Table of Content

12 January 2018, Volume 49 Issue 1

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EFFECT OF OPERATING CONDITIONS ON PRODUCTS PROPERTIES OF MILD HYDROCRACKING PROCESS

2018, 49(1):  1-7. 

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Mild hydrocracking process can give the diesel/gasoline ratio new flexibility for refinery. The effect of the operating conditions of hydrogen partial pressure, LHSV and H2/oil on the product properties were tested. Results indicated that at the same conversion, the qualities of the wax oil and diesel fractions are all improved and the high content of the mono-aromatic is easy to react when the hydrogen partial pressure increased; when the content of single cyclic aromatic hydrocarbons with different carbon number is consistent, the aromatic with lower carbon number is more likely to react as the hydrogen partial pressure increases, while the distribution changes of the carbon number of naphthene and chain alkane are small with the hydrogen partial pressure variation. Increasing SV, little changes of the product qualities are observed at the same conversion. At higher Sv, the maximum carbon number of each hydrocarbon in wax oil is higher significantly than that at lower Sv; At the same conversion, increasing H2/oil can only cause small quality changes, higher H2/oil ratio gives higher peak of carbon number than that at lower ratios. It is recognized that at the same conversion, higher PH2 is helpful to produce high quality diesel blending component and wax oil product, while higher H2/oil and Sv are benefit to the production of wax oil with higher carbon number, which can be used as feed for FCC or catalytic cracking process.

OPERATION ANALYSIS OF 2.2 Mt/a DCC-PLUS UNIT

2018, 49(1):  8-14. 

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中海石油宁波大榭石化有限公司采用中国石化石油化工科学研究院开发的增强型催化裂解（DCC-plus）专利技术建设了一套2.2 Mt/a的催化裂解装置。该装置以常压渣油和加氢裂化尾油为原料，以乙烯、丙烯等低碳烯烃为主要目标产物，副产富含轻芳烃的裂解石脑油。装置自开工以来运行平稳，专用催化剂具有较高的低碳烯烃产率、较好的抗金属污染性能以及优良的水热活性稳定性和流化输送性能，且随着系统中专用催化剂比例的增加，乙烯和丙烯的收率稳步提高，最高分别达到4.56%和20.08%，均超过了设计值。在装置运行过程中，通过调整操作参数能够有效地提高乙烯和丙烯的收率。

APPLICATION OF SELECTIVE HYDRODESULFURIZATION TECHNOLOGY (CDOS-FRCN Ⅱ)FOR FULL DCC GASOLINE DISTILLATE

2018, 49(1):  15-20. 

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The superiority of CDOS-FRCN Ⅱ technology applied for producing ultra-low sulfur gasoline was introduced. The splitter process (LCN/HCN) of gasoline was cut out in the technology. The technology has advantages in simple process, flexible operation, less investment, lower energy consumption. It used a new nano TiO2-based HDDO-100/HDOS-200/HDMS-100 catalyst system, which has high activity in desulfurization, selectivity and stability and is suitable for full distillate hydrodesulfurization. The catalyst system showed excellent activity and stability in treating DCC gasoline or FCC gasoline with high diene and olefin content. A new DCC gasoline hydrogenation unit with 0.5 Mt/a in CNOOC Dongfang Petrochemical Co. Ltd., achieves China V gasoline product using the technology.

OVERHEAD SYSTEM CORROSION PROTECTION

2018, 49(1):  21-25. 

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The technology for anti-corrosion of overhead system of atmospheric distillation tower was discussed. When two-stage condensation system is chosen, adding heat exchangers in front of the air coolers can avoid the difficulty of eliminating dew point caused by water misdistribution inside the air coolers. Extra water injection points can also be installed on branch pipes of air cooler inlets at the top of the column so as to minimize corrosion. Meanwhile, appropriate process can be set up for overhead product drum to discharge sour water to decrease damage from corrosion in the overhead system of the column. When one-stage condensation system is used, cancelling the overhead cold reflux flow can protect the column overhead system from corrosion. During operation, controlling either the temperature of overhead reflux drum or the temperature at the top of atmospheric column can meet the quality requirements of naphtha product.

EFFECTS OF IRON CONTAMINATION ON PERFORMANCE OF CATALYST IN HEAVY OIL CATALYTIC PYROLYSIS PROCESS AND COUNTERMEASURES

2018, 49(1):  26-29. 

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This paper focused on the reasons for deterioration of slurry quality in the heavy oil catalytic pyrolysis process, which leads to coking in fractionator, unqualified products, lower ethylene and propylene yields and the oil slurry system plugging, threatening the long term stable operation of the unit. By the operation data analysis and the catalyst characterization by NH3-TPD and BET, considering the reaction mechanism, it is concluded that high level of Fe in the feedstocks was the main cause of the above issues. The measures are suggested: substantial replacement of balance agent and iron removal from feedstocks.

