JP5454836B2 - Method for producing fatty acid monoester product using regenerated solid acid catalyst - Google Patents

Description

  The present invention relates to a method for producing a fatty acid monoester product by activating a sulfonic acid group-introduced amorphous carbon catalyst, which is a solid acid catalyst, by washing with water and reusing it in an ester exchange reaction or an esterification reaction.

Conventionally, attempts have been made to produce fatty acid monoesters using vegetable oils or animal oils as raw materials and to use these as fuels for diesel engines. Vegetable oils and animal oils have low sulfur content, so when used as fuel for diesel engines, almost no sulfur oxides (SO _x ) are generated. The generated carbon dioxide is once again fixed during crop growth and is considered as a CO ₂ zero-emission fuel, and is considered promising as contributing to environmental conservation.

  Such diesel engine fuel uses aliphatic triglycerides, which are the main components of vegetable oils and animal oils, as raw materials, and (1) transesterifies vegetable oils and animal oils in alcoholic solvents using alkali as a catalyst to produce the corresponding fatty acid monoesters. (2) Without using a catalyst, water is added to vegetable oil or animal oil and hydrolyzed under supercritical or subcritical conditions, and then alcohol is added to the resulting hydrolyzate to supercritical or subcritical. It is produced by a method of producing a fatty acid monoester by esterification under conditions, and (3) a method of producing a fatty acid monoester by adding an alcohol to a vegetable oil or animal oil and transesterifying under supercritical or subcritical conditions. .

  However, since vegetable oils and animal oils generally contain free fatty acids, in the method for producing a fatty acid monoester performed by adding the alkali catalyst described in (1) above, the free fatty acid and the alkali catalyst react with each other before the transesterification reaction. And water is produced. Water significantly reduces the alkali catalysis and the resulting soap acts as a surfactant, making it difficult to separate the product from the catalyst.

  On the other hand, as a method of transesterification or esterification under the supercritical or subcritical conditions of (2) and (3) above, a method for producing a fatty acid ester from fat and alcohol without adding a catalyst, Or there exists the manufacturing method of the fatty acid ester characterized by making it react on the conditions which alcohol becomes a supercritical state (patent document 1). In Example 1, waste soybean oil and methanol were reacted at a temperature of 300 ° C. and a pressure of 6.5 MPa to obtain a fatty acid methyl ester. Similarly, animal oil or vegetable oil is treated in the absence of a catalyst using an alcohol in a supercritical state or a subcritical state as a solvent, and a fatty acid monoester product corresponding to the alcohol used as the solvent selectively and in a short time There is also a method of obtaining (Patent Document 2). In Example 1 of Patent Document 2, used rapeseed oil and methanol are reacted at a temperature of 240 to 360 ° C. and a pressure of 40 MPa to obtain a monoester product.

In addition, as a method for producing a fatty acid monoester from a fatty acid ester, there is a method for producing a fatty acid monoester product by a transesterification reaction using a solid catalyst. A method using a catalyst comprising a metal oxide as a solid catalyst, comprising an amorphous zirconium oxide (A), a Group III element oxide, a Group V element oxide, and / or an IV other than zirconium or hafnium. A composite inorganic oxide catalyst containing a group element oxide (B) is used, and an esterified product is produced by bringing the composite inorganic oxide catalyst into contact with a raw material ester and an alcohol for transesterification. (Patent Document 3). By using the catalysts (A) and (B) in combination, the reaction can be allowed to proceed under a pressure of about normal pressure. In the embodiment, a composite inorganic oxide catalyst, catalyst obtained by mixing TiO ₂ or SiO ₂ to ZrO _2, or ZrO ₂ having a spinel structure ZnAl ₂ O ₄ or _{xZnO, yAl 2 O 3 (x} , y = 0~2 ) And the reaction is carried out at a reaction temperature of 200 to 250 ° C. for transesterification.

On the other hand, a method for producing ethyl acetate from acetic acid and ethyl alcohol using a proton conductive material containing amorphous carbon having a sulfonic acid group introduced as a solid catalyst is also disclosed (Patent Document 4). In the example of Patent Document 4, concentrated sulfuric acid is added to naphthalene, coronene, heavy oil, etc., heated at 250 ° C. for 15 hours, and excess concentrated sulfuric acid is removed by distillation under reduced pressure to obtain a black powder. It works with ethyl alcohol and sees the effect of the catalyst.
JP 2000-143586 A JP 2000-204392 A International Publication No. 2005/000782 International Publication No. 2005/029508

  However, the methods described in Patent Document 1 and Patent Document 2 are those in which fats and oils mainly composed of triglycerides and the like are reacted with alcohol, but transesterification is performed under supercritical conditions as reaction conditions, and the apparatus is simplified. Development of a method capable of producing a fatty acid monoester product under milder conditions is desired from the standpoints of conversion and safety. In addition, the fatty acid monoester product fraction obtained by the method described in Patent Document 2 does not satisfy the acid value standard of the fuel for biodiesel engines defined in European and American standards, and the acid value exceeds 0.5. There is a case. In the transesterification reaction, triglycerides contained in animal oils directly react with alcohols to produce fatty acid monoesters. At the same time, triglycerides are hydrolyzed to fatty acids in the presence of water, and water is further added by esterification of fatty acids. To be born. For this reason, the reaction equilibrium in which a fatty acid monoester is produced from a fatty acid and an alcohol shifts to the reverse reaction side due to the presence of water. This tendency increases as the temperature rises, especially in supercritical conditions. In order to lower the acid value, it is important to sufficiently reduce the water content in the reaction solution. However, when oils and fats containing fatty acids are used as raw materials, water is by-produced, so that an acid value of 0.5 or less must be achieved. Is very difficult. The same applies when the raw material contains moisture.

  On the other hand, it is only necessary to remove causative substances that can increase the acid value, such as free fatty acids and moisture contained in the raw material, but it is not easy to remove free fatty acids from a large amount of animal oil or vegetable oil as the raw material oil. Such pretreatment contributes to a reduction in product yield from fats and oils.

  In addition to triglyceride, diglyceride and monoglyceride are by-produced by transesterification reaction of triglyceride and alcohol, but monoglyceride is difficult to separate because it has a boiling point close to that of fatty acid monoester. It mixes in the monoesterified product. As shown in the following formula, when the mass percentage of the glycerin contained in the fatty acid monoester and the total amount of glycerin constituting the triglyceride, diglyceride and monoglyceride with respect to the total mass of the fatty acid monoester is defined as “total glycerin conversion amount”, When the esterified product is used as a fuel for a biodiesel engine, the product specification of a total glycerin conversion amount of 0.24% by mass or less may not be satisfied.

また、前記特許文献３は、脂肪酸モノエステル化物を製造し得る触媒として固体触媒として金属酸化物からなる触媒を使用する方法であるが、反応温度が２００〜２５０℃と高く、超臨界温度条件に近い反応であり、更に温和な条件での反応が望まれる。

Moreover, although the said patent document 3 is a method of using the catalyst which consists of a metal oxide as a solid catalyst as a catalyst which can manufacture a fatty-acid monoester, reaction temperature is as high as 200-250 degreeC, and it is supercritical temperature conditions. It is a near reaction and a reaction under milder conditions is desired.

  Similarly, Patent Document 4 only shows that a proton conductive material containing amorphous carbon having sulfonic acid groups introduced therein can be used as a solid catalyst for producing ethyl acetate from acetic acid and ethyl alcohol. It is not intended to transesterify triglycerides such as fats and oils.

