Zn改性ZRP沸石催化剂对催化裂化汽油芳构化性能的影响

以催化裂化汽油为原料,在固定床微反装置上考察Zn改性ZRP沸石催化剂对催化裂化汽油芳构化反应性能的影响,通过实验考察改性金属Zn在芳构化反应中的作用,并结合吡啶吸附红外吸收光谱分析改性前后催化剂的酸性变化,提出催化裂化汽油在Zn改性ZRP沸石催化剂上的反应机理。结果表明,Zn改性能够显著提高ZRP沸石催化剂的芳构化性能。分析认为催化裂化汽油芳构化反应在ZRP沸石催化剂上主要通过氢转移反应实现,在Zn改性的ZRP沸石催化剂上以环化、脱氢为主,氢转移反应为辅,并涉及到裂化、齐聚、异构化等反应。Zn改性的ZRP沸石孔道中可能存在[Zn(OH)]+活性位,它具有B酸和L酸的双重属性,芳构化反应在不同的反应步骤需要不同性质的活性位,因此Zn改性可提高ZRP沸石的芳构化性能。     

磷氧化物改性对ZSM—5沸石物化性质及择形催化性能的影响

采用磷氧化物对ZSM-5沸石进行修饰改性,用XRD、NMR、IR、BET等物化手段对改性后沸石的物质性质变化情况进行了表征,并采用轻油微反和小型固定流化床催化裂化装置对改性后的样品进行了反应性能评价。结果表明,采用磷氧化物对ZSM-5沸石的修饰改性能够抑制它在水热条件下的骨架脱铝,并延缓沸石在水热过程中的晶系转变,保持结构的对称性不下降,从而显著改善ZSM-5沸石的水热活性稳定性,而沸石的晶体形貌及孔体积等没有受到大的影响。磷化物的修饰改性还改善了ZSM-5沸石的酸强度分布状况,少量加入FCC催化剂中可使裂化反应中的择形催化性能得到改善,较好地提高了催化裂化汽油的辛烷值,特别是马达法辛烷值。     

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。     

磷改性对催化裂化催化剂抗磨损性能的影响

以磷元素为改性剂,采用等体积浸渍法对流化催化裂化(FCC)催化剂进行改性,考察了磷酸盐种类、浸渍量、焙烧温度、焙烧时间对FCC催化剂磨损指数影响,确定了最佳改性工艺条件,并将磷改性催化剂进行ACE评价。结果表明:4种磷酸盐改性FCC催化剂均表现出良好的抗磨损性能,磷浸渍量越多,催化剂磨损指数越低;随焙烧温度的升高,磷酸铵改性催化剂(Cat-B-P-3.2)磨损指数先减小后增大;随着焙烧时间的延长,Cat-B-P-3.2催化剂的磨损指数下降,在550℃下焙烧2.0 h后,Cat-B-P-3.2催化剂的性能较佳;以P_2O_5质量分数1.0%的磷酸铵浸渍的改性FCC催化剂与标准催化剂相比,其产物中焦炭和干气分别降低0.72,0.10个百分点,汽油收率增加0.91个百分点。     

重催催化剂最新技术

FCC（Fluid Catalytic Cracking)工艺原理是在流动床条件下使原料油与催化剂发生催化裂化反应，炼油厂一般采用拔头油装置把原料油常压蒸馏并根据不同沸点得到液态烃，石脑油，柴油和重油，其中分子量大，沸点高的物质（重油亦称渣油）需要进一步脱硫和脱金属才能成为FCC装置的原料油，最终从该原料油中得到收益较大的汽油，裂化柴油（LCO）。     

镁改性FCC催化剂抗镍污染性能和机理

以碱土元素镁为改性元素,采用原位加入方法制备了镁改性流化催化裂化(FCC)催化剂。着重考察并探究了镁改性FCC催化剂对重油催化裂化的抗镍污染性能和反应机理。催化剂理化性质表征结果表明,与常规FCC催化剂相比,镁改性对催化剂的比表面积、孔体积、磨损强度以及堆密度等理化性质没有明显影响。高级催化裂化评价装置(ACE)评价结果表明,相同镍污染条件下,与常规FCC催化剂相比,镁改性FCC催化剂的干气和焦炭产率分别下降了0.38和1.28百分点,而汽油和总液体收率则分别增加了1.38和1.49百分点,显示了优良的抗镍污染性能。抗镍污染机理分析结果表明:镁改性FCC催化剂一方面可以减少催化剂表面酸中心尤其是强酸中心数量,改善催化剂的干气和焦炭选择性,从而提高催化剂的容镍能力;另一方面,高温水热条件下,镁原子能够进入到氧化镍晶格中形成镁 镍固溶体,能够极大地提高氧化镍的还原温度,从而使得镁改性能够显著提高FCC催化剂的钝镍性能。     

