KR100983546B1 - Palm diesel with low pour point - Google Patents

Abstract

The invention particularly relates to esterification reactions of C18, C18: 1 and C18: 2 mixed fatty acids with methanol or ethanol, or fractional distillation of methyl or ethyl esters from palm oil, palm kernel oil, palm oil products or palm kernel oil products, or palm oil, Crystallization after fractional distillation of methyl or ethyl esters from palm kernel oil, palm oil product or palm kernel oil product, or crystallization of methyl or ethyl esters from palm oil, palm kernel oil, palm oil product or palm kernel oil product, or palm oil, palm kernel oil, palm oil product Or a process for producing palm oil of low flow point through fractional distillation after crystallization of methyl or ethyl esters from palm kernel oil products, but is not limited thereto.

Palm oil, palm kernel oil, palm oil product, palm kernel oil product, low flow point, palm diesel, crystallization, fractional distillation, methyl ester, ethyl ester

Description

 Palm diesel with low pour point

The present invention relates to biofuels having improved cold and hot flow properties without additional additives. The invention relates to, but is not limited to, improved biofuels obtained from palm oil, palm kernel oil, palm oil products or palm kernel oil products, in particular as alternatives for petroleum diesel.

Recently, due to increased environmental awareness, the concept of using vegetable oil as a fuel has been developed. In Malaysia, biofuels have been successfully derived from palm oil. Patent PJ1105 / 88 discloses a process for producing palm oil methyl ester (palm diesel) from palm oil. Palm oil is converted to palm oil methyl ester through a transesterification reaction, and the derived palm oil methyl ester or palm diesel has been demonstrated to show excellent fuel properties and can be used as a diesel substitute. Production and Evaluation of Palm Oil Methyl Esters as Diesel Substitutes, published in Publication Eis Special Issue, Elaeise Special Issue, November 1995, pp 15-25, announce the fuel properties of palm diesel and its potential as diesel substitutes. It became.

However, palm oil methyl esters known to have a pour point in the range of + 15 ° C. to + 18 ° C. have limitations for use or consumption as fuel, especially in cold climate countries. Although palm diesel shows good fuel characteristics and can meet fuel specifications, it causes some problems when used at low operating temperatures. This is because the pour point of palm oil methyl ester is from + 15 ° C to + 18 ° C. Pour point is the temperature of the oil 3 ° C above the point at which the specimen will not move when tilted horizontally.

Fuel flow in an engine or machine is very important under all circumstances. When running the engine in the cold, it is essential that the mechanical parts can move freely and that the fuel must not have difficulty moving through lines and pumps. Failure to do this will result in failures and engines and machines become inefficient and inoperable.

When the fuel is cooled to a low temperature, it undergoes a number of changes, so-called solidification, solidification with the formation of precipitates of the macrocrystals, and solidification with the formation of the macrocrystals. The expanding macrocrystals block the oil remaining in the crystal structure. Under these circumstances, the flow of fuel is limited. Therefore, good low temperature flow characteristics (flow points) are essential for fuels to ensure smooth operation and to be suitable for a variety of applications. The fuel should have a good pour point, which is the temperature of the oil 3 ° C above the point where the oil does not move when tilted horizontally. Pour points of all samples were analyzed using standard method ASTM D97. Pour point should be lower than operating temperature.

In order to improve the low temperature characteristics mentioned above, a pour point depressant is generally used. Pour point depressants act through surface adsorption onto the wax crystals. The resulting surface layer of the pour point depressant hinders the growth of wax and paraffin crystals. As a result, because there are no long inter-fixed crystals or expanded particles, the fuel can move freely. However, these additives are expensive even if mixed in a small amount in the fuel.

The present invention relates to biofuels having improved cold flow properties without additives (flow point lowering agents). The present invention relates in particular to, but is not limited to, improved biofuels obtained from palm oil, palm kernel oil, palm oil products or palm kernel oil products as alternatives for petroleum diesel.

The present invention discloses premium grade palm diesel compositions and their excellent low temperature properties. In contrast to palm oil methyl esters, the premium grade palm diesel (biodiesel) disclosed herein will be suitable for use in cold climate countries.

In addition, the present invention discloses a process of producing palm diesel having a low flow point, in particular, but is not limited thereto.

(1) esterifying a C18, C18: 1 and C18: 2 mixed fatty acid with methanol or ethanol, or

(2) fractionating distillation of methyl or ethyl esters of palm oil, palm kernel oil, palm oil product or palm kernel oil product, or

(3) fractionating and distilling methyl or ethyl esters of palm oil, palm kernel oil, palm oil product or palm kernel oil product, or

(4) crystallizing the methyl or ethyl ester of palm oil, palm kernel oil, palm oil product or palm kernel oil product, or

(5) A process of fractionating and distilling palm oil, palm kernel oil, palm oil product or methyl or ethyl ester of palm kernel oil product.

Biodiesel according to the present invention is a biodiesel obtained from palm oil, palm kernel oil, palm oil product or palm kernel oil product or mixtures thereof, which is composed of at least C18, C18: 1 and C18: 2 methyl or ethyl esters, or combinations thereof. It features.

