Absorbing oxygen carriers promotes phosphorus recovery from sludge via the microwave thermal conversion process.

This study aims to apply the Absorbing oxygen carriers (AOCs) to induce the migration and transformation of phosphorus compounds during the microwave thermal conversion of sludge so the hard-to-extract organic phosphorus (OP) can be converted to easy-to-extract inorganic phosphorus (IP) and be enriched onto the sludge char. The AOCs were recycled by screen separation from the IP-rich sludge char, with the latter being a renewable phosphorus source from sludge. The AOCs in this novel process enhanced the conversion efficiency of OP into non-apatite inorganic phosphorus (NAlP), which was further converted to apatite inorganic phosphorus (AP). Most phosphorus in the sludge char is presented in the form of orthophosphate.

Review on supported metal catalysts with partial/porous overlayers for stabilization.

Heterogeneous catalysts of supported metals are important for both liquid-phase and gas-phase chemical transformations which underpin the petrochemical sector and manufacture of bulk or fine chemicals and pharmaceuticals. Conventional supported metal catalysts (SMC) suffer from deactivation resulting from sintering, leaching, coking and so on. Besides the choice of active species (e.g. atoms, clusters, nanoparticles) to maximize catalytic performances, strategies to stabilize active species are imperative for rational design of catalysts, particularly for those catalysts that work under heated and corrosive reaction conditions. The complete encapsulation of metal active species within a matrix (e.g. zeolites, MOFs, carbon, etc.) or core-shell arrangements is popular. However, the use of partial/porous overlayers (PO) to preserve metals, which simultaneously ensures the accessibility of active sites through controlling the size/shape of diffusing reactants and products, has not been systematically reviewed. The present review identifies the key design principles for fabricating supported metal catalysts with partial/porous overlayers (SMCPO) and demonstrates their advantages versus conventional supported metals in catalytic reactions.

Insight into derivative Weibull mixture model in describing simulated distributed activation energy model and distillers dried grains with solubles pyrolysis processes.

The kinetics of biomass pyrolysis is fundamental for exploring its mechanisms and optimizing its processes, which is helpful for designing its systems. The derivative Weibull mixture model was proposed for kinetic description of the simulated distribution energy model (DAEM) processes and distillers dried grains with solubles (DDGS) pyrolysis processes. The conversion rate data of these processes at different heating rates could be accurately described by the derivative Weibull mixture model. Moreover, the proposed model could effectively smooth the noises contained in the experimental conversion rate data of DDGS pyrolysis. The derivative Weibull mixture model separated DDGS pyrolysis reactions into several individual processes, and provided some data required for further isoconversional kinetic analysis. The predicted curves from the derivative Weibull mixture model allowed us to obtain the effective activation energies of DDGS pyrolysis, which varied significantly from 170 to 330 kJ mol-1 in the conversion range between 0.1 and 0.9.

Investigation of product selectivity and kinetics of poplar sawdust catalytic pyrolysis over bi-metallic Iron-Nickel/ZSM-5 catalyst.

Py-GC/MS and thermogravimetric analysis were carried out to systematically explore product selectivity and kinetics of poplar sawdust catalytic pyrolysis over bi-metallic Fe-Ni/ZSM-5. The results showed that the Fe-Ni/ZSM-5 exhibited an additive effect on the production of monocyclic aromatic hydrocarbons compared to mono-metallic catalysts (Fe/ZSM-5 or Ni/ZSM-5). Fe-Ni/ZSM-5 further increased the yield of toluene (17.28 mg g-1), which was 41.4% and 80.9% higher than Fe/ZSM-5 and Ni/ZSM-5, respectively. According to the kinetic analysis, the average activation energy obtained from catalytic pyrolysis with Fe-Ni/ZSM-5 using the methods of Friedman, Starink, Flynn-Wall-Ozawa, and Kissinger-Akahira-Sunose was 156.19, 152.39, 154.30, and 152.11 kJ mol-1, respectively. Fe-Ni/ZSM-5 addition lowered the activation energy compared to non-catalytic pyrolysis at the conversion rate of 0.15-0.75. The overall catalytic pyrolysis process of poplar sawdust follows the diffusion and nucleation models. The thermodynamic parameters (enthalpy and entropy) showed positive and negative values, respectively, indicating non-spontaneous reactions during the catalytic pyrolysis process.

Stainless steel membranes for harvesting cyanobacteria: Performance, fouling and cleaning.

