菲美合作研发椰子“生物柴油”

菲律宾正在与美国共同开发一种椰油制成的“生物柴油”，预计这项研究将成为菲律宾替代能源研究中的一项技术突破。

Biodiesel production and its development strategy

Biodiesel, an environmentally friendly biofuel with similar flow and combustion properties as petroleum-based diesel and low emission profile, which is commonly prepared from triglyceride （TG） sources such as vegetable oils, animal fats, and waste greases, holds good promises as an alternative to diesel fuel. Alternate fuels for diesel engines have become increasingly important due to diminishing petroleum reserves and awareness of the increased environmental consequences of emissions from petroleum-fuelled engines, as the world is confronted with an energy crisis. Currently, the production of methyl or ethyl esters from edible oils is much more expensive than that of diesel fuels due to the relatively high costs of vegetable oils （about four times the cost of diesel in China）. Methyl esters produced from such oils can be expected to compete economically with diesel fuels, and there is a need to explore low cost alternate feedstocks for the production of biodiesel. Rapeseed is little sensitive to crop input levels, allowing reduction of tillage, irrigation, and weed control. Significant yield increases will be attained using new hybrids and better crop management. Rapeseed cultures in seasonal set-aside lands such as Dongting Lake surroundings can significantly decreases the amount of subsides spent for agricultural overproduction in China, which leads to an increase in farmer incomes as well as the creation of new employment. This significantly lowers production costs, reduces environmental impact, and increases final energy gains. Our rapeseed oil is good source for biodiesel with respect to high oil content and proper fatty acid composition.

市场瞭望

植物叶开发前景广阔箬竹叶,在国际市场上,箬竹叫包装备受发达国家青睐,被誉为'绿色包装'。利用高科技从箬竹叶中提取的高品质天然香精和食用天然防腐剂,在食品中广泛应州,箬竹叶还可以加工成饲料和用于造纸。杜仲叶,把它浸泡、清洗、榨取后,经过精加工而制成的杜仲茶,味道清香鲜美,色泽纯正浓郁。它不仅含钙、铁、钾等各种矿物质,而且营养物质平衡全面。

Simulation of biodiesel industrial production via solid base catalyst in a fixed-bed reactor

Biodiesel industrial production based on a solid base catalyst in a fixed-bed was simulated. The lab and bench scale experiments were carded out effectively, in which the kinetic model is established and it can describe the transesterification reaction well. The Antoine equation of biodiesel is regressed with the vapor-liquid data cited of literature. The non-random two liquid （NRTL） model is applied to describe the system of fatty acid methyl ester （FAME）, methanol and glycerol and parameters are obtained. The Ternary phase map is obtained from Aspen Plus via the liquid-liquid equilibrium （LLE） data. In order to describe the production in a fixed-bed performs in industrial scale after being magnified 1 000 times, the Aspen Plus simulation is employed, where two flowsheets are simulated to predict material and energy consumption. The simulation results prove that at least 350. 42 kW energy consumption can be reduced per hour to produce per ton biodiesel compared with data reported in previous references.

Studies on Production of Biodiesel by Esterification of Fatty Acids by a Lipase Preparation from Candida sp. 99-125

A self-made lipase preparation from Candida sp. 99-125 was used for the production of biodiesel through enzymatic esterification of fatty acids. The crude lipase powder and fermentation broth were immobilized on a cheap fiber cloth carrier. The conditions of lipase-catalyzed esterification between long-chain fatty acids and methanol in a solvent system were investigated in detail, including the temperature, pH value, substrate concentration, solvent, absorbent agent, enzyme dosage and purity, immobilization method, the mode of addition of substrate. The results show that reaction temperature, pH of lipase micro-environment, substrate concentration, enzyme dosage and purity affect the esterification strongly. Several new methods and enzymatic procedures for improving the enzymatic reaction involving the process cost are also discussed, such as fossil diesel fuel as reaction solvent, immobilization method, multi-step gradient addition of methanol. The esterification degree of 92.8% was obtained with oleic acid and methanol under the optimal reaction condition after 12.5 h reaction time. The half-life of the immobilized lipase preparation from crude free lipase powder for esterification was 15 days.