降低催化裂化汽油烯烃含量的中型试验研究

在中型提升管催化裂化试验装置上详细考察了原料油性质、催化剂类型以及操作条件对催化裂化汽油烯烃含量的影响.原料油性质是决定催化裂化汽油烯烃含量高低的关键,选择氢转移活性高的稀土Y型催化剂是降低催化裂化汽油烯烃含量的有效措施.选择适宜的反应温度和油气停留时间,适当提高剂油比和催化剂活性,均可以在一定程度上降低催化裂化汽油烯烃含量.     

催化裂化操作参数对降低汽油烯烃含量的影响

针对催化裂化汽油烯烃含量较高的情况,在中型提升管催化裂化装置上,考察了原料油性质、催化剂性质、反应条件、汽油馏程等对汽油烯烃含量的影响,提出了工业生产装置降低催化裂化汽油烯烃含量的措施。研究发现,催化裂化汽油烯烃含量与氢转移指数（异丁烷／丁烯及异丁烷／异丁烯）呈线性关系,氢含量高、K值大的原料油,汽油烯烃含量较高。使用降烯烃催化剂、提高催化剂活性、提高剂油比、降低反应温度、延长反应时间、提高烃分压、提高汽油终馏点等有利于降低催化裂化汽油烯烃含量。     

一种改进的催化剂添加剂提高了FCC装置烯烃收率

传统的FCC催化剂是基于USY型沸石（孔径大约为7．6A），该催化剂选择性地将长链碳氢化合物裂解成小分子碳氢化合物，汽油组分、轻和重催化裂化油以及其他产品。最近，人们使用ZSM-型沸石分子筛作为添加剂，由于其孔径（5．5A）较小使得该催化剂对于裂解直链和短链烯烃比USY-型沸石分子筛更有效。催化剂和化学品工业公司开发并推出了一种使用磷对其SAM-5型添加剂改性的产品。与传统的添加剂相比较，这种新型添加剂可以提高汽油的辛烷值和低级烯烃（包括丙烯和丁烯）的收率。OCTUP-11S与其前一代添加剂OCTUP-11相比，有更高的耐高温进料性能，对低级烯烃（C5-C12）的扩散来说，具有优化的孔径分布。     

催化裂化汽油的下行床催化转化

以循环下行床为反应器,催化裂化汽油为原料,在工业催化裂化(FCC)催化剂和催化裂解(DCC)催化剂作用下,研究了催化裂化汽油的催化转化过程。实验结果表明,在下行床反应器中,催化裂化汽油中的烯烃能显著降低,主要转化为低碳烯烃产品,同时得到富含芳烃的液体产品,副产干气和焦炭量很低。催化裂化汽油在FCC催化剂和DCC催化剂上表现出不同的反应机理。FCC催化剂孔道大,可以发生双分子裂化反应和单分子裂化反应,而DCC催化剂孔道小,以单分子裂化反应机理为主,同时DCC催化剂低碳烯烃选择性更高。     

EFFECT OF ZSM-5 ADDITION ON PRODUCT DISTRIBUTION IN A HIGH SEVERITY FCC MODE

The high-severity fluid catalytic cracking (HS-FCC) process is a novel FCC process that enhances light olefins yield under high severity reaction conditions. The process has been investigated by using a small-scale FCC pilot plant (0.1 BPD) with a down-flow reactor. High severity reaction conditions are preferable for enhancing the production of light olefins by catalytic cracking of heavy oils. As another option for the light olefin production, adoption of ZSM-5 additive in conventional FCC units is well known. This presentation describes the effect of ZSM-5 additive on the catalytic cracking of vacuum gas oil under high severity reaction conditions, particularly focusing on the synergistic effect with the base catalyst. Three kinds of FCC catalysts with different activity were used as base catalysts. Although the employment of a ZSM-5 additive resulted in significant increase in the light olefins yield at the expense of gasoline in each catalyst system tested, the effectiveness was varied depending on the nature of the base catalysts. By choosing a suitable base cracking catalyst, more than 20 wt% of propylene yield was obtained at a one-pass conversion of fresh feed.     

