反凝析作用对苏里格气田上古生界气藏开发的影响

鄂尔多斯盆地苏里格气田上古生界气藏在开发中产生一定量的凝析油,含量约为10g/m~3,属于微含凝析油气藏,如果生产初期配产过大,那压力下降就会过快。在反凝析作用下,凝析油在近井地带析出形成多相流,堵塞微孔隙和吼道,导致气相渗透率降低,使得气井产量大幅下降,部分被封闭的天然气无法采出,层内凝析对储层的伤害有可能是永久性的。为此,通过对该气藏层内反凝析机理、层内凝析影响因素的分析及室内试验.再使用新建立的三维数学模型对单井进行预测,结果表明该气藏"三低"(低孔、低渗、低产)特征加剧了凝析液对储层的伤害。同时还分析了气井产能降低的根本原因.并对气井生产管理提出了建议:①在保护开采阶段,投产初期应合理配产,以低于无阻流量的1/5~1/8配产,尽可能延长露点线以上开采时间,使凝析油尽可能不在地层中析出;②在反凝析阶段,要在系统研究的基础上得出准确的相态图,要快速通过该阶段尽早进入蒸发阶段,使已经凝析出来的凝析油再次蒸发汽化,从而降低储层污染。该研究成果对苏里格气田上古生界气藏的科学开发以及进一步提高采收率具有重要意义。     

制酸熔硫系统乏汽及其凝结水回收装置的优化设计

针对大型硫黄制酸熔硫系统乏汽及其凝结水温度、压力特点,开发一种可操作的乏汽及其凝结水回收方法。介绍需要的设备和工艺流程,对回收难点提出针对性的解决方法,最大限度实现余热的回收再利用。该方法可显著提高余热回收利用量,减少原始新蒸汽的用量,降低熔硫系统生产成本,年产生经济效益900万元以上。     

羟基新戊醛合成工艺及其动力学

羟基新戊醛是合成多种精细化学品的重要中间体。以叔胺溶液为催化剂,利用正交实验法优化了甲醛异丁醛缩合制备羟基新戊醛的工艺条件,并考察了缩合反应动力学。由正交实验结果得到最佳反应条件为:催化剂的用量为3%质量分数,反应温度75℃,甲醛与异丁醛的物质的量之比为1.1:1,反应压力0.3 MPa,反应时间80 min,在此条件下产物收率可达98.33%。动力学的研究结果表明:缩合主副反应的表观活化能分别为40.801 k J/mol和64.088 k J/mol;主反应对异丁醛、甲醛反应级数分别为1和1.2,副反应对羟基新戊醛的反应级数为2。通过残差分析和统计检验,表明动力学模型是适定的。     

Dual‐bed catalyst system for the direct synthesis of high density aviation fuel with cyclopentanone from lignocellulose

In this article, we demonstrated an integrated process for the direct production of tri(cyclopentane) with cyclopentanone which can be obtained from lignocellulose. The reaction was carried out in a dual‐bed continuous flow reactor. In the first bed, cyclopentanone was selectively converted to 2,5‐dicyclopentylcyclopentanol over the Pd‐MgAl‐HT (hydrotalcite) catalyst. Under solvent‐free and mild conditions (443 K, 0.1 MPa H₂), high carbon yield (81.2%) of 2,5‐dicyclopentylcyclopentanol was achieved. Subsequently, the 2,5‐dicyclopentylcyclopentanol was further hydrodeoxygenated to tri(cyclopentane) in the second bed. Among the investigated catalysts, the Ni‐Hβ‐DP prepared by deposition‐precipitation (DP) method exhibited the highest activity for the hydrodeoxygenation step. By using Pd‐MgAl‐HT as the first bed catalyst and Ni‐Hβ‐DP as the second bed catalyst, tri(cyclopentane) was directly produced at high carbon yield (80.0%) with cyclopentanone as feedstock. This polycycloalkane has high density (0.91 kg/L) and can be used as additive to improve the density and volumetric heating value of bio‐jet fuel. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2754–2761, 2016     

Mg-MOF-74在Knoevenagel缩合反应中的催化性能研究

在溶剂热条件下,使用四水合乙酸镁和2,5-二羟基对苯二甲酸合成Mg-MOF-74,通过元素分析、扫描电子显微镜（SEM）、X衍射衍射光谱（XRD）、红外光谱（FT-IR）和热重（TG）表征方法,分析和确定其结构和性质。碱土金属中心和酚酸氧配体的结合,极大地增强了金属有机骨架化合物（MOFs）材料的碱性。为了探索Mg-MOF-74的催化活性,将其用于催化苯甲醛与氰基乙酸乙酯的Knoevenagel缩合反应,生成（E）-α-氰基肉桂酸乙酯。通过改变反应时间、溶剂类型、底物浓度、催化剂的量、搅拌速率和反应温度等条件来提高转化率。在较温和的条件下,反应的转化率达到94.5%,选择性大于99.5%。催化剂易于从溶液中分离出来,表现出良好非均相性。在5次循环实验之后,催化效果没有明显的降低。     

