KR20100015881A - Antioxidant blends for fatty acid methyl esters (biodiesel) - Google Patents

Abstract

This invention provides stabilized biodiesels comprising (1) biodiesel, such as fatty acid methyl ester (FAME), (2) mono-or bis-hindered phenolic derived from 2,6-di-tert-butylphenol, and (3) N,N'-di-substituted para-phenylene diamine. Also methods of stabilizing biodiesel are provided involving adding (2) and (3) to (1).

Description

Antioxidant Blend for Fatty Acid Methyl Ester (Biodiesel) {ANTIOXIDANT BLENDS FOR FATTY ACID METHYL ESTERS (BIODIESEL)}

As global energy demand continues to increase and fossil fuel reserves decrease, diversification of energy resources becomes increasingly important. Biodiesel is one way to achieve diversification. Biodiesel is a common name for mono-alkyl esters of long-chain fatty acids derived from renewable lipid raw materials such as vegetable oils, animal fats or cooking oils and fats used. Biodiesel fuels have different names depending on the feedstock used to produce them, such as fatty acid methyl ester (FAME), rapeseed methyl ester (RME), vegetable oil methyl ester (UVOME) used, soybean oil methyl ester (SOME) or palm oil methyl ester (POME). Biodiesel feedstocks vary widely depending on the composition (chain length and saturation) of their fatty acids.

Biodiesel is typically produced by the reaction of vegetable oils or animal fats with alcohols such as methanol in the presence of a catalyst to produce methyl esters (biodiesel) and glycerin. The most commonly used catalyst, potassium hydroxide, is used to transesterify a wide range of oils and fats, including those with the highest acid content, from vegetable to animal, from unused to used. The biodiesel produced in this way can be distilled off to remove excess alcohol and other impurities. Other methods of producing biodiesel are known.

Freshly produced vegetable oils are protected from oxidation by the presence of natural antioxidants (eg tocopherols). However, biodiesel production methods tend to remove some natural antioxidants, leaving fuel less protected from degradation due to oxidation. In addition, the distillation of biodiesel tends to essentially remove all natural antioxidants, leaving fuel even more unprotected from degradation by oxidation. Oxidation of biodiesel by contact with air and metal surfaces results in the formation of peroxides. They induce free radical chain reactions that cause decomposition of low molecular weight highly oxidized species (aldehydes, ketones, acids) and high molecular weight polymeric materials (gum). The gums tend to cause poor combustion and other engine problems such as deposition on injectors and pistons. The presence of high molecular weight insoluble gums generally clogs the fuel filter.

The RANCIMAT test is a widely accepted method for measuring the oxidative stability of biodiesel. This test consists of bubbling air through biodiesel heated to 110 ° C. The amount of short chain acid (decomposition product of fatty acid oxidation) present in the distillate is a direct indicator of the oxidative stability of the biodiesel. In Europe and Brazil, biodiesel must meet the 6 hour RANCIMAT test requirement in production plants and pumps when refueling vehicles, regardless of the age of the biodiesel. Other countries may establish similar requirements. Although freshly produced biodiesel can exhibit oxidative stability of more than 6 hours (measured by the RANCIMAT method), this value will decrease over time under normal storage conditions in the absence of antioxidants.

Antioxidants are used in hydrocarbon fuels to increase oxidative stability. Oxidative stability of biodiesel can also be increased by the addition of antioxidants. However, because biodiesel fuel is relatively young compared to hydrocarbon fuels, antioxidant technology for biodiesel is also not well developed.

Therefore, there is a need for biodiesel compositions comprising such antioxidant compositions that are economically suitable for commercial use, and improved antioxidant compositions for use in biodiesel fuels.

