Optimization of Product Distribution for MIP Units Using Data Mining

Based on data from a petrochemical company’s MIP unit over the past three years,19 input variables and 2 output variables were selected for modeling using the maximum information coefficient and Pearson correlation coefficient among 155 variables,which included properties of feedstock oil and spent catalyst,operational variables,and material flows.The distillation range variables were reduced using factor analysis,and the feedstock oils were clustered into three types using the K-means++algorithm.Each feedstock oil type was then used as an input variable for modeling.An XGBoost model and a back propagation(BP)neural network model with a structure of 20-15-15-2 were developed to predict the combined yield of gasoline and propylene,as well as the coke yield.In the test set,the BP neural network model demonstrated better fitting and generalization abilities with a mean absolute percentage error and determination coefficient of 1.48%and 0.738,respectively,compared to the XGBoost model.It was therefore chosen for further optimization work.The genetic algorithm was utilized to optimize operational variables in order to increase the combined yield of gasoline and propylene while controlling the growth of coke yield.Seven commercial test results in the MIP unit showed an average increase of 1.39 percentage points for the combined yield of gasoline and propylene and an average decrease of 0.11 percentage points for coke yield.These results indicate that the model effectively improves the combined yield of gasoline and propylene while controlling the increase in coke yield.

Kinetic Study on Liquid-Phase Hydrodesulfurization of FCC Diesel in Tubular Reactors

According to the characteristics of FCC diesel, a technology of liquid-phase hydrodesulfurization of the diesel in tubular reactors was proposed and lab-scale experiments were carried out. A kinetic model for the hydrodesulfurization process was developed and verified. The model was utilized to predict the sulfur content of products under different operating conditions. The effects of temperature, space velocity, pressure, and hydrogen concentration on the dcsulfurization rate were investigated.

Nickel and potassium co-modified β-Mo_2C catalyst for CO conversion

Nickel and potassium co-modified β-Mo2C catalysts were prepared and used for CO hydrogenation reaction. The major products over β-Mo2C were C1-C4 hydrocarbons, only few alcohols were obtained. Addition of potassium resulted in remarkable selectivity shift from hydrocarbons to alcohols at the expense of CO conversion over β-Mo2C. Moreover, it was found that potassium enhanced the ability of chain propagation with a higher C2＋OH production. Modified by nickel,β-Mo2C showed a relatively high CO conversion, however, the products were similar to those of pure β-Mo2C. When co-modified by nickel and potassium,β-Mo2C exhibited high activity and selectivity towards mixed alcohols synthesis, and also the whole chain propagation to produce alcohols especially for the stage of C1 OH to C2OH was remarkably enhanced. It was concluded that the Ni and K had, to some extent, synergistic effect on CO conversion.

XPS study of potassium-promoted molybdenum carbides for mixed alcohols synthesis via CO hydrogenation

The X-ray photoelectron spectroscopy （XPS） was used to investigate the surface characteristic of potassium-promoted or un-promoted both β-Mo2C and α-MoC1-x pretreated by syngas at different temperatures,and the promotional effect of potassium on the catalytic performance was also studied.XPS results revealed that the content of surface Mo and its valence distribution between β-Mo2C and α-MoC1-x were quite different.Promoted by potassium,the remarkable changes were observed for surface composition and valence of Mo distribution over β-Mo2C.Potassium had strong electronic effect on β-Mo2C,which led to a higher Mo4＋ content.On the contrary,potassium had little electronic effect on α-MoC1-x,and K-Mo interaction was weak.Therefore,Mo0 and Mo2＋ became the dominant species on the catalyst surface,and the Mo4＋ content showed almost no increase as the pretreatment temperature enhanced.In terms of catalytic performance of molybdenum carbides,the increase in Mo0 most likely explained the increase in hydrocarbon selectivity,yet Mo4＋ might be responsible for the alcohols synthesis.

Catalytic performance of iron carbide for carbon monoxide hydrogenation

Novel iron carbide and potassium-promoted iron carbide catalysts were prepared and investigated for CO hydrogenation. The iron carbide showed high activity for CO hydrogenation under high pressures; with the addition of potassium, activity and selectivity to C5＋ hydrocarbons were greatly enhanced, and the selectivity to methane was suppressed under high pressure.

Transalkylation of Multi-secbutylbenzenes with Benzene over Hierarchical Beta Zeolite

A hierarchical beta zeolite synthesized by quasi-solid phase conversion method was characterized by BET, scanning electron microscope （SEM）, transmission electron microscope （TEM）, X-ray diffraction （XRD）, temperature-programmed desorption of ammonia （NH3-TPD）, 27A1 and 295i magic angle spinning nuclear magnetic resonance （27A1 and 29Si MAS NMR）, and its catalytic performance was compared with that of conventional microporous beta zeolite for liquid phase transalkylation of multi-secbutylbenzenes （MSBBs） with benzene. The results indicate that the hierarchical beta zeolite consists of nanosized crystals with a meso/ microporous structure and has stronger acid strength than the microporous beta zeolite. The higher conversion oftri-secbutylbenzene （TSBB） and selectivity ofsec-butylbenzene （SBB） are achieved on hierarchical beta zeolite than microporous beta zeolite, while the conversion of di-secbutylbenzene （DSBB） is slightly higher. The improvement of catalytic performance over hierarchical beta zeolite can be ascribed to the presence of mesopores, nanosized crystals and stronger acidity.

