Engineering an ultrathin amorphous TiO2 layer for boosting the weatherability of TiO2 pigment with high lightening power

TiO2 pigments are typically coated with inert layers to suppress the photocatalytic activity and improve the weatherability. However, the traditional inert layers have a lower refractive index compared to TiO2, and therefore reduce the lightening power of TiO2. In the present work, a uniform, amorphous, 2.9-nm-thick TiO2 protective layer was deposited onto the surface of anatase TiO2 pigments according to pulsed chemical vapor deposition at room temperature, with Ti Cl4 as titanium precursor. Amorphous TiO2 coating layers exhibited poor photocatalytic activity, leading to a boosted weatherability. Similarly, this coating method is also effective for TiO2 coating with amorphous SiO2 and SnO2 layers. However, the lightening power of amorphous TiO2 layer is higher than those of amorphous SiO2 and SnO2 layers. According to the measurements of photoluminescence lifetime, surface photocurrent density, charge-transfer resistance, and electron spin resonance spectroscopy, it is revealed that the amorphous layer can prevent the migration of photogenerated electrons and holes onto the surface, decreasing the densities of surface electron and hole, and thereby suppress the photocatalytic activity.

Superior resistance to alkali metal potassium of vanadium-based NH_(3)-SCR catalyst promoted by the solid superacid SO_(4)^(2-)-TiO_(2)

The significant decrease of acid sites caused by alkali metal poisoning is the major factor in the deactivation of commercial V_(2)O_(5)-WO_(3)/TiO_(2)NH_(3)-SCR catalysts.In this work,the solid superacid SO_(4)^(2-)-TiO_(2) modified by sulfate radicals,was selected as the catalyst support,which showed superior potassium resistance.The physicochemical properties and K-poisoning resistance of the V_(2)O_(5)-WO_(3)/SO_(4)^(2-)-TiO_(2)(VWSTi) catalyst were carried out by XRD,BET,H2-TPR,NH3-TPD,XPS,in situ DRIFTS and TG.The results pointed out that the introduction of SO_(4)^(2-)significantly increased the NH3-SCR catalytic activity at high temperatures,with an exceptionally high NO_(x) conversion over 90% between 275℃ and 500℃.When 0.5%(mass) K_(2)O was doped on the catalysts,the catalytic performance of the traditional V_(2)O_(5)-WO_(3)/TiO_(2)(VWTi) catalyst decreased significantly,while the VWSTi catalyst could still maintain a NOxconversion over 90%in the range of 300–500℃.The characterizations suggested that the support of SO_(4)^(2-)-TiO_(2) greatly increased the number of acidic sites,thereby enhancing the adsorption capacity of the reactant NH_(3).The results above demonstrated a potential approach to achieve superior potassium resistance for NH3-SCR catalysts using solid superacid.

Measurements of the effective mass transfer areas for the gas–liquid rotating packed bed

Rotating packed bed(RPB) is one of the most effective gas–liquid mass transfer enhancement reactors, its effective specific mass transfer area(ae) is critical to understand the mass transfer process. By using the NaOH–CO_(2) chemical absorption method, the aevalues of three RPB reactors with different rotor sizes were measured under different operation conditions. The results showed that the high gravity factor and liquid flow rate were major affecting factors, while the gas flow rate exhibited minor influence.The radius of packing is the dominant equipment factor to affect aevalue. The results indicated that the contact area depends on the dispersion of the liquid phase, thus the centrifugal force of rotating packed bed greatly influenced the aevalue. Moreover, the measured ae/ap(effective specific mass transfer area/specific surface area of packing) values were fitted with dimensionless correlation formulas. The unified correlation formula with dimensionless bed size parameter can well predict the experimental data and the prediction errors were within 15%.

