Table of Content

12 March 2018, Volume 49 Issue 3

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DEVELOPMENT AND COMMERCIAL APPLICATION OF FIXED BED HYDROTREATING CATALYSTS FOR LOW QUALITY RESIDUES

Qing-He YANG Zhi-Cai SHAO

2018, 49(3):  1-6. 

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According to the different characteristics of residues, catalyst RDM-36 with large holes for conversion of asphaltene, demetallization catalyst RDMA-31 with doublet holes, porous foam type protective catalyst RG-30 and honeycomb cylindrical type protective catalyst RG-20 and RG-30E with special shape and pore structure were developed by RIPP. Meanwhile layered catalyst bed processes were designed especially for processing residues with high content of Ni+V, asphaltene, and Fe+Ca, respectively. The industrial application results showed that the residue hydrotreating technology with RDMA-31 can be used to treat residue with high asphaltene content. The content of metal impurities in product meets the requirement of high quality raw material for FCC unit. The residue hydrotreating technology with RDM-36 can be used to treat residual oil with a (Ni+V) content close to 200 μg/g. The removal rate of metal impurities reaches the expected target. By reasonably graded RG-30, RG-20 and RG-30E, high (Fe+Ca) content residue can be processed with relatively low pressure drop and prolonged operating cycle.

CAUSE ANALYSIS OF HIGH IRON CONTENT ON FCC EQUILIBRIUM CATALYST

2018, 49(3):  7-12. 

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Aiming at the problem of excessive iron content on the FCC equilibrium catalyst of Sinopec Hainan Refining & Chemical Company, the sources and distribution characteristics of the iron on the equilibrium catalyst were analyzed. The analysis showed that the iron introduced by the catalyst production process (the iron contained in the fresh catalyst) is relatively low and stable, and its impact on the performance of equilibrium catalyst is small. The iron carried by FCC feedstock (exogenous iron) is the main source for iron on the equilibrium catalyst. It is found that the exogenous iron is from the crude oil transportation, storage and the corrosion of upstream processing units. The heavy oil without hydrogenation and the backwashing oil (bottom oil) from the residue hydrogenation unit became parts of FCC feedstock, which results in too high iron content in the FCC feedstock. Based on the analysis results, the improvement measures of reducing the iron content on the equilibrium catalyst were proposed.

PREPARATION OF MANGANESE DIOXIDE CATALYST WITH DIFFERENT MORPHOLOGIES AND PERFORMANCE OF ACTIVATING PMS FOR Rh B DEGRADATION IN AQUEOUS SOLUTIONS

2018, 49(3):  13-20. 

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Heterogeneous activation of peroxymonosulfate (PMS) becomes an important technology for degradation of organic compounds in aqueous solutions by generating sulfate radicals and hydroxyl radicals. In this study, three types of MnO2 catalysts were synthesized: two 1D manganese dioxides，nanorods and nanowires, and one α-MnO2 without a specific appearance. The catalytic performance of three MnO2 catalysts for Rh B degradation in aqueous solutions through activated PMS was compared. The results indicated that the nanowire MnO2 has the highest activity. By investigating the influence of different factors on the catalytic activity of nanowire MnO2, the best conditions for the degradation of Rh B in water are as follows: 35℃，pH=8, Rh B concentration of 10μg/g, PMS 0.5 g/L and nanowire MnO2 0.3 g/L. By the experiments of eliminating radicals, the mechanism for Rh B degradation in aqueous solution through activating PMS was studied, indicating that the sulfate radical from PMS activation plays an important role in degradation of organic compounds. The activation of PMS, the generation of sulfate radical and the process of Rh B degradation are illustrated in detail.

PREPARATION OF AuCl3-BiCl3/C AND PERFORMANCE OF CATALYSTS

2018, 49(3):  21-24. 

