PETROLEUM PROCESSING AND PETROCHEMICALS

ANALYSIS ON THE DEVELOPMENT PATHWAYS OF LOW-CARBON OIL REFINING INDUSTRY IN CHINA

2023, 54(1): 1-9.

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Carbon peaking and carbon neutrality goalsare challenges facing the petroleum processing industry and important opportunities for the industry to achieve high-quality development.The low-carbon development of petroleum processingindustry needs to coordinate the relationship between the whole and the part, development and emission reduction, short-term and long-term, and choose different emission reduction paths according to specific emission reduction scenarios.The technologies including energy efficient utilization, resource efficient utilization, resource recycling, renewable resource utilization, low-carbon refining process, green hydrogen refining, CO₂ chemical utilizationandintelligent technology can provide low-carbon development support at different stages of industry development, and help the refining industry to achieve the carbon peaking and carbon neutrality targets as soon as possible.

ENLIGHTENMENT OF INTERNATIONAL CARBON EMISSION TRADING PRACTICE TO CHINA

2023, 54(1): 10-16.

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In the era of "Post-epidemic" and "Dual-carbon targets", the focus of research on China's carbon trading market has changed from basic framework design to problem solving and development paths in the process of practice. Foreign carbon trading markets have developed for many years, and have experienced the financial crisis and the impact of the coronavirus epidemic. By analyzing the important problems and countermeasures encountered in the process of carbon trading market by representative organizations such as EU, USA, New Zealand, Korea and Japan, the valuable experience and reference significance of foreign carbon trading practice were summarized. At the same time, comparing the similarities and differences between Chinese and foreign carbon trading national conditions, and taking into account the current development of China's carbon trading market, this paper put forward some carbon trading strategies with Chinese characteristics and absorbing foreign advanced experience, such as choosing appropriate emission caps, balancing regulation, formulating price stabilization mechanism, and leaving interfaces for international cooperation.

RESEARCH PROGRESS ON SYNTHESIS METHODS OF SMALL CRYSTAL SAPO MOLECULAR SIEVES

2023, 54(1): 17-29.

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As an important class of inorganic porous materials, silicaluminophosphate molecular sieves (SAPO) have been widely used in catalysis, adsorption, separation and environmental protection in recent years. The narrow porous channels of SAPO molecular sieves bring great resistance to mass transfer, which are unfavorable to the contact between reactant molecules and active sites in the pores. Reducing the grain size of SAPO molecular sieves can shorten the residence time of reactant molecules in the pores, thus improving the utilization of active centers. The research progress of small crystal SAPO molecular sieve synthesis methods in recent years was reviewed, including the mixed-template method, seed-assisted method, and so on. Furthermore, the advantages and disadvantages of these synthesis methods were elucidated. The mixed-template method was a simple and mature process for the synthesis of small crystal SAPO molecular sieves, and the future research should focus on how to reduce the use of organic templates. Other synthesis methods were mostly in the theoretical research stage, and the future research should focus not only on the optimization of the synthesis process, but also on the development of molecular sieve synthesis equipments.

STUDY ON THE PERFORMANCE OF ZSM-22 FOR CATALYZING ETHYLENE OLIGOMERIZATION TO LIQUID FUELS

2023, 54(1): 30-37.

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Clean and high-quality liquid fuels could be prepared from low-carbon olefins derived from refinery dry gas, liquefied petroleum gas and biomass or CO₂ conversion by the oligomerization reaction. ZSM-22 and ZSM-22-A, modified by tetraethylammonium hydroxide (TEAOH), were used as the catalysts, using ethylene as the representative of low-carbon olefin. Their effects on the synthesis of fuel oil from ethylene and the reaction conditions were investigated, respectively. The results showed that TEAOH modified ZSM-22-A exhibited higher catalytic activity than ZSM-22 due to its desilication, pore enlargement and increase of acid content. The optimum reaction conditions for this reaction were: a reaction temperature of 280 ℃, a reaction pressure of 5 MPa, and a mass space velocity of 0.15 - 1.35 h^-1 according to the oil target. It was found that ZSM-22 began to deactivate after 280 h of reaction, but ZSM-22-A did not deactivate after 400 h of reaction, so the ZSM-22-A had higher stability than ZSM-22, which indicated that the modification ZSM-22 with TEAOH had a good application prospect in the synthesis of liquid fuels by ethylene oligomerization.

EFFECTS OF CATALYTIC MATERIALS ON ISOMERIZATION OF HYDROCRACKING TAIL OIL IN DEEP CATALYTIC CRACKING PROCESS

2023, 54(1): 38-43.

