三吡啶胺和四齿链酚胺配体与Cu(Ⅱ)配位性质及其配合物催化酯水解研究

运用 ｐＨ电位滴定法,在 ２５±０．１℃　Ｔ, Ｉ＝０．１（ＫＮＯ_３）条件下,研究了 Ｃｕ（Ⅱ）与三吡啶胺（Ｌ’）和队（２’－羟基苄基）－二乙二胺（ＨＬ~２）的配位行为。结果表明,Ｌ’以二齿的形式和 Ｃｕ（Ⅱ）形成稳定的 ２：１（Ｌ： Ｍ）配合物。其配位水分子的离解常数 ｐ Ｋａ为 ７．５４。对于 ＨＬ~２,三个氮原子和酚氧负离子与 Ｃｕ（Ⅱ）配位,酚羟基离解常数 ｐ Ｋａ为４．４４。在２５±０．１℃,Ｉ＝０．１（ＫＮＯ_３）条件下,ｐＨ＝６～９（５０ｍｏｌ·Ｌ~（－１））范围内,用紫外、可见分光光度法研究了Ｌ~１的Ｃｕ（Ⅱ）配合物催化对－硝基苯酚乙酸酯（ＮＡ）水解动力学行为,发现配合物催化ＮＡ酯水解反应速率常数ｋ_（ＮＰ）与溶液 ｐＨ呈 Ｓｉｇｍｏｉｄａｌ型曲线, ｋ_（ＮＰ）最大值为 ２． ５３×１０~（－２）Ｌ· ｍｏｌ(－１)· ｓ(－１)。说明 Ｌ~１的 Ｃｕ（Ⅱ）配合物中的 Ｃｕ（Ⅱ）－ＯＨ~－是有效的亲核试剂,对底物ＮＡ酯的水解有较好的催化作用。     

非催化动力学光度法测定铬的研究

研究了在ＨＣｌ介质中，Ｃｒ（Ⅵ）氧化碘离子显色反应的动力学条件，建立了测定Ｃｒ（Ⅵ）的非催化动力学分析法。方法的灵敏度７．２７×１０－７ｇ·Ｌ－１，检测限５．３３×１０－６ｇ·Ｌ－１，测定范围２×１０－５～３×１０－４ｇ·Ｌ－１。用于测定标钢中的铬，测定值与标准值基本一致     

甲醇在CM-3-1催化剂上脱水生成二甲醚的本征动力学

采用等温积分反应器研究了常压下甲醇在ＣＭ３１催化剂上脱水生成二甲醚反应的本征动力学，得到Ｌａｎｇｍｉｕｒ均匀吸附双曲型动力学方程：ｒＭ＝１．５８７×１０１２ｅｘｐ１２２９８４ＲＴＰＭ１ＰＤＰＷＫＰ２Ｍ１＋１．１０３×１０９ｅｘｐ８１７６０ＲＴＰＭ２，ｍｏｌ／（ｇ·ｈ）     

单茂钛催化剂的丙烯无规聚合反应及其动力学研究

比较了不同钛化合物／甲基铝氧烷（ＭＡＯ）催化体系的丙烯无规聚合，催化活性次序为ＣｐＴｉ（ＯＲ）３＞ＣｐＴｉ（ＯＰｈ）３＞ＣｐＴｉＣｌ３＞Ｃｐ２ＴｉＣｌ２＞Ｔｉ（ＯＢｕ）４＞ＴｉＣｌ４＞Ｔｉ（ＯＢｕ）２Ｃｌ２，所得聚丙烯用沸庚烷抽提８ｈ，溶解９５％以上，可溶部分经１３Ｃ ＮＭＲ、ＷＡＤＸ、ＦＴＩＲ等分析证明为无规聚丙烯（ａＰＰ），是没有结晶性的弹性体．ＧＰＣ测出其分子量Ｍｗ＝８．０～１０．０×１０４，Ｍｗ／Ｍｎ≈２．０．探索了催化体系ＣｐＴｉ（Ｏ ｎ Ｐｒ）３／ＭＡＯ中钛的浓度、［Ａｌ］／［Ｔｉ］摩尔比，丙烯聚合压力，聚合温度和时间对丙烯聚合反应的影响．研究了该催化体系丙烯聚合反应动力学规律，表观聚合反应速率对催化剂浓度和单体压力（浓度）都呈一级反应关系，表观聚合速率常数ＫＰ＝２９２×１０５ｍｏｌ／Ｌ·ｈ（４０℃）．活化能ΔＥ＝－７．８８×１０３Ｊ·ｍｏｌ－１，碰撞因子Ａ＝１．４１×１０－４ｍｏｌ／Ｌ·ｈ．     

