磷酸三乙酯作为乙基化剂

在指导研究合成,ω一双一[对一氨基苯氧基]—庚烷衍生物的过程中,曾根据二烷基氮基苯酚能与,ω—二溴烷烃相作用以及对烷氧基苯胺的氨基能被烷基化等等事实提出两种合成途径: 一、一个途径是先制成所需的对二取代氨基苯酚,然后令其与1,7—二溴庚烷相作用:

Synthesis of Methyl Acetate by Dimethyl Ether Carbonylation over Cu/HMOR： Effect of Catalyst Preparation Method

Dimethyl ether carbonylation to methyl acetate was comparatively investigated over mor- denite supported copper （Cu/HMOR） catalysts prepared by different methods including evaporation, urea hydrolysis, incipient wetness impregnation and ion-exchange. The results showed that Cu/HMOR prepared via iron-exchange method exhibited the highest catalytic activity due to the synergistic effect of active-site metal and acidic molecular sieve support. Conversion of 95.3% and methyl acetate selectivity of 94.9% were achieved under conditions of 210℃, 1.5 MPa, and GSHV of 4883 h-1. The catalysts were characterized by nitrogen absorption, X-ray diffraction, NH3 temperature program desorption, and CO temperature program desorption techniques. It was found that Cu/HMOR prepared by ion-exchange method possessed high surface area, moderate strong acid centers, and CO adsorption centers, which improved catalytic performance for the reaction of CO insertion to dimethyl ether.

Facile preparation of nanocrystal-assembled hierarchical mordenite zeolites with remarkable catalytic performance

The present study reports a novel strategy to fabricate nanocrystal-assembled hierarchical MOR zeolites. This is the first demonstration of hierarchical MOR without preferential growth along the c-axis, which facilitates mass transfer in the 12-membered ring channels of MOR zeolite for the conversions involving bulky molecules. The facile method involves the combined use of tetraethylammonium hydroxide （TEAOH） and commercial surfactants, in which TEAOH is essential for the construction of nanocrystal assemblies. The surfactant serves as a crystal growth-inhibiting agent to further inhibit nanocrystalline particle growth, resulting in enhanced mesoporosity. The hierarchical MOR assembled particles, constructed of 20-50-nm crystallites, exhibit superior catalytic properties in the alkylation of benzene with benzyl alcohol compared with the control sample, as the hierarchical MOR possesses a larger external surface area and longer c-axis dimension. More importantly, the material shows improved activity and stability in the dimethyl ether carbonylation to methyl acetate reaction, which is a novel route to produce ethanol from syngas.

Effects of porous oxide layer on performance of Pd-based monolithic catalysts for 2-ethylanthraquinone hydrogenation

Pd/oxide/cordierite monolithic catalysts(oxide = Al_2O_3, SiO_2 and SiO_2\\Al_2O_3) were prepared by the impregnation method. The results of ICP, XRD, SEM–EDX, XPS and N_2 adsorption–desorption measurements revealed that the Pd penetration depth increased with increasing the thickness of oxide layer, and the catalysts with Al_2O_3 layers had the larger pore size than those with SiO_2 and SiO_2\\Al_2O_3 layers. Catalytic hydrogenation of 2-ethylanthraquinone(eA Q), a key step of the H_2O_2 production by the anthraquinone process, over the various monolithic catalysts(60 °C, atmosphere pressure) showed that the monolithic catalyst with the moderate thickness of Al_2O_3 layer(about 6 μm) exhibited the highest conversion of e AQ(99.1%) and hydrogenation efficiency(10.0 g·L^(-1)). This could be ascribed to the suitable Pd penetration depth and the larger pore size, which provides a balance between the distribution of Pd and accessibility of active sites by the reactants.

Intermolecular Transalkylation of Isopropylnaphthalene and Its Application in the Production of 2,6-Diisopropylnaphthalene