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Using AuCl3 as active component, BiCl3 as additive and active carbon as carrier, AuCl3-BiCl3/C catalysts were prepared by impregnation method and were characterized by BET，XRD and TEM. The catalytic performance and selectivity to VCM were investigated in a fixed bed reactor. The results showed that adding BiCl3 is beneficial to enhancing the performance and inhibiting coke deposition during the reaction. Among catalysts prepared, the 0.3%AuCl3-0.9%BiCl3/C catalyst is the best one. The active components are highly dispersed on the surface of the carrier. Under the reaction conditions of C2H2 hourly space velocity of 20h-1, feed volume ratio V(HCl)/V(C2H2)=1:1.1, the conversion of acetylene is up to 98.9%, the selectivity to VCM is up to 99.7% after test for 24h.

STUDY ON REACTION CHEMISTRY OF NON-BASIC NITROGEN COMPOUNDS IN FCC PROCESS

2018, 49(3):  25-29. 

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The impact of non-basic nitrogen compounds represented by indole on FCC reaction and the contribution and conversion rule of these compounds during the process was studied in a fixed fluidized bed (FFB). The results showed that the addition of non-basic nitrogen compounds reduces the conversion of FCC process, and influences the product distribution. The higher the nitrogen content in feedstock, the greater the influence on the reactions. In the catalytic cracking reaction of indole, the nitrogen in the raw material oil was distributed in gasoline distillates, diesel distillates, coke and heavy oil fractions were 12.58%, 54.15% and 24.88% respectively. In addition, 4.46% nitrogen was converted into ammonia, and the nitrogen in the heavy oil distillate was less than 5%. Indole is the most susceptible to alkylation during catalytic cracking. Due to hydrogen transfer reaction, the nitrogen-containing heteroatomic ring of indole molecule is saturated, and then converted further into aniline or ammonia through the ring-opening cracking reaction. Ammonia reacts with olefin to form aniline and further quinoline. The macromolecular nitrogen compounds are generated from small molecule nitrogen compounds by cyclization and condensation reactions.

EFFECT OF MOLECULE COMPOSITIONS ON VISCOSITY INDEX OF LUBE BASE OIL

2018, 49(3):  30-34. 

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Well understanding the impact of molecule compositions on the viscosity index of lube base oil is very important for feedstocks selection and operation adjustment. With the combination of traditional and high resolution mass spectroscopy, nuclear magnetic resonance characterization methods, the relation of viscosity index and molecule compositions of four samples (feed A1 and A2, base oil product B1 and B2) was studied. The results showed that B1 and B2 have lower content of paraffin, lower iP/nP, but higher content of naphthene, resulting in lower viscosity index than A1 and A2. The content of alkanes in A1 and B1 is lower and the content of naphthene with different ring numbers is higher than in A2, B2, respectively, A1and B1 still have higher viscosity index because they have more carbon number in the same distillate range. The properties and constituents of narrow fractions indicated that the viscosity index of narrow fraction increases with the end point and the fraction with higher viscosity index has higher contents of paraffins and one ring naphthenes.

EFFECT OF REACTION CONDITIONS ON BASIC NITROGEN COMPOUND CONVERSION IN RESIDUE HYDROTREATING

2018, 49(3):  35-40. 

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Hydrotreating reactions of Dalian mixed residue were studied in an autoclave to investigate the effect of hydrogen pressure and catalyst-to-oil mass ratio on distribution and types of basic nitrogen compounds in the liquid product. The nitrogen compounds in product and raw material were characterized by electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FT - ICR MS). The results showed that N1 (one N atom) type alkaline compounds in the residue before and after the reaction account for most proportion, N1S1 (one N atom and one S atom) and O1 (one O atom) is next, the relative abundance of the other types are low. With increase of hydrogen pressure, most of the basic N species in product decrease. At the same time, hydrogenation breaks down the side chains of the compounds and makes the carbon number in N1 species reduce and molecular size become smaller. When catalyst-to-oil ratio increase, the relative abundance of most N compounds and molecular saturation decreases, the equivalent double bond (DBE) of N1 compounds has no significant change (DBE: 9 ~ 18) and the carbon numbers of Ni compounds decrease significantly.

STUDY ON CLASSIFICATION OF FEEDSTOCKS FOR FCC MIP PROCESS

2018, 49(3):  41-47. 