Biodiesel according to the invention is characterized in that C18, C18: 1 and C18: 2 methyl or ethyl esters, or mixtures thereof, are mixed at a rate such that they have a pour point in the range of -12 ° C to -21 ° C.

Biodiesel according to the invention is characterized in that C18, C18: 1 and C18: 2 methyl or ethyl esters, or mixtures thereof, are mixed at a rate such that they have a pour point in the range of 15 ° C to -24 ° C.

Biodiesel according to the invention is characterized in that C18, C18: 1 and C18: 2 methyl or ethyl esters, or mixtures thereof, are mixed at a rate such that they have a pour point in the range of 15 ° C to -33 ° C.

In biodiesel according to the invention, the ratio is less than 10% by weight of saturated methyl ester or ethyl ester or mixtures thereof and at least 90% by weight of C18: 1 methyl or ethyl ester, C18: 2 methyl or ethyl ester, or mixtures thereof Characterized in that consists of.

In the biodiesel according to the present invention, the methyl ester is characterized by consisting of methyl myristic acid salt, methyl palmitate salt, methyl oleate salt and methyl linolenic acid salt.

In the biodiesel according to the present invention, the methyl ester composition is composed of 0.5% by weight of methyl myristic acid salt, 4.9% by weight of methyl palmitate, 83.6% by weight of methyl oleate and 11.0% by weight of methyl linoleate, Pour point is characterized in that -21 ℃.

In the biodiesel according to the present invention, the methyl ester composition comprises 0.6% by weight of methyl myristic acid salt, 5.7% by weight of methyl palmitate, 2.0% by weight methyl stearate, 79.0% by weight methyl oleate and 12.7% by weight. It consists of methyl linolenic acid salt, and is characterized by a pour point of -15 占 폚.

In the biodiesel according to the invention, the mixture comprises 0.5% by weight of methyl myristic acid salt, 6.3% by weight of methyl palmitate, 2.9% by weight methyl stearate, 74.6% by weight methyl oleate and 15.7% by weight methyl linolenic acid. It consists of a salt, It is characterized by the pour point of -12 degreeC.

In the biodiesel according to the present invention, the mixture contains 0.7% by weight of methyl myristate, 6.7% by weight of methyl palmitate, 0.4% by weight of methyl stearate, 75.5% by weight of methyl oleate and 16.7% by weight of methyl linolenic acid. It consists of a salt, It is characterized by the pour point of -9 degreeC.

In the biodiesel according to the invention, the mixture is 1.6% by weight of methyl myristate, 5.0% by weight of methyl palmitate, 0.7% by weight methyl stearate, 72.9% by weight methyl oleate, 19.4% by weight methyl linolenic acid Salt, and 0.4% by weight of methyl arachidate, characterized by a pour point of -33 ° C.

Further, the biodiesel according to the present invention is a biodiesel obtained from palm oil, palm kernel oil, palm oil product or palm kernel oil product or mixtures thereof, and a mixture of methyl or ethyl esters of palm oil, palm kernel oil, palm oil product and / or palm kernel oil product. Less than 7% by weight total saturated methyl or ethyl esters and at least 70% by weight C18: 1 methyl or ethyl esters or mixtures thereof.

In the biodiesel according to the present invention, the total saturated methyl or ethyl ester is composed of C14 methyl or ethyl ester, C16 methyl or ethyl ester, or C18 methyl or ethyl ester.

The biodiesel synthesis method according to the present invention is a process for synthesizing biodiesel composed of C18, C18: 1 and C18: 2 methyl or ethyl esters, or mixtures thereof. Esterifying the mixture (a); Or fractionally distilling methyl or ethyl esters from palm oil, palm kernel oil, palm oil product or palm kernel oil product; Or (c) crystallizing methyl or ethyl esters from palm oil, palm kernel oil, palm oil product or palm kernel oil product; Or an integrated process (d) for fractionating and crystallizing methyl or ethyl esters of palm oil, palm kernel oil, palm oil product or palm kernel oil product; Or an integrated process (e) which crystallizes and fractionates distillation of palm oil, palm kernel oil, palm oil product or methyl or ethyl ester of palm kernel oil product.

In the biodiesel synthesis method according to the invention, the esterification process of step (a) is carried out in liquid or solid form at a temperature between 110 ° C. and 160 ° C. using at least C18: 1, C18: 2 fatty acids or mixtures thereof. Characterized in that it is carried out together with the acid catalyst.

In the biodiesel synthesis method according to the present invention, the acid catalyst is selected from concentrated sulfuric acid, concentrated hydrochloric acid and / or sulfonic acid or solid acid, and used at a concentration of 0.5% to 1% by weight of the total mixture. It features.

In the biodiesel synthesis method according to the invention, the fractional distillation process of step (b) is characterized in that it is carried out under a pressure of 5Pa to 30Pa.

In the biodiesel synthesis method according to the present invention, the crystallization process of step (c) and step (d) is characterized in that the drying or solvent fractionation.

In the biodiesel synthesis method according to the present invention, the solvent classification process is characterized in that an alcohol selected from the group consisting of methanol, ethanol, isopropanol and mixtures thereof is used.

