Ce-Ca-Mg-Al-O催化剂的制备、表征及其酯交换性能

以硝酸盐为原料,尿素为沉淀剂,采用均匀沉淀及焙烧的方法制备了Ce-Ca-Mg-Al-O固体碱催化剂,采用单因素实验考察了制备条件对催化剂活性的影响。应用Hammett指示剂滴定法,采用TG,BET,XRD,SEM等方法对催化剂及其前体进行了表征。实验结果表明,制备催化剂的优化条件为:n(Ce)∶n(Ca)∶n(Mg)∶n(Al)=0.100∶3.0∶3.0∶2、反应温度115℃、焙烧温度700℃及焙烧时间6 h;将优化条件下制备的催化剂用于蓖麻油与甲醇的酯交换反应,在n(醇)∶n(油)=9∶1、m(催化剂)∶m(油)=0.04∶1、搅拌转速为550 r/min、反应温度65℃及反应时间为4 h的条件下,蓖麻油转化率可达96.00%。表征结果显示,催化剂的碱强度为7.2~11.2;BJH脱附比表面积为52.20 m~2/g、BJH脱附孔体积为0.102 cm~3/g。     

CaO/Zn-Fe-O固体碱的制备、表征及油脂醇解催化活性

采用共沉淀、浸渍及高温焙烧的方法制备了CaO/Zn-Fe-O固体碱催化剂。采用正交试验考察了制备条件对CaO/Zn-Fe-O固体碱油脂醇解催化活性的影响,得到的优化条件为:n(Zn)/n(Fe)=5,Ca(Ac)_2浸渍液质量分数0.15、浸渍时间12h、焙烧温度800℃、焙烧时间3h。以优化条件下制备的CaO/Zn-Fe-O固体碱为催化剂,在n(醇)/n(油)=9、m(催化剂)/m(油)=0.04、搅拌速率400r/min、反应温度70℃、反应时间3h的条件下,蓖麻油转化率为84.21%。采用TG-DTA、FT-IR、BET及XRD技术对催化剂及其前驱体进行了表征。结果表明:Ca(Ac)_2/Zn-Fe水滑石TG曲线出现3个失重台阶,分别位于180~250℃、250~380℃及700~750℃温区;CaO/Zn-Fe-O固体碱催化剂BET比表面积为6.19m~2/g,BJH脱附累积孔容为0.011 6cm~3/g,BJH脱附平均孔半径为3.84nm;CaO/Zn-Fe-O固体碱中的活性组分CaO以无定形或微晶的形式高度分散于Zn-Fe-O复合氧化物载体表面。     

Ca-Mg-Zn-Al-O固体碱催化剂的制备及其催化性能

采用共沉淀和高温焙烧的方法制备了Ca-Mg-Zn-Al-O固体碱催化剂,并采用正交实验对催化剂的制备条件进行了优化;通过TG-DTA,BET,XRD,SEM等手段及Hammett指示剂法对催化剂及其前体进行了表征。实验结果表明,正交实验得到的较适宜的制备条件为:陈化温度80℃、陈化时间12 h、焙烧温度700℃、焙烧时间5 h。以在上述优化条件下制备的Ca-Mg-Zn-Al-O固体碱为催化剂,用于蓖麻油与甲醇的酯交换反应,在n(甲醇)∶n(蓖麻油)=9、m(催化剂)∶m(蓖麻油)=0.04、搅拌转速550 r/min、反应温度65℃、反应时间3 h的条件下,蓖麻油的转化率稳定在95%~99%之间。     

