A STUDY ON THE DEGRADATION MECHANISM OF PHOTOCROSSLINKING PRODUCTS FORMED BY CYCLIZED POLYISOPRENE-DIAZIDE SYSTEM UNDER THE INFLUENCE OF ALKYL BENZENE SULFONIC ACIDS

The degradation mechanism of photocrosslinking products formed by cyclized polyisoprene-diazide system under the influence of the different alkyl benzene sulfonic acids was studied. The effects of alkyl chain length and the concentration of alkyl benzene sulfonic acids on the rate of degradation reaction were discussed. It was found that in the initial stage of degradation, the cyclicity ratio and the average fused ring number did not change considerably, but the percentage of uncyclized parts content varied significantly. The suitable mechanism was supposed.

Understanding the interfacial behaviors of benzene alkylation with butene using chloroaluminate ionic liquid catalyst: A molecular dynamics simulation

To better understand the benzene alkylation with chloroaluminate ionic liquids(ILs) as catalyst, the interfacial properties between the benzene/butene binary reactants and chloroaluminate ILs with varying cation alkyl chain length and different anions were investigated using molecular dynamics(MD) simulations. The results indicate that ILs can obviously improve the interfacial width, solubility and diffusion of reactants compared to H_(2)SO_(4). The longer alkyl chains of cations present a density enrichment at the interface and protrude into the binary reactants phase. Furthermore, the ILs consisting of 1-octyl-3-methylimidazolium cations([Omim]^(+)) and the stronger acidity heptachlorodialuminate anions([Al_(2)Cl_(7)]^(-)) are more beneficial to promote the interfacial width and facilitate the dissolution and diffusion of benzene in both the IL bulk and the interfacial region in comparison to the ones with shorter alkyl chains cations and weaker acidity anions. The information gives us a better guideline for the design of ILs for benzene alkylation.

Some new progress on the light absorption properties of linear alkyl benzene solvent

Linear alkyl benzene （LAB） will be used as the solvent in a liquid scintillator mixture for the JUNO antineutrino experiment. Its light absorption properties should therefore be understood prior to its effective use in the experiment. Attenuation length measurements at a light wavelength of 430 nm have been performed on samples of LAB prepared for the JUNO experiment. Inorganic impurities in LAB have also been studied for their possibilities of light absorption in our wavelength of interest. In view of a tentative plan by the JUNO collaboration to utilize neutron capture with hydrogen in the detector, we also present in this work a preliminary study on the carbon-hydrogen ratio and the attenuation length of the samples.

The Retention Behaviors of Benzene and Its Alkyl Homologues in Microemulsion Electrokinetic Chromatography

The retention behaviors of benzene and its alkyl homologues in microemulsion electrokinetic chromatography were investigated in both anionic and cationic surfactant MEEKC systems. The effects of the composition of microemulsion on retention time and selectivity were studied. A good linear relationship was obtained between log k and the carbon number of alkyl chain.

Benzene alkylation with methanol over phosphate modified hierarchical porous ZSM-5 with tailored acidity

The acidity and acid distribution of hierarchical porous ZSM-5 were tailored via phosphate modification. The catalytic results showed that both benzene conversion and selectivity of toluene and xylene increased with the presence of appropriate amount of phosphorus. Meanwhile, side reactions such as methanol to olefins related with the formation of by-product ethylbenzene formation and isomerization of xylene to meta-xylene were suppressed efficiently. The acid strength and sites amount of Br?nsted acid of the catalyst were crucial for improving benzene conversion and yield of xylene, whereas passivation of external surface acid sites played an important role in breaking thermodynamic equilibrium distribution of xylene isomers.