Application of Choline Chloride·xZnCl2 Ionic Liquids for Preparation of Biodiesel

The inexpensive and moisture-stable Lewis-acidic ionic liquids were prepared and applied for transesterification of soybean oil to biodiesel.The influences of molar ratio of methanol to soybean oil,reaction temperature and amount of ionic liquids were investigated.The transesterification of soybean oil to biodiesel catalyzed by choline chloride·xZnCl2 ionic liquids showed many advantages such as mild conditions and lower cost.On the other hand,the non-ideal yield and complicated separation between biodiesel and soybean oil were also investigated and analyzed.The improvement on the systems of choline chloride·xZnCl2 was proposed for further investigation.

Modified graphene‐based materials as effective catalysts for transesterification of rapeseed oil to biodiesel fuel

Production of biodiesel by the transesterification process using different modified graphene‐based materials as catalysts was studied.Solid acid graphene‐based samples were prepared by grafting sulfonic or phosphate groups on the surface of thermally reduced graphene oxide.The obtained materials were thoroughly characterized using scanning electron microscopy,X‐ray diffraction,thermogravimetric analysis,X‐ray photoelectron spectroscopy,N2 adsorption‐desorption measurements,potentiometric titration,elemental analysis,and Fourier transform infrared spectroscopy.The prepared catalysts were tested in the transesterification of rapeseed oil with methanol at 130°C under pressure,and their activities were compared to the performance of a commercially available heterogeneous acidic catalyst,Amberlyst‐15.All modified samples were active in the transesterification process;however,significant differences were observed in the yield of biodiesel,depending on the method of catalyst preparation and strength of the acidic sites.The highest yield of fatty acid methyl esters of 70%was obtained for thermally reduced graphene oxide functionalized with 4‐benzenediazonium sulfonate after 6 h of processing,and this result was much higher than that obtained for the commercial catalyst Amberlyst‐15.The results of the reusability test were also promising.

Reaction Kinetics of Biodiesel Synthesis from Waste Oil Using a Carbon-based Solid Acid Catalyst

The kinetics of simultaneous transesterification and esterification with a carbon-based solid acid catalyst was studied.Two solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt.These catalysts were characterized on the basis of elemental analysis,acidity site concentration,the Brunauer-Emmett-Teller（BET）surface area and pore size.The kinetic parameters with the two catalysts were determined,and the reaction system can be described as a pseudo homogeneous catalyzed reaction.All the forward and reverse reactions follow second order kinetics.The calculated concentration values from the kinetic equations are in good agreement with experimental values.

Enzymatic Synthesis of Fatty Acid Methyl Esters from Crude Rice Bran Oil with Immobilized Candida sp. 99-125

The non-edible crude rice bran oil was extracted from white rice bran, and then was catalyzed by immobilized lipase for biodiesel production in this study. The effects of water content, oil/methanol molar ratio, temperature, enzyme amount, solvent,number of methanol added times and two-step methanolysis by using Candida sp. 99-125 as catalyst were investigated. The optimal conditions for processing 1 g rice bran oil were: 0.2 g immobilized lipase, 2 ml n-hexane as solvent, 20% water based on the rice bran oil mass, temperature of 40 °C and two-step addition of methanol. As a result, the fatty acid methyl esters yield was 87.4%. The immobilized lipase was proved to be stable when it was used repeatedly for 7 cycles.

Effect of carbon source on growth and lipid accumulation in Chlorella sorokiniana GXNN01

Heterotrophic culture of microalgae to develop methods of increasing biomass productivity and storage lipids has brought new insight to commercial biodiesel production. To understand the relationship between heterotrophy and lipid production, the effects of carbon sources on the growth and lipid accumulation of Chlorella sorokiniana GXNN01 was studied. The alga exhibited an increased growth rate in response to the addition of carbon sources, which reached the stationary phase after 48 h at 30℃. In addition, glucose and NaAc had a significant effect on the lipid accumulation during the early-stationary phase. Specifically, the lipid content was 0.237±0.026 g ·g^-1 cell dry weight and 0.272±0.041 g Ll when glucose was used as the carbon source, whereas the lipid content reached 0.287±0.018 g ·g^-1 cell dry weight and 0.2884-0.008 g Lz when NaAc was used as the carbon source. The neutral lipid content was found to first decrease and then increase over time during the growth phase. A glucose concentration of 20 mmol L^-1 gave the maximal lipid yield and the optimum harvest time was the early-stationary phase.

Effect of Biodiesel on Oxidation Stability, Detergency and Antiwear Ability of Diesel Oil

Different contents of biodiesel and petrodiesel were incorporated into diesel engine oils. The oxidative stability, detergency and antiwear performance of the formulated diesel oils were evaluated. The results indicated that, compared with petrodiesel, biodiesel was more liable to promote oxidation degradation of diesel oils, leading to worse oxidative stability, detergency and antiwear ability of the oils.

