Improvement strategies for Ni-based alcohol steam reforming catalysts

Steam reforming(SR)of fossil methane is already a well-known,documented and established expertise in the industrial sector as it accounts for the vast majority of global hydrogen production.From a sustainable development perspective,hydrogen production by SR of biomass-derived feedstock represents a promising alternative that could help to lower the carbon footprint of the traditional process.In this regard,bio-alcohols such as methanol,ethanol or glycerol are among the attractive candidates that could serve as green hydrogen carriers as they decompose at relatively low temperatures in the presence of water compared to methane,allowing for improved H_(2)yields.However,significant challenges remain regarding the activity and stability of nickel-based catalysts,which are most widely used in alcohol SR processes due to their affordability and ability to break C–C,O–H and C–H bonds,yet are prone to rapid deactivation primarily caused by coke deposition and metal particle sintering.In this state-of-the-art review,a portfolio of strategies to improve the performance of Ni-based catalysts used in alcohol SR processes is unfolded with the intent of pinpointing the critical issues in catalyst development.Close examination of the literature reveals that the efforts tackling these recurring issues can be directed at the active metal,either by tuning Ni dispersion and Ni-support interactions or by targeting synergistic effects in bimetallic systems,while others focus on the support,either by modifying acid-base character,oxygen mobility,or by embedding Ni in specific crystallographic structures.This review provides a very useful tool to orient future work in catalyst development.

Control system design for a pressure-tube-type supercritical water-cooled nuclear reactor via a higher order sliding mode method

Nuclear power plants exhibit non-linear and time-variable dynamics.Therefore,designing a control system that sets the reactor power and forces it to follow the desired load is complicated.A supercritical water reactor(SCWR)is a fourth-generation conceptual reactor.In an SCWR,the non-linear dynamics of the reactor require a controller capable of control-ling the nonlinearities.In this study,a pressure-tube-type SCWR was controlled during reactor power maneuvering with a higher order sliding mode,and the reactor outgoing steam temperature and pressure were controlled simultaneously.In an SCWR,the temperature,pressure,and power must be maintained at a setpoint(desired value)during power maneuvering.Reactor point kinetics equations with three groups of delayed neutrons were used in the simulation.Higher-order and classic sliding mode controllers were separately manufactured to control the plant and were compared with the PI controllers speci-fied in previous studies.The controlled parameters were reactor power,steam temperature,and pressure.Notably,for these parameters,the PI controller had certain instabilities in the presence of disturbances.The classic sliding mode controller had a higher accuracy and stability;however its main drawback was the chattering phenomenon.HOSMC was highly accurate and stable and had a small computational cost.In reality,it followed the desired values without oscillations and chattering.

Hydrogen generation from polyvinyl alcohol-contaminated wastewater by a process of supercritical water gasification

Gasification of polyvinyl alcohol （PVA）-contaminated wastewater in supercritical water （SCW） was investigated in a continuous flow reactor at 723-873 K, 20-36 MPa and residence time of 20-450 s. The gas and liquid products were analyzed by GC/TCD, and TOC analyzer. The main gas products were H2, CH4, CO and CO2. Pressure change had no significant influence on gasification efficiency. Higher temperature and longer residence time enhanced gasification efficiency, and lower temperature favored the production of H2. The effects of KOH catalyst on gas product composition were studied, and gasification efficiency were analyzed. The TOC removal efficiency （RTOC）, carbon gasification ratio （RCG） and hydrogen gasification ratio （RHG） were up to 96.00%, 95.92% and 126.40% at 873 K and 60 s, respectively, which suggests PVA can be completely gasified in SCW. The results indicate supercritical water gasification for hydrogen generation is a promising process for the treatment ofPVA wastewater.

Transient Heat Transfer Study of Direct Contact Condensation of Steam in Spray Cooling Water

We conducted a transient experimental investigation of steam–water direct contact condensation in the absence of noncondensible gas in a laboratory-scale column with the inner diameter of 325 mm and the height of 1045 mm. We applied a new analysis method for the steam state equation to analyze the molar quantity change in steam over the course of the experiment and determined the transient steam variation. We also investigated the influence of flow rates and temperatures ofcooling water on the efficiency ofsteam condensation. Our experimental results show that appropriate increasing of the cooling water flow rate can significantly accelerate the steam condensation. We achieved a rapid increase in the total volumetric heat transfer coefficient by increasing the flow rate of cooling water, which indicated a higher thermal convection between the steam and the cooling water with higher flow rates. We found that the temperature ofcooling water did not play an important role on steam condensation. This method was confirmed to be effective for rapid recovering ofsteam.