The present invention is a composition obtained from biodiesel, mono- or bis-disrupted phenolic derived from 2,6-di-tert-butylphenol, and N, N'-di-substituted para-phenylene diamine As described above, by providing a composition wherein the combined amount of mono- or bis-disrupted phenolic acid and N, N'-di-substituted para-phenylene diamine is from about 50 ppm to about 5000 ppm based on biodiesel. It meets the requirements. In addition, biodiesel is crude biodiesel, crude biodiesel derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil, or vegetable oil used, and the crude biodiesel is fatty acid methyl. The composition is provided which is an ester. Such compositions are provided wherein the biodiesel is distilled biodiesel and the distilled biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil or vegetable oil used. Also provided are such compositions wherein the combined amount of mono- or bis-disrupted phenolic acid and N, N'-di-substituted para-phenylene diamine is from about 100 ppm to 2500 ppm based on biodiesel. Furthermore, the ratio of mono- or bis-disrupted phenols to N, N'-di-substituted para-phenylene diamines is from about 10: 1 to about 1:10 by weight, in particular from about 5: 1 to about The composition is provided which varies at 1: 5. Furthermore, as a composition obtained from biodiesel, 2,4,6-tri-tert-butylphenol and N, N'-di-substituted para-phenylene diamine, N, N'-di-substituted para-phenyl Also provided are compositions wherein the ratio of 2,4,6-tri-tert-butylphenol to lene diamine varies from about 10: 1 to about 1:10 by weight. The invention also includes or combines biodiesel, mono- or bis-disrupted phenols derived from 2,6-di-tert-butylphenol, and N, N'-di-substituted para-phenylene diamines A composition prepared by providing a composition wherein the combined amount of mono- or bis-disrupted phenolic acid and N, N'-di-substituted para-phenylene diamine is from about 50 ppm to about 5000 ppm based on biodiesel. .

The invention also relates to biodiesel, such that the combined amount of mono- or bis-disrupted phenolic acid and N, N'-di-substituted para-phenylene diamine is from about 50 ppm to about 5000 ppm based on biodiesel. Biodiesel is included by combining a composition comprising a mono- or bis-disrupted phenol derived from 2,6-di-tert-butylphenol and N, N'-di-substituted para-phenylene diamine It provides a method for improving the oxidative stability of the composition. Wherein the biodiesel is crude biodiesel, the crude biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil or vegetable oil used, and the crude biodiesel is a fatty acid methyl ester. A method is also provided. Also provided is the biodiesel being distilled biodiesel, wherein the distilled biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil or vegetable oil used. Also provided is the process wherein the combined amount of mono- or bis-disrupted phenolic acid and N, N'-di-substituted para-phenylene diamine is from about 100 ppm to about 2500 ppm based on biodiesel. Furthermore, the ratio of mono- or bis-disrupted phenols to N, N'-di-substituted para-phenylene diamines is from about 10: 1 to about 1:10 by weight, in particular from about 5: 1 to about 1: The above method of varying to five is provided. Improving the oxidative stability of compositions comprising biodiesel by blending compositions comprising biodiesel, 2,4,6-tri-tert-butylphenol and N, N'-di-substituted para-phenylene diamine The method of claim 2 wherein the ratio of 2,4,6-tri-tert-butylphenol to N, N'-di-substituted para-phenylene diamine varies from about 5: 1 to about 1: 5 by weight. A method is provided.

In the present invention, mono- or bis-disrupted phenols derived from 2,6-di-tert-butylphenol are ortho-tert-butylphenol, 2,6-di-tert-butylphenol, 2, 4,6-tri-tert-butylphenol, 4,4'-methylenebis (2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxyphenylhydro Cinnamic acid, methyl ester, 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, C7-C9 branched alkyl ester, 2,6-di-tert-butyl-alpha-dimethylamino- p-cresol, butylated hydroxytoluene, or 2,4,6-tri-tert-butylphenol; N, N'-di-substituted para-phenylene diamine is N, N'-di-tert-butyl-p-phenylenediamine, N, N'-diisopropyl-p-phenylenediamine, or N , N'-bis- (1,4-dimethylpentyl) -p-phenylenediamine.

In some compositions and / or methods of the invention, the weight ratio of 2,4,6-tri-tert-butylphenol to N, N'-disubstituted para-phenylene diamine is greater than about 1, In some embodiments, greater than about 1.25, and in other embodiments, greater than about 1.5.

The glossary is provided in advance of the claims.

The inventors have surprisingly found a substantial increase in the oxidative stability of the biodiesel provided by the present invention. We could not anticipate that the combination of biodiesel and antioxidants described and claimed herein will provide the benefits demonstrated by the examples provided herein.

