高压加氢装置设计、施工、开工及运行总结

山东某炼油公司30万t/a高压加氢装置于2019年9月中交,次年3月产出合格产品,实现装置一次开车成功。该装置以加氢改质柴油为原料,生产低凝低芳变压器油及WI系列轻质白油。文章介绍了装置设计、施工及开车情况,包括设计过程中出现的问题,施工阶段管理要求,装置吹扫、气密、催化剂装填、催化剂干燥、催化剂硫化、引油开车等开工过程以及装置运行情况。装置运行部分着重对催化剂性能、产品收率、性质和能耗方面进行运行分析。结果显示:装置催化剂性能良好,整体处于设计初期水平。临氢降凝催化剂活性高于设计预期,其反应控制温度为279℃;补充精制剂反应控制温度280℃左右。在当前操作条件下可以生产合格的-40℃变压器油。白油产品除黏度外,其余指标均符合WI系列轻质白油国标要求。原料性质变化是造成装置运行过程中部分轻质白油产品黏度波动、重质产品收率高、氢耗高以及低负荷工况下能耗低于设计值的主要原因。     

重整切尾油催化加氢生产优质溶剂油

介绍了中国石油抚顺石化公司石油三厂以重整切尾油为原料,通过加氢微型试验装置,筛选出加氢精制催化剂3996与加氢脱芳催化剂FV-1,将上述2种催化剂按照体积比1︰1进行组合装填,在加氢微型试验装置进行一段加氢法生产塑胶溶剂油试验,并经过了工业生产运行。结果表明,在适宜的操作条件下,可以出合格的塑胶油产品,并获得较好的经济效益。     

HT-1／HIDW-1异构降凝催化剂工业应用

中国石油大庆石化分公司炼油厂年产210kt柴油加氢装置成功实现由加氢精制到异构降凝生产方案的切换，生产出-20^#柴油，标志着由中国石油大庆石化公司研究院开发研制的HT-1／HIDW-1柴油加氢精制-异构降凝催化剂组合技术在工业装置上应用成功。     

体相催化剂级配技术中催化剂装填研究

在小型加氢反应装置上进行了体相催化剂级配装填技术的研究,结果表明,原料油中二次加工油质量掺炼比从38%提高到70%,体相催化剂体积装填比例从25%提高到43%,可以加工生产超低硫柴油产品。当反应器氢气压力为6.4 MPa时,体相催化剂装填在反应器中部的超深度加氢脱硫活性好于其装填在反应器下部,氢气压力为9.2 MPa时,体相催化剂装填在反应器下部的超深度加氢脱硫活性好于其装填在反应器中部。工业应用结果表明,根据研究结果进行体相催化剂装填,体相催化剂级配技术在装置能力和炼油厂生产目的限制下发挥最大性能,可长期稳定生产超低硫柴油产品。     

常二线和减三线馏分油综合加工的可行性研究

以中海油环烷基常二线和减三线馏分油及其混合油作为原料,通过高压加氢处理、糠醛精制组合工艺制备变压器油和环保橡胶油。结果表明,常二线馏分油单独进料,通过单段高压加氢处理工艺可得到满足GB 2536—2011的变压器油。减三线馏分油单独进料,通过单段高压加氢处理工艺可直接生产CA为10%的环保橡胶油。2种馏分油混合进料,通过高压加氢处理和糠醛精制组合工艺可生产CA超过25%的高芳环保橡胶油,生产的变压器油CA较高,与深度精制石蜡基变压器油调和可得到满足GB 2536—2011的变压器油。2种馏分油混合进料可避免因原料切换产生过渡油,充分释放加工能力,提高装置利用率。     

催化剂脱油技术在沸腾床加氢装置中的应用

介绍了沸腾床加氢工艺的发展及在国内的应用情况,简述了沸腾床加氢装置卸出催化剂进行脱油的必要性。热氮气提脱油方法在国内首套沸腾床加氢装置的工业化应用表明:该脱油工艺流程简单,操作方便,脱油率高达98.65%,提高了资源回收利用率;脱油后的催化剂可达到国内催化剂再生技术的要求,具有较好的经济和环保效益。     

鲁奇炉宽馏分煤焦油加氢改质工艺研究

在100mL固定床加氢实验装置上,采用自制的不同性质的加氢催化剂组合对云南解放军化肥厂鲁奇炉副产的宽馏分煤焦油进行了加氢改质的工艺研究.结果表明,反应压力、温度、空速和氢油比等参数对煤焦油加氢改质的影响显著,并在反应压力12.0MPa,温度360℃,液时空速1.0h-1和氢油比1200∶1的优化条件下通过加氢改质和产品分馏,可以获得约9%的小于160℃石脑油馏分、78%的160℃～350℃柴油馏分和13%大于350℃尾油馏分.实验装置连续运行了1114h后仍能保持稳定,催化剂表现出良好的活性和稳定性.     

