Table of Content

12 December 2011, Volume 42 Issue 12

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加工工艺

CAUSE ANALYSIS OF SORBENT DEACTIVATION IN S Zorb UNIT FOR GASOLINE DESULFURIZATION

Xu Guangtong

2011, 42(12):  1-6.  doi:

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Aiming at investigating the causes of fast deactivation and high consumption of sorbent in S Zorb process, the physicochemical properties of various sorbent samples were characterized by SEM, XRD, XRF, XPS and MAS-NMR techniques systemically. During the operation of S Zorb unit, the amount of active ZnO decreases significantly, due to the formation of non-activated gahnite, such as zinc aluminate, Willemite and etc. As long as the amount of active ZnO is not enough to support the transfer of sulfur containing compounds in gasoline, the sorbent is deactivated and its desulfurization function diminishes. In addition, the formation of zinc aluminate in sorbent may cause the particles to be fragile, thus the consumption of sorbent increases. It is suggested that monitoring the phase changes of spent and regenerated sorbent will be helpful to ensure an effective and stable running of the S Zorb unit.

EFFECT OF H2S IN RECYCLE HYDROGEN ON SELECTIVE HYDRODESULFURIZATION OF HEAVY FCC NAPHTHA

Zhang Fu-Chun

2011, 42(12):  7-10.  doi:

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On a fix-bed hydrogenation pilot plant unit, the effect of H2S in recycle hydrogen on the hydrodesulfurization (HDS) and olefin saturation（HYD）reactions during FCC heavy naphtha selective hydrogenation process over Co-Mo catalyst was studied. The results showed that the existence of H2S could inhibit HDS reactions and promote HYD reactions, however, the selectivity of the catalyst decreased with the increase of H2S content in recycle hydrogen. Results also showed that the effect of H2S content in recycle hydrogen on HDS and HYD reactions was varied under various reaction severities: under relatively mild operation conditions to keep the total sulfur content of liquid product below 50 μg/g, the influence of H2S was significant; under relatively severe operation conditions to keep the total sulfur content of liquid product below 10 μg/g, the influence of H2S was less significant.

CATALYTIC CRACKING PERFORMANCES OF DAO AND ITS RAFFINATE OILS FROM FURFURAL EXTRACTION

2011, 42(12):  11-15.  doi:

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In this paper, pilot plant riser reactor was used to evaluate the catalytic cracking performances of desaphalted oil (DAO) and its raffinate oils (denoted as feed A and feed B), which were obtained by extracting DAO with furfural under the conditions of furfural/DAO mass ratio of 2, extraction temperature of 80 ℃ and 85 ℃, respectively. Experimental results indicated that compared with DAO, both feed A and feed B exhibited improved catalytic cracking performances: higher heavy oil conversion and light oil yield, lower yields of coke and slurry oil, besides, the properties of cracking products from feed A and feed B are also better in some ways.

STUDY ON THE PULSE ELECTRIC DESALTING TECHNIQUE OF CRUDE OIL

2011, 42(12):  16-22.  doi:

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The mechanism of pulse electric desalting/dehydration for crude oil was discussed. Seven factors related to the operation efficiency of pulse electric desalting technique were studied by orthogonal test design method，using a 10 L/h continuous two-stage desalting unit. The results showed that when the crude processing capacity increased by 60%, the contents of salt and water in the secondary desalted crude oil were less than 3.0 mg/L and 0.3%, respectively, furthermore, the oil content in waste water was less than 100 mg/L, which well met the requirements of deep desalting. The electricity-saving rate of pulse electric desalting technique could reach 58.9% as compared with conventional AC electric desalting technique under optimum operating conditions.

APPLICATION OF ULTRASONIC ONLINE CLEANING TECHNIQUE IN THE SLURRY OIL SYSTEM OF FCC UNIT

2011, 42(12):  23-26.  doi:

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Ultrasonic online cleaning technique was applied on the slurry oil heat exchanger of FCC unit in PetroChina Dagang Petrochemical Company to solve the fouling and coking problems happened there. The effect of ultrasonic technique on the heat transfer coefficient of heat exchanger, the operation of slurry oil system, product quality and product yields was investigated. Results indicated that by using ultrasonic online cleaning technique the heat transfer coefficient of heat exchanger increased 24.327 W/(m2·℃), the steam production of drum increased 0.404 t/h, the operation period of slurry oil heat exchanger was prolonged from 5-month to 8-month and the total operation status of the slurry oil system at the bottom of fractionation column was improved.