Mono or bis-disrupted phenols derived from 2,6-di-tert-butylphenol

Suitable mono or bis-disrupted phenols derived from 2,6-di-tert-butylphenol are 2,6-di-tert-butylphenols (e.g. 2 sold under the tradename ETHANOX 4701). , Products comprising 6-di-tert-butylphenol); 2,4,6-tri-tert-butylphenol; A combination of ortho-tert-butylphenol, 2,6-di-tert-butylphenol, and 2,4,6-tri-tert-butylphenol (e.g. sold under the tradename ethanox 4733, Products comprising ortho-tert-butylphenol, 2,6-di-tert-butylphenol and 2,4,6-tri-tert-butylphenol); Combinations of 2,6-di-tert-butylphenol and 2,4,6-tri-tert-butylphenol (e.g., 2,6-di-tert-butylphenol sold under the trade name Etanox 4735 And 2,4,6-tri-tert-butylphenol; 4,4'-methylenebis (2,6-di-tert-butylphenol) (e.g., 4,4'-methylenebis (2,6-di-tert-butyl) sold under the trade name ethanox 4702 Products comprising phenol; 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, methyl esters (e.g., 3,5-di-tert- sold under the tradename ethanox 4750) Butyl-4-hydroxyphenylhydrocinnamic acid, products comprising methyl esters; 3,5-di-tert-butyl-4-hydroxyphenylcinnamic acid, C7-C9 branched alkyl esters (eg, 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, a product comprising C7-C9 branched alkyl ester, sold under the trade name ethanox 4716); 2,6-di-tert-butyl -Alpha-dimethylamino-p-cresol (e.g., products comprising 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol sold under the tradename ethanox 4703); Oxytoluene (BHT); essentially 100% 2,4,6-tri-tert-butylphenol (TTBP) Or a combination thereof, In the present invention, the concentration of mono- or bis-disrupted phenols derived from 2,6-di-tert-butylphenol is from about 0.0025% by weight of the total biodiesel 0.25 weight percent.

N, N'-di-substituted para-phenylene diamine

Suitable N, N'-di-substituted para-phenylene diamines are N, N'-di-tert-butyl-p-phenylenediamine (PDA), N, N'-diisopropyl-p-phenylene Diamine, N, N'-bis- (1,4-dimethylpentyl) -p-phenylenediamine, or combinations thereof. The concentration of N, N'-di-substituted para-phenylene diamine in the present invention may be from about 0.0025% to about 0.25% by weight of the total biodiesel.

Biodiesel

Unless otherwise indicated, the term biodiesel as used herein includes crude biodiesel, distilled biodiesel, or any individual chemical component of any one of the foregoing. Crude biodiesel comprises fatty acid methyl esters of vegetable or animal origin or saturated, mono-unsaturated, di-unsaturated, or tri-unsaturated methyl esters having 8 to 22 carbon atoms. Methods of producing crude biodiesel are well known to those skilled in the art. Examples of individual chemical components of fatty acid methyl esters include methyl stearate (n-octadecanoic acid, methyl ester), methyl oleate (9-octadecenoic acid, methyl ester), methyl vasenate (11-octadecenoic acid methyl ester) , Methyl linoleate (9,12-octadecadienoic acid, methyl ester), or methyl linoleniate (9,12,15-octadecateric acid, methyl ester), caprylic acid methyl ester, methyl capric acid Esters, lauric acid methyl ester, myristic acid methyl ester, palmitic acid methyl ester, arachidic acid methyl ester, behenic acid methyl ester, lauroleic acid methyl ester, myristoleic acid methyl ester, palmitoleic acid methyl ester, l Lideic acid methyl ester, gadoleic acid methyl ester, arachidonic acid methyl ester, erucic acid methyl ester, and the like.

Distilled biodiesel comprises, for example, crude biodiesel in which one or more distillation steps have been carried out to remove excess alcohol, residual glycerin and other impurities, and specific cuts produced during the distillation of the crude biodiesel Or biodiesel obtained in fractions. Methods of distilling crude biodiesel are well known to those skilled in the art.

Crude biodiesel is, for example, soybean oil, lower erucic rapeseed oil (canola oil), higher erucic rapeseed oil, palm oil, cooking oil used, vegetable oil, coconut oil, corn oil, cottonseed oil. And any suitable plant or animal origin, including safflower oil, sunflower oil, peanut oil, sugarcane oil, swine oil, bovine oil, poultry fat, yellow grease and the like. Fatty acid methyl esters in crude biodiesel can be produced, for example, by transesterification reactions between vegetable or animal family triglycerides and methanol using catalysts as known to those skilled in the art.

Crude biodiesel or distilled biodiesel can be subjected to further chemical treatment, for example to reduce the degree of unsaturation.

Formulation

Biodiesel, mono- or bis-disrupted phenols derived from 2,6-di-tert-butylphenol (component (2)), and N, N'-di-substituted para-phenylene diamines (component ( A composition according to the invention prepared by comprising or combining 3)) may comprise from about 50 ppm to about 5000 ppm of components (2) and (3), or by combining them, based on the amount of biodiesel It may be prepared and the composition may comprise from about 100 ppm to about 2500 ppm of components (2) and (3) based on the amount of biodiesel or may be prepared by combining them.

