Kinetic studies on vapor phase carbonylation of methanol to acetic acid over Rh/Ys catalyst

A novel catalyst Rh/Ys for the carbonylation of methanol to acetic acid with CH3I as the promoter shows excellent activity and selectivity.The reaction is kinetically controlled.The reaction rate is in proportion to the concentration of Rh and CH3I but has nothing to do with those of CH3OHH and CO.The surface active energy is Ea ~51.02 kJ/mol.A mechanism is also proposed.     

2—乙烯基吡啶—甲基丙烯酸甲酯共聚物的链结构与其铑络合物对烯烃催化加氢性能的关系

本工作定量测定了2-乙烯基吡啶-甲基丙烯酸甲酯-铑络合物的烯烃催化加氢性能与共聚物配体序列结构的关系。同时根据共聚物的微结构三元组分布数据对催化剂的络合状态进行了探讨。实验结果证明,催化剂的活性随共聚物配体中以甲基丙烯酸甲酯为中心的三元组F_(MMM),F_(MMV+)含量增加而提高。而稳定性则随以2—乙烯基吡啶为中心的三元组F_(VVV),F_(VVM+)含量增加而提高。     

POLYKETONE FROM CO AND STYRENE: A USEFUL COPOLYMER CATALYZED BY A HIGHLY ACTIVE AND STABLE PALLADIUM CATALYST WITH 5-NITRO-1,10-PHENANTHROLINE LIGAND

A novel coordinated complex [(5-nitrophen)Pd(CF3CO2)2] (5-nitrophen = 5-nitro-l,10-phenanthroline) was first synthesized. By using XPS, IR, and 1H-NMR, its coordination unit was studied in comparison with those of complexes [(N- N)Pd(CH3CO2)2] and [(N - N)Pd(CF3CO2)2]. The H2,9 proton signals of 1H-NMR spectra of the complexes are excellent probes to monitor the evolution of the environment of the palladium atom. The state of anionic coordination was confirmed by the presence of IR absorption peaks of COO in complexes ([(N N)Pd(CH3CO2)2] and [(NN)Pd(CF3CO2)2]). Bonding energies of N1s and Pd3d5 obtained from XPS data testified to the strength of the N-Pd coordinating bond. The conclusion can be drawn by analyzing these data from IR, XPS and 1H-NMR that it is the unsymmetrical substitution of the 1,10-phenanthroline (phen) that makes the [(5-nitrophen)Pd(CF3CO2)2] more active.Experimental results showed that [(5-nitrophen)Pd(CF3CO2)2] exhibits much higher activity than [(bipy)Pd(CF3CO2)2] (1, l‘-bipyridine = bipy) and [(phen)Pd(CF3CO2)2] under the same conditions.     

Intramolecular reaction of polymer coordinated cationic rhodium complex

Ｓｑｕａｒｅｐｌａｎａｒｃｉｓｄｉｃａｒｂｏｎｙｌｒｈｏｄｉｕｍｃｏｍｐｌｅｘ,ａｐｒｅｃｕｒｓｏｒｏｆｃａｔａｌｙｔｉｃａｌｌｙａｃｔｉｖｅｃｏｍｐｏｕｎｄｉｎｃａｔａｌｙｔｉｃｒｅａｃｔｉｏｎ,ｉｓａｔｙｐｉｃａｌｋｉｎｄｏｆｃａｔａｌｙｓｔ[1].Ｉｔｉｓｕｓｕａｌｌｙｕｎｓｔａｂｌｅ.Ｆｏｒｅｘａｍｐｌｅ,ｗｉｔｈｏｕｔｅｆｆｉｃｉｅｎｔｐｒｏｔｅｃｔｉｏｎｏｆＣＯａｎｄｈｉｇｈｔｅｍｐｅｒａｔｕｒｅ,ｄｉｉｏｄｏｄｉｃａｒｂｏｎｙｌｒｈｏｄｉｕｍ,ａｎｅｆｆｅｃｔｉｖｅｃａｔａｌｙｓｔｆｏｒｔｈ…     

新型Ni－La催化剂催化甲醇气相羰基化反应

 制备和测试一种全新的甲醇气相羰基化催化剂。催化剂的活性金属为Ni, La为第二组分，本身无催化羰基化活性，采用一种我们自行开发的新型碳分子筛为载体。在制备过程中，采用了一种全新的负载路线，即：以Ni-La双核配合物为金属微晶的前体，使得Ni-La按确定的原子比混合，由此得到全新Ni-La羰基化催化剂。La有很强的助催化作用，与未添加La的Ni催化剂相比，Ni-La催化剂表现出更高的催化活性和选择性。     

A NOVEL COPOLYMER-BOUND CIS-DICARBONYLRHODIUM COMPLEX FOR THE CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE

A series of porous microspheres of linear and ethylene diacrylate (M') cross-linked copolymers of 2-vinylpyridine (V) and methyl acrylate (M) reacted with tetracarbonyldichlorodirhodium to form a series of cis-dicarbonylrhodium chelate complex (MVRh and MVM 'Rh). They are thermally stable yet very reactive in the carbonylation of methanol to acetic acid, and of methanol-acetic acid mixture to acetic acid and acetic anhydride with a selectivity of 100% under relatively mild and anhydrous conditions.     

STUDY OF CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE OVER A BIDENTATE POLYMER BOUND CIS-DICARBONYLRHODIUM COMPLEX AS CATALYST

Copolymer of 2-vinylpyridine and vinylacetate coordinated with dicarbonylrhodiumused as a catalyst for carbonylation of methanol to acetic acid and anhydride has beenstudied. The structural characteristics of the copolymer ligand and complex, and the in-fluences of the reaction conditions on the carbonylation catalyzed by this polymer complexhave been investigated. In comparison with small molecule catalyst of Rh complex, thebidentate copolymer coordinated complex has better thermal stability. The reactionmechanism of the carbonylation reaction is also illustrated.     

Improvement on stability of square planar rhodium (Ⅰ) complexes for carbonylation of methanol to acetic acid

A series of square planar cis-dicarbonyl polymer coordinated rhodium complexes with uncoordinated donors near the central rhodium atoms for carbonylation of methanol to acetic acid are reported. Data of IR, XPS and thermal analysis show that these complexes are very stable. The intramolecular substitution reaction is proposed for their high stability. These complexes show excellent catalytic activity, selectivity and less erosion to the equipment for the methanol carbonylation to acetic acid. The distillation process may be used instead of flash vaporization in the manufacture of acetic acid, which reduces the investment on the equipment.     

气相色谱的定量分析方法Ⅰ.以空气作标准的热导池气相色谱定量方法的研究

本文在相对灵敏度理论基础上,提出以空气作相对标准的气相色谱定量方法,并引进空气标定因子作为应用这一方法的定量参数.有关气体在热导池检测器中的空气标定因子,根据Novák提出的相对克分子响应关系式^[1]计算得到的结果,其准确度可以满足一般情况下热导池气相色谱定量分析的精度要求.