用于牛粪液厌氧消化的推流式和完全混合式反应器性能研究

对推流式反应器(PFR)和完全混合式反应器(CSTR)用于牛粪液厌氧消化的性能进行了比较研究。在中温35℃下，对进料浓度40、80和128 g/L的3种牛粪液分别进行了试验。结果表明，CSTR比PFR具有更好的去除VS(挥发性固体)和产生物气的性能，在进料浓度为40、80和128 g/L时，CSTR中VS去除率比PFR中分别提高了17.4%～21.5%，3.9%～21.5%和0.5%～5.3%。在最优进料浓度80 g/L下，CSTR获得了最高的容积产气率和单位VS产气量，比PFR中提高了9.8%～25.9%。研究认为，CSTR中的搅拌作用加强了微生物与物料之间物质的传递，提高了降解去除有机物和产生物气的消化效果。因此，在牛粪液厌氧消化时，推荐使用CSTR反应器。     

Modeling evaluation of carbaryl degradation in a continuously stirred tank reactor by anodic fenton treatment

Anodic Fenton treatment (AFT) has been shown to be effective in removing pesticides from aqueous solution in batch reactors with the formation of less toxic and more biodegradable products. To facilitate practical application of AFT, carbaryl degradation in a continuously stirred tank reactor (CSTR) by AFT was investigated under different experimental conditions, such as carbaryl inlet concentration, Fenton reagent concentration/ratio, and carbaryl feeding flow rate. A higher Fe2+ delivery rate and H2O2 to Fe2+ ratio (H2O2:Fe2+) were found to favor the carbaryl degradation process, whereas flow rate was shown to be a much less significant factor to influence the degradation rate under the evaluated experimental conditions. A kinetic-based semiempirical model was developed to simulate the experimental data, and a very good fit between the model and the raw data was found (R2 > 0.99). A dimensionless parameter (k/q2) was found to be a good indicator of the degradation rate; that is, the higher the k/q2value is, the faster the degradation process is. The rate parameter (k) can be used to evaluate the degradation rate when the flow rate is invariant for a given pesticide. The shape parameter (beta) is most likely related to the availability and reactivity of Fenton reagents and hydroxyl radicals. To compare the degradation rate of different pesticides, more information other than k/q2, k, and beta values, such as the instantaneous degradation rate vs time relationship, needs to be considered.     

Suppressive effect of saturated acyl L-ascorbate on the oxidation of linoleic acid encapsulated with maltodextrin or gum arabic by spray-drying

6-O-Palmitoyl L-ascorbate was added to linoleic acid at various molar ratios of the ascorbate to the acid, the mixtures were emulsified with a maltodextrin or gum arabic solution, and the emulsions were spray-dried to produce microcapsules. At higher molar ratios, the oil droplets in the emulsions were smaller, and the oxidative stabilities of the encapsulated linoleic acid were higher for both the maltodextrin- and gum arabic-based microcapsules. 6-O-Capryloyl, caproyl, and lauroyl L-ascorbates, which were synthesized through lipase-catalyzed condensation in acetone, were also used for the microencapsulation of linoleic acid. Except for capryloyl L-ascorbate, the addition of a saturated acyl ascorbate, especially caproyl ascorbate, to linoleic acid was effective for preparing oil droplets of small particle diameter and for suppressing the oxidation of the encapsulated linoleic acid.     

Characterization of ester sulphate in a gypsum-amended podzol using an immobilized sulphatase reactor

An immobilized sulphatase reactor column was successfully used to determine the biochemical stability of ester sulphate in soil organic matter extracted from a podzol amended with gypsum. The sulphatase from Helix pomatia was covalently attached to controlled-porosity glass beads, and the immobilized enzyme was packed into a small glass column. The optimum pH, the time required to reach equilibrium, and the percentage of substrate consumed for the enzymatic hydrolysis of soil ester sulphate (pH 7.7, 90 min, 23–59%) were substantially different from those of p-nitrophenyl sulphate at similar concentrations of substrate (pH 7.0, 40 min, 99%). The striking difference in the biochemical stability and kinetic behaviour between soil ester sulphate and the simple synthetic substrate reflected their different chemical nature and structural features. The amounts of enzymatically hydrolysable (labile) ester sulphate in soil organic matter extracted from the podzol amended with gypsum at rates of 0, 50, and 200 kg S ha^-1 were significantly different (P=0.0004), being 0.5, 1.1, and 1.4 g S ml^-1 soil extract (or 5, 11, and 14 g S g^-1 soil), respectively. The labile ester sulphate was not correlated with the total hydriodic acid-reducible organic sulphate with the soil organic matter extracts but with the hydriodic acid-reducible organic sulphate: organic C ratio, which increased as a result of gypsum amendment. This study revealed that input of inorganic sulphate as gypsum substantially increased the accumulation of labile ester sulphate in a podzol.     

