PETROLEUM PROCESSING AND PETROCHEMICALS

HYDROGENATION TECHNOLOGIES BASED ON CATALYST DEVELOPMENT PLATFORMS FOR FULL-HYDROGENATION REFINERY AND THEIR COMMERCIAL APPLICATIONS

2018, 49(11): 1-6.

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In view of the new situation of the current market demand, RIPP is committed to efficient utilization of oil resources to increase the yield of light oil, green production of clean oils at low cost, and application of the key technologies, e.g. the maximum production of gasoline and the integration of refining and petrochemical process. Through long-term applied basic research combined closely with industrial practice, RIPP has successfully established a platform for development of hydrogenation catalyst and relative technologies. It is an organic whole consisting of catalytic material platform, active phase study platform and catalyst production technology platform. Based on the platform, RIPP can quickly respond to the problems and technical requirements encountered in industrial practice and propose correct technical measures, creating greater economic and social benefits for enterprises.

FEASIBILITY STUDY OF FCC CATALYST BLENDING TECHNOLOGY

2018, 49(11): 7-11.

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The physicochemical properties and catalytic performances of the integrated FCC catalyst produced by traditional methods (contains a certain proportion of different zeolites) and the physical blending catalysts (from mixing the based catalyst which contains only Y zeolite or modified ZSM-5 with a close ratio as in the former were comparatively studied. The results showed that, at similar compositions, the physicochemical properties and catalytic performances of blended catalysts are close to the integrated one. Therefore, FCC catalysts could be flexibly tailor-made for refineries by blending base catalysts. In addition, some issues about the formulation and attrition property of base catalysts which should be cared were suggested.

ADSORPTIVE DENITRIOGENATION OF NaY MOLECULAR SIEVE MODIFIED BY Ni2+ AND Ba2+

2018, 49(11): 12-16.

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A series of Ni-Ba-Y molecular sieves was obtained by ion exchange method at different temperature and modifier concentrations, the adsorption denitrogenation experiments were conducted. Experimental results showed that the obtained Ni-Ba-Y molecular sieve prepared at modification temperature of 70 ℃ and the modifier concentration of 0.25 mol/L exhibits the best adsorption performance, the XRD and IR results showed a similar characteristic peak of modified Ni-Ba-Y to the standard NaY molecular sieve. The results of FT- IR indicated a decrease of 1 147 cm-1 peaks strength and a blue shift of the peak at 1024 cm-1, meaning Ni2+ and Ba2+ being successfully exchanged into the NaY zeolite framework. Experiment data of the quinoline adsorption isotherm were fitted by Langmuir, Freundlich and Langmuir-Freundlich mixed adsorption models, the results revealed that the R2 of three regression equations is close to each other, but the Langmuir-Freundlich mixed adsorption model is any better. The effects of adsorption time on denitrogenation from the simulated fuels over NaY, NiY and Ni-Ba-Y molecular sieves were compared. The adsorption capacity of NiY molecular sieve is significantly superior to that of NaY molecular sieve, while the adsorption capacity of Ni-Ba-Y is similar to that of NaY molecular sieve.

INFLUENCING FACTOTS FOR HIGH EFFICIENT RUNNING OF VRDS UNITS AND SOLUTIONS

2018, 49(11): 17-21.

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To extend the life cycle of VRDS unit, measures were proposed by RIPP base on the analysis of factors affecting the VRDS operation. Catalysts with higher activity and stability as well as better grading catalyst filling technology for varies feedstocks are developed. The higher efficient fluid distribution technology and an asymmetric switching guard reactor configuration are also developed to give full play to the performance of the whole catalysts system.

STUDY OF SEPARATION OF STYRENE BY EXTRACTIVE DISTILLATION WITH N,N-DIMETHYLACETAMIDE SOLVENT

Zhao Ming Tian Longsheng Tang Wencheng Gao Siliang

2018, 49(11): 22-26.

