Computer generation of detailed reaction networks in hydrocracking of Fischer-Tropsch wax

Fischer-Tropsch synthesis(FTS)wax is a mixture of linear hydrocarbons with carbon number from C7 to C70+.Converting FTS wax into high-quality diesel(no sulfur and nitrogen contents)by hydrocracking technology is attractive in economy and practicability.Kinetic study of the hydrocracking of FTS wax in elementary step level is very challenging because of the huge amounts of reactions and species involved.Generation of reaction networks for hydrocracking of FTS wax in which the chain length goes up to C70 is described on the basis of Boolean adjacency matrixes.Each of the species(including paraffins,olefins and carbenium ions)involved in the elementary steps is represented digitally by using a(N+3)N matrix,in which a group of standardized numbering rules are designed to guarantee the unique identity of the species.Subsequently,the elementary steps are expressed by computer-aided matrix transformations in terms of proposed reaction rules.Dynamic memory allocation is used in species storage and a characteristic vector with nine elements is designed to store the key information of a(N+3)N matrix,which obviously reduces computer memory consumption and improves computing efficiency.The detailed reaction networks of FTS wax hydrocracking can be generated smoothly and accurately by the current method.The work is the basis of advanced elementary-step-level kinetic modeling.

Mapping out the reaction network of humin formation at the initial stage of fructose dehydration in water

The formation of humins hampers the large-scale production of 5-hydroxymethylfurfural(HMF)in biorefinery.Here,a detailed reaction network of humin formation at the initial stage of fructose-to-HMF dehydration in water is delineated by combined experimental,spectroscopic,and theoretical studies.Three bimolecular reaction pathways to build up soluble humins are demonstrated.That is,the intermolecular etherification of β-furanose at room temperature initiates the C12 path,whereas the C-C cleavage of a-furanose at 130-150℃ leads to C11 path,and that of open-chain fructose at 180℃ to C11' path.The successive intramolecular dehydrations and condensations of the as-formed bimolecular intermediates lead to three types of soluble humins.We show that the C12 path could be restrained by using HCl or AlCl_(3) catalyst,and both the C12 and C110 paths could be effectively inhibited by adding THF as a co-solvent or accelerating heating rate via microwave heating.

Insights into the Reaction Network and Mechanism of Green Aerobic Oxidative Esterification of Methacrolein over Different Heterogeneous Catalysts

The oxidative esterification of methacrolein(MAL)is an important way to prepare high-valued methyl methacrylate(MMA),but this process is ultra-complex due to the high reactivity of both C=O and C=C bonds in MAL molecule.In order to further improve MMA selectivity,the reaction network and relevant mechanisms have been proposed and profoundly investigated in this paper.Five kinds of fundamental reactions are involved in this process,including(a)the acetal reaction;(b)the aerobic oxidation of hemiacetal;(c)the alkoxylation of C=C double bond;(d)the Diels-Alder reaction;and(e)the hydrogenation reaction of unsaturated double bond.Among them,the Diels-Alder reaction of MAL is non-catalyzed,and the Brönsted acid sites or the Lewis acid sites favor promoting acetal reaction of MAL with methanol,while the alkoxylation of C=C bond with methanol is enhanced under alkaline condition.In particular,by employing the Pd-based catalysts,hydrogenation products are formed in alkaline methanol solution,hence with lower than those obtained by the Au-based catalysts.Notably,it is necessary to match the hemiacetal fromation and aerobic oxidation of hemiacetal,which is relevant with the amount and strength of acid and redox sites.Consequently,this work can provide a good guidance for the further design of both catalysts and processes in future.

AN ENGINEERING MODEL FOR MULTICOMPONENT REVERSIBLE REACTION NETWORK

The treatment of a multicomponent reversible reaction network is extremely complicated because largenumber of rate constants must be precisely determined and because the calculation based on these rateconstants is tedious.In order to reduce the degrees of freedom of the process,the authors propose a methodin which the reactor and the separator are regarded as a whole.Based on this approach,an N-componentreversible reaction system can be dealt with as a two—component system.Consequently,a simple and ac-cessible way of the apparent rate determination is suggested.For fiist-order reactions,an explicit,simplifiedexpression has been derived for both lumped and distributed parameter reaction systems.

