Table of Content

12 May 2020, Volume 51 Issue 5

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DEVELOPMENT AND APPLICATION OF MEDIUM PRESSURE HYDROCRACKING TECHNOLOGY FOR PRODUCING QUALIFIED JET FUEL

Zhao Yang Zhao Guangle Mo Changyi Dong Songtao Mao Yichao Dai Lishun Hu Zhihai

2020, 51(5):  1-6. 

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In order to meet the market demand for jet fuel with the existing equipment of enterprises, developed a technology of medium-pressure hydrocracking to produce qualified jet fuel. The effects of reaction pressure, cracking catalyst, feedstock oil, conversion depth and LHSV on the properties of jet fuel product were investigated. The technology was applied in a medium pressure hydrocracker with capacity of 1.5 Mt/a in SINOPEC Shanghai Petrochemical Co. Ltd., and was certificated by the aviation certification committee in Nov. 2018. It was the first time to produce qualified jet fuel from vacuum gas oil under medium pressure in China. The commercial results showed that by the technology, the yield of jet fuel from feed VGO reached more than 20%, and the product met the quality requirements of No. 3 jet fuel, and the tail oil had BMCI of 10, a kind of excellent raw material for cracking to ethylene.

HIGH-EFFICIENCY SOLUTIONS FOR FIXED BED RESIDUE HYDROTREATING UNIT

Dong Changhong Wei Xiang

2020, 51(5):  7-13. 

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The fixed bed residue hydrotreating unit in SINOPEC Hainan Refining & Chemical Co. Ltd. has the characteristics of large volumetric space velocity and high reactor height to diameter ratio in the first reactor. Therefore，the catalyst grading of this unit is difficult. It is necessary to balance the catalyst activity，catalyst activity stability and reactor pressure drop simultaneously to get the best reaction efficiency. In order to achieve the above objectives，Hainan refinery screened and compared the residue hydrotreating catalysts of different catalyst manufacturers by operation data. The statistical results of industrial applications showed that comprehensive performance of RHT series catalysts for residue hydrotreating developed by SINOPEC Research Institute of Petroleum Processing was superior to foreign and domestic reference catalysts. The high efficient operation was realized by up-grading the unit and optimizing the operation conditions.

ANALYSIS OF LONG PERIOD OPERATION OF LIQUID PHASE DIESEL HYDROGENATION UNIT

2020, 51(5):  14-20. 

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A new liquid phase diesel hydrogenation unit with capacity of 0.60 Mt/a was built in CNOOC Oriental Petrochemical Co. Ltd., using atmospheric gas oil and lighe cycle oil from catalytic cracking unit as raw materials to produce diesel meeting China phase Ⅴ standard . The plant started to produce qualified products for the first time in January 2017 and has run smoothly since then. Due to the changes of the proportion of feed oils, the operation conditions had to switch at any time according to six working conditions, resulting in high energy consumption. By analyzing the different processing conditions and the problems affecting the long cycle operation, some solutions were suggested, which can provide reference for the operation of the same type of plant.

A REVIEW ON INDUSTRIAL APPLICATIONS OF CROSSER GRIDS IN DENSE FLUIDIZED BED REACTORS

2020, 51(5):  21-25. 

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The industrial applications of Crosser grids, a new type of internals for dense gas-solids fluidized bed reactors developed by China University of Petroleum(Beijing) were reviewed. The design principle of the Crosser grid and its effects on improving gas-solids contact and suppressing solids backmixing were described. The emphasis was on its industrial applications in the regenerators and strippers of fluid catalytic cracking (FCC) units in petroleum refineries. These successful applications proved the effectiveness of the Crosser grid on promoting the performances of both FCC regenerators and strippers due to its effective improvements on bed fluidization and suppression on axial solid backmixing. Finally, the application possibility of Crosser grid in MTO plant and the effect on product distribution and regenerator charing effect were analyzed and discussed.

THE PERFORMANCE AND APPLICATION OF NEW NAPHTHA HYDROCRACKING CATALYST RHC-210

2020, 51(5):  26-30. 

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New hydrocracking catalyst RHC-210 was developed for hydrocracking to produce heavy naphtha used as catalytic reforming feedstock. The processing parameters, adaptability to raw oils and the full-cycle hydrocracking process for producing reforming feed were investigated in a pilot plant. The pilot plant results showed that by using catalyst RHC-210, reforming feeds could be obtained under different technological processes from different raw materials, and could simultaneously produce the high quality jet fuel, diesel and tail oil, and the catalyst had high activity, selectivity and performance price ratio. The industrial application results of catalyst RHC-210 showed that the catalyst can be used to produce high-quality reforming raw materials, and at the same time, it can obtain jet fuel with high smoke point and tail oil with low BMCI .

