磁分离回收技术在催化裂化废催化剂研究中的应用

在催化裂化反应条件下,原料油中的重金属(如Ni,Fe,V等)不断地沉积在催化剂表面,使催化剂受到污染而中毒,降低了活性和选择性,导致氢气、焦炭量增加,目的产物汽柴油收率下降,影响装置经济效益。采用磁分离技术回收催化裂化废催化剂是一种简捷而有效的工艺。华北石化催化裂化废催化剂磁分离回收试验结果表明,回收率控制在35%-50%时,可使回收的催化剂微反活性提高6.4~10.2个单位,催化裂化总液体收率提高0.61%-2.09%,经济效益显著。     

AIC-950重油催化裂化催化剂的工业应用

介绍了重油催化裂化催化剂AIC-950在山东东明石化集团有限公司Ⅳ套催化裂化装置上工业应用的情况。结果表明,当AIC-950催化剂达到系统藏量的60%后,与对比剂相比,干气收率下降1.40百分点,同时,油浆收率下降0.11百分点,总液体收率上升1.40百分点,轻质油收率上升1.51百分点。由此可见,采用AIC-950催化剂时产品选择性好、轻质油收率高、总液体收率高、重油转化能力强。     

RE-Ⅱ助剂对CRMI-2催化剂催化裂化性能的影响

目前炼油工业实现重油轻质化的主要措施仍然是重油催化裂化工艺，借助催化裂化工艺可将低附加值重质油品转化为高附加值轻质油品。我国成品油市场中75%以上的汽油调和组分来自于催化裂化工艺。借助优化操作条件，改善进料喷嘴的雾化效果，提高汽提效率，虽能部分提高催化裂化反应产物中的轻油收率，但受自身工艺条件的限制，很难满足进一步提高轻油收率的要求。在FFB小型固定流化床反应装置上考察添加RE-Ⅱ助剂对CRMI-2催化剂催化裂化性能的影响，采用XRD、NH3-TPD和BET等对反应后CRMI-2催化剂的结构、酸性和比表面积进行表征。结果表明，与空白样品相比，添加质量分数0.6%RE-Ⅱ助剂的CRMI-2催化剂，催化裂化反应产物的总液收和轻油收率分别为88.99%和71.64%，与CRMI-2催化剂相比,提高了2.04个百分点和2.43个百分点，焦炭收率为3.70%，降低了0.48个百分点。     

苏丹高酸原油两段催化裂化初步研究

在小型提升管催化裂化实验装置上进行了苏丹高酸原油两段提升管催化裂化的实验研究,考察了LTB-2催化剂和ZC-7300催化剂对苏丹高酸原油的催化裂化效果.结果表明苏丹高酸原油虽然性质较差,但是很容易催化裂化.苏丹高酸原油在ZC-7300催化剂上的转化率很高,但产物分布较差,尤其是柴油的收率太低;采用LTB-2催化剂时,苏丹高酸原油的转化率较低,但柴油和低碳烯烃的收率较高,同时可以完全脱除其中的石油酸.在丙烯产率高达20.18%的情况下,柴油收率可以达到21.63%,而且汽油的烯烃含量非常低.由于原料的残炭很高,焦炭的产率非常高,将增加烧焦负荷.     

催化裂化汽油在多元沸石基催化剂上加氢改质研究

采用浸渍法分别制备了以丝光沸石（HM）、Hβ和HZSM-5及其组合为载体的沸石基Ni-Mo-P催化剂,考察了载体组成对催化裂化汽油加氢改质反应性能的影响。结果表明,由适宜比例的三者组合得到的沸石基Ni-Mo-P催化剂具有良好的加氢异构化、脱硫、芳构化活性及稳定性,可在催化裂化汽油脱硫降烯烃的同时保证产品的辛烷值不降低。考察了工艺条件对三元沸石基Ni-Mo-P催化剂反应性能的影响。在温度300 ℃、氢油体积比350、液相体积空速2.5 h-1和反应压力1.5 MPa反应条件下,催化裂化汽油异构烷烃收率、芳烃收率、脱硫率及液相收率分别达41.9%、31.7%、51.0%和98.3% 。     

