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.

Supercritical water oxidation for the destruction of toxic organic wastewaters:A review

The destruction of toxic organic wastewaters from munitions demilitarization and complex industrial chemical clearly becomes an overwhelming problem if left to conventional treatment processes. Two options, incineration and supercritical water oxidation （SCWO）, exist for the complete destruction of toxic organic wastewaters. Incinerator has associated problems such as very high cost and public resentment; on the other hand, SCWO has proved to be a very promising method for the treatment of many different wastewaters with extremely efficient organic waste destruction 99.99% with none of the emissions associated with incineration. In this review, the concepts of SCWO, result and present perspectives of application, and industrial status of SCWO are critically examined and discussed.

Degradation mechanism of 2,4,6-trinitrotoluene in supercritical water oxidation

The 2,4,6-trinitrotoluene （TNT） is a potential carcinogens and TNT contaminated wastewater, which could not be effectively disposed with conventional treatments. The supercritical water oxidation （SCWO） to treat TNT contaminated wastewater was studied in this article, The TNT concentration in wastewater was measured by high-performance liquid chromatograph （HPLC） and the degraded intermediates were analyzed using GC-MS. The results showed that SCWO could degrade TNT efficiently in the presence of oxygen. The reaction temperature, pressure, residence time and oxygen excess were the main contributing factors in the process. The decomposition of TNT was accelerated as the temperature or residence time increased. At 550℃, 24 MPa, 120 s and oxygen excess 300%, TNT removal rate could exceed 99.9%. Partial oxidation occured in SCWO without oxygen. It was concluded that supercritical water was a good solvent and had excellent oxidation capability in the existence of oxygen. The main intermediates of TNT during SCWO included toluene, 1,3,5-trinitrobenzene, nitrophenol, naphthalene, fluorenone, dibutyl phthalate, alkanes and several dimers based on the intermediate analysis. Some side reactions, such as coupled reaction, hydrolysis reaction and isomerization reaction may take place simultaneously when TNT was oxidized by SCWO.

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.

Supercritical water syntheses of transition metal-doped CeO_2 nano-catalysts for selective catalytic reduction of NO by CO:An in situ diffuse reflectance Fourier transform infrared spectroscopy study

In the present study,we synthesized CeO2 catalysts doped with various transition metals(M=Co,Fe,or Cu)using a supercritical water hydrothermal route,which led to the incorporation of the metal ions in the CeO2 lattice,forming solid solutions.The catalysts were then used for the selective catalytic reduction(SCR)of NO by CO.The Cu‐doped catalyst exhibited the highest SCR activity;it had a T50(i.e.,50%NO conversion)of only 83°C and a T90(i.e.,90%NO conversion)of 126°C.Such an activity was also higher than in many state‐of‐the‐art catalysts.In situ diffuse reflectance Fourier transform infrared spectroscopy suggested that the MOx‐CeO2 catalysts(M=Co and Fe)mainly followed an Eley‐Rideal reaction mechanism for CO‐SCR.In contrast,a Langmuir‐Hinshelwood SCR reaction mechanism occurred in CuO‐CeO2 owing to the presence of Cu+species,which ensured effective adsorption of CO.This explains why CuO‐CeO2 exhibited the highest activity with regard to the SCR of NO by CO.

COD Removal Efficiencies of Some Aromatic Compounds in Supercritical Water Oxidation

Some aromatic compounds, phenol, aniline and nitrobenzene, were oxidized in supercritical water. It was experimentally found that the chemical oxygen demand (COD) removal efficiency of these organic compounds can achieve a high level more than 90% in a short residence time at temperatures high enough. As temperature, pressure and residence time increase, the COD removal efficiencies of the organic compounds would all increase. It is also found that temperature and residence time offer greater influences on the oxidation process than pressure. The difficulty in oxidizing these three compounds is in the order of nitrobenzene ＞ aniline ＞ Phenol. In addition, it is extremely difficult to oxidize aniline and nitrobenzene to CO2 and H2O at the temperature lower than 873.15 K and 923.15 K, respectively. Only at the temperature higher than 873.15 K and 923.15 K, respectively, the COD removal efficiencies of 90% of aniline and nitrobenzene can be achieved.

