Table of Content

12 February 2012, Volume 43 Issue 2

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A STUDY OF THE HYDROCARBON COMPOSITION AND CATALYTIC CRACKING PERFORMANCE OF DIFFERENT VGO

2012, 43(2):  1-8. 

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Three VGO samples from different base of crude oil and processing mode were selected as feedstocks to study their catalytic cracking performance by a fixed fluidized bed device (ACE). The hydrocarbon compositions of feedstocks and their cracked products were determined by GC/MS. Test results were analyzed by using conversions with two definitions (221 conversion and 20+ conversion). Results show that the conversion of VGO feedstock mainly depends on its intrinsic properties and hydrocarbon compositions. However, using 20+ conversion to express the essential distinctions of selectivities to cracked products among various VGO feedstocks is rather better than using traditional 221 conversion. Due to the difference in product distributions and compositions of these VGO feedstocks, suitable product scheme for individual VGO feedstock should be varied.

AN INVESTIGATION ON THE REGENERATION OF ADSORBENT FOR REMOVING SOx & NOx IN FCC FLUE GAS

2012, 43(2):  9-14. 

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The adsorbing behaviors of SO2 and NOx over a solid adsorbent, the regeneration performance of spent adsorbent in the presence of hydrogen, and the hydrogen reduction of SO2 and NO in gas phase were studied by a continuous micro fluidized fixed-bed reactor. Results showed that SO2 and NOx interacted with the adsorbent through chemical adsorption under atmospheric pressure and 200℃. Under atmospheric pressure and 600℃, 12 % of SO2 and 14 % of NOx (based on the adsorbed amount) were released from unstable salts. The adsorption capability of the loaded adsorbent could be recovered under the conditions of atmospheric pressure, a reaction temperature of 600℃ and a reaction time of not less than 20 min. Under atmospheric pressure, the temperatures of complete conversion of SO2 and NO in gas phase were less than 500℃ when the excesses of hydrogen were 3 and 8 times over the stoichiometric ratio to SO2 and NO, respectively.

SYNTHESIS AND ANTI-WEAR PERFORMANCE OF MONOGLYCERIDES CATALYZED BY IONIC LIQUID

2012, 43(2):  15-18. 

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The synthesis of monoglycerides from fatty acids and glycerol catalyzed by self-made ionic liquid was investigated using 1,4-dioxane as solvent. The optimal process conditions were obtained by single factor experiments as follows: glycerin/ fatty acids molar ratio of 7, the amount of catalyst and solvent (based on the total materials) was 8% and 50%, respectively, reaction temperature in the range of 140—150℃ and a reaction time of 3 h. The abrasion resistance of monoglycerides was evaluated, and the results showed that when low sulfur diesel fuel containing 80 μg/g monoglycerides, it could meet the abrasion resistance requirement of EN 590 Standard for automobile diesel fuel in Europe.

IMPACT OF METAL PORPHYRINS IN HEAVY OIL ON CATALYTIC CRACKING

2012, 43(2):  19-27. 

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To study the impact of metalloporphyrins on the product distribution and catalyst performance in catalytic cracking process, nickel and vanadium porphyrins were separated from Venezuela 380 heavy oil and Yichang pipeline oil residue, and then added into feedstock with various proportions. The evaluation tests were conducted in a fixed fluidized bed device and the results showed that with the increase of nickel and vanadium porphyrins in heavy oil, the yields of gasoline and diesel fractions decreased significantly, at the same time, the yields of dry gas and coke increased. The selectivity to light oil trend to degrade, and the impact of nickel porphyrin seemed to be more significant. The relative crystallinity of the catalyst decreased due to the presence of nickel and vanadium porphyrins, in which the effect of vanadium porphyrin was greater. However, vanadium porphyrin exhibited negative impact on the activity of regenerated catalyst in someway while nickel porphyrin showed little.

ISOLATION OF AN ALKANE-DEGRADATION BACTERIUM AND STUDY ON ITS DEGRADATION PERFORMANCE AND KINETICS

2012, 43(2):  28-32. 