EFFECT OF ZSM-5 ADDITION ON PRODUCT DISTRIBUTION IN A HIGH SEVERITY FCC MODE

The high-severity fluid catalytic cracking (HS-FCC) process is a novel FCC process that enhances light olefins yield under high severity reaction conditions. The process has been investigated by using a small-scale FCC pilot plant (0.1 BPD) with a down-flow reactor. High severity reaction conditions are preferable for enhancing the production of light olefins by catalytic cracking of heavy oils. As another option for the light olefin production, adoption of ZSM-5 additive in conventional FCC units is well known. This presentation describes the effect of ZSM-5 additive on the catalytic cracking of vacuum gas oil under high severity reaction conditions, particularly focusing on the synergistic effect with the base catalyst. Three kinds of FCC catalysts with different activity were used as base catalysts. Although the employment of a ZSM-5 additive resulted in significant increase in the light olefins yield at the expense of gasoline in each catalyst system tested, the effectiveness was varied depending on the nature of the base catalysts. By choosing a suitable base cracking catalyst, more than 20 wt% of propylene yield was obtained at a one-pass conversion of fresh feed.     

催化裂化与芳构化反应耦合多产优质汽油催化剂的研究

以NiO／HZSM-5为增强芳构化助剂，通过催化裂化与芳构化反应耦合，使催化裂化汽油和裂化气中的部分烯烃转化为芳烃，以降低汽油馏分中的烯烃含量，改善催化裂化汽油的组成。考察了助剂添加量对催化裂化催化剂降烯烃性能的影响，并与以CoAPO-11分子筛和HZSM-5与APO-11复合分子筛为助剂的催化裂化催化剂进行了对比。结果表明，NiO／HZSM-5的芳构化降烯烃效果最好，当添加量为5％时，汽油馏分中烯烃含量降低了5．8个百分点，而芳烃含量提高了9．7个百分点。并对催化裂化与芳构化反应耦合的机理进行了初步探讨。     

降低汽油硫含量的重油裂化催化剂的开发

摘要：降低汽油硫含量和重油催化裂化系列催化剂DOS的开发针对降硫组元及活性组元进行了研究，开发了降硫功能组元L酸碱对化合物和筛选了与之相匹配的分子筛活性组元。评价结果表明，开发的L酸碱对化合物能增加催化剂对大分子硫化物的转化，促进脱硫反应的发生；筛选的分子筛与L酸碱对化合物协同作用具有较好的降烯烃和降硫功能。开发的降硫重油裂化催化剂DOS在ACE装置和固定流化床装置评价结果表明：与工业降烯烃催化剂相比，重油转化能力强，抗重金属污染能力强，汽油硫含量可降低20％以上。     

FCC Gasoline Hydroisomerization Over Pt/HZSM-5 Catalysts

Pt/HZSM-5 bifunctional catalyst of fluid catalytic cracking (FCC) gasoline hydroisomerization was prepared. The influence of calcinations and reduction conditions, the metal-incorporation technique, and metal loading on the hydroisomerization of FCC gasoline over the Pt/HZSM-5 bifunctional catalyst was studied. The process opinion catalyst of FCC gasoline hydroisomerization was obtained under the condition of temperature 290-300°C; pressure 1.5-2.5 Mpa; liquid hour space velocity (LHSV) 2.0-3.0 hr^-1; V(H₂)/V(Oil) = 2.0-3.0. The results showed that calcination conditions have a significant influence on ion-exchanged catalysts, as they control the final metal distribution. The reduction conditions and the method used for platinum incorporation were found to be important factors that affected both the activity and selectivity of the catalysts. Pt/HZSM-5 bifunctional catalyst possessed good activity for hydrogenation and isomerization. The olefin hydrocarbons of FCC gasoline were hydrogenated and the stability of FCC gasoline was improved under condition of unchanged octane number.     