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The separation of styrene from pyrolysis C8 fraction by extractive distillation, using N,N-dimethylacetamide as solvent, was studied by process simulation and pilot test. The effects of solvent ratio, reflux ratio, plate position of solvent feed and temperature on the purity and yield of styrene were investigated. The results showed that the styrene product purity can reach more than 99.8%，styrene recovery rate of 98.5% or more at the conditions of the feed plate position in the range of the 11th to 13th, the solvent ratio of 3.8-4.2, the reflux ratio 3.1-3.3, the solvent temperature 45-50 ℃. The pilot test results are consistent with the process simulation, proving that the process simulation system is reliable. Compared with the extraction distillation process by using sulfolane solvent, the operating temperature of the tower using N,N – dimethylacetamide solvent is only 113 ℃, beneficial to the long operation of the device.

FEASIBILITY OF RECONSTRUCTION EXISTING UNIT FOR PRODUCING GASOLINE FROM LCO

Li Zhengrong

2018, 49(11): 27-32.

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The LCO selective hydrocracking technology provides a new process to efficiently converse LCO, producing high-octane gasoline and low-sulfur diesel. It is an effective way to popularize this technology by reconstructing existing diesel hydrotreating unit to LCO hydrocracking unit. The main limiting factors for the reconstruction of diesel hydrotreating unit to LCO hydrocracking unit are the huge gaps in product slate and operating parameters. The reconstruction requires a significant reduction in the processing capacity and a large amount of project investment. However, the above gap is relatively small between medium pressure hydrocracking unit and LCO hydrocracking unit, the reconstruction can be done with small project investment and good economic benefits.

INFLUENCE OF BLENDING DIFFERENT FCC DIESELS ON VGO HYDROCRACKING PERFORMANCE

Cao Zhengkai Sun Hongjiang Mu Shuai Wu Ziming

2018, 49(11): 33-39.

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The influence of mixing FCC diesels with different distillation ranges on VGO hydrocracking performance was investigated. It was found that under the same reaction conditions, as the FCC diesel becomes heaver，the yield of light and heavy naphtha decreased, and the latent aromatic of heavy naphtha increased gradually；the yield of jet fuel was increased first and then decreased, while the smoking point of jet fuel decreased；the yield of ＞282℃ bottom oil was decreased and then increased with increase of BMCI value. The experiment results demonstrated that under the same reaction condition, as light FCC diesel blending ratio increases，the yields of jet fuel and heavy naphtha decreased, the latent aromatic of heavy naphtha increased, the BMCI value of ＞282℃ bottom oil gradually increased. When the mixing ratio of light FCC diesel was 30%，the BMCI value of ＞282℃ bottom oil was 13.31，which can be applied as a high-quality feedstock for SCR. Under the same conversion rate, with the increase of light FCC diesel ratio，the hydrogen consumption of hydrocracking reaction increases, the yields of light naphtha and heavy naphtha decreased. The yield of jet fuel, latent aromatics of heavy naphtha and BMCI value of bottom oil were increased, but the smoking point of jet fuel decreased.

INDUSTRIAL PRACTICE OF SR DIESEL BLENDING WITH FCC LCO AS MEDIUM PRESSURE HYDROCRACKING FEED

Zhao Chenxi Yang Jie Li Baoliang

2018, 49(11): 40-44.

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The technology of processing mixed feed of SR diesel and FCC diesel was commercially applied in a 3.6 Mt/a kerosene-diesel medium-pressure hydrocracking unit of CNOOC Huizhou Petrochemical Company. The catalyst has been running for 8 and half years without changing the structure of the device. However, even the mixing ratio is up to 21%（w），the device ran smoothly in such conditions，the comprehensive energy consumption increased from 777.121 MJ/t to 952.315 MJ/t. The qualities of heavy naphtha, jet fuel and diesel products are all on spec. Compared with the kerosene-diesel feed case, the yield of jet fuel decreased by 11.99 percentage points，and the smoke point decreased by 4.6 mm，the density（20 ℃）was increased by 12.8 kg/ m3 and the volume percent of the aromatic was increased by 8 percentage points；the cetane number of the diesel is 16.4 higher than the blending feed itself, but 5.5 lower than the diesel before blending，while the yield increased by 8.29 percentage points. The technology raises the volume of China V diesel, satisfy the need of the Company and provide a new way for the large refinery to optimize the material balance.

DEMULSIFICATION AND DEHYDRATION OF AGING OIL EMULSION UNDER HIGH FREQUENCY AND HIGH VOLTAGE PULSED ELECTRIC FIELD

2018, 49(11): 45-49.