STUDY OF N-HEPTANE CONVERSION RULE OVER Pt-Sn REFORMING CATALYST

Ren Yuelin Ma Aizeng Wang Jieguang

2018, 49(1):  30-36. 

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N-heptane, the paraffin that is difficult to convert, was used as a model compound to investigate the effect of potassium, mixture of rare earth cerium and potassium, and bi-rare earth metals (Ce,Eu) on n-heptane conversion. The results showed that adding potassium (0.045%, 0.060%) decreases the strong Lewis acidity of catalyst support, inhibiting the cracking reaction. At 510 ℃, cracking products decrease about 5 percentage points and the selectivity of iso-paraffins increases about 7 percentage points; adding mixture of cerium (0.28%) and potassium (0.010%, 0.030%) decreases the selectivity for cracking by 4.2-7.1 percentage points, while the iso-paraffin selectivity rises 7.4 - 9.8 percentage points at 510 ℃. Increasing reaction temperature has a weakened effect to certain extent on n-heptane conversion; Addition of bi-rare earth metals can effectively reduce the selectivity for cracking product at low temperature (510 ℃)，but the iso-parafin selectivety rises. The effect of addition of bi-rare metals on heptane transformation is weakened significantly with increasing the reaction temperature.

COMBUSTION OF SOOT PARTICULATE OVER Mn1-XAgXCo2O4 SPINEL OXIDE

2018, 49(1):  37-41. 

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A series of Mn1-xAgxCo2O4 spinel oxide catalysts were prepared by sol-gel method and characterized by XRD，FI-IR，O2-TPD, and TPO techniques. The performance of the catalysts was evaluated in a home-made device by temperature programme. The results showed that the as-prepared catalysts possess spinel structures and exhibit high catalytic activity for soot combustion. Mn0.6Ag0.4Co2O4 catalyst has the best activity with a T50（the temperature at which soot conversions is 50%）of 325 oC, 260 oC lower than the temperature needed in non-catalytic soot combustion.

PERFORMANCE OF METHANOL DECOMPOSITION AT HIGH TEMPERATURE ON COPPER CEMENT CATALYST MODIFIED BY NICKEL AND ZINC

2018, 49(1):  42-47. 

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Using the basic nickel carbonate, basic zinc carbonate, basic copper carbonate and cement as materials, the Cu-Ni, Cu-Zn and Cu-Ni-Zn cement catalysts were prepared, and their catalytic performance for methanol decomposition was studied. The evaluation results showed that the conversion of methanol over Cu-Ni catalyst exceeds 96% at 380-420℃, WHSV of 3.39h-1 and atmospheric pressure. The Cu-Zn catalyst shows lower catalytic activity, but higher selectivity for H2 and CO. After the Cu-Ni-Zn cement catalyst runs for 1600 h, little changes are observed in the conversion of methanol and the distribution of product, the conversion of methanol is basically above 81%, and the total molar fraction of H2+CO is more than 98%, indicating its good high temperature stability.

IR STUDY OF SOLID RESIDUES IN CO-PROCESSING OF COAL AND HEAVY OIL

2018, 49(1):  48-53. 

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The lignite and FCC slurry （FCCS） were co-processed in an autoclave using molybdenum naphthenate oil soluble catalyst in H2 atmosphare. Solid residues derived from the reaction at different time were obtained and analyzed by Fourier transform infrared spectroscopy（FT-IR）. The reaction process was speculated by combination of peaks fitting of the specific bands of different functional groups in FT-IR spectra using Peakfit software and the conversions and product distribution of different functional groups. Results showed there are five different types of hydrogen bonds in the solid residues, among which the hydrogen bond from hydroxyl association is at most, while the hydrogen bond formed through the association of the phenolic hydroxyl group and ether group in oxygen-containing functional groups account the maximum. The reaction process can be divided into three stages：in the first stage, the coal conversion raises rapidly, all kinds of the functional groups decreases and the fat chain breaks down a lot; the second stage is the stable phase of coal conversion, in which the amounts of phenolic hydroxyl groups and ether groups reduce, and the other oxygen-containing groups change little; in the third stage, the coal conversion reaches much deeper, the content of oxygen-containing compounds and aliphatics in solid residues further decreases, resulting in minimized association of hydrogen bonds.

QUANTITATIVE RELATIONSHIP BETWEEN CATALYST PROPERTIES AND HYDRODESULFURIZATION CONVERSION OVER NiMo/Al2O3

2018, 49(1):  54-59. 

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A series of NiMo/Al2O3 catalysts with different properties was obtained by controlling the metal loading. NiO loading, MoO3 loading and the MoS2 dispersion of the catalysts were considered and a “changing super geometric average” was applied to revise the existing model to establish a quantitative relationship between the catalyst properties and the HDS conversion. The results indicated that the average relative deviation for the modified model is only 1.13%. The optimum MoO3 and NiO loadings are 12%-14% and 3%-4%, respectively, as analyzed by the established model. The results also showed that hydrodesulfurization activity is more sensitive to the content of NiO loading.