Numerical Simulation of Water Droplets Deposition on the Last-Stage Stationary Blade of Steam Turbine

Based on the method of discrete phase, the law of droplets’ deposition in the last stage stationary blade of a supercritical 600 MW Steam Turbine is simulated in the first place of this paper by using the Wet-steam model in commercial software FLUENT, where the influence of inlet angle of water droplets of the stationary blades is also considered. Through the calculation, the relationship between the deposition and the diameter of water droplets is revealed. Then, the amount of droplets deposition in the suction and pressure surface is derived. The result is compared with experimental data and it proves that the numerical simulation result obtained in this paper is reasonable. Finally, a formula of the relationship between the diameter of water droplets and the inlet angle is fit, which could be used for approximate calculation in the engineering applications.

Determination of the Thermodynamic Properties of Water and Steam in the p-T and p-S Planes via Different Grid Search Computer Algorithms

The role of different grid search computer algorithms for the determination of the thermodynamic properties of water and steam in the p-T and P-S planes has been investigated via experimental and analytical methods.The results show that the spline interpolation grid search algorithm and the power grid search algorithm are more efficient,stable and clear than other algorithms.

Effects of Ovariectomy and 17<i>β</i>-Estradiol Replacement on Dopamine D2 Receptors in Female Rats: Consequences on Sucrose, Alcohol, Water Intakes and Body Weight

Background: Mechanisms underlying overeating-induced obesity in post-menopausal woman include functional lack of 17β-estradiol dysregulating dopamine D2 receptors, thereby inducing food addiction, glucose craving or alcohol dependence through reward circuitry. This study aimed at further understanding 17β-estradiol and dopamine D2 receptors interferences in the etiology of woman obesity. Method: Seventy-two Wistar female rats weighing 200 - 205 g, individually-housed, were divided into non-ovariectomized control (C = 6 groups) and ovariectomized rats (OVX = 6 groups) which were concurrently subjected to the following treatments: Non-drug-treated (DMSO vehicle), 17β-estradiol (E2, 5 μg/kg, s.c.), sulpiride (SUL, 20 mg/kg, i.p.), bromocriptine (BR, 0.1 mg/kg, i.p.), E2 + SUL or E2 + BR, designating the 6 constitutive groups of either control or ovariectomy. Within each experimental group, consumption of different solutions (10% alcohol, 10% sucrose and water) as well as food intake and body weight were daily measured, for 10 consecutive days. Results: This study indicated that D2S was a specific inducer of alcohol and food intakes, but reduced sugar consumption. In addition, 17β- estradiol regulated the body weight set point, modulating D2S functions towards increased food intake at lower weights and decreased food intake at higher weights. D2S met the slow genomic actions induced by 17β-estradiol. Conversely, D2L inhibited alcohol and food intakes, but induced specifically sugar consumption, thereby regulating blood glucose levels and promoting energy expenditure in reducing body weight. Indeed, 17β-estradiol exerted a tonic inhibition on D2L which was released by OVX, exacerbating sugar intake and increasing body weight. D2L mediated the rapid metabolic effects of 17β-estradiol. Conclusion: Our results supported physiological data reporting that activation of the mostly expressed presynaptically D2S-class autoreceptors decreased dopamine release stimulating food intake, whereas activation of the predominantly postsynaptic isoform D2L receptors increased dopamine activity inhibiting food intake. Our studies indicated that 17β-estradiol acted on the two types of D2 receptors showing opposite functions to equilibrate energy intake vs. expenditure for weight set point regulation. Our data also supported biochemical findings reporting that 17β-estradiol induced D2 genes transcriptional regulation, thereby involving both types of D2 receptors in the etiology of obesity. The combined dysregulated effects of D2L and D2S receptors, as 17β-estradiol was lacking, would be causal factors underlying the etiology of obesity.

A Novel Computerized Water Level Control System of PWR Steam Generator of Nuclear Power Plant

This paper presents a novel method to solve old problem of water level control system of pressurized water reactor (PWR) steam generator (SG) of nuclear power plant (NPP) .The level control system of SG plays an important role which effects the reliablity,safty,cost of SG and its mathematical models have been solved.A model of the conventional controller is presented and the existing problems are discussed. A novel rule based realtime control technique is designed with a computerized water level control (CWLC) system for SG of PWR NPP.The performance of this is evaluated for full power reactor operating conditions by applying different transient conditions of SG′s data of Qinshan Nuclear Power Plant (QNPP).

Numerical Study of Steam-Water Separators with Wave-type Vanes

Droplet behavior in the wave-type flow channel is discussed,especially with the secondary droplet gen- eration due to impingement of droplets on the wall considered.A numerical method is suggested to simulate the droplet behavior in the flow field.Calculations are compared with experimental data on the pressure drop and sepa- rating efficiency.Good agreement exists between the calculations and air-water experiments.The numerical method developed gives a reasonable description of the droplet deposition and secondary droplet generation,and it can be applied to predict the performance of wave-type vane separators.

