| 35% |
With 3,5-dimethylpyrazolium fluorochromate(VI) In dichloromethane at 20℃; for 1h; |
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| 14.6% |
With carbon dioxide; hydrogen; oxygen In water monomer at 30℃; for 6h; Autoclave; |
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With aspergillus niger-stem |
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With dihydrogen peroxide; FERROUS SULFATE |
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With Methylobacterium extorquens IMI 369321 alcohol dehydrogenase; NAD<SUP>+</SUP> In various solvent(s) |
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With dihydrogen peroxide In water monomer at 0 - 90℃; for 1.5h; |
1; 3; 4; 5
A 1.5 part quantity of ferrous sulfate heptahydrate catalyst was placed in an open reaction vessel equipped with a mechanical stirrer and chilled using an ice water bath. The catalyst was dissolved in 15 parts deionized water and 200 parts of a biodiesel-derived glycerol waste stream containing 85% glycerol obtained from Cargill Inc. (Minnetonka, Minn.). A second reaction mixture was similarly prepared using a reaction vessel whose temperature was controlled using an ambient temperature water bath instead of ice water. The two reaction vessels were designated as Cool (C) and Warm (W). A 50 part quantity of 35% hydrogen peroxide was added dropwise to each reaction vessel over a one hour period. The reaction vessels were allowed to stand for a 30 minute rest period during which the pH was measured and adjusted to 3.0 using 5N sodium hydroxide as needed and 20 parts of the reaction mixture were collected. A portion of the collected reaction mixture was analyzed to determine the reducing sugar content and reported as a weight percent equivalent of reducing moieties in the sample compared to a known glucose standard. The standard was prepared by dissolving 0.1439 g dry glucose in 500 mL deionized water. A 5 mL aliquot (viz., a portion containing 1.439 mg glucose) was combined with 5 mL of Copper Reagent (prepared by dissolving 53 g Na2HPO4.7H20 and 40 g NaKC4H4O6.4H2O in about 70 ml of water, followed by 100 mL portions of 1N sodium hydroxide, 8 g CuSO4.5H2O, 180 g Na2SO4, and 0.7134 g KIO3, and after everything had dissolved diluting the solution to 1 L) and heated to 100° C. for 40 minutes. The mixture was cooled, combined with potassium iodide and a starch indicator, and titrated with sodium thiosulfate. A net addition of 14.6 mL titrant was required compared to a blank prepared without glucose. The standard accordingly had a “Sugar Factor” of 0.0989 mg glucose/mL titrant. A portion of the collected reaction mixture sample (e.g., 1.01 g) was diluted to 500 mL and a 5 mL aliquot was combined with Copper Reagent, heated and titrated with thiosulfate in a similar manner. The net titrant required was multiplied by the Sugar Factor to determine the sample portion reducing sugar content.The hydrogen peroxide addition, rest, sampling and analysis procedures were repeated four more times (for a total of five hydrogen peroxide additions in all) by adding a hydrogen peroxide amount corresponding to 25% of the amount of glycerol-containing biodiesel waste stream remaining in the reaction vessel. The material balance and reducing sugar results for the Cool and Warm reaction vessels are shown below in Tables 1A and 1B.The individual samples from the Cool reaction vessel were identified as 1C, 2C, 3C and so on depending on whether the sample was collected at the first, second, third, etc. sample collection period shown in Table 1A. In similar fashion, the individual samples from the Warm reaction vessel were identified as 1W, 2W, 3W and so on depending on whether the sample was collected at the first, second, third, etc. sample collection period shown in Table 1B.During the reaction, the Cool reaction vessel temperature was about 20-30° C. and the Warm reaction vessel temperature was about 45-55° C. A strong exotherm occurred when making the initial hydrogen peroxide addition, with less strong exotherms being observed for subsequent peroxide additions. The results in Tables 1A and 1B show that the reaction was not greatly affected by temperature, but that the Warm reaction provided somewhat greater reducing sugar content than the Cool reaction after corresponding reaction times.The results in Tables 1A and 1B also show that the reducing sugar content peaked at around the third sample (3C or 3W) collection period. The ferrous ion catalyst may by that point have become sufficiently diluted so that further reaction would not take place without additional catalyst. The extent or rate of reaction may be improved by maintaining the concentration of ferrous ion at about 1000 ppm or more.Analysis of sample 3W showed that a 5 mL aliquot of a diluted 1.01 g sample portion contained the equivalent of 1.87 mg glucose. Factoring in dilution, the original 1.01 g sample portion must have contained 187 mg of glucose equivalent, or 1.04 mmoles. At the time sample 3W was collected, the Warm reaction mixture contained 321 g of reactants, corresponding to 333 mmoles of glucose equivalent. This may be presumed to be 0.33 moles glycerose, plus unreacted glycerol, side reaction products such as dihydroxyacetone, and potentially other species as well. Based on the material balance shown in Table 1B, this 321 g reactant mixture was derived from 173 g of the biodiesel waste stream and 130 g of hydrogen peroxide, corresponding to about 1.6 moles glycerol and 1.3 moles hydrogen peroxide. This indicates that about 21% of the starting glycerol amount formed the target aldehyde, and that the extent of reaction might be further improved. EXAMPLE 3 High Temperature Glycerol Oxidation and Feed PreparationOne part ferrous sulfate heptahydrate catalyst was placed in a reaction vessel equipped with a thermometer and mechanical stirrer and dissolved in 10 parts deionized water. 100 Parts of a biodiesel-derived glycerol waste stream containing 80% glycerol obtained from Freedom Fuels, LLC (Mason City, Iowa) were added to the vessel, followed by the dropwise addition of 50 parts of 35% hydrogen peroxide at a rate sufficient to bring the reaction mixture to 90° C. Following completion of the reaction, the resulting glycerose liquor (Liquor A) was analyzed for reducing sugar content using the method of Example 1 and found to contain 16.8% glucose equivalents.Using the method of Example 2, SBM was combined with sufficient Liquor A to add 2% glycerol or glycerol-derived oxidation products to the finished blend, and heated for 1, 5, 10 or 15 minutes. In comparison runs, SBM was combined with known solutions of glycerose dimer (Dimer A) or dihydroxyacetone dimer (Dimer B), using sufficient solution to add 0.5 wt. % dimer to the finished blend. These blends were heated using the method of Example 2 for 15 minutes. In a further comparison run, SBM was combined with 5 wt. % spent sulfite liquor (XYLIG lignosulfonate, LignoTech, USA, Rothschild, Wis.) and heated for 15 or 30 minutes. The resulting dried samples were sent to the FARME Institute for a 16 hour in situ protein degradation evaluation. The results are shown below in Table 3:The results in Table 3 show that addition of 2% Liquor A provided feed products whose RUP values were comparable to or better than the RUP values obtained using 5% spent sulfite liquor, and made using much shorter heating times. Treatment with glycerose dimer or with dihydroxyacetone dimer provided feeds having generally lower RUP values, suggesting that the test conditions did not permit the dimers to hydrolyze to their corresponding monomeric forms. EXAMPLE 4 Catalyst and Chelant EvaluationVarying amounts of ferrous sulfate heptahydrate catalyst and EDTA chelant were placed in a reaction vessel equipped with a thermometer, mechanical stirrer and cooling bath, and dissolved in 10 g deionized water. 100 grams of a biodiesel-derived glycerol waste stream containing 83% glycerol obtained from Minnesota Soybean Processors (Brewster, Minn.) were added to the vessel, followed by the addition at five minute intervals of five 1 mL aliquots of 35% hydrogen peroxide. The typical response to the initial 1 mL addition of hydrogen peroxide was an immediate color change from light yellow to reddish brown. At the same time an exothermic reaction occurred that increased the temperature by 6 to 9° C. This exothermic reaction was very rapid as the temperature began to decline after the first minute. During the second or third minute it was common to see small bubbles, presumed to be oxygen, forming in the glycerose liquor. The exothermic reaction appeared to take place before the appearance of bubbles. When the level of iron was 0.5 g or more the exotherm continued with each incremental addition of hydrogen peroxide. When iron was omitted, no heating occurred with addition of