Efficient synthesis of bioetheric fuel additive by combining the reductive and direct etherification of furfural in one-pot over Pd nanoparticles deposited on zeolites

Furfuryl ethers have been considered to be a promising fuel additive.One step reduction etherification of furfural over supported Pd catalysts provides a facile way for the preparation of furfuryl ether.However,the preparation of a reusable Pd catalyst for reductive etherification remains to be a great challenge.In this study,a series of Si O_(2)supported Pd catalysts with particle size ranging from 2.2 nm to 28 nm were prepared.Their textural properties and catalytic performance in furfural reductive etherification have been systematically studied.The results herein shed light on the particle size effect on the competition between hydrogenation/hydrogenolysis of C=O in furfural over Pd surface.We found out that Pd nanoparticles larger than 3 nm are preferred for one step reductive etherification.Based on this finding,we prepared a Pd/ZSM-5 bifunctional catalyst comprising Pd nanoparticles larger than 3 nm and decreased acidity in presence of amino organosilane,which served as a bifunctional catalyst succeeding in one-pot synthesis of ether via reductive-etherification and direct-etherification.This strategy showed significant advantage in efficiently converting furfuryl acohol,a major side-product,into ether,while suppressing the undesired side-reactions.

Etherification of HMF to biodiesel additives: The role of NH4+ confinement in Beta zeolites

The role of NH4^+ ion confinement in the catalytic etherification of HMF(5-hydroxymethylfurfural) with ethanol to biodiesel additives was evidenced by studying the catalytic behavior of NH4^+-Beta zeolites with SiO2/Al2O3 ratios of 25 and 75.In order to affect the strength and distribution of the acidic sites, as well as the mobility of NH4^+ ions in the zeolites cages, a secondary level of porosity was introduced in the NH4^+-Beta, presenting a different stability versus alkaline treatment, by using a thermal or an ultrasound assisted method.By analyzing the catalytic behavior in these two series of samples with respect to the changes in porosity by nonlocal density functional theory, structure by XRD, amount of acid sites by FT-IR and mobility of NH4^+ cations by measurements of reversible NH4^+ exchange capacity, was evidenced a decrease in catalytic performances both in terms of rate of HMF depletion and productivity to the main products, when confinement of the ammonium ions is lost due to the introduction of mesoporosity.The high capability of ammonium ions release, associated to the mono-dentate configuration,and the minor confinement effect inside the zeolite pore system, due to the more opened pores structure of mesoporous zeolites, hinders both the direct etherification of HMF to EMF [5-(ethoxymethyl)furan-2-carbaldehyde] and the parallel reaction pathway via acetalization, favoring the rapid desorption of the HMFDEA [5-(hydroxymethyl)furfural diethyl acetal] product out of the crystal and the consequent inhibition of the consecutive reactions to EMFDEA [5-(ethoxymethyl)furfural diethyl acetal] and EMF.

Etherification of Methanol with Propylene Oxide Catalyzed by Heteropolyacids

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Etherification of Alkali-pretreated Sugarcane Bagasse Cellulose in Tetrahydrofuran

Sugarcane bagasse(SCB)is an important by-product in the sugar industry.It is a source of cellulose fibers or cellulose for paper mills and textiles factories.In this study,SCB was ethyl etherified in tetrahydrofuran(THF)after alkali pretreatment.The alkali concentration for the pretreatment,the ratio of ethyl bromide(EtBr)to dried SCB in the reaction,reaction time,and temperature were investigated for the etherification of SCB.The ethoxyl content and characterization of the product were determined using headspace gas chromatography(HS-GC),Fourier Transform Infrared(FT-IR)and 13C-NMR spectroscopy,respectively.It was found that SCB was well-etherified with EtBr in alkali-THF.Upon ethylation of SCB,the ethoxyl content of the product was high when the alkali concentration and the ratio of EtBr to dried SCB were controlled from 50%to 75%and 4:1(V/w)to 6:1(V/w),respectively.The reaction occurred optimally when the temperature was controlled below 110℃;above this temperature,the degree of etherification decreased.The thermal stability of ethylated SCB was higher than that of SCB but slightly lower than that of commercial ethyl cellulose.Ethylated SCB has the potential to form composites with many materials because it is soluble in a wide variety of solvents.

