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期刊基本信息
主办单位：中国石油化工股份有限公司
　　　　　石油化工科学研究院
编辑出版：石油炼制与化工编辑部
主　　编：汪燮卿院士
执行主编：李才英教授
副 主 编：刘鸿洲 刘迎春
国际标准刊号：ISSN 1005-2399
国内统一刊号：CN 11-3399/TQ
邮发代号：2-332

Table of Content

    12 January 2024, Volume 55 Issue 1
    Previous Issue    Next Issue
    ACCELERATE THE PACE OF PREMIUMIZATION FOR POLYMER MATERIALS IN CHINA
    2024, 55(1):  1-6. 
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    The development status of polymer industry in China was summarized, and the existing problems such as similar product structure, low-end product structural overcapacity and insufficient technical support capacity were pointed out. It is necessary to accelerate the research and development of high-end polymer materials. The consumption trend of the three major general polymer materials was analyzed and eleven kinds of high-end polymer materials with fast growth of market demand in the near and medium term and stable market demand in the long term were predicted. A research and development approach for the high-end development of polymer materials was proposed: firstly, both the development of special materials and high-end general materials should be focused on; secondly, a profound study of the relationship between polymer material structure and performance should be made from qualitative analysis to quantitative modeling as soon as possible; thirdly, the optimization and selection of the technology path of high-end polymer materials should be emphasized, achieving low energy consumption, low investment, and low-cost premiumisation; fourthly, the monomer constraints of high-end molecular materials should be broken through; fifthly, the research and development of processing application technology and equipment should be strengthened.
    TECHNICAL STRATEGIES FOR TRANSFORMATION AND DEVELOPMENT OF CHINA PETROLEUM PROCESSING INDUSTRY
    2024, 55(1):  7-17. 
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    The present situation of refining industry in China and the challenges faced under the new situation were analyzed, and the necessity of transformation and development was elaborated. The development and application of clean transportation fuel production, low-cost production of basic organic chemical raw materials, high-value special chemicals production and carbon dioxide emission reduction technology are key to support the transformation and development of refining industry. The experimental and practical application of new technologies such as solid acid C4 alkylation for high-octane-gasoline production, biojet fuel production, diesel ultra-deep hydrodesulfurization (RTS), production of low sulfur marine fuel oil, adsorptive separation of n-alkanes from full fraction naphtha, combination of directional hydrotreating with selective deep catalytic cracking (DCC) process for maximum propylene (SHMP), residue to chemicals (RTC) process, light cycle oil (LCO) to aromatics and gasoline (LTAG) process, RHT-DCC bi-directional combined process for producing chemical raw materials from residual oil (RICP), high end needle coke production, low viscosity poly-α-olefins (PAO) production, integration of fluid catalytic cracking (FCC) gas oil hydrotreating and highly selective catalytic cracking for maximizing liquid yield (IHCC), low energy consumption continuous diesel liquid-phase hydrotreating (SLHTDR) process, were introduced.
    HOLLOW TITANIUM SILICATE MOLECULAR SIEVE CATALYTIC MATERIAL: FROM RATIONAL DESIGN TO COMMERCIAL APPLICATIONS
    2024, 55(1):  18-27. 
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    In response to the problems of traditional titanium silicate (TS-1) molecular sieve, such as poor selectivity, low activity and poor synthesis reproducibility, SINOPEC Corporation began to organize technical research starting with the “titanium state” and the“intracrystalline pore structure” in the 1990s, a series of hollow titanium silicate molecular sieves with independent intellectual property rights were developed, which supported the first industrialization of cyclohexanone ammoximation and propylene epoxidation technology in China. Furthermore, due to the intracrystalline reaction of propylene epoxidation and the fact that surface titanium is easy to decompose H2O2, the framework titanium is mainly distributed in the crystal of molecular sieve to reduce the ineffective decomposition of H2O2. It is found that the type and number of defects have an important effect on the size and distribution of the voids, that is, the regular bulk and irregular banded voids are produced by the skeleton point defects and the grain boundary defects, respectively. Because the template cationic TPA+ can not enter the crystal of molecular sieve, it is inferred that the defect-dissolved and dissolved silicon-titanium species recrystallization along the external surface of molecular sieve is the basic reason of the hollow and morphology change. The research progress of HTS in structural design, catalytic performance enhancement, and catalytic oxidation applications in recent yearsis aree reviewed, with a focus on summarizing the industrial applications of HTS.