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The effects of ZSP zeolite catalyst, Y zeolite catalyst and their mixture system on the product distribution in deep catalytic cracking (DCC) process of hydrocracking tail oil (HTO) were investigated in a fixed fluidized bed reactor, and the effects of different catalytic materials on the isomerization during catalytic cracking and on the cracking, aromatization and hydrogen transfer reaction during DCC process were explored. The isomerization index (ISOI) was proposed to characterize the isomerization degree of catalytic cracking products by the composition of gasoline distillates. The results showed that the degree of isomerization, the degree of cracking, the degree of hydrogen transfer reaction and the degree of aromatization decreased with the increase of the proportion of ZSP zeolite in the catalyst system, the isomerization index(BG1) of cracking gas in HTO was 1.13，the ISOI of gasoline was 0.83，the yield of isomerized hydrocarbons was 29.45%，the yield of ethylene was 7.22%，and the yield of propylene was 23.66%. Compared with Y zeolite, ZSP zeolite could reduce the yield of isomerization products and increased the yield of light olefins in the DCC of HTO.

DEVELOPMENT OF WATER-RESISTANT CATALYSTS FOR CATALYTIC OXIDATION OF NATURAL GAS VEHICLES EXHAUST

2023, 54(1): 44-51.

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A series of Pd/Al₂O₃-based catalysts for the purification of natural gas vehicle exhaust were developed and modified, and the effects of hydrothermal treatment, calcination temperature, and rare earth metal modification on the catalytic activity and water-resistant ability in methane oxidation were investigated by means of N₂ adsorption-desorption, XRD, thermal stability test and catalyst activity evaluation. The results showed that hydrothermal treatment could generate a large number of hydroxyl groups on the surface of synthesized catalysts, which could then be separated from the catalyst to form a large number of oxygen defect sites during in the subsequent calcinations process, and promote the dispersion of metal active sites and strengthen the interaction between metal and supports. In addition, increasing calcination temperature could significantly affect the activity as well due to the enlarged pore volume and surface areas. The introduction of rare earth metal promoters did not change the pore structure of the catalyst obviously, but enhanced the hydrothermal stability of Pd/Al₂O₃ catalysts to a certain extent. The 1%Pd/HTT-2La-B-Al2O3 catalyst with the best performance was prepared by hydrothermal treatment, calcination under 650 ℃ and modification with 2% of lanthanum using butanol as solvent. The conversion rate for methane oxidation on the catalyst was 90% at 305 ℃.

PREPARATION OF Y ZEOLITE WITH HIGH CRYSTALLINITY BY MIXING KAOLIN MICROSPHERES AND POWDER

2023, 54(1): 52-57.

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Kaolin microsphere (or powder) and metakaolin powder (or microsphere) were used as raw materials, the corresponding kaolin microsphere and metakaolin powder were obtained by high temperature and medium temperature calcination respectively. Y zeolite was synthesized and characterized by XRD, N₂ adsorption-desorption and SEM. The results showed that the crystallinity of metakaolin was higher in the mixed crystallization of kaolin and metakaolin. When the mass ratio of liquid to solid was 2.5 and the mass ratio of kaolin microsphere to metakaolin powder was 1:1, the crystallinity of the metakaolin product (named PK-1) was 81%, and the mesoporous pore volume and external surface area were 0.13 cm³/g and 53.3 m²/g respectively, which were higher than those of NaY (0.02 cm³/g and 28.8 m²/g). The grain size of PK-1 was 300-600 nm. ACE evaluation showed that the catalyst prepared by using PK-1 had better heavy oil conversion ability and better coke selectivity than by commercial NaY zeolite.

FIRST INDUSTRIAL APPLICATION OF FULLY SULFURIZED FHUDS-10 CATALYST

2023, 54(1): 58-62.

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The first commercial application of fully sulfurized FHUDS-10 catalyst in a 1.2 Mt/a diesel hydrogenation unit in Chambroad Petrochemical Co., Ltd. was introduced. The results showed that the start-up time of FHUDS-10 catalyst was shortened by about 20 hours compared with that of conventional oxidation-state catalyst. The sulfur mass fraction of refined diesel was 4.0μg/g and the mass fraction polycyclic aromatic was 4.2% under the conditions of a reaction pressure of 7.4 MPa, a reactor inlet temperature of 314 ℃,a reactor outlet temperature of 364 ℃, and a main catalyst volume space velocity of 0.85 h^-1 during calibration with the mixture of straight-run diesel and coker gasoline-diesel as raw material. Since its stable application for 7 months, the refined diesel can meet the quality standard of China standard VI, which indicates that the fully sulfurized FHUDS-10 catalyst has good activity.

