Table of Content

12 November 2019, Volume 50 Issue 11

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TECHNICAL CONSIDERATION AND RELEVANT TECHNOLOGICAL DEVELOPMENT ON MAXIMIZING CHEMICALS FROM CRUDE OIL

Xu Youhao Wang Xieqing Shu Xingtian

2019, 50(11):  1-10. 

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The maximum production of chemical raw materials from crude oil is a hot spot in petrochemical research field. Based on the domestic and foreign technical schemes for chemical raw materials production fromcrude oil and long-term research experiences of SINOPECResearch Institute of Petroleum Processing in this field, this paper summarizes five technical schemes for maximizing BTX and maximizing light olefins from crude oil. In BTX-based scheme, the residue hydrocracking process is the core technology, and the deep catalytic cracking（DCC） process is the core technology in light olefins-based scheme. When maximizinglight olefinsespecially propylene, thedevelopmentof higholefin-selectivitydeep catalytic cracking process(HOS) can greatly increase the yield of propylene. In the process of maximizing production ofchemical raw materials, solvent deasphalting and RGCT/POX processes have become an indispensable process.

EXPERIMENTAL STUDY OF REMOVING NICKEL AND VANADIUM FROM RESIDUE IN STRONG ELECTRIC FIELD

Jiang Xingjia Wang Xue Cui Xin'an

2019, 50(11):  11-15. 

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Based on the polarization effect of electrostatic field on polar components, the strong electric field was used to break the balance system of residue to remove nickel and vanadium. The effect of temperature (70-160℃)，residence time (0.5-4h)，solvent/residue mass ratio (0.5-6) and electric field intensity (1 500-7 500v/cm) on the removal ratio of nickel and vanadium were investigated. Results showed that increasing temperature and mass ratio of solvent/residue could reduce the viscosity of residue and facilitate movement and sedimentation of the nickel-containing and vanadium-containing components in the residue；increasing the electric field intensity was conducive to promote the agglomeration of polar components of nickel and vanadium compounds in the residue. The removal ratio of nickel and vanadium were 61.4% and 70.4%, respectively，under the optimum conditions of a temperature of 160 ℃，a solvent/residue mass ratio of 4，a residence time of 2 h and an electric field intensity of 4500 V/cm，and the yield of purified residue was 88.2%.

INDUSTRIAL APPLICATION OF DCC-PLUS TECHNOLOGY

Cai Jianchong Wan Tao

2019, 50(11):  16-20. 

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The concept of DCC-Plus technology developed by SINOPEC Research Institute of Petroleum Processing (RIPP) and the first industrial application of the technology were introduced. The results from DCC-Plus units showed that compared with DCC technology, the DCC-Plus could meet the demand of increasing the production of low carbon olefins while decreasing gasoline and diesel fuel. The yield of propylene rose to 18.22% in DCC-Plus process from 15.50% of the original design, the total yields of gasoline and diesel were reduced to 39.07% from 45.10%, respectively, and the yields of dry gas and coke remained low.

INDUSTRIAL APPLICATION OF JR-SA06 EFFICIENT SLURRY DEASH AGENT

2019, 50(11):  21-25. 

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The removal of solid catalyst powder from FCC slurry is a common technical challenge in the deep processing of FCC slurry. To realize deep purification for slurry and to improve the comprehensive utilization value of the slurry, the JR-SA06 efficient slurry deash agent was first applied in 2.3 Mt/a FCC unit of a company. The application results demonstrated that adding 500 μg/g deash agent based on the FCC slurry and settling at 90-95 ℃ for 72 hours, the ash content in the slurry decreased from 0.28% to 0.019%, removal rate of ash reached 93.16%, which is superior to the common deash agents and creates good conditions for the subsequent processing and utilization of slurry.

REGENERATION OF LUBE HYDROFINISHING NOBLE CATALYST RLF-10L

2019, 50(11):  26-29. 

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Through the analysis, regeneration and evaluation of the deactivated lube hydrofinishing catalyst RLF-10L of a lube hydroisomerization dewaxing unit, the primary deactivation causes were fixed, and the regeneration scheme of RLF-10L was proposed. Based on the scheme, the regeneration of RLF-10L was completed in commercial scale in SINOPEC Catalyst Company Changling Division . The analysis and evaluation results showed that the regenerated RLF-10L met the requirements of regeneration specification, and the hydrogenation activity after regeneration reached the same level of the catalyst regenerated in laboratory, indicating that the activity of the noble catalyst RLF-10L can be recovered well. This work is very important to the re-start up of the lube hydroisomerization dewaxing unit.