Methods for improving the oxidative stability of biodiesel according to the invention include biodiesel, mono or bis-disrupted phenols derived from 2,6-di-tert-butylphenol and N, N'-di-substituted Combining about 50 ppm to about 5000 ppm of an antioxidant component comprising para-phenylene diamine. The process also comprises about 100 biodiesel components and mono or bis-disrupted phenols derived from 2,6-di-tert-butylphenol and N, N'-di-substituted para-phenylene diamines. compounding from ppm to about 2500 ppm of the antioxidant component.

The following examples illustrate the principles of the present invention. It is to be understood that the present invention, whether in the examples or elsewhere in the present patent application, is not limited to any particular embodiment illustrated herein.

In each of the examples summarized in Table 1, the identified biodiesel samples and antioxidant compositions were combined. In some comparative examples, no antioxidant composition was added to the identified biodiesel. In the examples where biodiesel was distilled off, biodiesel was distilled using standard techniques known to those skilled in the art. In each example, the oxidative stability of the formulation (or only biodiesel in certain comparative examples) was tested by the RANCIMAT test using the RANCIMAT test method (DIN EN 14112). In each example, the sample size was 3 g, the temperature was 110 ° C., the air source was purified dry air, and the flow rate was 10 L / hr. The advantages of the present invention are clearly demonstrated from the data described in Table 1. For example, the highest RANCIMAT results for soybean oil methyl esters that were distilled but not added to antioxidants were 1.7 hours (see Comparative Examples 33-39), while antioxidants were added and distilled soybean oil methyl esters according to the present invention. For the above, RANCIMAT results within the range of 3.87 hours to 11.19 hours were obtained [see Examples 1 to 22]. The highest RANCIMAT results for soybean oil methyl esters that were not distilled and without antioxidants were 4.63 hours [see Comparative Examples 40 and 41], whereas for soybean oil methyl esters with antioxidants added and not distilled according to the invention. , RANCIMAT results within the range of 6.46 hours to 9.28 hours were obtained [see Examples 23 to 32]. Both, Comparative Examples 42 and 44, which show the results of combining distilled soybean oil methyl ester with 300 ppm ethanox 4733 and an antioxidant composition of 100 ppm of a component other than the present invention, were respectively distilled soybean oil methyl ester. Compared with Examples 1, 3, 5 and 6 of the present invention showing the result of combining the antioxidant composition of ethanox 4733 with less than 300 ppm and PDA, each of Examples 1, 3, 5 and 6 It can be seen that the RANCIMAT results (8.76 hours, 9.53 hours, 6.91 hours and 5.89 hours, respectively) are better than the RANCIMAT results (42.44 and 2.88 hours, respectively). Distilled soybean oil methyl ester is shown in Comparative Examples 43, 45 and 46 showing the results of combining distilled soybean oil methyl ester with 300 ppm of ethanox 4702 and an antioxidant composition of 100 ppm of a component other than the present invention. Compared with Example 2 of the present invention showing the result of combining 200 ppm of ethanox 4702 with 200 ppm of PDA, the RANCIMAT results of Comparative Examples 43, 45 and 46 (3.6 hours respectively) , 3.87 hours, and 4.06 hours), indicating better RANCIMAT results (10.52 hours). Comparative Examples 50, 51 and 52, respectively, showing the results of combining undistilled soybean oil methyl ester with various amounts (200 ppm to 600 ppm) of antioxidant composition of TTBP, respectively. Compared with Examples 27-32 of the present invention showing the results of combining the antioxidant composition of ppm or less of TTBP and PDA, each of Examples 27-32 showed the RANCIMAT results of Comparative Examples 50, 51 or 52, respectively. It can be seen that RANCIMAT results (8.1 hours, 9.28 hours, 8.38 hours, 7.77 hours, 6.95 hours, and 6.46 hours) are better than 5.28 hours, 5.53 hours and 5.84 hours, respectively. In particular, Comparative Example 50 (which shows 5.28 hours of RANCIMAT test results using an antioxidant composition of 200 ppm TTBP) was used in Example 28 of the present invention using an antioxidant composition of 200 ppm TTBP and 200 ppm PDA. , Which represents 9.28 hours of RANCIMAT test results, shows that the present invention provides a substantial advantage. Similar comparisons based on the antioxidant composition of ethanox 4703 compared to the antioxidant composition of the present invention comprising ethanox 4703 can be made between Comparative Example 48 and Examples 3, 7, 8, and 9 of the present invention. Comparative Example 47 shows the use of 381 ppm PDA as an antioxidant with distilled biodiesel, resulting in 6.39 hours of RANCIMAT results. Although some embodiments of the present invention using distilled biodiesel and antioxidants of PDA with mono or bis-disrupted phenols show lower RANCIMAT results, none of these examples are used in PDAs near 381 ppm. Not. Because of the relatively high cost of PDA and the relatively low cost of phenol, it may be advantageous to use a small amount of PDA with phenol in accordance with the present invention to obtain acceptable RANCIMAT results. See, for example, Examples 2 and 3 of the present invention where only 200 ppm PDA with distilled biodiesel is used with phenol and RANCIMAT results of 8.76 hours and 10.52 hours are obtained. In addition, in each embodiment of the present invention using an antioxidant and distilled biodiesel with PDA and phenols showing a RANCIMAT result of less than 6.39 hours, the phenol in antioxidants is ethanox 4733; The lowest value of the RANCIMAT results described above was 3.87 hours. This is compared with Comparative Examples 42 and 44 (2.94 hours and 2.88 hours of RANCIMAT results) in which ethanox 4733 is used with an amine other than the component of the present invention, whereby improved results are obtained using the antioxidant composition of the present invention. I can see your luggage. From Comparative Example 49 showing the use of 200 ppm PDA as antioxidant with biodiesel (not distilled), a RANCIMAT result of 9.01 hours is obtained. 5.28 hours of RANCIMAT results are obtained from Comparative Example 50 showing the use of 200 ppm of TTBP as an antioxidant with biodiesel (not distilled). When a combination of 100 ppm TTBP and 100 ppm PDA of the present invention was used as an antioxidant with biodiesel (not distilled), an RANCIMAT result of 8.1 hours was obtained (Example 27). The 8.1 hour results obtained with the TTBP / PDA blend are much better than the 5.28 hours obtained with TTBP alone. In addition, the 8.1 hour results obtained using the TTBP / PDA blend are only slightly lower than the 9.01 hours obtained using the PDA alone, and yet offer significant commercially significant cost advantages. Some embodiments of the present invention that use PDA as an antioxidant with biodiesel (not distilled) and mono or bis-disrupted phenols show lower RANCIMAT results, none of which show a PDA near 200 ppm. I do not use it.

