油品脱硫技术研究进展

目前油品的脱硫技术主要分为加氢脱硫技术和非加氢脱硫技术。本文主要介绍了加氢脱硫技术和萃取脱硫技术、络合脱硫技术、生物脱硫技术、氧化脱硫技术、吸附脱硫技术等几种非加氢脱硫技术的原理和最新的研究情况,并简单介绍了各种技术的优缺点。     

Adsorptive removal of acrylonitrile by commercial grade activated carbon: kinetics, equilibrium and thermodynamics

The potential of activated carbons--powdered (PAC) and granular (GAC), for the adsorption of acrylonitrile (AN) at different initial AN concentrations (50相似文献   

Adsorptive removal of chlorophenols from aqueous solution by low cost adsorbent--Kinetics and isotherm analysis

Adsorptive removal of parachlorophenol (PCP) and 2,4,6-trichlorophenol (TCP) from aqueous solutions by activated carbon prepared from coconut shell was studied and compared with activated carbon of commercial grade (CAC). Various chemical agents in different concentrations were used (KOH, NaOH, CaCO(3), H(3)PO(4) and ZnCl(2)) for the preparation of coconut shell activated carbon. The coconut shell activated carbon (CSAC) prepared using KOH as chemical agent showed high surface area and best adsorption capacity and was chosen for further studies. Batch adsorption studies were conducted to evaluate the effect of various parameters such as pH, adsorbent dose, contact time and initial PCP and TCP concentration. Adsorption equilibrium reached earlier for CSAC than CAC for both PCP and TCP concentrations. Under optimized conditions the prepared activated carbon showed 99.9% and 99.8% removal efficiency for PCP and TCP, respectively, where as the commercially activated carbon had 97.7% and 95.5% removal for PCP and TCP, respectively, for a solution concentration of 50mg/L. Adsorption followed pseudo-second-order kinetics. The equilibrium adsorption data were analysed by Langmuir, Freundlich, Redlich-Peterson and Sips model using non-linear regression technique. Freundlich isotherms best fitted the data for adsorption equilibrium for both the compounds (PCP and TCP). Similarly, acidic pH was favorable for the adsorption of both PCP and TCP. Studies on pH effect and desorption revealed that chemisorption was involved in the adsorption process. The efficiency of the activated carbon prepared was also tested with real pulp and paper mill effluent. The removal efficiency using both the carbons were found highly satisfactory and was about 98.7% and 96.9% as phenol removal and 97.9% and 93.5% as AOX using CSAC and CAC, respectively.     

One-step oxidative-adsorptive desulfurization of DBT on simulated solar light-driven nano photocatalyst of MoS2-C3N4-BiOBr @MCM-41

Using a catalyst-adsorbent for simultaneous oxidation and adsorption of sulphuric compounds in liquid fuels is an effective and economical way. Thus in this paper, the core–shell MoS₂-C₃N₄-BiOBr@MCM-41 photocatalyst-adsorbents with different percentages of MoS₂ (1, 3, and 5 wt%) were prepared and used in a one-step photo oxidative-adsorptive desulfurization under simulated solar light. The samples were characterized by XRD, FESEM, FTIR, EDX, BET-BJH, TEM, UV–Vis DRS, and PL analyses. The results indicated that the final C/C₀ decreased from 0.42 to 0.016 with increasing the MoS₂ percentage (98.4% conversion). Despite the lowest surface area (845 m²/g) and the broad bandgap energy (2.8 eV), the sample with 5 wt% of MoS₂ illustrated the most degree of desulfurization due to strong interaction between components, the highest coverage of MCM-41 with active phases, high population of structural defects, high capability of light absorption and low recombination rate of charge carriers. GC-MS analysis indicated no DBT, DBTO or DBTO₂ in the treated fuel. However, the presence of DBTO₂ on the surface of the photocatalyst was confirmed that reveals the successful one-step oxidative-adsorptive desulfurization on the MoS₂-C₃N₄-BiOBr@MCM-41. The adsorption mechanism was consistent with the pseudo-second-order kinetics, indicating that the rate-limiting step was chemical adsorption. Moreover, selectivity evaluations showed that while MoS₂-C₃N₄-BiOBr@MCM-41 photocatalyst had high activity in the desulfurization of DBT, its affinity for adsorption and photocatalytic oxidation of non-sulfur aromatic compounds such as benzene, xylene and toluene was very low.     