Li-Ca-Mg-Al-O固体碱催化制备生物柴油

以锂、钙、镁、铝的硝酸盐为原料,以尿素为沉淀剂,采用沉淀焙烧的方法制备了Li-Ca-Mg-Al-O固体碱催化剂。采用单因素实验考察了制备条件对催化剂活性的影响,得到制备优化条件为:元素配比n(Li)∶n(Ca)∶n(Mg)∶n(Al)=1∶2∶1∶1,焙烧温度800℃,焙烧时间6.5h。将优化条件下制备的Li-Ca-Mg-AlO固体碱用于催化蓖麻油和甲醇的酯交换反应,在n(醇)∶n(油)=9,m(催化剂)∶m(油)=0.04,搅拌速率为550r/min,反应温度为65℃,反应时间为3h的条件下,蓖麻油转化率可达85.7%。采用Hammett指示剂滴定法、TG、BET、XRD及SEM对催化剂及其前驱体进行了表征。结果表明:Li-Ca-Mg-Al-O固体碱的碱强度为7.2~11.2;Li-Ca-Mg-Al类水滑石在温度超过800℃后质量不再随温度升高而变化;Li-Ca-Mg-Al-O固体碱催化剂比表面积为11.93m~2/g、孔容为0.031 7cm~3/g,主要由CaO、MgO及Al_2O_3三种晶体组成。     

Li-Ca-Zn-Al-O催化油脂醇解反应

以锂、钙、锌、铝的硝酸盐为原料,尿素为沉淀剂,采用沉淀焙烧法制备了Li-Ca-Zn-Al-O复合氧化物催化剂,采用单因素试验考察了制备条件对催化剂活性的影响。制备复合氧化物催化剂的优化条件为:元素配比n(Li)∶n(Ca)∶n(Zn)∶n(Al)=1∶4∶2∶2,反应温度120℃,焙烧温度800℃,焙烧时间7.0h。将优化条件下制备的Li-Ca-Zn-Al-O复合氧化物用于催化蓖麻油和甲醇的醇解反应,在n(甲醇)∶n(蓖麻油)=9∶1、m(催化剂)∶m(蓖麻油)=0.04∶1、搅拌速率550r/min、反应温度65℃、反应时间3h的条件下,蓖麻油转化率可达91.9%。采用Hammett指示剂法、TG、BET及XRD对复合氧化物及其前躯体进行了表征。结果显示:Li-Ca-Zn-Al-O复合氧化物的碱强度为7.2~11.2;Li-Ca-Zn-Al类水滑石在温度升至800℃时质量趋于稳定;Li-Ca-Zn-Al-O复合氧化物催化剂比表面积为25.70m~2/g、孔体积为0.047 74cm~3/g,且主要由CaO及ZnO两种晶体构成。     

Li-Ca-Zn-Al-O催化油酯醇解反应

以锂、钙、锌、铝的硝酸盐为原料,尿素为沉淀剂,采用沉淀焙烧法制备了Li-Ca-Zn-Al-O复合氧化物催化剂,采用单因素试验考察了制备条件对催化剂活性的影响。找到的制备复合氧化物催化剂的优化工艺为：元素配比n(Li):n(Ca):n(Zn):n(Al)=1:4:2:2,反应温度120 ℃,焙烧温度800 ℃,焙烧时间7 h。将优化条件下制备的Li-Ca-Zn-Al-O复合氧化物用于催化蓖麻油和甲醇的醇解反应,在n(甲醇):n(蓖麻油)=9:1,m(催化剂):m(蓖麻油)=0.04:1,搅拌速率550 r/min,反应温度65 ℃,反应时间3 h的条件下,蓖麻油转化率可达91.9%。采用Hammett指示剂法、TG、BET及XRD对复合氧化物及其前驱体进行了表征。结果显示：Li-Ca-Zn-Al-O复合氧化物的碱强度为7.2～11.2;Li-Ca-Zn-Al类水滑石在温度升至800℃时质量趋于稳定;Li-Ca-Zn-Al-O复合氧化物催化剂比表面积为25.70 m2/g、孔容为0.0477 4 cm3/g,且主要由CaO及ZnO两种晶体构成。     

