Wet carbon-based solid acid/NaNO_3 as a mild and efficient reagent for nitration of aromatic compound under solvent free conditions

Nitro aromatic compound can be obtained in high yields via nitration of aromatic compound with wet carbon-based solid acid and NaNO_3 under solvent free oxidation at room temperature.

Wet carbon-based solid acid/potassium permanganate as an efficient heterogeneous reagents for oxidation of alcohols under mild conditions

Wet carbon-based solid acid and potassium permanganate were used as new reagents for oxidation of alcohols to their corresponding aldehydes and ketones in heterogeneous mixtures. The experiments were done moderately at mild condition and high yields in suitable times were obtained.

Reaction Kinetics of Biodiesel Synthesis from Waste Oil Using a Carbon-based Solid Acid Catalyst

有基于碳的稳固的酸催化剂的同时的 transesterification 和酯化作用的动力学被学习。二稳固的酸催化剂被使碳化的蔬菜油沥青和石油沥青的 sulfonation 准备。这些催化剂根据元素的分析，酸味地点集中， Brunauer-Emmett-Teller (赌注) 表面区域和毛孔尺寸被描绘。有二催化剂的运动参数被决定，并且反应系统能被描述为假同类的催化反应。所有前面、反向的反应跟随第二顺序动力学。从运动方程的计算集中价值在对试验性的价值的好同意。

Preparation of a Carbon-Based Solid Acid with High Acid Density via a Novel Method

A carbon-based solid acid with high acid density was successfully prepared using camphor tree branches as raw materials through a novel method including dilute sulfuric acid activation, carbonization in refluxing solvent and sulfonation. Physical characterization was detected to show that the carbon-based acid is amorphous with polycyclic aromatic carbon sheets attached plentiful -OH, -COOH, and -SO3H groups. The sulfonic acid density and total acid density of it reached 2.05 mmol·g-1 and 5.63 mmol·g-1, respectively by acid-base titration. As a solid acid catalyst, it showed excellent performance in the ketalization of cyclohexanone with glycol.

Carbon-Based Solid Acid as An Efficient and Reusable Catalyst for One-Pot Synthesis of Tetrasubstituted Imidazoles under Solvent-Free Conditions

Carbon-based solid acid catalyst was found to be highly efficient, eco-friendly and recyclable heterogeneous catalyst for the multicomponent reaction of benzil, aromatic aldehyde, primary amine and ammonium acetate, giving rise to 1,2,4,5-tetrasubstituted imidazoles in good to excellent yields. The present methodology offers several advantages, such as high yields, short reaction time, mild reaction condition and a recyclable catalyst with a very easy work up.

Superior resistance to alkali metal potassium of vanadium-based NH_(3)-SCR catalyst promoted by the solid superacid SO_(4)^(2-)-TiO_(2)

The significant decrease of acid sites caused by alkali metal poisoning is the major factor in the deactivation of commercial V_(2)O_(5)-WO_(3)/TiO_(2)NH_(3)-SCR catalysts.In this work,the solid superacid SO_(4)^(2-)-TiO_(2) modified by sulfate radicals,was selected as the catalyst support,which showed superior potassium resistance.The physicochemical properties and K-poisoning resistance of the V_(2)O_(5)-WO_(3)/SO_(4)^(2-)-TiO_(2)(VWSTi) catalyst were carried out by XRD,BET,H2-TPR,NH3-TPD,XPS,in situ DRIFTS and TG.The results pointed out that the introduction of SO_(4)^(2-)significantly increased the NH3-SCR catalytic activity at high temperatures,with an exceptionally high NO_(x) conversion over 90% between 275℃ and 500℃.When 0.5%(mass) K_(2)O was doped on the catalysts,the catalytic performance of the traditional V_(2)O_(5)-WO_(3)/TiO_(2)(VWTi) catalyst decreased significantly,while the VWSTi catalyst could still maintain a NOxconversion over 90%in the range of 300–500℃.The characterizations suggested that the support of SO_(4)^(2-)-TiO_(2) greatly increased the number of acidic sites,thereby enhancing the adsorption capacity of the reactant NH_(3).The results above demonstrated a potential approach to achieve superior potassium resistance for NH3-SCR catalysts using solid superacid.

