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HomeMy WebLinkAboutProduction Methyl Esters Using Salmon Oil Taku Renewable Resources LeeLitvin 04-27-2009               1.0 Abstract ................................................................ 2.0 Purpose ................................................................ 3.0 Introduction ................................................................ 4.0 Materials and Methods ................................ 4.1 Oil Characterization ................................ 4.2 Oil Pre-Treatment ................................ 4.3 Methyl Ester Production ................................ 4.4 Methyl Ester Purification ................................ 4.4.1 Water Wash ................................ 4.4.2 Silicate Wash ................................ 4.4.3 Distillation ................................ 4.5 Methyl Ester Analysis ................................ 5.0 Results and Discussion ................................ 5.1 Oil Characterization ................................ 5.2 Methyl Ester Production and Purification 5.3 Methyl Ester Analysis ................................ 6.0 Conclusions ................................................................ Appendix ................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ 5.2 Methyl Ester Production and Purification ................................................................................................ ................................................................................................................................ ................................................................................................ ................................................................................................................................ Page 2 of 10 .................................... 3 .................................... 3 ............................................................. 3 ............................................ 3 ............................................. 3 ................................................ 4 ...................................... 4 ..................................... 4 .................................................. 4 ................................................ 4 .................................................... 4 .......................................... 4 ............................................ 4 ............................................. 4 ............................................ 5 .......................................... 7 ............................................................. 8 ..................................... 10 1.0 Abstract Methyl esters were produced from salmon oil by transesterification with potassium methoxide. Three separate purification techniques were used, water wash, silicate wash, and distillation. After purification, the methyl esters were tested for parameters specified by ASTM D 6751 (B100) for Middle Distillate Fuels. The samples did not meet the requirements for oxidation stability index and carbon residue. The failing results are caused by the characteristics of the feedstock and not the method of production. Samples were not tested for cetane number and distil degree of unsaturation of the carbon chains could cause the salmon oil methyl esters to also fail to meet the specification for cetane number and distillation temperature. the specifications to be considered biodiesel. 2.0 Purpose The purpose of this project was to examine the effectiveness of using salmon oil as a feedstock for biodiesel production. Pacific Biodiesel Technologies study to assess the feasibility of biodiesel production from Juneau area waste cooking oil and Juneau area waste salmon oil. 3.0 Introduction Biodiesel is defined as a fuel comprised of mono animal fats.1 The production of biodiesel usually comprised of a reaction of vegetable oil or animal fat with alcohol, usually methanol, in the presence of a catalyst, usually sodium hydroxide or pota called transesterification and yields mono immiscible and naturally separate with the esters floating on top of the glycerin. and the esters are purified. In order for the resulting esters to be considered biodiesel, it must pass a series of tests specified in ASTM D 6751. Industrially, biodiesel is typically made from soy oil, canola oil, tallow, or yellow grease. are not any industrial producers of biodiese 4.0 Materials and Methods 4.1 Oil Characterization Approximately 55 gallons of salmon oil was delivered from to Pacific Biodiesel Technologies by freight in a sealed plastic bag. plastic bag. Tests were conducted on this sample salmon oil. The tests conducted include Moisture and Unsaponifiable Matter content, Free Fatty Acid content, Specific Gravity, Sulfur content, and Oxidation Stability Index. Moisture and Volatiles content, Insoluble Impurities content, and Unsaponifiable Matter content, commonly grouped together and called MIU, determine how much material is present in the sample that is not able to be converted into biodiesel. This value helps us determine ide to determine the degree of degradation of the triglyceride molecule. As a triglyceride molecule degrades, a fatty acid chain breaks off the glycerin backbone lead to excessive soap formation and yield loss feedstock because sulfur levels in the final fuel product must meet strict limits in order to be use Oxidation Stability Index tells us about the stability of the sample and how readily it oxidizes and breaks down. A higher Oxidation Stability Index value is preferable for fuels. 1 ASTM International, Standard D 6751 Middle Distillate Fuels Methyl esters were produced from salmon oil by transesterification with potassium methoxide. Three separate ication techniques were used, water wash, silicate wash, and distillation. After purification, the methyl esters were tested for parameters specified by ASTM D 6751-08, Standard Specification for Biodiesel Fuel Blend Stock . The samples did not meet the requirements for oxidation stability index and The failing results are caused by the characteristics of the feedstock and not the method of Samples were not tested for cetane number and distillation temperature. It is estimated that the high degree of unsaturation of the carbon chains could cause the salmon oil methyl esters to also fail to meet the specification for cetane number and distillation temperature. Methyl esters produced from salmon oil do not meet the specifications to be considered biodiesel. The purpose of this project was to examine the effectiveness of using salmon oil as a feedstock for biodiesel echnologies shall act as TRRi’s consultant in support of TRRi’s need to complete a study to assess the feasibility of biodiesel production from Juneau area waste cooking oil and Juneau area waste Biodiesel is defined as a fuel comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or The production of biodiesel usually comprised of a reaction of vegetable oil or animal fat with alcohol, usually methanol, in the presence of a catalyst, usually sodium hydroxide or potassium hydroxide. yields mono-alkyl esters and glycerin. These two products of transesterification immiscible and naturally separate with the esters floating on top of the glycerin. The two phases are th and the esters are purified. In order for the resulting esters to be considered biodiesel, it must pass a series of tests Industrially, biodiesel is typically made from soy oil, canola oil, tallow, or yellow grease. At the present time there are not any industrial producers of biodiesel using fish oil as a feedstock in the United States. Methods Approximately 55 gallons of salmon oil was delivered from Delta Pacific, 6001 60th Ave Delta, BC CN V4G OXO by freight in a sealed plastic bag. A one liter sample of oil was removed from the on this sample to first understand the physical and chemical char The tests conducted include Moisture and Volatiles content, Insoluble Impurities content, Unsaponifiable Matter content, Free Fatty Acid content, Specific Gravity, Sulfur content, and Oxidation Stability content, Insoluble Impurities content, and Unsaponifiable Matter content, commonly grouped together and called MIU, determine how much material is present in the sample that is not able to be converted into biodiesel. This value helps us determine ideal yield of the process. Free Fatty Acid content is a test to determine the degree of degradation of the triglyceride molecule. As a triglyceride molecule degrades, a fatty acid chain breaks off the glycerin backbone leaving behind a diglyceride molecule. High free fatty acid content can and yield loss during transesterification. Sulfur content is important to know sulfur levels in the final fuel product must meet strict limits in order to be used for on Oxidation Stability Index tells us about the stability of the sample and how readily it oxidizes and breaks down. A higher Oxidation Stability Index value is preferable for fuels. ASTM International, Standard D 6751-08 – Standard Specification from Biodiesel Fuel Blend Stock (B100) for Page 3 of 10 Methyl esters were produced from salmon oil by transesterification with potassium methoxide. Three separate ication techniques were used, water wash, silicate wash, and distillation. After purification, the methyl esters Standard Specification for Biodiesel Fuel Blend Stock . The samples did not meet the requirements for oxidation stability index and The failing results are caused by the characteristics of the feedstock and not the method of It is estimated that the high degree of unsaturation of the carbon chains could cause the salmon oil methyl esters to also fail to meet the on oil do not meet The purpose of this project was to examine the effectiveness of using salmon oil as a feedstock for biodiesel sultant in support of TRRi’s need to complete a study to assess the feasibility of biodiesel production from Juneau area waste cooking oil and Juneau area waste long chain fatty acids derived from vegetable oils or The production of biodiesel usually comprised of a reaction of vegetable oil or animal fat with alcohol, ssium hydroxide. This reaction is of transesterification are The two phases are then separated and the esters are purified. In order for the resulting esters to be considered biodiesel, it must pass a series of tests At the present time there BC CN V4G OXO A one liter sample of oil was removed from the to first understand the physical and chemical characteristics of the content, Insoluble Impurities content, Unsaponifiable Matter content, Free Fatty Acid content, Specific Gravity, Sulfur content, and Oxidation Stability content, Insoluble Impurities content, and Unsaponifiable Matter content, commonly grouped together and called MIU, determine how much material is present in the sample that is not able to be al yield of the process. Free Fatty Acid content is a test to determine the degree of degradation of the triglyceride molecule. As a triglyceride molecule degrades, a fatty . High free fatty acid content can during transesterification. Sulfur content is important to know in the d for on-road use. Oxidation Stability Index tells us about the stability of the sample and how readily it oxidizes and breaks down. A Standard Specification from Biodiesel Fuel Blend Stock (B100) for 4.2 Oil Pre-Treatment Because the oil was determined to have a high water content (see Table 1), it had to dried before transesterification. The oil was added to a rotary evaporator and heated to 80°C under vacuum conditions. The oil was dried to approximately 500ppm water before transesterifi 4.3 Methyl Ester Production Salmon oil was converted into methyl esters using the process of transesterification. Nine separate batches identified as SAL01 through SAL09, were produced. In all nine batches, were kept constant. Salmon oil reacted with potassium methoxide for approximately 16 hours. The solution was then allowed to settle and separate for approximately leaving the methyl ester. 4.4 Methyl Ester Purification The nine batches of salmon oil methyl esters were purified using three different methods. Three batches SAL03, were purified using a water wash technique. Three batches wash technique. Three batches, SAL07 4.4.1 Water Wash Water was added to each batch. The methyl ester and water completed, the methyl ester/water mixture was allowed to sett washing was performed three additional times for a total of four washes. ester, such as soaps, methanol, or glycerin, were The resulting washed ester was then placed in a rota purification of batches SAL01 – SAL03 4.4.2 Silicate Wash Batches SAL04 – SAL06 were separately placed in a rota Once each batch was dry, magnesium silicate was added and mixed for 30 minutes. The magnesium silicate attracts and bonds with polar contaminants, such as soap or remove the resulting cake. The remaining filtered methyl ester is the finished product. 