In addition, the biodiesel synthesis method according to the present invention is a process for synthesizing biodiesel obtained from palm oil, palm kernel oil, palm oil product or palm kernel oil product or mixtures thereof, wherein the biodiesel is transesterified with palm oil, methanol and ethanol, respectively. Methyl or ethyl esters or mixtures thereof synthesized through the reaction.

In the biodiesel synthesis method according to the present invention, the transesterification process using palm oil, palm kernel oil, palm oil product or palm kernel oil product with methanol or ethanol for 45 minutes to 1 hour at a temperature of 60 ℃ to 65 ℃ And an alkaline catalyst selected from the group consisting of sodium hydroxide, sodium methylate, and potassium hydroxide is used at 0.25% to 1%.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention relates to a premium grade palm diesel, which comprises methyl oleate (at least 98% pure) and methyl linoleate (at least 98% pure) or a mixture comprising a high proportion of methyl oleate and methyl linoleate (at least 90%). It starts. Premium grade palm diesel is encountered when palm oil methyl esters (consisting of C16 (45%), C18 (5%), C18: 1 (39%) and C18: 2 (11%)) are used in cold climate countries. Solve the pour point problem.

Methyl oleate, a component from palm oil methyl ester, exhibits excellent fuel properties like palm oil methyl ester, as well as a low flow point of -18 ° C. Methyl linolenic acid has a pour point of -39 ° C. This pour point is very low compared to palm oil methyl esters (a mixture of C16, C18, C18: 1 and C18: 2). Thus, methyl linoleate can be used in cold climate countries or during low operating temperatures. Similarly, mixtures containing high proportions of methyl oleate and methyl linoleate, such as C14 (0.5%), C16 (4.9%), C18: 1 (83.6%) and C18: 2 (11.0%), It showed a low flow point of 21 ° C. In contrast, the methyl ester mixture consisting of C14 (0.6%), C16 (5.7%), C18 (2.0%), C18: 1 (79.0%) and C18: 2 (12.7%) shows a pour point of -15 ° C. In addition, the methyl ester mixture consisting of C14 (0.5%), C16 (6.3%), C18 (2.9%), C18: 1 (74.6%) and C18: 2 (15.7%) has a pour point of -12 ° C. And the methyl ester mixture comprising C14 (0.7%), C16 (6.7%), C18 (0.4%), C18: 1 (75.5%) and C18: 2 (16.7%) has a pour point of -9 ° C.

General grade palm diesel, on the other hand, is a common palm oil methyl or ethyl ester (45% C16, 5% C18, 39% C18: 1, and 11% C18: 2) with a pour point of + 15 ° C. . This grade is not suitable for use in cold countries because it solidifies in cold countries. On the other hand, mixed methyl or ethyl esters of C18, C18: 1, and C18: 2 having a pour point below −15 ° C. may be used in cold climate countries.

 Mixtures of the methyl or ethyl esters with low flow points can be produced in particular by, but not limited to: (1) esterifying a mixed fatty acid of C18, C18: 1, and C18: 2 with methanol and ethanol, or (2) fractionating methyl or ethyl esters from palm oil, palm kernel oil, palm oil product or palm kernel oil product Distillation; or (3) fractionation and crystallization of methyl or ethyl esters from palm oil, palm kernel oil, palm oil product or palm kernel oil product, or (4) palm oil, palm kernel oil, palm oil product or palm kernel oil product. Crystallizing methyl or ethyl esters, or (5) fractionating and distilling the methyl or ethyl esters of palm oil, palm kernel oil, palm oil products or palm kernel oil products.

All the methyl and ethyl esters mentioned can be obtained by fractionating the methyl or ethyl esters of palm oil, palm kernel oil, palm oil product or palm kernel oil product or esterifying each fatty acid with methanol or ethanol respectively. Since fatty acids can be easily obtained from fat separation of palm oil, the acid-catalyzed esterification of each fatty acid (or cut of mixed fatty acids) with methanol or ethanol can be carried out to produce methyl or ethyl esters. C16 methyl or ethyl esters and C18, C18: 1 and C18: 2 mixed methyl or ethyl esters incorporate methyl or ethyl esters of palm oil, palm kernel oil, palm oil products or palm kernel oil products under fractional distillation, crystallization or controlled pressure and temperature. Fractional distillation and crystallization, ie, crystallization after fractional distillation, or by fractional distillation after crystallization can be obtained. The C16 methyl ester component is commercially available for oleochemical use. The C16 methyl ester component can be used as a feedstock for high quality white soaps and can also be used as feedstock for α-sulfonated methyl esters in additional mild hydrogenation processes. C18, C18: 1 and C18: 2 mixed methyl or ethyl ester components, having a pour point that satisfies the conditions (0 ° C. to -33 ° C.), can be used as biofuels in temperate countries.

The process disclosed by the present invention can be employed to produce low flow palm diesel from palm kernel oil methyl or ethyl esters, in addition to deriving low flow palm oil from palm oil methyl ester. Palm kernel oil methyl ester is C6 (0.3%), C8 (4.4%), C10 (3.6%), C12 (48.3%), C14 (15.6%), C16 (7.8%), C18 (2.0%), C18: 1 (15.1%), and C18: 2 (2.9%). The integrated process of fractional distillation and crystallization, i.e., the process of crystallization after fractional distillation or fractional distillation after crystallization, produces palm oil with a low flow point.