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Based on the commercial data from a FCC MIP process unit，seven properties of feedstock including density, saturated hydrocarbons content, aromatics content, asphaltene plus resin content, nickel content, vanadium content and residue carbon were used to cluster for the feedstock oils for MIP process by K-means clustering method and fuzzy c-means clustering（FCM）method, respectively. The ninety-five data of feedstock properties were classified into four categories by K-means clustering algorithm and into five categories by FCM clustering method. The results showed that the characteristic of every category of the feedstock oils is obvious, indicating the good applicability to the feedstock properties by each method. On the basis of the works above, the product distribution intelligent model for every category of feedstocks can be established to find the optical operation conditions for MIP process.

COLD MOLD STUDY OF A NOVEL DIAMETER-CHANGING RISER REACTOR

2018, 49(3):  48-53. 

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The effects of different operating conditions on the solid circulation and solid holdup distribution in the axial and radial directions of a novel diameter-changing riser were investigated in a cold-mold test using FCC equilibrium catalyst and room temperature air medium. The flow structure within the diameter expanded segment was described. Experimental results showed that the amount of solid circulation increases with the increase of the superficial gas velocity, and the bed height. When changing the ratio of intake air, the amount of circulation increases with the increase of the proportion of pre-lifting gas. Compared with the traditional riser, there are many kinds of flow patterns in the new structure riser, and the solid holdup in the expanded section is significantly increased. A dense phase turbulent flow pattern exists in the bottom region (εs is about 0.3—0.4) and a dilute phase pneumatic conveying form is observed in the upper region (εs is about 0.05—0.1) where the solid holdup has no obvious change. The novel variable diameter riser is able to redistribute the solid particles coming from the inclined pipe, resulting in inhibition of the traditional “ring-core” flow pattern, and making the radial distribution of solid holdup more uniform.

PRODUCTION OF CHINA V DIESEL BY REVAMPING CONTINUOUS LIQUID PHASE DIESEL HYDROTREATING UNIT

Dong Xiaomeng Yu Yang

2018, 49(3):  54-60. 

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The 2.2 Mt/a of continuous liquid phase diesel hydrotreating unit in SINOPEC Anqing Petrochemical Company was revamped to meet the requirements for the production of China V diesel in September 2016. Two hydrotreating reactors were applied in the reaction sector, and two fractionators were used instead of single distillation column. The full load calibration results in Jun, 2017 showed that the upgrading of the device is successful; the RS-2000 catalyst system exhibits a good activity and can meet the requirements for production of China V standard diesel.

PROBLEMS IN S ZORB PROCESS AND COUNTERMEASURES

Ning Wei, Peng Chen, Zhang Xueheng, WAng Xiaoqiang

2018, 49(3):  60-65. 

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Taking the S-Zrob gasoline desulfurization unit (1.5 Mt/a) in a Sinopec company as a research subject, this study introduced the running conditions after improvement of the unit. Two typical problems during operation were analyzed: (i) coking in feed heat exchanger E101 and (ii) degassing line wear leakage of D105 for receiving the used catalyst. The results showed that (i) strictly controlling the raw material source and prohibiting the gasoline with high content of gum or the non-transparent gasoline entering into the S-Zorb equipment are important to ensure the long period operation for feed heat exchanger E101; (ii) controlling the hydrogen flow rate of D105 for extraction and line speed in a reasonable range, at the same time, upgrading the material of degassing line. And (iii) in addition, strictly controlling the amount of fine powder in the system; and periodically measuring the thickness of the weak point of pipeline to ensure the long period operation of the unit.

RESEARCH OF PRODUCTION PROCESS OF ENVIRONMENT-FRIENDLY RUBBER OIL AND INDUSTRIAL APPLICATION

2018, 49(3):  66-70. 

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The relationship between CA value, PCA and contents of eight kinds of specific aromatics in SZ36-1 vacuum narrow distillate was investigated. Result showed that the distillates (≥480 ℃) have advantages of producing high CA environmental-friendly rubber oils. A new furfural extraction process named gradual fining-separation process was self-developed in which the furfural is injected at upper and lower parts of the tower instead of only at the top position injection. The new process greatly increases the yield of target rubber oils on the premise of the same product quality compared with the traditional technology. The industrial application of the new technology verifies the results of the laboratory research and greatly reduces the production cost of the product.

