K/MgO-Al_2O_3催化大豆油酯交换制备生物柴油动力学研究

以大豆油为原料,考察了固定床反应器内K/Mg O-Al_2O_3催化大豆油与甲醇酯交换制备生物柴油反应过程的宏观动力学。结果表明:大豆油与甲醇的固定床酯交换反应在甲醇过量时可当作单步反应处理,反应速率方程为rA=-d CA/dt=kAC0.4A,活化能E为28.081 4 k J/mol,指前因子A为5.933 6×103L/(mol·h)。采用动力学方程计算值与实验值的相对误差绝对值均在4%以内,进一步验证了动力学方程的可靠性和实用性。     

钙基固体碱催化剂用于花生油酯交换制备生物柴油

将钙基固体碱催化剂CaO和CaO/MgO用于催化花生油与甲醇酯交换制备生物柴油,考察了催化剂的制备条件,优化了CaO和CaO/MgO催化花生油酯交换反应工艺.研究表明,利用廉价碳酸钙作为原料,在800～900℃下N2气氛中煅烧制备的CaO具有比较好的催化活性;而CaO/MgO催化剂比较适宜的制备条件是用22.6%的Ca(Ac)2溶液浸渍MgO载体1次,在600℃下煅烧.CaO/MgO在空气中存放易失去活性,需在800～900℃下N2气氛活化.CaO和CaO/MgO催化剂均可使花生油与甲醇的酯交换反应在醇油摩尔比12:1、催化剂用量2%、反应温度65℃、反应时间2 h的条件下获得80%以上的酯交换转化率.与CaO相比,CaO/Mgo催化剂具有较高的抗水性和抗酸性,以及较好的重复使用性.     

K_2CO_3/Al_2O_3催化餐饮废油酯交换制备生物柴油的动力学

以餐饮废油和甲醇为原料,固体碱K2CO3/Al2O3为催化剂进行酯交换反应。考察了反应温度和反应时间对酯交换反应的影响。实验结果表明,酯交换反应速率随反应温度的升高而加快,最佳反应温度为65℃,反应时间为2 h,废油转化率最高可达95.7%。通过改变反应温度得到了酯交换反应动力学数据,即酯交换反应级数为1.94级,平均活化能为36.49 kJ/mol,指前因子为2.17×105 L/(mol·min),建立了酯交换反应动力学方程,并对动力学方程进行了验证。验证结果表明,废油转化率的计算值与实验值的相对误差均小于4%,说明所建立的反应速率方程在实验条件范围内能较好地描述该酯交换反应。该研究为固体碱催化餐饮废油与甲醇酯交换反应的动力学提供了理论基础。     

K3PO4催化酯交换制备生物柴油

研究了磷酸三钾作为固体催化剂催化米糠油酯交换反应制备生物柴油。考察了反应温度和催化剂用量对脂肪酸甲酯转化率的影响,并通过采用凝胶渗透色谱法对测定反应物中甘油三酯、甘油二酯、甘油单酯和脂肪酸甲酯的含量,对米糠油酯交换反应动力学进行了研究。由试验数据绘制出的动力学曲线表明酯交换反应为一级反应。由试验数据求出酯交换反应的反应速率常数k和酯交换反应的活化能已,结果显示反应速率常数和活化能大小依次为kTG〉kDG〉kMG和EaMG〉EaDG〉EaTG。     

微碱超/近临界法制备无甘油生物柴油动力学及其性能研究

对微碱超/近临界条件下,棕榈油与碳酸二甲酯(DMC)酯交换制备无甘油生物柴油的动力学进行了考察,并测试了无甘油生物柴油与0号柴油混合燃料的低温流动性能以及燃烧性能。结果表明:该反应在260~300℃的温度范围内呈拟一级反应,其反应活化能Ea为43.0 k J/mol,远低于常压碱催化的反应活化能79.1 k J/mol;当生物柴油的掺混比例低于5%时,其对0号柴油的冷滤点、倾点以及基本燃烧特性参数影响不大;通过低温结晶以及流变性能的测试,发现生物柴油中的饱和脂肪酸可以与石化柴油中的正构烷烃形成最低共熔物,从而延缓低温下燃料蜡晶的析出。     