4.4.3 Distillation Batches SAL07 – SAL09 were vacuum distilled. temperatures that did not exceed 240°C, and vapor te was then mixed for one hour with Amberlite. The purpose of the Amberlite was to remove any glycerin that may have distilled over with the ester. After the Amberlite has finished mixing, the decanted methyl ester is the final profuct. 4.5 Methyl Ester Analysis For methyl esters to be considered biodiesel, they first must pass a series of tests listed in the specification ASTM D 6751. All of the tests in ASTM D 6751 were performed on the batches of methyl esters except for cetane number D 613 and distillation temperature D 1160. There was not enough of each sample made to complete these two tests. 5.0 Results and Discussion 5.1 Oil Characterization The results of the oil characterization are listed in Table 1. have a high water content (see Table 1), it had to dried before transesterification. The oil was added to a rotary evaporator and heated to 80°C under vacuum conditions. The oil was dried to transesterification. Salmon oil was converted into methyl esters using the process of transesterification. Nine separate batches were produced. In all nine batches, the transesterification process parameters constant. Salmon oil reacted with potassium methoxide for approximately 16 hours. The solution was then allowed to settle and separate for approximately two hours. The polar, glycerin, layer was then removed The nine batches of salmon oil methyl esters were purified using three different methods. Three batches were purified using a water wash technique. Three batches, SAL04 – SAL06, were purifies using a silicate , SAL07 – SAL09, were purified using distillation. Water was added to each batch. The methyl ester and water mixture were then stirred. After the methyl ester/water mixture was allowed to settle and separate. The water was then removed. This washing was performed three additional times for a total of four washes. Any polar contaminants in the methyl or glycerin, were removed in the water phase. washed ester was then placed in a rotary evaporator to remove any residual water. This completed the SAL03. were separately placed in a rotary evaporator to remove any residual met magnesium silicate was added and mixed for 30 minutes. The magnesium silicate attracts bonds with polar contaminants, such as soap or glycerin molecules. The mixture was then vacuum filte The remaining filtered methyl ester is the finished product. were vacuum distilled. The distillation equipment operated at conditions of 0mbar, pot °C, and vapor temperatures that did not exceed 200°C. The resulting distillate was then mixed for one hour with Amberlite. The purpose of the Amberlite was to remove any glycerin that may After the Amberlite has finished mixing, the methyl ester is decanted. The decanted methyl ester is the final profuct. For methyl esters to be considered biodiesel, they first must pass a series of tests listed in the specification ASTM D 751 were performed on the batches of methyl esters except for cetane number D 613 and distillation temperature D 1160. There was not enough of each sample made to complete these two tests. Results and Discussion s of the oil characterization are listed in Table 1. Page 4 of 10 have a high water content (see Table 1), it had to dried before transesterification. The oil was added to a rotary evaporator and heated to 80°C under vacuum conditions. The oil was dried to Salmon oil was converted into methyl esters using the process of transesterification. Nine separate batches, the transesterification process parameters constant. Salmon oil reacted with potassium methoxide for approximately 16 hours. The solution was hours. The polar, glycerin, layer was then removed The nine batches of salmon oil methyl esters were purified using three different methods. Three batches, SAL01 – were purifies using a silicate the stirring step was . The water was then removed. This Any polar contaminants in the methyl evaporator to remove any residual water. This completed the evaporator to remove any residual methanol or water. magnesium silicate was added and mixed for 30 minutes. The magnesium silicate attracts glycerin molecules. The mixture was then vacuum filtered to The distillation equipment operated at conditions of 0mbar, pot mperatures that did not exceed 200°C. The resulting distillate was then mixed for one hour with Amberlite. The purpose of the Amberlite was to remove any glycerin that may methyl ester is decanted. The For methyl esters to be considered biodiesel, they first must pass a series of tests listed in the specification ASTM D 751 were performed on the batches of methyl esters except for cetane number D 613 and distillation temperature D 1160. There was not enough of each sample made to complete these two tests. Table Test Moisture and Volitiles Insoluble Impurities Usaponifiable Matter Free Fatty Acid content Water Content Specific Gravity Sulfur content Oxidation Stability Index The water content of the salmon oil is a concern. The transesterification reaction is hindered by the pr water. A feedstock with water contents processing. A characteristic of the oil that may cause difficulty with the final ester product meeting ASTM specification is the Oxidation Stability Index (OSI) value of 1.65 hours. Soybean oil, which is a commonly used feedstock for biodiesel has an OSI value of 9.4 hours feedstock will have an OSI less than the ASTM spec adverse effect on the transesterification of salmon oil. 5.2 Methyl Ester Production and Purification There was very little variability in the reaction yields for all nine batches. The resul Figure 1 displays the ester glycerin separation after the batch has settled. Notice the distinct color change between the two phases. Figure 2 Casmir C. Akoh, Oxidative Stability of Fat Substitutes and Vegetable Oils by the Oxidative Stability Index Method. JAOCS, Vol. 71, no. 2 (February 1994) Table 1. Salmon Oil Characterization Results Result Units Moisture and Volitiles 1.62 % mass Insoluble Impurities 0.04 % mass Usaponifiable Matter 0.97 % mass Free Fatty Acid content 0.52 % mass as oleic acid 1.60 % mass 0.91 8.8 ppm Oxidation Stability Index 1.65 hours lmon oil is a concern. The transesterification reaction is hindered by the pr contents this high will not react efficiently. Therefore, the oil must be dried before that may cause difficulty with the final ester product meeting ASTM he Oxidation Stability Index (OSI) value of 1.65 hours. Soybean oil, which is a commonly used feedstock for biodiesel has an OSI value of 9.4 hours.2 It is estimated that methyl esters produced from this feedstock will have an OSI less than the ASTM specified three hours. All other tested parameters will not have an adverse effect on the transesterification of salmon oil. Methyl Ester Production and Purification There was very little variability in the reaction yields for all nine batches. The results are displayed in Table 2. Figure 1 displays the ester glycerin separation after the batch has settled. Notice the distinct color change between Figure 1. Separation of Ester and Glycerin ir C. Akoh, Oxidative Stability of Fat Substitutes and Vegetable Oils by the Oxidative Stability Index Method. JAOCS, Vol. 71, no. 2 (February 1994) Page 5 of 10 % mass as oleic acid lmon oil is a concern. The transesterification reaction is hindered by the presence of . Therefore, the oil must be dried before that may cause difficulty with the final ester product meeting ASTM he Oxidation Stability Index (OSI) value of 1.65 hours. Soybean oil, which is a commonly used It is estimated that methyl esters produced from this All other tested parameters will not have an ts are displayed in Table 2. Figure 1 displays the ester glycerin separation after the batch has settled. Notice the distinct color change between ir C. Akoh, Oxidative Stability of Fat Substitutes and Vegetable Oils by the Oxidative Stability Index Batch Reaction Yield, % mass Purification Technique SAL01 98.3 SAL02 98.1 SAL03 98.4 SAL04 97.8 SAL05 97.7 SAL06 97.8 SAL07 97.7 SAL08 98.0 SAL09 97.4 The differences in final processing yields can be attributed to the different purification techniques used. wash purification technique has a slightly higher efficiency wit The three different purification techniques did yield very different final product colors. A representative sample of each technique is displayed in Figure 2. red color. The silicate wash resulted in an ester with a bright orange color. The distillation resulted in an ester with a bright yellow color. Figure 2. Color Differences in Purification Techniques The silicate wash removed much of the pigment in the ester. T was used to purify the ester the cake had a deep red Table 2. Reaction and Processing Yields Purification Technique Loss From Purification, % mass Final Processing Yield, % mass Final Processing Yield, % volume* Water 4.0 94.3 97.1 Water 3.8 94.3 97.1 Water 3.6 94.8 97.6 Silicate 4.5 93.3 96.1 Silicate 4.3 93.4 96.2 Silicate 4.3 93.5 96.3 Distillation 5.8 91.9 94.7 Distillation 4.5 93.5 96.3 Distillation 5.5 91.9 94.7 *calculated The differences in final processing yields can be attributed to the different purification techniques used. wash purification technique has a slightly higher efficiency with respect to final yields. The three different purification techniques did yield very different final product colors. A representative sample of . From left to right, the water wash resulted in an ester with a deep color. The silicate wash resulted in an ester with a bright orange color. The distillation resulted in an ester with Color Differences in Purification Techniques removed much of the pigment in the ester. The silicate begins as a pure white powder. After it was used to purify the ester the cake had a deep red-orange color. See Figure 3. Page 6 of 10 Final Processing Yield, % volume* 97.1 97.1 97.6 96.1 96.2 96.3 94.7 96.3 94.7 The differences in final processing yields can be attributed to the different purification techniques used. The water The three different purification techniques did yield very different final product colors. A representative sample of he water wash resulted in an ester with a deep orange- color. The silicate wash resulted in an ester with a bright orange color. The distillation resulted in an ester with he silicate begins as a pure white powder. After it The residue left behind after the distillation was deep brown in color and had the physical characteristics of a wax. See Figure 4. 5.3 Methyl Ester Analysis Table 3 displays the results of the analysis for purification technique. Results for each individual batch can be found in the Appendix. exceeded the specified ASTM D 6751 limit. Figure 3. Silicate Cake after the distillation was deep brown in color and had the physical characteristics of a wax. Figure 4. Distillate Bottoms Table 3 displays the results of the analysis for the finished products. The values have been averaged for each type of purification technique. Results for each individual batch can be found in the Appendix. The values in bold have exceeded the specified ASTM D 6751 limit. The fuel passes most of the specifications, regardless of the Page 7 of 10 after the distillation was deep brown in color and had the physical characteristics of a wax. The values have been averaged for each type of The values in bold have regardless of the purification technique, with the exceptions of Oxidation Stability Index (OSI) and Table 3. Final Ester Analysis Results Test Method Ca & Mg, combined EN 14538 Na & K, combined EN 14538 Phosphorus content D4951 Flash Point D93 Water and Sediment D2709 Kinematics Viscosity D445 Sulfated Ash D874 Sulfur D5453 Cu Strip Corrosion D130 Cloud Point D5773 Carbon Residue D4530 Acid Number D664 Free Glycerin D6584 Total Glycerin D6584 Oxidation Stability Index EN 14538 Cold Soak Filtration Time D6751 Annex As discussed in Oil Characterization, the (OSI) of the salmon oil was low relative to soybean oil. Therefore, it surprising that the OSI of the resulting ester is also low, with and average of 0. 