劣质催化裂化柴油加氢改质技术的开发及工业应用

在中型试验装置上对劣质催化裂化柴油 ,在氢分压 6.4MPa条件下进行加氢改质 ,通过应用加氢精制催化剂RN 1和加氢裂化催化剂RT 5的加氢改质工艺可以生产质量收率在 90 %～95%的优质柴油馏分 ,其十六烷值较原料可提高 1 0～ 1 5.7个单位 ,副产品石脑油馏分油的芳烃潜含量在 70 %左右。该技术于 1 998年初在武汉石油化工厂 30 0kt/a加氢改质装置上实现了首次工业应用 ,工业结果与中型结果一致。

A Survey of Novel Processes to Produce Ultra Low Sulfur Gasoline

The restriction on sulfur level in gasoline has been increasingly tightened. The U.S.Tier 22222 regulation requires a reduction from average 340ppm to 30ppm from 2004 to 2008. Recently significant progress has been made in effective high sulfur removal, such as post treatment of FCC gasoline by selective hydrotreating, S Zorb sulfur removal technology, OATS process etc. The sulfur content of FCC gasoline can be deceased to less than 10ppm. With regard to gasoline pool composition in China, it is very important to look for effective desulfurization processes that are simple, straightforward, with less hydrogen consumption. Post-treatment of FCC gasoline is a preferred option. From the point of view of comprehensive utilization, alkylation, polymerization, isomerisation etc. can be added to desulfurization process to meet the requirement of ultra low sulfur, premium.

Development of FCC Naphtha Hydrodesulfurization and Aromatization Process

This articles refers to the development of the technology for hydrodesulfurization (HDS) and aromatization of FCC naphtha This technology adopts a catalyst with aromatization performance, which does not reduce the octane rating of gasoline in the course of HDS of FCC naphtha. Experimental results have shown that the sulfur removal rate of FCC naphtha could reach over 85%, with the RON of gasoline increased by 0.2-0.6 units, the MON increased by 1.3-1.8 units and the antiknock index of the gasoline increased by around one unit. The total C5+ liquid yield was over 95%. The activity of regenerated catalyst could be restored to be equal to that of fresh one after coke burning on the spent catalyst.

Development and Application of DCC Catalysts to Meet New Demands

The new generation of DCC catalysts, the DMMC/RMMC series catalysts developed by RIPP are introduced in this paper. The large molecule cracking ability is enhanced by increasing the portion of large pores; and the coke selectivity is improved by adjusting the acidity site density on the matrix surface, while the selective cracking reactions are increased. The sphericity of catalysts is improved by adopting new preparation method. The commercial application results have shown that applying DMMC/RMMC series catalysts with the mixed VGO, VGO plus AR, and hydrotreated VGO feed can increase the propylene yield by 2.43, 1.3 and 0.8 percentage points, respectively, as compared to the previous catalysts along with improvement in some products yields. The refining enterprises can make more profits after applying new series of DCC catalysts.

Development of Light Cycle Oil(LCO) Hydrocracking Technology over a Commercial W-Ni Based Catalyst

Because of its high density and low cetane number, the light cycle oil(LCO) containing heavy aromatics(60%—80%) can hardly be transformed through the conventional hydro-upgrading technology. In this report, a novel LCO hydrocracking technology(FD2G) was proposed for the utilization of LCO to manufacture high value-added products. Through the ingenious combination of hydroprocessing catalyst and the hydrocracking process, the high octane gasoline and the ultra-low sulfur diesel(ULSD) blendstocks were produced simultaneously. The influence of catalyst type, reaction temperature, pressure, respectively, on the research octane number(RON) of produced gasoline was studied in a fixed bed hydrogenation reactor. It indicated that high reaction temperature and medium pressure would favor the production of highoctane gasoline through the conversion of bi-aromatic and tri-aromatic hydrocarbons. The typical results of FD2 G technology on commercial units showed that it could produce clean diesel with a sulfur content of less than 10 μg/g and clean gasoline with a research octane number(RON) of up to 92. It would be contributed to the achievement of the maximum profit of a refinery, the FD2 G technology could provide a higher economic efficiency than the other diesel quality upgrading technology under the current gasoline and diesel price system.

