Triolein and preparation method thereof

Abstract

The invention discloses glyceryl oleate and a preparation method thereof, glycerol and oleic acid are taken as reaction raw materials, melamine is taken as a reaction solvent, esterification reaction is carried out to generate glyceryl oleate, and glyceryl oleate is obtained; wherein the mass parts of the glycerol, the oleic acid and the grease are respectively 20 to 50 parts, 50 to 70 parts and 0.02 to 1.0 part; the preparation method comprises the following steps: putting reaction raw materials and a reaction solvent into a first container, stirring, putting into a high-pressure kettle, introducing argon, and pressurizing and heating, with the temperature in the high-pressure kettle being 105-110 DEG C, the pressure being 0-40 MPa and the flow being 51 pm; after the pressurizing and heating time in the high-pressure kettle is a first preset time for 2-2.5 hours, temperature rise is ended, and after the constant temperature is kept for a second preset time, the high-pressure kettle is cooled to the room temperature.

Description

Technical Field

[0001] The invention relates to the technical field of material processing, and in particular to olein and a preparation method thereof. Background Art

[0002] Oleic acid glyceride is a new type of energy and chemical raw material with broad application prospects. It is used as an emulsifier and wetting agent in the daily chemical industry to prepare new polymers, liquid crystals, ceramides, etc. It can also be used in surfactants, pharmaceutical raw materials and other applications.

[0003] The preparation of olein can be carried out by chemical synthesis, biological fermentation and hydrolysis. Among them, chemical synthesis is one of the main methods for preparing olein. The chemical synthesis steps of olein include catalytic distillation of oleic acid, esterification reaction of glycerol and acid deesterification reaction. During the synthesis process, the reaction conditions, such as temperature, catalyst type and concentration, need to be controlled to ensure the stability and purity of the synthesis results.

[0004] However, the conversion rate of the reaction process when chemical synthesis is used in the prior art is low.

[0005] The above contents are only used to assist in understanding the technical solution of the present invention and do not constitute an admission that the above contents are prior art. Summary of the invention

[0006] The main purpose of the present invention is to provide an olein and a preparation method thereof, aiming to solve the problem of low conversion rate of preparation of olein in the prior art.

[0007] In order to achieve the above object, the present invention provides a method for preparing olein, which comprises:

[0008] Using glycerol and oleic acid as reaction raw materials and melamine as reaction solvent, an esterification reaction occurs to generate oleic acid glyceride, thereby obtaining oleic acid glyceride;

[0009] The mass fractions of glycerol, oleic acid and oil are 20-50 parts, 50-70 parts and 0.02-1.0 parts respectively;

[0010] The preparation method comprises:

[0011] The reaction raw materials and the reaction solvent are placed in a first container, stirred, placed in an autoclave, introduced with argon gas and pressurized and heated, wherein the temperature in the autoclave is 105-110° C., the pressure is 0-40 MPa, and the flow rate is 51 pm;

[0012] After the pressurized heating time in the autoclave reaches a first preset time, the heating is stopped, and the temperature is maintained at a constant temperature for a second preset time, and then cooled to room temperature, wherein the first preset time is 2-2.5 hours.

[0013] Preferably, in the preparation method of olein, the mass fractions of glycerol and oleic acid are 30-40 parts and 60-70 parts respectively.

[0014] Preferably, in the method for preparing olein, the temperature in the autoclave is 105°C.

[0015] Preferably, in the method for preparing olein, the first preset time length is 2 hours.

[0016] In order to achieve the above object, the present invention provides a method for preparing olein, which comprises:

[0017] Glycerol and oleic acid are used as reaction raw materials, melamine is used as reaction solvent, esterification reaction occurs to generate oleic acid glyceride, and argon gas is introduced during the reaction process to obtain oleic acid glyceride.

[0018] Preferably, in the preparation method of olein, the mass fractions of glycerol and oleic acid are 30-40 parts and 60-70 parts respectively.

[0019] Preferably, in the method for preparing olein, the reaction temperature is 105-110° C., the pressure is 10 MPa-30 MPa, and the heating time is 2-2.5 hours.

