Table of Content

12 December 2018, Volume 49 Issue 12

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DEVELOPMENT AND APPLICATION OF SLG-1 CATALYST FOR LTAG TECHNOLOGY

2018, 49(12):  1-5. 

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The high accessibility Y zeolite with an abundant mesoporous structure and strong B acid activity were designed according to the reaction features of hydrotreated light circulating oil (LCO). The resulting Y zeolite has an improved ring-opening ability. Combined with the matrix with heavy oil pre cracking capacity and strong carbon tolerance, a special catalytic cracking catalyst SLG-1 for processing hydrotreated LCO was developed. The industrial application results showed that the yield of LPG is reduced by 1.58 percentage points, the gasoline yield increases by 4 percentage points, and the total liquid yield improves by 2.17 percentage points.

EFFECT OF FLUORINE ON Pt-Sn/Al2O3 CATALYST PERFORMANCE

2018, 49(12):  6-9. 

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The Pt-Sn/γ-Al2O3 catalyst with different content of Fluorine was prepared, and the influence of F on the performance of reforming catalysts was investigated. The results of BET, Py-IR, NH3-TPD tests showed that the introduction of F has no significant effect on specific surface area and pore volume of catalyst. But the catalyst acidity is significantly improved. Both Lewis and Bronsted acid sites exist on the F-modified γ-Al2O3 carrier surface, and the acid amount increases with increasing F content. The reaction performance of n-heptane and naphtha showed that LPG yield increases significantly with the increase of fluorine content, the yield of C5+ and aromatics decrease, while coking rate on the catalyst increases. When the fluorine content is greater than 1%, the catalysts exhibit a high selectivity of LPG（C3+C4）.

IMPROVED RFS SOx TRANSFER ADDITIVE AND ITS APPLICATION FOR CONTROLLING BLUE SMOKE PLUME FROM WET SCRUBBER

2018, 49(12):  10-15. 

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To resolve the problem of blue smoke and plume tailing from scrubber, a commercial trail of improved RFS SOx transfer additive was performed on a MIP-CGP unit of SINOPEC. After the initial rapid accumulation, the system storage is about 1.5% of catalyst inventory and then the additive is steadily added with rate of 0.024 kg/t based on fresh feed, the industrial application was summed up. The results showed that the application of RFS additive has little influence on product distribution, product properties and unit operation. SO2 and SO3 in flue gas is significantly decreased, therefore the consumption of NaOH solution is also decreased. Furthermore, TDS and COD in waste water and circulating water decline obviously. Blue smoke is diminished and plume tailing is well controlled.

STUDY ON PERFORMANCE OF MAGNESIUM-PROMOTED HYDROISODEWAXING CATALYST

Zheng Xiuxin Yu Wendong Liu Youpeng Sun Guofang

2018, 49(12):  16-21. 

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Pt/ZSM-23, Pt-Mg/ZSM-23-1% and Pt-Mg/ZSM-23-2% hydroisomerization catalysts were prepared by loading Pt and Mg on H-ZSM-23 molecular sieve by incipient co-impregnation method. The influences of magnesium on the acidity and hydroisomerization of catalysts were studied using hydrocracking tail oil as feed from Huizhou Petrochemical Company. The results showed that the introduction of the magnesium promoter resulted in the decrease of medium-strong acids, while increases their selectivities. The layered Pt/ZSM-23 and Pt-Mg/ZSM-23-2% (volume ratio of 1:1) catalyst system showed a higher yield (from 75.0% to 79.0%) and selectivity at conditions of 325 ℃, hydrogen pressure of 13 MPa, the hydrogen to oil ratio 500 and the LHSV 1.1 h-1. After 1000 h running, the catalyst exhibited a stable hydroisomerization performance. The pour point of 150N base oil is-18 ℃, the yield of 150N and total lube base oil is 48.0% and 79.3% respectively. The results indicate the good hydroisomerization performance and good industrialization prospect.

APPLICATION OF SULFUR TRANSFER AGENT APPLIED IN FCC UNIT

2018, 49(12):  22-26. 

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The sulfur transfer additive RFS09 was used in a 1.2 Mt/a FCCU (MIP) in CNOOC Huizhou Petrochemical Company. The application results showed that, at excessive oxygen content of 4.2%~5.5%, and when the accumulation amount of RFS09 reaches 2.56% of the catalyst inventory, the contents of SO3 and SO2 in the flue gas reduce from 527.5 mg/Nm3 and 263.0 mg/Nm3 to 16.0 mg/Nm3 and 14.0 mg/Nm3, respectively, the remove rate reaches 96.97% and 94.67% respectively. Meanwhile, the caustic consumption is decreased by over 90%. The cost accounting of benefit shows that, using the sulfur transfer agent to eliminate the acid mist will not increase the running cost of the company.