Synthesis of Modified β-Zeolite Under Microwave Irradiation and Its Use on Etherification

zeolite was synthesized by using tetraethyl ammonium hydroxide as the template reagent andmicrowave radiation as the heat source. The effect of the sol composition and the radiation temperature onzeolite crystallinity was investigated. The zeolite was tested and compared with the commercial product, whichwas produced by conventional hydrothermal synthesis method. The physico-chemical properties of the syn-thesized samples, the specific surface area of the samples synthesized under microwave irradiation and porevolume measured by X-ray diffraction apparatus, were better than the conventional samples. The etherificationexperiment on FCC light naphtha in the presence of transition metals modified Hβ-zeolite, which was synthe-sized firstly under microwave irradiation, was studied in a fixed-bed reactor. The effect of catalyst preparationconditions on its activity, stability and the effect of reaction temperature, methanol/tertiary-carbon olefin molarratio and liquid hourly space velocity on the etherification reaction were discussed. The experimental resultsshowed that the different metals modified Hβ-zeolite had different etherification performances. And theconversion of tertiary carbon-olefins of the molybdenum modified Hβzeolite, which was loaded at a concen-tration of 3 percents, was higher than that on 6.0 percent of Hβzeolite. The modified Hβzeolite catalystspossessed favorable prospects for its higher stability.

STUDY ON ETHERIFICATION OF TERMINAL HYDROXY GROUP OF POLYETHYLENE GLYCOL MONOALKYL ETHERS

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Study on the Adaptability of Etherification Feedstock to Reactor Type

A reactive C5 olefins and methanol etherification kinetic model based on E-R mechanism was established and three different types of reactors including the adiabatic fixed-bed liquid reactor, the external loop reactor and the mixedphase reactor were constructed by Aspen Plus. The adaptability of reactive C5 olefins to these reactors was studied and simulated using various gasoline fractions with different olefins content. After the theoretical model was validated by the experimental data of the etherification of three C5 light cut fractions from different gasoline sources in different reactors, the simulated isoamylene conversion with reactive C5 olefin contents increasing from 10% to 60% was studied in the three different types of reactors for etherification with methanol, respectively. Test results show that there is an obvious adaptability of the feedstock composition to the reactor type to achieve a high conversion.

Preparation and Catalytic Properties of Various Oxides and Mesoporous Materials Containing Niobium and Sulfate Ions, in the Etherification Reaction of 2-Naphtol

Several types of solid acid catalysts were prepared based on oxides like (ZrO2, TiO2, HfO2, MCM-41 and SBA-15), using two main preparation methods: the precipitation and the sol-gel methods. Each catalyst was subjected to two types of impregnations: sulfate ions using sulfuric acid as precursor and niobium using niobium oxalate as precursor. These prepared catalysts were tested in the etherification reaction of 2-naphtol, where the catalysts showed both acidic and redox properties. The acidic character was manifested through the formation of 2-butoxynaphtalene (with moderate yields) when oxide is sulfated, and the redox character (when impregnated with niobium) manifested through the formation of the interesting product 2-ethylnaphtofuran (with low yields) and other products that were a result of oxidative coupling of two 2-naphtol molecules (binol and acetal of binol). However despite the effort, several attempts to increase the yield of 2-ethylnaphtofuran did not work. All products prepared were obtained in pure form and characterized by 1H and 13C NMR, GC and MS.