The Addition of ZSM-5 to a Fluid Catalytic Cracking Catalyst for Increasing Olefins in Fluid Catalytic Cracking Light Gas

Abstract

The second largest source of propylene supplied for petrochemical application is from fluid catalytic cracking (FCC) units. The primary function of the FCC unit has typically been to produce gasoline. However, refiners have been taking advantage of opportunity to produce and recover more propylene from their FCC unit by increasing reaction severity via riser temperature, adding shape selective catalyst, and installing a propylene recovery unit (PRU). At a conventional FCC process propylene exists in the off gas of FCC and it is about 6 wt% of off gas by changing the FCC process parameter quantity of propylene in off gas can be more than 20 wt% by using ZSM-5 additives and increasing temperature The effects of operating parameters, such as reaction temperature, and ZSM-5 as FCC catalyst additive, on the distribution of the product and the yield of propylene were investigated on a bench-scale fluidized bed reactor. It is the aim of this work to perform an overall analysis of the yields and selectivity of hydrocarbons obtained in the vacuum gas-oil conversion over FCC and ZSM-5 catalysts. The effectiveness of ZSM-5 additive in the FCC process was investigated by doing experimental work in a bench-scale setup. The experiment data of off gas analysis showed that vacuum gas oil cracking at high reaction temperatures of 450–550°C increases the yield of propylene. Similar behavior is observed with the addition of 10–25 wt% ZSM-5 additive. The combination of the two effects (high temperature and ZSM-5 addition) makes the FCC unit an excellent source of light olefins for downstream petrochemical units. Higher FCC reactor temperatures (600–650°C) would not have positive effects for increasing propylene yield.     

小晶粒ZSM-5的表征、磷改性及其在多产丙烯FCC催化剂中的应用

ZSM 5是催化裂化催化剂中的重要组分,对于增加丙烯产率有显著作用。采用XRD、SEM和粒度分析(SDP) 表征了常规(大晶粒)和小晶粒2种ZSM 5分子筛。对这2种ZSM 5分子筛进行磷改性,并对它们进行水洗实验,考察改性元素流失情况。以上述2种磷改性ZSM 5分子筛制备FCC催化剂,采用磨损指数、固定流化床装置(FFB)等方法评价催化剂催化性能。结果表明,小晶粒ZSM 5分子筛与常规ZSM 5分子筛相比,相对结晶度高,平均粒度显著小,颗粒分散均匀,条状物少。对小晶粒ZSM 5分子筛进行磷改性,可以减少改性元素的流失,进而大幅提高催化剂活性稳定性;磷改性小晶粒ZSM 5分子筛在800℃下水热处理17 h,结晶度保留率达到976%。采用磷改性小晶粒ZSM 5分子筛制备FCC催化剂,可以大大降低催化剂的磨损指数,同时增加对丙烯的选择性,提高丙烯产率。工业应用表明,丙烯产率可以提高074百分点。     

增产丙烯的催化裂化工艺进展

介绍了催化裂化( FCC)工艺增产丙烯的主要思路,围绕这些思路综述了增产丙烯的工艺改造进展.包括深度催化裂化(DCC),催化热裂解技术(CPP),重质油接触裂解(HCC),PetroFCC,选择性组分裂化(SCC),Maxofin,高苛刻度FCC(HS-FCC),Superflex等工艺,并将这些工艺流程特点、使用的催化剂、产品分布和烯烃产品收率与常规FCC工艺相比较,结果表明,丙烯收率均有明显提高.并指出通过FCC工艺技术改造增产丙烯是适合当前我国国情的技术路线.     

催化裂化催化剂的发展历程及研究进展

介绍了催化裂化催化剂在国内外的发展历程,详细阐述了重油裂化催化剂、生产高辛烷值催化裂化催化剂、生产清洁燃料催化剂、增产低碳烯烃催化剂、多产液化气和柴油等催化剂的研究进展。并对催化剂的发展前景进行展望,今后催化裂化催化剂仍然是重油高效转化、增产丙烯、高温化学改性、降低汽油烯烃含量和高固含量成胶技术的方向发展。     

大庆蜡油在酸性催化剂上反应机理的研究

以大庆蜡油为原料，采用两种不同类型的催化剂，在流化床反应器实验装鬣上进行催化裂化反应。结果表明，大庆蜡油在酸性催化剂上反应所产生的干气组成与高烯烃催化裂化汽油相同，干气的产生主要是单分子裂化反应所造成的。从干气产率、组成以及液化气组成可以看出，大庆蜡油在不同类型的催化剂上明显地表现出裂化反应类型的差异。