Influence of subsequent curing on water sorptivity and pore structure of steam-cured concrete

Steam-cured condition is found to cause larger porosity and worse properties of concrete compared with normal curing condition.For the sake of seeking effective measurements to eliminate this bad effect of steam-cured condition on concrete,the water sorptivity and pore structure of steam-cured concretes exposed to different subsequent curing conditions were investigated after steam-curing treatment.The capillary absorption coefficient and porosity of the corresponding concretes were analyzed,and their mechanisms were also discussed.The results indicate that water sorptivity and pore structure of steam-cured concrete are greatly influenced by the curing condition used in subsequent ages.Exposure steam-cured concrete to air condition has an obviously bad effect on its properties and microstructures.Adopting subsequent curing of immersing steam-cured concrete into about 20 °C water after steam curing period can significantly decrease its capillary absorption coefficient and porosity.Steam-cured concrete with 7 d water curing has minimum capillary absorption coefficient and total porosity.Its water sorptivity is decreased by 23% compared with standard curing concrete and the porosity is 9.6% lower.Moreover,the corresponding gradient of water sorptivity and porosity of steam-cured concrete both decrease,thus microstructure of concrete becomes more homogeneous.

Swelling behaviour of amphiphilic poly(methacryloxyethyl dimethylalkane ammonium bromide) gels in alcohol/water solvent systems

Three kinds of amphiphilic PMADAB gels were prepared through radiation-induced polymerization and crosslinking of methacryloxyethyl dimethylalkane ammonium bromide(MADAB) with different alkyl side chains(butyl,octyl and dodecyl).The length of alkyl side chains had significant influence on swelling behavior of the PMADAB gels in alcohol/water solvent.Equilibrium swelling degree(EDS) of PMBDAB(butyl) gel in water was ca.160 and decreased with increasing alcohol content(x),whereas EDS of PMODAB(octyl)and PMDDDAB(dodecyl) gels showed a convex-upward function of x,i.e.,these two gels barely swelled in pure water and swelled with increasing x and then shrank gradually.This phenomenon was explained by the hydrophobic association of long alkyl chains and a cosolvency effect of PMADAB in alcohol and water.The swelling behavior of PMADAB gels in methanol,ethanol and isopropanol were similar,and their EDS are related with the dielectric constant of alcohol solvents.The results suggest that PMADAB gels may be potential absorbents for various kinds of alcohols.

Studies of Process and Mechanism for Preparing Nano-Sized CeO_2 Powders via Homogeneous Precipitation in Alcohol-Water Solvent

Nano-sized CeO_2 powders were synthesized by homogeneous precipitation method in alcohol-water solution with HMT as precipitator and the nano-particles were characterized by TEM and BET. The process parameters which influenced the sizes and agglomeration of nanometer CeO_2 powders were studied and the influence mechanism was discussed. The results show that the average size of the particles prepared by the above method with the best process parameters is about 8 nm, and the particles are of smaller size and better dispersion than those obtained from the ordinary powders synthesized by homogeneous precipitation in water solution.

Gibbs Density Surface of Water and Steam: 2nd Debate on the Absence of Van Der Waals’ “Critical Point”

A revised phase diagram for water shows three distinct fluid phases. There is no continuity of liquid and gas, and no “critical point” on Gibbs’ density surface as hypothesized by van der Waals. A supercritical colloidal mesophase bounded by percolation transition loci separates supercritical liquid water and gas-phase steam. The water phase is bounded by a percolation transition (PA) of available volume, whereas steam is bounded by the loci of a percolation transition (PB) at a density whereupon a bonded molecular cluster suddenly percolates large distances. At the respective percolation densities, there is no barrier to nucleation of water to steam (PA) or steam to water (PB). Below the critical temperature, the percolation loci become the metastable spinodals in the two-phase coexistence region. A critical divide is defined by the interception of PA and PB the p-T plane. Critical parameters are obtainable from slopes and intercepts of pressure-density supercritical isotherms within the mesophase. The supercritical mesophase is a fourth equilibrium state besides ice, water and steam. A thermodynamic state function rigidity (dp/dρ)T defines a distinction between liquid and gas, and shows a remarkable symmetry due to an equivalence in number density fluctuations, arising from available volume and molecular clusters, in liquid and gas respectively. Following an earlier debate in these pages [“Fluid phases of argon: A debate on the absence of van der Waals’ critical point” Natural Science 5 (2) 194-206 (2013)], we here report further debate on a science of criticality applied to water and steam (APPENDIX 1).