Isopropylation of naphthalene with propene resulted in a variety of isomers having different alkylation levels.The most important isomer is 2,6-DIPN,which is the precursor of important monomer 2,6-naphthalene di- carboxylic acid used for making liquid crystal polymers.In order to increase the yield of 2,6-DIPN,the intermo- lecular transalkylation with naphthalene was applied to the mixture of other DIPNs and PIPN to obtain MIPN en- riched product,which underwent isopropylation with propene to produce 2,6-DIPN in a higher yield.The experi- mental study showed that the preferable conditions for transalkylation were reaction temperature of 325℃,the mo- lar ratio of isopropyl group to naphthyl group(IP/N)of 0.8︰1—0.9︰1,reaction time of 4h and 5%of amorphous silica-alumina by mass.The conversions of DIPN and PIPN in its mixture were 62%—69%and 87%—88%respec- tively and the yield of MIPN was greater than 40%.The mixture of MIPN enriched product and recovered MIPN from rectification was subject to isopropylation with propene at 275℃over a shape-selective catalyst to produce 2,6-DIPN in a yield up to 38%.A recycled process of recovered components was established,through one cycle the yield of 2,6-DIPN based on naphthalene may be 2.8 times higher than before,and the utilization ratio of raw naph- thalene was increased by 46%.

Stabilizing copper species using zeolite for ethanol catalytic dehydrogenation to acetaldehyde

The selective dehydrogenation of ethanol to acetaldehyde is a promising route for acetaldehyde production.Although Cu-based catalysts exhibit high activity in ethanol dehydrogenation,a rapid deactivation due to Cu sintering always occurs.In this study,highly dispersed Cu species were stabilized using the silanol defects in Beta zeolite(denoted as Beta)resulting from dealumination,and applied as robust catalysts for ethanol-to-acetaldehyde conversion.Typically,a long catalyst lifetime of 100 h with an acetaldehyde yield of^70%could be achieved over 5%Cu/Beta.The presence of Cu^+and Cu0 species and the agglomeration of Cu particles after a long-term reaction for 180 h were revealed by transmission electron microscopy,thermogravimetric analysis,and CO-diffuse-reflectance infrared Fourier transform spectroscopy,and were responsible for the deactivation of the Cu/Beta catalyst in the ethanol-to-acetaldehyde conversion.

Laboratory simulated dissipation of metsulfuron methyl and chlorimuron ethyl in soils and their residual fate in rice, wheat and soybean at harvest

Two sulfonylurea herbicides, metsulfuron methyl （Ally 20 WP） and chlorimuron ethyl （Classic 25 WP） were evaluated for their dissipation bchaviour in alluvial, coastal saline and laterite soils under laboratory incubated condition at 60% water holding capacity of soils and 30 ℃ temperature was maintained. In field study herbicides were applied twice for the control of grasses, annual and perennials broad leaves weeds and sedges in rice, wheat and soybean to find out the residual fate of both the herbicides on different matrices of respective crops after harvest. Extraction and clean up methodologies for the herbicides were standardized and subsequently analyzed by HPLC. The study revealed that the half-lives of metsulfuron methyl and chlorimuron ethyl ranged from 10.75 to 13.94 d irrespective of soils and doses applied. Field trials with rice, wheat and soybean also revealed that these two herbicides could safely be recommended for application as no residues were detected in the harvest samples.

Solar energy‐driven C−H activation of methanol for direct C−C coupling to ethylene glycol with high stability by nitrogen doped tantalum oxide

Direct photocatalytic coupling of methanol to ethylene glycol(EG)is highly attractive.The reported photocatalysts for this reaction are all metal sulfide semiconductors,which may suffer from photocorrosion and have low stability.Thus,the development of non‐sulfide photocatalysts for efficient photocatalytic coupling of methanol to EG and H2 with high stability is urgent but extremely challenging.Herein,the first metal oxide photocatalyst,tantalum‐based semiconductor,is reported for preferential activation of C−H bond within methanol to form hydroxymethyl radical(•CH_(2)OH)and subsequent C−C coupling to EG.Compared with other metal oxide photocatalysts,such as TiO2,ZnO,WO_(3),Nb_(2)O_(5),tantalum oxide(Ta_(2)O_(5))is unique in that it can realize the selective photocatalytic coupling of methanol to EG.The co‐catalyst free nitrogen doped tantalum oxide(2%N‐Ta_(2)O_(5))shows an EG formation rate as high as 4.0 mmol gcat−1 h−1,about 9 times higher than that of Ta_(2)O_(5),with a selectivity higher than 70%.The high charge separation ability of nitrogen doped tantalum oxide plays a key role in its high activity for EG production.This catalyst also shows excellent stability longer than 160 h,which has not been achieved over the reported metal sulfide photocatalysts.Tantalum‐based photocatalyst is an environmentally friendly and highly stable candidate for photocatalytic coupling of methanol to EG.

