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.

Chiral fluorescent sensor Tb^(3+)@Cd‑CP based on camphoric acid for the enantioselective recognition of R‑and S‑propylene glycol

Herein,a layered chiral coordination polymer,[Cd2(D‑cam)_(2)(2,2′‑bipy)_(2)]_(n)(Cd‑CP),was synthesized using a solvothermal method with camphoric acid(D‑H_(2)cam),2,2′‑bipyridine(2,2′‑bipy)and Cd^(2+),and Tb^(3+)@Cd‑CP was in‑situ synthesized introducing Tb^(3+)ions.The fluorescence experiments revealed that compared to Cd‑CP,Tb^(3+)@Cd‑CP exhibited ultra‑high fluorescence performance.The luminescence sensing performance demonstrated that Tb^(3+)@Cd‑CP could distinguish R/S‑propylene glycol(R/S‑PG)by fluorescence responses,with fluorescence quenching constant of 5.3×10^(3)and 2.0×10^(3)L·mol^(-1)respectively and the enantioselectivity factor(α)of 2.65.Moreover,Tb^(3+)@Cd‑CP demonstrated limits of detection of 9.3 and 19.0μmol·L^(-1)for R‑PG and S‑PG,respectively,and showed good reproducibility.

Tailoring the microenvironment of Ti sites in Ti-containing materials for synergizing with Au sites to boost propylene epoxidation

Au sites supported on Ti-containing materials(Au/Ti-containing catalyst)are currently considered as a promising catalyst for the propylene epoxidation owing to the synergistic effect that hydrogen peroxide species formed on Au sites diffuses to the Ti sites to form the Ti-hydroperoxo intermedi-ates and contributes to the formation of propylene oxide(PO).In principle,thermal treatment will significantly affect the chemical and physical structures of Ti-containing materials.Consequently,the synergy between tailored Ti sites with different surface properties and Au sites is highly expected to enhance the catalytic performance for the reaction.Herein,we systematically studied the intrinsic effects of different microenvironments around Ti sites on the PO adsorption/desorption and conversion,and then effectively improved the catalytic performance by tailoring the number of surface hydroxyl groups.The Ti^(Ⅵ) material with fewer hydroxyls stimulates a remarkable enhancement in PO selectivity and H_(2) efficiency compared to the Ti^(Ⅵ) material that possessed more hydroxyls,offering a 7-fold and 4-fold increase,respectively.As expected,the Ti^(Ⅵ+Ⅳ) and Ti^(Ⅳ) materials also exhibit a similar phenomenon to the Ti^(Ⅵ) materials through the same thermal treatment,which strongly supports that the Ti sites microenvironment is an important factor in suppressing PO con-version and enhancing catalytic performance.These insights could provide guidance for the rational preparation and optimization of Ti-containing materials synergizing with Au catalysts for propylene epoxidation.

The Oxyalkylation of Hydrophilic Black Alder Bark Extractives with Propylene Carbonate with a Focus on Green Polyols Synthesis

The isolated hydrophilic black alder(Alnus glutinosa)bark extractives were characterized in terms of component and functional composition and converted at 150℃-170℃ into liquid green polyols using solvent-free and lowtoxic base-catalyzed modification with propylene carbonate(PC).FTIR spectroscopy,HP-LC,GC,GPC,and wet chemistry methods were used to characterize the starting constituents,intermediate and final products of the reaction and to monitor the different pathways of PC conversion.The reaction of extractives as well as the model compounds,including catechol,xylose,PEG 400,and benzoic acid,with PC indicated the ability of OH groups of different origins present in the extractives to condense with equivalent amounts of PC.The polyols obtained consist of a copolymer fraction with one oxypropyl unit grafted per OH functionality of extractive components on average and oligo oxypropyl diols with a small number of carbonate linkages in the chain,obtained as a result of remaining PC homopolymerization.The domination of the oxypropylation mechanism vs.transcarbonation for PC ring opening was observed for both copolymerization and homopolymerization processes,making the process of oxypropylation with PC similar to that of conventional oxypropylation.At optimal reaction conditions,including a PC/OH ratio of 3.0 and a 24-h duration at 150°C,uniform polyols with low viscosity of~900 mPa·s^(-1),a biomass content of~27%,and an OHV of~500 mg KOH·g^(-1) were obtained.Increasing the temperature of modification allows shortening the process but drastically increases the polyol viscosity.At fixed temperature values,increasing the PC/OH ratio not only decreases the biomass content but also strongly prolongs the processing.The significantly increased duration of the process using PC as an alternative oxyalkylation agent compared to that of oxyalkylation with propylene oxide is a reasonable trade-off for using a safer and more environmentally friendly technology.

