Development of index system for inherently safer process design using an integrated approach

With a growing population, an increasing number of petrochemical facilities are built with larger capacity and more complexity, which pose a great risk to assets, community and environment. The value of inherently safer design is recognized with time by all stakeholders, and an effective tool is needed to evaluate and compare inherent safety of alternative technologies. This study developed a safety index to evaluate existing technologies for their safety levels and guide inherently safer design. The Integrated Risk-based Safety Index(IRSI) was developed based on a comprehensive review of petrochemical processes, incident cases from Sinopec and US Chemical Safety Board, and existing safety index systems. The IRSI included all major hazards, including fire, explosion,toxic release, dust explosion, physical explosion, and runaway. Also, the integrated life cycle approach considered chemical hazards, equipment failure rates and safety measures in this risk-based index. Advanced modeling techniques, PHAST simulation and Neural Network, were used in the development of three novel sub-indices in the projects, fire, explosion and toxic release. The index system could be easily incorporated into a user friendly tool for the ease of application. A case study of hydrogen dioxide was conducted using the IRSI, which showed its capability for evaluating the safety level of process facilities.

One-step synthesis of inherently chiral p-tert-butylcalix[4]azacrown

A one-step procedure is developed to synthesize inherently chiral p-tert-butylcalix[4]azacrown 1 through etherification between p-tert-butylcalix[4]arene and compound 3, which can be amplifed to efficiently prepare more inherently cbiral calix[4]arenes in ABHH substitution pattern.

A Signed Digraphs Based Method for Detecting Inherently Unsafe Factors of Chemical Process at Conceptual Design Stage

Digraph-based causal models have been widely used to model the cause and effect behavior of process systems. Signed digraphs （SDG） capture the direction of the effect. It should be mentioned that there are loops in SDG generated from chemical process. From the point of the inherent operability, the worst unsafe factor is the SDG having positive loops that means any disturbance occurring within the loop will propagate through the nodes one by one and are amplified gradually, so the system may lose control, which may lead to an accident. So finding the positive loops in a SDG and treating these unsafe factors in a proper manner can improve the inherent safety of a chemical process. This article proposed a method that can detect the above-mentioned unsafe factors in the proc- ess conceptual design stage automatically through the analysis of the SDG generated from the chemical process. A case study is illustrated to show the working of the algorithm, and then a complicated case from industry is studied to depict the effectiveness of the proposed algorithm.

Catalytic Asymmetric Synthesis of Inherently Chiral Saddle- Shaped Dibenzo[b,fI[1,5]diazocines

Dibenzo[b,fi[1,5]diazocines are a class of eight-membered heterocycles,which exhibit unique rigid saddle-shaped structure and possess inherent chirality.In this study,we report a convenient and straightforward method for the catalytic enantioselective synthesis of these unique chiral molecules through chiral phosphoric acid-catalyzed dimerization of 2-acylbenzoisocyanates.Notably,the addition of corresponding 2-acylaniline as the co-catalyst significantly improved the efficiency of these reactions,and a simple phase separation operation resulted in products with excellent enantiopurity.Experimental studies were performed to elucidate the mechanism behind these reactions,leading to the proposal of a plausible reaction mechanism based on the study findings.

Inherently Chiral 6,7-Diphenyldibenzo [e,g][1,4]diazocine: Enantioselective Synthesis and Application as a Ligand Platform

Inherently chiral 6,7-diphenyldibenzo[e,g][1,4]diazocine(DDD)has been synthesized enantioselectively for the first time via chiral phosphoric acid(CPA)-catalyzed cyclocondensation of readily available[1,1′-biphenyl]-2,2′-diamine(1a)and benzil(2a)in 82%yield,with 98%ee under mild reaction conditions.The strategy could also be applied to racemic biaryl diamines through kinetic resolution.The unexpectedly high interconversion energy barriers between the enantiomers(ΔG=39.5 kcal/mol)and the chemical stability rendered DDD an ideal platform for developing new chiral ligands and catalysts.Unique inherently chiralDDD-based phosphoramidites,phosphoric acid,mono-and diphosphine ligands were prepared from optically pure diphenol derivative DDDOL as a common precursor.Preliminary asymmetric reactions catalyzed by Pd or Rh in the presence of newly developed ligands exhibited comparable or even better enantioselectivities than the corresponding BINOLor SPINOL-derived ligands.Density functional theory calculation revealed the origin of the enantioselectivity during the process.

