Fluid catalytic cracking feed hydrotreatment and its severity impact on product yields and quality

This paper investigates the effect of fluid catalytic cracking (FCC) feed hydrotreatment and its severity increase on product yields and quality obtained in a commercial and a laboratory MAT FCC units. The hydrotreatment of Ural heavy vacuum gas oil reduces not only sulfur, nitrogen, Conradson carbon and metals content in the FCC feed but also increases the mononuclear aromatic hydrocarbons content by 8% absolute at almost no change in the total aromatics content. Regardless of this 8% increase of the mononuclear aromatics in the hydrotreated FCC feed the conversion increase in both commercial and laboratory MAT units was only 2%. The severity increase in the FCC feed hydrotreater leads to a higher conversion in the FCC, higher hydrogen transfer rate that results in higher isobutane/butylenes ratio, lower gasoline olefins content, and higher gasoline motor octane number. The hydrotreatment of the Ural heavy vacuum gas oil exhibited the same changes in FCC catalyst selectivities: lower coke and LCO selectivities and higher gasoline selectivity in both commercial riser FCC unit that has between 2 and 3 s time on stream, and the fixed bed reactor MAT unit, that has 30 s time on stream.     

Synthesis, characterization and evaluation of a novel resid FCC catalyst based on in situ synthesis on kaolin microspheres

A new way was provided for in situ synthesized FCC catalyst. Characterization and evaluation results indicated the catalyst is more suitable for cracking resid feed because of its unique manufacturing process which makes this catalyst has appropriate pore structures in which large resid molecules are more accessible to the active sites. The high zeolite content (above 40%) keeps the catalyst having higher activity and selectivity. These advantages ensure the in situ catalyst developed more adaptable for cracking resid and resid-containing feedstocks, particularly the feed containing large amounts of contaminant metals.     

Fluid Catalytic Cracking Catalyst Evaluation: The Short Contact Time Resid Test

Abstract

The latest state‐of‐the‐art innovation in realistic fluid catalytic cracking (FCC) catalyst testing is the short contact time resid test (SCTRT). This unit has been especially developed for residual hydrocarbon feed and solves limitations of other lab‐scale testing units by allowing instantaneous mixing (injection time of 1 second) of catalyst and feed. Its unique features make the SCTRT an excellent tool for catalyst development and for screening and evaluating FCC short contact time operations in the laboratory.     

催化裂化原料加氢预处理催化剂的研制

为满足FCC原料预处理的要求,开发了一种高脱硫、脱氮活性的FCC原料预加氢处理催化剂。该催化剂以氟改性氧化铝为载体,Ni Mo为活性组分,比表面积为169 m2·g-1,孔容为0.31 m L·g-1,平均孔径为6.5 nm,最可几孔径为3.35 nm和8.00 nm,孔径(4~10)nm占71%,具有大孔容、高比表面积和活性金属组分分散性好等特点。在100 m L固定床加氢试验装置上,以中国石化青岛炼化公司的高硫低氮混合蜡油和江苏新海石化有限公司的高硫高氮焦化蜡油为原料进行加氢活性评价。结果表明,在反应温度370℃、反应压力10.0 MPa、空速1.0 h-1和氢油体积比700∶1条件下,高硫低氮混合蜡油的脱硫、脱氮率分别为98.0%和96.5%,对高硫高氮焦化蜡油的脱硫、脱氮率分别为93.2%和90.0%。催化剂表现出原料适应性强,能有效脱除原料中的硫氮化合物,具有较高的加氢活性。     

Cracking catalyst additives for sulfur removal from FCC gasoline

FCC catalyst additives for sulfur-compound cracking with the ability to reduce sulfur in gasoline have been produced by depositing various metals and metal oxides on different supports using the microemulsion technique. Three groups of additives have been studied. First, Zn on different supports: alumina, titania, and hydrotalcite. Second, different metals on alumina: Zn, Mn and Zr, and third, two different metals on hydrotalcite: Zn and Co. The additives were blended to 10 wt% with a reference FCC-catalyst. All the additives give lower yields of gasoline than the reference catalyst itself. The loss in gasoline is due to an increased amount of gas production and/or increase in coke production. Concerning the sulfur reduction, the order of activity of the four best additives is the following: Zn/hydrotalcite > ZrO/alumina > Zn/titania > Mn/alumina. Zn/hydrotalcite has a value of ≈80% reduction of sulfur in sulfur-spiked gasoline at the microactivity test (MAT)-level.     

Review on the deactivation of FCC catalysts by cyclic propylene steaming

The deactivation of FCC catalysts in small-scale units in the presence of contaminant metals has been the industry workhorse for a number of years due to the robustness and simplicity of such methods.