Influence of the post-treatment of HZSM-5 zeolite on catalytic performance for alkylation of benzene with methanol

The porous material HZSM-5 zeolite with micro-mesopore hierarchical porosity was prepared by post-treatment （combined alkali treatment and acid leaching） of parent zeolite and its catalytic performance for benzene alkylation with methanol was investigated. The effect of post-treatment on the textural properties was characterized by various techniques （including ICP-AES, XRD, nitrogen sorption isotherms, SEM, NH3-TPD, Py-IR and TG）. The results indicated that the post-treatment could modify the structural and acidic properties of HZSM-5 zeolite. In this procedure, not only additional mesopores were created by selective extraction of silicon but also the acidity was tuned. Consequently, the modified HZSM-5 zeolite showed larger external surface area with less acid sites as compared to the parent zeolite. It was found out that the modified zeolite exhibited a higher benzene conversion and xylene selectivity for alkylation of benzene with methanol as well as excellent life span of the catalyst than conventional ones. This can be explained by the facts that the presence of additional mesopores improved the diffusion property in the reactions. Furthermore, the modified zeolite showed an appropriate Bronsted acidity for effective suppression of the side reaction of methanol to olefins, thus reduced the accumulation of coke on the HZSM-5 zeolite, which was favorable for the catalyst stability. In comparison with the parent HZSM-5 zeolite, the modified zeolite by alkali treatment and acid leaching showed better performance for the benzene alkylation with methanol.

Surface Acidity of Aluminum Phosphate and Its Catalytic Performance in Benzene Alkylation with Long Chain Olefin

The acidic properties of aluminum phosphate （A1PO4-5） solid acid catalyst were characterized by tem- perature programmed desorption （TPD） of ammonia （NH3）, n-propylamine （n-C3HTNH2）, iso-propylamine [（CH3）2CHNH2] and n-dipropylamine [（C3H7）2NH] separately, and its catalytic performance in benzene alkylation with long chain olefin was studied in a fixed-bed reactor. The characterized acid amount of catalyst increased with the basicity of adsorbates. With increase of the activation temperature of catalyst, the acid amount characterized by NHa-TPD decreased, however, it increased when characterized by TPD using three other adsorbates. The desorption kinetics of TPD process and the deactivation kinetics of catalyst were investigated. The acidity and catalytic per- formance of catalyst was also correlated. The results showed that the acid amount and strength are well correlated with the activity and stability using NH3 as adsorbate, respectively, which indicated NH3 was a better basic adsorbate. It was also found that the catalyst with higher acid amount and lower acid strength on the surface exhibited the better catalytic performance and stability.

Efficient conversion of benzene and syngas to toluene and xylene over ZnO-ZrO_(2)&H-ZSM-5 bifunctional catalysts

A series of ZnO-ZrO_(2) solid solutions with different Zn contents were synthesized by the urea coprecipitation method,which were coupled with H-ZSM-5 zeolite to form bifunctional catalysts.As a new benzene alkylation reagent,syngas was used instead of methanol to realize the efficient conversion of syngas and benzene into toluene and xylene.A suitable ratio of ZnO-ZrO_(2) led to the significant improvement in the catalytic performance,and a suitable amount of acid helped to increase the selectivity of toluene/xylene and reduce the selectivity of the by-products ethylbenzene and C^(9+) aromatics.The highest benzene conversion of 89.2%and toluene/xylene selectivity of 88.7%were achieved over 10%ZnO-ZrO_(2)&H-ZSM-5(Si/Al=23)at a pressure of 3 MPa and a temperature of 450℃.In addition,the effect of the zeolite framework structure on product distribution was examined.Similar to the molecular dynamics of aromatic hydrocarbons,H-ZSM-5 zeolites comprise 10-membered-ring pores,which are beneficial to the activation of benzene;hence,the conversion of benzene is higher.H-ZSM-35 and HMOR zeolites exhibited small eight-membered-ring channels,which were not conducive to the passage of benzene;hence,the by-product ethylbenzene exhibits a higher selectivity.The distance between the active centers of the bifunctional catalysts was the main factor affecting the catalytic performance,and the powder mixing method was more conducive to the conversion of syngas and benzene.

