Table of Content

12 January 2022, Volume 53 Issue 1

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FUTURE PROSPECTS FOR REFINING INDUSTRY IN THE ERA OF “CARBON PEAK AND CARBON NEUTRALIZATION”

2022, 53(1):  1-6. 

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Under the background that China formally proposed the grand goal of "carbon peak and carbon neutralization", the development status of refining and chemical enterprises is evaluated with respect to the potential problems in their upper, middle and lower reaches. The development direction and technologies that can be applied in refining and chemical enterprises are reviewed, including bio-oil and fossil crude oil co-processing technology, low-level heat utilization technology and carbon capture technology,and their application prospect are analyzed. The refining and chemical enterprises should persist in the sustainable development, ensuring the national energy security. Meanwhile, the courage for the future development is necessary in leading innovations and accomplishing the industrialization of key technologies and materials.

DEACTIVATION OF TITANIUM SILICALLITE UNDER ACID CONDITION AND ITS REACTIVATION BY RECRYSTALLIZATION WITH THE EXISTENCE OF Ti SPECIES

Peng Xinxin Qiu Limei Xia Changjiu Zhu Bin Lin Min Shu Xingtian

2022, 53(1):  7-13. 

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The accelerated deactivation of hollow titanium silicalite (HTS) under acid conditions and its reactivation by recrystallization with the existence of Ti source was studied. The samples were characterized by XRD, XRF, ICP-OES, FT-IR, UV-Raman, XPS, 29Si MAS NMR and TEM. The results show that the framework Si—O—Ti bond is hydrolyzed during the deactivation process, and the 4-coordinated Ti is converted into to 6-coordinated Ti and lost, which lead to a significant decrease of its catalytic performance. During the rearrangement and replacement of titanium, a part of Ti is inserted into the framework vacant site and generates new active center, which makes the catalytic performance return to the level of the fresh HTS zeolite, and the conversion of allyl chloride, the selecltiviety and the mass fraction of dichloropropanol reach to 99.1%, 99.0% and 26.1%, respectively; the other part of introduced Ti is converted into anatase species.

STUDY ON THE EFFECT OF Fe ON COKE FORMATION AND MICROSTRUCTURE IN RESIDUE HYDROTREATING PROCESS

2022, 53(1):  14-20. 

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Under the same temperature as the operation end of fixed-bed residue hydrogenation unit, the effect of different Fe species on the coking behavior of the residue hydrogenation process is observed using the unloaded catalyst from a refinery to carry out a series of batch tests in autoclave. The effects of Fe on the composition,type and microstructure of coke are investigated by many characterization methods including thermogravimetry, Raman spectroscopy, and scanning electron microscopy. The results show that the existence of large amounts of iron naphthenate and FeS leads to the increase of coke amount in residue hydrogenation reaction. The addition of iron naphthenate leads to the decrease of coke condensation degree, while the addition of FeS leads to the increase of coke condensation degree. This is mainly related to the fact that iron naphthenate needs to be transformed to Fe_1-xS, which can affect coke formation reaction, and part of iron naphthenate directly participates in coke formation.

CATALYTIC CRACKING REACTION CHARACTERISTICS OF KEY COMPOUNDS OF HYDROGENATED LCO

2022, 53(1):  21-28. 

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Four key components of hydrogenated LCO,including tetralin,indan,decalin and 3-ethyltoluene,were used as model compounds.A small fixed fluidized bed (ACE) unit and Y zeolite catalyst was used to study the catalytic cracking performance.The results showed that the model compounds showed their unique reaction characteristics at the two conversion depths, tetralin mainly underwent hydrogen transfer reaction, and the alkylation/alkylation transfer and dehydrogen-condensation of indan were more likely to generate heavy aromatic hydrocarbons above C₉. Although decalin has high ring-opening and cracking selectivity，the selectivity of aromatic hydrocarbon products is low. The light efficiency of 3-ethyltoluene is mainly affected by isomerization reaction.The BTEX mass selectivity of tetralin,indan,decalin and 3-ethyltoluene were 22.65%,19.66%,15.70% and 34.36%,respectively.Tetralin and indan are prone to the continuous α-C-C bond fracture to form benzene;decalin is more inclined to form xylene due to the existence of two tert-carbenium ions;3-ethyltoluene has a higher molar selectivity of toluene and ethylbenzene.