煤直接液化油催化加氢制备环烷基油

在300 mL连续加氢实验装置上,以神华鄂尔多斯直接液化工厂生产的加氢稳定油为原料,以加氢精制剂RNC-2为催化剂,考察了不同反应温度和体积空速对加氢产物性质及加氢精制反应过程的影响.结果 表明:升高反应温度或降低体积空速,芳烃加氢饱和反应过程中的氢耗增大,产品油的密度、运动黏度及馏程降低;从不同反应条件加氢产品油中芳...     

DZD-1柴油加氢精制催化剂载体的研究

介绍了DZD-1柴油加氢精制催化剂载体的选择、扩孔以及改性.利用研制的载体制备出DZD-1柴油加氢催化剂,并在10 mL小型加氢装置上进行了活性评价,结果表明,其活性优于国内参比剂,加氢生成油的硫质量分数＜50×10-6.     

中低温煤焦油加氢改质工艺研究

在小型固定床加氢装置上,用加氢精制催化剂和加氢裂化催化剂对陕北的中低温煤焦油进行加氢改质工艺研究.着重考察反应温度、反应压力、氢油体积比和液体体积空速对加氢效果的影响,得到了优化的工艺条件:反应压力14 MPa,反应温度390℃,氢油体积比1 600:1,液体体积空速0.25 h-1.加氢改质产品切割得到汽油、柴油和尾油馏分,分别占产物质量的9.82%,73.12%和16.43%.汽柴油馏分经过简单处理后可以得到合格的产品,加氢尾油可以作为优质的催化裂化或加氢裂化原料.     

Evaluation of hydrogenation catalyst activity

The AOCS Recommended Practice for testing activity of hydroge-nation catalysts was used to compare activity and properties of a number of commercial catalysts with the AOCS standard catalyst. Four of five commercial catalysts tested were similar to the standard but one commercial catalyst was markedly more active and more selective. It also was very difficult to filter after hydrogenation. Selectivity of the catalysts in hydrogenation of soybean oil was determined from change in fatty acid composition. The most selective catalyst produced the highest level oftrans isomers and the highest dropping point. Solid fat contents measured after 30 and 40 min of hydrogenation time were determined by wide-line nuclear magnetic resonance. The Recommended Practice and standard catalyst were useful tools in evaluating activity and selectivity of hydrogenation catalysts.     

CLA formation in oils during hydrogenation process as affected by catalyst types,catalyst contents,hydrogen pressure,and oil species

The effects of types and amount of catalysts, hydrogen pressure, and kinds of vegetable oils on the formation of CLA isomers were studied during hydrogenation. CLA isomers were identified by using a silver ion-impregnated high-performance liquid chromatograph and 100-m cyano-capillary column gas chromatograph. A selective catalyst (SP-7) produced a considerably higher content of CLA in soybean oil than nonselective catalysts. The maximal quantity of CLA produced in soybean oil during hydrogenation increased greatly with increasing amount of catalyst. By increasing the amount of selective catalyst from 0.05 to 0.3%, the quantity of total CLA obtained was about 1.9 times higher. Changes in hydrogen pressure also greatly influenced total CLA formed. By decreasing hydrogen pressure from 0.24 to 0.024 MPa, the quantity of CLA obtained was about 1.3 times higher. With different oil species (soybean, cottonseed, and corn oils), the time to reach the maximal quantity of CLA was different under the same hydrogenation conditions. However, the maximal quantity of CLA and proportion of CLA isomers formed were almost identical, regardless of oil species tested, under the same hydrogenation conditions.     

宽馏分油加氢制取溶剂油和白油的研究

以洛阳金达石化有限责任公司特种油品厂10×104 t/a宽馏分装置的宽馏分油为原料,采用催化剂a和催化剂b组合工艺,在金达研发中心200 m L加氢装置上进行高压加氢制取溶剂油和白油等特种油品的研究。考察了反应压力(16.5~18.5 MPa)、反应温度(315~355℃)、质量空速(WHSV)(0.3~0.6 h-1)和氢油体积比(1 000:1~1 800:1)对加氢精制产物油性质的影响,并确定最佳的工艺参数。结果表明,产物油硫含量随着反应温度、压力、氢油体积比的增大而减小,随着空速的增大而增大;产物油芳烃含量随着反应压力、氢油体积比的增大而减小,随着反应温度和空速的增大而增大。对加氢产物油进一步蒸馏切割得到25%溶剂油馏分、60%白油馏分和11%减底尾油馏分。对产物油馏分进行含量分析,生成的产品油分别满足溶剂油和白油标准。     

Supported gold catalysis in the hydrogenation of canola oil

The catalytic activity of gold supported on silica orγ-alumina has been studied in the hydrogenation of canola oil. In the hydrogenation of butadiene and pentene using these catalysts, high stability, low yield oftrans-isomers and high monoene selectivity have been reported in the literature. Catalysts containing 1% and 5% Au w/w on porous silica andγ-alumina were active in hydrogenating canola oil in the range of 150 to 250 C and 3550 to 5620 kPa. The activity level of these catalysts was about 30 times lower than that shown by the standard AOCS Ni catalyst based on the concentration of metal (g Au/L oil). Up to 91% monoene content was obtained using these catalysts in comparison with a maximum of 73% for the AOCS standard Ni catalysts. Gold catalysts can be recovered easily by filtration and reused several times without a decrease in activity. The hydrogenated oil was nearly colorless. No gold was detectable in the oil. Contrary to claims in the patent literature, the gold catalyst produces higher concentrations oftrans-isomers than does nickel. However, using gold catalysts the complete reduction of linolenic acid in canola oil can be achieved at a lowertrans-isomer content in the products than that obtained by using the AOCS standard nickel catalyst.     

