FT合成沉淀Fe／Cu／K催化剂有效因子的计算：I.工业颗粒催化剂有…

用包括水抑制作用的动力学方程，根据建立的反应扩散模型和ＦＴ合成化学计量关系，计算了工业原颗粒ＦＴ合成沉淀Ｆｅ／Ｃｕ／Ｋ催化剂在工业操作条件下的有效因子。根据不同的产物组成，建立了三种化学计量关系式，比较了气相反应和气液反应的有效因子，确立了ＦＴ合成沉淀Ｆｅ／Ｃｕ／Ｋ催化剂有效因子的计算方法。在ＦＴ合成反应条件下，产物蜡充满了催化剂的微孔，各组分在蜡中的扩散系数要比纯气相中的扩散系数小得多。在工况操     

FT合成沉淀Fe／Cu／K催化剂有效因子的计算Ⅰ．工业颗粒催化剂有效因子的计算

用包括水抑制作用的动力学方程，根据建立的反应扩散模型和ＦＴ合成化学计量关系，计算了工业原颗粒ＦＴ合成沉淀Ｆｅ／Ｃｕ／Ｋ催化剂在工业操作条件下的有效因子。根据不同的产物组成，建立了三种化学计量关系式，比较了气相反应和气液反应的有效因子，确立了ＦＴ合成沉淀Ｆｅ／Ｃｕ／Ｋ催化剂有效因子的计算方法。在ＦＴ合成反应条件下，产物蜡充满了催化剂的微孔，各组分在蜡中的扩散系数要比纯气相中的扩散系数小得多。在工况操作条件下（５２３Ｋ，２．５ＭＰａ，５００ｈ￣（－１），尾气循环比３．０），工业原颗粒（ｄ＿ｐ＝２．５ｍｍ，ｌ＿ｐ＝５～１０ｍｍ）催化剂的实际有效因子是纯气相反应的一半左右，计算的平均有效因子分别为０．４０和０．４２。     

焙烧温度对合成低碳醇用Cu/Mn/Ni/ZrO2催化剂性能的影响

 研究了焙烧温度对合成低碳醇用Cu／Mn／Ni／ZrO2催化剂结构及催化性能的影响．随着焙烧温度的升高，催化剂的催化活性和产物分布都发生较大的变化．催化剂在较低的温度下焙烧，低温下反应液相产物的分布符合S－F方程；反应温度升高时，液相产物中主要是甲醇和异丁醇；在高温下焙烧的催化剂，其催化活性较低，但即使在较低的反应温度下，异丁醇在液相高级醇（C2＋OH）中也是主要的产物．结合其他的一些反应结果与XRD，BET，TPR及EXAFS等表征结果，认为焙烧温度使催化剂的结构发生了较大的变化，进而影响催化剂各组分之间的相互作用，从而使催化剂对合成低碳醇反应表现出不同的催化性能．     

STUDY OF Cu-Mu CATALYST FOR THE SYNTHESIS OF METHYL FORMATE AND METHANOL FROM SYNTHESIS GAS

将一种新型的ＣｕＭｎ催化剂用于由合成气合成甲酸甲酯和甲醇，该催化剂表现出良好的反应活性和甲酸甲酯选择性。考察了反应温度、合成气压力及催化剂制备方法等对合成甲酸甲酯和甲醇的反应活性及选择性的影响。在反应条件下，产物收率最高达６０．１０ｇ／（Ｌ·ｈ），产物甲酸甲酯的选择性很高。用ＢＥＴ、ＸＲＤ及ＸＰＳＡｕｇｅｒ等测试方法对催化剂的比表面、晶相组成以及铜、锰在催化剂中的价态进行了表征，并探讨了催化剂失活的原因。     

复合床合成低碳醇的研究

采用了三种不同的合成醇催化剂分别作为第一段催化床层,以ＺｎＯ／Ｃｒ２Ｏ３催化剂作为第二段催化床层,研究了复合催化剂床对合成低碳醇反应行为的影响。结果表明,采用复合床层技术可以提高反应产物中低碳醇的选择性,但是烃类的转化率增加,液收减小。同时发现,第一段催化床层的反应产物分布与第二段催化床层的反应条件直接影响最终的反应结果。第一段催化剂床层中ＣＯ的转化率或甲醇的选择性过高都不利于提高反应产物中低碳醇的选择性     

尿素水解均匀沉淀法制Cu/ZnO/Al2O3甲醇合成催化剂

甲醇是富氯液体，可通过水蒸气重整制氢用于燃料电池的氢源，是最有希望成为燃料电池电动汽车的燃料，目前这方面的研究颇受重视。现代甲醇工业是通过合成气在催化剂作用下反应制得的，所用催化剂主要为Cu／ZnO／Al2O3。为了进一步提高催化剂的性能，近年来关于催化剂制备方法的文献发表较多。吴晓晖等考察了草酸盐胶体法制备Cu／ZnO／Al2O3甲醇合成催化剂的性能，洪中山等用凝胶网格共沉淀法制得Cu／ZnO／Al2O3甲醇合成催化剂，郭宪吉等则考察了添加Mn助剂对Cu／ZnO／Al2O3甲醇合成催化剂的影响。     

