3，9-双（1，1-二甲基-2-羟基乙基）-2，4，8，10-四氧杂螺环[5，5]十-烷的合成

以2-甲基-2-羟甲基丙醛、季戊四醇为原料，盐酸作催化剂，通过羟醛缩合和环化脱水反应，合成了3，9-双（1，1-二甲基-2-羟基乙基）-2，4，8，10-四氧杂螺环[5，5]十-烷。通过正交试验和单因素试验，确定反应的较佳条件为：n（2-甲基-2-羟甲基丙醛）：n（季戊四醇）：n（HCl）=2．3：1：0．06，反应温度60℃，反应时间12h。在上述条件下，产物收率为94．0％，纯度可达99．0％。采用红外光谱和核磁共振等技术对产物结构进行了表征。     

Synthesis of unsaturated fulfides from 1,1-bis(methylthiomethyl)propan-2-one

4-Hydroxymethyl-2-methyl-2-(1-methylthiomethyl)vinyl-1,3-dioxolane, 2-methyl-2-(1-methylthiomethyl)vinyl-1,3-dioxolane, and 3-methylthiomethyl-3-buten-2-one were synthesized from bis(methylthiomethyl)propan-2-one, including ketolization, and thiol elimination steps followed by acid hydrolysis. The synthesized compounds are of interest as biocides and intermediate products in organic synthesis.     

Dienes from the C5 pyrolyzate fraction in thermal and catalytic [4 + 2]-cycloaddition reactions

Different functional alicyclic derivatives of cyclohexene and bicyclo[2.2.1]hept-5-ene have been synthesized from 1,3-dienes of the C₅ pyrolyzate fraction. The adducts obtained have been tested as antimicrobial drugs.     

Enhanced Oil Recovery: The Synthesis of Anthraquinone [1, 2-C] Alkylisoxazole

Abstract

Anthraquinone [1, 2-C] methylisoxazole is synthesized from 2-ethylanthraquinone through nitration and treating with oleum. The different methods of 2-ethylanthraquinone nitrated were discussed. The optimum conditions were determined. The structure of the product was confirmed by MS and ¹H NMR.     

Enhanced Oil Recovery: The Synthesis of Anthraquinone [1, 2-C] Alkylisoxazole

Anthraquinone [1, 2-C] methylisoxazole is synthesized from 2-ethylanthraquinone through nitration and treating with oleum. The different methods of 2-ethylanthraquinone nitrated were discussed. The optimum conditions were determined. The structure of the product was confirmed by MS and ¹H NMR.     

ZrO_2在二甲醚合成催化剂CuO-ZnO-ZrO_2/HZSM-5中的作用

采用并流共沉淀法制备了一系列不同ZrO2含量的CuO-ZnO-ZrO2甲醇合成催化剂,与HZSM-5分子筛机械混合制备了一步法合成二甲醚的双功能催化剂CuO-ZnO-ZrO2/HZSM-5,在固定床反应器中进行合成气直接制二甲醚的研究,考察了ZrO2在催化剂中的作用。结果表明,ZrO2的加入能显著提高催化剂性能,当ZrO2含量达到x(ZrO2)=0.06时,催化剂的活性、选择性较高并且耐热性能较强。而过量的ZrO2会降低催化剂的耐热性能。利用TPR?XRD对催化剂进行了表征,发现适量ZrO2的加入不仅有助于提高Cu活性组分在催化剂表面的分散,使催化剂不容易高温烧结,而且有利于促进催化剂还原。     

CO_2加氢合成C_1~C_5醇反应体系热力学分析

对CO2加氢合成C1~C5醇反应体系进行了热力学分析。反应体系中各独立反应的吉布斯自由能变化分析表明,较低的反应温度对C1~C5醇的生成有利。采用最小G值法计算得到不同温度、压力、进料氢与CO2摩尔比下体系的平衡组成、醇的平衡收率及CO2和H2的平衡转化率,并讨论了反应条件对反应的影响。此热力学分析可以为评价C1~C5醇合成催化剂的催化效果以及确定CO2加氢合成C1~C5醇的工艺条件提供重要依据。     

Synthesis of 2,3-(bicyclo[2.2.1]hept-5-ene)dimethanol dialkanoates and their investigation as lubricating oils

A series of esters of 2,3-(bicyclo[2.2.1]hept-5-ene)dimethanol and C₄–C₉ aliphatic monocarboxylic acids were synthesized. The physicochemical, viscosity-temperature, thermo-oxidative, and lubricating properties of these compounds were determined, and a correlation between the chemical structure and the performance characteristics of the compounds was established.     