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A high effective alkane-degradation bacterial strain C18 was isolated from oil-contaminated soil of a refinery, and it was identified as Pseudomonas plecoglossicida based on its morphological feature, biochemical & physiological characteristics and partial 16S sDNA sequence analysis. The ability of degrading n-hexadecane/diesel and growth kinetics of said strain were studied by shaking flask tests. It was found that the optimum conditions for the growth of strain C18 were under 30-37 ℃, system pH=7 and containing 1% NaCl. Even at pH=6-9 and system containing 5% NaCl, its ability to degrade n-hexadecane was still high. The growth kinetics research showed that when the concentration of n-hexadecane was 10-300 mg/L under optimum conditions, Michaelis equation could be acquired by calculation with being 15.22 mg/L and being 11.22 mg/(L·h). Under a diesel concentration of 3 000 mg/L, dominant bacterial strain C18 not only could degrade n-alkanes in diesel fuel effectively, but also could well degrade the cyclanes and aromatic hydrocarbons in diesel fuel within 60 h.

EXPERIMENTAL STUDY ON REMOVING ORGANIC SULFIDE IN REFINERY C4 FRACTION BY SOLVENT EXTRACTION

2012, 43(2):  33-37. 

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Using C4 fraction from PetroChina Lanzhou Petrochemical Company as raw material, desulfurization tests by solvent extraction were carried out to select optimum desulfurization agent and method, as well as to study the process conditions and agent regeneration conditions. Results showed that SW-I was the optimum desulfurization agent, which had a C4 fraction solubility of 6.53×10-5 g/g only. By comparing liquid-liquid extraction method and gas-liquid absorption method, it was shown that gas-liquid absorption method was more suitable. When adopting 3-stage gas-liquid absorption method and SW-I desulfurization agent, under a reaction temperature of 20 ℃, an extractant space velocity of 0.15 h-1 and C4 fraction space velocity of 350 h-1, the sulfur content of treated C4 fraction dropped from 198.9 μg/g to 7.5 μg/g with a desulfurization rate of 96.23%. The sulfur-rich absorption agent could be regenerated by hot air stripping. When regeneration temperature was 70 ℃, solvent space velocity was 1.02 h-1 and hot air space velocity was 291 h-1, the desulfurization rate of regenerated agent was 96.03%, indicating that the regeneration rate of the desulfurization agent reached 99.80%.

A PRELIMINARY STUDY ON THE TECHNOLOGY OPTIONS FOR UPGRADING THE QUALITY OF DIESEL FUEL

2012, 43(2):  38-40. 

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In order to meet the needs of upgrading diesel fuel quality, based on analyzing the makeup and properties of hydrotreating feedstocks in Tianjin Petrochemical Corporation, considering the present status of hydrotreating units and integrating optimization of hydrotreating feedstocks, three technical options to upgrade the quality of diesel fuel were proposed. By comparing these options from the technical and economic aspects and based on the total investment plan of construction, technical option with establishing a 1.8 Mt/a hydrotreating unit for treating poor quality feedstocks mainly was chosen, which could be used to produce clean diesel fuel meeting the requirements of National Emission Standard IV and V.

A SELECTION OF LOW POISONOUS SOLVENT FOR DETERMINING POTENTIAL CONTENT OF LUBRICATING OIL

2012, 43(2):  41-45. 

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An investigation of selecting less poisonous dewaxing solvent (butanone/toluene) to substitute the conventional dewaxing solvent (acetone/benzene/toluene), which is more volatile and poisonous, in the determination of lubricating oil potential content (RIPP9-90) was carried out. A suitable proportion of butanone to toluene was obtained based on the variation of dewaxed oil yield with the mixed solvent composition. The dewaxing processes of VGO samples from various crude oils using this less poisonous solvent and the conventional one were conducted and qualities of these obtained dewaxed oil samples were compared. It was found that their properties and compositions (by mass spectrometry) were very close. Therefore, in the determination of lubricating oil potential content (RIPP9-90), the conventional dewaxing solvent could be substituted by this less poisonous one with butanone/toluene volume ratio of 60:40.

STUDY ON THE CATALYTIC DISTILLATION PROCESS FOR ALKYLATION DESULFURIZATION OF FCC GASOLINE

2012, 43(2):  46-50. 

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Sulfur containing compounds in FCC gasoline could be removed by alkylation with olefins and then enriched in the heavy fraction by distillation. Based on the reaction conditions obtained in laboratory research, catalytic distillation process for alkylation desulfurization of FCC gasoline was investigated by using catalytic distillation tower. Test results showed that with resin catalyst, under atmospheric pressure, bottom feeding mode, reflux mass ratio of 2.0, reaction temperature in the range of 96-117 ℃, test results of 2 016 h continuous operation showed that the sulfur content of gasoline at the top of the tower was in the range of 30－40 μg/g with an average desulfurization rate of 91.14%, the performance of the catalyst was stable.

