Method for producing alcohol and method for producing tetraalkoxysilane

Abstract

To provide a method for producing an alcohol, which has high safety, does not need time and effort, and is excellent in cost.SOLUTION: A method for producing an alcohol comprises: step (1) of carrying out a hydrolysis reaction and condensation reaction of tetraalkoxysilane under an alkali catalyst to obtain a dispersion of silica particles comprising the alcohol; step (2) of isolating a solution comprising the alkali catalyst and the alcohol from the dispersion of silica particles obtained in the step (1); and step (3) of passing the solution comprising the alcohol, obtained in the step (2), through an ion exchange resin to obtain the alcohol with the alkali catalyst removed.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing an alcohol and a method for producing a tetraalkoxysilane. [Background technology]

[0002] Alcohol is used in a variety of applications, including chemicals, daily necessities, and food and beverages, and is consumed in a variety of industries. It is an indispensable material in the industry. There are a wide variety of manufacturing methods, and the cost and production They are used according to production volume and purpose.

[0003] For example, Patent Document 1 relates to a method for producing methanol, Or, by reacting vaporized liquid hydrocarbons with water vapor, hydrogen, carbon monoxide and diacid By generating synthesis gas, which is mainly composed of oxidized carbon, and reacting it on a catalyst, A method for producing nol is disclosed.

[0004] Patent Document 2 relates to a method for producing ethanol, and describes a method for producing ethanol from starch-containing raw materials. Ethanol is produced by fermenting the saccharified pellets obtained by infusing koji mold into the pellets. A method for this is disclosed. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 01-180841 [Patent Document 2] Japanese Patent Application Laid-Open No. 2005-65695 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the method for producing methanol described in Patent Document 1, for example, requires high-temperature reaction at temperatures of 800°C or higher. It requires the reaction of hydrocarbons with water vapor under high temperature conditions and generates highly toxic carbon monoxide. Therefore, there are concerns about costs and risks. In addition, the ethanol production method described in Patent Document 2 takes 5 days from the start of fermentation to completion. Not only does it take more than 10 hours, but it also requires the effort of cultivating koji mold, so there are concerns about the effort and cost involved.

[0007] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to It does not require high-temperature steam reactions, does not generate carbon monoxide, and does not require fermentation or koji mold. To provide a method for producing alcohol that does not require laborious work such as culturing.

[0008] Therefore, the present invention does not require the reaction of hydrocarbons with steam at high temperatures and does not generate carbon monoxide. This is a method of producing alcohol that does not require the labor of fermentation or koji mold cultivation. In other words, we provide a highly safe, hassle-free, and cost-effective method for producing alcohol. The purpose is to provide [Means for solving the problem]

[0009] In order to solve the above problems, the present inventors have conducted extensive research and have found that tetraalkoxysilane is used as a starting material. The present invention was completed based on the discovery that the above problems can be solved by using .

[0010] The gist of the present invention is as follows. A first aspect of the present invention relates to a method for producing an alcohol, which comprises the following steps (1) to (3). Step (1): Hydrolysis and condensation of tetraalkoxysilane in the presence of an alkali catalyst to obtain a dispersion of silica particles containing the alcohol. Step (2): The dispersion of silica particles obtained in step (1) is subjected to the alkali catalyst treatment. separating the solvent and the solution containing the alcohol. Step (3): The alcohol-containing solution obtained in step (2) is passed through an ion exchange resin to obtain the pre- A step of obtaining alcohol through a step of removing the alkali catalyst.

[0011] Aspect 2 of the present invention relates to the alcohol production method of aspect 1, wherein the steps (2) and (3) The following step (2-1) is included between the steps. Step (2-1): A reaction mixture containing the alkali catalyst and the alcohol separated in the step (2) distilling the solution to reduce the alkali catalyst concentration;

[0012] Aspect 3 of the present invention relates to the alcohol production method according to Aspect 1 or Aspect 2, wherein in step (3), The resulting alcohol is methanol.

[0013] A fourth aspect of the present invention relates to a method for producing an alcohol according to any one of the first to third aspects, The alkaline catalyst includes ammonia.

[0014] A fifth aspect of the present invention relates to a method for producing an alcohol according to any one of the first to fourth aspects, wherein The tetraalkoxysilane is tetramethoxysilane.

[0015] A sixth aspect of the present invention relates to a method for producing an alcohol according to any one of the first to fifth aspects, comprising: The alkali in the solution containing the alkali catalyst and alcohol separated in the step (2) The concentration of the catalyst is 0.1% by mass to 3% by mass.

[0016] A seventh aspect of the present invention relates to a method for producing an alcohol according to any one of the first to sixth aspects, wherein The alcohol in the solution containing the alkali catalyst and the alcohol separated in the step (2) The concentration is 60% by mass to 90% by mass.

