PETROLEUM PROCESSING AND PETROCHEMICALS

DEVELOPMENT AND COMMERCIAL APPLICATION OF PACKAGED TECHNOLOGY FOR CATALYTIC DECARBOXYLATION AND CRACKING OF HIGH ACID CRUDE OIL

Jun Long,TIAN Songbai

2011, 42(3): 1-6. doi:

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The charge distributions, bond orders on the atoms of various petroleum acids and their reaction behaviors over different catalytic materials were studied by means of molecular simulation technology and quantum chemistry theory. It was found that the carboxyl of petroleum acid could be removed over acidic catalysts to form noncorrosive carbon dioxide and hydrocarbons rapidly. A set of novel technologies to directly process high acid crude oil after desalting and dewatering was developed, which involves using FCC riser reactor and proprietary cracking catalyst to realize the catalytic decarboxylation and cracking reactions happened simultaneously, and high valuable products were produced. The commercial results showed that the rate of catalytic decarboxylation was more than 99%, the obtained gasoline and diesel fractions could be used as related blending components directly. Compared with conventional processing technology, at an equilibrium catalyst having a metal content of 40 620 μg/g (in which Ni 24 000 μg/g), the total light oil yield increased by 1.36 percentage points, the energy consumption (based on crude) decreased by 271.7 MJ/t and without special anticorrosion requirements for the processing unit. This technology could provide effective technical support for the refining enterprises to expand the selection of crude oil resources, to reduce production cost and increase profit for better competition.

INTEGRATED TECHNOLOGY (IHCC) OF HYDROTREATING FCC GAS OIL AND HIGHLY SELECTIVE CATALYTIC CRACKING FOR MAXIMIZING LIQUID YIELD

lishun dai,Jun Long,Hong Nie

2011, 42(3): 7-12. doi:

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The integrated technology of hydrotreating FCC gas oil and selective catalytic cracking was studied on pilot plant units using Qilu hydrogenated residue and Daqing vacuum residue as feedstocks respectively. Test results showed that with similar hydrogenated residue feedstocks, as compared with MIP process the liquid yield of IHCC technology was 11.58 percentage points higher, the yields of dry gas, slurry and coke were reduced significantly. As compared with VRFCC process, using feedstocks with similar properties the liquid yield of IHCC technology was 9.10 percentage points higher. The olefin content of gasoline in IHCC technology was higher than that of in MIP process, yet lower than that of in VRFCC process. In addition, the sulfur containing compounds in feedstock were mostly converted to H2S in IHCC technology. IHCC technology was in favor of processing inferior FCC feedstocks.

A DISCUSSION ON THE PROCESS DESIGN OF LIGHT FCC GASOLINE ETHERIFICATION

Liu Chengjun,Xiangling Zhang

2011, 42(3): 13-17. doi:

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Issues related with processing scheme and equipment selection of the etherification of FCC gasoline light fraction were discussed based on engineering design standpoint. When non-noble metal catalysts are selected for selective hydrogenation of diolefin, full-range FCC gasoline hydrogenation process is preferred. Adopting Johnson screen in fixed-bed etherification reactor could significantly reduce the equipment size and investment cost. In order to obtain ideal etherification conversion and to improve the unit operation flexibility, two (or even more) etherification reactors in series are required. However, the application of catalytic distillation in etherification is depended on the individual conditions.

A PROCESS ANALYSIS OF PRODUCING HYDROGEN FROM NATURAL GAS WITH DRY GAS BLENDING

2011, 42(3): 18-23. doi:

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By analyzing the process of natural gas to hydrogen post to blending dry gas in feedstock, the effect of changes in feedstock properties on the unit operation was investigated, and optimization measures were proposed. After revamping, the unit could process dry gas blended feedstock in a safe and stable operation mode for long term running, meeting the requirements of recovering dry gas and clean production. At the same time, good economic and social benefit was achieved; a 14.4 million RMB economic effect was obtained annually.