Study on Disproportionation Reaction of FCC Gasoline on Acid Catalyst

Based on the experimental data relating to the reaction of FCC gasoline on acid catalyst the analysis of product distribution, and composition of gasoline and diesel fractions have been analyzed. The occurrence of disproportionation reaction of FCC gasoline on acid catalyst and the network of disproportionation reaction have been identified. Study has also shown that different reaction temperatures can result in different pathways of disproportionation reactions on acid catalyst.

Light-Controlled Chemical Reaction Pathways in Disulfide-Based Nonequilibrium Systems

Pathway selection in a complex chemical reaction network(CRN)enables organisms to adapt,evolve,and even learn in response to changing environments.Inspired by this,herein we report an artificial system,where light signal was used to manipulate the reaction pathways in a disulfide-based nonequilibrium CRN.By changing the photon energy and irradiation window,the anion or new radical-mediated pathways were selectively triggered,resulting in a user-defined evolution pathway.Additional photodissipative cycles were achieved by UV(365 nm)irradiation,increasing the total number of reactions from 3 to 7.The emerging pathway selection of the CRN is accurately predictable and controllable even in complex organo-hydrogel materials.We demonstrate up to five-state autonomous sol-gel transitions and the formation of fuel-driven dissipative organo-hydrogel through both chemical and light input.This work represents a new approach to allowing CRNs to communicate with the environment that can be used in the development of materials with lifelike behaviors.

DNA Reaction Network Mimicking the Basic Steps of Synaptic Communication

Biological systems use intricate networks of chemical reactions to exchange information. How to simulate complex systems with simple strand-displacement reactions is crucial to broaden the application scenario of the DNA reaction network. Here, we report the artificial DNA reaction network to mimic the operation and function of biological information transfer via strand-displacement reaction. DNA is used as simple artificial analogs to schematize structures and transmit information. Using chemical synapses in neural networks as an example, we show that the proposed network enables core functions of biological systems, such as the long-term potential of synapses, which underpin learning and memory. Also, we performed the simple “silicon mimetic” to link electronic circuits to chemical network-based biological structures. As such, synaptic communication simulated by the DNA reaction network provides a complete demonstration for designing artificial reaction networks based on the essence of information interaction.

Integration strategies of hydrogen network in a refinery based on operational optimization of hydrotreating units

Inferior crude oil and fuel oil upgrading lead to escalating increase of hydrogen consumption in refineries.It is imperative to reduce the hydrogen consumption for energy-saving operations of refineries.An integration strategy of hydrogen network and an operational optimization model of hydrotreating(HDT)units are proposed based on the characteristics of reaction kinetics of HDT units.By solving the proposed model,the operating conditions of HDT units are optimized,and the parameters of hydrogen sinks are determined by coupling hydrodesulfurization(HDS),hydrodenitrification(HDN)and aromatic hydrogenation(HDA)kinetics.An example case of a refinery with annual processing capacity of eight million tons is adopted to demonstrate the feasibility of the proposed optimization strategies and the model.Results show that HDS,HDN and HDA reactions are the major source of hydrogen consumption in the refinery.The total hydrogen consumption can be reduced by 18.9%by applying conventional hydrogen network optimization model.When the hydrogen network is optimized after the operational optimization of HDT units is performed,the hydrogen consumption is reduced by28.2%.When the benefit of the fuel gas recovery is further considered,the total annual cost of hydrogen network can be reduced by 3.21×10~7CNY·a^(-1),decreased by 11.9%.Therefore,the operational optimization of the HDT units in refineries should be imposed to determine the parameters of hydrogen sinks base on the characteristics of reaction kinetics of the hydrogenation processes before the optimization of the hydrogen network is performed through the source-sink matching methods.

From Chemical Langevin Equations to Fokker-Planck Equation: Application of Hodge Decomposition and Klein-Kramers Equation

The stochastic systems without detailed balance are common in various chemical reaction systems, such as metabolic network systems. In studies of these systems, the concept of potential landscape is useful However, what are the su^cient and necessary conditions of the existence of the potential function is still an open problem. Use Hodge decomposition theorem in differential form theory, we focus on the general chemical Langevin equations, which reitect complex chemical reaction systems. We analysis the conditions for the existence of potential landscape of the systems. By mapping the stochastic differential equations to a Hamiltonian mechanical system, we obtain the Fokker-Planck equation of the chemical reaction systems. The obtained Fokker-Planck equation can be used in further studies of other steady properties of complex chemical reaction systems, such as their steady state entropies.