[0017] Aspect 8 of the present invention is a method for producing an alcohol according to any one of aspects 2 to 7, further comprising the steps of: The step (2-1) is a step of reducing the concentration of the alkali catalyst to 1000 mass ppm or less. R

[0018] A ninth aspect of the present invention relates to a method for producing an alcohol according to any one of the first to eighth aspects, The concentration of the alkali catalyst in the alcohol obtained in the step (3) is 30 mass ppb or less. be.

[0019] A tenth aspect of the present invention relates to a method for producing an alcohol according to any one of the first to ninth aspects, wherein The ion exchange resin used in the step (3) is at least one selected from strongly acidic cation exchange resins. Includes one.

[0020] Aspect 11 of the present invention relates to the alcohol production method of Aspect 10, wherein the step (3) is The ion exchange resin includes at least one selected from strongly acidic cation exchange resins of H type.

[0021] A twelfth aspect of the present invention is a method for producing tetraalkoxysilane, which comprises the steps of any one of the first to eleventh aspects. A tetraalkoxy compound is produced by using an alcohol obtained by any one of the methods for producing alcohols. Manufactures silane. [Effects of the Invention]

[0022] According to this embodiment, alcohol can be produced in a highly safe, hassle-free, and cost-effective manner. Specifically, it is possible to produce olefins without the need for a high-temperature reaction between hydrocarbons and steam. It does not generate carbon monoxide and does not require the labor of fermentation or koji mold cultivation. be. DETAILED DESCRIPTION OF THE INVENTION

[0023] The present invention will be described in detail below, but the present invention is not limited to the following embodiments. It should be noted that the present invention can be practiced with various modifications within the scope of its gist. When using the expression "~", it is used as an expression that includes the numerical values ​​or physical properties before and after it.

[0024] <<How alcohol is produced>> The method for producing an alcohol according to this embodiment includes the following steps (1) to (3). Step (1): Hydrolysis and condensation of tetraalkoxysilane in the presence of an alkali catalyst to obtain a dispersion of silica particles containing the alcohol. Step (2): The dispersion of silica particles obtained in step (1) is subjected to the alkali catalyst treatment. separating the solvent and the solution containing the alcohol. Step (3): Passing the alcohol-containing solution obtained in step (2) through an ion exchange resin, A step of obtaining alcohol from which the alkali catalyst has been removed.

[0025] Each step of this embodiment will be described below.

[0026] <Process (1)> In this embodiment, step (1) is a process for the dehydration of tetraalkoxysilane in the presence of an alkali catalyst. This is a process in which a decomposition reaction and a condensation reaction are carried out to obtain a dispersion of silica particles containing alcohol. The tetraalkoxysilane is hydrolyzed to obtain an alcohol derived from the alkoxy group. For example, tetramethoxysilane can be treated with methanol, and tetraethoxysilane can be treated with If so, you can get ethanol.

[0027] The above-mentioned alkali catalyst is, for example, prepared by preparing a solution (A) containing an alcohol and an alkali catalyst. Then, the solution (A) is mixed with the solution (B) containing tetraalkoxysilane and, if necessary, with the solution ( This can be achieved by adding a solvent such as A) or solution B. In addition to the solution (B), a solution (C) containing an alkali catalyst or water is added to the solution (A). This can also be achieved.

[0028] In the solution (A) containing an alkali catalyst and an alcohol in this embodiment, Examples of the catalyst include ethylenediamine, diethylenetriamine, and triethylenetetramine. Examples include amines, ammonia, urea, ethanolamine, and tetramethylammonium hydroxide. Among them, it has excellent catalytic action, can suppress metal contamination, and is highly volatile and can be easily added. Ammonia is preferred because it is easily removable after the hydrolysis reaction and the condensation reaction. The alkali catalyst may be used alone or in combination of two or more kinds.

[0029] In the solution (A) of this embodiment, examples of the alcohol include methanol, Examples include ethanol, propanol, isopropanol, and ethylene glycol. However, it is easy to dissolve tetraalkoxysilane and is used in hydrolysis and condensation reactions. Since the products produced are the same as those produced by methanol and ethanol, it is easy to manufacture. is more preferred, and methanol is even more preferred. The alcohol may be used alone or in combination of two or more kinds.

[0030] The solution (A) in this embodiment further has the advantage of promoting the hydrolysis of alkoxysilane. From this viewpoint, it is preferable that the composition contains water. Furthermore, the solution (A) may contain a solvent other than alcohol and water.

[0031] In this embodiment, the combination of alcohol and alkali catalyst in solution (A) is A combination of at least one of methanol and ethanol and ammonia is preferred. A combination of methanol and ammonia is more preferred.

[0032] In this embodiment, the concentration of the alkali catalyst in the solution (A) is 0% by mass to 10.0% by mass. Here, it is preferable to suppress the aggregation of silica particles and to improve the dispersion stability of silica particles in the silica sol. From this viewpoint, the concentration is preferably 0% by mass or more, and more preferably 0.1% by mass or more. The concentration of the alkali catalyst in the liquid (A) may be 0 mass %, that is, the liquid (A) may not contain an alkali catalyst. In that case, a solution containing an alkaline catalyst, such as solution (C) described below, should be added. The reaction may be carried out in the presence of an alkali catalyst. From the viewpoint of controllability, the concentration is preferably 10.0% by mass or less, and more preferably 8.0% by mass or less. preferable.

