Table of Content

12 January 2013, Volume 44 Issue 1

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OUTLOOK OF AROMATICS PRODUCTION TECHNOLOGY

2013, 44(1):  1-10. 

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The recent technology improvements worldwide for aromatics production are reviewed such as various aromatics separation, aromatics formation processes, toluene disproportionation and transalkylation, alkylation of methyl group, as well as combination of processes to maximize aromatics production. Following the analysis, the recent technology advances and innovations for aromatics production can be summarized as follows: 1) improvement of catalysts and adsorbents; 2) development and application of new reaction and separation processes; 3) implementation of combined process solution; 4) enhancement of energy and material utilization efficiency and 5) economy of scale. Then, recommendations to expedite the development of technology for entire aromatics complex with proprietary intellectual property and features like flexible feedstock, easy switch of product slate and lower consumption are presented. In order to face the challenge of feedstock shortage, aromatization technology of light hydrocarbons (LPG, light olefins and raffinate oil) should be developed. Finally, additional ideas for further increase of aromatics production are proposed, such as highly integration of refining-petrochemical-ethylene units for better utilization of feedstocks including FCC LCO, pyrolysis heavy gasoline components, heavy aromatics and coal tar oil for BTX production; integrating aromatics complex with coal chemical plant; and developing technology using unconventional feedstock, e.g. methanol, cellulose and so on.

DEVELOPMENT AND COMMERCIAL APPLICATION OF THE THIRD GENERATION CATALYSTS FOR RESID HYDROTREATING

2013, 44(1):  11-15. 

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By optimizing the relations between activity and stability, diffusion and reactivity, cost and performance, a 3rd generation catalyst series for resid hydrotreating was developed by Research Institute of Petroleum Processing. Comparing with the 2nd generation RHT series of catalysts, this new series of catalysts exhibited an overall improvement in HDS, HDM and HDCCR performance, as well as much better stability for long-term running. The commercial results demonstrated that the new series of catalysts perform better than the reference catalyst series. Thus, it is helpful to increase the total economic benefit of the combined process of resid hydrotreating and catalytic cracking.

SYNTHESIS OF SAPO-5 MOLECULAR SIEVE HAVING HIERARCHICAL PORE STRUCTURE AND ITS APPLICATION IN HYDROREFINING CATALYST FOR DIESEL FUEL

2013, 44(1):  16-21. 

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SAPO-5 molecular sieve having hierarchical pore structure (HI-SAPO-5) was synthesized by one-step hydrothermal crystallization method using 3-(trimethoxysilyl) propyl hexadecyldimethyl ammonium chloride (TPHAC) as mesopore directing surfactant. Samples were analyzed by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption-desorption and pyridine-adsorbed infrared (Py-IR). Characterization results showed that pure HI-SAPO-5 molecular sieve was obtained by introducing THPAC into the synthesis system of normal SAPO-5 molecular sieve (N-SAPO-5). Compared with N-SAPO-5 molecular sieve, HI-SAPO-5 molecular sieve possessed much higher external specific surface area, larger mesopore volume, more suitable acid amount and acid strength. As a result, these advantages were in favor of the mass transfer and conversion of bulky sulfur compounds and polyaromatic hydrocarbons. Evaluation results showed that when coker gas oil was hydrotreated over catalyst containing HI-SAPO-5 molecular sieve, improved hydrodesulfurization, hydrodenitrogenation and hydrodearomatization performance were exhibited. The mass fractions of sulfur and above two-ring aromatic hydrocarbons in the treated oil were 8 μg/g and 1.1 %, respectively.

EFFECT OF BASIC METAL ADDITIVES ON Cu-Fe CATALYST WITH BIMODAL PORE SUPPORT FOR HIGHER ALCOHOLS SYNTHESIS

2013, 44(1):  22-27. 

