Pt supported on Zn modified silicalite-1 zeolite as a catalyst for n-hexane aromatization

Platinum(Pt)supported on Zinc(Zn)modified silicalite-1(S-1)zeolite(denoted as Pt-Zn/S-1)was prepared by using a wetness-impregnation method and applied in the n-hexane aromatization reaction for the first time.Both Lewis and Bronsted acid sites were detected in Pt-Zn/S-1 catalyst by means of FT-IR adsorption of NH3 experiment,which were identified as mostly weak and medium ones.Besides,Pt and Zn species showed strong interaction,as revealed by the TPR(Temperature-programmed reduction)and XPS(X-ray photoelectron spectroscopy)experiments.Pt-Zn/S-1 catalyst exhibited excellent aromatization function rather than isomerization and cracking side reactions in the conversion of n-hexane.Pulse experimental study showed that 75.6%of n-hexane conversion and 76.8%of benzene selectivity were obtained over Pt0.1-Zn60/S-l catalyst at 550℃ and under atmospheric pressure.By spectroscopy tests and pulse experimental results,it was concluded that the n-hexane aromatization over Pt-Zn/S-1 catalyst follows a metal-acid bifunctional mechanism.Furthermore,with the assistance of Zn,the electron-deficient Pt species in Pt-Zn/S-1 showed good sulfur tolerance performance.

Study on Pt/KL Zeolite Catalyst for n-Hexane Aromatization Modified by Lanthanum

Xe-129-NMR and TEM were used to study the location and dispersion of Pt particles in KL zeolite with lanthanum incorporation. Owing to the interaction between Pt and La, more Pt particles accompanying La3+ were located in the inner channels of KL zeolite, rather than agglomerated in the external surface. The dispersion of Pt particles was therefore improved. Pt/KL zeolite modified by La showed a little lower reactivity for aromatization of n-hexane, but much higher resistance to sulfur-poisoning because of the existence of new acidic sites.

Effect of Rare Earths on n-Hexane Aromatization over HZSM-5 Catalyst

The cracking and aromatization of n hexane over H ZSM 5 modified by various rare earths were investigated by means of continuous flow micro reactor. The surface properties of modified H ZSM 5 catalysts were obtained from IR, XRD and XPS. The results show that the rare earths enhance the aromatizing properties of the catalysts which are prepared by mechanical mixture method. The results of n hexane cracking and aromatization are correlated with the acidity. The Brnsted acidic sites are the active sites of n hexane aromatization, while Lewis acid site plays an important role in n hexane cracking.

Effect of mesopore spatial distribution of HZSM-5 catalyst on zinc state and product distribution in 1-hexene aromatization

1-hexene aromatization is a promising technology to convert excess olefin in fluid catalytic cracking(FCC)gasoline to high-value benzene(B),toluene(T),and xylene.Besides,the increasing market demand of xylene has put forward higher requirements for new generation of catalyst.For increasing xylene yield in 1-hexene aromatization,the effect of mesopore structure and spatial distribution on product distribution and Zn loading was studied.Catalysts with different mesopore spatial distribution were prepared by post-treatment of parent HZSM-5 zeolite,including NaOH treatment,tetra-propylammonium hydroxide(TPAOH)treatment,and recrystallization.It was found the evenly distributed mesopore mainly prolongs the catalyst lifetime by enhancing diffusion properties but reduces the aromatics selectivity,as a result of damage of micropores close to the catalyst surface.While the selectivity of high-value xylene can be highly promoted when the mesopore is mainly distributed interior the catalyst.Besides,the state of loaded Zn was also affected by mesopores spatial distribution.On the optimized catalyst,the xylene selectivity was enhanced by 12.4%compared with conventional Zn-loaded parent HZSM-5 catalyst at conversion over 99%.It was attributed to the synergy effect of mesopores spatial distribution and optimized acid properties.This work reveals the role of mesopores in different spatial positions of 1-hexene aromatization catalysts in the reaction process and the influence on metal distribution,as well as their synergistic effect two on the improvement of xylene selectivity,which can improve our understanding of catalyst pore structure and be helpful for the rational design of high-efficient catalyst.