3 hours. Carbon Residue is a test which measures the certain rates and temperatures in a nitrogen filled environment. The material that has not evaporated and remains is the carbon residue or coke. The carbon residue results ASTM limit. Therefore it is inferred that this fuel will have a tendency to form coke deposits when used. Cetane number and distillation temperature were not performed on the salmon methyl esters because of available sample. It can be estimated that salmon methyl esters may have a cetane number which is below the ASTM limit for biodiesel. Cetane values decrease as the amount of double bonds increase in a carbon chain salmon oil is comprised of a high percentage of unsaturated (many double bonds) carbon chains. cetane numbers tend to cause diesel knocking and show increased gaseous and particulate exhaust emissions due to incomplete combustion. Moreover, excessive engine deposits 6.0 Conclusions Salmon can be converted into methyl esters by transesterification, but the resulting fuel does not pass ASTM D 6751 specification for biodiesel. The oxidation stability can be oxidation stability agent or antioxidant. The dosage amount that would raise the OSI above the limit would be experimentally determined and would vary on the type of antioxidant the methyl ester cannot be improved. It is a function of the characteristics of the feedstock. A way to to blend the fuel with biodiesel made fr refined soy, or tallow. Blending ratios would need to be experimentally determined. The purification process used did not have a great effect on the techniques yielded very similar results. The distillation technique yielded some differenc 3 Martin Mittelbach, Biodiesel The Comprehensive Handbook p. 141. purification technique, with the exceptions of Oxidation Stability Index (OSI) and Carbon Residue Units ASTM D6751 Limit Water Wash Silicate Wash ppm 5 max <2 <2 ppm 5 max <2 <2 ppm 10 max <1 <1 °C 93 min 178 173 % volume 0.050 max <0.005 <0.005 mm2/s 1.9 – 6.0 4.42 4.45 % mass 0.020 max <0.002 <0.002 ppm 15 max 1.0 0.9 3 max 1a 1a °C report -0.1 -0.2 % mass 0.050 max 0.145 0.154 mg KOH/g 0.50 max 0.180 0.145 % mass 0.020 max <0.005 <0.005 % mass 0.240 max 0.068 0.069 hours 3 min 0.6 0.7 D6751 Annex seconds 360 max 85 84 the (OSI) of the salmon oil was low relative to soybean oil. Therefore, it surprising that the OSI of the resulting ester is also low, with and average of 0.6 hours, and below the ASTM limit of Carbon Residue is a test which measures the non-volatile compounds present in the fuel. Samples are heated a nitrogen filled environment. The material that has not evaporated and remains is The carbon residue results in this study are in approximately three times higher than the Therefore it is inferred that this fuel will have a tendency to form coke deposits when used. Cetane number and distillation temperature were not performed on the salmon methyl esters because of available sample. It can be estimated that salmon methyl esters may have a cetane number which is below the ASTM limit for biodiesel. Cetane values decrease as the amount of double bonds increase in a carbon chain a high percentage of unsaturated (many double bonds) carbon chains. cetane numbers tend to cause diesel knocking and show increased gaseous and particulate exhaust emissions due to incomplete combustion. Moreover, excessive engine deposits are reported.3 Salmon can be converted into methyl esters by transesterification, but the resulting fuel does not pass ASTM D 6751 specification for biodiesel. The oxidation stability can be improved with the addition of a commonly avai . The dosage amount that would raise the OSI above the limit would and would vary on the type of antioxidant and feedstock used. The carbon reside of ot be improved. It is a function of the characteristics of the feedstock. A way to the fuel with biodiesel made from different feedstock which has a low carbon residue, such as virgin canola, os would need to be experimentally determined. not have a great effect on the ASTM test results. The water wash and silicate wash techniques yielded very similar results. The distillation technique yielded some differences. There was a slight Biodiesel The Comprehensive Handbook, Martin Mittelbach (Publisher), Graz, Austria, Page 8 of 10 Carbon Residue. Silicate Wash Distillation <2 <2 <1 176 <0.005 <0.005 4.41 <0.002 <0.002 0.5 1a -1.5 0.158 0.330 <0.005 0.014 0.067 0.5 247 the (OSI) of the salmon oil was low relative to soybean oil. Therefore, it is not hours, and below the ASTM limit of volatile compounds present in the fuel. Samples are heated at a nitrogen filled environment. The material that has not evaporated and remains is re in approximately three times higher than the Therefore it is inferred that this fuel will have a tendency to form coke deposits when used. Cetane number and distillation temperature were not performed on the salmon methyl esters because of lack of available sample. It can be estimated that salmon methyl esters may have a cetane number which is below the ASTM limit for biodiesel. Cetane values decrease as the amount of double bonds increase in a carbon chain and a high percentage of unsaturated (many double bonds) carbon chains. Fuels with low cetane numbers tend to cause diesel knocking and show increased gaseous and particulate exhaust emissions due to Salmon can be converted into methyl esters by transesterification, but the resulting fuel does not pass ASTM D 6751 improved with the addition of a commonly available . The dosage amount that would raise the OSI above the limit would need to The carbon reside of ot be improved. It is a function of the characteristics of the feedstock. A way to manage this is a low carbon residue, such as virgin canola, test results. The water wash and silicate wash es. There was a slight , Martin Mittelbach (Publisher), Graz, Austria, 2004, decrease in sulfur, a decrease in cloud point, an increase in acid number, an increase in free glycerin, a decrease in OSI, and an increase in cold soak filterability time can be attributed to the degradation of the fatty acid chains or polymerization at high temperatures. The high degree of unsaturation yields thermal instability and negative performance characteristics of the fuel. One unexpected benefit to using the silicate was technique was the removal of the deep red pigment in the ester. The final product from the silicate wash was a bright orange color as opposed to the water wash product which was a deep orange-red color. Because the salmon oil used in this study had Before using salmon oil as a feedstock for biodiesel production, it is imperative that the water content is known and if it is too wet, steps are taken to dry the oil. High reduced production yields. Salmon oil is not an ideal feedstock for the production of on feedstock, it must be blended with other oil methyl esters could however be used as an fuel in any manner, it should first be treated with an antioxidant. Witho degrade. decrease in sulfur, a decrease in cloud point, an increase in acid number, an increase in free glycerin, a decrease in , and an increase in cold soak filterability time. The decrease in OSI and increase in cold soak filterabilit can be attributed to the degradation of the fatty acid chains or polymerization at high temperatures. The high degree of unsaturation yields thermal instability and negative performance characteristics of the fuel. the silicate was technique was the removal of the deep red pigment in the ester. The final product from the silicate wash was a bright orange color as opposed to the water wash product which was s study had a high water content, it needed to be dried before it was processed. Before using salmon oil as a feedstock for biodiesel production, it is imperative that the water content is known and if it is too wet, steps are taken to dry the oil. High water contents in feedstock oils can lead to soap formation and Salmon oil is not an ideal feedstock for the production of on-road biodiesel. For salmon oil to be used as a biodiesel feedstock, it must be blended with other oils which produce biodiesel with low carbon residue values. could however be used as an effective off-road fuel substitute. If salmon methyl esters are used for should first be treated with an antioxidant. Without an antioxidant added, the fuel will quickly Page 9 of 10 decrease in sulfur, a decrease in cloud point, an increase in acid number, an increase in free glycerin, a decrease in The decrease in OSI and increase in cold soak filterability time can be attributed to the degradation of the fatty acid chains or polymerization at high temperatures. The high degree the silicate was technique was the removal of the deep red pigment in the ester. The final product from the silicate wash was a bright orange color as opposed to the water wash product which was it needed to be dried before it was processed. Before using salmon oil as a feedstock for biodiesel production, it is imperative that the water content is known and water contents in feedstock oils can lead to soap formation and For salmon oil to be used as a biodiesel s which produce biodiesel with low carbon residue values. Salmon road fuel substitute. If salmon methyl esters are used for ut an antioxidant added, the fuel will quickly Appendix Table A1. Test Results for Individual Batches Table A1. Test Results for Individual Batches Page 10 of 10                1.0 Abstract ................................................................ 2.0 Purpose ................................................................ 3.0 Introduction ................................................................ 4.0 Materials and Methods ................................ 4.1 Oil Characterization ................................ 4.2 Oil Pre-Treatment ................................ 4.3 Methyl Ester Production ................................ 4.4 Methyl Ester Purification ................................ 4.4.1 Water Wash ................................ 4.4.2 Silicate Wash ................................ 4.4.3 Distillation ................................ 4.5 Methyl Ester Analysis ................................ 5.0 Results and Discussion ................................ 5.1 Oil Characterization ................................ 5.2 Methyl Ester Production and Purification 5.3 Methyl Ester Analysis ................................ 6.0 Conclusions ................................................................ Appendix ................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ 5.2 Methyl Ester Production and Purification ................................................................................................ ................................................................................................................................ ................................................................................................ ................................................................................................................................ Page 2 of 10 .................................... 3 .................................... 3 ............................................................. 3 ............................................ 3 ............................................. 3 ................................................ 4 ...................................... 4 ..................................... 4 .................................................. 4 ................................................ 4 .................................................... 4 .......................................... 4 ............................................ 4 ............................................. 4 ............................................ 5 .......................................... 7 ............................................................. 8 ..................................... 10 1.0 Abstract Methyl esters were produced from salmon oil by transesterification with potassium methoxide. Three separate purification techniques were used, water wash, silicate wash, and distillation. After purification, the methyl esters were tested for parameters specified by ASTM D 6751 (B100) for Middle Distillate Fuels. The samples did not meet the requirements for oxidation stability index and carbon residue. The failing results are caused by the characteristics of the feedstock and not the method of production. Samples were not tested for cetane number and distil degree of unsaturation of the carbon chains could cause the salmon oil methyl esters to also fail to meet the specification for cetane number and distillation temperature. the specifications to be considered biodiesel. 