Table of Content

12 May 2014, Volume 45 Issue 5

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CHALLENGES IN CLEAN AND EFFECTIVE PRODUCTION OF HIGH VALUE PRODUCTS FROM INFERIOR CRUDE FOR EUROPEAN REFINING INDUSTRY

2014, 45(5):  1-10. 

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The challenges and the countermeasures were paid close attention to European refining industry in the 18th ERTC Annual Meeting hold in Budapest，Hungary in 2013. The advance technologies and their applications for enhancing competitiveness of European refineries were presented. The topics discussed include plant and feedstock flexibility improvement and the product slate expansion, technologies processing inferior crudes and bottom of the barrel, production of more diesel fuel and petrochemicals, profit maximization, emission control and capture, energy efficiency, biofuels and biomass, petrochemicals, asset optimal utilization, technologies and processes. The meeting represented that despite the gloomy prospect of the industry, European refiners are in the hope of increasing profit by investment in technology. Key Words：inferior crude; heavy oil; diesel; profit; emission; energy efficiency

STUDY ON STYRENE POLYMERIZATION MECHANISM IN EXTRACTION DISTILLATION PROCESS

2014, 45(5):  11-15. 

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Through analyzing the composition and structure of both oligomers and polymers of styrene by GCMS and FT-ICR MS methods, a mechanism of styrene polymerization occurred in the extraction distillation process was proposed. It is concluded that the styrene polymerization is triggered along the radical initiation and thermal initiation with the latter one as a dominate way. It is found that 1,3,5-triphenylcyclohexane is participated in the chain initiation reaction and that the ethylbenzene in extraction feedstock is involved in the chain transfer reaction of styrene polymerization, resulting in more ethyl phenyl free radicals in the system.

STUDY ON VISCOSITY REDUCTION MECHANISM OF TAHE HEAVY OIL BY CATALYTIC AQUATHERMOLYSIS

2014, 45(5):  16-20. 

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By comparison of the characters and compositions of Tahe heavy oil before and after aquathermolysis with or without viscosity reducer and a model compound aquathermolysis reaction, a mechanism of viscosity reduction was established. The test results show that the viscosity of Tahe heavy oil can be reduced up to 65.8% by catalytic aquathermolysis, 32% higher than that of aquathermolysis without viscosity reducer. The heavy component is decreased, the light one is increased, and the molecular weight and the sulfur content are reduced after treatment. The aquathermolysis experiments of dodecyl mercaptan and dioctyl sulfide with viscosity reducer indicate that the bond breakage of C-S, S-H，C-C，S-S are happened. The reasons for the irreversible viscosity reduction are the weakened molecular interactions like hydrogen bond and coordination bond and bond breakages after treatment, resulting in smaller aggregation of resins and asphaltenes and thus the reduced viscosity.

INFLUENCE OF INITIAL HYDROGEN PRESSURE ON ASPHALTENE HYDROCONVERSION

2014, 45(5):  21-24. 

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The influence of initial hydrogen pressure on hydroconversion of C7-insoluble asphaltene in THAR (Tahe atmospheric residue) was studied by autoclave with decalin as a solvent. The results show that the yield of gas plus gasoline increases, the coke yield decreases when the initial hydrogen pressure increases from 8.0 MPa to 14.0 MPa. The maximum asphaltene conversion and diesel yield and the minimum hydrotreated residue are obtained at 12.0 MPa. The increase of initial hydrogen pressure is beneficial to the conversion of asphaltene, but the exorbitant initial hydrogen pressure has adverse effect to the conversion because the oil-film on catalyst become thicker and is harmful to the diffusion of reactant into catalyst. With the increase of initial hydrogen pressure, the desulfurization rate, denitrification rate, and the molecule weight of hydrotreated asphaltene are decreased, but the change decreases with the increase of hydrogen pressure.

STUDY ON STABILITY OF VACUUM RESIDUE BLENDING COAL TAR AND HYDROCRACKING OF MIXTURE

2014, 45(5):  25-28. 

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The hydro-conversion properties and product distribution of vacuum residue mixed with coal tar were tested by ebullated bed. The spot test and instability parameter test were used to investigate the stability of the mixed oil before and after hydrocracking. The results indicate that the compatibility of vacuum residue is better than the mixed oil before hydrocracking. However, the stability of the hydrotreated blending oil is improved significantly, while the hydrotreated vacuum residue is the opposite. After hydrocracking of the mixed oil with a ratio of 7:3(residue to coal tar), the yield of distillate less than 500 ℃ increases and the coke yield decreases clearly.

SYNTHESIS OF MeAPO-5 MOLECULAR SIEVES AND THEIR CATALYTIC PERFORMANCE FOR CYCLOHEXANE OXIDATION

2014, 45(5):  29-33. 

