Physicochemical and catalytic properties of iron- and indium-containing zeolites

The influence of the preparation procedure of Fe- and In-containing zeolites on their physicochemical and catalytic properties in methanol conversion to hydrocarbons and the upgrading of the straight-run gasoline fraction of crude oil has been studied. The introduction of In and Fe into a zeolite increases the on-stream time of the catalysts in methanol conversion and increases their selectivity for the formation of alkenes and isoalkanes. Zeolites containing iron and indium nanopowders are the most effective catalysts for the manufacturing of high-octane gasolines from straight-run gasoline.     

直馏柴油催化裂化生产轻质芳烃的研究

采用小型固定流化床催化裂化装置,考察了分子筛类型和反应条件对直馏柴油催化裂化反应的影响以及不同烃类组成的直馏柴油催化裂化产物分布特点。结果表明:选用富含环烷烃和单环芳烃的直馏柴油有利于提高轻质芳烃收率;在Y型分子筛催化剂作用下的直馏柴油催化裂化转化率最高,轻质芳烃收率可达13.22%;反应温度对轻质芳烃收率影响显著,反应温度由510℃提高到610℃时,转化率增加12.95百分点,轻质芳烃收率增加7.16百分点,提高原料的转化深度有利于增加轻质芳烃收率,但是汽油收率降低;剂油比对轻质芳烃收率影响较小,剂油比过高时,汽油收率下降。与直馏柴油相比,其催化裂化产物烃类组成中环烷烃质量分数减少26.4百分点,环烷烃参与反应的比例高达80.49%,环烷烃环数越多,参与反应的比例越高。     

加氢轻循环油裂化反应规律研究

以加氢轻循环油（LCO）为原料,采用含Y型分子筛、活性中孔材料以及含β或MFI结构分子筛的不同类型催化剂在小型固定流化床ACE Model Rt装置上进行裂化反应实验,考察不同类型催化剂对加氢LCO中各组分的转化能力,并考察反应条件对加氢LCO裂化反应的影响。结果表明：采用含高活性Y型分子筛的催化剂能够得到较高的汽油收率及C6～C9芳烃收率,有利于提高汽油辛烷值或者获得较多的苯、甲苯、二甲苯等化工产品,但反应过程同时会生成双环及多环芳烃,抵消了部分加氢前处理的效果;反应温度和剂油比对加氢LCO裂化转化率影响较小;汽油收率随反应温度的提高而降低,剂油比对汽油收率的影响较小;提高反应温度会促进重质产物的生成,而提高剂油比则会抑制重质产物的生成;反应温度和剂油比的提高均有利于增加汽油中芳烃含量。     

NK-2非临氢重整催化剂性能评价及工业应用

在固定床试验装置上以直馏汽油、油田轻烃混合物为原料,对NK-2型非临氢重整催化剂进行了中试评价。工业装置应用表明,该催化剂对直馏汽油、油田轻烃等表现出很好的改质效果。原料在非临氢状态下,经过重整和异构化反应,改质汽油的辛烷值提高30个单位,苯、烯烃含量略有升高,芳烃含量小于30％,改质汽油收率73．12%,液化石油气收率24．26％,干气及损失2．62％。该催化剂具有良好的活性及稳定性,工艺过程简单,为炼油厂汽油的升级换代开辟了新的途径。     

Catalytic activity in the hydrocarbon conversion of systems containing platinum,nickel, iron,and zinc nanoparticles (communication 2)

The catalytic activity of metal-containing zeolites modified by nanosized Pt, Ni, Fe, and Zn powders was studied in the process of upgrading the petroleum straight-run gasoline fractions. It was found that the introduction of metal nanoparticles into the zeolite increases the catalyst activity and allows the desired product to be obtained at a lower processing temperature. An enhancement of the aromatization reactions of the hydrocarbon feedstock was revealed on the catalyst samples deactivated in the first reaction cycle and calcined in air.     

