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.

Effect of TS-1 Treatment by Mixed Alkaline on Propylene Epoxidation

Titanium silicate-1(TS-1) was treated with a mixed alkaline of tetrapropyl ammonium hydroxide(TPAOH) and NaOH. It was characterized by XRD, nitrogen physical adsorption, SEM, FT-IR, UV-Vis and ICPOES, and studied in propylene epoxidation. The mixed alkaline treatment with TPAOH/NaOH solution did not destroy the MFI structure of TS-1. With increasing NaOH concentrations, the relative crystallinity and the framework titanium decreased to some extent while the mesopore volume, mesopore diameter, and extra-framework titanium increased appreciably. When NaOH concentration was 0.0333 mol L^(-1), the best catalytic performance was obtained.

Green and efficient epoxidation of methyl oleate over hierarchical TS-1

The epoxidation of methyl oleate(MO)was conducted in the presence of aqueous H2O2 as the oxidant and hierarchical TS-1(HTS-1)as the catalyst;the catalyst was synthesized using polyquaternium-6 as the mesopore template.The effects of various parameters,i.e.,H2O2/C=C molar ratio,oxidant concentration,amount of the catalyst,reaction temperature,and time,were systematically studied.Furthermore,response surface methodology(RSM)was used to optimize the conditions to maximize the yield of epoxy MO and to evaluate the significance and interplay of the factors affecting the epoxy MO production.The H2O2/C=C molar ratio and catalyst amount were the determining factors for MO epoxidation,wherein the maximum yield of epoxy MO reached 94.9%over HTS-1 under the optimal conditions.

Synergetic photo-epoxidation of propylene with molecular oxygen over bimetallic Au–Ag/TS-1 photocatalysts

Au-Ag bimetallic nanoparticle‐supported microporous titanium silicalite‐1catalysts were prepared via a hydrothermal‐immersion method,and their structures were examined.These materials serve as efficient catalysts for the photosynthesis of propylene oxide via the epoxidation of propene.The Au/Ag mass ratio and reaction temperature were demonstrated to have significant effects on the catalytic activity and selectivity of propylene oxide.The optimal formation rate(68.3μmol/g·h)and selectivity(52.3%)toward propylene oxide were achieved with an Au:Ag mass ratio of4:1.Notably,the strong synergistic effect between Au and Ag resulted in superior photocatalysis of the bimetallic systems compared with those of the individual systems.A probable reaction mechanism was proposed based on the theoretical and experimental results.

Engineering three-layer core–shell S-1/TS-1@dendritic-SiO_(2) supported Au catalysts towards improved performance for propene epoxidation with H_(2) and O_(2)

The advocacy of green chemical industry has led to the development of highly efficient catalysts for direct gas-phase propene epoxidation with green,sustainable and simple essence.The S-1/TS-1@dendritic-SiO_(2) material with three-layer core–shell structure was developed and used as the support for Au catalysts,which showed simultaneously fantastic PO formation rate,PO selectivity and stability(over 100 h)for propene epoxidation with H_(2) and O_(2).It is found that silicalite-1(S-1)core and the middle thin layer of TS-1 offer great mass transfer ability,which could be responsible for the excellent stability.The designed dendritic SiO_(2) shell covers part of the acid sites on the external surface of TS-1,inhibiting the side reactions and improving the PO selectivity.Furthermore,three kinds of SiO_(2) shell morphologies(i.e.,dendritic,net,mesoporous shell)were designed,and relationship between shell morphology and catalytic performance was elucidated.The results in this paper harbour tremendous guiding significance for the design of highly efficient epoxidation catalysts.

Synthesis of 1-Octene Oligomer by Rare Earth Coordination Catalyst

The polymerization of 1-octene with Nd(P_(204))_3-AlEt_3 catalyst has been successfully carried out for the first time.Some features of polymerization of 1-octene are described.The 1-octene oligomer prepared has an average molecular weight of about 10~3 with molecular weight distribution of about 2.It has a terminal double bond,which can be transferred into terminal carboxy group by direct oxidation with KMnO_4 in acidic solution, and then can be esterified with polyglycol.

