固定床轻石脑油催化加氢脱硫研究

在200 mL固定床催化加氢装置上考察了Co-Ni-Mo-W四元复合催化剂在轻石脑油催化加氢的脱硫效果,考察了反应温度,氢气分压、空速、氢油体积比等工艺条件对加氢脱硫反应的影响。实验结果表明：Co-Ni-Mo-W四元复合催化剂具有良好的脱硫脱烯效果,脱硫效率平均为99%,烯烃脱除率可达98.6%。在中低压低温时有效脱除...     

柱撑粘土在加氢脱硫中的应用研究

以柱撑粘土为载体,制备了Mo-Ni／A1-Fe-PILC和Mo—Ni／AbPILC加氢脱硫催化剂,在50m愀型固定床反应评价装置中对FCC汽油进行加氢脱硫研究。结果表明：Mo-Ni／A1-Fe-PILC和Mo-Ni／A1-PILC2种催化剂具有较好的加氢脱硫效果,脱硫率达到75％以上,最佳的工艺条件为反应温度340℃,反应压力6．0MPa,空速为4．0h-1。     

邻苯二甲酸二异丁酯脱硫-加氢工艺

以邻苯二甲酸二异丁酯(DIBP,工业级)为原料,采用固定床高压反应器,对DIBP脱硫-加氢制备环己烷-1,2-二甲酸二异丁酯反应的催化剂和工艺进行了研究,增加了DIBP原料中痕量硫的脱除工艺,考察了反应压力、温度、空速、氢油比等工艺参数对DIBP脱硫及加氢反应的影响。试验结果表明:在反应压力14MPa、温度110℃(脱硫段)、温度160℃(加氢段)、空速0.3h~–1、氢油比600∶1的最佳条件下,装置稳定运行1000h,DIBP中的硫含量为3.5μg/g,DIBP转化率99.94%,脱硫和加氢性能稳定。     

DFL-1煤油深度加氢精制催化剂性能评价

在200 mL连续加氢固定床装置上,以煤油为原料,对DFL-1催化剂进行催化剂活性评价实验。采用该催化剂可使煤油中的硫含量降至0.5μg·g~(-1)以下,溴指数小于150 mg·(100g)~(-1),达到深度精制目的。相同工艺条件下,DFL-1催化剂比国内传统催化剂加氢深度较深,脱硫效果显著,若达到相同的精制效果,DFL-1比国内同类型催化剂的反应温度降低10℃以上。     

FCC汽油馏分在Ni/Al_2O_3催化剂上加氢脱硫醇的研究

以改性氧化铝为载体,采用等体积浸渍法制备Ni/改性Al_2O_3催化剂。以FCC选择加氢脱硫后的重汽油馏分加正庚硫醇为原料,在100 m L固定床加氢评价装置上对所制备催化剂进行加氢脱硫改质活性评价。结果表明,加氢脱硫后重FCC汽油馏分在加氢脱硫醇过程中除脱硫醇和脱硫反应外,还存在烯烃加氢饱和反应、烯烃环化脱氢反应以及烯烃的异构化反应等,这些反应与工艺条件密切相关,并影响加氢生成油的辛烷值和改质效果。对所研制的重汽油馏分加氢脱硫醇改质催化剂适宜的工艺参数为:压力2. 0 MPa、反应温度340～360℃、反应氢油体积比200～250∶1、体积空速3. 5～4. 5 h-1。     

水热处理对体相加氢催化剂活性的影响

体相催化剂经水热处理后,催化剂孔结构发生了改变,孔容、孔径和比表面积增加。采用小型加氢装置加工处理不同超深度脱硫难度的柴油原料,对水热处理后的催化剂进行超深度加氢脱硫活性评价。评价结果表明,体相催化剂经水热处理后,提高体相催化剂的超深度加氢脱硫活性和芳烃饱和性能,加工处理超深度脱硫难度大的劣质柴油时,加氢活性提高更加明显。以直馏柴油为原料,在相同工艺条件下,精制油中硫含量小于10μg/g时,对比没经水热处理的催化剂,水热处理后催化剂的反应温度降低了5℃。而以催化柴油为原料,在相同工艺条件下,精制油中硫含量小于10μg/g时,水热处理后催化剂的反应温度比水热处理前的反应温度降低了13℃。水热处理后的体相催化剂具有良好的活性稳定性。     

