乙酸乙酯原装置主体不动扩产节能技术改造新方法

乙酸乙酯技术改造新方法:在酯化塔体不动的情况下,改变操作条件,用精酯回流,使酯化塔产粗酯量提高83.3%;在精镏塔体不动情况下,用丝网填料代替鲍尔环填料,使精镏塔的处理能力提高50%;施工时间短,节能效果明显。

阳图PS版用重氮萘醌系感光组成物研究进展

目前PS版在印刷领域仍占有较重要地位,重氮萘醌系感光组成物自20世纪应用以来,经久不衰。文章主要介绍了PS版用重氮萘醌系感光组成物的研究进展情况,包括重氮类感光化合物,与之配合使用的版基、成膜树脂、酯化体。同时产酸剂、背景染料、溶剂及其它添加剂简单进行了归纳,并研究了重氮萘醌系阳图PS版的配方化学及发展趋势。

Esterification of cyclohexene with formic acid over a peanut shell-derived carbon solid acid catalyst

A carbon solid acid catalyst was prepared by the sulfonation of partially carbonized peanut shell with concentrated H2SO4. The structure and acidity of the catalyst were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, thermogravimetric analysis, X‐ray photoelectron spectroscopy, and elemental analysis, which showed that it was an amorphous carbon material composed of aromatic carbon sheets in random orientations. Sulfonic acid groups were present on the surface at a density of 0.81 mmol/g. The carbon solid acid catalyst showed better performance than HZSM‐5 for the esterification of cyclohexene with formic acid. At a3：1 molar ratio of formic acid to cyclohexene, catalyst loading of 0.07 g/mL of cyclohexene, and reaction time of 1 h at 413 K, the cyclohexene conversion was 88.4% with 97.3% selectivity to cyclohexyl formate. The carbon solid acid catalyst showed better reusability than HZSM‐5 because its large pores were minimally affected by the accumulation of oligomerized cyclohexene, which deactivated HZSM‐5. The activity of the carbon solid acid catalyst decreased somewhat in the first two recycles due to the leaching of polycyclic aromatic hydrocarbon containing –SO3H groups and then it remained constant in the following reuse.

Study on ternary polymerization of toluene diisocyanate

For the production of reactive polyurethane cross-linkinger and curing agents, 2, 4-diisocyanate toluene （TDI） terpolymer, which possesses the rigid structures of hexatomic ring and three reactive functional groups, was synthesized and characterized by the Fourier transform infrared （FFIR）, the gel permeation chromatography （GPC） and the chemical analysis methods. The reaction conditions were studied and optimized. A tracking research on the polymerization process of TDI was taken by using the GPC. The formation processes of the terpolymer, oligomers and higher-polymers were also dealt with. Results show that the TDI terpolymer can be prepared in the presence of Cat-3 catalyst and at the reaction temperature of （60 ±2）℃. The reaction time is short, its outcomes have narrow molecular weights distribution, namely molecular weights from 530 to 550, Mw/Mn =1.10, and the mass fraction of NCO is （25. 0 ± 0. 5）%. With the reaction time prolonging, however, TDI can be further higher-polymedzed to form higher-polymers. Benzoyl chloride （0. 4%, mass fraction）, as the stabilizing agent, can effectively inhibit the occurrence of higher-polymerization. The obtained TDI terpolymer can be stable for more than half a year.

One Step Preparation of Sulfonated Solid Catalyst and Its Effect in Esterification Reaction

A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization （in moderate conditions：200 ＆#176;C, 12 h） of red liquor solids, a by-product of paper-making process. The prepared sulfonated cata-lyst （SC） had aromatic structure, composed of carbon enriched inner core, and oxygen-containing （SO3H, COOH, OH） groups enriched surface. The SO3H, COOH, OH groups amounted to 0.74 mmol·g^-1, 0.78 mmol·g^-1, 2.18 mmol·g^-1, respectively. The fresh SC showed much higher catalytic activity than that of the traditional solid acid catalysts （strong^-acid 732 cation exchange resin, hydrogen type zeolite socony mobile-five （HZSM-5）, sulfated zir-conia） in esterification of oleic acid. SC was deactivated during the reactions, through the mechanisms of leaching of sulfonated species and formation of sulfonate esters. Two regeneration methods were developed, and the catalytic activity can be mostly regenerated by regeneration Method 1 and be fully regenerated by regeneration Method 2, respectively.

