Table of Content

12 November 2022, Volume 53 Issue 11

Previous Issue    Next Issue

HIGH-EFFICIENCY AND HIGH-CLEAN GASOLINE AND DIESEL STANDARDS SUPPORTING LOW-CARBON AND ULTRA-LOW EMISSION FUEL VEHICLES

Cao Xianghong

2022, 53(11):  1-10. 

Asbtract ( 225 )   PDF  

Related Articles | Metrics

This paper analyzed the challenges faced by electric vehicles and hydrogen fuel cell vehicles in the future development process, and the role of oil electric hybrid vehicles in fuel saving and carbon reduction and ultra-low emission of pollutants in tail gas. It is pointed out that electricity, hydrogen and oil will coexist in automobile power in a long time in the future. In view of the future market demand for gasoline and diesel, it is proposed that oil refining enterprises should devote themselves developing high-efficiency and high-clean gasoline and diesel, and support the realization of low carbon and ultra-low emission of fuel vehicles. Based on the research results of the impact of oil quality on pollutants and carbon emissions both at domestic and abroad and the demands of major foreign automobile manufacturers for future oil quality indicators, the main technical indicators, standard formulation research, main technical development topics and promotion strategies of high-efficiency and high-clean gasoline and diesel in China were put forward.

PROGRESS AND COST ANALYSIS OF DISTRIBUTED HYDROGEN PRODUCTION TECHNOLOGY

2022, 53(11):  11-16. 

Asbtract ( 608 )   PDF  

References | Related Articles | Metrics

At present, hydrogen for transportation energy in China is mainly transported by 20 MPa long tube trailers, which has low transportation efficiency and high cost, so the large-scale application of hydrogen energy is limited to a certain extent. Distributed hydrogen production has attracted more and more attention due to the lack of long-distance transportation troubles of hydrogen. In this paper, the technical progress of hydrogen production from distributed methanol, natural gas, alkaline electrolytic water, PEM electrolytic water and ammonia decomposition were introduced, and the cost of hydrogen production was analyzed. The technology of hydrogen production from distributed methanol and natural gas reforming hydrogen production technologies was mature, and the price of raw materials had a great influence on the cost of hydrogen production. For distributed water electrolysis hydrogen production, both methods of hydrogen production have achieved commercial application. The price of electricity was an important factor affecting the cost of hydrogen production. In addition, the initial investment of PEM water electrolysis hydrogen production equipment was relatively high, which further increased the cost of hydrogen production. For hydrogen production by distributed ammonia decomposition, there is room for further improvement of commercial technology. At the current stage, the economic competitiveness of ammonia decomposition hydrogen production is lower than that of methanol reforming hydrogen production, but it has certain application potential under the background of carbon neutrality.

STATUS AND PROSPECT OF SLURRY BED RESIDUE HYDROCRACKING TECHNOLOGY

Shao Zhicai

2022, 53(11):  17-23. 

Asbtract ( 511 )   PDF  

References | Related Articles | Metrics

In recent years, the domestic demand of crude has depended on importing foreign crude at a high level, and the resource of crude needs to be utilized efficiently, slurry bed hydrocracking technology is a good choice to convert heavy oil into high-value transportation fuel and petrochemical products because of its high conversion rate and low quality feedstock. Several slurry bed residue hydrocracking technologies were introduced as follows: HDH plus technology of PDVSA, Uniflex technology of UOP, LC-Slurry technology and VRSH technology of CLG, EST technology of Eni, RMAC technology of RIPP. The technical characteristics of above processes were compared, and the technical difficulties of slurry bed residue hydrocracking were analyzed. It is suggested that the study of slurry bed residue hydrotreating process, engineering and catalyst should be strengthened．

RESEARCH ON SELECTIVE HYDRODESULFURIZATION TECHNOLOGY OF RESIDUE

2022, 53(11):  24-29. 

