直馏柴油的选择性催化氧化脱硫

柴油非加氢脱硫技术已成为研究热点。采用专用的柴油均相催化氧化脱硫催化剂TS-1和纯O2对直馏柴油进行催化氧化脱硫，可达到很好的脱硫效果，且投资小，容易操作。但此法得到的脱硫柴油酸值较大。加入硼酸可以选择性地催化氧化柴油脱硫，抑制烃类化合物的深度氧化，降低脱硫柴油的酸值，且其硫含量也可达到欧洲Ⅱ类柴油标准（总硫的质量分数少于300μg／g）。实验结果表明，选择性催化氧化脱硫（硼酸用量为2％）使柴油中硫的质量分数从2217．2μg／g下降到271μg／g，酸值下降了89．2％；与非选择性催化氧化脱硫相比，脱硫柴油收率提高了2．2％。     

直馏柴油选择催化氧化脱硫催化剂的制备与评价

制备了直馏柴油催化氧化脱硫催化剂苯甲酸锌、B2O3和复合催化剂FTS-1。以O2为氧化剂,考察了3种催化剂催化氧化直馏柴油中的硫化物的脱硫效果。研究结果发现,苯甲酸锌催化剂脱硫效果明显,脱硫后直馏柴油中的硫含量达到小于300μg/g的欧洲Ⅱ类排放标准;B2O3催化剂脱硫效果差,但萃取柴油的收率较高;复合催化剂FTS-1可选择催化氧化直馏柴油,抑制烃类化合物的深度氧化,降低氧化柴油的酸值,极大地改善了脱硫柴油的质量,提高脱硫柴油的收率。在搅拌转速700r/m in、苯甲酸锌质量分数0.15%、B2O3质量分数2%、反应温度150℃、氧气压力1.3M Pa、反应时间60m in的条件下,复合催化剂FTS-1脱硫后直馏柴油中硫含量可降到271μg/g,脱硫率达到87.8%。     

柴油氧化萃取脱硫工艺研究

以过氧化氢为氧化剂，甲酸为氧化反应的催化剂，甲醇为萃取剂，对柴油选择性氧化萃取法脱硫技术的工艺条件进行了研究。实验结果表明，在O与S摩尔比为10，氧化时间为40min，氧化温度为70℃，萃取剂为甲醇，剂油比为1．0，萃取时间为30min，萃取温度为室温的最佳工艺条件下，一级萃取柴油的脱硫率为78．2％；三级萃取柴油的脱硫率为97．7％，柴油硫含量为18μg／g，小于50μg／g，达到欧Ⅳ排放标准的要求。     

催化裂化柴油氧化萃取脱硫工艺研究

以氧气作氧化剂,甲酸作催化剂,N-甲基吡咯烷酮（NMP）作萃取剂,采用催化氧化反应与溶剂萃取相结合的方法对催化裂化柴油进行了氧化萃取脱硫实验。通过单因素实验考察了催化剂用量,催化氧化温度、时间、氧气压力及萃取剂的用量等对催化裂化柴油硫含量的影响。通过实验得出最适宜的脱硫条件为：反应温度80℃;反应时间90min;充氧压力0．6MPa;催化剂体积分数为10％。经催化氧化,柴油硫质量分数可从1694．2μg/g降到190．8μg/g,脱硫率达到88．7％;在剂油比为1．0和室温条件下,用NMP三级萃取,柴油硫质量分数为37．5μg/g,小于50μg/g,达到欧Ⅳ排放标准的要求。     

用H2O2/乙酸酐氧化脱除直馏柴油中的含硫化合物

用H2O2／乙酸酐氧化处理直馏柴油,然后用乙腈萃取、吸附剂吸附或蒸馏等方法将柴油中含硫化合物的氧化产物除去。结果表明,氧化-萃取法效果较好。当柴油：H2O2：乙酸酐的体积比为10：1：1,80℃：,反应2h,乙腈萃取,可将直馏柴油的硫含量从2623．6μg／g降到270．3μg／g,脱硫率达90％,脱硫油收率95％。苹取剂乙腈可回收并循环使用。对氧化产物的IR分析表明,含硫化合物的氧化产物主要为砜类,且大部分被乙腈萃取出来,一部分进入氧化剂层,氧化剂层中有少量氧化产物SO4^2-存在。     