Process development of continuous glycerolysis in an immobilized enzyme-packed reactor for industrial monoacylglycerol production

Continuous and easily operated glycerolysis was studied in different lipase-packed columns to evaluate the most potential process set-ups for industrial monoacylglycerol (MAG) production. Practical design-related issues such as enzyme-filling degree, required reaction time, mass transfer investigations, and capacity and stability of the enzyme were evaluated. A commercially available immobilized Candida antarctica lipase B was used to catalyze the glycerolysis reaction between glycerol and sunflower oil dissolved in a binary tert-butanol: tert-pentanol medium. Considering easy handling of the enzyme and measured expansion when wetted with a reaction mixture, a filling degree of 52 vol % dry enzymes particles per column volume seemed appropriate. Twenty minutes was required to reach equilibrium conditions with a MAG content of 50-55 wt %. Only insignificant indications of mass transfer limitations were observed. Hence, the commercial lipase seemed adequate to use in its available particle size distribution ranging from 300 to 900 microm. A column length-to-diameter ratio of less than 25 did not interfere with the transfer of the fluid mixture through the column. Under the tested conditions, the enzyme could be active for approximately 92 days before enzyme renewal was needed. This corresponds to a very high enzyme capacity with approximately 2000 L pure MAG produced per kg enzyme.     

Production of Brassica carinata protein hydrolyzates with a high Fischer's ratio using immobilized proteases

Brassica carinata protein isolates were hydrolyzed using the digestive enzymes trypsin, chymotrypsin, and carboxypeptidase A in order to obtain hydrolyzates with a high Fischer's ratio. The proteases were immobilized using two glyoxyl-agarose supports of different porosity, 4 and 10% agarose gels, in order to evaluate the effect of substrate diffusion into the support containing the enzyme on the hydrolytic process. Reaction time, substrate concentration, and the enzyme to substrate ratio were optimized in an attempt to increase the Fischer's ratio in the resulting hydrolyzates. Gel filtration chromatography of a hydrolyzate with a degree of hydrolysis of 36% yielded a fraction that represented 31% of the total hydrolyzed proteins and had a Fischer's ratio of 28.3 with a phenylalanine + tyrosine content below 1.5%. This material could be used for preparing special diets when there is a need to increase the supply of branched amino acids and/or reduce the intake of aromatic amino acids.     

Examination of ester sulfates in Podzolic and Regosolic soils using an immobilized arylsulfatase reactor

The enzyme kinetics of an immobilized arylsulfatase reactor were examined. We found that the optimum operating conditions for the reactor were pH 7.0 and 25°C, using p-nitrophenyl sulfate in acetate buffer. The Michaelis constant (K _m) of immobilized arylsulfatase was 5.29 mM, compared with a K _m of 2.18 mM for soluble arylsulfatase from the same source (Helix pomatia). Since arylsulfatase hydrolyzes organic ester sulfate linkages, the immobilized arylsulfatase reactor was used to examine ester sulfate compounds in two soils subjected to different fertility management schemes. Soil samples were obtained from the Ap horizons of a Podzol from S-amended wheat plots and a Regosol from dykeland hayfield plots which had received additions of NH₄NO₃ and compost. The distribution of S in these soils was examined in the fall of 1993 and the spring of 1994. Soil organic matter was extracted and separated into three molecular weight fractions (<500, 500–10 000, >10 000). There was no difference in the ester sulfate content for the >10 000 fraction of control and S-amended Podzol soils; however, the S-amended samples had significantly higher quantities of hydrolysable ester sulfates than controls for the 500–10 000 range, indicating that S amendments resulted in the incorporation of ester sulfate into this lower molecular weight fraction. Both control and NH₄NO₃ treatments to the Regosol showed significantly higher quantities of hydrolysable ester sulfates in the >10 000 fraction, while compostamended plots showed no difference between the >10 000 and 500–10 000 fractions due to suspected microbial degradation of high molecular weight organic S compounds in the compost. Since there was no significant effect of sampling time, this study indicated that naturally occurring low molecular weight ester sulfate compounds accumulate in soil and persist during storage. Hydrolysable ester sulfates constituted 35–55% of the hydriodic acid-reducible S in these different soils and probably represent an important and easily mineralizable portion of total ester sulfates.     