Dimerization of Hexadecene with Acid Mesoporous Silica-Alumina Catalysts

Catalytic dimerization of 1-hexadecene is shown to be a promising path to make high quality base oil. The base oil is produced by hexadecene dimerization with acid mesoporous silica-alumina catalyst, followed by distillation and hydrogenation. The base oil stock had a high viscosity index (typically 140–150) and a low volatility (Noack typically less than 8 %). The best performance in hexadecene dimerization was achieved with the MCM-22 zeolite embedded MCM-41 catalyst within the silica-alumina catalysts compared. Commercial mesoporous silica-alumina catalysts behaved similarly to a non-commercial MCM-41 catalyst. Y-zeolite and ion exchange resin Amberlyst-35 deactivated fast.     

Pilot-plant selective hydrogenation of soybean oil: Activation and evaluation of copper-containing catalysts

In pilot-plant tests, the linolenate content of soybean oil was reduced to less than 1% without increasing the saturates, by hydrogenation to an IV of about 115 with an active copper-chromite catalyst. The linolenate-linoleate selectivity ratio (K_Le/K_Lo) was from 9 to 12. Several commercial copper-chromite catalysts were used in hydrogenation tests. The activities of four of five commercial catalysts tested were improved to various degrees by heating in air at 350 C (one was inactive both before and after heating). Examination by differential thermal analysis (DTA) of each catalyst, just as received and then after being heated at 350 C, demonstrated that heating greatly diminished or removed peak areas from the DTA curve. Studies made with one commerical copper-chromium-barium catalyst showed that heating the catalyst was also necessary to gain maximum linolenate-linoleate selectivity in hydrogenating soybean oil. Presented at the AOCS Meeting, New Orleans, May 1967. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Effect of phospholipid structure on kinetics and chemistry of soybean oil hydrogenation with nickel catalysts

Phospholipids (PL) are one of the compounds which poison nickel catalysts during the hydrogenation process. It was affirmed that even trace amounts of PL (5—10 ppm P) cause a decrease in catalyst activity. Quantities over 50 ppm P almost totally inhibit the reaction. In bleached oils used for hydrogenation, PL exist as native compounds as well as products of their transformation. In the present work, the effect of native phospholipids, lysophospholipids (LPL) and phosphatidic acids (PA) on the kinetics and chemistry of soybean oil hydrogenation was investigated. It was found that PA were more toxic to nickel catalysts than LPL and native PL. Fine‐grained catalyst was more active and resistant to the poisoning effect of phospholipids than moderate‐grained catalyst. No changes in the oil hydrogenation chemistry were observed in the presence or absence of PL; thus, linoleic and linolenic selectivity and specific isomerization did not undergo any change.     

An evaluation of commercial nickel catalysts during hydrogenation of soybean oil

The activities of several commercial nickel catalysts were determined by measuring their activation energies. Among these catalysts, G95E, Resan 22, Nysosel 222 and 325, all with low activation energy, were more active than DM3 and G95H, which had higher activation energy. However, the less active catalysts increased the linoleate selectivity of soybean oil during hydrogenation. The yields of bothtrans isomers and winterized oil were higher for the more selectively hydrogenated oil catalyzed by the less active catalysts. In the sensory evaluation, the fractionated solid fat that contained moretrans isomers was lower in flavor scores than the fractionated liquid oil after hydrogenation and winterization of soybean oil.     

NiW/Al-PILC催化剂的页岩油加氢性能

采用铝柱撑粘土为载体制备了NiW/Al—PILC催化剂,研究了在页岩油加氢中的催化性能,与催化剂NiW/γ-Al_2O_3的催化性能进行比较。对催化剂进行表征,并对页岩油加氢所得柴油馏分[(180～350)℃]进行分析,结果表明,NiW/Al—PILM催化剂催化性能优于NiW/γ—Al_2O_3催化剂,其铝柱撑粘土层间距d_(001)=1.962 nm、比表面积为264.3 m~2·g~(-1),在该催化剂上页岩油加氢柴油收率达52.8%,20℃运动黏度5.025 mm~2·s~(-1),凝点-3℃,冷凝点1℃,闪点84℃,十六烷值64.3,20℃密度0.832 7 g·cm~(-3)。