Influence of water vapor on the separation of volatile organic compound/nitrogen mixture by polydimethylsiloxane membrane

In the industrial treatment of waste volatile organic compound(VOC)streams by membrane technology,a third impurity,generally,water vapor,coexists in the mixture of VOC and nitrogen or air,and can affect membrane performance and the design of the industrial process.This study focused on the investigation of the effect of water vapor on the separation performance of the separation of VOC/water/nitrogen mixtures by a polydimethylsiloxane(PDMS)membrane.Three types of VOCs:water-miscible ethanol,water-semi-miscible butanol,and water-immiscible cyclohexane,were selected for the study.Different operating parameters including,concentration of the feed VOC,feed temperature,and concentration of the feed water were compared for the separation of binary and ternary VOC/nitrogen mixtures.The interaction between the VOC and water was analyzed to explain the transportation mechanism after analyzing the difference in the membrane performance for the separation of binary and ternary mixtures.The results indicated that the interaction between the VOC(or nitrogen)and water is the key factor affecting membrane performance.Water can promote the permeation of hydrophilic VOC but prevent hydrophobic VOC through the membrane for the separation of ternary VOC/water/nitrogen mixtures.These results will provide fundamental insights for the design of the recovery application process for industrial membrane-based VOCs,and also guidance for the investigation of the separation mechanism in vapor permeation.

基于低压数据对高压鼓泡塔中传质系数的预测(英文)

鼓泡塔中质量传递系数受压力的影响 ,在高压操作下测定传质系数比在低压操作下更加困难 .本文提出了一种预测高压操作下鼓泡塔中传质系数的方法 :利用高压下获得的气含率及气含率分布的数据 ,结合低压下传质系数的研究成果来预测高压下的传质系数 .采用本方法来预测文献报道的数据 (压力在 0 .1～ 1 .1 MPa) ,误差小于 2 0 %.

CO_(2) mineralization of carbide slag for the production of light calcium carbonates

The production of polyvinyl chloride by calcium carbide method is a typical chemical process with high coal consumption,leading to massive flue gas and carbide slag emissions.Currently,the carbide slag with high CaO content is usually stacked in residue field,easily draining away with the rain and corroding the soil.In this work,we coupled the treatment of flue gas and carbide slag to propose a facile CO_(2)mineralization route to prepare light calcium carbonate.And the route feasibility was comprehensively evaluated via experiments and simulation.Through experimental investigation,the Ca^(2+) leaching and mineralization reaction parameters were determined.Based on the experiment,a process was built and optimized through Aspen Plus,and the energy was integrated to obtain the overall process energy and material consumption.Finally,the net CO_(2)emission reduction rate of the entire process through the life-cycle assessment method was analyzed.Moreover,the relationship between the parameters and the CO_(2)emission life-cycle assessment was established.The final optimization results showed that the mineralization process required 1154.69 kW·h·(t CO_(2))^(-1) of energy(including heat energy of 979.32 kW·h·(t CO_(2))^(-1) and electrical energy of 175.37 kW·h·(t CO_(2))^(-1)),and the net CO_(2)emission reduction rate was 35.8%.The light CaCO_(3)product can be sold as a high value-added product.According to preliminary economic analysis,the profit of mineralizing can reach more than 2,100 CNY·(t CO_(2))^(-1).

Selective oxidation of cyclopentene with H2O2 by using H3PW12O40 and TBAB as a phase transfer catalyst

The selective oxidation of cyclopentene by aqueous H2O2 using H3PW12O40 and tetrabutyl ammonium bromide(TBAB) as a phase transfer catalyst has been investigated. The results show that the presence of TBAB significantly improved the oxidation selectivity of cyclopentene. The effects of the reaction conditions on the conversion of cyclopentene were investigated in detail. The optimal reaction conditions are as follows: the H3PW12O40 to TBAB molar ratio, 1:1–1:3;H3PW12O40 to cyclopentene molar ratio,0.54:100–0.64:100;and molar ratio of H2O2 to cyclopentene, 1.6:1. The conversion reached to 59.8% in 4h at 35.0 ℃, while the selectivity of glutaraldehyde was 38.0% and the selectivity of 1,2-cyclopentanediol was 55.6%. In addition, a route for oxidation of cyclopentene by aqueous H2O2 using a heteropoly acid and quaternary ammonium salt as a phase transfer catalyst was proposed.