    BIOMASS-DERIVED PARAXYLENE: THE BRIDGE FROM LOW-COST LIGNOCELLULOSE TO SUSTAINABLE POLYESTER
    2024, 55(1):  28-41. 
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    Paraxylene (PX) is the leading raw material of polyester industry in China and an important bulk product in chemical industry. With the popularization of ‘Double Carbon’ strategy in China, the raw materials of chemical manufacturing industry are gradually changing from non-renewable resources (petroleum and coal) to renewable resources. The development of bio-based PX production process from lignocellulosic biomass can not only promote the comprehensive utilization of lignocellulose as a renewable resource, but also promote the development of green and low-carbon manufacture of polyethylene terephthalate (PET) polyester monomer, connect the two. Based on this, the research status of various preparation routes of bio-PX was reviewed, and their advantages and disadvantages were analyzed. Combined with process simulation and economic analysis, the problems of high production cost and low production capacity in bio-based PX process were pointed out.
    RESEARCH PROGRESS IN ELECTROCATALYTIC ORGANIC OXIDATION COUPLED WITH HYDROGEN PRODUCTION
    2024, 55(1):  42-51. 
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    Electrocatalytic water splitting driven by clean energy (e.g., solar, wind) is the most promising green ways for hydrogen（H2） production. However, this process still suffers from the problem of high energy consumption. One of the main “bottlenecks” for water splitting is the sluggish four-electron OER while the generated O2 is not of significant value. Electrocatalytic organic oxidation coupled with H2 production has been proven to be an attractive approach to produce high-value-added chemicals at anode and facilitate coupled H2 production at cathode. This review provided a comprehensive summary of the recent advances in electrocatalytic organic oxidation coupled with H2 production, including the types of “active oxygen” and the reaction mechanism for catalytic organic oxidation, the strategies to enhance the reaction rate by reactants enrichment, and the design of appropriate reaction equipment. Finally,the potential prospects and challenges in this emerging electrocatalytic field were discussed ,aiming to stimulate the development of H2 production from electrocatalytic water splitting
    ADVANCES IN SELECTIVE HYDROGENATION OF BIOMASS DERIVATIVES CATALYZED BY MONATOMIC CATALYSTS
    2024, 55(1):  52-61. 
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    Biomass is a kind of renewable resource in the form of carbon source, and its platform compounds and derivatives can be used to upgrade energy and fine chemical products. Heterogeneous catalysts play an important role in the conversion of biomass resources, many of which involve nano-catalysts and monatomic catalysts. Because of the high oxygen content of lignocellulose, it can not be directly used as industrial raw material, so reduction reaction is needed to reduce its oxygen content. Hydrogenation is an important method to decrease the ratio of O/C and increase the ratio of H/C in lignocellulosic molecules. The application of monatomic catalysts in selective hydrogenation of furans, unsaturated aldehydes and lignin platform compounds would be comprehensively discussed.
    CARBON NEUTRALITY PATHWAY OUTLOOK FOR CHINA’S PETROCHEMICAL INDUSTRY
    2024, 55(1):  62-67. 
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    China's petrochemical industry has a high proportion of carbon emissions. The industry is still in a period of growth and has a need to increase its carbon emissions, so it faces a major challenge to realize the "double carbon" goal. We must clarify the development of ideas, and actively and steadily promote the industry's low-carbon transformation and high-quality development. Currently, the petrochemical industry is facing a lot of situations, including the rapid development of alternative energy in the field of transportation, the role of hydrogen energy carrier highlights the "double carbon" policy continues to make efforts. Continued efforts are needed in several areas, such as promoting industrial upgrading, energy saving and carbon reduction, promoting clean alternatives, highlighting innovation and leadership, and strengthening safeguard measures. By analyzing and judging the key paths of industrial structural adjustment, implementation of green hydrogen refining, and integration with CCUS, we propose a possible combination of paths and trends that can achieve the carbon neutral target, analyze the characteristics of development at different stages, and make recommendations.
