聚丙烯新型外给电子体聚合评价的研究

采用液相本体聚合法,以硅醚9-(甲氧甲基)-9-[(三甲基硅基)氧基甲基]芴(DTSF)、甲基环己基二甲氧基硅烷(CHMMS)、二环戊基二甲氧基硅烷(DCPDMS)为外给电子体,以DTSF/CHMMS和DTSF/DCPDMS为复配外给电子体,考察了聚丙烯NG催化剂的丙烯聚合性能。实验结果表明,DTSF外给电子体的氢调敏感性较好,但聚合活性和聚丙烯等规度与CHMMS和DCPDMS外给电子相比偏低;DTSF/CHMMS复配外给电子体可明显提高NG催化剂的氢调敏感性、聚丙烯等规度及聚合活性,较适宜的配比为n(CHMMS)∶n(DTSF)=1∶1;将DTSF与DCPDMS外给电子体进行复配无实际意义。     

外给电子体对DQC催化剂聚合性能的影响

采用4种不同外给电子体,在5L不锈钢高压反应釜中对DQC催化剂进行丙烯液相本体聚合的研究。实验结果表明,以二环戊基二甲氧基硅烷(DCPDMS)和二异丙基二甲氧基硅烷(DIPDMS)为外给电子体时可得到较高等规度的聚合物,且聚合物具有较宽的相对分子质量分布;以DCPDMS为外给电子体时得到的聚合物的数均相对分子质量和重均相对分子质量最大;在生产低熔体流动指数聚合物时,以甲基环己基二甲氧基硅烷(CHMMS)为外给电子体时聚合物具有更敏感的氢调性能;以二异丁基二甲氧基硅烷(DIBDMS)和DCPDMS为外给电子体时,预络合时间对催化剂活性的影响较小;以DIBDMS为外给电子体时,DQC催化剂在氢调敏感性、高氢加入量时催化剂活性、预络合时间对催化剂活性的影响以及催化剂活性衰减等方面均优于另外3种外给电子体。     

外给电子体对新型球形聚丙烯催化剂性能的影响

采用常压淤浆聚合法研究了4种二甲氧基硅烷化合物外给电子体对新型球形聚丙烯(HQ)催化剂聚合行为的影响,利用GPC和DSC等方法考察了外给电子体种类对HQ催化剂及聚丙烯性能的影响。实验结果表明,外给电子体对HQ催化剂活性影响的高低顺序为:二环戊基二甲氧基硅烷(DCPMS)二异丙基二甲氧基硅烷(DIPS)二异丁基二甲氧基硅烷环己基甲基二甲氧基硅烷(CHMMS)。使用DCPMS时,HQ催化剂活性衰减速率最慢;使用CHMMS时,HQ催化剂活性衰减速率最快。随外给电子体用量的增大,聚丙烯等规度呈先急剧后缓慢增大的趋势。当用量相同时,使用DCPMS时得到的聚丙烯的等规度和熔点最高;使用DIPS时得到的聚丙烯的重均相对分子质量最大;使用CHMMS时得到的聚丙烯的重均相对分子质量最小。     

硅烷类外给电子体对Ziegler-Natta催化剂催化丙烯聚合的影响

研究了硅烷类外给电子体对Ziegler-Natta催化剂催化丙烯聚合的影响,并利用DSC,GPC,WAXRD等方法分析了外给电子体对聚丙烯性能的影响。实验结果表明,二烷氧基硅烷类外给电子体具有较高的聚合活性和立构定向性;多烷氧基硅烷类外给电子体比二烷氧基硅烷类外给电子体具有更好的氢调敏感性;在相同聚合条件下,采用二烷氧基硅烷类外给电子体制得的聚丙烯的相对分子质量分布较宽;加氢量对聚丙烯的晶型无影响,相对分子质量低和等规度低的聚丙烯发生多重熔融的几率较大。二烷氧基硅烷类外给电子体的最高占据轨道能级较高,因此具有较好的立构定向性。     