氧化锌脱除H_2S穿透时间的理论预测和实验研究

固定床氧化锌脱硫是目前燃料电池重整系统普遍采用的脱硫工艺。针对氧化锌脱除H2S的固定床反应体系,采用微分方程递推的方法建立脱硫反应的数学模型,计算了不同反应温度、空速条件下固定床脱硫反应器的穿透时间,并用穿透法测定的实验结果对该模型进行验证。研究结果表明,理论模型预测的穿透时间与实验研究结果规律一致,特别是在低空速、高温反应条件下的二者吻合良好。研究还证实了在适当的温度空速范围内,提高温度、降低空速对提高脱硫剂的硫容有利。本研究可为脱硫反应器设计和最优化操作提供参考依据。     

PRIME G+技术工艺参数的选择

探讨反应温度、压力、停留时间、氢烃比等工艺操作参数对Prime G+工艺选择性加氢和加氢脱硫的影响.在压力一定条件下,该工艺应尽可能在低温下操作.选择性加氢部分可提高氢烃比,满足适宜二烯烃加氢限制烯烃加氢并保持催化剂的稳定性.加氢脱硫部分提高氢/烃比增加了加氢脱硫的活性和选择性.在加氢脱硫的过程中要注意循环气中硫化氢的...     

Ni-Mo/γ-Al_2O_3催化剂加氢处理工艺条件的优化

采用固定床加氢装置对原料油(蜡油)进行加氢精制研究,采用控制变量法,考察了反应温度,液时空速,氢油比等对加氢效果的影响。以Ni-Mo/γ-Al_2O_3作为催化剂对加氢工艺进行优化,由数据表明升高温度、适当降低液时空速、增大氢油体积比,均有助于提高催化剂的脱硫和脱氮效果。Ni-Mo/γ-Al_2O_3催化剂在中高压条件下,反应温度为400℃,液时空速为0.25 h~(-1),氢油体积比在2 000左右时,加氢精制的效果最好。     

催化裂化汽油加氢脱硫工艺条件优化研究

针对催化裂化(FCC)汽油含硫量较高的缺点,对FCC重汽油进行加氢脱硫工艺条件的优化研究。以脱硫率(X_S)、烯烃加氢转化率(X_H)、选择性因子(α)为考察目标,分别从反应温度、反应压力、氢油比和空速四个方面对工艺条件进行了考察。实验结果表明:FCC汽油重组分进行加氢脱硫具有良好的脱硫率;较优的工艺条件为反应温度为240~250℃,反应压力为1.0~1.5 MPa,氢油体积比为300~350,空速控制为3.0 h~-1。     

Hydrodesulfurization of diesel in a slurry reactor

The need for more complete removal of sulfur from fuels is due to the lower allowable sulfur content in gasoline and diesel, which is made difficult by the increased sulfur contents of crude oils. This work reports an experimental study on the hydrodesulfurization (HDS) of diesel in a slurry reactor. HDS of straight-run diesel using a NiMoS/Al₂O₃ catalyst was studied in a high-pressure autoclave for the following operating conditions: 4.8–23.1 wt% catalyst in the reactor, 320–360 °C, 3–5 MPa pressure, and 0.56–2.77 L/min hydrogen flow rate. It was found that the reaction rate was proportional to the catalyst amount and increased with temperature, pressure and hydrogen flow rate. The reaction kinetics for the HDS reaction in the slurry reactor was obtained. As compared with HDS in a fixed bed reactor, HDS in a slurry reactor is promising because of the uniform temperature profile, high catalyst efficiency, and online removal and addition of catalyst.     

