The effect of catalyst properties on residue oil hydroconversion was studied at moderate operating conditions(at a temperature of 400 ℃, an initial hydrogen pressure of 10 MPa, and a reaction time of 4 h) in a batch mode slurry phase with different catalyst samples. The results showed that the catalyst acidity had a good effect on residue conversion and MCR(micro carbon residue) conversion but brought about higher coke yield. Residue conversion was thermally induced but the catalyst acidity changed its conversion route. A catalyst with higher metal loading, higher hydrogenation activity and appropriate pore size had higher sulfur and metal removal rate, higher MCR conversion and also a lower coke formation. The activity of spent commercial catalyst AS1 and DS1 was slightly lower than the corresponding fresh ones but was still high enough for residue oil hydroconversion. It assumes that the role of the catalyst is to activate hydrogen species toward reaction with an aromatic carbon radical to yield a cyclohexadienyl type intermediate which will turn into liquid and also to absorb the mesophase which can easily aggregate to form coke.
The microstructure and properties of the coke samples collected from 4 different wall regions of the cyclone in the reactor of a residue fluid catalytic cracking unit(RFCCU) were analyzed by using the scanning-electron microscope(SEM), and the possible coke formation processes were investigated as well. The results showed that some of the heavy nonvolatile oil droplets entrained in the flowing oil and gas mixture could possibly deposit or collide on the walls by gravity settling or turbulence diffusion, and then were gradually carbonized into solid coke by condensing and polymerization along with dehydrogenation. Meanwhile some of fine catalyst particles also built up and integrated into the solid coke. The coke can be classified into two types, namely, the hard coke and the soft coke, according to its property, composition and microstructure. The soft coke is formed in the oil and gas mixture’s stagnant region where the oil droplets and catalyst particles are freely settled on the wall. The soft coke appears to be loose and contains lots of large catalyst particles. However, the hard coke is formed in the oil and gas mixture’s flowing region where the oil droplets and catalyst particles diffuse towards the wall. This kind of coke is nonporous and very hard, which contains a few fine catalyst particles. Therefore, it is clear that the oil and gas mixture not only carries the oil droplets and catalyst particles, but also has the effects on their deposition on the wall, which can influence the composition and characteristics of deposited coke.
The desulfurization performance of the UDS solvents was investigated at an industrial side-stream plant and was compared with that of MDEA solvent.A mass transfer performance model was employed for explaining the COS absorption into different solvents.Meanwhile,the regeneration performance of the UDS solvents was evaluated in side-stream tests.Results indicate that under the conditions covering an absorption temperature of 40℃,a pressure of 8.0 MPa,and a gas to liquid volume ratio(V/L)of around 230,the H2S content in purified gas can be reduced to 4.2 mg/m3 and 0 by using solvents UDS-II and UDS-III,respectively.Moreover,the total sulfur content in both purified gases is less than 80 mg/m3.As a result,the UDS-III solvent shows by 30 percentage points higher in COS removal efficiency than MDEA.In addition,the total volume mass transfer coefficient of UDS solvent is found to be twice higher than that of MDEA.Furthermore,the UDS solvents exhibit satisfactory thermal stability and regeneration performance.
The denitrifying sulfide removal（DSR） process with bio-granules comprising both heterotrophic and autotrophic denitrifiers can simultaneously convert nitrate, sulfide and acetate species into di-nitrogen gas, elemental sulfur and carbon dioxide, respectively, at high loading rates. This study has determined that the reaction rate of sulfide oxidized into sulfur could be enhanced in the presence of 1,2-naphthoquinone-4-sulphonate（NQS）. The presence of NQS mitigated the inhibition effects of sulfide species on denitrification. Furthermore, the reaction rates of nitrate and acetate to nitrogen gas and CO2, respectively, were also promoted in the presence of NQS, thereby enhancing the performance of DSR granules. The advantages and disadvantages of applying the NQS-DSR process are discussed.
A well core-shell composite of [email protected] with a mesoporous alumina shell and a Y zeolite core was synthesized. The mesoporous alumina shell has a wormhole-like structure with large mesopores. The prepared catalytic cracking catalyst using this composite has exhibited excellent catalytic performance for heavy oil cracking thanks to its favorable physicochemical properties, such as high surface area, large pore volume and outstanding acid sites accessibility for large molecules provided by the composite. In comparison with the reference catalyst using pure Y zeolite, the oil conversion achieved by the above-mentioned catalyst increased by 2.73 percentage points, while the heavy oil yield and coke yield decreased by 2.23 percentage points and 1.28 percentage points, respectively, with the light oil yield increasing by 2.27 percentage points.