Influence of Steam Treating on Deethylating Type Isomerization Catalyst

This article mainly worked on methods to reduce side reactions of the de-ethylating type catalyst for xylene isomerization. In laboratory the de-ethylating type catalyst for xylene isomerization was subjected to steam treatment at different temperatures and durations to achieve dealumination of the ZSM-5 zeolite to some extent, which could affect the change in BrФnsted acid content to decrease xylene loss along with reduction of side reactions. Test results showed that the degree for reducing side reactions by steam treatment depended upon two important parameters-treating temperature and duration. The optimal condition required treating the catalyst at 500℃ for 8 hours.

Study on Performance of Hydrocracking Catalyst CHC-1

Evaluation of hydrocracking catalyst CHC-1 showed superior qualities ofcatalyst CMC-1. When it was used for hydrocracking reaction, the yield of middle distillates (jetfuel and diesel fuel) can reach more than 71 m%. When it was used for medium-pressurehydro-upgrading of Daqing FCC diesel fuel, diesel density was decreased by 0.0284―0.0365 g/cm^3(20℃). Cetane number increased by 7.8―10.5 and the contents of sulphur and nitrogen wereremarkably reduced. The storage stability of the upgraded diesel was improved.

Selective Hydrogen Transfer Reaction in FCC Process:Characterization and Application

The product distribution and gasoline quality of FCC process, especially the olefin content,heavily depends on the catalyst performance in terms of selective/non-selective hydrogen transfer reaction selectivity. A reliable experimental protocol has been established by using n-dodecane as a probe molecule to characterize the selective hydrogen transfer ability of catalytic materials. The results obtained have been correlated with the performance of the practical catalysts.

Study on Expansion of Steam Cracking Unit to 660 kt/a at Yanshan Petrochemical Company

Yanshan Petrochemical Company after having expanded its 300 kt/a steam cracking unit to 450 kt/a in 1994 is still experiencing such problems as low feedstock flexibility, high energy consumption and smaller scale of ethylene unit.In order to fully improve technical capability of steam crackers, reduce energy consumption, improve feedstock flexibility and increase production capacity, a lot of technical revamp cases on steam cracking were studied and compared.Revamp of relevant facilities has expanded the ethylene capacity to the target of 660 kt/a with the actual capacity reaching 710 kt/a. This revamp project has remarkably reduced the energy consumption, which is capable of using naphtha, light diesel fuel, heavy diesel fuel and the hydrocracked tail oil as the steam cracking feedstock. This project is the first to apply refrigeration by means of a mixed cooling agent and has succeeded in using C, catalytic rectification/hydrogenation technology, which has given an impetus to the progress of steam cracking industry in the world.

Characterization and Modification of Indonesian Natural Zeolite for Hydrocracking of Waste Lubricant Oil into Liquid Fuel Fraction

Modification and characterization of natural zeolite under some various methods for hydrocracking catalyst of waste lubricant to gasoline and diesel fractions have been conducted. Natural zeolite from Klaten was activated using hydrothermal treatment at temperature 500 ℃ for 6 h （produced ZAAHd）, the ZA sample was treated with hydrothermal followed by Microwave （produced ZAAHdM）, the ZA sample was treated with HCI 3 N at temperature of 90 ℃ for 30 min （produced ZAAH）, the ZAAH sample was heated in to microwave （produced ZAAHM）, the ZAAHM was treated hydrothermal （produced ZAAHMHd）, the ZAAHMHd sample was heated in to microwave （produced ZAAHMHdM）, soaking of natural zeolit activated by HCl-microwave-hydrothermal-microwave in NH4NO3 1 N which was stirred using stirer at room temperature for 24 h （produced ZAAHMHdMN） and the ZAAHMHdMN sample was heated into microwave （ZAAHMHdMNM）. The heating process by microwave was conducted at 550 watt for 15 rain. Catalyst characterization involved determination of the number of total acid sites using gravimetric method with vapour adsorption of NH3 and pyridine, catalyst crystallinity by XRD （X-ray diffraction） and TO4 （T= Si and AI） site by infra red spectrophotometer （IR）. Hydrocracking of waste lubricants oil was performed in a fixed bed reactor of stainless steel at temperature of 450 ℃, H2 flow rate of 15 mL/min., feed/catalyst ratio of 5. Liquid products of the hydrocracking were analyzed using GC （gas chromatography）. The characterization results showed that various modification of natural zeolite increased acidity and dealumination degree of the catalysts. Products of the hydrocracking were liquid, coke, and gas fractions. Liquid products consisted of gasoline fraction （C5-C12）, diesel fraction （C12-C20）, and heavy oil fraction （〉 C20）.Thc conversion of liquid products was increased with the increase of catalyst acidity. The greatest liquid product conversion was produced by the ZAAHMHdMNM catalyst, i.e., 56.80%, with selectivity towards gasoline, diesel, and heavy oil fractions was 88.37%, 8.61% and 3.02%, respectively. The increase of catalyst acidity increased the selectivity of gasoline fraction.

