新型给电子体聚丙烯催化剂的研究

A P-substituted sulfonyl-containing compound was synthesized in the lab. The structure of the compound was demonstrated by 1H and 31P NMR. The propylene polymerization catalysts were prepared by incorporating an internal donor, and the content of Ti, H and C in the catalysts was also checked by elemental analysis. The effect of dosage of the donor, the Al/Ti ratio and the polymerization temperature on the catalyst activity were studied, the results suggested that the dosage of donor, the Al/Ti ratio and the polymerization temperature could affect not only the activity of catalyst but also the isotacticity index of the polymer. A catalyst with high activity was selected, and the polypropylene formed in the presence of this catalyst had high isotacticity index.     

FCC Catalysts to Meet Demand of New Era

The CGP series FCC catalysts for manufacture of clean gasoline and propylene and the catalyst RSC-2006 for processing inferior residuum with high yield of light distillates are novel catalysts jointly developed by Qilu Catalyst Branch Company of SINOPEC Corp. and the Research Institute of Petroleum Processing （RIPP）. The results of commercial application of these catalysts have revealed that they can satisfactorily meet the requirements for environmental protection, good economic benefits and capability for processing inferior FCC feed under new circumstances.     

Studies on the Reaction Mechanism of CPP and the Factors Affecting the Yields of Ethylene and Propylene

The reaction mechanisms of Catalytic Pyrolysis Process and the ethylene and propylene forma-tion reaction are analyzed,and ethylene and propylene are produced through both the free radical reac-tion and carbenium ion reaction.The factors affecting the yields of ethylene and propylene are discussed.The results showed that greater yields of ethylene and propylene can be obtained on ZSM-5 catalysts rather than USY and REY catalysts,and the modified ZSM-5 could improve the ethylene yield.A higher temperature is favorable for enhancement of the free radical reaction as opposed to carbenium ion reaction,and change in temperature can adjust the ratio of ethylene and propylene production.A higher steam amount could produce more ethylene and propylene and less coke,and lowering the catalyst/oil ratio is favorable for producing ethylene.     

制备乙烯聚合球形MgCl2/SiO2/THF负载的后过渡金属催化剂

A facile and user friendly technique to immobilize the late-transition metal complexes on spherical MgCl2/SiO2/THFsupport has been developed. The spherical MgCl2/SiO2/THF-supported late-transition metal catalysts 2,6-bis-[1-（2,6-dimethylphenylimino）ethyl]pyridine iron （II） dichloride （SC-A） and 1,4-bis（2,6-dimethylphenyl）- acenaphthene diimine nickel （II）dibromide （SC-B） for ethylene polymerization has been prepared by spray-drying technique using tetrahydrofuran suspensioncontaining MgCl2, SiO2 and late-transition metal complexes. The catalysts were characterized by BET, XRD, SEMand the polymers were analyzed using GPC, DSC and 13C-NMR. The test results show that spray-drying is a very effectivemethod for immobilizing late-transition metal catalysts for ethylene polymerization. Among six kinds of cocatalysts for olefinpolymerization, TMA and TEA were confirmed to be more effective than other compounds for the ethylene polymerizationsystem using the catalyst SC-A. For the case of the catalyst SC-B, DEAC showed the best performance as cocatalysts inethylene polymerization. The replication of the catalyst morphology was found in the resultant polyethylene.     

满足新时期需求的催化裂解催化剂

The new generation of DCC catalysts, the DMMC/RMMC series catalysts developed by RIPP are introduced in this paper. The large molecule cracking ability is enhanced by increasing the portion of large pores; and the coke selectivity is improved by adjusting the acidity site density on the matrix surface, while the selective cracking reactions are increased. The sphericity of catalysts is improved by adopting new preparation method. The commercial application results have shown that applying DMMC/RMMC series catalysts with the mixed VGO, VGO plus AR, and hydrotreated VGO feed can increase the propylene yield by 2.43, 1.3 and 0.8 percentage points, respectively, as compared to the previous catalysts along with improvement in some products yields. The refining enterprises can make more profits after applying new series of DCC catalysts.     

Commercial Application of CPP for Producing Ethylene and Propylene from Heavy Oil Feed

A new process named CPP (Catalytic Pyrolysis Process) for producing ethylene and propylene from heavy oil feedstock has been developed. The catalyst CEP was specially designed for this process, which has bi-functional catalytic activities for both carbonium ion reaction and free radical reaction, so as to maximize the yields of ethylene and propylene. The commercial trial showed that the yield of ethylene and propylene was 20.37% and 18.23% respectively in maximum ethylene operation with Daqing AR as feedstock, and the yield of ethylene and propylene was 9.77% and 24.60% respectively in maximum propylene operation by using the same feedstock.Compared with steam cracker, the feed cost of CPP is much lower for producing ethylene and propylene.     