Synthesis of TS-1 Films on Porous Supports for Epoxidation ofAllyl Chloride by Hydrogen Peroxide

Titanium silicalite-1(TS-1)films were synthesized on stainless steel plate,glass slide and monolith supports via an in-situ hydrothermal method.Characterization data showed that the formation of TS-1 films was easier on the porous flat support with rough surface such as monolith than on the smooth non-porous supports like glass slide and stainless steel plate.The film on the monolith had the highest uniformity and smallest size of crystals.The catalytic property of monolithsupported film was tested for epoxidation of allyl chloride(ACH)by H2O2in a fixed bed reactor.Under the condition of a methanol(solvent)/ACH(90% )/H2O2(30% )ratio of 12:1:1,a LHSV of 1.35 h-1and a temperature of 318 K,the conversion of allyl chloride and the selectivity to epichlorohydrin reached 79% and 51% ,respectively.

Highly Effective Propylene Epoxidation over TS-1/SiO_(2) Hydrothermally Treated

The propylene epoxidation over TS-1/SiO2 catalyst hydrothermally treated was investigated. It was found by EPR characterization that two types of Ti (IV)-superoxide radicals, A (gz=2.0271; gy=2.0074; gx=2.0010) and B (gz=2.0247; gy= 2.0074; gx= 2.0010), were observed for TS-1/SiO2. The superoxo species A converted to B after TS-1/SiO2 catalyst was hydrothermally treated. The results show that over TS-1/SiO2 catalyst hydrothermally treated at 170℃, about 95% conversion of H2O2 with above 94% PO selectivity is obtained during continuous running for 300 h under the conditions of reaction temperature 45℃, 0.5 h-1WHSV of propylene.

Post-treatment of TS-1 with Mixtures of TPAOH and Ammonium Salts and the Catalytic Properties in Propylene Epoxidation

TS-1/SiO_2 extrudate was post-treated with mixed solution of tetrapropyl ammonium hydroxide(TPAOH)and various ammonium salts solution(NH_4F,(NH_4)_3PO_4,(NH_4)_2CO_3,(NH_4)_2SO_4,NH_4CH_3CO_2,NH_4NO_3,NH_4Cl and(NH_4)_2TiF_6).The obtained hierarchical TS-1 catalysts were characterized by many techniques and tested for propylene epoxidation using hydrogen peroxide as an oxidant in a fixed-bed reactor.It was shown that the physicochemical and catalytic properties of the treated TS-1/SiO_2 extrudate depended on the types of ammonium salts added.Compared to the treatment with TPAOH alone,the treatment with a mixed solution of TPAOH and some ammonium salts can greatly improve the catalytic properties of the treated TS-1/SiO_2 extrudate.Some of these ammonium salts were favorable for the incorporation of titanium in the framework,and the beneficial effect depended on the types of ammonium salt.TS-1/SiO_2 extrudate treated with a mixed solution of TPAOH and(NH_4)_3PO_4 exhibited the highest catalyst stability in propylene epoxidation.Such catalytic property can be correlated to high crystallinity,more framework titanium,large specific surface area and large external surface area.

COPOLYMERIZATION OF 1-OCTENE WITH STYRENE BY RARE EARTH COORDINATION CATALYSTS

The copolymerization of l-octene with styrene catalyzed by rare earth coordination catalysts has been studied for the first time. Some features and kinetic behavior are described. The overall activation energy of the copolymerization was 22.2 KJ/mol and the copolymerization rate could be expressed as R_p=K_p [Nd] [M]~2. (=1.68×10^(-3) L^2/mol^2. S, 50℃, [Oct]/[St]=1). The catalytic activity of various rare earth elements in Ln (naph)_3 for the copolymerization was compared and shows the following sequence: Dy, Y, Yb>Ho>Sm, Gd, Nd>Pr>Ce>La>Tm. Both monomers of l-octene and styrene in the copolymerization by Nd (naph)_3-AlEt_3 have the tendency of constant proportion copolymerization. The structure of the copolymers was studied by ~1H-NMR.