Preparation, Characterization and Catalytic Activity of Alkyl Benzene Sulfonic Acid Carbon-Based Acid Catalyst

Based on starch and series of alkyl benzene sulfonic acid as the materials, a novel carbon-based solid acid catalyst is synthesized using hydrothermal method. This catalyst exhibits much higher catalytic activity in the reaction of esterification of Mono-fatty alcohol polyoxyethylene maleate esters with 1,4-butanediol. The structure of carbon-based solid acid catalyst was charactered by IR and XRD, characterizations showed that this catalyst exhibited high –SO3H loading. Reusability of the carbon-based solid acid catalyst for esterification showed that after recycling five times the activity remained unchanged.

Chemiluminescence Determination of Benzoic Acid Using A Solid-Phase Verdigris Reactor

A new chemiluminescence flow system has been developed for sequential determina-tion of benzoic acid based on the reaction of the compound with copper carbonate entrapped in a solid-phase reactor. It was found that the unsaturated complex of Cu(II) and benzoic acid (1:1) has strong catalytic effect on the luminol-H2O2 chemiluminescence reaction. The calibration graph is linear over the range of 0.025 ~ 60 g/mL of benzoic acid, with a relative standard deviation of less than 3.0 %, and the detection limit is 0.01礸穖L-1. The proposed method was applied to the determination of benzoic acid content in different pharmaceutical formulations.

Preparation and Catalytic Application of Novel Water Tolerant Solid Acid Catalysts of Zirconium Sulfate/HZSM-5

Esterification of acrylic acid（AA） to produce AA esters has widespread application in the chemical industry. A series of water tolerant solid acid catalysts was prepared, and characterized by XRD, nitrogen adsorption, TGA-DTA, XPS, and ammonia adsorption FTIR. The effects of Si/Al ratio, zirconium sulfate（ZS） loading on HZSM-5 and calcination temperature on the esterification were investigated. When 20% （mass fraction） ZS is loaded on HZSM-5, the conversion of AA reaches 100%. XRD analysis indicates that ZS is highly dispersed on HZSM-5 because no crystalline structure assigned to ZS is found. Catalytic activity and hydrophobicity of ZS supported on HZSM-5 are higher compared with those of parent ZS or HZSM-5. Results show that this kind of novel catalysts is an efficient water tolerant solid acid catalyst for esterification reactions.

Hydrolysis of mechanically pre-treated cellulose catalyzed by solid acid SO4^2--TiO2 in water–ethanol solvent

An efficient catalyst SO4^2--TiO2(ST) from industrial metatitanic acid has been successfully prepared to catalyze hydrolysis of ball-milling cellulose. The results show that the highest catalytic efficiency is obtained for ST calcined at 450 ℃(ST-450) with the yield of 21.8% glucose, 13.0% 5-HMF and 4.2% furfural at 200 ℃ for30 min. The ball milling of cellulose and solid acid catalyst significantly enhances the cellulose hydrolysis. The high Lewis to Bronsted acid sites ratio for ST-450 induced by bidentate ligands between SO4^2-and TiO2 benefits high organics yield, and high total acid sites contribute to the high cellulose conversion. The large pore volume of 0.29 cm^3·g^-1 and appropriate pore size of 7.35 nm of ST-450 also contribute to the high performance. High reaction temperature over 200 ℃ exhibits negative effect on glucose and 5-HMF yield due to undesired side reactions, while furfural product is stable in the reaction system. The bidentate ligands between SO4^2-and TiO2 are considered as active acid sites for cellulose hydrolysis in water–ethanol solvents.