Asbtract ( 232 )   PDF  

References | Related Articles | Metrics

The selective hydrodesulfurization technology of residue from the Middle East high-sulfur crude was deeply researched and developed from the aspects of catalyst development, process condition optimization, catalyst gradation and activity stability. The results showed that the hydrodesulfurization activity of the newly developed hydrodemetallization and hydrodesulfurization catalysts for selective hydrodesulfurization of residue was significantly higher than that of conventional hydrodemetallization and hydrodesulfurization catalysts. When the sulfur content of the hydrogenated oil was equal, proper hydrogen partial pressure, lower volumetric space velocity and higher hydrogen-to-oil ratio, as well as lower reaction temperature could improve the hydrodesulfurization selectivity. Compared with the conventional technology, the reaction temperature of the newly developed residue selective hydrodesulfurization technology was lower by 7 ℃, the CCR of hydrogenated oil was higher by 11.5%, and the hydrogen consumption was lower by 7%-11% under the condition of comparable hydrodesulfurization rate.

COMMERCIAL APPLICATION OF HIGHLY SELECTIVE CATALYTIC CRACKING TECHNOLOGY FOR LOW-QUALITY HEAVY OIL（RTC-G）

2022, 53(11):  30-35. 

Asbtract ( 250 )   PDF  

References | Related Articles | Metrics

In order to convert low-quality heavy raw materials into high-quality clean oil products and chemicals with high selectivity and low energy consumption, the highly selective catalytic cracking (RTC-G) technology was developed by SINOPEC Research Institute of Petroleum Processing Co.,Ltd.and applied in SINOPEC Jinan Company for the first time. Compared with blank calibration, under the same conversion rate, the yield of LPG increased by 1.96 percentage points, the yield of gasoline decreased by 0.51 percentage point, the yields of dry gas and coke reduced by 0.49 percentage point and 0.80 percentage point,respectively, the yield of slurry decreased by 2.18 percentage points, and the product distribution was significantly improved. By appropriately increasing the conversion rate, the yield of liquefied gas was basically unchanged, the yield of gasoline increased by 3.73 percentage points, the yield of slurry decreased by 3.21 percentage points, and the selectivity of coke decreased by 0.78 percentage point. After using RTC-G technology, the selectivity of high-value products was improved, and the product structure was further improved. RTC-G technology has become an effective means for enterprises to reduce carbon emission and to increase benefits under the background of “Double Carbon” target.

COMMERCIAL APPLICATION OF COMBINATION TECHNOLOGY FOR LUBRICATING OIL HYDROGENATION TREATMENT

Song Yichang Wang Luqiang

2022, 53(11):  36-41. 

Asbtract ( 199 )   PDF  

References | Related Articles | Metrics

The new lube oil hydrotreating unit of SINOPECYanshan Company adopted the combined technology of RLT hydrotreating technology developed by SINOPEC Research Institute of Petroleum Processing Co., Ltd. and MSDW selective dewaxing technology of ExxonMobil, and the whole process was successfully started in September 2021. API Ⅲ 6 and API Ⅲ 4 base oil is stably produced by processing the third side-drawVGOand the secondside-draw VGO of high sulfur crude oil, respectively. The results show that, adopting combined technology, the lube oil hydrotreating unit has strong adaptability of raw materials, good selectivity of target products with stable quality.

STUDY ON PREDICTION MODEL OF DIESEL CETANE NUMBER

2022, 53(11):  42-45. 

Asbtract ( 211 )   PDF  

References | Related Articles | Metrics

At present, the testing engine for measuring the cetane number of diesel is very expensive, and the prediction accuracy of the existing cetane index is low. It is urgent to establish a diesel cetane number prediction model with high prediction accuracy. Based on 450 representative samples of diesel, a database including physical and chemical properties, hydrocarbon group composition and cetane number of diesel was established. Using stepwise regression analysis, statistical product and service solutions (SPSS) software, two cetane number prediction models based on physical and chemical properties of diesel and based on hydrocarbon group composition of diesel were established, respectively. F-test, T-test and residual analysis were used to verify the validity of the models. The accuracy of the two models was compared by calculating root mean square error.The results showed that two models were all valid,and the accuracy of the model based on physical and chemical properties ofdiesel was better than that of the model based on hydrocarbon group composition of diesel.

