煤焦油悬浮床加氢装置反应温度的影响及控制

对反应器入口温度以及相应的平均反应温度进行综合性的探究,并且对反应器出口温度变化所产生的影响进行综合性分析。悬浮床加氢有强制循环悬浮床加氢以及非强制循环悬浮床加氢两种模式运行,对相应的温度控制方式进行了分析与探究。非强制循环悬浮床加氢装置反应温度的控制方式与固定床的方式具有一定程度的类似性,其主要的模式是通过对加热炉负荷进行调节,并且对反应器床层冷氢注入量调整,而强制循环悬浮床加氢装置,对加热炉负荷、反应器入口冷氢注入量以及反应器底循环泵循环量调整,以此对反应温度进行有效的调节。     

温度对粗苯加氢脱硫反应的研究

在低温条件下,使用2段预加氢反应和1段主加氢脱硫反应工艺条件,研究了温度对粗苯加氢脱硫反应的影响,并分析了反应产物的烃组成、双烯值和GC-SCD。研究结果表明:3段反应中,温度的变化对烃组成影响甚微,在第一段预加氢反应中,随着温度的升高,硫含量变化不大,但是双烯值变化明显,在体积空速1.0 h-1,反应压力为3.0 MPa,氢油比400∶1,反应温度为160℃时,双烯值为1.35 g I/100 g,下降了76.23%;第二段预加氢反应中,随着温度的变化,产物的烃组成、双烯值和硫含量变化均不明显;第三段主加氢脱硫反应中,在体积空速1 h-1,反应压力3.0 MPa,氢油比为400∶1,反应温度300℃时,产物中硫质量浓度为21.16 mg/L,脱硫率99.27%,噻吩脱除率为99.87%。     

实用新型专利ZL201621393255.X 预加氢反应的中低温煤焦油加氢系统

<正>一种增设预加氢反应的中低温煤焦油加氢系统,该系统精制进料缓冲罐、加氢精制反应器、精制热高分罐、精制冷高分罐、加热炉、裂化进料缓冲罐、加氢裂化反应器、裂化热高分罐、裂化冷高分罐、热低分罐、冷低分罐、脱硫化氢汽提塔(稳定塔)、分馏塔、循环氢压缩机和新氢压缩机;还包括预加氢进料缓冲罐和预加氢反应器,所述的预加氢进料缓冲罐和预加氢反应器通过管路连接,所述的预加氢反应器的底部通过管路与加氢精制反应器连接,所述的加热炉通过管路与预加氢反     

汽油加氢脱硫装置催化剂毒物对产品质量的影响及原因分析

针对大庆石化公司炼油厂GARDES工艺催化汽油加氢脱硫装置在2021年5～6月连续出现汽油产品硫含量不合格的情况，详细论述催化汽油加氢脱硫装置产品硫含量不合格时的排查过程及原因分析。结果表明，循环氢中CO含量上升对催化剂脱硫效果抑制非常明显，当循环氢中CO含量高于200 mL·m^-3,催化剂脱硫活性明显降低。     

NiW/Al2O3催化剂上二苯并噻吩的加氢脱硫宏观动力学

以二苯并噻吩(DBT)为含硫模型化合物,在实验室中压滴流床反应装置中研究了工业NiW/Al2O3催化剂RN-10上的加氢脱硫反应的动力学规律,详细考察了工艺条件:氢分压2.4～4.5 MPa、氢油比150～700(v/v)、液时空速(WHSV)15～60 h-1、反应温度300～380C对DBT转化率的影响.实验结果表明:提高反应温度可大大提高DBT的转化率,但反应温度达到330℃后,再提高反应温度,对DBT转化率的提升有限;在较高氢分压的条件下,DBT的转化率受氢分压的影响很小;当氢油比较小时,随着氢油比的提高,DBT转化率逐渐增加,但当氢油体积比大到一定程度(500)时,继续增大氢油比对脱硫率几乎没有影响.采用修正了的2级反应动力学模型对实验数据进行拟合,求得了二苯并噻吩加氢脱硫反应的表观活化能为75.95 kJ·mol-1.经检验,模型计算结果与实验结果能较好地吻合.     