The process of crystallizing the palm oil, palm kernel oil, methyl oil or ethyl ester of palm oil product or palm kernel oil product is achieved by (a) dry fractionation or (b) solvent fractionation under gradual cooling and controlled conditions.

Saturated methyl or ethyl esters, ie methyl or ethyl palmitate and methyl or ethyl stearate, can be classified through dry fractionation (crystallization) from unsaturated methyl or ethyl esters, ie methyl or ethyl oleate and methyl or ethyl linoleate. Gradually cooling and slowly stirring palm oil methyl or ethyl ester results in the formation of fine crystals. Filtering the suspension of fine crystals produces C16 and C18 methyl or ethyl esters with a purity of at least 80%. Application of the resulting component to the second stage fractionation further improves the purity of saturated methyl or ethyl esters. To produce palm diesel with low flow point, a small amount of methyl or ethyl palmitate (C16 methyl or ethyl ester) and methyl or ethyl stearate (C18 methyl), using a similar approach to the filtrate obtained from the first stage fractionation Or ethyl esters), and a high composition of methyl or ethyl oleate (C18: 1 methyl ester) and methyl or ethyl linolenic acid salt (C18: 2 methyl ester). It is preferred to collect the remaining components obtained from the various second stage crystallizations of the filtrate rich in unsaturated methyl or ethyl esters for further crystallization. On the other hand, it is also desirable to collect the filtrate components obtained from the various second stage crystallizations of the residue rich in saturated methyl or ethyl esters for further crystallization. Thus, this method eliminates the loss of starting materials (palm oil, palm kernel oil, palm oil product, and methyl or ethyl esters of palm kernel oil product).                     

The present invention also discloses another classification route, namely solvent classification. Saturated methyl esters, ie methyl or ethyl palmitate, methyl or ethyl stearate, can be effectively classified from unsaturated methyl or ethyl esters, ie methyl or ethyl oleate and methyl or ethyl linoleate. Methanol, ethanol and isopropanol have proven to be excellent as solvents for crystallizing saturated methyl or ethyl esters from unsaturated methyl or ethyl esters. Typical compositions of the unsaturated methyl ester components obtained are 1-2% methyl myristate, 4-6% methyl palmitate, 0-1% methyl stearate, 70-72% methyl oleate, 20-22% methyl linoleate And 0-1% methyl arachidate. On the other hand, the saturated methyl ester component is 0-0.4% methyl myristate, 86-89% methyl palmitate, 6-7% methyl stearate, 3-5% methyl oleate, 1-2% methyl linoleate, and 0-2% methyl arachidate.

The present invention also discloses compositions of methyl or ethyl esters (methyl or ethyl esters of C8, C10, C12, C14, C16, C18, C18: 1 and C18: 2), carbon chain lengths and respective pour points. The pour point depends on the composition of methyl or ethyl esters with different chain lengths. Compositions comprising a high proportion of methyl oleate and methyl linoleate, such as C14 (0.5%), C16 (4.9%), C18: 1 (83.6%) and C18: 2 (11.0%), have a high ratio of -21. It was confirmed to have a low flow point of ℃. In contrast, the methyl ester mixture of C14 (0.6%), C16 (5.7%), C18 (2.0%), C18: 1 (79.0%) and C18: 2 (12.7%) shows a pour point of -15 ° C. In addition, the methyl ester compositions of C14 (0.5%), C16 (6.3%), C18 (2.9%), C18: 1 (74.6%) and C18: 2 (15.7%) show a pour point of -12 ° C. In contrast, methyl ester mixtures containing C14 (0.7%), C16 (6.7%), C18 (0.4%), C18: 1 (75.5%) and C18: 2 (16.7%) show a pour point of -9 ° C. . Low flow palm diesel has a mixture of methyl or ethyl esters of palm oil, palm kernel oil, palm oil product or palm kernel oil product (1) less than 10% total saturated methyl or ethyl ester, ie C14 methyl or ethyl ester, C16 methyl or ethyl Esters, and C18 methyl or ethyl esters, and (2) at least 90% of C18: 1 and C18: 2 mixed methyl or ethyl esters or can be achieved.

C18, C18: 1 and C18: 2 mixed methyl or ethyl esters, except those with low flow points, have other fuel characteristics similar to those of petroleum diesel (viscosity, flash point, sulfur content, total heat of combustion, residual carbon content (Conradson Carbon Residue) CCR), specific gravity and boiling point), showing the suitability as a diesel substitute. The overall performance of the C18 mixed methyl esters was tested in fixed engine and field tests.

The present invention is explained in more detail through the following examples.

≪ Example 1 >

Premium grade palm diesel has a pour point of 15 ° C. or less, depending on its composition.

(a) A mixture of methyl esters, the so-called methyl myristic acid salt (0.5%), methyl palmitate (4.9%), methyl oleate salt (83.6%), and methyl linolenic acid salt (11.0%), have a low temperature of -21 ° C. Pour point. This methyl ester mixture was obtained by acid ester direct esterification of industrial grade oleic acid (about 80% purity) with methanol.