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Cu-Fe bimodal pore catalysts modified with basic metal additives for higher alcohols synthesis (HAS) were prepared by an ultrasonic impregnation method. The study was undertaken to investigate the effects of various basic metal additives on the microstructures and HAS performances of catalysts. Several techniques, including N2 physical adsorption, temperature programmed reduction of hydrogen, X-ray diffraction and X-ray photoelectron spectroscopy, were combined to characterize these catalysts. The characterization results indicated that bimodal pore support was formed with the addition of small pore silica sol into the macroporous silica gel. Adding additives containing Ca and Li into Cu-Fe bimodal catalyst increased the amount of CuO and decreased that of Fe2O3 on the surface layer of the catalyst, which could weaken the interaction of Cu-Fe-O and promote the formation of methanol. The addition of Na and K additives increased the amounts of copper and iron species on the surface layer, enhancing the synergistic effect of Cu-Fe and improving the HAS activity and selectivity of C2+OH. Among these four basic metal additives, catalyst with K additive exhibited the best activity and space time yield of higher alcohols.

STUDY ON THE PROCESS CONDITIONS OF FURFURAL HYDROGENATION CATALYZED BY NANOMETER CUPRIC HYDROXIDE

2013, 44(1):  28-30. 

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Studing the optimized nanometer cupric hydroxide catalyst on the reaction of synthesis furfuryl alcohol from furfural hydrogenation, discussing the effects of temperature, reactor, catalyst dosage and reaction time on the resultant of reaction, The conversion rate and selectivity were tested by gas chromatography, The optimum reaction conditions were temperature 200℃, pressure 6MPa, 200g of catalyst loading dose ( furfural / g catalyst . H ) , 3h of reaction time.Through the spectrum analysis and calculation, furfuryl alcohol conversion rate had reached 97%, the selectivity was 96.6%.

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COMMERCIAL APPLICATION OF FHUDS-2 CATALYST IN HYDROTREATING UNIT PROCESSING COKER GAS OIL AND COKER NAPHTHA

2013, 44(1):  31-35. 

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The application of FHUDS-2 catalyst in hydrotreating unit processing coker gas oil mixed with coker naphtha at Lanzhou Petrochemical Company was introduced. The operation results showed that the hydrodesulphurization activity of FHUDS-2 catalyst was better than that of the imported catalyst in the base case. Using FHUDS-2 catalyst under the operation conditions of a processing capacity of 75 t/h, reactor inlet temperature of 300 ℃, a purity of recycle hydrogen over 86% and coker naphtha of the mixed feed in the range of 10%—20%, the sulfur removal rate reached 92%—95%. The sulfur mass fraction of the treated diesel fuel was less than 0.035%, which could meet the requirement of National Emission Standard III for automobile diesel fuels.

STUDY ON KINETIC MODELS FOR HYDRODESULFURIZATION OF JET FUEL

2013, 44(1):  36-40. 

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Various jet fuels were hydrotreated over novel catalyst RSS-2 on a 30 mL fixed bed reactor to obtain sulfur contents of products under different reaction conditions. Based on these data kinetic parameters were calculated and a kinetic model for low pressure hydrodesulfurization reaction of jet fuel was established and validated. Results show that this hydrodesulfurization reaction model is close to piston flow reaction model with an apparent reaction order of 1.1. Under the testing conditions, the influence of reaction pressure and H2/oil ratio on the hydrodesulfurization reaction is a little, the order of reaction is 0.273 and 0.375, respectively. The influence of reaction temperature on hydrodesulfurization reaction can be expressed by Arrhenius equation with activation energy of 114.5 kJ/mol. This kinetic model can be used to predict the sulfur content of product under given conditions and it is useful as reference for refinery to adjust operation parameters.

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CHARACTERIZATIONS OF NITROGEN COMPOUNDS IN COKER GAS OIL AND STRAIGHT RUN DIESEL OIL

2013, 44(1):  41-45. 

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Nitrogen compounds were extracted from coker gas oil and straight run diesel oil by chromatography with neutral silica adsorption column. Then the nitrogen compounds were concentrated and separated into basic and non-basic types using acid-modified silica column. The identification of nitrogen compounds in the extracts was performed by gas chromatography-mass spectrometer (GC-MS) and gas chromatography-nitrogen chemiluminescence detection (GC-NCD), as well as verification of peak assignments with those reported by others. Results showed that in straight-run diesel, neutral nitrogen compounds, mainly benzocarbazole nitrogen compounds, occupied more than 70% (mass fraction) of the total nitrogen compounds; in coker gas oil, nitrogen compounds including pyridine, aniline, indole, quinoline, and carbazole were found, and the mass fraction of total neutral nitrogen compounds was slightly over that of basic nitrogen compounds occupied more than 50% of the total nitrogen compounds.