EFFECT OF NAPHTHENATE ON POLYCYCLIC AROMATIC HYDROGENATION VIA IN SITU GENERATED H2 FROM WATER GAS SHIFT REACTION

2018, 49(1):  60-64. 

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The effect of nickel and iron naphthenate on anthracene hydrogenation by using in situ hydrogen generated through the water gas shift reaction was investigated in an autoclave. The factors of the concentration of nickel and iron naphthenate each, the mixed system of iron and nickel naphthenate were tested. The reaction conditions are follows: 400℃, 2.0MPa CO, and CO/H2O molar ratio of 1:2.5. The reaction samples were took out at different reaction time and analyzed. The results showed that iron and nickel naphthenate are catalytic active for both anthracene hydrogenation and water gas shift reaction. Nickel naphthenate is more conducive to the water gas shift reaction, while the catalytic effect of iron naphthenate on anthracene hydrogenation is more effective. The conversion of anthracene hydrogenation is the highest when the concentration of Ni in nickel naphthenate is 0.08w% and Fe in iron naphthenate is 0.05w%. There is a synergistic effect of iron and nickel naphthenate, which can effectively promote the reactions of the water gas shift and anthracene hydrogenation. Addition, the results indicated that there is a positive synergy between these two reactions.

NUMERICAL SIMULATION STUDY ON TUBULAR GAS-LIQUID DISTRIBUTOR

2018, 49(1):  65-69. 

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Gas-liquid distributor is an important internal component of fixed bed hydrogenation reactors. Performance of tubular distributors was simulated using Euler multiphase model and RNG turbulence model. Three types of tubular distributors were studied and each distributor with broken flow plate or not was compared. The results showed that the distribution performance of the distributor is improved significantly after adding the broken flow plate. However, the pressure drop of the distributor is increased. The distribution performance of the inclined pipe distributor with a broken flow plate and cross arrangement of side hole with 90o is the best. The broken flow plate greatly reduces the influence of the way the gas entering the distributor and the arrangement of overflow hole on distribution performance.

INFLUENCE OF S-P TYPE ANTI-WEAR AGENTS ON ANTI-MICROPITTING

2018, 49(1):  70-74. 

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The effect of anti-wear agents of trialkyl phosphorodithioate (P1) and trialkylphenyl phosphorothionate (P2) on anti-micropitting for gear oil was tested by analysis of the change rate of track width, CLA curve and surface topography of the roller using MPR test machine. The result showed that the MPR test machine has a good distinction to the anti-micropitting for gear oil. Compared with sample P1, the change rate of the track width of P2 is small; fewer pits on the surface of roller are found and are relatively shallow; the CLA curve is relatively steady and smooth. These results showed that P2 has better anti-micropitting ability and could lower the occurrence of micropitting for gear oil.

STUDY ON BLENDING OF HYDROCRACKING NAPHTHACOAL FROM INDIRECT LIQUEFACTION WITH BY-PRODUCT GASOLINE OF MTP PROCESS

2018, 49(1):  75-78. 

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Both the hydrocracking naphtha of coal indirect liquefaction and the by-product gasoline of MTP process are good components for gasoline blending. The blended coal-based gasoline with 50uL/L antioxidant can meet the requirements of standard GB/T17930-2016, which is characterized by low sulfur, nitrogen, iron and manganese, and is a clean and environmental friendly gasoline.

DETERMINATION OF IRON SPECIES IN RESIDUUM

2018, 49(1):  79-82. 

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A method was established for the determination of iron species in residue by inductively coupled plasma optical emission spectrometry (ICP-OES). Four representative iron compounds: ferric chloride, iron naphthenate, iron 2-ethlhexannoate, and iron meso-tetraphenylporphine chloride were employed as model chemicals to investigate the extraction efficiency and conditions. The results showed that the extraction rate of ferric chloride reaches 100% by pure water. In the case of dilute acid is used as the extraction agent, the irons in residue can be divided into acid extracted iron, residual iron in oil and other iron irons. The acid extracted iron includes water soluble iron, majority of oil acid iron and a small amount of ferroporphyrins. Hydrochloric acid solution(5%) was found to be the best extraction solvent for iron naphthenates. The spiked recoveries of iron naphthenates and iron 2-ethlhexannoate in residue are 100.5% and 93.2%, respectively after extraction for 3h with the HCL solution. It is found that the other iron compounds disappear after hydrogenation, indicating they are easy to remove by hydrogenation. However, the removal rate of the residue iron in oil is far lower than the total iron removal rate.