[0033] In this embodiment, the concentration of the alcohol in the solution (A) is preferably 10% by mass to 96% by mass. From the viewpoint of dispersibility of the tetraalkoxysilane in the reaction liquid, the above concentration is preferably It is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. In addition, from the viewpoint of dispersibility in the reaction liquid of silicic acid produced by the hydrolysis reaction, the above-mentioned concentrated The concentration is preferably 96% by mass or less, more preferably 94% by mass or less, and even more preferably 90% by mass or less. It is most preferable that the content is 85 mass % or less, and even more preferable that the content is 85 mass % or less.

[0034] In this embodiment, the concentration of water in the solution (A) is preferably 3% by mass to 90% by mass. From the viewpoint of dispersibility of silicic acid produced by the hydrolysis reaction in the reaction solution, the above concentration is set to 3. The content of tetraalkoxysilane in the reaction mixture is preferably 5% by mass or more, and more preferably 5% by mass or more. From the viewpoint of dispersibility of the silane, the concentration is preferably 90% by mass or less, and more preferably 50% by mass or less. More preferable.

[0035] When the solution (A) in this embodiment contains a solvent other than alcohol and water, the concentration of the solvent is The balance is preferably an alkali catalyst, an alcohol and water.

[0036] The solution (B) containing tetraalkoxysilane in this embodiment is There is no particular limitation as long as it includes orchids. Preferred tetraalkoxysilanes are tetramethoxysilane and tetraethoxysilane. Tetramethoxysilane is preferable because it allows for the production of methanol at low cost and safely. Tetraethoxysilane can be used to produce ethanol efficiently and at low cost. Among the tetraalkoxysilanes, tetramethoxysilane is more preferable.

[0037] The solution (B) has excellent dispersibility of tetraalkoxysilane in the reaction liquid, It is preferred that the solvent is contained.

[0038] Examples of the solvent in the solution (B) include methanol, ethanol, propanol, Alcohols such as isopropanol and ethylene glycol; acetone and methyl ethyl ketone and esters such as ethyl acetate. The product produced is the same as the product used in the reaction, and it is convenient for manufacturing. Preferred is ethanol, more preferred is methanol and ethanol, and even more preferred is methanol. These solvents may be used alone or in combination of two or more.

[0039] The concentration of the tetraalkoxysilane in the solution (B) is preferably 76% by mass to 89% by mass. Here, from the viewpoint of reducing the amount of solvent used and reducing the water content in the solvent, The concentration is preferably 76% by mass or more, more preferably 77% by mass or more. From the viewpoint of dispersibility of the tetraalkoxysilane, the concentration is preferably 89% by mass or less, and more preferably 89% by mass or less. It is more preferably 8% by mass or less.

[0040] The concentration of the solvent in the solution (B) is preferably 11% by mass to 24% by mass. From the viewpoint of dispersibility of the tetraalkoxysilane in the liquid, the concentration is preferably 11% by mass or more. It is preferable that the amount of the solvent used is reduced, and more preferable that the amount of the solvent used is reduced. From the viewpoint of productivity of silica particles, the concentration is preferably 24% by mass or less, and more preferably 23% by mass or less. preferable. The concentration of the solvent in the solution (B) is the remainder of the tetraalkoxysilane in the solution (B). It is preferable.

[0041] The solution (C) containing an alkali catalyst in this embodiment is not particularly limited as long as it contains an alkali catalyst. It will not be done. The solution (C) is used as a solvent from the viewpoint of efficiently proceeding with the hydrolysis reaction and the condensation reaction. The mixture may contain water.

[0042] The alkali catalyst in the solution (C) may be, for example, ethylenediamine, diethylenetriamine, Triamine, triethylenetetraamine, ammonia, urea, ethanolamine, tetramethyl Among them, ammonium hydroxide has excellent catalytic action and is easy to control particle shape. It is easy to use, can suppress metal contamination, and is highly volatile, making it suitable for removal after hydrolysis and condensation reactions. Ammonia is preferred because of its excellent scavenging properties. These alkali catalysts may be used alone or in combination of two or more.

[0043] The solution (C) may contain a solvent other than water. Examples of the solvent other than water in the solution (C) include methanol, ethanol, propanol, etc. Examples of the solvents include alcohols such as alcohol, isopropanol, and ethylene glycol. The solvent may be used alone or in combination of two or more.

[0044] The concentration of water in the solution (C) is preferably 75% by mass to 100% by mass. From the viewpoint of dispersibility in the reaction liquid of silicic acid produced by the decomposition reaction, the above concentration is 75 mass% or more. The upper limit is not particularly limited, and is preferably 100 mass % or more. %, that is, it may consist of only water, or it may be 99 mass % or less.