Catalytic Reaction Kinetics of Propylene Dimerization to 4-Methyl-1-Pentene Using Cu-K/K_(2)CO_(3) Solid Base Catalyst

The catalysis technology of propylene dimerization to form 4-methyl-1-pentene(4MP1)using a Cu-K/K_(2)CO_(3) solid base catalyst is a well-known heterogeneous catalytic reaction.In this study,the intrinsic kinetics of propylene dimerization were studied in a fixed-bed continuous reactor.Internal and external diffusion during the dimerization reaction experiments were eliminated by adjusting the flow rate of the carrier gas and the particle size of the catalyst support.Then,the concentration changes of each substance at the outlet of the catalyst bed under different residence times were investigated.Moreover,the suitable reaction kinetics equations was derived using the Langmuir Hinshelwood-Hougen-Watson kinetic model.Finally,the activation energy for each reaction involved in the dimerization reaction was calculated.The activation energies of 4MP1,branched by-products,and 1-hexene were 115.0,150.8,and 177.4 kJ/mol,respectively.The effect of process conditions on propylene dimerization with solid base catalysts was studied through kinetic model simulation.By comparing the theoretical values obtained from the simulation with the experimental results,the applicability and accuracy of the kinetic model were verified.

Catalytic cracking of light diesel over Au/ZSM-5 catalyst for increasing propylene production

The catalytic cracking of light diesel oil （235–337 ＆#176;C） over gold‐modified ZSM‐5 was investigated in a small confined fluidized bed at 460 ＆#176;C and ambient pressure. Different Au/ZSM‐5 catalysts were prepared by a modified deposition‐precipitation method by changing the preparation procedure and the amount of gold loading and were characterized by X‐ray diffraction, N2 adsorp‐tion‐desorption, temperature‐programmed desorption of NH3, transmission electron microscopy and inductively coupled plasma spectrometer. It was found that a small amount of gold had a posi‐tive effect on the catalytic cracking of light diesel oil and increased propylene production at a rela‐tively low temperature. The maintenance of the ZSM‐5 MFI structure, pore size distribution and the density of weak and strong acid sites of the Au/ZSM‐5 catalysts depended on the preparation pa‐rameters and the Au loading. Simultaneous enhancement of the micro‐activity and propylene pro‐duction relies on a synergy between the pore size distribution and the relative intensity of the weak and strong acid sites. A significant improvement in the micro‐activity index with an increase of 4.5 units and in the propylene selectivity with an increase of 23.2 units was obtained over the Au/ZSM‐5 catalyst with an actual Au loading of 0.17 wt%.

Study on kinetics of propylene polymerizationat different temperatures via Monte Carlo simulation

The elementary reactions of propylene polymerization catalyzed by conventional Ziegler-Natta catalysts was proposed according to the comprehensive view and without considering the effect of any impurity in the material on propylene polymerization. The Monte Carlo simulation technique was employed to investigate the kinetics of propylene polymerization in order to determine the validity of the stationary state assumption and the effects of the polymerization temperature on the polymerization. The simulated total amount of active species, which only increases quickly at the beginning of the polymerization, indicates that the stationary state assumption in the studied system is valid. Moreover, significant effects of polymerization temperature on the polymerization conversion, and the molecular weight and its distribution were also analyzed. The simulated results show that the consumption rate of propylene increases with the increase of polymerization temperature; the maximum values of the number-average degree of polymerization are constant at different polymerization temperatures, however, the peak appears earlier with the higher temperature; as the polymerization temperature increases, the average molecular weight decreases and the molecular weight distribution changes greatly.