Table 1

Example number Biodiesel Sample Antioxidant composition (Ppm based on biodiesel) Result (hrs) One  Distilled, Soybean Oil Methyl Ester  200 ppm ethanox 4733, 200 ppm pda 8.76 2  Distilled, Soybean Oil Methyl Ester  200 ppm PDA, 200 ppm ethanox 4702 10.52 3  Distilled, Soybean Oil Methyl Ester  200 ppm PDA, 200 ppm ethanox 4703 9.53 4  Distilled, Soybean Oil Methyl Ester  85 ppm ethanox 4733, 295 ppm pda 5.85 5  Distilled, Soybean Oil Methyl Ester  183 ppm Etanox 4733, 206 ppm PDA 6.91 6  Distilled, Soybean Oil Methyl Ester  296 ppm Etanox 4733, 98 ppm PDA 5.89 7  Distilled, Soybean Oil Methyl Ester  318 ppm PDA, 104 ppm ethanox 4703 9.3 8  Distilled, Soybean Oil Methyl Ester  204 ppm PDA, 202 ppm ethanox 4703 7.88 9  Distilled, Soybean Oil Methyl Ester  105 ppm PDA, 297 ppm ethanox 4703 6.56 10  Distilled, Soybean Oil Methyl Ester  100 ppm ethanox 4733, 100 ppm pda 4.45 11  Distilled, Soybean Oil Methyl Ester  200 ppm ethanox 4733, 200 ppm pda 6.5 12  Distilled, Soybean Oil Methyl Ester  300 ppm ethanox 4733, 300 ppm pda 8.35 13  Distilled, Soybean Oil Methyl Ester  150 ppm ethanox 4733, 50 ppm PDA 3.87 14  Distilled, Soybean Oil Methyl Ester  300 ppm ethanox 4733, 100 ppm PDA 5.47 15  Distilled, Soybean Oil Methyl Ester  450 ppm ethanox 4733, 150 ppm PDA 6.78 16  Distilled, Soybean Oil Methyl Ester  100 ppm ethanox 4733, 100 ppm pda 4.34 17  Distilled, Soybean Oil Methyl Ester  200 ppm ethanox 4733, 200 ppm pda 6.54 18  Distilled, Soybean Oil Methyl Ester  300 ppm ethanox 4733, 300 ppm pda 8.42 19  Distilled, Soybean Oil Methyl Ester  400 ppm ethanox 4733, 400 ppm pda 9.69