Development of New Generation Catalysts for Selective Hydrodesulfurization of FCC Naphtha

The influence of active metal components of catalyst, additives and catalyst preparation method on the reactivity of catalyst for selective hydrodesulfurization (HDS) of FCC naphtha was investigated, and the RSDS-21 catalyst with high HDS performance and the RSDS-22 catalyst with high selectivity were developed by RIPP. The composite loading of a new series of catalysts for selective HDS of FCC gasoline has demonstrated excellent desulfurization activity and selectivity and can under conventional hydrotreating conditions manufacture clean gasoline product meeting the national IV emission standard and the Euro V emission standard with less loss in antiknock index. The finalized new series of FCC catalysts upon being adopted for selective HDS of FCC naphtha have good adaptability to different feedstocks along with good stability.

Suitability of Sour Crude Processing and Resid Hydrotreating Technologies

This article has analyzed the environment and tasks confronting China's petroleum refining industry, and has referred to principles for selecting the resid processing technologies and viability of various combination technologies for resid processing. Taking into account the actual commercial practice of resid hydrogenation units, this article has also discussed methods for processing high-sulfur inferior crudes as well as the suitability of resid hydrogenation technology.

In situ FT-IR spectroscopy investigations of carbon nanotubes supported Co-Mo catalysts for selective hydrodesulfurization of FCC gasoline

To better understand the nature of carbon nanotubes supported Co-Mo catalysts （Co-Mo/CNTs） for selective hydrodesulfurization （HDS） of fluid catalytic cracking （FCC） gasoline, studies are carried out using in situ Fourier transform infrared spectroscopy （FT-IR）. The catalytic performances of Co-Mo/CNTs catalysts were evaluated with a mixture of cyclohexane, diisobutylene, cyclohexene, 1-octene （60 ： 30 ： 5 ： 5, volume ratio） and thiophene （0.5%, ratio of total weight） as model compounds to simulate FCC gasoline. The HDS experimental results suggested that the HDS activity and selectivity of Co-Mo/CNTs catalysts were affected by Co/Mo ratio; the optimal Co/Mo atomic ratio is about 0.4, and the optimum reaction temperature is 260 ℃. The in situ FT-IR studies revealed that 1-octene can be completely saturated at 200 ℃. In the FT-IR spectra of diisobutylene, the characteristic absorption peak around 3081 cm^-1 for the stretching vibration peak of =C-H bond was still clear at 320 ℃ indicating that diisobutylene is difficult to be hydrogenated. As for the thiophene, no characteristic absorption peak could be found around 3092 cm^-1 and 835 cm^-1 when the reaction temperature was raised to 280 ℃, indicating that thiophene had been completely hydrodesulfurized. On the basis of FT-IR results, it can be deduced that thiophene HDS reaction occurred mainly through direct hydrogenolysis route, whereas thiophene HDS and diisobutylene hydrogenation reaction over Co-Mo/CNTs catalysts might occur on two different kinds of active sites.

Hydrocracking of Goudron in the Presence of a Suspended Natural Catalyst

The main results of hydrocracking of goudron under reduced pressure in the presence of a suspended catalyst have beenanalyzed. It was investigate the influence of temperature to hydrocracking process of goudron. It was determined that with increasing of temperature from 400 ℃ to 440 ℃ （0.5 MPa pressure） the yield of light oil products increased from 31.39% to 61% mass.

Development Forecast of Catalytic Reforming in China

The current status of catalytic reforming in China is reviewed and a forecastof the development in a couple of years or a decade is given. Distinguished from the past decade,the future trend will be focused on revamps, expansions, higher severity, diversified feeds,combination with other processes for higher product quality, and novel catalysts and equipment.