DETEEMINATION OF PHENOLIC COMPOUNDS IN DIESELS USING LIQUID-LIQUID EXTRACTION AND GC-OXYGEN SELECTIVE DETECTOR

2018, 49(1):  83-87. 

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A method for determination of phenolic compounds in diesels was established by using liquid-liquid extraction combined with gas chromatograph equipped with oxygen selective flame ionization detector（GC-OFID）. Diesel samples were first extracted with 10% sodium hydroxide. The extracted water phase was neutralized to Ph 5-6 with dilute hydrochloric acid and then re-extracted with dichloromethane. The phenolic compounds-containing dichloromethane were evaporated to get concentrated phenolic compounds and were then detected by GC-MS and GO-OFID. The structures or types of 54 peaks or groups of phenolic compounds were identified by GC-MS, chromatography retention time and boiling points. Benzyl alcohol was added into the concentrated samples as internal standard for quantification test. When 50 mL diesel sample is treated，the detection limits of phenol，2，5-dimethyl-phenol and 2，3，5-trimethyl phenol are 0.5，1.0，1.5 mg/L respectively. The relative standard deviations of five consecutive results are less than 8.0% in the phenolic compound concentration range of 8-40 mg/L，which meet the requirement of routine analysis.

COMPOSITIONS AND STRUCTURES AGGREGATION BEHAVIORS OF RESIN IN FENGCHENG HEAVY OIL

2018, 49(1):  88-93. 

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Resin in Fengcheng heavy crude was separated by silica gel column chromatography. The compositions and structures of the resin were characterized by elemental analysis, FT-IR, NMR and XPS. The average structural parameters and average molecular formulas of the resin were determined by 1H NMR/IR method. The results showed that the resin in Fengcheng heavy crude is polar molecules containing heterocyclic aromatics, n-alkanes and N, O and S atoms. Oxygen atoms exist mainly in the form of ether oxygen and N atoms are mostly in the form of pyrrole and pyridine. The average molecular weight of the resin is 3 773, the number of average structural units (n) is 6.57 and the average structure unit formula is C39H55O2N. In addition, the aggregation behaviors of the resin in heptane and toluene were also discussed by molecular dynamics simulation method. It is showed that the resin can form stable aggregate system in heptane, however toluene is good for diffusion of resin molecules.

COST ANALYSIS AND DEVELOPMENT SUGGESTION FOR HYDROGEN PRODUCTION FROM COAL AND NATURAL GAS

Zhang Caili

2018, 49(1):  94-98. 

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Starting from the low cost raw material sources for hydrogen production and according to all hydrogenation process of refinery that need an independent hydrogen plant, the factors affecting hydrogen cost and competition were analyzed to quantify the influence of carbon dioxide emission and national carbon tax on the processing route. Based on the raw material availability, economy and feasibility, suggestions for hydrogen production from different raw materials at different refineries are proposed.

PROBLEMS AND OPTIMIZATION OF CONTACTING COOLING SYSTEM IN DELAYED COKING UNIT

yang junjun Leyi WANG

2018, 49(1):  99-102. 

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The main function of the contacting cooling system as a part of delayed coking unit is to cool the high temperature steam, oil and gas during the large blow steaming, the water feeding and the oil and gas preheating from the treatment tower of the coke tower. Some problems exist, such as the corrosion of cooling water tank in the bottom of contacting cooling tower, the water containing oil in the bottom of the tower and the cavitation corrosion of the bottom pump. A series of optimized measures were adopted for contacting cooling system: stop using the cooling water tank; using the cross line process, and adding an atomization spray system and heat exchangers in entrance and bottom of the cooling tower, respectively to effectively solve the problems, and to save the equipment maintenance investment and reduce the processing costs about 75 000 RMB/a.

NEW TECHNOLOGIES OF DENITRATION, DESULPHURIZATION AND DUST REMOVAL FOR FCC FLUE GAS

2018, 49(1):  103-108. 

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FCC is an important emission source of oil refinery. In view of the characteristics of FCC flue gas, a combined technology of denitration and desulfurization and dust removal was developed by SINOPEC with completely independent intellectual property rights. It includes SCR(selective catalytic reduction) - heat recovery-CO oxidation process, new type of turbulent impulse Venturi for FCC flue gas dust removal and desulfurization, high mechanical strength honeycombed SCR catalyst for flue gas denitrification, key equipments and patented internal components such as ammonia spraying component, venturi grid, spraying nozzle, high-efficient demister. The first unit for denitration and desulfurization and dust removal of FCC flue gas was built in Zhenhai. The industrial results showed that the dust,SO2,NOx concentration in purified flue gas is less than 20 mg/m3, 10 mg/m3, 50 mg/m3 ,respectively,with the minimum NOx concentration less than 20 mg/m3, and the concentration of ammonia escaped less than 2.0 mg/m3.