Enantiopure inherently chiral calix[4]arene derivatives containing quinolin-2-yl-methanol moiety:Synthesis and application in the catalytic asymmetric addition of diethylzinc to benzaldehyde

A series of novel N,O-type chiral ligands derived from enantiopure inherently chiral calix[4]arenes containing quinolin-2-yl-methanol moiety in the cone or partialcone conformation have been synthe-sized and characterized. Moreover,they have been applied to the catalytic asymmetric addition of diethylzinc to benzaldehyde,which represents the first example that the inherently chiral calixarene can be used as the chiral ligands for the catalytic asymmetric synthesis.

“Blocking and rebalance”mechanism-guided design strategies of bimetallic doped 2D a-phosphorus carbide as efficient catalysts for N_(2) electroreduction

Compared to single atom catalysts(SACs),the introduction of dual atom catalysts(DACs)has a significantly positive effect on improving the efficiency in the electrocatalytic nitrogen reduction reaction(NRR)which provides an environmental alternative to the Haber-Bosch process.However,the research on the mechanism and strategy of designing bimetallic combinations for better performance is still in its early stages.Herein,based on"blocking and rebalance"mechanism,45 combinations of bimetallic pair dopedα-phosphorus carbide(TM_(A)TM_(B)@PC)are investigated as efficient NRR catalysts through density functional theory and machine learning method.After a multi-step screening,the combinations of TiV,TiFe,MnMo,and FeW exhibit highly efficient catalytic performance with significantly lower limiting potentials(-0.17,-0.18,-0.14,and-0.30 V,respectively).Excitingly,the limiting potential for CrMo and CrW combinations is 0 V,which are considered to be extremely suitable for the NRR process.The mechanism of"blocking and rebalance"is revealed by the exploration of charge transfer for phosphorus atoms in electron blocking areas.Moreover,the descriptorφis proposed with machine learning,which provides design strategies and accurate prediction for finding efficient DACs.This work not only offers promising catalysts TM_(A)TM_(B)@PC for NRR process but also provides design strategies by presenting the descriptorφ.

Effect of Rigid Pitch Motion on Flexible Vibration Characteristics of a Wind Turbine Blade

Adynamic pitch strategy is usually adopted to improve the aerodynamic performance of the blade of awind turbine.The dynamic pitch motion will affect the linear vibration characteristics of the blade.However,these influences have not been studied in previous research.In this paper,the influences of the rigid pitch motion on the linear vibration characteristics of a wind turbine blade are studied.The blade is described as a rotating cantilever beam with an inherent coupled rigid-flexible vibration,where the rigid pitch motion introduces a parametrically excited vibration to the beam.Partial differential equations governing the nonlinear coupled pitch-bend vibration are proposed using the generalized Hamiltonian principle.Natural vibration characteristics of the inherent coupled rigid-flexible system are analyzed based on the combination of the assumed modes method and the multi-scales method.Effects of static pitch angle,rotating speed,and characteristics of harmonic pitch motion on flexible natural frequencies andmode shapes are discussed.It shows that the pitch amplitude has a dramatic influence on the natural frequencies of the blade,while the effects of pitch frequency and pith phase on natural frequencies are little.

