Phosphotungstic acid immobilized on amino-functionalized TS-1 zeolite as a solid acid catalyst for the synthesis of tributyl citrate

The amino-functionalization of TS-1 zeolite followed by immobilization of phosphotungstic acid(HPW)was presented to prepare a strong solid acid catalyst for the synthesis of bio-based tributyl citrate from the esterification of citric acid and n-butanol.γ-Aminopropyltriethoxysilane(APTES)was first grafted on the TS-1 zeolite via the condensation reactions with surface hydroxyl groups,and subsequently the HPW was immobilized via the reaction between the amino groups and the protons from HPW-forming strong ionic bonding.The Keggin structure of HPW and MFI topology of TS-1 zeolite were well maintained after the modifications.The amino-functionalization generated abundant uniformly distributed active sites on TS-1 for HPW immobilization,which promoted the dispersity,abundance,as well as the stability of the acid sites.The tetrahedrally coordinated framework titanium and non-framework titania behaved as weak Lewis acid sites,and the protons from the immobilized HPW acted as the moderate or strong Brønsted acid sites.An optimized TBC yield of 96.2%(mol)with a conversion of-COOH of 98.1%(mol)was achieved at 150℃for 6 h over the HPW immobilized on amino-functionalized TS-1.The catalyst exhibited good stability after four consecutive reaction runs,where the activity leveled off at still a relatively high level after somewhat deactivation possibly caused by the leaching of a small portion of weakly anchored APTES or HPW.

Synthesis of zeolite A and zeolite X from electrolytic manganese residue,its characterization and performance for the removal of Cd^(2+)from wastewater

Electrolytic manganese residue(EMR)can cause serious environmental and biological hazards.In order to solve the problem,zeolite A(EMRZA)and zeolite X(EMRZX)were synthesized by EMR.The pure phase zeolites were synthesized by alkaline melting and hydrothermal two-step process,which had high crystallinity and excellent crystal control.And the optimum conditions for synthesis of zeolite were investigated:NaOH-EMR mass ratio=1.2,L/S=10,hydrothermal temperature=90℃,and hydrothermal time=6 h.Then,EMRZA and EMRZX showed excellent adsorption of Cd^(2+).When T=25℃,time=120min,pH=6,C0=518 mg·L^(-1),and quantity of absorbent=1.5 g·L^(-1),the adsorption capacities of EMRZA and EMRZX reached 314.2 and 289,5 mg·g^(-1),respectively,In addition,after three repeated adsorption-desorption cycles,EMRZA and EMRZX retained 80%and 74%of the initial zeolites removal rates,respectively.Moreover,adsorption results followed quasi-second-order kinetics and monolayer adsorption,which was regulated by a combination of chemisorption and intra-particle diffusion mechanisms.The adsorption mechanism was ions exchange between Cd^(2+)and Na+.In summary,it has been confirmed that EMRZA and EMRZX can be reused as highly efficient adsorbents to treat Cd^(2+)-contaminated wastewater.

Hydration Characteristics and Mechanical Properties of Cement-Based Materials Modified by Calcined Zeolite and Montmorillonite

Montmorillonite and clinoptilolite zeolite were used as representative materials to prepare calcined clay-cement binary cementitious materials in order to study the effect of calcination treatment on the activation of clay minerals and the activity difference between layered and framed clays in this research.The influence of different calcined clay content(2%,4%,6%,8%,10%)on the fluidity,compressive strength,microstructure,phase change,and hydration heat of cement-based materials were analyzed.The calcined clay improves the fluidity of cement-based materials as compared with the uncalcined group.The addition of calcined montmorillonite(CMT)improves the development of mechanical strength,and the optimal compressive strength reaches 85 MPa at 28 days with 8%CMT.However,the activity of calcined clinoptilolite zeolite(CZL)is weak with few reaction sites,which slightly reduced the mechanical strength as compared to the blank sample.The addition of CMT changes the microscopic morphology of hydration products such as C-S-H and C-A-H,leading to the formation and transformation of ettringite in the early stage.It promotes the gradual polymerization of Si-O bonds into Si-O-Si bonds simultaneously,which accelerates the early hydration process.However,CZL acts mainly as a filling function in the cementitious system.In brief,CMT as an admixture can improve the mechanical properties of cement,but CZL has little effect.This work provides a guideline for the applications of calcined clay in cement,considering the influence of clay type on workability and mechanical strength.