Stainless steel membranes with 0.45, 1 and 2 µm pore sizes were applied to harvest cyanobacteria. Their critical fluxes were determined and continuous filtration tests were conducted. Two novel transition-combined models for constant flux filtration were developed and applied to describe observed variations in fouling. A pyrolysis cleaning method was proposed and tested. The results showed that the 2 µm membrane was preferable for practical applications as it could process more than twice the filtrate volume before clogging than the other two membranes, with an 8% reduction in rejection rate. The transition-cake-intermediate model predicted fouling better than the combined models, and the fouling mainly resulted from cake formation. Pyrolysis cleaning removed the foulants more effectively and quicker while converting the foulants into desirable products, making it a promising cleaning method for heat-resisting membranes fouled by algae. But both cleaning methods could lead to the enlargement of pore sizes and porosity.

Sustainable and scalable in-situ synthesis of hydrochar-wrapped Ti3AlC2-derived nanofibers as adsorbents to remove heavy metals.

To ensure a sustainable future, it is imperative to efficiently utilize abundant biomass to produce such as platform chemicals, transport fuels, and other raw materials; hydrochar is one of the promising candidates derived by hydrothermal carbonization of biomass in pressurized hot water. The synthesis of "hydrochar-wrapped Ti3AlC2-derived nanofibers" was successfully achieved by a facile one-pot hydrothermal reaction using glucose as the hydrochar precursor. Meanwhile, cellulose and pinewood sawdust as raw materials were also investigated. Products were characterized by XRD, N2 adsorption-desorption isotherms, SEM, TEM and FT-IR to investigate their crystal structures, textural properties, morphologies, and surface species. In the adsorption test to remove Cd(II) and Cu(II) in aqueous solution, hydrochar-wrapped nanofibers outperformed pure nanofibers derived from Ti3AlC2, hydrothermal carbon derived from glucose and commercial activated carbon. Finally, the regeneration, sorption kinetics, and possible adsorption mechanism were also explored.

Synergetic effects during co-pyrolysis of biomass and waste tire: A study on product distribution and reaction kinetics.

The synergetic effects during co-pyrolysis of biomass and waste tire (WT) were investigated concerning the product distribution and reaction kinetics. Two biomass feedstocks were separately mixed with WT at different effective hydrogen/carbon ratio (H/Ceff), and analytical co-pyrolysis of mixtures was conducted using pyrolysis gas chromatography/mass spectroscopy at 500 °C. Product distributions were similar between different biomass feedstocks but varied significantly at different H/Ceff values. The percentage of hydrocarbons increased significantly when increasing H/Ceff, and the optimal H/Ceff was determined considering the correspondingly higher yield of polycyclic aromatic hydrocarbons and char residuals at higher percentage of WT. The experimental derivative thermogravimetric curves of mixtures at the optimal H/Ceff were compared with the calculated results based on kinetic analysis of three individual components using the distributed activation energy model. Significant synergetic effects were observed at the initial and final stages of the pyrolysis process.

Kinetic compensation effect in logistic distributed activation energy model for lignocellulosic biomass pyrolysis.

The kinetic compensation effect in the logistic distributed activation energy model (DAEM) for lignocellulosic biomass pyrolysis was investigated. The sum of square error (SSE) surface tool was used to analyze two theoretically simulated logistic DAEM processes for cellulose and xylan pyrolysis. The logistic DAEM coupled with the pattern search method for parameter estimation was used to analyze the experimental data of cellulose pyrolysis. The results showed that many parameter sets of the logistic DAEM could fit the data at different heating rates very well for both simulated and experimental processes, and a perfect linear relationship between the logarithm of the frequency factor and the mean value of the activation energy distribution was found. The parameters of the logistic DAEM can be estimated by coupling the optimization method and isoconversional kinetic methods. The results would be helpful for chemical kinetic analysis using DAEM.

Sensitivity analysis of three-parallel-DAEM-reaction model for describing rice straw pyrolysis.

The three-parallel-DAEM-reaction model was used to study the slow pyrolysis kinetics of rice straw based on thermogravimetric analysis (TGA) data. The kinetic parameters of the model were calculated using the pattern search method. A comparison between the predicted DTG data and experimental values showed good agreement. The influences of the kinetic parameters on the model for describing the experimental data of rice straw were analyzed by means of local parametric sensitivity analysis. The results indicated that the frequency factor and the mean value of the activation distribution for cellulose decomposition affect the model more strongly than other parameters, followed by the corresponding parameters for hemicellulose and lignin. The sensitivity of the model to the standard deviations of the activation energy distributions for all pseudocomponents is very slight.

Iterative linear integral isoconversional method: theory and application.