Solid components and acid buffering capacity of soils in South China

The effects of soil solid components on soil sensitivity to acid deposition by sequential extraction method were studied. A multiple regression equation of soil sensitivity was set up on the basis of stepwise regression analysis. The results showed that organic matter expressed dual effects that were decided by soil original pH value and exchangeable cation composition on acid buffering reactions. The hydrolysis of activated oxides was a very important proton buffering reaction when in low pH situation. The crystalline oxides also played a role in the buffering reactions, but the role was restricted by the rate of activation of oxides. Meanwhile, the results by stepwise analysis showed that factors that had significant effect on soil acid buffering capacity were content of montmorillite, soil original pH value, Al 0, Mn 0 and CEC in decreasing order. Finally, sixteen soils were classified into four types of sensitive with single index cluster and multiple fuzzy cluster analysis respectively.

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.

Acid Mine Drainage and Heavy Metal Pollution from Solid Waste in the Tongling Mines, China

Based on investigation of the characteristics of solid waste of two different mines, the Fenghuangshan copper mine and the Xinqiao pyrite mine in Tongling, Anhui province in central-east China, the possibility and the differences of acid mine drainage （AMD） of the railings and the waste rocks are discussed, and the modes of occurrence of heavy metal elements in the mine solid waste are also studied. The Fenghuangshan copper mine hardly produces AMD, whereas the Xinqiao pyrite mine does and there are also differences in the modes of occurrence of heavy metal elements in the railings. For the former, toxic heavy metals such as Cu, Pb, Zn, Cd, As and Hg exist mostly in the slag mode, as compared to the latter, where the deoxidization mode has a much higher content, indicating that large amounts minerals in the waste rocks have begun to oxidize at the earth surface. AMD is proved to promote the migration and spread of the heavy metals in mining waste rocks and lead to environmental pollution of the surroundings of the mine area.

Preparation of solid acid catalyst SO4^2-/TiO2/γ-Al2O3 for esterification: A study on catalytic reaction mechanism and kinetics

In this work, a series of SO4^2-/TiO2/γ-Al2O3 solid acid catalysts were synthesized by impregnation method, in which nano-TiO2 was prepared by sol–gel method, and then the nano-TiO2 sol was loaded on porous γ-Al2O3 supporter through impregnation. The structure and property of catalyst were characterized by XRD, N2-BET,SEM, TEM, XPS, NH3-TPD, Pyridine-IR and FT-IR. In addition, the catalyst of chelate bidentate coordination acid center model was established. The catalytic performance test was carried out in the esterification of n-butyl alcohol with lauric acid and the catalyst showed excellent activity. The experimental results showed that the medium strength acid sites were more dominant active sites than the strong and weak acid sites for the rapid esterification reaction. Its kinetic behaviors and activation energy were studied for the esterification under the catalytic reaction condition.

CATIONIC RING-OPENING POLYMERIZATION OF TETRAHYDROFURAN WITH KEGGIN-TYPE HETEROPOLYCOMPOUNDS AS SOLID ACID CATALYSTS

Three Keggin-type heteropolyanions, namely H3PMo12O40-13H2O, （NH4）3PMo12O40·4H2O and H3PW12O40·13H2O were prepared and tested in the ring-opening polymerization reaction of tetrahydrofuran. The effects of the counter-cation （H＋, NH4＋） and the peripheral atoms （Mo, W） on the polymerization were investigated. It has been found that when the protons of H3PMo12O40·13H2O were replaced by the ammonium cations the polymerization rate decreased dramatically. Whereas, when the peripheral atoms （Mo） were replaced by their homologous （W）, the polymerization rate increased twofold. As for the viscosity average molecular weight （My） of polymer products, it was found that the high molecular weight （7930） was obtained by using H3PW12O40·13H2O. The molecular weight （My） obtained by H3PMo12O40·13H2O and （NH4）H3PMo12O40·13H2O was 6470 and 6810, respectively.

