3.2.3. Hydroformylation 2467 3.2.4. Dimerization 2468 3.2.5. Oxidative Cleavage and Ozonolysis 2469 3.2.6. Metathesis 2470 4. Terpenes 2472 4.1. Pinene 2472 4.1.1. Isomerization: R-Pinene 2472 4.1.2. Epoxidation of R-Pinene 2475 4.1.3. Isomerization of R-Pinene Oxide 2477 4.1.4. Hydration of R-Pinene: R-Terpineol 2478 4.1.5. Dehydroisomerization 2479 4.2. Limonene 2480 4.2.1. Isomerization 2480 4.2.2. Epoxidation: Limonene Oxide 2480 4.2.3. Isomerization of Limonene Oxide 2481 4.2.4. Dehydroisomerization of Limonene and Terpenes To Produce Cymene 2481

Chemical Routes for the Transformation of Biomass into Chemicals

This critical review provides a survey illustrated by recent references of different strategies to achieve a sustainable conversion of biomass to bioproducts. Because of the huge number of chemical products that can be potentially manufactured, a selection of starting materials and targeted chemicals has been done. Also, thermochemical conversion processes such as biomass pyrolysis or gasification as well as the synthesis of biofuels were not considered. The synthesis of chemicals by conversion of platform molecules obtained by depolymerisation and fermentation of biopolymers is presently the most widely envisioned approach. Successful catalytic conversion of these building blocks into intermediates, specialties and fine chemicals will be examined. However, the platform molecule value chain is in competition with well-optimised, cost-effective synthesis routes from fossil resources to produce chemicals that have already a market. The literature covering alternative value chains whereby biopolymers are converted in one or few steps to functional materials will be analysed. This approach which does not require the use of isolated, pure chemicals is well adapted to produce high tonnage products, such as paper additives, paints, resins, foams, surfactants, lubricants, and plasticisers. Another objective of the review was to examine critically the green character of conversion processes because using renewables as raw materials does not exempt from abiding by green chemistry principles (368 references).

Conversion of biomass to selected chemical products

UV-Visible ار راد ن .د TiO2 ( تیفرظ راون مان هب نورتکلا یاراد یژرنا زارت لماش VB و ) رگید زارت ی یژرنا اب ( ییاناسر راون مان هب نورتکلا زا یلاخ و رتلااب VB یم ) .دشاب ت ود نیا نیب یژرنا توافت یژرنا فاکش زار ، پگ دناب هدیمان یم .دوش هک ینامز زا نورتکلا لاقتنا VB هب VB یم ماجنا دریگ ، TiO2 اب ودح یژرنا بذج د ev 2 / 3 ، نورتکلا تفج کی دیلوت یم هرفح .دیامن و نورتکلا هرفح ی نا اب هدش دیلوت یم کرتشم حطس هب لاقت ثعاب دناوت شنکاو ماجنا اه یی ددرگ . TiO2 دربراک ،دراد یدایز یاه هلمج زا یم ناوت اوه یگدولآ هیفصت یارب (CO2) و بآ و ... نآ زا هدافتسا درک .

Advanced Nanoarchitectures for Solar Photocatalytic Applications

Conversion of Biomass into Chemicals over Metal Catalysts

Biodiesel is a promising alternative, and renewable, fuel. As its production increases, so does production of the principle co-product, crude glycerol. The effective utilization of crude glycerol will contribute to the viability of biodiesel. In this review, composition and quality factors of crude glycerol are discussed. The value-added utilization opportunities of crude glycerol are reviewed. The majority of crude glycerol is used as feedstock for production of other value-added chemicals, followed by animal feeds.

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Value-added uses for crude glycerol--a byproduct of biodiesel production.

Glycerolysis of crude fatty acid methyl esters (FAME) with crude glycerol derived from biodiesel production was performed. The reaction was accomplished at temperatures ranging between 160 and 200 °C and molar ratios of FAME to glycerol ranging between 1.5 and 3.0. Increasing the temperature improved the formation rate of monoglycerides (MG) and diglycerides (DG). However, increasing both the temperature and the molar ratio of glycerol to FAME diminished the formation of MG. Best results (43 % MG and 26 % DG in 10 min) were obtained at 200 °C using the lowest concentration of glycerol. The effects of soap and NaOH present in crude glycerol were controlled by carrying out the reaction with pure glycerol. In comparison with NaOH-catalyzed reactions, soap-catalyzed reactions resulted in a slower formation rate of products. However, soap-catalyzed reactions were less prone to secondary reactions, affording maximum yields of MG and DG, which were higher than those obtained with NaOH-catalyzed reactions at 180 and 200 °C.