peroxide.After 25 minutes, additional hydrogen peroxide was added to each reaction mixture in a continuous dropwise stream at approximately 1 nL/min while cooling the reaction vessel sufficiently to maintain the reaction mixture at 50 to 60° C., until a total of 44.4 mL (50 g) of hydrogen peroxide had been added. Effervescence was common to most treatments, with audible fizzing occurring as the bubbles broke the surface. This is most likely oxygen and represents a waste of hydrogen peroxide, the single most expensive ingredient. The peroxide might be used more efficiently if the addition rate were slower or if the reaction were carried out at elevated pressure. In a commercial setting, a slower addition rate might provide additional time for the removal of heat.Acidity was measured using a pH meter. Following completion of the reaction, the resulting glycerose liquors (Liquors B through H) were analyzed for reducing sugar content using the method of Example 1 but with comparison to a glycerose standard rather than a glucose standard. The liquors were also analyzed for carboxyl content using conductometric titration.Using the method of Example 2, a 10 minute heating time and an add-on rate sufficient to provide 1% glycerol-derived product in the finished blends, glycerose liquors B through G were used to treat SBM and determine their potential to generate RUP. A SBM sample was also treated with sufficient water to increase the moisture content to 20% and heated for ten minutes. The resulting samples were exposed to air to allow cooling and drying, and sent to the FARME Institute for a 16 hour in situ protein degradation evaluation. The results are shown below in Table 4: Increasing the level of ferrous sulphate (Fe++ catalyst) tended to reduce the observed aldehyde level (reported in Table 4 as the Glycerose Equivalent) and lower the pH, suggesting that some of the aldehyde may have been further oxidized to a carboxylic acid. Addition of EDTA tended to increase the observed aldehyde level, raise the pH, and reduce the carboxyl level, all favourable responses. EDTA additions thus seemed to reverse the effect of high catalyst levels, suggesting that the EDTA was chelating the ferrous ion. A combination of 0.5 g ferrous sulfate and 1.0 g of EDTA appeared to provide a desirable level of RUP and suggested that the chelated iron remained effective as a catalyst. A reduced RUP value was observed for SBM treated with Liquor F (made using 1 g each of catalyst and EDTA). Increased glycerose equivalent and RUP levels were observed for SBM treated with Liquor E (made using 0.5 g catalyst and 1 g EDTA), suggesting additional improvements might be obtained by adjusting the catalyst and EDTA amounts or the ratio of EDTA to catalyst. For example, 100 g crude glycerol and 10 g water might be combined with about 0.5 g catalyst and 0.7 g EDTA to provide a starting mixture containing about 900 ppm iron and about 0.6 wt. % EDTA.Biodiesel-derived glycerol often contains a small amount of fatty acid, and the Minnesota Soybean Processors glycerol used in this Example is said to include a 0. 15% fatty acid content. Fatty acids may be capable of combining with divalent cations to form insoluble salts analogous to those responsible for bath tub ring formation. In some of the runs noted above a reddish brown scum was observed to have adhered to the sides of the reaction vessel, possibly due to a combination of fatty acid(s) (e.g., linoleic acid) with the ferrous ion catalyst. If carried out on a commercial scale a similar combination might lead to formation of greasy globs capable of blocking filters or nozzles. The addition of EDTA appeared to reduce or eliminate scum formation and was thought to be due to chelation of the ferrous ion and consequent reduction or prevention of its interaction with fatty acids.For Liquor G, the low initial catalyst level appeared to provide a milder exotherm, and the temperature began to decline 30 minutes after start of the initial peroxide addition even as the peroxide addition continued. This suggested that the additional peroxide was not reacting due to iron depletion or deficiency in the reaction mixture. At t=35 minutes, a further 0.1 g of ferrous sulfate was added to the reaction mixture. Over the next 5 minutes no further peroxide was added but the temperature increased, indicating that unreacted peroxide had been present in the liquor. The peroxide