Production of biodiesel from waste vegetable oil using impregnated diatomite as heterogenous catalyst

In this study, biodiesel was produced from waste vegetable oil using a heterogeneous base catalyst synthesized by impregnating potassium hydroxide(KOH) onto diatomite. Response surface methodology based on a central composite design was used to optimize four transesterification variables: temperature(30–120 °C), reaction time(2–6 h), methanol to oil mass ratio(10%–50%) and catalyst to oil mass ratio(2.1%–7.9%). A quadratic polynomial equation was obtained to correlate biodiesel yield to the transesterification variables. The diatomite–KOH catalyst was characterized using X-ray diffraction(XRD), Fourier transform infra-red spectroscopy(FTIR) and a scanning electron microscope(SEM) equipped with an energy dispersive X-ray detector(EDS). A maximum biodiesel yield of 90%(by mass) was obtained. The reaction conditions were as follows: methanol to oil mass ratio 30%, catalyst to oil mass ratio 5%, reaction time 4 h, and reaction temperature 75 °C. The XRD, FTIR and SEM(EDS) results confirm that the addition of KOH modifies the structure of diatomite. During impregnation and calcination of the diatomite catalyst the K2 O phase forms in the diatomite structural matrix and the active basicity of this compound facilitates the transesterification process. It is possible to recycle the diatomite–KOH catalyst up to three times. The crucial biodiesel properties from waste vegetable oil are within the American Standard Test Method specifications.

Effect of ethanol addition on flame characteristics of waste oil biodiesel

Biodiesel is a kind of clean and renewable energy. The effect of ethanol addition on the flame characteristics of waste oil biodiesel is studied by using OH-PLIF technique from the perspective of OH radical evolution. Ethanol addition leads to the appearance of diffusion flame reaction interface ahead of schedule and shortens the diffusion flame height. The experimental results show a linear correlation between the flame height and the fuel flow rate for a given fuel and oxidant. The same conclusion is drawn from the theoretical analysis of the approximate model. In addition. ethanol addition makes the average OH signal intensity of flame at different fuel flow rate tend to be consistent and the fuel flow rate enlarge where the flame field shows the strongest oxidation performance. Average OH signal intensity begins to weaken at larger fuel flow rate, which indicates that fuel flow rate of fuels blended with ethanol can change in larger range and does not significantly affect the uniformity of combustion.

Solid Acid Used as Highly Efficient Catalyst for Esterification of Free Fatty Acids with Alcohols

Anovel solid acid catalyst, which was prepared from sodium alginate (SA) and metal chlorides and characterized with XRD and FT-IR spectrometry, was used for the preparation of biodiesel via esterification reaction. The study results showed that the aluminum-alginate complex prepared in a cheap and easy way exhibited high catalytic activity, and a 92.6% conversion of methyl oleate was obtained in the presence of 4m% of catalyst dosage upon refluxing for 3h of methanol and acid mixed in a molar ratio of 10:1. It should be noted that the catalyst can be applied to the esterification reaction of fatty acids with various carbon chain length on methanol or different short chain alcohols, indicating that the catalyst is suitable for the preparation of biodiesel from waste oils with a high acid value.

Biodiesel Production from Waste Edible Oils and Grease Containing Free Fatty Acids

Till now, most part of the biodiesel is produced from the refined vegetable oils using methanol as feedstock in the presence of an alkali catalyst. However, large amount of waste edible oils and grease are available. The difficulty with alkali-catalyzed esterification of these oils is that they often contain large amount of free fatty acids （FFA）, polymers and decomposition products. These free fatty acids can quickly react with the alkali catalyst to produce soaps that inhibit the separation of the ester and glycerine. An esterification and transesterification process is developed to convert the high FFA oil to its monoesters, The first step, the acidcatalyzed esterification with glycerine and these FFA reduces the FFA content of the oil and grease to less than 3%, and then an azeotropic distillation solvent is used to remove the water. The major factors affecting the conversion efficiency of the process such as glycerol to free fatty acid molar ratio, catalyst amount, reaction temperature and reaction duration are analyzed, The second step, alkali-catalyzed transesterificatiou process converts the products of the first step to its monoesters and glycerol, and then the glycerol is recycled for utilization in the first step. Technical indicators of the biodiesel product can meet the ASTM 6751 standard.