COMMERCIAL APPLICATION OF ADSORBENT FOR PURIFICATION OF HYDROGEN IN TAIL GAS FROM METHYL ETHYL KETONE UNIT

2012, 43(2):  51-53. 

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QMS-01 adsorbent for removing methyl ethyl ketone and sec-butyl alcohol from hydrogen were developed and used for the purification of hydrogen in tail gas from methyl ethyl ketone unit. The commercial application results showed that using QMS-01 adsorbent, under appropriate conditions of tail gas space velocity in the range of 90-100 h－1, reaction pressure in the range of 2.4-3.0 MPa and reaction temperature in the range of 5-10 ℃, the mass fraction of methyl ethyl ketone and sec-butyl alcohol in the tail gas could be both less than 1 μg/g. The purified hydrogen could well meet the requirements of hydrogen for hydrogenation processes, and the adsorbent could be regenerated having a service life of about 3-5 years.

COMMERCIAL APPLICATION OF HIGH-EFFICIENCY PROPYLENE ADDITIVE KHP IN A RFCC UNIT

2012, 43(2):  54-57. 

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KHP additive produced by a domestic company was an additive to enhance propylene yield in FCC process. The application of KHP propylene additive was carried out in a 3.5 Mt/a RFCC unit of PetroChina Guangxi Petrochemical Company. Test results showed that when the amount of KHP additive in the total catalyst inventory reached 5.8 %, the yields of propylene and LPG increased 1.66 and 3.08 percentage points, respectively; meanwhile, the yields of gasoline and LCO dropped 1.75 and 1.53 percentage points, respectively. The overall light products yield remained basically unchanged. The RON of gasoline increased by 0.5 units with no significant changes observed in other gasoline properties. KHP high-efficiency propylene additive demonstrated good compatibility with the primary catalyst LDO-75 during the test.

STRUCTURE DETERMINATION OF SRM-2 MOLECULAR SIEVE FROM POWDER X-RAY DIFFRACTION DATA

2012, 43(2):  58-60. 

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Based on high resolution experimental X-ray powder diffraction spectra of SRM-2 molecular sieve, the patterns of its polycrystalline structure were indexed, analyzed and simulated by molecular structure analysis software, which provided important information on its crystal structure, such as space group, and crystal lattice parameters. From the known crystal structure parameters, an approximate structure was first assembled and refined with Rietveld method subsequently. Results show that in SRM-2 molecular sieve, α cage is consisted of 48 framework atoms (twelve 4-membered rings, eight 6-membered rings and six 8-membered rings) and α cages are connected by double 8-membered rings with pore diameter of 0.419 nm. The crystal structure of SRM-2 molecular sieve belongs to cubic crystal system, 123 space groups. Its unit cell parameters are a = b = c = 1.511 1 nm，∠ =∠ =∠ = 90.00°.

INDUSTRIAL APPLICATION OF THE SECOND GENERATION RHT SERIES CATALYSTS FOR RESID HYDROTREATING

2012, 43(2):  61-64. 

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Industrial application of the second generation RHT series residue hydrotreating catalysts developed by Research Institute of Petroleum Processing was carried out at the 3.1 Mt/a RDS unit of SINOPEC Hainan Company for FCC feedstock pretreatment. The operation results showed that this new generation RHT series catalysts exhibited high hydrordesulfurization activity and good performance of removing carbon residue in feedstocks, especially during the mid and late operation period as compared with imported catalysts. The operation period of this new generation RHT series catalysts was prolonged for more than two months due to the good stabilities of catalysts.

STUDY ON THE AROMATIZATION PERFORMANCE OF Ga/HZSM-5 CATALYST

2012, 43(2):  65-70. 

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Ga/HZSM-5 catalysts were prepared using nano-scale HZSM-5 hydrothermally treated under various temperatures as base materials. The aromatization performances of Ga/HZSM-5 catalysts were investigated using full rang FCC gasoline as feed. Results showed that Ga/HZSM-5 catalyst prepared with nano-HZSM-5 hydrothermally treated under 600 ℃ followed by HNO3 washing exhibited the best aromatization performance: under a reaction temperature of 480 ℃ and WHSV of 1 h-1，the volume fraction of aromatics and (C3+C4 ) in the product was 58.3% and 7.6%, respectively. When a second metal, such as Fe, Cu and Cr, was introduced into Ga/HZSM-5 catalyst, without positive effect on its aromatization performance was observed under the testing conditions.