α－蒎烯选择性二聚合及低聚反应研究 Ⅰ．不同催化剂体系的聚合行为和产物构成

从聚合动力学、异构化和产物构成等方面检讨了质子酸、Ｌｅｗｉｓ酸和质子酸／Ｌｅｗｉｓ酸复合酸三类，多种催化剂和各种反应条件对α－蒎烯的二聚合及低聚反应的影响，结果表明，活性种为质子Ｈ＾＋的这三类催化剂主要生成二、三、四聚体产物，发现质子酸与Ｌｅｉｗｓ酸组成的复合催化剂比单独时聚合活性大幅度提高，异构化作用显著减少，可以高选择性地合成二聚体，如复合催化剂ＡｌＣｌ３／ＣＦ３ＣＯＯＨ异构化率仅０．５％；聚     

工业固定床Fe-Cu-K催化剂浆态床F-T合成适应性研究

采用连续搅拌釜式反应器,在接近F-T合成实际工况下考察了工业固定床Fe-Cu-K催化剂浆态床F-T合成反应性能,研究反应温度、压力、原料气空速和氢碳摩尔比等操作参数对催化剂反应活性、产物选择性和稳定性的影响,实验总运转时间达2 500 h;同时采用扫描电镜技术（SEM）对催化剂的抗磨损性能进行了研究,结果表明,操作参数对催化剂的活性、选择性和目标产物产率有较大的影响,工业固定床Fe-Cu-K催化剂具有一定的抗磨损性能,F-T合成烃产物分布合理;催化剂具有较高的稳定性,在589 h的稳定条件运行内,催化剂的失活速率为0.23%/d（以CO转化率的降低计）;在整个运行期间CH4选择性维持在较低的水平。     

浆态反应器中铁／活性炭催化剂上还原研究

众所周知，费托合成（Fischer-Tropsch synthesis,FTS)反应是一个有理论与应用价值的研究课题。数十年来，学者们已发现了铁系，钴系和钌系等具有优良FTS反应性能的催化剂体系，铁／活性炭（Fe/Activated Carbon,AC)催化剂是中国科学院大连化学物理研究所八十年代末开发的一类费托合成催化剂，由于活性炭载体发达的孔结构使得该催化剂上FTS反应产物中汽油，柴油选择性高（烃类碳数小于20）和油收率大（C5^ ,112g/m^3 sysgaa)^[1,2]，具有工业放大前景。本文采用1L浆态床反应器，应用不同的还原方法（原位高压还原和反应器外还原）和XRD物相表征手段，了铁／活性炭催化剂在浆态床中的还原与反应问题，得到了一些有用的信息。     

Co-CeO2/SiO2催化剂上的费-托反应性能

 考察了反应条件对Co－CeO2／SiO2催化剂上费－托合成反应性能的影响，并对催化剂进行了1000h稳定性和再生性能实验．结果表明，添加铈助剂后，催化剂具有良好的稳定性和再生性能，整个过程中CO转化率为89．7％，C5＋烃类（主要组成为C10～C20直链烃）选择性为81．0％，链增长几率为0．90．催化剂的活性表面被反应产物蜡覆盖时，阻碍了反应物与活性中心的结合，是导致催化剂活性降低的主要原因．     

α-松油烯-马来酸酐加成物的气相色谱分析

气相色谱法直接测定α－松油佛－马来酸酐加成物，不但免去了容量滴定法测定时必先分离共存马来酸酐的繁琐手续，而且方法简便、快速，能满足合成过程中跟踪分析的需要。     

An investigation of the adduct of poly(vinyl furfural acetal) and maleic anhydride by IR spectroscopy

The IR spectra of films of PVA subjected to acetalation with furfural and to coupling with maleic anhydride by the diene synthesis have been obtained, and an assignment of absorption bands is given. The alkali treatment of the adduct of poly(vinyl furfural acetal) with maleic anhydride is apparently accompanied by the epimerization of one carboxyl group.     

