阅读说明：本技术 环氧脂肪酸甲酯氢化改性工艺和含羟基饱和脂肪酸甲酯 (Epoxy fatty acid methyl ester hydrogenation modification process and hydroxyl-containing saturated fatty acid methyl ester ) 是由 潘鹤潮 陈文� 蔡熙扬 陈武渊 侯君辉 卢志敏 于 2018-06-19 设计创作，主要内容包括：本发明公开了一种环氧脂肪酸甲酯氢化改性工艺。其系对环氧脂肪酸甲酯进行加氢工艺处理,得到含羟基饱和脂肪酸甲酯；其中,加氢工艺的反应温度为100-150℃、反应压力为≤4MPa、反应时间为1-4小时；所述加氢工艺中的催化剂有效成分为金属镍,所述催化剂的载体成分为氧化铝。本发明还公开了采用上述工艺得到的含羟基饱和脂肪酸甲酯。本发明与现有技术相比,虽然多了一个环氧脂肪酸甲酯合成工艺才能获得饱和脂肪酸甲酯,但由于最终得到的含羟基饱和脂肪酸甲酯具有特殊功效,因此在整个表面活性剂生产工艺上存在更高的经济效益。(The invention discloses a hydrogenation modification process of epoxy fatty acid methyl ester. Carrying out hydrogenation process treatment on epoxy fatty acid methyl ester to obtain saturated fatty acid methyl ester containing hydroxyl; wherein the reaction temperature of the hydrogenation process is 100-150 ℃, the reaction pressure is less than or equal to 4MPa, and the reaction time is 1-4 hours; the catalyst in the hydrogenation process comprises the effective component of metallic nickel, and the carrier component of the catalyst is alumina. The invention also discloses the saturated fatty acid methyl ester containing hydroxyl obtained by the process. Compared with the prior art, the method has the advantages that although saturated fatty acid methyl ester can be obtained only by one more epoxy fatty acid methyl ester synthesis process, the finally obtained saturated fatty acid methyl ester containing hydroxyl has special efficacy, so that higher economic benefit exists in the whole surfactant production process.)

1. The hydrogenation modification process of the epoxy fatty acid methyl ester is characterized in that the epoxy fatty acid methyl ester is subjected to hydrogenation process treatment to obtain saturated fatty acid methyl ester containing hydroxyl; wherein the reaction temperature of the hydrogenation process is 100-150 ℃, the reaction pressure is less than or equal to 4MPa, and the reaction time is 1-4 hours; the catalyst in the hydrogenation process comprises the effective component of metallic nickel, and the carrier component of the catalyst is alumina.

2. The process for hydrogenating and modifying epoxy fatty acid methyl ester according to claim 1, wherein the epoxy fatty acid methyl ester is a fatty acid methyl ester having at least one epoxy group having a three-membered ring.

3. The process for hydrogenation modification of epoxy fatty acid methyl ester according to claim 2, wherein the epoxy fatty acid methyl ester is any one of epoxy soybean oil methyl ester, epoxy palm oil methyl ester, epoxy cottonseed oil methyl ester, epoxy rapeseed oil methyl ester, epoxy oleic acid methyl ester, epoxy castor oil methyl ester and epoxy hogwash oil methyl ester, or a combination of at least two of them.

4. The hydrogenated modification process of epoxidized fatty acid methyl ester according to claim 1, wherein the epoxidized fatty acid methyl ester has an epoxy value of 3-8%.

5. The hydrogenation modification process of epoxidized fatty acid methyl ester according to claim 1, wherein the BET specific surface area of the catalyst used in the hydrogenation process is 100-200m²The pore volume is 0.4-0.5mL/g, the compaction density is 700-³The average grain diameter is 2.0-3.0 mm; the mass content of the metallic nickel in the catalyst is 15-25%; the average size of the alumina is 1.0-2.0 mm.

6. Saturated fatty acid methyl esters containing hydroxyl groups, characterized in that they are prepared by the process for the hydrogenation modification of epoxidized fatty acid methyl esters according to any one of claims 1 to 5.

Technical Field

The invention belongs to the technical field of oil industrial production, and particularly relates to a hydrogenation modification process of epoxy fatty acid methyl ester and saturated fatty acid methyl ester containing hydroxyl.

Background

At present, anionic surfactant fatty acid methyl ester sulfonate MES and nonionic surfactant fatty acid methyl ester ethoxylate FMEE commonly used in the daily chemical industry are mainly synthesized by adopting saturated fatty acid methyl ester. The saturated fatty acid methyl ester is synthesized by using unsaturated fatty acid methyl ester containing carbon-carbon double bonds as a raw material through hydrogenation reaction, and the oxidation resistance stability of the fatty acid methyl ester is improved while the carbon-carbon double bonds are eliminated.

Epoxy fatty acid methyl esters are generally prepared by reacting unsaturated double bonds in fatty acid methyl esters with peroxy organic acids in the presence of catalysts, and because they contain epoxy groups, they are often used as intermediates for the production of chemicals having a variety of industrial uses. Although the iodine value in the product index of the epoxy methyl ester is reduced and the degree of unsaturation of a carbon chain is also reduced, the ring opening of the epoxy fatty acid methyl ester influences the synthesis of a target product, so that no published research data reports an industrial process for preparing a surfactant product by using the epoxy fatty acid methyl ester as a production raw material.