[0045] The concentration of the alkali catalyst in the solution (C) is preferably 0% by mass to 25% by mass. In order to prevent the reaction from proceeding too quickly and to facilitate reaction control, the concentration is preferably 25% by mass or less. The concentration of the alkali catalyst is preferably 0 mass %, more preferably 20 mass % or less. It does not have to be contained, but if it is contained, it may be, for example, 1% by mass or more.

[0046] The concentration of the solvent other than water in the solution (C) is preferably the balance of water and the alkali catalyst. It's nice.

[0047] In step (1) of this embodiment, the solution (A) is mixed with the solution (B) according to the circumstances. By adding the solution (C) to the reaction mixture, the reaction of tetraalkoxysilane under an alkali catalyst is carried out. The hydrolysis reaction and condensation reaction proceed stably. This allows the silica particles containing alcohol to be A dispersion of the formula:

[0048] In the above step (1), the amount of solution (B) added was 5 parts by volume per 100 parts by volume of solution (A). From the viewpoint of production efficiency, the amount of solution (B) added is preferably 5 parts by volume to 80 parts by volume. Parts by volume or more is preferred, 30 parts by volume or more is more preferred, and 50 parts by volume or more is even more preferred. From the viewpoint of reaction control, the amount of solution (B) added is preferably 80 parts by volume or less, and more preferably 70 parts by volume or less. Parts by volume or less is more preferred, and 60 parts by volume or less is even more preferred.

[0049] In the above step (1), the amount of solution (C) added was 5 parts by volume per 100 parts by volume of solution (A). From the viewpoint of production efficiency, the amount of solution (C) added is preferably 5 parts by volume to 40 parts by volume. Parts by volume or more is preferred, 10 parts by volume or more is more preferred, and 15 parts by volume or more is even more preferred. From the viewpoint of reaction control, the amount of solution (C) added is preferably 40 parts by volume or less, and more preferably 30 parts by volume or less. Parts by volume or less is more preferred, and 20 parts by volume or less is even more preferred.

[0050] The concentration of water in the reaction solution in the hydrolysis and condensation reaction systems changes significantly during the reaction. This is because the concentration of water changes during step (1). The dispersibility of the intermediate product, silicic acid, in the reaction solution changes, and the stability of the alcohol production is impaired. The rate of change in water concentration is preferably 75% or less, and 50% or less. It is more preferable to set it to below.

[0051] The concentration of water in the reaction system is the concentration of the liquid and the liquid in the reaction system in the hydrolysis reaction and the condensation reaction. The total amount of water in the total amount of dissolved substances. The total amount of liquid and dissolved substances in the reaction system is only solution (A) at the start of the reaction. During the reaction, the total amount of solution (A), solution (B), solution (C) and the alcohol produced in the reaction is In addition, silica particles dispersed in the liquid are mixed with the liquid and the substance dissolved in the liquid in the reaction system. Does not include.

[0052] The concentration of the alkali catalyst in the reaction system for the hydrolysis reaction and the condensation reaction is It is preferable to maintain the content of 0.01% by mass to 10.0% by mass in the range of 0.0% by mass to 10.0% by mass. (2) To lower the boiling point of the above-mentioned alkaline catalyst, in order to reduce energy costs, The concentration is preferably 0.01% by mass or more, more preferably 0.1% by mass or more. ) to reduce the content of alkaline catalyst in the separated liquid, that is, the content of the ion exchange resin in step (3) From the viewpoint of extending the breakthrough time, the concentration of the alkali catalyst to be maintained is preferably 10.0 mass % or less. It is preferably 8.0 mass % or less, and more preferably 8.0 mass % or less.

[0053] The concentration of the alkali catalyst in the reaction system is the concentration of the alkali catalyst in the reaction system during the hydrolysis reaction and the condensation reaction. This refers to the total amount of alkali catalyst in the total amount of substances dissolved in the body and liquid.

[0054] The reaction temperature of the hydrolysis reaction and condensation reaction of tetraalkoxysilane (the reaction liquid in the reaction system) The reaction temperature is preferably 15°C to 50°C. Here, the reaction does not proceed too slowly and from the viewpoint of controllability. From this viewpoint, the reaction temperature is preferably 15°C or higher, more preferably 20°C or higher. From the viewpoint of the balance between the decomposition reaction rate and the condensation reaction rate, the reaction temperature is preferably 50°C or less. The temperature is preferably 45°C or lower.

[0055] <Process (2)> In the step (2) of this embodiment, the dispersion of silica particles obtained in the step (1) is This is a step of separating the solution containing the alkaline catalyst and the alcohol.

[0056] In the step (2), for example, the dispersion of silica particles obtained in the step (1) is heated. The solution containing the alkali catalyst and alcohol can be separated by the heating. You can do this while doing other things.

[0057] The heating temperature should be equal to or higher than the boiling point of the dispersion medium of the silica particle dispersion, and is in the range of 50°C to 100°C. is preferred.