Towards understanding the mechanism of n-hexane tolerance in Synechocystis sp.PCC 6803

Synthetic biology efforts have also led to the development of photosynthetic cyanobacteria as"autotrophic cell factories"for biosynthesis of various biofuels directly from CO_(2).However,the low tolerance to toxicity of biofuels has restricted the economic application of cyanobacterial hosts.In this study,RNAseq transcriptomics was employed to reveal stress responses to exogenous n-hexane in Synechocystis sp.PCC 6803.Functional enrichment analysis of the transcriptomic data showed that signal transduction systems were induced significantly.To further identify regulatory genes related to n-hexane tolerance,a library of transcriptional regulators(TRs)deletion mutants was then screened for their roles in nhexane tolerance.The results showed that a knockout mutant of slr0724 that encodes an Hta R suppressor protein was more tolerant to n-hexane than the wild type,indicating the involvement of slr0724 in nhexane tolerance.This study provides the foundation for better understanding the cellular responses to n-hexane in Synechocystis sp.PCC 6803,which could contribute to the further engineering of nhexane tolerance in cyanobacteria.

Intensified shape selectivity and alkylation reaction for the two-step conversion of methanol aromatization to p-xylene

Two-step conversion of methanol to aromatics via light hydrocarbons can significantly improve the conversion stability compared with direct aromatization of methanol,but it remains a challenge to achieve a high p-xylene(PX)selectivity.Herein,silica coating was firstly used to passivate external acid sites of ZSM-5 catalyst for the aromatization of light hydrocarbons by the chemical liquid deposition method.With the increase of SiO_(2) deposition,the density of the external acid sites of the catalyst was decreased from 0.1 to 0.03 mmol·g^(-1),which inhibited the surface secondary reactions and increased the PX/X from 34.6% to 60.0%.In view of the fact that the aromatization process in the second step was partly inhibited as methanol was consumed in advance in the upper methanol-to-light hydrocarbons catalyst layer,part of methanol was directly introduced into the lower aromatization catalyst layer to promote the alkylation process during the aromatization,which decreased the toluene selectivity from 34.5% to 14.3% but increased the xylene selectivity from 40.0%to 55.3%.It was also found that an appropriate external acid density was needed for aromatization catalyst to strengthen the alkylation process and improve the selectivity of xylene under the conditions of methanol introduction.

Extend ethylene aromatization single-event kinetic modeling with physical and chemical descriptor based on ZSM-5 catalyst

The ethylene aromatization is critical for the methanol to aromatics and light alkane dehydroaromatization process.The single-event microkinetic(SEMK)model combining the linear free energy theory and solid acid distribution concept were established and extend for the ethylene aromatization process,which can reduce the kinetic parameters and simplify the reaction network by comparison with the SEMK model including subtype elementary steps based on the type of carbenium ions.Further introducing deactivation parametersφinto the model and applying the linear free energy model to the deactivation experimental data,the obtained deactivation parametersφindicate that the carbon deposition precursors have the greatest impact on reducing the reaction rate of single-molecular reactions and the smallest impact on the hydrogen transfer reaction.Meanwhile,according to the change of reaction enthalpy,effect of carbenium ion structure on methylation,ethylation,cyclization and endo-βscission was investigated by introducing linear free energy concept into the SEMK model.The effect of different acid strengths on elementary steps was investigated based on the acid strength distribution model,it was found that the methylation and oligomerization reactions,the ali-βscission reaction,endo-βscission reaction and the cyclization reaction were more sensitive to strong acidity sites.The physisorption and chemisorption heat are separated from the protonation heat in the linear free energy kinetic model and the acid strength distribution kinetic model,and the absolute values of the obtained physisorption and chemisorption heat increase with the carbon number of carbenium ions.Furthermore,the parameters of the acid strength distribution kinetic model were applied to propane dehydroaromatization on H-ZSM-5 and the ethane dehydroaromatization on Zn/ZSM-5 to confirm the independence of parameters in the SEMK model with the similar reaction network.