PREPARATION OF POLYUREA GREASE BY PREMADE THICKENER METHOD

2012, 43(2):  71-75. 

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In conventional production process of urea-based grease, direct reaction between amines and isocyanates in the base oil is a required step. However, the toxicity of isocyanates poses as a significant challenge for industrial safety. In this paper, a new route of producing polyurea based grease was studied through a two step method. The first step is to prepare polyurea thickener through reacting organic amines and isocyanates in selected organic solvent systems. The obtained thickener was then dried and can be used to prepare polyurea grease. The structure and toxicity of the premade thickener was analyzed by IR, and the results showed that this thickener having the typical structure of polyurea thickener was nontoxic. Polyurea grease prepared with this premade thickener had high drop point and exhibited good colloid stability, as well as thermal and oxidation stability, with low leakage and corrosion when use in bearing.

STUDY ON THE REGENERATION OF WASTE LUBRICATING OILS BASED ON SOLVENT REFINING WITH FOUR CARBON ALCOHOLS

2012, 43(2):  76-80. 

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Solvent refining is not only an environmental-friendly process but also one of the cheapest and most efficient processes for waste lubricating oils recycling. In this work, single factor experimental design was adopted, four carbon alcohols were used as polar extraction solvents, polyacrylamide (PAM) was used as flocculant to regenerate waste lubricating oil. The optimal process conditions were obtained as follows: using isobutyl alcohol as extraction solvent, a solvent/oil mass ratio of 5, a PAM amount of 1.0%, a refining time of 15 min and refining temperature of 25℃ (room temperature). The yield of the recovered oil under such conditions was 82.1%, some of the physicochemical properties of this recovered oil were improved significantly, such as viscosity index reached more than 130, the flash point was over 200℃, the content of carbon residue was less than 0.01% and the acid number was 0.01 mgKOH/g, which indicated that this technology for waste lubricating oil recycling is feasible and may have a promising application future.

ENERGY CONSUMPTION ANALYSIS AND ENERGY SAVING MEASURES OF 3.2 Mt/a HYTROTREATING UNIT

2012, 43(2):  81-86. 

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An energy consumption analysis of the 3.20 Mt/a hydrotreating unit in Qingdao Refining ＆ Chemical Company was carried out based on the unit performance test data (under full capacity). Some energy saving measures were proposed based on the production status of the plant. Through adopting advanced technology, optimizing operation conditions, implementing technical renovation and enhancing management, the energy consumption of the plant was reduced significantly, in 2010 the energy consumption of the plant reached as low as 198.13 MJ/t, which is the new record of low energy consumption within the same type of units in Sinopec. It also provides energy saving thoughts for new unit design and existing unit revamping.

APPLICATION OF ENERGY NETWORK DIAGRAM IN A LARGE SCALE REFINING & PETROCHEMICAL PROJECT

Kefeng Hou

2012, 43(2):  87-91. 

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It is an effective tool and method to use energy balance table and energy network diagram to assess a project in energy efficiency. A case study of adopting energy network diagram in the energy assessment for a large scale refining and petrochemical project was carried out, and some pertinence analysis and theoretical discussion were given taking into account the project characters. Finally, the scientific rationality of energy utilization in this project was assessed.

DEVIATION IN NEAR-INFRARED ONLINE BLENDING OF GASOLINE AND COUNTER MEASURES

2012, 43(2):  92-96. 

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The application of near-infrared online automatic blending system (BRC, BPC) in gasoline blending at Hainan Refining & Chemical Company is briefly introduced focusing on analyzing some cases that blending deviation occurred by operating with BRC or BPC, and counter measures are proposed. Since these counter measures are realized, the deviations of gasoline blending reduce significantly, and the utilization of high octane blending components is more effective, resulting in a better economic benefit.

PROGRESS IN COKE INHIBITION STUDY OF ETHYLENE CRACKER

2012, 43(2):  97-103. 

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In this review article, three major coke formation mechanisms in ethylene cracking furnace are introduced briefly, and then the key influencing factors on coke formation are discussed. Based on the discussion, a number of methods and new technology developed in recent years worldwide to suppress coke formation in the cracking process are summarized in detail, including optimization of feedstock and process conditions, use of coke inhibitive additives, surface pretreatment of furnace tube, advances in new alloy for tubes and technologies for enhanced heat transfer. However, it seems that using coke inhibitive additives in cracking system is easy to be realized in commercial unit, and with the development of high temperature coating technologies, pretreatment of tube surface becomes promising.