SELECTION OF FIXED-BED RESIDUE HYDROTREATING TECHNOLOGY TAILORED FOR REFINERY STRUCTURE TRANSFORMATION

2023, 54(1): 63-68.

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The technology of the fixed bed residue deep hydrogenation was developed, which could use heavy oil to provide feedstock for DCC and produce more propylene. High sulfur content and low nitrogen content atmospheric residue had higher value added of hydrogen content after hydrogenation, so it was more suitable to be used as feedstock for residue deep hydrogenation to produce high-quality catalytic cracking feedstock. The process of low sulfur petroleum coke production by fixed-bed residue hydrotreating-delayed coking combination was developed by using the Middle East vacuum residual oil with sulfur content of 4.95%. The result showed that the mass fraction in the petroleum coke was 2.8% when the mass fraction of sulfur in the hydrogenated residual oil was decreased to 0.52%, and the sulfur transfer coefficient increased with the increase of residue hydrogenation depth. The effect of residue hydrogenation depth on the distribution of delayed coking products was obvious, with the increase of desulfurization depth, the yield of petroleum coke decreased gradually and the yield of liquid products increased obviously. The advanced desulfurization technology of high sulfur residual oil producing low sulfur heavy fuel oil for marine was developed, and the corresponding catalyst gradation technology was put forward in combination with the development of the residue hydrodesulfurization catalyst with slow-released activity, the desulfurization activity stability of the integral catalyst has been greatly improved. Company A has realized the stable production of low sulfur heavy marine fuel oil by using this technology.

OPTIMIZATION OF AROMATICS EXTRACTION PROCESS FROM STRAIGHT-RUN DIESEL

2023, 54(1): 69-75.

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Using simulated straight-run diesel as feedstock, several solvents were screened for the most appropriate extracting agent, and the operation conditions of the extraction process were optimized. Moreover, the impact of stripping agent types, the ratio of stripping agent to solvent, and the ratio of washing water to solvent on the stripping agent process was investigated. The results showed that increasing the ratio of solvent to feed was beneficial to both extraction selectivity and aromatics removal rate, while raising temperature would lead to decrease of selectivity and increase of aromatics removal rate. Increasing the ratio of water to solvent, the ratio of stripping agent to solvent and the temperature of the distillation column pot were beneficial to the purity of the recovered solvent. Under the optimized conditions of solvent/feed ratio of 3.0 and extraction temperature of 60 ℃, 3-methyl sulfoxide (3-SUL) was used to carry out 7-stage countercurrent extraction for straight-run diesel, the mass fraction of aromatics in the raffinate oil reduced to 6.6%, and the removal rate of aromatics reached 78.2%. Under the optimum conditions of 20 ℃, 0.5 mass ratio of stripping agent to solvent and 0.15 mass ratio of water to solvent, cyclopentane was used to carry out a three-stage reverse extraction for the solvent-rich solvent with soluble extractant, the mass fraction of 3-SUL in the recovered solvent was 99.01%.

STUDY ON CHARACTERISTICS OF RESIDUE HYDROCONVERSION IN FLUIDIZED BED BASED ON MOLECULAR STRUCTUR

2023, 54(1): 76-82.

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Two kinds of residue with different nitrogen content were taken as the research object, and the fluidized bed hydroconversion experiments were carried out under the same process conditions, and the properties and structure of feedstock oils and their hydrotreated oils were analyzed; the characteristics of two kinds of residue hydroconversion in fluidized bed were investigated, and their molecular structures were explained. The results showed that the average molecular structure of residue with higher nitrogen content had higher condensation degree, more aromatic rings and more naphthenic rings than that of the residue with lower nitrogen content. With the increase of the reaction temperature, the sulfur bridge bond of the archipelagic molecules of the higher nitrogen residue broke, the molecular diffusion resistance decreased, which made it easier to approach the catalyst active center for conversion. At the same time, the residue with higher nitrogen content was more likely to undergo naphthenic dehydrogenation and aromatic condensation reactions, resulting in coking precursors, this was just the reason why it was necessary to strictly control the conversion depth in the fluidized bed process for treating residue with high-nitrogen content.

INFLUENCE OF MIXING LIGHT DEASPHALTED OIL ON DCC-PLUS UNIT AND COUNTERMEASURES

2023, 54(1): 83-89.