  On the other hand, the activity of the catalyst may decrease due to continuous use, and the yield of the target product may decrease. The amount of the catalyst used is small but expensive compared to the raw material, and it is desired to extend the catalyst life. However, the activity generally decreases with continued use, especially at elevated temperatures and pressure conditions. Therefore, it is efficient if the catalyst can be reactivated and used.

  The present invention has been made under these circumstances, and its object is to produce a fatty acid monoester product having a low acid value using a catalyst having excellent transesterification efficiency and esterification rate. An object of the present invention is to provide a method for producing a fatty acid monoester product stably and continuously by washing and regenerating the catalyst and reusing it for transesterification and esterification.

  The present inventors examined a catalyst capable of producing a fatty acid monoester by an ester exchange reaction of animal oil and / or vegetable oil and alcohol. When a specific sulfonic acid group-introduced amorphous carbon catalyst is used, the ester exchange rate is improved. By reacting in the presence of water, in particular, by-products of fatty acid monoglycerides, which are difficult to separate and purify from the target fatty acid monoester product, can be suppressed very efficiently. It has been found that a monoesterified product can be produced by a simple process, and that the above catalyst can also efficiently carry out an esterification reaction between a fatty acid and an alcohol. Furthermore, the activity of this transesterification reaction and esterification decreases with time, but when the catalyst is washed with water, the transesterification rate and esterification rate are recovered and can be reused. It has been found that a fatty acid monoester product can be efficiently produced using an amorphous carbon catalyst, and the present invention has been completed.

The present invention reuses the sulfonic acid group-introduced amorphous carbon catalyst after washing with water, and can extend the life of an expensive catalyst, so that the production cost can be reduced.
In addition, in the production process of the fatty acid monoester product, by combining the washing step of the sulfonic acid group-introduced amorphous carbon catalyst with the transesterification reaction with the water-washed sulfonic acid group-introduced amorphous carbon catalyst, the fatty acid monoester product can be stably and It can be manufactured continuously.

  In the present invention, the washed sulfonic acid group-introduced amorphous carbon catalyst can also be used for transesterification of triglyceride and alcohol and esterification reaction of remaining fatty acid and alcohol. An esterified product can be produced.

  The present invention relates to a sulfonic acid group-introduced amorphous carbon used for the reaction of animal oil and / or vegetable oil with an alcohol represented by ROH (R represents a saturated or unsaturated fatty acid group having 1 to 24 carbon atoms). A first step of obtaining a fatty acid monoester product reaction solution by using a water-washed sulfonic acid group-introduced amorphous carbon catalyst obtained by washing the catalyst in the esterification and / or transesterification reaction of the animal oil and / or vegetable oil with an alcohol. This is a method for producing a fatty acid monoester product.

  When the sulfonic acid group-introduced amorphous carbon catalyst is used for the transesterification reaction of triglyceride and alcohol contained in animal oil or the like, or the esterification reaction of fatty acid and alcohol, the transesterification rate and esterification rate decrease over time. It has been found that the activity can be recovered by washing the amorphous carbon catalyst having a sulfonic acid group introduced therein with water. Hereinafter, the present invention will be described in detail.

(1) Sulfonic acid group-introduced amorphous carbon catalyst The "sulfonic acid group-introduced amorphous carbon catalyst" used in the present invention is a carbon having a sulfonic acid group and not having a clear crystal structure such as diamond or graphite. Say.

  The sulfonic acid group-introduced amorphous carbon to be used is not particularly limited as long as it can catalyze the transesterification reaction between animal oil and / or vegetable oil and alcohol and / or catalyze the esterification reaction between alcohol and fatty acid. What obtained by heat-processing an organic compound at the temperature of 0-350 degreeC in concentrated sulfuric acid or fuming sulfuric acid can be used conveniently. Examples of the organic compound include aromatic hydrocarbons such as benzene, naphthalene, anthracene, perylene and coronene; monosaccharides such as glucose, fructose and galactose, and saccharides such as starch, cellulose, agarose and oligosaccharide. . These have a carbon 6-membered ring structure in the structure, and a sulfonic acid group is introduced by heat treatment with concentrated sulfuric acid or fuming sulfuric acid, and can exhibit excellent esterification or transesterification activity.

  The sulfonic acid group-introduced amorphous carbon used in the present invention preferably has a sulfonic acid density of 1 to 8 mmol / g, more preferably 1 to 7 mmol / g, and 1.2 to 6 mmol / g. It is particularly preferred. This is because within this range, the reaction efficiency of a fatty acid monoester product using triglyceride and alcohol as raw materials is high, the byproduct rate of monoglyceride is low, and the efficiency of producing a fatty acid ester from alcohol and fatty acid is excellent.

  The sulfonic acid group-introduced amorphous carbon used in the present invention can be obtained by heat-treating the above organic compound in concentrated sulfuric acid or fuming sulfuric acid at a temperature of 0 ° C to 350 ° C, preferably 60 ° C to 250 ° C. . When the treatment temperature is less than 0 ° C., condensation and carbonization of the organic compound may not be sufficient. On the other hand, when the treatment temperature exceeds 350 ° C., thermal decomposition of the sulfonic acid group may occur. Although heat processing time can be suitably selected according to the organic compound to be used, processing temperature, etc., it is 15 minutes-50 hours normally, Preferably it is 1 to 20 hours. Within the range of this reaction time, partial carbonization, cyclization, condensation and the like of the organic compound can proceed and sulfonation can occur. Preferably, the organic compound in concentrated sulfuric acid or fuming sulfuric acid is heated in an inert gas stream such as nitrogen or argon or in a dry air stream. Thereby, amorphous carbon having a high sulfonic acid density can be produced. More preferably, heating is performed while blowing an inert gas such as nitrogen or argon or dry air into concentrated sulfuric acid or fuming sulfuric acid to which the organic compound is added. Aromatic sulfonic acid and water are produced by the reaction of concentrated sulfuric acid and aromatic hydrocarbons. This reaction is an equilibrium reaction, and as the amount of water in the reaction system increases, the reverse reaction proceeds faster and is introduced into amorphous carbon. This significantly reduces the amount of sulfonic acid. However, it has a high sulfonic acid density by actively removing water from the reaction system by reacting in an inert gas or in a dry air stream or by blowing these gases into the reaction system. Amorphous carbon can be synthesized.

  Although the quantity of the concentrated sulfuric acid and fuming sulfuric acid to be used is not specifically limited, It is 0.1-100 mass parts normally with respect to 1 mass part of organic compounds, It is 10-30 mass parts suitably. When sugars such as glucose and cellulose are used as raw materials, these raw materials are heated in an inert gas stream at 100 to 350 ° C. for 1 to 20 hours before heat treatment in concentrated sulfuric acid or fuming sulfuric acid. It is preferable to partially carbonize.

  In addition, aromatic hydrocarbons, heavy oils containing them, pitch, tar, asphalt, etc. can be used as raw materials. In this case, the product is heated in vacuo after heat treatment in concentrated sulfuric acid or fuming sulfuric acid. Is preferred. Excess sulfuric acid can be removed, and carbonization and solidification of the product can be promoted to increase the yield of the product. Vacuum evacuation is preferably performed at an exhaust rate of 10 L / min or more, an ultimate pressure of 100 torr or less, a heating temperature of 140 to 300 ° C., more preferably 200 to 280 ° C., for 2 to 20 hours.