Quantization of Action for Elementary Particles and the Principle of Least Action

The uncertainty principle is a fundamental principle of quantum mechanics, but its exact mathematical expression cannot obtain correct results when used to solve theoretical problems such as the energy levels of hydrogen atoms, one-dimensional deep potential wells, one-dimensional harmonic oscillators, and double-slit experiments. Even after approximate treatment, the results obtained are not completely consistent with those obtained by solving Schrödinger’s equation. This indicates that further research on the uncertainty principle is necessary. Therefore, using the de Broglie matter wave hypothesis, we quantize the action of an elementary particle in natural coordinates and obtain the quantization condition and a new deterministic relation. Using this quantization condition, we obtain the energy level formulas of an elementary particle in different conditions in a classical way that is completely consistent with the results obtained by solving Schrödinger’s equation. A new physical interpretation is given for the particle eigenfunction independence of probability for an elementary particle: an elementary particle is in a particle state at the space-time point where the action is quantized, and in a wave state in the rest of the space-time region. The space-time points of particle nature and the wave regions of particle motion constitute the continuous trajectory of particle motion. When an elementary particle is in a particle state, it is localized, whereas in the wave state region, it is nonlocalized.

Discrete element modeling of inherently anisotropic granular assemblies with polygonal particles

In the present article, we study the effect of inherent anisotropy, i.e., initial bedding angle of particles and associated voids on macroscopic mechanical behavior of granular materials, by numerical simulation of several biaxial compression tests using the discrete element method （DEM）. Particle shape is considered to be irregular convex-polygonal. The effect of inherent anisotropy is investigated by following the evolution of mobilized shear strength and volume change during loading. As experimental tests have already shown, numerical simulations also indicate that initial anisotropic condition has a great influence on the strength and deformational behavior of granular assemblies. Comparison of simulations with tests using oval particles, shows that angularity influences both the mobilized shear strength and the volume change regime, which originates from the interlocking resistance between particles.

Size effect of fracture characteristics for anisotropic quasi-brittle geomaterials

Understanding the size effect exhibited by the fracture mechanism of anisotropic geomaterials is important for engineering practice. In this study, the anisotropic features of the nominal strength, apparent fracture toughness, effective fracture energy and fracture process zone(FPZ) size of geomaterials were first analyzed by systematic size effect fracture experiments. The results showed that the nominal strength and the apparent fracture toughness decreased with increasing bedding plane inclination angle.The larger the specimen size was, the smaller the nominal strength and the larger the apparent fracture toughness was. When the bedding inclination angle increased from 0° to 90°, the effective fracture energy and the effective FPZ size both first decreased and then increased within two complex variation stages that were bounded by the 45° bedding angle. Regardless of the inherent anisotropy of geomaterials,the nominal strength and apparent fracture toughness can be predicted by the energy-based size effect law, which demonstrates that geomaterials have obvious quasi-brittle characteristics. Theoretical analysis indicated that the true fracture toughness and energy dissipation can be calculated by linear elastic fracture mechanics only when the brittleness number is higher than 10;otherwise, size effect tests should be adopted to determine the fracture parameters.

Study of residual stresses and distortions from the Ti6Al4V based thinwalled geometries built using LPBF process

The current paper focuses on the prediction of residual stresses and distortions in the Laser Powder Bed Fusion(LPBF)built Ti6Al4V thin-walled geometries using Ansys Additive Print(AAP)software which employs a layer-by-layer accumulation of inherent strain to calculate the deformations.Isotropic and anisotropic strain scaling factors were calibrated initially within the APP software for the Ti6Al4V based single cantilever beam geometry.Subsequently,the numerical simulations were performed in APP software and computed the residual stresses and distortions for the varied process parameters including laser power,scan speed and hatch distance while maintaining the layer thickness constant for all the design iterations.The numerical predictions were compared;they were found to match reasonably well with the XRD measurements within the calibrated regime.