A major advance in the deactivation of metallated catalysts on a small-scale that better simulated the performance of commercial FCC catalyst, was the introduction of the cyclic propylene steaming (CPS) method. In the CPS protocol, FCC catalyst is impregnated with vanadium and nickel prior to deactivation in reduction–oxidation cycles and the latter provides significant advantages over traditional methods such as the Mitchell approach. In certain situations, however, the contribution of vanadium to catalyst deactivation is over-emphasized in the CPS method, and therefore this method has been developed further.

This paper describes a number of modifications that have been made to the CPS method to further attenuate the destructive effects of vanadium on the FCC catalyst during deactivation. This includes exposing the metallated catalyst to pre-stabilisation steps with reduction-oxidation cycles and changing the ratio of the time the catalyst spends in reducing and oxidising environments during the CPS cycles. The comparison of activity and selectivity data obtained from FCC catalysts having age distribution with those obtained from CPS showed that both scenarios gave the same catalyst ranking.

These investigations have also shown that the use of reduction–oxidation cycles better simulates the deactivation of FCC catalysts in the absence of contaminant metals. These investigations have also shown that the use of reduction–oxidation cycles better simulates the deactivation of FCC catalysts in the absence of contaminant metals “the part” than traditional deactivations in a 100% steam atmosphere.     

Equilibrium catalyst from a fluidized catalytic cracking unit separated by metal content by using carbon nanotubes and a biphasic system

During fluid catalytic cracking (FCC) operations FCC catalyst particles become contaminated with various metals. These metals impact FCC performance and currently requires equilibrium catalyst (ECAT) mixtures consisting of a blend of FCC particles with a time spent in the reactor ranging from minutes to several months to be continuously extracted and sold as low value products or sent to landfills. Here a unique method to recycle FCC ECAT particles is presented, which separates ECAT particles by metal content by synthesizing carbon nanotubes and nanofibers on the ECAT particles surface and using a biphasic system. ECAT with low metal content can be sent back to the FCC unit for further use while ECAT with high metal content can be used for other purposes. Further, we show these treated ECAT materials of high metals content will absorb oil on the surface of water and may prove useful for oil spill clean-up applications.     

Active Catalysts for the NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Reduction in a FCC unit

Additives, without noble metals, based in Ce–Al mixed oxides supported on γ-alumina have been investigated as potential catalysts for the NO _x reduction in the FCCU regenerator. The best results were obtained with clusters of Sn–Cu–Al–O interacting with Ce–Al mixed oxides highly dispersed on the γ-Al₂O₃. The strong interaction between the two complex oxides provides a stable catalyst with high activity at high temperature. These additives would be active in the dense phase of the FCC regenerator, being deactivated at oxygen concentrations higher than 2%, but they would be regenerated in the FCC reactor. A. Uzcátegui is in leave to Laboratorio de cinética y catálisis del Departamento de Química, Facultad de Ciencias, Universidad de los Andes, La Hechicera, Merida, Venezuela.     

影响FCC再生立管输送催化剂影响因素的分析

再生立管是FCC装置再生器和提升管反应器之间再生催化剂循环的输送管,其操作复杂性在于立管内催化剂的流态受多种因素影响。本文中在1.0Mt/a FCC装置上,通过测量立管改造前后不同操作条件时的轴向压力分布,考察再生立管输送催化剂的影响因素。生产运行结果表明,影响立管操作的主要因素包括催化剂密度和平均粒径、立管几何结构、滑阀安装位置、松动风性质和流量等;选用低密度催化剂和高黏度流化介质可以减小气泡尺寸,维持反应温度稳定;松动风流量应根据立管推动力、滑阀压降和反应温度及时调整,避免填充流。另外,立管结构和滑阀的安装位置对立管推动力影响较大,分析结果可供立管设计和装置改造参考。     

Adsorption and desorption kinetics of hydrocarbons in FCC catalysts studied using a tapered element oscillating microbalance (TEOM). Part 1: experimental measurements

An experimental procedure to measure the adsorption and desorption kinetics of hydrocarbons in fluid catalytic cracking (FCC) catalysts using a tapered element oscillating microbalance is described. It enables adsorption rates to be measured on a timescale of about . Experiments using n-hexane, n-heptane, n-octane, toluene and p-xylene were performed on both a commercial FCC catalyst and a pure rare-earth exchanged zeolite Y sample under non-reacting conditions (temperatures of 373-). Heats of adsorption for these hydrocarbons are reported. The overall adsorption and desorption kinetics are found to depend on carrier gas flowrate in cases when adsorption is strong indicating that the length of the catalyst bed can have a significant influence on the observed kinetics. However, at high carrier gas flowrates the overall adsorption and desorption kinetics do not depend on the amount of catalyst present. It is found that the rates of adsorption and desorption of the hydrocarbons studied are the same for the FCC catalyst as for the pure zeolite Y sample. This means that mass transport in the matrix component of the FCC catalyst is rapid and not a limiting step in the adsorption process for the hydrocarbons studied in this work.     