Adsorption of copper (II), chromium (III), nickel (II) and lead (II) ions from aqueous solutions by meranti sawdust

The present study proposed the use of meranti sawdust in the removal of Cu(II), Cr(III), Ni(II) and Pb(II) ions from synthetic aqueous solutions. Batch adsorption studies showed that meranti sawdust was able to adsorb Cu(II), Cr(III), Ni(II) and Pb(II) ions from aqueous solutions in the concentration range 1–200 mg/L. The adsorption was favoured with maximum adsorption at pH 6, whereas the adsorption starts at pH 1 for all metal ions. The effects of contact time, initial concentration of metal ions, adsorbent dosage and temperature have been reported. The applicability of Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) isotherm was tried for the system to completely understand the adsorption isotherm processes. The adsorption kinetics tested with pseudo-first-order and pseudo-second-order models yielded high R² values from 0.850 to 0.932 and from 0.991 to 0.999, respectively. The meranti sawdust was found to be cost effective and has good efficiency to remove these toxic metal ions from aqueous solution.     

Removal of Cu(II) from aqueous solution by adsorption onto acid-activated palygorskite

A series of activated palygorskite clay by HCl with different concentrations was prepared and applied as adsorbents for removal of Cu(II) from aqueous solutions. The effects of contact time, adsorbent dosages and pHs of suspension on the adsorption capacities for Cu(II) were investigated. The results showed that adsorption capacity of activated palygorskites increased with increasing the HCl concentration and the maximum adsorption capacity with 32.24 mg/g for Cu(II) is obtained at 12 mol/L of HCl concentration. The variations in IR spectra and pH of solution after adsorption Cu(II) confirmed that the numerous amount of silanol groups (Si-OH) originated by acid treatment were mainly responsible for Cu(II) adsorption onto acid-activated palygorskite. Kinetic studies indicated that the adsorption mechanisms in the Cu(II)/acid-activated palygorskite system followed the pseudo-second-order kinetic model with a relatively small contribution of film diffusion. Equilibrium data fitted well with Freundlich isotherm model compared to Langmuir isotherm model, indicating that adsorption takes place on heterogeneous surfaces of the acid-activated palygorskite. Adsorption-desorption studies presented that activated palygorskite has lower adsorption and desorption efficiencies using Cu(CH3COO)2 than that of other inorganic copper salts, such as CuSO4, Cu(NO3)2, and CuCl2.     

Adsorption behavior and mechanism of Cd(II) on loess soil from China

Cadmium is a toxic heavy metal that has caused serious public health problems. It is necessary to find a cost effective method to deal with wastewater containing Cd(II). Loess soils in China have proven to be a potential adsorbent for Cd(II) removal from wastewater. The adsorption capacity of loess towards Cd(II) has been determined to be about 9.37 mg g⁻¹. Slurry concentration, initial solution pH, reaction time and temperature have also been found to significantly influence the efficiency of Cd(II) removal. The adsorption isotherms and kinetics of loess soil from China can be best-fit with the Langmuir model and pseudo-second order kinetics model, respectively. The thermodynamic analysis revealed that the adsorption process was spontaneous, endothermic and the system disorder increased with duration. The natural organic matter in loess soil is mainly responsible for Cd(II) removal at pH < 4.2, while clay minerals contribute to a further gradual adsorption process. Chemical precipitation dominates the adsorption stage at pH > 8.97. Further studies using X-ray diffraction, Fourier transform infrared spectra of Cd(II) laden loess soil and Cd(II) species distribution have confirmed the adsorption mechanism.     