[0020] Preferably, in the method for preparing olein, the reaction temperature is 105°C.

[0021] Preferably, in the preparation method of olein, the heating time is 2 hours.

[0022] In order to achieve the above object, the present invention provides a kind of olein, and the olein is synthesized by the above-mentioned preparation method of olein.

[0023] The present invention has at least the following beneficial effects:

[0024] The invention uses glycerol and oleic acid as reaction raw materials and melamine as reaction solvent to generate oleic acid glyceride through esterification reaction, thereby obtaining oleic acid glyceride; wherein the mass fractions of glycerol, oleic acid and oil are 20-50 parts, 50-70 parts and 0.02-1.0 parts respectively; the reaction raw materials and reaction solvent are put into a first container, stirred and then put into an autoclave, argon gas is introduced and pressurized and heated, wherein the temperature in the autoclave is 105-110° C., the pressure is 0-40MPa and the flow rate is 51pm; after the pressurized heating time in the autoclave is a first preset time, the temperature is stopped, and the temperature is kept constant for a second preset time, and then cooled to room temperature, wherein the first preset time is 2-2.5 hours, so that the preparation esterification rate of oleic acid glyceride reaches more than 97%.

[0025] Furthermore, by adding CHN as a reaction solvent to generate an acid-base neutralization reaction, the oleic acid reaction can be completed and the reaction rate can be accelerated; then argon gas is introduced to increase the melting point to protect the reactants and products, improve the problem of oleic acid and glycerol being insoluble before the reaction, and improve the conversion rate of the reaction process.

[0026] Furthermore, the process of the present invention can achieve a glycerol conversion rate of more than 95% during the reaction, and a selectivity of the target product oleic acid glyceride of more than 80%. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The present invention provides a flow chart of the method for preparing olein.

[0028] The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0029] In the embodiments of the present invention, the term "and / or" describes the association relationship of associated objects, indicating that three relationships may exist. For example, A and / or B may represent three situations: A exists alone, A and B exist at the same time, and B exists alone. The character " / " generally indicates that the associated objects before and after are in an "or" relationship.

[0030] It should be noted that the terms "first", "second", etc. in the specification and claims of the present invention and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence.

[0031] In the embodiments of the present invention, the term "plurality" refers to two or more than two, and other quantifiers are similar.

[0032] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings. However, it can be understood by those skilled in the art that in the embodiments of the present invention, many technical details are proposed in order to enable the reader to better understand the present invention. However, even without these technical details and various changes and modifications based on the following embodiments, the technical scheme claimed in the present invention can also be implemented. The division of the following embodiments is for the convenience of description and should not constitute any limitation on the specific implementation of the present invention. The various embodiments can be combined and referenced with each other under the premise of no contradiction.

[0033] The present invention provides a method for preparing oleic acid glyceride, wherein glycerol and oleic acid are used as reaction raw materials, melamine is used as reaction solvent, and oleic acid glyceride is generated by esterification reaction to obtain oleic acid glyceride, wherein the mass fractions of glycerol, oleic acid, and oil are 20-50 parts, 50-70 parts, and 0.02-1.0 parts, respectively.

[0034] Oleic acid glyceryl ester (1-oleylglycerol) is an organic compound with the molecular formula C 21 H 40 O4. It is the product of the polymerization of oleic acid (octadecenoic acid) and glycerol (propylene glycol), and is an unsaturated glyceride. It can be hydrolyzed under acidic and alkaline conditions, and can also react with hydrogen and nitrate with nitric acid. It is often used as a surfactant, food stabilizer, and plastic rubber additive.

[0035] Figure 1 A process 100 for preparing olein is shown schematically, see Figure 1 .

[0036] At step 101, the reaction raw materials and the reaction solvent are placed in a first container, stirred, placed in an autoclave, argon is introduced, and pressurized and heated, wherein the temperature in the autoclave is 105-110°C, the pressure is 0-40MPa, and the flow rate is 51pm. The mass fractions of glycerol, oleic acid, and oil are 20-50 parts, 50-70 parts, and 0.02-1.0 parts, respectively. In other embodiments, the mass fractions of glycerol and oleic acid are 30-40 parts and 60-70 parts, respectively.