Friedlnder缩合反应合成C-2-β-D-葡萄糖基喹啉

采用葡萄糖和2,4-戊二酮经Knoevenagel缩合反应制备得到β-丙酮基葡萄糖,β-丙酮基葡萄糖与苯环取代的邻氨基苯甲醛经Friedlnder缩合反应,以高达90%的产率合成了4个结构新颖的葡萄糖基喹啉类化合物.目标化合物的结构均经1HNMR,13CNMR和元素分析确证。     

瑞德南特的合成研究

以4-（4’-羟基苯基）-1-乙酰哌嗪（Ⅰ）为原料,经醚化和水解合成了中间体1-（4’-甲氧乙氧苯基）哌嗪（Ⅲ）;从2-呋喃甲酸甲酯（Ⅳ）出发,经酰化、闭环和卤代反应合成了具有氮杂稠环结构中间体（Ⅶ）;最后,中间体（Ⅲ）和中间体（Ⅶ）经缩合反应合成了瑞德南特。采用FT-IR、1HNMR和ESI-MS对中间体及目标化合物进行了结构确认。采用常规合成方法,六步反应的收率分别为99.0%、95.4%、98.0%、78.9%、86.9%（以Cl计）和52.5%。为了提高反应总产率,采用超声合成对最后一步缩合反应进行了改进。结果表明,在150 W超声条件下,n（中间体2）：n（中间体5）=1.2:1,DMSO为溶剂,碳酸钠为缚酸剂,反应温度90 ℃,反应时间1.5 h,缩合反应的收率为85.4%,产率得到了大幅度提高。     

A Nanochannel Platform for Single DNA Studies: From Crowding,Protein DNA Interaction,to Sequencing of Genomic Information

The study of nanochannel-confined DNA is important from biotechnological and biophysical points of view. We produce nanochannels in elastomer with soft lithography and proton beam writing. Issues concerning DNA confined in such quasi one-dimensional channels are discussed. We describe DNA stretching via the control of channel diameter and buffer conditions and how the extension can be interpreted with theory and computer simulation. We then discuss the conformation of nano-confined DNA crowded by neutral polymers and like-charged proteins. As an example of a protein that has an affinity to DNA, the effect of heat-stable nucleoid-structuring protein, H-NS, on the folding and compaction of DNA is reviewed. Compaction of DNA by eukaryotic protamine and unpacking of pre-compacted DNA through an increase in salt concentration are discussed. We review results obtained with a novel, cross-channel device that allows the monitoring of the dynamic, conformational response of DNA after exposure to a ligand or protein and/or a change in buffer conditions in situ. As a biotechnological application, linearization of DNA by bottlebrush coating with a polypeptide copolymer is discussed. It is demonstrated that large-scale genomic organization can be sequenced using single DNA molecules on an array of elastomeric nanochannels. Overall, our results show that the effects of ligands and proteins on the conformation, folding, and condensation of DNA are not only related to classical controlling factors, such as osmotic pressure, charge, and binding, but that the interplay with confinement in a nanospace is of paramount importance.     

1-（2-呋喃基）-2-丙酮的合成

1-（2-呋喃基）-2-丙酮具有水果、辛香、焦糖样和小萝卜样的香气。以糠醛为原料,将其与硝基乙烷缩合得到2-（2-硝基-1-丙烯基）呋喃,然后用硼氢化钠还原得到2-（2-硝基-1-丙基）呋喃,最后采用Nef反应,得到1-（2-呋喃基）-2-丙酮。所有产物的结构通过IR和1H NMR进行了表征。该合成路线原料易得,操作简便,三步反应总收率可以达到54%。     

高含量哒螨灵原药合成研究

以叔丁基肼水溶液、糠氯酸为原料,在甲苯做溶剂、冰乙酸做催化剂条件下经成腙、闭环、脱溶,然后在水相结晶制得高含量2-叔丁基-4,5-二氯-3(2H)-哒嗪酮(以下简称哒嗪酮);哒嗪酮再与对叔丁基苄硫醇在甲醇做溶剂的条件下经缩合、脱甲醇、水相结晶制得高含量哒螨灵原药。反应具有操作稳定、收率高的优点,缩合反应在低温下进行,有利于提高产品质量及收率;哒螨灵在一定浓度的稀碱水溶液中结晶,其含量可达到96%以上。该方法具有产品质量高、成本低的优点,适合工业化生产。