Amino-N compounds found in soil organic matter hydrolysates of a loamy sand using an immobilized protease reactor column

Summary Soil organic matter (OM) from seven different fertility plots of a loamy sand was extracted and fractionated into high- and low-molecular-weight (HMW, LMW) fractions using gel filtration. The fractions were acid-hydrolyzed to determine the amino sugar and amino acid contents. The same fractions were hydrolyzed with an immobilized protease reactor column. Reverse-phase high-performance liquid chromatography (HPLC) was used to identify the soil amino-N compounds. With the HMW fraction as substrate, the enzyme released less than 1% of 11 amino-N compounds determined by acid hydrolysis. Phenylalanine and leucine, however, were recovered in quantities of 2% and 4%, respectively. Immobilized protease hydrolysis of the LMW fraction recovered considerably more amino-N compounds compared with acid hydrolysis of the same fractions. Each system of hydrolysis produced some amino-N compounds not found in the other. We conclude that an immobilized enzyme reactor column will allow a researcher to perform time-course hydrolysis, so that hydrolysis intermediates, e.g. peptides, can be separated and identified.     

Production of hard-type cheese using free or immobilized freeze-dried kefir cells as a starter culture

This study provides a contribution to hard-type cheese starter culture production through the use of a freeze-dried culture in the ripening of hard-type cheeses. The effect of initial cell concentration, ripening temperature, and cell immobilization of kefir on the degree of openness, mold spoilage, microbial associations, physicochemical characteristics, and aroma-related compounds was studied. Use of kefir starter cultures resulted in cheese with an increased shelf life and resistance to spoilage as compared to control cheeses without kefir inoculants. Furthermore, the freeze-dried kefir culture improved aroma, taste, and texture characteristics while increasing the degree of openness in comparison to traditional hard-type cheese products. The kefir culture resulted in an increase in counts of total aerobic bacteria, yeasts and molds, lactococci, and lactobacilli until the 15th day of ripening. From then on, only lactobacilli counts increased, reaching levels up to 9.17 log CFU/g in cheeses ripened at 5 degrees C using freeze-dried kefir cells immobilized on casein. SPME-GC/MS analysis revealed major differences in volatile composition, especially with regard to alcohols (up to 75%), carbonyl compounds (up to 75%), and esters (up to 64%) between cheeses made with kefir cells and cheeses made without kefir inoculants.     

Production of ascorbyl palmitate by surfactant-coated lipase in organic media

The surface of a lipase from Burkholderia cepacia was coated with a nonionic surfactant, propylene glycol monostearate, and was used as a biocatalyst in the production of ascorbic acid in tert-butyl alcohol. The influence of various factors such as the type of surfactant, the pH of the buffer used for coating, the amount of surfactant in the coating, the organic solvent, and the temperature and molar ratio of the substrates used in the reaction on the conversion of ascorbyl palmitate were studied. After 24 h of reaction at 50 degrees C, a conversion of 47% was obtained using an ascorbic acid to palmitic acid molar ratio of 1:6. The native lipase showed only 6% conversion.     