[0037] At step 102, after the time of pressurized heating in the autoclave reaches the first preset time, the temperature rise is terminated, and the temperature is kept constant for the second preset time, and then cooled to room temperature, wherein the first preset time is 2-2.5 hours. The second preset time can be 10 minutes, or can be set according to specific needs. Preferably, the first preset time is 2 hours.

[0038] With glycerol and oleic acid as the reaction raw materials and melamine as the reaction solvent, an esterification reaction is carried out to generate oleic acid glyceride, and oleic acid glyceride is obtained, and the structural formula is:

[0039]

[0040] The molecular formula of oleic acid is: 17 H 33 COOH.

[0041] The molecular formula of glycerol (propylene glycol) is: HOCH2CH(OH)CH2OH.

[0042] Oleic acid and glycerol undergo esterification to form oleylglycerol, and the chemical reaction equation is:

[0043]

[0044] The present invention also provides a method for preparing oleic acid glyceride, which comprises: using glycerol and oleic acid as reaction raw materials, using melamine as reaction solvent, performing esterification reaction to generate oleic acid glyceride, and introducing argon gas during the reaction to obtain oleic acid glyceride. The mass fractions of the glycerol and oleic acid are 30-40 parts and 60-70 parts, respectively.

[0045] Among them, the reaction temperature is 105-110°C, the pressure is 10MPa-30MPa, and the heating time is 2-2.5 hours.

[0046] It should be noted that this embodiment includes the contents of the above embodiments, and the contents of the above embodiments can also be applied to this embodiment.

[0047] The influencing factors in the above preparation method are explained below through examples and comparative examples.

[0048] (1) Impact of reaction time

[0049] It should be noted that, when other reaction conditions are the same, the esterification rate increases with the increase of reaction time; however, when the reaction time is too long, the esterification rate remains unchanged, while the color of the reactant becomes darker, and side reactions occur, resulting in a decrease in the quality of the product. In this embodiment, when the reaction time is less than 4 hours, the esterification rate is too low, and when the reaction time reaches 2-2.5 hours, the esterification rate is the highest; when the reaction time exceeds 2.5 hours, side reactions occur, resulting in a decrease in the quality of the product, as shown in Table 1. The calculation of the esterification rate can be calculated by calculating the acid value.

[0050] Table 1 Effect of reaction time on esterification rate

[0051] Reaction time Esterification rate% Example 1 2 97.2 Example 2 2.2 98.3 Example 3 2.5 99.5 Comparative Example 1 1.5 84.1％

[0052] Example 1

[0053] Using glycerol and oleic acid as reaction raw materials and melamine as reaction solvent, an esterification reaction is carried out to generate oleic acid glyceride, thereby obtaining oleic acid glyceride; wherein the mass fractions of the glycerol, oleic acid, and oil are 30 parts, 50 parts, and 0.02 parts, respectively;

[0054] S1, putting the reaction raw materials and the reaction solvent into a first container, stirring, putting them into an autoclave, introducing argon gas and pressurizing and heating, wherein the temperature in the autoclave is 105°C, the pressure is 40MPa, and the flow rate is 51pm;

[0055] S2, after the pressurized heating time in the autoclave reaches a first preset time, the heating is terminated, and the temperature is maintained at a constant temperature for a second preset time, and then cooled to room temperature, wherein the first preset time is 2 hours.

[0056] Example 2

[0057] Using glycerol and oleic acid as reaction raw materials and melamine as reaction solvent, an esterification reaction is carried out to generate oleic acid glyceride, thereby obtaining oleic acid glyceride; wherein the mass fractions of the glycerol, oleic acid, and oil are 30 parts, 50 parts, and 0.02 parts, respectively;

[0058] S1, putting the reaction raw materials and the reaction solvent into a first container, stirring, putting them into an autoclave, introducing argon gas and pressurizing and heating, wherein the temperature in the autoclave is 105°C, the pressure is 40MPa, and the flow rate is 51pm;

[0059] S2, after the pressurized heating time in the autoclave reaches a first preset time, the heating is stopped, and the temperature is maintained at a constant temperature for a second preset time, and then cooled to room temperature, wherein the first preset time is 2.2 hours.