Scavenging behaviour of meranti sawdust in the removal of methylene blue from aqueous solution

Meranti (Philippine mahogany) sawdust, an inexpensive material, showed strong scavenging behaviour through adsorption for the removal of methylene blue (MB) from aqueous solution. Batch studies were performed to evaluate and optimize the effects of various parameters such as contact time, pH, initial dye concentrations and adsorbent dosage. Langmuir, Freundlich and Temkin isotherms were used to analyze the equilibrium data at different temperatures. The experimental data fitted well with the Langmuir adsorption isotherm, indicating thereby the mono layer adsorption of the dye. The monolayer sorption capacity of meranti sawdust for MB was found to be 120.48, 117.64, 149.25 and 158.73 mg/g at 30, 40, 50 and 60 °C, respectively. Thermodynamic calculations showed that the MB adsorption process is endothermic and spontaneous in nature. Kinetic studies showed that the adsorption followed a pseudo-second-order kinetic model. The results indicated that the meranti sawdust could be an alternative material in place of more costly adsorbents used for dye removal.     

Adsorption of 4-chlorophenol from aqueous solutions by xad-4 resin: isotherm, kinetic, and thermodynamic analysis

Removal of 4-chlorophenol (4-CP) from synthetic aqueous solutions through adsorption on Amberlite XAD-4 resin, a non-ionic macroreticular resins, under batch equilibrium experimental conditions at 298, 308 and 318K was investigated. It is necessary to propose a suitable model to a better understanding on the mechanism of 4-CP adsorption. For this purpose, Langmiur, Freundlich, Toth, and Redlich-Peterson (RP) isotherm models were compared. The two and three parameters in the adopted adsorption isotherm models were determined by the help of MATLAB package program. It was determined that best fitted adsorption isotherm models were obtained to be in the order: Redlich-Peterson>Langmuir>Toth>Freundlich isotherms. The pseudo-second-order kinetic model provided the best correlation to the experimental results. Results of the intra-particle diffusion model show that the pore diffusion is not the only rate limiting step. The lower correlation of the data to the Bangham's equation also represents that the diffusion of the adsorbate into pores of the sorbent is not the only rate-controlling step. The thermodynamic constants of adsorption phenomena; DeltaG degrees, DeltaH degrees, and DeltaS degrees were found as -4.17 (at 298K) kJ/mol, -42.01 kJ/mol, and -0.127 kJ/(mol K), respectively. The results showed that adsorption of 4-CP on Amberlite XAD-4, a nonionic polymeric resin was exothermic and spontaneous.     

Removal of congo red from aqueous solution by adsorption onto acid activated red mud

The objective of this study is to remove the congo red (CR) anionic dye, from water by using the acid activated red mud in batch adsorption experiments. The effects of contact time, pH, adsorbent dosage and initial dye concentration on the adsorption were investigated. The pH of the dye solution strongly affected the chemistry of both the dye molecules and activated red mud in an aqueous solution. The effective pH was 7.0 for adsorption on activated red mud. It was found that the sufficient time to attain equilibrium was 90 min. The adsorption isotherms were analyzed using the Langmuir, the Freundlich, and the three parameter Redlich-Peterson isotherms. The Langmuir isotherm was the best-fit adsorption isotherm model for the experimental data obtained from the non-linear chi-square statistic test.     