  The sulfonic acid group-introduced amorphous carbon used in the present invention is, for example, carbon in which both the G band and the D band are detected in the spectrum by Raman spectroscopy, and the integrated intensity ratio of the G band to the D band (I Carbon with (D) / I (G)) of 0.1 to 0.7 can be preferably used. When the integrated intensity ratio (I (D) / I (G)) is less than 0.1, the number of aggregated carbon six-membered rings is small and does not become solid, and when it exceeds 0.7, the graphene sheet becomes large At the same time, the density of the sulfonic acid is lowered, so that it may not function as a catalyst. The integral intensity ratio (I (D) / I (G)) may be 0.1 to 0.7, preferably 0.1 to 0.65, and preferably 0.2 to 0.65. More preferably. In this specification, the D band, the G band, and their integrated intensities are defined as follows.

The D band is Alg breathing mode vibration in a carbon six-membered ring, and its peak top appears at 1350 cm ^{−1 to} 1360 ⁻¹ cm. G band is a vibration of E2g mode of six-membered carbon ring, the peak top appears at 1580cm ^-1 ~ soil 5cm ^-1. The Raman spectrum consisting of the sum of both peaks was divided into two peaks by Gaussian or Gaussian-Lorentzian, and the obtained integrated intensities of the D band and G band were used as the integrated intensities.

(2) Animal oil, vegetable oil and fatty acid In the present invention, the corresponding fatty acid obtained by transesterification of animal oil and / or vegetable oil and alcohol using the catalyst for transesterification reaction comprising the sulfonic acid group-introduced amorphous carbon catalyst. Monoesterified products can be produced.

  The “animal oil” to be used is an oil derived from animals and is a concept including fats and oils. Animal oils that can be used in the present invention include fish oil obtained from the body of fish such as sardine oil, mackerel oil, herring oil, saury oil, tuna oil, cod liver oil; lard fat, chicken fat, butter fat, beef fat, beef bone fat, There are deer fat, dolphin fat, horse fat, pork fat, bone oil, sheep fat, cow leg oil, murine dolphin oil, shark oil, sperm whale oil, whale oil, etc., selected from the group consisting of fish oil, beef tallow and pork fat One or more oils are preferable, and a mixture of a plurality of these oils, oils and fats containing diglycerides or monoglycerides, and oils that have undergone modification such as oxidation or reduction may be used.

  Further, in the present invention, “vegetable oil” is a plant-derived oil and is a concept including fats and oils. Vegetable oils that can be used in the present invention include cocoa butter fat, corn oil, peanut oil, coconut oil, soybean oil, coconut oil, olive oil, safflower oil, oilseed oil, linseed oil, coconut oil, oak oil, almond oil, Apricot seed oil, castor oil, garlic oil, Chinese oil, cottonseed oil, cottonseed stearin, sesame oil, palm oil, palm kernel oil, rice oil, kapok oil, etc., more preferably sunflower oil, safflower oil , Paulownia oil, linseed oil, soybean oil, rapeseed oil, cottonseed oil, olive oil, coconut oil, coconut oil and palm oil, but are not limited thereto. As described above, a mixture of a plurality of these oils, oils and fats containing diglycerides and monoglycerides, and oils that have undergone modification such as oxidation or reduction may be used.

  Even when the animal oil and / or vegetable oil used in the present invention contains oils and fats containing diglycerides or monoglycerides other than triglycerides, and oils partially modified such as oxidation and reduction, the sulfonic acid group-introduced amorphous carbon catalyst is This is because, when the reaction is carried out in the presence of water under predetermined conditions, a fatty acid monoester product reaction solution having a monoglyceride byproduct rate of 0 to 1.3% by mass can be obtained. In addition, in this invention, a monoglyceride byproduct rate shall mean the ratio which a monoglyceride byproduces when the case where all the raw materials become fatty acid esterified shall be 100 mass%.

  The animal oil or vegetable oil may be collected directly from the raw animal or plant, but may be discarded after being used as edible oil. This is because a triglyceride represented by the following formula is contained as a main component in these, and a fatty acid monoester product can be efficiently produced by transesterification.

上記トリグリセリドに含まれるＲ¹、Ｒ²およびＲ³の置換基としては、水酸基、アミノ基、カルボニル基、カルボキシル基などがあり、上記トリグリセリドに含まれる脂肪酸基としては、原料の動物種や植物種によって適宜選択することができる。

Examples of the substituents for R ¹ , R ² and R ³ contained in the triglyceride include a hydroxyl group, an amino group, a carbonyl group, and a carboxyl group. Examples of the fatty acid group contained in the triglyceride include animal species and plant species as raw materials. Can be appropriately selected.

  The animal oils and vegetable oils may contain free fatty acids and moisture. A fatty acid monoester product is produced by using this, and finally the fatty acid monoester product that can be suitably used as a fuel for a diesel engine is also removed by the second step and the third step described later, This is because the acid value can be reduced. In general, animal oil and vegetable oil collected from animals and plants, or waste animal oil and waste vegetable oil after being used for food, etc. contain 1 to 5 mass% free fatty acid and 0 mass% to saturated water. It is. The dark oil by-produced from the edible oil refining process contains 50 to 100% by mass of free fatty acids. Rather, according to the method for producing a fatty acid monoester product of the present invention, a fatty acid monoester product having a low acid value can be efficiently produced in a simple process without removing free fatty acids and moisture from such raw materials. There is a feature in the point.

  In the present invention, the above sulfonic acid group-introduced amorphous carbon catalyst is used, and a fatty acid and ROH (R is carbon atoms) having 8 to 24 carbon atoms, more preferably 12 to 22 carbon atoms, and particularly preferably 14 to 22 carbon atoms. A fatty acid monoester product can be produced by an esterification reaction with an alcohol represented by the formula (1-24). Examples of such fatty acids include free fatty acids obtained by hydrolyzing the animal oil and / or vegetable oil.

(3) Alcohol The alcohol used in the present invention is represented by ROH (R represents a saturated or unsaturated fatty acid group having 1 to 24 carbon atoms), and among R, saturated or unsaturated having 1 to 24 carbon atoms. Examples of the saturated fatty acid group include an alkyl group, an aralkyl group, an alkenyl group, and an alkynyl group.

  Examples of the alcohol in which R is an alkyl group include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol, hexanol, cyclohexanol, heptanol and the like.

Examples of the alcohol in which R is an aralkyl group include benzyl alcohol, α-phenethyl alcohol, and β-phenethyl alcohol, and benzyl alcohol is preferred.
Examples of the alcohol in which R is an alkenyl group include allyl alcohol, 1-methylallyl alcohol, 2-methylallyl alcohol, 3-buten-1-ol, 3-buten-2-ol, and the like. Alcohol is preferred.

Examples of alcohols in which R is an alkynyl group include 2-propyn-1-ol, 2-butyn-1-ol, 3-butyn-1-ol, 3-butyn-2-ol, and the like. Is done.
Among these, as the alcohol, R is preferably an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, 2-butanol, t-butanol, and allyl alcohol. More preferred are methanol and ethanol, and even more preferred is methanol. Alcohols may be used alone or in admixture of two or more. Moreover, alcohol may contain an optical isomer, when an optical isomer exists.

(4) First step The first step of the present invention is a water-washed sulfonic acid group-introduced amorphous carbon catalyst obtained by washing the sulfonic acid group-introduced amorphous carbon catalyst used in the reaction of the animal oil and / or vegetable oil with alcohol. This is a step for obtaining a fatty acid monoester product reaction solution by use in the esterification and / or transesterification reaction of the animal oil and / or vegetable oil and alcohol.