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In this paper, based on the prepared aging oil W/O emulsion from Liuhua 11-1 oilfield, the influence of electric field intensity, frequency, waveform and moisture content on electric demulsification and dehydration under high frequency and high voltage electric field was investigated. A static electrostatic coalescing device with a centrifuge assisted to enhance the dehydration rate. The experiment results indicated that the phase inversion point of aging oil emulsion is between 40% and 50%, the optimal electric field parameter for W/O emulsion demulsification and dehydration is field strength (voltage) of 6 kV, frequency 2 kHz and AC square wave. The dehydration efficiency of stable W/O emulsion is 74.074% when the moisture content reaches 40%. These optimal electric field parameters do not vary with moisture content. This study can provide design references for the modification of aging oil treatment process in Liuhua oil field and a foundation for the improvement of production.

DISCUSSION ON PROCESSING SCHEME FOR HEAVY DISTILLATE WITH HIGH AROMATIC CONTENT

2018, 49(11): 50-54.

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The comparative studies of schemes were introduced for processing CNOOC SZ36-1 vacuum No.3 cut with high aromatic content to produce rubber plasticizer. The results showed that the rubber plasticizer with CA value of 12.9% was produced by a combined process of medium pressure hydrotreating and furfural extraction; the rubber plasticizer with CA of 13.4% could be obtained by one stage high pressure hydrotreating process with a light fuel as by-products. While the rubber plasticizer with CA 18.2% was gained by the combined process of high pressure hydrotreating and one stage furfural extraction, then the furfural raffinate oil could be used to produce naphthene-base rubber plasticizer having CN above 40% by hydro-dewaxing. The 3 stage all hydro-processing technology, consisting of high pressure hydrotreating-hydrodewaxing-hydrofinishing can produce naphthene-base rubber plasticizer having CN above 40%. Among these schemes, the combined process of high pressure hydrotreating process-one stage furfural extraction -raffinate oil hydrodewaxing is recommended as the best process.

APPLICATION OF DSO TECHNOLOGY IN FCC GASOLINE HYDROGENATION UNIT

2018, 49(11): 55-60.

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The application of DSO technology in 1.4 Mt/a gasoline hydrogenation unit of Yunnan refinery was introduced. The data showed that at the conditions of feed S content of 103μg/g, the processing load 102%, and mass ratio of light gasoline and heavy gasoline of 0.36:0.64, the final gasoline product has sulfur content of 11.4μg/g. Mercaptan sulfur content reduces from 18μg/g to less than 3μg/g. The RON loss of gasoline is 1.4, lower than the design value 1.7, the induction period increases from 168 min to 505 min. The energy consumption is 675 MJ/t, less than the design value 838 MJ/t. After 7 months of operation, the unit runs smoothly, the gasoline product can be used as the China VI standard gasoline blending component.

STUDY ON METAL-SUPPORT INTERACTION SITES OVER Mo/γ-Al2O3 CATALYSTS

2018, 49(11): 60-65.

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Metal-support interaction imposes a great influence on the structure and catalytic activity of the hydrogenation catalysts, and meanwhile it directly depends on the surface properties of the support. In this article, for deeply understanding the influencing mechanism of the support properties on the interaction, the support used for industrial RS-2100 catalyst was first hydrothermally treated under different temperatures (from 20 ℃ to 180 ℃) and the relative concentration of sites on support surface (including basic hydroxyl groups, neutral hydroxyl groups, acidic hydroxyl groups and coordinatively unsaturated sites) were modified. The obtained samples were then characterized by IR-OH and Py-IR, and the strength of metal-support interaction was evaluated according to the equilibrium adsorption contents of MoO3 on the support surface. IR-OH and Py-IR analysis results indicate that, with the increase of the hydrothermal temperature, the relative concentration of either basic hydroxyl groups or acidic hydroxyl groups first increases and then decreases, and reaches the maximum at 100 ℃. While the relative concentration of acidic hydroxyl groups decreases slightly after 100 ℃, and whereas that of either the neutral hydroxyl groups or Al-CUS gradually decreases. Meanwhile, according to the results of equilibrium adsorption contents of MoO3, it can be seen that, with the increase of temperature, the metal-support interaction first increases and then decreases. Based on the above analysis results, the suggestion that the metal-support interaction is mainly originated from the basic hydroxyl groups on the alumina surface can be given.