MOLECULAR STRUCTURE, CORROSION INHIBITION AND MOLECULAR DYNAMICS SIMULATION OF MORPHOLINE CORROSION INHIBITORS

2022, 53(1):  29-35. 

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Three kinds of morpholine derivatives MLPP, MLMBT and MLMB were synthesized and characterized by FT-IR and 1H NMR. The corrosion inhibition effects of three synthesized inhibitors and one commercial inhibitor on carbon steel were evaluated in simulated oils with the same acid value containing naphthenic acid, fatty acid, aromatic acid and mixed acids. The results show that MLMBT and MLMB have excellent corrosion inhibition properties to 20 steel test pieces in all simulated oils with 1% corrosion inhibitor at 190 °C, and MLMBT can effectively inhibit the synergistic corrosive effect of fatty acid and naphthenic acid. Molecular dynamics simulations show that there are strong interactions between three inhibitor molecules and iron surface. The addition of thiadiazole and benzotriazole can strengthen the adsorption effect. The adsorption energies calculated by molecular dynamic simulation（MD) verify that the increasing order of corrosion inhibitors performance is dodecylamine, MLPP, MLMB and MLMBT.

EXPLORATIONS ON CALCULATION METHOD OF REACTION HEAT IN CATALYTIC CRACKING

2022, 53(1):  36-40. 

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A method for calculating reaction heat of catalytic cracking by typical reactions was proposed on the basis of analysis of the existed calculation methods. Chemical reactions in the reactor of fluidized catalytic cracking unit （FCCU） were divided into six kinds of typical reactions: cracking，dehydrogenation，hydrogen transfer，isomerization，coking and formation of hydrogen sulfide，so that the amount and thermal effect data of each kind of typical reaction could be used to calculate the reaction heat. The reaction heat data of six large-scale commercial FCCUs was calculated by this method and compared with calculation results of the molecular expansion method，the catalytic coke method and the heat balance method. The results show that the reaction heat calculated by the typical reaction method is 45.8% and 31.8% lower than that by the molecular expansion method and the catalytic coke method, and is 77.8% higher than that calculated by the reactor-regenerator system heat balance，but the reaction heat calculated by the heat balance method is lower than that calculated by the reactor system based on the catalyst circulation quantity of carbon difference method.

STUDY ON REACTION KINETICS OF SYNTHESIZING PROPYLENE CARBONATE FROM CARBON DIOXIDE AND PROPYLENE OXIDE CATALYZED BY IONIC LIQUIDS

2022, 53(1):  41-45. 

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The synthesis of propylene carbonate (PC) using carbon dioxide and 1,2-epoxypropane catalyzed by the composite-modified ionic liquid (CMIL) catalyst was studied. According to the mechanism of nucleophilic reaction, the kinetic equation of the reaction process was established, the parameters of the kinetic equation were obtained by regression. The results show that CMIL has good catalytic performance. Under the conditions of a temperature of 95℃, a pressure of 1.5 MPa, a catalyst dosage of 2.0%, the PO conversion rate is 99.98%,and the PC selectivity is 98.87%. The reaction rate of propylene carbonate is linear relationship with the concentration of catalyst and 1,2-epoxypropane.

DEVELOPMENT OF THE LCO HYDROTREATING TECHNOLOGY TO PRODUCE HIGH-DENSITY JET FUEL

2022, 53(1):  46-52. 

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The monocyclic and bicyclic aromatic hydrocarbons,rich in FCC light cycle oil （LCO）, can be hydrogenated into naphthenes which are high-density jet fuel components. By analyzing the hydrocarbon composition of the narrow fractions of LCO, the range of feedstock fraction suitable for producing high density jet fuel was determined. A high density jet fuel component with a density (20 ℃) greater than 0.835 g/cm³ was obtained with the optimized light fraction of LCO as feedstock under suitable hydrogenation conditions. Furthermore, the effect of process conditions on the properties of high density jet fuel was studied. The technology of producing high density jet fuel by catalytic hydrogenation of LCO can provide more choices for refinery enterprises on the processing route of LCO.