(I) Washed sulfonic acid group-introduced amorphous carbon catalyst In the “reaction of the animal oil and / or vegetable oil and alcohol” in the first step, the transesterification reaction of animal oil and / or vegetable oil and alcohol, the animal oil and / or It is a concept including an esterification reaction between a fatty acid and an alcohol mixed in vegetable oil, and a combined use of the transesterification reaction and the esterification reaction. The sulfonic acid group-introduced amorphous carbon catalyst can catalyze a transesterification reaction between an animal oil and / or vegetable oil and an alcohol, and can catalyze an esterification reaction between the alcohol and a fatty acid. The animal oil and / or vegetable oil includes This is because the fatty acid can also be contained, so that the above three modes can exist. Accordingly, the water-washed sulfonic acid group-introduced amorphous carbon catalyst is used for any of the above three reactions. Although the said reaction conditions are not specifically limited, For example, the reaction conditions of the transesterification mentioned later may be sufficient.

  In the present invention, the catalyst used in the above reaction is washed with water. Since the transesterification reaction is a reaction system that generally does not contain water, there is a problem with the resistance when the catalyst is treated with water. However, when various activation methods were examined, the introduction of sulfonic acid groups used in the present invention was considered. It was found that the activity of the amorphous carbon catalyst was recovered most by washing with water.

  Although there is no limitation in the regeneration method by water washing, for example, 1 to 20 mass times the amount of catalyst is added, and the mixture is stirred at a temperature of 0 to 100 ° C for 5 minutes to 1 hour, and after stirring at a temperature of 50 to 150 ° C. It can be regenerated by drying. You may wash | clean by flowing 0.5-20 mass times water of a catalyst amount at a flow rate of 3-200 mm / min, without stirring in water. Since the sulfonic acid group-introduced amorphous carbon catalyst is used as a slurry or fixed bed in the reactor, water is added after the reaction solution is withdrawn after the completion of the above reaction, and the catalyst remaining in the reactor is batch-typed. It is possible to wash with water or to continuously wash with water.

  In the present invention, the “water” used for washing the catalyst with water may contain the alcohol in an amount of 20% by mass or less. This is because if the alcohol content is within the above range, the activity of the sulfonic acid group-introduced amorphous carbon catalyst can be recovered after washing with water. In addition, the water discharged in the production process of the fatty acid monoester product may contain alcohol used in the reaction system and can be fractionated in the process and reused as water and alcohol. By relaxing and recovering the alcohol-containing water and using it for catalyst cleaning, the production cost can be reduced.

  The sulfonic acid group-introduced amorphous carbon catalyst used in the present invention recovers its activity by washing with water, but the water-washed sulfonic acid group-introduced amorphous carbon catalyst also has activity over time by a batch or continuous transesterification reaction. descend. Such a catalyst can also be used as an amorphous carbon catalyst with an introduced sulfonic acid group in the present invention by washing with water again.

  Although the reason for the recovery of the sulfonic acid group-introduced amorphous carbon catalyst by washing with water is not clear, the sulfonic acid group-introduced amorphous carbon catalyst is thought to catalyze transesterification and esterification reactions by the introduced sulfonic acid group. It is done. However, since a large amount of alcohol is contained in the reaction system, the sulfonic acid group becomes alkoxy due to this alcohol, and the activity is lowered. Therefore, it is considered that the activity is recovered by converting the alkoxy to the original sulfonic acid group by washing with water. It is done.

(Ii) Esterification and transesterification In the present invention, the animal oil and / or vegetable oil and alcohol are subjected to a temperature of 60 to 200 ° C., more preferably 70 in the presence of a water-washed sulfonic acid group-introduced amorphous carbon catalyst and water. The reaction is carried out at ˜180 ° C., particularly preferably 90˜160 ° C., pressure atmospheric pressure˜5 MPa, more preferably atmospheric pressure˜4 MPa, particularly preferably atmospheric pressure˜3 MPa. Even if the temperature is lower than 60 ° C., the swelling or transesterification proceeds, but it may take time and the productivity may decrease. On the other hand, even if it exceeds 200 ° C., the conversion rate is not improved, and by-products may be generated, which is disadvantageous. Even if the reaction pressure is lower than atmospheric pressure, esterification and transesterification proceed, but it is disadvantageous because it becomes a boiling state and the reaction capacity increases. On the other hand, even if it exceeds 5 MPa, the conversion rate does not improve, and it is economically disadvantageous because it becomes a thick-walled container because it is necessary to increase the pressure resistance of the reactor.

  The reaction time is a time sufficient for the fatty acid triglyceride contained in the animal oil and / or vegetable oil to transesterify with the alcohol to obtain the corresponding fatty acid monoester product and glycerin. As described above, the animal oil and / or vegetable oil may contain a fatty acid, or when the animal oil and / or vegetable oil generates a free fatty acid according to the above conditions, the fatty acid and the alcohol are esterified. It is sufficient time to produce a fatty acid ester product. In general, the reaction time is 10 minutes to 50 hours, more preferably 30 minutes to 30 hours, depending on the reaction conditions.

  In the transesterification reaction, when 1 mol of alcohol is reacted with 1 mol of fatty acid group contained in animal oil or vegetable oil, a corresponding 1 mol of fatty acid monoester product is formed. However, in the present invention, the molar ratio of alcohol to 1 mol of fatty acid group constituting the free fatty acid, triglyceride and monoglyceride contained in animal oil and vegetable oil (fatty acid group contained in alcohol / animal oil and vegetable oil) is 1 to 40, more preferably 2. Alcohol is added in the range of -30, particularly preferably 4-25. The animal oil and / or vegetable oil may contain a fatty acid, and a fatty acid monoester product can be efficiently produced by adding an alcohol in the above range. If the molar ratio is less than 1, esterification or transesterification reaction becomes insufficient. On the other hand, if it exceeds 40, the reaction apparatus becomes enormous and uneconomical.

  The present invention is characterized in that water is included in the esterification and / or transesterification reaction. In the transesterification reaction of triglyceride and alcohol contained in animal oil, etc., if water is present, the triglyceride is hydrolyzed to produce free fatty acids, which are then esterified to produce water as a by-product. The equilibrium of is transferred to the reverse reaction side. In addition, esterification reaction of fatty acid and alcohol is reversed by the by-product water. Therefore, conventionally, water is not added to the transesterification reaction system or the esterification reaction system. However, when the water-washed sulfonic acid group-introduced amorphous carbon catalyst is used as an esterification and / or transesterification catalyst, by adding a small amount of water to the reaction system, the by-product of fatty acid monoglyceride can be suppressed very efficiently. I found. In addition to the target fatty acid monoester, water and glycerin, the reaction solution may contain fatty acid monoglyceride, fatty acid diglyceride, unreacted triglyceride, etc., but separation and purification from the target fatty acid monoester In the present invention, a fatty acid monoester product having a low acid value can be produced.

  The compounding amount of water is 0.1 to 20 mol, more preferably 0.15 to 15 mol, and particularly preferably 0.2 to 10 mol with respect to 1 mol of triglyceride contained in animal oil or vegetable oil. Theoretically, when 1 mol of triglyceride is reacted with 3 mol of water, 1 mol of glycerin and 3 mol of fatty acid are produced by hydrolysis. In the present invention, water is added for the purpose of hydrolysis. is not. It is found that by adding water, by-product of monoglyceride can be suppressed, and subsequent purification can be facilitated, and the fuel for diesel engines with low total glycerin conversion amount and low acid value can be produced. Because it became clear. When water is less than 0.1 mol, the effect of suppressing monoglyceride by-product is insufficient, while when it exceeds 20 mol, the amount of free fatty acid may increase due to hydrolysis, which is disadvantageous.