STUDY ON TRANSESTERIFICATION CATALYZED BY POLYMER COATED ENZYME

2020, 51(5):  31-36. 

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Aiming at the stability and cost of enzyme catalyst in enzymatic reactive distillation technology, Candida antarctica Lipase B (CALB) was immobilized on the macroporous adsorption resin NKA by hydrophobic interaction, and the immobilized lipase NKA-CALB-PEG was prepared by PEGylation. Compared with the commercial immobilized lipase Novozyme435, the stability and cost of NKA-CALB-PEG were significantly improved. The optimal reaction conditions for NKA-CALB-PEG catalytic transesterification of EtAC and BuOH were as follows: the stirring speed was 300 r/min, the amount of catalyst was 10%, the molar ratio of BuOH/EtAC was 1∶1, the temperature was 65 ℃. At 333.15-348.15 K, the experimental data were fitted to obtain the kinetic equation of the reaction. Comparing the experimental values with the calculated results showed that the macro kinetic equation was reasonable.

INVESTIGATION ON BUBBLE CHARACTERISTICS IN GAS-LIQUID CONCURRENT UP-FLOW REACTOR

2020, 51(5):  37-41. 

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The bubble characteristics in the gas-liquid concurrent up-flow reactor and the effect of gas flow rate and liquid flow rate on the bubble Sauter mean diameter, bubble rising velocity and pressure drop was investigated. Results showed that the bubble Sauter mean diameter and bubble rising velocity both increased with increasing gas flow rate and decreasing liquid flow rate. The bubble diameter distribution and rising velocity distribution in the radial direction both increased with increasing radial distance firstly and then decreased. The pressure drop increased with increasing gas flow rate firstly and then decreased, but the effect of liquid flow rate on it was negligible. Through the dimensionless analysis of the experimental data, the relationship between the average diameter of bubble Sauter and the Reynolds number in liquid phase and gas phase was put forward.

RESEARCH ON BUBBLE GENERATION PERFORMANCE OF GAS-LIQUID DISTRIBUTOR IN UP-FLOW REACTOR

2020, 51(5):  42-47. 

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The gas-liquid distributor is an important internal component of up-flow liquid phase hydrogenation reactor, generally with porous plate distributors with multi-group gas-liquid riser tubes. This article studied the bubble generation performance of cylindrical riser tube and Venturi riser tube by high-speed camera method in an up-flow three-dimensional bed cold model device. Furthermore, the effects of superficial gas and liquid velocities on the bubble generation performance of the Venturi riser tube were investigated. The results showed that under the same operating conditions, compared with the cylindrical riser tube, the Venturi riser tube produced more bubbles, and the average diameter of bubbles was smaller, which is more conducive to the uniform distribution of bubbles, so that the bubble generation performance is better. It is found that at the same liquid velocity, as the gas velocity increased, the microbubble fraction increased slightly, the Satue average diameter of bubbles became larger, and the bubble size distribution was wider. While at the same gas velocity, as the liquid velocity increased, the microbubble fraction increased, the Satue average diameter of bubbles became smaller, and the bubble size distribution was narrower.

SYNTHESIS, EVALUATION AND ANALYSIS OF MIXED ALKYLBENZENE SULFONATES

2020, 51(5):  48-54. 

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Tertiary oil recovery requires a large number of cost-effective sulfonate surfactants. Mixed alkylbenzene sulfonates were synthesized with fuming sulphuric acid using different distillate oils as raw materials and anhydrous aluminum trichloride as catalyst. The comprehensive properties of synthetic samples were evaluated. The interfacial tension between the mixed alkylbenzene sulfonate and the typeⅠ and Ⅱ crude oil of four blocks in Shengli oil field was less than 5×10^-3 mN/m and the interfacial tension was 3×10^-2 mN/m for the type Ⅲ crude oil. Moreover, the synthesized sulfonate has a wider concentration window, higher salt tolerance, lower adsorption performance, better compatibility with polymer and better comprehensive performance than similar products. The analysis of infrared, mass spectrum and carbon distribution showed that the composition is more complex than that of petroleum sulfonate and more similar to that of crude oil.