ANALYSIS OF OPERATION STATUS OF CATALYTIC CRACKING UNIT IN SINOPEC

2022, 53(1):  53-59. 

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The operation of 50 FCC units in SINOPEC refinery over the past two years is systematically summarized. In view of the operation of the plant, adjustment of product structure, energy conservation and emissions reduction, and the operation condition of new technology and new process, the operation experience was summarized and the optimization suggestions were put forward. The technical measures for increasing propylene and LPG production were introduced emphatically. In order to realize the long-term operation, green production and lower carbon emission of FCC unit, some suggestions on the next work were put forward.

INDUSTRIAL PRACTICES OF INCREASING PRODUCTION OF No.－35 LOW POUR POINT DIESEL BY LUBE BASE OIL HYDROTREATING UNIT

2022, 53(1):  60-63. 

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In order to meet the market demand for low-pour point diesel and to improve the utilization ratio of the unit, the feasibility of increasing the production of low pour point diesel No. －35 by using the existing 0.15 Mt/a lub base oil hydrotreating unit was studied in PetroChina Karamay Petrochemical Co.,Ltd. The results of commercial production and calibration show that the freezing point of product diesel is decreased from －22 ℃ to －58 ℃, and the cold filter plugging point is decreased from －1 ℃ to －32 ℃, the cold flow properties of the product diesel are significantly improved. The economic accounting results show that the unit can produce 54 kt of low pour point diesel in the whole year, and the economic benefit is increased by 12.1 million Yuan/a.

ECONOMIC EVALUATION OF SR-1000 CATALYST REPLACEMENT FOR SEMI-REGENERATIVE REFORMER

2022, 53(1):  64-67. 

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Nearly 10 years after using semi-regenerative reforming catalysts PRT-C/PRT-D in 500 kt/a catalytic reforming unit of PetroChina Dushanzi Petrochemical Company, because of the increase of the carbon and iron content on the catalyst, the yield of C₅+ stabilized gasoline was decreased by 2—3 percentage points and the benefit of the unit was decreased. The simulation calculation of the processing effect of SR-1000 catalyst, which was newly developed by the SINOPEC Research Institute of Petroleum Processing, was carried out. The results show that the RON of C₅+ stabilized gasoline reaches 95 under the same conditions. Compared with PRT-C/PRT-D catalyst, the liquid yield, the pure hydrogen yield, recycle hydrogen purity of SR-1000 catalyst are increased by 3, 0.4 and 3.9 percentage points, respectively. The SR-1000 catalyst has obvious advantages in increasing the C₅+ gasoline and hydrogen. The economic profit of SR-1000 catalyst will be increased by 20.775 million yuan per year.

SYNTHESIS OF Pt/PTA-MIL-101(Cr) AND ITS CATALYTIC PERFORMANCE FOR n-HEPTANE ISOMERIZATION

2022, 53(1):  68-75. 

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The 0.4%Pt/PTA-MIL-101(Cr) metal-acid bifunctional catalysts with different doping amounts of PTA were prepared by modifying organometallic skeleton material MIL-101(CR) with phosphotungstic acid (PTA) and were first applied to n-heptane isomerization. The synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), N2 adsorption-desorption, thermal gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), X-ray fluorescence (XRF) and acid-base titration. The results show that the synthesized samples are mesoporous-microporous composite materials with typical octahedral structure, regular pore structure and high specific surface area; the framework and thermal stability of MIL-101(Cr) are not damaged; the Keggin structure of PTA can be maintained in the catalyst, which can provide a good acidic environment for the catalytic reaction and the higher dispersity of Pt in MIL-101(Cr). Through the evaluation of n-heptane isomerization performance of the catalyst, it was found that the best match between the acid sites and metal sites of the catalyst was the most suitable for catalyzing n-heptane isomerization, when the reaction temperature was 260 ℃ and the doping content of PTA was 30%, and the conversion of n-heptane and the selectivity of iso-heptane could reach 69.1% and 93.7%,respectively.