助催化剂和外给电子体对丙烯聚合性能的影响

考察助催化剂加入量(Al/Ti摩尔比)和外给电子体加入量(Si/Ti摩尔比)的变化对MgCl2负载的Ziegler-Natta催化体系催化丙烯聚合时的聚合性能的影响.发现Al/Ti摩尔比增大会使催化剂的活性增加,并存在最佳的助催化剂用量.同时,Al/Ti摩尔比增大还会使聚丙烯的等规度下降,但当存在外给电子体时,下降速率稍缓;而外给电子体的加入通常在提高聚合物等规度的同时会使催化剂的活性降低.     

1,3-二醇酯为内给电子体的丙烯聚合催化剂

研究了1,3-二醇酯为内给电子体的丙烯聚合ND-01系列催化剂的活性、氢调敏感性、定向性及动力学行为。实验结果表明,ND-01系列催化剂的活性较高;定向性易调;不加外给电子体时,所得聚丙烯的等规度也可达94.2%;与不同外给电子体配合使用的ND-01系列催化剂的性能与现有以邻苯二甲酸二丁酯为内给电子体的催化剂A的性能有较大的不同,使用二异丙基二甲氧基硅烷为外给电子体时,ND-01系列催化剂的氢调敏感性比催化剂A好,聚合所得聚丙烯的相对分子质量分布较宽;动力学行为实验结果表明,ND-01系列催化剂的活性衰减较慢。ND-01系列催化剂与三乙基铝/环己基甲基二甲氧基硅烷进行预络合反应时,ND-01系列催化剂中1,3-二醇酯的损失量小于催化剂A中邻苯二甲酸二丁酯的损失量。延长预络合时间,ND-01系列催化剂的聚合活性下降。     

国产硅烷外给电子体在气相聚丙烯装置上的应用

在Novolen气相聚丙烯装置上,通过连续试验考察了进口和国产甲基环己基二甲氧基硅烷(CHMMS)外给电子体的平均单耗,以及CHMMS外给电子体对催化剂活性、聚丙烯等规度及聚丙烯产品质量的影响。试验结果表明,国产CHMMS外给电子体的平均单耗较低;国产和进口CHMMS外给电子体对聚丙烯等规度均有较好的调控性能,生产的聚丙烯等规度均在97%以上;采用国产CHMMS外给电子体生产的聚丙烯与采用进口CHMMS外给电子体生产的聚丙烯的性能差别不大,质量符合标准。     

ClMg(OR)·ROH负载的高效丙烯聚合催化剂及其聚合行为

以含镁配合物ClMg(OR).ROH为载体制备了高效丙烯聚合催化剂,对催化剂进行了聚合反应动力学研究,考察了聚合温度、铝钛比、铝硅比和氢气加入量对催化剂聚合反应性能的影响。实验结果表明,该催化剂具有良好的氢调敏感性和立体定向性,动力学行为呈现典型的上升-衰减型,聚合过程中聚丙烯形态复现了催化剂的形态。在三乙基铝为助催化剂、甲基环己基二甲氧基硅烷为外给电子体、n(Al):n(Ti)=300、n(Al):n(Si)=15、氢气加入量(质量分数)为0.0200%、温度为70℃的条件下,该催化剂具有较高的活性(12.0kg/g),聚丙烯等规度可达97%以上。     