催化剂

EFFECT OF HYDROTHERMAL TREATING TEMPERATURE ON THE SELECTIVE HYDRODESULFURIZATION PERFORMANCE OF CoMo/nano-HZSM-5 CATALYSTS

Cao Zhan-guo,Xiangsheng Wang,Xinwen Guo

2011, 42(12):  27-32.  doi:

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A series of modified nanosized HZSM-5 samples were prepared by hydrothermal treatment under various temperatures. The effects of hydrothermal treating temperatures on the structure and properties of nanosized HZSM-5 samples, such as acidity, surface area and pore volume were investigated by XRD, NH3-TPD, pyridine FT-IR and N2 adsorption/desorption techniques. The catalytic performance of these nanosized HZSM-5 samples incorporated with CoMo active components was evaluated on a continuous-flow fixed bed micro-reactor using full range FCC gasoline as feedstock. Results showed that nanosized HZSM-5 exhibited good hydrothermal stability; after hydrothermal treatment its acid amount and acid strength reduced, the interreaction of active components and support enhanced. With the increase of hydrothermal treating temperature, the hydrodesulfurization activity of the catalyst decreased, however, the olefin saturation activity decreased as well, more olefins remained in the treated gasoline. When the hydrothermal treating temperature was more than 600 ℃, the olefin saturation rate was less than 5%, so that the group compositions of the treated gasoline were basically unchanged.

EFFECT OF PRESULFURIZATION TEMPERATURE ON THE SELECTIVE HYDRODESULFURIZATION OF MoCo/Al2O3 CATALYST

Zhao Le-Ping,Bai-Ling You,Hong Pang

2011, 42(12):  33-35.  doi:

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The effect of presulfurization temperature(230-400℃)of MoCo/Al2O3 catalyst on its selective hydrodesulfurization(HDS) performance, such as HDS rate, hydro-saturation(HYD) rate and gasoline octane(RON) loss, was studied on a pilot plant unit using full range FCC gasoline as feed. The test results indicated that under reaction temperature of 260℃,with the increase of presulfurization temperature, the HDS rates of these catalysts increased from 84.4% to 91.1%;under reaction temperature of 280℃,the HDS rates of these catalysts were all over 96.0%,presulfurization temperature had less influence. However, in these two cases, MoCo/Al2O3 catalyst sulfurized at 250℃,exhibited the minimum HYD rate and gasoline RON loss, which indicated said catalyst possessed the best HDS selectivity. It was found that MoCo/Al2O3catalyst could be well sulfurized at 250℃ and with less coke deposit, which would be favorable to provide good HDS selectivity when treating FCC gasolien.

STUDY ON THE PREPARATION OF Pt/Al2O3-TiO2 CATALYST FOR HYDROGENATION OF REFORMATE RAFFINATE

LIU Chen-Guang

2011, 42(12):  36-41.  doi:

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Pt/Al2O3-TiO2 catalysts were prepared by impregnation method using Al2O3-TiO2 supports calcined under various temperatures. The prepared catalysts were characterized by BET, XRD, TPR, TEM and H2-O2 titration techniques, and the activity of catalysts for olefin and aromatic hydrocarbon hydrogenation was evaluated using reformate raffinate as feedstock. Results showed that the optimum preparation conditions of Pt/Al2O3-TiO2 catalyst for hydrogenation of reformate raffinate were as follows: support calcination temperature of 900 ℃, catalyst calcination temperature of 350 ℃ and reduction temperature of 200 ℃. The hydrogenation activity of Pt/Al2O3-TiO2 catalyst increased with the increase of reaction temperature. Under a reaction temperature of 200 ℃, a reaction pressure of 3.0 MPa, hydrogen/oil volume ratio of 200 and LHSV of 2.0 h－1, over Pt/Al2O3-TiO2 catalyst prepared with optimum conditions, the conversions of olefin and aromatic hydrocarbon in reformate raffinate reached 100%.