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.

Seed-solution-induced Synthesis of FER Zeolite and Its Catalytic Application in the Skeletal Isomerization of n-Butene

A series of Ferrierite(FER)zeolites were prepared via hydrothermal synthesis in the absence of organic templates with the aid of sodium-type FER zeolite(NaFER)or NaFER suspensions(NaFERsus)acquired by NaOH solution treatment as seeds.The differences in the structures and acid sites of the obtained FER zeolite catalysts arising from the choice of seed were investigated,and the catalytic performances of the obtained FER zeolites were evaluated in the skeletal isomerization of n-butene.The results indicate that the samples synthesized using NaFERsus feature more Br?nsted acid sites(BAS)in the 10-membered-ring(10-MR)at the expense of strong acid and Lewis acid sites(LAS),compared with samples derived from NaFER.Therefore,the FER samples synthesized using NaFERsus outperformed the NaFER counterparts as the BAS in 10-MR and LAS were the main active sites,while BAS in 8-MR and LAS were responsible for side reactions,such as polymerization,cracking,and carbon deposition in n-butene isomerization.The optimized FER catalyst was continuously used for 720 h at 350℃ at 0.1 MPa under an n-butene space velocity of 2.0 h^(-1),during which the n-butene conversion remained at>40%,and the isobutylene yield was>37.5%.

Zeolite A Synthesized from Geothermal Waste Using Conventional and Microwave Heating for the Hydrothermal Treatment

Zeolite A has been successfully synthesized from geothermal waste with natrium aluminate and natrium silicate using conventional(C-H)and microwave heating(M-H)for the hydrothermal treatment.The products obtained for different aging times have been characterized using X-Ray Diffraction(XRD),Fourier transformation infrared spectroscopy(FTIR),and scanning electron microscopy(SEM).It is shown that with the M-H process,zeolite can be formed at relatively low temperature(100°C)in a relatively short time(40 min).The crystallization of zeolite A has been found to be generally promoted by an increase of aging and synthesis time;however,it has also been observed that relative long aging times can transform it into sodalite.Zeolite A produced through the M-H process generally displays a smaller and more homogeneous crystal size with respect to that obtained with the C-H method.

Phosphate removal from wastewater by model-La(Ⅲ)zeolite adsorbents

Phosphorus is one of the primary nutrients which leads to eutrophication and accelerates aging process in enclosed water bodies. Because of the poor phosphorus selectivity of other adsorbents, the novel La（Ⅲ）-modified zeolite adsorbent （LZA） was prepared by modifying 90 nm zeolite with lanthanide to selectively remove phosphate in the presence of various omnipresent anions, such as sulfates, bicarbonates, and chlorides. Through batch and fixed bed operation, the following optimum conditions were obtained： concentration of lanthanum chloride solution 0.05 mol/L; solid/liquor ratio 1/25; pH 10; calcination temperature 550℃; time 1 h. The value of the Freundlich model constants Kf and 1/n were found to be 16.76 mg/L and 0.2209, respectively. In addition, when calculated at pH 6.0, distribution coefficient KD could be as high as 36.6. Furthermore, in the alkaline pH range, solution of 0.8 mol/L NaCl was used to regenerate the saturated LZA, which could reach the high regeneration efficiency as high as 100%. Because of the good selectivity and regenerability of LZA, it might serve as a potential way for advanced phosphate removal from the sewage containing other anions.

Effect of combining the metals of group VI supported on H-ZSM-5 zeolite as catalysts for non-oxidative conversion of natural gas to petrochemicals

The most prestigious catalyst applied in natural gas （methane） non-oxidative conversion to petrochemicals is 6%Mo/H-ZSM-5. Chromium, molybdenum and tungsten are the group VI metals. Hence, in this work, 6%Mo/H-ZSM-5 was correlated with 3%Cr＋3%Mo/H-ZSM-5 and 3%W＋3%Mo/H-ZSM-5 as catalysts to examine their promoting or inhibiting effects on the various reactions taking place during methane conversion. The catalytic activities of these catalysts were tested in a continuous flow fixed bed reactor at 700℃ and a GHSV of 1500 ml·g^-1·h^-1 Characterization of the catalysts using XRD, TGA and TPD were investigated. XRD and NH3-TPD showed greater interaction between the W-phase and the Bronsted acid sites in the channels of the zeolite than between Cr-phase and the acid sites in the zeolite.