Thermoregulated Organic Biphasic Hydrogenation of 1-Octene Catalyzed by Ru/PETPP Complex

Thermoregulated organic biphasic system composed of triethylene glycol monomethyl ether （TGME） and n-heptane was first applied to the hydrogenation of 1-octene. Under the optimal conditions： P（H2）=5.0MPa, T=80℃, t=3h, 1-octene/Ru=1000 （molar ratio）, the yield of n-octane reached up to 99.6%. Furthermore, the simply decanted catalyst could be reused for 10 times without apparent loss of catalytic activity.

STUDY ON THE MECHANISM OF 1-OCTENE ZIEGLER-NATTA POLYMERIZATION BASED ON THE NUMBER OF ACTIVE CENTERS

The number of active centers (C_p)-t and k_p-t profiles of Solvay type TiCl_3 - AlR_3 (R=C_2H_5, i-C_4H_9) or Stauffer AA TiCl_3-Al (C_2H_5)_3 catalyzed 1-octene polymerization were determined by using an acetyl chloride quenching method as well as kinetic data. The results show that in the studied systems k_p decreases when C_p increases, indicating the presence of two or more types of different active centers. The C_(p^(-t)) plots of the Solvay TiCl_3-AlR_3 systems show the presence of both stable active centers and unstable centers which decay in the polymerization process. The phenomena are explained based on a model of active center plurality. The increases of C_p in the induction periods are also discussed.

COPOLYMERIZATION OF ETHYLENE WITH 1-OCTENE USING Et(Ind)_2ZrCl_2/MAO CATALYST

Copolymerization of ethylene/1-octene was carried out in toluene withvarious concentrations of comonomer in the feed using Et(Ind)_2ZrCl_2/MAO (methyl alu-minoxane) as catalyst. It was found that with the increase of 1-octene concentration in thefeed the content of 1-octene in the copolymer increases, while the density, melting point,crystallinity and intrinsic viscosity of copolymer decrease. A copolymer with very lowdensity, containing 11.5 mol% of 1-octene (VLLDPE) can be produced with this catalystsystem. The effect of temperature and zirconium aluminum mole ratio of the catalyst onthe copolymerization was also investigated. The results of ^(13)C NMR determination of thecopolymer showed that the 1-octene units in the copolymer are principally isolated.

^(13)C-NMR STUDY OF ETHYLENE-1-OCTENE COPOLYMERS

A ^(13)C-NMR method is presented for a quantitative determination of the respective monomercomposition and sequence distributions in ethylene-1-octene copolymers prepared with supportedtitanium/magnesium catalyst. On the basis of the sequence distributions, the ethylene-1-octenecopolymerization mechanism was studied. It was found that the observed sequence distributions inethylene-1-octene copolymers are satisfactorily predicted by the two-site model M/M,in whichthe copolymerization proceeds according to first-order Markovian statistics at the two differentsites.

Effects of the Water in Mixed Solvent on the Epoxidation Reaction of Propylene with TS-1 Catalyst

The epoxidation reaction of propylene and hydrogen peroxide with zeolite catalyst containing titaniumsilicalite (TS-1)has been studied, and the reaction in the mixed solvent of water/methanol has been discussed. It is shown that the selective of epoxidation propylene decreases while the selective of propylene glycol increases, when the water content increases in the mixed solvent of methanol/water.

多级孔TS-1分子筛的制备及催化1-辛烯环氧化性能研究

以P123为辅助试剂,制备了一系列分级孔TS-1分子筛.利用红外、紫外、XRD、BET、ICP等对所得样品进行了表征.对样品在过氧化氢环氧化1-辛烯反应中的催化性能进行了评价.结果表明,所得分级孔TS-1沸石均具有典型的MFI结构,其形貌和结构随P123分子量不同有一定的变化.在优化的反应条件下,用P123(MW=5800)合成的样品可以有效地将1-辛烯转化为相应的环氧化物,相应产率可达56.05%,环氧化物选择性可达59.2%.