Understanding the interfacial properties of benzene alkylation with 1-dodecene catalyzed by immobilized chloroaluminate ionic liquids using molecular dynamics simulation

Benzene alkylation catalyzed by immobilized ionic liquids(ILs)on solid carriers is considered as a heterogeneous reaction,in which the interfacial properties play an important role.Hence,the interfacial characteristics between benzene/1-dodecene mixture and immobilized chloroaluminate ILs with different alkyl chain length on the silica substrate were investigated by molecular dynamics simulation.The grafted ILs can obviously promote the enrichment of benzene near the interface,leading to a higher ratio of benzene to dodecene,and the interfacial width increases slightly with increased alkyl chain of grafted cations.At the same time,the grafted cations can also enhance the benzene diffusion and suppress the dodecene diffusion at the interface,which probably helps to inhibit the inactivation of catalysts.This work provides deeply insights into the rational design of novel immo-bilized ILs catalysts for the benzene alkylation.

Zn_(x)Zr/HZSM-5 as efficient catalysts for alkylation of benzene with carbon dioxide

Alkylation of benzene with carbon dioxide and hydrogen to produce toluene and xylene could increase the added-value of surplus benzene as well as relieve environmental problems like green-house effect.In this work,the alkylation benzene with carbon dioxide and hydrogen reaction was proceeded by using the mixture of zinc-zirconium oxide and HZSM-5 as bifunctional catalyst.The equivalent of Zn/Zr=1 displays the best catalytic performance at 425℃ and 3.0 MPa,and benzene conversion reaches 42.9%with a selectivity of 90%towards toluene and xylene.Moreover,the carbon dioxide conversion achieves 23.3%and the carbon monoxide selectivity is lower than 35%,indicating that more than 50%carbon dioxide has been effectively incorporated into the target product,which is the best result as far as we know.Combined with characterizations,it indicated that the Zn and Zr formed a solid solution under specific conditions(Zn/Zr=1).The as-formed solid solution not only possesses a high surface area but also provides a large amount of oxygen vacancies.Additionally,the bifunctional catalyst has excellent stabilities that could keep operating without deactivation for at least 80 h.This work provides promising industrial applications for the upgrading of aromatics.

Recent Development on Zero-Phosphate Spray Dried Detergent Powders Incorporated with Palm C16 Methyl Ester Sulfonates

Palm C16 methyl ester sulphonate （C16MES）is an anionic surfactant that has the potential as active ingredient in the production of laundry detergent powders. Although C16MES has been successfully applied in the production of high-density laundry detergent powders （HDDP）, it coulingd not be employed directly as it is in the spray drying process for the production of low-density laundry detergent powders （LDDP） without compromising the detergency and other significant properties. This research paper highlights the pilot-scale experimental study, which performed to produce phosphate-free laundry detergent （PFD） powders incorporated with binary anionic surfactants of C16MES and linear alkyl benzene sulphonic acid （LABSA）. Past laboratory experiments revealed that PFD powders resulted from C16MES/LABSA of 50：50 ratio and of pH 7-8 have good detergency stability upon one-week of continuous heating in an oven at 50~C with 85% relative humidity. Based on these laboratory results, subsequent experiments were carded in a 5 kg/hr capacity co-current pilot spray dryer using PFD formulations comprising six different ratios of C16MES/LABSA （0：100, 20：80, 40：60, 80：20 and 100：0） under the same pH condition. Three PFD formulations were selected for further evaluation based on their characteristics in the spray drying process. The cleaning properties and particle properties of the resulting spray dried detergent powders from these selected formulations were analyzed. Based on the overall evaluation, C16MES/LABSA in 40：60 ratio was selected as the ideal PFD formulation. Further tests confirmed that spray dried detergent powder （SDDP） from the ideal formulation has high level of biodegradability （60% in 13 d）, low eco-toxicity properties （LC50 of 11.3 mg/L） and moderate flowability charactedsUcs （Hausner ratio of 1.27 and Carr＇s index of 21.3）.