addition was resumed at t=40 minutes but the temperature began to decline again after t=50 minutes. The concentrations of ferrous ion when the temperature began to decline were 430 and 520 ppm, suggesting that for this reaction vessel and under these conditions, a possible minimum catalyst level might be about 500 to about 600 ppm. Analysis of Liquor G showed it to have a high carboxyl content and very little aldehyde, suggesting that a low ferrous ion concentration may favor further oxidation of aldehydes and formation of carboxylic acids. EXAMPLE 5 The method of Example 4 was repeated using the Freedom Fuels, LLC glycerol waste stream employed in Example 3. The resulting dried samples were sent to the FARME Institute for a 16 hour in situ protein degradation evaluation. The results are shown below in Table 5: Like the results in Table 4, the results in Table 5 demonstrated high RUP levels. |
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With dihydrogen peroxide In water monomer at 40 - 88℃; for 3h; |
8; 10
Ferrous sulfate heptahydrate (0.5 g) was combined with 1.0 g tetra sodium EDTA and 10 mL of distilled water in a 500 mL round bottom flask, followed by the addition of 100 g crude glycerol from Minnesota Soybean Processers. The flask was placed in a water bath to warm the mixture and maintain various target processing temperatures. The flask was fitted with a thermometer and mechanical stirrer. Fifty grams of 35% hydrogen peroxide were added to the flask in a dropwise manner over a period of three hours. This process was repeated five times at target processing temperatures of 40, 60, 70, 80, and 88° C., yielding glycerose liquors containing about 50% glycerol products. The glycerose equivalents in each glycerose liquor were determined by titration against known standards and reported as a percentage of total liquid weight. Yields tended to decline with increasing processing temperature and the decline became severe when the processing temperature exceeded 80° C. At the highest processing temperature, strong effervescence was observed with each added drop of peroxide. Under these circumstances, the peroxide may be decomposing to form oxygen before it can react with glycerol. Based on this work and subsequent confirmatory runs, processing temperatures of about 50 to about 60° C. appear to provide especially desirable glycerose yields.EXAMPLE 10 Oxidant:Glycerol RatioTwo hundred grams of a biodiesel-derived glycerol waste stream containing 82% glycerol obtained from Minnesota Soybean Processors and 5.6 g of a 40% tetrasodium EDTA solution (DISSOLVINE E-39, Akzo Nobel) were added to a round bottom flask. The flask was first agitated by hand and then stirred continuously using a magnetic stirrer. Ferrous sulfate heptahydrate (1.6 g) was dissolved in 5.0 g of warm water and the resulting solution was added to the flask. Hydrogen peroxide (35%) was added to the reaction flask using a burette. Initially, 2 mL increments were added rapidly at five minute intervals. When the hydrogen peroxide addition is initiated the reaction liquor is dense and viscous and the hydrogen peroxide may not mix well. Local concentrations may heat up such that the reaction liquor may boil and the peroxide will disproportionate. As further hydrogen peroxide is added the reaction liquor warms and become diluted, reducing its viscosity. Care was taken to provide strong mixing at the point of hydrogen peroxide addition. A thermometer was also placed in the reaction liquor and the temperature recorded at one-minute intervals. After 10 mL of peroxide had been added, the addition was changed to a continuous mode at a rate of about 1 mL per minute. During the continuous addition period water was placed in a containment vessel surrounding the flask. Approximately one liter of cool tap water was used. This was changed every time another 50 mL of peroxide had been added. Heat generation during a similar reaction was estimated to be approximately 730 kcal/liter of 35% hydrogen peroxide added to the reaction flask.Sub-samples (25 mL) were pipetted from the reaction liquor at intervals corresponding to peroxide:glycerol (viz., oxidant:glycerol) ratios of 0.4, 0.6, 0.8, 0.9, 1.0, 1.1, and 1.2, on a liquid weight basis. These corresponded to collections made when 71, 103, 131, 144, 156, 166, and 176 mL of peroxide had been added. The sub-samples were weighed and stored for later testing. The pH