GDmax-Per催化剂在海外炼厂的工业应用

介绍中国石化催化剂有限公司齐鲁分公司生产的GDmax-Per催化裂化催化剂在印度尼西亚A炼厂催化裂化装置的工业应用情况,运行结果表明:使用GDmax-Per催化剂,其装置裂化产物分布均优于投标保证值,汽油收率质量分数高于保证值0.5%,丙烯收率质量分数高于保证值1.3%;同时汽油辛烷值达到92.2,高于保证值要求的91.0,生产出的高辛烷值汽油可以直接出厂,进一步提升了企业效益。GDmax-Per催化剂的成功应用,充分展示了齐鲁分公司催化裂化催化剂的国际竞争力。     

柴油非临氢降凝催化剂的中试应用

研制新型柴油降凝催化剂,在常压﹑非临氢条件下以抚顺石油二厂催化裂化柴油和辽化加氢裂化尾油为原料,考察了温度、空速对降凝效果的影响。催化裂化柴油凝点可降低5~25℃,液体收率98%以上,柴油收率85%以上;加氢裂化尾油凝点可降低36~56℃,液体收率在95%左右,润滑油基础油的收率在90%左右,裂解气产量很少,降凝效果显著。     

LZR-20催化剂在催化裂化装置的工业应用

介绍了LZR-20高效重油转化催化剂在某石化公司3.0 Mt/a流化催化裂化装置的工业应用情况。结果表明,与原催化剂相比,总液体收率增加2.39%,油浆收率降低3.04%,焦炭收率增加0.42%,丙烯收率增加1.16%,汽油RON提高0.86个单位。LZR-20催化剂表现出良好的重油转换能力和产品选择性,具有增产丙烯和提高汽油辛烷值的特点。     

CC-20DF催化剂在灵活多效催化裂化装置上的应用

在双提升管催化裂化装置(FDFCC)上,使用长岭催化剂厂生产的CC-20DF催化剂,液态烃收率及烃中的丙烯含量增加,当CC-20DF催化剂占总藏量40%时液态烃收率达到13.5%,丙烯收率达到4.52%(收率均相对于总进料,以下同).     

LDO-75重油催化裂化催化剂的工业应用

介绍了LDO-75重油裂化催化剂在中国石油大连石化公司年产3.5 Mt重油催化裂化装置的工业应用.结果表明,LDO-75催化剂达到系统总藏量50%后,装置催化剂单耗由1.34kg·t-1降至1.04 kg·t-1,干气和油浆收率分别降低0.03%和1.36%,液化气收率增加1.19%,总液收提高1.42%.     

新型CDCM催化剂在两段提升管催化裂化装置上的应用

CDCM催化剂在800 kt·a^－1两段提升管重油催化裂化装置（TSRFCC）上的应用结果表明,该催化剂具有活性高、目的产品选择性好、重油裂解能力强和抗重金属污染能力强的特点。能显著改善产品分布和提高产品质量，在操作条件基本不变的情况下，液态烃收率和总液收分别可提高2.80和0.60个百分点，同时汽油辛烷值和诱导期提高，液态烃中丙烯含量增加。     

TMP工艺与催化剂的配套性分析

在重油催化裂解多产丙烯（简称TMP）技术中,将两段催化裂解工艺与配套的增产丙烯催化剩结合,以大庆常压渣油为原料可以得到20％的丙烯收率,并能够很好兼顾汽柴油的质量。试验结果表明：以大庆常压渣油为原料,使用配套开发的LCC-300催化剂,干气加焦炭收率。小于15％、丙烯的收率大于20％、汽油的辛烷值RON96、烯烃30％（v）左右。     

Recovery of liquid fuel from hydrocarbon-rich microalgae by thermochemical liquefaction

Liquefaction of Botryococcus braunii, a colony-forming microalga, with high moisture content was performed with or without sodium carbonate as a catalyst for conversion into liquid fuel and recovery of hydrocarbons. A greater amount of oil than the content of hydrocarbons in B. braunii (50 wt% db) was obtained, in a yield of 57–64 wt% at 300 °C. The oil was equivalent in quality to petroleum oil. The recovery of hydrocarbons was a maximum (>95%) at 300 °C.     