Highly selective extraction of aromatics from aliphatics by using metal chloride-based ionic liquids

The separation of aromatics from aliphatics is essential for achieving maximum exploitation of oil resources in the petrochemical industry.In this study,a series of metal chloride-based ionic liquids were prepared and their performances in the separation of 1,2,3,4-tetrahydronaphthalene(tetralin)/dodecane and tetralin/decalin systems were studied.Among these ionic liquids,1-ethyl-3-methylimidazolium tetrachloroferrate([EMIM][FeCl_(4)])with the highest selectivity was used as the extractant.Density functional theory calculations showed that[EMIM][FeCl_(4)]interacted more strongly with tetralin than with dodecane and decalin.Energy decomposition analysis of[EMIM][FeCl_(4)]-tetralin indicated that electrostatics and dispersion played essential roles,and induction cannot be neglected.The van der Waals forces was a main effect in[EMIM][FeCl_(4)]-tetralin by independent gradient model analysis.The tetralin distribution coefficient and selectivity were 0.8 and 110,respectively,with 10%(mol)tetralin in the initial tetralin/dodecane system,and 0.67 and 19.5,respectively,with 10%(mol)tetralin in the initial tetralin/decalin system.The selectivity increased with decreasing alkyl chain length of the extractant.The influence of the extraction temperature,extractant dosage,and initial concentrations of the system components on the separation performance were studied.Recycling experiments showed that the regenerated[EMIM][FeCl_(4)]could be used repeatedly.

Sensory Phenotypic and Molecular Identification of Aromatic Rice Accessions Cultivated in Benin

Rice is one of the most widely cultivated cereals in the world, and its aroma is increasingly in demand. With the advancement of research, a major rice flavor gene has been identified on rice chromosome 8. It encodes non-functional betaine aldehyde dehydrogenase leading to the accumulation of 2-acetyl-1-pyrroline which is the major olfactory compound that confers the fragrant character to rice. The aroma of rice is considered a special trait of enormous economic importance that determines the prime price in world trade. To satisfy the needs of the population and reduce rice imports into Benin, we conducted this study to identify aromatic rice accessions grown in Benin. Seventy-two rice accessions collected across Benin were PCR amplified with three SSR markers RM 7049, Aro 7, and RM 223, linked to the fgr (fragrance of rice) aroma gene. Molecular analysis revealed that 12 of the 72 accessions, namely Bagou 19, Bagou 22, Tchaka 34, Foun 15, Tchaka 41, Nana 32, Kan 61, Kung 69, Kung 67, Bagou 20, Agbab 101 and Koum 55 possess the fgr gene and can be considered as aromatic rice accessions. A sensory phenotypic test using KOH was carried out on rice accessions carrying fgr gene. Of the twelve positives, only one had the smell of aromatic rice, like the Azucena control. These results show that Benin also has aromatic rice varieties that can be sold on national and international markets.

Controllable Condensation of Aromatics and Its Mechanisms in Carbonization

In order to obtain liquefied products with higher yields of aromatic molecules to produce mesophase pitch,a good understanding of the relevant reaction mechanisms is required.Reactive molecular dynamics simulations were used to study the thermal reactions of pyrene,1-methylpyrene,7,8,9,10-tetrahydrobenzopyrene,and mixtures of pyrene with 1-octene,cyclohexene,or styrene.The reactant conversion rates,reaction rates,and product distributions were calculated and compared,and the mechanisms were analyzed and discussed.The results demonstrated that methyl and naphthenic structures in aromatics might improve the conversion rates of reactants in hydrogen transfer processes,but their steric hindrances prohibited the generation of high polymers.The naphthenic structures could generate more free radicals and presented a more obvious inhibition effect on the condensation of polymers compared with the methyl side chains.It was discovered that when different olefins were mixed with pyrene,1-octene primarily underwent pyrolysis reactions,whereas cyclohexene mainly underwent hydrogen transfer reactions with pyrene and styrene,mostly producing superconjugated biradicals through condensation reactions with pyrene.In the mixture systems,the olefins scattered aromatic molecules,hindering the formation of pyrene trimers and higher polymers.According to the reactive molecular dynamics simulations,styrene may enhance the yield of dimer and enable the controlled polycondensation of pyrene.