of each sub-sample was also measured by inserting a pH instrument probe directly into the reaction liquor.Two portions of glyceraldehyde (0.0400 and 0.0520 g) were dissolved in 200 mL of warm deionized water to make glyceraldehyde standards with concentrations of 200 and 260 mg/L. Five milliliter aliquots of each standard and a 5 mL aliquot of deionized water were pipetted into 25×200 mm PYREX test tubes to provide two standard solutions and a deionized water blank. Five mL of Copper Reagent were added to each test tube. The three tubes were heated in boiling water for 40 minutes and cooled. Each tube was treated by addition of 2 mL 2.5% KI and 1.5 mL 2N H2SO4. About 10 mL of 0.005 N sodium thiosulfate solution was added to each tube, followed by 4 mL of 0.4% dissolved starch, which turned the solution dark blue. Additional sodium thiosulfate was added to titrate the samples until the solutions were clear and colorless. The net difference between the volumes of titrant used for the glyceraldehyde standard solutions and the deionized water blank was used to calculate the titrant strength.The glycerose liquor sub-samples were next titrated to determine their glycerose content. About 0.7 g of each liquor was weighed into a 500-mL volumetric flask and diluted with deionized water to volume. A 5 mL aliquot of this solution was transferred to a PYREX test tube, combined with Copper Reagent, heated for 40 minutes, and titrated with sodium thiosulfate as described above. The volume of titrant was recorded and used to calculate the amount of glycerose in each sub-sample.As shown in FIG. 1 and FIG. 2, the addition of hydrogen peroxide to glycerol generates increasing amounts of glycerose (FIG. 1) but also dilutes the reaction liquor (FIG. 2). The rate of glycerose production and liquor dilution may be balanced so that the percentage of glycerose in the reaction liquor reaches a plateau (FIG. 2). The shape and nature of the plateau may be altered by using a more concentrated (e.g., 50%) or less concentrated (e.g., 30%) oxidant solution. The oxidant:glycerol ratio may be altered over wide ranges as desired (e.g., 60 to 100 parts or 80 to 100 parts of hydrogen peroxide per 100 parts of glycerol) and may affect variables including production cost, glycerose yield, product viscosity and acidity. The occurrence of possible side reactions may also be taken into account. For example, if one mole of hydrogen peroxide reacted with one mole of glycerol to produce one mole of glycerose there would be 100% conversion of glycerol to glycerose at an oxidant:glycerol ratio of 0.865. However, for the reactions shown in FIG. 1 only about 50% conversion was observed at that ratio. Some portion of the hydrogen peroxide may have decomposed to oxygen without reacting with glycerol, and another portion of the hydrogen peroxide may have reacted with glycerose to oxidize it further. The production of additional glycerose at oxidant:glycerol ratios >0.9 indicates the continued presence of unreacted glycerol.The sub-samples were also used to treat SBM to determine their potential to generate RUP. In each case 150 g of SBM was combined, using the method of Example 2, with an amount of sub-sample sufficient to provide 1% glycerol-containing product in the finished blend. The samples contained 80% DM and were heated in a 105° C. oven for 9 minutes. The resulting feed products were sent to the FARME Institute for in situ determination of crude protein and RUP. The results are shown below in Table 11: |
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With dihydrogen peroxide In water monomer at 6 - 60℃; |
9
Using the method of Example 4, varying amounts of ferrous sulfate heptahydrate catalyst and EDTA chelant were reacted with 100 grams of the Minnesota Soybean Processors biodiesel-derived glycerol waste stream. The resulting glycerose liquors were combined with SBM as in Example 4 and Example 2, using a 10 minute feed heating time. The results are shown below in Table 9:In Run Nos. 9-2 and 9-3, a small quantity of black floating scum appeared in the 5 glycerose liquor. This is believed to be due to formation of an iron-fatty acid salt, and may have lowered the glycerose equivalent yield. The scum was eliminated when the ratio of sodium EDTA to ferrous sulfate heptahydrate exceeded about 8:5.The Run No. 9-7 glycerose liquor (Liquor S) was stored for five months to evaluate its shelf stability, then applied along with water to a 100 g SBM sample in amounts sufficient to provide 1% glycerol-derived product in the finished blends and bring the total moisture level to 20, and heated for 10 or 30 minutes. The resulting feed products were sent to the FARME Institute for in situ determination of crude protein and RUP. The results are shown below in Table 10:The results in Table 10 show that the glycerose liquor solution continued to provide bypass protein protection after lengthy storage. |