制备WO_(3)/TS-1分子筛及催化环戊烯环氧化反应研究

利用湿法浸渍制备了一系列WO_(3)/TS-1分子筛.利用SEM、TEM、XRD、IR、UV-Vis、XPS、BET、ICP等多种分析手段对催化剂的结构、形貌和性质等进行了表征.考察了这一系列分子筛对环戊烯环氧化反应的催化性能,其中以W占分子筛质量分数为4%时浸渍制备的分子筛的催化性能最好.催化剂循环4次后,1,2-环氧环戊烷的选择性和产率保持在68.7%和55.5%左右.

Decreased Expression of Vitamin K Epoxide Reductase Complex Subunit 1 in Kidney of Patients with Calcium Oxalate Urolithiasis

Urinary prothrombin fragment 1 （UPTFl） is a potent inhibitor of urinary stone formation. UPTF1 exerts such inhibitory effect by effective 7-carboxylation in which vitamin K epoxide reductase complex subunit 1 （VKORC1）, the rate-limiting enzyme, is involved. This study examined the correlation between VKORC1 expression and calcium oxalate urolithiasis. The renal cortex samples were obtained from patients undergoing nephrectomy and then divided into 3 groups： urolithiasis group, control group A [hydronephrosis-without-stone （HWS） group], control group B （normal control group）, The localization and expression of VKORC1 in renal tissues were determined by using immunohistochemistry, immunofluorescence microscopy, Western blotting and SYBR Green I real-time reverse-transcription PCR. The rapid amplification of cDNA ends （RACE） were conducted to obtain the 3＇- and 5＇-untranslated region （UTR） of VKORC1. The results showed that VKORC1 was located in the cytoplasm of renal tubular epithelial cells. The expression of VKORC1 in the uro- lithiasis group was significantly lower than that in the other two control groups （P〈0.05）. Moreover, the 3＇- and 5＇-UTR sequence of the VKORC1 gene was successfully cloned. No insertion or deletion was found in the 3＇- and 5＇-UTR. However, a 171-bp new base sequence was discovered in the up- stream of 5＇-UTR end in the urolithiasis group. It was concluded that the decreased expression of VKORC 1 may contribute to the development of calcium oxalate urolithiasis in the kidney.

Selective propylene epoxidation in liquid phase using highly dispersed Nb catalysts incorporated in mesoporous silicates

Selective propylene epoxidation to propylene oxide(PO) with hydrogen peroxide(H_2O_2) was carried out in a catalytic semi-batch reactor.High propylene epoxidation activity(44 h^(-1)) was observed over Nb based mesoporous silicate materials Nb-TUD-1 under mild operating conditions.The physical and chemical properties of the Nb based silicates characterized using BET,FTIR,TPD,TEM and UV–Vis revealed that the site isolation and surface acidity are crucial for PO production.Catalyst synthesis methods were investigated for their effects on PO productivity,PO selectivity and H_2O_2 utilization efficiency.It is found that Nb-TUD-1 material synthesized by the sol–gel method is more active and selective than impregnated materials for liquid phase propylene epoxidation.Surface characterization confirms that thus synthesized Nb-TUD-1 catalysts have more Lewis acidity and less Bronsted acidity compared to the catalysts by impregnation.

Assignment of cis-Epoxides and Crystal Structure of cis-4-Nitro-N-(7-oxabicyclo[4.1.0]hept-2-yl)benzamide

The conformations and relative configurations of four epoxides of α-amido cyclohexenes have been determined by the combination of molecular modeling and NMR decoupling technique, cis-Epoxides were deduced from the vicinal coupling constants calculated from the torsional angles H（1）-C（1）-C（2）-H（2） in modeling models by means of Karplus equation and observed by decoupling technique. The crystal structure of cis-4-nitro-N-（7-oxabicyclo[4.1.0]hept-2-yl）benzamide further confirms this assignment.