Effects of Oral Administration of Propylene Glycol and Ca-P-Mg Mixture on Milk Quality and SCC of Dairy Cows after Birth

In order to further study the postpartum care technology of dairy cows,the effects of oral administration of propylene glycol or Ca-P-Mg mixture and compound oral rehydration salts on milk quality and SCC of dairy cows after birth were investigated. The results showed that the milk fat and dry matter contents in the dairy cows administered with Ca-P-Mg mixture and compound oral rehydration salts were higher than those in the dairy cows administered with propylene glycol（P 〈0.05）. However, there were no significant differences in milk sugar and protein contents and SCC between the two administration groups.

VAPOR-LIQUID EQUILIBRIA FOR PROPYLENE -METHANOL-WATER SYSTEM

In this article VLE data for a ternary system (propylene-methanol-water) under 30～60 C,0. 3～0. 9 MPa with a mass ratio of methanol to water of 9:1, 8: 2, 7: 3 were determined with a static equilibrium still, and were correlated by using Peng-Robinson model. The average relative error ofpropylene concentration in liquid phase is 1. 46 %. The results indicate that the models are very suitablefor the ternary system and the data are reliable.

Effects of ammonium exchange and Si/Al ratio on the conversion of methanol to propylene over a novel and large partical size ZSM-5

One type of ZSM-5 zeolite with large partical size was prepared and characterized by XRD, SEM, N2 adsorption-desorption, XRF, Py-IR and NH3-TPD techniques. Effects of ammonium exchange and SiO2/Al2O3 molar ratios on the reaction of methanol to propylene （MTP） over Na-ZSM-5 and H-ZSM-5 zeolites have been studied in a fixed-bed flow reactor under the operating conditions of T = 500 °C, P = 1 atm, and WHSV = 6 h-1. Ammonium exchange led to a rapid decrease in Na content for Na-ZSM-5 zeolite. The reaction results indicated that Na-ZSM-5 and H-ZSM-5 with different SiO2/Al2O3 molar ratios all exhibited high activity for methanol conversion. Ammonium exchange and the decreased SiO2/Al2O3 molar ratio of ZSM-5 zeolite led to an increase both in strong acid sites and weak acid sites. Na-ZSM-5 with high SiO2/Al2O3 molar ratio was favorable for the formation of propylene. The highest propylene selectivity （45.9%） was obtained over Na-ZSM-5 zeolite catalyst with SiO2/Al2O3 molar ratio of 220.

Synthesis of propylene carbonate from urea and 1,2-propanediol

The production of propylene carbonate （PC） from urea and 1,2-propanediol （PG） was investigated in a batch process. The catalytic performances of zinc chloride and magnesium chloride were investigated for this reaction system. The influences of various operation conditions on the PC yield were explored. In this work, MgCl2 and ZnCl2 showed the excellent catalytic activity toward PC synthesis, and the yields of propylene carbonate reached 96.5% and 92.4%, respectively. The optimum reaction conditions were as follows： ethanol/urea molar ratio of 4, catalyst concentration of 1.5%, reaction temperature of 160 ℃, reaction time of 3 h, respectively. The route from urea and 1,2-propanediol shows advantages, such as mild reaction condition and safe operation. The catalytic system is environmentally benign.