2.0 Purpose The purpose of this project was to examine the effectiveness of using salmon oil as a feedstock for biodiesel production. Pacific Biodiesel Technologies study to assess the feasibility of biodiesel production from Juneau area waste cooking oil and Juneau area waste salmon oil. 3.0 Introduction Biodiesel is defined as a fuel comprised of mono animal fats.1 The production of biodiesel usually comprised of a reaction of vegetable oil or animal fat with alcohol, usually methanol, in the presence of a catalyst, usually sodium hydroxide or pota called transesterification and yields mono immiscible and naturally separate with the esters floating on top of the glycerin. and the esters are purified. In order for the resulting esters to be considered biodiesel, it must pass a series of tests specified in ASTM D 6751. Industrially, biodiesel is typically made from soy oil, canola oil, tallow, or yellow grease. are not any industrial producers of biodiese 4.0 Materials and Methods 4.1 Oil Characterization Approximately 55 gallons of salmon oil was delivered from to Pacific Biodiesel Technologies by freight in a sealed plastic bag. plastic bag. Tests were conducted on this sample salmon oil. The tests conducted include Moisture and Unsaponifiable Matter content, Free Fatty Acid content, Specific Gravity, Sulfur content, and Oxidation Stability Index. Moisture and Volatiles content, Insoluble Impurities content, and Unsaponifiable Matter content, commonly grouped together and called MIU, determine how much material is present in the sample that is not able to be converted into biodiesel. This value helps us determine ide to determine the degree of degradation of the triglyceride molecule. As a triglyceride molecule degrades, a fatty acid chain breaks off the glycerin backbone lead to excessive soap formation and yield loss feedstock because sulfur levels in the final fuel product must meet strict limits in order to be use Oxidation Stability Index tells us about the stability of the sample and how readily it oxidizes and breaks down. A higher Oxidation Stability Index value is preferable for fuels. 1 ASTM International, Standard D 6751 Middle Distillate Fuels Methyl esters were produced from salmon oil by transesterification with potassium methoxide. Three separate ication techniques were used, water wash, silicate wash, and distillation. After purification, the methyl esters were tested for parameters specified by ASTM D 6751-08, Standard Specification for Biodiesel Fuel Blend Stock . The samples did not meet the requirements for oxidation stability index and The failing results are caused by the characteristics of the feedstock and not the method of Samples were not tested for cetane number and distillation temperature. It is estimated that the high degree of unsaturation of the carbon chains could cause the salmon oil methyl esters to also fail to meet the specification for cetane number and distillation temperature. Methyl esters produced from salmon oil do not meet the specifications to be considered biodiesel. The purpose of this project was to examine the effectiveness of using salmon oil as a feedstock for biodiesel echnologies shall act as TRRi’s consultant in support of TRRi’s need to complete a study to assess the feasibility of biodiesel production from Juneau area waste cooking oil and Juneau area waste Biodiesel is defined as a fuel comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or The production of biodiesel usually comprised of a reaction of vegetable oil or animal fat with alcohol, usually methanol, in the presence of a catalyst, usually sodium hydroxide or potassium hydroxide. yields mono-alkyl esters and glycerin. These two products of transesterification immiscible and naturally separate with the esters floating on top of the glycerin. The two phases are th and the esters are purified. In order for the resulting esters to be considered biodiesel, it must pass a series of tests Industrially, biodiesel is typically made from soy oil, canola oil, tallow, or yellow grease. At the present time there are not any industrial producers of biodiesel using fish oil as a feedstock in the United States. Methods Approximately 55 gallons of salmon oil was delivered from Delta Pacific, 6001 60th Ave Delta, BC CN V4G OXO by freight in a sealed plastic bag. A one liter sample of oil was removed from the on this sample to first understand the physical and chemical char The tests conducted include Moisture and Volatiles content, Insoluble Impurities content, Unsaponifiable Matter content, Free Fatty Acid content, Specific Gravity, Sulfur content, and Oxidation Stability content, Insoluble Impurities content, and Unsaponifiable Matter content, commonly grouped together and called MIU, determine how much material is present in the sample that is not able to be converted into biodiesel. This value helps us determine ideal yield of the process. Free Fatty Acid content is a test to determine the degree of degradation of the triglyceride molecule. As a triglyceride molecule degrades, a fatty acid chain breaks off the glycerin backbone leaving behind a diglyceride molecule. High free fatty acid content can and yield loss during transesterification. Sulfur content is important to know sulfur levels in the final fuel product must meet strict limits in order to be used for on Oxidation Stability Index tells us about the stability of the sample and how readily it oxidizes and breaks down. A higher Oxidation Stability Index value is preferable for fuels. ASTM International, Standard D 6751-08 – Standard Specification from Biodiesel Fuel Blend Stock (B100) for Page 3 of 10 Methyl esters were produced from salmon oil by transesterification with potassium methoxide. Three separate ication techniques were used, water wash, silicate wash, and distillation. After purification, the methyl esters Standard Specification for Biodiesel Fuel Blend Stock . The samples did not meet the requirements for oxidation stability index and The failing results are caused by the characteristics of the feedstock and not the method of It is estimated that the high degree of unsaturation of the carbon chains could cause the salmon oil methyl esters to also fail to meet the on oil do not meet The purpose of this project was to examine the effectiveness of using salmon oil as a feedstock for biodiesel sultant in support of TRRi’s need to complete a study to assess the feasibility of biodiesel production from Juneau area waste cooking oil and Juneau area waste long chain fatty acids derived from vegetable oils or The production of biodiesel usually comprised of a reaction of vegetable oil or animal fat with alcohol, ssium hydroxide. This reaction is of transesterification are The two phases are then separated and the esters are purified. In order for the resulting esters to be considered biodiesel, it must pass a series of tests At the present time there BC CN V4G OXO A one liter sample of oil was removed from the to first understand the physical and chemical characteristics of the content, Insoluble Impurities content, Unsaponifiable Matter content, Free Fatty Acid content, Specific Gravity, Sulfur content, and Oxidation Stability content, Insoluble Impurities content, and Unsaponifiable Matter content, commonly grouped together and called MIU, determine how much material is present in the sample that is not able to be al yield of the process. Free Fatty Acid content is a test to determine the degree of degradation of the triglyceride molecule. As a triglyceride molecule degrades, a fatty . High free fatty acid content can during transesterification. Sulfur content is important to know in the d for on-road use. Oxidation Stability Index tells us about the stability of the sample and how readily it oxidizes and breaks down. A Standard Specification from Biodiesel Fuel Blend Stock (B100) for 4.2 Oil Pre-Treatment Because the oil was determined to have a high water content (see Table 1), it had to dried before transesterification. The oil was added to a rotary evaporator and heated to 80°C under vacuum conditions. The oil was dried to approximately 500ppm water before transesterifi 4.3 Methyl Ester Production Salmon oil was converted into methyl esters using the process of transesterification. Nine separate batches identified as SAL01 through SAL09, were produced. In all nine batches, were kept constant. Salmon oil reacted with potassium methoxide for approximately 16 hours. The solution was then allowed to settle and separate for approximately leaving the methyl ester. 4.4 Methyl Ester Purification The nine batches of salmon oil methyl esters were purified using three different methods. Three batches SAL03, were purified using a water wash technique. Three batches wash technique. Three batches, SAL07 4.4.1 Water Wash Water was added to each batch. The methyl ester and water completed, the methyl ester/water mixture was allowed to sett washing was performed three additional times for a total of four washes. ester, such as soaps, methanol, or glycerin, were The resulting washed ester was then placed in a rota purification of batches SAL01 – SAL03 4.4.2 Silicate Wash Batches SAL04 – SAL06 were separately placed in a rota Once each batch was dry, magnesium silicate was added and mixed for 30 minutes. The magnesium silicate attracts and bonds with polar contaminants, such as soap or remove the resulting cake. The remaining filtered methyl ester is the finished product. 4.4.3 Distillation Batches SAL07 – SAL09 were vacuum distilled. temperatures that did not exceed 240°C, and vapor te was then mixed for one hour with Amberlite. The purpose of the Amberlite was to remove any glycerin that may have distilled over with the ester. After the Amberlite has finished mixing, the decanted methyl ester is the final profuct. 4.5 Methyl Ester Analysis For methyl esters to be considered biodiesel, they first must pass a series of tests listed in the specification ASTM D 6751. All of the tests in ASTM D 6751 were performed on the batches of methyl esters except for cetane number D 613 and distillation temperature D 1160. There was not enough of each sample made to complete these two tests. 5.0 Results and Discussion 5.1 Oil Characterization The results of the oil characterization are listed in Table 1. have a high water content (see Table 1), it had to dried before transesterification. The oil was added to a rotary evaporator and heated to 80°C under vacuum conditions. The oil was dried to transesterification. Salmon oil was converted into methyl esters using the process of transesterification. Nine separate batches were produced. In all nine batches, the transesterification process parameters constant. Salmon oil reacted with potassium methoxide for approximately 16 hours. The solution was then allowed to settle and separate for approximately two hours. The polar, glycerin, layer was then removed The nine batches of salmon oil methyl esters were purified using three different methods. Three batches were purified using a water wash technique. Three batches, SAL04 – SAL06, were purifies using a silicate , SAL07 – SAL09, were purified using distillation. Water was added to each batch. The methyl ester and water mixture were then stirred. After the methyl ester/water mixture was allowed to settle and separate. The water was then removed. This washing was performed three additional times for a total of four washes. Any polar contaminants in the methyl or glycerin, were removed in the water phase. washed ester was then placed in a rotary evaporator to remove any residual water. This completed the SAL03. were separately placed in a rotary evaporator to remove any residual met magnesium silicate was added and mixed for 30 minutes. The magnesium silicate attracts bonds with polar contaminants, such as soap or glycerin molecules. The mixture was then vacuum filte The remaining filtered methyl ester is the finished product. were vacuum distilled. The distillation equipment operated at conditions of 0mbar, pot °C, and vapor temperatures that did not exceed 200°C. The resulting distillate was then mixed for one hour with Amberlite. The purpose of the Amberlite was to remove any glycerin that may After the Amberlite has finished mixing, the methyl ester is decanted. The decanted methyl ester is the final profuct. For methyl esters to be considered biodiesel, they first must pass a series of tests listed in the specification ASTM D 751 were performed on the batches of methyl esters except for cetane number D 613 and distillation temperature D 1160. There was not enough of each sample made to complete these two tests. Results and Discussion s of the oil characterization are listed in Table 1. Page 4 of 10 have a high water content (see Table 1), it had to dried before transesterification. The oil was added to a rotary evaporator and heated to 80°C under vacuum conditions. The oil was dried to Salmon oil was converted into methyl esters using the process of transesterification. Nine separate batches, the transesterification process parameters constant. Salmon oil reacted with potassium methoxide for approximately 16 hours. The solution was hours. The polar, glycerin, layer was then removed The nine batches of salmon oil methyl esters were purified using three different methods. Three batches, SAL01 – were purifies using a silicate the stirring step was . The water was then removed. This Any polar contaminants in the methyl evaporator to remove any residual water. This completed the evaporator to remove any residual methanol or water. magnesium silicate was added and mixed for 30 minutes. The magnesium silicate attracts glycerin molecules. The mixture was then vacuum filtered to The distillation equipment operated at conditions of 0mbar, pot mperatures that did not exceed 200°C. The resulting