Glycerolysis of Crude Methyl Esters with Crude Glycerol from Biodiesel Production

Kinetics of curing of maleated castor oil glycerides with styrene was studied by differential scanning calorimetry and rhe- ology. The resin was synthesized from biodiesel-derived crude glycerol. Curing rates were fitted to several empirical models (autocata- lytic model, Kamal's model and a model with vitrification). The three models showed a good fitting with experimental data at conversions lower than 0.55 for temperatures ranging from 30 to 50 � C. However, the model that includes vitrification showed a bet- ter fitting in the entire range of conversions and the same temperatures. At higher temperatures (50-60 � C), some deviations were observed for the three models at low and high conversions. Gel times were obtained from rheological studies and the apparent activa- tion energies were calculated thereof. Gel times were 300-2700 s. The values of apparent activation energy obtained for this castor oil-based copolymer (47.2-52.3 kJ/mol) were within range of commercial unsaturated polyester resins. V C 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41344.

Curing copolymerization kinetics of styrene with maleated castor oil glycerides obtained from biodiesel‐derived crude glycerol

Modifications to the double bonds of plant oils were done by addition of alcohols, using the corresponding epoxides as intermediates. Both, crystalline and amorphous aluminosilicates were studied as catalysts and they were thoroughly characterized using 29 Si and 27 Al MAS NMR as well as FT-IR, XRD, inductive couple plasme atomic emission spectroscopy (ICP-AES) and nitrogen adsorption, to link catalyst properties to catalytic behavior. Aluminosilicates where found to be suitable catalysts for the nucleophilic addition of alcohols to epoxidized oils. Zeolites with higher mesopores content, such as steamed ones, were more active because the active Bronsted sites are more accessible to the bulky substrate. Aluminosilicates in lamellar form, like clays of the type montmorillonite, showed to be the most active aluminosilicates for the epoxide alcoholysis. Clays with a higher degree of Al3+ substitution for Si4+ in the SiO2 layers proved to be superior to those with a higher degree of Fe2+ or Mg2+ substitution for Al3+ in the Al2O3 layers. The analysis indicate that this better performance is due to a higher Bronsted acid strength present in the former clays.

Modification and characterization of aluminosilicates used for nucleophilic addition of alcohols to epoxidized oils

BACKGROUND
Cyclic fatty carbonates can be obtained from epoxidized vegetable oils and CO2 under mild conditions. The main application of these bio-derivatives is the production of thermoset polymers and non-isocyanate polyurethanes. Castor oil has a different chemical structure from the other oils that have been used for carbonation. In this work, a kinetic model was developed for high CO2 pressure carbonation of epoxidized castor oil.

RESULTS
The highest epoxide group conversion (93%) was obtained at 130 °C and 480 min. However, the highest content of carbonate groups (1.5 carbonates/molecule) was obtained at 115 °C and 180 min. A kinetic model was proposed which included carbonation of epoxide as well as etherification of the oxirane ring as a competitive reaction. Both reactions were best fitted to pseudo-first-order kinetics. Activation energy of carbonation and etherification of the oxirane ring were estimated as 37.41 and 33.25 kJ mol−1, respectively.

CONCLUSION
Carbonated castor oil was produced from the epoxidized oil at 100–130 °C and a constant pressure of CO2 (0.5 MPa). Because of the polyfunctional character of the product, it could find applications as a monomer and as a synthetic building block for other bio-based chemicals. This product and the reaction pathway have not previously been disclosed. © 2016 Society of Chemical Industry

Carbonation of epoxidized castor oil: a new bio‐based building block for the chemical industry

Lycopene, to which tomato owes its red coloration, besides presenting great properties like colorant, is a powerful antioxidant that helps to combat degenerative diseases. Due to the importance that has been given to lycopene, because of its properties, in this investigation both steam-dragging and solvent extraction methods are compared based on the obtained yield and the pre-treatment given to the vegetable sample, characterizing the obtained extracts by means of visible UV spectrometry. Extractions are also carried out to determine the lycopene content in tomato chonto Lycopersicum esculentum , as well as other parameters of the extraction process: temperature, ratio mass of tomato pulp to solvent volume, time of extraction and number of stages. With these parameters, a basic design of a pilot plant is proposed for the extraction of this carotenoid, arranging the equipment according to the corresponding flow diagram and under the necessary operation conditions to avoid the degradation and decomposition of lycopene along the process and that allow to obtain a yield of 6 g of oleoresin / Kg of pulp.

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Luis A. Rios

Papers

Glycerolysis of Crude Methyl Esters with Crude Glycerol from Biodiesel Production

Curing copolymerization kinetics of styrene with maleated castor oil glycerides obtained from biodiesel‐derived crude glycerol

Modification and characterization of aluminosilicates used for nucleophilic addition of alcohols to epoxidized oils

Carbonation of epoxidized castor oil: a new bio‐based building block for the chemical industry

EXTRACCIÓN DEL CAROTENOIDE LICOPENO DEL TOMATE CHONTO (Lycopersicum esculentum)