Structural changes imposed on whey proteins by UV irradiation in a continuous UV light reactor

The objective of this study was to investigate the structural changes of whey proteins during exposure in a continuous-flow UV reactor. Varying UV irradiation dosages were obtained by controlling the flow rate and the mixing speed. Whey protein isolate (WPI) solutions at concentrations of 1% and 5% (w/v) were circulated at flow rates ranging from 30 to 800 mL·min(-1), and changes in physicochemical properties of the proteins were investigated. Intrinsic fluorescence spectra and surface hydrophobicity measurements suggested changes in the tertiary structure of the proteins with UV exposure. The UV treatment also increased the concentration of total and accessible thiol groups in 1% WPI solutions, while no change was measured in 5% WPI solutions. Size-exclusion chromatography demonstrated the formation of UV-induced aggregates and oxidation products (N-formylkynurenine and dityrosine) of aromatic amino acids. Furthermore, the UV-induced changes in protein conformation increased the susceptibility of whey proteins to pepsin hydrolysis.     

Production of organically bound selenium yeast by continuous fermentation

This paper describes a protocol for incorporation of sodium selenite or sodium selenate into Saccharomyces cerevisiae biomass by continuous fermentation in a medium with minimal sulfur and methionine concentrations. Selenium incorporation was followed by atomic absorption analysis and methylene blue reduction time (MBRT). Continuous fermentation at 0.2 h(-1) dilution rate and sodium selenite addition gradient up to 0.69 g/L of Na(2)SeO(3) yielded 1. 89 g/L of biomass with 1904 microg of selenium/g of dry biomass. However, MBRT was 0.1 min, which indicated that the majority of selenium was in the inorganic form. On the other hand, continuous fermentation at 0.2 h(-1) dilution rate and sodium selenate gradient up to 0.28 g/L of Na(2)SeO(4) yielded 0.76 g/L of dry biomass with 687 microg of selenium/g of dry biomass, and MBRT was 26 min, which indicated a high concentration of organically bound selenium. Overall, the results indicate a Se/S ratio of 3.9:1 and a dry biomass/Se ratio of 5.5:1 as optimal for continuous production of organically bound selenium.     

Enzymatic interesterification of butterfat with rapeseed oil in a continuous packed bed reactor

Lipase-catalyzed interesterification of butterfat blended with rapeseed oil (70/30, w/w) was investigated both in batch and in continuous reactions. Six commercially available immobilized lipases were screened in batch experiments, and the lipases, Lipozyme TL IM and Lipozyme RM IM, were chosen for further studies in a continuous packed bed reactor. TL IM gave a fast reaction and had almost reached equilibrium with a residence time of 30 min, whereas RM IM required 60 min. The effect of reaction temperature was more pronounced for RM IM. TL IM showed little effect on the interesterification degree when the temperature was raised from 60 degrees C to 90 degrees C, whereas RM IM had a positive effect when the temperature was increased from 40 degrees C to 80 degrees C. Even though TL IM is an sn-1,3 specific lipase, small changes in the sn-2 position of the triacylglycerol could be seen. The tendency was toward a reduction of the saturated fatty acid C14:0 and C16:0 and an increase of the long-chain saturated and unsaturated fatty acids (C18:0 and C18:1), especially at longer residence times (90 min). In prolonged continuous operation the activity of TL IM was high for the first 5 days, whereafter it dramatically decreased over the next 10 days to an activity level of 40%. In general, the study shows no significant difference for butterfat interesterification in terms of enzyme behavior from normal vegetable oils and fats even though it contains short-chain fatty acids and cholesterol. However, the release of short-chain fatty acids from enzymatic reactions makes the sensory quality unacceptable for direct edible applications.     

Production of high hydroxytyrosol yields via tyrosol conversion by Pseudomonas aeruginosa immobilized resting cells

An immobilized whole cell system was successfully performed to produce the most powerful antioxidant, hydroxytyrosol. Bioconversion of tyrosol into hydroxytyrosol was achieved via the immobilization of Pseudomonas aeruginosa resting cells in calcium alginate beads. Immobilization was advantageous as it allows immobilized cells to tolerate a greater tyrosol concentration than free cells. The bioconversion yield reached 86% in the presence of 5 g L-1 of tyrosol when cells immobilized in alginate beads were carried out in single batches. Evaluation of kinetic parameters showed the maintenance of the same catalytic efficiency expressed as Kcat/Km for both free and immobilized cells. The use of immobilized cells in repeated batches demonstrated a notable activity stabilization since the biocatalyst reusability was extended for at least four batches with a molar yield greater than 85%.     