The effect of FER zeolite acid sites in methanol-to-dimethyl-ether catalytic dehydration

In this paper, the effect of acidity of zeolites with FER framework was studied in the methanol dehydration to dimethyl ether reaction, by comparing catalysts with different Si/Al ratios(namely 8, 30 and60). The aim of this work was to investigate how the acid sites concentration, strength, distribution and typology(Br?nsted and Lewis) affect methanol conversion, DME selectivity and coke formation. It was found that the aluminium content affects slightly acid sites strength whilst a relevant effect on acid sites concentration and distribution(Br?nsted/Lewis) was observed as 24% of Lewis sites were found on Alrichest samples, whilst less than 10% of Lewis acid sites were observed on FER at higher Si/Al ratio. All the investigated catalyst samples showed a selectivity toward DME always greater than 0.9 and samples with the lowest Si/Al ratio exhibit the best performances in terms of methanol conversion, approaching the theoretical equilibrium value(around 0.85) at temperatures below 200 °C. Turnover-frequency analysis suggests that this result seems to be related not only to the higher amount of acid sites but also that the presence of Lewis acid sites may play a significant role in converting methanol. On the other hand, the presence of Lewis acid sites, combined with a high acidity, promote the formation of by-products(mainly methane) and coke deposition during the reaction. As final evidence, all the investigated catalysts exhibit very high resistance to deactivation by coke deposition, over 60 h continuous test, and a GC–MS analysis of the coke deposited on the catalyst surface reveals tetra-methyl benzene as main component.

Performance of a double-layer BAF using zeolite and ceramic as media under ammonium shock load condition

An experiment was carried out to investigate the anti-ammonium shock load capacity of a biological aerated filter （BAF） composed of a double-layer bed. This bed was made up of a top layer of ceramic and a bottom layer of zeolite. The experiment shows that the anti-ammonium shock load process can be divided into two processes： adsorption and release. In the adsorption process, the total removal efficiency of ammonia nitrogen by zeolite and ceramic was 94%. In the release process, the ammonia nitrogen concentration increased significantly and then gradually returned to the normal level four hours after the shock load. The results indicated that the double-layer BAF had a high level of adaptability to the short-term ammonium shock load and long-term operation. The main factors influencing the dynamic process of ammonia nitrogen adsorption were the filter bed height, ammonia nitrogen concentration of influent, and flow rate. The bed depth service time （BDST） model was used to predict the relationship between the filter bed height and breakthrough time at different flow rates, and the results are reliable.

Redistributing Cu species in Cu-SSZ-13 zeolite as NH3-SCR catalyst via a simple ion-exchange

The nature and distribution of Cu species in Cu-SSZ-13 play a vital role in selective catalytic reduction of NO by NH3(NH3-SCR),but existing methods for adjusting the Cu distribution are complex and difficult to control.Herein,we report a simple and effective ion-exchange approach to regulate the Cu distribution in the one-pot synthesized Cu-SSZ-13 that possesses sufficient initial Cu species and thus provides a“natural environment”for adjusting Cu distribution precisely.By using this proposed strategy,a series of Cu-SSZ-13x zeolites with different Cu contents and distributions were obtained.It is shown that the dealumination of the as-synthesized Cu-SSZ-13 during the ion-exchange generates abundant vacant sites in the double six-membered-rings of the SSZ-13 zeolite for relocating Cu2+species and thus allows the redistribution of the Cu species.The catalytic results showed that the ion-exchanged Cu-SSZ-13 zeolites exhibit quite different catalytic performance in NH3-SCR reaction but superior to the parent counterpart.The structure–activity relationship analysis indicates that the redistribution of Cu species rather than other factors(e.g.,crystallinity,chemical composition,and porous structure)is responsible for the improved NH3-SCR performance and SO_(2) and H_(2)O resistance.Our work offers an effective method to precisely adjust the Cu distribution in preparing the industrial SCR catalysts.