Synthesis, characterization, and catalytic performance of hierarchical ZSM-11 zeolite synthesized via dual-template route

Hierarchical zeolite materials were prepared via one‐pot synthesis of ZSM‐11zeolites with different molar ratios(R)of a mesoporogen,i.e.,cetyltrimethylammonium bromide template(CTAB),to a microporogen,i.e.,tetra‐n‐butylammonium bromide(TBABr).The structures,morphologies,and textural properties of the resultant materials were investigated.Initially,with increasing R,the crystal size of the synthesized product decreased,the number of intercrystalline mesopores increased,and a pure ZSM‐11zeolite phase was present.Then an MCM‐41‐like phase was produced and embedded in the ZSM‐11zeolite phase.Finally,an MCM‐41‐like phase was obtained.The alkalinity had important effects on the physicochemical and textural properties of the prepared samples.A possible mechanism of formation of the hierarchical ZSM‐11zeolite was proposed on the basis of a combination of various characterization results.The role of CTAB varied depending on the R value,and it showed a capping effect,micellar effect,and template effect.These effects of CTAB were synergetic in ZSM‐11synthesis,but they were competitive with the structure‐directing effect of TBABr.In addition,the impact of the acidic properties and porosities of the hierarchical ZSM‐11catalysts on their performances in the alkylation of benzene with dimethyl ether was investigated.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Nitridation:A simple way to improve the catalytic performance of hierarchical porous ZSM-5 in benzene alkylation with methanol

Nitrided hierarchical porous ZSM-5 was synthesized by nitridation of hierarchical porous ZSM-5 with flowing ammonia at elevated temperature.The samples were characterized by XRD,SEM,Nitrogen sorption isotherms,NH3-TPD and Py-IR,and evaluated in alkylation of benzene and methanol.The result indicated that the high specific surface area of parent ZSM-5 was maintained,while the Bronsted acidity was effectively adjusted by nitridation.Moreover,the high suppression of ethylbenzene was observed on nitrided catalyst and this could be attributed to the decrease of Bronsted acidity which suppressed the methanol to olefins reactions.

Timing properties and pulse shape discrimination of LAB-based liquid scintillator

Linear Alkyl Benzene （LAB） is a promising liquid scintillator solvent in neutrino experiments because it has many appealing properties. The timing properties of LAB-based liquid scintillator have been studied through ultraviolet and ionization excitation in this study. The decay time of LAB, PPO and bis-MSB is found to be 48.6 ns, 1.55 ns and 1.5 ns, respectively. A model can describe the absorption and re-emission process between PPO and bis-MSB perfectly. The energy transfer time between LAB and PPO with different concentrations can be obtained via another model. We also show that the LAB-based liquid scintillator has good （n, γ） and （α, γ） discrimination power.

Temperature dependence of the light yield of the LAB-based and mesitylene-based liquid scintillators

We studied the temperature dependence of the light yield of linear alkyl benzene （LAB）-based and mesitylene-based liquid scintillators. The light yield increases by 23% for both liquid scintillators when the temper- ature is lowered from 26 ℃ to -40 ℃, correcting for the temperature response of the photomultiplier tube. The measurements help to understand the energy response of liquid scintillator detectors. Especially, the next generation reactor neutrino experiments for neutrino mass hierarchy, such as the Jiangmen Underground Neutrino Observatory （JUNO）, require very high energy resolution. As no apparent degradation on the liquid scintillator transparency was observed, lowering the operation temperature of the detector to ～4 ℃ will increase the photoelectron yield of the detector by 13%, combining the light yield increase of the liquid scintillator and the quantum efficiency increase of the photomultiplier tubes.

GEOCHEMICAL CHARACTERISTICS OF SUPERGENE ORGANIC MATTER IN HYPERSALINE ENVIRONMENT

The source rocks and crude oils from the Qianjiang Formation (Eocene) in the Jiangban basin have been systematically studied in the present work. Supergene hydrocarboholds are characterized by (ⅰ) high alteration ratio of soluble organic matter over organic carbon and middle ratio of hydrocarbon over organic carbon; (ⅱ) high content of non-hydrocarbon plus asphahene in extracts or crude oils; (ⅲ) sulfur-rich crude oils being an important immature crude oil; (ⅳ) alkane showing high content of phytane, gammacerane and marked even-carbon predominance or odd-carbon predominance; (ⅴ) aromatic biomarkers being distinctly classified into four groups; (ⅵ) pronounced evencarbon predominance in alkyl henzenes. In combination of all geochemical data. it is extrapolated that exploration of immature crude oil in hypersaline environment should be noticed.