Hydrothermal decomposition of pentachlorophenol in subcritical and supercritical water with sodium hydroxide addition

Hydrothermal decomposition of pentachlorophenol （PCP, C6HC150）, as the probable human carcinogen, was investigated in a tubular reactor under subcritical and supercritical water with sodium hydroxide （NaOH） addition. The experiments were conducted at a temperature range of 30（0-420℃ and a fixed pressure of 25 MPa, with a residence time that ranged from 10 s to 70 s. Under the reaction conditions, the initial PCP concentrations were varied from 0.25 to 1.39 mmol/L, and the NaOH concentrations were varied from 2.5 to 25 times of the concentrations of PCP. The result of this study showed that PCP conversion in supercritical water was highly dependent on the reaction temperature, residence time, and NaOH concentration. PCP conversion in subcritical water is, however, only dependent on reaction temperature. NaOH concentration and residence times were found to have little effect on PCP conversion in subcritical condition. It was found that NaOH concentration affected the dechlorinations of PCP in the supercritical water. The intermediates detected were proposed to be tetrachlorophenol and trichlorophenol, respectively.

Decomposition kinetics of dimethyl methylphospate(chemical agent simulant) by supercritical water oxidation

Supercritical water oxidation （SCWO） has been drawing much attention due to effectively destroy a large variety of high-risk wastes resulting from munitions demilitarization and complex industrial chemical. An important design consideration in the development of supercritical water oxidation is the information of decomposition rate. In this paper, the decomposition rate of dimethyl methylphosphonate（DMMP）, which is similar to the nerve agent VX and GB（Sarin） in its structure, was investigated under SCWO conditions. The experiments were performed in an isothermal tubular reactor with a H2O2 as an oxidant. The reaction temperatures were ranged from 398 to 633℃ at a fixed pressure of 24 MPa. The conversion of DMMP was monitored by analyzing total organic carbon （TOC） on the liquid effluent samples. It is found that the oxidative decomposition of DMMP proceeded rapidly and a high TOC decomposition up to 99.99% was obtained within 11 s at 555℃. On the basis of data derived from experiments, a global kinetic equation for the decomposition of DMMP was developed. The model predictions agreed well with the experimental data.

Hydrogen production by glycerol reforming in supercritical water over Ni/MgO-ZrO_2 catalyst

Nano ZrO2 and MgO-ZrO2 were prepared by a self-assembly route and were employed as the support for Ni catalysts used in hydrogen production from glycerol reforming in supercritical water （SCW）. The reforming experiments were conducted in a tubular fixed-bed flow reactor over a temperature range of 600-800 ℃. The influences of process variables such as temperature, contact time, and water to glycerol ratio on hydrogen yield were investigated and the catalysts were charactered by ICP, BET, XRD and SEM. The results showed that high hydrogen yield was obtained from glycerol by reforming in supercritical water over the Ni/MgO-ZrO2 catalysts in a short contact time. The MgO in the catalyst showed significant promotion effect for hydrogen production likely due to the formation of the alkaline active site. Even when the glycerol feed concentration was up to 45 wt%, glycerol was completely gasified and transfered to the gas products containing hydrogen, carbon dioxide, and methane along with small amounts of carbon monoxide. At a diluted feed concentration of 5 wt%, near theoretical yield of 7 mole of H2/mol of glycerol could be obtained.

Effect of Increasing Course of Temperature and Pressure on Polypropylene Degradation in Supercritical Water

The effect of increasing course of temperature and pressure on polypropylene （PP） degradation in supercritical water was investigated for developing a process of recycling waste plastic. A group of experiments was carded out in a reaction system at a pressure of 26MPa, temperature of 380℃ or 400℃ for 30min, 70min, and 120min by Course One （the increasing course of temperature and pressure is via gaseous regions to supercritical regions）, and the other group was carried out at corresponding holding conditions by Course Two （the increasing course of temperature and pressure is via liquid regions to supercritical regions）. The time of the increasing courses was about 30min. Products were analyzed by Ostward-type viscometer, gaseous chromatography, and mass spectrometers （GC/MS）. Characterization results suggested that different increasing courses of temperature and pressure would give rise to different results, although they were treated under the similar holding conditions. It was also found that Course Two was more effective on PP degradation in supercritical water.

Energetic analysis of gasification of biomass by partial oxidation in supercritical water

Partial oxidation gasification in supercritical water could produce fuel gases(such as H2, CO and CH4) and significantly reduce the energy consumption. In this work, an energetic model was developed to analyze the partial oxidative gasification of biomass(glucose and lignin) in supercritical water and the related key factors on which gasification under autothermal condition depended upon. The results indicated that the oxidant equivalent ratio(ER) should be over 0.3 as the concern about energy balance but less than 0.6 as the concern about fuel gas production. Feedstocks such as glucose and lignin also had different energy recovery efficiency. For materials which can be efficiently gasified, the partial oxidation might be a way for energy based on the combustion of fuel gases. Aromatic materials such as lignin and coal are more potential since partial oxidation could produce similar amount of fuel gases as direct gasification and offer additional energy. Energy recovered pays a key role to achieve an autothermal process. Keeping heat exchanger efficiency above 80% and heat transfer coefficient below15 k J·s-1is necessary to maintain the autothermal status. The results also indicated that the biomass loading should be above 15% but under 20% for an autothermal gasification, since the increase of biomass loading could improve the energy supplied but decrease the efficiency of gasification and gaseous yields. In general,some specific conditions exist among different materials.