[0060] Example 3

[0061] Using glycerol and oleic acid as reaction raw materials and melamine as reaction solvent, an esterification reaction is carried out to generate oleic acid glyceride, thereby obtaining oleic acid glyceride; wherein the mass fractions of the glycerol, oleic acid, and oil are 30 parts, 50 parts, and 0.02 parts, respectively;

[0062] S1, putting the reaction raw materials and the reaction solvent into a first container, stirring, putting them into an autoclave, introducing argon gas and pressurizing and heating, wherein the temperature in the autoclave is 105°C, the pressure is 40MPa, and the flow rate is 51pm;

[0063] S2, after the pressurized heating time in the autoclave reaches a first preset time, the heating is stopped, and the temperature is maintained at a constant temperature for a second preset time, and then cooled to room temperature, wherein the first preset time is 2.5 hours.

[0064] Comparative Example 1

[0065] Using glycerol and oleic acid as reaction raw materials and melamine as reaction solvent, an esterification reaction is carried out to generate oleic acid glyceride, thereby obtaining oleic acid glyceride; wherein the mass fractions of the glycerol, oleic acid, and oil are 30 parts, 50 parts, and 0.02 parts, respectively;

[0066] S1, putting the reaction raw materials and the reaction solvent into a first container, stirring, putting them into an autoclave, introducing argon gas and pressurizing and heating, wherein the temperature in the autoclave is 105°C, the pressure is 40MPa, and the flow rate is 51pm;

[0067] S2, after the pressurized heating time in the autoclave reaches a first preset time, the heating is stopped, and the temperature is maintained at a constant temperature for a second preset time, and then cooled to room temperature, wherein the first preset time is 1.5 hours.

[0068] (2) Effect of reaction temperature

[0069] When other reaction conditions are the same, as the reaction temperature increases, the esterification rate gradually increases; but when the reaction temperature is too high, the side reactions will intensify, the color of the reaction product will darken, and the product quality will be affected. At the beginning of the temperature increase, the esterification rate is relatively low. When the temperature is increased to 105-110°C, the reaction rate is fast and the esterification rate gradually increases. However, when the reaction temperature continues to increase, the reaction rate increases slowly, the esterification rate does not increase significantly, and side effects occur, and the color of the system turns yellow. Therefore, the reaction temperature of the present invention is 105-110°C for the best effect.

[0070] (3) Effect of the distribution ratio of each group

[0071] When other conditions are the same, the mass fraction of the reaction raw material glycerol increases, and the oleic acid reacts completely. However, when the mass fraction of glycerol is too large, the reaction amount of oleic acid is not obvious, indicating that the best effect is achieved when the mass fractions of glycerol and oleic acid are 20-50 parts and 50-70 parts, respectively.

[0072] (4) Effect of reaction solvent

[0073] The selection of the reaction solvent in the present invention is very important. When the melamine provided by the present invention is selected as the reaction solvent, not only the reaction speed is significantly improved, but also the reaction temperature is significantly reduced, and the esterification rate is improved.

[0074] The following is a comparative description of using melamine as a reaction solvent and not using melamine as a reaction solvent.

[0075] Example 4

[0076] Using glycerol and oleic acid as reaction raw materials and melamine as reaction solvent, an esterification reaction is carried out to generate oleic acid glyceride, thereby obtaining oleic acid glyceride; wherein the mass fractions of the glycerol, oleic acid, and oil are 30 parts, 50 parts, and 0.02 parts, respectively;

[0077] S1, putting the reaction raw materials and the reaction solvent into a first container, stirring, putting them into an autoclave, introducing argon gas and pressurizing and heating, wherein the temperature in the autoclave is 105°C, the pressure is 40MPa, and the flow rate is 51pm;

[0078] S2, after the pressurized heating time in the autoclave reaches a first preset time, the heating is stopped, and the temperature is maintained at a constant temperature for a second preset time, and then cooled to room temperature, wherein the first preset time is 2.5 hours.