PREPARATION AND PERFORMANCE OF Ni2P/TiO2-Al2O3 CATALYST FOR HYDRODENITROGENATION

2011, 42(12):  42-45.  doi:

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TiO2-Al2O3 mixed supports were prepared by sol-gel method and used in preparation of Ni2P/TiO2-Al2O3 catalysts by co-impregnation．Hydrodenitrogenation(HDN) activity of the catalysts was tested in a fixed bed reactor after in-situ reduction．The results showed that titanium-to-aluminium molar ratio and Ni loadings had remarkable influence on activity of the catalysts．The result showed that the hydrodesulfurization activity of the Ni2P/TiO2-Al2O3 catalyst reached the best HDN activity when the ratio of n(Ti)/n(Al) was 1 to 4 and Ni loadings of 25%. the catalyst exhibited the highest HDS activity, with desulfurization rate of 98%.

基础研究

STUDY ON THE THERMOGRAVIMETRIC ANALYSIS AND PYROLYSIS KINETICS OF COKE FROM DELAYED COKING

2011, 42(12):  46-49.  doi:

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Pyrolysis of coke from delayed coking was performed by thermogravimetric analysis (TGA) in argon and carbon dioxide atmosphere from room temperature to 1000 ℃ respectively. The mechanism of pyrolysis was discussed. TGA results showed that during the pyrolysis of coke dehydration happened at 50－100 ℃; then significant weight loss started from 400 ℃ and reached a maximum value around 620－640 ℃, which is commonly attributed to the release of volatile matter due to the rupture of side chains from organic compounds; above 800 ℃, weight loss increased remarkably, indicating rapid pyrolysis occurred. The average activation energy was determined using a third-order chemical reaction model to simulate the pyrolysis of coke from delayed coking. In the temperature range of 433－904 ℃, the average activation energy under CO2 and Ar atmosphere was 29.70-44.81 kJ/mol and 57.68－69.44 kJ/mol, respectively.

NUMERICAL SIMULATION OF FLOW FIELD AND SEPARATION EFFICIENCY OF CYCLONE SEPARATOR WITH OBLIQUE TANGENTIAL DOUBLE INLETS

WU Cai-Jin,Zhengfei Ma

2011, 42(12):  50-55.  doi:

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A new type of cyclone with oblique tangential double inlets was proposed, and RSM Model was employed to simulate the three-dimensional flow field and separation efficiency of said cyclone separator. Results showed that cyclone with oblique tangential double inlets improved the flow field nonsymmetry of single entry cyclone greatly and the partial vortex flow inside the flow field was minished. With the increase of obliquity, both tangential and axial velocities exhibited the trends of firstly increased and then decreased, the maximum axial velocity and maximum tangential velocity was obtained at a obliquity of 12 degree and 10 degree, respectively. Same trend was observed with pressure drop, but the maximum value was far below that of single entry cyclone, the change of radial velocity was not significant. Cyclone with oblique tangential double inlets could improve the separation efficiency significantly, and the optimal obliquity angle was 10 degree.

节能减排

RESEARCH AND APPLICATION OF RECYCLING FIBER WASTEWATER TREATED BY MBR TO CIRCULATING WATER SYSTEM

Ben-Gao LI,FU Xiao-Ping

2011, 42(12):  56-59.  doi:

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According to the characteristics of wastewater treated by member bioreactor (MBR) and operation conditions of circulating water system in chemical fiber unit, a technology of water quality stabilization for recycling wastewater to circulating water system was developed involving self-developed bactericides and compound corrosion-scale inhibitor. The 2-year application results of said technology in the circulating water system of a chemical fiber unit show that the average corrosion rate and adhering rate of this waste-reused circulating water is 0.042 mm/a and 133.20 mg/(cm2·a), respectively, which is better than the SINOPEC performance assessment index of circulating system with fresh water. Adopting said water stabilized technology for MBR treated wastewater could well meet the requirements of production unit for circulating water; good economic and social benefits are obtained.