    GREEN CHEMICAL TECHNOLOGY STATUS AND DEVELOPMENT PROPOSAL IN CHINA
    2024, 55(1):  68-81. 
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    The rapid development of the chemical industry has contributed to global economic growth and improved people's quality of life. However, the massive consumption of fossil energy in the chemical production process has also caused environmental pollution and climate change that cannot be ignored. China has taken the initiative to set the targets of carbon peaking and carbon neutrality goals, requiring all industries to follow the path of green and high-quality development, which will promote the green transformation of China's chemical industry. Green chemical industry should include the greening of the whole industrial chain and innovation chain from chemical raw materials, catalysts, reaction engineering and energy to products, which is the general trend of industry development. It is recommended to strengthen the oriented support to the applied basic research of green chemical technology, advocate the inclusion of green indexes in the evaluation standard of technological advancement, promote the integration of the green development concept into the whole process of technology development and application in the chemical industry, and accelerate the digital transformation and integrated development of China's chemical industry, so as to realize more green chemical technological innovation and sustainable development of the industry at an early date.
    RESEARCH PROGRESS OF SAFETY RISK ANALYSIS AND PREVENTION AND CONTROL TECHNOLOGY IN GREEN HYDROGEN INDUSTRY CHAIN
    2024, 55(1):  82-88. 
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    The development of large-scale green hydrogen industry is a strategic choice to promote the transformation of China's energy structure and achieve the goal of carbon peak and carbon neutrality. Using renewable energy to produce green hydrogen will replace fossil energy to produce hydrogen on a large scale, effectively reduce carbon emissions during energy production and consumption, and support the construction of a new energy system. The green hydrogen industry chain mainly includes the upstream production of green hydrogen, the midstream storage and transportation of green hydrogen and the downstream application of green hydrogen. Based on the analysis of the technological development status of green hydrogen production, storage, transportation and application process, the safety risks existing in all aspects of green hydrogen industry were summarized. From the concept of technologies, standards, policies and regulations, and innovation platforms and so on, the corresponding risk prevention and control suggestions were put forward to lay a solid foundation for the safe utilization of large-scale green hydrogen, to ensure the safe and high-quality development of the green hydrogen industry chain.
    RESEARCH AND APPLICATION PROGRESS OF ECO-FRIENDLY RUBBER EXTENDER OIL
    2024, 55(1):  89-97. 
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    The classification, development status, production process and research progress of eco-friendly rubber extender oil (rubber oil) at domestic and overseas were summarized. The rubber oil mainly includes five categories: distillate aromatic extract (TDAE), heavy naphthenic oil (NAP), mildly extract solvate (MES), residual aromatic extract (RAE) and blended oil. Taking by-product extracted oil from lube oil refining unit, FCC slurry and residue, etc. as raw materials, the production process of eco-friendly rubber oil mainly included solvent refining process, double solvent extraction process, hydrorefining-solvent extraction process, etc., these processes produced eco-friendly rubber oil by selective removal of polycyclic aromatic hydrocarbons from raw materials and retention of aromatic hydrocarbons and alkyl-aromatic hydrocarbons with less rings. The main problems were low production volume and low CA of eco-friendly rubber oil, which influenced the large scale application of eco-friendly rubber oil in China and the improvement of the quality of the eco-friendly rubber tire. It was urgent to develop a new production process of eco-friendly rubber oil on the original technical scheme and explore a new processing route.
    APPLICATION AND POTENTIAL VALUE OF MICROALGAE BIO-CARBON FIXATION TECHNOLOGY IN CARBON NEUTRALITY
    2024, 55(1):  98-111. 