  The amount of the washed sulfonic acid group-introduced amorphous carbon catalyst of the present invention is not particularly limited, but is preferably 10 to 1000 g, more preferably 20 to 500 g, relative to 1 mol of triglyceride.

  The type of the apparatus for carrying out the production method of the present invention is not particularly defined, and for example, a batch type reactor, a continuous tank type reactor, a piston flow type flow type reactor, a column type flow type reactor or the like can be used. . It can select suitably according to the fats and oils and alcohol to be used.

  For example, a fixed bed is formed by, for example, filling a column with a washed sulfonic acid group-introduced amorphous carbon catalyst, and the oil, fat, alcohol and water are supplied to the fixed bed and reacted under the reaction conditions. The obtained fatty acid monoester product reaction liquid contains an excess of alcohol, by-product glycerin and water in addition to the product fatty acid monoester product, but according to the present invention, the monoglyceride byproduct rate is 0. A fatty acid monoester product reaction liquid of ˜1.3 mass%, more preferably 0-1.0 mass% can be obtained.

(5) Second Step The second step is a step of obtaining the fatty acid monoester fraction by removing the alcohol, glycerin and water from the fatty acid monoester product reaction liquid obtained in the first step. The fatty acid monoester product reaction liquid contains alcohol added excessively together with glycerin, in addition to the fatty acid monoester fraction mainly composed of the fatty acid monoester product.

  As a method of fractionating the fatty acid monoester fraction, (1) introducing the fatty acid monoester product reaction liquid of the first step into a distillation column, selecting distillation conditions, and distilling alcohol and water from the top of the column Glycerin is extracted from the column, and the fatty acid monoester product is recovered from the bottom of the column. (2) The fatty acid monoester product reaction liquid is introduced into the distillation column, the distillation conditions are selected, and alcohol is added from the column top. And distilling off water and glycerin and recovering the fatty acid monoester product from the bottom of the column, (3) introducing the fatty acid monoester product reaction liquid into the first distillation column, selecting the distillation conditions, Distill off alcohol and water, extract glycerin and fatty acid monoester from the bottom of the tower, then introduce the bottom liquid into the second distillation tower to separate the glycerin and fatty acid monoester product. (4) Introducing the fatty acid monoester product reaction liquid into the distillation tower, distilling methanol and water, liquid-liquid separation of the fatty acid monoester product and glycerin, and any other method Also good. The method (4) is preferred. In the present invention, a fraction obtained by removing the glycerin, water, and alcohol from the fatty acid monoester product reaction solution is defined as a fatty acid monoester fraction.

(6) Third Step In the present invention, the fatty acid monoester fraction and the alcohol are then contacted and reacted in the presence of a solid catalyst comprising a cation exchange resin and / or a sulfonic acid group-introduced amorphous carbon catalyst. Is preferred. When free fatty acids are contained in animal and / or vegetable oils used as raw materials, water is produced as a by-product by reaction with alcohol, and fatty acid monoesters produced by this by-product water are hydrolyzed to produce free fatty acids. There is. This free fatty acid can be mixed in the fatty acid monoester fraction in the second step, but is esterified when alcohol is contacted in the presence of the solid catalyst, and free fatty acid is removed from the fatty acid monoester fraction. Is esterified, so that the esterification rate can be improved.

  In the present invention, a solid catalyst comprising a cation exchange resin or a sulfonic acid group-introduced amorphous carbon catalyst can be used as such a solid catalyst. This is because the sulfonic acid group-introduced amorphous carbon catalyst has a transesterification and a catalysis of the esterification reaction. The amorphous sulfonic acid group-introduced amorphous carbon catalyst may be the above-described washed sulfonic acid group-introduced amorphous carbon catalyst or an unused sulfonic acid group-introduced amorphous carbon catalyst.

The cation exchange resins, sulfonic acid functional group _{^{(R-SO 3 - H +}} ) or strongly acidic cation exchange resin, those containing carboxylic acid groups as functional group, a sulfonic acid group, phosphine acid group, a phenoxide group, nitrous Weakly acidic cation exchange resins having arsenic acid groups and the like can be suitably used. In the present invention, any resin may be used as long as it can esterify the fatty acid contained in the fatty acid monoester fraction. Preferably, pK value (25 degreeC) is 0-7, More preferably, it is 0-5. Among them, a sulfonic acid group in the functional group _{^{(R-SO 3 - H +}} ) strongly acidic cation exchange resin those with are preferred. Moreover, in this invention, it is preferable to use the cation exchange resin which consists of a styrene type crosslinked polymer or a (meth) acrylic acid ester type crosslinked polymer. Examples of the styrene-based crosslinked polymer include a crosslinked polymer of styrene-divinylbenzene (hereinafter abbreviated as DVB). The resin structure may be a gel type obtained by simply polymerizing styrene and DVB, or may be a porous type or a high porous type which is porous and has a resin surface area much larger than that of the gel type. In the present invention, the product names “organoamberlist 15DRY”, “organoamberlist 15JS-HG / dry”, “organoamberlist 35Dry”, “amberlist 36Dry”, “amberlist 70”, etc. manufactured by Organo Corporation are suitable. Can be used for The solid catalyst may be used as a fixed bed or may be used after stirring.

  In the third step of the present invention, the fatty acid monoester fraction and the alcohol are contacted and reacted in the presence of the solid catalyst, and the free fatty acid that can be contained in the fatty acid monoester fraction is reesterified. Is. In this re-esterification, for example, re-esterification may be performed while sequentially removing water. The esterification reaction time can be further shortened by performing the esterification reaction by sequentially removing water.

  The amount of alcohol used relative to the fatty acid monoester fraction is 0.007 to 2 parts by mass of alcohol, more preferably 0.01 to 1.5 parts by mass, particularly preferably 1 part by mass of the fatty acid monoester fraction. 0.015 to 1 part by mass. Only a small amount of free fatty acid is mixed in the fatty acid monoester fraction fractionated in the second step, and the esterification can be carried out sufficiently efficiently within the above range. When the amount is less than 0.007 parts by mass, the fatty acid may increase due to hydrolysis reaction with water in which the fatty acid monoester fraction is slightly present. On the other hand, if it exceeds 2 parts by mass, excessive energy is required in the alcohol recovery step, which is disadvantageous.

  The reaction temperature during esterification is 25 to 200 ° C, more preferably 30 to 160 ° C, and particularly preferably 35 to 140 ° C. Esterification itself is possible even if it exceeds 200 ° C., but if it exceeds this, the solid catalyst may deteriorate. On the other hand, when the temperature is lower than 25 ° C., the reaction time becomes long, which is disadvantageous. Moreover, there is no restriction | limiting in reaction pressure.

  When the solid catalyst is used as a fixed bed, esterification can be carried out in a short time by gas-liquid-solid contact in which alcohol is supplied in gas or by bringing the fatty acid monoester fraction and alcohol into solid-liquid contact with the solid catalyst. The reaction can be performed.

  The type of equipment used in the third step is not specified, but as in the first step, a batch type reactor, a continuous tank type reactor, a piston flow type flow type reactor, a tower type flow type reactor, etc. Can be used. For example, the fatty acid monoester fraction and alcohol are supplied to a reactor charged with a solid catalyst, the reactor is controlled at a predetermined temperature and pressure, and the solid catalyst is suspended and stirred to make a solid-liquid contact with the ester. The reaction can be carried out. The solid catalyst may be charged into the reactor as a fixed bed.