DQS-1催化剂的丙烯聚合性能研究

以环己基甲基二甲氧基硅烷(CHMMS)、二环戊基二甲氧基硅烷(DCPMS)、二异丁基二甲氧基硅烷(DIBMS)和二异丙基二甲氧基硅烷(DIPMS)为外给电子体,考察了DQS-1催化剂在不同铝硅比和不同加氢量条件下的丙烯聚合性能及聚合活性衰减速率,着重探索了DQS-1/CHMMS催化体系聚合温度对丙烯本体聚合的影响及乙丙抗冲共聚能力。实验结果表明,以CHMMS或DIPMS为外给电子体时,DQS-1催化剂同时兼具高的立构定向性和好的氢调敏感性,且丙烯聚合活性衰减速率明显低于现有DQC催化剂;提高聚合温度,可提高DQS-1催化剂的聚合活性及聚丙烯树脂的等规度,但其熔体流动指数不降低;用于乙丙抗冲共聚时,DQS-1催化剂的乙丙共聚能力相比DQC-602催化剂提高约30%。     

聚合温度对聚丙烯性能的影响

采用连续釜式预聚和卧式釜气相串联聚合工艺,利用BCM催化剂,二乙氨基三乙氧基硅烷外给电子体进行了丙烯聚合,考察了聚合温度对聚丙烯性能的影响。实验结果表明,随聚合温度的升高,催化剂的聚合活性降低,聚丙烯的相对分子质量分布变窄、等规度先增大后减小、结晶温度和熔点逐渐降低。聚丙烯的热变形温度、拉伸强度、弯曲强度和弯曲模量与等规度的变化趋势相同,即先增大后减小,在95℃时为最大值。当聚合温度在85~95℃时,催化剂的氢调敏感性比较好,聚丙烯的相对分子质量分布较窄、等规度高、热性能较好、力学性能优异。     

阿姆河右岸酸性气田井口冲蚀及对策

中亚土库曼斯坦阿姆河右岸气田群为高含H_2S和CO_2的碳酸盐岩气藏,单井产量高,井口设备均出现了不同程度的腐蚀。初步分析认为其原因是生产过程中仅考虑酸性介质对气井井口的化学腐蚀,而没有考虑气体流速对井口的冲蚀作用,极大地影响了气田的安全生产。为此,通过对节流阀上下游阀道、法兰面均出现明显坑状腐蚀的进一步分析,明确了化学腐蚀和气体冲蚀的交互作用是井口磨损的主要影响因素,气流冲刷腐蚀坑的化学腐蚀产物会加速冲蚀损害;进而借鉴冲蚀与腐蚀运行环境下的多相管流管道的磨损计算理论,计算了该运行环境下的冲蚀极限速度,得到了不同生产工况下节流阀的抗冲蚀流量;最后,根据气田生产情况,针对性地提出了按气井配产要求来选择采气树类型、节流阀通径及类型冲蚀的技术控制策略。此举为气田安全生产提供了工程技术保障。     

山前地区深井超深井套管防磨与减磨技术研究

针对山前地区深井超深井钻井过程中套管磨损严重的问题,在分析套管磨损机理的基础上,开展了山前地区套管防磨与减磨技术研究,基于技术研究成果及应用实践,得到如下结论:1应用Power V等垂直钻井系统控制井眼轨迹,特别是上部井段的狗腿度和井斜,可明显减小侧向力和磨损量,缩短套管磨损时间;2应综合考虑套管磨损率、磨损系数以及钻杆耐磨带本身的磨损量,优选出效果最优的耐磨带;在狗腿度严重的位置,可考虑采用一定数量的橡胶钻杆卡箍来减轻对套管的磨损;3山前地区钻井液采用CX-300减磨剂能够显著降低磨损速率,减轻套管磨损程度,但在不同钻井液体系使用之前应进行优化分析以确定最佳使用量;4在迪那204井使用高密度钻井液体系,全部采用优选的高密度重晶石粉代替铁矿粉作为加重剂,整个钻进过程中未出现钻具及套管磨损,迪那204井易损件消耗量仅为邻井迪那203井的左右,防磨减磨效果非常显著。     

Biodiesel Projects Helpful to Ease Energy Shortage

Nearly 7,000 hectares of biodiesel forest will take shape in the northern province of Hebei in 2008, part of a national campaign to fuel the fast growing economy in a green way. In no more than five years, the Pistacia chinensis Bunge, whose seeds have an oil content of up to 40 percent, will yield five tons of fruit and contribute about two tons of high-quality biological diesel oil, according to the provincial forestry administration.     

