PETROLEUM PROCESSING AND PETROCHEMICALS

OUTLOOK ON GLOBAL REFINING AND TRANSPORTATION FUEL MARKET IN THE FUTURE - A Review of 2010 HART Energy Conference

2010, 41(11): 1-7. doi:

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The highlights presented in the 2010 HART Energy Conference including outlook of global petroleum market, transportation fuel and biofuels market are summarized. It is concluded that the demand for petroleum products is below the production capacity as a result of the exceptional high crude price in 2008 and subsequent recession. However, it is generally believed that the demand for petroleum products in particular transportation fuel will rebound as global economy is recovering and the growth of demand will become evident by 2015. The fuel production capacity will continually increase with the demand from Asia and the Middle East, though eventually, this would lead to overproduction in fuels market. With respect to the trend in the future of product slates, diesel/middle distillates is well regarded as the most important product, while ultra low sulfur gasoline and diesel fuel will become standard. On the other hand, reducing CO2 emission will be the main driving force when developing new fuel requirements and regulations. It is quite certain that the fuels market will be diversified in the future due to limited petroleum resource and need for sustainable growth. Biofuels has great potential to play a more important role in the market. But the development of biofuels still needs to be optimized and will face challenges from some complicated social and economic issues.

ADVANCES ON THE CONTROLLABLE SYNTHESIS OF SAPO-34

2010, 41(11): 8-14. doi:

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SAPO-34 molecular sieve with moderate acidity and characteristic small pore structure exhibits super selectivity to C2-C3 olefins during the conversion of methanol to light olefins (MTO). However, the catalytic performance of SAPO-34 molecular sieve catalyst mainly depends on its physicochemical characteristics, such as pore structure, surface acidity, crystal size and chemical compositions. Thus, a fully understanding of the relationship between physicochemical property and catalytic performance of the catalyst is helpful for an optimum catalyst design. In this paper the effects of physicochemical properties of SAPO-34 on the catalytic performance including activity, selectivity, thermal and hydrothermal stability of the catalyst in MTO process are analyzed, as well as various methods for adjusting the acidity, crystal size, pore structure and chemical compositions of SAPO-34 are summarized.

APPLICATION STUDY OF SFT418 CATALYST FOR FISCHER-TROPSCH SYNTHESIS BY SLURRY BED REACTION SYSTEM

yulin shi

2010, 41(11): 15-21. doi:

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SFT418 catalyst, a Fe-Co-Cu-K-SiO2 catalyst having dual active centers for low temperature Fischer-Tropsch (F-T) synthesis process, was developed by China Shenhua Coal to Liquid and Chemical Beijing Institute. An application performance test of SFT418 catalyst obtained from a commercial trial was carried out on a self-developed pilot plant of F-T synthesis process (CEU) under the commercial operation conditions of indirect coal liquefaction. The CEU evaluation results show that SFT418 catalyst exhibits excellent catalytic performance for F-T synthesis, under the optimized commercial conditions the CO conversion is more than 92% and the selectivity to C3+ hydrocarbons reaches more than 93%, indicating that the catalyst is ready to be used commercially.

PREPARATION OF MODIFIED ATTAPULGITE SUPPORTED Ni-B AMORPHOUS ALLOY CATALYST FOR THE SELECTIVE HYDROGENATION OF MALEIC ANHYDRIDE TO γ-BUTYROLACTONE

XU Jian

2010, 41(11): 22-26. doi:

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A series of sulfuric acid modified attapulgite supported Ni-B amorphous alloy catalysts were prepared by chemical reduction method. The obtained catalysts were characterized by XRD, TEM, XPS and BET. The effect of catalyst preparation conditions and reaction conditions on the selective hydrogenation of maleic anhydride to γ-butyrolactone was investigated. Results showed that over Ni-B/PAL-8 catalyst, under the conditions of a reaction temperature of 200℃, a reaction pressure of 3 MPa and a reaction time of 2 h, the conversion of maleic anhydride reached 100% and the selectivity to γ-butyrolactone was 97.1%. The high activity of Ni-B/PAL-8 catalyst could be attributed to the rod-like and needle-like structure of the sulfuric acid modified attapulgite support and the relatively high surface area of the catalyst.