COMMERCIAL APPLICATION OF FV-10 CATALYST IN PARAFFIN WAX HIGH-PRESSURE HYDROGENATION UNIT

2022, 53(1):  76-78. 

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The characteristics of paraffin wax hydrogenation catalyst FV-10, and its ex-situ presulfiding and application in paraffin wax high-pressure hydrogenation unit in Panjin North Asphalt Fuel Co.,Ltd. were introduced. The application results show that under the conditions of 12 MPa, 252-255 ℃ and 10 t/h, the pressure drop of catalyst bed is less than 0.02 MPa, the reaction temperature rise is less than 2.5 ℃, and the product can meet the requirements of refined paraffin wax. The color of product is +30, the light stability is +3, and the thermal stability is +28, which reflects advantages of high pressure hydrogenation.

STUDY ON APPLICATION PERFORMANCE OF AROMATIC ENVIRONMENT-FRIENDLY RUBBER PLASTICIZER A1820

2022, 53(1):  79-85. 

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The production process and product properties of Jinan A1820 aromatic environment-friendly rubber plasticizer from SINOPEC Jinan Company were studied, and the application performance of reference products with higher market share in the current period was compared. Jinan A1820 produced by physical refining process has excellent thermal stability and light stability. When used as filling oil, Jinan A1820 and reference products have the same effect in styrene butadiene rubber; as an operating oil, the former gives the rubber material relatively better processing performance, dynamic performance, and better anti-aging performance; the tire products with the same formula of the two operating oils have good performance, but the wet brake performance of the tire with Jinan A1820 is better. The research results have been widely accepted by the market, and the proportion of Jinan A1820 in the high-end tire rubber manufacturing field is gradually increasing.

RAPID PREDICTION OF HYDROCARBON MOLECULAR COMPOSITION OF NAPHTHA BASED ON NEAR INFRARED SPECTROSCOPY

2022, 53(1):  86-92. 

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A rapid method for the determination of molecular level composition of naphtha was provided. Based on the data samples of group composition (PINA) and single hydrocarbon composition of naphtha by gas chromatography in laboratory, the distribution ratio library of single hydrocarbon in naphtha was established. A large number of virtual samples were generated by sample enhanced (DA) method. A prediction model of naphtha PINA composition was established by using near infrared spectroscopy (NIR) as input variables and partial least squares (PLS) method. A prediction model of naphtha mono-hydrocarbon distribution ratio was established by K-nearest neighbor regression (KNR) method. The prediction results show that within the range of experimental data samples, the model can be used to quickly determine the monomer hydrocarbon molecular composition of naphtha.

NITROGEN BALANCE AND TRANSMISSION IN CRUDE OIL PROCESSING

YANG xiaoyan

2022, 53(1):  93-98. 

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21 units including atmospheric and vacuum distillation, hydrocracking, continuous reforming, diesel hydrogenation, residue hydrogenation, ketone-benzol dewaxing, furfural refining, and heavy oil catalysis etc. in a domestic refinery were comprehensively sampled and analyzed. The distribution and transmission of nitrogen-containing crude oil in various processes of refinery were investigated, the balance and distribution of nitrogen elements in each unit were determined, and the nitrogen diagram of the whole plant was drawn, in order to provide technical support for deep denitrification in refinery, anticorrosion protection in key units and process upgrading.

EXTRACTION AND ANALYSIS OF ORGANIC POLLUTIONS IN OIL SLUDGE OF REFINERY

2022, 53(1):  99-104. 