Hydrogenation of 2‐ethylanthraquinone with bimetallic monolithic catalysts: An experimental and DFT study

We studied the hydrogenation of 2‐ethylanthraquinone（eAQ） over Pd/SiO2/COR（COR = cordierite） monometallic and Pd‐M/SiO2/COR（M = Ni, Fe, Mn, and Cu） bimetallic monolithic catalysts, which were prepared by the co‐impregnation method. Detailed investigations showed that the particle sizes and structures of the Pd‐M（M = Ni, Fe, Mn, and Cu） bimetallic monolithic catalysts were great‐ly affected by the second metal M and the mass ratio of Pd to the second metal M. By virtue of the small particle size and the strong interaction between Pd and Ni of Pd‐Ni alloy, Pd‐Ni bimetallic monolithic catalysts with the mass ratio of Pd/Ni = 2 achieved the highest H2O2 yield（7.5 g/L） and selectivity（95.3%）. Moreover, density functional theory calculations were performed for eAQ ad‐sorption to gain a better mechanistic understanding of the molecule‐surface interactions between eAQ and the Pd（1 1 1） or PdM（1 1 1）（M = Ni, Fe, Mn, and Cu） surfaces. It was found that the high activity of the bimetallic Pd‐Ni catalyst was a result of strong chemisorption between Pd3Ni1（1 1 1） and the carbonyl group of eAQ.

Selective extraction of In(Ⅲ),Ga(Ⅲ) and Zn(Ⅱ) using a novel extractant with phenylphosphinic acid

A new extractant, [N,N-di（2-ethylhexyl）aminolmethylphenylphosphinic acid （DEAPP）, was synthesized to de- velop the mutual separation techniques of In（Ⅲ）, Ga（Ⅲ） and Zn（Ⅱ）. The extraction selectivity for In（Ⅲ）, Ga（Ⅲ） and Zn（Ⅱ） with DEAPP was higher than that of the commercial phosphorus acid extractants such as D2EHPA and PC-88A. The extraction selectivity for metal ions in 1 mob L 1 aqueous ammonium nitrate solution with DEAPP was in the following order： In（Ⅲ） 〉 Ga（Ⅲ） 〉 Zn（Ⅱ）. These selective extraction behaviors indicate that the amino moiety of DEAPP plays an important role in the mutual separation of ln（Ⅲ）, Ga（Ⅲ） and Zn（ll）. The extraction equilibria of In（Ⅲ）, Ga（Ⅲ） and Zn（Ⅱ） with DEAPP （ = HR） were expressed by the following reactions： In3＋ ＋ 2（HR）2 InR3（HR） ＋ 3H＋, Ga3＋ ＋ 1.5（HR）2 ＋ N- = GaR2（HR）（NO3） ＋ 2H＋, and Zn2＋ 4- 2（HR）2 ZnR2 （HR） 2 determined 4- 2H＋. The extraction equilibrium constants of In（Ⅲ）, Ga（Ⅲ） and Zn（Ⅱ） with DEAPP were to be Kex, M = 1.7 × 104 [dm3.mol 1], 4.17 [（dm3.mol-1）s], and 1.55 × 10 2 [-], respectively.

SYNTHESIS AND PROPERTIES OF SULFHYDRYL CHITOSAN

A new adsorbent for heavy metal ions, sulfhydryl chitosan (S chitosan), was produced by treatment of chitosan with sulhydryl acetic acid in the presence of sulfuric acid as a catalyst. Its structure was confirmed by elemental analysis and FT IR spectra analysis. The adsorption properties of sulfhydryl chitosan for Cu(Ⅱ), Cd(Ⅱ), Pb(Ⅱ), Cr(Ⅲ) and Ni(Ⅱ) were investigated, and the effect of pH value on adsorption, adsorption kinetics, and selective adsorption was examined. It was shown that S chitosan has good adsorption for Pb(Ⅱ), Cu(Ⅱ) and Cd(Ⅱ) like chitosan, is also insoluble in acid solution; has good adsorption kinetic properties for heavy metal ions; and can be used in acid solution. The adsorption capacities of S chitosan can be affected by media acidity. The adsorbed Cu(Ⅱ) Cd(Ⅱ)and Pb(Ⅱ) could be eluted by diluted chlorhydric acid.