Physiology of medicinal and aromatic plants under drought stress

Drought poses a significant challenge,restricting the productivity of medicinal and aromatic plants.The strain induced by drought can impede vital processes like respiration and photosynthesis,affecting various aspects of plants’growth and metabolism.In response to this adversity,medicinal plants employ mechanisms such as morphological and structural adjustments,modulation of drought-resistant genes,and augmented synthesis of secondary metabolites and osmotic regulatory substances to alleviate the stress.Extreme water scarcity can lead to leaf wilting and may ultimately result in plant death.The cultivation and management of medicinal plants under stress conditions often differ from those of other crops.This is because the main goal with medicinal plants is not only to increase the yield of the above-ground parts but also to enhance the production of active ingredients such as essential oils.To elucidate these mechanisms of drought resistance in medicinal and aromatic plants,the current review provides a summary of recent literature encompassing studies on the morphology,physiology,and biochemistry of medicinal and aromatic plants under drought conditions.

Rational design of new in situ reduction of Ni(II)catalytic system for low-cost and large-scale preparation of porous aromatic frameworks

Porous aromatic framework 1(PAF-1)is an extremely representative nanoporous organic framework owing to its high stability and exceptionally high surface area.Currently,the synthesis of PAF-1 is catalyzed by the Ni(COD)2/COD/bpy system,suffering from great instability and high cost.Herein,we developed an in situ reduction of the Ni(II)catalytic system to synthesize PAF-1 in low cost and high yield.The active Ni(0)species produced from the NiCl_(2)/bpy/NaI/Mg catalyst system can effectively catalyze homocoupling of tetrakis(4-bromophenyl)methane at the room temperature to form PAF-1 with high Brunauer-Emmett-Teller(BET)-specific surface area up to 4948 m^(2) g^(−1)(Langmuir surface area,6785 m2 g−1).The possible halogen exchange and dehalogenation coupling mechanisms for this new catalytic process in PAF's synthesis are discussed in detail.The efficiency and universality of this innovative catalyst system have also been demonstrated in other PAFs'synthesis.This work provides a cheap,facile,and efficient method for scalable synthesis of PAFs and explores their application for high-pressure storage of Xe and Kr.

Changes in the Non-targeted Metabolomic Profile of Three-year-old Toddlers with Elevated Exposure to Polycyclic Aromatic Hydrocarbons

Objective To investigate changes in the urinary metabolite profiles of children exposed to polycyclic aromatic hydrocarbons(PAHs)during critical brain development and explore their potential link with the intestinal microbiota.Methods Liquid chromatography-tandem mass spectrometry was used to determine ten hydroxyl metabolites of PAHs(OH-PAHs)in 36-month-old children.Subsequently,37 children were categorized into low-and high-exposure groups based on the sum of the ten OH-PAHs.Ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry was used to identify non-targeted metabolites in the urine samples.Furthermore,fecal flora abundance was assessed by 16S rRNA gene sequencing using Illumina MiSeq.Results The concentrations of 21 metabolites were significantly higher in the high exposure group than in the low exposure group(variable importance for projection>1,P<0.05).Most of these metabolites were positively correlated with the hydroxyl metabolites of naphthalene,fluorine,and phenanthrene(r=0.336–0.531).The identified differential metabolites primarily belonged to pathways associated with inflammation or proinflammatory states,including amino acid,lipid,and nucleotide metabolism.Additionally,these distinct metabolites were significantly associated with specific intestinal flora abundances(r=0.34–0.55),which were mainly involved in neurodevelopment.Conclusion Higher PAH exposure in young children affected metabolic homeostasis,particularly that of certain gut microbiota-derived metabolites.Further investigation is needed to explore the potential influence of PAHs on the gut microbiota and their possible association with neurodevelopmental outcomes.