THEORETICAL STUDY OF INFLUENCE OF EXTRA-FRAMWORK ALUMINUM SPECIES ON BRONSTED ACID STRENGTH IN HY ZEOLITES

2018, 49(11): 66-71.

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The extra-framework aluminum species on the acidity of HY molecular sieve has a major influence on the properties of modified molecular sieves. The effect of [AlO]+ and [Al(OH)]2+ extra-framework Al species on the acidity of Br?nsted acid in HY zeolites was studied by using the periodic Density Functional Theory. By analyzing the deprotonation energy and the ammonia adsorption energy, it was recognized that the [Al(OH)]2+ species can strengthen the Br?nsted acid more effectively than the [AlO]+ species. The attached ammonia molecule can grab the H atoms of Br?nsted acid and turn into NH4+ species, NH3 works as an electron donor to transfer part of the electrons to the active center of HY zeolite. The more strength of Br?nsted acid, the more electrons transferred. Through geometric and electronic analysis, it was found that the influence of extra-framework Al species on the structure of Br?nsted acid is insignificant, but affects the electron structure of the molecular sieve skeleton, thus affecting its acidity.

MOLECULAR SIMULATION STUDY ON ADSORPTION BEHAVIOR OF OCTANE AND 1-OCTENE ON CeY ZEOLITE

2018, 49(11): 72-79.

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The adsorption and diffusion behaviors of octane and 1-octene molecules on CeY zeolite were simulated by the Grand Canonical Monte Carlo method and molecular dynamics method. To investigate the discipline of the adsorption isotherms of octane and octene on CeY, The Langmuir-Freundlich fitting curve, distribution curve of energy, contour maps of density and isosteric heat of adsorption at 303K and 423K were used. The results showed that the adsorption confirms to Langmuir-Freundlich model for octane. The interaction between octane or 1-octene and Na+ in the hierarchical pores of CeY zeolite is stronger, and the strength with Ce(OH)2+is the next and becomes weaker as the adsorption pressure raises. Octane is much easy to adsorb on CeY and has a stronger interaction with it, getting a larger saturation adsorbance than octene, the energy change of octane adsorption is more significant with the change of temperature. The adsorption heat of octane is higher than octene in the beginning of adsorption and turns lower than octene in the end stage, because the π-π interaction between octene becomes more obviously than octane with the increase of adsorbance and temperature.

PREPARATION OF HIGH ALKALINE CALCIUM SULFONATE

2018, 49(11): 80-85.

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The high alkaline calcium sulfonate was prepared by multistep method using acid materials from different sources. The parameters of ratio of domestic and foreign sulfonic acids, the amount of water added, the flow rate of carbon dioxide and the volume of methanol were changed to test the effect on the performance of the sulfonate products. The results showed that the best systhetic conditions are: the ratio of domestic sulfonic acid D and foreign one of 9:1, water 2.5g, CO2 flow rate 400ml/min, dosage of methanol 26ml. At these conditions, the obtained sulfonate has a high TBN, low turbidity, low motion viscosity and the product is easy to filter.

PREPARATION AND PROPERTIES OF BIODEGRADABLE LUBRICATING OIL ADDITIVE PIPERAZINE DERIVATIVES

2018, 49(11): 86-90.

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In order to reduce the environmental pollution caused by oil, new biodegradable lubricating oil additives 1,4-bis (dithiocarbamoyl-n-hexylamine) piperazine (NP) and 1,4-bis (dithiocarbamate) piperazine (DP) were synthesized with piperazine (PP) as a precursor, dichloromethane as solvent, triethylamine as acid binding agent, n-hexylamine, dodecylamine and chloroacetyl chloride as raw materials. The structures and thermal stability of products were characterized by FT-IR, 1HNMR and TG techniques. Using rapeseed oil as lubricating base oil, the anti-wear performance and biodegradabilities, BDI index of additives were tested. The results showed that the thermal decomposition temperature is 305℃, and the solubility in rapeseed oil is better(up to 2.58%). The anti-wear performance of DP is better than NP, while the anti-friction performance of NP is better than DP. Both NP and DP have excellent biodegradability (BDI> 80%).

TECHNICAL AND ECONOMIC COMPARISON OF ALKYLATION PROCESS

Wan Hui

2018, 49(11): 91-95.

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