distillate was then mixed for one hour with Amberlite. The purpose of the Amberlite was to remove any glycerin that may methyl ester is decanted. The For methyl esters to be considered biodiesel, they first must pass a series of tests listed in the specification ASTM D 751 were performed on the batches of methyl esters except for cetane number D 613 and distillation temperature D 1160. There was not enough of each sample made to complete these two tests. Table Test Moisture and Volitiles Insoluble Impurities Usaponifiable Matter Free Fatty Acid content Water Content Specific Gravity Sulfur content Oxidation Stability Index The water content of the salmon oil is a concern. The transesterification reaction is hindered by the pr water. A feedstock with water contents processing. A characteristic of the oil that may cause difficulty with the final ester product meeting ASTM specification is the Oxidation Stability Index (OSI) value of 1.65 hours. Soybean oil, which is a commonly used feedstock for biodiesel has an OSI value of 9.4 hours feedstock will have an OSI less than the ASTM spec adverse effect on the transesterification of salmon oil. 5.2 Methyl Ester Production and Purification There was very little variability in the reaction yields for all nine batches. The resul Figure 1 displays the ester glycerin separation after the batch has settled. Notice the distinct color change between the two phases. Figure 2 Casmir C. Akoh, Oxidative Stability of Fat Substitutes and Vegetable Oils by the Oxidative Stability Index Method. JAOCS, Vol. 71, no. 2 (February 1994) Table 1. Salmon Oil Characterization Results Result Units Moisture and Volitiles 1.62 % mass Insoluble Impurities 0.04 % mass Usaponifiable Matter 0.97 % mass Free Fatty Acid content 0.52 % mass as oleic acid 1.60 % mass 0.91 8.8 ppm Oxidation Stability Index 1.65 hours lmon oil is a concern. The transesterification reaction is hindered by the pr contents this high will not react efficiently. Therefore, the oil must be dried before that may cause difficulty with the final ester product meeting ASTM he Oxidation Stability Index (OSI) value of 1.65 hours. Soybean oil, which is a commonly used feedstock for biodiesel has an OSI value of 9.4 hours.2 It is estimated that methyl esters produced from this feedstock will have an OSI less than the ASTM specified three hours. All other tested parameters will not have an adverse effect on the transesterification of salmon oil. Methyl Ester Production and Purification There was very little variability in the reaction yields for all nine batches. The results are displayed in Table 2. Figure 1 displays the ester glycerin separation after the batch has settled. Notice the distinct color change between Figure 1. Separation of Ester and Glycerin ir C. Akoh, Oxidative Stability of Fat Substitutes and Vegetable Oils by the Oxidative Stability Index Method. JAOCS, Vol. 71, no. 2 (February 1994) Page 5 of 10 % mass as oleic acid lmon oil is a concern. The transesterification reaction is hindered by the presence of . Therefore, the oil must be dried before that may cause difficulty with the final ester product meeting ASTM he Oxidation Stability Index (OSI) value of 1.65 hours. Soybean oil, which is a commonly used It is estimated that methyl esters produced from this All other tested parameters will not have an ts are displayed in Table 2. Figure 1 displays the ester glycerin separation after the batch has settled. Notice the distinct color change between ir C. Akoh, Oxidative Stability of Fat Substitutes and Vegetable Oils by the Oxidative Stability Index Batch Reaction Yield, % mass Purification Technique SAL01 98.3 SAL02 98.1 SAL03 98.4 SAL04 97.8 SAL05 97.7 SAL06 97.8 SAL07 97.7 SAL08 98.0 SAL09 97.4 The differences in final processing yields can be attributed to the different purification techniques used. wash purification technique has a slightly higher efficiency wit The three different purification techniques did yield very different final product colors. A representative sample of each technique is displayed in Figure 2. red color. The silicate wash resulted in an ester with a bright orange color. The distillation resulted in an ester with a bright yellow color. Figure 2. Color Differences in Purification Techniques The silicate wash removed much of the pigment in the ester. T was used to purify the ester the cake had a deep red Table 2. Reaction and Processing Yields Purification Technique Loss From Purification, % mass Final Processing Yield, % mass Final Processing Yield, % volume* Water 4.0 94.3 97.1 Water 3.8 94.3 97.1 Water 3.6 94.8 97.6 Silicate 4.5 93.3 96.1 Silicate 4.3 93.4 96.2 Silicate 4.3 93.5 96.3 Distillation 5.8 91.9 94.7 Distillation 4.5 93.5 96.3 Distillation 5.5 91.9 94.7 *calculated The differences in final processing yields can be attributed to the different purification techniques used. wash purification technique has a slightly higher efficiency with respect to final yields. The three different purification techniques did yield very different final product colors. A representative sample of . From left to right, the water wash resulted in an ester with a deep color. The silicate wash resulted in an ester with a bright orange color. The distillation resulted in an ester with Color Differences in Purification Techniques removed much of the pigment in the ester. The silicate begins as a pure white powder. After it was used to purify the ester the cake had a deep red-orange color. See Figure 3. Page 6 of 10 Final Processing Yield, % volume* 97.1 97.1 97.6 96.1 96.2 96.3 94.7 96.3 94.7 The differences in final processing yields can be attributed to the different purification techniques used. The water The three different purification techniques did yield very different final product colors. A representative sample of he water wash resulted in an ester with a deep orange- color. The silicate wash resulted in an ester with a bright orange color. The distillation resulted in an ester with he silicate begins as a pure white powder. After it The residue left behind after the distillation was deep brown in color and had the physical characteristics of a wax. See Figure 4. 5.3 Methyl Ester Analysis Table 3 displays the results of the analysis for purification technique. Results for each individual batch can be found in the Appendix. exceeded the specified ASTM D 6751 limit. Figure 3. Silicate Cake after the distillation was deep brown in color and had the physical characteristics of a wax. Figure 4. Distillate Bottoms Table 3 displays the results of the analysis for the finished products. The values have been averaged for each type of purification technique. Results for each individual batch can be found in the Appendix. The values in bold have exceeded the specified ASTM D 6751 limit. The fuel passes most of the specifications, regardless of the Page 7 of 10 after the distillation was deep brown in color and had the physical characteristics of a wax. The values have been averaged for each type of The values in bold have regardless of the purification technique, with the exceptions of Oxidation Stability Index (OSI) and Table 3. Final Ester Analysis Results Test Method Ca & Mg, combined EN 14538 Na & K, combined EN 14538 Phosphorus content D4951 Flash Point D93 Water and Sediment D2709 Kinematics Viscosity D445 Sulfated Ash D874 Sulfur D5453 Cu Strip Corrosion D130 Cloud Point D5773 Carbon Residue D4530 Acid Number D664 Free Glycerin D6584 Total Glycerin D6584 Oxidation Stability Index EN 14538 Cold Soak Filtration Time D6751 Annex As discussed in Oil Characterization, the (OSI) of the salmon oil was low relative to soybean oil. Therefore, it surprising that the OSI of the resulting ester is also low, with and average of 0. 3 hours. Carbon Residue is a test which measures the certain rates and temperatures in a nitrogen filled environment. The material that has not evaporated and remains is the carbon residue or coke. The carbon residue results ASTM limit. Therefore it is inferred that this fuel will have a tendency to form coke deposits when used. Cetane number and distillation temperature were not performed on the salmon methyl esters because of available sample. It can be estimated that salmon methyl esters may have a cetane number which is below the ASTM limit for biodiesel. Cetane values decrease as the amount of double bonds increase in a carbon chain salmon oil is comprised of a high percentage of unsaturated (many double bonds) carbon chains. cetane numbers tend to cause diesel knocking and show increased gaseous and particulate exhaust emissions due to incomplete combustion. Moreover, excessive engine deposits 6.0 Conclusions Salmon can be converted into methyl esters by transesterification, but the resulting fuel does not pass ASTM D 6751 specification for biodiesel. The oxidation stability can be oxidation stability agent or antioxidant. The dosage amount that would raise the OSI above the limit would be experimentally determined and would vary on the type of antioxidant the methyl ester cannot be improved. It is a function of the characteristics of the feedstock. A way to to blend the fuel with biodiesel made fr refined soy, or tallow. Blending ratios would need to be experimentally determined. The purification process used did not have a great effect on the techniques yielded very similar results. The distillation technique yielded some differenc 3 Martin Mittelbach, Biodiesel The Comprehensive Handbook p. 141. purification technique, with the exceptions of Oxidation Stability Index (OSI) and Carbon Residue Units ASTM D6751 Limit Water Wash Silicate Wash ppm 5 max <2 <2 ppm 5 max <2 <2 ppm 10 max <1 <1 °C 93 min 178 173 % volume 0.050 max <0.005 <0.005 mm2/s 1.9 – 6.0 4.42 4.45 % mass 0.020 max <0.002 <0.002 ppm 15 max 1.0 0.9 3 max 1a 1a °C report -0.1 -0.2 % mass 0.050 max 0.145 0.154 mg KOH/g 0.50 max 0.180 0.145 % mass 0.020 max <0.005 <0.005 % mass 0.240 max 0.068 0.069 hours 3 min 0.6 0.7 D6751 Annex seconds 360 max 85 84 the (OSI) of the salmon oil was low relative to soybean oil. Therefore, it surprising that the OSI of the resulting ester is also low, with and average of 0.6 hours, and below the ASTM limit of Carbon Residue is a test which measures the non-volatile compounds present in the fuel. Samples are heated a nitrogen filled environment. The material that has not evaporated and remains is The carbon residue results in this study are in approximately three times higher than the Therefore it is inferred that this fuel will have a tendency to form coke deposits when used. Cetane number and distillation temperature were not performed on the salmon methyl esters because of available sample. It can be estimated that salmon methyl esters may have a cetane number which is below the ASTM limit for biodiesel. Cetane values decrease as the amount of double bonds increase in a carbon chain a high percentage of unsaturated (many double bonds) carbon chains. cetane numbers tend to cause diesel knocking and show increased gaseous and particulate exhaust emissions due to incomplete combustion. Moreover, excessive engine deposits are reported.3 Salmon can be converted into methyl esters by transesterification, but the resulting fuel does not pass ASTM D 6751 specification for biodiesel. The oxidation stability can be improved with the addition of a commonly avai . The dosage amount that would raise the OSI above the limit would and would vary on the type of antioxidant and feedstock used. The carbon reside of ot be improved. It is a function of the characteristics of the feedstock. A way to the fuel with biodiesel made from different feedstock which has a low carbon residue, such as virgin canola, os would need to be experimentally determined. not have a great effect on the ASTM test results. The water wash and silicate wash techniques yielded very similar results. The distillation technique yielded some differences. There was a slight Biodiesel The Comprehensive Handbook, Martin Mittelbach (Publisher), Graz, Austria, Page 8 of 10 Carbon Residue. Silicate Wash Distillation <2 <2 <1 176 <0.005 <0.005 4.41 <0.002 <0.002 0.5 1a -1.5 0.158 0.330 <0.005 0.014 0.067 0.5 247 the (OSI) of the salmon oil was low relative to soybean oil. Therefore, it is not hours, and below the ASTM limit of volatile compounds present in the fuel. Samples are heated at a nitrogen filled environment. The material that has not evaporated and remains is re in approximately three times higher than the Therefore it is inferred that this fuel will have a tendency to form coke deposits when used. Cetane number and distillation temperature were not performed on the salmon methyl esters because of lack of available sample. It can be estimated that salmon methyl esters may have a cetane number which is below the ASTM limit for biodiesel. Cetane values decrease as the amount of double bonds increase in a carbon chain and