高温气相色谱法分析油脂随机酯交换反应程度研究

以大豆油和极度氢化棕榈油为原料进行酯交换反应,利用高温气相色谱法分析反应前后各种三酰甘油组成的变化,研究了不同催化剂催化酯交换反应的酯交换率,从而评判催化剂催化效果。采用此方法,利用单因素试验对Lipozyme 435脂肪酶催化大豆油与极度氢化棕榈油酯交换的参数进行了研究,得到适合的反应条件为:反应温度90℃、反应时间4 h、加酶量4%(占油脂总质量)、大豆油与氢化棕榈油质量比4∶3。在此条件下反应随机酯交换率为98.3%。     

钙基负载型固体碱催化菜籽油酯交换反应动力学

菜籽油与甲醇在钙基负载型固体碱催化下进行酯交换反应生成生物柴油（脂肪酸甲酯）,用气相色谱法跟踪分析产品中脂肪酸甲酯的含量。菜籽油与甲醇酯交换反应的主要产物为十六酸甲酯、十八酸甲酯、二十酸甲酯和二十二酸甲酯,生成反应动力学研究表明,产物的生成反应可以分为3个阶段,引发阶段、增长阶段和反应后期平衡阶段。酯交换反应速率对菜籽油浓度由开始引发阶段得拟0．5级反应。逐步转变为增长阶段的拟2级反应,最终又很快转化为平衡阶段的0级反应;酯交换反应速率对甲醇浓度为0级。引发阶段十六酸甲酯、十八酸甲酯、二十酸甲酯和二十二酸甲酯生成反应活化能分别为90．80kJ／mol、86．38kJ／mol、92．02kJ／mol、98．88k1／mol。增长阶段其十六酸甲酯、十八酸甲酯、二十酸甲酯和二十二酸甲酯生成反应活化能分别为58．48kJ／mol、66．05kJ／mol、60．07kJ／mol、52．78kJ／mol。     

助溶剂法制备生物柴油的动力学研究

菜籽油和甲醇在碱催化下通过酯交换反应制备生物柴油,因油和甲醇不能完全互溶,反应速度较慢,而助溶剂的加入解决了这一问题。当催化剂KOH用量为0．15％,醇油摩尔比为27：1,助溶剂甲基叔丁基醚和油的体积比为1．6：1时,反应物能形成均相。在反应温度分别为30、40、50℃时,对助溶剂法酯交换反应进行动力学研究,结果表明反应在30min内基本达到平衡,转化率最高为99．4％。反应基本遵循1级反应,反应活化能为52．17kJ／mol。     

大豆油脚浸出油制备生物柴油及性能研究

大豆油脚浸出油与甲醇在催化剂KOH作用下通过酯交换反应制得生物柴油(BDF)。用气相色谱法跟踪研究醇油摩尔比、反应温度、反应时间及催化剂用量对产物生物柴油浓度的影响,正交实验得到大豆油脚浸出油制备生物柴油最佳工艺条件为:反应温度45℃、催化剂用量1%、醇油摩尔比6∶1、反应时间45 min,生物柴油含量为96.8%。生物柴油的主要性能指标符合0#柴油标准(GB 252-1994)。考察了大豆油脚浸出油酯交换反应的动力学,由实验数据绘制的动力学曲线呈现出酯交换反应在开始阶段为二级反应,并逐步转变为一级反应,反应后期为零级反应。由动力学实验数据求出酯交换反应的动力学参数,酯交换反应的活化能为47.71 kJ/mol,频率因子为6.01×107L/(mol.min)。     

对甲苯磺酸催化制备生物柴油的研究

本文研究了花生油与甲醇在催化剂对甲苯磺酸存在下通过单次酯交换反应制备生物柴油的最佳反应条件和两次酯交换对反应的影响.研究结果表明,催化剂用量为油脂质量的0.5%、醇油摩尔比为10∶1、反应温度为150℃、反应1.5h,单次酯交换制备生物柴油,收率可达到93.6%;总催化剂用量为0.5%(占油脂质量)、醇油摩尔比为14∶1、反应温度为150℃、反应4.0h,两次酯交换法制备生物柴油,收率可达到97.9%.     