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。     

固定床加氢装置开工过程中要点和难点

加氢装置开工是每套装置最重要的环节,其中涉及的油联运、烘炉、氢气气密、硫化、钝化、循环氢量控制以及反应温度的控制都是要点、难点。供氢溶剂油加氢是将原料油适度加氢饱和转化为部分饱和的双环芳烃和部分饱和的多环芳烃,独立的芳烃饱和过程反应物的碳数不变(即不产生小分子),为加氢装置提供芳碳率适度的供氢溶剂油。此论文以溶剂油加氢与加氢精制、加氢裂化共用一套循环氢系统为例,首先对固定床加氢装置的开工要点和难点进行介绍,其次结合国内多套加氢装置实际开工过程以及开工中出现问题总结较好的开工经验,为以后新建装置开工提供借鉴^[1]。     

循环氢脱硫系统带液分析

介绍了山东京博石油化工有限公司柴油加氢装置运行情况,以及存在问题解决。循环氢脱硫系统在运行过程中带液,影响安全生产,分析脱硫系统胺液发泡,胺液浓度、清洁度和硫化氢含量等因素,最终问题点聚焦在反应系统的脱盐效率上,装置原料实际氮含量高于方案设计氮含量。在原料氮含量较高的情况下,操作未采取相应措施,实际注水量低于设计值,针对因素及时调整,适当调整贫胺液温度、注水量,使装置平稳运行。     

汽油加氢装置降辛烷值损失优化控制

针对吉林石化PRIME G+汽油加氢脱硫装置国Ⅴ质量升级改造后,存在脱硫深度较同类装置大,辛烷值损失大的实际问题,通过对影响装置辛烷值损失的因素进行深入分析,在保证催化剂使用寿命的前提下,通过调整选择性加氢反应温度、氢烃比、轻汽油采出比例、急冷烃以及加氢脱硫反应温度等工艺控制手段,尽量减少装置的辛烷值损失,提出降低装置辛烷值损失的优化控制方案,以期在今后较好地指导生产。     

煤焦油轻质油加氢制清洁燃料油试验研究

我国石油短缺,对数量可观的煤焦油进行加氢生产燃料油和精细化学品具有重要意义。以煤焦油预处理后的3种轻质馏分油混合油为原料,在固定床加氢装置上进行了轻质油全馏分加氢提质试验研究,考察了反应温度、反应压力、空速和氢油比对原料油脱硫脱氮及芳烃加氢饱和的影响。最后对加氢提质产物油性质进行分析。结果表明,产物氮、硫及芳烃含量均随着反应温度、压力、氢油比的增大而减少,随着空速的增大而增大;在反应温度为360℃,反应压力为16 MPa,液体体积空速为0.25 h~(-1),氢油比为1 800的最优工艺条件下,液体收率达到98.03%。对加氢后全馏分油进行精密蒸馏切割得到170℃的石脑油馏分和170℃的柴油馏分;石脑油馏分20℃密度为776.9 kg/m~3,几乎不含硫、氮,芳烃潜含量67.6%,可以作为优质的催化重整原料;加氢后的柴油馏分不含硫、氮,芳烃含量低,闪点高,凝点低,馏程适宜,可以作为柴油的调和油。     

Wasserstoff-Erzeugung und Kreislaufgas-Zerlegung für die Kohleverflüssigung

Hydrogen generation and recycle gas separation for coal liquefaction . Just as 40 years ago, low-temperature processes are now again being considered for recycle gas separation in today's large scale coal liquefaction projects. Hydrogen can be generated by gasification of heavy residues and by steam reforming of ethane. Alternatives for recycle gas separation into hydrogen and gas products are butane and methane absorption or low-temperature condensation processes at high or medium pressure. These processes employ several additional absorption and adsorption steps for gas purification. They are proven on a large technical scale, and fulfill the requirements of environmental legislation.     

甲烷水蒸汽催化转化的动力学模型

在常压下使用内循环式无梯度反应器研究了Z102镍催化剂上甲烷水蒸汽催化转化反应的动力学。实验条件如下:反应温度500—700℃,H_2O/CH_4=2.5—4.5（克分子比）,甲烷空速为2000—10000ml/h·g-cat。根据实验结果的分析,作者认为在反应过程中一氧化碳和二氧化碳是同时生成的,即甲烷水蒸汽催化转化反应可用平行反应模型来表示。所得到的一氧化碳及二氧化碳的生成速度方程分别为: rco=k,p_(CH_4)~(0.8)及 rco_2=k_2p_(CH_4)~(0.8) p_(H_2O)~(1.5)反应速度常数k_1及k_2与温度的关系均符合阿累尼乌斯方程。一些研究者认为在通常的操作条件下,甲烷水蒸汽催化转化反应过程中,水煤气变换反应很快就达到平衡,我们的实验数据计算证明这个见解是不妥的。     