固体酸催化氧化脱硫的实验室研究

用浸渍法制备了固体酸催化剂H3PW12O40／SiO2，以催化裂化汽油为原料，进行催化氧化脱硫实验，考察了催化剂用量、氧化剂（特丁基过氧化氢）用量、反应温度及反应时间对脱硫效果的影响。实验结果表明，在催化剂用量为5％，氧化剂中氧与硫的摩尔比为5，反应温度70℃，反应时间3h的最佳反应条件下，H3PW12O40／SiO2催化剂可将催化裂化汽油中的硫含量由100μg／g降低到3．5μg／g，脱硫率可达96．5％，汽油收率为83．5%，并且催化剂具有较好的再生性。     

超声波作用下柴油深度氧化脱硫的研究

催化氧化脱硫是降低柴油硫含量的非加氢脱硫工艺，在催化氧化溶剂抽提的基础上，引入超声波为反应提供能量，考察了超声频率、声强等因素对脱硫效果的影响。结果表明。以H2O2-有机酸为氧化剂，在室温，剂油比为0．05，搅拌速率为300r／min，反应时间为15min，频率为28kHz，声强为0．408W／cm^2的条件下进行柴油催化氧化反应，将得到的产品与萃取剂（DMF）在室温下按照1：1混合，萃取两次后进行分离，其脱硫率为94．8％，而未加超声波的脱硫率仅为67．2％，说明超声氧化脱硫效果明显优于未加超声波的氧化脱硫反应。     

FCC柴油氧化萃取深度脱硫工艺研究

以氧气作氧化剂、甲酸作催化剂、N-甲基吡咯烷酮作萃取剂,采用催化氧化反应与溶剂萃取相结合的方法对催化裂化柴油进行了氧化萃取脱硫实验。考察了催化剂用量、催化氧化温度、反应时间、氧气压力及萃取剂的用量等对催化裂化柴油脱硫率的影响。结果表明,在反应温度为80℃、反应时间为90min、充氧压力为0.6MPa、催化剂与油体积比为10%的条件下,柴油经催化氧化脱硫后,硫含量可从1694.2μg/g降到190.8μg/g,脱硫率达到88.7%;在萃取剂油体积比为1.0和室温条件下,用N-甲基吡咯烷酮萃取3次,再经硅胶吸附后柴油硫含量为37.5μg/g,柴油收率为94%,达到欧Ⅳ排放标准小于50μg/g的要求。     

亚铁离子及甲酸催化过氧化氢氧化柴油深度脱硫研究

将噻吩和二苯并噻吩溶解于正辛烷配制成模型油,在Fe^2＋和甲酸的催化作用下,用过氧化氢氧化脱硫。研究了Fe^2＋的催化氧化性能及反应条件对其催化性能的影响。实验结果表明：30％H2O2-HCOOH-Fe^2＋产生的过氧甲酸和羟基自由基能迅速将模型有机硫化合物氧化,氧化脱硫率可达到96％以上,Fe^2＋和甲酸的催化氧化性能明显优于单纯使用甲酸。甲酸浓度、Fe^2＋／H2O2摩尔比、过氧化氢加量及反应温度对氧化脱硫率均有影响。30％H2O2-HCOOH-Fe^2＋体系氧化FCC柴油,然后经过萃取能达到深度脱硫,柴油硫含量从0．7268％（ω）降至0．0114％（ω）,脱硫率达到98．43％,油回收率为85．53％。     

直馏柴油应用离子液体“一锅法”脱硫

以实验室合成的Zn[C6H11NO]3Cl2、N-甲基咪唑溴化物、Zn[CO(NH3)2]3Cl2、1-丁基-3-甲基咪唑四氟硼酸盐和磷酸酯类离子液体作为脱硫萃取剂,H2O2-冰醋酸体系作为氧化剂,采用"一锅法"对直馏柴油进行脱硫,考察了离子液体种类和用量、H2O2和冰醋酸用量、反应时间及氧化温度对脱硫率的影响.结果表明,磷酸酯类离子液体对直馏柴油的脱硫效果相对较好,在离子液体体积分数为20%、H2O2体积分数为8%、冰醋酸体积分数为4%、20 min、80℃条件下,柴油中硫质量分数由1425 μg/g降至676μg/g,脱硫率达到52.6%;且回收的离子液体使用5次,其脱硫效率仍达到40%以上.     

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.