20  Distilled, Soybean Oil Methyl Ester  500 ppm Etanox 4733, 500 ppm PDA 11.19 21  Distilled, Soybean Oil Methyl Ester  375 ppm Etanox 4733, 125 ppm PDA 6.15 22  Distilled, Soybean Oil Methyl Ester  375 ppm Etanox 4733, 125 ppm PDA 6.07 23  Undistilled, soybean oil methyl ester  100 ppm ethanox 4733, 100 ppm pda 7.74 24  Undistilled, soybean oil methyl ester  200 ppm ethanox 4733, 200 ppm pda 9.04 25  Undistilled, soybean oil methyl ester  150 ppm ethanox 4733, 50 ppm PDA 6.82 26  Undistilled, soybean oil methyl ester  300 ppm ethanox 4733, 100 ppm PDA 8.3 27  Undistilled, soybean oil methyl ester  100 ppm PDA, 100 ppm TTBP 8.1 28  Undistilled, soybean oil methyl ester  200 ppm PDA, 200 ppm TTBP 9.28 29  Undistilled, soybean oil methyl ester  100 ppm PDA, 300 ppm TTBP 8.38 30  Undistilled, soybean oil methyl ester  100 ppm PDA, 100 ppm TTBP 7.77 31  Undistilled, soybean oil methyl ester  75 ppm PDA, 75 ppm TTBP 6.95 32  Undistilled, soybean oil methyl ester  50 ppm PDA, 50 ppm TTBP 6.46 33 (Comparative Example)  Distilled, Soybean Oil Methyl Ester none 1.57 34 (Comparative Example)  Distilled, Soybean Oil Methyl Ester none 1.58 35 (comparative)  Distilled, Soybean Oil Methyl Ester none 1.7 36 (comparative)  Distilled, Soybean Oil Methyl Ester none 1.58 37 (comparative)  Distilled, Soybean Oil Methyl Ester none 1.56 38 (Comparative)  Distilled, Soybean Oil Methyl Ester none 1.59 39 (Comparative)  Distilled, Soybean Oil Methyl Ester none 1.61 40 (comparative)  Undistilled, soybean oil methyl ester none 4.63 41 (Comparative Example)  Undistilled, soybean oil methyl ester none 4.49 42 (Comparative)  Distilled, Soybean Oil Methyl Ester  300 ppm ethanox 4733, 100 ppm didecylmethylamine 2.94 43 (Comparative Example)  Distilled, Soybean Oil Methyl Ester  300 ppm ethanox 4702, 100 ppm didecylmethylamine 3.6 44 (Comparative)  Distilled, Soybean Oil Methyl Ester  300 ppm ethanox 4733, 100 ppm dilauryl thiodipropionate 2.88

45 (Comparative)  Distilled, Soybean Oil Methyl Ester  300 ppm ethanox 4702, 100 ppm dilauryl thiodipropionate 3.87 46 (Comparative)  Distilled, Soybean Oil Methyl Ester  300 ppm ethanox 4702, 100 ppm N, N'-disalicylidene propylenediamine 4.06 47 (Comparative Example)  Distilled, Soybean Oil Methyl Ester  381 ppm PDA 6.39 48 (Comparative)  Distilled, Soybean Oil Methyl Ester  471 ppm ethanox 4703 3.14 49 (Comparative)  Undistilled, soybean oil methyl ester  200 ppm PDA 9.01 50 (comparative)  Undistilled, soybean oil methyl ester  200 ppm TTBP 5.28 51 (Comparative)  Undistilled, soybean oil methyl ester  400 ppm TTBP 5.53 52 (Comparative)  Undistilled, soybean oil methyl ester  600 ppm TTBP 5.84

Reactants and components referred to in the chemical names or formulas in any of the specification or claims, whether or not they are referred to in the singular or plural, these reactants and components may be other substances (e.g., other reactants, Solvent or other) prior to compounding or contact. It does not matter what chemical change, transformation and / or reaction, if present, occurs in the combination or solution or reaction medium in which the reaction is to be made, as long as the above-described modifications, transformations and / or reactions are required under certain conditions according to the invention and Because it is a natural consequence of the ingredients. Thus, the reactants and components are considered to be components that are bound together in connection with the practice of the desired chemical reaction or in forming the combination used to carry out the desired reaction. Thus, although the claims hereafter refer to materials, components, and / or components of the present tense ("comprises," "is", etc.), one or more other materials, components, and / or components in accordance with the present invention; It is based on those materials, components, or components that are first contacted, combined, blended, or just before being mixed. If present, the claims are intended to cover whatever conversion takes place in situ with the reaction being performed. Thus, a substance, component or component may lose its unique identity through chemical reactions or transformations during contact, combination, blending or mixing operations performed in accordance with the present invention and by applying common sense and conventional techniques of the chemist. The fact that it is, is of total importance for the true meaning of this specification and its claims, and for the correct understanding and evaluation of the material.