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Five kinds of MeAPO-5 molecular sieves containing Ce, Fe, Cr, Ti, and Sn, respectively were synthesized by hydrothermal method in the absence of HF. The successful synthesis of the MeAPO-5 molecular sieves was verified by the characterization of X-ray fluorescence spectrometry, N2 adsorption-desorption isotherm, XRD, FT-IR, and NMR of 31P and 27Al. The catalytic performance of the five MeAPO-5 molecular sieves in the cyclohexane oxidization reaction with air was investigated. Using the CeAPO-5molecular sieve, at the reaction conditions: 1.25 MPa and 165 ℃ for 0.5 h, the cyclohexane conversion is 10.9%, and the selectivity for cyclohexanol, cyclohexanone, and cyclohexylhydroperoxide is 40.0%, 29.3%, and 10.2%, respectively, and the total yield of the three products is up to 8.7%, which is evidently the highest among all MeAPO-5 molecular sieves tested, showing the CeAPO-5 molecular sieve is a more proper catalyst for the oxidizing reaction of cyclohexane with air.

COMMERCIAL APPLICATION OF FCC GASOLINE PRE-HYDROTREATING CATALYST GHC-32

2014, 45(5):  34-37. 

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A FCC gasoline pre-hydrotreating catalyst is developed and commercialized. The calibration results demonstrate that the mercaptans content in FCC gasoline is reduced to 2.7 μg/g from 21.6 μg/g, the diene value is lowered to 0.20 gI/(100 g) from 0.64 gI/(100 g) and the olefin content loss is 0.3%. No octane number loss is observed. The results confirm that the pre-hydrotreating catalyst has advantages of high hydrogenation activity and selectivity in minimizing the hydrogenation of olefins.

PREPARATION、CHARACTERIZATION OF UDH MULTIPLE COMPONENT MERCURY-FREE CATALYST AND COMPARISON WITH HgCl2 FOR ACETYLENE HYDROCHLORINATION

Lei Wang Benxian Shen Ruofan Ren Jigang Zhao

2014, 45(5):  38-43. 

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The UDH mercury-free catalyst was prepared in a 10 L synthesis tank and was characterized by ICP-AES, BET, SEM and TEM. The comparison test for acetylene hydrochlorination with an industrial HgCl2 catalyst was conducted in a single pipe reactor under the same experimental conditions. The characterization results show that the UDH mercury-free catalyst has a micropore structure, the pore diameter is 2 nm, and the particle size of active component is 4 nm. The catalytic tests indicate that the VCM selectivity of UDH mercury-free catalyst is more than 99% which equals to that of the industrial HgCl2 catalyst. The C2H2 conversion of industrial HgCl2 catalyst is more than 98% in the first 900 hours, but declines in the following 700 hours; while the C2H2 conversion of UDH mercury-free catalyst reduced slowly from 98% to 89% in the whole 1 600 hours runing, thus the mercury-free catalyst has better stability.

PREPARATION，CHARACTERIZATION AND PROPYLENE EPOXIDATION PERFORMANCE OF TITANIUM SILICALITE

2014, 45(5):  44-49. 

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Titanium silicalite-1(TS-1) molecular sieves with different Si/Ti were hydrothermally synthesized with tetraethyl orthosilicate as Si source, tetrabutyl titanate as Ti source and tetrapropyl ammonium hydroxide as template and modified with organic base. The structure and morphology of TS-1 sieves were characterized by XRD, UV-Vis, FI-IR and SEM. The Si-Ti sieves prepared are proved to have the typical MFI structure. At Ti/Si of 70(TS-1-70), no non-framework anatase is observed. It is found that after treatment with propyl ammonium hydroxide for TS-1-70, hierarchical pores with 2-6 nm meso-pores appear with broad pore size distribution, while still retaining the original MFI topology. The propylene epoxidation with modified TS-1-70 was conducted in a continuous slurry bed reactor. Under the optimal conditions, the catalyst can steadily run for over 160 h with high activity, demonstrating the good stability of the modified catalyst.

SYNTHESIS AND CHARACTERIZATION OF TI-MSU MESOPOROUS MOLECULAR SIEVES AND THEIR CATALYTIC PERFORMANCE

2014, 45(5):  50-53. 

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Ti-MSU molecular sieve catalysts were prepared by hydrothermal synthesis and impregnation method, respectively. The samples were characterized by TG, X-ray diffraction, N2 adsorption-desorption and FT-IR. The epoxidation performance for 1- butylene was studied. The results show that the Ti atom species are the catalyst active component and the activity of Ti-MSU catalyst with 5.5w% Ti by impregnated method is much higher than the hydrothermal one.

SYNTHESIS OF ZSM-5 ZEOLITE FROM DIATOMITE BY HYDROTHERMAL CRYSTALLIZATION METHOD

2014, 45(5):  54-59. 

