Enzymatic biodiesel production: Technical and economical considerations

It is well documented in the literature that enzymatic processing of oils and fats for biodiesel is technically feasible. However, with very few exceptions, enzyme technology is not currently used in commercial‐scale biodiesel production. This is mainly due to non‐optimized process design and a lack of available cost‐effective enzymes. The technology to re‐use enzymes has typically proven insufficient for the processes to be competitive. However, literature data documenting the productivity of enzymatic biodiesel together with the development of new immobilization technology indicates that enzyme catalysts can become cost effective compared to chemical processing. This work reviews the enzymatic processing of oils and fats into biodiesel with focus on process design and economy.     

在以纯碱为原料的非强酸性水溶液体系中采用酸碱滴定分析的误差来源及分析方法的改进

以三聚磷酸钠生产过程为例,论述了在以纯碱为原料的非强酸性水溶液体系中,由于反应不完全导致反应物中存在少量的碳酸盐,这部分碳酸盐干扰了用酸碱滴定法测量的中和度,并据此提出中和度分析改进方法.由此可以推广到其它以纯碱为原料的非强酸性水溶液体系中.     

Separation of weak and strong acids by electro-electrodialysis—Experiment and theory

The experimental results of the separation of acetic acid (HA) from the sulfuric acid by the electro-electrodialysis (EED) method and the modeling of process have been presented. The Neosepta membranes CMX and ACM have been used. It has been found that the efficiency of retention of HA is high (>0.9) when the process is conducted below the limiting current density with respect to HSO₄⁻ or SO₄²⁻ anions. The observed current efficiency of the H₂SO₄ removal was rather low (CE_S = ca. 0.7, when the initial concentration of H₂SO₄ in the mixture was 1 or 2 M) which was caused by the nonideal selectivity of the anion-exchange membrane. The experimental results have been described by the model based on the extended Nernst-Planck equation and the Donnan equilibrium. Since the efficiency of the process depended mainly on the selectivity of anion-exchange membrane (ACM), the concentration of fixed charges of that membrane, , and the ratio of volume fraction of pores to their squared tortuosity, V_p/θ², have been chosen as the main fitting parameters. It has been found that the fitting of the EED data depends mainly on , whereas in the modeling of diffusion experiment (or an EED experiment conducted at low current density) both parameters are important. The best fit has been obtained for , i.e. ca. one order smaller than that determined experimentally. The obtained optimal value of V_p/θ², equal to 0.013, is consistent with those previously obtained for other Neosepta anion-exchange membrane.     

固体超强酸S_2O_8~(2-)/SnO_2-SiO_2催化合成环己酮1,2-丙二醇缩酮

采用沉淀-浸渍法制备了固体超强酸S2O28-/SnO2-SiO2,以它为催化剂催化环己酮和1,2-丙二醇合成了环己酮1,2-丙二醇缩酮;考察了带水剂种类及用量、酮醇摩尔比、催化剂用量、反应时间对产品收率的影响,并用正交实验对反应条件进行了优化。实验结果表明,适宜的反应条件为:n(环己酮)∶n(1,2-丙二醇)=1∶1.6、催化剂用量为反应物料总质量的2.0%、带水剂环己烷用量5.0mL、反应时间50min。在此条件下,环己酮1,2-丙二醇缩酮收率达到91.47%;催化剂的稳定性良好,在重复使用5次后环己酮1,2-丙二醇缩酮收率为82.20%,活性下降的主要原因为催化剂表面积碳和吸附了有机物;经傅里叶变换红外光谱和气相色谱质谱分析表明,产物为环己酮1,2-丙二醇缩酮,纯度为100%。     

Methacrylic acid–acrylamide-g-poly(ethyleneterephthalate) fibres for urea hydrolysis

This paper presents the results of urease immobilization onto methacrylic acid–acrylamide grafted poly(ethyleneterephthalate) fibres. The graft yield strongly affected the maximum activity of the immobilized enzyme up to a value of 70·2%. Higher grafting caused a decline in urease activity and led to the degradation of the fibres. The minor changes observed in K_m and V_max demonstrated that the conformational changes existed during immobilization were not extensive. However, 70·2% methacrylic acid–acrylamide-g-fibres containing urease were more stable towards acidic and alkaline pH, high temperature and storage conditions compared with free enzyme. Apart from the increase in stability to heat inactivation, the initial enzymatic activity of the urease–fibre system remained almost unchanged even after 40 repeated assays corresponding to 10 h of operation in 4 months, indicating the excellent durability of the system.     

Pyrene oxidation as a model reaction for characterizing the mechanism of coke oxidation on Y zeolites

The same effect of temperature on the production of CO, CO₂ and H₂O was found during oxidative treatment of HY zeolites either impregnated with pyrene or coked. Therefore, pyrene oxidation can be used to specify the mechanism of coke oxidation. Three types of reactions can be distinguished: (a) condensation of polyaromatic molecules, (b) oxidation of polyaromatics into aldehydes, ketones, acids and anhydrides and (c) decarbonylation or decarboxylation of oxygenated compounds, all these reactions involving protonic sites.     

In situ13C NMR study of tert-butanol interaction with moderately concentrated sulfuric acid

An in situ NMR study of tert-butanol dehydration in 95 and 85% sulfuric acid did not indicate the formation of tert-butyl cations as active reaction intermediates. Instead, only NMR lines from oxonium ions under the condition of fast exchange with water and the acid were observed. It is most likely that, in the concentrated acid, the active intermediates of this reaction are represented by tert-butyl sulfuric ester which probably is a precursor of invisible tert-butyl carbenium ions representing short-lived excited or transition states.     

Effect of harvesting time and fruit size on titratable acidity, soluble solid and distribution of limonin in Thai tangerine juice

The effect of fruit size and harvesting of Thai tangerine fruit ( Citrus reticulata , Blanco) at different growth stages, 8–12 months after fruit set, on the distribution of limonin in whole fruit as well as in the individual fruit parts and extracted juice was investigated. The highest limonin concentration was observed in seed, followed by albedo, flavedo, segment membrane and juice sacs in decreasing order. The limonin concentration in juice as well as in whole fruit was decreased when fruit was harvested 8–12 months of fruit set. Increasing harvesting time from 8 to 12 months showed corresponding decreases in the amount of limonin in flavedo, albedo and seed. There was a decrease in titrable acidity and increase in total soluble solid and total soluble solid/titrable acidity ratio of juice with a later than normal harvesting time. However, fruit size showed no effect on limonin content and other properties of juice extracted from tangerine.