While the present invention has been described in terms of one or more preferred embodiments, it will be understood that other modifications may be made without departing from the scope of the invention as set forth in the claims below.

Glossary

Biodiesel comprises crude individual biodiesel, distilled biodiesel, or any individual chemical component of either.

Crude biodiesel comprises fatty acid methyl esters of vegetable or animal origin, or saturated, mono-unsaturated, di-unsaturated, or tri-unsaturated methyl esters having 8 to 22 carbon atoms.

Distilled biodiesel comprises, for example, crude biodiesel in which one or more distillation steps have been carried out to remove excess alcohol, residual glycerin and other impurities, and certain fragments or fractions produced during the distillation of the crude biodiesel Biodiesel obtained as a.

TTBP essentially comprises 100% 2,4,6-tri-tert-butylphenol.

Claims (24)

From biodiesel, mono- or bis-hindered phenols derived from 2,6-di-tert-butylphenol, and N, N'-di-substituted para-phenylene diamines As the obtained composition, Wherein the combined amount of mono- or bis-disrupted phenol and N, N'-di-substituted para-phenylene diamine is from about 50 ppm to about 5000 ppm based on biodiesel. The method of claim 1, (a) the biodiesel essentially comprises crude biodiesel; (b) mono- or bis-disrupted phenols derived from 2,6-di-tert-butylphenol, (i) ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii) 2,4,6-tri-tert-butylphenol, (iv) 4,4'-methylenebis (2,6-di-tert-butylphenol), (v) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, methyl esters, (vi) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, C7-C9 branched alkyl ester, (vii) 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated hydroxytoluene; (c) N, N'-di-substituted para-phenylene diamine, (i) N, N'-di-tert-butyl-p-phenylenediamine, (ii) N, N'-diisopropyl-p-phenylenediamine, or (iii) a composition comprising N, N'-bis- (1,4-dimethylpentyl) -p-phenylenediamine. The composition of claim 2 wherein the crude biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil or vegetable oil used. The composition of claim 2 wherein the crude biodiesel is a fatty acid methyl ester. The method of claim 1, (a) the biodiesel essentially comprises distilled biodiesel; (b) mono- or bis-disrupted phenols derived from 2,6-di-tert-butylphenol, (i) ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii) 2,4,6-tri-tert-butylphenol, (iv) 4,4'-methylenebis (2,6-di-tert-butylphenol), (v) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, methyl esters, (vi) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, C7-C9 branched alkyl ester, (vii) 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated hydroxytoluene; (c) N, N'-di-substituted para-phenylene diamine, (i) N, N'-di-tert-butyl-p-phenylenediamine, (ii) N, N'-diisopropyl-p-phenylenediamine, or (iii) a composition comprising N, N'-bis- (1,4-dimethylpentyl) -p-phenylenediamine. The composition of claim 5 wherein the distilled biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil or vegetable oil used. The composition of claim 1 wherein the combined amount of mono- or bis-disrupted phenolic acid and N, N′-di-substituted para-phenylene diamine is from about 100 ppm to 2500 ppm based on biodiesel. The weight ratio of 2,4,6-tri-tert-butylphenol to N, N'-di-substituted para-phenylene diamine is as follows: a) greater than about 1, b) about 1.25 Or, c) greater than about 1.5. A composition obtained from biodiesel, 2,4,6-tri-tert-butylphenol, and N, N'-di-substituted para-phenylene diamine, wherein the composition is N, N'-di-substituted para-phenylene A composition wherein the weight ratio of 2,4,6-tri-tert-butylphenol to diamine is greater than about 1). The composition of claim 9 wherein the ratio of 2,4,6-tri-tert-butylphenol to N, N'-disubstituted para-phenylene diamine is from about 10: 1 to about 1:10 by weight. . As a composition prepared by combining biodiesel, mono- or bis-disrupted phenols derived from 2,6-di-tert-butylphenol, and N, N'-di-substituted para-phenylene diamines, Wherein the combined amount of mono- or bis-disrupted phenol and N, N'-di-substituted para-phenylene diamine is from about 50 ppm to about 5000 ppm based on biodiesel. The method of claim 11, (a) the biodiesel essentially comprises crude biodiesel; (b) mono- or bis-disrupted phenols derived from 2,6-di-tert-butylphenol, (i) ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii) 