Catalytic performance of Fe modified K/Mo_2C catalyst for CO hydrogenation

Fe modified and un-modified K/Mo2C were prepared and investigated as catalysts for CO hydrogenation reaction. Compared with K/Mo2C catalyst, the addition of Fe increased the production of alcohols, especially the C2＋OH. Meanwhile, considerable amounts of C5＋ hydrocar- bons and C2= -C4= were formed, whereas methane selectivity greatly decreased. Also, the activity and selectivity of the catalyst were readily affected by the reaction pressure and temperature employed. According to the XPS results, Mo4＋ might be responsible for the production of alcohols, whereas the low valence state of Mo species such as Mo^0 and/or Mo^2＋ might be account for the high activity and selectivity toward hydrocarbons.

Computational Fluid Dynamics Simulation of Liquid-Phase FCC Diesel Hydrotreating in Tubular Reactor

The computational fluid dynamics(CFD) code, FLUENT, was used to simulate the liquid-phase FCC diesel hydrotreating tubular reactor with a ceramic membrane tube dispenser. The chemical reaction and reaction heat were added to the model by user-defined function(UDF), showing the distribution of temperature and content of sulfides, nitrides, bicyclic aromatics and monocyclic aromatics in different parts of the reaction bed. When the pressure was 6.5 MPa, the amount of mixing hydrogen was 0.84%(m), the space velocity was 2 h-1 and the inlet temperature was 633 K, the temperature reached a maximum at a height of 0.15 m, and the range of radial temperature reached its maximum(2.5 K) at a height of 0.15 m. It indicated that the proper ratio of height to diameter of catalyst bed in the tubular reactor was 5-6. The increase of inlet temperature, the mixing hydrogen and the decrease of space velocity led to the decrease in the content of bicyclic aromatics, sulfides and nitrides, and the increase in monocyclic aromatics content, while the high temperature increased. The results were in good agreement with experimental data, indicating to the high accuracy of the model.

A Selective Octane-Enhancing FCC Catalyst Using ZRP Zeolite as an Active Component

A hetero-crystalline seeding method to prepare a unique MFI type zeolite with mesopores of ca. 4 nm diameter designated as the ZRP zeolite, which possesses high stability and selectivity and is used as component of FCC catalysts to produce high-octane gasoline and light olefins, was developed. With the DOCR and DOCP catalysts containing the ZRP zeolite modified by phosphorus-incorporation as the octaneenhancing catalysts, the commercial trial was carried out in a 0.8Mt/a RFCC unit with a feedstock composed of Daqing atmospheric residue. As compared to the base catalyst, the LPG+gasoline+LCO product yield obtained from this catalyst was increased by 0.53m%. Meanwhile, the RON and MON of gasoline was increased by 1.4 and 2.4 units, respectively. The higher increment of MON is attributable to the higher isoparaffines content in gasoline. This result indicates that the ZRP zeolite possesses higher isomerization selectivity.

Single-step thermal carburization synthesis of supported molybdenum carbides from molybdenum-containing methyl-silica

A novel synthesis route to obtain highly dispersed molybdenum carbides in porous silica is described. The synthesis was carried out by a single-step heat treatment of molybdenum-containing and methyl-modified silica （Mo-M-SiO2） in argon atmosphere at 973 K. Mo-M-SiO2 precursor was facilely obtained via a one-pot synthesis route, using （NH4）6Mo7O24 4H2O （AHM） as molybdenum sources and polymethylhydrosiloxane （PMHS） as silica sources at the initial synthetic step. The optimal C/Mo molar ratio in reaction system for complete carburization of molybdenum species was 7. The carburization process of molybdenum species followed a nontopotactic route involving a MoO2 intermediate phase, which was evidenced by XRD, N2 adsorption-desorption and in situ XPS. Formation mechanism of Mo-M-SiO2 precursor was also proposed by observation of the reaction between AHM and PMHS with TEM. Furthermore, by adding TEOS into silica sources and adjusting TEOS/PMHS mass ratio, crystal phase of molybdenum carbides transferred from β-Mo2C to α-MoC1-x, and SiO2 structure changed from microporous to micro/mesoporous. Catalytic performances of samples were tested using CO hydrogenation as a probe reaction. The supported molybdenum carbides exhibited high selectivity for higher alcohol synthesis compared with bulk β-Mo2C and α-MoC1-x.

Supercritical carbon dioxide extraction of CLA-ethyl ester

Supercritical carbon dioxide(SC-CO_(2))extraction of Conjugated linoleic acid(CLA)ethyl ester was investigated at pressures in the range of 9 to 10.5 MPa and temperature gradients ranging from 0℃ to 21℃.The content of CLA-ethyl ester in the fraction was analyzed with gas chromatography(GC).The experimental results indicated that the rate of extraction would rise with the increase of pressure when temperature gradient was given.Moreover,the extraction pressure had insignificant influence on the selectivity of CLA-ethyl ester in SCCO_(2).When pressure was fixed,setting certain temperature gradient can improve the selectivity of CLA-ethyl ester in SC-CO_(2),and CLA-ethyl ester can be concentrated more effectively than without a temperature gradient.The acid value and peroxide value of the fractions were reduced obviously,compared to the raw material.The optimal condition is pressure at 10 MPa and temperature gradient at 11℃.