Effect of supercritical water on the stability and activity of alkaline carbonate catalysts in coal gasification

The stability and activity of alkaline carbonate catalysts in supercritical water coal gasification has been investigated using density functional theory method. Our calculations present that the adsorption of Na2CO3 on coal are more stable than that of K2CO3, but the stability of Na2CO3 is strongly reduced as the cluster gets larger. In supercritical water system, the dispersion and stability of Na2CO3 catalyst on coal support is strongly improved. During coal gasification process, Na2CO3 transforms with supercritical water into NaOH and NaHCO3, which is beneficial for hydrogen production. The transformation process has been studied via thermodynamics and kinetics ways. The selectively catalytic mechanism of NaOH and the intermediate form of sodium-based catalyst in water-gas shift reaction for higher hydrogen production has also been investigated. Furthermore, NaOH can transform back to Na2CO3 after catalyzing the water-gas shift reaction. Thus, the cooperative effects between supercritical water and Na2CO3 catalyst form a benignant circle which greatly enhances the reaction rate of coal gasification and promotes the production of hydrogen.

Decomposition of oil cleaning agents from nuclear power plants by supercritical water oxidation

Oil cleaning agents generated from nuclear power plants(NPPs)are radioactive organic liquid wastes.To date,because there are no satisfactory industrial treatment measures,these wastes can only be stored for a long time.In this work,the optimization for the supercritical water oxidation(SCWO)of the spent organic solvent was investigated.The main process parameters of DURSET(oil cleaning agent)SCWO,such as temperature,reaction time,and excess oxygen coefficient,were optimized using response surface methodology,and a quadratic polynomial model was obtained.The determination coefficient(R^(2))of the model is 0.9812,indicating that the model is reliable.The optimized process conditions were at 515 C,66 s,and an excess oxygen coefficient of 211%.Under these conditions,the chemical oxygen demand removal of organic matter could reach 99.5%.The temperature was found to be the main factor affecting the SCWO process.Ketones and benzene-based compounds may be the main intermediates in DURSET SCWO.This work provides basic data for the industrialization of the degradation of spent organic solvents from NPP using SCWO technology.

Investigation on adsorption and regeneration performances of multi-walled carbon nanotubes by supercritical water technique

In this paper, adsorption and regeneration characteristics of multi-walled carbon nanotubes （MWNTs） used as adsorbent were investigated for the removal of 1,3-beuzenediol （BDO） from water by the supercritieal water （SCW） technique. FFIR, XPS, SEM and dispersion stability tests were used to characterize the structure and surface morphology of CNTs. The results showed that CNTs surfaces were slightly activated and strongly etched in supercritieal water system. The adsorption capacity of SCW-treated CNTs was higher than that of raw CNTs. The adsorbed amounts for treated CNTs and raw CNTs samples at the same initial concentration of 60 mg/L were ca. 16.42 and 7.30 mg/g, respectively. The BDO adsorption of treated CNTs was due to the physical adsorption. The experimental data fit Freundlich isotherm model better than Langmuir one. The loaded adsorbent could be efficiently desorbed and regenerated by SCW technique. Therefore, SCW is a promising and environmentally friendly technique for the improvement of adsorption and regeneration of CNTs.

Supercritical Water as a Reaction Medium for Nitrogen-Containing Heterocycles

Supercritical water has been focused on as an environmentally attractive reaction media, in which organic materials can be decomposed into smaller molecules. The reaction behavior of pyrrole as a simple model compound of nonbasic nitrogen compounds found in petroleum residua was studied in supercritical water with a batch type reactor. The reaction was carried out at temperatures of 698-748 K and at various pressures under an argon atmosphere. The chemical species in the aqueous products were identified by GCMS （gas chromatography mass spectrometry） and quantified using GC-FID （gas chromatography flame ionization detector）. The effect of temperature and reaction time on the conversion process of pyrrole is presented. Under supercritical water conditions, pyrrole underwent successful decomposition in water into its derived compounds. The conversion of pyrrole could approach 81.12 wt% at 723 K and 40 MPa within 240 min of reaction time. The decomposition process was accelerated with the existence of water at the same temperature. Ultimate analysis of solid products was also conducted using a CHN analyzer. The process investigated in this study may form the basis for an efficient method of nitrogen compound decomposition in future.