EFFECT OF PORE STRUCTURE AND ACIDIC PROPERTY ON CATALYTIC PROPERTIES OF POROUS ALUMINA MATERIALS

Zheng Jinyu Luo Yibin Shu Xingtian

2018, 49(12):  27-33. 

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Two alumina materials prepared in lab and three industrial alumina materials before and after hydrothermal aging treatment were characterized by XRD、XRF、BET、FT-IR and NH3-TPD, and evaluated in a heavy oil micro reactor. The results indicated that the selected alumina materials possess pseudo-boehmite structure and average pore diameter of 5～16 nm belonging to mesopore. All the materials only have Lewis acid centres. The preparation method leads to an obvious difference in crystallinity, pore parameter, acidic property, hydrothermal stability and cracking activity. The cracking property and product distribution depend on both pore parameter and acidic property of the alumina material after hydrothermal aging treatment, and the effect degree of pore parameter and acidic property differs from each other in size of pore diameter. For the alumina material with pore diameter about 10 nm, the pore structure is the main influence factor. When the pore diameter increases to 13～25 nm, the influence of total acid content is relatively higher than the pore diameter.

CATALYTIC SYNTHESIS OF 1,5-BIS(2-FURANYL)-1,4-PENTADIEN-3-ONE

2018, 49(12):  34-38. 

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1,5-bis(2-furanyl)-1,4-pentadien-3-one was synthesized by the aldol condensation reaction of furfural and acetone in inorganic base medium and is identified by FT-IR,1H-NMR and XRD. The optimum conditions for the reaction are: reaction medium of 0.1 mol?L-1 KOH (aq), reaction temperature 20℃, reaction time 10h, the molar ratio of furfural to acetone 2:1. Under the optimum conditions, the yield of product is 98.5 % with a purity of 98%.

EFFECT OF PORE VOLUME ON CRACKING PERFORMANCE OF RFCC CATALYST

2018, 49(12):  39-42. 

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X-ray diffraction (XRD), N2 physical adsorption, infrared spectra of pyridine (Py-IR), mercury intrusion porosimetry (MIP), field emission scanning electron microscopy (FE-SEM) and an advanced cracking evaluation (ACE) equipment were used to study the physicochemical properties and cracking performance of the RFCC catalysts with different pore volume. The results showed that the catalyst Cat-1 with pore volume of 0.46cm3/g has a conversion rate 6.86% higher than that of the catalyst Cat-2 with pore volume of 0.36cm3/g. The yields of LPG and C5+ gasoline increase remarkably and the selectivity of by-product (coke and dry gas) declines at reaction conditions of 530℃ and catalyst/oil ratio 5.

COMPOSITIONS AND STRUCTURES OF DIFFERENT ASPHALTENES IN TAHE ATMOSPHERIC RESIDUE

2018, 49(12):  43-47. 

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The samples of C5-As, C6-As and C7-As asphaltene were separated from the Tahe atmospheric residue (THAR) by n-pentane, n-hexane and n-heptane solvent, respectively. The surface morphology, crystal structure, functional groups and pyrolysis performance of samples were characterized by SEM, XRD, FT-IR and TG-DTG techniques. The results showed that with increase of solvent carbon chain length, the yield of C5-As, C6-As and C7-As becomes 33.57 %, 26.98 % and 21.12 %, respectively; the surface of three samples were gradually more rough, the particle size decreases; the layer number of aromatic ring and aromatization degree in the molecular structure cell are increased; aromatic ring substitution decreases and condensation extent increases; the thermal stability and the residual carbon of the samples are increased.

ADSORPTION OFAROMATIC HYDROCARBON IN LIQUID WAX OIL

2018, 49(12):  48-52. 

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The presence of aromatic hydrocarbon in liquid wax has a serious effect on the quality of downstream products. The separation of the aromatic compounds in liquid wax by adsorption method was studied. The adsorption effect of modified porous carbon, molecular sieve, silica gel and polystyrene resin on aromatic hydrocarbons was investigated, and the structure of the modified adsorbent was characterized. The results showed that the porous carbon material modified with NaOH has a higher specific surface area, the adsorption capacity of aromatic hydrocarbons can reach up to 37.025 mg?g-1, much greater than that of molecular sieve, silica gel and resin. The adsorption performance of the resin is the worst, the adsorption capacity is only 16.025 mg?g-1.

INDUSTRIAL PRACTICE ON ADJUSTING DIESEL/GASOLINE RATIO BY PROCESSING LCO WITH RLG TECHNOLOGY

Li Guijun Liu Qing Yuan Deming Fan Yijun Xiao Yunpeng Hua Chuanlun

2018, 49(12):  53-57. 