By this third step, the free fatty acid contained in the fatty acid monoester fraction becomes a fatty acid monoester product, and the acid value can be further reduced.
(7) Fourth Step On the other hand, the esterification reaction liquid obtained in the third step may contain an alcohol together with a fatty acid monoesterified product and further contain by-product water generated by the esterification reaction. Therefore, it is possible to produce a fatty acid monoester product having a higher purity, that is, a fatty acid monoester product having a lower acid value, by removing alcohol from the reaction solution and removing by-product water present in a trace amount. it can. In particular, even if the unreacted animal oil and / or vegetable oil or diglyceride is contained in the esterification reaction liquid obtained in the third step, a high-boiling component or unreacted component is obtained by performing the fourth step of fractionating the fatty acid monoester product. The reaction animal oil and / or vegetable oil, diglyceride and triglyceride can be removed, and the total amount of glycerin can be reduced.

  As a method for separating and removing alcohol, water, triglyceride and the like from a part of the reaction solution, the reaction solution is introduced into a distillation column, distillation conditions are selected according to the second step, and alcohol and water are introduced from the top of the column. The fatty acid monoester product can be recovered from the bottom of the column and introduced into a vacuum distillation facility to distill the fatty acid monoester product, and any other method can be employed.

(8) Esterification reaction In the present invention, the water-washed sulfonic acid group-introduced amorphous carbon catalyst obtained by washing the sulfonic acid group-introduced amorphous carbon catalyst used in the esterification reaction of the fatty acid having 8 to 24 carbon atoms and the alcohol, When the molar ratio of the alcohol to 1 mol of the fatty acid is in the range of 4 to 50 mol, it can be reused in the esterification reaction to produce a fatty acid monoester product.

The washing method of the sulfonic acid group-introduced amorphous carbon catalyst can be performed in the same manner as the washing method.
The conditions for the esterification reaction using the sulfonic acid group-introduced amorphous carbon catalyst or the water-washed sulfonic acid group-introduced amorphous carbon catalyst are not particularly limited. For example, the reaction temperature is 25 to 200 ° C, more preferably 30 to 160 ° C. Especially preferably, it is 35-140 degreeC. Although esterification itself is possible even if it exceeds 200 degreeC, when it exceeds this, the said catalyst may deteriorate. On the other hand, when the temperature is lower than 25 ° C., the reaction time becomes long, which is disadvantageous. Moreover, although there is no restriction | limiting in reaction pressure, it is a pressure which can ensure the amount of alcohol liquids required for a fatty-acid monoesterified product and the said alcohol to react in a liquid phase.

  Moreover, the usage-amount of the alcohol with respect to the said fatty acid is 4-50 mass parts of alcohol with respect to 1 mass part of fatty acids, Preferably it is 5-50 mass parts, More preferably, it is 5-40 mass parts, Most preferably, it is 7-40 mass. Part. When the amount is less than 4 parts by mass, esterification does not proceed sufficiently. On the other hand, when the amount exceeds 50 parts by mass, excessive energy is required in the alcohol recovery step, which is disadvantageous. In particular, in order to reduce the acid value of the resulting fatty acid monoester product, it is necessary to reduce the amount of water and unreacted fatty acid, and in the above range, the esterification reaction rate is improved, the amount of unreacted fatty acid is reduced, A fatty acid monoester having an acid value of 0.5 or less can be obtained. In addition, in the esterification reaction, when the acid value cannot be satisfied by one-stage esterification reaction, the esterification reaction may be performed in multiple stages while removing water. Thereby, a fatty acid monoester product having a low acid value can be obtained efficiently.

  The type of the apparatus used in the esterification reaction is not particularly limited, but a batch type reactor, a continuous tank type reactor, a piston flow type flow type reactor, a column type flow type reactor, or the like can be used. For example, the fatty acid and alcohol are supplied to a reactor charged with the water-washed sulfonic acid group-introduced amorphous carbon catalyst, the reactor is controlled to a predetermined temperature and pressure, and the catalyst is suspended and stirred for solid-liquid contact. The esterification reaction can be carried out. The water-washed sulfonic acid group-introduced amorphous carbon catalyst may be charged as a fixed bed in the reactor.

(9) Fuel for diesel engine When the fatty acid monoester product of the present invention is produced by the first step to the third step, and further to the fourth step, the total amount of glycerin converted is 0.24 or less and the acid The value is 0.5 or less. In particular, since the by-product rate of monoglyceride is extremely low in the first step, the step of separating the monoglyceride from the fatty acid monoester product becomes unnecessary, and the acid value and the total amount of glycerin can be reduced. For this reason, the obtained fatty acid monoester product can be suitably used as a diesel engine fuel.

Moreover, even when prepared by an esterification reaction of the above fatty acid and alcohol, since it has a high esterification rate and a low acid value, it can be suitably used as a fuel for diesel engines.
For use as a diesel engine fuel, the total amount of glycerin is 0.24% by mass or less, the acid value is 0.5 or less, low viscosity, high volatility, no bad odor, black smoke Although and SO _X is preferably less components, raw materials less SOx component because it is vegetable oil or animal oil, after the esterification reaction, since the fatty acid monoester fraction is isolated, no bad smell, and fatty acid esterified Is highly volatile and can be suitably used as a fuel for diesel engines. Moreover, the fatty acid monoester product produced by the present invention can be used as a fuel for diesel engines, or can be used for other fuels by adding to light oil, kerosene, heavy fuel oil A or the like.

  The fatty acid monoester product produced by the present invention uses biomass resources incorporated in the earth's circulation system as a raw material, and greatly contributes to a reduction in environmental burden as compared with light oil derived from fossil resources. The production method of the present invention can be greatly expected as a technology for mass treatment of industrial and household waste such as waste edible oil used for cooking and the like, particularly a technology for selectively and effectively converting them into useful compounds.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are not intended to limit the present invention, and any design changes in accordance with the gist of the preceding and following descriptions are technical technical features of the present invention. It is included in the range.

Production Example 1: Preparation of Catalyst Carbonaceous powder was obtained by heating 20 g of D-glucose at 400 ° C. for 15 hours under a nitrogen gas flow. This powder was heated at 150 ° C. for 15 hours with stirring in 200 ml of 15% by mass fuming sulfuric acid to obtain a black powder. This was repeatedly washed with distilled water to remove sulfuric acid contained in the powder, and sulfonic acid group-introduced amorphous carbon (I) was obtained.

  The sulfonic acid density of this sulfonic acid group-introduced amorphous carbon was 1.5 mmol / g. In addition, the integrated intensity ratio (I (D) / I (G)) of the G band to the D band in the Raman spectrum was 0.59.

The sulfonic acid density was measured by the following method.
Since most of the sulfur element contained in the sulfone is based on sulfonic acid groups, elemental analysis with fuel (SX-Elements Micro Analyzer YS-10 (yanaco) was used to determine the amount of sulfur in the sample and convert it to the amount of sulfonic acid. .

Further, the measurement of the integrated intensity ratio (I (D) / I (G)) of the G band to the D band in the Raman spectrum was performed by the following method.
The sample powder was placed on a sample holder of an NRS-2100 triple monochromator Raman spectrophotometer (JASCO), and the Raman spectrum was measured. The Raman spectrum in which two bands of the G band for the D band are observed is divided into two peaks of the G band for the D band by Gaussian or Gaussian-Loren-Ruien, and the integrated intensity of the obtained D band and G band is obtained. Each integrated intensity was used.

Production Example 2
Instead of D-glucose, cellulose having a crystallinity of 80% and a polymerization degree of 200 to 300 was used, and the operation was performed in the same manner as in Production Example 1 except that the conditions were changed to those shown in Table 1. Carbon (II) was produced.