Investigation of N-（Hydroxylethyl）pyrrolidone Dehydration over REOx-doped Nano-ZrO2 Catalyst

Catalyst plays an important role in the dehydration of N-（hydroxylethyl）pyrrolidone （NHP） to prepare N-vinyl-pyrrolidone （NVP）. At present, NVP yield is only about 30% on commercial ZrO2 catalyst. A coupled precipitation and solid dispersion technique was designed to prepare the nano-ZrO2 catalyst, in which rare earth metal oxides （REOx） was used as electronic promoter. The results indicated that the catalyst doped REOx （S-1.0） exhibits the optimum performance of NHP dehydration at moderate conditions. NHP conversion and NVP selectivity are respectively 97.0%, 82.3%. Of special interest is that the indexes of the catalyst （S-1.0-1.0） are up to 98.4% and 89.2% respectively. Furthermore, this catalyst bears the good stability. It means that nano-ZrO2 doped REOx catalyst might be a potential commercial catalyst for the NHP dehydration.

Synthesis of Methyl 3-Hydroxypropanoate by Hydroesterification of Ethylene Oxide over Dicobalt Octacarbonyl Catalyst

Methyl 3-hydroxypropanoate was synthesized via hydroesterification of ethylene oxide with CO in the presence of dicobalt octacarbonyl catalyst and methanol solvent. The catalyst exhibited high catalytic activity. The effect of reaction temperature, CO pressure, methanol dosage, catalyst dosage and reaction time on catalytic reaction was investigated. The test results revealed that this reaction was greatly affected by reaction temperature, but it was not significantly affected by the CO pressure, the methanol dosage, the catalyst dosage and the reaction time. Under the optimal conditions, the conversion of ethylene oxide was equal to 92.24%, while the selectivity and yield of methyl 3-hydroxypropanoate reached 88.99% and 84.35%, respectively.

Preparation and Catalytic Oxidation Activity on 2-mercaptoethanol of a Novel Catalytic Cellulose Fibres

Cobalt tetra（N-carrbonylacrylic） aminophthalocyanine was supported on cellulose fibres by graft reaction to obtain a novel polymer catalyst, catalytic cellulose fibres （CCF）, and the optimal supporting conditions were pH = 6,80℃, t = 120 min. The catalytic oxidation activity of CCF towards oxidation of 2-mercaptoethanol （MEA） in aqueous solution was investigated. The experimental results demonstrated that CCF had good catalytic oxidation activity on MEA at room temperature, causing no secondary pollution and remaining efficient for the repetitive tests with no obvious decrease of catalytic activity.

The effect of copper valence on catalytic combustion of styrene over the copper based catalysts in the absence and presence of water vapor

Catalysts CuOx/γ,-Al2O3-IH and CuOx/γ/-Al2O3-IM were prepared, characterized, and tested for styrene combustion in the absence and presence of water vapor. The effect of copper valence of the catalysts on the catalytic activity for styrene combustion was discussed using the theory of hard soft acids and bases （HSAB）. The results showed that the existence of water vapor in feed stream inhibited the catalytic activity for styrene combustion due to the competition adsorption of water molecule. HSAB theory confirmed that the local soft acidity of the catalyst CuOx/^-AI203-1H was much stronger than that of the catalyst CuOx/^-AI203-1M because of the higher content of soft acid Cu＋ on its surface, which increased the adsorption ability toward soft base of styrene and reduced the adsorption toward hard base of water vapor, and thus increased the catalytic activity for styrene combustion and weakened the negative influence of water vapor.

Chiral BINAP-based hierarchical porous polymers as platforms for efficient heterogeneous asymmetric catalysis

Two vinyl‐functionalized chiral2,2'‐bis(diphenylphosphino)‐1,1'‐binaphthyl(BINAP)ligands,(S)‐4,4'‐divinyl‐BINAP and(S)‐5,5'‐divinyl‐BINAP,were successfully synthesized.Chiral BINAP‐based porous organic polymers(POPs),denoted as4‐BINAP@POPs and5‐BINAP@POPs,were efficiently prepared via the copolymerization of vinyl‐functionalized BINAP with divinyl benzene under solvothermal conditions.Thorough characterization using nuclear magnetic resonance spectroscopy,thermogravimetric analysis,extended X‐ray absorption fine structure analysis,and high‐angle annular dark‐field scanning transmission electron microscopy,we confirmed that chiral BINAP groups were successfully incorporated into the structure of the materials considered to contain hierarchical pores.Ru was introduced as a catalytic species into the POPs using different synthetic routes.Systematic investigation of the resultant chiral Ru/POP catalysts for heterogeneous asymmetric hydrogenation ofβ‐keto esters revealed their excellent chiral inducibility as well as high activity and stability.Our work thereby paves a path towards the use of advanced hierarchical porous polymers as solid chiral platforms for heterogeneous asymmetric catalysis.