a high percentage of unsaturated (many double bonds) carbon chains. Fuels with low cetane numbers tend to cause diesel knocking and show increased gaseous and particulate exhaust emissions due to Salmon can be converted into methyl esters by transesterification, but the resulting fuel does not pass ASTM D 6751 improved with the addition of a commonly available . The dosage amount that would raise the OSI above the limit would need to The carbon reside of ot be improved. It is a function of the characteristics of the feedstock. A way to manage this is a low carbon residue, such as virgin canola, test results. The water wash and silicate wash es. There was a slight , Martin Mittelbach (Publisher), Graz, Austria, 2004, decrease in sulfur, a decrease in cloud point, an increase in acid number, an increase in free glycerin, a decrease in OSI, and an increase in cold soak filterability time can be attributed to the degradation of the fatty acid chains or polymerization at high temperatures. The high degree of unsaturation yields thermal instability and negative performance characteristics of the fuel. One unexpected benefit to using the silicate was technique was the removal of the deep red pigment in the ester. The final product from the silicate wash was a bright orange color as opposed to the water wash product which was a deep orange-red color. Because the salmon oil used in this study had Before using salmon oil as a feedstock for biodiesel production, it is imperative that the water content is known and if it is too wet, steps are taken to dry the oil. High reduced production yields. Salmon oil is not an ideal feedstock for the production of on feedstock, it must be blended with other oil methyl esters could however be used as an fuel in any manner, it should first be treated with an antioxidant. Witho degrade. decrease in sulfur, a decrease in cloud point, an increase in acid number, an increase in free glycerin, a decrease in , and an increase in cold soak filterability time. The decrease in OSI and increase in cold soak filterabilit can be attributed to the degradation of the fatty acid chains or polymerization at high temperatures. The high degree of unsaturation yields thermal instability and negative performance characteristics of the fuel. the silicate was technique was the removal of the deep red pigment in the ester. The final product from the silicate wash was a bright orange color as opposed to the water wash product which was s study had a high water content, it needed to be dried before it was processed. Before using salmon oil as a feedstock for biodiesel production, it is imperative that the water content is known and if it is too wet, steps are taken to dry the oil. High water contents in feedstock oils can lead to soap formation and Salmon oil is not an ideal feedstock for the production of on-road biodiesel. For salmon oil to be used as a biodiesel feedstock, it must be blended with other oils which produce biodiesel with low carbon residue values. could however be used as an effective off-road fuel substitute. If salmon methyl esters are used for should first be treated with an antioxidant. Without an antioxidant added, the fuel will quickly Page 9 of 10 decrease in sulfur, a decrease in cloud point, an increase in acid number, an increase in free glycerin, a decrease in The decrease in OSI and increase in cold soak filterability time can be attributed to the degradation of the fatty acid chains or polymerization at high temperatures. The high degree the silicate was technique was the removal of the deep red pigment in the ester. The final product from the silicate wash was a bright orange color as opposed to the water wash product which was it needed to be dried before it was processed. Before using salmon oil as a feedstock for biodiesel production, it is imperative that the water content is known and water contents in feedstock oils can lead to soap formation and For salmon oil to be used as a biodiesel s which produce biodiesel with low carbon residue values. Salmon road fuel substitute. If salmon methyl esters are used for ut an antioxidant added, the fuel will quickly Appendix Table A1. Test Results for Individual Batches Table A1. Test Results for Individual Batches Page 10 of 10                1.0 Abstract ................................................................ 2.0 Purpose ................................................................ 3.0 Introduction ................................................................ 4.0 Materials and Methods ................................ 4.1 Oil Characterization ................................ 4.2 Oil Pre-Treatment ................................ 4.3 Methyl Ester Production ................................ 4.4 Methyl Ester Purification ................................ 4.4.1 Water Wash ................................ 4.4.2 Silicate Wash ................................ 4.4.3 Distillation ................................ 4.5 Methyl Ester Analysis ................................ 5.0 Results and Discussion ................................ 5.1 Oil Characterization ................................ 5.2 Methyl Ester Production and Purification 5.3 Methyl Ester Analysis ................................ 6.0 Conclusions ................................................................ Appendix ................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ ................................................................................................................................ 5.2 Methyl Ester Production and Purification ................................................................................................ ................................................................................................................................ ................................................................................................ ................................................................................................................................ Page 2 of 10 .................................... 3 .................................... 3 ............................................................. 3 ............................................ 3 ............................................. 3 ................................................ 4 ...................................... 4 ..................................... 4 .................................................. 4 ................................................ 4 .................................................... 4 .......................................... 4 ............................................ 4 ............................................. 4 ............................................ 5 .......................................... 7 ............................................................. 8 ..................................... 10 1.0 Abstract Methyl esters were produced from salmon oil by transesterification with potassium methoxide. Three separate purification techniques were used, water wash, silicate wash, and distillation. After purification, the methyl esters were tested for parameters specified by ASTM D 6751 (B100) for Middle Distillate Fuels. The samples did not meet the requirements for oxidation stability index and carbon residue. The failing results are caused by the characteristics of the feedstock and not the method of production. Samples were not tested for cetane number and distil degree of unsaturation of the carbon chains could cause the salmon oil methyl esters to also fail to meet the specification for cetane number and distillation temperature. the specifications to be considered biodiesel. 2.0 Purpose The purpose of this project was to examine the effectiveness of using salmon oil as a feedstock for biodiesel production. Pacific Biodiesel Technologies study to assess the feasibility of biodiesel production from Juneau area waste cooking oil and Juneau area waste salmon oil. 3.0 Introduction Biodiesel is defined as a fuel comprised of mono animal fats.1 The production of biodiesel usually comprised of a reaction of vegetable oil or animal fat with alcohol, usually methanol, in the presence of a catalyst, usually sodium hydroxide or pota called transesterification and yields mono immiscible and naturally separate with the esters floating on top of the glycerin. and the esters are purified. In order for the resulting esters to be considered biodiesel, it must pass a series of tests specified in ASTM D 6751. Industrially, biodiesel is typically made from soy oil, canola oil, tallow, or yellow grease. are not any industrial producers of biodiese 4.0 Materials and Methods 4.1 Oil Characterization Approximately 55 gallons of salmon oil was delivered from to Pacific Biodiesel Technologies by freight in a sealed plastic bag. plastic bag. Tests were conducted on this sample salmon oil. The tests conducted include Moisture and Unsaponifiable Matter content, Free Fatty Acid content, Specific Gravity, Sulfur content, and Oxidation Stability Index. Moisture and Volatiles content, Insoluble Impurities content, and Unsaponifiable Matter content, commonly grouped together and called MIU, determine how much material is present in the sample that is not able to be converted into biodiesel. This value helps us determine ide to determine the degree of degradation of the triglyceride molecule. As a triglyceride molecule degrades, a fatty acid chain breaks off the glycerin backbone lead to excessive soap formation and yield loss feedstock because sulfur levels in the final fuel product must meet strict limits in order to be use Oxidation Stability Index tells us about the stability of the sample and how readily it oxidizes and breaks down. A higher Oxidation Stability Index value is preferable for fuels. 1 ASTM International, Standard D 6751 Middle Distillate Fuels Methyl esters were produced from salmon oil by transesterification with potassium methoxide. Three separate ication techniques were used, water wash, silicate wash, and distillation. After purification, the methyl esters were tested for parameters specified by ASTM D 6751-08, Standard Specification for Biodiesel Fuel Blend Stock . The samples did not meet the requirements for oxidation stability index and The failing results are caused by the characteristics of the feedstock and not the method of Samples were not tested for cetane number and distillation temperature. It is estimated that the high degree of unsaturation of the carbon chains could cause the salmon oil methyl esters to also fail to meet the specification for cetane number and distillation temperature. Methyl esters produced from salmon oil do not meet the specifications to be considered biodiesel. The purpose of this project was to examine the effectiveness of using salmon oil as a feedstock for biodiesel echnologies shall act as TRRi’s consultant in support of TRRi’s need to complete a study to assess the feasibility of biodiesel production from Juneau area waste cooking oil and Juneau area waste Biodiesel is defined as a fuel comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or The production of biodiesel usually comprised of a reaction of vegetable oil or animal fat with alcohol, usually methanol, in the presence of a catalyst, usually sodium hydroxide or potassium hydroxide. yields mono-alkyl esters and glycerin. These two products of transesterification immiscible and naturally separate with the esters floating on top of the glycerin. The two phases are th and the esters are purified. In order for the resulting esters to be considered biodiesel, it must pass a series of tests Industrially, biodiesel is typically made from soy oil, canola oil, tallow, or yellow grease. At the present time there are not any industrial producers of biodiesel using fish oil as a feedstock in the United States. Methods Approximately 55 gallons of salmon oil was delivered from Delta Pacific, 6001 60th Ave Delta, BC CN V4G OXO by freight in a sealed plastic bag. A one liter sample of oil was removed from the on this sample to first understand the physical and chemical char The tests conducted include Moisture and Volatiles content, Insoluble Impurities content, Unsaponifiable Matter content, Free Fatty Acid content, Specific Gravity, Sulfur content, and Oxidation Stability content, Insoluble Impurities content, and Unsaponifiable Matter content, commonly grouped together and called MIU, determine how much material is present in the sample that is not able to be converted into biodiesel. This value helps us determine ideal yield of the process. Free Fatty Acid content is a test to determine the degree of degradation of the triglyceride molecule. As a triglyceride molecule degrades, a fatty acid chain breaks off the glycerin backbone leaving behind a diglyceride molecule. High free fatty acid content can and yield loss