Solid base catalysts derived from Ca-M-Al(M = Mg, La, Ce, Y) layered double hydroxides for dimethyl carbonate synthesis by transesterification of methanol with propylene carbonate

Composite solid base catalysts derived from Ca‐M‐Al(M=Mg,La,Ce,Y)layered double hydroxides(LDH)were synthesized,characterized and applied to the transesterification of methanol with propylene carbonate.X‐ray diffraction analyses of the catalysts show that all of the catalysts were in the form of composite oxides.Compared with the Ca‐Al LDH catalyst,the specific surface areas and pore volumes of the catalysts were increased with the introduction of Mg,La or Ce.The catalytic performance of these catalysts increases in the order of Ca‐Y‐Al<Ca‐Al<Ca‐Ce‐Al<Ca‐La‐Al<Ca‐Mg‐Al,which is consistent with the total surface basic amounts of these materials and the formation of especially strong basic sites following modification with Mg and La.The Ca‐Mg‐Al catalyst shows the highest(Ca+Mg):Al atomic ratio,indicating that it likely contains more unsaturated O2?ions,providing it with the highest concentration of very strong basic sites.The recyclability of these catalysts is improved following the addition of Mg,La,Ce or Y,with the Ca‐Mg‐Al maintaining a high level of activity after ten recycling trials.X‐ray diffraction analyses of fresh and used Ca‐Mg‐Al demonstrate that this catalyst is exceptionally stable,which could be of value in practical applications related to heterogeneous catalysis.

D-β-hydroxybutyrate inhibits microglial activation in a cell activation model in vitro

Microglial activation plays an important role in a panel of neurological disorders such as multiple sclerosis(MS) and Parkinson's disease(PD),and is a key target for developing therapeutic strategies for these diseases.Ketogenic diet (KD),which is able to inhibit microglial activation in substantia nigra pars compacta of mice,has been shown effective in a mouse model of PD,possibly through increasing D-β-hydroxybutyrate(D-β-HB),a major component of ketone bodies.To verify this,we developed an in vitro model of microglia activation with a microglia line,BV-2,and investigated how D-β-HB have an effect on the LPS-stimulated BV-2 cells.We found D-β-HB is able to recover the cell viability,and inhibit the production of inflammatory mediators and cytokines such as ROS,nitrite,IL-1β,TNF-α,and IL-6,which otherwise were increased in LPS-stimulated BV-2 cells.We conclude that the LPS induced BV-2 cells activation is a valid in vitro model of microglia activation.D-β-HB is able to suppress the activation of BV-2 cells, which might account for one of the possible reasons of KD therapy on the PD model.

Resolution of Ibuprofen Ester by Catalytic Antibodies in Water-miscible Organic-solvents

The asymmetric hydrolysis of racemic ibuprofen ester is one of the most important methods for chiral separation of ibuprofen. In this work, a catalytic antibody that accelerates the rate of enantioselective hydrolysis of ibuprofen methyl ester was obtained against an immunogen consisting of tetrahedral phosphonate hapten attached to bovine serum albumin (BSA). The catalytic activity of the catalytic antibody in the water-miscible organic-solvent system composed of a buffer solution and N, N-dimethylformamide (DMF) was studied. With 6% DMF in the buffer solution (containing catalytic antibody 0.25 μmol, 0.2 mol·L-1 phosphate buffer, pH 8) at 37°C for 10 h, a good conversion (48.7%) and high enantiomeric excess (>99%) could be reached. The kinetic analysis of the cata-lytic antibody-catalyzed reaction showed that the hydrolysis in the water-miscible organic-solvent system with DMF in buffer solution followed the Michaelis-Menten kinetics. The catalytic efficiency (Kcat/Km) was enhanced to 151.91 L·mmol-1·min-1, twice as large as that for the buffer solution only.