A New Interpretation of the Higgs Vacuum Potential Energy Based on a Planckion Composite Model for the Higgs

We present a new interpretation of the Higgs field as a composite particle made up of a positive, with, a negative mass Planck particle. According to the Winterberg hypothesis, space, i.e., the vacuum, consists of both positive and negative physical massive particles, which he called planckions, interacting through strong superfluid forces. In our composite model for the Higgs boson, there is an intrinsic length scale associated with the vacuum, different from the one introduced by Winterberg, where, when the vacuum is in a perfectly balanced state, the number density of positive Planck particles equals the number density of negative Planck particles. Due to the mass compensating effect, the vacuum thus appears massless, chargeless, without pressure, energy density, or entropy. However, a situation can arise where there is an effective mass density imbalance due to the two species of Planck particle not matching in terms of populations, within their respective excited energy states. This does not require the physical addition or removal of either positive or negative Planck particles, within a given region of space, as originally thought. Ordinary matter, dark matter, and dark energy can thus be given a new interpretation as residual vacuum energies within the context of a greater vacuum, where the populations of the positive and negative energy states exactly balance. In the present epoch, it is estimated that the dark energy number density imbalance amounts to, , per cubic meter, when cosmic distance scales in excess of, 100 Mpc, are considered. Compared to a strictly balanced vacuum, where we estimate that the positive, and the negative Planck number density, is of the order, 7.85E54 particles per cubic meter, the above is a very small perturbation. This slight imbalance, we argue, would dramatically alleviate, if not altogether eliminate, the long standing cosmological constant problem.

On the Cosmic Evolution of the Quantum Vacuum Using Two Variable G Models and Winterberg’s Thesis

We work within a Winterberg framework where space, i.e., the vacuum, consists of a two component superfluid/super-solid made up of a vast assembly (sea) of positive and negative mass Planck particles, called planckions. These material particles interact indirectly, and have very strong restoring forces keeping them a finite distance apart from each other within their respective species. Because of their mass compensating effect, the vacuum appears massless, charge-less, without pressure, net energy density or entropy. In addition, we consider two varying G models, where G, is Newton’s constant, and G-1, increases with an increase in cosmological time. We argue that there are at least two competing models for the quantum vacuum within such a framework. The first follows a strict extension of Winterberg’s model. This leads to nonsensible results, if G increases, going back in cosmological time, as the length scale inherent in such a model will not scale properly. The second model introduces a different length scale, which does scale properly, but keeps the mass of the Planck particle as, ± the Planck mass. Moreover we establish a connection between ordinary matter, dark matter, and dark energy, where all three mass densities within the Friedman equation must be interpreted as residual vacuum energies, which only surface, once aggregate matter has formed, at relatively low CMB temperatures. The symmetry of the vacuum will be shown to be broken, because of the different scaling laws, beginning with the formation of elementary particles. Much like waves on an ocean where positive and negative planckion mass densities effectively cancel each other out and form a zero vacuum energy density/zero vacuum pressure surface, these positive mass densities are very small perturbations (anomalies) about the mean. This greatly alleviates, i.e., minimizes the cosmological constant problem, a long standing problem associated with the vacuum.

Inherent Criteria of Brand Name Translation

This thesis takes the Skopostheorie as the guiding principle,analyzes and explains some important yet tend-to-be neglected standards,that is,the inherent characteristics unique to each product or service category.By means of analyzing cases,either successful or undesirable,it suggests the brand name translation had better imply their underlying features.Such principles may result in amazing translations.

Recent developments in the use of single-atom catalysts for water splitting

Electrochemical water splitting is regarded as the most promising approach to produce hydrogen.However,the sluggish electrochemical reactions occurring at the anode and cathode,namely,the oxygen evolution reaction(OER)and the hydrogen evolution reaction(HER),respectively,consume a tremendous amount of energy,seriously hampering its wide application.Recently,single-atom catalysts(SACs)have been proposed to effectively enhance the kinetics of these two reactions.In this minireview,we focus on the recent progress in SACs for OER and HER applications.Three classes of SACs have been reviewed,i.e.,alloy-based SACs,carbon-based SACs and SACs supported on other compounds.Different factors affecting the activities of SACs are also highlighted,including the inherent element property,the coordination environment,the geometric structure and the loading amount of metal atoms.Finally,we summarize the current problems and directions for future development in SACs.