MOLECULAR SIMULATION OF ADSORPTION BEHAVIOR OF BUTANE ISOMERS IN TON ZEOLITE

2022, 53(11):  46-53. 

Asbtract ( 197 )   PDF  

References | Related Articles | Metrics

The adsorption behavior of n-butane and isobutane in TON zeolite was simulated by using the Grand Canonical Monte Carlo method. The adsorption isotherms of n-butane and isobutane in the TON zeolite at 273 K, 303 K and 373 K were simulated and fitted with the Langmuir, Langmuir-Freundlich and Toth adsorption isotherm models; the adsorption potential, density distribution, adsorption heat were analyzed; the adsorption selectivity of butane isomers was also investigated by simulating the adsorption of n-butane/isobutane mixture with equal mass ratio. The results showed that the adsorption of n-butane and isobutane in TON zeolite was more in accordance with Toth adsorption model, and n-butane had higher adsorption amount in TON zeolite than isobutane. When the mixture of n-butane and isobutane was competitive adsorbed in TON zeolite, the adsorption amount of n-butane was much larger than that of isobutane, it can be concluded that TON zeolite has better adsorption separation effect for n-butane than isobutane.

THERMODYNAMIC ANALYSIS OF THE COMPLEX REACTION SYSTEM FOR HYDRODECHLORINATION IN WASTE PIASTICS PYROLYSIS OIL

2022, 53(11):  54-64. 

Asbtract ( 262 )   PDF  

References | Related Articles | Metrics

The thermodynamics of the complex hydrodechlorination reaction system of 13 kinds of organochlorides identified from the waste plastics pyrolysis oil was analyzed by using Aspen Plus software. First, simulations were performed using a Gibbs reactor in Aspen Plus software using thermodynamic analysis based on the principle of Gibbs free energy minimization, determining the equilibrium composition of the various organic chlorides under the specified initial composition and reaction conditions; then using the sensitivity analysis tool, the effects of the hydrogen-oil volumetric ratio, reaction temperature and pressure on the equilibrium composition of the complex reaction system were investigated. The results showed that the hydrodechlorination reaction of 13 kinds of organochlorides in the complex reaction system could be carried out spontaneously and completely under the given reaction conditions. For a given initial composition of organochlorides, hydrodechlorination effect was the best when the hydrogen-oil volumetric ratio was 3.7, the reaction temperature was 300-320 ℃, the reaction pressure was 3-5 MPa. Under the condition of excess hydrogen, the reaction degree of chloroalkanes was lower than that of chloroalkenes and arylchlorides.

PREPARATION OF Ni-BASED BIMETALLIC CATALYSTS AND THEIR CATALYTIC PERFORMANCE OF HYDRODEOXYGENATION

2022, 53(11):  65-69. 

Asbtract ( 233 )   PDF  

References | Related Articles | Metrics

A series of Ni-based bimetallic catalysts supported on γ-Al₂O₃ were prepared by impregnation method. The effects of metal promoters (Mo, Co and Ce ) on the hydrodeoxygenation（HDO）performance of Ni-based catalysts were investigated. The catalysts were characterized by XRD, N₂ physical adsorption at low temperature, NH₃-TPD, H₂-TPR and XPS. Using n-butanol as model compound, the HDO performance of catalysts was evaluated in a fixed-bed micro-reactor. The results showed that the promoter Ce had most significant effect on the HDO performance of the catalyst, the complete conversion of n-butanol was achieved at 210 ℃, while the activation of C-O bond by Mo was stronger, and the selectivity of n-butane was higher than that of other promoters.

APPLICATION OF BULK PHASE CATALYST IN HYDROCRACKING UNIT

2022, 53(11):  70-76. 