催化裂化汽油加氢改质催化剂的改进

针对催化裂化汽油加氢脱硫降烯烃组合工艺技术中，芳构化降烯烃改质催化剂M应用于重馏分汽油加氢时，存在因反应温度高而影响催化剂长周期运行及液体总收率等问题，对催化剂进行优化升级改进研究。结果表明，在M催化剂基础上，通过对HZSM-5分子筛原料改进及调变活性金属组分，研制出活性高和稳定性好的催化裂化重汽油芳构化降烯烃改质催化剂M-Ⅱ，与M催化剂相比，烯烃降低幅度相当时，芳烃增加1.5个百分点，研究法辛烷值提高0.8个单位。     

Five-lump kinetic model with selective catalyst deactivation for the prediction of the product selectivity in the fluid catalytic cracking process

The effective simulation of the fluid catalytic cracking (FCC) operation requires a good understanding of many factors such as, reaction kinetics, fluid dynamics, and feed and catalyst effects. The different product slates that can be obtained are the consequence of a complex reaction scheme including cracking, isomerization, hydrogen transfer, oligomerization, etc. Furthermore, the catalyst deactivation may affect each one of the reactions in different ways, which creates an additional reason for different variation with time-on-stream of the yield to each product. On the basis of the experimental data of the FCC pilot plant operated in Chemical Process Engineering Research Institute (CPERI, Thessaloniki, Greece), a lumping model was developed for the prediction of the FCC product distribution. The lumped reaction network involved five general lumps (gas oil, gasoline, coke, liquefied product gas, and dry gas) to simulate the cracking reactions and to predict the gas oil conversion and the product distribution. The paths of catalyst deactivation were studied and a selective deactivation model was adopted that enhances the fundamentality and accuracy of the lumping scheme. The hypothesis of selective catalyst deactivation was found to improve the product slates prediction. Models with different assumptions were examined, regarding the behavior of the catalyst, as deactivated, and its effect on the reactions of the lumping scheme. A large database of experiments, performed in the FCC pilot plant of CPERI was used to verify the performance of the models in steady state unit operation. The simulation results depict the importance of incorporating selective catalyst deactivation functions in FCC lumping models.     

Dependence of Fluid Catalytic Cracking Unit Performance on H-Oil Severity,Catalyst Activity,and Coke Selectivity

The effect of the quality of ebullated bed vacuum residue H-Oil hydrocracking gas oils cracked in a commercial fluid catalytic cracking unit (FCCU) on its performance was studied. Six different catalysts were employed in this study. Four catalysts were tested in a commercial FCCU, and two in a laboratory FCCU. An increase of the H-Oil hydrocracker reaction temperature was associated with a decrease in the K_W factor of the H-Oil gas oils. The diminished K_W factor of H-Oil gas oils resulted in lower FCCU conversion and higher regenerator temperatures. The FCC conversion at maximum gasoline yield is best predicted by the feed K_W factor. The higher-activity, higher-Δcoke catalyst is unfavorable for FCCU performance because the excessive regenerator temperature excursions require reduction of the throughput.     

From waste to best: excellent desulfurization performance of spent FCC catalyst

Fluidized catalytic cracking (FCC) is an important link in heavy oil processing. Industrial FCC catalyst which mainly consists of molecular sieves, substrates and adhesives is used in large quantities every year. Spent FCC catalyst is one kind of hazardous solid waste that is hard to handle. In this paper, we used a spent FCC catalyst as a desulfurization adsorbent, and show that it displays advanced desulfurization property. Furthermore, regeneration experiment showed that calcination was an effective method to remove the sulfides adsorbed in spent FCC catalyst, after four cycles it still owned a high sulfur adsorption ability. The results of metal impregnation indicated that the high ability to remove sulfur in LPG was due to those metals deposited on WC. The sulfur removal further increased by calcination of the spent catalyst since carbon deposition on the catalyst surface which blocked the active sites was minimized by calcination, thus leading an increase in the number of active sites available.     

Selective catalytic reduction of NOx, by propene over copper-exchanged pillared clays

Copper-exchanged pillared clays were examined as an SCR catalyst for NO_x, removal by propene. Both micropores and mesopores were simultaneously developed by pillaring a bentonite with TiO₂. Therefore, TiO₂-pillared clay has about 8 to 9 times higher surface area and 3 times higher pore volume than the parent unpillared bentonite. The presence of water in the feed gas stream caused a small and reversible inhibition effect on NO removal activity of Cu/Ti-PILC. The water tolerance of Cu/Ti-PILC was higher than copper-exchanged zeolites such as CuHM and Cu/ZSM-5 due to its high hydrophobicity as confirmed by H₂O-TPD experiment. Copper-exchanged PILC was confirmed to be an active catalyst for NO_x, removal by propene. The addition of copper to TiO₂-pillared clay greatly enhanced the catalytic activity for NO removal. Cupric ions on Ti-PILC were active reaction sites for the present reaction system. The state of copper species on the surface of Ti-PILC varied with the content of copper and TiO₂. The catalyst having more easily reducible cupric ions showed maximum NO conversion at relatively lower reaction temperatures. It indicates that the redox behavior of cupric ions is directly related to NO removal mechanism. The redox property of cupric ions depended on the copper content and dehydration temperature of PILC.     

