Method for reforming palm acid oil by skeletal isomerization

Abstract

[Problem] To develop a solid acid catalyst for use in a method for reforming palm acid oil by skeletal isomerization in the presence of a solid acid catalyst. [Solution] A method for reforming palm acid oil by skeletal isomerization in the presence of a solid acid catalyst, wherein one or more components selected from ZrO2 / Al2O3 / SO4 2-, Al-SBA-15, SAPO-11, and H-Beta are the solid acid catalyst.

Description

Modification method of palm acid oil by skeletal isomerization

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

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

[0003]

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

[0005] The present inventors have previously proposed a method for producing biofuel using a solid acid catalyst in which transesterification of triglycerides in fats and oils with lower alcohols hardly occurs, and esterification of FFAs with a small amount of lower alcohols is preferentially carried out (Japanese Patent No. 6770554, Japanese Patent No. 7045775).

[0006] Patent No. 6770554 Patent No. 7045775

[0007] However, the biofuel obtained by this method has the problem of being difficult to handle due to its low cold flowability.

[0008] Figure 1 illustrates the PAO modification reaction via skeletal isomerization. When PAO is reacted with a lower alcohol, transesterification of TG is suppressed and skeletal isomerization occurs to produce isomerized TG. Meanwhile, FFA is converted to fatty acid methyl esters (FAME) via esterification, and then skeletal isomerization occurs again to produce isomerized FAME.

[0009] Therefore, the present inventors have conducted research with the aim of developing a solid acid catalyst for a method of modifying palm acid oil by skeletal isomerization in the presence of a solid acid catalyst.

[0010] The present invention relates to a method for modifying palm acid oil by skeletal isomerization in the presence of a solid acid catalyst, in which ZrO2 / Al2O3 / SO4 2-This paper proposes a modification method using one or more of Al-SBA-15, SAPO-11, and H-Beta.

[0011] The present invention also provides a method for modifying palm acid oil by skeletal isomerization in the presence of a solid acid catalyst, in which a calibration curve of the degree of modification versus the degree of isomerization is prepared, with the degree of modification of palm acid oil and the degree of isomerization as coordinate axes, and the degree of isomerization corresponding to the optimum degree of modification is determined from the calibration curve. The degree of isomerization is used as a standard, and the solid acid catalyst is selected from SAPO-11, H-Beta, ZrO2 / Al2O3 / SO4 2- , and propose a modification method using one or more of Al-SBA-15.

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

[0013] In the present invention, the skeletal isomerized palm acid oil is improved in all of acid value, kinematic viscosity, and slip point (° C.) compared to untreated palm acid oil.

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

[0015] Diagram showing the modification reaction of PAO due to skeletal isomerization of PAO. Diagram showing the calibration curve of modification degree vs. isomerization degree, with the slip point and isomerization degree as the coordinate axes.

[0016] In the process of upgrading palm acid oil by skeletal isomerization in the presence of a solid acid catalyst, ZrO2 / Al2O3 / SO4 2- A modification method using one or more of Al-SBA-15, SAPO-11, and H-Beta.

[0017] Examples of the present invention will be described below.

[0018] Table 2 shows the reaction conditions and results for reforming PAO in a solid-bed flow reactor.

[0019] In the table, Conversion rate 1): Conversion rate (%) of triglycerides in the raw oil Conversion rate 2): Conversion rate (%) of free fatty acids (FFA) in the raw oil Isomerization rate 3): Isomerization rate of unsaturated FFA and TG in the raw oil Slip point is the temperature at which fat solidifies at low temperatures and begins to flow when heated

[0020] The quality and quantity of PAO isomers are determined by GC-MS. In this example, the degree of isomerization is determined by the following formula:

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

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

[0023]

[0024] In the table, Conversion rate 1): Conversion rate (%) of triglycerides in the raw oil Conversion rate 2): Conversion rate (%) of free fatty acids (FFA) in the raw oil Isomerization rate 3): Isomerization rate of unsaturated FFA and TG in the raw oil Slip point is the temperature at which fat solidifies at low temperatures and begins to flow when heated

[0025] Summary of Tables 2 and 3 1. Modification of PAO In Table 2, Feedstock PAO (139): Palm acid oil (PAO) containing approximately 67.84% free fatty acids, with an acid value of 139 mg KOH / g feedstock and a kinematic viscosity of 74.2 mPg.s. Slip point (°C) was 47.3. Feedstock PAO (110): Palm acid oil (PAO) containing approximately 47.94% free fatty acids, with an acid value of 110 mg KOH / g feedstock and a kinematic viscosity of 81.42 mPg.s. Solid acid catalysts used were ZrO2 / Al2O3 / SO4 2-When PAO was modified using Al-SBA-15 and SAPO-11, the PAO had an unsaturated acid value of 110-130 mgKOH / g, a kinematic viscosity of 74.2-81.4 mPg·s, and a slip point (°C) of 47.3. The resulting oil was modified to an acid value of 6.1-21.2 mgKOH / g, a kinematic viscosity of 3.6-8.8 mPg·s, and a slip point (°C) of 8.3-11.7. In Table 3, Feedstock PAO (139): Palm acid oil (PAO) containing approximately 67.84% free fatty acids, had an acid value of 139 mgKOH / g, and a kinematic viscosity of 74.2 mPg·s. PAO (110) feedstock: Palm acid oil (PAO) containing approximately 47.94% free fatty acids, with an acid value of 110 mg KOH / g feedstock and a kinematic viscosity of 81.42 mPg·s. When the PAO was modified using SAPO-11 and H-Beta as solid acid catalysts at a reaction temperature of 220-280°C for a reaction time of 1-6 hours, the resulting PAO had an acid value of 110-139 mg KOH / g PAO and a kinematic viscosity of 74.2-81.4 mPg·s. The resulting oil had an acid value of 29.8-59.6 mg KOH / g, a kinematic viscosity of 4.3-11.72 mPg, and a slip point (°C) of 5.8. 2. Correlation between the degree of modification (slip point, kinematic viscosity, etc.) and the degree of isomerization. (Table 2) Correlations were observed between the degree of modification (slip point, kinematic viscosity, etc.) and the degree of isomerization. Figure 2 shows a calibration curve of the modification degree versus isomerization degree, with the slip point and isomerization degree plotted on the coordinate axis. 3. Discussion PAO is a composition of unsaturated fatty acids or their esters, as shown in Table 1, and it is assumed that the effects of PAO isomerization described above in 1.2 also apply to individual unsaturated fatty acids or their esters.

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

Claims

1. In the method for upgrading palm acid oil by skeletal isomerization in the presence of a solid acid catalyst, ZrO2 / Al2O3 / SO4 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 reforming palm acid oil by skeletal isomerization in the presence of a solid acid catalyst, a calibration curve of reforming degree-isomerization degree is prepared with the coordinate axis being the reforming degree of palm acid oil and the isomerization degree, and the isomerization degree corresponding to the optimum reforming degree is determined from the calibration curve. Using the isomerization degree as a standard, SAPO-11, H-Beta, ZrO2 / Al2O3 / SO4 are selected as solid acid catalysts. 2- A method for modifying palm acid oil using one or more of Al-SBA-15.

3. A 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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