STUDY ON THE DELAYED COKING OF RESIDUE OIL WITH WASTE ROAD ASPHALT

2013, 44(1):  46-50. 

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The coking of a mixture containing residue oil and waste road asphalt was calculated by a delayed coking kinetic model built by structure oriented lumping method, and the results showed that waste road asphalt could be used as a blending material for delayed coking. Experimental results indicated that under the operating conditions of 470 ℃, 0.15 MPa and without recycle, as compared with the 80% yields of total residue oil coking, for coking of this residue oil mixed with 20% waste road asphalt, the yield increase of gas, liquid and coke was 2.30, 2.91 and 14.79 percentage point, respectively. By comparing products properties and economic estimation, it was confirmed that waste road asphalt as delayed coking blending material could be a new approach for its recycling.

VAPOR-PHASE SYNTHESIS OF N-METHYL-2-PYRROLIDONE CATALYZED BY ZSM-5 ZEOLITE

2013, 44(1):  51-55. 

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A process for vapor-phase synthesis of N-mehtyl-2-pyrrolidone (NMP) from γ-butyrolactone (GBL) and aqueous methylamine over ZSM-5 molecular sieve was studied. The effects of liquid hourly space velocity (LHSV), reaction temperature, silica to alumina ratio of ZSM-5 molecular sieve and molar ratios of raw materials on the yield of NMP were investigated. Test results showed that using ZSM-5 molecular sieve catalyst with silica to alumina ratio of 120, under the conditions of molar ratios of methylamine: GBL: water was optimized to 1.5: 1.0: 30, LHSV of 0.5 h-1, under atmospheric pressure and a reaction temperature of 300 ℃, the yield of NMP could reach about 99%.

COMMERCIAL TRIAL OF CPP COMPLETE TECHNOLOGY FOR PRODUCING LIGHT OLEFINS FROM HEAVY FEEDSTOCK

2013, 44(1):  56-59. 

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The first commercial unit worldwide of heavy feed catalytic pyrolysis process (CPP) was set up and put into operation in June 2009 at Shenyang Chemical Group Shenyang Paraffin and Chemical Company with a capacity of 500 kt/a. This unit is designed for processing paraffinic atmospheric residue feedstock to obtain main products, ethylene and propylene, with cracked naphtha having high light aromatics as by-product. The results of performance test show that using Daqing atmospheric residue feedstock, under ethylene plus propylene operation mode, at a reaction temperature of 610℃ and without recycle of ethane and propane, the yields of ethylene and propylene reach 14.84% and 22.21%, respectively; the aromatics mass fraction of cracked naphtha is 82.46%, which all well meet the design targets. The successful running of this unit opens a novel light olefins and aromatics production route from heavy feedstock, which is also a good example of refining and petrochemical integration.

MEASURES FOR UPGRADING THE PROCESSING CAPACITY OF S ZORB UNIT

2013, 44(1):  60-64. 

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The main causes of lower processing capacity than the design value of the 900 kt/a S Zorb unit in SINOPEC Jinan Company were analyzed and counter measures were discussed. Since adopting measures, such as adding another feed filter, cleaning heat exchanger of feed, increase the riser outlet temperature of FCC unit, increase the direct feed supply temperature from FCC unit to S Zorb unit, adjusting the cycle rate of sorbent and frequency of regeneration, using heavy gas as fuel of heating furnace, reducing the reaction temperature and using high-purity hydrogen, the processing capacity of said S Zorb unit has an increment of about 11 t/h and the gasoline product also well meets the requirement of National Emission Standard III.

