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Table of Content

    12 September 2018, Volume 49 Issue 9
    EXPERIMENTAL STUDY ON CATALYTIC CRACKING OF HYDROGENATED LCO MIXED WITH HYDROGENATED VGO
    2018, 49(9):  1-5. 
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    The catalytic cracking performance of mixtures of HVGO and heavy fractions from different hydrotreated depths LCOs (denoted as HLCO-M, moderate depth hydrotreated LCO and HLCO-H, deep hydrotreated LCO)was investigated in a bench scale fixed fluidized bed device. The test results showed that, with increasing the ratio of the moderate depth hydrotreated LCO, the yields of dry gas, coke, LPG, and gasoline are gradually decreased compared with the calculation values of mixed feed with the same composition. When the HLCO-M mixing ratio is 90%, 50% and 10%, the dry gas yield decreases by 22.22%,13.13% and 3.17%, respectively, the coke yield decreases by 23.68%, 22.05% and 17.11%, respectively. For HLCO-H, the increase of mixing ratio causes the yield reduction of dry gas, coke and LPG, while the gasoline yield increases compared with the calculation values of mixed feed with the same composition. In case of HLCO mixing ratio of 90%, 50% and 10%, the dry gas yield decreases by 4.34%, 16.49% and 9.52%, respectively, the coke yield decreases by 10.52%, 30.16% and 29.30%, respectively.
    TECHNOLOGY FOR INCREASING NO.3 JET FUEL BY LOW PRESSURE HYDROFINING OF KEROSENE FRACTION
    Zhang Rui Xi Yuanbing Ding Shi Dai Lishun Nie Hong
    2018, 49(9):  6-10. 
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    Broadening the final distillation point of straight-run kerosene is an important way to increase jet fuel production. However, the broadened fraction has higher content in sulfur and nitrogen, lower smoke point and higher freezing point. The hydrofining test showed that the high reaction temperature and low space velocity under low pressure are favor to removal nitrogen compounds, but not for saybolt color of the product. A new low pressure hydrofining process was developed to process the broadened SR fraction. The results indicated that the new process has a better performance for improving the color of jet fuel product, compared with the conventional process.
    DEVELOPMENT AND COMMERCIAL APPLICATION OF ENVIRONMENT-FRIENDLY LPG DEEP DESULFURIZATION(LDS)TECHNOLOGY
    2018, 49(9):  11-15. 
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    The development and application of environment-friendly LPG deep desulfurization(LDS)technology were introduced. Through Higee process intensification,the oxidation reaction of mercaptan sodium to disulfide and the separation process of disulfide from caustic were coupled into one step,while both high oxidation conversion rate as above 95% and high separation ratio as above 98% were achieved. Results of commercial application in a 0.3 Mt/a LPG sweetening unit in Company A of PetroChina showed that FCC LPG after amine washing with 80 μg/g of mercaptan was taken as the feed, low sulfur content of LPG product with less than 10 μg/g is gained,while the amount of fresh caustic is reduced by more than 90% compared with the Merox process and nearly zero spent caustic is discharged. The economic benefit of the whole factory increases by nearly ¥ 11 million yuan /a
    OPERATION ANALYSIS OF 1.0 Mt/a COUNTER-CURRENT CCR UNIT
    Chen Xiang Li Jianguo Tian Xilei
    2018, 49(9):  16-21. 
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    The 1.0 Mt/a counter-current CCR unit in CNOOC Taizhou Petrochemical Company was designed with the improved countercurrent moving bed continuous reforming technology. The operation data exhibited good pressure drop distribution and smooth performance. Although the catalyst was slightly poisoned by sulfur and nitrogen and the potential aromatics content of feed was 5.7% lower than the design value,the hydrogen yield reaches 3.53%,the yield of C5+ is 89.63%,the mass fraction of the aromatics in the depentanizer bottom is 77.44% and the catalyst dust is only 3.99 kg/d. The PS-Ⅵ CCR catalyst showed excellent activity,selectivity,and good abrasion resistance and anti-poisoning ability.
    INDUSTRIAL PRACTICE OF PROCESSING ATMOSPHERIC RESIDUE OF LIAOHE THIN OIL IN RFCC UNIT
    2018, 49(9):  22-26. 
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    The crude for Liaohe refinery changed from Daqing crude to Liaohe thin oil, leading to production instability. By optimizing the feed composition and amount of recycling oil, choosing low active and anti- nickel catalyst LRC-30, adding dull nickel agents and increasing the replacement rate of equilibrium catalyst, the nickel content in the feed and equilibrium catalyst are controlled in 17.9 μg/g and 13 265 μg/g, respectively, and the processing volume and liquid yield return to normal. However, the diesel yield increases by 7.44 percentage points due to the limitation of existing hardware equipment of two stage riser technology.