(b) a mixture of methyl esters synthesized with 0.6% methyl myristate, 5.7% methyl palmitate, 2.0% methyl stearate, 79.0% methyl oleate, and 12.7% methyl linoleate; It has a pour point of ℃. Thus, mixtures of these C18, C18: 1 and C18: 2 methyl esters can be used when the operating temperature drops below 15 ° C. in temperate countries.

 <Example 2>

A mixture of C18, C18: 1 and C18: 2 methyl esters consists of palm oil methyl esters (consisting of C16 (45%), C18 (5%), C18: 1 (39%), and C18: 2 (11%)). It can also be obtained by vacuum fractional distillation. Under a pressure of 30 Pa, 90% of methyl palmitate is fractionated at 139 ° C. and a mixture of C18, C18: 1 and C18: 2 methyl esters is fractionated at 154-156 ° C. This methyl ester component shows a pour point below 0 ° C.

<Example 3>

Another way to produce different grades of palm diesel is to use partial vacuum fractionation of palm oil methyl esters. A mixture of methyl esters consisting of 6.0% methyl palmitate, 8.5% methyl stearate, 69.5% methyl oleate, and 16.0% methyl linoleate was obtained under a pressure of 25 Pa, at a temperature ranging from 145 ° C to 154 ° C. Could. This methyl ester component shows a pour point below 0 ° C.

<Example 4>

Crystallization of the palm oil methyl ester was carried out using 1 part by weight palm oil methyl ester in 2 parts by weight methanol. When cooled in two steps from 22 ° C. to −12 ° C., most C 16 methyl esters crystallize out of the palm oil methyl ester. The remaining unsaturated (C18: 1 and C18: 2) mixed methyl esters have a pour point of -33 ° C. This unsaturated mixed methyl ester consists of 1.6% methyl myristate, 5.0% methyl palmitate, 0.7% methyl stearate, 72.9% methyl oleate, 19.4% methyl linoleate and 0.4% methyl arachidate. It is composed.

<Example 5>

Crystallization of the palm oil methyl ester was performed using 1 weight part palm oil methyl ester in 2 weight parts methanol. The mixture was cooled to + 5 ° C. for 30 minutes. The mixture was filtered using suction filtration to collect both residue and filtrate. The filtrate was then cooled to −11 ° C. for 2.5 hours to effect second stage crystallization. The filtrate following this step consists of a high proportion of unsaturated methyl esters, such as 70-72% C18: 1 methyl ester and 20-22% C18: 2 methyl ester. The filtrate has a pour point of -12 ° C. To obtain a high proportion of saturated methyl ester, the residue collected in the first crystallization step was washed with cold methanol (+ 5 ° C.).

<Example 6>

Solvent crystallization of the distilled palm oil methyl ester using methanol as the solvent may also be performed by one step cooling. The mixture was cooled to -9 ° C for 2 h. After suction filtration, the collected filtrate contains 68-69% C18: 1 methyl ester and 18-19% C18: 2 methyl ester and shows a pour point of -9 ° C.

<Example 7>

Crystallization of palm oil methyl ester was performed using 1 weight part palm oil methyl ester in 2 weight parts ethanol. In the first crystallization step, the mixture was cooled to + 3 ° C. for 30 minutes. In the second crystallization step, the filtrate was cooled to -9 ° C for 2.5 hours. After filtration, a filtrate comprising a high proportion of unsaturated methyl esters such as 63-64% C18: 1 methyl ester and 15-16% C18: 2 methyl ester was obtained with a pour point of 0 ° C.

<Example 8>

Crystallization of palm oil methyl ester was performed using 1 weight part palm oil methyl ester in 3 weight parts methanol. In the first crystallization step, the mixture was cooled to + 2 ° C. for 1 hour. In the second crystallization step, the filtrate was cooled to -12 ° C for 2.5 hours. After filtration to remove the residue, high proportions of unsaturated methyl esters are obtained, such as 71-72% C18: 1 methyl ester and 18-19% C18: 2 methyl ester. This mixture shows a pour point of -12 ° C. Meanwhile, in order to obtain high purity saturated methyl esters such as 91-92% C16 methyl ester and 6-7% C18: 0 methyl ester, the residue collected from the first and second stage crystallization was washed with cold methanol. .

Example 9

Crystallization was performed on the components obtained from the partial fractionation. The component was cooled from + 26 ° C. to 0 ° C. for 30 minutes while the component consisting of 3.4% C 16 methyl ester, 8.8% C 18 methyl ester, 71.6% C 18: 1 methyl ester and 16.2% C 18: 2 methyl ester, Crystallized in a water bath at -5 ° C. One weight part of methanol was used for one weight part of the components mentioned above. The residue consists of 5.6% C16 methyl ester, 84.0% C18 methyl ester, 5.8% C18: 1 methyl ester, 1.2% C18: 2 methyl ester, and 3.4% C20 methyl ester.