Equilibrium, kinetic and thermodynamic studies on the adsorption of m-cresol onto micro- and mesoporous carbon

Investigations were conducted in batch mode to study the adsorption behaviour of m-cresol on a porous carbon prepared from rice husk (RHAC) by varying the parameters such as agitation time, m-cresol concentration (50-300 mg/l), pH (2.5-10) and temperature (293-323 K). Studies showed that the adsorption decreased with increase in pH and temperature. The isotherm data were fitted to Langmuir, Freundlich, and Dubinin-Radushkevic (D-R) models. The kinetic models such as pseudo-first-order, pseudo-second-order and intraparticle diffusion models were selected to understand the reaction pathways and mechanism of adsorption process. The thermodynamic equilibrium coefficients obtained at different temperatures were used to evaluate the thermodynamic constants DeltaG degrees, DeltaH degrees and DeltaS degrees. The sorption process was found to be exothermic in nature (DeltaH degrees : -23.46 to -25.40 kJ/mol) with a decrease in entropy (DeltaS degrees: -19.44 to -35.87 J/(mol K)). The negative value of Gibbs free energy, DeltaG degrees indicates that the adsorption occurs via a spontaneous process. The decrease in the value of -DeltaG degrees from 17.70 to 13.54 kJ/mol with increase in pH and temperature indicates that the adsorption of m-cresol onto activated carbon is less favourable at higher temperature and pH range. The influence of mesopore and a possible mechanism of adsorption is also suggested.     

Adsorption of dyes from aqueous solutions on activated charcoal

Adsorption of industrially important dyes namely bromophenol blue, alizarine red-S, methyl blue, methylene blue, eriochrome black-T, malachite green, phenol red and methyl violet from aqueous media on activated charcoal has been investigated. The effect of shaking time, pH and temperature on the adsorption behaviour of these dyes has been studied. It was noted that adsorption of all the dyes on activated charcoal decreases with an increase in the pH and the temperature. The adsorption isotherms at different temperatures were found to be of L-type. Adsorption data was fitted to Freundlich, BET and Langmuir isotherms and various adsorption parameters have been calculated. The thermodynamic parameters such as DeltaG, DeltaH and DeltaS were calculated from the slopes and intercepts of the linear variation of lnK against 1/T, where K is the adsorption coefficient obtained from Langmuir equation, was used. The calculated values for the heat of adsorption and the free energy indicate that adsorption of dyes is favored at low temperatures and the dyes are chemisorbed on activated charcoal.     

Adsorption of divalent heavy metal ions from water using carbon nanotube sheets

Removal of some divalent heavy metal ions (Cu(2+), Zn(2+), Pb(2+), Cd(2+), Co(2+)) from aqueous solutions using carbon nanotube (CNT) sheets was performed. CNT sheets were synthesized by chemical vapor deposition of cyclohexanol and ferrocene in nitrogen atmosphere at 750°C, and oxidized with concentrated nitric acid at room temperature and then employed as adsorbent for water treatment. Langmuir and Freundlich isotherms were used to describe the adsorption behavior of heavy metal ions by oxidized CNT sheets. The obtained results demonstrated that the oxidized CNT sheets can be used as an effective adsorbent for heavy metal ions removal from water. It was found out that kinetics of adsorption varies with initial concentration of heavy metal ions. Preference of adsorption onto the oxidized CNT sheets can be ordered as Pb(2+)>Cd(2+)>Co(2+)>Zn(2+)>Cu(2+). Using the oxidized CNT sheets, waste water treatment without CNT leakage into water is economically feasible. Therefore, CNT sheets have good potential application in environmental protection.     

Adsorptive desulfurization by zinc-impregnated activated carbon: characterization,kinetics, isotherms,and thermodynamic modeling

Sulfur oxides emission because of burning of liquid fuels has become a global environmental challenge. Refineries need to meet ever-stringent liquid fuel standards by using newer desulfurization methods. Present paper reports the results of the studies on adsorptive removal of sulfur compounds from model fuel by zinc-impregnated granular activated carbon (GAC). Zn-loaded adsorbent (Zn-GAC) prepared by wet impregnation method was characterized for its textural, morphological, and structural characteristics by different techniques like liquid nitrogen adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). The adsorbent was further used for the removal of dibenzothiophene (DBT), a sulfur compound, from iso-octane. Equilibrium adsorption was obtained in 6 h. The equilibrium adsorption data were well represented by the Redlich–Peterson isotherm. Thermodynamic parameters were calculated by applying the van’t Hoff and Clausius–Clapeyron equations. Values of change in enthalpy and entropy were found to be 4.89 kJ/mol and 30 J/mol K, respectively. Isosteric heat of adsorption was correlated with surface coverage and heterogeneous nature of the Zn-GAC.     