Purification of Crude Glycerol from Waste Cooking Oil Based Biodiesel Production by Orthogonal Test Method

Purification of original crude glycerol obtained from biodiesel production was conducted in a laboratory scale equipment by means of a combined chemical and physical treatment method based upon repeated cycles of acidification of liquid phase to the desired pH value by using 5.85% H3PO4 solution for pH value adjustment, and the mixture was kept at 70 ℃ for 60 rain to make phase separation for obtaining a glycerol-rich middle phase. The yield of crude glycerol reached 81.2%. Subsequently, upon reaction of the obtained glycerol phase with 0.03% of sodium oxalate at 80 ℃ for 30 min the impurity removal rate was equal to 19.8%. The fraction boiling between 164 ℃ and 200 ℃ was collected by vacuum distil- lation followed by decolorization with 2% of active carbon at 80 ℃ for two times to yield the product glycerol with an ac- ceptable purity of 98.10%.

Spectroscopic Analysis of Structural Transformation in Biodiesel Oxidation

The oxidation behavior of three biodiesels of different origins,viz.rapeseed oil derived biodiesel,soybean oil derived biodiesel and waste oil based biodiesel,were tested on an oxidation tester.The chemical compositions of the biodiesels were characterized by gas chromatography.Thereafter,the structural transformation of fatty acid methyl ester(FAME)of the biodiesels was analyzed by an infrared spectrometer and an ultraviolet absorption spectrometer.The results demonstrated that the oxidation behavior of biodiesels of different origins was closely related to the composition and distribution of FAMEs.Higher concentration of unsaturated FAME with multi-double bonds exhibited poorer oxidation resistance.Furthermore,cis-trans isomerization transformation occurred in the unsaturated FAME molecules and conjugated double-bond produced during the oxidation process of biodiesel.Greater cis-trans variations corresponded to deeper oxidation degree.The higher the content of unsaturated FAME with multi-double bonds in a biodiesel,the more the conjugated double bonds was formed.

Continuous Production of Biodiesel from Soybean Oil Using Supercritical Methanol in a Vertical Tubular Reactor：I.Phase Holdup and Distribution of Intermediate Product along the Axial Direction

Production of biodiesel with supercritical methanol is a green synthesis process.A study was carried out in a vertical tubular reactor with a length of 3700 mm and a diameter of 20 mm at 275-375°C,15 MPa,and molar ratio of methanol to soybean oil of 40︰1.The phase holdup,intermediate product,yield and axial distribution of methyl ester(ME) were investigated.Methanol and oil were mixed non-uniformly due to the formation of biodiesel and difference in their densities,even when the reaction system was in the supercritical state.From top to bottom,the phase holdup of methanol increased and that of oil decreased.As temperature increased,the concentrations of monoglyceride and diglyceride decreased gradually and the ME yield increased.When the temperature reached 300°C,the critical temperature of the system,the ME yield was 50%.Further increase in temperature led to a sharp in-crease of ME yield.However,at 375°C after 1200 s of reaction time,the decomposition rate of ME was greater than its formation rate,reducing the ME yield.

Synthesis of Biodiesel Using ZrO_2 Polycrystalline Ceramic Foam Catalyst in a Tubular Reactor

With the help of the ceramic foam research efforts and preparation techniques, the ZrO2 polycrystalline ceramic foam catalyst was synthesized, and its characteristics, including the crystal structure, the phase composition, the acid–base properties, and the microstructure, were analyzed by XRD, SEM, Py-IR, and BET techniques. The performance of the ZrO2 polycrystalline ceramic foam catalyst in a tubular reactor was investigated via biodiesel synthesis using S. wilsoniana oil and methanol. The effects of reaction conditions(i.e., reaction temperature, reaction pressure, and volume ratio of methanol to S. wilsoniana oil) on transesterification efficiency were investigated, and the reaction conditions were optimized using RSM. The optimum reaction temperature, reaction pressure, and volume ratio of methanol to S. wilsoniana oil were determined to be 290 ℃, 10 MPa, and 4:1, respectively. Under this condition, the FAME content in the product oil reached 98.38%. The performance of the ZrO2 polycrystalline ceramic foam catalyst synthesized in this work for biodiesel synthesis from S. wilsoniana oil with a moisture content of 7.1% and an acid value of 130.697 mg KOH/g was examined, and the FAME content in the product oil was found to be 93% and 97.67%, respectively. The FAME content in the product oil exceeded 97% after five consecutive cycles(12 h per cycle of use) of the catalyst. The proposed catalyst represents a new type of solid catalyst with excellent acid resistance, water resistance, esterification efficiency, and catalytic stability.