Antibacterial Activity of Cu^(2+)-ZnO-modified 13X Zeolite against E.coli and S.aureus

A new type of zeolite composite antibacterial agents was prepared by introducing zinc oxide and copper ions into 13 X zeolite through the coprecipitation and ion-exchange methods. The structural properties of the tested antibacterial material were characterized and the antibacterial activity was evaluated. In Cu^(2+)/ZnO-13 X(CZ-13), zinc oxide and copper ions were either embedded in the interlayer space or dispersed on surface of 13 X zeolite. Excellent antimicrobial activity of CZ-13 was observed on Escherichia coli(E. coli) and Staphylococcus aureus(S.aureus). In the case of Cu^(2+)/ZnO-13 X, both MIC and MBC against E.coli were 0.2 mg/mL and 0.8 mg/mL. For S.aureus, CZ-13 also showed similar antibacterial properties. The bacterial cells turned from normal rod-shape into irregular shapes after treatment with the tested CZ-13. An increase of the intracellular enzyme activity after CZ-13 addition suggested that the permeability of the cell membrane increased and bacteria were damaged.

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.

Ultrafine tuning of the pore size in zeolite A for efficient propyne removal from propylene

The removal of trace propyne(C_(3)H_(4))from propyne/propylene(C_(3)H_(4)/C_(3)H_(6))mixtures is a technical and challenging task during the production of polymer-grade propylene in view of their very similar size and physical properties.While some progress has been made,it is still very challenging to use some highly stable and commercially available porous materials via an energy-efficient adsorptive separation process.Herein,we report the ultrafine tuning of the pore apertures in type-A zeolites for the highly efficient removal of trace amounts of C_(3)H_(4)from C_(3)H_(4)/C_(3)H_(6)mixtures.The resulting ion-exchanged zeolite 5 A exhibits a large C_(3)H_(4)adsorption capacity(2.3 mmol g^(-1)under 10^(-4)MPa)and high C_(3)H_(4)/C_(3)H_(6)selectivity at room temperature,which were mainly attributed to the ultrafine-tuned pore size that selectively blocks C_(3)H_(6)molecules,while maintaining the stro ng adsorption of C_(3)H_(4)at low pressure region.High purity of C_(3)H_(6)(>99.9999%)can be directly obtained on this material under ambient conditions,as demonstrated by the experimental breakthrough curves obtained for both 1/99 and 0.1/99.9(V V)C_(3)H_(4)/C_(3)H_(6) mixtures.

Quasi-solid state synthesis of EU-1 zeolite and its catalytic properties for the isomerization of C_8 aromatics

In this study,EU-1 zeolite was successfully synthesized via a quasi-solid state approach and assembled to catalyst for the C 8 aromatics isomerization process.The catalytic properties were tuned through careful modification of the acidity of EU-1 zeolites and metal-doping of the catalyst.It was shown that EU-1 was an excellent candidate for the C 8 aromatics isomerization process due to its unique structure.In addition,steam treatment of EU-1 at 450-500 ℃ could optimize the acidic properties of the catalyst,hence enhance its catalytic performance.The effect of the amount of Pt on ethylbenzene conversion was studied and the optimum amount was determined to be about 0.3-0.4 wt%.It was confirmed that EU-1 zeolite prepared via a quasi-solid state approach and then dealuminated by steam treatment had better activity and selectivity than conventional mordenite（MOR） zeolite and could be an excellent candidate for C 8 aromatics isomerization.

Synthesis of Zeolite a from Natural Ca-Bentonite Using a Direct Alkali Hydrothermal Approach

Ca-bentonite can be converted into zeolites A through hydrothermal alkaline treatment by varying the synthetic parameters. This study focuses on the effect of initial Si/Al molar ratio, NaOH concentration on the type of formed zeolite A. The Ca-bentonite (China, Fuxin)were mixed with an aqueous NaOH solution, Al(OH)3 powder and hydrothermally treated at about 90 ℃,12 h. Different types of zeolites (zeolite X, P, and A),sodalite were synthesized after the treatment. Zeolites were characterized and quantified by means of XRD and SEM analysis. Zeolite A predominantly formed with 0.5≤Si/Al≤2.0 was produced and zeolite X, P formed with Si/Al>2.0 under the 2.2mol/LNaOH concentration; Sodalite was also formed under high NaOH molarities. Shape of zeolite A is show the cube by the SEM micrograph.