Low dielectric thermoset. II. Synthesis and properties of novel 2,6‐dimethyl phenol–dipentene epoxy

A 2,6‐dimethyl phenol–dipentene adduct was synthesized from dipentene (DP) and 2,6‐dimethyl phenol, and then a 2,6‐dimethyl phenol–DP epoxy was synthesized from the reaction of the resultant 2,6‐dimethyl phenol–DP adduct and epichlorohydrin. The proposed structures were confirmed by Fourier transform infrared, elemental analysis, mass spectra, NMR spectra, and epoxy equivalent weight titration. The synthesized 2,6‐dimethyl phenol–DP adduct was cured with 4,4‐diamino diphenyl methane, phenol novolac, 4,4‐diamino diphenyl sulfone, and 4,4‐diamino diphenyl ether. The thermal properties of the cured epoxy resins were studied with differential scanning calorimetry, dynamic mechanical analysis, dielectric analysis, and thermogravimetric analysis. These data were compared with those for the bisphenol A epoxy system. The cured 2,6‐dimethyl phenol–DP epoxy exhibited a lower dielectric constant (ca. 3.1), a lower dissipation factor (ca. 0.065), a lower modulus, lower thermal stability (5% degradation temperature = 366–424 °C), and lower moisture absorption (1.21–2.18%) than the bisphenol A system but a higher glass‐transition temperature (ca. 173–222 °C) than that of bisphenol A system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4084–4097, 2002     

Donor-Acceptor Complexes in Copolymerization. XXXVII. Alternating Diene-Dienophile Copolymers. 5. Formation of Conjugated Diene-Maleic Anhydride Copolymers through Retrograde Dissociation of Furan-Maleic Anhydride Diels-Alder Adduct

Abstract

The equimolar, alternating copolymer of isoprene, as well as other conjugated dienes, and maleic anhydride is formed by the radical catalyzed reaction of the conjugated diene with maleic anhydride in the presence of furan as well as with the furan-maleic anhydride Diels-Alder adduct. The retrograde dissociation of the cyclic adduct above 60°C regenerates furan and maleic anhydride which in the presence of isoprene forms the isoprene-maleic anhydride ground state complex. The latter yields the corresponding cyclic adduct in the absence of a radical catalyst and undergoes excitation and homopolymerization in the presence of a catalyst.     

A stereoselective total synthesis of nat (−) prostaglandin E1 and its optical antipode

A stereoselective total synthesis of nat (?) prostaglandin E₁ and its optical antipode employing the Diels-Alder adduct oftrans-piperylene and maleic anhydride as starting material is described.     

Synthesis and characterization of a novel non-linear optical (NLO) material

Anthracene is one of the organic molecular crystals, which exhibits peculiar optical and electronic properties. Since the 9, 10 positions are very reactive in anthracene, it undergoes the Diel’s–Alder reaction with maleic anhydride in 99% yield. The synthesis of Diel’s–Alder adduct has been carried out by adopting standard procedure. The product was subjected to various characterization studies such as FTIR, UV and ¹H NMR spectroscopy, and thermal studies to check its purity and determine the applicability of adduct in various applications. The second harmonic generation (SHG) efficiency of the adduct has been observed using Nd:YAG laser.     

Convergent total synthesis of the racemic HIF-1 inhibitor laurenditerpenol

The convergent total synthesis of the HIF-1 inhibitor laurenditerpenol 1a is reported. The key step is the Julia olefination-reduction process between the two components, the sulfone 4 (prepared from the dimethylfuran-maleic anhydride Diels-Alder adduct) and the aldehyde 3 (prepared from 3-methylcyclohexenone).     

Le dimethyl-1,1 germole

The first synthesis of an unsubstituted germole is described. Catalytic vacuum-flow dehydration (Al₂O₃, 300°C, 0.01 mmHg) of 1,1-dimethyl-1-germacyclopent-4-ene-3-ol gives monomeric 1,1-dimethylgermole, which is characterized by its PMR spectrum at room temperature and by its Diels—Alder adduct with maleic anhydride.     

Donor–acceptor complexes in copolymerization. LVIII. Alternating diene–dienophile copolymers. 12. Structure of furan–maleic anhydride copolymers prepared from the monomers and the diels-Alder adduct

The copolymerization of furan with maleic anhydride in the presence of a perester or azobisiso-butyronitrile at 50 or 70°C yields an unsaturated equimolar, alternating copolymer in which the furan units have 3,4 unsaturation and 2,5 linkages. The furan–maleic anhydride Diels-Alder adduct undergoes retrograde dissociation in solution at 70°C and, in the presence of radical catalysts, yields the same unsaturated alternating copolymer as is obtained from the monomers. The adduct undergoes homopolymerization in the presence of a rapidly decomposing perester at 50°C to yield a saturated polymer having a rearranged structure containing 3-oxabicyclo[2.2.1]heptane-5,6-dicarboxylic anhydride repeating units with 2,7 linkages.     

Isomeric maleic anhydride adducts of phthalazine and pyridazine and their partial stereochemistry

The addition of maleic anhydride to phthalazine is confirmed to form a five-membered pyrrolidino ring fusion to phthalazine VI, rather than a pyridophthalazine II, by means of synthetic and degradative experiments, and proton and carbon-13 nmr. Two of probable three isomers obtained have been isolated and the stereochemistry partially established. Comparison of the data obtained for this adduct with the data obtained for the adduct of maleic anhydride with pyridazine demonstrates that it too possesses the pyrrolidino ring fusion. Electron impact fragmentations of the two adducts are compared and are related to the breakdown of 1H,2H-pyridazinone.