Enriching Iodine and Regulating Grain Aroma,Appearance Quality,and Yield in Aromatic Rice by Foliar Application of Sodium Iodide

Applying iodine fertilizers to cultivate iodine-rich crops for daily intake is an effective approach for iodine supplementation,especially for aromatic rice.Field experiments were conducted during the early growing seasons of 2021 and 2022 to evaluate the impacts of foliar application of iodine fertilizer on aromatic rice and to explore the optimal iodine fertilizer concentration.At the full heading stage,six different concentrations of sodium iodide solutions of 0%(CK),0.010%(T1),0.025%(T2),0.050%(T3),0.075%(T4),and 0.100%(T5)were applied to indica aromatic rice cultivars Meixiangzhan 2 and Xiangyaxiangzhan.The results showed that sodium iodide treatments significantly increased the iodine and sodium contents in both leaves and grains.Compared with the CK,the T1 and T2 treatments increased the 2-acetyl-1-pyrroline(2-AP)content in mature grains by 8.41%-101.66%and 13.58%-74.60%,respectively.Improvements in the contents of 1-pyrroline-5-carboxylic acid,proline,1-pyrroline,and methylglyoxal,as well as the activity of proline dehydrogenase were also detected.Additionally,sodium iodide treatments remarkably decreased the chalky grain rate,chalkiness area,and chalkiness degree of aromatic rice,with the T2 treatment exhibiting a 17.79%-47.42%decrease in chalkiness degree compared with the CK.Meanwhile,T1 and T2 treatments showed beneficial impacts on chlorophyll content,photosynthetic characteristics,and yield components,while T3,T4,and T5 treatments exhibited adverse effects on leaf and grain yields.The linear discriminant analysis revealed significant differences between treatments.The correlation analysis and piecewise structural equation modeling showed that the iodine and sodium influenced the photosynthetic characteristics and chlorophyll content of the leaves,thereby regulating the 2-AP biosynthesis and yield components,ultimately affecting the 2-AP content and yield.Overall,this study suggests that foliar application of 0.025%sodium iodide is an effective method to enrich the iodine content in rice grains,improve the grain aroma and appearance quality of aromatic rice,without detrimental effects on grain yield.

Research Progress of Aromatic Bed Curtains for Aiding Sleep Based on Lavender Microcapsule Technique

In this paper, the preparation technique of lavender essential oil microcapsules and the construction method of aromatic textiles were expounded, and the research status of bed curtains and lavender microcapsules at home and abroad was analyzed and studied from the perspective of application in textiles. The application of lavender essential oil to bed curtains through the microcapsule technique was put forward to allow lavender essential oil to play its role of helping sleep in bed curtains. This paper expounded the material selection and preparation technique of lavender microcapsule agents, and put forward the preparation method of microcapsules with mixed solutions of pure Chinese medicine extracts and natural essences as core material and high-viscosity epoxy resin as wall materials. The post-processing techniques and the spray ironing method for clothing were studied and developed, and these techniques and methods were applied to bed curtains, and good results were obtained.

Heterogeneously elevated branched-chain/aromatic amino acids among new-onset type-2 diabetes mellitus patients are potentially skewed diabetes predictors

BACKGROUND The lack of specific predictors for type-2 diabetes mellitus(T2DM)severely impacts early intervention/prevention efforts.Elevated branched-chain amino acids(BCAAs:Isoleucine,leucine,valine)and aromatic amino acids(AAAs:Tyrosine,tryptophan,phenylalanine)show high sensitivity and specificity in predicting diabetes in animals and predict T2DM 10-19 years before T2DM onset in clinical studies.However,improvement is needed to support its clinical utility.AIM To evaluate the effects of body mass index(BMI)and sex on BCAAs/AAAs in new-onset T2DM individuals with varying body weight.METHODS Ninety-seven new-onset T2DM patients(<12 mo)differing in BMI[normal weight(NW),n=33,BMI=22.23±1.60;overweight,n=42,BMI=25.9±1.07;obesity(OB),n=22,BMI=31.23±2.31]from the First People’s Hospital of Yunnan Province,Kunming,China,were studied.One-way and 2-way ANOVAs were conducted to determine the effects of BMI and sex on BCAAs/AAAs.RESULTS Fasting serum AAAs,BCAAs,glutamate,and alanine were greater and high-density lipoprotein(HDL)was lower(P<0.05,each)in OB-T2DM patients than in NW-T2DM patients,especially in male OB-T2DM patients.Arginine,histidine,leucine,methionine,and lysine were greater in male patients than in female patients.Moreover,histidine,alanine,glutamate,lysine,valine,methionine,leucine,isoleucine,tyrosine,phenylalanine,and tryptophan were significantly correlated with abdominal adiposity,body weight and BMI,whereas isoleucine,leucine and phenylalanine were negatively correlated with HDL.CONCLUSION Heterogeneously elevated amino acids,especially BCAAs/AAAs,across new-onset T2DM patients in differing BMI categories revealed a potentially skewed prediction of T2DM development.The higher BCAA/AAA levels in obese T2DM patients would support T2DM prediction in obese individuals,whereas the lower levels of BCAAs/AAAs in NW-T2DM individuals may underestimate T2DM risk in NW individuals.This potentially skewed T2DM prediction should be considered when BCAAs/AAAs are to be used as the T2DM predictor.