Hydrogen production from fluidized bed steam reforming of hydrocarbons

Steam reforming of methane, kerosene and heavy oil over a nickel/alumina commercial catalyst and other materials such as limestone, dolomite and iron ore, was studied using a 5 cm i.d. fluidized bed reactor. The effects of operating parameters on conversion, hydrogen yield, product gas composition and elutriation of fine catalysts were investigated. It was found that a fluidized bed is flexible enough to handle various feedstocks, including hydrocarbons heavier than naphtha, because it permits the addition of catalyst to, or withdrawals of, coked catalyst from the bed. The yield of hydrogen obtained from fluidized bed steam reforming of heavy oil at 800‡C over limestone was similar to that obtained over commercial nickel-based catalyst. This indicates that limestone could be a promising catalyst for the production of hydrogen from heavy oil. However, hydrogen yield decreased with reaction time in the experiments using the limestone catalyst. The main cause of the decrease in hydrogen yield was elutriation of fine catalysts from the bed during the reaction.     

页岩灰和FCC催化剂调控油页岩热解产物二次反应特性

采用两段反应器对油页岩热解初级挥发分进行二次催化反应特性研究,考察了第2段反应器内不同的催化载体、反应气氛与停留时间对油气收率及品质的影响。结果表明,在考察的停留时间范围内页岩灰具有相对适中的催化活性来调控热解挥发分产物的二次反应,水蒸气气氛能够进一步提高热解油收率约5%,并能够在一定程度上抑制裂解气体中C₂~C₃组分的生成。页岩灰作为催化载体能够转化热解油中VGO（馏程>350℃）等重质组分,随停留时间增加油品馏程向轻组分转移。油品组分GC-MS结果表明,较短停留时间内（<3 s）,水蒸气添加能够有效抑制热解油中脂肪烃类的过度裂解,与氮气相比提高汽柴油馏分含量20%以上。过长的停留时间（3~5 s）会造成VGO等馏分缩聚生成焦炭,从而大幅降低热解油收率。     

重质芳烃油选择性加氢工艺研究

以油浆抽提得到的重质芳烃油为原料,通过选择性加氢工艺降低其中有害的稠环芳烃(PAHs)化合物,得到的精制油为橡胶用环保芳烃油。实验分别对反应温度、压力、时间以及一段、二段加氢工艺对PAHs转化率的影响进行了考察,同时运用BET及EDS对2种硫化态催化剂进行了表征,以考察催化剂的活性及选择性。结果表明,Ni-W/γ-Al2O3催化剂活性及选择性较Ni-Mo/γ-Al2O3高。实验证明:通过选择性加氢可大幅度降低重质芳烃油中PAHs质量分数,一段加氢采用Ni-W/γ-Al2O3催化剂,在反应温度280℃、压力8 MPa、时间6 h的条件下,原料PAHs转化率达到46.24%;二段加氢采用Ni-Mo/γ-Al2O3催化剂,在与一段相同的反应条件下,PAHs转化率达到32.94%。经2段加氢后,产物中PAHs质量分数由起始的58.13%降到21.05%,总转化率达到63.79%,液体总收率91.72%。     