自搅拌厌氧折流板反应器连续处理猪场废水的效果

该研究以猪场废水为处理对象,采用自搅拌厌氧折流板反应器（self-agitation anaerobic baffled reactor,SaABR）开展200 d的连续中温厌氧消化试验,考察在水力停留时间（hydraulic retention time,HRT）3、2、1和0.5 d梯度缩短的过程中,SaABR截留微生物的效果以及反应器的产气性能、稳定性和污泥比产甲烷活性（specific methanogenic activity,SMA）。同时,该研究还开展了全混式反应器（completely stirred tank reactor,CSTR）78 d的连续对比试验。试验发现,SaABR具有良好的截留微生物的作用,在HRT 3 d时SaABR第1至第4取样口污泥挥发性固体（volatile solid,VS）浓度分别为10.2、4.1、44.2和2.5 g/L,而CSTR污泥VS质量浓度仅为2.6 g/L。较高的微生物量显著提高了有机物的降解率并降低了出水的有机酸浓度。随着HRT的缩短,SaABR的降解率也呈现下降。在HRT 1 d时,SaABR的单位VS产甲烷率为0.43 L/g,即使在HRT 缩短到0.5 d时,仍然可实现稳定的发酵产气（单位VS产甲烷率为0.24 L/g）,而CSTR反应器由于微生物洗出不能在HRT 1 d时连续产气。该研究的结果显示,SaABR反应器所具有截留微生物的良好特性,为养殖粪水的处理提供参考。     

盐度对序批式生物反应器污泥膨胀的影响

为了研究盐度对污泥膨胀的影响,采用序批式生物反应器（sequencing batch reactor,SBR）处理含盐废水,考察NaCl、NA₂SO₄和Na₃PO₄盐度变化对污泥沉降性和污染物去除效果的影响。结果表明,当NaCl和NA₂SO₄盐度由0升高至30 g/L时,污泥容积指数（sludge volume index,SVI）由135 mL/g下降至71⁷3 mL/g,总氮（total nitrigen,TN）去除率由80%下降到60%,胞外聚合物（extracellular polymeric substance,EPS）质量浓度由521⁵23 mg/L升高到896⁹17 mg/L,污泥沉降性良好;当Na₃PO₄盐度由0升高至8 g/L时,SVI由135 mL/g升高至198 mL/g,TN去除率由80%下降至60%,EPS质量浓度由549 mg/L升高到674 mg/L,发生污泥膨胀。随着NaCl和NA₂SO₄盐度的提高,污泥沉降性能提高,TN去除率下降,EPS质量浓度升高。随着Na₃PO₄盐度的提高,污泥沉降性能和TN去除率均下降,EPS质量浓度升高。然而,随着NaC（l30⁰ g/L）、NA₂SO₄（30⁰ g/L）和Na₃PO₄（8⁰ g/L）盐度的降低,SVI值分别由71 mL/g升高至298 mL/g,73 mL/g升高至291 mL/g和198 mL/g升高至241 mL/g,TN去除率分别由62%下降至43%,65%下降至44%,70%下降至35%,EPS质量浓度分别由917 mg/L升高至1 092 mg/L,896 mg/L升高至1 078 mg/L,674 mg/L升高至759 mg/L。随着NaCl、NA₂SO₄和Na₃PO₄盐度由高降低后,污泥沉降性能和TN去除率均下降,EPS质量浓度继续升高,盐度降低后发生了污泥膨胀。     

Characteristics of structured lipid prepared by lipase-catalyzed acidolysis of roasted sesame oil and caprylic acid in a bench-scale continuous packed bed reactor

Structured lipid (SL) was prepared from roasted sesame oil and caprylic acid (CA) by Rhizomucor miehei lipase-catalyzed acidolysis in a bench-scale continuous packed bed reactor. Total incorporation and acyl migration of CA in the SL were 42.5 and 3.1 mol %, respectively, and the half-life of the lipase was 19.2 days. The SL displayed different physical and chemical properties, less saturated dark brown color, lower viscosity, lower melting and crystallization temperature ranges, higher melting and crystallization enthalpies, higher smoke point, higher saponification value, and lower iodine value, in comparison to those of unmodified sesame oil. The oxidative stability of purified SL was lower than that of sesame oil. There were no differences in the contents of unsaponifiables including tocopherols and phytosterols. However, total sesame lignans content was decreased in SL due to the loss of sesamol when compared to sesame oil. Most of the 70 volatiles present in roasted sesame oil were removed from SL during short-path distillation of SL. These results indicate that the characteristics of SL are different from those of original sesame oil in several aspects except for the contents of tocopherols and phytosterols.     