Catalytic hydrogenation is an appropriate method for the improvement of C9 petroleum resin（C9PR） quality. In this study, the Ni2P/SiO2（containing 10% of Ni） catalyst prepared by the temperature-programmed reduction（TPR） method was used for hydrogenation of C9 petroleum resins. The effect of reaction conditions on catalytic performance was studied, and the results showed that the optimum reaction temperature, pressure and liquid hourly space velocity（LHSV） was 250 ℃, 6.0 MPa, and 1.0 h-1, respectively. The bromine numbers of hydrogenated products were maintained at low values（250 mg Br/100g） within 300h, showing the high activity and stability of Ni2P/SiO2 catalyst. The fresh and spent catalysts were characterized by X-ray diffraction（XRD）, BET surface area（BET） analysis, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, Fourier transform infrared（FTIR） pyridine adsorption, and X-ray photoelectron spectroscopy（XPS）. Compared with the traditional sulfurated-Ni W catalysts, Ni2P possessed globe-like structure instead of layered structure like the active phase of Ni WS, thereof exposing more active sites, which were responsible for the high activity of Ni2P/SiO2 catalyst. The stability of Ni2P/SiO2 catalyst was probably attributed to its high sulfur tolerance, antisintering, anti-coking and carbon-resistance ability. These properties might be further ascribed to the special Ni-P-S surface phase, high thermal stability of Ni2P nanoparticles and weak surface acidity for the Ni2P/SiO2 catalyst.更多还原
Effects of silylation on surface properties and catalytic performance of Zn-IM5 for butane aromatization were studied in this paper. Collidine-IR and NH3-TPD analyses revealed that the silylation treatment not only decreased the quantity of both strong and weak acid sites but also led to a slightly reduced intensity of weak acidity. Silylation of the catalyst promoted the selectivity of BTX by narrowing the channel and cutting the acidity. The effect of temperature of silylation and amount of Si loading were evaluated. The best condition has specified a temperature of 50 ℃ and a SiO2 loading of 4.0%.
The performance of the two newly developed bimetallic catalysts based on the precursor, Mo/Al2O3, was compared for reverse water gas shift（RWGS） reaction. The structures of the precursor and the catalysts were studied using X-ray diffraction（XRD）, Brunauer–Emmett–Teller（BET） analysis, inductively coupled plasma-atomic emission spectrometry（ICP-AES）, CO chemisorption, temperature programmed reduction of hydrogen（H2-TPR） and scanning electron microscopy（SEM） techniques. The activity of Fe-Mo and Co-Mo catalysts was compared in a fixed bed reactor at different temperatures. It is shown that the Co-Mo catalyst has higher CO2 conversion at all temperature level. The time-on-stream（TOS） analysis of the activity of catalysts for the RWGS reaction was carried out over a continuous period of 60h for both catalysts. The Fe-Mo/Al2O3 catalyst exhibits good stability within a period of 60h, however, the Co-Mo/Al2O3 is gradually deactivated after 50h of reaction time. Existence of（Fe2（MoO4））3 phase in Fe-Mo/Al2O3 catalyst makes this catalyst more stable for RWGS reaction.
The linkage of aromatic ring structures in vacuum residues was important for the refining process. The Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) combined with collision-induced dissociation(CID) is a powerful method to characterize the molecular structure of petroleum fractions. In this work, model compounds with different aromatic ring structures were measured by CID FT-ICR MS. The cracking of the parent ions and the generated fragment ions were able to distinguish different linkage of the model compounds. Then, vacuum residues were separated into saturates, aromatics, resins and asphaltenes fractions(SARA), and each fraction was characterized by CID technology. According to the experimental results, the aromatic rings in saturates and aromatics fractions were mainly of the island-type structures, while the aromatic rings in resins and asphaltenes fractions had a significant amount of archipelago-type structures.
Recently, a kind of hybrid solution MEA-methanol shows a better CO2 capture performance over aqueous MEA solution. However, the vaporization of methanol is the biggest disadvantage that hinders its application, so it is necessary to minimize the vaporization of methanol during both the absorption and regeneration processes. In this work, two kinds of hybrid solutions were studied and compared with aqueous MEA solution and MEA-methanol solution, including MEA/TEA/methanol solution and MEA/glycerol/methanol solution. The absorption property of MEA/glycerol/methanol solution is better than aqueous MEA solution within a certain period of time and the absorption property of MEA/TEA/methanol solution is too poor to be used in CO2 capture. By increasing the concentration of TEA and decreasing the concentration of MEA, the absorption rate, CO2 capture efficiency and absorption capacity all decreased. Upon adding glycerol, the cyclic capacity decreased and the generation temperature increased, and moreover, the density and viscosity also increased considerably. So after adding TEA and glycerol, the CO2 capture performance of MEAmethanol solvent cannot be improved.