钇对甲烷芳构化催化剂Mo／HZSM—5性能影响的研究

研究了稀土钇的含量对Ｍｏ／ＨＺＳＭ－５催化剂的活性和选择性的影响，发现稀土钇的加入，不同程度上提高了Ｍｏ／ＨＺＳＭ－５的活性和选择性。特别是，当Ｙ／Ｍｏ＝０．０４时，活性最佳。甲烷在１０２３Ｋ芳构化反应，转化率达１９．６％，苯的选择性达９６．５％，且活性较稳定。     

Combination of Sorption-Enhanced Steam Methane Reforming and Electricity Generation by MCFC: Concept and Numerical Simulation Analysis

Abstract

Reformed gas made by the steam methane reforming(SMR) process is used as fuel feed to MCFC, but it is not as good as pure hydrogen due to the presence of CO₂ and CO. The sorption-enhanced steam methane reforming(SE-SMR) process can reduce CO₂ and CO to a low level and produce high purity hydrogen. Considering the merits of similar operating temperatures (about 500°C) and carbon dioxide recycle, a novel concept of a six-step sorption-enhanced steam methane reforming (SE-SMR) combined with electricity generation by molten carbonate fuel cell (MCFC) is proposed. In the present paper, a cycle of the SE-SMR process, which include the steps of reaction/adsorption, depressurization, gas purges (nitrogen and reformed gas, respectively), and pressurization with reformed gas, is modeled and analyzed. The process stream in the SE-SMR process is used as anode feed in MCFC. According to the result of numerical simulation, a fuel cell grade hydrogen product (above 80% purity) at the SE-SMR temperature of 450°C can be obtained. A carbon dioxide recycle mechanism is developed for cathode feed of MCFC from flue gas by burning with excess air to achieve a proper CO₂/air ratio (about 30:70). The novel electricity generation system, which can operate at lower energy consumption and high purity hydrogen feed is helpful for the MCFC'S performance and life time.     

水合物法分离低浓度煤层气中的甲烷

向模拟煤层气(13.11vol% CH4+86.89vol% N2)中添加5.8mol%四氢呋喃(THF)?0.03mol%十二烷基硫酸钠(SDS)促进剂溶液分离提纯煤层气,考察了压力、温度、反应时间对气体消耗量、反应速率、分解气中甲烷浓度、甲烷回收率和甲烷分离因子的影响,采用色谱分析法分别测定了CH4在剩余气相和分解气相中的浓度。结果表明,压力增加,CH4回收率增大,CH4分离因子增大,CH4分离效果越好;温度是影响甲烷分离因子的关键因素,温度降低,氮气和甲烷竞争进入水合物晶体中,导致水合物相中甲烷浓度降低;温度升高有利于提高水合物对甲烷的选择性。甲烷回收效率最高可达98.65%,分离因子最大为14.83。随反应时间增加,分解气中CH4浓度升高。     

Hydrogen separation from the H2/N2 mixture by using a single and multi-stage inorganic membrane

The separation characteristics of hydrogen from a gas mixture were investigated by using a single and two-stage inorganic membrane. Three palladium impregnated membranes were prepared by using the sol-gel, hydrolysis, and soaking-and-vapor deposition (SVD) techniques. A two-stage gas separation system without a recycling stream was constructed to see how much the hydrogen separation factor would be increased. Numerical simulation for the separation system was conducted to predict the separation behavior for the multi-stage separation system and to determine the optimal operating conditions at which the highest separation factor is obtained. Gas separation through each prepared membrane was achieved mainly by Knudsen diffusion. The real separation factor for the H₂/ N₂ mixture was increased with the pressure difference and temperature for a single stage, respectively. For the twostage separation system, there was a maximum point at which the highest separation factor was obtained and the real hydrogen separation factor for H₂/N₂ mixture was increased about 40 % compared with a single stage separation. The numerical simulation for the single and two-stage separation system was in a good agreement with the experimental results. By numerical simulation for the three-stage separation system, which has a recycle stream and three membranes that have the same permeability and hydrogen selectivity near to the Knudsen value, it is clear that the hydrogen separation factors for H₂/N₂ mixture are increased from 1.8 to 3.65 and hydrogen can be concentrated up to about 80 %. The separation factors increased with increasing recycle ratio. Optimal operating conditions exist at which the maximum real separation factor for the gas mixture can be obtained for three-stage gas separation and they can be predicted successfully by numerical simulation.     