    OPERATION ANALYSIS AND COUNTERMEASURES OF HIGH PRESSURE HYDROGENATION DEVICE FOR PARAFFIN LUBE BASE OIL PRODUCTION
    2018, 49(9):  27-31. 
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    The high-pressure hydroprocessing unit for production of paraffin base oil in CNOOC is a key unit for company`s benefit. The CLG proprietary catalysts, process package were used. The problems of low yield of base oil, and unqualified heavy product in some indicators appeared in operation. This paper analyzes the causes of the problem. The results showed that the presence of large nitrogen compounds in the feed, which are difficult to remove, increases the cracking reaction and reduces the base oil yield. The high content waxes with rings in the feed add the difficulty for isomerization, and aggravate the cracking reaction, leading to a low base oil yield, and a higher pour point and turbidity point. Some short-term improvement measures, such as reducing space velocity, processing more No.3 VGO time and lowering the dry point of No.4 VGO were proposed. The measures of using appropriate crude oils, blending feeds and adopting more efficient catalyst grading are suggested for medium and long term production.
    STUDY OF IMPROVING CATALYTIC CRACKING SELECTIVITY OF NAPHTHENE IN STRAIGHT-RUN NAPHTHA
    2018, 49(9):  32-36. 
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    A cracking reaction network for cyclohexane and methyl-cyclohexane model compounds was established by using molecular simulation and micro-reaction tests to analyze the reasons for poor selectivity of naphthene cracking in catalytic cracking process of straight-run naphtha. It is found that, by using IM-5 zeolite with specific pore structure the ring-opening reaction selectivity of naphthene can be strengthened effectively, and more low carbon olefin obtain can be produced.
    INFLUENCE OF NEW TYPE H2S SCAVENGER ON CRUDE OIL DEMULSIFICATION AND DESALINATION
    Zhang Feng Wang Zhenyu
    2018, 49(9):  37-42. 
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    Three kinds of H2S scavenger for crude oil were comprehensively compared in H2S removal performance, the influence on demulsification kinetics and desalination for crude oil in electric field. The three scavengers for comparison include a self-developed H2S scavenger FHSS, hexahydro-1,3,5-tris-s-triazine TRIAZINE and a new amine-type Bis(2-dimethylaminoethyl)ether, BDMAEE. The results indicated that H2S content in desulfurized crude oil is not more than 0. 55 μg/g if FHSS in crude oil is ≥ 36 μg/g. FHSS presents the similar removal performance for H2S to TRIAZINE,and has slightly advantage over BDMAEE. Within the experimental range of additive amount(0~100 μg/g),FHSS,TRIAZINE and BDMAEE have no influence on demulsification rates of cured oil emulsions in electrostatic field,and the demulsification kinetics could be approximatively represented by the first-order kinetics equation for chemical reactions. Meanwhile,the three scavengers all do not affect crude oil desalination.
    MECHANISM OF BINARY COMPLEX SURFACTANT IN OIL - WATER INTERFACE
    2018, 49(9):  43-48. 
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    Mesoscopic simulation was used to study the distribution of binary compound surfactant molecules in oil-water interface. It is found that SDBS and TX100 were all distributed in the interface of oil and water. When used alone, there is an extremum of decrease of interfacial tension. However, the synergistic effect of the two is complementary to each other, increasing the distribution density of surfactant molecules at the oil-water interface and occupying more oil-water interfacial layer, and reducing the interfacial tension of the interface; polyacrylamide cannot reduce the interfacial tension, but it can form a spatial network structure and extend itself through the entanglement of molecular chains, which can connect the surrounding oil droplets and make the oil molecules gather more easily.
    ADSORPTION STUDY OF ETHYLBENZENE AND PARA-XYLENE ON EUO ZEOLITE BY MONTE CARLO SIMULATION
    2018, 49(9):  49-53. 
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    The adsorption behavior of ethyl benzene and para-xylene on four EUO zeolites with different Si/Al ratio was studied under high temperature conditions by means of the macro-canonical statistics ensemble Monte Carlo simulation and validated by the catalytic reaction of industrial samples. GCMC simulation shows that the adsorption energy of PX in EUO zeolite is slightly higher than that of EB; PX is mainly adsorbed in the straight pore channel, while EB is adsorbed in the side cage, the Bronsted acid produced by Al atom can block the diffusion of adsorbed mass, which leads to more ladder platform in the adsorption isotherm of PX; the blockage caused by carbon deposition has a greater effect on PX diffusion, so the generation of by-product toluene will decay more rapidly than that of ethylbenzene.
    STUDY ON PROPERTIES OF DIESEL HYDRODESULFURIZATION CATALYST WITH MESOPOROUS ZSM-5 ZEOLITE
    2018, 49(9):  54-58. 