Reliable identification of grapevine rootstock varieties using RAPD PCR on woody samples

Since grapevine ( Vitis spp .) rootstock material is being traded increasingly as disbudded woody material a lack of distinctive morphological features on such material necessitates an alternative and reliable means of identification. Methods described here were developed for rapid and efficient extraction of DNA from woody samples rich in phenolic compounds and polysaccharides, and for subsequent identification of varieties by RAPD PCR. Using these methods, and with the application of only one selected RAPD primer, we were able to differentiate sixteen rootstock varieties, including the seven varieties most commonly used in Germany. Problems commonly encountered with reproducibility of RAPD patterns were avoided by choosing primers with a dinucleotide sequence and a high G/C content that allowed a rather high annealing temperature of 45°C. Methods described here should also be useful for other horticultural crops, especially those with woody tissues rich in phenolic compounds and polysaccharides.     

An internet compendium of analytical methods and spectroscopic information for monomers and additives used in food packaging plastics

An internet website (http://cpf.jrc.it/smt/) has been produced as a means of dissemination of methods of analysis and supporting spectroscopic information on monomers and additives used for food contact materials (principally packaging). The site which is aimed primarily at assisting food control laboratories in the European Union contains analytical information on monomers, starting substances and additives used in the manufacture of plastics materials. A searchable index is provided giving PM and CAS numbers for each of 255 substances. For each substance a data sheet gives regulatory information, chemical structures, physico-chemical information and background information on the use of the substance in particular plastics, and the food packaging applications. For monomers and starting substances (155 compounds) the infra-red and mass spectra are provided, and for additives (100 compounds); additionally proton NMR are available for about 50% of the entries. Where analytical methods have been developed for determining these substances as residual amounts in plastics or as trace amounts in food simulants these methods are also on the website. All information is provided in portable document file (PDF) format which means that high quality copies can be readily printed, using freely available Adobe Acrobat Reader software. The website will in future be maintained and up-dated by the European Commission's Joint Research Centre (JRC) as new substances are authorized for use by the European Commission (DG-ENTR formerly DGIII). Where analytical laboratories (food control or other) require reference substances these can be obtained free-ofcharge from a reference collection housed at the JRC and maintained in conjunction with this website compendium.     

Chlorohydrins of bisphenol A diglycidyl ether (BADGE) and of bisphenol F diglycidyl ether (BFDGE) in canned foods and ready-to-drink coffees from the Japanese market

BADGE.2HCl and BFDGE.2HCl were determined in 28 samples of ready-to-drink canned coffee and 18 samples of canned vegetables (10 corn, 5 tomatoes and 3 others), all from the Japanese market. HPLC was used as the principal analytical method and GCMS for confirmation of relevant LC fractions. BADGE.2HCl was found to be present in one canned coffee and five samples of corn, BFDGE.2HCl in four samples of canned tomatoes and in one canned corn. No sample was found which exceeded the 1mg/kg limit of the EU for the BADGE chlorohydrins. However the highest concentration was found for the sum of BFDGE.2HCl and BFDGE.HCl.H₂O at a level of 1.5mg/kg. A Beilstein test confirmed that all cans containing foods contaminated with BADGE.2HCl or BFDGE.2HCl had at lest one part coated with a PVC organosol.     

European priorities for research to support legislation in the area of food contact materials and articles

A strong science base is required to underpin the planning and decision-making process involved in determining future European community legislation on materials and articles in contact with food. Significant progress has been made in the past 5 years in European funded work in this area, with many developments contributing to a much better understanding of the migration process, and better and simpler approaches to food control. In this paper this progress is reviewed against previously identified work-areas (identified in 1994) and conclusions are reached about future requirements for R&D to support legislation on food contact materials and articles over the next 5 or so years.     

Aroma characterization of various apricot varieties using headspace–solid phase microextraction combined with gas chromatography–mass spectrometry and gas chromatography–olfactometry

The characterization of the aromatic profile of several apricot cultivars with molecular tracers in order to obtain objective data concerning the aromatic quality of this fruit was undertaken using headspace–solid phase microextraction (HS–SPME). Six apricot cultivars were selected according to their organoleptic characteristics: Iranien, Orangered, Goldrich, Hargrand, Rouge du Roussillon and A4025. The aromatic intensity of these varieties measured by HS–SPME–Olfactometry were defined and classified according to the presence and the intensity of grassy, fruity and apricot like notes. In the six varieties, 23 common volatile compounds were identified by HS–SPME–GC–MS. Finally, 10 compounds, ethyl acetate, hexyl acetate, limonene, β-cyclocitral, γ-decalactone, 6-methyl-5-hepten-2-one, linalool, β-ionone, menthone and (E)-hexen-2-al were recognized by HS–SPME–GC–O as responsible of the aromatic notes involved in apricot aroma and considered as molecular tracers of apricot aromatic quality which could be utilized to discriminate apricot varieties.     