The fouling properties of SiO2-CaO-P2O5 system in high-temperature rotary kiln phosphoric acid process

Kiln phosphoric acid(KPA)technology could produce P2O5 with high purity and has been applied in thermal phosphoric acid industry;however the formation of fouling in the high-temperature rotary kiln restricts the stable and long-term operation.In this paper,the reaction of phosphate ores with gaseous P2O5 was investigated in a high-temperature reactor,and the Ca O-SiO2-P2O5 ternary phase diagram was analyzed to understand the fouling formation mechanism.The results showed that the low-melting-point products,such as Ca(PO3)2and Ca2P2O7,are responsible for the fouling in the KPA process.In addition,a small amount of impurities,e.g.,aluminum and iron,could facilitate the generation of the low-melting-point products and cause serious fouling.Based on the high-temperature SiO2-P2O5 and CaO-SiO2-P2O5 phase diagram analysis,the control of Si/Ca molar ratio(e.g.,Si/Ca=2.0)was found to avoid fouling formation in the kiln.These results could provide the operation parameters of reaction temperature and feeds composition to suppress the fouling in the kiln reactor for the phosphoric acid production in industry.

Effects of mechanical activation on the digestion of ilmenite in dilute H_2SO_4

The commercial sulfate process for pigment production uses concentrated sulfuric acid(N 85 wt% H_2SO_4) as feeding material and discharges 8–10 tons of spend dilute acid(20 wt% H_2SO_4) per ton of product. Re-using spend acid to leach ilmenite can cut the waste emission and save fresh feeding acid. However, the leaching reaction with dilute acid is very slow and the digestion efficiency is fairly low. This paper describes a wet-milling process to enhance the dilute-acid leaching of ilmenite that makes it possible to produce TiO_2 pigment in a more environmentally benign routine. The leaching kinetic study of unmilled ilmenite, dry milled 60 min ilmenite and wet milled 60 min ilmenite was conducted by revision of the shrinking core model(SCM), incorporation of particle size distribution(PSD) into SCM. The results revealed that mechano-chemical activation method significantly increased the leaching efficiency of titanium from 36% to 76% by reducing the particle size and increasing the reaction contact area. On the other hand, the milling process increased the lattice deformation and amorphization of crystalline, which lowered the activation energies in the leaching process. Compared with dry milling operation, wet milling is more effective, the particle size distribution of wet-milled ilmenite was much narrower, smaller, and more uniform. Wet milling of ilmenite makes the leaching reaction with dilute acid(60 wt% H_2 SO_4) practicable and the re-use of spend acid becomes possible and economical.

Simulation of the hydrodynamics and mass transfer in a falling film wavy microchannel

The flow in a liquid falling film is predominantly laminar,and the liquid-side mass transfer is limited by molecular diffusion.The effective way to enhance the mass transfer is to improve the liquid film flow behavior.The falling film behaviors of water,ethanol and ethylene glycol in nine different wavy microchannels were simulated by Computational Fluid Dynamics.The simulation results show that the falling film thickness exhibits a waveform distribution resulting in a resonance phenomenon along the wavy microchannel.The fluctuation of liquid film surface increases the gas-liquid interface area,and the internal eddy flow inside the liquid film also improves the turbulence of liquid film,the gas-liquid mass transfer in falling film microchannels is intensified.Compared with flat microchannel,the CO_(2) absorption efficiency in water in the wavy microchannel is improved over 41%.Prediction models of liquid film amplitude and average liquid film thickness were established respectively.

Modeling of a Demethanizer Tower Using Statistical Tools

Monitoring of industrial plant performance and detection on flaws is important to the successful operation on industrial production units. Malfunctioning equipment can greatly impact plant performance by reducing the efficiency and increasing the production cost. Phenomenological equations cannot properly describe industrial processes. Thus, it is necessary to develop new equations for model industrial operations. The purpose of this study is to develop an empirical model for industrial demethanizer tower which is malfunctioning due to an error in the design in one of its plates. A nonlinear statistical model was designed to predict the pressure variation in the column, and consequently, the flooding conditions. This model was validated using industrial data to predict the maximum loads in the column.

