发展FCC轻汽油醚化工艺

我国FCC汽油作为车用汽油的主要调合组分，其比例已占70％以上，是车用汽油质量不能进一步提高的瓶颈所在．FCC轻汽油醚化工艺将其中的叔碳烯烃转化为醚，在一定程度上弥补了MTBE产量的不足，除提高辛烷值和增加含氧量外，还可降低汽油的烯烃含量和蒸气压，一举多得，值得开发、推广。     

Etherification of FCC Light Gasoline over Mo-Modified β Zeolite Catalyst

Abstract

Etherification activity of several molecular sieve catalysts for FCC light gasoline was studied in a fixed-bed reactor. H-Beta zeolite was found to be high active than that of others and close to cation exchanged resin catalyst. H-Beta zeolite also showed good activity and selectivity and could not be deactivated easily, and could be easily regenerated after deactivation. In order to further improve etherification activity, the surface acidity and pore structure of zeolite could be modified, by loading different metal oxides. The result showed that the highest conversion of tert-olefin was obtained over Mo/Hβ (1%). The influence of reaction temperature, methanol and tert-olefin molar ratio, reaction pressure, and LHSV on the conversion was investigated. At optimized reaction conditions, tert-olefin conversion of 57.42% had been reached with Mo/Hβ (1%).     

FCC汽油在ZSM-5分子筛上的芳构化反应

考察了全馏分催化裂化（FCC）汽油的芳构化改质反应，结果表明，在三种不同硅铝比的分子筛中，以硅铝比为50的分子筛为载体所制备的催化剂性能较好。对Ni、Mo、Zn、Co4种金属活性组分的选择考察，以Zn为活性组分的催化剂芳构化性能最好，以Ni为活性组分的催化剂液收最高。分析了FCC汽油中不同烃类的芳构化反应历程．得出金属组分应有适宜的含量。     

制备因素对催化裂化汽油加氢脱硫催化剂性能的影响

针对催化裂化汽油脱硫技术要求,介绍了一种以共沉淀法制备的载体负载Co、Mo活性金属组分的催化汽油加氢脱硫催化剂,考察了载体Mg／Al原子比、焙烧温度、活性金属含量对催化剂活性及选择性的影响,并对本研究的催化剂进行了1000h的稳定性试验。实验结果表明,采用Mg／Al=X 0、5、焙烧温度(y 200)℃所制备的载体,在其活性金属MoO3含量8％、CoO含量2.0％时,催化剂具有适宜的酸性中心数和最佳的脱硫选择性;本研究催化剂在1000h的试验运转过程中,具有较高的脱硫率和较低的烯烃饱和率,其活性稳定性良好。     

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。     

Etherification Performance of Transition Metals Modified β-Zeolite Catalyst

The etherification experiment for FCC light gasoline on transition metals modified Hβ zeolite was studied in a fixed-bed reactor. The effect of preparation condition of catalyst on the catalyst's activity, stability, and the effect of reaction temperature, methanol/tert-olefin molar ratio, and liquid hour space velocity on the etherification reaction were discussed. The experimental results showed that the different metals modified Hβ zeolite had different etherification performances. And the conversion of tertiary carbon-olefins of the molybdenum modified Hβ zeolite, which was loaded 3%, was higher 6.0% than the Hβ zeolite. The optimal reaction conditions were temperature 70-80°C, liquid hour space velocity 1.0 h^-1 and methanol/tert-olefin molar ratio 1.05. The modified Hβ zeolite catalysts possessed favorable prospect for its higher stability.     

FCC汽油加氢改质催化剂研究开发进展

综述了FCC汽油加氢改质催化剂的研究开发进展,分析比较了各种催化剂的特点,讨论了其适用范围,指出了目前汽油改质催化剂研究开发存在的问题,认为具有高度加氢异构-适度芳构化双功能和长期稳定性的新型催化剂将是FCC汽油改质催化剂今后发展的趋势。     

FCC轻汽油醚化装置催化剂失活原因分析

南充炼油化工总厂轻汽油醚化装置醚化催化剂和异构化催化剂超过使用寿命后均出现了床层压降增大和转化率降低等问题,通过分析,找到了催化剂失活原因,提出了解决方案,大大延长了催化剂的使用寿命,获得了良好的经济效益。     

催化汽油醚化装置的控制方案

国内某炼厂新建的催化汽油醚化装置采用CDHydro（催化汽油选择性加氢）、CDEthers（催化轻汽油醚化）和ISOMPLUS（碳五烯烃异构化）技术,其工艺流程和自动控制方案和其他汽油醚化技术相比均具有一定的特点。主要介绍了该装置的技术特点和各单元典型的控制方案,包括加氢蒸馏塔顶内回流控制、轻汽油/甲醇比值控制、醚化蒸...     

催化裂化汽油馏分在P—Zn／HZSM-5催化剂上的芳构化

以50～100℃的FCC汽油馏分为原料,在连续固定床反应器上考察了工艺条件对P-Zn／HZSM-5催化剂在芳构化反应中性能的影响。结果表明,在反应温度410℃、反应压力0．5MPa、液时空速1．0h^-1的操作条件下,液相产物中的烯烃、异构烷烃和芳烃的含量分别为8．56％,13．07％,73．39％。催化剂P-Zn／HZSM-5具有较好的芳构化降烯烃效果。     

Study on Disproportionation Reaction of FCC Gasoline on Acid Catalyst

Based on the experimental data relating to the reaction of FCC gasoline on acid catalyst the analysis of product distribution, and composition of gasoline and diesel fractions have been analyzed. The occurrence of disproportionation reaction of FCC gasoline on acid catalyst and the network of disproportionation reaction have been identified. Study has also shown that different reaction temperatures can result in different pathways of disproportionation reactions on acid catalyst.     

Aromatization of FCC Gasoline Over Modified HZSM-5 Catalyst

Zinc and phosphorus incorporated HZSM-5 catalyst was prepared by adopting incipient wet co-impregnation (Zn-P/HZSM-5). Zn-P/HZSM-5 catalyst exhibited the lowest acidity but the highest aromatization activity with stable performance in the studied period of 16 hr. The process conditions on aromatization reaction and the coke deactivation mechanism of Zn-P/HZSM-5 catalyst were studied on a small-scale, fixed bed reactor using FCC naphtha (75-120°C). The weight contents of ZnO and P₂O₅ were 2% and 4%, respectively. Results showed that Zn-P/HZSM-5 catalyst under a temperature of 450°C, liquid hourly space velocity of 1.0 h^-1, and pressure of 0.1 MPa, the conversions of olefins and alkanes are 96.77% and 88.94%, respectively, the contents of olefins, aromatics in liquid product are 6.79% and 74.57%, respectively. Carbon deposition was the major reason for catalyst deactivation due to the catalyst's good performance as a fresh catalyst after regeneration. All of the blending products fitted the standards of Chinese gasoline.     

Aromatization of FCC Gasoline Over Modified HZSM-5 Catalyst

Abstract

Zinc and phosphorus incorporated HZSM-5 catalyst was prepared by adopting incipient wet co-impregnation (Zn-P/HZSM-5). Zn-P/HZSM-5 catalyst exhibited the lowest acidity but the highest aromatization activity with stable performance in the studied period of 16 hr. The process conditions on aromatization reaction and the coke deactivation mechanism of Zn-P/HZSM-5 catalyst were studied on a small-scale, fixed bed reactor using FCC naphtha (75–120°C). The weight contents of ZnO and P₂O₅ were 2% and 4%, respectively. Results showed that Zn-P/HZSM-5 catalyst under a temperature of 450°C, liquid hourly space velocity of 1.0 h^?1, and pressure of 0.1 MPa, the conversions of olefins and alkanes are 96.77% and 88.94%, respectively, the contents of olefins, aromatics in liquid product are 6.79% and 74.57%, respectively. Carbon deposition was the major reason for catalyst deactivation due to the catalyst's good performance as a fresh catalyst after regeneration. All of the blending products fitted the standards of Chinese gasoline.     

FCC废催化剂细粉合成超细Y型分子筛

以FCC废催化剂细粉为原料,通过向合成体系中引入无机盐、调变碱度和结晶温度,可以控制Y型分子筛的粒径,得到了大比表面积超细Y型分子筛。以减压蜡油（VGO）为原料油,考察了超细Y型分子筛粒径对催化剂催化裂化反应性能的影响。结果表明,合成体系中引入NaCl可以显著降低Y型分子筛的粒径,较高的碱度和较低的合成温度有利于构建超细Y分子筛的骨架结构;减小分子筛的粒径可以提高轻油的选择性和重油转化率,以及催化剂的抗积炭性能;合成的超细分子筛还显示了优良的水热稳定性。     

气液相法干气制乙苯工艺研究

研究了革与催化裂化于气中体积分数为10％～20％的乙烯在FX－02改性β沸石催化剂上进行烷基化反应合成乙苯的工艺条件,提出适宜的工艺条件为：干气分三段并联进料,反应温度140～160℃,本质量空速2h～(-1),苯与乙烯摩尔比6～8。在此条件下,乙烯转化率可达到80％～90％,催化剂经1000h运转,乙烯转化率未出现明显的降低。     

醚化用树脂催化剂QRE-02的性能评价

考察了QRE -0 2型树脂催化剂在碳五、轻汽油醚化反应中的活性及长周期耐高温情况。结果表明 :由于该催化剂具有较高的交换容量和较大的孔径 ,因而在轻烃醚化反应中表现出了较高的活性 ,在最佳反应条件下叔戊烯转化率可达 74%以上 ,叔己烯转化率可达 43 % ;而且其高温脱磺速率较低 ,可以满足碳五、轻汽油醚化生产的需求     

MCM22/ZSM35共结晶分子筛上催化裂化汽油改质

采用MCM22分子筛、ZSM35分子筛、MCM22/ZSM35共结晶分子筛为催化剂,在固定床反应装置上对催化裂化汽油进行改质。实验结果表明,MCM22/ZSM35共结晶分子筛催化剂表现出最好的芳构化性能。在温度330～430℃、空速1.0h-1、压力0.1～2.0MPa的实验条件下,在MCM22/ZSM35共结晶分子筛催化剂300h的汽油改质中,原料汽油中芳烃的质量分数由19.99%提高到30%左右,烯烃的质量分数由36.76%降至18%以下。失活后的催化剂在空气气氛下可以再生。     

The Aromatization of Different FCC Naphtha Fractions over a P-Zn/HZSM-5 Catalyst

Abstract

The aromatization reaction performance of P-Zn/HZSM-5 catalyst was investigated on a fixed bed reactor using five fluid catalytic cracked (FCC) gasoline fractions (<100°C, 50°C–100°C, <120°C, 75°C–120°C, and full fraction) as feedstock, and the effect of feedstock on aromatization is discussed. The results showed that the activity and stability of P-Zn/HZSM-5 catalyst for the aromatization of the 50°C–100°C fraction were high in definite reaction conditions. After 16 hr, the content of olefin and aromatics in liquid product were 5.23 and 79.9%, respectively. The liquid product of low olefin and high aromatics was obtained. The distribution of benzene, toluene, and xylene in liquid product of 50°C–100°C fraction was investigated during aromatization, and the result showed that the toluene content was maximum among the three aromatics contents, the benzene content was minimum at the beginning of the reaction, xylene content became maximum, and benzene was still minimum after reacting for 20 hr. The content of C₉ ⁺ aromatics increased at the first stage of the reaction and then decreased with the increasing reaction time.     

应用“RICC-Ⅱ+GOR-Ⅱ”催化剂降低FCC汽油烯烃含量

南阳石蜡精细化工厂在催化裂化装置上应用＂RICC-Ⅱ＋GOR-Ⅱ＂催化剂进行汽油降烯烃试验,试验结果表明,FCC汽油烯烃含量降低7%～15%（φ）,与单纯使用GOR-Ⅱ催化剂相比,汽油产率提高5.45个百分点,汽油辛烷值损失0.5～1个单位,馏程变化很小,芳烃、烷烃略上升,汽油质量合格。RICC-Ⅱ与GOR-Ⅱ催化剂混合比例控制在2～3∶7～8较适宜。     

FCC Gasoline Sulfur Reduction by Additives: A Review

This review covers publications in the open literature and patents issued during the last 10 years on issues related to fluid catalytic cracking (FCC) gasoline sulfur reduction. Emphasis was placed on FCC additives, their composition and performance. An attempt was made to elucidate the mechanism for sulfur reduction at FCC cracking conditions. Fluid catalytic cracking technology advances, both process and catalyst, have historically worked together to achieve significant improvements in FCC performance. There is every reason to expect that this will continue to be the case in the future. These advances will have an impact on the volume and quality of the FCC gasoline produced and will offer additional operating flexibility.