EFFECT OF THE REDUCTION OF Fe3+ ON THE ACTIVITY OF ACRYLONITRILE CATALYST

Jiang Jiale

2010, 41(11): 27-31. doi:

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XRD, IR and chemical analysis were applied to the investigation of a decline in catalyst activity of an acrylonitrile unit. It was found that an exceeding reduction of the key element Fe3+ in acrylonitrile catalyst and the changes of catalyst structure during the process were the main causes of catalyst deactivation. Lab test results showed that the acrylonitrile yield could be increased significantly by applying ex-situ regeneration of the used catalyst, the acrylonitrile yield of catalyst prior and post to regeneration was 76.11% and 81.62%, respectively. In commercial unit, adopting partial substitution of used catalyst by regenerated catalyst, the acrylonitrile yield of catalyst prior and post to partial substitution was 75.01% and 78.82%, respectively, which indicated that a 3.81 percentages increase of yield was obtained.

SYNTHESIS AND CATALYTIC PERFORMANCE OF Cr-SUBSTITUTED MESOPOROUS ALUMINOPHOSPHATE MOLECULAR SIEVE

Li Xin-zhu Li Xin-zhu

2010, 41(11): 32-36. doi:

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A Cr-substituted mesoporous aluminophosphate molecular sieve (Cr-MAP) was synthesized by hydrothermal crystallization method using cetyltrimethylammonium chloride as templating agent. The obtained Cr-MAP sample was characterized by XRD, N2 adsorption, EPR and etc. to show that the sample was a typical mesoporous molecular sieve, which was short of long-range ordered crystal structure. Results of evaluation indicated that Cr-MAP exhibited excellent catalytic performance for selective oxidation of ethylbenzene with tertbutyl hydroperoxide to acetophenone and the influences of reaction conditions were studied. Under the conditions of using 8 mmol ethylbenzene, 5 mL chlorobenzene as solvent, 16 mmol TBHP as oxidant, over 40 mg Cr-MAP catalyst, a reaction temperature of 100℃ and a reaction time of 8 h, the conversion of ethylbenzene, the selectivity to acetophenone and the yield of acetophenone reached 72.8%, 85.4%, and 62.2%, respectively.

CATALYTIC PERFORMANCE OF Ni/Al2O3 CATALYST ON MERCAPTAN AND ISOPRENE THIOETHERIFATION

SHEN Zhi-Bing

2010, 41(11): 37-42. doi:

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Ni/Al2O3 catalysts were prepared and characterized by XRD and SEM. Under the presence of H2, the catalytic performance of thioetherifying mercaptan and isoprene over Ni/Al2O3 catalyst using model FCC gasoline was studied on a continuous fixed-bed micro reaction system, as well as the effect of reaction conditions and gasoline components on the thioetherifation was investigated. Results showed that Ni/Al2O3 catalyst having a NiO loading amount of 15% exhibited good catalytic performance for thioetherifying mercaptan and diene, using a model FCC gasoline with a mercaptaneous sulfur content of 107.4 μg/g, under the conditions of a reaction pressure of 1.0 MPa, a reaction temperature of 80 ℃, a LHSV of 2.0 h-1 and a H2/oil volume ratio of 300, the mercaptaneous sulfur content of the treated oil reduced to 1.2 μg/g, reaching a mercaptan removal rate of more than 98%. The olefin content of gasoline had little effect on the thioetherifation, yet the presence of aniline and phenolic compounds had significant effect.

LIQUID PHASE SELECTIVE OXIDATION OF CYCLOHEXANE WITH MODIFIED VPO CATALYSTS

SONG Hua

2010, 41(11): 43-47. doi:

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Four vanadium phosphorus oxides (VPO) catalysts modified by Fe, Co, Ni and Bi respectively were prepared and characterized by XRD and SEM. The average oxidation values of vanadium in these catalysts were determined by oxidation-reduction titration. The synthesis of cyclohexanone from cyclohexane using hydrogen peroxide as oxidant over various modified VPO catalysts was carried out in the liquid phase to compare the catalytic performance of these catalysts. Test results showed that the catalytic activities for cyclohexane to cyclohexanone of these catalysts from high to low were in the order of Bi-VPO> Fe-VPO > Ni-VPO> Co-VPO > VPO. Under the conditions of a cyclohexane amount of 0.6 mL, an acetone amount of 10 mL, a Bi-VPO catalyst dosage of 0.015 g, a hydrogen peroxide amount of 3 mL, a reaction temperature of 65℃ and a reaction time of 8 h, the conversion of cyclohexane reached 81.4%, the yields of cyclohexanone and cyclohexanol were 58.2% and 23.2%, respectively.