Synthesis of propylene glycol ethers from propylene oxide catalyzed by environmentally friendly ionic liquids

A series of acetate ionic liquids were synthesized using a typical two‐step method.The ionic liquids were used as environmentally benign catalysts in the production of propylene glycol ethers from propylene oxide and alcohols under mild conditions.The basic strengths of the ionic liquids were evaluated by determination of their Hammett functions,obtained using ultraviolet‐visible spectroscopy,and the relationship between their catalytic activities and basicities was established.The catalytic efficiencies of the ionic liquids were higher than that of the traditional basic catalyst NaOH.This can be attributed to the involvement of a novel reaction mechanism when these ionic liquids are used.A possible electrophilic‐nucleophilic dual activation mechanism was proposed and confirmed using electrospray ionization quadrupole time‐of‐flight mass spectrometry.In addition,the effects of significant reaction parameters such as concentration of catalyst,molar ratio of alcohol to propylene oxide,reaction temperature,and steric hindrance of the alcohol were investigated in detail.

Optimization of conjugated linoleic acid triglycerides via enzymatic esterification in no-solvent system

We compared four esterifiable enzymes. The lipase Novozym 435 possessed the highest activity for the conjugated linoleic acid esterification during the synthesis of triglycerides. The triglycerides were synthesized by esterification of glycerol and conjugated linoleic acid （CLA） in a no-solvent system using lipase catalysis. We investigated the effects of temperature, enzyme concentration, water content, and time on esterification. Enzyme and water concentrations of up to 1% of the total reaction volume and a system temperature of 60℃ proved optimal for esterification. Similarly, when the esterification was carried out for 24 h, the reaction ratio improved to 94.11%. The esterification rate of the rotating screen basket remained high （87.28%） when the enzyme was re-used for the 5th time. We evaluated the substrate selectivity of lipase （NOVO 435） and determined that this lipase prefers the 10,12-octadacadienoic acid to the 9,11-octadecadienoic acid.

Lipase-catalyzed Synthesis of Caffeic Acid Phenethyl Ester in Ionic Liquids： Effect of Specific Ions and Reaction Parameters

Caffeic acid phenethyl ester(CAPE)is a rare,naturally occurring phenolic food additive.This work systematically reported fundamental data on conversion of caffeic acid(CA),yield of CAPE,and reactive selectivity during the lipase-catalyzed esterification process of CA and phenylethanol(PE)in ionic liquids(ILs).Sixteen ILs were selected as the reaction media,and the relative lipase-catalyzed synthesis properties of CAPE were measured in an effort to enhance the yield of CAPE with high selectivity.The results indicated that ILs containing weakly coordinating anions and cations with adequate alkyl chain length improved the synthesis of CAPE.[Emim][Tf2N]was selected as the optimal reaction media.The optimal parameters were as follows by response surface methodology(RSM):reaction temperature,84.0°C;mass ratio of Novozym 435 to CA,14︰1;and molar ratio of PE to CA,16︰1.The highest reactive selectivity of CAPE catalyzed by Novozym 435 in[Emim][Tf2N]reached 64.55%(CA conversion 98.76%and CAPE yield 63.75%,respectively).Thus,lipase-catalyzed esterification in ILs is a promising method suitable for CAPE production.

