Recycling of physically refined deodorizer distillate into useful products.

Wong Yiu Kwong Kenji.Thesis (M.Phil.)--Chinese University of Hong Kong, 2005.Includes bibliographical references (leaves 189-204).Abstracts in English and Chinese.Acknowledgement --- p.iAbstract --- p.ii摘要 --- p.ivContents --- p.viList of Figure --- p.xiiList of Table --- p.xviIntroduction --- p.1Chapter 1.1. --- Vegetable oil production and their refining --- p.1Chapter 1.1.1. --- Vegetable oil production and consumption --- p.1Chapter 1.1.2. --- Vegetable oil refining steps --- p.2Chapter 1.2. --- Chemical refining vs. Physical refining --- p.3Chapter 1.2.1. --- Differences between chemical and physical refining --- p.3Chapter 1.2.2. --- Pros and Cons of the two refining practices --- p.4Chapter 1.2.3. --- Adoption criteria and popularity of refining methods --- p.6Chapter 1.3. --- Deodorizer distillate (DODc vs. DODp) --- p.7Chapter 1.3.1. --- Compositions of DODc and DODp --- p.7Chapter 1.3.1.1. --- Squalene --- p.9Chapter 1.3.1.2. --- Tocopherols --- p.10Chapter 1.3.1.3. --- Phytosterols --- p.12Chapter 1.3.2. --- Usages of DODc and DODp and purification of phytochemicals --- p.14Chapter 1.3.2.1. --- Concentration of tocopherols and phytosterols --- p.15Chapter 1.3.2.2. --- Purification of tocopherols and phytosterols --- p.18Chapter 1.3.3. --- Alternative usage of DODp --- p.20Chapter 1.4. --- Usages of fatty acid mono-alkyl esters --- p.20Chapter 1.4.1. --- As intermediate for Bio-surfactants --- p.21Chapter 1.4.2. --- Bio-lubricants --- p.21Chapter 1.4.3. --- Biodiesel --- p.22Chapter 1.5. --- Production of biodiesel and its advantages and disadvantages --- p.23Chapter 1.5.1. --- Production of biodiesel --- p.23Chapter 1.5.1.1. --- Use of catalyst --- p.25Chapter 1.5.1.2. --- "Molar ratios between methanol, sample and catalyst" --- p.26Chapter 1.5.1.3. --- Temperature and pressure --- p.27Chapter 1.5.1.4. --- Biodiesel purification --- p.27Chapter 1.5.2. --- Pros and Cons of using biodiesel --- p.27Chapter 1.5.3. --- Sources of Biodiesel production --- p.29Chapter 1.6. --- Proposed strategy --- p.33Chapter 1.6.1. --- Summary of the literatures reviewed --- p.33Chapter 1.6.2. --- Hypothesis making --- p.34Chapter 1.6.3. --- Aim and objectives --- p.34Chapter 1.6.4. --- Significance of study --- p.34Chapter 1.6.5. --- Study scheme --- p.35Chapter 2. --- Methodology --- p.36Chapter 2.1. --- Characterization of physically refined Deodorizer Distillate (DODp) --- p.36Chapter 2.1.1. --- Collection & storage of DODp --- p.36Chapter 2.1.2. --- Determination of fatty acids composition --- p.36Chapter 2.1.3. --- Determination of acid number (ASTM D 664) --- p.37Chapter 2.1.4. --- Determination of free fatty acid contents --- p.38Chapter 2.1.5. --- Determination of unsaponifiable matter content --- p.38Chapter 2.1.6. --- "Determination of squalene, tocopherol and phytosterol contents." --- p.39Chapter 2.1.7. --- Deduction of natural glyceride contents --- p.40Chapter 2.1.8. --- "Other physical, chemical and biological analyses" --- p.40Chapter 2.1.8.1. --- Elemental analysis --- p.40Chapter 2.1.8.2. --- Nitrogen --- p.41Chapter 2.1.8.3. --- Water and volatile matter content --- p.41Chapter 2.1.8.4. --- Melting point and specific gravity --- p.41Chapter 2.1.8.5. --- Microbial counts --- p.42Chapter 2.2. --- Production of fatty acid methyl esters (FAMEs) - Protocol A --- p.42Chapter 2.2.1. --- Optimization of Esterification --- p.42Chapter 2.2.1.1. --- Molar ratio of methanol: DODp --- p.43Chapter 2.2.1.2. --- Molar ratio of DODp: sulfuric acid --- p.43Chapter 2.2.1.3. --- Reaction temperature --- p.44Chapter 2.2.2. --- Optimization of Molecular Distillation --- p.44Chapter 2.2.2.1. --- Feed rate --- p.45Chapter 2.2.2.2. --- Distillation temperature --- p.45Chapter 2.2.2.3. --- Speed of rotary