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    In the context of “Dual-carbon targets”, carbon neutrality will have a profound impact on the development of economy, society, technology and lifestyle of human in the next thirty years. To achieve the goal of carbon peaking and carbon neutrality, carbon capture, utilization and storage (CCUS) is a key measure to reduce CO2 emissions. The CCUS technology based on microalgae could convert CO2 to high value-added biomass through photosynthesis, which has the advantages of environmentally-friendly and resource sustainability. Based on the current status of numerous carbon capture and utilization technologies, this article focused on summarizing the application potential of CO2 removing by microalgae, the dissolution, transport and transformation process of CO2 in the aquaculture system. The effective methods to improve the carbon sequestration efficiency of microalgae were discussed, including enhancing CO2 mass transfer and optimizing the regulation of efficient reactor, and the assistance of information technology in the efficient cultivation and production of microalgae was also introduced. The diversified utilization pathways of microalgae biomass in many fields such as bio-energy, protein substitution and high-value products were summarized. Finally, the economic feasibility, market prospects, and cost optimization strategies were systematically discussed in order to promote the application of CCUS technology by microalgae in carbon neutrality.
    FABRICATION OF UIO-66 MEMBRANE BY TWO-STEP DRY GEL CONVERSION FOR EFFICIENT SEPARATION OF HEXANE ISOMER
    2024, 55(1):  112-121. 
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    Hexane isomer is an important basic chemical raw material in the petrochemical industry, so it is of great strategic significance to separate it efficiently and with low energy consumption. Metal-organic frameworks (MOF) have attracted much attention in solving the challenging problem of hexane isomer separations due to their precisely adjustable pore structure and surface function. A two-step dry gel conversion method for the preparation of continuous dense UiO-66 membranes was reported. The characterization of the formation process and microstructure of UiO-66 membranes were analyzed by combining various characterization techniques. The results showed that the introduction of zirconium gel twice was the key to the formation of dense membranes, on the one hand, the mixed phase of zirconium gel and UiO-66 seed crystal, as precursor layer, provided homogeneous and abundant nucleation sites for the initial growth of the membrane, on the other hand, the second self-transformation of zirconium gel could seal the inter-crystalline defects of the membrane layer. The pervaporation experiment proved that UiO-66 membrane prepared by the two-step dry gel conversion method could permeate straight-chain and mono-branched alkanes preferentially, while repelling di-branched alkanes.
    THE PRACTICE FROM FUNDAMENTAL RESEARCH TO COMMERCIAL APPLICATION – RESEARCH AND DEVELOPMENT OF SMTO TECHNOLOGY FOR METHANOL-TO-OLEFINS
    2024, 55(1):  122-129. 
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    Methanol-to-olefins (MTO) conversion is one of the critical technologies for the clean utilization of coal, which has important strategic significance for ensuring national energy security. SINOPEC has continuously innovated in the area of catalytic reaction mechanism, high-performance zeolite catalysts and reaction-regeneration process for more than 20 years, and developed the SMTO catalytic technology with high efficiency for industrialization. The tandem innovation from oriented fundamental research to industrial application was thus demonstrated using SMTO as a case in this account.
    KEY SCIENTIFIC PROBLEMS AND INDUSTRIAL DEVELOPMENT OF SINOPEC HPPO TECHNOLOGY FOR GREEN PROPYLENE OXIDE PRODUCTION
    2024, 55(1):  130-134. 
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    In order to overcome the disadvantages of the existing technologies for propylene oxide (PO) production, SINOPEC has developed a new hydrogen peroxide propylene oxide (HPPO) process by using silicon-rich surface hollow titanium silicalite molecular sieves as catalytic component, and the first 100 kt/a HPPO industrial plant in China has been built. The surface silicon-rich multi-hollow titanium-silicon molecular sieve was invented, and the high-efficiency hydroxyl coupling binder was developed, which could simultaneously increases the active component content and the catalyst strength under low-temperature reaction conditions. A composite auxiliary agent was developed, which regulated the formation of a "five-member ring" transition state between hydrogen peroxide and framework titanium, thus greatly improving PO selectivity. The separation and purification technology of PO by low temperature separation, extractive distillation and chemical de-impurity coupling was explored to enhance the product quality. PO wastewater was used as terminator in catalytic cracking unit to make organic matter cracking into low carbon hydrocarbons such as ethylene and propylene. Compared with foreign reference technologies, the impurity total aldehyde is 80% lower, the moisture content is 50% lower, the hydrogen peroxide conversion rate is 3.3% higher, the PO selectivity is 3.6% higher, the purity of PO product is 99.99% , and the rate of high grade product is 100%.