Asbtract ( 181 )   PDF  

References | Related Articles | Metrics

The hydrofining catalyst FF-66 and combined hydrocracking catalysts FC-16B/FC-14 were used in the sixth cycle of the hydrocracking unit of SINOPEC Jinling Company. After 36 months of operation，the oxidation stability of the product transformer oil reduced, pour point increased，and the viscosity index of tail oil could no longer meet the demand of lube base oil. In order to improve the product quality and enhance the hydrogenation ability，FF-66 grading the bulk phase catalyst FTX-1 were used for refining catalyst and FC-16B/FC-14 grading the bulk phase catalyst FTXC-1 were used for cracking catalyst in the seventh cycle. The calibration data of the unit showed that compared with the sixth cycle, the sulfur content of heavy naphtha in the seventh cycle decreased from 4.0 μg/g to 1.3 μg/g，the smoke point of aviation kerosene increased from 25.4 mm to 26.8 mm, and the pour point of transformer oil decreased from －9 ℃ to －12 ℃. The high content of aromatics was the main reason for the poor oxidation stability of transformer oil. The aromatics content of transformer oil decreased from 10% to 0.5% by hydrosaturation treatment of further low temperature aromatics and the oxidation stability was improved. The viscosity index of tail oil in the seventh cycle was 91, which could not meet the requirement of the lube base oil. It can be increased by blending paraffin base oil and improving aromatics ring-opening ability of hydrocracking catalyst.

PREPARATION AND PERFORMANCE OF SURFACE SILICA-RICH USY ZEOLITE

2022, 53(11):  77-81. 

Asbtract ( 197 )   PDF  

Related Articles | Metrics

In order to improve the properties and catalytic cracking performance of USY zeolite modified by conventional “Hydrothermal hyperstability” process, the conventional “Two-exchange-two-calcination” process was combined with in-situ silica modification method, and the silica-rich USY zeolite was prepared and used for the preparation of FCC catalyst, which was characterized by XRD, N₂ adsorption-desorption, NH₃-TPD, SEM and so on, and the performance of the FCC catalyst was evaluated by ACE unit. The results showed that the crystallinity, crystal lattice parameter, specific surface area, pore volume, surface acidity and micro cracking activity of surface silica-rich USY zeolite were better than those of conventional USY zeolite. Compared with the FCC catalyst made by conventional USY zeolite, the conversion of heavy oil cracked on the FCC catalyst prepared by USY zeolite with silicon-rich surface increased by 3.70 percentage points, and the yield of gasoline and the total yield of liquid products increased by 2.31 percentage points and 1.32 percentage points, respectively, which indicate that the FCC catalyst prepared by USY zeolite with silicon-rich surface layer has excellent catalytic performance.

STUDY ON LIQUID ALKYLATION OF BENZENE WITH ETHYLENE CATALYZED BY ALKALI-TREATED Hβ ZEOLITE

2022, 53(11):  82-88. 

Asbtract ( 229 )   PDF  

Related Articles | Metrics

Hβ zeolites were modified with different concentrations of sodium hydroxide solution and characterized by XRD, XRF, NH₃-TPD, SEM, N₂ adsorption-desorption and other techniques,and used as catalyst in the alkylation reaction of benzene and ethylene. Compared with the original Hβ zeolite, the modified Hβ zeolites showed higher catalytic activity, which was mainly due to the removal of the amorphous particles on the surface of the modified Hβ crystals and the enhancement of the diffusion effect of reactants and products. Even though the structure of zeolite collapsed due to the high concentration of alkali solution, the obtained alkali-treated zeolite still showed good catalytic selectivity. The Hβ zeolite treated in 0.08 mol/L NaOH solution at 60 ℃ for 60 min had the highest catalytic performance, with the ethylene conversion rate of 87.29% and the ethylbenzene selectivity of 91.67%.

SYNTHESIS AND TRIBOLOGICAL PROPERTIES OF XANTHOGEN POLYSULFIDE

Qing NI Long Jun Duan Qinghua

2022, 53(11):  89-95. 