Solvent-based fatty alcohol synthesis using supercritical butane. Thermodynamic analysis

Conventional liquid-phase fatty ester hydrogenolysis processes are necessarily operated at high pressures owing to the limited solubility of hydrogen in the reaction medium. In a solvent-based process this problem can be overcome, but recycling and product-solvent separation may turn out to be difficult. An alternative is the use of supercritical solvents, for which the solubility of fatty esters and fatty alcohols is high. Dropping the pressure into the subcritical domain allows for easy product separation and reactant recycle. In the present work we have analyzed the hydrogenolysis of methyl palmitate in supercritical butane. A reliable estimation of properties of the supercritical mixture can be obtained by fitting experimental vapor-liquid equilibrium data with Schwatzentruber-Renon cubic equation of state. The reaction mixture remains supercritical for a maximum pressure of 9 MPa and temperature of 470 K for mole fractions of hydrogen and methyl palmitate of 0.1 and 0.025, respectively. In these conditions an equilibrium conversion of more than 99% can be reached. An industrial process is feasible.     

Investigation on the structure and the oxidation activity of the solid carbon produced from catalytic decomposition of methane

The structure and the oxidation activity of the solid carbon produced from catalytic decomposition of methane at different temperatures were investigated using TEM, XRD, Raman and TPO techniques. The results show that the graphitization degree of the solid carbon is increased with decomposition reaction temperature. The addition of ethylene or acetylene to methane can change the growth way of the solid carbon and decrease their graphitization degree. The average oxidation temperature of the solid carbon has a close relationship with the corresponding graphitization degree. The addition of ethylene or acetylene to methane can decrease the average oxidation temperature of the solid carbon.     

Inhibition of hydrogasification of brown coals by moisture: Influence of heating rate, temperature and pressure

Two types of Rheinische Braunkohle with different mineral matter contents, each with two different moisture contents plus a coke produced from the coal with the lower ash content, were gasified at total pressures between 0.2 and 5 MPa with pure or dry hydrogen, hydrogen/water vapour and argon/water vapour mixtures. In studies with controlled heating (4 K min⁻¹ up to 850 °C) it was found that: 1. methane formation rates and methane yields during gasification in dry hydrogen are drastically lowered with increased moisture of the coals but only at high pressures which reduce evaporation of water; 2. methane formation rates and methane yields during gasification with wet hydrogen (x_H2o = 0.02) are generally lowered with all materials; 3. increasing the water content does not further lower the yields or lead to water vapour gasification. Studies at constant temperature (after rapid heating, 100 K s⁻¹) confirmed these results. It was found that increasing the temperature to 950 °C does not eliminate the inhibiting effect of moisture (in hydrogen) if hydrogen pressure is low ≈ ≤ 1 MPa. It was also determined that raising the temperature above 850 °C with a simultaneous increase in pressure up to 5 MPa hydrogen effectively prevented the inhibition by moisture. It was concluded that extremely stable ether bridges are blocking the active sites at the carbon suface and are therefore responsible for the inhibitory effect of moisture in hydrogasification.     

基于Aspen Plus的焦炉气制甲烷工艺模拟与分析

利用Aspen Plus模拟软件对焦炉煤气制甲烷工艺进行了流程模拟。分析了甲烷化反应压力、过热蒸汽与反应进料气质量比对反应器出口温度和甲烷产量的影响。结果显示,当反应压力在10×103kPa³0×103kPa时,可调控两个反应器出口温度范围均为0℃30×103kPa时,可调控两个反应器出口温度范围均为0℃⁵0℃,甲烷产量变化很大;当过热蒸汽与反应进料气质量比在0.0550℃,甲烷产量变化很大;当过热蒸汽与反应进料气质量比在0.05⁰.40时,可调控第一、二级反应器出口温度范围分别为0℃0.40时,可调控第一、二级反应器出口温度范围分别为0℃⁵0℃和0℃50℃和0℃²5℃,甲烷产量变化不大。