The black water around the Changjiang (Yangtze) Estuary in the spring of 2003

The Changjiang （Yangtze） Estuary is located in the East China Sea shelf with shallow water. Affected by the tide mixing and the runoff of the Changjiang River and the Qiantang River the turbidity is very high. Generally, the water-leaving radiance is high in the turbid water because of the large particle scattering. Based on the in-situ data and ocean color remote sensing data of SeaWiFS, it was found that there was a black water region with the normalized water-leaving radiances less than 0.5 mW/（cm2-μm2-sr）. The optical principle of the occurrence of this black water was analyzed by the inherent optical properties and the ocean color components. The results show that black water is caused by the relative low values of the suspended particle matter concentration and the back scattering ratio. In the black water region, the percentage of the phytoplankton absorption was relatively high, and the large size of the phytoplankton caused the low value of the particle backscattering ratio.

Comparative study on evaluation of tendon force for welding distortion prediction in thin plate fabrication

Tendon force is an essential concept to predict welding distortion such as longitudinal shrinkage and welding induced buckling in thin plate fabrication. In this study,three approaches with experimental,theoretical and computational analysis,are examined to evaluate the magnitude of tendon force. In detail,inherent deformation theory is introduced first,the theoretical analysis to obtain the inherent strain solution is also reviewed; and then analytical solution for tendon force is achieved. Also,the theory of FE analysis for welding is introduced and implemented in a computation to obtain the transient temperature distribution,plastic strain,residual stress and welding distortion in a bead-on-plate welded joint with 2. 28 mm in thickness. The longitudinal displacement is employed to evaluate tendon force directly,and these computed inherent strain and inherent stress can also be employed to evaluate tendon force by integration approach later. All the evaluated magnitudes of tendon force have a good agreement with each other.

Retrieval of inherent optical properties of the Yellow Sea and East China Sea using a quasi-analytical algorithm

We tested and modified the quasi-analytical algorithm （QAA） using 57 groups of field data collected in the spring of 2003 in the Yellow Sea and East China Sea. The QAA performs well in deriving total absorption coefficients of typical coastal waters. The average percentage difference （APD） is in a range of 13.9%-38.5% for the total absorption coefficient （13.9% at 440 nm）, and differences in particle backscattering coefficient bbp（2） are less than 50% （in the case of the updated QAA）. To obtain improved results, we modified the QAA by adjusting the empirical relationships. The modified algorithm is then applied to the field data to test its performance. The APDs were 44.7%-46.6% for bbp（λ） and 9.9%-32.8% （9.9% at 555 nm） for the total absorption coefficient. This indicates that the modified QAA derives better results. We also used the modified model to derive phytoplankton pigment absorption （aph） and detritus and CDOM absorption （aug） coefficients. The APDs for aph and a dg at 440 nm are 37.1% and 19.8%. In this paper, we discuss error sources using the measured dataset. More independent field data can improve this algorithm and derive better results.

PREDICTION OF WELDING DEFORMATIONS BY FEM BASED ON INHERENT STRAINS

Welding deformations can be predicted by inherent strains that are assumed to be distributed in the welds and nearby area. This method is more convenient compared with the thermo elasto plastic finite element method because only elastic analysis is necessary. The problem is how to know the inherent strains in advance during deformation analysis. The relations between inherent strains and welding parameters based on some experimental curves and a 3 D FEM model were introduced. According to this study, the longitudinal and transverse inherent strains that are the most important factors on welding deformations can be determined. The effectiveness of the proposed methods is demonstrated through the deformation analysis of a large welded cylinder with multipass welds as an example.