    RESEARCH ON THE HIGH-QUALITY DEVELOPMENT PATH OF REFINING AND PETROCHEMICAL BASED ON MULTI-ENERGY INTEGRATION UNDER THE "DUAL CARBON" GOAL
    2024, 55(1):  135-144. 
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    The refining and petrochemical industry is a process industry based on fossil fuels as the main raw materials, which consumes a lot of energy and emits a lot of CO2. Thus it is urgent to accelerate the development of multi-energy integration in order to support the green and low-carbon transformation of the industry with high efficiency. Herein, the idea of multi-energy integration with high quality development of petrochemical industry in China was proposed based on the characteristics of petrochemical process and new energies. Two integration modes were established, with one called energy integration, including electricity, heat and hydrogen, and the other named resource integration, including carbon, hydrogen and oxygen. The new power-thermal system, new hydrogen system and new production process system were investigated and constructed to provide guidance for the high-quality development of refining and petrochemical industry, the multi-disciplinary industrial integration and technological innovations, etc. in China. The case study of multi-energy integration shows that the coupling of new energies with refiners plays an important role in facilitating carbon reduction transitions in refining process. Therefore, the development and application of the corresponding engineering technologies should be accelerated to further to reduce costs, promote the substitution of green electricity and green hydrogen, and synergistically achieve the goal of the carbon emission reduction, pollution reduction and efficiency increase.
    PREPARATION OF NON-THIOPHENE SULFIDE ADSORBENT AND INFLUENCE OF OLEFIN ON ADSORPTION EFFECT
    guohao Zhang liang zhao Jin-sen Gao
    2024, 55(1):  145-151. 
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    In order to develop high efficiency adsorbents for non-thiophene sulfides, CuY, CrY, CoY and NiY adsorbents were prepared by maceration method, and the effects of different metals on the morphology and acidity of adsorbents were investigated by using relative characterization techniques. The results showed that Cu and Ni could increase the acidity of Lewis and form the S-M bond, so the adsorbent had better adsorption desulfurization effect. However, the metal Ni tended to agglomerate and block the pore of adsorbent, which affected the sulfide diffusion and made the adsorption desulfurization effect weaker than that of CuY. When the mass fraction of Cu was 10%, the sulfur capacity of Cu10/Y was highest (14.24 mg/g). In addition, the effect of olefin on the adsorption and removal of non-thiophene sulfides was also investigated. With the increase of olefin content, the adsorption capacity of the adsorbent decreased. According to the calculation of dipole moment and electrostatic potential, 1-hexene and sulfide could form complexes with metal, which could lead to competitive adsorption and affect the adsorption desulfurization effect.
    FACILE STNTHESIS OF NANOSIZED LEV MOLECULAR SIEVE
    2024, 55(1):  152-157. 
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    In this contribution, we reported facile preparation of nano-sized LEV molecular sieve with various n（SiO2）/n（Al2O3） by using isopropyltrimethylammonium as structure-directing agent for the first time. The effect of aluminum sources, alkali cations, initial n（SiO2）/n（Al2O3）and alkalinity on the products outcome was investigated. It turns out that sodium aluminate and sodium hydroxide are beneficial to the crystallization of nano-sized LEV molecular sieve. LEV molecular sieve could be obtained with initial n（SiO2）/n（Al2O3） ranging from 20 to 150, by modulating the alkalinity of the initial gel. The total acid amount drops with the increasing of n（SiO2）/n（Al2O3）, while the acid strength enhances. The nano-sized LEV molecular sieve has high specific area and micropore volume. Moreover, the total pore volume exceeds 1.0 cm3/g, which is extremely high. This type of molecular sieve material is endowed with high application potential in adsorptive separation and selective conversion of organic molecules, thanks to its nano-sized dimension, strong acidity as well as high surface area and pore volume.
