阅读说明：本技术 一种十四酸甲酯的制备方法及装置 (Preparation method and device of methyl myristate ) 是由 周政 刘颖 陈磊 闫瀚钊 董旺来 曹志 于 2020-06-11 设计创作，主要内容包括：本发明提供了一种十四酸甲酯的制备方法及装置。所述制备方法包括如下步骤：将十四酸与甲醇按照1:(2-6)的摩尔比混合搅拌形成混合物,加热到50-60℃,添加所述混合物质量的10-30wt％的固体酸催化剂进行酯化反应。本发明的制备方法使用固体酸催化剂替代液体酸催化剂,固体酸催化剂的比表面积及孔体积均比较大,确保了良好的选择性以及反应活性,易于产物分离和提纯,且可反复使用多次,避免了设备腐蚀和环境污染,使企业能够连续性生产；并且在混合物10-30wt％的催化剂用量的特定条件下,提高了反应效率,抑制了副反应的发生,使得产品的转化率达到了97.8％-99.7％,提高了最终产物十四酸甲酯的收率。(The invention provides a method and a device for preparing methyl myristate. The preparation method comprises the following steps: mixing and stirring the tetradecanoic acid and the methanol according to the molar ratio of 1 (2-6) to form a mixture, heating to 50-60 ℃, and adding a solid acid catalyst accounting for 10-30 wt% of the mixture for esterification reaction. The preparation method uses the solid acid catalyst to replace the liquid acid catalyst, the specific surface area and the pore volume of the solid acid catalyst are large, good selectivity and reaction activity are ensured, the product is easy to separate and purify, the product can be repeatedly used, the equipment corrosion and the environmental pollution are avoided, and the enterprise can continuously produce the product; under the specific condition of the catalyst dosage of 10-30 wt% of the mixture, the reaction efficiency is improved, the occurrence of side reaction is inhibited, the conversion rate of the product reaches 97.8% -99.7%, and the yield of the final product, namely methyl myristate, is improved.)

1. A preparation method of methyl myristate is characterized by comprising the following steps:

mixing and stirring the tetradecanoic acid and the methanol according to the molar ratio of 1 (2-6) to form a mixture, heating to 50-60 ℃, and adding a solid acid catalyst accounting for 10-30 wt% of the mixture for esterification reaction.

2. The method according to claim 1, wherein the solid acid catalyst is used in an amount of 15 to 25 wt% based on the mass of the mixture;

preferably, the solid acid catalyst is used in an amount of 20 wt% of the mass of the mixture.

3. The method according to claim 1, wherein the solid acid catalyst is at least one of a cation exchange resin and a solid super acid;

preferably, the solid acid catalyst is a cation exchange resin;

preferably the type of cation exchange resin is at least one of Amberlyst39wet, Amberlyst36wet, Amberlyst35 wet;

preferably, the cation exchange resin is of the type Amberlyst39 wet.

4. The method of claim 1, wherein the mixing and stirring rate is 400rpm to 600 rpm.

5. The method according to claim 1, further comprising a step of performing quantitative analysis of the reaction product after the esterification reaction, wherein the quantitative analysis is performed by using a gas chromatograph;

preferably, the gasification temperature of the gas chromatograph is 270-280 ℃, and the detection temperature is 280-290 ℃.

6. A preparation device adopting the preparation method of methyl myristate according to any one of claims 1-5, characterized by comprising a premixing tank for premixing raw materials, wherein the premixing tank is connected with a full mixing kettle, the full mixing kettle is provided with a catalyst inlet for introducing a solid acid catalyst and a raw material inlet for introducing raw materials, and the full mixing kettle is provided with a temperature control device.

7. The preparation device of claim 6, wherein the side wall of the complete mixing kettle is provided with a product outlet, and reaction products enter the catalyst separator from the product outlet for separation and recovery of the catalyst;

preferably, a liquid phase outlet is arranged at the top of the catalyst separator, and a membrane filter is connected to the liquid phase outlet for separating the catalyst in the liquid phase material;

preferably, the bottom of the membrane filter is provided with a catalyst recovery port, the side wall of the membrane filter is provided with a product outlet for discharging purified products, and the catalyst recovery port is connected with the side wall of the catalyst separator for returning part of materials to the catalyst separator to continue purification and separation.