<Example 10>

20 components consisting of 0.3% C12 methyl ester, 2.2% C14 methyl ester, 64.5% C16 methyl ester, 2.1% C18 methyl ester, 24.7% C18: 1 methyl ester and 6.2% C18: 2 methyl ester Crystallized in a water bath at -5 ° C while cooling from + 26 ° C to + 5 ° C for minutes. This process produced a residue consisting of 0.9% C14 methyl ester, 91.5% C16 methyl ester, 1.6% C18 methyl ester, 5.1% C18: 1 methyl ester, and 0.9% C18: 2 methyl ester. One weight part of methanol was used for the one weight part of the component.

<Example 11>

A component consisting of 0.3% C12 methyl ester, 2.2% C14 methyl ester, 64.5% C16 methyl ester, 2.1% C18 methyl ester, 24.7% C18: 1 methyl ester and 6.2% C18: 2 methyl ester Crystallized in a water bath at -5 ° C while cooling from + 26 ° C to + 5 ° C for minutes. This process produced a residue consisting of 0.9% C14 methyl ester, 91.4% C16 methyl ester, 2.1% C18 methyl ester, 4.7% C18: 1 methyl ester, and 0.9% C18: 2 methyl ester. 2 parts by weight of methanol were used for 1 part by weight of the component. While the filtrate consists of 10.7% C16 methyl ester, 4.5% C18 methyl ester, 68.6% C18: 1 methyl ester, 15.6% C18: 2 methyl ester, and 0.6% C20 methyl ester, Pour point of 6 ° C is shown.                     

<Example 12>

A component consisting of 0.3% C12 methyl ester, 2.2% C14 methyl ester, 64.5% C16 methyl ester, 2.1% C18 methyl ester, 24.7% C18: 1 methyl ester and 6.2% C18: 2 methyl ester, Dry crystallization was carried out in a water bath at -5 ° C while cooling from + 25 ° C to + 10 ° C for 5 minutes. This process produced a residue consisting of 1.5% C14 methyl ester, 83.0% C16 methyl ester, 2.0% C18 methyl ester, 11.4% C18: 1 methyl ester, and 2.1% C18: 2 methyl ester. While the filtrate consists of 10.5% C16 methyl ester, 2.4% C18 methyl ester, 70.2% C18: 1 methyl ester, 16.1% C18: 2 methyl ester, and 0.8% C20 methyl ester, Pour point of 6 ° C is shown.

Example 13

Palm oil methyl ester consisting of C14 (1.0%), C16 (45.0%), C18 (4.1%), C18: 1 (39.9%), C18: 2 (9.7%), and C20 (0.3%) + The dry fractionation was carried out by gradually cooling from 40 ° C. to + 8 ° C. and held at that temperature for 3 hours. The crystal suspension was filtered through a membrane filtration process, and the resulting residues were C14 (0.8%), C16 (86.0%), C18 (1.8%), C18: 1 (8.8%), and C18: 2. (2.6%), ie 88.6% saturated methyl ester and 11.4% unsaturated methyl ester. In contrast, the filtrate was C12 (0.7%), C14 (2.0%), C16 (25.0%), C18 (2.4%), C18: 1 (53.6%), C18: 2 (15.9%), and C20 (0.4 %), Ie 30.5% saturated methyl ester and 69.5% unsaturated methyl ester, with a pour point of 6 ° C.                     

<Example 14>

Palm oil methyl ester consisting of C14 (1.0%), C16 (45.0%), C18 (4.1%), C18: 1 (39.9%), C18: 2 (9.7%), and C20 (0.3%) + The dry fractionation was carried out with gradual cooling from 40 ° C. to + 9 ° C. and held at that temperature for 12 hours. The crystal suspension was filtered through a membrane filtration process, and the resulting residues were C14 (0.9%), C16 (79.7%), C18 (1.9%), C18: 1 (13.5%), and C18: 2. (4.0%), ie 82.5% saturated methyl ester and 17.5% unsaturated methyl ester. In contrast, the filtrate was C12 (0.7%), C14 (2.1%), C16 (25.1%), C18 (2.4%), C18: 1 (53.2%), C18: 2 (16.0%), and C20 (0.5) %), Ie 30.8% saturated methyl ester and 69.2% unsaturated methyl ester, with a pour point of 6 ° C.

<Example 15>

The second dry crystallization step for the residue or saturated methyl ester was carried out using the residue obtained from the process as described in Example 14 to improve purity. Filtration consisting of C14 (0.9%), C16 (79.7%), C18 (1.9%), C18: 1 (13.5%), and C18: 2 (4.0%), i.e. 82.5% saturated methyl ester and 17.5% unsaturated methyl ester The liquid was gradually cooled from + 40 ° C. to + 24 ° C. for 4.5 hours and held at that temperature for 2.5 hours. The crystalline suspension was filtered through a membrane filtration process, and the resulting residue was C14 (0.3%), C16 (95.2%), C18 (1.0%), C18: 1 (2.7%), and C18: 2. (0.8%), i.e. 96.5% saturated methyl ester and 3.5% unsaturated methyl ester. The residue with a high proportion of saturated methyl esters (96.5%) was subjected to a further gentle hydrogenation process (pressure below 50 MPa, temperature below 300 ° C., using conventional catalysts such as nickel). The resulting product has an iodine value of less than 0.5 and can be used as feedstock for α-sulfonated methyl esters. On the other hand, the filtrate was C12 (0.3%), C14 (2.1%), C16 (68.6%), C18 (2.4%), C18: 1 (20.6%), and C18: 2 (6.0%), i.e. 73.4% Composed of saturated methyl ester and 26.6% unsaturated methyl ester.