CAUSES OF CATALYST DEPOSITS IN THE FLUE GAS EXPANDER OF RFCCU AND COUNTERMEASURES

2011, 42(3): 24-28. doi:

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The causes of catalyst deposits in flue gas expander of a 3.5 Mt/a RFCC unit were analyzed. It was found that with the increase of catalyst fines in flue gas, heavy deposition of catalyst in cyclone separation system and flue gas expander could be happened. In order to avoid increasing catalyst fines in flue gas, keeping the catalyst discharge of cyclones in good conditions, evading overloading and keeping balance loading of individual pipe for the third cyclone separator were essential. By optimizing the design of cyclone separator to smoothly discharge of catalyst and to increase the recovery rate of catalyst fines, the flue gas expander was kept running in good conditions for three years. Besides, some monitoring and control measures in daily operation were also introduced.

MICRO ACTIVITY OF ADSORBENT FOR REMOVING SOx AND NOx IN FCC FLUE GAS

GUO Da-Wei

2011, 42(3): 29-32. doi:

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The micro activity of FCC catalyst used as adsorbent for removing SOx and NOx in flue gas (adsorbent-catalyst) was evaluated using light diesel distillate and n-hexadecane as feeds respectively, and the feasibility of reuse said adsorbent-catalyst in FCC unit was discussed. Test results showed that the micro activities of used adsorbent-catalysts were equal or even a bit higher than those of the reference catalysts. Further evaluation was performed on ACE unit using VGO feed and composite catalyst based on catalyst MLC-500. Results showed that within a mass fraction of used adsorbent-catalyst in the range of 5% to 10%, the feed conversion and coke yield increased with the increase of adsorbent-catalyst amount, yet the increment of coke selectivity was just half of that of the fresh catalyst.

PREPARATION AND COMMERCIAL APPLICATION OF LS-981 MULTIFUNCTION CATALYST FOR SULFUR RECOVERY

2011, 42(3): 33-37. doi:

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The development and commercial application of LS-981 catalyst, a new multifunction sulfur recovery catalyst, were introduced. LS-981 catalyst possessed high Claus reaction activity, high CS2 hydrolysis activity, good oxygen removal activity and excellent structure stability. LS-981 catalyst was applied in the 4 kt/a sulfur recovery unit of SINOPEC Shengli Petrochemical Complex successfully. The application results showed that LS-981 catalyst could process hydrocarbon containing sour gas, the total sulfur conversion over LS-981 catalyst was more than 96%, CS2 hydrolysis rate was over 90% and the operation cycle of the unit was prolonged.

EFFECT OF pH VALUE ON THE PERFORMANCE OF Pd/C CATALYST FOR HYDROPURIFICATION OF CRUDE TEREPHTHALIC ACID

wenbin du,WANG Ji-Yuan,qingfen zhu,shaohui chen

2011, 42(3): 38-41. doi:

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A series of Pd/C catalysts for hydropurification of crude terephthalic acid (CTA) were prepared by impregnating with solutions having various pH values, and the prepared catalysts were characterized by XRD and TEM techniques. Effects of impregnation pH values on the performance of catalyst during removing p-carboxy benzaldehyde (4-CBA), the main impurity in CTA, were investigated. Results showed that catalyst prepared with an impregnation solution pH value of 3.0 exhibited the best catalytic activity, under a reaction temperature of 280 ℃, H2 partial pressure of 0.6 MPa and a reaction time of 1.0 h, the conversion of 4-CBA over said Pd/C catalyst was almost 100%. In this catalyst the palladium particles were highly dispersed on the surface of active carbon and presented as microcrystalline structure. A comparison study was carried out between said Pd/C catalyst (prepared at pH value of 3.0) and an import catalyst. Under severe testing conditions and after repeating testing, the deactivation tendency and palladium sintering behavior of these two catalysts were similar, which indicated that the hydropurification performance of these two catalysts was in the same level.