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ZSM-5 zeolites were synthesized from diatomite by hydrothermal crystallization method. The resulting samples were characterized by X-ray diffraction, FT-IR and scanning electron microscopy. The preparation factors were investigated such as crystallization time and temperature, pH of the synthesis system and the amount of NaAlO2. The results show that the optimal synthesis conditions are: 170 ℃ for 48 h in a solution with a pH value of 13.0 and the amount of NaAlO2 is about 4% of purified diatomite. The possible formation process of the ZSM-5 zeolite from diatomite during the hydrothermal crystallization is put forward based on the XRD and SEM analysis.

EFFECT OF PHOSPHORUS PRETREATMENT ON γ-Al2O3 AND ACTIVITY OF ITS NICKEL PHOSPHIDE HDS CATALYST

2014, 45(5):  60-65. 

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A series of phosphorus modified γ-Al2O3 supports using diammonium phosphate were prepared by incipient wetness impregnation method. The supported nickel phosphide catalysts based on the modified supports were prepared by incipient wetness impregnation followed by in situ H2 reduction. Their hydrodesulfurization (HDS) performance were evaluated in a continuous flow fixed-bed reactor using thiophene as a model molecule. The obtained phosphorus modified supports and catalysts were characterized by XRD, N2 adsorption-desorption and temperature-programmed desorption of ammonia (NH3-TPD). The results show that the surface area of the phosphorus modified γ-Al2O3 first increases and then declines with increasing of phosphorus content. The pore size distribution, surface acidity and acid strength distribution of the γ-Al2O3 can be effectively adjusted by the addition of phosphorus. Pure phase of Ni2P were easily formed on the phosphorus-containing alumina support after in situ H2 reduction. The amount of medium-strong acid, total amount of acid and catalytic activity are maximum when phosphorus content on the modified γ-Al2O3 is 3.6%.

PREPARATION AND PERFORMANCE OF SULFONATED CHARCOAL-BASED SOLID ACID CATALYST FOR SYNTHESIS OF DIBUTYL SEBACATE

2014, 45(5):  66-71. 

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A novel charcoal-based sulfonated solid acid was synthesized through carbonation and then sulfonation of the bamboo charcoal using chlorosulfonic acid. The esterification of sebacic acid and n-butyl alcohol was taken as the model reaction to investigate the impact of preparation parameters on the catalyst activity. Fourier transform infrared spectroscopy（FT-IR）、X-ray diffraction（XRD）、scanning electron microscope（SEM）and thermo gravimetric analysis（TGA）were used to characterize the catalyst. The results show that the charcoal-based solid acid catalyst has amorphous carbon structure and the catalyst prepared at the optimal conditions of carbonization at 325 ℃ for 1h and then sulfonation at room temperature for 2 h with acid-bamboo charcoal ratio of 2.5ml/g exhibits a higher catalytic activity. Its acid group can be reached 1.77 mmol/g. The conversion rate of sebacic acid reached 99.14 % at the following conditions: n-butyl alcohol to sebacic acid mole ratio 3.0, the amount of charcoal-based sulfonated solid acid for 2% of sebacic acid, 3 ml n-butyl alcohol, and reaction time 100min. After repeated use 4 times, sebacic acid conversion rate remains above 80%, indicating the good regeneration performance.

STUDY ON SUPERCRITICAL FLUID EXTRACTION AND PROPERTIES OF NARROW FRACTIONS OF HYDROTREATED RESIDUE

2014, 45(5):  72-76. 

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The feed residue and hydrotreated residue of Qilu VRDS unit were separated by supercritical fluid extraction technology. The extraction information under the same treating conditions, and the properties of narrow fractions from the two residues were analyzed. The results show that hydrotreated residue can be effectively separated by the supercritical fluid extraction technology. The removal rates of metals and Conradson carbon residue and desulfurization rate of hydrotreated residue are all significantly higher than the feedstock residue. The hydrotreated residue is more suitable for solvent deasphalting process to produce deasphalting oil.

OPERATION ANALYSIS OF 3.9 Mt/a RESIDUE HYDROTREATING UNIT

2014, 45(5):  77-82. 