Acetalization of carbonyl compounds with 2,2,4-trimethyl-1,3-pentanedio catalyzed by novel carbon based solid acid catalyst

The synthesis of 2, 4-diisopropyl-5,5-dimethy1- 1.3-dioxane through the acetalization of isobutyraldehyde with 2, 2, 4-trimethy1-1,3-pentanediol （TMPD） catalyzed by the novel carbon based acid was first carried out. High conversion （≥98%） and specific selectivity were obtained using the novel carbon based acid, which kept high activity after it was reused 5 times. Moreover. the catalyst could be used to catalyze the acetalization and ketalization of different aldehydes and ketones with superior yield. The yield of several products was over 90%. The novel heterogeneous catalyst has the distinct advantages of high activity, strikingly simple workup procedure, non-pollution, and reusability, which will contribute to the success of the green process greatly.

Glucose-derived solid acids and their stability enhancement for upgrading biodiesel via esterification

Utilization of biomass-derived materials or chemicals plays a significant role in reducing the dependence of unsustainable resources of petroleum and coal. A series of sulfonated glucose-derived solid acids(SGSAs) were developed in this study through a one-step method. These catalysts were characterized by XRD, FT-IR, SEM,and BET to determine their physiochemical properties, and their acid content was measured by acid–base titration. The catalytic performances of SGSA catalysts were evaluated in two esterification reactions: propionic acid or oleic acid with methanol(a typical reaction to upgrade biodiesel). Conversion of oleic acid and selectivity of methyl oleate can reach as high as 93.3% and 94.7% respectively over SGSA-6, which has the highest -SO3 H density. Moreover, regeneration of spent catalysts by sulfuric acid solution can significantly enhance their stability and reusability.

Fries Rearrangement of Phenyl Acetate over Solid Acid Catalyst

A silica-supported zirconium based solid acid (ZS) has been used as catalyst for the Fries rearrangement of phenyl acetate (PA). The catalyst showed a higher PA conversion activity and a much higher selectivity for o-hydroxyacetophenone (o-HAP) than for strongly acidic zeolite catalysts. The supported catalyst was characterized by XRD, IR, XPS, pyridine-TPD and the surface area measurements. The catalytic properties were influenced significantly by pretreatment temperature.

ENCAPSULATION OF STRONG SOLID ACID NANOPARTICLES IN MESOPOROUS CHANNEL HOSTS

Mesoporous molecular sieve with Al-promoted sulfated rirconia (SZA) based strong solid acid nano-particles within its mesoporous channels was synthesized by using a one-step incipient wetness impregnation method with zirconium sulfate and aluminum sulfate as the precursors. The assemblies of SZA/MCM-41 were obtained by thermal decomposition of the precursors in air.The resultant composite was characterized with various techniques such as nitrogen physisorption, X-ray diffraction, SEM and TEM. It was shown that the well-ordered channels of MCM-41 arranged in hexagonal arrays as well as the hollow tubular morphology was retained. The strong solid acid nanoparticles were isolated born each other and highly, dispersed in the channels. Nitrogen sorption showed the expected decrease in pore volume. The catalytic activity of SZA/MCM-41 composite in the isomerization of n-butane was dramatically improved in comparison to bulk SZA or SZA/silica.

Microwave-induced synthesis and characterization of nanometer Ce_(0.5)Zr_(0.5)O_2 solid solution for the acidic catalytic reaction

Ce0.5Zr0.5O2 solid solution was successfully synthesized using cerium nitrate, zirconium nitrate, and urea as raw materials by the microwave irradiation method and characterized by X-ray diffraction, fluorescence spectrum, transmission electron microscopy, and infrared spectrum. Its acid catalytic activity was evaluated in the esterification reaction of acetic acid and n-butyl alcohol. The results show that Ce0.5Zr0.5O2 solid solution has cubic fluorite structure, and its particle diameter is in the nanometer scale. As a sort of solid acid, it possesses a higher acid catalytic activity and can be easily separated from reaction liquids. It can be used for several times, and basically, its activity keeps constant. The proton acid sites and Lewis acid sites exist in the structure of Ce0.5Zr0.5O2 solid solution.