[0079] Comparative Example 2

[0080] Using glycerol and oleic acid as reaction raw materials and a fixed acid as a reaction solvent, an esterification reaction is performed to generate oleic acid glyceride, thereby obtaining oleic acid glyceride; wherein the mass fractions of the glycerol, oleic acid, and oil are 30 parts, 50 parts, and 0.02 parts, respectively;

[0081] S1, putting the reaction raw materials and the reaction solvent into a first container, stirring, putting them into an autoclave, introducing argon gas and pressurizing and heating, wherein the temperature in the autoclave is 105°C, the pressure is 40MPa, and the flow rate is 51pm;

[0082] S2, after the pressurized heating time in the autoclave reaches a first preset time, the heating is stopped, and the temperature is maintained at a constant temperature for a second preset time, and then cooled to room temperature, wherein the first preset time is 2.5 hours.

[0083] Comparative Example 3

[0084] Melamine was not used as the reaction solvent, and other steps were the same as those in Example 4.

[0085] Table 2 Effect of reaction solvent on esterification rate

[0086] Reaction solvent Esterification rate% Example 4 Melamine 99.6 Comparative Example 2 Solid Acid 90％ Comparative Example 3 / 85.1％

[0087] It can be seen from Table 2 that under the same conditions, when melamine solution is used as the reaction solvent, the esterification rate is significantly higher than that when no reaction solvent is used or other reaction solvents are used.

[0088] (4) Effect of introducing argon gas

[0089] Example 5

[0090] Using glycerol and oleic acid as reaction raw materials and melamine as reaction solvent, an esterification reaction is carried out to generate oleic acid glyceride, thereby obtaining oleic acid glyceride; wherein the mass fractions of the glycerol, oleic acid, and oil are 30 parts, 50 parts, and 0.02 parts, respectively;

[0091] S1, putting the reaction raw materials and the reaction solvent into a first container, stirring, putting them into an autoclave, introducing argon gas and pressurizing and heating, wherein the temperature in the autoclave is 105°C, the pressure is 40MPa, and the flow rate is 51pm;

[0092] S2, after the pressurized heating time in the autoclave reaches a first preset time, the heating is stopped, and the temperature is maintained at a constant temperature for a second preset time, and then cooled to room temperature, wherein the first preset time is 2.5 hours.

[0093] Comparative Example 4

[0094] Using glycerol and oleic acid as reaction raw materials and melamine as reaction solvent, an esterification reaction is carried out to generate oleic acid glyceride, thereby obtaining oleic acid glyceride; wherein the mass fractions of the glycerol, oleic acid, and oil are 30 parts, 50 parts, and 0.02 parts, respectively;

[0095] S1, putting the reaction raw materials and the reaction solvent into a first container, stirring, putting them into an autoclave, introducing nitrogen and pressurizing and heating, wherein the temperature in the autoclave is 105°C, the pressure is 40MPa, and the flow rate is 51pm;

[0096] S2, after the pressurized heating time in the autoclave reaches a first preset time, the heating is stopped, and the temperature is maintained at a constant temperature for a second preset time, and then cooled to room temperature, wherein the first preset time is 2.5 hours.

[0097] Comparative Example 5

[0098] Using glycerol and oleic acid as reaction raw materials and melamine as reaction solvent, an esterification reaction is carried out to generate oleic acid glyceride, thereby obtaining oleic acid glyceride; wherein the mass fractions of the glycerol, oleic acid, and oil are 30 parts, 50 parts, and 0.02 parts, respectively;

[0099] S1, putting the reaction raw materials and the reaction solvent into a first container, stirring and then putting them into an autoclave for pressurized heating, wherein the temperature in the autoclave is 105° C., the pressure is 40 MPa, and the flow rate is 51 pm;

[0100] S2, after the pressurized heating time in the autoclave reaches a first preset time, the heating is stopped, and the temperature is maintained at a constant temperature for a second preset time, and then cooled to room temperature, wherein the first preset time is 2.5 hours.