Co-Mo／SBA-15柴油加氢脱硫研究

以介孔分子筛SBA-15为载体,担载Co—Mo双金属活性组分制备了深度加氢脱硫催化剂。通过XRD和BET表征表明,负载金属后SBA-15分子筛仍然保持二维晶相结构,表面积略有下降。以直馏柴油为原料,在固定床反应器上评价了催化剂的脱硫反应活性的结果表明,SBA-15介孔分子筛Co—Mo的负载量为W（CoO）=5％,w（MoO3）=25％;脱硫适宜的反应条件为：反应温度360℃,压力4．0MPa,氢油体积比400．0,空速2．0h^-1。在此条件下,柴油硫含量可由1350μg／g降至39μg／g。     

移动床中内构件对煤热解反应过程调控作用

在外热式内构件（多级折流板和多段集气管）移动床反应器内研究了淖毛湖煤的热解特性,并与常规固定床反应器中煤热解行为进行对比,考察了两反应器内的传热速率以及热解温度对产物分布、热解气组成、焦油组成和品质等影响规律。结果表明：在450℃低温热解时,煤颗粒在内构件移动床内的升温时间比固定床缩短了60%以上,内构件具有显著提高反应器内颗粒间传热速率的作用。随着热解温度的升高,热解气中的C₂H₄/C₂H₆和C₃H₆/C₃H₈的比值变大,挥发分的二次反应程度加大,但裂解程度低于固定床。内构件移动床中的焦油产率随温度的升高先增加后降低,在550℃时达到最高为10.8%（质量分数）,比固定床增高约28.6%。当热解温度越高时,移动床所产焦油中的沥青质组分含量越低,在750℃时焦油中轻质组分质量分数达到85.17%,脂肪烃含量降低到了28.00%。通过与固定床对比,揭示了内构件（多级折流板和集气管）调控淖毛湖煤热解反应并提高热解焦油产率和品质的作用。     

Coupling non-isothermal trickle-bed reactor with catalyst pellet models to understand the reaction and diffusion in gas oil hydrodesulfurization

In this work, a trickle-bed reactor coupled with catalyst pellet model is employed to understand the effects of the temperature and catalyst pellet structures on the reaction–diffusion behaviors in gas oil hydrodesulfurization(HDS). The non-isothermal reactor model is determined to be reasonable due to non-negligible temperature variation caused by the reaction heat. The reaction rate along the reactor is mainly dominated by the temperature,and the sulfur concentration gradient in the catalyst pellet decreases gradually along the reactor, leading to the increased internal effectiveness factor. For the fixed catalyst bed volume, there exists a compromise between the catalyst reaction rate and effectiveness factor. Under commonly studied catalyst pellet size of 0.8–3 mm and porosity of 0.4–0.8, an optimization of the temperature and catalyst pellet structures is carried out, and the optimized outlet sulfur content decreases to 7.6 wppm better than the commercial level at 0.96 mm of the catalyst pellet size and 0.40 of the catalyst porosity.     

Activity of hydroprocessing catalysts prepared by reprocessing spent catalysts

In this study, two spent catalysts from the 3rd and 4th fixed beds of the atmospheric residue desulfurization (ARDS) process and one spent catalyst from the H-Oil process employing the expanded bed were used as the starting material for preparation of hydroprocessing catalysts. The spent catalysts were used either in a coked or decoked form. The procedures involved pulverizing the spent catalysts before mixing, kneading and extruding with boehmite in the presence of peptizing agent such as HNO₃. The hydrodesufurization (HDS) and hydrodemetallization (HDM) activities of the new catalysts were evaluated in the microreactor using the atmospheric residue derived from Kuwait crude. The new catalysts prepared from the spent catalysts used in the fixed bed reactors exhibited higher activity than that of commercial catalysts. The HDS activity of the new catalysts prepared from spent catalysts used in the ebullated bed reactor was much lower than that of the other catalysts. This was attributed to a high content of vanadium in the former spent catalyst. At the same time, the adverse effect of vanadium on HDM was much less evident.     

Intensification of Deep Hydrodesulfurization Through a Two-stage Combination of Monolith and Trickle Bed Reactors

Deep hydrodesulfurization (HDS) is an important process to produce high quality liquid fuels with ultra-low sul-fur. Process intensification for deep HDS could be implemented by developing new active c...     