APPLICATION OF DOMESTIC CCR WHOLE SET TECHNOLOGY IN UNIT REVAMPING

Bin Li

2010, 41(11): 48-52. doi:

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The application of domestic CCR whole set technology in the revamping of the 700 kt/a CCR unit of SINOPEC Luoyang Company was introduced, as well as analyzing the start up of unit, performance test results and existing problems, such as surge of recycle hydrogen compressor, difficulty in catalyst circulation, corrosion in regeneration system and insufficient heat duty of heater. Countermeasures for ensuring the unit running in full capacity steadily were summarized. Final results showed that this revamping was successful, the unit throughput and the qualities of reformate were improved significantly, which could be a reference for the revamping of other similar units.

DEVELOPMENT AND COMMERCIAL TRIAL OF DSO TECHNOLOGY FOR FCC GASOLINE HYDRODESULFURIZATION

2010, 41(11): 53-56. doi:

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A FCC gasoline hydrodesulfurization technology (DSO) was developed by PetroChina Petrochemical Research Institute and its commercial trial was carried out on a 320 kt/a hydrotreating unit of Yumen Refinery successfully. Performance test results showed that the sulfur content of FCC gasoline (having high olefin volume content of 57.5%) was decreased from 320.3 μg/g to 59.3 μg/g, i.e. a sulfur removal rate of 81.3%, and the average RON loss was only 0.7 units. This treated gasoline could be blended with other gasoline components of said refinery to form a gasoline product meeting the requirements of National Standard Ⅳ for clean gasoline (sulfur content less than 50 μg/g).

STEAM CRACKING PERFORMANCE OF FEEDSTOCKS RICH IN NORMAL PARAFFINS GATHERED BY ADSORPTION PROCESS

2010, 41(11): 57-60. doi:

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The ethylene yields of straight-run naphtha, hydrotreated coker naphtha, condensate oil from natural gas and their related desorption oil samples (post to 5A molecular sieve adsorption, rich in normal paraffins) were studied in order to optimize the utilization of cracking feeds and improve the ethylene yield of steam cracking process. The effect of cracking conditions on the cracking performance was also investigated. Under typical industry cracking conditions the ethylene yields of straight-run naphtha, related adsorption raffinate and desorption oil are 29.9%, 23.0% and 41.1%, respectively. It can be seen that the ethylene yield of the desorption oil increases 11.2 percentages as compared with that of naphtha. The total yields of ethylene, propylene and butadiene of desorption oil are 8.4 percentages higher than that of naphtha. For the hydrotreated coker naphtha and the condensate oil, the ethylene yields of their related desorption oils increase 11.1 and 6.5 percentages, respectively. With the increase of cracking temperature, the ethylene and butadiene yields of naphtha and related desorption oil increase notably, yet the propylene yields remain approximately constant.

STUDY ON THE KINETIC MODEL FOR HYDROSATURATION OF AROMATIC HYDROCARBON IN VGO

Zhihai Hu

2010, 41(11): 61-65. doi:

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Based on the reaction characteristics of hydrotreating process, the effect of process conditions on the hydro-saturation of aromatic hydrocarbon in VGO feed was investigated and a basic kinetic equation of aromatic hydrocarbon hydro-saturation was proposed. In order to extend the application of this equation, the effect of various VGO feeds on the activation energy of hydro-saturation reactions was studied and corresponding empirical correlations were obtained. Finally, a better kinetic model for hydro-saturation of aromatic hydrocarbon in VGO was set up, and the validated result showed that the calculated value agreed well with the test datum.

PREPARATION OF METHYL ISOBUTYL CARBINOL BY CATALYTIC HYDROGENATION OF MESITYL OXIDE IN GAS PHASE

2010, 41(11): 66-70. doi:

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The process of preparing methyl isobutyl carbinol by catalytic hydrogenation of mesityl oxide in gas phase over Mn-modified Cu-Zn-Al catalyst was studied. The influence of catalyst compositions and the reaction conditions on the conversion of mesityl oxide and the selectivity to methyl isobutyl carbinol was investigated. The Cu-Zn-Al-Mn catalysts were characterized by XRD, TPR and BET method. Results showed that under the optimum conditions of using a catalyst with Mn mass fraction of 5% and Cu/Zn molar ratio of 1.2, a reaction temperature of 160℃, a H2/mesityl oxide molar ratio of 3.5 and mesityl oxide feeding rate of 90.0 mL/h, the conversion of mesityl oxide reached 99.4% and the selectivity to methyl isobutyl carbinol was 96.6%.