Preparation and shaping of solid acid SO_4^(2-)/TiO_2 and its application for esterification of propylene glycol monomethyl ether and acetic acid

The solid acid SO_4^(2-)/TiO_2 was prepared by immersion method and applied for synthesis of propylene glycol methyl ether acetate(PMA) through esterification reaction of propylene glycol monomethyl ether(PM)and acetic acid(HAc). The optimal catalyst preparation condition was determined by orthogonal analysis of parameters in a five-factor and four-level test. The obtained solid acid catalysts were characterized in detail by means of X-ray powder diffraction, thermogravimetry, pyridine adsorbed IR analysis, scanning electron microscopy, and BET surface area method. Synthesis of PMA was studied in this paper through experimental investigation of reaction conditions such as temperature, molar ratio of reactants, catalyst dosage and agitation speed. Based on its possible reaction mechanism, a pseudo-homogeneous kinetic model was established and its activation energies E_a^+ and E_a^-,65.68 × 10~3J·mol^(-1) and 57.78 × 10~3J·mol^(-1), were estimated. To prepare shaped solid acid catalyst SO_4^(2-)/TiO_2, the shaping method of impregnation–shaping–impregnation was applied. The optimal molding formulation of solid acid catalyst, obtained from the orthogonal test, was found to be binder 7 wt%, reinforcing agent 20 wt%, pore forming material 2.5 wt%, and lubricant 4 wt%.The results of performance test of catalyst demonstrated that the shaped solid acid catalyst exhibited high activity and stability.

Effects of Temperature and Catalyst to Oil Weight Ratio on the Catalytic Conversion of Heavy Oil to Propylene Using ZSM-5 and USY Catalysts

It is useful for practical operation to study the rules of production of propylene by the catalytic conversion of heavy oil in FCC （fluid catalytic cracking）. The effects of temperature and C/O ratio （catalyst to oil weight ratio） on the distribution of the product and the yield of propylene were investigated on a micro reactor unit with two model catalysts, namely ZSM-5/Al2O3 and USY/Al2O3, and Fushun vacuum gas oil （VGO） was used as the feedstock. The conversion of heavy oil over ZSM-5 catalyst can be comparable to that of USY catalyst at high temperature and high C/O ratio. The rate of conversion of heavy oil using the ZSM-5 equilibrium catalyst is lower compared with the USY equilibrium catalyst under the general FCC conditions and this can be attributed to the poor steam ability of the ZSM-5 equilibrium catalyst. The difference in pore topologies of USY and ZSM-5 is the reason why the principal products for the above two catalysts is different, namely gasoline and liquid petroleum gas （LPG）, repspectively. So the LPG selectivity, especially the propylene selectivity, may decline if USY is added into the FCC catalyst for maximizing the production of propylene. Increasing the C/O ratio is the most economical method for the increase of LPG yield than the increase of the temperature of the two model catalysts, because the loss of light oil is less in the former case. There is an inverse correlation between HTC （hydrogen transfer coefficient） and the yield of propylene, and restricting the hydrogen transfer reaction is the more important measure in increasing the yield of propylene of the ZSM-5 catalyst. The ethylene yield of ZSM-5/A1203 is higher, but the gaseous side products with low value are not enhanced when ZSM-5 catalyst is used. Moreover, for LPG and the end products, dry gas and coke, their ranges of reaction conditions to which their yields are dependent are different, and that of end products is more severe than that of LPG. So it is clear that maximizing LPG and propylene and restricting dry gas and coke can be both achieved via increasing the severity of reaction conditions among the range of reaction conditions which LPG yield is sensitive to.

The Function of β Zeolite for Enhancing the Propylene Yield in FCC Process

The ultra-stable Y zeolite, modified β zeolite, and modified ZSM-5 zeolite were characterized by NH3-TPD analysis. The results showed that the acidic substance of modified β zeolite is between that of the Y zeolite and the ZSM-5 zeolite. These three kinds of zeolites were evaluated by using hexane, decane and light diesel serving as feedstocks with different molecular size. The results showed that these three kinds of zeolites had different cracking capability and product distribution obtained for cracking hydrocarbons with different molecular sizes as a result of the difference in pore structure and acidic substances. The modified β zeolite can produce much more C_5~= —C_8~= olefins, which are excellent precursors of propylene. Then the mixed samples of these three kinds of zeolites were tested in the VGO microreactor unit, and the test results showed that the modified β zeolite played a ‘relay role' between the ultra-stable Y zeolite and the modified ZSM-5 zeolite, so that the composite made of the ultra-stable Y zeolite, the modified β zeolite, and the modified ZSM-5 zeolite showed a highest propylene yield and selectivity.