超细Mo-Co-K催化剂合成低碳醇性能的研究

采用类凝胶法和超临界干燥技术制得超细Ｍｏ－Ｃｏ－Ｋ催化剂。研究了还原态催化剂上ＣＯ加氢合成低碳醇的反应性能,考察了不同钼钴比、钾盐助剂呈和反应条件对合成低碳醇性能的影响,在３００℃、６．０ＭＰａ,１００００ｈ＾－１的反应条件下,超细Ｍｏ－Ｃｏ－Ｋ（Ｍｏ／Ｃｏ＝７：１,Ｋ含量为１％）催化剂上低碳醇的时空产率达到６２４．４ｇ／ｋｇ－ｃａｔ．ｈ,醇选择性与４８．５％,ＯＨ／Ｃ１ＯＨ＝１．０８。     

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。     

Cu(Ⅱ)KIO_4胭脂红-1,10-菲罗啉体系催化动力学光度法测定人发中痕量铜

基于ｐＨ６．５ 的Ｎａ２ＨＰＯ４ＮａＨ２ＰＯ４ 缓冲介质中铜离子对高碘酸钾氧化胭脂红褪色反应的催化作用,提出了催化动力学光度法测定痕量铜的新方法。研究了该方法的适宜反应条件,方法的检出限为１．１×１０－ ７ｇ／ＬＣｕ（Ⅱ）,表观摩尔系数ε＝ ７．８×１０５Ｌ·ｍ ｏｌ－ １·ｃｍ － １,线性范围为０～０．５μｇ／１０ｍ ＬＣｕ（Ⅱ）,方法已用于人发中痕量铜的测定     

稀土助剂对Zr－Mn－K催化剂上甲醇、异丁醇合成的影响

在Ｚｒ－Ｍｎ－Ｋ催化剂中添加稀土氧化物助剂Ｐｒ６Ｏ_（１１）、Ｓｍ_２Ｏ_３可以显著提高合成气合成甲醇、异丁醇的活性，特别是异丁醇的时空产率在４００℃、１０ＭＰａ、５０００~（－１）的反应条件下，由原来的５．９分别增加到１１．５、９．８ｍｌ／ｈ·ｌｃａｔ．。催化剂的ＸＲＤ、ＬＲＳ、ＴＰＲ、ＴＥＭ图和比表面测定结果一致表明，稀土元素可使催化剂晶粒细化、高度分散，稳定了四方相。ＸＰＳ结果表明：ＲＥＯ的加入使表面Ｍｎ富集，且催化剂表面Ｍｎ和Ｋ的比例影响其合成甲醇、异丁醇的活性与选择性。     