    STEP SIMULATION TECHNIQUE AND EXPERIMENTAL VERIFICATION OF CATALYST SPRAY FORMING ATOMIZATION PROCESS
    2024, 55(1):  158-163. 
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    The atomization process is the key control step in catalyst forming by spray drying technology, and the atomization results directly affect the particle size distribution of the final product. Aiming at the problem that it was difficult to measure the intermediate process of the transient atomization process by the experimental method, and it was difficult to simulate the process effectively because of the complexity of the process, the atomization process was divided into two parts: the first stage atomization and the second stage atomization, and the liquid film tearing process of the first-stage atomization was simulated by the volume of fluid (VOF) model, the volume of fluid-deformable component model (VOF-TO-DPM) was used to simulate the secondary atomization, which greatly reduced the computational load. The results showed that when the feeding pressure was over 4 MPa, the primary atomization was sufficient and the droplet size was basically unchanged. The droplet size presented a bimodal distribution, and the smaller droplet size was mainly concentrated in about 40 μm, and the large droplet size was mainly concentrated in 95~100 μm. The higher the feed pressure was, the fuller the primary atomization and the larger the initial velocity of the droplets was, and the more the small droplets were produced by the secondary atomization. The comparison between the simulation results and the test results showed that they were in good agreement, indicating that the simulation results had a good accuracy.
    THEORETICAL INNOVATION AND PRACTICE APPLICATION OF HYDROCRACKING TECHNOLOGY
    2024, 55(1):  164-170. 
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    SINOPEC (Dalian) Petrochemical Research Institute Co., Ltd. (FRIPP) found that the induced dipole moment of hydrocarbon molecule and the stability of the reaction intermediate carbocation were key factors that affected the adsorption and reaction of hydrocarbon molecule. On this basis, the gradual reaction theory was proposed to guide the development and upgrading of hydrocracking processes and catalytic materials. The application of the gradual reaction theory avoided the occurrence of low-efficient and disorderly reactions and made the hydrocracking process reasonally and orderly, thus, the product selectivity and quality of the hydrocracking process were improved under the reaction environment of low energy consumption and low hydrogen consumption. The gradual reaction theory will effectively promote the refinery configuration adjustment in China, to achieve a reasonal and orderly "oil to chemicals" and "oil to special oil products" transformation and development.
    DEVELOPMENT STRATEGY AND INDUSTRIAL PRACTICE OF PETROLEUM REFINING TECHNOLOGY UNDER THE GOAL OF "CARBON PEAK AND CARBON NEUTRALITY"
    2024, 55(1):  171-179. 
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    The century-old petroleum refining industry is facing the dual challenges of "carbon peak and carbon neutrality" goals and the continuous reduction of fuel demand due to the third energy transformation, while the traditional oil refining technology prioritizes high conversion rates, it leads to low hydrocarbon utilization efficiency and high CO2 emissions from petroleum resources, which is contrary to development goal of “emission reduction and efficiency enhancement”. Therefore, based on the concept of petroleum molecule management, and taking the product high selectivity as the research strategy for petroleum refining technology, revolutionary technologies for small molecule alkane processing, heavy oil processing, and low-carbon olefin production has been developed and put into industrial practice, to reduced carbon at source and in process, and meet the increasingly urgent needs of the petroleum refining industry for transformation towards green, low-carbon, oil reduction, and clean production.
    PREDICTION OF PHYSICAL PROPERTIES OF WORKING FLUID BASED ON ARTIFICIAL NEURAL NETWORK
    2024, 55(1):  180-188. 