2,4,6-tri-tert-butylphenol, (iv) 4,4'-methylenebis (2,6-di-tert-butylphenol), (v) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, methyl esters, (vi) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, C7-C9 branched alkyl ester, (vii) 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated hydroxytoluene; (c) N, N'-di-substituted para-phenylene diamine, (i) N, N'-di-tert-butyl-p-phenylenediamine, (ii) N, N'-diisopropyl-p-phenylenediamine, or (iii) a composition comprising N, N'-bis- (1,4-dimethylpentyl) -p-phenylenediamine. The method of claim 11, (a) the biodiesel essentially comprises distilled biodiesel; (b) mono- or bis-disrupted phenols derived from 2,6-di-tert-butylphenol, (i) ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii) 2,4,6-tri-tert-butylphenol, (iv) 4,4'-methylenebis (2,6-di-tert-butylphenol), (v) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, methyl esters, (vi) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, C7-C9 branched alkyl ester, (vii) 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated hydroxytoluene; (c) N, N'-di-substituted para-phenylene diamine, (i) N, N'-di-tert-butyl-p-phenylenediamine, (ii) N, N'-diisopropyl-p-phenylenediamine, or (iii) a composition comprising N, N'-bis- (1,4-dimethylpentyl) -p-phenylenediamine. A composition comprising biodiesel, 2,4,6-tri-tert-butylphenol, and N, N'-di-substituted para-phenylene diamine, wherein N, N'-di-substituted para-phenyl A weight ratio of 2,4,6-tri-tert-butylphenol to lene diamine is greater than a) about 1. 15. The composition of claim 14, wherein the ratio of 2,4,6-tri-tert-butylphenol to N, N'-di-substituted para-phenylene diamine is from about 10: 1 to about 1:10 by weight. . A composition comprising biodiesel such that the combined amount of mono- or bis-disrupted phenolic acid and N, N'-disubstituted para-phenylene diamine is from about 50 ppm to 5000 ppm based on biodiesel, and 2 By combining the mono- or bis-disrupted phenols and N, N'-di-substituted para-phenylene diamines derived from, 6-di-tert-butylphenol, the oxidative stability of the composition comprising biodiesel How to improve. The method of claim 16, wherein (a) the biodiesel essentially comprises crude biodiesel; (b) mono- or bis-disrupted phenols derived from 2,6-di-tert-butylphenol, (i) ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii) 2,4,6-tri-tert-butylphenol, (iv) 4,4'-methylenebis (2,6-di-tert-butylphenol), (v) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, methyl esters, (vi) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, C7-C9 branched alkyl ester, (vii) 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated hydroxytoluene; (c) N, N'-di-substituted para-phenylene diamine, (i) N, N'-di-tert-butyl-p-phenylenediamine, (ii) N, N'-diisopropyl-p-phenylenediamine, or (iii) a method comprising N, N'-bis- (1,4-dimethylpentyl) -p-phenylenediamine. 18. The method of claim 17, wherein the crude biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil or vegetable oil used. 18. The method of claim 17, wherein the crude biodiesel is a fatty acid methyl ester. The method of claim 16, (a) the biodiesel essentially comprises distilled biodiesel; (b) mono- or bis-disrupted phenols derived from 2,6-di-tert-butylphenol, (i) ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii) 2,4,6-tri-tert-butylphenol, (iv) 4,4'-methylenebis (2,6-di-tert-butylphenol), (v) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, methyl esters, (vi) 3,5-di-tert-butyl-4-hydroxyphenylhydrocinnamic acid, C7-C9 branched alkyl ester, (vii) 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated hydroxytoluene; (c) N, N'-di-substituted para-phenylene diamine, (i) N, N'-di-tert-butyl-p-phenylenediamine, (ii) N, N'-diisopropyl-p-phenylenediamine, or (iii) a method comprising N, N'-bis- (1,4-dimethylpentyl) -p-phenylenediamine. The method of claim 20 wherein the distilled biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil or vegetable oil used. The method of claim 16, wherein the combined amount of mono- or bis-disrupted phenolic acid and N, N′-di-substituted para-phenylene diamine is from about 100 ppm to 2500 ppm based on biodiesel. 17. The process of claim 16, wherein the weight ratio of 2,4,6-tri-tert-butylphenol to N, N'-di-substituted para-phenylene diamine is greater than about a). The process of claim 16 wherein the ratio of 2,4,6-tri-tert-butylphenol to N, N'-di-substituted para-phenylene diamine is from about 10: 1 to about 1:10 by weight. .