Asbtract ( 197 )   PDF  

Related Articles | Metrics

Two kinds of lubricating oil additives containing bisxanthate structure were synthesized and characterized by nuclear magnetic resonance (NMR), infrared spectroscopy (IR), elemental analysis and other technical means. The odor grade, oil solubility, and copper corrosion properties were tested, and the tribological properties in 150N base oil were investigated by a four-ball friction and wear tester. The elemental composition and chemical state of the wear scar surface were analyzed by X-ray photoelectron spectroscopy (XPS). The results showed that both xanthogen polysulfides had good oil solubility and low odor as lubricant additives, and had good copper corrosion properties and extreme pressure and antiwear properties. The antiwear properties of xanthate disulfides were better than those of xanthate polysulfides. The extreme pressure properties of xanthate polysulfides were better than those of xanthate disulfides. The extreme pressure and antiwear properties of both additives were better than that of isobutenyl sulfide under the same conditions.

OPTIMIZATION OF PREPARATION PROCESS FOR HIGH ALKALINE COMPLEX CALCIUM SULFONATE GREASE

2022, 53(11):  96-101. 

Asbtract ( 267 )   PDF  

References | Related Articles | Metrics

The effects of base oil type, feeding sequence, reaction temperature and reaction time in the conversion stage on the properties of the prepared grease were investigated by single factor experiment, to optimize the preparation process of calcium sulfonate complex grease with high base number. The results showed that when base oil A was used as the base oil of grease, high alkaline calcium sulfonate and fatty acid D were added in the conversion stage, under the conditions of a conversion temperature of 85 ℃ and a reaction time of 2.5 h, the performance of the high alkaline complex calcium sulfonate grease was the best, and its dropping point exceeded 343 ℃, which was higher than the dropping point height limit of GB/T 3498—2008 standard. The working cone penetration (0.1 mm) was 279, and the oil separation rate of steel mesh was 2.17%. The extreme pressure and anti-wear performance is excellent, and many properties are better than those of similar greases on the market.

PHOTOCATALYTIC DEGRADATION OF THE REFRACTORY ORGANIC CONTAMINANT IN AN INTERNAL LOOP AIRLIFT REACTOR

2022, 53(11):  102-109. 

Asbtract ( 186 )   PDF  

References | Related Articles | Metrics

he photocatalytic degradation of reactive brilliant red X-3B was investigated in an internal loop airlift photocatalytic reactor. The effects of initial substrate concentration, catalyst load, initial solution pH, aeration amount, temperature, and UV intensity on the photocatalytic degradation reaction were systematically analyzed. The results showed that the degradation rate of active brilliant red X-3B could reach more than 85% under the conditions of a pH of 4-10, a catalyst dosage of 0.5 g/L ,an air flowrate of 2.5 m³/h, an active brilliant red X-3B concentration of 50 mg/L for 3 h of photocatalytic reaction. The results of the reaction kinetic studies indicate that the degradation of reactive brilliant X-3B by photocatalytic treatment can be described by the Langmuir-Hinshelwood model. An empirical model was established to predict the photocatalytic degradation performance of active brilliant X-3B with the variables of reaction time, substrate concentration, UV light intensity and aeration amount. The coefficient of determination between the predicted and experimental value was 0.958, which can provide theoretical guidance and experience for the following amplification experiments.

STUDY ON RECYCLING AND PERFORMANCE OF SPENT SCR

2022, 53(11):  110-116. 

Asbtract ( 197 )   PDF  

References | Related Articles | Metrics

There are a lot of valuable metals such as titanium, vanadium and tungsten in the spent catalyst of ammonia selective catalytic reduction (SCR). The recycling of these metals can not only prevent the waste of valuable metal resources, but also reduce environmental pollution and the production cost of denitration catalyst. A new kind of honeycomb denitration catalyst was prepared by extrusion method with titanium dioxide mixed with acid-washed spent SCR catalyst as the carrier. The catalyst was characterized by X-ray diffraction (XRD), specific surface area analyzer (BET) and scanning electron microscope (SEM). The influence of the mixed amount of acid-washed spent SCR catalyst on the mechanical properties, denitration performance and stability of honeycomb denitration catalyst was investigated. The results showed that the crystal structure of the catalyst was not changed when the catalyst was mixed with pickling spent SCR catalyst; the specific surface area and pore volume of the catalyst decreased with the increase of the mixed amount of acid washing spent SCR catalyst;and when the amount of mixed SCR catalyst was large, the catalyst had high mechanical strength and strong anti-wear performance; when the mixed amount（w）of acid washing spent SCR catalyst was 30%, the prepared honeycomb denitration catalyst could still maintain the denitration efficiency and activity as the catalyst prepared with pure titanium dioxide, and it had good denitration stability.