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OPTIMIZING THE UTILIZATION OF RAW MATERIALS FOR STEAM CRACKING TO ETHYLENE WITH THE ADVANTAGE OF REFINING-CHEMICAL INTEGRATION

2013, 44(1):  65-70. 

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The optimization of raw materials for steam cracking to ethylene with the advantage of refining-chemical integration at Zhenghai Refining & Chemical Company was introduced, focusing on expanding the raw material resources. The advantages of using light feedstock for ethylene production were discussed and feasible scheme of producing appropriate blending components for steam cracking and reforming were proposed. Since optimization, the ratio of light naphtha in ethylene feedstock reduced, gaseous feeds and high quality hydrocracked tail oil increased, thus the mass fraction of paraffin in ethylene feedstock increased 1.8 percentage points. About 15%—25% of low value products were converted to high value products in the refinery.

AN ANALYSIS OF A HYDROCRACKING UNIT PROCESSING HIGH SULFUR WAX OIL

2013, 44(1):  71-75. 

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In this paper, the operation status of the 1.4 Mt/a hydrocracking unit at Sinopec Shanghai Gaoqiao Company is discussed including matters occurred and might happen. The effect of processing high sulfur feed on the process conditions, equipment corrosion and product quality is analyzed, so that, some suggestions for maintaining long-term production are put forward. It can be seen that with appropriate revamping, this unit could process feed having sulfur mass fraction below 1.96%, yet it should avoid processing high sulfur and high acid feeds heavily, optimization of feed constitution is appreciated. Monitoring the corrosion of pipeline and equipment should be carried on routinely. When processing high sulfur feed, the sulfur content of tail oil should be checked more often to provide reference data for increasing the temperature of post treating catalyst.

PERFORMANCE EVALUATION AND POTENTIAL ANALYSIS OF A 3.2 Mt/a HYDROTREATING UNIT AFTER LONG TERM RUNNING

2013, 44(1):  76-79. 

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A 3.2Mt/a hydrotreating unit after a long running cycle was evaluated. The operation performance of this running cycle was summarized and some suggestions were proposed. During this 1st running cycle, the average deactivation rate of catalyst was 0.026 ℃/d, the average rising rate of pressure drop in the 1st stage of reactor was 9.9×10-5 MPa/d and the scale resistance in the high pressure heat exchanger reached 1.2×10-3 m2.K/W by the end of this operation cycle. Based on the above data and the predicted values of catalyst service life, the rising rate of pressure drop in reactor, as well as the fouling in high pressure heat exchanger calculated by the modified deactivation model, it can say comprehensively that the next running cycle could be 1 417 days.

COMMERCIAL APPLICATION OF RSDS-II TECHNOLOGY FOR PRODUCING GASOLINE MEETING NATIONAL Ⅲ AND Ⅳ EMISSION STANDARD

2013, 44(1):  80-82. 

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The commercial application of RSDS-II technology in Sinopec Qingdao Petrochemical Company is introduced. Results show that the sulfur content of the treated catalytic cracking gasoline can be dropped to less than 150 μg/g, which meets the requirement of National Emission Standard III, and it can even be less than 50 μg/g, which meets the requirement of National Emission Standard IV. In addition, the RON loss of the product is only a little. It is shown from the data of long term running, the product quality is stable and the unit is running steadily, although the sulfur content of feed varied significantly (217—1 400 μg/g), in conclusion, RSDS-II technology can well meet the need of upgrading gasoline quality.

TECHNICAL MEASURES FOR REDUCING THE RADIAL TEMPERATURE DIFFERENCE OF FIXED-BED RESIDUE HYDROTREATING REACTOR

2013, 44(1):  83-85. 

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Due to the high viscosity of residue feedstock, in residue hydrotreating unit the distribution of feed along the catalyst bed could be non-uniform sometimes, which might lead to a great radial temperature difference of the catalyst bed and even hotspot occurred during the early stage of start-up. The performance of the catalyst could be affected and it also could be a hidden danger in operation. Thus, countermeasures should be conducted in time. By optimizing startup procedure and operation, adopting a more efficient feed inlet distributor, the fluid distribution in the residue hydrotreating reactor of SINOPEC Hainan Petrochemical Company was improved significantly, so that the radial temperature difference of the catalyst bed was less and the catalyst could be used more efficiently.

