Orientational Separation of Sulfur in Petroleum Coke by Alkali Calcining and Reflux Washing

The application of high-sulfur petroleum coke after desulfurization in aluminum electrolysis anodes is an important development trend. However, removing sulfur from high-sulfur petroleum coke is still a significant challenge.This study proposes alkali calcining and reflux washing to examine the impacts of temperature, particle size, the mass ratio of Na₂CO₃ to NaOH, and total sodium addition on the desulfurization efficiency and mechanism. The results show that the desulfur...     

改性Y型分子筛对石脑油脱硫效果的研究

NH4Y zeolite was prepared through ion-exchange of NaY zeolite with an ammonium salt. Then LaY zeolite was obtained through a secondary ion-exchange of NH4Y zeolite with a rare earth salt solution followed by calcination of the zeolite product. Dynamic adsorptive desulfurization of naphtha was conducted in the presence of the modified LaY zeolite, and the sulfur content of the treated naphtha samples was analyzed by microcoulometry. The test results showed that under dynamic conditions the LaY zeolite prepared through secondary ion-exchange of NH4Y zeolite, which was prepared using 1.0 mol/L ammonium salt, with the rare earth salt exhibited a better desulfurization efficiency. Furthermore, the LaY zeolite achieved a best desulfurization effect at an adsorption temperature of 45 ℃ and an adsorbent/oil ratio of 1:2.     

Adsorptive Desulfurization of Propylmercaptan and Dimethyl Sulfide by CuBr_2 Modified Bentonite

Adsorptive desulfurization for removing propylmercaptan(PM) and dimethyl sulfide(DMS) over CuBr2 modified bentonite was investigated under ambient conditions in this work. A saturated sulfur capacity as high as 196 mg of Spergram of adsorbent was demonstrated. The influence of loading amount of Cu(II) and calcination temperature on adsorptive desulfurization was investigated. Test results revealed that the optimum loading amount of Cu(II) was 15%, and the calcination temperature was 150 ℃. The pyridine-FTIR spectroscopy showed that a certain amount of Lewis acid could contribute to the increase of adsorption capacity. Spectral shifts of the ν(C-S) and ν(Cu-S) vibrations were detected from the Raman spectra of the Cu(II) complex which was a reaction product of CuBr2 with DMS. According to the hybrid orbital theory and the complex adsorption reaction, the desulfurization of PM and DMS over the CuBr2 modified bentonite is ascribed to the formation of S-M(σ) bonds.     

Effect of Mixed Oxide Support for Ni/ZnO in Reactive Adsorption Desulfurization

The effect of mixed oxide support on the performance of Ni/ZnO in the reactive adsorption desulfurization(RADS) reaction was investigated in a fixed bed reactor by using thiophene as the sulfur-containing compound in the model gasoline. A series of oxide supports for Ni/ZnO were synthesized by the co-precipitation method and characterized by XRD, N_2-adsorption, TPR and NH_3-TPD techniques. It was found that the desulfurization capacity of Ni/ZnO was enhanced greatly when active components were supported on the proper mixed oxide. Ni/ZnO supported on oxides exhibited much higher desulfurization efficiency and sulfur adsorption capacity than the unsupported Ni/ZnO and the synthesized Ni/ZnO-SA adsorbent exhibited the highest efficiency for thiophene removal. The higher desulfurization activity and sulfur capacity of Ni/ZnO supported on SiO_2-Al_2O_3 with small particle size, high specific surface area and large pore volume could promote the high dispersion of active metal phase and the transfer of sulfur to ZnO with lower mass transfer resistance. γ-Al_2O_3 species could weaken the interaction of active phases and SiO_2 as well as could increase greatly the amount of weak acids. Therefore, these oxides could impose a great influence on the structure and chemical properties of the catalyst.     

银离子改性白土对模拟油品的深度脱硫研究

In order to further reduce the sulfur content in liquid hydrocarbon fuels,a desulfurization process by adsorption for removing alkyl dibenzothiophenes was investigated.Desulfurization of model gasoline by bentonite adsorbents loaded with silver nitrate was studied.The test results indicated that the bentonite adsorbents loaded with Ag + ions were effective for adsorbing the alkyl dibenzothiophenes.The crystal structure of bentonite adsorbents was characterized by X-ray diffraction (XRD) and their acidity was measured by Fourier transform infrared (FT-IR) spectroscopy.Several factors influencing the desulfurization capability,including the Ag + loading,the baking temperature,as well as the reaction temperature,were investigated.The desulfurization efficiency was enhanced by increasing the Ag + loading and the best result was obtained at a silver loading of 7 m%.It was found that the adsorption capacity of the alkyl dibenzothiophenes on bentonite loaded with Ag + ions increased with a decreasing temperature.Baking of the adsorbent could also improve the desulfurization capacity,and the optimum baking temperature was 423 K.     