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The effects of toluene, petroleum ether,compound solvent of hydrocarbon and alcohol, naphtha and gasoline as solvent on the extraction of organic pollutants from tank bottom oil sludge were investigated. The optimum extractants were selected to obtain a compound extractant with high extraction rate. The effects of the ratio of extractant to sludge, extraction temperature, extraction time and stirring rate on the extraction efficiency were studied, and the content of polycyclic aromatic hydrocarbons (PAHs) in the extracted organic pollutants and tailings was also determined. The results showed that the extraction rate could reach more than 95%, and the extraction volume could reach 0.159 0 g/mL, when the compound extractant ratio (toluene/compound solvent of hydrocarbon and alcohol) was 6:4, the ratio of extractant to sludge was 3, the extraction temperature was 70 ℃, the extraction time was 30 min, and the stirring rate was 1 000 r/min. The total content of PAHs in the extracted organic pollutants was 1 579.87 μg/g, and carcinogens (∑CPAHs) accounted for 44%, indicating that there was a great potential carcinogenic risk. The PAHs of tailings was less than 6 μg/g, which could be directly discharged or used as garden land and pasture soil without harm to the environment.

COMBINED PROCESS OF HNO3/H2O2 FOR FLUE GAS DENITRATION AND MICROALGAE CULTIVATION

2022, 53(1):  105-111. 

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The HNO₃/H₂O₂ oxidation absorption solution is used to denitrate the simulated flue gas containing NO_x, and the absorption solution after denitration is used as the nitrogen source for microalgae cultivation. The effects of different heights of the packing on the denitration of flue gas, the contents metal ions in flue gas, trace elements in the microalgae medium and pH of the medium on the decomposition rate of H₂O₂ in the absorption solution were investigated to explore the feasibility of using HNO₃/H₂O₂ as a nitrogen source for the growth of Chlorella pyrenoidosa. The results show that the addition of packing in the absorption column can strengthen the gas-liquid contact and effectively reduce the liquid-gas volume ratio under the premise of ensuring a certain denitration rate. The iron, cobalt, and nickel ions in the flue gas can easily cause the decomposition of H₂O₂. The microalgae medium containing trace elements and weakly acidic environment are conducive to the decomposition of H₂O₂. The growth rate of Chlorella pyrenoidosa is higher when HNO₃ is used as the nitrogen source than that of NaNO₃, and the growth of microalgae is not affected when there is a small amount of H₂O₂ in the absorption solution of nitrogen source.

APPLICATION OF WASTE FCC CATALYST IN CATALYTIC OZONATION OF AMINE-CONTAINING WASTEWATER AND ITS KINETICS STUDY

2022, 53(1):  112-117. 

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The waste FCC catalyst was used as catalyst for catalytic ozonation of amine-containing wastewater. The effects of ozone concentration, waste FCC catalyst addition, wastewater initial pH value, and reaction temperature on the reduction efficiency of COD in amine-containing wastewater were investigated, and the catalytic oxidation effect of waste FCC catalyst was compared with conventional ozonation catalysts used in industry. The factors affecting the kinetics of the ozone catalytic oxidation of organic amines by waste FCC catalyst were analyzed, and the apparent reaction rate constants under different conditions were determined. The results show that increasing the ozone concentration and the amount of waste catalyst can accelerate the reduction rate of COD in wastewater; alkaline conditions will promote the decomposition of ozone to produce hydroxyl radicals (.OH) and speed up the oxidation reaction rate; the appropriate increase of the reaction temperature is beneficial to the oxidation reaction, but too high temperature will reduce the solubility of ozone; the synergistic catalytic oxidation effect of waste FCC catalyst is obviously better than conventional ozonation catalysts. The results of kinetic analysis show that ozone catalytic oxidation of wastewater containing amine at different pH, temperature and the amount of waste catalyst addition is consistent with the first-order reaction kinetics.

QUANTITATIVE ANALYSIS OF CYCLOHEXANOL/CYCLOHEXANONE SYNTHESIS PROCESS BY ATOM ECONOMY

2022, 53(1):  118-122. 

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The "dual carbon" goal promotes China's chemical industry green development to a new level. To optimize the production route of cyclohexanol and cyclohexanone in producing caprolactam, this article introduces the main industrial synthesis process of cyclohexanol and cyclohexanone. The traditional processes such as cyclohexane oxidation, cyclohexene hydration and phenol hydrogenation as well as the new esterification hydrogenation process have been quantitatively evaluated for the degree of greenness by introducing index of atomic economy. It is found that the novel process of esterification hydrogenation has more advantages in atomic economy, high single-pass conversion and good economic benefits.