EFFECTS OF DESULFURIZATION AND DENITRATION ADDITIVES ON CATALYTIC CRACKING REACTIONS

2019, 50(11):  30-34. 

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The influence of the addition of three different RESN additives on the catalytic cracking reaction performance was investigated. The feasibility returning to FCC unit of the catalytic cracking catalyst with additive was discussed. The results of fixed fluidized bed（FFB）showed that the addition of 4.2% different RESN additives has a certain influence on the yield of cracking gas and diesel oil and the content of S in FCC fluid products. The results of the ACE evaluation indicated that the addition of RESN-3 had little or no effect on the catalytic cracking reaction when the mass fraction of the additive was no more than 2%。It is feasible for the mixture to be regenerated in FCC unit.

SYNTHESIS OF [N, O]-ZIRCONIUM COMPLEX AND ITS CATALYTIC PERFORMANCE FOR ETHYLENE OLIGOMERIZATION

2019, 50(11):  35-39. 

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The Zirconium dichloride (zirconium salicylaldehyde aniline), a [N,O] zirconium nonallocene complex, was synthesized. The structure of the complex was investigated by means of spectrum analysis. The catalytic activities and selectivities of the zirconium complex with Et2AlCl as co-catalyst in ethylene oligomerization were studied under different reaction temperatures, Al/Zr ratio, and various electron donors. Under optimal reaction conditions, the activity was 11 636 g / (gZr?h )，and selectivity of the α- olefin was 97.8%.

THE FIRST INDUSTRIAL APPLICATION OF SEMI-REGENERATIVE CATALYTIC REFORMING CATALYST SR-1000

2019, 50(11):  40-44. 

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The first application of semi-regenerative reforming catalyst SR-1000 developed by SINOPEC Research Institute of Petroleum Processing was conducted in the 250 kt/a reforming unit of SINOPEC Qingdao Petrochemical Company. The application results showed that the catalyst SR-1000 had good activity，selectivity，stability and excellent regeneration performance for gasoline or aromatics production. After long term operation，the catalyst still showed good temperature sensitivity. The coke deposition rate was slow, which satisfies with the long term stable operation of the unit under severe operation conditions.

CHARACTERIZATION AND EVALUATION OF PRESULFURIZED NiO/Al2O3 CATALYSTS UNDER DIFFERENT SULFURIZATION CONDITIONS

2019, 50(11):  45-49. 

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The NiO/Al2O3 catalysts with 20% NiO loading were prepared by stepwise impregnation method with industrial Al2O3 as support. The sulfided catalysts were characterized by BET, XRD, XPS and TEM. The effect of presulfidation conditions on the selective hydrogenation performance of the catalyst was studied in a 10 mL fixed-bed hydrogenation reactor using toluene/n-heptane solution containing dicyclopentadiene (DCPD) and styrene as the model compound. The results showed that sulfidity increased first and then decreased with the increase of presulfidation temperature in the range of 280 -320 ℃. The optimum presulfidation temperature for NiO/Al2O3 catalyst was 300 ℃. The nickel sulfide grains were small and uniformly dispersed when sulfided at 300 ℃. At 180 ℃, 3.5 MPa, space velocity of 3.5 h-1, H2/oil volume ratio of 400:1, the styrene conversion was 97.32%, DCPD conversion was 94.78%, and DCD selectivity was 76.63%.

EFFECT OF ARSENIDE IN FCC GASOLINE ON THE PERFORMANCE OF CoMo/Al2O3 HDS CATALYST

2019, 50(11):  50-55. 

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The influence of arsenic compounds on the HDS activity of CoMo/Al2O3 catalyst was tested using a model oil with high content of Triphenyl arsenic or Triethyl arsenic as arsenic source. The catalyst was conducted the spiked treatment of arsenic. XRF, BET, XRD and Py-IR were used to characterize the physicochemical properties of CoMo/Al2O3catalysts before and after arsenic poisoning. The hydrogenation activity of CoMo/Al2O3 before and after arsenic poisoning as well as the deactivation temperature of the fouled catalyst was evaluated. The results indicated that after arsenic poisoning, the hydrogenation activity of CoMo/Al2O3 decreased significantly due to the loss of B and L acidities of the catalysts.

DEVELOPMENT OF LOW BASIC CALCIUM POLYISOBUTYLENE THIOPHOSPHONATE

Liu Yinong Duan Qinghua

2019, 50(11):  56-60. 