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A 1.0 Mt/a LCO hydrocracking unit was built using RLG technology developed by RIPP in SINOPEC Anqing Company to produce gasoline with RON 90 and 10 μg/g sulfur as well as clean diesel blending components with sulfur less than 10μg/g, while the cetane index increases by 10 units. With the RLG technology, the mass ratio of diesel to gasoline is decreased from 0.97 to 0.74; the production of car diesel increases greatly, while the regular diesel is just opposite. The economic benefits is greatly improved

TECHNOLOGY FOR WAXMAKING FROM COAL TAR

2018, 49(12):  58-63. 

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The light oil from middle and low temperature coal tar was used to make wax by hydrofining and then solvent dewaxing process. The effect of reaction temperature，pressure，LHSV on the properties and content of paraffin of the waxes were investigated using three hydrofining reactors in series. The melting point and content of n-alkanes of the waxes obtained by solvent dewaxing process were determined. The optimal reaction conditions of the process are as follows：reaction temperature of 380 ℃，reaction pressure 13 MPa，LHSV 0.3 h-1, the ratio of ketone-benzene and solvent-oil is 8:1 and 5:1，respectively. The final wax product has a melting point of 50.7℃，n-alkane content of 93.7%.

HIGH CONCENTRATION WASTEWATER INSTEAD OF STEAM FOR COOLING COKE IN DELAYED COKING

2018, 49(12):  64-66. 

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The commercial application of high concentration wastewater in cooling coke process instead of 1.0 MPa steam in a 2.4 Mt/a delayed coking unit of CNOOC Zhoushan Petrochemical Company was introduced, which not only can reduce the use of steam and unit energy consumption, and also can handle some high concentration wastewater that is difficult to treat in swage water treatment plant. The application results showed that the reduction of energy consumption is about 237.02 x 103 MJ/d, the discharged out wastewater is reduced about 75 t/d.

ANALYSIS FOR SUPER LONG-TERM RUNING OF 1.7 Mt/a RHT UNIT IN CHANGLING COMPANY

2018, 49(12):  67-70. 

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A residual oil hydrotreating unit in SINOPEC Changling Company successfully ran for four cycles. The first cycle ran for 426 days, processing residue with high content of iron and calcium; the 2nd cycle was up to 471 days. Due to the overhaul, the 3rd cycle only worked for 326 days. By optimizing catalysts grading, blending LCO and decreasing VR ratio, the fourth cycle was even longer, as long as 693 days. Compared with the second cycle, the total amount of feed and VR processed, utilization efficiency of the catalyst, and the impurities removal rate in the fourth cycle were all higher, thought the blending ratio of VR was less than in the former.

DEVELOPMENT AND COMMERCIALIZATION OF LIGHT WHITE OIL PRODUCED FROM DIESEL BY HIGH-PRESSURE HYDROGENATION TECHNOLOGY

Sun Peng Sun Guoquan Zhang Pengfei Quan Hui

2018, 49(12):  71-75. 

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The low sulfur and low aromatic light white oil production technology developed by Dalian Research Institute of Petroleum and Petrochemicals (FRIPP) was introduced, where the bench scale high-pressure hydrogenation device was adopted and the diesel fraction was used as material. The commercial application results showed that at conditions of PH2 pressure of 15.0 MPa, hydrogen-to-oil ratio 800 (v), reaction temperature of 60 ℃+base, and the optimized liquid space velocity, the mass fraction of the aromatics is 0.004%, 0.007%, 0.015%, 0.021%, 0.046% for 160-18 ℃, 185-215 ℃, 215-245 ℃, 245-280 ℃, 280-310 ℃ fractions, respectively, all meeting with the industry standard of NB/ST/T 0913-2015（Light White Oil II）. The fraction heavier than 310 ℃ gives pour point of －9 ℃ and Saybolt color of ＋30，meeting the industry standard of NB/SH/T 0006-2017( Industrial Mineral Oil II).

STUDY ON PREDICTION OF CARBON NUMBER DISTRIBUTION OF DIESEL DISTILLATE

Ren Xiaotian Chu Xiaoli Tian Songbai

2018, 49(12):  76-80. 

