Synthesis of spherical nano-ZSM-5 zeolite with intergranular mesoporous for alkylation of ethylbenzene with ethanol to produce m-diethylbenzene

Catalytic synthesis of m-diethylbenzene(m-DEB)through alkylation of ethylbenzene(EB)may be a promising alternative route in comparison with traditional rectification of mixed DEB,for which the top priority is to develop efficient and stable heterogeneous catalysts.Here,the spherical nano-ZSM-5 zeolite with abundant intergranular mesoporous is synthesized by the seed-mediated growth method for alkylation of EB with ethanol to produce m-DEB.The results show that the spherical nano-ZSM-5 zeolite exhibits better stability and higher alkylation activity at a lower temperature than those of commercial micropore ZSM-5.And then,the spherical nano-ZSM-5 is further modified by La_(2)O_(3) through acid treatment followed by immersion method.The acid treatment causes nano-ZSM-5 to exhibit the increased pore size but decreased the acid sites,and subsequent La_(2)O_(3) loading reintroduces the weak acid sites.As a result,the HNO_(3)-La_(2)O_(3)-modified catalyst exhibits a slight increase in EB conversion and DEB yield in comparison with unmodified one,and meanwhile,it still maintains high m-DEB selectivity.The catalyst after acid treatment achieves higher catalytic stability besides maintaining the high alkylation activity of EB with ethanol.The present study on the spherical nano-HZSM-5 zeolite and its modification catalyst with excellent alkylation ability provides new insights into the production of mDEB.

Covalently tethering disulfonic acid moieties onto polyoxometalate boosts acid strength and catalytic performance for hydroxyalkylation/alkylation reaction

Solid acid catalysts are widely used in the production of various high-value added and industrially important chemicals.Although the use of organosilicon compounds to modify the vacancy site has been extensively studied,the covalent tethering-SO_(3)H functionalized organosilicon modified polyoxometalates(POMs)has been rarely reported.In this work,two catalysts(TBA_(4)[SiW_(11)O_(39)(O(SiC_(3)H_(6)SO_(3)H)_(2))](compound 2)and TBA_(4)[SiW_(11)O_(39)(O(SiC_(8)H_(8)SO_(3)H)_(2))](compound 3))were synthesized successfully through covalently grafting different sulfonic acid(-SO_(3)H)groups onto[SiW_(11)O_(39)]^(8−)cluster,respectively.Compound 2 was achieved by surface grafting and in situ oxidation(3-mercaptopropyl)-trimethoxysilane,while compound 3 was achieved by surface grafting of 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane.Strong Brønsted acid strength of compounds 2 and 3 can be demonstrated by different methods including potentiometric titration,pyridine adsorption studies,and the ^(31)P trimethylphosphine oxides(TMPO)nuclear magnetic resonance(NMR).The systematic investigation of the relationship among POM structures,acid strength,and electron density was carried out based on density functional theory(DFT)calculation and experimental results,which revealed that covalent modification of compounds 2 and 3 decreased the electron density of the O-H bond,and promoted the release of H^(+).When applied in hydroxyalkylation/alkylation(HAA)reaction of 2-methylfuran(2-MF)with cyclohexanone,compound 2 exhibited better catalytic performance with conversion of ~93%,monocyclic fuel precursors(1a)yield of 79.9% and selectivity of 85.7% than compound 3,which can be attributed to strong Brønsted acid and the intramolecular hydrogen-bonding interactions between the neighboring -SO_(3)H moieties in compound 2.Finally,compound 2 also showed excellent catalytic activity in the HAA reaction of 2-MF with several different aldehydes and ketones(e.g.,furfuraldehyde,5-methylfurfuraldehyde,acetone,butyraldehyde and 4-methoxybenzaldehyde).This result opens a new pathway for design and fabrication of novel solid acid catalysts.

Non-cross-linked Polystyrene Supported Cyclosulfamide： A New Chiral Auxiliary for Highly Stereoselective Alkylation Reactions

The asymmetric alkylation reactions induced by non-cross-linked polystyrene supported cyclosulfamide chiral auxiliary occurred in moderate to good yields with a very high stereoselectivity（e.e.〉99%）. Compared to non-supported cyclosulfamide chiral auxiliary, this chiral auxiliary can be recovered by simple precipitation and filtration, and could be reused at least four cycles without appreciable reduction in the yield or stereoselectivity.

Alkylation of naphthalene with n-butene catalyzed by liquid coordination complexes and its lubricating properties

With the development of coal chemical industry,large amounts of naphthalene and n-butene are produced,and converting them into high value-added products through alkylation has gained particular importance and interest.In this work,liquid coordination complexes(LCCs)were used as acid catalysts for the first time in the naphthalene alkylation reaction under mild conditions to obtain multibutylnaphthalenes with high yield.Various reaction conditions were thoroughly investigated.The LCC consisting of urea and AlCl_(3) showed excellent catalytic performance under optimal reaction conditions,giving 100%conversion of naphthalene and 99.66%selectivity towards multi-butylnaphthalenes.Combining the catalyst properties and catalytic results,a plausible reaction mechanism was proposed.The lubricating properties of the synthesized products were investigated for their potential application as lubricating base oils.The synthesized multi-butylnaphthalenes showed comparable physicochemical properties and tribological performances as the commercial cycloalkyl base oil.

REACTIONS OF ORGANODILITHIUM COMPOUND WITH ALKYL HALIDES

The mechanism of the electron transfer reaction of 1,4-dilithio- tetraphenyl-1,3-butadiene with methyl iodide was studied.

Active precursor promoting nucleation/growth of MwW zeolite and controlling its morphology

MWW zeolites is an important catalyst in petrochemical industry.However,the efficient preparation of Mww zeolites still faces challenges,and the origin of influential factors for regulating its structure properties also remains obscure.Herein,we designed a nanoscale amorphous silica-alumina species denoted as active precursor(APS),and adopt the APS in the HMI mixture to synthesize MCM-22 zeolite(APS-MWW)successfully.To reveal the distinctive role of APS in promoting the crystallization of MWW zeolites,two crystal materials(ITQ-1 and MCM-22)and one mother liquor(ML)as seeds to synthesize three types of MWW zeolites.Typically,when adding APS in the synthetic mixture,the HMI amount was reduced to less than a quarter and crystallization time was reduced to 36 h.APS-MWW sample provides a smaller particle size(2-4μm)and thinner stacked layer thickness(5-20 nm).Synchrotron radiation Small Angle X-ray Scattering(SAXS)shows each seed has a different impact on the species'fractal structure and size distribution in the mixture,which is highly related to the nucleation and growth of MWW zeolites.APS shows a large number of 6 membered ring(MR)structure units which play a sig-nificant role in boosting the rapid nucleation and growth of APS-MwW zeolite.Among the synthesized MWW zeolites,the APS-MWW performs the highest ethylbenzene yield in the alkylation reaction of benzene-ethylene,which is attributed to its moderate flake thickness,appropriate texture properties and more external surface acidity.The results will provide a new perspective for producing MwW-types zeolites by using the available and effective active precursor.

Direct a-Alkylation of Aldehydes by Brensted-Acid Catalysis

A Bronsted acid catalyzed direct alkylation reaction of aldehydes was described. The 3,5-dinitrobenzoic acid promoted the reaction between aldehydes and diarylmethanols to afford the corresponding alkylation products with middle to high yields （up to 91% yield）.