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The preparation process of calcium polyisobutylene thiophosphonate，including polyisobutylene thiophosphonic acid and calcium polyisobutylene thiophosphonate were developed. The reaction parameters for synthesis of polyisobutylene thiophosphonic acid, such as reaction temperature，reaction time，the dosage of P2S5 and catalyst，the dosage of water for hydrolysis were investigated. The optimized reaction parameters covered a reaction temperature of T0，a reaction time of 10 h，a mass ratio of P2S5 to polyisobutylene of 21%，a mass ratio of catalyst to polyisobutylene of 0.5% and a mass ratio of water to polyisobutylene thiophosphonic anhydride of 0.1%. The low basic calcium polyisobutylene thiophosphonate were synthesized by calcification process. The synthesis of polyisobutylene thiophosphonate in pilot reactor indicated that the preparation conditions were controllable with good test repeatability. The product, calcium polyisobutylene thiophosphonate, has a base value of 40-50mgKOH/g，while the mass fractions of P and S are greater than 0.9% and 3.0%, respectively. The product has good cleaning, dispersion and oxidation resistance, and can be used in internal combustion engine oil.

STUDY ON STRUCTURE AND PERFORMANCE OF MANNICH DETERGENTS

Xin Shihao Huang Zuoxin

2019, 50(11):  61-65. 

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Mannich base detergents with different structures were synthesized and their detergency properties for gasoline and diesel fuel were evaluated. The relationship between the molecular structure, thermal stability, solubilization and bond energy of Mannich base with detergency property was discussed. The results showed that Mono and Bis Mannich base had better detergencies, but Diamine had worse detergency. Increasing the number of nitrogen atom in Mannich base amines could not further improve its cleaning performance. The higher the thermal stability of Mannich base, the better the cleaning performance. When the thermal stability was equal, the stronger the solubility, the better the cleanliness. The carbon-nitrogen bond energy generated by secondary amine in Mannich base molecule was less than that generated by primary amine, and it is easy to break at high temperature, resulting in poor cleaning performance of mannich base.

SYNERGISTIC PROPERTY OF SODIUM ION - EXCHANGED LAYERED ZIRCONIUM PHOSPHATE AS ADDITIVE IN LITHIUM - BASED GREASE

2019, 50(11):  66-72. 

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The tribological properties of sodium ion-exchanged layered zirconium phosphate (Na-α-ZrP) combined with molybdenum dialkyldithiophosphate (MoDDP) as a lithium-based grease additive was investigated by a four-ball tester. The morphologies, elemental distributions and chemical state of the worn surfaces were analyzed by 3D optical profiler, scanning electron microscope, X-ray energy spectrometer and X-ray photoelectron spectroscopy. The results indicated that Na-α-ZrP and MoDDP had outstanding synergistic effects on extreme pressure, friction-reducing and antiwear properties and the synergistic effects were enhanced with the increase of the tester load. The formation of Na-α-ZrP physical adsorption film and Mo, S and P elements chemical reaction film formed on the friction pair is the reason for outstanding synergistic effects.

TRIBOLOGICAL PROPERTIES AND MECHANISM OF LUBRICATING OIL CONTAINING NANO-COPPER IN MAGNETIC FIELD

2019, 50(11):  73-78. 

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The nano-copper lubricating oil additive modified by oleic acid was synthesized. The tribological properties of nano-Cu lubricating oil in different magnetic fields were investigated by modified four-ball machine. The results showed that the wear spot diameter and friction coefficient of the steel ball in the lubricating oil containing nano-Cu were smaller than those in the environment without magnetic field. Scanning electron microscopy (SEM) and X ray photoelectron spectroscopy (XPS) were used to analyze the wear spots, and the tribological mechanism of nano-Cu in magnetic field was discussed. It is concluded that on the one hand, induced current caused by external magnetic field promotes the softening of Cu; on the other hand, the applied magnetic field may promote the participation of Cu in the tribochemical reaction to form CuO.

EFFECT OF BASE OIL ON PROPERTIES OF TITANIUM COMPLEX GREASE

2019, 50(11):  79-86. 

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Titanium complex grease was prepared from single mineral base oil, synthetic oil and compound mineral base oil, respectively. The consistency, shear stability, colloidal stability, thermal stability, anti-wear and anti-friction properties of titanium-base composite grease were investigated. The results showed that the type of base oil had a great influence on the performance of titanium complex grease, and mineral base oil is more suitable as base oil for preparing titanium composite grease. The drop point of titanium-base composite grease prepared by T110 mineral oil was 326 °C, the steel mesh oil separation rate was 0.8%, the average friction coefficient was 0.073, and its physical and chemical properties are excellent, however, the anti-wear and anti-friction properties need to be improved; the physical and chemical properties and anti-wear of the titanium-base composite grease prepared by the composite of mineral base oils had a good anti-friction performance with an excellent comprehensive performance. The mixed mineral base oil of 600N and MVI500 mineral base oil at a ratio of 1:1 was proved an ideal compound base oil for preparing titanium-base composite grease, and the prepared titanium base grease had a dropping point of 333 °C, a steel mesh oil separation rate of only 0.7%, an average friction factor of 0.061, showing good performance in all aspects.