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    Traditional working fluids in thermodynamic cycles, such as refrigeration and waste heat power generation, have been associated with issues such as ozone layer depletion and global warming. The development of efficient and environmentally friendly novel working fluids has become a research focus. Hydrocarbons and halogenated hydrocarbons are ideal candidates, but their large number and many unknown thermophysical properties make it crucial to establish accurate models for predicting these properties in order to screen new working fluids effectively. In this study, the basic thermophysical parameters of more than 2 500 hydrocarbons and halogenated hydrocarbons containing C, H, F, and Cl atoms were collected from various public databases, including normal boiling point(Tb) , critical temperature(Tc) , critical pressure (pc) and acentric factor (ω), and furtherly, by improving the method of group contribution-artificial neural network (GC-ANN), a neural network model for predicting Tb,Tc,pc,and ω of hydrocarbons and halogenated hydrocarbons containing C, H, F, and Cl atoms was established by adding relative molecular mass, Tb and approximate wiener index to the input parameters of the model. The prediction errors of the models developed in this study were smaller than those of the traditional GC-ANN.
    BASE CATALYTIC TECHNOLOGY FOR LOW CARBON AND EFFICIENT PETROLEUM PROCESSING WITH ENHANCED CHEMICAL PRODUCTION
    2024, 55(1):  189-201. 
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    Base catalytic technology and converting crude oil to chemicals is getting more attention recently. In this paper, CNOOC DPC (Direct Petroleum Cut to Chemicals & Materials) base catalytic technology was thoroughly reported for the first-time including catalyst properties, industrial experiment performances, comparison of base catalytic technology and acid catalytic technology, and reaction characteristics and mechanisms. The key of DPC basic catalysis technology is to synthesize mesoporous materials with high hydrothermal stability and base catalyst with high base activity stability on the basis of the discovery of new catalytic materials that can greatly reduce the yields of coke and dry gas, and develop a new intensified reaction-regeneration catalytic process. The DPC base catalysis process has more advantages than delayed coking (DC) process and fluid catalytic cracking (FCC) technology in terms of processing heavy oil and inferior feedstock. Furthermore, the DPC base catalysis process also has more advantages than heavy oil atmospheric residue or vacuum residue hydrotreating process such as atmospheric residue desulfurization (ARDS) and vacuum residue desulfurization (VRDS) technologies. DPC technology leads to a much higher chemical yield, lower dry gas yield and coke formation. It is the only technology in petrochemical industry that is suitable for various types of feedstocks such as crude oil, vacuum gas oil, atmospheric residue, vacuum residue, and oil sands bitumen. It was preliminarily confirmed that the DPC base catalysis technology followed the reaction mechanism of carbanion, and almost did not occur hydrogen transfer and aromatic condensation reaction. However, it also showed a certain ability of cracking and isomerization reaction. It is a subversive technology of the current catalytic treatment of heavy oil with molecular sieve solid acid, which can replace DC, FCC, ARDS and VRDS processes, and provide theoretical and technical guidance, support and guidance for the direct production of chemicals from crude oil.
    GREEN PRODUCTION TECHNOLOGY FOR NYLON-6 MONOMER: CAPROLACTAM
    2024, 55(1):  202-207. 
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    After 30 years of continuous innovation, SINOPEC Research Institute of Petroleum Processing Co., Ltd. has successfully developed green production technology for nylon-6 monomer caprolactam, it included a new green synthesis pathway for cyclohexanone by cyclohexene esterification and hydrogenation, the integration of hollow TS-1 zeolite with the slurry-bed reactor for the ammoximation of cyclohexanone, the integration of silicalite-1 zeolite with the moving-bed reactor for the gas-phase rearrangement of cyclohexanone oxime and the integration of an amorphous nickel catalyst with the magnetically stabilized bed reactor for the purification of caprolactam. Compared with the import technology of caprolactam production, the utilization rate of carbon atom and nitrogen atom were obviously increased, the emission of “three wastes” was significantly reduced, no low-value by-product ammonium sulfate was produced, the investment of the plant was greatly reduced, and the production cost was obviously reduced.
    STUDY ON IN-SITU ENRICHMENT PROCESS OF CARBON DIOXIDE IN FLUID CATALYTIC CRACKING REGENERATOR
    2024, 55(1):  208-217. 