新试剂N-间甲苯基-N′-(氨基对苯磺酸钠)硫脲(MMPT)的合成及其在分析化学中的应用

本文合成新试剂Ｎ－间甲苯基－Ｎ′－（氨基对苯磺酸钠）硫脲（ＭＭＰＴ），经红外、紫外、核磁、元素分析等测试，确定其结构。研究测定了试剂与４０多种离子的反应及其配合物的表观摩尔吸光系数，它可作为Ｃｕ２＋（ｍ＝０．０１５μｇ，ｃ＝０．５μｇ／ｍＬ）、Ａｇ＋（ｍ＝０．１μｇ，ｃ＝３．３μｇ／ｍＬ）的新鉴定试剂和光度法测定Ｐｄ２＋（ε３０９．７＝６．３２×１０４Ｌ·ｍｏｌ－１·ｃｍ－１）、Ｐｔ（Ⅳ）（ε７５４．４＝８．５８×１０４Ｌ·ｍｏｌ－１·ｃｍ－１）等的显色剂，方法灵敏度高、选择性好，用于阳极泥、人发、矿石及催化剂中上述元素的鉴定或测定，均获满意结果。     

用卡尔曼滤波-分光光度法测定无机铬的形态

利用Ｋａｌｍａｎ滤波技术和二溴苯基荧光酮－溴化十六烷基三甲基铵－Ｃ_２Ｈ_５ＯＨ分光光度测定体系,同时对Ｃｒ（Ⅲ）和Ｃｒ（Ⅳ）进行测定。Ｃｒ（Ⅲ）的表观摩尔吸光系数为１．９６ × １０~５ Ｌ· ｍｏｌ~（－１）·ｃｍ~（－１）,线性范围为０～ ４．０ ｘ１０－６ｍｏｌ／Ｌ;Ｃｒ（Ⅵ）的表观摩尔吸光系数为４．１６ ×１０~５Ｌ· ｍｏｌ~（－１）· ｃｍ~（－１）,线性范围为０～５．２×１０~（－１）ｍｏｌ／Ｌ。     

甲醇气固相合成甲酸甲酯

利用甲醇合成甲酸甲酯（ＭＦ）是一个很有研究和开发价值的新课题,受到人们的普遍重视［１～４］。在人们把合成气和甲醇视为一种具有竞争力的Ｃ１化工原料的今天,甲酸甲酯的应用前景不可估量。本文着重介绍了在连续稳定操作条件下,采用共沉淀法制备的Ｖ２Ｏ５／ＴｉＯ...     

Catalytic Preparation of Methyl Formate from Methanol over Silver

A catalytic reaction over a silver catalyst performed in an unregarded temperature region（473-873 K） with a long catalytic lifetime for the production of methyl formate from methanol was provided as a potential preparing route. The optimal yield of methyl formate（ca. 14. 8% ） with a selectivity 〉90% was obtained at about 573 K. Because α- oxygen species and bulk oxygen species coexist in the unregarded temperature region, a synergistic process concerning α-oxygen species and bulk oxygen species was proved over Oα -rich and Oγ-rich samples.     

合成甲醇和甲酸甲酯的Cu-Cr催化剂(英文)

以甲酸钠作为羰化催化剂,未还原的铜－铬作为氢解催化剂,在３８３ Ｋ,初始压力为５．０ＭＰａ的条件下浆态相合成甲醇。铜－铬催化剂采用三种方法制备：Ａ,ＣｕＯ和Ｃｒ_２Ｏ_３的简单混合;Ｂ,共沉淀法：Ｃ,络合法。结果表明,采用Ａ制得的铜－铬催化剂没有活性,络合法比共沉淀法活性高。在以络合法制备的催化剂中加入第三金属组分可改变催化剂的选择性,加入Ｃｏ、Ａｇ、Ｌａ和ＺｒＯ_２后甲醇的选择性得以提高,而加入Ｍｎ、Ｂａ和Ｍｇ,则甲酸甲酯的选择性高于甲醇的选择性。     

CONCURRENT SYNTHESIS OF METHANOL AND METHYL FORMATE CATALYZED BY COPPER-BASED CATALYSTS II.INFLUENCES OF SOLVENTS AND H2/CO MOLE RATIOS

The concurrent synthesis of methanol and methyl formate (MF) from synthesis gas at low temperature and under low pressure in a slurry reactor has been investigated. The influences of the solvents and H2/CO mole ratios on the activity and methyl formate selectivity of CuCl and Cu-Cr oxide catalysts have been examined. The experimental results demonstrate that the solvents have remarkable influences on the activity and methyl formate selectivity of CuCl and Cu-Cr oxide catalysts.     