RECYCLING DIESEL FOR INCREASING JET FUEL AND NAPHTHA IN HYDROCRACKING UNIT

2018, 49(3):  71-74. 

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The industrial application of the new process, where the diesel products, are hydrocracking again was conducted to increase jet fuel and naphtha in a 3.6Mt/a hydrocracking unit of CNOOC Huizhou Petrochemical Co, Ltd. Without changing the device structure and the catalyst, the conversion rate of diesel reach 75%, target products (jet fuel, naphtha) yield increases by 3.29%, the smoke point of jet fuel has no significant change, the cetane number of diesel increases by 3.9 units,. The quality of the products meets their respective standards. The energy consumption of the device is slightly increased from 856.21 MJ/t to 859.72MJ/t raw material.

INVESTIGATION OF HYDRO-TREATED FCC RECYCLE OIL AS HYDROGEN DONOR FOR COKING REACTION

2018, 49(3):  75-79. 

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The hydrogen-donating indexes of the three narrow fractions of FCC recycle oil were measured. Among these fractions, the one which has the highest hydrogen-donating index was chosen to be used as hydrogen donor after being hydro-treated. The hydrogen-donating effect of the hydro-treated fraction was investigated in pilot tests. The results showed that the fraction (IBP-400℃) has the best hydrogen-donating capacity among the three narrow fractions of FCC recycle oil, and the hydrogen-donating capacity can be further improved by hydrotreatment. When the fraction (IBP-400 ℃) hydrotreated was used as hydrogen donor, the liquid yield can increase by 1.32% and coke yield can decrease by 2.45%.

INDUSTRIAL APPLICATION OF GARDES TECHNOLOGY IN CATALYTIC CRACKING GASOLINE HYDROGENATION

Yang Lifeng Liu Xin Liu Telin Liu Jianlong

2018, 49(3):  80-84. 

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GARDES technology developed by PetroChina Petroleum and Petrochemical Research Institute and China University of Petroleum (Beijing) was adopted in the 1.1 Mt/a catalytic cracking gasoline hydrogenation unit of PetroChina Sichuan Petrochemical co. Ltd，using catalytic cracking gasoline as the raw material to produce motor gasoline blending component in compliant with GB 17930—2016. The calibration results indicated that the mixed gasoline products with the mass fraction of sulfur of 7.1 μg/g can be obtained from the raw material of FCC gasoline with the mass fraction of sulfur of 69.6 μg/g，volume fraction of olefin of 30.3%，volume fraction of aromatics of 18.4%，and the octane number（RON） of 91.7. The loss of octane number（RON）is 0.5 unit. The yield of mixed gasoline is 99.41%, which is better than the control index, and the integrated energy consumption is slightly higher than the control index.

STUDY ON COMPREHENSIVE UTILIZATION OF CNOOC VACUUM RESIDUE

2018, 49(3):  85-88. 

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Comprehensive utilization of CNOOC Vacuum Residue was studied by the propane deasphalting technology. The vacuum residue is divided into DAO and DOA. 150BS can be obtained from DAO by hydrotreating-atmospheric/vacuum distillation-ketone benzene dewaxing or isomerization dewaxing-hydrofinishing; while by two stage furfural refinings, the high aromatic eco-friendly rubber oil with CA value up to 25.3% can be produced; The SZ36-1 furfural extract oil can be blended into DOA to produce heavy traffic road asphalt and meets the GB/T 15180-2010 technical requirements

EVALUATION OF INTERFACIAL TENSION AND EMULSIFYING PROPERTIES OF COMPOSITE SYSTEM OF HEAVY ALKYL BENZENE SULFONATE

Jing TIAN

2018, 49(3):  89-93. 