TRIBOLOGICAL PROPERTIES OF SERPENTINE POWDER/SOFT METAL NANOPARTICLES AS COMPLEX LITHIUM-BASED GREASE ADDITIVE

2020, 51(5):  55-59. 

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Serpentine powder and soft metal nanoparticles (Ag, Ni and Cu) were used as lubricating greases additives. The tribological properties of the complex lithium-based grease containing various mass ratios of Serpentine powder to soft metal nanoparticle were investigated by reciprocating friction and wear tester. Scanning electron microscope and energy-dispersive X-ray spectroscopy were employed to analyze the worn surfaces and typical elements. The results showed that the composite powder could improve the tribological performance of the complex lithium-based grease. When the mass ratio of serpentine powder to nano particle of sliver, nickel and copper was 4∶1, 2∶1 and 4∶1, respectively, the lubricating greases showed the optimum tribological properties. Under different loads, the Serpentine powder/nano-sliver lubricating grease had the best friction reduction and anti-wear performance than Serpentine powder/ nano-nickel and serpentine powder/ nano-copper lubricating greases.

PREPARATION AND PROPERTIES OF BENTONITE-TITANIUM COMPLEX GREASE

2020, 51(5):  60-66. 

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In order to optimize the performance of titanium complex grease and reduce the preparation cost of titanium complex grease，the synthetic route of bentonite-titanium complex grease was explored by combining the preparation methods of bentonite grease and titanium complex grease. The preparation process and raw material formula are further optimized to produce bentonite-titanium complex grease with excellent performance. It was found that the two greases have good compatibility. The bentonite-titanium complex grease prepared by high-temperature refined titanium complex grease plus pre-formed bentonite grease not only maintains the high dropping point and anti-wear anti-friction performance of the two single greases，but also improves the mechanical stability of the bentonite grease and the structural stability of the titanium complex grease.

STUDY ON FOAMING TENDENCY OF NO. 65 AVIATION COOLANT

2020, 51(5):  67-72. 

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In view of foaming in the filtration cycle of No. 65 aviation coolant, the foaming propensity of the aviation coolant was explored. According to the SH / T 0066-2002 (Engine coolant foam tendency measurement method), the coolant foam tendency tester was used to evaluate the tendency of the coolant foaming and the water glycol fluids control test was used as a reference. The results showed that the aviation coolant had a higher foaming tendency in the case of low temperature and long cycle time, and the foaming tendency was reduced to some extent with the increase of temperature and the shortening of the cycle time. It is concluded that the foaming in the filtration cycle of aviation coolant is caused by the added additives.

DETERNINATION METHOD OF SULFUR COMPOUNDS IN LIGHT HYDROCARBON AND ITS EFFECT ON METAL CORROSION

2020, 51(5):  73-78. 

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The lamp method, microcoulometry method, ultraviolet fluorescence method, and X-ray fluorescence spectrometry method are commonly used for determination of sulfur compounds in light hydrocarbon oil. Ultraviolet fluorescence and X-ray fluorescence spectrometry methods will dominate in the future, the traditional chemical isolation and analysis methods gradually being replaced by more effective means—gas chromatography-sulfur selective detection method. Different forms of sulfides have different corrosion properties on metal products. Hydrogen sulfide and elemental sulfur showed strong corrosion to Silver and Copper stip. Thiols and organic acids can enhance the corrosion degree of elemental sulfur. Other forms of alkylated sulfur compounds have little effect on the corrosion of metals.

INFLUENCE OF TRACE IMPURITIES ON PROPERTIES OF CAPROLACTAM

2020, 51(5):  79-84. 

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In order to evaluate the influence of impurity on the quality of caprolactam product, 10 kinds of impurities, such as aromatic amines, ketones, oximes, ethers and caprolactam homologs, were added to purified caprolactam, and the influences on volatile basicity, chromaticity, ultraviolet absorption at 290 nm, alkalinity and acidity, potassium permanganate value was investigated. The results showed that the aromatic amines had a sigenificant effect on all five indexes, and the presence of trace aromatic amines would lead to the unqualified caprolactam products. The in-crease of 2-methoxy cyclohexanone and 2,3-epoxy cyclohexanone would lead to the increase of the volatile basicity, ultraviolet absorption at 290 nm and potassium per-manganate value, leading to a worse product quality. Trace caprolactim methyl ether in caprolactam would cause the unqualified alkalinity caprolactam, and the alkalinity increased by 0.1 mmol/kg for every 25μg/g increase in its mass fraction. Cyclohexanone oxime had a medium effect on the volatile basicity and potassium permanganate value. Cyclohexanone and N-methyl caprolactam had no effect on those indexes of caprolactam.