Novel process for synthesis of 1,1,3,3-tetrabutyl-1-methoxy-3-isocyanatodistannoxane

A new process for synthesis of 1,1,3,3-tetrabutyl-1-methoxy-3-isocyanatodistannoxane (TBMI) from dibutyltin oxide (DSnO), methyl carbamate and methanol was proposed. The structure of the TBMI was confirmed by UV-Vis, elemental analyses, FTIR and HPLC. The effects of various conditions, such as reaction temperature, pressure, reaction time, molar ratio of the reactants and the stirring speed were investigated in the terms of TBMI yield. The experimental results indicated that the optimal reaction conditions were the molar ratio of methyl carbamate:DSnO of 2:1, the reaction time of 3 h, the reaction temperature of 433 K, the methanol:DSnO molar ratio of 2:1, the initial pressure of 0.4 MPa and the stirring speed of 1000 rpm, respectively. TBMI yield of 96.9% was obtained in the optimal reaction conditions. This process shows some advantages like easy to operate, higher yield, shorter reaction time and lower cost.     

CONCURRENT SYNTHESIS OF METHANOL AND METHYLFORMATE CATALYZED BY COPPER-BASED CATALYSTS III. INFLUENCES OF CONCENTRATIONS OF CATALYSTSAND PROMOTERS

The influences of concentrations of catalysts and promoters on the catalytic activity and methyl formate selectivity in the cocurrent synthesis of methanol and methyl formate from synthesis gas at low temperature and pressure in a slurry phase catalyzed heterogeneously by copper-based catalysts have been studied. The experimental results exhibit that the catalytic activity goes up regularly with the increase of catalyst concentration and promoter concentration in the experimental range over all the tested catalysts.     

PRELIMINARY EXAMINATION OF THE CONCURRENT SYNTHESIS OF METHANOL IN SLURRY PHASE

本文报道了ｌ升浆液搅拌釜内一体化甲醇合成反应过程中涉及的甲醇连续羰基化、甲酸甲酯氢解和低温甲醇合成反应的初步考察结果。     

锆对低温液相合成甲醇Cu-Cr催化剂性能的影响

Cu-Cr and Cu-Cr-Zr catalysts for the low temperature methanol synthesis slurry phase, with the surface area of 77.9 and 113.2 m2/g respectively, were prepared by the co precipitation approach. The activity and selectivity of these catalysts were evaluated in a stainless steel autoclave at 5.5 MPa and at different temperatures of 383 and 423 K separately. It was found that the activity of Cu-Cr-Zr catalyst was obviously higher than that of Cu-Cr catalyst, whereas the methanol selectivity of Cu-Cr-Zr catalyst was a little lower. The concentration of sodium compounds in the solution after reaction was also measured. The results showed that the concentration of sodium formate after reaction is much lower than that before reaction, which is quite different from the observations from the Cu-Cr catalyst previously. This implies that the conversion of sodium methoxide to sodium formate has been completely suppressed in the presence of zirconia in Cu-Cr-Zr catalyst. This finding is more beneficial to improve the performance of Cu-Cr catalyst and to increase the life of catalyst system as well.     

相转移法制备Cu-Mn合成气一步法合成甲酸甲酯催化剂

采用月桂酸作表面活性剂相转移制备了Ｃｕ－Ｍｎ合成甲酸甲酯催化剂,结果发现相转移法制得的催化剂粒径比采用共沉淀法要小得多,已经达到了纳米超细粒子水平。同时,比表面积也显著增大,用于由合成气一步法合成甲酸甲酯的活性显著高于共沉淀法及浸渍法制得的催化剂。