Textural Properties of Cold-set Gels Induced from Heat-denatured Whey Protein Isolates

A 9% whey protein (WP) isolate solution at pH 7.0 was heat-denatured at 80°C for 30 min. Size-exclusion HPLC showed that native WP formed soluble aggregates after heat-treatment. Additions of CaCl2 (10–40 mM), NaCl (50–400 mM) or glucono-delta-lactone (GDL, 0.4–2.0%, w/v) or hydrolysis by a protease from Bacillus licheniformis caused gelation of the denatured solution at 45°C. Textural parameters, hardness, adhesiveness, and cohesiveness of the gels so formed changed markedly with concentration of added salts or pH by added GDL. Maximum gel hardness occurred at 200 mM NaCl or pH 4.7. Increasing CaCl2 concentration continuously increased gel hardness. Generally, GDL-induced gels were harder than salt-induced gels, and much harder than the protease-induced gel.     

Tests of potential functional barriers for laminated multilayer food packages. Part I: Low molecular weight permeants

The advent of the functional barrier concept in food packaging has brought with it a requirement for fast tests of permeation through potential barrier materials. In such tests it would be convenient for both foodstuffs and materials below the functional barrier (sub-barrier materials) to be represented by standard simulants. By means of inverse gas chromatography, liquid paraffin spiked with appropriate permeants was considered as a potential simulant of sub-barrier materials based on polypropylene (PP) or similar polyolefins. Experiments were performed to characterize the kinetics of the permeation of low molecular weight model permeants (octene, toluene and isopropanol) from liquid paraffin, through a surrogate potential functional barrier (25 μm-thick oriented PP) into the food simulants olive oil and 3% (w/v) acetic acid. These permeation results were interpreted in terms of three permeation kinetic models regarding the solubility of a particular model permeant in the post-barrier medium (i.e. the food simulant). The results obtained justify the development and evaluation of liquid sub-barrier simulants that would allow flexible yet rigorous testing of new laminated multilayer packaging materials.     

Occurrence of bisphenol-F-diglycidyl ether (BFDGE) in fish canned in oil

The levels of bisphenol-F-diglycidyl ether (BFDGE) were quantified as part of a European survey on the migration of residues of epoxy resins into oil from canned fish. The contents of BFDGE in cans, lids and fish collected from all 15 Member States of the European Union and Switzerland were analysed in 382 samples. Cans and lids were separately extracted with acetonitrile. The extraction from fish was carried out with hexane followed by re-extraction with acetonitrile. The analysis was performed by reverse phase HPL C with fluorescence detection. BFDGE could be detected in 12% of the fish, 24% of the cans and 18% of the lids. Only 3% of the fish contained BFDGE in concentrations considerably above 1mg/kg. In addition to the presented data, a comparison was made with the levels of BADGE (bisphenol-A-diglycidyl ether)analysed in the same products in the context of a previous study.     

Contribution of European research to risk analysis

The European Commission's, Quality of Life Research Programme, Key Action 1—Health, Food & Nutrition is mission-oriented and aims, amongst other things, at providing a healthy, safe and high-quality food supply leading to reinforced consumer confidence in the safety of European food. Its objectives also include the enhancing of the competitiveness of the European food supply. Key Action 1 is currently supporting a number of different types of European collaborative projects in the area of risk analysis. The objectives of these projects range from the development and validation of prevention strategies including the reduction of consumers risks; development and validation of new modelling approaches; harmonization of risk assessment principles, methodologies, and terminology; standardization of methods and systems used for the safety evaluation of transgenic food; providing of tools for the evaluation of human viral contamination of shellfish and quality control; new methodologies for assessing the potential of unintended effects of genetically modified (genetically modified) foods; development of a risk assessment model for Cryptosporidium parvum related to the food and water industries; to the development of a communication platform for genetically modified organism, producers, retailers, regulatory authorities and consumer groups to improve safety assessment procedures, risk management strategies and risk communication; development and validation of new methods for safety testing of transgenic food; evaluation of the safety and efficacy of iron supplementation in pregnant women; evaluation of the potential cancer-preventing activity of pro- and pre-biotic ('synbiotic') combinations in human volunteers. An overview of these projects is presented here.