POTENTIAL APPROACHES FOR WATER SAVING AND SEWAGE REDUCTION OF REFINING AND CHEMICAL ENTERPRISES

Wang Boyu

2020, 51(5):  85-89. 

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Water saving and emission reduction is an inevitable requirement for the development of refining and chemical enterprises. After summarizing the achievements of SINOPEC in water saving and sewage reduction in recent 20 years and comparing with industry-leading level，the in-depth analysis of water usage compositions and water saving potential of refining and chemical enterprises was performed. In conclusion, the approaches, including reusing sewage，improving the condensate recovery，raising concentration factor，enhancing heat integration of units and using indirect cooling with sea water, for further reducing water intake for enterprises were proposed.

APPLICATION OF SULFUR TRANSFER AGENT RSF09 IN RFCC FLUE GAS DESULPHURIZATION

Zhou Ziyang Pan Tao Guan Yongheng

2020, 51(5):  90-94. 

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In order to decrease the SO₂ content in the regenerated flue gas of the heavy oil catalytic cracking unit (RFCC) and reduce the processing load of the subsequent flue gas desulfurization and dust removal device, SINOPEC Guangzhou Company adopted RFS09 sulfur transfer agent. The results of industrial tests showed that the SO₂ concentration of the flue gas was reduced significantly after the application of RFS09, the COD concentration of the sulfur-containing external drainage was decreased, and the SO₂ concentration of the purified flue gas was decreased from 3.56 g/m³ to 2.28 g/m³. The use of sulfur transfer additive did not adversely affect the yield of major products, such as gasoline and liquefied gas, and the quality of the equilibrium catalyst.

MODELLING AND ANALYSIS OF DELAYED COKER FURNACE

2020, 51(5):  95-99. 

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Based on computer simulation and analysis, the dynamics, physical properties and reactor of the coking furnace in a refinery were discussed, and the mathematical model of the furnace was established. The distributions of temperature, pressure, flow rate, composition of gas and liquid were obtained by analyzing working conditions after verifying model in field. The results showed that the deviation between simulation results and field values was small, and the distribution trend of temperature, pressure and other parameters were consistent with the macroscopic understanding. The established mathematical model can be used to analyze the running parameters of the heating furnace in field and provide theoretical support for design, operation and optimization of the delayed coking heating furnace.

SIMULATION AND ANALYSIS OF HEAT PUMP PROCESS BASED ON ISOBUTYLENE PURIFICATION REACTION DISTILLATION

2020, 51(5):  100-104. 

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Based on the characteristics of isobutylene purification reaction distillation, a steam compression heat pump energy saving process was designed. In this work, the whole isobutylene purification reaction distillation process simulated by Aspen Plus, and the simulation strategy of heat pump distillation for partial condensation process was proposed. From the point of view of exergy analysis and technical economy, energy consumption and economical efficiency were evaluated comprehensively. A case study showed that the reaction distillation process using heat pump energy saving technology was compared with the conventional process. When the compression ratio was 1.6, the energy consumption per unit product decreased by 87.5%, effective energy efficiency increased by 32.7%, annual operating cost decreased by 64.4%, project investment payback period was 1.5 years.

PROPERTIES AND MECHANISM OF NON-PHOSPHORUS ORGANIC SCALE INHIBITORS

2020, 51(5):  105-109. 

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The scale inhibition properties and mechanism of three kinds of phosphate-free organic scale inhibitors, including carboxylate polymer, sulfonate polymer and polyether polymer, on calcium carbonate and calcium phosphate were reviewed from the relationship between structure and scale inhibition performance. The carboxylate chelates with the calcium ions on the surface of the calcium carbonate crystal, which distorts the calcium carbonate crystal into a loose structure and inhibits the scaling of calcium carbonate. The carboxylate is anchored to the surface of amorphous calcium phosphate nanoparticles by chelation, the sulfonate makes amorphous calcium phosphate negatively charged and disperses calcium phosphate scale, and the polyvinyl oxy chain increases the solubility of calcium phosphate. In this context, the directions of developing scale inhibitors were prospected.