PROBLEMS AND SOLUTIONS IN THE APPLICATION OF SCR DENITRIFICATION TECHNOLOGY IN FCC UNIT

2022, 53(11):  117-122. 

Asbtract ( 190 )   PDF  

References | Related Articles | Metrics

In order to ensure long-term operation of catalytic cracking unit, the reasons of increasing the pressure drop of the waste heat boiler in selective catalytic reduction (SCR) unit were analyzed, and the solutions were put forward. The results indicated that the formation of ammonia hydrogen sulfate (NH₄HSO₄) with strong viscosity and easy deposition was the main reason for the increase of pressure drop of waste heat boiler. Reducing the concentration of nitrogen oxide (NO_x) and sulfur oxide (SO_x) in the inlet flue gas of SCR unit could greatly reduce the amount of ammonia injected into the SCR unit and effectively inhibit the formation of NH₄HSO₄. The results of industrial application showed that the NO_x conversion rate in the reaction-regeneration system was 69.08%-81.27%, and the concentration of NO_x and SO₂ in flue gas was significantly reduced after the use of SDJF-A1 type desulfurization and denitrification auxiliary agent. The methods of optimizing operation of the soot blowing system and increasing the temperature of economizer to decompose NH₄HSO₄ are effective in controlling the pressure drop rise in the waste heat boiler. Further measures such as optimizing SCR ammonia injection system, increasing the reaction temperature of SCR and improving soot blowing system can be taken to ensure the long-term operation of the plant.

DETERMINATION METHOD OF MOLYBDENUM CONTENT IN SLURRY BED RESIDUE HYDROCRACKING MATERIALS

2022, 53(11):  123-127. 

Asbtract ( 179 )   PDF  

Related Articles | Metrics

A method for the determination of molybdenum (organic molybdenum and inorganic molybdenum) in slurry bed residue hydrocrackting materials was established by using a dry ashing pretreatment method and an inductively coupled plasma optical emission spectrometry. The effects of ashing time, ashing temperature and acid treatment on the determination of molybdenum element were investigated. The results showed that the content of molybdenum (organic molybdenum and inorganic molybdenum) could be accurately determined when the ashing temperature was 430-480 ℃, ashing time was not less than 10 h, the acid dissolving the ash was hydrochloric acid or nitric acid. The relative standard deviation of this method was less than 1%, and the recovery was 97%-102%, met the general requirements of elemental analysis. Compared with GB/T 37160—2019, this method can reduce the ashing temperature, reduce the amount of acid, and determine the molybdenum content more accurately.

MODELING AND FULL PROCESS SIMULATION OF SULFURIC ACID ALKYLATION REACTOR BASED ON CAPE-OPEN STANDARD

2022, 53(11):  128-134. 

Asbtract ( 452 )   PDF  

References | Related Articles | Metrics

Based on the mechanism model of sulfuric acid alkylation established by Stratco process of the DuPont company, the unit operation module of sulfuric acid alkylation reactor was developed by using C++ and COM technology, which conformed to CAPE-OPEN standard, the model could interact with the general chemical process simulation software through unit operation interface and the thermodynamic physical property interface, and a convenient and friendly user interface was established. The module of sulphuric acid alkylation reactor was embedded in Aspen Plus, and the whole process simulation of the sulfuric acid alkylation process could be realized by means of Aspen Plus's physical property data, thermodynamic method and conventional unit operation module of the simulation software itself. The simulation results are in good agreement with the actual industrial data, which shows that the CAPE-OPEN sulfuric acid alkylation reactor module is stable and reliable, it will plays an important role in the process simulation and parameter optimization of the sulfuric acid alkylation unit.