8. The preparation device of claim 7, wherein the bottom of the complete mixing kettle is provided with a first catalyst outlet; a second catalyst outlet is formed in the bottom of the catalyst separator, and the second catalyst outlet is communicated with the first catalyst outlet for common recovery;

preferably, the preparation device further comprises a catalyst regenerator, and the side wall of the catalyst regenerator is respectively connected with the first catalyst outlet and the second catalyst outlet;

preferably, the side wall of the catalyst regenerator is connected to the catalyst inlet for the regenerated catalyst to be returned to the complete mixing tank.

9. The production apparatus according to claim 7, wherein the product outlet is connected to a first rectification column for separating a product from methanol; and a tower top condenser is arranged at the tower top of the first rectifying tower, part of condensate coming out of the tower top condenser returns to the first rectifying tower, and part of condensate goes to the premixing tank.

10. The device as claimed in claim 7, wherein a heavy component outlet is arranged at the bottom of the first rectifying tower, and an extraction tower is connected to the heavy component outlet for product extraction and purification;

preferably, the top of the extraction tower is provided with an extraction solvent spray nozzle, the bottom of the extraction tower is provided with an extraction liquid outlet, and the extraction liquid outlet is connected with the second rectification tower to remove the extraction solvent.

Technical Field

The invention relates to the field of preparation of methyl myristate, and particularly relates to a preparation method and a device of methyl myristate.

Background

Due to exhaustion of conventional non-renewable diesel and increase of artificial emission of greenhouse gases, biodiesel is regarded as a promising alternative energy source and has received wide attention in recent years. Methyl myristate, as one of the main components of biodiesel, has the advantages of high cetane number, high flash point, good emission characteristics, reproducibility and excellent biodegradability, and is considered as a diesel additive and a fuel substitute with great potential. Besides being used for biodiesel, the methyl myristate can also be used for edible essences such as honey, coconut and the like, daily essences and can also be used for preparing organic chemicals. Therefore, the methyl myristate serving as an important fatty acid methyl ester has great application value, and the development of a green and economic methyl myristate process route is of great practical significance.

At present, myristic acid and methanol are generally adopted in industrial production of methyl myristate, and concentrated sulfuric acid is used as a catalyst to perform esterification reaction, has quite high activity, but has the defects of serious equipment corrosion, difficulty in continuous production, strict acidity requirement, serious environmental pollution and the like, is difficult to separate and purify a product, has a plurality of byproducts, and greatly reduces the yield.

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

The invention aims to provide a preparation method of methyl myristate, which uses a solid acid catalyst to replace a liquid acid catalyst, has larger specific surface area and pore volume, ensures good selectivity and reaction activity, is easy for product separation and purification, can be repeatedly used for many times, avoids equipment corrosion and environmental pollution, and enables enterprises to continuously produce; under the specific condition of the specific solid acid catalyst dosage, the reaction efficiency is greatly improved, the occurrence of side reactions is inhibited, the conversion rate of the product can reach 97.8-99.7%, and the yield of the final product, namely methyl myristate, is improved.

The second purpose of the invention is to provide a device adopting the preparation method, which has low cost and convenient operation and can obtain the methyl myristate with high yield by utilizing the device.

In order to achieve the above purpose of the present invention, the following technical solutions are adopted:

the invention provides a preparation method of methyl myristate, which comprises the following steps:

mixing and stirring the tetradecanoic acid and the methanol according to the molar ratio of 1 (2-6) to form a mixture, heating to 50-60 ℃, and adding a solid acid catalyst accounting for 10-30 wt% of the mixture for esterification reaction.

Drawings

Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:

FIG. 1 is a schematic structural diagram of a preparation apparatus for methyl myristate according to an embodiment of the present invention;

FIG. 2 is a graph showing the influence of the amount of the catalyst used in examples 1 to 5 on the esterification reaction of tetradecanoic acid;

FIG. 3 is a graph showing the relationship between the effects of different catalysts on the esterification reaction of tetradecanoic acid in examples 6 to 9;

FIG. 4 is a gas chromatogram of the reaction product obtained in example 3 of the present invention;

FIG. 5 is a gas chromatogram of the product obtained in example 10 of the present invention.

Detailed Description

The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.

In order to more clearly illustrate the technical solution of the present invention, the following description is made in the form of specific embodiments.