直馏汽油掺碳四非临氢改质技术的工业应用

介绍了石油化工科学研究院开发的直馏汽油非临氢改质工艺在沈阳石蜡化工有限公司70kt／a直馏汽油非临氢改质装置上的工业应用情况。结果表明，该技术性能可靠，各项工艺指标均达到或超过设计要求。直馏汽油掺碳四馏分原料改质后，可以增加汽油产率，汽油RON提高38个单位以上，烯烃含量小于3％，成为品质优良的汽油降烯烃调合组分；改质后液化气的烷烃含量达95％以上，烯烃含量小于5％，经脱硫后可作为车用液化气，经济效益显著。     

直馏柴油催化裂化加工技术探索

采用小型固定流化床实验装置,探索研究了直馏柴油催化裂化加工技术路线的可行性。结果表明：催化裂化是将直馏柴油转化为高附加值产物的切实可行的工艺技术;采用催化裂化技术路线时,直馏柴油直接催化裂化反应具有较高的汽油和丙烯收率,分别可达48%和8%左右;采用催化裂解技术路线时,直馏柴油直接催化裂解反应具有较高的低碳烯烃和BTX（苯、甲苯和二甲苯）收率,在反应温度为620℃时乙烯、丙烯和BTX总收率可达39%以上,并可副产22％以上的高辛烷值汽油,其 RON在99以上;重油原料掺炼直馏柴油时,直馏柴油掺入比例较高时催化裂化反应性能较好,但会导致汽油产物中芳烃含量增加。     

焦化汽油催化裂解反应特性探析

分析了典型焦化汽油烃类组成特点,重点研究焦化汽油催化裂解反应过程中反应转化率以及低碳烯烃的产率和选择性的主要影响因素。结果表明,催化裂解反应条件下焦化汽油转化率较低,提高反应温度是提高低碳烯烃产率的有效手段,但是目标产物的选择性变化不大;采用高选择性的催化剂可以在提高乙烯和丙烯产率的同时提高其选择性,并达到少产丁烯的目的。焦化汽油的正构烷烃转化程度低,尤其是C5～C7正构烷烃转化程度不足60％,是因其分子碳链短,所形成的正碳离子的β断裂反应不易发生所致。     

煤制合成油工业单管试验

在工业单管上对改进的Ｆ－Ｔ合成一段催化剂（Ｆｅ／Ｃｕ／Ｋ型）进行预处理，考察了反应温度、原料气Ｖ（Ｈ２）／Ｖ（ＣＯ）的影响，试验数据表明，催化剂的性能发挥与工艺条件密切相关，所开发的一段催化剂具有良好的水汽变换性能。另外，由改进的Ｆ－Ｔ合成产物分布规律还说明两段分子筛催化剂改性的重要性。     

Catalyst Innovation for Reducing Olefin Content in MGG Gasoline

In order to reduce the olefin content in gasoline manufactured by the MGG (Maximizing Liquefied Gas and Gasoline) process while retaining the LPG yield, RIPP has developed a novel catalyst consisting of a more pore-opened matrix and the modified Y-zeolite and the ZRP zeolite modified with metal oxides. Test results have revealed that compared with the commercial catalyst RAG under comparable reaction conditions the reaction conversion rate and product distribution provided by the novel catalyst were similar, but the olefin content in gasoline obtained thereof was decreased with the octane rating unchanged along with a slight reduction of olefin content in the LPG fraction. The hydrothermal stability of the novel catalyst was better than the commercial catalyst RAG.     

柴油加氢裂化转化的切割方案

以直馏柴油和催化裂化柴油为原料,选用柴油加氢精制催化剂与柴油缓和加氢裂化催化剂的复合催化体系,采用固定床双反应器串联、一次通过工艺进行加氢裂化转化实验。结果表明:在直馏柴油加氢裂化多产乙烯裂解原料过程中,若能将重石脑油馏分中低于90 ℃的轻组分,以及柴油馏分中高于250 ℃馏分段分离出来,可有效提高乙烯裂解原料的品质。在催化裂化柴油加氢裂化生产高辛烷值汽油和高十六烷值柴油过程中,与大于220 ℃馏分相比,200～220 ℃馏分的密度和链烷烃质量分数较低,收率约为前者的16.4%;200～220 ℃馏分单环芳烃质量分数较高,可以作为回炼组分用以提高汽油中芳烃质量分数。     