実施例１
東京理科器械株式会社のパーソナル有機合成装置（ケミステーション）ＰＰＳ−２５１０の加圧型のガラス試験管に、グリセリントリオレイン酸エステル２．６６ｇ、製造例２で調製したエステル交換反応用触媒０．３６ｇを量りとり、メタノール４．１６ｇと水０．１８ｇとを加えて蓋をして密封した。これを１３０℃で圧力７００ｋＰａで５時間加熱して脂肪酸モノエステル化物反応液を得た。脂肪酸モノエステル収率は９５．８（％）、オレイン酸２．４７（％）であり、オレイン酸モノグリセリド０（％）であった。脂肪酸モノエステル化物反応液の組成を表２に示す。

Example 1
2.66 g of glycerol trioleate and 0.36 g of a transesterification catalyst prepared in Production Example 2 were added to a pressure glass test tube of a personal organic synthesizer (Chemical Station) PPS-2510 of Tokyo Science Instruments Co., Ltd. Weighed and added 4.16 g of methanol and 0.18 g of water, sealed with a lid. This was heated at 130 ° C. and a pressure of 700 kPa for 5 hours to obtain a fatty acid monoester product reaction liquid. The yield of fatty acid monoester was 95.8 (%), oleic acid 2.47 (%), and oleic acid monoglyceride 0 (%). The composition of the fatty acid monoester product reaction solution is shown in Table 2.

  Next, the catalyst was washed with water 10 to 15 times the capacity of the catalyst for about 10 minutes, drained with a filter paper, and dried at 130 ° C. for 3 hours to prepare a washed sulfonic acid group-introduced amorphous carbon catalyst. Subsequently, this water-washed sulfonic acid group-introduced amorphous carbon catalyst was used for transesterification twice under the conditions shown in Table 2. The composition of the resulting fatty acid monoester product reaction solution is shown in Table 2.

Comparative Example 1
After the ester exchange reaction with the water-washed sulfonic acid group-introduced amorphous carbon catalyst of Example 1, the ester exchange reaction was carried out three times under the conditions shown in Table 2 without washing the catalyst with water. The composition of the resulting fatty acid monoester product reaction solution is shown in Table 2.

As is clear from the transesterification reactions of 4, 5, and 6 times in Table 2, the activity was extremely reduced unless water was washed after the reaction.
Example 2
After the transesterification reaction of Comparative Example 1, the above catalyst was washed with water 10 to 15 times the capacity of the catalyst for about 10 minutes, drained with a filter paper, dried at 130 ° C. for 3 hours, and then washed with sulfonic acid groups. An amorphous carbon catalyst was prepared. Subsequently, this water-washed sulfonic acid group-introduced amorphous carbon catalyst was used for transesterification twice under the conditions shown in Table 2. The composition of the resulting fatty acid monoester product reaction solution is shown in Table 2. When the transesterification was performed after washing the catalyst used 6 times in Comparative Example 1 with the water, the transesterification rate at the seventh time recovered to the reaction efficiency at the second time.

比較例２
東京理科器械株式会社のパーソナル有機合成装置（ケミステーション）ＰＰＳ−２５１０の加圧型のガラス試験管に、オレイン酸４．２６ｇ、製造例１で調製したエステル交換反応用触媒０．３ｇを量りとり、メタノール４．８ｇとを加えて蓋をして密封した。これを６４℃、大気圧で６時間加熱してエステル化した。オレイン酸メチルの収率は９９．５％であった。

Comparative Example 2
Weighed 4.26 g of oleic acid and 0.3 g of the catalyst for transesterification prepared in Production Example 1 into a pressurized glass test tube of a personal organic synthesizer (Chemical Station) PPS-2510 from Tokyo Science Instrument Co., Ltd. Methanol 4.8g was added and sealed with a lid. This was esterified by heating at 64 ° C. and atmospheric pressure for 6 hours. The yield of methyl oleate was 99.5%.

  Next, the catalyst was placed in a beaker together with 10 ml of room temperature methanol, washed with hand stirring for 10 minutes, allowed to stand to remove methanol, dried at a temperature of 100 ° C. for 1 hour, and reused. The yield of oleic acid methyl ester was 84.3%. Similarly, methanol washing was performed and esterification reaction was performed 5 times in total. The yield is shown in Table 3.

Methanol washing decreased the esterification reaction activity.
Example 3
After the esterification reaction of Comparative Example 2, the used catalyst was placed in a beaker together with 10 ml of room temperature water, washed with hand stirring for 10 minutes, allowed to stand to remove water, and dried at a temperature of 100 ° C. for 1 hour. Reused. The yield of oleic acid methyl ester was 91.3%. The yield is shown in Table 3. Washing with water recovered the esterification activity from washing with methanol.

比較例４
実施例１と同じ加圧型のガラス試験管に、オレイン酸４．２６ｇ、製造例１で調製したスルホン酸基導入無定形炭素（I）０．３ｇを量りとり、メタノール１．４５ｇとを加えて蓋をして密封した。これを６４℃、大気圧で６時間加熱してエステル化した。オレイン酸メチルの収率は６９．４％であった。メタノール／脂肪酸モル比＝３ではエステル化反応は充分ではない。
実施例４
東京理科器械株式会社のパーソナル有機合成装置（ケミステーション）ＰＰＳ−２５１０の加圧型のガラス試験管に、オレイン酸１．７７５ｇ、製造例２で調製したスルホン酸基導入無定形炭素（II）０．３０７ｇを量りとり、メタノール５．２１ｇとを加えて蓋をして密封した。これを９５℃、圧力は成り行き（約１５０ｋＰａゲージ）に保ちながら、４時間加熱してエステル化した。オレイン酸メチルの収率は９９．９％であった。

Comparative Example 4
To the same pressure-type glass test tube as in Example 1, weigh 4.26 g of oleic acid and 0.3 g of sulfonic acid group-introduced amorphous carbon (I) prepared in Production Example 1, and add 1.45 g of methanol. Sealed with a lid. This was esterified by heating at 64 ° C. and atmospheric pressure for 6 hours. The yield of methyl oleate was 69.4%. When the methanol / fatty acid molar ratio is 3, the esterification reaction is not sufficient.
Example 4
To a pressurized glass test tube of a personal organic synthesizer (chemistation) PPS-2510 manufactured by Tokyo Science Instrument Co., Ltd., 1.775 g of oleic acid, sulfonic acid group-introduced amorphous carbon (II) prepared in Production Example 2 was added. 307 g was weighed, 5.21 g of methanol was added, and the cap was sealed. This was esterified by heating for 4 hours while maintaining the temperature at 95 ° C. and the pressure (about 150 kPa gauge). The yield of methyl oleate was 99.9%.

  The catalyst was then placed in a beaker with 10 ml of room temperature water, washed with hand stirring for 10 minutes, allowed to stand to remove water, dried at a temperature of 130 ° C. for 3 hours, and reused. The yield of oleic acid methyl ester was 99.8%. Similarly, washing with water was performed, and esterification reaction was performed three times in total. The yield is shown in Table 4. The activity of the esterification reaction could be kept high by washing with water.

実施例５
図１に示す装置を使用して、脂肪酸モノエステル化物を製造した。

Example 5
The apparatus shown in FIG. 1 was used to produce a fatty acid monoester product.