第三代渣油加氢催化剂的开发及工业应用

Based on the mechanism of resid hydrotreating reaction by coordinating the catalyst activity and stability, the diffusion mechanism and catalyst reactivity, the cost and catalyst performance, and the production and application requirements, the third-generation series catalysts for residue hydrotreating have been developed by Research Institute of Petroleum Processing, SINOPEC. The new series RHT catalysts possess higher activity for HDS, HDM and HDCCR performance as well as longer run length. The commercial results for application of these catalysts have demonstrated that the new catalyst system performs better than the reference ones.     

MMC——High Propylene Selectivity DCC Catalyst

RIPP has developed the third generation novel DCC catalysts aimed at increasing the propylene yield, named as the MMC series catalysts. This catalyst is of the MFI structure composed of the ZSP zeolite as the main active component, which has higher capability for producing low-carbon olefins, in particular the propylene. The commercial application of this catalyst at SINOPEC Anqing Petrochemical Company has revealed that the adoption of the MMC-2 catalyst has resulted in a 1.6-4.0 percentages increase in propylene yield under basically similar conditions in terms of the feedstock property and process operating regime coupled with reduction in gasoline olefin COntent and increase in aromatic content to improve the gasoline quality.     

环烷氧基硅为内给电子体的负载型Ziegler-Natta催化剂合成宽分子量分布聚乙烯

Two kinds of cycloalkoxy silane compounds were synthesized and used as the internal electron donors （IEDs） of supported Ziegler-Natta catalyst for ethylene polymerization to produce polyethylene with broader molecular weight distribution （MWD）, The effect of the structure and the amount of these IEDs on the polymerization performance was in- vestigated. The results implied that the molecular weight distribution of the obtained polyethylene could be adjusted by the incorporation of IEDs. SEM result showed that the morphology of catalyst particle was spherical and uniform in size distribution. The titanium content of these catalysts was higher, the active TiCl4 species were easily anchored on the support than that without adding IED, which was determined by ICE The GPC result confirmed that the polyethylene with broader molecular weight distribution in the range of from 23.4 to 25.6 was obtained using triethoxy-（-cyclopentyloxy）-silane （ED1） and triethoxy-（-cyclohexyloxyl）- silane （ED2） as the internal electron donors.     

新型硅溶胶基质在催化裂化反应中应用研究

A new silica sol binder was obtained by mixing the acid-modified aluminium sulfate and water glass. The effect of SiO2 concentration in sodium silicate, pH value and polymerization was investigated. The new silica sol binder, which possessed abundant pore volume and suitable acid amount, was an ideal component for preparing cracking catalyst. As a result, the corresponding catalyst comprising the new binder showed excellent performance. Compared with the reference sample, the liquefied petroleum gas （LPG） and propylene yield obtained over this catalyst increased by 3.49 and 1.20 percentage points, respectively. The perfect pore structure and suitable Lewis acid amount of new silica sol were the possible reason leading to its outstanding performance.     

聚丙烯催化剂的研发进展

综述了用于丙烯聚合的Ziegler-Natta催化剂在给电子体技术及催化剂制备工艺等方面,茂金属催化剂在制备丙烯均聚物、丙烯共聚物及特殊聚丙烯等方面,非茂单活性中心催化剂在丙烯活性聚合、丙烯与极性单体共聚及水介质聚合等方面的研发进展;讨论了聚丙烯催化剂的前景。     

以磺酰胺类为内给电子体的丙烯聚合催化剂

Three sulfonyl aliphatic amines [(R2SO2)2NR1, viz.: compound 1, in which R1=Me, and R2=Ph; compound 2, in which R1=n-Bu, and R2=CF3; and compound 3, in which R1=C8H17, and R2=CF3] have been synthesized and employed as internal electron donors (IED) for the preparation of Ziegler-Natta catalysts for the polymerization of propylene. The contents of Ti, H and C in these catalysts have been determined by elemental analysis and UV-vis spectrophotometry. The effect of the structure and dosage of the electron donor, the Al/Ti ratio and the polymerization temperature on the catalyst performance has been studied. Under optimized conditions, the catalyst with a highest activity yielded polypropylene with high isotacticity in the absence of external electron donors.     

BCND催化剂催化丙烯聚合的动力学研究

研究了在常压淤浆聚合条件下聚合温度对以1,3-二醇酯为内给电子体的BCND催化剂的丙烯聚合动力学行为的影响,并与目前工业生产装置上常用的几种以邻苯二甲酸酯为内给电子体的丙烯聚合催化剂进行了比较。实验结果表明,丙烯低温(10~20℃)聚合时,不同催化剂催化丙烯聚合的动力学行为近似,随聚合温度的升高,聚合反应速率增加,与N催化剂和YS-842催化剂相比,BCND催化剂的丙烯聚合活性受聚合温度的影响较小;丙烯在较高温度(70~90℃)聚合时,随聚合温度的升高,BCND催化剂活性中心的衰减速率加快,聚合反应速率下降,但与参比催化剂相比,BCND催化剂催化丙烯聚合的反应速率仍为最大。     

