Modification method by bone isomerization of palm acid oil

Abstract

To develop a solid acid catalyst in a modification method by bone isomerization of palm acid oil in the presence of a solid acid catalyst.SOLUTION: In a modification method by bone isomerization of palm acid oil in the presence of a solid acid catalyst, one or more kinds of ZrO2 / Al2O3 / SO42-, Al-SBA-15, SAPO-11, and H-Beta are used as the solid acid catalyst.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] The present invention relates to a reforming method by skeletal isomerization of palm acid oil (PAO).

Background Art

[0002] Palm acid oil (PAO) is a composition of unsaturated fatty acids and their esters as shown below.

[0003]

Table 1

[0004] PAO is widely used as a raw material oil for biodiesel fuel (BDF: registered trademark).

[0005] The inventor of the present application previously proposed a method for producing biofuel in which transesterification between triglycerides in fats and oils and lower alcohols hardly occurs, and esterification of FFA by a small amount of lower alcohol is preferentially performed using a solid acid catalyst (Japanese Patent No. 6770554, Japanese Patent No. 7045775).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, the biofuel obtained by this method has a problem that its low-temperature fluidity is low and it is difficult to handle.

[0008] Figure 1 illustrates the modification reaction of PAO by skeletal isomerization of PAO. Regarding Figure 1, when reacting PAO with lower alcohols, for TG, the transesterification reaction is suppressed and the skeletal isomerization reaction is carried out to generate isomerized TG. On the other hand, for FFA, it is converted to fatty acid methyl (FAME) by esterification, and further, isomerized FAME is generated by the skeletal isomerization reaction.

[0009] Therefore, the inventors of the present application conducted research aiming at the development of a solid acid catalyst in the modification method by skeletal isomerization of palm fatty acid oil in the presence of a solid acid catalyst.

Means for Solving the Problems

[0010] The present invention proposes a modification method in the modification method by skeletal isomerization of palm fatty acid oil in the presence of a solid acid catalyst, using one or more of ZrO 2 / Al 2 O 3 / SO 4 2- , Al-SBA-15, SAPO-11, H-Beta as the solid acid catalyst.

[0011] Further, the present invention creates a calibration curve of the modification degree - isomerization degree with the modification degree and isomerization degree of palm fatty acid oil as the coordinate axes in the modification method by skeletal isomerization of palm fatty acid oil in the presence of a solid acid catalyst, determines the isomerization degree corresponding to the optimal modification degree from the calibration curve, and proposes a modification method using one or more of SAPO-11, H-Beta, ZrO 2 / Al 2 O 3 / SO 4 2- , Al-SBA-15 as the solid acid catalyst based on the isomerization degree.

[0012] Examples of the lower alcohol include methanol and ethanol.

Effects of the Invention

[0013] In the present invention, the palm acid oil with skeletal isomerization is modified compared to the untreated palm acid oil in terms of acid value, kinematic viscosity, and Slip Point (°C).

[0014] Moreover, according to the present invention, the pour point of PAO can be lowered by skeletal isomerization to enhance the low-temperature fluidity of PAO.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0016] In the modification method by skeletal isomerization of palm acid oil in the presence of a solid acid catalyst, a modification method using one or more of ZrO 2 / Al 2 O 3 / SO 4 2- , Al-SBA-15, SAPO-11, H-Beta as the solid acid catalyst.

Examples

[0017] Hereinafter, examples of the present invention will be shown.

Examples

[0018] Table 2 shows the modification reaction conditions and results of PAO in a fixed-bed flow reactor.

Table 2

[0019] In the table, Conversion rate 1): Conversion rate (%) of triglycerides in the source oil Conversion rate 2): Conversion rate (%) of free fatty acids (FFA) in the raw material oil Degree of isomerization 3): Degree of isomerization of unsaturated FFA and TG in the raw material oil The slip point is the temperature at which fat solidifies at low temperature and begins to flow upon heating.

[0020] The qualitative and quantitative analysis of PAO isomers is carried out by GC-MS. In this example, the degree of isomerization is calculated by the following formula.

[0021] ISOmol[X]=isoFAME18:1[n] / All[n] isoFAME18:1[n]:: The number of moles of methyl oleate isomers in 1 g of the reformed oil All[n]: The number of moles of all substances in 1 g of the reformed oil

Example

[0022] Table 3 shows the results of the reforming reaction of PAO in a batch reactor.