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With dihydrogen peroxide In water monomer at 6 - 60℃; |
4; 5
Varying amounts of ferrous sulfate heptahydrate catalyst and EDTA chelant were placed in a reaction vessel equipped with a thermometer, mechanical stirrer and cooling bath, and dissolved in 10 g deionized water. 100 grams of a biodiesel-derived glycerol waste stream containing 83% glycerol obtained from Minnesota Soybean Processors (Brewster, Minn.) were added to the vessel, followed by the addition at five minute intervals of five 1 mL aliquots of 35% hydrogen peroxide. The typical response to the initial 1 mL addition of hydrogen peroxide was an immediate color change from light yellow to reddish brown. At the same time an exothermic reaction occurred that increased the temperature by 6 to 9° C. This exothermic reaction was very rapid as the temperature began to decline after the first minute. During the second or third minute it was common to see small bubbles, presumed to be oxygen, forming in the glycerose liquor. The exothermic reaction appeared to take place before the appearance of bubbles. When the level of iron was 0.5 g or more the exotherm continued with each incremental addition of hydrogen peroxide. When iron was omitted, no heating occurred with addition of peroxide.After 25 minutes, additional hydrogen peroxide was added to each reaction mixture in a continuous dropwise stream at approximately 1 nL/min while cooling the reaction vessel sufficiently to maintain the reaction mixture at 50 to 60° C., until a total of 44.4 mL (50 g) of hydrogen peroxide had been added. Effervescence was common to most treatments, with audible fizzing occurring as the bubbles broke the surface. This is most likely oxygen and represents a waste of hydrogen peroxide, the single most expensive ingredient. The peroxide might be used more efficiently if the addition rate were slower or if the reaction were carried out at elevated pressure. In a commercial setting, a slower addition rate might provide additional time for the removal of heat.Acidity was measured using a pH meter. Following completion of the reaction, the resulting glycerose liquors (Liquors B through H) were analyzed for reducing sugar content using the method of Example 1 but with comparison to a glycerose standard rather than a glucose standard. The liquors were also analyzed for carboxyl content using conductometric titration.Using the method of Example 2, a 10 minute heating time and an add-on rate sufficient to provide 1% glycerol-derived product in the finished blends, glycerose liquors B through G were used to treat SBM and determine their potential to generate RUP. A SBM sample was also treated with sufficient water to increase the moisture content to 20% and heated for ten minutes. The resulting samples were exposed to air to allow cooling and drying, and sent to the FARME Institute for a 16 hour in situ protein degradation evaluation. The results are shown below in Table 4: Increasing the level of ferrous sulphate (Fe++ catalyst) tended to reduce the observed aldehyde level (reported in Table 4 as the Glycerose Equivalent) and lower the pH, suggesting that some of the aldehyde may have been further oxidized to a carboxylic acid. Addition of EDTA tended to increase the observed aldehyde level, raise the pH, and reduce the carboxyl level, all favourable responses. EDTA additions thus seemed to reverse the effect of high catalyst levels, suggesting that the EDTA was chelating the ferrous ion. A combination of 0.5 g ferrous sulfate and 1.0 g of EDTA appeared to provide a desirable level of RUP and suggested that the chelated iron remained effective as a catalyst. A reduced RUP value was observed for SBM treated with Liquor F (made using 1 g each of catalyst and EDTA). Increased glycerose equivalent and RUP levels were observed for SBM treated with Liquor E (made using 0.5 g catalyst and 1 g EDTA), suggesting additional improvements might be obtained by adjusting the catalyst and EDTA amounts or the ratio of EDTA to catalyst. For example, 100 g crude glycerol and 10 g water might be combined with about 0.5 g catalyst and 0.7 g EDTA to provide a starting mixture containing about 900 ppm iron and about 0.6 wt. % EDTA.Biodiesel-derived glycerol often contains a small amount of fatty acid, and the Minnesota Soybean Processors glycerol used in this Example is said to include a 0. 