose lignin using light energy, and the lignin which reaches only 20 to 30% of the non-effective resources of wood can be obtained by a simple method, such as an alcohol such as an alcohol such as methanol or an organic acid such as formic acid. Hydrogen ions can expand the use of lignin, which is difficult to decompose in nature. That is, the alcohol extracted from lignin can be used as a substitute fuel for fossil fuels such as petroleum, and in the field of the fuel industry, organic acids can be utilized in various industrial fields, and hydrogen ions obtained from lignin can be used, for example. It is used in fuel cells and can be used in the field of the power industry. Further, the catalyst for decomposing an aromatic hydrocarbon of the present invention can be decomposed into an aromatic hydrocarbon in which a benzene ring is bonded to an oxygen atom, so that it is possible to treat harmful industrial waste or to purify contaminated soil or the surface. Therefore, it can be used in the field of industrial waste treatment or in the field of purification such as soil. BRIEF DESCRIPTION OF THE DRAWINGS [The structural formula of the product obtained in Production Example 1 is shown. Fig. 2 shows the spectrum of the result of the absorbance analysis for the product obtained in Production Example 1. [Fig. 3] The η N M R spectrum of the sample 1 obtained in Production Example 1. Fig. 4 is a 13 C NMR spectrum of Sample 1 obtained in Production Example 1. Fig. 5 is a view showing the HSQC spectrum of Sample 1 obtained in Production Example 1. Fig. 6 is a COSY spectrum of Sample 1 obtained in Production Example 1. Fig. 7 is a HMBC spectrum of Sample 1 obtained in Production Example 1. -42 - 201038737 [Fig. 8] Ν E S Y spectrum of Sample 1 obtained in Production Example 1. Fig. 9 shows the NOESY spectrum of the sample 1 obtained in Production Example 1. 10] The NMR spectrum of Sample 2 obtained in Production Example 1. [The NMR spectrum of the sample 2 obtained in Production Example 1 [Fig. 12] shows the n Ε Ο S Y spectrum of the sample 2 obtained in Production Example 1. [Fig. 13] shows the spectrum of the relative amount of the sample 2 obtained in Production Example 1. Fig. 14 shows the results of analysis by ESI-MS.

[Fig. 15] shows the results of analysis of the product obtained in Production Example 1 by thermal decomposition of 〇 C - M S .

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Claims (1)