Disclosure of Invention

The first purpose of the invention is to provide a hydrogenation modification process of epoxidized fatty acid methyl ester, aiming at the defects of the prior art, so that the epoxidized fatty acid methyl ester can be suitable for preparing a surfactant product.

The second purpose of the invention is to provide the saturated fatty acid methyl ester containing hydroxyl prepared by the process.

In order to achieve the first purpose, the invention adopts the following technical scheme:

the hydrogenation modification process of the epoxy fatty acid methyl ester comprises the steps of carrying out hydrogenation process treatment on the epoxy fatty acid methyl ester to obtain saturated fatty acid methyl ester containing hydroxyl; wherein the reaction temperature of the hydrogenation process is 100-150 ℃, the reaction pressure is less than or equal to 4MPa, and the reaction time is 1-4 hours; the catalyst in the hydrogenation process comprises the effective component of metallic nickel, and the carrier component of the catalyst is alumina.

Further, the epoxy fatty acid methyl ester is a fatty acid methyl ester containing an epoxy group having at least one three-membered ring,

preferably, the epoxidized fatty acid methyl ester is any one of epoxidized soybean oil methyl ester, epoxidized palm oil methyl ester, epoxidized cottonseed oil methyl ester, epoxidized rapeseed oil methyl ester, epoxidized oleic acid methyl ester, epoxidized castor oil methyl ester and epoxidized hogwash oil methyl ester, or a combination of at least two of them.

Preferably, the epoxy value of the epoxidized fatty acid methyl ester is 3 to 8%.

Preferably, the BET specific surface area of the catalyst used in the hydrogenation process is 100-200m²The pore volume is 0.4-0.5mL/g, the compaction density is 700-³The average grain diameter is 2.0-3.0 mm; the mass content of the metallic nickel in the catalyst is 15-25%; the average size of the alumina is 1.0-2.0 mm.

In order to achieve the second purpose, the invention adopts the following technical scheme:

saturated fatty acid methyl ester containing hydroxyl is prepared by the hydrogenation modification process of the epoxy fatty acid methyl ester.

Compared with the prior art, the method has the advantages that although saturated fatty acid methyl ester can be obtained only by one more epoxy fatty acid methyl ester synthesis process, the finally obtained saturated fatty acid methyl ester containing hydroxyl has special efficacy, so that higher economic benefit exists in the whole surfactant production process.

Detailed Description

The invention relates to a hydrogenation modification process of epoxy fatty acid methyl ester, which is to carry out hydrogenation process treatment on the epoxy fatty acid methyl ester to obtain saturated fatty acid methyl ester containing hydroxyl.

The epoxy fatty acid methyl ester is a general commercial industrial product, and the product indexes are as follows:

item	Standard requirements
		Epoxy value (%)	≥3.0，≤8.0
Moisture Moisture (%)	≤0.5
		Acid Value (mgKOH/g)	≤1
Color number color (APHA)	≤30
		Iodine Value Iodine Value (g/150g)	≤5
Density (e20 ℃/cm3)	0.92-0.95

The epoxy fatty acid methyl ester meeting the product index requirements can be any one of epoxy soybean oil methyl ester, epoxy palm oil methyl ester, epoxy cottonseed oil methyl ester, epoxy rapeseed oil methyl ester, epoxy oleic acid methyl ester, epoxy castor oil methyl ester and epoxy hogwash oil methyl ester, or the combination of at least two of the epoxy soybean oil methyl ester, the epoxy palm oil methyl ester, the epoxy cottonseed oil methyl ester, the epoxy rapeseed oil methyl ester, the epoxy oleic acid methyl ester, the epoxy castor.

The hydrogenation modification process has the following process key points:

1. hydrogenation catalyst:

the catalyst has effective component of metal nickel and carrier component of alumina. Wherein, the metallic nickel is granular, and the mass content in the catalyst is 15-25%, preferably 20%. The alumina is solid particles with an average size of 1.0-2.0 mm.

The BET specific surface area of the catalyst is 100-²The pore volume is 0.4-0.5mL/g, the compaction density is 700-³The average particle diameter is 2.0-3.0 mm.

2. A hydrogenation reactor:

a batch kettle type reactor or a tower type continuous reactor can be adopted.

3. The technological parameters are as follows:

internal pressure of the reactor: 2-4 Mpa.

The temperature of the reaction mass is 100-150 ℃.

The residence time of the reaction mass is 1-4 hours.

In the process, the reaction temperature of the hydrogenation process is low, so that the chain scission of methyl ester in epoxy fatty acid methyl ester can be avoided to generate fatty acid and methanol; the catalyst carrier alumina is an acidic carrier, which is beneficial to ring opening of an epoxy group and improvement of the reaction rate; the obtained saturated fatty acid methyl ester containing hydroxyl has higher saturation, the iodine value of the product is lower than 0.5, and the epoxy value is lower than 0.1%.

The following illustrates an example of the synthesis of a hydroxyl-containing saturated fatty acid methyl ester by the process of hydrogenating and modifying an epoxy fatty acid methyl ester: