The Aromatization Properties of Nano-HZSM-5 Catalyst

In this article, the influence of reaction conditions on the aromatization over nano-HZSM-5 zeolite catalyst was investigated. The experimental results showed that nano-HZSM-5 catalyst has the best aromatization properties under the optimal conditions: reaction temperature 430°C, reaction pressure 0.3 MPa, and liquid hourly space velocity 1 h^-1. At the optimal operational conditions, the conversion of olefins in the feedstock was 76.15%. Aromatics yield and the content of olefins, content of aromatics, and content of isoparaffins in liquid product were up to 84.98%, 12.11%, 39.58%, and 35.23%, respectively.     

Reducing Olefins Content of FCC Gasoline Using a NANO-HZSM-5 Catalyst

Abstract

The study of reducing olefins properties on nano-HZSM-5 catalyst was investigated with a continuous fixed reactor using fraction of fluid catalytic cracking gasoline (75N120°C). The experimental results showed that nano-HZSM-5 catalyst has the best reducing olefins properties under the optimal conditions: temperature 430°C, pressure 0.3 MPa, and liquid hourly space velocity 1 h^?1, and the content of olefins in the feed stock decreased to 12.11% and dropped 31 percentage points. The yield of liquid product, the content of aromatics, and the content of isoalkane in liquid product are up to 84.98%, 39.58%, and 35.23% respectively.     

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。     

Reducing Olefins Content of FCC Gasoline Using a NANO-HZSM-5 Catalyst

The study of reducing olefins properties on nano-HZSM-5 catalyst was investigated with a continuous fixed reactor using fraction of fluid catalytic cracking gasoline (75N120°C). The experimental results showed that nano-HZSM-5 catalyst has the best reducing olefins properties under the optimal conditions: temperature 430°C, pressure 0.3 MPa, and liquid hourly space velocity 1 h^-1, and the content of olefins in the feed stock decreased to 12.11% and dropped 31 percentage points. The yield of liquid product, the content of aromatics, and the content of isoalkane in liquid product are up to 84.98%, 39.58%, and 35.23% respectively.     

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.     

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。     

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.     

An Orthogonal Method for Aromatization Reactions of Shenghua FCC Gasoline

Abstract

Using a confined fluidized bed reactor and aromatization catalysts (LBO-A and LBO-16), the aromatization performance of Shenghua fluid catalytic cracking (FCC) gasoline has been studied in an orthogonal method. The experimental results reveal that the optimum reaction condition for the light oil yield was reaction temperature 420°C, WHSV 40 h^?1, mass ratio catalyst to oil 4 and 75% LBO-A and 25% LBO-16; the optimum reaction condition for aromatics amount in the light oil was reaction temperature 420°C, WHSV 30 h^?1, mass ratio catalyst to oil 5 and 65% LBO-A and 35% LBO-16, the olefin content is remarkably reduced from about 54.7% to 12.8% and 8.7% (by mass), respectively, at the same time the reaction mechanism of aromatization reaction is put forward based on the experimental result.     

Ga改性HZSM-5催化剂芳构化性能的考察

以不同温度水热处理的纳米HZSM-5为母体制备了Ga/HZSM-5催化剂,并对该催化剂在FCC汽油芳构化上的性能进行考察。结果表明：以600 oC水热处理、硝酸洗涤的HZSM-5为母体制备的Ga/HZSM-5（GaHS600）的芳构化性能最优,当温度为480 oC,WHSV为1 h-1时,GaHS600上所得产品中芳烃和（C3+C4）体积分数分别为58.3%和7.6%。在本实验考察条件下,金属二次改性对Ga/HZSM-5芳构化性能的提高并无有利影响。     

FCC馏分油在MoP/HZSM-5催化剂上临氢芳构化研究

制备了MoP/HZSM-5催化剂，采用XRD进行表征。在反应温度400℃、压力1.0MP、体积空速1.0h-1、氢油比400:1的条件下，在小型固定床反应装置上进行催化裂化汽油中间馏分(50～100℃)的芳构化反应，考查了不同钼质量分数、n(Mo):n(P)的摩尔比和温度对反应的影响。结果表明，钼质量分数及n(Mo):n(P)的摩尔比对反应有明显的影响，适当增加磷含量能提高催化剂性能。MoP/HZSM-5在钼的质量分数为3%、n(Mo):n(P)=1.5，反应温度为400℃时，改性催化剂芳构化活性最佳,液相产品中芳烃质量分数为65.43%,烯烃质量分数为5.42%，液收为61.04%。     

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.     

芳烃抽提返洗液常压芳构化研究

以扬子石化公司芳烃抽提返洗液为原料,以改性ZSM-5分子筛为催化剂,在200 mL气固相催化反应装置上进行常压芳构化研究,考察反应温度、进料空速对芳构化反应的影响以及催化剂的稳定性及再生情况。结果表明,在常压、体积空速为4.0h-1、反应温度为450℃时,芳构化效果最佳,此时催化剂单程寿命约为12 h;再生多次的催化剂具有与原始催化剂同样的催化性能;芳烃抽提返洗液常压芳构化可同时降低返洗液中的烯烃和环烷烃含量,增加目标产物芳烃含量。     

Influence of Aromatization Reaction Conditions in the Presence of HZSM-5 Catalyst

Abstract

The reaction conditions include temperature, weight hourly space velocity (WHSV), catalyst loading amount Ga and Si/Al, vapor, calcination temperature, soaking order, pretreatment, oxygen, and microwave heating method. The study introduces the influence of aromatization reaction conditions over HZSM-5 catalyst in detail. The proper temperature, low weight hourly space velocity (WHSV), modified HZSM-5, non-oxygen and microwave heating method are beneficial to the aromatization reaction.     

裂解C_9常压芳构化的研究

以裂解C_9为原料、改性ZSM-5分子筛为催化剂,在40mL固定床催化反应装置上进行了裂解C_9芳构化的探索实验,实验结果表明,反应温度在450～500℃内,苯、甲苯、二甲苯(三者简称为BTX)的含量迅速增加、茚和茚满的总含量快速下降。在200mL固定床催化反应装置上进行了芳构化放大实验,实验结果发现,在改性的ZSM-5分子筛用量115.3g、常压、反应温度500℃、WHSV=0.30h~(-1)的条件下,得到了无色透明的可作芳烃原料的液相产物,液相产物中BTX的质量分数大于71%、茚和茚满的总质量分数小于2%,液体收率的平均值为75%。改性ZSM-5分子筛催化剂可重复使用。     

FCC汽油不同馏分在P-Zn／HZSM-5上的芳构化研究

 在连续固定床反应器上考察了P-Zn/HZSM-5催化剂对FCC汽油不同馏分芳构化的反应性能，探讨了原料对芳构化反应的影响。结果表明，在一定的反应条件下，P-Zn/HZSM-5催化剂对50～100℃馏分芳构化反应具有很高的活性和稳定性。在反应16 h后，液相产品中烯烃及芳烃的质量分数分别为 5.23%和79.9%，得到了低烯烃、高芳烃的汽油调合产品。在50～100℃馏分芳构化反应中，液相产品中的苯、甲苯和二甲苯的含量分布会发生变化。反应进行4 h后，苯、甲苯和二甲苯的含量以甲苯、二甲苯、苯的顺序递减，而反应进行20 h后，由于催化剂积炭，改变为以二甲苯、甲苯、苯的顺序递减；C9+芳烃的含量则先增加后降低。     

Study on Olefin Decrement Reformulation and Increasing Light Olefins of FCC Gasoline by Catalytic Cracking

Abstract

Catalytic upgrading of fluid catalytic cracked (FCC) gasoline obtained from Huabei Petrochemical Company, PetroChina (Renqiu, Hebei, China), was investigated using a microreactor and gas chromatograph integrated unit in order to decrease the content of olefins in gasoline and increase the light olefins (ethylene, propylene, and butylene) content. The experimental results showed that the olefin content in upgraded gasoline can be decreased from 42.6% in raw material to nearly 10%, meeting the requirements of the new gasoline standard, whereas iso-alkane and aromatics contents were markedly increased, from 28.4 and 18.2% to 47 and 36.1%, respectively, so the octane number of gasoline should not be reduced. In addition, higher yields of light olefins were obtained after FCC gasoline was reformulated under laboratory conditions. Higher reaction temperature, longer reaction time, higher weight ratio of catalyst to oil, and higher catalyst activity were beneficial to decrease the olefin content of FCC gasoline and increase the yields of light olefins.     

Olefin Reduction of FCC Naphtha Using β-zeolite Catalyst in the Absence of Hydrogen

Abstract

In order to fulfill the requirement of environmental protection, experimentation of reducing FCC gasoline olefin content and optimization of the process operating conditions were studied in a small fixed vector. Under the action of a macroporous molecular sieve catalyst, which consists of active composition of Ni and Mo metal in β-zeolite supporter, when the reaction temperature was 140°C, reaction pressure was 2.0 MPa, and space velocity was 1.0 h^?1–2.0 h^?1, aromatization reactions, isomerization reactions, and hydrogen transfer reactions happened, so that the olefin, benzene, and arene in product gasoline were no more than 35%, 2.5%, and 40%, respectively. The octane number of petroleum is slightly increased. And it overcomes the disadvantage of losing octane by hydrogenation process. The catalyst could be regenerated using a multi-cycle with an average running cycle of about 96 hr. The results show that the process reaction condition is relaxation, process is non-hydrogenation, process flow is simple, technical and economic target is advanced, benefit is high, and cost is low.     

Zn-Ga/HZSM-5分子筛芳构化催化剂

以硝酸锌或硝酸镓为改性剂,纳米HZSM-5分子筛为原料,采用浸渍法可制备单(双)金属改性HZSM-5分子筛催化剂(负载Zn,Ga质量分数分别为6.0%,0.1%)。以正丁烷或异丁烷为原料,在反应温度为400～550℃,反应压力为0.8 MPa,质量空速为0.60 h^-1的条件下,研究了不同金属离子负载顺序对所制备催化剂芳构化反应性能的影响。结果表明：在反应温度为550℃的条件下,以异丁烷为研究对象,采用Zn-Ga/HZSM-5分子筛催化剂,转化率达到93.75%,芳烃选择性达到46.54%;以正丁烷为研究对象,选用Ga-Zn/HZSM-5分子筛催化剂,上述各值依次为62.18%,49.52%;与单金属改性HZSM-5分子筛催化剂相比,双金属改性不仅可以提高异丁烷和正丁烷芳构化反应性能,还能够降低干气收率,抑制小分子烃的生成。     

Transformation of Cycloparaffin over Zeolite-Supported Metal Catalyst for Improving the Octane Number of Gasoline

Abstract

In order to improve the octane number of gasoline, Ni/HZSM-5 and NiMo/HZSM-5 catalysts were prepared by impregnation method, and their activities for hydrocracking, hydroisomerization, and aromatization were investigated by the transformation of cylcohexane. The experimental results show that the conversion of cyclohexane is affected greatly by the reaction temperature. The production of methyl-cyclopentane is the result of the hydroisomerization of cyclohexane. The olefin distribution reveals that the hydrocracking reaction of cyclohexane over acidic zeolite catalyst probably obeys the dimolecular mechanism and the C₅ and C₇ olefins come from the cracking of the dimer of cyclohexane. The activities of the presulfided Ni/HZSM-5 and NiMo/HZSM-5 catalyst for the transformation of cyclohexane were evaluated and the product selectivities for two presulfided catalysts are similar to those obtained over reduced Ni/HZSM-5 catalyst.     

SiO_2改性HZSM-5催化剂催化C_4烯烃裂解生产丙烯

利用硅油对HZSM-5分子筛进行液相沉积S iO2改性,制备了S iO2/HZSM-5催化剂(简称催化剂);考察了S iO2沉积量及反应条件对催化剂催化C4烯烃裂解生产丙烯性能的影响;采用X射线衍射、N2等温吸附-脱附、透射电子显微镜、扫描电子显微镜、吡啶吸附-脱附红外光谱等方法对催化剂进行了表征。实验结果表明,在HZSM-5分子筛上沉积SiO2调变了催化剂的孔结构和酸性,SiO2沉积量影响催化剂的性能,当SiO2沉积量为7.0%(质量分数)时,催化剂具有适当的孔结构和酸性,催化剂的性能较好。在530℃、0.1MPa、原料重时空速2.0 h-1、催化剂中SiO2沉积量7.0%的条件下,C4烯烃转化率为42.9%,丙烯收率为28.3%。