[0023]

Table 3

[0024] In the table, Conversion rate 1): The conversion rate (%) of triglycerides in the feedstock oil Conversion rate 2): The conversion rate (%) of free fatty acids (FFA) in the feedstock oil Degree of isomerization 3): The degree of isomerization of unsaturated FFA and TG in the feedstock oil The slip point is the temperature at which fat solidifies at low temperature and begins to flow upon heating.

[0025] 〈Summary of Table 2 and Table 3〉 1. Reforming of PAO In Table 2 Feedstock oil PAO(139): Palm acid oil (PAO) containing about 67.84% free fatty acids, acid value 139 mg KOH / g of feedstock oil, kinematic viscosity 74.2 mPa·s. Slip Point (°C) was 47.3 Feedstock oil PAO(110): Palm acid oil (PAO) containing about 47.94% free fatty acids, acid value 110 mg KOH / g of feedstock oil, kinematic viscosity 81.42 mPa·s. As the solid acid catalyst, ZrO2 / Al 2 O 3 / SO 4 2- , When using Al-SBA-15 and SAPO-11 to carry out the reforming reaction of PAO, the produced oil treated with respect to the unsaturated acid value of PAO being 110 - 130 mgKOH / g, kinematic viscosity being 74.2 - 81.4 mPa·s, and Slip Point (°C) being 47.3 has been reformed to an acid value of 6.1 - 21.2 mgKOH / g, kinematic viscosity of 3.6 - 8.8 mPa·s, and Slip Point (°C) of 8.3 - 11.7. In Table 3 Raw material oil PAO(139): Palm acid oil (PAO) containing about 67.84% free fatty acids, with an acid value of 139 mgKOH / g for the raw material oil and a kinematic viscosity of 74.2 mPa·s. Raw material oil PAO(110): Palm acid oil (PAO) containing about 47.94% free fatty acids, with an acid value of 110 mgKOH / g for the raw material oil and a kinematic viscosity of 81.42 mPa·s. When using SAPO-11 and H-Beta as solid acid catalysts to reform PAO under the conditions of reaction temperature 220 - 280 °C and reaction time 1 - 6 hr, the produced oil treated with respect to the acid value of PAO being 110 - 139 mgKOH / g PAO and kinematic viscosity being 74.2 - 81.4 mPa·s has been reformed to an acid value of 29.8 - 59.6 mgKOH / g, kinematic viscosity of 4.3 - 11.72 mPa, and Slip Point (°C) of 5.8. 2. Correlation between the degree of reforming and isomerization degree such as Slip Point and kinematic viscosity In Table 2, a correlation is recognized between the degree of reforming such as Slip Point and kinematic viscosity and the isomerization degree. Figure 2 is a diagram for creating a calibration curve of the degree of reforming - isomerization degree with Slip point and isomerization degree as coordinate axes. 3. Discussion As shown in Table 1, PAO is a composition of unsaturated fatty acids or their esters, and it is assumed that the effects of the above 1.2. due to the isomerization of PAO are also applicable to individual unsaturated fatty acids or their esters.

Industrial Applicability

[0026] According to the present invention, palm acid oil is modified by skeletal isomerization.

Claims

1. In the process of upgrading palm acid oil by skeletal isomerization in the presence of a solid acid catalyst, ZrO 2 / Al 2 O 3 / SO 4 2- A method for modifying palm acid oil using one or more of Al-SBA-15, SAPO-11, and H-Beta.

2. In a method for modifying palm acid oil by skeletal isomerization in the presence of a solid acid catalyst, a calibration curve of modification degree-isomerization degree is prepared with the coordinate axis being the modification degree of palm acid oil and the isomerization degree, and the isomerization degree corresponding to the optimum modification degree is determined from the calibration curve. Using the isomerization degree as a standard, SAPO-11, H-Beta, ZrO 2 / Al 2 O 3 / SO 4 2- A method for modifying palm acid oil using one or more of Al-SBA-15.

3. 3. The method for modifying palm acid oil by skeletal isomerization according to claim 1 or 2, wherein the lower alcohol is methanol or ethanol.

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