[0058] The concentration of the alkali catalyst in the solution containing the separated alkali catalyst and alcohol is 0.1 mass %. From the viewpoint of simplifying the operation of step (2), the above The concentration is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and more preferably 0.3% by mass or more. The above is more preferable. In the subsequent step (3), the breakthrough time of the ion exchange resin is extended. From this viewpoint, the concentration is preferably 3% by mass or less, more preferably 1% by mass or less, and more preferably 0.5% by mass or less. It is more preferably % by mass or less.

[0059] The concentration of alcohol in the solution containing the separated alkali catalyst and alcohol is 60% by mass. From the viewpoint of recovering alcohol with higher purity, it is preferable that the content of the alcohol is 90 mass % or less. The concentration is preferably 60% by mass or more, more preferably 65% ​​by mass or more, and more preferably 70% by mass or more. From the viewpoint of reducing the cost of the separation operation, the concentration is more preferably 90% by mass or less. is preferable, more preferably 80% by mass or less, and even more preferably 75% by mass or less. The component concentrations of the alkali catalyst and alcohol-containing solution in the specification are based on the evaluation results in the examples described below. The concentration of each component can be measured by gas chromatography as described in the titration method.

[0060] <Process (2-1)> In this embodiment, step (2-1) is performed between step (2) and step (3) described later. The solution containing the alkali catalyst and alcohol separated in the above step (2) is distilled to obtain the alkali. The process may include a step of reducing the catalyst concentration.

[0061] The distillation can be carried out by a conventionally known method. For example, the distillation can be carried out by using a vessel having a jacket. The term "having a jacket" means that the solution can be heated easily. This refers to the two-layer structure that allows for temperature adjustment, and is usually located on the outside of the inner tank. The two-layered hollow part of the jacket can be filled with steam, water, oil, etc. to control the temperature. can.

[0062] In the step (2-1), the alkali catalyst and alcohol separated in the step (2) are The solution containing the compound is distilled by heating it, and the temperature is preferably 65°C to 100°C. From the viewpoint of recovering as high a concentration of alcohol as possible in a short time, the temperature is set to 65℃. Preferably, the temperature is 80°C or higher, and more preferably 80°C or higher. The temperature is preferably 100°C or lower, more preferably 90°C or lower.

[0063] The distillation time is preferably 0.5 to 6 hours. Here, in order to recover more alcohol, From this viewpoint, the time is preferably 0.5 hours or more, and more preferably 1 hour or more. From the viewpoint of reducing costs in the distillation operation, the time is preferably 6 hours or less, and more preferably 4 hours or less. The following is more preferred:

[0064] The pressure for distillation is preferably 0.01 MPa to 1.0 MPa. From the viewpoint of recovering alcohol, the pressure is preferably 0.05 MPa or more, and more preferably 0.0 It is more preferable that the pressure is 8 MPa or more. From this viewpoint, the pressure is preferably 0.5 MPa or less, and more preferably 0.3 MPa or less.

[0065] The above step (2-1) can provide a solution containing the target alcohol. The concentration of the alkali catalyst contained in the solution containing alcohol is 1000 mass ppm or less. Preferably, the content is 100 mass ppm or less, more preferably 100 mass ppm or less, and the lower the content, the better. When the tetraalkoxysilane described below is produced using the obtained alcohol, The concentration of the alkali catalyst contained in the alcohol to be used is preferably 1 mass ppm or more, and 10 mass ppm or more. Amounts of ppm or more are more preferable.

[0066] <Process (3)> In the present embodiment, step (3) is carried out by condensing the alcohol obtained in step (2) or step (2-1) above. The alkali catalyst is removed by passing the solution containing the alkali through an ion exchange resin. This is the process of obtaining a call.

[0067] In the step (3), the alkali catalyst and The alkali catalyst is removed by passing a solution containing the alkali and alcohol through an ion exchange resin. Any known ion exchange resin can be used as long as it can remove the alkaline catalyst. Among these, it is preferable to use a strongly acidic cation exchange resin. It is more preferable to use H-type. Commercially available products include Diaion ( Registered trademark) SK1BH, Diaion PK216LH, Diaion RCP160M, etc. However, from the viewpoint of cost, Diaion SK1BH and Diaion PK216L H is preferred, and Diaion SK1BH is more preferred. Usually, when water or other liquid is passed through the above ion exchange resin, polystyrene sulfonic acid (hereinafter referred to as polystyrene sulfonic acid) is released from the resin. However, in the above step (3), the alkaline catalyst is removed without dissolving the PSS. This allows for the removal of contaminants, resulting in the production of alcohol with minimal contamination. Although the mechanism is unclear, alcohols such as methanol have a greater effect on the ionic strength of resins than water. The resin is less likely to swell due to the small effect on the ion exchange groups, so the cross-linking of the resin is less likely to be broken. The sulfur content derived from PSS is generally used in industrial applications such as solvents. If so, it is preferable to keep the concentration below 1 ppm, and 0.2 ppm to avoid contamination of the product. Less than pm is more preferable.