利用CT数字图像和网络模型预测近饱和土壤水力学性质

在近饱和状态下,土壤的有效水力学性质主要取决于较大孔隙的结构特征,而这又决定了土壤中的优势流通道以及溶质的运移。基于孔隙形态学特征的网络模型可以很好的表现出较大孔隙的几何形态与拓扑特征对有效水力学性质的影响。本文通过对连续土壤切片CT图像的分析,定量获取了土壤孔隙的大小分布以及连通性参数。在此基础上建立了相关网络模型,在孔隙尺度上模拟了土壤中的水分运动过程并预测了近饱和土壤水力学性质。实验结果表明,虽然随机网络模型对室内填装土样本水力学性质的预测结果要优于相关网络模型,但是结合了实测孔隙形态特征的相关网络模型能够表现出田间原状土样本的双重孔隙度结构,其预测结果更符合实际的土壤结构特征。     

Efficient hydrolysis of tuna oil by a surfactant-coated lipase in a two-phase system

A surfactant-coated lipase (SCL) prepared by mixing Candida rugosa lipase with emulsifier in ethanol was used to hydrolyze tuna oil in a two-phase aqueous-organic system. Both enzyme (SCL) and substrate (tuna oil) were soluble in the organic phase, and the hydrolysis could occur with water molecules from the aqueous phase. This hydrolysis could promptly proceed compared to that catalyzed by native lipases which only occurred at the interface between the two phases. Michaelis-Menten kinetics in the two-phase reactions showed that the K(m) value of the SCL was half that of the native lipase, while the maximum velocity (V(max)) was 11.5 times higher. The hydrolysis method resulted in enrichment of n-3 polyunsaturated fatty acid (n-3 PUFA) content in glyceride mixtures from 26.4% to 49.8% and DHA from 19.1% to 38.9%. The SCL acted as an efficient hydrolytic catalyst for tuna oil.     

采用不同监测数据组合反演饱和均质石英砂水热运移参数

土壤及含水层的水力参数与热参数对于定量描述土壤水、地下水迁移规律及其伴生的热运移过程十分重要。为探讨不同监测数据类型组合对多孔介质水热参数估计的影响,该研究基于热示踪方法,开展了3种不同粒径条件下的饱和均质石英砂的热示踪试验,并结合HYDRU-2D模型对介质的饱和导水率、导热系数和纵向、横向热弥散度进行反演。参数估计时分别设置3种情景对介质水热参数进行估计：仅采用观测点温度（R1）、观测点温度+水流通量（R2）、观测点温度+水流通量+热量损失（R3）。并对R1情景设置3种不同参数反演组合,即同时对2组参数（饱和导水率和导热系数）、3组参数（饱和导水率、纵向和横向热弥散度）和4组参数（饱和导水率、导热系数、纵向和横向热弥散度）进行估计。研究结果表明：同时对介质饱和导水率、导热系数与热弥散度进行估计,有利于提高介质水热参数的估计精度;对导热系数的合理估计可减小R1情景中介质饱和导水率的估计误差。4组参数中饱和导水率是敏感性最高的参数,增加用于参数反演的水流运动和热量传递信息时,粗砂、中砂、细砂的累积流量相对误差分别减少了9.74、6.65和12.53个百分点,显著提高了介质饱和导水率的反演精度。饱和导水率的估计值随介质粒径增大而增大,而纵向热弥散度随粒径的变化则呈相反的变化规律,横向热弥散度估值基本不变。增加水流和热量传递信息还能显著提高中砂的导热系数反演精度,导热系数的估计值随着介质孔隙度增大而逐渐降低。研究可为基于不同数据类型的均质介质参数反演提供。