Effect of Olefins on Formation of Sulfur Compounds in FCC Gasoline

The effect of olefins on formation of sulfur compounds in FCC gasoline was studied in a small-scale fixed fluidized bed （FFB） unit at temperatures ranging from 400℃ to 500℃, a weight hourly space velocity （WHSV） of 10 h-1, and a catalyst/oil ratio of 6. The results showed that C4--C6 olefins contained in the FCC gasoline could react with HzS to form predominantly thiophenes, alkyl-thiophenes as well as a fractional amount of thiols, while large molecular olefins such as heptene could react with hydrogen sulfide to form benzothiophenes. The amount of sulfur compounds formed at different tem- peratures over different catalysts were in proportion to the mass fractions of olefins in the feedstock, with the amount of sulfur compounds formed over REUSY catalyst exceeding those formed over the shape selective zeolite catalyst owing to the effect of catalyst performance and the impact of catalyst on the degree of olefin conversion. The amount of sulfur compounds generated and their increase reached a maximum at 450℃ and a minimum at 400℃ because of the influence of temperature on the thermodynamic and kinetic constants for formation of sulfur compound as well as on the olefin conversion degree. Based on the above-mentioned study, a reaction network and a model for prediction of sulfur compounds generated upon reaction of olefins in FCC gasoline with HES were established.

Reaction decoupling in thermochemical fuel conversion and technical progress based on decoupling using fluidized bed

Thermochemical conversion of fuels via pyrolysis/carbonization,cracking,gasification and combustion has to involve a number of individual reactions called attribution reactions to form an intercorrelated reaction network for any conversion process.By separating one or some attribution reactions from the others to decouple their interactions existing in the reaction network,the so-called reaction decoupling enables a better understanding of the complex thermal conversion process and further the optimization of the conditions for attribution reactions as well as the entire conversion process to realize advanced performances.The dual bed conversion and two-stage conversion are the two representative types of fuel conversion technologies developed in recent years based on reaction decoupling.Many technical advantages have been proven for such decoupling fuel conversion technologies,such as poly-generation of products,low-cost production of high-grade products,elimination of undesirable products or pollutants,easy operation and control,and so on.The treated fuels with decoupling conversion technologies mainly include solid biomass and coal,as well as liquid petroleum oil.This paper is devoted to reiteration of the reaction decoupling concept and further to reviewing the research,developments and successful applications of several decoupling fuel conversion technologies of two such types by using fluidized bed as their major reactors.

Kinetic model for hydroisomerization reaction of C_(8)-aromatics

Based on the reported reaction networks,a novel six-component hydroisomerization reaction net-work with a new lumped species including C_(8)-naphthenes and C_(8)-paraffins is proposed and a kinetic model for a commercial unit is also developed.An empirical catalyst deactivation function is incorporated into the model accounting for the loss in activity because of coke forma-tion on the catalyst surface during the long-term opera-tion.The Runge-Kutta method is used to solve the ordinary differential equations of the model.The reaction kinetic parameters are benchmarked with several sets of balanced plant data and estimated by the differential vari-able metric optimization method(BFGS).The kinetic model is validated by an industrial unit with sets of plant data under different operating conditions and simulation results show a good agreement between the model predic-tions and the plant observations.

Fluctuation theorem for entropy production in a chemical reaction channel

Fluctuation theorem for entropy production in a mesoscopic chemical reaction network is discussed. When the system size is sufficiently large, it is found that, by defining a kind of coarse-grained dissipation function, the entropy production in a reversible reaction channel can be approximately described by a type of detailed fluctuation theorem. Such a fluctuation relation has been successfully tested by direct simulations in a linear reaction model consisting of two reversible channels and in an oscillatory model wherein only one channel is reversible.

Nuclear uncertainties in the s-process simulation

The heavy elements in the Universe are formed during the s- and r-processes mainly in AGB stars and supernovae, respectively. Simulation of s- and r-nucleosynthesis critically depends on the neutron capture and weak decay rates for all the nuclei on the reaction chain. The present work analyzes systematically the neutron capture rates (cross sections) for the s-process nuclei, including ～3000 rates on ～200 nuclei. The network calculations for the constant temperature s-process have been performed using the different data sets selected as the nuclear inputs to investigate the uncertainties in the predicted s-abundances. We show that the available cross sections of neutron capture on many s-process nuclei still carry large uncertainties, which lead to low accuracy in the determination of s-process isotope abundances. We analyze the neutron capture cross section data for the same unique isobar nucleus accorded by year from previous work. Such an analysis indicates that the s-process has been studied for more than fifty years and there exist two research stages around 1976 and 2002, respectively. The needs and opportunities for future experiments and theoretical tools are highlighted to remove the existing shortcomings in the neutron capture rates.