[0068] The average exchange capacity of the above ion exchange resins is 1.00 mmol / mL-Resin~2 0.00 mmol / mL-Resin is preferred. The above mmol / mL-Resin is It represents the number of moles of ion exchange that can be performed per mL of ion exchange resin. From the viewpoint of recovery, the average exchange capacity of the ion exchange resin is 1.25 mmol / mL-R. Resin or higher is preferable, and 1.50 mmol / mL-Resin or higher is more preferable. In addition, in order to reduce the chance of contact with dangerous alkaline catalysts, Resin or less is preferred, and 1.90 mmol / mL-Resin or less is more preferred.

[0069] The temperature of the solution when passing through the ion exchange resin is preferably 0°C to 65°C. From this viewpoint, the temperature is preferably 25°C or higher, and more preferably 35°C or higher. From the viewpoint of reducing the occurrence of oxidative stress, the temperature is preferably 60°C or less, more preferably 50°C or less. .

[0070] The amount of liquid passed through the ion exchange resin is preferably 1 to 20 times the amount of the ion exchange resin. From the viewpoint of shortening the time required for the ion exchange resin treatment, the amount of the liquid passing through the ion exchange resin is preferably at least twice as large as the amount of the ion exchange resin, and more preferably at least four times as large as the amount of the ion exchange resin. In order to increase the time that the liquid and the resin are in contact with each other, the above-mentioned amount of liquid passing through the resin is more preferable. is preferably 15 times or less, more preferably 12 times or less, of the ion exchange resin.

[0071] The flow rate when passing the liquid through the ion exchange resin is 1L / L-Resin to 20L / L-Resin. The above L / L-Resin represents the amount of liquid passing through per 1 L of the ion exchange resin capacity. In order to shorten the liquid passing time and improve productivity, the flow rate is set at 2L / L-Res. in or more is preferable, and 4 L / L-Resin or more is more preferable. From the viewpoint of extending the time required for the resin to be removed, the pressure is preferably 15 L / L-Resin or less. 2L / L-Resin or less is more preferable.

[0072] The target alcohol can be obtained by the above step (3), but the obtained alcohol The concentration of the alkali catalyst contained in the fuel is preferably 30 mass ppb or less, and more preferably 10 mass ppb or less. By carrying out step (3), it is possible to reduce the amount of the distillation product. This method allows for a stable and consistent production of high-purity alcohol with a more consistent quality than conventional purification methods. On the other hand, it is of sufficient purity for general industrial uses such as solvents and fuels. Therefore, from the viewpoint of production cost and production efficiency, the alkali contained in the obtained alcohol is The concentration of the catalyst may be 0.1 mass ppb or more, or 5 mass ppb or more. The alcohol and alkali catalyst in the alcohol-containing solution obtained in step (3) of the specification The concentration of each component was measured by gas chromatography as described in the evaluation method of the Examples below. It can be measured with a The concentration of the alkali catalyst is determined by the ion exchanger having the effect of removing the alkali catalyst under appropriate conditions. This can be reduced by passing the liquid through a resin.

[0073] According to the production method of this embodiment, a high-temperature reaction between hydrocarbon and water vapor is not required, It does not generate carbon monoxide and does not require laborious fermentation or koji mold cultivation. You can get alcohol without any hassle. The alcohol obtained by the production method according to this embodiment can be used for any purpose. However, it is preferably used, for example, in the production of tetraalkoxysilanes.

[0074] <Method for producing tetraalkoxysilane> That is, the present invention provides a method for producing an alcohol by using the alcohol obtained by the above-mentioned "Production method of alcohol" The present invention relates to a method for producing tetraalkoxysilane.

[0075] The method for producing tetraalkoxysilane according to this embodiment uses the above alcohol. Conventional process methods can be used. For example, a silicon-containing compound is reacted with the alcohol in the presence of an alkali catalyst. Thus, tetraalkoxysilane can be obtained.

[0076] The silicon-containing compound in this embodiment includes, in addition to silicon itself, iron silicide containing iron and the like. Among them, the silicon-containing alloys (called silicon alloys) can be used to make the reaction more efficient. From the viewpoint of efficient operation, the silicon purity of the silicon-containing compound is preferably 85% by mass or more. , and more preferably 95% by mass or more.

[0077] The alcohol in this embodiment is obtained by the step (1) in the above "Method of Producing Alcohol". Therefore, the alkali catalyst used in the production of tetraalkoxysilane may be included. It is suitable as a raw material that serves both as an alkaline catalyst and an alcohol. The solvent may be further added as needed.

[0078] The alkali catalyst is, for example, the catalyst used in step (1) of the above-mentioned "Method for Producing Alcohol." Similarly, ethylenediamine, diethylenetriamine, triethylenetetraamine, ammonia These include urea, ethanolamine, and tetramethylammonium hydroxide. It may be contained in alcohol.