<Example 16>

Dry classification of palm oil methyl ester consisting of C14 (1.0%), C16 (45.0%), C18 (4.1%), C18: 1 (39.9%), C18: 2 (9.7%), and C20 (0.3%) It was carried out under gradual cooling from + 40 ° C. to + 12 ° C. for hours and held at that temperature for 3 hours. The crystal suspension was filtered through a membrane filtration process, and the resulting residues were C14 (0.7%), C16 (87.9%), C18 (1.6%), C18: 1 (7.7%), and C18: 2. (2.1%), ie 90.2% saturated methyl ester and 9.8% unsaturated methyl ester. In contrast, the filtrate was C12 (0.7%), C14 (1.9%), C16 (32.1%), C18 (2.4%), C18: 1 (48.3%), C18: 2 (14.3%), and C20 (0.3) %), Ie 37.4% saturated methyl ester and 62.6% unsaturated methyl ester, with a pour point between 9 and 12 ° C. A second dry crystallization step was performed on the filtrate.

<Example 17>

The second dry crystallization step for the filtrate or unsaturated methyl ester was carried out using the filtrate obtained from the process as described in Example 16 to improve purity. C12 (0.7%), C14 (1.9%), C16 (32.1%), C18 (2.4%), C18: 1 (48.3%), C18: 2 (14.3%), and C20 (0.3%), or 37.4% The filtrate consisting of saturated methyl ester and 62.6% unsaturated methyl ester was gradually cooled from + 40 ° C. to + 2 ° C. for 13 hours and held at that temperature for 6 hours. The crystal suspension was filtered through a membrane filtration process, and the resulting residues were C12 (1.0%), C14 (1.6%), C16 (54.0%), C18 (2.8%), C18: 1 (31.3%). ), And C18: 2 (9.3%), i.e. 59.4% saturated methyl ester and 40.6% unsaturated methyl ester. In contrast, the filtrate was C12 (0.8%), C14 (2.2%), C16 (17.8%), C18 (2.3%), C18: 1 (58.9%), C18: 2 (17.7%), and C20 (0.3) %), Ie 23.4% saturated methyl ester and 76.6% unsaturated methyl ester, with a pour point of 3 ° C.

&Lt; Example 18 >

One mole of industrial grade oleic acid (having a fatty acid composition of 0.5% C14, 5.5% C16, 80.2% C18: 1 and 13.8% C18: 2) was esterified with 6 moles of methanol at 160 ° C. 0.5 wt% concentrated sulfuric acid was used as catalyst. After reacting for 4.5 hours, the original product was washed with water until the decanted aqueous layer was neutralized. The dry product was subjected to a second esterification reaction (reesterification reaction) step. The esterification step is similar to the first esterification step except that 0.3 wt% of catalyst is used. The resulting methyl esters from the first and second stage esterifications exhibit pour points of -15 ° C and -21 ° C, respectively.

&Lt; Example 19 >

Having the composition of C14 (0.3%), C16 (95.2%), C18 (1.0%), C18: 1 (2.7%), and C18: 2 (0.8%), i.e. 96.5% saturated methyl ester and 3.5% unsaturated methyl ester The components obtained from the crystallization were further subjected to fractional distillation and / or hydrogenation processes (pressure below 50 MPa, temperature below 300 ° C., using conventional catalysts such as nickel). This integration process yielded C16 methyl esters and / or C16 and C18 mixed methyl esters with a purity greater than 97% and an iodine value of less than 0.5. The resulting product is suitable for use as feedstock for α-sulfonated methyl esters.

Example 20

The second dry crystallization step for the filtrate or unsaturated methyl ester was carried out using the filtrate obtained from the process described in Example 16 to improve purity. C12 (0.7%), C14 (1.9%), C16 (32.1%), C18 (2.4%), C18: 1 (48.3%), C18: 2 (14.3%), and C20 (0.3%), or 37.4% The filtrate having a composition of saturated methyl ester and 62.6% unsaturated methyl ester was gradually cooled from + 40 ° C. to −4 ° C. for 16 hours and held at that temperature for 6 hours. After filtration of the crystal suspension through the membrane filtration process, the resulting residues were C14 (1.5%), C16 (46.5%), C18 (3.9%), C18: 1 (37.5%), and C18: 2 ( 10.6%), i.e. 51.9% saturated methyl ester and 48.1% unsaturated methyl ester. On the other hand, the filtrate was C12 (0.8%), C14 (2.0%), C16 (8.5%), C18 (1.6%), C18: 1 (67.9%), and C18: 2 (19.2%), i.e. 12.9% It has a composition of saturated methyl ester and 87.1% unsaturated methyl ester and shows a pour point of -9 ° C.