Optimizing the Synthesis of Ethyl tert-Butyl Ether in Continuous Catalytic Distillation Column Using New Ion Exchange Resin Catalyst

Liquid phase synthesis of one of the important fuel oxygenate, ethyl tert-butyl ether （ETBE）, from etha-nol and tert-butyl alcohol （TBA） has been studied in catalytic distillation column （CDC） using ion exchange resin catalyst CT-145H. A packed CDC of 1.2 m height and 50 mm diameter with indigenously developed reactive sec-tion packing was used to generate experimental data. Effect of different key variables on product purity in distillate, was investigated to find the optimum operating conditions for ETBE synthesis. The optimum conditions for 0.2 kg·s-1 of ethanol feed were found：reboiler duty of 375 W, molar feed ratio of 1︰1.3 of reactants, and reflux ratio of 7. Concentration profiles for each component along each column section at optimum conditions were also drawn. Neither output nor input multiplicity was observed at experimental conditions.

Investigation of Propoxylation and Ethoxylation of 2-Ethylhexanol in the Presence of an Alkaline and DMC Type Catalyst at Initial Stages of the Syntheses

This paper reports the results of monopropoxylation and monoethoxylation of ethylhexyl alcohol performed in the presence of KOH and a DMC type catalyst, respectively. The existing differences are discussed in terms of kinetic performance of the syntheses, as well as the obtained products＇ compositions. The investigated DMC type catalyst showed 60 to 70 times as high conversion rates, narrower homolog distributions and higher selectivity, in comparison with KOH. Interpretation of the experimental results was performed using kinetic parameters of the WeibulI-Nycander-Gold model and the Natta Mantica relationships. In spite of any differences between the reactivity of the investigated catalysts and alkylene oxides, a significant contribution ofpolymerisation parallel to the target polyaddition was determined, absorbing a major part of the converted adducts, both in the presence of DMC and KOH.

Kinetics of Vapor-Phase Carbonylation of Ethanol on Ni-Zn/C Catalyst

A novel heterogeneous Ni-Zn/C catalyst was used for vapor-phasecarbonylation of ethanol under at- mospheric pressure. Experimentswere designed with the elimination of mass-transfer resistances. Thedata of primary reactions in the carbonylation were collected with adifferential tubular reactor. Power law rate models were employed toexpress the conversion of ethanol and the yields of ethyl propionateand diethyl ether. The results obtained with the models were inagreement with the experimental data.

Antioxidant activity of N-acetyl-glucosamine based thiazolidine derivative

N-acetyl-glucosamine, the monomer of chitin, was cyclo-condensed with L-cysteine to prepare thiazolidine derivative： 2-N-acetyl-glucosamine-thiazolidine-4（R）-carboxylic acid （GlcNAcCys）. The stability of GlcNAcCys was evaluated by high performance liquid chromatography （HPLC） measurement. The results showed that GlcNAcCys was more stable than other TCA derivatives, especially in alkaline condition. The direct in vitro antioxidative properties of GlcNAcCys were investigated by using UV radiation-induced lipid peroxidation （LPO） in mitochondria and nuclei and . OH-induced LPO in red blood cell （RBC） ghosts models. UV radiation caused dose-dependent LPO in both mitochondria and nuclei. This effect was catalyzed by addition of Fe^2 ＋ while prevented by co-incubation with GlcNAcCys. When nuclei and mitochondria was treated with 100μl, 300μl, 500μl of GlcNAcCys and co-incubated at 37℃ for 30min, LPO was decreased to 96%, 72%, 68% in nuclei and 95%, 72%, 68% in mitochondria when compared to the UV radiation group respectively. Hydroxyl radicals （. OH） generated by Fenton reaction induced LPO in RBC ghosts. Pretreatment of RBC ghosts with GlcNAcCys could induce antioxidant RBC ghosts and inhibit concentration-dependent malondialdehyde （MDA） formation in antioxidant RBC ghosts. Its inhibition percent was 14%, 35%, 36%, 42% at 10, 20, 30, 40mg/ml respectively. In a conclusion, the data suggest that GlcNAcCys has antioxidant ability and can significantly inhibit lipid peroxidation in biological samples tested in vitro.