Production of biodiesel from palm fatty acid distillate using sulfonated-glucose solid acid catalyst:Characterization and optimization

A palm fatty acid distillate （PFAD） has been used for biodiesel production. An efficient sulfonated-glucose acid catalyst （SGAC） was prepared by sulfonation to catalyze the esterification reaction. The effect of three variables i.e. methanol-to-PFAD molar ratio, catalyst amount and reaction time, on the yield of PFAD esters was studied by the response surface methodology （RSM）. The optimum reaction conditions were： 12.2：1 methanol-to- PFAD molar ratio, 2.9% catalyst concentration and 134 rain of time as predicted by the RSM. The reaction under the optimum conditions resulted in 94.5% of the free fatty acid （FFA） conversion with 92.4% of the FAME yield. The properties of the PFAD esters were determined according to biodiesel standards.

Simulation for Transesterification of Methyl Acetate and n-Butanol in a Reactive and Extractive Distillation Column Using Ionic Liquids as Entrainer and Catalyst

A new reactive and extractive distillation process with ionic liquids as entrainer and catalyst （RED-IL）was proposed to produce methanol and n-butyl acetate by transesterification reaction of methyl acetate with n-butanol. The RED-IL process was simulated via a rigorous model, and high purity products of methanol and n-butyl acetate can be obtained in such a process. The effects of reflux ratio, feed mode, holdup, feed location, entrainer ratio and catalyst concentration on RED-IL process were investigated. The conversion of methyl acetate and purities of products increase with the holdup in column, entrainer ratio and catalyst content. An optimal reflux ratio exists in RED-IL process. Comparing to the mixed-feed mode, the segregated-feed mode is more effective, in which the optimal feed locations of reactants exist.

Novel MgCl2-supported Catalysts Containing Succinate Donors for Propylene Polymerization

A novel MgCl2-supported Ziegler-Natta catalyst containing diethyl diisopropylsuccinate donor was prepared and propylene polymerizations with the combination of such catalyst and four external donors were investigated in detail. The catalyst was compared with a commercial one with phthalate as internal donor in terms of catalytic activity, hydrogen sensitivity and stereospecificity in propylene polymerization. The molecular weight,molecular weight distribution and microstructure of the produced polypropylenes were compared also. It was found that the novel catalyst containing succinate internal donor showed higher activity and higher stereospecificity than those with phthalate as internal donor. Consequently, polypropylenes obtained by the succinate-based catalyst showed high molecular weight, high melting temperature, high isotactic index and broad molecular weight distribution than those obtained with the commercial catalyst.

Complete Valorization of Olive Mill Wastewater through an Integrated Process for Poly-3-hydroxybutyrate Production

An economical and environmental sustainability of bioplastic production is dependent on the use of low cost and waste C-sources as raw materials. OMW （Olive Mill Wastewater） with its high organic load represents a dangerous polluting waste. Herein the authors present an integrated process for the simultaneous recovery of polyphenols, high value natural antioxidants, production of PHAs （polyhydroxyalkanotes）, thermoplastic bio-polymers, in particular of PHB （poly-3-hydroxybutyrate） starting from OMW. The combination of membrane filtration and bacterial digestion of OMW resulted in very high yields of polyphenols （3 2.5 g/L） and PHB （31.4 mg/L.h） if compared with the state of the art. These results make the technical approach described here effective for reducing the polluting effect of OMW and maximizing the valuable product yield. Moreover the process is readily suitable for an industrial scale PHB production from OMW.

Epoxidation of Unsaturated Fatty Acid Methyl Esters in the Presence of SO_3H-functional Brφnsted Acidic Ionic Liquid as Catalyst

The epoxidation of unsaturated fatty acid methyl esters(FAMEs)by peroxyacetic acid generated in situ from hydrogen peroxide and acetic acid was studied in the presence of SO3H-functional Brnsted acidic ionic liquid (IL)[C3SO3HMIM][HSO4]as catalyst.The effects of hydrogen peroxide/ethylenic unsaturation ratio,acetic acid concentration,IL concentration,recycling of the IL catalyst,and temperature on the conversion to oxirane were studied.The kinetics and thermodynamics of unsaturated FAMEs epoxidation and the kinetics of oxirane cleavage of the epoxidized FAMEs by acetic acid were also studied.The conversion of ethylenic unsaturation group to oxirane, the reaction rate of the conversion to oxirane,and the rate of hydrolysis(oxirane cleavage)were higher by using the IL catalyst.