STUDY ON THE CATALYST FOR CATALYTIC CRACKING OF C4 ALKENES TO PROPYLENE AND ETHYLENE

ｗａｎｇＤｉｎｇ－Ｂｏ

2011, 42(3): 42-46. doi:

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Using ultra-fine silica as carrier and ZRP-5 molecular sieve with high Si/Al ratio and good hydrothermal stability as active component, catalysts for catalytic cracking of C4 alkenes to propylene and ethylene were prepared by extrusion. The relationship between the catalytic activities and the acidic properties of the catalysts were investigated by modifying the catalysts with alkaline earth oxides. Results showed that the catalytic activities and acidities of catalysts modified by MgO, CaO and SrO decreased with the increase of atomic radius of Mg, Ca and Sr. The catalyst modified by MgO-CaO was evaluated on a fixed-bed reactor under a reaction temperature of 500 ℃, a reaction pressure of 0.1 MPa, a H2O/mixed C4 mass ratio of 0.2, a WHSV of 3 h-1 and a continuous operation of 50 d, the conversion of C4 alkenes was more than 65%, the yields of propylene and ethylene were more than 31% and more than 6%, respectively. The catalytic activity of the regenerated MgO-CaO/ZRP-5/SiO2 catalyst was about 98% of that of the fresh catalyst.

A BRIEF ANALYSIS OF CATALYST DEACTIVATION IN OXIDIZING ACROLEIN TO PREPARE ACRYLIC ACID

2011, 42(3): 47-50. doi:

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Catalysts of oxidizing acrolein to acrylic acid were developed by Lanzhou Petrochemical Research Center and applied in some industrial units. However, with the prolongation of operation period the yield of acrylic acid was gradually reduced. In order to investigate the main causes of catalyst deactivation, the physical-chemical properties of fresh catalyst and catalyst used for 2.5-year were compared using XRD, X-fluorescence, TGA and other techniques. Results showed that the loss of main active components, Mo and V, and co-components, Cu and Sr, was one of the main causes for catalyst deactivation. Besides, the phase transition of Sb+3Sb+5O4 to Sb2O3 might also have negative effect on catalyst activity. However, the yield of acrylic acid could be increased after used catalyst regeneration.

INDUSTRIAL APPLICATION OF LDO-70 FCC CATALYST PROCESSING RESIDUE FEED

2011, 42(3): 51-54. doi:

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LDO-70 catalyst was a catalyst developed for reducing olefin content of FCC gasoline．The commercia1 tria1 of LDO-70 catalyst was carried out successfully in the FCC unit of PetroChina Liaohe Petrochemical Company. Results showed that LDO-70 catalyst could significantly reduce the olefin content of FCC gasoline, when olefin content reduced 5 percentage points, the RON loss was only 0.6 units. As compared with the base case under similar operation conditions, it can be seen that the yields of gasoline and light oil increased 1.63 and 1.02 percentage points, respectively; the yields of slurry oil and coke reduced 0.99 and 0.50 percentage points, respectively; the product distributions were improved significantly．

INFLUENCE OF MoO3 CONTENT ON THE CATALYTIC PERFORMANCE OF CATALYST FOR PREPARING PROPENE FROM COMBINED FEED OF FCC DRY GAS AND MIXED C4

LI Chunyi Li

2011, 42(3): 55-60. doi:

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In order to enhance the utilization of olefins and to produce more propene, FCC dry gas was introduced as partial feed in the process of preparing propene from mixed C4. A series of ZSM-5 zeolite catalysts loaded with various MoO3 contents were prepared by incipient wetness procedure to realize the coupling of cracking reactions and metathesis reactions. The MoO3/ZSM-5/Al2O3 catalysts were characterized by XRD，Py-FT-IR and BET method to study the effect of MoO3 content on the catalyst performance．Test results showed that the acidity, surface property and pore structure of the catalyst were affected by the loading of MoO3．Based on correlating the evaluation results of fixed bed micro-reactor and the MoO3 contents，it was found that under the conditions of a reaction temperature of 450 oC, a dry gas/mixed C4 volume ratio of 4 and a GHSV of 120 min-1, MoO3/ZSM-5/Al2O3 catalyst with suitable MoO3 content was in favor of promoting metathesis reactions between ethene and 2-butene, and thus the propene yield was increased．A maximum propene yield of 27.85% was obtained over a catalyst with a MoO3 content of 4%．