甲醇与C_(2~5)醇合成醚的热力学分析

为了降低石油的依赖性和提高甲醇燃料油品的适应性,提出了以甲醇为主要原料的醚类的合成路线。采用UNIFAC模型对甲醇与C2~5醇合成醚的反应体系进行热力学分析,得到了273~423 K内的反应摩尔焓变、摩尔Gibbs自由能变以及平衡常数与温度的关系。考察了温度和原料n(甲醇)∶n(C2~5醇)对反应过程的影响。计算结果表明,醚类合成反应的最佳温度范围为333~363 K,原料n(甲醇)∶n(C2~5醇)的适宜范围为(1~3)∶1。在此条件下,甲醇与C2~5醇的转化率均大于95%,合成甲基乙基醚的收率最高。     

Keggin型杂多酸催化合成1-乙酰胺基苯甲基-2-萘酚

以2-萘酚、苯甲醛和乙酰胺为原料、Keggin型杂多酸及磷钨酸盐为催化剂,采用无溶剂一步法经多组分缩合反应合成了1-乙酰胺基苯甲基-2-萘酚(AAN);比较了一系列Keggin型杂多酸及磷钨酸盐的催化效果。实验结果表明,磷钨酸的催化活性最高。同时考察了在磷钨酸催化剂作用下,催化剂用量、反应温度、原料配比和反应时间对AAN收率的影响,确定了适宜的反应条件:磷钨酸用量为反应物总质量的8.0%、n(苯甲醛)∶n(乙酰胺)∶n(2-萘酚)=1.15∶1.00∶1.00、反应温度120℃、反应时间40min;在此条件下,AAN的收率达到100.0%。该工艺具有催化剂用量较少、AAN收率高、反应速率快、后处理简单及产物色泽好等优点。     

合成酚类抗氧剂1010的新工艺Ⅱ．四－［3－（3，5－二叔丁基－4－羟基苯基）丙酸］季戊四醇酯的合成

在１５升的不锈钢反应釜中，以２，６－二叔丁基苯酚、丙烯酸甲酯为原料，在叔丁酸钾催化剂存在下，对一步法合成四－［３－（３，５－二叔了基－４－羟基苯基）丙酸］季成四醇酯（抗氧剂１０１０）的酯交换反应工艺进行了研究，优化了反应条件。结果表明，在较佳的条件下，反应的选择性及收率分别达９２％、８３％。反应产物经结晶等后处理，抗氧剂１０１０产品质量及其应用效果与国外同类产品相当。     

甲醇乙醇催化合成异丁醛的宏观动力学研究

在固定床微型反应器中测定了甲醇乙醇一步催化合成异丁醛的宏观动力学，实验反应温度为200℃～300℃，原料甲醇与乙醇摩尔比为3：1，体积空速为4h^-1，常压，实验采用自制V2O5催化剂。体系的宏观反应速率方程式为：（-rA）=0．385e-16650/8.314T，反应体系的活化能Ea=16．65kJ／mol，指前因子k0=0．385s^-1。     

Synthesis and studies of some metal-containing derivatives of [2-Hydroxy-3,5-di-(1-phenylethyl)phenyl]methylaminodiacetic acid

[2-Hydroxy-3,5-di-(1-phenylethyl)phenyl]methylaminodiacetic acid and its complexes with transition metals, Cu(II), Co(II), and Ni(II), were synthesized and studied. Protonated (MeHL) and deprotonated (MeL) complexes were prepared. It was found that of copper(II), cobalt(II), and nickel(II), [2-hydroxy-3,5-di-(1-phenylethyl)phenyl]methylaminodiacetates are effective as antiwear and antiscore agents.     

N,N’-双[3-(3’,5’-二叔丁基-4’-羟基苯基)丙酰]六甲撑二胺的合成

以 3 (3’ ,5’ 二叔丁基 4 羟基苯基 )丙酸甲酯 (简称 3,5 甲酯 )与己二胺为原料 ,有机锡为催化剂 ,二甲苯为溶剂合成了N ,N’ 双 [3 (3’ ,5’ 二叔丁基 4’ 羟基苯基 )丙酰 ]六甲撑二胺。通过实验考察了反应温度、催化剂及催化剂用量、反应时间及物料配比等因素对反应的影响。结果表明 ,最佳的反应条件是 :反应温度 135～ 14 5℃ ,催化剂为有机锡 ,催化剂用量0 6 0 g ,反应时间 3 5h ,3,5 甲酯与己二胺摩尔比 2 10∶1。在此条件下 ,收率在 97%以上 ,放大到 10 0 0ml,收率在 99%以上 ,产品熔点为 16 1～ 16 2℃ ,产品纯度较高 ,通过元素分析、红外光谱分析、核磁氢谱对产品进行了结构表征     