Zeolite A enhanced chitosan films with high water absorption ability and antimicrobial activity

Zeolite A/CS xerogel hybrid films were prepared by in-situ crystallization method with uniform structure and good strength.The hybrid films prepared from the precursor films dried at 50℃showed zeolite A was well crystallized.The hybrid films show high water absorption,good elastic strength and Young modulus.The antimicrobial ability of the hybrid films was investigated after Ag^(+)-ion exchanged.The Ag^(+)-exchanged hybrid films with 35%(mass)content of zeolite A showed the highest antimicrobial activity,which could reduce the concentration of the microbial to zero after 7 h.

Synthesis of highly active Cu(Ⅰ)-Y(Ⅲ)-Y zeolite and its selective adsorption desulfurization performance in presence of xylene isomers

A bimetal-exchanged NaY zeolite(Cu(Ⅰ)-Y(Ⅲ)-Y)with a desirable adsorptive desulfurization(ADS)performance was prepared and characterized by means of X-ray diffraction,specific surface area measurements,X-ray fluorescence spectrometer,X-ray photoelectron spectroscopy,thermal gravity analysis and Fourier transform infrared spectroscopy.The effect of Y(Ⅲ)ions on ADS in the presence of the xylenes was investigated.Results indicated that the ADS performance of Y(Ⅲ)-Y is higher than that of most reported CeY.The Y(Ⅲ)-based Cu(Ⅰ)-Y(Ⅲ)-Y demonstrated the higher breakthrough loading than those of reported Ce(Ⅲ)/Ce(Ⅳ)-based transition metal Y zeolites,showing that Y(Ⅲ)ions play a promoting role in improving the ADS selectivity.For Cu(Ⅰ)-Y(Ⅲ)-Y,a new strong S-M interaction(S stands for sulfur,while M stands for metal)active site was formed,which might be caused by the synergistic effect between Cu(Ⅰ)and Y(Ⅲ).The Cu(Ⅰ)-Y(Ⅲ)-Y,which combined the advantages of Cu(I)-Y and Y(Ⅲ)-Y,is a kind of promising adsorbent.The breakthrough loading decreased in the order of Cu(Ⅰ)-Y(Ⅲ)-Y>Y(Ⅲ)-Y>Cu(Ⅰ)-Y,and the effect of xylene isomers on the sulfur removal was in the order of ortho-xylene>meta-xylene>para-xylene,which exhibited the same trend with the bond order of xylenes.

A Selective Octane-Enhancing FCC Catalyst Using ZRP Zeolite as an Active Component

A hetero-crystalline seeding method to prepare a unique MFI type zeolite with mesopores of ca. 4 nm diameter designated as the ZRP zeolite, which possesses high stability and selectivity and is used as component of FCC catalysts to produce high-octane gasoline and light olefins, was developed. With the DOCR and DOCP catalysts containing the ZRP zeolite modified by phosphorus-incorporation as the octaneenhancing catalysts, the commercial trial was carried out in a 0.8Mt/a RFCC unit with a feedstock composed of Daqing atmospheric residue. As compared to the base catalyst, the LPG+gasoline+LCO product yield obtained from this catalyst was increased by 0.53m%. Meanwhile, the RON and MON of gasoline was increased by 1.4 and 2.4 units, respectively. The higher increment of MON is attributable to the higher isoparaffines content in gasoline. This result indicates that the ZRP zeolite possesses higher isomerization selectivity.

Effect of the Composite of Natural Zeolite and Fly Ash on Alkali-Silica Reaction

The effect of the composite of natural zeolite and fly ash on alkali-silica reaction (ASR) was studied with natural alkali-reactive aggregate and quartz glass aggregate respectively.The expansive experiment of mortar bar and concrete prism was completed.The results show that ASR can be suppressed effectively by the composite of natural zeolite and fly ash.