STUDY ON THE CHARACTERIZATION OF BACTERIAL STRAIN FOR DIESEL OIL DESULFURATION

2011, 42(12):  60-64.  doi:

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Due to the conventional hydrodesulfurization are less effective to remove thiophene and dibenzothiophene (DBT) types of sulfur containing compounds in diesel fuel, bio-desulfurization is being concerned. A kind of bacterial strain, HT1, using DBT as sole sulfur source and having high DBT degradation function is screened out. The optimal ferment conditions for HT1 strain are obtained by orthogonal test design as follows: treating at 30 ℃, DBT concentration of 102.0 mg/L, NH4NO3 concentration of 2.0 g/L, glycerol concentration of 5 g/L, cultivation time of 4 d with pH value of 7.0. The effect of various sulfur sources on the growth and desulfurization performance of HT1 strain is investigated. Results show that the growth of HT1 strain with various sulfur sources is similar, yet the influence of sulfur sources on the DBT degradation is significant, the best degradation performance was observed with HT1 strain using DBT as sulfur source. However, the degradation of sulfur containing compounds by HT1 strain is also depended on the structure of the compound, and the sulfur removal rate of catalytic cracking diesel fraction by HT1 strain still needs to be improved.

油品与添加剂

STUDY ON THE COMPOSITION OF SOLID HYDROCARBON IN FOOTS OIL FROM KETONE-BENZOL DEWAXING UNIT

2011, 42(12):  65-67.  doi:

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Two foots oil samples from processing 2nd and 5th vacuum side cuts at the No.3 ketone-benzol dewaxing unit of SINOPEC Shanghai Gaoqiao Branch were used as feedstocks and treated by low temperature sweating deoiling and solvent dewaxing-deoiling respectively. From the source of light fraction (2nd vacuum side cut), low melting point wax was obtained, its solid hydrocarbons were mainly consisted of normal paraffins. The thermal analysis of this low melting point wax showed that it exhibited the characteristics of narrow heat absorption temperature arrange, high heat absorption and moderate phase transition temperature, so that it can be developed to phase transition wax products. From the source of heavy fraction (5th vacuum side cut), low melting point microcrystalline wax was obtained, its solid hydrocarbons were mainly consisted of cycloparaffins and isoparaffins, which can be an explanation of the phenomenon of "good light fraction and bad heavy fraction" in commercial production, on the other hand, it can provide technical support to produce high melting point and low oil content wax.

RESEARCH ON THE PERFORMANCE OF α-OLEFIN POLYMER AS DRAG REDUCTION AGENT

Ying-Lu LU

2011, 42(12):  68-72.  doi:

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A drag reducing agent (DRA), α-hexylene/α-dodecene, was synthesized by bulk polymerization using TiCl4/Al(i-Bu)3 as catalyst. The obtained polymer was characterized by means of IR, 1HNMR and TG. The effect of main catalyst and co-catalyst dosages on the intrinsic viscosity of the synthesized DRA was investigated and its drag reducing efficiency was tested with a loop evaluation device. Results showed that under the optimum conditions of a main catalyst dosage of 0.09 g, a co-catalyst dosage of 0.12 ml, α-dodecene/α-hexylene volume ratio of 2 (a total volume of 40 mL), a reaction temperature of -5 ℃ and a reaction time of 48 h, the intrinsic viscosity of the synthesized DRA was 11.21 dL/g; by adding said DRA to diesel fuel at a dosage of 10 g/g, its drag reducing rate reached 50.81%.

分析与评定

RESEARCH ON THE DETERMINATION OF CRUDE OIL DENSITY BY MID-INFRARED SPECTROSCOPY RAPIDLY

TIAN Songbai

2011, 42(12):  73-77.  doi:

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The combined use of mid-infrared attenuated total reflection spectroscopy and multivariate calibration to determine the density of crude oil was carried out. Calibration models for crude oil density were established by partial least squares (PLS) based on 280 crude oil samples collected worldwide. Results show that the standard deviation of cross-verification is 0.005 1 g/cm3 and the predicted standard deviation is 0.004 4 g/cm3, which are all close to the requirements of standard method, which indicates that the results predicted by this method are very close to those determined by standard method. As compared with the U-tube vibration method this method is quick and easy to operate, its result could meet the requirements of fast analysis/process control analysis, and in certain cases it could substitute the U-tube method for fast prediction of crude oil density.