Liquid Etherification of Alkoxybenzyl Alcohols, Cinnamyl Alcohols and Fluorinated Phenylalkenols with Platinum on Carbon (Pt/C) and Palladium on Carbon (Pd/C)

In the presence of either Pd/C or Pt/C, 4-alkoxybenzyl alcohols, 4-alkoxy-phenylalkyl alcohols and cinnamyl alcohols undergo liquid etherification to bis(4-alkoxybenzyl) ethers, bis[(4-alkoxybenzyl)alkyl] ethers and bis(cin-namyl) ethers at temperatures of 100°C - 135°C. In a number of cases, Pt/C and Pd/C as catalysts, also when they are doped with Ru, show distinct differences when the reactions run in air, with an oxidative dehydrogenation of the alcohols as side-reaction, yielding the corresponding ketones and aldehydes as by-products. Also, the reactivity of fluorinated phenylalkenols under these conditions has been investigated. Furthermore, the immobilization of alkyl aryl ethers on silica within a column with passage of hexane as solvent was found to lead to the formation and elution of styrenes from the column in fair yield.

Copper-Catalyzed Oxidative Dearomatization of 2-Naphthols via Etherification

Copper-catalyzed intermolecular oxidative-etherification type dearomatization reaction of 2-naphthols was developed.With air as the terminal oxidant,the reaction proceeded in excellent yields under mild conditions.In addition,the reaction between two different naphthol substrates occurred smoothly.A series of multifunctionalized β-naphthalenones,important scaffold existed widely in natural products and biologically active molecules,were synthesized efficiently.

Highly Stereocontrolled Total Syntheses of Cedrane Sesquiterpenes via Cascade [5+2] Cycloaddition/Etherification

Cedrane sesquiterpenes possess common tricyclo[5.3.1.0^(1,5)]undecane core structure.The varied oxa-five-membered ring decorating their core structure to form 8-oxa-tetracyclo[7.2.2.0^(1,5).0^(6,13)]tridecane framework,containing six consecutive chiral centers(including two all-carbon quaternary centers and one oxygenated quaternary carbon center),has proven to be a synthetic challenge and a biosynthetic mystery to date.

Walking Cations: Transition-Metal Free Benzyl Cation-Triggered sp^(2) C—H Phosphorylation and Etherification

A novel benzyl cation-triggered site-selective sp^(2) C—H phosphorylation and etherification was developed. This reaction was conducted under the transition metal-free conditions through cation migration via dearomatization. Under the reaction conditions, the derivatives of naphthalenes, benzofurans and benzo[b]thiophenes all can be transformed into the corresponding products in good to excellent yields. It provides a method to construct sp^(2) C—P and sp^(2) C—O bonds as well as a new strategy for benzylic activation-triggered sp^(2) C—H functionalization.

Regioselective etherification of 1,2-O-isopropylidene-4,6-di-O-benzyl myo-inositol

During the etherification of 1,2-O-isopropylidene-4,6-di-O-benzyl myo-inositol, the specific regioselectivity on 3- or 8-hydroxyl group was showed to be determined by the nature of the O-alkylating agents used. As demonstrated by MM and MNDO calculation, the regioselectivity of the reaction mentioned can be rationalized by steric and/or electronic effect.

Concise synthesis of xanthones by the tandem etherification——Acylation of diaryliodonium salts with salicylates

An efficient synthetic method for multi-substituted xanthones was developed. The reaction of diaryliodonium salts and salicylates was employed for the preparation of the xanthones. This method proceeded through an intermolecular etherification-acylation to give target heterocycles in good yields（up to 91%）. Multi-substituted xanthones were gained by shifting the substituent of salicylates or diaryliodonium salts

Surface Properties and Etherification in Microemulsion Systems of Novel Bronsted Acid Surfactants

Novel Bronsted acid-surfactants with different alkyl chains were synthesized via a two-step process, and their surface properties were studied. The critical micelle concentration（cmc）, surface tension at the cmc（γcmc）, and ability of these compounds to lower the surface tension by 0.02 N/re（C20 and pC20） were investigated at 25 and 40 ℃. The molecular architecture of the compounds strongly influenced these physicochemical parameters. The ability of these compounds to lower surface tension was found to be good. Etherification in microemulsions formed by these surfactants as well as dodecylbenzenesulfonic acid（DBSA） was performed; surfactants 3a and 3b were found to be much more efficient than dodecylbanzenesulfonic acid（DBSA）.