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    The effect of mesoporous ZSM-5 zeolite on the hydrodesulfurization activity of MoO3-CoO catalyst was investigated. Al2O3 with different content of mesoporous ZSM-5 zeolite was used as supports. The straight-run diesel was used for hydrodesulfurization (HDS) evaluation. The results indicated that the HDS activity of the catalysts firstly increased and then decreased with the increase of the mesoporous ZSM-5 zeolite. The catalyst with 12% mesoporous ZSM-5 zeolite has the highest activity, higher than that of the catalyst without ZSM-5 and the catalyst with 12% non-mesoporous ZSM-5. The result indicated that the mesoporous ZSM-5 zeolite greatly improves the HDS activity of the catalyst.
    INDUSTRIAL APPLICATION OF H2S SELECTIVE OXIDATION CATALYST LS-06
    2018, 49(9):  59-63. 
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    LS-06 catalyst for selective oxidation of hydrogen sulfide with good hydrogen sulfide conversion rate and sulfur recovery yield was developed by optimizing the active component, the preparation process,and the carrier. The catalyst was manufactured in industrial scale and applied in a commercial unit. The commercial calibration indicated that the conversion rate of hydrogen sulfide is more than 98.08%, the sulfur recovery rate 91.04% under the conditions of H2S concentration of 0.5% in inlet of super-Claus process. The sulfur dioxide concentration of purified flue gas is below 500 mg/m3, less than 550 mg/m3 of the design requirement, lower than the 960 mg/m3 emissions standards of the national environmental protection regulations.
    PREPARATION OF Pd/Ca-Al2O3 CATALYST AND ITS HYDROGENATION ACTIVITY FOR C5 RAFFINATE
    He Long Feng Liangjing Zhao Cunsheng
    2018, 49(9):  64-68. 
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    The Pd catalysts, using Al2O3 and alkali metal additives as carrier, were prepared by the kneading-impregnation method. The suitable alkali metal additive was chosen, the effects of additive amount and Pd loading on the olefin saturation activity of the catalyst were investigated. The process reaction conditions and activity stability of the selected catalyst were investigated. The results showed that the best alkali metal additive for the catalyst is Ca,and the best additive amount of Ca is 2.5% (w),meanwhile the best Pd loading is 0.15%(w). The catalyst containing the additives has a less acid amount, and can reduce the aggregation of the diolefin on the catalyst surface, improving the stability of the catalyst. It is concluded by tests that the suitable reaction conditions for Pd/Ca-Al2O3 catalyst for hydrogenation of C5 raffinate are: 40 ℃,1.0 MPa, LHSV of 11 h-1,and the ratio of hydrogen to oil of 110. The olefin saturation rate of C5 raffinate under the optimal condition is not less than 99.5%,and the catalyst was continuously operated for 600 h with stable activity.
    EFFECTS OF TEMPLATE AND ADDITIVES ON HYDROISOMERIZATION PERFORMANCE OF Pt/MOR CATALYST
    2018, 49(9):  69-74. 
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    Hierarchical pore MOR zeolites were synthesized by using sodium dodecyl benzene sulfonate(SDBS), composite polyethylene glycol 20000(PEG20000) and cetyltrimethylammonium bromide(CTAB) as templates, respectively. Pt/MOR catalysts were prepared by loading Pt on MOR zeolites and the second metal components Ni and Cr were respectively introduced into the obtained catalyst by sequential impregnation method. The samples were characterized by XRD, BET, CO pulse chemical adsorption, H2-TPR, NH3-TPD and Py-IR. The results showed that the mesoporous are effectively introduced by the addition of composite templates, the mesoporous surface area and volume of the MOR prepared increase from 36.4% and 52.9% to 54.2% and 76.5%, respectively, and its average pore diameter increases from 2.1 nm to 3.9nm. The introduction of Ni or Cr significantly increases the total acidity and Lewis acid of the catalyst, and remarkably improves the dispersity of the Pt species, and the effect of Cr is better than that of Ni. Over the Pt/MOR catalyst with 1% Cr, the n-octane conversion reaches to 59.3% with the isomerization selectivity of 94.9%.
     
    2018, 49(9):  75-78. 
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    To meet the refineries’ requirements for reducing diesel-to-gasoline ratio, Lanzhou Petrochemical Research Center, PetroChina, has successfully developed LPC-70 cracking catalyst for improving gasoline yield. In this catalyst, the hierarchical matrix material APM-7 with high content of Br?nsted acidities has been employed. It can improve gasoline yield and propylene content in LPG greatly as well as heavy oil conversion rate. Recent application of LPC-70 in Lanzhou Petrochemical Company has demonstrated that compared to the blank rating, with the lowing quality of feed oil and catalyst consumption, bottom yield decreased by 0.71%; gasoline yield increased by 2.53%; diesel-to-gasoline mass ratio of the unit decreased from 0.46 to 0.39 and the propylene content in liquid hydrocarbon increased by 6.10 percent point.