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According to the process characteristics of DCC-plus unit, in order to increase economic benefits and widen the source of feed for DCC-plus unit, based on the laboratory evaluation results of cracking performance of light deasphalted oil, a company has developed a new type of DCC-plus unit, and the optimum blending mass ratio of no more than 20% was determined. According to the company's production and operation deployment, the company started blending light deasphalted oil into the mixed feed of DCC-plus unit from May 2022. In view of the deterioration of the properties of the mixed raw materials after blending light deasphalted oil, the effects on the product distribution, product properties, operating parameters, catalysts, energy consumption and flue gas pollutant concentration of the DCC-plus unit after blending light deasphalted oil were analyzed. At the same time, the corresponding countermeasures were put forward, which not only ensured the smooth operation of the DCC-plus unit, but also obtained better economic benefits. The CDU could reduce the processing amount of high-priced paraffinic-base crude oil, and obtained 540 CNY/t (for light deasphalted oil) benefit，with an annual benefit of 190 million CNY.

WEAR RESISTANCE OF ALUMINA MICROSPHERES MODIFIED BY DIFFERENT ELEMENT

2023, 54(1): 90-94.

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The modified alumina with different elements, such as zinc, magnesium, phosphorus and silicon,respectively,were prepared by saturation impregnation method, and the wear resistance of the modified alumina microspheres was determined by turbidity analysis. The results showed that the physical wear resistance of modified alumina microspheres was not changed, but the wear resistance of the modified alumina microsphere was improved under hydrothermal condition, among them, the wear resistance of silicon-modified alumina with tetraethyl orthosilicate as raw material was the best. X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy were used to analyze the cause of the difference, it was found that the silicon hydroxyl group formed by silicon modification could replace the aluminum hydroxyl group on the surface of alumina to form Al-O-Si bond, which weakened the adsorption of water and improved the hydration resistance of alumina, furthermore, the wear resistance of silicon-modified alumina microspheres was improved under hydrothermal condition.

STUDY ON COLLISION COALESCENCE PROCESS OF OIL DROPLETS BASED ON FLUID PARTICLE MODEL

2023, 54(1): 95-103.

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In the process of oil water separation by deoiling hydrocyclone, the separation effect of emulsion oil droplets and dispersed phase oil droplets whose particle sizes are less than 20 μm is not ideal. A fluid particle model was established to reflect the coalescence law of oil droplets, and collision coalescence process of oil droplet particles was simulated by using the standard k-ε turbulence model and the CLSVOF multiphase flow model coupled with the surface tension model. The results showed that the probability of positive collision and coalescence of non-uniform size oil droplets was greater than that of uniform size oil droplets under the condition of approaching velocity of 0.50 m/s. The probability of positive collision coalescence of oil droplets with uniform size increased nonlinearly with the approaching velocity, and when the approaching velocity increased from 0.16 m/s to 0.80 m/s, the probability of forward collision coalescence increased by 17%. When the approach velocity of oil droplets with uniform particle size was 0.50 m/s, there was a negative correlation between the probability of collision coalescence and the angle of collision, and the effective collision angle for collision coalescence was 0°- 45°. The research results can improve the ability of the deoiling hydrocyclone for oil water elaborately separation.

STUDY ON REGENERATION KINETICS OF CATALYTIC CRACKING CATALYSTS IN OXYGEN/CARBON DIOXIDE ATMOSPHERE

2023, 54(1): 104-108.

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The coke-burning regeneration tests of FCC spent catalyst in air (conventional regeneration) and oxygen/carbon dioxide atmosphere were carried out in the fixed fluidized bed test equipment. Based on the results, the kinetics of conventional regeneration and oxygen/carbon dioxide atmosphere regeneration were studied. The results showed that the apparent activation energy of the reaction in O₂/CO₂ atmosphere regeneration was similar to that in conventional regeneration, which was 108 kJ/mol and 105kJ/mol, respectively; the apparent reaction rate constant in O₂/CO₂ atmosphere regeneration was higher than that in conventional regeneration, and the coke-burning performance of the catalyst was better than that of conventional regeneration, which could allow the catalyst to contain more carbon. For the regeneration in O₂/CO₂ atmosphere, with the increase of the initial O₂ content in the mixed gas, the coke-burning performance of the catalyst was significantly enhanced.

SYNERGISTIC EFFECT OF NANO-ZINC OXIDE AND ANIONIC SURFACTANT AND NONIONIC SURFACTANT TO REDUCE VISCOSITY OF HEAVY CRUDE OIL

2023, 54(1): 109-117.