[0101] Table 3 Effect of introducing argon

[0102] Gas Esterification rate% Example 5 Argon 99.6 Comparative Example 4 Nitrogen 90％ Comparative Example 4 / 80％

[0103] It can be seen from Table 3 that under the same conditions, adding argon has a better effect.

[0104] The invention uses glycerol and oleic acid as reaction raw materials and melamine as reaction solvent to generate oleic acid glyceride through esterification reaction, thereby obtaining oleic acid glyceride; wherein the mass fractions of glycerol, oleic acid and oil are 20-50 parts, 50-70 parts and 0.02-1.0 parts respectively; the reaction raw materials and reaction solvent are put into a first container, stirred and then put into an autoclave, argon gas is introduced and pressurized and heated, wherein the temperature in the autoclave is 105-110° C., the pressure is 0-40MPa and the flow rate is 51pm; after the pressurized heating time in the autoclave is a first preset time, the temperature is stopped, and the temperature is kept constant for a second preset time, and then cooled to room temperature, wherein the first preset time is 2-2.5 hours, so that the preparation esterification rate of oleic acid glyceride reaches more than 97%.

[0105] Furthermore, by adding CHN as a reaction solvent to generate an acid-base neutralization reaction, the oleic acid reaction can be completed and the reaction rate can be accelerated; then argon gas is introduced to increase the melting point to protect the reactants and products, improve the problem of oleic acid and glycerol being insoluble before the reaction, and improve the conversion rate of the reaction process.

[0106] Furthermore, the process of the present invention can achieve a glycerol conversion rate of more than 95% during the reaction, and a selectivity of the target product oleic acid glyceride of more than 80%.

[0107] Obviously, the embodiments described above are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, ordinary technicians in this field can make other different forms of changes or modifications without creative work, which should fall within the scope of protection of the present invention.

Claims

1. A method for preparing olein, characterized in that: include: Using glycerol and oleic acid as reaction raw materials and melamine as reaction solvent, an esterification reaction occurs to generate oleic acid glyceride, thereby obtaining oleic acid glyceride; Wherein, the mass fractions of glycerol, oleic acid and oil are 20-50 parts, 50-70 parts and 0.02-1.0 parts respectively; The preparation method comprises: The reaction raw materials and the reaction solvent are placed in a first container, stirred, placed in an autoclave, introduced with argon gas and pressurized and heated, wherein the temperature in the autoclave is 105-110° C., the pressure is 0-40 MPa, and the flow rate is 51 pm; After the pressurized heating time in the autoclave reaches a first preset time, the heating is stopped, and the temperature is maintained at a constant temperature for a second preset time, and then cooled to room temperature, wherein the first preset time is 2-2.5 hours.

2. The method for preparing olein as claimed in claim 1, wherein The mass fractions of the glycerol and oleic acid are 30-40 parts and 60-70 parts respectively.

3. The preparation method of olein as claimed in claim 1, characterized in that, The temperature in the autoclave was 105°C.

4. The method for preparing olein as claimed in claim 1, wherein The first preset duration is 2 hours.

5. A method for preparing olein, characterized in that: include: Glycerol and oleic acid are used as reaction raw materials, melamine is used as reaction solvent, esterification reaction occurs to generate oleic acid glyceride, and argon gas is introduced during the reaction process to obtain oleic acid glyceride.

6. The method for preparing olein as claimed in claim 5, characterized in that: The mass fractions of the glycerol and oleic acid are 30-40 parts and 60-70 parts respectively.

7. The method for preparing olein as claimed in claim 5, characterized in that: The reaction temperature is 105-110°C, the pressure is 10MPa-30MPa, and the heating time is 2-2.5 hours.

8. The method for preparing olein as claimed in claim 7, characterized in that: The reaction temperature was 105°C.

9. The method for preparing olein as claimed in claim 7, wherein: The heating time is 2h.

10. A kind of olein, characterized in that: The olein is synthesized by the preparation method of any one of claims 1 to 9.

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