The New-Generation Technology for Making Petroleum Needle Coke

The current technology for producing the petroleum needle coke is apt to cause overflow of feedstock from the coke drums, instability in operation of.coking unit, low mechanical strength of petroleum coke, and high percentage of coke powder, leading to difficulties in improving the overall quality of needle coke. Therefore, we have developed a new technology for producing the needle coke, featuring the manipulation of temperature range in a narrow scale at high pressure coupled with feedstock alternations. This new kind of technology has been successfully applied in a 60kt/a commercial coking unit. Provided that demand for the feedstock quality is satisfied, petroleum needle coke meeting the international quality standard can be manufactured using RIPP‘s technology for producing petroleum needle coke.     

Preparation of WO_3/C Composite and Its Application in Oxidative Desulfurization of Fuel

The WO_3/C composite was successfully prepared by calcination of a mixture of WO_3 and g-C_3N_4 at 520 ℃. The as-synthesized samples were analyzed by X-ray diffraction(XRD), electronic differential system(EDS), scanning electron microscopy(SEM), infrared spectrometry(IR) and the Brunner-Emmet-Teller(BET) techniques. The WO_3/C composite, in comparison with the WO_3 and C_3N_4, features smaller particle size, bigger surface area and higher desulphurization performance. The influence of the reaction temperature, the catalyst dosage, the reaction time, the oxidant dosage, the sulfide type and the extractant dose on desulfurization reaction was studied. The results showed that the WO_3/C composite revealed a higher desulfurization activity than the WO_3. The desulfurization rate could reach up to 95.8% under optimal conditions covering a catalyst dosage of 0.02 g, a H_2O_2 amount of 0.2 mL, a 1-ethyl-3-methylimidazolium ethyl sulfate(EMIES) amount of 1.0 mL, a reaction temperature of 70 ℃ and a reaction time of 180 min. After five recycles, the desulfurization activity of catalyst did not significantly decline.     

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.     

Effect of Olefins on Formation of Sulfur Compounds in FCC Gasoline

The effect of olefins on formation of sulfur compounds in FCC gasoline was studied in a small-scale fixed fluidized bed （FFB） unit at temperatures ranging from 400℃ to 500℃, a weight hourly space velocity （WHSV） of 10 h-1, and a catalyst/oil ratio of 6. The results showed that C4--C6 olefins contained in the FCC gasoline could react with HzS to form predominantly thiophenes, alkyl-thiophenes as well as a fractional amount of thiols, while large molecular olefins such as heptene could react with hydrogen sulfide to form benzothiophenes. The amount of sulfur compounds formed at different tem- peratures over different catalysts were in proportion to the mass fractions of olefins in the feedstock, with the amount of sulfur compounds formed over REUSY catalyst exceeding those formed over the shape selective zeolite catalyst owing to the effect of catalyst performance and the impact of catalyst on the degree of olefin conversion. The amount of sulfur compounds generated and their increase reached a maximum at 450℃ and a minimum at 400℃ because of the influence of temperature on the thermodynamic and kinetic constants for formation of sulfur compound as well as on the olefin conversion degree. Based on the above-mentioned study, a reaction network and a model for prediction of sulfur compounds generated upon reaction of olefins in FCC gasoline with HES were established.     

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%.     

Progress in the Technology for Desulfurization of Crude Oil

The poor quality of crude oil obviously leads to high sulfur contents of oil products,and the technology for desulfurization of crude oil is urgently needed so that the sulfur contents in petroleum product could be reduced from the root.This paper describes the progress in technology for desulfurization of crude oil.The present technologies for desulfurization of crude oil include caustic washing,dry gas desulfurization,hydrodesulfurization(HDS),etc.The new combined technologies for desulfurization of cr...     