State Energy Base Proposed in Inner Mongolia

Experts recently suggested China set up a state energy base in lnner Mongolia Autonomous Region to ease its energy thirst. The survey was co-conducted by senior researchers from the National Development and Reform Commission, Development Research Center of the State Council, Chinese Academy of Sciences and the Ministry of Finance. To plan and establish strategic energy bases at state level is in line with the principle of ＂giving priority to energy saving and diversifying energy consumption with the utility of coal at the core.＂     

Influence of Shale Oil Boom in North America upon nternational Crude Price Flucturation

正Current stituation of shale oil development in the world The US The country is blessed with abundant shale oil resources and had matersed whole sets of theories and technologies needed for their exploration and development after years of practices.According to an assessment of shale oil resources in major countries and regions of the world issued by the U.S.Energy Information Agency(EIA),the US ranks the second in the world with its 6.8 billion tons of technically recoverable shale oil(shale oil in place is about 136.3 tons).About 8plays had been confirmed to have     

A Sintering-resistant Pd/C Composite Catalyst for Ethylbenzene DehydrogenationDeveloped by CAS Institute of Metals

Carbon deposition is a commonplace phenomenon occurringin the catalytic reaction process, in particular inthe system of direct dehydrogenation of ethylbenzene,because the reactant - ethylbenzene molecules on thesurface of metal oxide catalysts are prone to quickly formcarbon deposits, leading to deactivation of catalysts. Recently,the associate research fellow Mr. Liu Hongyangand the research fellow Mr. Su Dangsheng of the StateShenyang Material Science （United ） Laboratory of theInstitute of Metal Research, CAS by taking advantageof the carbon deposition process during direct dehydrogenationof ethylbenzene have ingeniously designeda Pd/C composite catalyst. This catalyst in comparisonwith the traditional commercial carbon nanotubesupported Pd catalyst shows a significantly improved performancein terms of its catalytic activity and sinteringresistantability.     

ZPEB Overseas Markets Keep Steady and Efficient Development

In recent years, Zhongyuan Petroleum Exploration Bureau （ZPEB） has made rapid development in overseas petroleum markets through its integrated reorganization. A new international business plattbrm established, aimed at becoming a highly ranked contractor with international petroleum engineering technology. ZPEB has expanded its business scope and scale, regulated the market structure,     

New Era for China-Brazil Relations

China and Brazil celebrated the 40th anniversary of establishing diplomatic relations between the two countries in July this year. Bilateral relations between China and Brazil have entered a new stage, and experts expect the already extensive cooperation between the two countries to deepen and broaden as Chinese President Xi Jinping made a state visit to Brazil in mid-July, which is his first state visit to Brazil since he assumed the office last year. The visit to China＇s largest trade partner in Latin America is at the invitation of Brazilian President Dilma Rousseff.     

Large Scale Ethylene Production Package Technology SuccessfullyDeveloped by CNPC

The CNPC Group has successfully developed a largescaleethylene production package technology with independentintellectual property rights, which has beensuccessfully applied in the 1.2 Mt/a ethylene revamp andexpansion project at the Daqing Petrochemical Complex（DPC）.     

Recent Advancements in Petroleum E & P Equipments in China

The role of equipments in oil and gas exploration and development had never been attached with so much importance as that in shale oil and gas boom in the U.S. With the help of massive hydraulic fracturing and horizontal drilling techniques, the U.S., the world＇s No. 1 oil importer even started to dream about energy self-sufficiency with its proudly high production of shale oil and gas from several major shale plays in the country. However, what behind this remarkable achievement are powerful multi-stage hydraulic fracturing machinery and smart tools for directional drilling.