STUDY ON THE PREPARATION OF EMULSIFIED SBS MODIFIED ASPHALT EMULSION

XuChuan-Jie,CAI Hong-mei,Zhang Xiao-Ying

2010, 41(11): 71-75. doi:

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A novel modification agent, emulsified SBS, was developed to prepare modified asphalt emulsion. The effect of emulsifier dosage on the storage stability of modified asphalt emulsion was studied and the results showed that the optimum emulsifier dosage was 1%. By investigating the effect of emulsified SBS dosage on the softening point, ductility and penetration of modified asphalt emulsion, an optimum emulsified SBS dosage of 6% was obtained. It was shown by the analysis results of optical microscope that when the particle size and density of the particles of SBS and asphalt were similar, the SBS particles could be dispersed uniformly in the system. Based on the above optimum dosages of emulsifier and modification agent, a modified asphalt emulsion having excellent performance was prepared.

STUDY ON THE TRIBOLOGICAL BEHAVIORS OF OIL-SOLUBLE DITHIOCARBAMATE MOLYBDENUM AS ADDITIVE IN HYDROGENATED BASE OIL

2010, 41(11): 76-79. doi:

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A oil-soluble dithiocarbamate molybdenum (MoDTC) was synthesized in lab and its tribological behaviors as additive in hydrogenated base oil (HVIH 6) and in self-owned additive package of API SL gasoline engine oil prior and post to oxidation were evaluated, using four-ball tester，SRV tester and PDSC method. Results indicated that MoDTC additive exhibited certain antiwear performance in HVIH 6 base stock and good extreme anti-friction performance in API SL gasoline engine oil. However, it was found that said additive was easy to be oxidized during service and thus lead to the decrease of anti-friction performance.

THE APPLICATION OF NANOPARTICLES IN COLD ROLLING EMULSION FOR STEEL STRIP

WANG Yi-Zhu

2010, 41(11): 80-84. doi:

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In the presence of ultrasonic, Fe3O4 nano-particles having an average particle size of 20 nm and modified with oleic acid, were dispersed in an emulsion, which was a selected base oil compounded with appropriate additives, such as surfactants, rust inhibitors and defoamers. The tribological properties of the newly developed cold-rolling emulsion containing nano-Fe3O4 were evaluated using MRS-10A four-ball test machine. The worn surfaces of the steel balls were investigated by optical microscope. Besides, the lubricity of this cold-rolling emulsion was evaluated on a cold-rolling tester using conventional emulsion as reference. Results indicate that Fe3O4 nano-particles as additive in cold-rolling emulsion could significantly improve the friction-reducing, anti-wear and surface quality of the friction pair. The new emulsion containing nano-Fe3O4 shows good lubricity performance during cold-rolling steel strips, the surface quality of the rolled strip is improved, and at the same time, the rolling force and energy parameters are decreased.

TECHNICAL ANALYSIS OF ENERGY SAVING AND CONSUMPTION REDUCTION OF A DIESEL FUEL HYDRO-UPGRADING UNIT

2010, 41(11): 85-88. doi:

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The basic status and energy consumption of the diesel fuel hydro-upgrading unit of Jinxi Petrochemical Company was introduced. A series of energy-saving measures related with furnace, pump and the recovery of low-temperature heat were applied to solve the existed problems in production, since then the energy consumption of the unit was reduced significantly.

EXPERIMENTAL STUDY ON THE DESULFURIZATION OF OIL PRODUCTS BY CELL ENGINEERING BACTERIA

Suo-Qi ZHAO

2010, 41(11): 89-92. doi:

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Biodesulfurization experiments were carried out to compare the sulfur removal rates of various oil products using cell engineering bacteria obtained by inter-kingdom protoplast fusion. Test results show that benzothiophene, dibenzothiophene, 4,6-dimethyl dibenzothiophene and diphenyl sulfide can be degradated by cell engineering bacteria simultaneously. Organic sulfur containing compounds in various oil products can be removed by cell engineering bacteria directly, especially, the removal of residue sulfur containing compounds in hydrotreated oil products was significant.

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