blade --- p.45Chapter 2.2.3. --- Crystallization --- p.46Chapter 2.3. --- Production of fatty acid methyl esters (FAMEs) - Protocol B --- p.46Chapter 2.3.1. --- Optimization of Saponification --- p.47Chapter 2.3.1.1. --- Saponification number --- p.47Chapter 2.3.1.2. --- Saponification --- p.47Chapter 2.3.2. --- Extraction of unsaponifiable matter --- p.48Chapter 2.3.3. --- Acidification --- p.49Chapter 2.3.4. --- Esterification --- p.49Chapter 2.3.5. --- Hot water washing --- p.49Chapter 2.3.6. --- Crystallization --- p.49Chapter 2.4. --- Quantity and quality assessments of FAMEs --- p.50Chapter 2.4.1. --- Determination of purity and yield of FAMEs --- p.50Chapter 2.4.2. --- Quality of FAMEs: Biodiesel Specifications in USA --- p.50Chapter 2.4.2.1. --- Sulfated Ash (ASTM D 874) --- p.50Chapter 2.4.2.2. --- Copper strip corrosion test (ASTM D 130) --- p.51Chapter 2.4.2.3. --- Water and Sediment (ASTM D 2709) --- p.52Chapter 2.4.2.4. --- Conradson Carbon Residue of Petroleum Products (ASTM D 189) --- p.52Chapter 2.4.2.5. --- Determination of Free and Total Glycerine in B-100 Biodiesel Methyl Esters By Gas Chromatography (ASTM D 6584) --- p.53Chapter 2.4.2.6. --- Flash point (modified from ASTM D 93) --- p.54Chapter 2.4.2.7. --- Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectrometry (ASTM D 4951) --- p.54Chapter 2.4.2.8. --- Kinematic Viscosity --- p.55Chapter 2.4.2.9. --- "Cetane index, Cloud Point and Distillation Temperature (ASTM D 613, ASTM D 2500 and ASTM D 90)" --- p.55Chapter 2.4.3. --- Toxicity assays of FAMEs --- p.55Chapter 2.4.3.1. --- Acute toxicity to mice --- p.56Chapter 2.4.3.2. --- Seed germination test --- p.56Chapter 2.4.3.3. --- Acute toxicity to aquatic invertebrate --- p.56Chapter 2.5. --- Quantity and quality assessments of phytochemical products --- p.57Chapter 2.5.1. --- Determination of purity and yield of phytochemicals in phytosterol and desterolized fractions --- p.57Chapter 2.5.2. --- Antioxidants activity of desterolized fraction --- p.58Chapter 2.5.2.1. --- ABTS scavenging activity --- p.58Chapter 2.5.2.2. --- Free radical scavenging activity --- p.58Chapter 2.5.3. --- Anti-proliferative effect on cancer cells of phytosterols --- p.59Chapter 2.5.3.1. --- Cell culture --- p.59Chapter 2.5.3.2. --- Determination of optimal cell density for antiproliferative assays --- p.59Chapter 2.5.3.3. --- Anti-proliferative effect of phytosterols on H1299 and Hep G2. --- p.60Chapter 2.5.3.4. --- Detection of action mechanism(s) of the anti-proliferative effects of β-sitosterol on H1299 and Hep G2 cancer cells --- p.61Chapter 3. --- Result --- p.70Chapter 3.1. --- Characterization of Physically Refined Deodorizer Distillate (DODp) --- p.70Chapter 3.1.1. --- Free fatty acids composition --- p.70Chapter 3.1.2. --- Acid number --- p.75Chapter 3.1.3. --- "Free fatty acids, natural glyceride and unsaponifiable matter contents" --- p.75Chapter 3.1.4. --- "Squalene, tocopherol and phytosterol contents" --- p.77Chapter 3.1.5. --- Other physicochemical and biological analyses --- p.81Chapter 3.2. --- Production of fatty acid methyl esters (FAMEs) - Protocol A --- p.83Chapter 3.2.1. --- Optimization of Esterification --- p.83Chapter 3.2.1.1. --- Methanol to DODp molar ratio --- p.83Chapter 3.2.1.2. --- DODp to sulfuric acid molar ratio --- p.85Chapter 3.2.1.3. --- Reaction temperature --- p.87Chapter 3.2.1.4. --- Calculation of esterification efficiency --- p.87Chapter 3.2.2. --- Optimization of Molecular Distillation --- p.89Chapter 3.2.2.1. --- Feed rate --- p.89Chapter 3.2.2.2. --- Distillation temperature --- p.91Chapter 3.2.2.3. --- Rotating blade speed --- p.93Chapter 3.2.3. --- Crystallization --- p.97Chapter 3.2.3.1. --- Phytosterol preparations --- p.97Chapter 3.2.3.2. --- Desterolized fractions --- p.97Chapter 3.3. --- Production of fatty acid methyl