In the transesterification reactor A (25A) and the transesterification reactor B (25B) having a capacity of 9 m ³ , fixed beds were prepared with 522 kg of the catalyst of Production Example 2, respectively.
The transesterification reactor A was charged with 1395 kg of methanol, 3853 kg of triglyceride, and 79 kg of water, and reacted at a temperature of 130 ° C. and a gauge pressure of 800 kPa for 5 hours. In order to promote the reaction, a circulation line facility having a heat exchanger was provided and circulated from the bottom to the top of the transesterification reactor A, and stirring and temperature control were performed. After completion of the reaction, the reaction product was discharged into the reactor receiving tank. Thereafter, water was passed through the transesterification reactor A at 15000 kg / h for 20 minutes, and the catalyst in the transesterification reactor A was washed by circulating a cleaning solution using an external circulation pipe. The washing liquid is discharged from the transesterification reactor A, introduced into the water-alcohol separation tower (73), distilled methanol from the top of the tower, temporarily stored in the alcohol storage tank (75), and then the alcohol re-distilling tower. Purified in (77). Methanol distilled from the top of the alcohol re-distillation tower (77) was circulated to the alcohol storage tank (20 ′). The bottom liquid of the water-alcohol separation tower (73) was water and was circulated to the water storage tank (15 ′).

  On the other hand, after completion of the reaction in the transesterification reactor A, while washing the catalyst, the same amount of methanol, triglyceride and water as in the transesterification reactor A are charged into the transesterification reactor B (25B), and the transesterification reaction is performed. When the reaction in the transesterification reactor B is completed, the catalyst in the transesterification reactor B is washed, and the transesterification reaction between the transesterification reactor B and the transesterification reactor A is performed alternately. And switched to catalyst washing.

  The reaction liquid of transesterification reactor A (25A) and transesterification reactor B (25B) is introduced into a distillation column (35) for separation of fatty acid monoester fractions, and methanol and water are distilled off from the top of the column to produce alcohol. It introduce | transduced into the storage tank (75) and the tower bottom liquid was introduce | transduced into the glycerol separation tank (45). In the glycerin separation tank (45), two layers are separated into a lower layer mainly composed of glycerin and an upper layer of the fatty acid monoester fraction (10) mainly composed of the fatty acid esterified product, and the lower layer glycerin is removed from the system. It discharged | emitted and it introduce | transduced into the esterification reactor A and the esterification reactor B which were arrange | positioned in parallel with the upper layer.

  Each of the esterification reactors A and B has a capacity of 503 L, and 350 L of a cation exchange resin (manufactured by Organo, trade name “organoamberlist 15JS-HG / dry”) is used as an esterification catalyst. Formed. Methanol was fed to the esterification reactor A (50A) or B (50B) at 164 kg / h, and the product was introduced into the distillation column (91) from the top of the reactor. Similarly to the transesterification reaction, the esterification reactors A and B were switched for use.

  Methanol and water were distilled from the top of the distillation column (91), and the bottom liquid was introduced again into the distillation column (100) for purification, and a diesel engine fuel was obtained from the top. A heavy substance with a high boiling point was obtained from the bottom of the tower.

  The liquid compositions in the steps I to X in FIG.

  ADVANTAGE OF THE INVENTION According to this invention, the fuel for diesel engines with a continuously low acid value can be manufactured using the regenerated | regenerated sulfonic acid group introduction | transduction amorphous carbon catalyst.

It is explanatory drawing which shows an example of the manufacturing process of the fatty-acid monoester product of this invention including the washing process of a catalyst.

Explanation of symbols

5 ... animal oil and / or vegetable oil,
5 '... animal oil and / or vegetable oil reservoir,
10: Fatty acid monoester fraction,
15 ... water,
15 '... water storage tank,
20 ... alcohol,
20 '... an alcohol reservoir,
25A, 25B ... transesterification reactor,
27. Amorphous carbon catalyst having a sulfonic acid group introduced therein,
30 ... Reboiler,
31 ... Heat exchanger 33 ... Waste water,
35... Distillation tower for separation of fatty acid monoester fraction,
45 ... Glycerin separation tank,
50A, 50B ... esterification reactor,
60 ... cation exchange resin,
73: Water-alcohol separation tower,
75 ... an alcohol reservoir,
77 ... Alcohol re-distilling tower,
80 ... Esterification reaction solution used in the fourth step,
91, 100: Distillation tower.

Claims (9)

The sulfonic acid group-introduced amorphous carbon catalyst used for the reaction of animal oil and / or vegetable oil with the alcohol represented by ROH (R represents a saturated or unsaturated fatty acid group having 1 to 24 carbon atoms) was washed with water. Washed sulfonic acid group-introduced amorphous carbon catalyst,
Including the first step of obtaining a fatty acid monoester product reaction solution by esterification and / or transesterification of the animal oil and / or vegetable oil and alcohol, wherein the sulfonic acid group-introduced amorphous carbon catalyst comprises an organic compound. It is obtained by heat treatment in concentrated sulfuric acid or fuming sulfuric acid at a temperature of 0 to 350 ° C., has a sulfonic acid density of 1 to 8 mmol / g, and has an integrated intensity ratio (I ( D) / I (G)) is a method for producing a fatty acid monoester product having a value of 0.1 to 0.7 . Following the first step,
A second step of obtaining a fatty acid monoester fraction by removing glycerin, the alcohol and water from the reaction mixture of the fatty acid monoester product,
The method according to claim 1 , further comprising a third step of obtaining an esterification reaction solution by contacting and reacting the fatty acid monoester fraction with the alcohol in the presence of a cation exchange resin and / or a sulfonic acid group-introduced amorphous carbon catalyst . A method for producing a fatty acid monoester product.   The method for producing a fatty acid monoester product according to claim 2, further comprising a fourth step of obtaining the fatty acid monoester product from the esterification reaction liquid obtained in the third step. Sulfonic acid group-introduced amorphous carbon used for the esterification reaction of a fatty acid having 8 to 24 carbon atoms and an alcohol represented by ROH (R represents a saturated or unsaturated aliphatic group having 1 to 24 carbon atoms) A water-washed sulfonic acid group-introduced amorphous carbon catalyst obtained by washing the catalyst with water,
It is characterized by being reused in the esterification reaction in a molar ratio of alcohol to 1 mol of the fatty acid in the range of 4 to 50 mol, wherein the amorphous sulfonic acid group-introduced amorphous carbon catalyst contains an organic compound in concentrated sulfuric acid or fuming sulfuric acid. It is obtained by heat treatment at a temperature of 0 to 350 ° C., has a sulfonic acid density of 1 to 8 mmol / g, and an integrated intensity ratio of G band to D band in Raman spectrum (I (D) / I (G) ) Is a method for producing a fatty acid monoester product having a value of 0.1 to 0.7 . In the first step, the animal oil and / or vegetable oil and the alcohol are reacted at a temperature of 60 to 200 ° C. and a pressure of atmospheric pressure to 5 MPa in the presence of the water-washed sulfonic acid group-introduced amorphous carbon catalyst and water. The manufacturing method of the fatty-acid monoester product in any one of Claims 1-3 which is a thing . The method for producing a fatty acid monoester product according to claim 3 , wherein the fatty acid monoester product has an acid value of 0.5 or less. The manufacturing method of the fatty acid monoesterified product of Claim 3 whose total glycerin conversion amount of the fatty acid monoesterified product obtained at the said 4th process is 0.24 mass% or less. The method for producing a fatty acid monoester product according to any one of claims 1 to 7 , wherein the fatty acid monoester product is a fuel for a diesel engine. The method for producing a fatty acid monoester product according to any one of claims 1 to 8 , wherein water used for washing the sulfonic acid group-introduced amorphous carbon catalyst contains 0 to 20% by mass of the alcohol.

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