ECONOMIC ANALYSIS OF FCC DIESEL PROCESSING AND CONVERSION PROCESS

2019, 50(11):  87-92. 

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Based on the molecular structure of diesel components, the relationship of compositions of various diesel raw materials with hydrogenation products was analyzed; the dearomatization reaction rules in the hydrotreating process of diesel components and the impacts of different hydrogenation depths on LCO recycle conversion were discussed; the different processing routes of LCO from the economic point of view were compared. The results showed that the H2 consumption of hydrogenation saturation reaction accounted for about 50% of the total hydrogen consumption of the reaction in the hydrotreating process for producing China VI standard vehicle diesel fuel. Due to high density and high content of polycyclic aromatic hydrocarbons of raw material LCO, deep dearomatization is required for the production of China VI standard diesel fuel, resulting in large hydrogen comsumption and the poor economy. The combined process of selective hydrotreating and catalytic cracking (LTAG) can reduce the hydrogenation depth and greatly decrease the hydrogen cost. The technologies such as hydroconversion to produce gasoline, hydroconversion to produce aromatics, hydrocracking mixed blending feedstock, and combined process of residue hydrocracking and catalytic cracking reycling to realize efficient utilization of LCO resources rich in aromatics.

STUDY OF COMPREHENSIVE UTILIZATION OF NAPHTHENIC HEAVY VACCUM GAS

2019, 50(11):  93-96. 

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The high value added products were prepared by high pressure hydrogenation-isomerization dewaxing- hydrofinishing and then precision fractionation process using naphthenic heavy vacuum gas oil as feedstock. The test results showed that by controlling the hydroprocess depth and the cutting temperature of precision fractionation, the high value added rubber plasticizer, transformer oil and light white oil could be obtained. The product distribution can be adjusted according to market demand, leading to maximized benefits of enterprises.

GASOLINE UPGRADING AND GASOLINE POOL COMPOSITION OPTIMIZATION TO MEET CHINA VI STANDARD

2019, 50(11):  97-101. 

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In the gasoline pool of PetroChina Karamay Petrochemical Company, the proportion of reformer gasoline and hydrogenated FCC gasoline was similar, and the blending proportion of high-octane, low-aromatic and low-olefin gasoline was relatively low, resulting in that the aromatics and olefin contents could not meet the requirements of China VI gasoline standards. To solve the above bottlenecks, a plan for upgrading the gasoline product and optimizing the structure of gasoline pool was presented. During the overhaul in 2018, the catalytic cracking unit, FCC gasoline HDS unit, diesel hydroupgrading unit and continuous reforming unit were revamped and expanded, and a light gasoline isomerization and an etherification unit were newly built. After the implementation of the plan, the aromatics and olefin content in the gasoline pool decreased by 5.0 and 2.2 percentage points, respectively. The gasoline product met the National VI gasoline standard. The diesel to gasoline ratio was flexible and controllable. I t is estimated that the annual economic benefit will increase by 265.38 million Yuan in 2019, with a diesel/gasoline ratio of 1.25.

EXPERIMENTAL STUDY OF PRETREATMENT OF PTA WASTEWATER BY AEROBIC BIOLOGICAL FLUIDIZED BED

2019, 50(11):  102-105. 

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Biological fluidized bed technology was used to conduct side-stream test for PTA (p-terephthalic acid) wastewater treatment with a handling capacity of 300 ~ 400L/h. The results showed that in the case of inlet COD of 1000 ~ 3600 mg/L and hydraulic retention time of 7-8h, the average removal rate of the COD reached 91%, and the average volumetric load of BOD was 3.82kg COD/(m3?d). The process has strong impact resistance, and the COD of the treated material was less than 500 mg/L, meeting the requirements of enterprise pretreatment.

STUDY OF CHEMICAL OXIDATION TREATMENT OF SOIL POLLUTED BY PAHs

2019, 50(11):  106-110. 

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The effects of additives, FeSO4 and NaClO, on the chemical oxidation treatment efficiency of soils contaminated by polycyclic aromatic hydrocarbons using Na2S2O8 as oxidant were investigated. The different roles of the additives were compared. Results showed that removal efficiency of PAHs was enhanced by addition of little FeSO4 as catalysts in NaS2O8 system. NaS2O8 and NaClO could be used in coordination with sodium persulfate to achieve the purpose of cooxidation. It is concluded that the test results can provide some references for the selection of site restoration technology and chemical oxidation process design.