Expected and unexpected etherification of 2-per(poly)fluoroethyl 4-substitutedphenol with β-haloethanol

Under different reaction conditions, the expected and unexpected reaction products (of which X-ray crystallographic structure was presented) of etherification of 2-per(poly)fluoroethyl 4-substituted phenol with β-haloethanol can be obtained respectively.

Preparation of a new animal glue binder for foundry use

A new casting binder was prepared based on an animal bone glue. In order to overcome the disadvantages of the animal glue agglomeration at room temperature, an alkaline decomposition process was used, with acrylic acid, ammonium persulfate, and glucose as modifiers of the animal glue to obtain a high strength of binding. In the process of alkaline decomposition, Na OH was used as the catalyst with the addition of 3, 4, 5, 6, 7, 8wt.%, respectively, into 100 g of animal glue and the alkaline decomposition temperature was set for 30, 40, 50, 60, and 70 °C, with an identical decomposition time of 30 min, in order to reduce viscosity of the animal glue and maintain a liquid state at room temperature. The added acrylic acid, ammonium persulfate and glucose were determined through an orthogonal experiment. The experimental results are as fol ows: the optimal amount of NaOH addition is 5wt.%; alkaline decomposition temperature is 50 °C; the optimal weight ratio of three kinds of modifiers to animal glue is acrylic acid : ammonium persulfate : glucose : animal glue = 30:3:15:100; the modification reaction should be performed at 75 °C with a reaction time of 90 min. With the addition of 3% binder to sand, a final tensile strength of about 3.36 MPa and surface tension value of about 25.387 m N·m^(-1) are achieved; the gas evolution at 850 °C is 19 ml·g^(-1) and the residual strength after high temperature(700 ■× 10 min) is 0 MPa. Finally, the new binder was characterized and analyzed by means of element analysis and an IR infrared spectrum.

Effect of Alkali Treatment on the Structure and Catalytic Properties of ZSM-5 Zeolite

Catalytic properties of ZSM-5 zeolite samples pretreated with NaOH solution have been investigated. The samples are characterized by XRD, SEM, chemical analysis, and N2 adsorption. The results indicate that mesopores are created in ZSM-5 crystals under alkali treatment without change the microporous structure and acidic strength of the zeolite, but the crystallinity is greatly decreased under severe treatment. IR indicates that the concentration of silanol is greatly enriched by alkali treatment. The etherification activities of ZSM-5 zeolites are greatly increased by alkali-treatment. The noticeably improved catalytic activity of treated samples is ascribed to the formation of mesopores and greatly enriched silanol group.

Preparation of Carboxymethylcellulose from Waste Paper

We aimed at producing sodium carboxymethylcellulose (CMC) from waste paper cellulose.For this etherification,the raw material was waste paper,the cellulose was initially alkalized with NaOH,the etherifying agent was sodium chloroacetate,and the reaction medium was water or ethanol.The method provided by us,i e,a method for preparing CMC from waste paper,was environment-friendly,could be easily implemented,and could be conveniently applied to make waste paper efficiently used with high profit,and to expand the range of usable raw materials for CMC production.We successfully synthesized CMC and prepared CMC plastic membrane.This practice changes waste into valuables,which is beneficial to our living environment.For preparation of CMC,one of the crucial factors is appropriate pretreatment of the cellulose from waste paper.The pretreatment was done with a self-built hydrolysis method.We experimentally examined the effects of the mass ratios of reactants,reaction temperature,time,and reaction environment of homogeneous or heterogeneous on CMC yield.The innovative points of this research could be stated as follows:the reaction activity of cellulose was improved by pre-hydrolysis;synthesizing CMC with cellulose from waste paper changes waste into valuables is beneficial to our living environment;and a freezing treatment for the cellulose-alkali mixture was innovatively added.The effects were exhibited by a desired final conversion efficiency.