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The calibration results，daily operation data, unit energy consumption，and the problems in operation of 3.9 Mt/a residue hydrotreating unit with RHT series catalysts in Shanghai petrochemical Co. LTD. was introduced. Industrial operation shows that RHT series catalysts have higher HDS, HDCCR, and HDM activity as well as lower deactivation rate and can provide RFCC feedstocks with low sulfur, low carbon and low metal under the reaction conditions of 15.5 MPa in cold high pressure separator and space velocity 0.2 h-1. The mid-term calibration results show that the average removal rates of HDS, HDCCR, and HDM are 89.82%, 65.01%, 86.39% respectively. The unit runs smoothly with lower reaction temperature, less radical temperature difference and pressure drop rising and can meet the requirements for long term operation. The problem is that the two series of residue hydrotreating reactor system cannot reach the ideal hydrogen to oil ratio due to the difficulties to adjust revolutions of circulating hydrogen compressor, which may become the bottleneck for full capacity operation at the end-of-run. Key Words：residue hydrotreating; catalyst; industrial calibration; application

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STUDY ON HYDRO-DEACIDIFICATION OF SZ36-1 THIRD LINE VACUUM DISTILLATE

2014, 45(5):  83-86. 

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A series of Ni-W based catalysts with different NiO content were prepared by incipient wetness method for hydro-deacidification of Suizhong36-1 crude third line vacuum distillate. The effect of operating conditions was investigated. The test results show that the optimum NiO content is around 4.9%. At the conditions of 315℃, 3.2 MPa, hydrogen to oil ratio 300, and volume space velocity 1.5 h-1, the acid value of Suizhong36-1 third line vacuum distillate is reduced to 0.05 mgKOH/g from 3.48 mgKOH/g of feed. A long term stability test for more than 2 000 h is conducted. The results indicate that compared with reference catalyst, the catalyst prepared has a lower cracking degree and is more stable under the moderate conditions.

SPOT TEST OF DEEP TREATMENT OF WASTEWATER FROM COAL-WATER SLURRY GASIFICATION

2014, 45(5):  87-90. 

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The wastewater from coal-water slurry gasification in Jinling Petrochemical Branch, sinopec was deeply treated on-site by sequencing batch reactor process (SBR) with bio-activated sludge. In the case of volumetric loading of COD and ammonia nitrogen is 1.5 times greater than the industrial wastewater treatment system, the treated effluent COD concentration is lower than 60 mg/L, and ammonia nitrogen concentration is lower than 15 mg/L, and the total nitrogen concentration is lower than 20 mg/L, the average conductivity declines to 1 397 μS/cm from 3102μS/cm (55% reduction) when COD of feed is 400?600 mg/L and NH4-nitrogen concentration is 200?260 mg/L. The average effluent conductivity is 989μS/cm when the wastewater mixed with life sewage at a ratio of 1:1 was treated. All the properties of the effluent water meet the refinery water-saving assessment indicators and the requirements for the water reuse.

STUDY ON EFFECT OF TRACE WATER ON PERFORMANCE OF FROZEN PAO

2014, 45(5):  91-93. 

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The amount of trace water in poly alpha-olefin (PAO) was measured by Karl Fischer Coulometric Titration method. The detergent turbidity method，the petroleum products color measurement, infrared, and TGA were used respectively to determine the physical and chemical properties of PAO before and after refrigeration. The frozen PAO’s interface phenomenon was analyzed. No influence on the physical and chemical properties of PAO before and after freezing was observed. The results indicate that the trace water is the main reason for the appearance of PAO after freezing.

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STUDY ON HYDROCARBON COMPOSITIONS OF PARAFFIN IN HYDROCRACKING TAIL OIL BY MASS SPECTROMETRY

2014, 45(5):  94-100. 

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Based on the SH/T 0659 method for analyzing saturate distillate in gas oil and GC-MS technique, a new method was established to measure the total content of normal paraffin, iso-paraffin, and the carbon number distribution of normal paraffin in hydrocracking tail oil. The GC-field ionization time-of-flight high-resolution mass spectrometry (GC-FI TOFMS) was used to calculate the carbon number distribution of the sample and then the carbon number distribution of iso-paraffin. Three hydrocracking tail oil samples at different conversion levels were studied by the new method to investigate the impact of conversion depth on the paraffin structure of tail oil. The results show that n- and iso-paraffin and total paraffin content are increased with the degree of conversion, while the ratio of normal one in total paraffin decreases. The carbon numbers in n-and iso-paraffin as well as in total paraffin are normally distributed. At high conversion level, more low carbon n- and iso-paraffin is in the tail oil, while high carbon paraffin becomes more at lower level.

CHANGES OF GASOLINE GUM DETERMINATION METHOD AND GASOLINE QUALITY

2014, 45(5):  101-104. 

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Based on the composition and properties of gasoline gum, the standard determination method for measuring existent gum，solvent washed gum and unwashed gum were systematically analyzed to find the reasons for the different analysis results of gum content. The changes of quoted standard for gasoline gum test method and the interactions between additives and solvent washed gum were introduced. It is found that the abuse of gasoline additives is the primary reason that causes the superstandard of unwashed gum and abnormal work of engine. The rational and efficient use of additives with lower polarity, less non-hydrocarbon element and lower unwashed gum is the foundation of effective running of engine.