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    In a typical refinery, nearly 30%-50% of carbon dioxide (CO2) is emitted from the regenerator of fluid catalytic cracking (FCC). As the main source of CO2, The regenerated flue gas has the characteristics of large volume flow rate and low CO2 concentration, this results in high operating cost of the traditional post-combustion carbon capture technology. In order to capture CO2 with high efficiency and low cost, an in-situ enrichment process of CO2 in regenerator was proposed in this work. Computational fluid dynamics and process simulation were used to explore the feasibility of the new process and the potential impact of the new process on the existing equipment. The results showed that the new process could ensure the normal fluidization of gas-solid flow field in the regenerator. The volume fraction of CO2 in flue gas and dry flue gas exceeded 85% and 93%, respectively. The change of component concentration of regenerated flue gas had little influence on the following key equipment, such as waste heat boiler, flue gas turbine, coal economizer, desulfurization and denitrification tower, etc., so there was no need to replace the existing equipment. This work will provide a new process idea for CO2 enrichment and capture of regenerated flue gas.
    DEVELOPMENT OF RAPID CONTINUOUS CATALYST-FREE SYNTHESIS PROCESS OF MORPHOLINE ETHANOL USING MORPHOLINE AND ETHYLENE OXIDE AS RAW MATERIALS
    2024, 55(1):  218-225. 
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    In order to solve the problems of the synthesis of morpholine ethanol from morpholine and ethylene oxide, such as low yield, long reaction time, poor safety and the use of catalysts, in a microchannel reactor consisting of SIMM-V2 micro-mixer and a stainless steel tube, the continuous and rapid preparation of morpholine ethanol was studied, and the effects of reaction temperature, residence time, system pressure, molar ratio of raw materials and flow rate were investigated. The results showed that the yield of the reactor was almost equal comparable to that of the kettle reactor under the condition of no catalyst and shorter reaction time. With the increase of reaction temperature, residence time, and molar ratio, the yield of the product increased first and then decreased, there was a wide window of reaction conditions, that was, given a certain condition, the other conditions could be adjusted to obtain the same yield. Under typical reaction conditions, such as a temperature of 150 ℃, a morpholine to ethylene oxide molar ratio of 1:1.08, a residence time of 3 min, a total flow rate of 1 mL/min, and a system pressure of 2.5 MPa, the conversion of morpholine could reach 99.55%, and the selectivity of morpholine ethanol was 97.1%, which was much higher than that of the batch reaction.
    PROCESS SIMULATION AND MULTI-OBJECTIVE OPTIMIZATION OF UPC PROCESS FOR DIRECT CATALYTIC CRACKING OF CRUDE OIL
    2024, 55(1):  226-232. 
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    The direct catalytic cracking technology of crude oil can realize a one-step leap from crude oil to olefins and aromatics, which is of great significant implications for the transformation and upgrading of the refining industry in China. Using total fractions of paraffin-base crude oil (159-780 ℃) as raw materials, the modeling strategy of the structure of mixed fractions and molecular composition lumped-block was used to model and calibrate the process parameters of direct catalytic cracking of crude oil to olefin (UPC). The accuracy of this method was validated by using industrial test data. In order to produce more olefin and control coke formation, the model was optimized by using the NSGA-Ⅲ multi-objective optimization algorithm, and the optimized operational parameters were obtained. The optimized operating conditions were as follows: first-stage preheating flash temperature at 194.32 ℃, second-stage preheating flash temperature at 228.16 ℃, first-stage riser reactor outlet temperature at 615.73 ℃, and second-stage riser reactor outlet temperature at 622.59 ℃. The total yield of ethylene and propylene by UPC process was 53.367%, and that of coke was 8.311%. In addition, due to the fact that the tax contribution of fuel-based process was obviously higher than that of chemical process, the olefin yield was greatly increased and the fuel oil yield was greatly decreased after the optimization of UPC process parameters, and the gross value of crude oil production decreased by RMB 44.30 Yuan/t.