In this work, the theory of the iterative linear integral isoconversional method was illustrated in detail. This method allows the dependence of the activation energy (Eα) on the conversion degree to be accurately determined in a short time. Moreover, the method can yield the term [Aαf(α)] (Aα: the frequency factor at conversion α, f(α): the reaction model). The obtained Eα and [Aαf(α)] values can be used to reconstruct the kinetic conversion data at experimental and extrapolated conditions. The suggested method was applied to the experimental data of combustion of biomass fast pyrolysis char, and the corresponding kinetic parameters were obtained.

A critical study of the Miura-Maki integral method for the estimation of the kinetic parameters of the distributed activation energy model.

Using some theoretically simulated data constructed from known sets of the activation energy distribution f(E) (assumed to follow the Gaussian distribution [Formula in text] where E is the activation energy, E(0) is the mean value of the activation energy distribution, and σ is the standard deviation of the activation energy distribution) and the frequency factor k(0), a critical study of the use of the Miura-Maki integral method for the estimation of the kinetic parameters of the distributed activation energy model has been performed from three cases. For all cases, the use of the Miura-Maki integral method leads to important errors in the estimation of k(0). There are some differences between the assumed and calculated activation energy distributions and the differences decrease with increasing the assumed k(0) values (for Case 1), with increasing the assumed σ values (for Case 2), and with decreasing the b values (for Case 3).

Logistic distributed activation energy model--part 2: application to cellulose pyrolysis.

The pyrolysis behavior of cellulose has been investigated by using thermogravimetric analysis (TGA). The non-isothermal TGA data obtained at different heating rates have been analyzed simultaneously. Pattern Search Method has been proposed for the estimation of the model parameter values. Predicted values from the logistic distributed activation energy model have been compared with the experimental data and the results have indicated that the model describes the kinetic behavior of cellulose pyrolysis very well. The mean value and standard deviation of the logistic activation energy distribution for cellulose pyrolysis are found to be 258.5718 kJ mol(-1) and 2.6601 kJ mol(-1), the reaction order is 1.1101 and the k(0) is 1.6218×10(17) s(-1).

Logistic distributed activation energy model--Part 1: Derivation and numerical parametric study.

A new distributed activation energy model is presented using the logistic distribution to mathematically represent the pyrolysis kinetics of complex solid fuels. A numerical parametric study of the logistic distributed activation energy model is conducted to evaluate the influences of the model parameters on the numerical results of the model. The parameters studied include the heating rate, reaction order, frequency factor, mean of the logistic activation energy distribution, standard deviation of the logistic activation energy distribution. The parametric study addresses the dependence on the forms of the calculated α-T and dα/dT-T curves (α: reaction conversion, T: temperature). The study results would be very helpful to the application of the logistic distributed activation energy model, which is the main subject of the next part of this series.

A new iterative linear integral isoconversional method for the determination of the activation energy varying with the conversion degree.

The conventional linear integral isoconversional methods may lead to important errors in the determination of the activation energy when the significant variation of the activation energy with the conversion degree occurs. Vyazovkin proposed an advanced nonlinear isoconversional method, which allows the activation energy to be accurately determined [Vyazovkin, J Comput Chem 2001, 22, 178]. However, the use of the Vyazovkin method raises the problem of the time-consuming minimization without derivatives. A new iterative linear integral isoconversional method for the determination of the activation energy as a function of the conversion degree has been proposed, which is capable of providing valid values of the activation energy even if the latter strongly varies with the conversion degree. Also, the new method leads to the correct values of the activation energy in much less time than the Vyazovkin method. The application of the new method is illustrated by processing of theoretically simulated data of a strongly varying activation energy process.

New distributed activation energy model: numerical solution and application to pyrolysis kinetics of some types of biomass.

In the present paper, a new distributed activation energy model has been developed, considering the reaction order and the dependence of frequency factor on temperature. The proposed DAEM cannot be solved directly in a closed from, thus a method was used to obtain the numerical solution of the new DAEM equation. Two numerical examples to illustrate the proposed method were presented. The traditional DAEM and new DAEM have been used to simulate the pyrolytic process of some types of biomass. The new DAEM fitted the experimental data much better than the traditional DAEM as the dependence of the frequency factor on temperature was taken into account.

Weibull mixture model for modeling nonisothermal kinetics of thermally stimulated solid-state reactions: application to simulated and real kinetic conversion data.

The possibility of applying Weibull mixture model for the fitting of the nonisothermal kinetic conversion data has been investigated. It has been found that the kinetic conversion data at different heating rates can be successfully described by one or the linear combination of few Weibull distribution functions. Several simulated and real kinetic conversion traces have been analyzed. An optimal fitting of the kinetic conversion data has been obtained by a mixture of Weibull distribution functions. The results obtained have shown that the obtained conversion curves calculated by the model proposed in this paper are in agreement with the raw kinetic conversion data.