程序升温法制备WP催化剂及其催化性能

以偏钨酸铵和磷酸氢二铵为原料,采用程序升温还原法制备体相WP催化剂,用质量分数0. 8%二苯并噻吩(DBT)溶液为模型化合物,考察磷化钨(WP)催化剂的加氢脱硫反应性能。采用XRD对催化剂进行表征,制备的WP催化剂移入固定床反应器前用体积分数10%H2S-Ar混合气体钝化,保证其结构未被破坏。实验表明,程序升温还原法成功制备出WP催化剂。WP催化剂具有良好的加氢性能,在WP催化剂上,二苯并噻吩主要以直接脱硫路径为主。     

Fe-5A催化亚甲基蓝溶液湿式H2O2氧化

以九水硝酸铁[Fe(NO3)3?9H2O]和柱状5A分子筛为原料采用湿法浸渍法制备Fe?5A催化剂,催化湿式H2O2氧化亚甲基蓝溶液,考察了间歇反应器中pH值和温度对亚甲基蓝转化率的影响及在连续固定床反应器中床层催化剂装填量、进料液流量、温度和亚甲基蓝入口浓度对亚甲基蓝降解性能的影响. 结果表明,在间歇反应中,在亚甲基蓝浓度50 mg/L、温度70℃、pH为2、反应20 min的条件下,亚甲基蓝的转化率为95.9%. 固定床反应中,随温度降低及进料液流量增加,亚甲基蓝转化率降低;随亚甲基蓝入口浓度增加,亚甲基蓝和化学需氧量(COD)的转化率变化幅度很小. 在温度70℃及pH=2、进料液流量4 mL/min、Fe?5A催化剂装填量1.25 g、亚甲基蓝浓度50?300 mg/L、固定床连续运转5 h的条件下,亚甲基蓝的转化率超过98%,COD转化率大于82%,铁浸出浓度低于3.5 mg/L,相同条件下,装填2.5 g 5A分子筛的固定床中50 mg/L亚甲基蓝的转化率仅为73.3%.     

Deep desulfurization of diesel oil: kinetic studies and process-improvement by the use of a two-phase reactor with pre-saturator

Desulfurization of liquid fuels is usually obtained by heterogeneous catalyzed hydrodesulfurization (HDS). Improvement of this process is needed, particularly with respect to future low residual S-contents of about . Up to now HDS of diesel oil is performed in a trickle bed reactor equipped with an expensive H₂-recycle, although the H₂-supply is far beyond the amount chemically consumed, at least for deep HDS of an already hydrotreated feed. In addition, scale up of trickle bed reactors is in general problematic. In this work kinetic studies and above all a new HDS-concept using a two-phase reactor is presented. Thereby the oil is externally pre-saturated with H₂ and only the liquid phase is passed over the catalytic fixed bed. The H₂-recycle is then redundant, the intrinsic reaction rate can be utilized, and scale-up problems do not occur. In addition, this concept can also be used for HDS of oils with a higher content of sulfur and/or unsaturated hydrocarbons by installing a liquid recycle.     

Upgrading Siberian (Russia) crude oil by hydrodesulfurization: Kinetic parameter estimation in a trickle-bed reactor

Hydrodesulfurization(HDS) of sour crude oil is an effective way to address the corrosion problems in refineries and is an economic way to process sour crude oil in an existing refinery built for sweet oil.Siberian crude oil transported through the Russia-China pipeline could be greatly sweetened and could be refined directly in local refinery designed for Daqing crude oil after the effective HDS treatment.In this study,the HDS of Siberian crude oil was carried out in a continuous flow isothermal trickle-bed reactor over Ni-Mo/γ-Al_2 O_3.The effects of temperature,pressure and LHSV were investigated in the ranges of 320-360℃,3-5 MPa and 0.5-2 h~(-1),keeping constant hydrogen to oil ratio at 600 L·L~(-1).The HDS conversion could be up to 92.89% at the temperature of 360℃, pressure of 5 MPa,and LHSV of 0.5 h~(-1), which is sufficient for local refineries(84%).A three phase heterogeneous model was established to analyze the performance of the trickle-bed reactor based on the two-film theory using Langmuir-Hinshelwood mechanism.The order of sulfur component is estimated as 1.28,and the order of hydrogen is 0.39.By simulating the reactor using the established model,the concentration of H_2, H_2 S and sulfur along the catalyst bed is discussed.The model is significantly useful for industrial application with respect to reactor analysis,optimization and reactor design,and can provide further insight of the HDS of Siberian crude oil.