High Efficieney Synthesis of Isotaetie Polypropylene and Linear Polyethylene Using a New C_2-symmetric Carbon-bridged Zirconocene Catalyst

Ansa-Cyclohexyl-bis（4,5,6,7-tertrahydro-l-indenyl） zirconium dichloride （5） was used as catalyst for propylene and ethylene polymerization together with methyl aluminoxane （MAO） as the cocatalyst. Isotactic polypropylene （PP） was obtained with the highest activity of 6.37× 107g PP （molZr）^-1h^-1. The mesomeso （mmmmm） pentads sequence content of PP was determined by 13C NMR spectroscopy. The dependence of the microstructure on the reaction temperature and the AI/Zr molar ratio was examined and the catalytic activity of complex 5 was compared with that of the similar ansa-zirconocene 3. The high activity of the new zirconocene 5 for propylene isospectic polymerization at high temperature （60℃） is the result of its unique bridged-group structure. Complex 5/MAO displays also high catalytic activity of 0.46× 10^6 to 9.87× 10^6g PE（molZr）^-h^-in the homo-polymerization of ethylene, The visometric molecular weight of PE ranges from 0.97×10^4 to 11.16×10^4 g.mol^- under the given conditions.^13C NMR spectroscopy analysis proves the PE to be linear polyethylene （LPE）.

State-of-the-art catalysts for direct dehydrogenation of propane to propylene

With growing demand for propylene and increasing production of propane from shale gas,the technologies of propylene production,including direct dehydrogenation and oxidative dehydrogenation of propane,have drawn great attention in recent years.In particular,direct dehydrogenation of propane to propylene is regarded as one of the most promising methods of propylene production because it is an on-purpose technique that exclusively yields propylene instead of a mixture of products.In this critical review,we provide the current investigations on the heterogeneous catalysts(such as Pt,CrOx,VOx,GaOx-based catalysts,and nanocarbons)used in the direct dehydrogenation of propane to propylene.A detailed comparison and discussion of the active sites,catalytic mechanisms,influencing factors(such as the structures,dispersions,and reducibilities of the catalysts and promoters),and supports for different types of catalysts is presented.Furthermore,rational designs and preparation of high-performance catalysts for propane dehydrogenation are proposed and discussed.

INFLUENCE OF DIALKYLZINC IN RARE-EARTH TERNARY CATALYST ONTHE COPOLYMERIZATION OF CARBON DIOXIDE AND PROPYLENE OXIDE

Rare-earth ternary catalysts Y（CCl3COO）3-ZnR2-glycerin were prepared for the copolymerization of carbon dioxide and propylene oxide （PO）, where dialkylzincs （ZnR2） were diethylzinc, di（n-propyl）zinc, di（n-butyl）zinc, di（i-propyl）zinc, di（i-butyl）zinc, di（s-butyl）zinc,respectively. The Y（CCl3COO）3-ZnR2-glycerin catalysts displayed the highest catalytic activity at the molar ratio of Y（CCl3COO）3：ZnR2：glycerin = 1：20：10. In the same copolymerization condition, catalysts containing dialkylzincs with branched alkyl group showed lower catalytic activity than that with primary alkyl group. For those catalysts including dialkylzincs with primary alkyl group, their catalytic activity decreases with increasing number of carbon atom in the alkyl group with the following sequence： Y（CCl3COO）3-ZnEt2-glycerin 〉 Y（CCl3COO）3-Zn（n- Pr）2-glycerin〉Y（CCl3COO）3-Zn（n-Bu）2-glycerin. However, the alkyl group in the dialkylzinc does not influence the insertion of PO into the propagation chain end.