Qualitative analysis of aromatic compounds via 1D TOCSY techniques

The aromatic compounds,including o-xylene,m-xylene,p-xylene,and ethylbenzene,primarily originate from the catalytic reforming of crude oil,and have a wide variety of applications.However,because of similar physical and chemical properties,these compounds are difficult to be identified by gas chromatography(GC)without standard samples.With the development of modern nuclear magnetic resonance(NMR)techniques,NMR has emerged as a powerful and efficient tool for the rapid analysis of complex and crude mixtures without purification.In this study,the parameters of one-dimensional(1D)total correlation spectroscopy(TOCSY)NMR techniques,including 1D selective gradient TOCSY and 1D chemicalshift-selective filtration(CSSF)with TOCSY,were optimized to obtain comprehensive molecular structure information.The results indicate that the overlapped signals in NMR spectra of nonpolar aromatic compounds(including o-xylene,m-xylene,p-xylene and ethylbenzene),polar aromatic compounds(benzyl alcohol,benzaldehyde,benzoic acid),and aromatic compounds with additional conjugated bonds(styrene)can be resolved in 1D TOCSY.More importantly,full molecular structures can be clearly distinguished by setting appropriate mixing time in 1D TOCSY.This approach simplifies the NMR spectra,provides structural information of entire molecules,and can be applied for the analysis of other structural isomers.

Study on Adsorption Removal of Polycyclic Aromatic Hydrocarbons by Modified Mussel Shells

Polycyclic aromatic hydrocarbons(PAHs)are typical persistent organic pollutants(POPs)that are commonly found in the environment.They are carcinogenic,teratogenic,mutagenic and biodegradable obviously.In this paper,the modified mussel shells were used to adsorb and remove anthracene.The results show that the adsorption removal rate of the mussel shells was higher after calcination at 600℃.5%H_(3)PO_(4) solution was more suitable for shell treatment than 3 mol/L ZnCl_(2) solution.As the dosage of the modified shells was 0.5 g/L,the adsorption reached a stable state,and the removal rate of PAHs was about 69.44%;the adsorption efficiency rose with the increase of time.It can be seen that as a new and cheap biological adsorbent,the modified shells can be used to remove PAHs from wastewater.

Coking kinetics and influence of reaction-regeneration on acidity, activity and deactivation of Zn/HZSM-5 catalyst during methanol aromatization

The coking kinetics and reaction-regeneration on Zn/HZSM-5 （Zn/HZ） catalyst in the conversion of methanol to aromatics were investigated. The highest initial benzene, toluene and xylene （BTX） yield of ca. 67.7% was obtained on fresh Zn/HZ catalyst, which showed the worst catalytic stability. The cycle of reaction-regeneration significantly modified the texture and acidity of Zn/HZ catalyst, which in turn affected its catalytic performance and coking behavior in methanol conversion to BTX. The residual carbon located on the surface of Zn/HZ catalyst led to the decrease of acid sites and the change on the acid sites distribution, which played an important roles on its activity and deactivation. It was found that the high B/L ratio and the low total acid sites concentration of the Zn/HZ catalyst favored to the high BTX yield and good catalytic stability in methanol conversion.