Application of High Shear Agitation for Desulfurization of Gasoline Using Ionic Liquids

The high shear agitation device was first adopted for gasoline desulfurization by ionic liquids. The effect of benzylimidazol fluoborate in desulfurization of gasoline and the influence of moisture on deuslfurization rate were investigated. The experimental results showed that the ionic liquid could effectively decrease the sulfur content of gasoline and the optimal conditions were as follows: The reaction could be carried out at room temperature, a volumetric ratio between oil and the liquid of 2∶1, a volumetric ratio between water and ionic liquid of 0.04∶1, a rotational speed of 5 krad/s, and a reaction time of 1 minute. The desulfurization rate of gasoline reached 53.6%, and the gasoline yield was up to 97.3%. The ionic liquid could be recycled for repeated use, and the use of high shear agitation for gasoline would have good prospects.     

Study on Reduction of Sulfur Content in FCC Gasoline

Reduction of sulfur content in FCC gasoline was studied in a fixed fluid bed (FFB) unit by using metal-modified LV-23 FCC catalyst. The results showed that the sulfur content in FCC gasoline could be reduced with LV-23 catalyst modified with zinc, palladium, zinc-palladium, zinc-cobalt, and zinc-nickel. Among these metals or metal combinations, palladium-containing catalyst was the most effective. Desulfufization of the heavy fraction of FCC gasoline was more effective than full-range gasoline under the same conditions with palladium-containing catalysts. A high reaction temperature was favorable to desulfurization, but it would reduce the yield of liquid product. After desulfurization reaction, the olefm content of product gasoline decreased while the aromatic and iso-alkane contents increased. Removal of thiophene and benzothiophene is higher.     

Study on Removing Trace Olefins in Aromatic Hydrocarbons with HPMo-loaded Y Zeolites

HPMo-loaded Y-zeolites were prepared for the removal of trace olefins from aromatic hydrocarbons. The temperature of calcination and the proportion of phospho-molybdic acid in the catalyst were studied. The catalytic activity for olefins removal and the service life of the catalyst were tested in a fixed bed microreactor. The results showed that the catalyst containing 3% phospho-molybdic acid, which was calcined at 550℃, demonstrated the best activity for olefins removal. The catalyst could be regenerated and could perform still very well. Catalyst characterization was performed by XRD and measured by pyridine-FTIR spectrometry. The test results indicated that the activity of the catalyst was related with the effect of acid concentration and acid strength. Besides, the deactivation of the catalyst was associated with the formation of coke deposits and the deactivated catalyst could recover its activity by oxidation with air under a proper temperature.     

Study on Desulfurization of Gasoline by Electrochemical Oxidation and Extraction

In order to further reduce the sulfur content in gasoline, a new desulfurization process was proposed by using catalytic oxidation and extraction realized in an electrochemical fluidized reactor. The fluidized layer of loaded catalyst particles consisted of lead dioxide (PbO2) supported on activated carbon particles (PbO2/C) and the electrolyte was aqueous NaOH solution. The PbO2/C particle anodes could remarkably accelerate the electrochemical reaction rate and promote the electrochemical catalysis of sulfur compounds. The sulfur compounds were at first oxidized to sulfones or sulfoxides, which were then re- moved after extraction. The experimental results indicated that the optimal desulfurization conditions were as follows: The cell voltage was 3.2 V, the concentration of hydroxyl ions in electrolyte was 0.12 mol/L, and the feed rate was 300 mL/min. Under these conditions the concentration of sulfur in gasoline was reduced from 310 ppm to 70 ppm. Based on these experimental results, a mechanism of indirect electrochemically catalytic oxidation was proposed.     

Preparation of Cu-, Zn-, Co-Zeolites and Application for Adsorptive Desulfurization of Saudi Arabian Medium Crude

A series of Cu(II)-, Zn(II)-, Co(II)-loaded zeolites were successfully prepared by liquid phase ion-exchange method and characterized by X-ray diffraction(XRD), N2-adsorption specific surface area measurement(BET), X-ray fluorescence(XRF), and scanning electron microscopy(SEM) techniques. The adsorptive desulfurization performance of different adsorbents for treating Saudi Arabian medium crude oil was investigated, and the results showed that desulfurization efficiency declined in the following order: Zn(II)X Cu(II)Y Co(II)X Cu(II)X Co(II)Y Zn(II)Y. The best desulfurization efficiency of 41.01% was achieved by using Zn(II)X as the adsorbent under the optimized conditions.The desulfurization performance of Zn(II)X in different distillates showed that a better performance was obtained in heavy petroleum fractions. Furthermore, the distribution of sulfur compounds in distillates after desulfurization was analyzed and the results showed that the adsorbent Zn(II)X could preferably adsorb aromatic sulfides such as thiophenes,benzothiophenes, and dibenzothiophenes. These results suggested that the π-complexation between zinc ions and sulfides would be crucial to the excellent desulfurization efficiency of Zn(II)X. In addition, the used adsorbent could be regenerated by heating at 700 °C in air, and around 84% of desulfurization capacity was recovered after the first cycle of regeneration.     