15% fatty acid content. Fatty acids may be capable of combining with divalent cations to form insoluble salts analogous to those responsible for bath tub ring formation. In some of the runs noted above a reddish brown scum was observed to have adhered to the sides of the reaction vessel, possibly due to a combination of fatty acid(s) (e.g., linoleic acid) with the ferrous ion catalyst. If carried out on a commercial scale a similar combination might lead to formation of greasy globs capable of blocking filters or nozzles. The addition of EDTA appeared to reduce or eliminate scum formation and was thought to be due to chelation of the ferrous ion and consequent reduction or prevention of its interaction with fatty acids.For Liquor G, the low initial catalyst level appeared to provide a milder exotherm, and the temperature began to decline 30 minutes after start of the initial peroxide addition even as the peroxide addition continued. This suggested that the additional peroxide was not reacting due to iron depletion or deficiency in the reaction mixture. At t=35 minutes, a further 0.1 g of ferrous sulfate was added to the reaction mixture. Over the next 5 minutes no further peroxide was added but the temperature increased, indicating that unreacted peroxide had been present in the liquor. The peroxide addition was resumed at t=40 minutes but the temperature began to decline again after t=50 minutes. The concentrations of ferrous ion when the temperature began to decline were 430 and 520 ppm, suggesting that for this reaction vessel and under these conditions, a possible minimum catalyst level might be about 500 to about 600 ppm. Analysis of Liquor G showed it to have a high carboxyl content and very little aldehyde, suggesting that a low ferrous ion concentration may favor further oxidation of aldehydes and formation of carboxylic acids. EXAMPLE 5 The method of Example 4 was repeated using the Freedom Fuels, LLC glycerol waste stream employed in Example 3. The resulting dried samples were sent to the FARME Institute for a 16 hour in situ protein degradation evaluation. The results are shown below in Table 5: Like the results in Table 4, the results in Table 5 demonstrated high RUP levels. |
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With NaNO3 aq. phosphate buffer; Electrochemical reaction; solid phase reaction; Enzymatic reaction; |
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With dihydrogen peroxide |
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With [2,2]bipyridinyl; sulfuric acid; chromic acid In water monomer at 30℃; |
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With 4-Amino-2,2,6,6-tetramethylpiperidino-1-oxyl; recombinant oxalate decarboxylase from Bacillus subtilis In aq. phosphate buffer at 25℃; Electrochemical reaction; Enzymatic reaction; |
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With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In aq. buffer at 25℃; Electrochemical reaction; Green chemistry; |
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With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; 4-amino-2,2,6,6-tetramethyl-1-piperidine-1-oxyl Electrochemical reaction; |
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With tert.-butylhydroperoxide; [Co(4'-(4-pyridyl)-2,2':6',2''-terpyridine)(tBuPO<SUB>3</SUB>H)<SUB>2</SUB>(H<SUB>2</SUB>O)]·H<SUB>2</SUB>O In acetonitrile at 80℃; for 3h; |
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With dihydrogen peroxide; sodium hydroxide at 60℃; for 6h; |
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With potassium hydroxide Electrochemical reaction; |
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With sulfuric acid; quinolinium dichromate In water monomer at 19.84℃; |
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With ~5 wt% Pt supported on graphitic multi-walled carbon nanotubes at 60℃; for 2h; |
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