Optimal design of heat exchanger header for coal gasification in supercritical water through CFD simulations

Heat exchangers play an important role in supercritical water coal gasification systems for heating feed and cooling products. However, serious deposition and plugging problems always exist in heat exchangers. CFD modeling was used to simulate the transport characteristics of solid particles in supercdtical water through the shell and tube of heat exchangers to alleviate the problems. In this paper, we discuss seven types of exchangers CA, B, C D, E, F and G）, which vary in inlet nozzle configuration, header height, inlet pipe diameter and tube pass distribution. In the modeling, the possibility of deposition in the header was evaluated by accumulated mass of particles; we used the velocity contour of supercritical water （SCW） to evaluate the uniformity of the velocity dis- tribution among the tube passes. Simulation results indicated that the optimum heat exchanger had structure F, which had a rectangular configuration of tube pass distractions, a bottom inlet, a 200-mm header height and a 10-ram inlet pipe diameter.

Forced Convective Heat Transfer Experiment of Supercritical Water in Different Diameter of Tubes

Forced convective experiment of supercritical water was performed in Inconel-625 tubes of 4.62 mm, 7.98 mm and 10.89 mm in diameter. The water flowed upward, covering the ranges of pressure of 23.4 MPa to 25.8 MPa, mass flux of 90 kg/m^2s to 3,281 kg/m^2s, local bulk temperature of 102-384 ℃, inner wall temperature of 167-669℃ and heat flux of up to 2.41 MW/m^2. The results exhibited severe deteriorated and enhancement heat transfer. The experimental results can be calculated by the Jackson＇s correlation and the Bishop＇s correlation mostly. But some data with strong effects of the buoyancy force and the variations of flow regimes can not be predicted properly.

Molecular Dynamics Investigation of Benzene in Supercritical Water

Microscopic structure and diffusion properties of benzene in ambient water (298 K, 0.1 MPa) and super critical water (673－773 K, 25－35 MPa) are investigated by molecular dynamics simulation with site-site models. It is found that at the ambient condition, the water molecules surrounding a benzene molecule form a hydrogen bond network. The hydrogen bond interaction between supercritical water molecules decreases dramatically under supercritical conditions. The diffusion coefficients of both the solute molecule and solvent molecule at supercritical conditions increase by 30－180 times than those at the ambient condition. With the temperature approaching the critical temperature, the change of diffusion coefficient with pressure becomes pronounced.

Study on the Diffusion Coefficient of Sodium Chloride at Infinite Dilution in Supercritical Water

The molecular dynamics (MD) was employed to simulate the diffusion coefficient of sodium chloride at infinite dilution in supercritical water from 703.2 K to 763.2 K and from 30 MPa to 45 MPa. Based on the simulated data and the Patel-Teja(PT) equation of state and the Liu-Ruckenstein equation, an equation for calculating the diffusion coefficient of NaCl at infinite dilution in supercritical water is proposed. Both the agreement between the simulated and correlated data, and that between the simulated and predicted data of diffusion coefficients for NaCl in supercritical water ranging from 703.2K to 803.2 K and from 25 MPa to 50 MPa show that this equation is applicable for the calculation of diffusion coefficients.

Effects of oxidants on the degradation of tributyl phosphate under supercritical water oxidation conditions

The effects of additional oxidants,such as NaNO_(3),Na_(2)S_(2)O_(3),KClO_(4),and K_(2)Cr_(2)O_(7),on the supercritical water oxidation(SCWO)of tributyl phosphate(TBP)were studied.The coupling of an ionic oxidant with SCWO can effectively enhance the oxidative degradation ability of the system,thus increasing its organic-matter-removal efficiency at a reduced reaction temperature.Moreover,the addition of NaNO_(3),KClO_(4),or K_(2)Cr_(2)O_(7)could improve this efficiency at a reaction temperature of 500℃compared with that of the original system at 550℃.Additionally,based on the conditions adopted in this study,the addition of either of these oxidants could reduce the final total organic carbon(TOC)of the effluent from~500 to<100 ppm.Concurrently,the ionic oxidants could effectively improve the processing capacity of the SCWO system to reduce the scale of the equipment,as well as the amount of produced wastewater.Compared with KClO_(4)and Na_(2)S_(2)O_(3),the addition of 10 mmol/L NaNO_(3)and K_(2)Cr_(2)O_(7)to the organic feed could increase the processing capacity of the system from 4 to 10%while maintaining the TOC removal at>99%.The effects of the ionic oxidants on the gas products,including CO_(2),CO,H_(2),and CH_(4),as well as other organic gases,have also been studied.Among these gas products,CO_(2)accounted for the main gas product with a proportion of more than half.At<500℃,temperature significantly affected the as products(CO,H_(2),CH_(4),and other organic gases).However,the gas product was mainly CO_(2)when the temperature was increased to≥500℃.This study initially revealed the enhancement effect of ionic oxidants on SCWO,which still requires further research.