FAST DETERMINATION OF BOUND ETHYLENE CONTENT OF ETHYLENE-PROPYLENE RUBBER BY FT-IR COMBINED WITH PARTIAL LEAST SQUARE REGRESSION

Xu Guangtong

2011, 42(12):  78-81.  doi:

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Quantitative calibration models for fast determination of bound ethylene content in ethylene-propylene rubber were established by partial least square regression based on data of 13C NMR measurement combined with information from mid-infrared spectroscopy. Parameters affected the models were optimized and the correlation between spectra and bound ethylene content was analyzed. Results show that in the wave number range of 600-1 300 cm-1, the absorption of -CH2- group, the vibrational absorption between end group of ethylene and -C-C- have great coherence with the bound ethylene content, models based on second order derivative spectra are in better quality. The results of validation show that under the model application scope, the deviation of bound ethylene contents between predicted value and actual measurement is within ±1.5%, which could meet the requirement of quantitative analysis during industrial production.

COMPARISON STUDY ON TWO STANDARD METHODS FOR DETERMINATION OF VOLATILE PHENOLIC COMPOUNDS IN WATER BY BROMINE METHOD

2011, 42(12):  82-85.  doi:

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Two standards for determination of volatile phenolic compounds with bromine method, GB 7491-1987 and HJ 502-2009, were compared including determination range, analysis procedure, consumption of potassium bromated-potassium bromide solution and titrant, precision and accuracy. Comparison results show that in HJ 502-2009 standard method, the determination range of volatile phenolic compounds (0.1-45.0 mg/L) is definite, which is not clear in GB 7491-1987; the content of precision and accuracy is added, and sample pre-distillation is only once, which is twice in GB 7491-1987. According to HJ 502-2009 standard method, for 100 mL distillate, the adding volume of potassium bromated-potassium bromide solution is fixed to 3 mL, thus one blank test is enough for multiple samples analysis, which is more suitable to batch analysis. When the content of volatile phenolic compounds in 100 mL distillate is 2.35 mg, the consumptions of potassium bromated-potassium bromide solution of these two standard method are the same; when the content of volatile phenolic compounds in 100 mL distillate is less than 2.35 mg, the consumption of potassium bromated-potassium bromide solution and sodium thiosulfate standard solution in HJ 502-2009 standard method is more than those in GB 7491-1987; however, it is contrary when the content of volatile phenolic compounds in 100 mL distillate is more than 2.35 mg. It is suggested to change the fixed volume of potassium bromated-potassium bromide solution from 3 mL to 2.5 mL, and the content of volatile phenolic compounds in 100 mL distillate should be less than 2.35 mg for easy operation and better accuracy.

综述

METHODS FOR REMOVING NITROGEN COMPOUNDS IN FCC LIGHT GASOLINE

2011, 42(12):  86-89.  doi:

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The etherification of FCC light gasoline is an ideal process to reduce olefin content in gasoline and with minimum octane loss, but trace amount of nitrogen compounds in the gasoline may lead deactivation of etherification catalyst, so these nitrogen compounds should be removed. In this paper, methods for removing nitrogen compounds in FCC light gasoline, such as extraction, adsorption, pre-hydrogenation and etc. are summarized including the benefits and limitations of each process and new progresses in denitrogenation technology. The future developing trend of removing nitrogen compounds in FCC light gasoline is also discussed.

CURRENT STATUS AND PROSPECTS OF PATENT PROTECTION CONCERNING DELAYED COKING TECHNOLOGY IN CHINA

2011, 42(12):  90-93.  doi:

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In order to fully understand the patent protection status concerning delayed coking technology，Chinese patents in this field which have been made public since 1985 are systematically analyzed. On this basis, proposals related to the research, patent application and key protection area of future advanced delayed coking technology are put forward.