磷钨介孔分子筛催化直馏柴油氧化脱硫工艺条件及反应动力学研究

以介孔分子筛SBA-15为载体,磷钨酸为活性组分,采用一锅法工艺制备出磷钨介孔催化剂,使用X射线衍射、透射电子显微镜等分析手段表征了催化剂的结构与性能。在磷钨介孔催化剂存在下,以过氧化氢为氧化剂,研究了工艺条件对辽河油田直馏柴油催化氧化脱硫效果的影响并获得了反应动力学数据。结果表明,磷钨酸负载SBA-15分子筛催化剂具有完整二维六方介孔结构。最佳负载量(质量分数)为30%时,在V(双氧水溶液)/V(直馏柴油)为0.05,m(催化剂)/V(直馏柴油)为0.03 g/mL,氧化温度为70℃,氧化时间为1.5 h的最佳工艺条件下,直馏柴油的脱硫率为80.08%;直馏柴油的氧化脱硫反应为一级反应,表观活化能为37.86 kJ/mol,指前因子为7 210.47。     

直馏汽油在纳米ZSM-5上的异构化反应研究

在固定床反应器中研究了不同反应条件下纳米HZSM-5和微米HZSM-5在直馏汽油异构化反应中的催化性能,并对纳米HZSM-5和微米HZSM-5进行了XRD、NH3–TPD及低温N2吸附等表征。结果表明：纳米HZSM-5粒径小、外表面酸量丰富、扩散路径短,直馏汽油异构化反应性能优于微米HZSM-5,具体表现在环烷烃和芳烃的生成量大。由于纳米颗粒之间的二次孔可以大量容纳积炭,纳米HZSM5的稳定性好;当反应温度为320?360 ℃、质量空速为1 h-1时,纳米HZSM-5的催化性能最佳。     

流化催化裂化汽油含硫化合物生成规律的考察

在小型固定流化床装置上采用流化催化裂化(FCC)催化剂、以FCC汽油轻馏分和H2S标准气为原料,考察了催化剂类型、原料组成和反应条件(反应温度、催化剂与原料油的质量比(剂油比)和重时空速)对硫化物生成的影响。实验结果表明,FCC汽油中的烯烃与H2S反应主要生成噻吩类硫化物和部分硫醇;在REUSY分子筛催化剂(催化剂A)上的硫化物收率比在ZRP型择形分子筛催化剂(催化剂B)上的高;且硫化物收率随H2S和烯烃含量的增加呈线性增长。受反应温度对烯烃转化程度的影响,较高的反应温度有利于抑制烯烃与H2S反应。因为反应机理及催化剂性质对噻吩类硫化物和硫醇的生成影响不同,两者收率随剂油比和重时空速的变化趋势不同,但变化幅度均不大,因而总硫化物收率随重时空速和剂油比的变化幅度也不大。     

Development and Commercial Application of RFCC Catalyst for Reducing Sulfur Content in Gasoline

The sulfur-reducing functional component the Lewis acid-base pair compound and associated active zeolite component were developed to prepare the RFCC catalyst DOS for reducing sulfur content in gasoline. The results of catalyst evaluation have revealed that the Lewis acid-base pair compound developed hereby could enhance the conversion of macromolecular sulfur compounds by the catalyst to promote the proceeding of desulfurization reactions, and the synergetic action of the selected zeolite and the Lewis acid-base pair compound could definitely reduce the olefins and sulfur contents in gasoline. The heavy oil conversion capability of the catalyst DOS thus developed was higher coupled with an enhanced resistance to heavy metals contamination to reduce the sulfur content in gasoline by over 20%. The commercial application of this catalyst at the SINOPEC Jiujiang Branch Company has revealed that compared to the GRV-C catalyst the oil slurry yield obtained by the catalyst DOS was reduced along with an improved coke selectivity, an increased total liquid yield, and a decreased olefin content in gasoline. The ratio of sulfur in gasoline/sulfur in feed oil could be reduced by 20.3 m%.     