焙烧态类水滑石/HZSM-5双功能催化剂的制备及催化CO_2加氢合成二甲醚

采用并流共沉淀法制备了不同Zr O2含量的Cu O-Zn O-Al2O3-Zr O2类水滑石前体,焙烧后与HZSM-5分子筛物理混合得到Cu O-Zn O-Al2O3-Zr O2/HZSM-5双功能催化剂,采用XRD、N2物理吸附、H2-TPR等技术对催化剂的物相、结构特征及还原性进行了表征,考察了催化剂对CO2加氢直接合成二甲醚(DME)反应的催化性能。实验结果表明,所有前体试样均具有结晶相为Cu3Zn3Al2(OH)16·4H2O的水滑石结构,Zr O2的加入改善了催化剂的还原性和活性,DME合成速率主要取决于甲醇的合成速率。在533 K、3.0 MPa、n(H2)∶n(CO2)=3∶1、GHSV=2 400 h-1的反应条件下,当n(Zr O2)∶n(Al2O3+Zr O2)=0.10时,催化剂的反应性能最佳,CO2转化率达25.87%,DME选择性达48.15%;反应30 h后,催化剂仍表现出较高的活性及稳定性。     

Fe修饰V_2O_5催化剂催化甲醇与乙醇一步合成异丁醛

<正>异丁醛主要来源于丙烯与合成气羰基化反应制正丁醛的副产物,产量很少,难以满足日益增长的需求,严重限制了异丁醛相关产业的发展[1]。甲醇与乙醇在催化剂作用下可一步合成异丁醛,这是一条以储量丰富的煤炭、天然气和可再生的生物质资源为源头的合成路线,该路线不仅克服了对石油资源的依赖,而且对进一步推动甲醇、乙醇产业的     

Preparation and Properties of 2,4,8,10-Tetranitro-5H-Pyrido[3′,2′:4,5][1,2,3] Triazolo[1,2–a]Benzotriazol-6-ium Inner Salt as a Thermally Stable High Explosive

The synthesis and explosive properties of 2,4,8,10-tetranitro-5H-pyrido[3′, 2′:4, 5] [1,2,3] triazolo [1,2-a] benzotriazol-6-ium inner salt (7) are given. This material is a very thermally stable high explosive that has a differential scanning calorimetry (DSC) onset of 365°C with fast decomposition occurring at 375°C. The material is readily prepared in three steps from inexpensive starting materials. The final compound is insensitive to initiation by spark and friction and has a drop height of 59 cm (Type 12, 2.5 kg weight, HMX = 23 cm). In addition, it has a failure diameter of less than 3 mm. A detonation velocity of 7.43 km/s and detonation pressure of 294 kbar were determined on 0.5 inch pellets at a density of 1.78 g/cm³.     

甲醇乙醇催化合成异丁醛催化剂V2O5的失活研究

研究了在V2O5催化剂上,在常压、反应温度375℃,原料甲醇与乙醇摩尔比为3:1,体积空速为2 h-1条件下一步催化合成异丁醛.考察了催化剂的稳定性和催化剂失活的原因.实验结果表明,反应至330 min后催化荆活性几乎不再变化,此时乙醇转化率在70%左右,而异丁醛的选择性仅为10%左右,催化剂几乎不再具有活性.表征测试结果表明,催化剂失活的原因是:反应过程中结焦;V2O5,在反应过程中被还原为V2O3;V2O5在反应过程结构的变化导致酸量的增加.催化剂失活为可逆失活,高温烧炭再生能使失活催化剂恢复其催化活性.     

Removal of basic nitrogen compounds from fuel oil with [C4mim]Br/ZnCl2 ionic liquid

Metal-based ionic liquid [C₄mim]Br/ZnCl₂ was synthesized, and its structure was characterized using FTIR spectroscopy and a mass spectrometer. The denitrogenation performance of the ionic liquid was investigated using coker diesel oil as feedstock. Experiment results showed that [C₄mim]Br/ZnCl₂ presented a good denitrogenation performance, obtaining about 94.95% basic N-removal efficiency under the condition with a temperature of 50°C, 1:1 (w/w) IL:oil, extraction time of 30 min. In addition, the basic N-removal efficiency can still reach above 50% at 1:7 IL/oil (w/w) during four recycles of the ionic liquid.