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STUDY ON THE AGING TEST CONDITIONS AND STABILITY OF FLUOROSILICONE OILS

2013, 44(1):  86-89. 

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Using a modified aging tester to age two types of fluorosilicone oil, FSO-2 and FSO-A, suitable aging test conditions were investigated. Gel chromatography (GPC) was used to analyze the molecular weight of fluorosilicone oil and to observe the changes of oil properties during aging test. Test results showed that when aging temperature was below 250℃, gelation did not occur in these two types of oil; testing under 250—300℃, aging happened in both oils. With prolonging aging time at 300℃, the increase of molecular weight and molecular weight distribution in both oils became significant. It can be seen from the GPC analysis results that the aging mechanisms of these two oils were similar; however, FSO-2 seemed to be more stable and should have a longer service life time.

INFLUENCE OF CHEMICAL VISCOSITY REDUCERS ON THE DEMULSIFICATION OF HEAVY OIL PRODUCED FLUIDS

2013, 44(1):  90-94. 

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A method for evaluating the stability of crude emulsion system was established based on Turbiscan stability analyzer and the influence of chemical viscosity reducers, including three water-soluble one and seven oil-soluble one, on the demulsification of Tahe oilfield produced fluids was studied. Test results indicated that all these three water-soluble viscosity reducers showed negative effect on demulsification, yet oil-soluble one did not show negative effect, in which THY-3 even showed significant positive effect on demulsification. It was found that the influence of water-soluble viscosity reducer on the demulsification of oilfield produced fluid was depended on its viscosity reduction performance, e.g. THS-1 viscosity reducer exhibited the best viscosity reduction performance with a reduction rate of 95.35%, it could improve the stability of crude emulsion significantly, at the same time, its negative effect on demulsification was also significant; the viscosity reduction rate of THS-2 was 82.58% and it showed less negative effect on demulsification of oilfield produced fluid.

COMPREHENSIVE MONITORING AND ASSESSMENT OF ODOUR EMISSION SOURCES FROM REFINERYⅠ. MONITORING OF ODOROUS SOURCES

2013, 44(1):  95-101. 

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A set of techniques integrated sampling and analysis was developed to monitor and identify offensive odour emissions from refinery, such as emissions from various storage tanks, wastewater treatment facilities and oxidative sweetening units. The monitoring items nearly covered all the typical refining odorous pollutants and hydrocarbons. Waste gases from odour emission sources were sampled and collected by aspirator bulbs and PTFE bags. Odorous compounds and hydrocarbons in waste gases were identified and semi-quantitatively analyzed by gas chromatography-mass spectrometry. Volatile sulfur compounds in waste gases were analyzed using a wide-bore capillary gas chromatography with sulfur chemiluminescence detection. The contents of total hydrocarbons and C1~C3 hydrocarbons in waste gases were determined by total hydrocarbon analyzer and flame ionization detection-packed column gas chromatography, respectively. The contents of benzene homologues and ammonia were determined according to the relative national standard methods. Some typical odour emission sources were sampled and analyzed from refineries of SINOPEC and the characteristics of odour emissions derived from petroleum refining were investigated systematically and comprehensively.

ENERGY CONSUMPTION ANALYSIS AND ENERGY SAVING MEASURES OF FURFURAL REFINING UNIT

2013, 44(1):  102-105. 

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The energy consumption of furfural refining unit in Karamay Petrochemical Company was analyzed. It was found that the energy consumption of the unit was mainly depended on the consumptions of fuel gas, self produced steam, electricity and circulating water. Some countermeasures to reduce the energy consumption were put forward and realized during revamping, such as energy saving reform of heating furnace, optimizing heat exchange flow, stop using the cooler for return stream at the bottom of extraction tower, adding frequency convertor on pumps and so on. Since then, the consumptions of fuel gas, self produced steam, electricity and circulating water reduced significantly, the total energy consumption of the unit dropped to 639.95 MJ/t, which is a reduction of 27.64% compared with the base case.