纳米HZSM-5沸石催化剂上催化裂化轻汽油的芳构化

利用小型固定床加压反应器在纳米 HZSM-5沸石催化剂上进行了流化催化裂化(FCC)轻汽油(馏出温度小于等于85℃的馏分)的芳构化反应。实验结果表明,在反应温度为360～400℃、反应压力为1.0～3.0 MPa、重时空速为1.0～4.0 h~(-1)、V(H_2)∶V(原料)为260、反应时间48 h 的条件下,FCC 轻汽油中的 C_5~+烯烃转化率为39.11%～97.92%,产物中芳烃净增量为2.59%～19.05%,说明 FCC 轻汽油可在纳米 HZSM-5沸石催化剂上有效进行芳构化反应。汽油收率低和催化剂失活快是 FCC轻汽油在纳米 HZSM-5沸石催化剂上进行芳构化反应需要解决的两个主要问题。对纳米 HZSM-5沸石催化剂进行必要的改性处理及脱除原料中的二烯烃杂质呵以改进 FCC 轻汽油芳构化催化剂的性能。     

USY分子筛催化噻吩烷基化性能的研究

以模拟汽油为原料,在小型固定床反应装置上,对4种硅铝比不同的USY型分子筛催化噻吩烷基化反应性能进行了评价。结果表明,硅铝摩尔比为11.15的USY 1分子筛具有较为适中的B酸量和L酸量,其总B,总L,强B,强L酸量分别为616.5,170.9,589.1,120.0μmol/g,USY 1分子筛催化噻吩烷基化的活性和稳定性明显优于其他3种USY分子筛。USY 1分子筛催化噻吩烷基化的最佳工艺条件为:反应温度140℃、反应压力0.4 MPa、模拟汽油质量空速3 h-1。在此优化条件下,模拟汽油的噻吩转化率达89.28%,催化剂的使用寿命为35 h。     

RECENT ADVANCES IN FLUID CATALYTIC CRACKING PROCESS

Abstract

Fluid Catalytic Cracking (FCC) is one of the processes applied world-wide for upgrading of heavy petroleum cuts by converting them into lighter products in the gasoline, light, and heavy cycle oil ranges. Catalytic cracking process was developed in the early stages of petroleum refining. It started by utilizing chemically treated natural clays as catalysts. In the early 1960s the introduction of zeolite containing catalysts, mainly the wide pore faujasite family (X-and Y-type) has significantly contributed to the yield as well as FCC process design consideration. The overall process performance is strongly dependent the catalyst characteristics. Therefore, FCC catalyst manufacturers and researchers are continuously searching for modified catalyst characteristics (improved thermal and hydrothermal stability, higher Activity and better selectivity for high barrel-octane gasoline production). This research activity resulted in this introduction of several FCC catalyses with enhanced performance to suit the steadily increasing emand for high quality refined FCC products.

The present review is aimed at throwing a light on the FCC process with special emphasis on the recent advances made in the field of catalysts design and its impact on the whole FCC process performance as related to the production of high octane gasoline.     

RECENT ADVANCES IN FLUID CATALYTIC CRACKING PROCESS

Fluid Catalytic Cracking (FCC) is one of the processes applied world-wide for upgrading of heavy petroleum cuts by converting them into lighter products in the gasoline, light, and heavy cycle oil ranges. Catalytic cracking process was developed in the early stages of petroleum refining. It started by utilizing chemically treated natural clays as catalysts. In the early 1960s the introduction of zeolite containing catalysts, mainly the wide pore faujasite family (X-and Y-type) has significantly contributed to the yield as well as FCC process design consideration. The overall process performance is strongly dependent the catalyst characteristics. Therefore, FCC catalyst manufacturers and researchers are continuously searching for modified catalyst characteristics (improved thermal and hydrothermal stability, higher Activity and better selectivity for high barrel-octane gasoline production). This research activity resulted in this introduction of several FCC catalyses with enhanced performance to suit the steadily increasing emand for high quality refined FCC products.

The present review is aimed at throwing a light on the FCC process with special emphasis on the recent advances made in the field of catalysts design and its impact on the whole FCC process performance as related to the production of high octane gasoline.     

催化裂化汽油流化床非临氢改质工艺研究

介绍了一种使用ZSM-5沸石催化剂对催化裂化汽油进行改质的流化床反应工艺.此工艺可有效降低汽油烯烃和硫含量,同时提高汽油辛烷值,改质汽油收率高,干气和焦炭产率较低.研究了不同反应条件下以及不同馏分汽油改质后产物分布的变化和烯烃、硫含量等汽油性质的改善情况.研究结果表明,采用低反应温度、高催化剂循环量条件,改质汽油烯烃含量、硫含量降低幅度大;相反,则裂化气产率和丙烯选择性提高.加工重馏分汽油时改质汽油收率高,但较全馏分汽油改质烯烃含量降幅稍低.