STUDY ON THE SELECTION OF STABILIZERS IN INSOLUBLE SULFUR PRODUCTION AND THEIR EFFECTS

2011, 42(3): 61-65. doi:

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The effects of adding various stabilizers in the production steps, such as polymerization, quenching, extraction and oil treatment, on the insoluble sulfur (IS) content and stability of product were studied. Test results showed that the IS content and the stability of product could be improved by adding stabilizers in each step; the optimum selections were adding alcoholic stabilizer D in polymerization, water soluble organic stabilizer A in quenching and ester type liquid stabilizer X in extraction and oil treatment. Besides, based on the single stabilizer test results, optimization tests of two-stabilizer combination were carried out, yet no positive synergetic effect was observed.

TRIBOLOGICAL BEHAVIOR OF THIADIAZOLE DIMER DERIVATIVES

2011, 42(3): 66-70. doi:

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Three thiadiazole dimer derivatives (TDD-7，TDD-10 and TDD-15) were synthesized and their structures were characterized by FT-IR. The tribological properties of these derivatives used as additives in distilled water were evaluated with a four-ball machine, and the chemical states of some typical elements on the worn surface were analyzed by XPS. Results indicated that these additives possessed excellent load carrying capacity and extreme pressure property in distilled water, and the antiwear and friction reducing performance of distilled water with additives were improved in some extent. Among these three additives, TDD-10 exhibited the best load carrying capacity and TDD-15 exhibited the best antiwear performance. The improved tribological behavior of distilled water by these additives could be attributed to the formation of adsorption film containing nitrogen, chemical reaction film containing Fe2O3, FeS and FeSO4, and the synergetic effect of these two types of films led to a further improvement.

STUDY ON THE SIMULATING TEST METHOD FOR ANTIWEAR PERFORMANCE OF HEAVY-DUTY DIESEL ENGINE OIL

ZHANG Qian

2011, 42(3): 71-74. doi:

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With the upgrading of heavy-duty diesel engine oil, the requirement for properties of engine oil is strengthening, especially for antiwear property. Thus, selecting optimum antiwear testing method in lab to simulate the operation conditions of Mack T-9 engine test is essential for the development of heavy-duty diesel engine oil. Test results show that SRV bench test is suitable to be used to evaluate the antiwear properties of various diesel engine oils. Furthermore, the effect of five additives on the antiwear properties of heavy-duty diesel engine oil was investigated by SRV testing, and the results show that properly adding more zinc dialkyldithiophosphate and using suitable anti-wear agents could improve the antiwear performance of diesel engine oil significantly.

A COMPARISON STUDY OF THE IMPROVEMENT SCHEMES FOR OPTIMIZING ENERGY CONSERVATION IN THE ABSORPTION-STABILIZATION SYSTEM OF A FCC UNIT

2011, 42(3): 75-79. doi:

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Using process simulation software Pro/Ⅱ, a case study for the improvement schemes of an absorption-stabilization system of a FCC unit was carried out from the energy-saving and optimization standpoint, and an optimal improvement idea was proposed consequently. The impact of various operation parameters on the process and energy consumption was investigated, finally, measures for optimizing process operation was put forward, such as set a reboiler at the middle part of desorption tower to realize the optimal cold feeding mode of desorption tower, the reboiler duty at the bottom could be reduced, the amount of desorption gas and supplemental absorbent could be decreased significantly and the operation load of the unit would be lowered.