Study of cracking FCC naphtha in a secondary riser of the FCC unit for maximum propylene production

To satisfy the increasing propylene demand, reprocessing FCC naphtha in a secondary riser of the FCC unit was investigated. To this aim, a full range FCC naphtha was cracked over a mixture of two kinds of commercial equilibrium FCC catalysts, which contained 95 t.% Y zeolite-based catalyst and 5 wt.% ZSM-5 zeolite-based additive. The effects of operating parameters such as reaction temperature (temperature of the riser outlet), catalyst-to-oil ratio and residence time on FCC naphtha cracking were studied in a continuous pilot plant. This work demonstrates that FCC naphtha requires high operating severities to crack, and approximately 12–19 wt.% FCC naphtha can be transformed into propylene. The conversion and yield of propylene showed a rapid increase with increasing reaction temperature, and the increase of catalyst-to-oil ratio also enhanced FCC naphtha cracking, even at high reaction temperature. However, at high catalyst-to-oil reactions, hydrogen-transfer reactions constrain further increases in light olefin yields. At these high operating severities, shortening residence time is an appropriate way to obtain high yields of propylene combined with (i) lower yields of dry gas and (ii) a lower apparent hydrogen-transfer coefficient.     

Catalytic behaviour of nickel and iron metal contaminants of an FCC catalyst after oxidative and reductive thermal treatments

The catalytic effects of nickel and iron deposited on an FCC (fluidized catalytic cracking) catalyst via metal naphthenates were studied in a micro activity test (MAT) unit after both oxidative and reductive treatments of the catalyst samples.The dehydrogenation activity of nickel was found to be close to the dehydrogenation activity of vanadium – and not several times higher than that of vanadium as is often reported – when deposited on the commercial FCC catalyst used in this study followed by steam deactivation (oxidative treatment) at 760 °C. However, the dehydrogenation activity of nickel was significantly intensified after post-treatment with a CO/N₂ mixture at this temperature (reductive treatment).The results show that iron did not have a dehydrogenation activity after steaming, but had a significant dehydrogenation activity after steaming when followed by exposure to the CO/N₂ mixture at 760 °C. The results indicate that the presence of deposited iron was inducing an additional catalytic cracking activity for the FCC catalyst.It was observed that co-impregnation of equal loadings of nickel, iron and vanadium on the FCC catalyst led to a considerably higher dehydrogenation activity than could be expected from the catalytic behaviour of the separate elements. The dehydrogenation activity was however slightly reduced by the reductive treatment as the reduced dehydrogenation activity from the lower oxidation state of vanadium (V³⁺) more than compensated the increased dehydrogenation activity of iron and nickel. A slightly increased gasoline production after the reductive treatment of the co-impregnated sample was a result of the increased production of gasoline from the FCC catalyst itself, which more than compensated for the reduced gasoline production from nickel.     

废FCC催化剂在LPG吸附脱硫中的资源化利用

金属污染是导致流化催化裂化（FCC）催化剂失活的重要因素,充分利用沉积的重金属是废FCC催化剂资源化的关键。本文将废FCC催化剂引入到轻质油品吸附脱硫领域,以脱除液化石油气（LPG）中的二甲基二硫醚作为考核目标,验证了废FCC催化剂作为脱硫剂的可行性。除去废FCC催化剂表面积炭后,其脱硫性能得到明显改善,在常温、质量空速为4.0h^-1的条件下,LPG中硫化物质量分数从382mg/m³脱除至40mg/m³。镧、铁、镍、钒、钙、锑6种金属在新鲜催化剂和焙烧后废催化剂上的总质量分数从10.2%升高至46.6%,6种金属按照对应含量分别固载在新鲜催化剂上,脱硫效果较未改性新鲜催化剂均有明显提升。验证实验表明,导致FCC催化剂失活的金属具有较高脱硫活性,废FCC催化剂作为轻质油品脱硫剂具备工业前景。     

重油催化裂化装置抗重金属镍污染的措施

重金属镍和钒在催化裂化催化剂上的沉积会导致催化剂的失活和选择性下降。大港油田炼油厂针对催化原料中重金属镍含量高的实际情况,采取了使用金属钝化剂、干气预提升、定期卸出部分平衡剂并补充新鲜剂、选用抗镍能力强的催化剂等一系列钝镍措施,取得了较好的工业应用效果。