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.

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 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.

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.

Supercritical gasification for the treatment of o-cresol wastewater

The supercritical water gasification of phenolic wastewater without oxidant was performed to degrade pollutants and produce hydrogen-enriched gases. The simulated o-cresol wastewater was gasified at 440-650℃ and 27.6 MPa in a continuous Inconel 625 reactor with the residence time of 0.42-1.25 min. The influence of the reaction temperature, residence time, pressure, catalyst, oxidant and the pollutant concentration on the gasification efficiency was investigated. Higher temperature and longer residence time enhanced the o-cresol gasification. The TOC removal rate and hydrogen gasification rate were 90.6% and 194.6%, respectively, at the temperature of 650℃ and the residence time of 0.83 min. The product gas was mainly composed of H2, CO2, CFL and CO, among which the total molar percentage of H2 and CFL was higher than 50%. The gasification efficiency decreased with the pollutant concentration increasing. Both the catalyst and oxidant could accelerate the hydrocarbon gasification at a lower reaction temperature, in which the catalyst promoted H2 production and the oxidant enhanced CO2 generation. The intermediates of liquid effluents were analyzed and phenol was found to be the main composition. The results indicate that the supercritical gasification is a promising way for the treatment of hazardous organic wastewater.

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.

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.

Stress corrosion cracking behavior of 310S in supercritical water with different oxygen concentrations

The effect of dissolved oxygen(DO) on the stress corrosion cracking(SCC) of 310 S in supercritical water was investigated using slow-strain-rate tensile tests.The tensile properties, fracture morphology, and distribution of the chemical composition of the oxide were analyzed to evaluate the SCC susceptibility of 310 S. The results showed that the rupture elongation decreased significantly as the degree of DO increased. A brittle fracture mode was observed on the fracture surface, and only intergranular cracking was observed on the surface of the gauge section, regardless of the DO. Cracks were widely distributed on the gauge surface near the fracture surface.Oxides were observed in the cracks with two-layered structures, i.e., a Cr-rich inner oxide layer and an Fe-rich outer oxide layer.

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.

Comparative evaluation for catalytic gasification of petroleum coke and asphaltene in subcritical and supercritical water

Subcritical and supercritical water gasification of petroleum coke and asphaltene was performed at variable temperatures(350–650°C),feed concentrations(15–30 wt%)and reaction times(15–60 min).Nickel-impregnated activated carbon(Ni/AC)was synthesized as a catalyst for enhancing syngas yields at optimal gasification conditions(650°C,15 wt%and 60 min).Structural chemistry of precursors and chars developed at different gasification temperatures was studied using physicochemical and synchrotronbased approaches such as carbon–hydrogen–nitrogen–sulfur(CHNS)analysis,thermogravimetric and differential thermogravimetric analysis(TGA/DTA),scanning electron microscopy(SEM),Fourier-Transform Infrared spectroscopy(FTIR),Raman spectroscopy,X-ray diffraction(XRD)and X-ray absorption spectroscopy(XAS).Asphaltene testified to be a better precursor for catalytic hydrothermal gasification leading to 11.97 mmol/g of total gas yield compared to petroleum coke(8.04 mmol/g).In particular,supercritical water gasification using 5 wt%Ni/AC at 650°C with 15 wt%feed concentration for 60 min resulted in 4.17 and 2.98 mmol/g of H_2from asphaltene and petroleum coke,respectively.Under the same conditions,the respective CH_4yields from catalytic gasification of asphaltene and petroleum coke were 2.54and 1.07 mmol/g.Nonetheless,asphaltene also seemed to an attractive feedstock for the production of highly aromatic chars through hydrothermal gasification.

Improving supercritical water gasification of sludge by oil palm empty fruit bunch addition: Promotion of syngas production and heavy metal stabilization

The co-gasification of sewage sludge and palm oil empty fruit bunch(EFB) in supercritical water(SCW) was conducted at 400 °C with a pressure of over 25 MPa. This study aimed to investigate the influence of EFB addition on the syngas production and its composition. The heavy metal distribution and the leaching potential of the solid residue were also assessed. The results showed that syngas yield significantly increased with the addition of EFB into the feedstock. The cold gas efficiency(CGE) and carbon efficiency(CE) of co-gasification were higher than those of individual gasification. The actual syngas production from co-gasification of sludge and EFB was 45% higher than the theoretical total volume. The results indicated that the addition of EFB to sludge had the synergetic promotion effect on syngas production from sludge and EFB in supercritical water. This enhancement might be due to the dissolution of alkali metals from EFB and the adjustment of organic ratio. In addition, higher percentage of heavy metals were deposited and stabilized in the solid residue after SCWG. The leaching concentration of heavy metals from the solid residues was decreased to a level below the standard limit which enables it to be safely disposed of in landfill. In conclusion, the EFB addition has been proved to promote syngas production,as well as, stabilize the heavy metal in solid residues during co-SCWG.

Co-liquefaction of Coal and Used Tire in Supercritical Water

The co-liquefaction of lignite coal and used tire was performed in a 250-ml batch reactor, in supercritical water under a nitrogen atmosphere to investigate the effects of temperature (380-440℃), water/feedstock ratio (4/1-10/1 (wt./wt.)) and the % used tire content in the feedstock (0-100 wt.%) on the conversion efficiency, liquid yield and oil composition attained. The maximum conversion and oil yield were 67 and 50%, respectively, obtained at 400℃ at 1 min, with water/feedstock ratio of 10/1 and 80% used tire content. The distillation characteristics of the oil products, analyzed by simulated distillation gas chromatography, revealed that the oil composition depended significantly on the reaction temperature. The co-liquefaction of coal and used tire yielded a synergistically increased level of oil production. Moreover, the total conversion level obtained with co-liquefaction alone was almost equal to those obtained in the presence of either Fe2O3 or NiMo as catalysts, under the same conditions. Therefore, supercritical water is a good medium for the dissolution of the volatile matter from a coal and used tire matrix.

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.

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.

Slag-washing water of blast furnace power station with supercritical organic Rankine cycle

Organic Rankine cycle(ORC) power plant operating with supercritical parameters supplied by low temperature slag-washing water(SWW) of blast furnace was investigated.A schematic of such installation was presented with a description of its operation and the algorithm of calculations of a supercritical power plant.Two typical organic fluids with sufficiently low critical parameters were selected as candidate working fluids in the plant to study the efficiency of the system with different organic fluids.An analysis of the influence on the effectiveness of operation of a plant was carried out.With the same temperature of slag-washing water,the specific work in turbine of fluid R143a is 45% higher than that obtained for the fluid R125,however,the specific work in pump of fluid R143a is approximate equal into that one of the fluid R125.

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.

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.

有机废水处理工艺CSCWO中多相催化剂研究进展

总结了有机废水处理工艺CSCWO中多相催化剂的研究进展,包括论述了难降解有机废水的特点和传统处理方法的局限性,介绍了SCWO和CSCWO的原理和优势,评述了CSCWO中多相催化剂的种类、性能、合成方法和影响因素,展望了CSCWO技术在未来的发展前景。开发新型高效催化剂,特别是金属氧化物催化剂和非贵金属催化剂,对于推动CSCWO技术的广泛应用具有重要意义。同时,还需要优化多相催化剂的合成工艺和参数,揭示多相催化剂在CSCWO中的反应机理和动态变化,为催化剂的设计提供指导。