Removal of chromium (VI) from aqueous solution using treated oil palm fibre

This study proposed an oil palm by-product as a low-cost adsorbent for the removal of hexavalent chromium [Cr (VI)] from aqueous solution. Adsorption of Cr (VI) by sulphuric acid and heat-treated oil palm fibre was conducted using batch tests. The influence of pH, contact time, initial chromium concentration and adsorbent dosage on the removal of Cr (VI) from the solutions was investigated. The optimum initial pH for maximum uptake of Cr (VI) from aqueous solution was found to be 1.5. The removal efficiency was found to correlate with the initial Cr (VI) concentration, adsorbent dosage as well as the contact time between Cr (VI) and the adsorbent. The adsorption kinetics tested with pseudo first order and pseudo second order models yielded high R(2) values from 0.9254 to 0.9870 and from 0.9936 to 0.9998, respectively. The analysis of variance (ANOVA) showed significant difference between the R(2) values of the two models at 99% confidence level. The Freundlich isotherm (R(2)=0.8778) described Cr (VI) adsorption slightly better than the Langmuir isotherm (R(2)=0.8715). Difficulty in desorption of Cr (VI) suggests the suitability of treated oil palm fibre as a single-use adsorbent for Cr (VI) removal from aqueous solution.     

Quantifying effects of pH and surface loading on arsenic adsorption on NanoActive alumina using a speciation-based model

Arsenic (As) poses a significant water quality problem and challenge for the environmental engineers and scientists throughout the world. Batch tests were carried out in this study to investigate the adsorption of As(V) on NanoActive alumina. The arsenate adsorption envelopes on NanoActive alumina exhibited broad adsorption maxima when the initial As(V) loading was less than a 50 mg g⁻¹ sorbent. As the initial As(V) loading increased to 50 mg g⁻¹ sorbent, a distinct adsorption maximum was observed at pH 3.2–4.6. FTIR spectra revealed that only monodentate complexes were formed upon the adsorption of arsenate on NanoActive alumina over the entire pH range and arsenic loading conditions examined in this study. A speciation-based adsorption model was developed to describe arsenate adsorption on NanoActive alumina and it could simulate arsenate adsorption very well in a broad pH range of 1–10, and a wide arsenic loading range of 0.5–50 mg g⁻¹ adsorbent. Only four adjustable parameters, including three adsorption constants, were included in this model. This model offers a substantial improvement over existing models in accuracy and simplification in quantifying pH and surface loading effects on arsenic adsorption.     

Arsenate removal from aqueous solution by cellulose-carbonated hydroxyapatite nanocomposites

Microwave-assisted synthesis of the cellulose-carbonated hydroxyapatite nanocomposites (CCHA) with CHA nanostructures dispersed in the cellulose matrix was carried out by using cellulose solution, CaCl(2), and NaH(2)PO(4). The cellulose solution was previously prepared by the dissolution of microcrystalline cellulose in NaOH-urea aqueous solution. Study was carried out to evaluate the feasibility of synthetic CCHA for As(V) removal from aqueous solution. Batch experiments were performed to investigate effects of various experimental parameters such as contact time (5 min - 8h), initial As(V) concentration (1-50mg/L), temperature (25, 35 and 45°C), pH (2-10) and the presence of competing anions on As(V) adsorption on the synthetic CCHA. Kinetic data reveal that the uptake rate of As(V) was rapid at the beginning and equilibrium was achieved within 1h. The adsorption process was well described by pseudo-first-order kinetics model. The adsorption data better fitted Langmuir isotherm. The maximum adsorption capacity calculated from Langmuir isotherm model was up to 12.72 mg/g. Thermodynamic study indicates an endothermic nature of adsorption and a spontaneous and favorable process. The optimum pH for As(V) removal was broad, ranging from 4 to 8. The As(V) adsorption was impeded by the presence of SiO(3)(2-), followed by PO(4)(3-) and NO(3)(-). The adsorption process appeared to be controlled by the chemical process.     