Electrocatalytic Synthesis of Propylene Carbonate from CO_2 and Propylene Oxide

The electrocatalytic synthesis of propylene carbonate（PC） from CO2 and propylene oxide（PO） was studied under mild conditions（PCO2=1.01×105 Pa, t=25 ℃）. Influences of solvents, supporting electrolytes, the passed charge, the nature of electrodes and the current density（j） on the yield of PC were investigated to optimize the electrolytic conditions, with the maximal yield to be 46.2%, the selectivity of propylene carbonate is 100%. The reduction of propylene oxide in the absence and presence of CO2 was examined by cyclic voltammetry. The mechanism of the reaction initiated by the synergistic effect of halides ions of supporting electrolytes with nucleophilicity and the metal ions from scarification anode with Lewis acid acidity was proposed on the basis of our results.

Numerical Investigation on 1,3-Butadiene/Propyne Co-pyrolysis and Insight into Synergistic Effect on Aromatic Hydrocarbon Formation

A numerical investigation on the co-pyrolysis of 1,3-butadiene and propyne is performed to explore the synergistic effect between fuel components on aromatic hydrocarbon formation. A detailed kinetic model of 1,3-butadiene/propyne co-pyrolysis with the sub-mechanism of aromatic hydrocarbon formation is developed and validated on previous 1,3-butadiene and propyne pyrolysis experiments. The model is able to reproduce both the single component pyrolysis and the co-pyrolysis experiments, as well as the synergistic effect between 1,3- butadiene and propyne on the formation of a series of aromatic hydrocarbons. Based on the rate of production and sensitivity analyses, key reaction pathways in the fuel decomposition and aromatic hydrocarbon formation processes are revealed and insight into the synergistic effect on aromatic hydrocarbon formation is also achieved. The synergistic effect results from the interaction between 1,3-butadiene and propyne. The easily happened chain initiation in the 1,3-butadiene decomposition provides an abundant radical pool for propyne to undergo the H-atom abstraction and produce propargyl radical which plays key roles in the formation of aromatic hydrocarbons. Besides, the 1,3-butadiene/propyne co-pyrolysis includes high concentration levels of C3 and C4 precursors simultaneously, which stimulates the formation of key aromatic hydrocarbons such as toluene and naphthalene.

Effects of the Amount of Tetrapropyl Ammonium Hydroxide in Synthesis on TS-1 Properties and Catalytic Performance in Epoxidation of Propylene

Titanium silicalite-1(TS-1) was synthesized by a hydrothermal synthesis method with different amounts of tetrapropyl ammonium hydroxide(TPAOH) as template.The as-prepared TS-1 was characterized by scanning electron microscopy,X-ray powder diffraction,Fourier-transform infrared resonance spectroscopy,ultravioletvisible diffuse reflectance spectroscopy and nitrogen physical adsorption and desorption,and studied in the propylene epoxidation with hydrogen peroxide in a fixed bed reactor.The results showed that the amount of TPAOH had a strong influence on the grain morphology,the amount of framework Ti,and the average particle sizes of TS-1.With the increase of TPAOH amount in the synthesis(the molar ratio of TPAOH/SiO_2 increasing from 0.25 to 0.45),the morphology changed gradually from ellipsoids to cubes,the particle sizes of TS-1 decreased slightly,the amount of the framework Ti increased appreciably,and the catalytic stability in the propylene epoxidation increased markedly.Moreover,all the catalysts had the same selectivity to propylene epoxide.However,when the molar ratio of TPAOH/SiO_2 was further increased to 0.55,the particles became large hexagons with the size distribution in a wide range,and the catalytic stability decreased sharply although the amount of the framework Ti increased further,which can be attributed to the long diffusion paths of the reactants in the zeolite.