[0079] When an alkaline catalyst is further added, copper catalyst such as copper chloride or potassium, sodium Alkoxides or hydroxides of alkali metals such as aluminum, rubidium, and lithium are examples. Among them, potassium-containing alkaline catalysts such as copper chloride, potassium methoxide, and caustic potassium are More preferred are copper chloride and potassium hydroxide from the viewpoints of reactivity and cost.

[0080] The reaction solution contains the silicon-containing compound, alcohol, alkali catalyst, and a solvent. That's fine. Examples of the solvent include tetraalkoxysilane, which is also the product, octane, nonane, Paraffin hydrocarbons such as decane and dodecane, octylbenzene, dodecylbenzene, etc. Examples of the product include alkylbenzene hydrocarbons. When used as a solvent, it is not necessary to separate the solvent from the product, which is a major advantage in the process. This is preferable.

[0081] The alcohol concentration in the reaction solution is preferably 1% by mass to 20% by mass. From the viewpoint of making the catalyst easily soluble and suppressing precipitation of the catalyst in the system, the concentration is preferably 1% by mass or more. In addition, when the heat of reaction decreases at the end of the reaction, the liquid temperature drops and the reaction rate slows down. From the viewpoint of suppressing the generation of ions, the concentration is preferably 20% by mass or less.

[0082] The concentration of the alkali catalyst in the reaction liquid is preferably 1% by mass to 20% by mass relative to silicon. From the viewpoint of catalytic activity, the concentration is preferably 1% by mass or more. Therefore, from an economical point of view, the concentration is preferably 20% by mass or less.

[0083] The reaction temperature is preferably 120° C. to 200° C. Here, from the viewpoint of obtaining a high reaction rate, The reaction temperature is preferably 120°C or higher, more preferably 150°C or higher. To proceed efficiently, a high reaction temperature is preferable, but from the viewpoint of energy costs, The temperature is preferably 200°C or lower, and more preferably 185°C or lower.

[0084] The reaction is preferably carried out under pressure, and the absolute pressure is 0.1×10 5Pa~10×10 5 Here, from the viewpoint of obtaining a practically sufficient reaction rate, the pressure is preferably 0.1 × 10 5 Pa or more is preferable, 2 × 10 5 Pa or more is more preferable. From the viewpoint of preventing this, the pressure is 10 × 10 5 Pa or less is preferable, and 8×10 5 Pa or below is better More preferable. [Example]

[0085] The present invention will be described in more detail below using examples. Unless otherwise stated, the following examples are not intended to be limiting.

[0086] Evaluation Method (Measurement of concentration of each component) Measurement of the concentration of methanol (alcohol) contained in the solution obtained by the distillation operation in each example The determination was carried out by gas chromatography. Specifically, 1 g of sample was weighed into a 10 mL sample tube and acetonitrile, the internal standard, was added. The mixture was mixed with 0.1g of HCl and placed in a gas chromatograph vial. Measurements were performed using a 7820A (model name, manufactured by Agilent). The sample was used, and the temperature was raised to 40°C for 2 minutes, then increased to 150°C at 10°C per minute. The temperature is raised to °C and the measurement is carried out.

[0087] The concentration of water contained in the solution obtained by the distillation operation in each example was measured by the same method as above. The measurement was carried out in the same manner as for the concentration measurement.

[0088] The ammonia contained in the solution obtained by the distillation operation and the ion exchange resin The concentration of Nia (alkali catalyst) was measured by ion chromatography. Specifically, the sample solution is diluted appropriately to a concentration that falls within the calibration curve range, and the Integr Measurements were performed using a ThermoScientific ion HPIC (model name). .

[0089] The concentration of sulfur contained in the solution obtained by passing the solution through the ion exchange resin was measured as follows: This was done by ion chromatography. Specifically, the sample solution was placed in an automatic combustion and absorption apparatus AQF-2100H (model name: Nitto Seiki). The combustion gas is absorbed in an absorbing solution, which is then used for ion exchange. Chromatography ICS-5000+ (Model name, ThermofisherScient Measurements were taken using a FiC (manufactured by FiC).

[0090] <Test Example> Example 1 Solution (A) was prepared by mixing pure water at a concentration of 7.5 mass %, ammonia at a concentration of 1.2 mass %, and the remaining The solution was prepared so that the remaining part was methanol. Solution (B) was prepared by mixing tetramethoxysilane and methanol at a ratio of 85:15 (by mass). A solution was prepared. As solution (C), a 4 mass % aqueous ammonia solution was prepared. Then, the solution (A) was added to a reaction vessel equipped with a thermometer, a stirrer, a supply pipe, and a distillation line. The temperature of the reaction solution was adjusted to 23°C, and the above solution ( 58 parts by volume of B) and 16 parts by volume of the above solution (C) were added at equal speeds, and methanol was added. A dispersion of silica particles containing the silica particles was obtained (step (1)).