Dye@MOF composites(RhB@1): Highly sensitive dual emission sensor for the detection of pesticides, Fe^(3+) and ascorbate acid

With the rapid development of economy, industrial and agricultural pollutants have caused great damage to the ecological environment and the normal development of organisms, posing a serious threat to global public health. Therefore, rapid and sensitive detection of pollutants is very important for environmental safety and people’s health. A stable multi-response fluorescence sensor(RhB@1) with dual emission characteristics was constructed by embedding Rh B guest molecules in Zn-MOF using a simple one-pot method. XRD, IR, XPS, Raman and other characterization methods were used to demonstrate the formation of composite materials. The sensor has two fluorescence emission peaks at 415 nm and 575nm under the excitation of 316 nm. It has high sensitivity and low detection limit(7.94 and 7.82 nmol/L,respectively) in the detection of fluazinam(FLU) and Fe^(3+). The mechanism of fluorescence quenching may be due to the synergistic effect of IFE and PET. Outstandingly, when ascorbate acid(AA) was added to the quenching system of Fe^(3+) and Rh B@1, its fluorescence gradually recovered, forming the unique“on-off-on” sensor. Therefore, RhB@1 has a fast fluorescence response and good stability, making it potentially useful in practical application and biosensors. More significantly, using Fe^(3+)and AA as chemical input signals, a binary intelligent logic gate device has been developed based on the “on-off-on” response mode of RhB@1, which extends the application of logic gate switching devices in the chemical field. In addition, a visual portable test paper with good selectivity and high sensitivity was developed, which can be used for rapid detection of FLU, showing its broad application prospect.

Fluidization of binary mixtures of sisal residue and sand:A new model for deriving the final fluidization velocity

The influence of different factors on the fiuidization of a binary mixture of sisal residue and sand was investigated.The particle sizes of the sand and sisal residue were varied from 0.2to 0.8mm and the biomass mass fractions from 2% to 9%.Some segregation was noted,and a significant relationship was found among the final fluidization velocity (Uff),the biomass and sand sizes,and the biomass mass fraction.A novel model was developed for predicting Uff,leading to an average discrepancy of 12.69% between the measured and predicted Uff compared with the best match of 15.32% when using a model from a previous paper.The new model was applied to data from studies using other biomass and a broad range of particle characteristics.The average divergences from measured values when using the new model were 7.9% for corn cob and walnut shell,and 20.5% for sweet sorghum bagasse,tobacco residue, and soy hulls.These were superior to the values derived using other models.Our results confirm the accuracy of the model developed in this work and show that it represents a viable alternative way to calculate Uff for a binary mixture of sand and biomass.

Hydrotreating of light gas oil using a NiMo catalyst supported on activated carbon produced from fluid petroleum coke

Nitric acid functionalized steam activated carbon （NAFSAC） was prepared from waste fluid petroleum coke （FPC） and used as a support material for the synthesis ofa NiMo catalyst （2.5 wt-% Ni and 13 wt-% Mo）. The catalyst was then used for the hydrotreatment of light gas oil. The support and catalysts were characterized by Brunauer-Emmett-Teller （BET） gas adsorption method, X-ray diffraction, H2-temperature programmed reduction, NH3-temperature programmed desorption, CO-chemisorption, mass spetrography, scanning electron microscopy （SEM）, Boehm titration, and Fourier transform infrared spectroscopy （FTIR）. The SEM results showed that the carbon material retained a needle like structure after functionalization with HNO3. The Boehm titration, FTIR, and BET results confirmed that the HNO3 functionalized material had moderate acidity, surface functional groups, and mesoporosity respectively. The produced NAFSAC had an inert nature, exhibited the sink effect and few metal support interactions, and contained functional groups. All of which make it a suitable support material for the preparation of a NiMo hydrotreating catalyst. Hydrotreating activity studies of the NiMo/NAFSAC catalyst were carried out under industrial operating conditions in a laboratory trickle bed reactor using coker light gas oil as the feedstock. A parallel study was performed on the hydrotreating activity of NiMo/7-A1203 as a reference catalyst. The hydrodesulfurization and hydrodenitrogena- tion activities of the NiMo/NAFSAC catalyst were 62% and 30%, respectively.