制备参数对CaO-ZrO_2结构及CuO/CaO-ZrO_2催化剂合成甲酸甲酯性能的影响

采用溶胶-凝胶法制备介孔Ca O-Zr O2固体碱,考察了制备参数对Ca O-Zr O2固体碱结构的影响,用TEM和CO2-TPD方法表征了固体碱的结构和碱性。采用浸渍法在Ca O-Zr O2固体碱上引入活性组分Cu O,制备Cu O/Ca O-Zr O2双功能催化剂。该催化剂用于合成气在浆态床反应器中合成甲酸甲酯(MF)的反应时,Ca O-Zr O2固体碱的制备参数对Cu O/Ca O-Zr O2催化剂合成MF的性能有重要影响。Ca O-Zr O2固体碱的最佳制备条件为:溶液p H=6.4,n(P123)∶n(Zr)=0.02,晶化温度60℃,晶化时间24 h,后处理介质为0.5 mol/L的Na OH溶液。以最佳条件下制备的Ca O-Zr O2固体碱为载体制备的Cu O/Ca O-Zr O2催化剂,在170℃、5.0 MPa、n(H2)∶n(CO)=2.0下进行合成MF的反应,MF的时空产率和选择性分别可达89.4 g/(L h)和27.4%。     

用于蓖麻油甲醇解催化剂KF-MgO/Al_2O_3的制备和表征

为了提高蓖麻油甲醇解反应速率,分别以MgAc_2水溶液、KF水溶液作为浸渍液,Al_2O_3作为载体,采用二次浸渍、二次焙烧的方法制备了KF-MgO/Al_2O_3催化剂。将其用于蓖麻油甲醇解反应,通过正交实验优化的催化剂制备条件为:一次焙烧温度500℃,一次焙烧时间3h,二次焙烧温度450℃,二次焙烧时间5h。利用哈密特指示剂滴定法、TG-DTG(热重-微分热重)、XRD(X射线衍射)、SEM(扫描电镜)、低温N_2吸附-脱附技术对催化剂及其前驱体进行了表征。结果显示:催化剂碱强度在7.2～18.4;催化剂由负载于Al_2O_3载体表面的MgO、KF及反应产物构成;其比表面积为20.40m~2/g、孔体积为0.048 9cm~3/g。该催化剂能有效提高蓖麻油甲醇解反应速率,使蓖麻油转化率在3h内达到98.79%。     

工艺条件对K_2WO_4-ZnCl_2/γ-Al_2O_3催化剂上合成甲硫醇的影响

采用浸渍法制备了K2WO4-Zn Cl2/γ-Al2O3催化剂,利用XRD,SEM,BET,TPD等方法对该催化剂进行了表征。表征结果显示,K2WO4-Zn Cl2/γ-Al2O3催化剂保持了典型γ-Al2O3晶体结构的特征,活性组分的分散度较高,孔道为典型的圆柱型介孔结构且孔分布较集中,同时具有弱酸位和弱碱位。考察了工艺条件对硫化氢和甲醇在K2WO4-Zn Cl2/γ-Al2O3催化剂上生成甲硫醇的影响。实验结果表明,硫化氢和甲醇在该催化剂上生成甲硫醇适宜的条件为:n(硫化氢)∶n(甲醇)=2∶1、空速2.0 h-1、反应温度400℃、反应压力1.0 MPa。在此条件下,甲醇转化率、甲硫醇选择性和甲硫醇收率分别为87.85%,91.43%,80.32%。     

Ce-SO_4~(2-)/Al_2O_3催化合成乙酸正丁酯的研究

以拟薄水铝石在500℃焙烧制取的γ-Al_2O_3为载体,利用Ce(SO_4)_2-H_2SO_4溶液浸渍法用对γ-Al_2O_3改性,制备Ce-SO_2-4/Al_2O_3固体催化剂。通过X射线衍射(XRD)、红外光谱(IR)、扫描电镜(SEM)、N_2吸附-脱附等分析方法对催化剂进行了表征。结果表明活性组分的负载对载体Al_2O_3的结构产生了较大的影响,由原来的片状结构变为粒状结构,BET表面积由原来314.3m~2/g增大到346.3m~2/g。颗粒堆积后产生介孔范围的孔道,平均孔径约为5.29nm。将Ce-SO_4~(_2)/Al_2O_3催化剂应用于催化合成乙酸正丁酯具有良好的催化活性,在n(冰乙酸)∶n(正丁醇)=1∶1.0、m(催化剂)∶m(冰乙酸)=0.05∶1、反应3h条件下,酯化率可达93.42%。     

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.