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The dispersion and viscosity reduction effects of seventeen surfactants and nano-ZnO and nano-Fe₃O₄ on Xinjiang heavy crude were studied, the surfactants including Tween-80 and dodecylbenzene sulfonic acid, etc. The composition and structure of the asphaltene in Xinjiang heavy crude were characterized by element analysis, gel permeation chromatography, Fourier transform infrared spectroscopy,etc,and the mechanism of viscosity reduction was discussed based on the rheological test results of heavy crude. The results showed that the YTSZ-2 dispersion viscosity reducer composed of Tween-80, sodium dodecylbenzene sulfonate and nano-ZnO had good dispersion viscosity reduction effect, the viscosity reduction rate of Xinjiang heavy crude reached 44.34% at the condition of 65 ℃ and dosage of 200 mg/L. The thickness, diameter and number of aromatic layers decreased with the increase of asphaltene lamellar spacing, and the asphaltene particle size decreased, thus the viscosity of heavy oil decreased.

SYNTHESIS AND CHARACTERIZATION OF MONOESTER SUCCINATE ANTI-WEAR AGENT FOR DIESEL FUEL

2023, 54(1): 118-122.

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In order to overcome the deficiency of fatty acid type diesel anti-wear agent, a kind of succinic acid monoester diesel anti-wear agent was synthesized by esterification reaction of succinic anhydride and 7-octene-1-alcohol. The reaction parameters such as feed ratio, reaction temperature and reaction time were optimized, and the best synthesis process was obtained. The structure and lubrication anti-wear performance of the synthesized products were characterized by infrared spectroscopy and high-frequency reciprocating test. The results showed that when the mass fraction of the additive was only 150 μg/g, it could meet the anti-wear requirements of diesel (the diameter of wear spot of steel ball in high frequency reciprocating test is no more than 420 μm), and the additive dosage was 40% lower than that of fatty acid type anti-wear agent. Moreover, the synthetic succinic acid monoester as diesel anti-wear agent had little effect on other physical and chemical properties of diesel, and the quality of diesel could meet the China VI standard.

EFFECT OF BIODIESEL ON OXIDATION RESISTANCE OF ENGINE OIL

2023, 54(1): 123-127.

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The research status of effect of biodiesel on anti-oxidation performance of engine oils was introduced, and a biodiesel formula with the same rigor as CEC L-109 was independently designed to evaluate the anti-oxidation performance of engine oils. The effects of palm oil biodiesel, gutter oil biodiesel and self-designed biodiesel on the anti-oxidation performance of engine oil according with ACEA specification and API specification were investigated. The results showed that the higher the content of unsaturated fatty acids in biodiesel, the greater the effects on anti-oxidation performance of biodiesel. The effect of biodiesel prepared from different raw materials on the anti-oxidation performance of engine oil was similar, which was mainly related to the content of unsaturated fatty acids in biodiesel, the type of based oil and the content of additives in engine oil.

SEPARATION AND DETERMINATION OF PETROLEUM HYDROCARBONS IN SOIL BY TLC-FID METHOD

2023, 54(1): 128-134.

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The separation and determination of petroleum hydrocarbon components in soil samples can be realized by thin layer chromatography with hydrogen flame ionization detector (TLC-FID). TLC-FID analysis of a series of distillate samples showed that the sample loss occurred mainly in the first development stage. The method has good applicability to the fractions with boiling point greater than 300 ℃, while the samples with low boiling point will have different degrees of loss. In addition, combined with TLC-FID analysis and determination of the total content of the petroleum hydrocarbon (C₁₀—C₄₀) , the changes of hydrocarbon components contents in petroleum hydrocarbon contaminated soil after chemical oxidation treatment with different amounts of sodium persulfate were studied. The results showed that sodium persulfate mainly acted on saturated hydrocarbon and aromatic hydrocarbon in soil, but had no obvious removal effect on colloid and asphaltene.

CAUSE ANALYSIS AND COUNTERMEASURES FOR THE LEAKAGE OF REBOILER TUBE BUNDLES IN STABILIZER OF DCC UNIT

2023, 54(1): 135-139.

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In view of the leakage of the reboiler tube bundles of the stabilizer of deep catalytic cracking (DCC-plus) unit in a petrochemical enterprise, which seriously affected the long-term safe operation of the unit, the reasons were analyzed from the aspects of equipment structure, process operation, equipment corrosion, etc. By taking emergency measures such as optimizing the control scheme of the reboiler heat exchange system and optimizing the process parameters, the internal leakage of the reboiler tube bundles was restrained and the running period of the reboiler was prolonged. The problem of internal leakage of reboiler tube bundles was solved through structure reform of reboiler and optimization of process pipeline during overhaul, it not only eliminated hidden trouble of safety, but also saved 3.5 MPa medium-pressure steam 9.7 t/h, benefit about 23.9 million Yuan per year.

CORROSION ANALYSIS AND COUNTERMEASURES FOR LONG-TERM OPERATION OF ATMOSPHERIC DISTILATION UNIT

2023, 54(1): 140-144.

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