Experimental Study of UDS Solvents for Purifying Highly Sour Natural Gas at Industrial Side-stream Plant

The desulfurization performance of the UDS solvents was investigated at an industrial side-stream plant and was compared with that of MDEA solvent.A mass transfer performance model was employed for explaining the COS absorption into different solvents.Meanwhile,the regeneration performance of the UDS solvents was evaluated in side-stream tests.Results indicate that under the conditions covering an absorption temperature of 40℃,a pressure of 8.0 MPa,and a gas to liquid volume ratio(V/L)of around 230,the H2S content in purified gas can be reduced to 4.2 mg/m3 and 0 by using solvents UDS-II and UDS-III,respectively.Moreover,the total sulfur content in both purified gases is less than 80 mg/m3.As a result,the UDS-III solvent shows by 30 percentage points higher in COS removal efficiency than MDEA.In addition,the total volume mass transfer coefficient of UDS solvent is found to be twice higher than that of MDEA.Furthermore,the UDS solvents exhibit satisfactory thermal stability and regeneration performance.     

Commercial Application of RMC Technology in the 1.5 Mt／a Hydrocracking Unit at Shanghai Petrochemical Company

The RMC technology developed by RIPP has been applied in a 1.5Mt/a medium pressure hydrocracking unit at Shanghai Petrochemical Company. The unit was successfully put on stream in September 2002. Calibration of the performance of the commercial unit has shown that the RMC technology has higher hydrogenation activity and selectivity, and high quality product can be obtained under lower reaction temperature. The heavy naphtha with less than 0.5 ppm of sulfur and 58.5 m% potential aromatic content is a good feedstock for catalytic reforming unit. The diesel with less than 0.5 ppm of sulfur, 6.6 m% aromatics and cetane rating of 56 is a high-grade diesel fuel. The hydrocracked tail oil containing more than 14 m% hydrogen and mere 1.7m% aromatics could be used as a good feedstock for steam cracking process to produce ethylene.     

Preparation of Bi_2WO_6 and Its Ultra-Deep Oxidative Desulfurization Performance in Ionic Liquids

The micro-spheric Bi_2WO_6 was synthesized by a simple one-step hydrothermal method. Bi_2WO_6 crystals were characterized using XRD, SEM, EDS and BET techniques. Bi_2WO_6, H_2O_2 and [HMIM][BF_4] served as catalyst, oxidant and extracting agent in the oxidative desulfurization system(ODS), respectively. The influence of extraction agent type, oxidant usage, catalyst dosage, temperature, sulfur compound type and other factors on the oxidative desulfurization was studied in the present work. The experimental results demonstrate that Bi_2WO_6 possesses high activity for desulfurization of dibenzothiophene(DBT) and benzothiophene(BT). The desulfurization rate of DBT and BT in model oil could reach 98.1% in 80 minutes and 96.2% in 120min at 70℃, respectively. Moreover, the desulfurization performance of catalyst for DBT hardly changed after being recycled for 10 times.     

Ce4+与H2O2对FCC汽油氧化脱硫比较研究

This article describes two kinds of model oil samples made of a benzothiophene/octane mixture and a 2-me- thylthiophene/octane mixture. Furthermore, this paper investigates the oxidative desulfurization selectivity and reaction efficiency when Ce4+ compound and H2O2 having identical electron equivalent weight were used as oxidants. The test re- sults showed that the two kinds of oxidants were more effective to remove benzothiophene in the model oil samples. For oxidative desulfurization of 2-methylthiophene, Ce4+ compound was obviously superior than H2O2. This paper by means of quantum chemistry analyses elaborates the complex formed between Ce4+ species and 2-methylthiophene and FT-IR spec- trograms of model oil samples before and after oxidation by Ce4+ compound and H2O2, respectively. The results demonstrat- ed that Ce4+ compound could remove sulfur compounds not only through oxidation reaction but also through complexation reaction.