Isobaric Vapor–Liquid Equilibrium for tert-Butyl Alcohol + Water + Propane-1,3-Diol + 1-Ethyl-3-Methylimidazolium Chloride at 101.3 kPa

In this study, we used a mixture of organic liquid propane-1,3-diol and ionic liquid 1-ethyl-3-methylimidazolium chloride([emim]Cl) as the entrainer to separate tert-butyl alcohol(TBA) + water. We measured the isobaric vapor–liquid equilibrium(VLE) for the quaternary system TBA + water + propane-1,3-diol + [emim]Cl at 101.3 kPa, and found the VLE data to be well correlated with the nonrandom two-liquid model. These results show that the mixed solvent of propane-1,3-diol + [emim]Cl can increase the relative volatility of TBA to water and break the azeotropic point. We found no notable synergetic effect between them, and observed that the liquid mixed solvent of propane-1,3-diol and [emim]Cl had lower viscosity than [emim]Cl, which makes it a promising entrainer for separating the TBA + water azeotrope in industrial applications.

Feasibility Analysis of Back-Pressure Steam Feeding Water Pump for Direct Air-Cooled Unit

As the performance of an air-cooled condenser is apt to be affected by the fluctuating ambient condition, some difficulties are brought to the use of a steam feeding water pump in an air-cooled unit. This paper introduces a new design of for steam feeding the water pump of an air-cooled unit using the back-pressure steam turbine as the prime motor. Using variable condition analysis on a 600 MW direct air-cooled unit, and with consideration of the effect on the ambient conditions, the feasibility, economy, and adaptability of the design are verified.

Effect of Reaction Conditions on Production of Catechinone Hair Dyestuff in Water/Alcohol Mixed Solution

Catechinone hair dyestuff was produced chemically from (+)-catechin by the oxidation with O2 in basic water/alcohol mixed solution. The effects of reaction conditions such as basicity, sorts of added base, temperature, alcohol molar fraction of solvent and sorts of added alcohols on the catechinone formation were studied in order to increase the efficiency of the dyestuff production. The amount of obtained catechinone increases with increasing basicity of the reaction solution. The dyestuff is obtained by adding monoethanol amine, diethanol amine, triethanol amine, l-arginine, Na2CO3, K2CO3, Na3PO4 or NaOH into the solution as a base and the most preferable base is monoethanol amine. The optimum temperature for the production in water/ethanol solution is 30&deg;C. It was found that water-soluble alcohols such as methanol, ethanol, 2-propanol, 1-propanol and tert-butyl alcohol are available for preparing the dyestuff. The optimum alcohol molar fraction of the mixed solvent used for the dye formation is 0.45 for methanol, 0.25 for ethanol and 0.20 for 2-propanol, 0.15 for 1-propanol and 0.10 for tert-butyl alcohol. The amount of the obtained dyestuff reaches a maximum at 1) 0.35 and 0.59, 2) 0.35 or 3) 0.35 mol&middot;kg¨1 of the concentration of (+)-catechin for the 1) water/methanol, 2) water/ethanol or 3) water/1-propanol system, respectively.

Experimental study on steam-water two-phase flow frictional pressure drops in helical coils

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PREPARATION OF PERFLUOROOCTANOYL-MODIFIED POLY(VINYL-ALCOHOL)S AND THEIR ADSORPTION AT AN AIR-WATER INTERFACE

Perfluorooctanoyl modified poly(vinyl alcohol)s (FPVA) were prepared by means of substituting a small amount of hydroxyl groups on the backbone of poly(vinyl alcohol), for which the initial degree of polymerization is equal to 1750. The substitution extent, defined by the number of substituting units in a chain, for the four FPVA samples was in the range of 0.5-5 perfluorooctanoyl groups per chain. The FPVA samples with the highest substitution extent still had good solubility in water. It was shown by experimental measurement at 30.0 +/- 0.1 degreesC that the surface tension of the aqueous solution of the highest substituted FPVA decreased to 16.6 mN/m at a higher concentration, e.g. about 0.1 g/mL. Obviously, macromolecules of FPVA exhibit a very strong tendency to adsorb at the air-water interface, because the hydrophobic perfluorooctanoyl groups in FPVA have a very high surface activity as they are in small molecular fluorinated surfactants. The chain conformation of such a model polymer adsorbed on the air-water interface was also discussed.

水汽系统积盐问题分析及处理

尿素水解制氨技术已广泛应用于火电机组脱硝还原剂的制备。然而,若出现尿素质量不合格,尿素水解器发生泄漏以及水解器疏水回用至凝汽器的情况,会对热力系统造成巨大危害。对某燃煤机组尿素水解器泄漏致水汽系统严重积盐及过热器爆管进行了分析,并提出了补充处理方案。实施后机组各项水汽指标均达到《火力发电机组及蒸汽动力设备水汽质量》(GB/T 12145—2016)要求,为水汽系统积盐的原因分析及处理提供了解决方案。