End-to-end computational approach to the design of RNA biosensors for detecting miRNA biomarkers of cervical cancer

Cervical cancer is a global public health subject as it affects women in the reproductive ages,and accounts for the second largest burden among cancer patients worldwide with an unforgiving 50%mortality rate.Relatively scant awareness and limited access to effective diagnosis have led to this enormous disease burden,calling for point-of-care,minimally invasive diagnosis methods.Here,an end-to-end quantitative unified pipeline for diagnosis has been developed,beginning with identification of optimal biomarkers,concurrent design of toehold switch sensors,and finally simulation of the designed diagnostic circuits to assess performance.Using miRNA expression data in the public domain,we identified miR-21-5p and miR-20a-5p as blood-based miRNA biomarkers specific to early-stage cervical cancer employing a multi-tier algorithmic screening.Synthetic riboregulators called toehold switches specific to the biomarker panel were then designed.To predict the dynamic range of toehold switches for use in genetic circuits as biosensors,we used a generic grammar of these switches,and built a neural network model of dynamic range using thermodynamic features derived from mRNA secondary structure and interaction.Second-generation toehold switches were used to overcome the design challenges associated with miRNA biomarkers.The resultant model yielded an adj.R^(2)~0.71,outperforming earlier models of toehold-switch dynamic range.Reaction kinetics modelling was performed to predict the sensitivity of the second-generation toehold switches to the miRNA biomarkers.Simulations showed a linear response between 10 nM and 100 nM before saturation.Our study demonstrates an end-to-end computational workflow for the efficient design of genetic circuits geared towards the effective detection of unique genomic/nucleic-acid signatures.The approach has the potential to replace iterative experimental trial and error,and focus time,money,and efforts.All software including the toehold grammar parser,neural network model and reaction kinetics simulation are available as open-source software(https://github.com/SASTRA-iGEM2019)under GNU GPLv3 licence.

Cross-interaction of volatiles from co-pyrolysis of lignin with pig manure and their effects on properties of the resulting biochar

Biomass and pig manure have distinct compositions and the co-pyrolysis of them has gained much attention.However,the influence of volatiles interaction on the properties of the char was still unclear.In this study,lignin was selected as the model component of biomass with pig manure for co-pyrolysis at 600°C.The results indicate that volatiles from co-pyrolysis promoted re-condensation reaction,resulting in the higher char yield(48.0%in co-pyrolysis versus 31.0%in pyrolysis of single manure)and the formation of more aromatics in bio-oil.The co-pyrolysis also facilitated the dehydrogenation and dehydration reactions,which accounted for the elimination of oxygen and nitrogen contents and thus a higher carbon content(64.7%in the co-pyrolysis versus the averaged value of 46.4%from the pyrolysis of single feedstock),higher crystallinity and thermal stability of the char.The in-situ diffuse reflection infrared Fourier transform spectroscopy(DRIFTS)characterization results demonstrated that the functionalities abundances of char with temperature was influenced by volatiles interaction via accelerating the carbonization reaction.In addition,the high heating value(HHV)of char was obviously improved by cross-interaction of volatiles during co-pyrolysis(24.4 MJ/Kg in co-pyrolysis versus averaged value of 15.1 MJ/Kg from single pyrolysis),implying that the co-pyrolysis enhanced the energy density of the resulting char.

Stochastic equations for a self-regulating gene

Expression of cellular genes is regulated by binding of transcription factors to their promoter, either activating or inhibiting transcription of a gene. Particularly interesting is the case when the expressed protein regulates its own transcription. In this paper, the features of this self-regulating process are investigated. In the presented model here, the gene can be in two states. Either a protein is bound to its promoter or not. The steady state distributions of protein during and just before switching from one state to the next state are analyzed. Moreover, a powerful numerical method based on the corresponding master equation to compute the protein distribution in the steady state is presented and compared to an already-existing method. Additionally the special case of self-regulation, in which protein can only be produced, if one of these proteins is bound to the promoter region, is analyzed. Furthermore, a self-regulating gene is compared to a similar gene, which also has two states and produces the same amount of proteins but is not regulated by its protein-product.