Microencapsulation of phase change materials(Micro PCMs) has been paid special attention because of their extensive applications in saving and releasing energy. Micro PCMs containing paraffin with a melting point of 55 ℃ in polystyrene-divinylbenzene(P(St-DVB)) were prepared by suspension-like polymerization. The characterization of microcapsules by FTIR, DSC and TG proved that paraffin had been successfully encapsulated and the proportion of encapsulated paraffin was 49.8%—58.5%. The effects of polyvinylpyrrolidone(PVP) with different molecular weights serving as the suspension stabilizer were investigated in detail. The results illustrated that the type of PVP had a significant influence on the particle size of Micro PCMs. The average diameter of Micro PCMs decreased with an increasing molecular weight of PVP. Moreover, the crosslinker-postaddition method was adopted in this study to improve the morphology of P(St-DVB) Micro PCMs. SEM images showed that when the DVB was added at the 2nd hour of polymerization the morphology of obtained P(St-DVB) Micro PCMs exhibited good sphericity since it could avoid the influence of cross-linker agent during the nucleation period.
The efficiencies of 6 kinds of macromolecules with dendritic structure in improving the flow properties of crude oil were investigated. The dendritic additives were synthesized using low-generation dendritic poly(amidoamine) and alkyl longchain acrylic esters as starting materials, and their structures were characterized by the Fourier transform infrared spectroscopy, 1H-nuclear magnetic resonance and elemental analysis. The effects on the pour point and rheological properties of crude oil samples were studied. Efficiencies of dendritic long-chain esters were not only influenced by the alky chain length, but also by the generation of dendrimer. The longer the alkyl chain of dendritic long-chain ester was, the better the effect in the reduction of pour point and apparent viscosity was. Efficiencies of 1.5 generation dendritic long-chain ester with 8 branched chains for the reduction of pour point and apparent viscosity were superior to those of 0.5 generation dendritic long-chain ester with 4 branched chains. Under the same conditions, efficiencies of 1.5 generation dendritic eighteen ester were superior to those of other 1.5 generation dendritic long-chain esters for the reduction of pour point and viscosity of crude oil.
This work aims to investigate the intrinsic kinetics of thermal dimerization of C5 fraction in the reactive distillation process. Experiments are conducted in an 1000-m L stainless steel autoclave under some selected design conditions. By means of the weighted least squares method, the intrinsic kinetics of thermal dimerization of C5 fraction is established, and the corresponding pre-exponential factor as well as the activation energy are determined. For example, the pre-exponential factor A is equal to 4.39×105 and the activation energy E4 a is equal to 6.58×10J/mol for the cyclopentadiene dimerization reaction. The comparison between the experimental and calculated results shows that the kinetics model derived in this work is accurate and reliable, which can be used in the design of reactive distillation columns.
Adsorption of FCC dry gas components, hydrogen（H2）, nitrogen（N2）, methane（CH4）, ethane（C2H6） and ethylene（C2H4） in zeolite Y was studied by performing the Grant Canonical Monte Carlo（GCMC） simulations at 298K and 823K and under a pressure range up to 10 MPa. Simulation results were analyzed using the Langmuir model, which presented fitting of dry gas components adsorption to be suggested as the monolayer adsorption. C2H4 presented most single adsorption amount, which reached 7.63 mol/kg at 298K under a pressure of 200kPa. Thermodynamic parameters of the Gibbs free energy change, enthalpy change and entropy change were analyzed based on adsorption equilibrium constant obtained from the GCMC simulations. The results suggested that it was more favorable for C2H4 to be adsorbed in zeolite Y. Adsorption molecules were in ordered arrangement in the zeolite, and C2H4 exhibited a more orderly arrangement than other components. Additionally, a competition in the adsorption of a mixture of dry gas components was found, and supercages were the priority adsorption space. The competition was favorable to CH4 and C2H6, and the competitive power was affected by temperature.
An attempt was made to extend mild combustion to forward flow furnace, such as the refinery and petrochemical tube furnace. Three dimensional numerical simulation was carried out to study the performance of this furnace. The Eddy Dissipation Concept（EDC） model coupled with the reaction mechanism DRM-19 was used. The prediction showed a good agreement with the measurement. The effect of air nozzle circle（D）, air nozzle diameter（d）, air nozzle number（N）, and air preheating temperature（Tair） on the flow, temperature and species fields, and the CO and NO emissions was investigated. The results indicate that there are four zones in the furnace, viz.: a central jet zone, an ignition zone, a combustion reaction zone, and a flue gas zone, according to the distribution profiles of H2 CO and OH. The central jet entrains more flue gas in the furnace upstream with an increasing D while the effect of D is negligible in the downstream. The air jet momentum increases with a decreasing d or an increasing Tair, and entrains more flue gas. The effect of N is mainly identified near the burner exit. More heat is absorbed in the radiant section and less heat is discharged to the atmosphere with a decreasing d and an increasing N as evidenced by the flue gas temperature. The CO and NO emissions are less than 50 μL/L and 10 μL/L, respectively, in most of conditions.