新一代功能性聚丙烯催化剂的研发进展

为适应聚丙烯树脂高性能化和功能化的发展需求,提出了基于MgCl2负载的高效Ziegler-Natta催化剂,借助于茂金属及非茂金属单中心催化剂丰富多样且明确可控的烯烃聚合催化能力,通过多重载体化制备了Ziegler-Natta/(非)茂金属复合型催化剂,从而获得兼具高活性、高立体定向性和可调、可控的共聚性能的新一代功能性聚丙烯催化剂,用于以聚丙烯/乙丙多相共聚物、高熔体强度聚丙烯和极性改性的功能化聚丙烯等为代表的高性能聚丙烯树脂的制备。通过对聚丙烯催化剂与聚合物结构性能之间对应关系的分析,及Ziegler-Natta/(非)茂金属复合型催化剂在制备多相共聚聚丙烯和高熔体强度聚丙烯等树脂中的实践,指出了以获得催化功能性为目标的Ziegler-Natta/(非)茂金属复合型催化剂是今后聚丙烯催化剂的发展方向。     

丙烯聚合TiCl_4/MgCl_2催化剂制备过程中原位生成邻苯二甲酸二正丁酯的研究

采用红外光谱、紫外-可见光谱、气相色谱和色谱-质谱联用等技术对不同条件下磷酸三丁酯和环氧氯丙烷溶解体系制备的丙烯聚合TiCl4/MgCl2催化剂的结构进行了表征。表征结果显示,在TiCl4/MgCl2催化剂的制备过程中,原位生成了少量的内给电子体邻苯二甲酸二正丁酯(DNBP)。TiCl4/MgCl2催化剂的丙烯淤浆聚合结果表明,在该催化剂体系中原位生成的少量DNBP对其催化性能产生一定的影响,通过降低无规活性中心的含量来提高TiCl4/MgCl2催化剂的定向能力;外加大量的DNBP,既降低了TiCl4/MgCl2催化剂中无规活性中心的含量,又使TiCl4/MgCl2催化剂的定向能力进一步提高。     

聚丙烯催化剂载体制备的研究进展

概述了聚丙烯催化剂载体发展历程。综述了当前国际上聚丙烯工业应用效果较好的Ziegler-Natta催化剂载体体系及其制备方法,包括MgCl_2·ROH体系、镁化合物溶液析出体系、醇镁体系、MgCl_2/SiO_2体系以及一些新型复合载体体系等。载体制备工艺的研究改进,有助于推动聚丙烯催化剂在高活性、高定向性的基础上向系列化、高性能化、专用化方向发展,从而不断开发性能更好的聚丙烯新产品。     

聚丙烯技术新进展

综述了近年来用于丙烯聚合的Z ieg ler-Natta催化剂,特别是以1,3-二醚、琥珀酸酯及1,3-二醇酯类化合物为内给电子体的催化剂的最新研究进展情况。同时介绍了丙烯聚合工艺的研究和应用现状,对Basell公司的Spherizone工艺、Borealis公司的Borstar工艺和超临界技术在烯烃聚合中的应用进行了重点介绍。综述了聚丙烯新产品———高熔体强度聚丙烯、高结晶聚丙烯、高流动共聚聚丙烯和高透明聚丙烯的开发情况。最后针对我国聚丙烯工业的发展现状提出了发展建议。     

硼酸酯类给电子体在淤浆法制备聚乙烯催化剂中的应用

以硼酸酯类化合物为给电子体制备了聚乙烯催化剂。利用SEM和粒度分布仪表征了含不同给电子体的催化剂的粒径与形态。表征结果显示,含硼酸酯类给电子体的催化剂颗粒呈球形,粒径分布均匀且平均粒径随给电子体上烷氧基数目的增大而增大。考察了含不同给电子体的催化剂的聚合性能。实验结果表明,含硼酸酯类给电子体的催化剂的聚合活性较高,其中,含硼酸三丁酯给电子体的催化剂氢调性能优异,共聚性能与商业催化剂相当。硼酸酯类给电子体的使用有利于开发高性能的高密度聚乙烯串联牌号。     

球形聚丙烯PC-2催化剂的性能

借助分光光度计、气相色谱、体式显微镜等仪器对聚丙烯PC-2催化剂的物理性质进行了表征,并采用模试及中试聚合(均聚或共聚)对催化剂的性能进行了评价。结果表明,PC-2催化剂粒径分布较窄,具有较高的比表面积,物理性质与国内外对比催化剂(二者分别由辽宁营口向阳化工厂和荷兰Basell公司生产)相当。对比模试及中试均聚可知,PC-2催化剂聚合活性高于国内外对比催化剂。通过中试共聚得到的聚合物与中国石油兰州石化公司生产的汽车保险杠专用料(牌号为SP 179)相比,二者结合乙烯质量分数及橡胶相质量分数相当,前者总体性能达到了后者的要求。     

聚丙烯生产技术和市场应用的新方向

聚丙烯催化剂和聚合工艺不断推陈出新，聚丙烯产品的创新使得聚丙烯的应用领域得以拓宽。基于此，建议我国聚丙烯工业发展的方向和重点。