Are Polymers Toxic？ Case Study： Environmental Impact of a Biopolymer

In this paper, the analysis of the environmental impacts of a biopolymer based on starch is presented. These impacts were calculated from a cradle to gate LCA （Life Cycle Assessment）, based on UNEEN ISO 14040：2006 and UNEEN ISO 14044, using as functional unit 1 kg of produced biomaterial. The impact categories analyzed were global wanning, ozone depletion, acidification and eutrophication. The results indicate that the electricity causes the highest impacts in the global warming and ozone depletion categories, but compared to synthetic polymers, the emissions are low. Finally, in the case of eutrophication, the impacts are similar to other biopolymers but higher in comparison with petroleum-based polymers like HDPE （High Density Polyethylene）, LDPE （Low Density Polyethylene）, PP （Polypropylene）, PS （Polystyrene） and PET （Polyethylene Terephthalate）.

The structure and properties of Fe_3O_4/P (NaUA-St-BA) magnetic composite nano particles

Fe3O4/P （NaUA-St-BA） core-shell composite micro spheres were in situ prepared by soapless polymerization of styrene and butyl acrylate, with Fe3O4magnetic colloidal particles coated with NaUA. The results of IR and XRD analysis demonstrated that the desired polymer chains have been covalently bonded to the surface of Fe3O4 nano particles. The morphology analysis by TEM confirmed that the composite particles have the core-shell structure and a relatively uniform diameter of about 100nm. The magnetic properties of the obtained composite latex particles were measured by VSM and found that they exhibited super paramagnetic properties. Finally, the prepared magnetic composite particles latex is stable for several months.

Highly efficient nickel/phosphine catalyzed cross-couplings of diarylborinic acids with aryl tosylates and sulfamates

Highly efficient cross-couplings of diarylborinic acids with aryl tosylates and sulfamates are reported for construction of biaryls using a tri(4-methoxyphenyl)phosphine-supported nickel catalyst system: Ni[P(4-MeOC6H4)3]2Cl2/2P(4-MeOC6H4)3 in the presence of K3PO4·3H2O in toluene. A variety of unsymmetrical biaryls could be obtained in good to excellent yields with1.5–3 mol% or 3–5 mol% catalyst loadings for aryl sulfamates and tosylates, respectively. In sharp contrast to the conventional nickel-catalyzed Suzuki coupling with arylboronic acids, arylsulfamates unexpectedly displayed a higher reactivity than the corresponding tosylates in coupling with diarylborinic acids catalyzed by the nickel/phosphine catalyst system.

Transesterification of glyceryl tributyrate with methanol using strontium borate as the solid base catalyst

Four kinds of strontium borates were prepared and characterized by XRD, SEM, EDS, TG-DTA and Hammett titration method and their catalytic activities were examined in the transesterification of glyceryl tributyrate with methanol for the first time. The separate effects of the molar ratio of methanol to oil, the reaction time, and reusability were investigated. In addition, the catalytic activities of Sr（OH）2 and SrCO3 were also examined for the comparison. The results showed that the basicity and catalytic activity of these catalysts were decreased as the following order： Sr（OH）2 〉 SrB2O4·4H2O 〉 SrB6O10·5H2O 〉 SrB2O4 〉 SrB6O10 〉 SrCO3, and the reusability decreases as the following order： anhydrous strontium borates （SrBgO4, SrB6O10） 〉 hydrated strontium borates （SrB2O4·4H2O, SrB6O10·5H2O） 〉 Sr（OH）〉 The results indicate that the SrB2O4·4H2O with regular morphology, which was obtained at low temperature by a simple preparation method, might be as one kind of good potential alkaline earth salts catalyst for transesterification. Moreover, the possible reaction mechanism is proposed and analyzed.