esters (FAMEs) 一 Protocol B --- p.99Chapter 3.3.1. --- Optimization of Saponification --- p.99Chapter 3.3.1.1. --- Saponification number --- p.99Chapter 3.3.1.2. --- Saponification --- p.99Chapter 3.3.2. --- Extraction of unsaponifiable matter --- p.101Chapter 3.3.3. --- FAMEs product after esterification --- p.101Chapter 3.3.4. --- Crystallization --- p.104Chapter 3.3.4.1. --- Phytosterol preparations --- p.104Chapter 3.3.4.2. --- Desterolized fractions --- p.104Chapter 3.4. --- Quantity and Quality assessments of FAMEs --- p.106Chapter 3.4.1. --- "FAMEs yield, purity and appearance" --- p.106Chapter 3.4.2. --- Specifications for Biodiesel in U.S.A --- p.106Chapter 3.4.3. --- Acute Toxicity assays of FAMEs --- p.109Chapter 3.4.3.1. --- Acute toxicity to mice --- p.109Chapter 3.4.3.2. --- Seed germination test --- p.109Chapter 3.4.3.3. --- Acute toxicity to aquatic invertebrate --- p.109Chapter 3.5. --- Quantity and Quality assessments of phytochemicals --- p.113Chapter 3.5.1. --- Phytochemicals recoveries and compositions in phytosterol preparations and desterolized fractions --- p.113Chapter 3.5.1.1. --- Phytosterols recoveries and compositions in phytosterol preparations --- p.113Chapter 3.5.1.2. --- Squalene and tocopherols recoveries and compositions in desterolized fraction --- p.115Chapter 3.5.2. --- Antioxidant activities of desterolized fractions --- p.118Chapter 3.5.2.1. --- ABTS scavenging activity --- p.118Chapter 3.5.2.2. --- Scavenging Activities of DPPH radicals --- p.120Chapter 3.5.3. --- Anti-proliferative effect of phytosterols on cancer cells --- p.123Chapter 3.5.3.1. --- Determination of optimal cell density for antiproliferative assays --- p.123Chapter 3.5.3.2. --- Anti-proliferative effect of phytosterols on H1299 --- p.126Chapter 3.5.3.3. --- Anti-proliferative effect of phytosterols on Hep G2 --- p.132Chapter 3.5.3.4. --- Further investigation of anti-proliferative mechanism of β-sitosterol --- p.138Chapter 4. --- Discussion --- p.149Chapter 4.1. --- Characteristics of Physically Refined Deodorizer Distillate (DODp) --- p.149Chapter 4.1.1. --- Fatty acid contents and compositions --- p.149Chapter 4.1.2. --- "Squalene, tocopherol and phytosterol contents" --- p.153Chapter 4.1.3. --- Other physical and chemical analyses --- p.155Chapter 4.2. --- Production of fatty acid methyl esters (FAMEs) 一 Protocol A --- p.156Chapter 4.2.1. --- Optimization of Esterification --- p.156Chapter 4.2.2. --- Optimization of Molecular Distillation --- p.158Chapter 4.3. --- Production of fatty acid methyl esters (FAMEs) 一 Protocol B --- p.159Chapter 4.3.1. --- Optimization of Saponification --- p.159Chapter 4.3.2. --- Extraction of unsaponifiable matter --- p.160Chapter 4.3.3. --- Production of FAMEs --- p.161Chapter 4.4. --- Purification of phytosterols --- p.162Chapter 4.4.1. --- Purity and recovery of phytosterols --- p.162Chapter 4.4.2. --- Purity and recovery of squalene and tocopherols in desterolized fractions --- p.163Chapter 4.5. --- Quantification of the Loss of Valuable products during Processing --- p.165Chapter 4.6. --- Quality assessment of FAMEs and phytochemicals --- p.170Chapter 4.6.1. --- Specifications for Biodiesel in USA --- p.170Chapter 4.6.2. --- Acute toxicities of FAMEs --- p.171Chapter 4.6.3. --- Antioxidant activities of desterolized fractions --- p.172Chapter 4.6.4. --- Anti-proliferative effects of phytosterols on cancer cells --- p.173Chapter 4.7. --- Comparisons of the two protocols --- p.182Chapter 4.7.1. --- Products from protocol A and B --- p.182Chapter 4.7.2. --- Characteristics of protocol A and B --- p.183Chapter 4.7.3. --- Sustainable recycling technology --- p.184Chapter 4.7.4. --- Life cycle analysis --- p.185Chapter 4.8. --- Further investigation --- p.186Chapter 5. --- Conclusion --- p.187Chapter 6. --- Reference --- p.18