Example 21

The second dry crystallization step for the filtrate or unsaturated methyl ester was carried out using the filtrate obtained from the process described in Example 16 to improve purity. C12 (0.7%), C14 (1.9%), C16 (32.1%), C18 (2.4%), C18: 1 (48.3%), C18: 2 (14.3%), and C20 (0.3%), or 37.4% The filtrate having a composition of saturated methyl ester and 62.6% unsaturated methyl ester was gradually cooled from + 40 ° C. to −10 ° C. for 16 hours and held at that temperature for 6 hours. After filtration of the crystal suspension through the membrane filtration process, the filtrate consists of at least 90.0% of unsaturated methyl ester and shows a pour point of -24 ° C.

<Example 22>

With compositions of C12 (0.7%), C14 (2.1%), C16 (25.1%), C18 (2.4%), C18: 1 (53.2%), C18: 2 (16.0%), and C20 (0.5%), The methyl ester component obtained from crystallization was fractionated. Under 20-50 Pa pressure and temperature below 145 ° C., the C16 methyl ester is distilled off and the remaining methyl ester consists of at least 90% of C18: 1 and C18: 2 methyl esters and shows a pour point of −21 ° C.

<Example 23>

C18, C18: 1 and C18: 2 mixed esters not only have a low flow point, but also show good fuel properties comparable to palm oil methyl esters. Table 1 summarizes the fatty acid composition of the mixed methyl esters and Table 2 summarizes the respective fuel characteristics.

Fatty acid composition of C18, C18: 1 and C18: 2 mixed methyl esters (% by weight methyl ester) Methyl ester Fatty acid composition
(% Methyl ester) Methyl Palmitate (C16) 4.2 Methyl Stearate (C18) 0.4 Methyl Oleate (C18: 1) 81.6 Methyl Linoleate (C18: 2) 13.8

Fuel Properties of C18, C18: 1 and C18: 2 Methyl Ester, Palm Diesel, and Malaysian Diesel exam Palm diesel Methyl ester
(C18, C18: 1 & C18: 2 mixture) Malaysian Diesel ^* importance
ASTM D1290 0.8700
74.5 ^o F 0.8803
60 ^o F 0.8330
60 ^o F Sulfur content (wt%)
IP 242 0.04 0.04 0.10 Viscosity 40 ° C (cSt)
ASTM D445 4.5 4.5 4.0 Pour point (℃)
ASTM D97 16.0 -15.0 15.0 Total combustion heat (kJ / kg)
ASTM D2332 40,335 39,160 45,800 Flash point (℃)
ASTM D93 174 153.0 98 Residual carbon content (wt%)
ASTM D198 0.02 0.1 0.14 Distillation (℃)
Initial boiling point
ASTM D86 324.0 282.2 228

* Samples obtained from PETRONAS petrol kiosk

As described above, palm diesel having a low flow point disclosed by the present invention not only solves the pour point problem encountered when conventional palm oil methyl ester is used in cold climate countries, but also exhibits excellent fuel characteristics.

Claims (21)

delete delete delete delete Biodiesel obtained from palm oil, palm kernel oil, palm oil product, palm kernel oil product or mixtures thereof, C18, C18: 1 and C18: 2 methyl or ethyl esters, or mixtures thereof, Less than 10% by weight of saturated methyl ester or ethyl ester or mixtures thereof and at least 90% by weight of C18: 1 methyl or ethyl ester, C18: 2 methyl or ethyl ester, or mixtures thereof, Biodiesel, characterized in that the pour point of the biodiesel is -9 ℃ to -33 ℃. The method of claim 5, The methyl ester is biodiesel, characterized in that consisting of methyl myristic acid salt, methyl palmitate, methyl oleate salt and methyl linoleate. The method of claim 6, The methyl ester is composed of 0.5% by weight methyl myristic acid salt, 4.9% by weight methyl palmitate, 83.6% by weight methyl oleate and 11.0% by weight methyl linolenic acid, characterized in that the pour point is -21 ℃ Biodiesel. The method of claim 6, The methyl ester consists of 0.6 wt% methyl myristate, 5.7 wt% methyl palmitate, 2.0 wt% methyl stearate, 79.0 wt% methyl oleate and 12.7 wt% methyl linoleate, with a pour point − Biodiesel, characterized in that 15 ℃. The method of claim 6, The methyl ester consists of 0.5% by weight methyl myristate, 6.3% by weight methyl palmitate, 2.9% by weight methyl stearate, 74.6% by weight methyl oleate and 15.7% by weight methyl linolenic acid, with a pour point- Biodiesel, characterized in that 12 ℃. The method of claim 6, The methyl ester consists of 0.7 wt% methyl myristate, 6.7 wt% methyl palmitate, 0.4 wt% methyl stearate, 75.5 wt% methyl oleate and 16.7 wt% methyl linolenic acid, with a pour point of − Biodiesel, characterized in that 9 ℃. The method of claim 6, The methyl ester is 1.6 wt% methyl myristate, 5.0 wt% methyl palmitate, 0.7 wt% methyl stearate, 72.9 wt% methyl oleate, 19.4 wt% methyl linoleate, and 0.4 wt% methyl Biodiesel comprising an arachidate and having a pour point of -33 ° C. delete delete delete delete delete delete delete delete delete delete