during transesterification. Sulfur content is important to know sulfur levels in the final fuel product must meet strict limits in order to be used for on Oxidation Stability Index tells us about the stability of the sample and how readily it oxidizes and breaks down. A higher Oxidation Stability Index value is preferable for fuels. ASTM International, Standard D 6751-08 – Standard Specification from Biodiesel Fuel Blend Stock (B100) for Page 3 of 10 Methyl esters were produced from salmon oil by transesterification with potassium methoxide. Three separate ication techniques were used, water wash, silicate wash, and distillation. After purification, the methyl esters Standard Specification for Biodiesel Fuel Blend Stock . The samples did not meet the requirements for oxidation stability index and The failing results are caused by the characteristics of the feedstock and not the method of It is estimated that the high degree of unsaturation of the carbon chains could cause the salmon oil methyl esters to also fail to meet the on oil do not meet The purpose of this project was to examine the effectiveness of using salmon oil as a feedstock for biodiesel sultant in support of TRRi’s need to complete a study to assess the feasibility of biodiesel production from Juneau area waste cooking oil and Juneau area waste long chain fatty acids derived from vegetable oils or The production of biodiesel usually comprised of a reaction of vegetable oil or animal fat with alcohol, ssium hydroxide. This reaction is of transesterification are The two phases are then separated and the esters are purified. In order for the resulting esters to be considered biodiesel, it must pass a series of tests At the present time there BC CN V4G OXO A one liter sample of oil was removed from the to first understand the physical and chemical characteristics of the content, Insoluble Impurities content, Unsaponifiable Matter content, Free Fatty Acid content, Specific Gravity, Sulfur content, and Oxidation Stability content, Insoluble Impurities content, and Unsaponifiable Matter content, commonly grouped together and called MIU, determine how much material is present in the sample that is not able to be al yield of the process. Free Fatty Acid content is a test to determine the degree of degradation of the triglyceride molecule. As a triglyceride molecule degrades, a fatty . High free fatty acid content can during transesterification. Sulfur content is important to know in the d for on-road use. Oxidation Stability Index tells us about the stability of the sample and how readily it oxidizes and breaks down. A Standard Specification from Biodiesel Fuel Blend Stock (B100) for 4.2 Oil Pre-Treatment Because the oil was determined to have a high water content (see Table 1), it had to dried before transesterification. The oil was added to a rotary evaporator and heated to 80°C under vacuum conditions. The oil was dried to approximately 500ppm water before transesterifi 4.3 Methyl Ester Production Salmon oil was converted into methyl esters using the process of transesterification. Nine separate batches identified as SAL01 through SAL09, were produced. In all nine batches, were kept constant. Salmon oil reacted with potassium methoxide for approximately 16 hours. The solution was then allowed to settle and separate for approximately leaving the methyl ester. 4.4 Methyl Ester Purification The nine batches of salmon oil methyl esters were purified using three different methods. Three batches SAL03, were purified using a water wash technique. Three batches wash technique. Three batches, SAL07 4.4.1 Water Wash Water was added to each batch. The methyl ester and water completed, the methyl ester/water mixture was allowed to sett washing was performed three additional times for a total of four washes. ester, such as soaps, methanol, or glycerin, were The resulting washed ester was then placed in a rota purification of batches SAL01 – SAL03 4.4.2 Silicate Wash Batches SAL04 – SAL06 were separately placed in a rota Once each batch was dry, magnesium silicate was added and mixed for 30 minutes. The magnesium silicate attracts and bonds with polar contaminants, such as soap or remove the resulting cake. The remaining filtered methyl ester is the finished product. 4.4.3 Distillation Batches SAL07 – SAL09 were vacuum distilled. temperatures that did not exceed 240°C, and vapor te was then mixed for one hour with Amberlite. The purpose of the Amberlite was to remove any glycerin that may have distilled over with the ester. After the Amberlite has finished mixing, the decanted methyl ester is the final profuct. 4.5 Methyl Ester Analysis For methyl esters to be considered biodiesel, they first must pass a series of tests listed in the specification ASTM D 6751. All of the tests in ASTM D 6751 were performed on the batches of methyl esters except for cetane number D 613 and distillation temperature D 1160. There was not enough of each sample made to complete these two tests. 5.0 Results and Discussion 5.1 Oil Characterization The results of the oil characterization are listed in Table 1. have a high water content (see Table 1), it had to dried before transesterification. The oil was added to a rotary evaporator and heated to 80°C under vacuum conditions. The oil was dried to transesterification. Salmon oil was converted into methyl esters using the process of transesterification. Nine separate batches were produced. In all nine batches, the transesterification process parameters constant. Salmon oil reacted with potassium methoxide for approximately 16 hours. The solution was then allowed to settle and separate for approximately two hours. The polar, glycerin, layer was then removed The nine batches of salmon oil methyl esters were purified using three different methods. Three batches were purified using a water wash technique. Three batches, SAL04 – SAL06, were purifies using a silicate , SAL07 – SAL09, were purified using distillation. Water was added to each batch. The methyl ester and water mixture were then stirred. After the methyl ester/water mixture was allowed to settle and separate. The water was then removed. This washing was performed three additional times for a total of four washes. Any polar contaminants in the methyl or glycerin, were removed in the water phase. washed ester was then placed in a rotary evaporator to remove any residual water. This completed the SAL03. were separately placed in a rotary evaporator to remove any residual met magnesium silicate was added and mixed for 30 minutes. The magnesium silicate attracts bonds with polar contaminants, such as soap or glycerin molecules. The mixture was then vacuum filte The remaining filtered methyl ester is the finished product. were vacuum distilled. The distillation equipment operated at conditions of 0mbar, pot °C, and vapor temperatures that did not exceed 200°C. The resulting distillate was then mixed for one hour with Amberlite. The purpose of the Amberlite was to remove any glycerin that may After the Amberlite has finished mixing, the methyl ester is decanted. The decanted methyl ester is the final profuct. For methyl esters to be considered biodiesel, they first must pass a series of tests listed in the specification ASTM D 751 were performed on the batches of methyl esters except for cetane number D 613 and distillation temperature D 1160. There was not enough of each sample made to complete these two tests. Results and Discussion s of the oil characterization are listed in Table 1. Page 4 of 10 have a high water content (see Table 1), it had to dried before transesterification. The oil was added to a rotary evaporator and heated to 80°C under vacuum conditions. The oil was dried to Salmon oil was converted into methyl esters using the process of transesterification. Nine separate batches, the transesterification process parameters constant. Salmon oil reacted with potassium methoxide for approximately 16 hours. The solution was hours. The polar, glycerin, layer was then removed The nine batches of salmon oil methyl esters were purified using three different methods. Three batches, SAL01 – were purifies using a silicate the stirring step was . The water was then removed. This Any polar contaminants in the methyl evaporator to remove any residual water. This completed the evaporator to remove any residual methanol or water. magnesium silicate was added and mixed for 30 minutes. The magnesium silicate attracts glycerin molecules. The mixture was then vacuum filtered to The distillation equipment operated at conditions of 0mbar, pot mperatures that did not exceed 200°C. The resulting distillate was then mixed for one hour with Amberlite. The purpose of the Amberlite was to remove any glycerin that may methyl ester is decanted. The For methyl esters to be considered biodiesel, they first must pass a series of tests listed in the specification ASTM D 751 were performed on the batches of methyl esters except for cetane number D 613 and distillation temperature D 1160. There was not enough of each sample made to complete these two tests. Table Test Moisture and Volitiles Insoluble Impurities Usaponifiable Matter Free Fatty Acid content Water Content Specific Gravity Sulfur content Oxidation Stability Index The water content of the salmon oil is a concern. The transesterification reaction is hindered by the pr water. A feedstock with water contents processing. A characteristic of the oil that may cause difficulty with the final ester product meeting ASTM specification is the Oxidation Stability Index (OSI) value of 1.65 hours. Soybean oil, which is a commonly used feedstock for biodiesel has an OSI value of 9.4 hours feedstock will have an OSI less than the ASTM spec adverse effect on the transesterification of salmon oil. 5.2 Methyl Ester Production and Purification There was very little variability in the reaction yields for all nine batches. The resul Figure 1 displays the ester glycerin separation after the batch has settled. Notice the distinct color change between the two phases. Figure 2 Casmir C. Akoh, Oxidative Stability of Fat Substitutes and Vegetable Oils by the Oxidative Stability Index Method. JAOCS, Vol. 71, no. 2 (February 1994) Table 1. Salmon Oil Characterization Results Result Units Moisture and Volitiles 1.62 % mass Insoluble Impurities 0.04 % mass Usaponifiable Matter 0.97 % mass Free Fatty Acid content 0.52 % mass as oleic acid 1.60 % mass 0.91 8.8 ppm Oxidation Stability Index 1.65 hours lmon oil is a concern. The transesterification reaction is hindered by the pr contents this high will not react efficiently. Therefore, the oil must be dried before that may cause difficulty with the final ester product meeting ASTM he Oxidation Stability Index (OSI) value of 1.65 hours. Soybean oil, which is a commonly used feedstock for biodiesel has an OSI value of 9.4 hours.2 It is estimated that methyl esters produced from this feedstock will have an OSI less than the ASTM specified three hours. All other tested parameters will not have an adverse effect on the transesterification of salmon oil. Methyl Ester Production and Purification There was very little variability in the reaction yields for all nine batches. The results are displayed in Table 2. Figure 1 displays the ester glycerin separation after the batch has settled. Notice the distinct color change between Figure 1. Separation of Ester and Glycerin ir C. Akoh, Oxidative Stability of Fat Substitutes and Vegetable Oils by the Oxidative Stability Index Method. JAOCS, Vol. 71, no. 2 (February 1994) Page 5 of 10 % mass as oleic acid lmon oil is a concern. The transesterification reaction is hindered by the presence of . Therefore, the oil must be dried before that may cause difficulty with the final ester product meeting ASTM he Oxidation Stability Index (OSI) value of 1.65 hours. Soybean oil, which is a commonly used It is estimated that methyl esters produced from this All other tested parameters will not have an ts are displayed in Table 2. Figure 1 displays the ester glycerin separation after the batch has settled. Notice the distinct color change between ir C. Akoh, Oxidative Stability of Fat Substitutes and Vegetable Oils by the Oxidative Stability Index Batch Reaction Yield, % mass Purification Technique SAL01 98.3 SAL02 98.1 SAL03 98.4 SAL04 97.8 SAL05 97.7 SAL06 97.8 SAL07 97.7 SAL08 98.0 SAL09 97.4 The differences in final processing yields can be attributed to the different purification techniques used. wash purification technique has a slightly higher efficiency wit The three different purification techniques did yield very different final product colors. A representative sample of each technique is displayed in Figure 2. red color. The silicate wash resulted in an ester with a bright orange color. The distillation resulted in an ester with a bright yellow color. Figure 2. Color Differences in Purification Techniques The silicate wash removed much of the pigment in the ester. T was used to purify the ester the cake had a deep red Table 2. Reaction and Processing Yields Purification Technique Loss From Purification, % mass Final Processing Yield, % mass Final Processing Yield, % volume* Water 4.0 94.3 97.1 Water 3.8 94.3 97.1 Water 3.6 94.8 97.6 Silicate 4.5 93.3 96.1 Silicate 4.3 93.4 96.2 Silicate 4.3 93.5 96.3 Distillation 5.8 91.9 94.7 Distillation 4.5 93.5 96.3 Distillation 5.5 91.9 94.7 *calculated The differences in final processing yields can be attributed to the different purification techniques used. wash purification technique has a slightly higher efficiency with respect to final yields. The three different purification techniques did yield very different final product colors. A representative sample of . From left to right, the water wash resulted in an ester with a deep color. The silicate wash resulted in an ester with a bright orange color. The distillation resulted in an ester with Color Differences in Purification Techniques removed much of the pigment in the ester. The silicate begins as a pure white powder. After it was used to purify the ester the cake had a deep red-orange color. See Figure 3. Page 6 of 10 Final Processing Yield, % volume* 97.1 97.1 97.6 96.1 96.2 96.3 94.7 96.3 94.7 The differences in final processing yields can be attributed to the different purification techniques used. The water The three different purification techniques did yield very different final product colors. A representative sample of he water wash resulted in an ester with a deep orange- color. The silicate wash resulted in an ester with a bright orange color. The distillation resulted in an ester with he silicate begins as a pure white powder. After it The residue left behind after the distillation was deep brown in color and had the physical characteristics of a wax. See Figure 4. 