APPLICATION OF SURPLUS HEAT RECOVERY SYSTEM WITH WATER HEAT MEDIUM IN DISPROPORTIONATION UNIT

2011, 42(3): 80-83. doi:

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A surplus heat recovery system with water heat medium was set up to recover heat in flue gas from the furnaces of disproportionation unit in SINOPEC Yangzi Company. The water supply to the medium-pressure boilers was used as heat carrier, the heat recovered from flue gas was used to preheat the combustion air, and two heat exchangers were involved in realizing the heat exchange among flue gas, water and air, so as to reduce the temperature of exhaust flue gas and to enhance the thermal efficiency of furnaces. After revamping, the thermal efficiency of furnaces was increased from 85.0% to 91.4%; an economic effect of 5.7172 million RMB was obtained annually.

EFFECT OF CHLORIDE ION CONTENT IN CIRCULATING WATER ON THE CORROSION BEHAVIOR OF CARBON STEEL

2011, 42(3): 84-87. doi:

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The effect of chloride ion content in simulated circulating water on the corrosion behavior of 20# carbon steel and 08 carbon steel was investigated by means of laboratory immersion and electrochemical methods. The results showed that with the increase of chloride ion content, the corrosion resistance of both 20# and 08 carbon steel materials decreased. When the chloride ion content was less than 750 g/g, corrosion resistance performance of the two materials in the simulation solution were similar; however, when the chloride ion content was more than 750 g/g, 08 carbon steel exhibited superior corrosion resistance in simulation solution as compared with 20 # carbon steel.

AN ANALYSIS OF THE COMPOSITIONS OF NITROGEN AND OXYGEN COMPOUNDS IN DIESEL DISTILLATE FROM HUADIAN SHALE OIL

2011, 42(3): 88-92. doi:

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The nitrogen and oxygen compounds in diesel distillate from Huadian shale oil were separated and concentrated by acid-base extraction and column chromatogram separation. The compositions of these nitrogen and oxygen compounds were analyzed by GC-MS. Results indicated that the nitrogen compounds in said diesel distillate were mainly composed of 1-3 ring compounds, such as pyridine, quinoline, indole, carbazole and their alkylated derivatives, as well as aliphatic nitriles. The majority of oxygen compounds found in the distillate were acidic oxides, for example, phenol, naphthol and their alkylated derivatives.

AN EXPERIMENTAL STUDY OF REMOVING ANILINE FROM REFINERY WASTEWATER WITH MACROPOROUS RESIN D151

2011, 42(3): 93-96. doi:

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The removal of aniline from refinery wastewater was studied using macroporous resin D151. Results showed that under the conditions of an adsorption temperature of 25℃，a pH range of 8-10 and an adsorption time of 35 min the adsorption rate of aniline in simulated wastewater could reach 86.6%; using 4% HCl as desorption agent and a desorption time of 90 min, the desorption rate could reach 85.7%. When using macroporous resin D151 to treat refinery wastewater, the removal rates of aniline for untreated sewage discharge and treated wastewater were over 99% and almost 100%, respectively.

STUDY ON TREATING NITROBENZENE WASTEWATER BY ELECTROCHEMISTRY-BIODEGRADATION

2011, 42(3): 97-100. doi:

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Electrochemical method was used to pretreat the nitrobenzene containing wastewater. A set of orthogonal experiments was carried out to study the influencing factors. Test results showed that under the optimum conditions of an electrolysis voltage of 15 V, an electrolysis current of 0.30 A, a pH value of 3 and a reaction time of 50 min, the removal rate of nitrobenzene was 100%. The pretreated wastewater was easy to be biodegraded. By treating with microorganism for 14 h, the removal rates of aniline and COD reached 99.5% and 82%, respectively. After 18 h biodegradation, the COD removal rate could reach 94%, indicating that most of the organic compounds in the wastewater were biodegraded to CO2 and H2O.

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