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Full range heavy alkyl benzene sulfonates were cut into a series of narrow fractions of HABS and then sulfonated. According to their molecular weight, the sulfonated narrow fractions are called HABS-1, 3, 5, 7, 9. The crude oil from Xinjiang 530 oilfield reservoir was used as oil phase, and its formation water in this oilfield as water phase. The effect of full range HABS and narrow fractions on emulsifying stability and interfacial tension (IFT) were measured, respectively. The results showed that the IFT value goes down firstly and then up with the increase of its molecular weight. The HABS with average alkyl carbon chain length of C15 (molecular weight of 398) can reduce the IFT level to 0.002 3 mN/m. The results of stability of oil-in-water emulsion showed that when HABS-3 mixed with HABS-1 (HABS-3:HABS-1=85:15) or with nonionic primary alcohol ethoxylate AEO-9 (HABS-3:AEO-9=85:15), the systems attain strong emulsion stability with emulsion composite index of 89.51% and 88.70%, while the IFT value is 0.009 8 mN/m and 0.005 9 mN/m, respectively, both are at 10-3 mN/m (ultra low) level.

SYNTHESIS AND PROPERTIES OF A NOVEL REVERSED DEMULSIFIER OF POLYQUATERNARYAMMONIUM SALT

2018, 49(3):  94-97. 

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A novel polyquaternary ammonium reversed demulsifier was synthesized with Jeffamine D-230, epichlorohydrin and N, N-dimethylethanolamine as raw materials. According to the molar ratio of Jeffamine D-230 to epichlorohydrin (1:2 and 1:4), The synthesized products with n(D-230)/n(epichlorohydrin)=1:2 and 1:4 are named Y-562 and Y-564,respectively. They were evaluated by bottle test with fresh crude oil from a petroleum platform in Bohai. The results indicated that when the demulsification temperature is 70℃, the demulsification time is 20 min and the amount of Y-564 is 15 mg/L, the water content in the oil is 0.7% and the amount of oil in the water is 80mg/L. The water layer in lower part is clear and the oil and water interface is clear, it means to achieve the optimum dehydration effect.

STUDY ON INFLUENCE OF NITROGEN CONTENT ON DETERMINATION OF TOTAL SULFUR IN DIESEL FUEL DETERGENTS AND ELIMINATION METHOD

2018, 49(3):  98-102. 

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Nitrogen element exerts strong interference in the ultraviolet fluorescence method for determination of total sulfur content in detergent additives for diesel fuel and results in great inaccuracy. This problem was investigated and solved by using high nitrogen suppressor. The effects of the installation of high nitrogen suppressor on elimination of the interference were studied. The working curve was established and the linearity of the working curve was investigated after the test condition was set up. The accuracy and the lower limit of detection of sulfur content were also investigated. The results showed that the strong interference problem is solved and the accuracy of the method is improved in determination of total sulfur content in diesel detergent additives. The working curve is linear up to 0.9998; the practical detection the lower limit is 0.2 mg?L-1. The relative standard deviation is less than 5% in the determination of practical samples.

INVESTIGATION OF CORROSION INHIBITION PERFORMANCE OF ORGANIC AMINES IN CRUDE UNIT OVERHEAD COOLING SYSTEM

Hai BoWang

2018, 49(3):  103-106. 

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The corrosion inhibition performance through neutratiing corrosive material of five organic amines (Triethylamine, N, N-Dimethylethanolamine, 3-Methoxypropylamine, Morpholine and Ethylenediamine) was investigated by acid-base neutralization titration, gas-liquid equilibrium, weight loss and the electrochemical technology. The neutralized performance order for the amines is Ethylenediamine > Morpholine > 3-Methoxypropylamine > N, N-Dimethylethanolamine > Triethylamine. The dissolved ability trend is Triethylamine < Ethylenediamine < 3-Methoxypropylamine < Morpholine < N,N-Dimethylethanolamine. The corrosion inhibition performance for the amines is Ethylenediamine > N,N-Dimethylethanolamine > Triethylamine> 3-Methoxypropylamine > Morpholine. When the mixture concentration rate of N, N-Dimethylethanolamine and Ethylenediamine is 7:1, the corrosion inhibition rate is 91.78%.