Adsorption of reactive dye from an aqueous solution by chitosan: isotherm, kinetic and thermodynamic analysis

The adsorption of Remazol black 13 (Reactive) dye onto chitosan in aqueous solutions was investigated. Experiments were carried out as function of contact time, initial dye concentration (100-300mg/L), particle size (0.177, 0.384, 1.651mm), pH (6.7-9.0), and temperature (30-60 degrees C). The equilibrium adsorption data of reactive dye on chitosan were analyzed by Langmuir and Freundlich models. The maximum adsorption capacity (qm) has been found to be 91.47-130.0mg/g. The amino group nature of the chitosan provided reasonable dye removal capability. The kinetics of reactive dye adsorption nicely followed the pseudo-first and second-order rate expression which demonstrates that intraparticle diffusion plays a significant role in the adsorption mechanism. Isotherms have also been used to obtain the thermodynamic parameters such as free energy, enthalpy and entropy of adsorption. The positive value of the enthalpy change (0.212kJ/mol) indicated that the adsorption is endothermic process. The results indicate that chitosan is suitable as adsorbent material for adsorption of reactive dye form aqueous solutions.     

Equilibrium and kinetic studies on the removal of Acid Red 114 from aqueous solutions using activated carbons prepared from seed shells

The use of low-cost and ecofriendly adsorbents has been investigated as an ideal alternative to the current expensive methods of removing dyes from wastewater. This paper deals with the removal of Acid Red 114 (AR 114) from aqueous solutions using activated carbons prepared from agricultural waste materials such as gingelly (sesame) (Sp), cotton (Cp) and pongam (Pp) seed shells. Optimum conditions for AR 114 removal were found to be pH 3, adsorbent dosage=3g/L of solution and equilibrium time=4h. Higher removal percentages were observed at lower concentrations of AR 114. The adsorption isotherm data were fitted to Langmuir and Freundlich equation, and the adsorption capacity of the studied adsorbents was in the order Sp>Cp>Pp. Kinetic studies showed that the adsorption followed both pseudo-second-order and Elovich equation. The thermodynamics parameters such as DeltaG degrees, DeltaH degrees, DeltaS degrees were also evaluated. The activated carbons prepared were characterized by FT-IR, SEM and BET analysis.     

Kinetics of adsorption of dyes from aqueous solution using activated carbon prepared from waste apricot

Adsorbent (WA11Zn5) has been prepared from waste apricot by chemical activation with ZnCl(2). Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by N(2) adsorption and DFT plus software. Adsorption of three dyes, namely, Methylene Blue (MB), Malachite Green (MG), Crystal Violet (CV), onto activated carbon in aqueous solution was studied in a batch system with respect to contact time, temperature. The kinetics of adsorption of MB, MG and CV have been discussed using six kinetic models, i.e., the pseudo-first-order model, the pseudo-second-order model, the Elovich equation, the intraparticle diffusion model, the Bangham equation, the modified Freundlich equation. Kinetic parameters and correlation coefficients were determined. It was shown that the second-order kinetic equation could describe the adsorption kinetics for three dyes. The dyes uptake process was found to be controlled by external mass transfer at earlier stages (before 5 min) and by intraparticle diffusion at later stages (after 5 min). Thermodynamic parameters, such as DeltaG, DeltaH and DeltaS, have been calculated by using the thermodynamic equilibrium coefficient obtained at different temperatures and concentrations. The thermodynamics of dyes-WA11Zn5 system indicates endothermic process.