    MODELING AND LIFE TEST OF SOLID SUPERACID CATALYST FOR n-C50/C60 ISOMERIZATION
    2018, 49(9):  79-86. 
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    The Pt/SO42-/ZrO2-Al2O3 (PtSZ/A) catalyst with binders were prepared by extrusion method. The effects of binders, dosage and calcination temperature on the isomerization and physicochemical properties of PtSZ/A catalysts were studied to determine the best conditions for preparation. The catalysts prepared were further treated by solvent. The crystal structures and sulfur contents of the catalysts were characterized by XRD and TG, respectively. The life test of the catalyst was conducted in a micro-fixed bed reactor. The results indicated that the PtSZ/A catalyst with pseudo-boehmite as binder showed higher n-C50/C60 isomerization activity and mechanical strength. The suitable calcination temperature is 650 ℃. After solvent treatment, the isomerization performance of PtSZ/A catalyst is further improved. Using refined naphtha as feed, the conversion rate of n-C50 and n-C60 is 62.5% and 90%, respectively in 1 400 h running. The selectivity of 2,2-dimethylbutane achieves 35% or more.
    STUDY ON OXIDATION RESISTANCE OF 150BS BRIGHT STOCKS FROM DIFFERENT SOURCES
    2018, 49(9):  87-91. 
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    The effect of anti-oxidation properties of three 150BS bright stocks (150BS-1,150BS-2 and 150BS-3) from different sources on performance of gear oils blended with the bright stocks were studied by RPVOT, oven oxidation test (OOT) and extreme pressure performance test. The results showed that, compared with the solvent refined 150BS-2, the hydrotreated stocks of the domestic 150BS-1 and the imported 150BS-3 have the better anti-oxidant sensibility to antioxidant. The saturated polycyclic naphthene has a negative effect on the oxidation resistance of 150BS hydrotreated. The better of the oxidation stability of the 150BS is, the better the anti-oxidation resistance of the industrial gear oil with bright stock.
    EFFECT OF GRAPHENE ADDITIVE ON TRIBOLOGICAL PROPERTIES OF LUBE BASE OIL
    2018, 49(9):  91-95. 
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    The effect of graphene additives on the tribological properties of lube base oil was studied. The dispersion and storage stability of graphene additives in lube base oil was studied by static sedimentation method. The anti-wear, friction-reducing ability and extreme pressure load-carrying capacity were investigated by a four-ball friction and wear tester. The worn surfaces were analyzed by SEM. The results showed that compared with the PAO 10 lube base oil, the graphene additives could reduce the friction coefficient of 13% and the wear scar diameter of 17% under the same test conditions. The wear mechanisms of both lube base oil and graphene additives are particle wear.
    DETERMINATION OF PHENOLIC COMPOUNDS IN FCC DIESEL OIL BY SOLID PHASE EXTRACTION-GAS CHROMATOGRAPHY
    2018, 49(9):  96-100. 
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    Solid phase extraction (SPE) was used for sample pretreatment to enrich phenolic compounds from FCC diesel oil. The sample was separated into two classes: phenolic compounds and hydrocarbons. The elution conditions of the SPE column were optimized with the standard sample. The recovery and repeatability were tested under the optimized conditions. The qualified and quantified analysis of the compositions of phenolic compounds in fraction rich in phenolic compounds by gas chromatography-mass spectrometry, gas chromatography-flame ionization was conducted. It was shown that the recoveries of the standard compounds are 93%~108% and the relative standard deviation is less than 5% after repeated separation of the same sample for 5 times, indicating a good repeatability of the method. It was revealed that the flame ionization detection has a good linear response in the range of 2~300 μg/g of phenolic compounds; the difference among the relative response factor of phenolic compounds is not significant. It was found that phenols, naphthols and phenanthrols are the main components, of which the phenols account for 69.4%. It is concluded that the phenolic compounds in FCC diesel could be effectively enriched by the SPE method, which could be used for the qualified and quantified analysis of phenolic compounds.
    EFFECT OF OLEIC DIETHANOLAMIDE ON ADSORPTION BEHAVIOR OF LUBRICATING OIL IN WATER-SOIL SYSTEM
    2018, 49(9):  101-106. 
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    The adsorption behavior of oleic diethanolamide (ODEA) in water - soil system was studied by oscillating equilibrium method. The adsorption kinetic characteristics and adsorption isotherm curves of ODEA lubricating oil in the system were investigated. The lube oil and the ODEA lube both are absorbed by soil quickly. The adsorption dynamic curve conforms to the Lagergren pseudo-second-order dynamics equation, and the adsorption isothermal curve accords with the Freundlich adsorption isothermal model and the Henry liner adsorption isothermal model. ODEA can inhibit the adsorption capacity and rate of lubricating oil in the soil, while the concentration of ODEA of 4mg/L is the best.