Computational Fluid Dynamics Simulation of Liquid-Phase FCC Diesel Hydrotreating in Tubular Reactor

The computational fluid dynamics(CFD) code, FLUENT, was used to simulate the liquid-phase FCC diesel hydrotreating tubular reactor with a ceramic membrane tube dispenser. The chemical reaction and reaction heat were added to the model by user-defined function(UDF), showing the distribution of temperature and content of sulfides, nitrides, bicyclic aromatics and monocyclic aromatics in different parts of the reaction bed. When the pressure was 6.5 MPa, the amount of mixing hydrogen was 0.84%(m), the space velocity was 2 h-1 and the inlet temperature was 633 K, the temperature reached a maximum at a height of 0.15 m, and the range of radial temperature reached its maximum(2.5 K) at a height of 0.15 m. It indicated that the proper ratio of height to diameter of catalyst bed in the tubular reactor was 5-6. The increase of inlet temperature, the mixing hydrogen and the decrease of space velocity led to the decrease in the content of bicyclic aromatics, sulfides and nitrides, and the increase in monocyclic aromatics content, while the high temperature increased. The results were in good agreement with experimental data, indicating to the high accuracy of the model.

Development and CommercialApplication of RSDS-II Technology for Selective Hydrodesulfurization of FCC Naphtha

The FCC naphtha selective hydrodesulfurization technology(RSDS-II)has been tested with different feedstocks in pilot scale.The results show that RSDS-II technology is viable in terms of its adaptability to different feedstocks.To produce gasoline with a sulfur content of less than 50μg/g by the RSDS-II technology,the gasoline RON loss is less than 1.8,0.9and 0.2 units,respectively,upon processing the conventional high-sulfur and high-olefin FCC naphtha,the high-sulfur MIP naphtha,and the medium-sulfur or low-sulfur MIP naphtha.Upon using the naphtha produced from pre-hydrotreated FCC feedstock as the RSDS-II feedstock to manufacture gasoline with a sulfur content of lower than 10μg/g,the RON loss does not exceed 1.0 unit.The RSDS-II technology has been commercialized successfully at many refineries.The result of operating commercial RSDS-II unit at the Shanghai Petrochemical Company has revealed that upon processing a feedstock containing 38.7 v% —43.3 v% of olefins and 250—470 mg/g of sulfur,the sulfur content in the treated gasoline ranges from 33μg/g to 46μg/g and the RON loss is equal to only 0.3—0.6 units.Till now this RSDS-II unit has been operating smoothly over 30 months.Thanks to its high HDS activity and good selectivity,the RSDS-II technology can meet the refinery’s needs for adequate upgrading of gasoline.

Deep Hydrodesulfurization of Diesel Fuel over Diatomite-dispersed NiMoW Sulfide Catalyst

Diatomite-dispersed NiMoW catalyst was prepared and characterized,and the activity of catalyst samples was tested during the HDS reaction of FCC diesel.Sulfur compounds in the feedstock and the hydrogenated products obtained over different catalysts were determined by GC-PFPD.The test results showed that the diatomite-dispersed NiMoW catalyst had high hydrodesulfurization activity for FCC diesel,which could be contributed to the excellent hydrogenation performance of the said catalyst.Characterization of catalyst by TEM and XRD indicated that the diatomite-dispersed NiMoW catalyst possessed higher layer stacking,larger curvature of MoS2or WS2,and segregated Ni3S2crystals relative to the supported catalyst.This kind of structure leads to high hydrogenation activity of the diatomite-dispersed NiMoW catalyst.

LTAG Technology Passed Appraisal

Recently the LTAG technology combining selective hydro-saturation of LCO with selective catalytic cracking technology for producing high-octane gasoline or light aromatic hydrocarbons has passed technical appraisal.

Influence of Crystal Size of USY Zeolite on Performance of Hydro-upgrading Catalysts

The effect of crystal size of USY zeolite on the performance of hydro-upgrading catalysts for treating catalytically cracked(FCC) LCO(light cycle oil) was studied.Three W-Ni catalysts supported on USY zeolites with different crystal sizes and Al2O3 were prepared by impregnation method.The catalysts were characterized by XRD and BET methods,and evaluated in a micro-reactor using tetralin as the model compound and in an 100-mL hydrogenation test unit using FCC LCO as the feedstock.By contrast,catalyst made from smaller crystal-size USY zeolite had higher external surface area and shorter pore length,having more hydrogenation activity sites and short contact time of reactant molecules with acidity sites.The evaluation results showed that the catalyst prepared on the basis of small crystal-size USY zeolite had higher tetralin conversion and better hydro-upgrading performance for treating FCC LCO.