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For the purpose of obtaining the detailed carbon number distribution of diesel distillate from its bulk properties and hydrocarbon group compositions，a new method was proposed based on the k-nearest neighbor regression algorithm （KNR） and over-sampling. With the standard methods，bulk properties，group compositions and carbon number distribution of the representative samples were obtained to build the data bank. As to a new sample to be measured，the nearest 6 samples were confirmed according to the bulk properties and group compositions, a massive virtual samples were obtained around this new sample using over-sampling technique on the 6 samples. With the KNR，the carbon number distribution of the new sample can be determined by linear weighted summing of the 4 virtual neighbors. A prediction model was established for the straight-run diesel，the contents of 312 carbon number lumps can be calculated simultaneously from the content of sulfur，nitrogen，acid number and the compositions of 11 type hydrocarbons（paraffin，monocycloalkane，bicycloalkane，tricycloalkane，alkylbenzene，indan/tetrahydronaphthalene，indene，naphthalene，acenaphthene，acenaphthlene and tricyclic aromatic hydrocarbon）. The model was accurate，fast and easy to maintain，which made it more useful and valuable in practical implement.

RAPID DETERMINATION OF DIESEL OXIDATION STABILITY

2018, 49(12):  81-85. 

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To establishing a simple and rapid method for determining diesel oxidation stability, a new type of instrument was developed, the oxidation induction period and oxidation inflection point were used as the symbol of oxidation stability. By means of the single-factor test and orthogonal test, the factors that impact on the diesel oxidation stability are explored. The optimal experimental conditions for the new instrument are 140℃，and O2 pressure of 700kPa. Meanwhile, a correlation model between the filterable insoluble substance at 140°C and the symbol was established. The results showed that the oxidation inflection point can be used to predict the filterable insoluble substance at 140°C. The method has good repetition and differentiation and can be used for evaluation of diesel oxidation stability.

OPTIMIZATION OF FRACTIONATION SYSTEM IN VGO HYDROCRACKING UNIT

2018, 49(12):  86-91. 

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A model for 4.0 Mt/a wax oil hydrocracking unit fractionation system of CNOOC Huizhou Petrochemical Company Limited is established by process simulation software. A comprehensive systematic analysis and diagnosis for the fractionation system was conducted to find out the unreasonable or operation parameter optimization space. Optimization measures are proposed and implemented such as reducing the pressure of the main fractionator, minimizing the flow of the recirculated tail oil to the furnace, and optimizing the stripping steam volume, resulting in improved the clarity of cutting, the separation of products, and the yield of high-value products such as heavy naphtha and aviation kerosene. The economic benefit of the unit is increased. At the same time, the energy of the fractionation system is comprehensively optimized. The load of the heating furnace is vacated through the reduction of operation pressure of the fractionation tower and the optimization of the heat distribution, which solves the bottleneck of insufficient heating furnace load and increases the production flexibility of the unit.

DENTIFICATION AND ANALYSIS OF KEY PARAMETERS FOR ENERGY CONSERVATION PROCESS OF ABSORPTION AND STABILIZATION SYSTEM WITH INTENSIFYING ABSORPTION PROCESS

2018, 49(12):  92-96. 

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By comparing the effect of changing parameters in a range on overall cost of an absorption tower with a side-draw in the energy conservation process, key parameters which influence the economic benefit of the absorption-stabilization system were indentified. The effect of changes of olefin and energy prices on parameters identification was also studied. Case study showed that, regardless of how the olefin prices and energy prices changed, the condensed oil tank temperature and supplementary absorbent flow rate are two key parameters. Desorption tower pressure, feed temperature of stabilization tower, and side draw flow rate and location of absorption tower have larger effects on the total cost. While the feed location on stabilization tower and hot feed proportion of desorption tower have little effect.

SYNTHESIS OF MANNICH BASE INHIBITOR AND THEIR EFFECTIVENESS AGAINST CORROSION

2018, 49(12):  97-102. 

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In this paper, imidazoline (IMTT) was synthesized through amidation and cyclization reactions by using oleic acid, triethylene tetramine as raw material. IMTT, which is reacted with formaldehyde and acetone, is used to prepare mannich base inhibitor (IMTTM). The structure of product was identified by IR. By using dynamic weight loss method, polarization curve method, AC impedance technique (EIS) and SEM-EDS, the corrosion inhibition of number 10 steel in HCl aqueous solution was studied. The results showed that at 60 ℃, the corrosion inhibition rate of IMTT and IMTTM is 96.11% and 97.75%%, respectively, and the effect of IMTTM is more significant. Polarization curve indicated that both IMTT and IMTTM are a mixed corrosion inhibitor of anode. The EIS test results are basically as same as the ones of polarization curve and weight loss method. SEM-EDS study demonstrated that the corrosion products are mainly different valence oxides of Fe, Cr and Mn. In addition, the corrosion product formed by IMTTM is denser, resulting in better corrosion resistance. It is found through simulated isotherm curves that both inhibitor IMTT and IMTTM follow Langmuir isotherm adsorption.