5.3 Methyl Ester Analysis Table 3 displays the results of the analysis for purification technique. Results for each individual batch can be found in the Appendix. exceeded the specified ASTM D 6751 limit. Figure 3. Silicate Cake after the distillation was deep brown in color and had the physical characteristics of a wax. Figure 4. Distillate Bottoms Table 3 displays the results of the analysis for the finished products. The values have been averaged for each type of purification technique. Results for each individual batch can be found in the Appendix. The values in bold have exceeded the specified ASTM D 6751 limit. The fuel passes most of the specifications, regardless of the Page 7 of 10 after the distillation was deep brown in color and had the physical characteristics of a wax. The values have been averaged for each type of The values in bold have regardless of the purification technique, with the exceptions of Oxidation Stability Index (OSI) and Table 3. Final Ester Analysis Results Test Method Ca & Mg, combined EN 14538 Na & K, combined EN 14538 Phosphorus content D4951 Flash Point D93 Water and Sediment D2709 Kinematics Viscosity D445 Sulfated Ash D874 Sulfur D5453 Cu Strip Corrosion D130 Cloud Point D5773 Carbon Residue D4530 Acid Number D664 Free Glycerin D6584 Total Glycerin D6584 Oxidation Stability Index EN 14538 Cold Soak Filtration Time D6751 Annex As discussed in Oil Characterization, the (OSI) of the salmon oil was low relative to soybean oil. Therefore, it surprising that the OSI of the resulting ester is also low, with and average of 0. 3 hours. Carbon Residue is a test which measures the certain rates and temperatures in a nitrogen filled environment. The material that has not evaporated and remains is the carbon residue or coke. The carbon residue results ASTM limit. Therefore it is inferred that this fuel will have a tendency to form coke deposits when used. Cetane number and distillation temperature were not performed on the salmon methyl esters because of available sample. It can be estimated that salmon methyl esters may have a cetane number which is below the ASTM limit for biodiesel. Cetane values decrease as the amount of double bonds increase in a carbon chain salmon oil is comprised of a high percentage of unsaturated (many double bonds) carbon chains. cetane numbers tend to cause diesel knocking and show increased gaseous and particulate exhaust emissions due to incomplete combustion. Moreover, excessive engine deposits 6.0 Conclusions Salmon can be converted into methyl esters by transesterification, but the resulting fuel does not pass ASTM D 6751 specification for biodiesel. The oxidation stability can be oxidation stability agent or antioxidant. The dosage amount that would raise the OSI above the limit would be experimentally determined and would vary on the type of antioxidant the methyl ester cannot be improved. It is a function of the characteristics of the feedstock. A way to to blend the fuel with biodiesel made fr refined soy, or tallow. Blending ratios would need to be experimentally determined. The purification process used did not have a great effect on the techniques yielded very similar results. The distillation technique yielded some differenc 3 Martin Mittelbach, Biodiesel The Comprehensive Handbook p. 141. purification technique, with the exceptions of Oxidation Stability Index (OSI) and Carbon Residue Units ASTM D6751 Limit Water Wash Silicate Wash ppm 5 max <2 <2 ppm 5 max <2 <2 ppm 10 max <1 <1 °C 93 min 178 173 % volume 0.050 max <0.005 <0.005 mm2/s 1.9 – 6.0 4.42 4.45 % mass 0.020 max <0.002 <0.002 ppm 15 max 1.0 0.9 3 max 1a 1a °C report -0.1 -0.2 % mass 0.050 max 0.145 0.154 mg KOH/g 0.50 max 0.180 0.145 % mass 0.020 max <0.005 <0.005 % mass 0.240 max 0.068 0.069 hours 3 min 0.6 0.7 D6751 Annex seconds 360 max 85 84 the (OSI) of the salmon oil was low relative to soybean oil. Therefore, it surprising that the OSI of the resulting ester is also low, with and average of 0.6 hours, and below the ASTM limit of Carbon Residue is a test which measures the non-volatile compounds present in the fuel. Samples are heated a nitrogen filled environment. The material that has not evaporated and remains is The carbon residue results in this study are in approximately three times higher than the Therefore it is inferred that this fuel will have a tendency to form coke deposits when used. Cetane number and distillation temperature were not performed on the salmon methyl esters because of available sample. It can be estimated that salmon methyl esters may have a cetane number which is below the ASTM limit for biodiesel. Cetane values decrease as the amount of double bonds increase in a carbon chain a high percentage of unsaturated (many double bonds) carbon chains. cetane numbers tend to cause diesel knocking and show increased gaseous and particulate exhaust emissions due to incomplete combustion. Moreover, excessive engine deposits are reported.3 Salmon can be converted into methyl esters by transesterification, but the resulting fuel does not pass ASTM D 6751 specification for biodiesel. The oxidation stability can be improved with the addition of a commonly avai . The dosage amount that would raise the OSI above the limit would and would vary on the type of antioxidant and feedstock used. The carbon reside of ot be improved. It is a function of the characteristics of the feedstock. A way to the fuel with biodiesel made from different feedstock which has a low carbon residue, such as virgin canola, os would need to be experimentally determined. not have a great effect on the ASTM test results. The water wash and silicate wash techniques yielded very similar results. The distillation technique yielded some differences. There was a slight Biodiesel The Comprehensive Handbook, Martin Mittelbach (Publisher), Graz, Austria, Page 8 of 10 Carbon Residue. Silicate Wash Distillation <2 <2 <1 176 <0.005 <0.005 4.41 <0.002 <0.002 0.5 1a -1.5 0.158 0.330 <0.005 0.014 0.067 0.5 247 the (OSI) of the salmon oil was low relative to soybean oil. Therefore, it is not hours, and below the ASTM limit of volatile compounds present in the fuel. Samples are heated at a nitrogen filled environment. The material that has not evaporated and remains is re in approximately three times higher than the Therefore it is inferred that this fuel will have a tendency to form coke deposits when used. Cetane number and distillation temperature were not performed on the salmon methyl esters because of lack of available sample. It can be estimated that salmon methyl esters may have a cetane number which is below the ASTM limit for biodiesel. Cetane values decrease as the amount of double bonds increase in a carbon chain and a high percentage of unsaturated (many double bonds) carbon chains. Fuels with low cetane numbers tend to cause diesel knocking and show increased gaseous and particulate exhaust emissions due to Salmon can be converted into methyl esters by transesterification, but the resulting fuel does not pass ASTM D 6751 improved with the addition of a commonly available . The dosage amount that would raise the OSI above the limit would need to The carbon reside of ot be improved. It is a function of the characteristics of the feedstock. A way to manage this is a low carbon residue, such as virgin canola, test results. The water wash and silicate wash es. There was a slight , Martin Mittelbach (Publisher), Graz, Austria, 2004, decrease in sulfur, a decrease in cloud point, an increase in acid number, an increase in free glycerin, a decrease in OSI, and an increase in cold soak filterability time can be attributed to the degradation of the fatty acid chains or polymerization at high temperatures. The high degree of unsaturation yields thermal instability and negative performance characteristics of the fuel. One unexpected benefit to using the silicate was technique was the removal of the deep red pigment in the ester. The final product from the silicate wash was a bright orange color as opposed to the water wash product which was a deep orange-red color. Because the salmon oil used in this study had Before using salmon oil as a feedstock for biodiesel production, it is imperative that the water content is known and if it is too wet, steps are taken to dry the oil. High reduced production yields. Salmon oil is not an ideal feedstock for the production of on feedstock, it must be blended with other oil methyl esters could however be used as an fuel in any manner, it should first be treated with an antioxidant. Witho degrade. decrease in sulfur, a decrease in cloud point, an increase in acid number, an increase in free glycerin, a decrease in , and an increase in cold soak filterability time. The decrease in OSI and increase in cold soak filterabilit can be attributed to the degradation of the fatty acid chains or polymerization at high temperatures. The high degree of unsaturation yields thermal instability and negative performance characteristics of the fuel. the silicate was technique was the removal of the deep red pigment in the ester. The final product from the silicate wash was a bright orange color as opposed to the water wash product which was s study had a high water content, it needed to be dried before it was processed. Before using salmon oil as a feedstock for biodiesel production, it is imperative that the water content is known and if it is too wet, steps are taken to dry the oil. High water contents in feedstock oils can lead to soap formation and Salmon oil is not an ideal feedstock for the production of on-road biodiesel. For salmon oil to be used as a biodiesel feedstock, it must be blended with other oils which produce biodiesel with low carbon residue values. could however be used as an effective off-road fuel substitute. If salmon methyl esters are used for should first be treated with an antioxidant. Without an antioxidant added, the fuel will quickly Page 9 of 10 decrease in sulfur, a decrease in cloud point, an increase in acid number, an increase in free glycerin, a decrease in The decrease in OSI and increase in cold soak filterability time can be attributed to the degradation of the fatty acid chains or polymerization at high temperatures. The high degree the silicate was technique was the removal of the deep red pigment in the ester. The final product from the silicate wash was a bright orange color as opposed to the water wash product which was it needed to be dried before it was processed. Before using salmon oil as a feedstock for biodiesel production, it is imperative that the water content is known and water contents in feedstock oils can lead to soap formation and For salmon oil to be used as a biodiesel s which produce biodiesel with low carbon residue values. Salmon road fuel substitute. If salmon methyl esters are used for ut an antioxidant added, the fuel will quickly Appendix Table A1. Test Results for Individual Batches Table A1. Test Results for Individual Batches Page 10 of 10