[0091] The silica particle dispersion obtained above was diluted to a content of about 20% by mass. The temperature is increased to separate the solution containing ammonia and methanol in the dispersion of silica particles. The mixture was separated and collected (step (2)). The concentration of ammonia in the recovered solution was 0.36 mass%, and the concentration of methanol was 73.6 mass%. The concentration of the water was 26.0 mass %.

[0092] The solution containing ammonia and methanol separated above is distilled in a distillation column. A solution with an ammonia concentration of 23 ppm by mass was obtained (step (2-1)).

[0093] To evaluate under more severe conditions, the ammonia concentration was set to 50 mass pp for ion exchange resin flow. The sample solution was prepared with the aim of obtaining a concentration of about 1000 ppm. Add 30 ml of purified SK1BH, remove the air, and let it stand. Then, run water through the jacket and heat it up to 40°C. After confirming that the internal temperature was 40°C, the mixture was pumped into the jacketed column at a flow rate of 150 ml / hr. Methanol was obtained by elution (Step (3)). Sampling was carried out every 4 hours, and the ammonia concentration of the obtained methanol was measured. The solution was prepared approximately every 8 hours and continued to be added to the same column. The ammonia concentration before flowing into the column and the ammonia concentration after 200 hours had passed were The concentration of the eluted polystyrene was the same as that of the ion exchange resin (Table 1). The sulfur content, which indicates the content of toluenesulfonic acid, was less than 0.2 ppm by mass, which was below the detection limit.

[0094] Example 2 In step (3) of Example 1, the ammonia concentration was increased by 10 times to 500 mass ppm. The sample solution was prepared so that the flow rate was about 300 ml / hr. Except for this, the same procedure as in Example 1 was used to transfer the solution to the jacketed column to obtain methanol. Sampling was carried out every hour, and the ammonia concentration of the resulting methanol was measured. After a certain period of time, the ammonia concentration before and after passing through the column became the same (Table 1) The sulfur content of polystyrene sulfonic acid, which is the eluted part of the ion exchange resin, is measured. The concentration was below the detection limit of less than 0.2 ppm by mass.

[0095] A table was prepared showing the ammonia concentration in the alcohol obtained in each example for each liquid passing time. (Table 1). [Table 1] [Industrial Applicability]

[0096] According to the alcohol production method of this embodiment, a hydrocarbon and water vapor are reacted at high temperatures. It does not require any fermentation or koji mold, and does not generate toxic gases such as carbon monoxide. Alcohol can be obtained without the need for laborious cultivation or the like. Furthermore, the alcohol obtained by the production method according to this embodiment is highly pure and can be used in a variety of applications. It can be used for industrial purposes, for example, it is suitable for use in the production of tetraalkoxysilane. I can.

Claims

1. A method for producing an alcohol, comprising the following steps (1) to (3): Step (1): Hydrolysis and condensation of tetraalkoxysilane in the presence of an alkali catalyst to obtain a dispersion of silica particles containing the alcohol. Step (2): The dispersion of silica particles obtained in step (1) is subjected to the alkali catalyst treatment. separating the solvent and the solution containing the alcohol. Step (3): Passing the alcohol-containing solution obtained in step (2) through an ion exchange resin, A step of obtaining an alcohol through a step of removing the alkali catalyst.

2. The method according to claim 1, further comprising the following step (2-1) between steps (2) and (3): Manufacturing method of the ball. Step (2-1): A reaction mixture containing the alkali catalyst and alcohol separated in the step (2) distilling the solution to reduce the alkali catalyst concentration;

3. The alcohol according to claim 1, wherein the alcohol obtained in step (3) is methanol. Manufacturing method.

4. The method for producing an alcohol according to claim 1 , wherein the alkaline catalyst comprises ammonia.

5. 2. The alkoxysilane of claim 1, wherein the tetraalkoxysilane is tetramethoxysilane. Manufacturing method of the ball.

6. The alkali catalyst and the alcohol in the solution separated in the step (2) The method for producing alcohol according to claim 1, wherein the concentration of the potassium catalyst is 0.1% by mass to 3% by mass. Law.

7. The alcohol in the solution containing the alkali catalyst and the alcohol separated in the step (2) The method for producing an alcohol according to claim 1, wherein the concentration of the alcohol is 60% by mass to 90% by mass.

8. The step (2-1) is a step of reducing the concentration of the alkali catalyst to 1000 mass ppm or less. The method for producing alcohol according to claim 2,

9. The concentration of the alkali catalyst in the alcohol obtained in the step (3) is 30 mass ppb or less. The method for producing an alcohol according to claim 1,

10. The ion exchange resin used in the step (3) is at least selected from strongly acidic cation exchange resins. The method for producing alcohol according to claim 1 , further comprising the steps of:

11. The ion exchange resin used in the step (3) is selected from the strongly acidic cation exchange resin H type. The method for producing alcohol according to claim 10, comprising at least one of:

12. The alcohol obtained by the method for producing alcohol according to any one of claims 1 to 11 A method for producing tetraalkoxysilane, comprising the steps of:

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