201038737 Seven' patent application scope: 1. A catalyst for lignin decomposition, which is characterized by containing a porphyrin which exhibits a catalytic function by light irradiation. 2. A catalyst for lignin decomposition, which comprises a porphyrin which exhibits a catalytic function in an alkali solution. 3. A catalyst for lignin decomposition, which comprises a porphyrin which exhibits a catalytic function by irradiation with light in an alkali solution. 4. The catalyst for lignin decomposition according to any one of claims 1 to 3, wherein the porphyrin is a tetramethyl or ethyl acetate or a propionic acid group (propionic acid group) in the porphyrin ring. Pyrrole compound. 5. The catalyst for lignin decomposition according to any one of claims 1 to 3, wherein the porphyrin contains 4 methyl groups, 4 ethyl esters or acetate groups (propionic acid) in the porphyrin ring. a tetrapyrrole compound. 6. The catalyst for lignin decomposition according to any one of claims 1 to 3, wherein the porphyrin is a porphyrin having a carboxyl group in the molecule. 7. The catalyst for lignin decomposition according to item 6 of the patent application, wherein the porphyrin is a porphyrin oxime having a total of 2, 4 or 8 carboxyl groups in the molecule, as in the wood of claim 6 The catalyst for decomposition of a substance, wherein the porphyrin is at least one selected from the group consisting of urinary porphyrin, protoporphyrin, and coproporphyrin. 9. The catalyst for lignin decomposition according to any one of claims 1 to 3, wherein the porphyrin is a porphyrin ring structure obtained from the culture medium after the Escherichia coli is cultured in the medium. Pyrrole compound. 10. The catalyst for the decomposition of wood-44 - 201038737 according to any one of claims 1 to 3, wherein the catalyst comprises a porphyrin ring structure obtained by culturing Escherichia coli in a culture medium. The medium of the tetrapyrrole compound is formed. For example, in the lignin decomposition catalyst of item 9 or item 10 of the patent application, Escherichia coli is an unexpressible Escherichia coli which is transformed by the mutation of the gene ypjD (b2611). 1 2 . The catalyst for decomposing wood quality of any one of items 9 to 1 of the patent application, wherein E. coli is a transposon of the gene ypjD (b2611) inserted into the mutant strain. A method for producing an alcohol or an organic acid, which comprises adding a solution containing an alkali compound to the lignin, and separating the alcohol and the organic acid from the lignin-base compound solution. 1 4 . The method for producing an alcohol and an organic acid according to claim 13 of the patent application, wherein the lignin-alkali compound solution is used to separate alcohol and organic acids from the lignin-base compound solution. . 〇 15. The method for producing an alcohol and an organic acid according to item 14 of the patent application, wherein the light irradiation is irradiated with ultraviolet rays or sunlight. 1) A method for producing an alcohol and an organic acid as described in claim 13 of the patent application, wherein the lignin/base compound solution further comprises a wood according to any one of claims 1 to 12 After the catalyst for the decomposition of the mass acts, the alcohol and the organic acid are separated from the lignin-base compound solution. 1 7 · A method for producing an alcohol and an organic acid as described in claim 16 of the patent application, wherein for the lignin-alkali compound solution, any one of items 1 to 12 of the scope of the application-45-201038737 is applied. After the lignin decomposition catalyst acts, the light is further irradiated, and the alcohol and the organic acid are separated from the lignin-base compound solution. 1 8 · A method for producing alcohols and organic acids as claimed in claim 17 wherein the light irradiation is by ultraviolet light or sunlight. The method for producing an alcohol or an organic acid according to any one of the items 1 to 3, wherein the alkali compound is at least one of KOH and NaOH. 20. A method for producing an alcohol and an organic acid, which is characterized in that lignin is acted upon by a catalyst for lignin decomposition according to any one of claims 1 to 2, wherein lignin is used. Separation of alcohols and organic acids. A method for producing an alcohol or an organic acid, which is characterized in that light is irradiated to lignin, and alcohols and organic acids are separated from lignin. 22. A method for producing an alcohol and an organic acid, which is a method for illuminating lignin by separating light alcohols and organic acids from lignin, and is characterized in that, for lignin, the first to the first claims are in the range of In the case where the catalyst for lignin decomposition of any of the items acts, the light is irradiated, and the alcohol and the organic acid are separated from the lignin. 23. A method of producing an alcohol or an organic acid according to claim 21 or 22, wherein the light irradiation is by ultraviolet light or sunlight. 24. The method for producing an alcohol and an organic acid according to any one of the claims 1 to 2, wherein the alcohol is methanol and the organic acid is -46 - 201038737 formic acid, acetic acid, malic acid, amber Acid and pyruvic acid. 25. The method for producing an organic acid according to any one of claims 13 to 24, wherein the separation of the alcohol is carried out. A method for producing a lignin decomposition product, which is characterized in that the method for producing an alcoholic acid according to any one of claims 13 to 25, wherein the alcohol is recovered and the organic acid is recovered Quality decomposition product. 〇 2 7. A catalyst for decomposing an aromatic hydrocarbon, which is a catalyst for decomposing an aromatic hydrocarbon which bonds an oxygen atom to a benzene atom, and is characterized by a porphyrin. 28. Decomposition of aromatic hydrocarbons according to item 27 of the patent application 'wherein porphyrins' is a tetrapyrrole compound having a porphyrin ring structure obtained by cultivating Escherichia coli in a culture medium. 2 9. Decomposition of aromatic hydrocarbons in the 27th item of the patent application scope Q ' wherein the catalyst is a medium in which Escherichia coli is cultured in a medium for all tetrapyrrolidone compounds having a porphyrin ring structure. Patent application No. 28 or Item 29 of the aroma solution catalyst, in which Escherichia coli is the gene ypjD (b2611) which becomes unsuccessful in E. coli. 3 1 _ A transposon insertion transfectant of a catalyst for the decomposition of aroma hydrocarbons, wherein Escherichia coli is a gene ypjD, as in any of claims 28 to 30. 32. The alcohol distillation in accordance with any one of the 27th to the 31st claims of the patent application is classified as the carbon of the ring produced, and the hydrocarbon containing the catalyst is obtained from the catalyst containing the catalyst. Fractional and fragrant; b2611 XI Zhi-47- 201038737 A catalyst for the decomposition of aromatic hydrocarbons, wherein the porphyrin is a tetrapyrrole compound containing a methyl group and an ethyl ester or an acetate group (propionic acid group) in the porphyrin ring. . The catalyst for the decomposition of aromatic hydrocarbons according to any one of claims 27 to 3, wherein the porphyrin is 'the porphyrin ring contains 4 methyl groups, 4 ethyl esters or A tetrapyrrole compound of an acetate group (propionic acid group). The catalyst for the decomposition of aromatic hydrocarbons according to the 27th item of the patent application, wherein the porphyrin is at least one selected from the group consisting of urinary porphyrin, protoporphyrin, coproporphyrin, and etioporphyrin. 3 5. A catalyst for the decomposition of aromatic hydrocarbons according to the 27th item of the patent application, wherein the porphyrin is a porphyrin having a carboxyl group in the molecule. 36. A catalyst for the decomposition of aromatic hydrocarbons according to claim 35, wherein the porphyrin is a porphyrin having a total of two, four or eight carboxyl groups in the molecule. The catalyst for the decomposition of aromatic hydrocarbons in any one of claims 27 to 36 wherein the aromatic hydrocarbon is a dioxin. 38. A free method for hydrogen ions, characterized in that the lignin-lignin-test compound solution acts as a catalyst for lignin decomposition according to any one of claims 1 to 11. 'The light is irradiated to the solution to make the hydrogen ions free. 39. A porphyrin characterized by having a catalytic function for converting lignin into an alcohol and an organic acid. A porphyrin characterized by having a catalytic function for decomposing a compound containing an aromatic hydrocarbon bonded to an oxygen atom on a carbon forming a benzene ring. 41. A porphyrin characterized by culturing a gene ypjD (b2611) which is mutated by -48-201038737 and which is rendered incapable of expression. 4 2. A catalyst for lignin decomposition, which is characterized by the fact that the culture gene ypjD (b261 1 ) is transformed into a non-expressible Escherichia coli. X -49 -