混合废塑料与焦化蜡油共催化裂解制取燃料油

以混合废塑料和焦化蜡油为原料,共催化裂解制备燃料油,克服了废塑料裂解中塑料粘稠度大且传热效率低、裂解炉中温度极不均匀、反应时间长、气体和固体收率高、液体收率低和易结焦等难题。详细考察焦化蜡油与混合废塑料质量比和催化剂用量对产物组成的影响以及FCC催化剂的重复使用性能。结果表明,在焦化蜡油与混合废塑料质量比为2、FCC催化剂用量为混合废塑料质量的10%、终温460 ℃并保持4 h条件下,燃料油收率达到96.67%,气体收率和釜残率分别仅有0.27%和1.53%。焦化蜡油的添加使液相产物中重组分增多,轻组分减少。FCC催化剂的重复使用性能好,催化剂重复使用5次,液体收率大于85%。采用混合废塑料与焦化蜡油共催化裂解的工艺不仅为“白色污染”的处理开辟了一条新途径,而且扩大了焦化蜡油的应用范围。     

Conversion of plastics/HVGO mixtures to fuels by two-step processing

A blend containing 20 wt.% low density polyethylene (PE) and 5 wt.% polyvinylchloride (PVC) in heavy vacuum gas oil was pyrolyzed at 623 K (dechlorination step). This mixture was then thermally and catalytically cracked in the presence of hydrogen at 673–723 K in a batch reactor (hydrocracking step). The liquid products from hydrocracking contained no chlorine compounds although the chlorine amount in the dechlorinated mixture was 700 ppm. Experiments have shown that the dechlorination step and the temperature had great effect on the product distribution from the hydrocracking step. It was observed that the dechlorination step led to both degradation of PE and dechlorination of PVC and that PE could be completely cracked with/without a catalyst by hydrocracking even though at 673 K. The use of a catalyst decreased the gas yield and led to an increase in coke yield at 723 K. The effect of the catalyst on the boiling point range of liquid product obtained from hydrocracking depended on the reaction temperature. The chlorine compounds in dechlorinated mixture affected the catalytic activity of the catalyst especially at 723 K. 75% and 55% of the liquid products obtained at 723 K with and without a catalyst, respectively, were hydrocarbons having boiling points ranging from 323 to 473K.     

油浆抽余油FCC反应

油浆经萃取分离得到以饱和烃为主的理想组分——抽余油。利用该油作为原料进行FCC反应,并与石蜡基重油从原料性质、反应工艺条件、产品分布及性质、再生剂性能等方面进行对比研究。结果表明：抽余油具有良好的FCC性能,其合适的反应条件为剂油比6.0、反应温度520 ℃、重时空速12.0 h?1;在各自最优工艺条件下,抽余油比重油液体收率增加1.69%,生焦率上升0.02%;在相同工艺条件即剂油比5.0、反应温度500 ℃、空速14.4 h?1,抽余油比重油液体收率增加0.19%,生焦率上升2.55%;与重油相比,抽余油FCC汽油辛烷值相当,FCC柴油十六烷值降低3.7,其再生剂失活程度较小。因此,抽余油完全可以替代重油作为FCC的原料,具有很好的工业应用前景。     

Investigating the process of heavy crude oil steam cracking in the presence of dispersed catalysts. II: Investigating the effect of Ni-containing catalyst concentration on the yield and properties of products

The process of heavy crude oil (HCO) steam cracking under a batch regime at 425°C in the presence of Ni-containing nanodispersed catalyst (0.3–2.0 wt % with respect to Ni) is investigated. It is established that using this catalyst facilitates the upgrading of semi-synthetic oil produced from HCO: the Н: С ratio rises (in comparison to steam cracking with no catalyst), and the sulfur content and viscosity are reduced. The Н: С ratio in the liquid products grows slightly along with the catalyst content, but the yield of liquid products falls from 81 to 76% during the process with a simultaneous increase in the yield of coke and gaseous products (from 8 to 13 and from 2 to 4 wt %, respectively). Catalyst with coke residue is investigated by means of XRD and TEM. It is shown that nanosized particles of the Ni9S8 phase with sizes of 15–40 nm form from the catalyst precursor (Ni(NO₃)₂ · 6H₂O) under the process conditions. The selection and investigation of catalytic systems for heavy crude oil cracking in the presence of superheated steam, along with optimization of the process conditions, are required to further enhance the efficiency of the upgrading process.