Ca-Al Hydrotalcites as Catalysts for Methanolysis and Ethanolysis of Soybean Oil

The use of heterogeneous catalysts in the transesterification reaction of vegetable oils has getting emphasis in recent years, mainly by the alternative of obtaining clean fuel derived from renewable sources. Metal oxide such as MgO or CaO, supported ones like ?and zeolites are often applied in transesterification process. Among them, hydrotalcite has shown potential as catalysts on this reaction due to their physicochemical properties, such as: thermal stability, porosity, specific surface area, memory effect, basicity, acidity and anion exchange capacity. This work studies the catalytic performance of the calcium and aluminum based hydrotalcite in the transesterification reaction of soybean oil in methanol and ethanol. The hydrotalcite samples treated at 450?C were impregnated with KOH. The efficiency of impregnated and non- impregnated samples was compared and the non-impregnated one showed the best performance. This property was attributed to the higher availability of active sites used in the transesterification process.

The NO_xStorage and Desorption Activity of Mg/Al/Cu-NH₃·H₂O Hydrotalcites at Low Temperature

Ammonium containing catalyst Mg/Al/Cu-NH3·H2O hydrotalcite (HT) is prepared via co-precipitation, which is effective for NOx storage under 160℃. XRD and FT-IR are employed to characterize its structure and show that ammonium is successfully incorporated into HT. Meanwhile, the HT still retains the typical structure of hydrotalcite-like compounds. NOx storage activity tests indicate Mg/Al/Cu-NH3·H2O HT shows the significant NOx removal activity at 156℃ with a little Oxygen existence. TGA and DTG reveal the reaction of the released ammonium with NOx and storage NOx as nitrates will be responsible for the high NOx storage activity. Additionally, the temperature programmed desorption test of NOx adsorbed sample under 175℃ proves NOx is stored successfully into Mg/Al/Cu-NH3·H2O HT further.

Aqueous-phase catalytic hydrogenation of furfural to cyclopentanol over Cu-Mg-Al hydrotalcites derived catalysts:Model reaction for upgrading of bio-oil

A series of Cu-Mg-Al hydrotalcites derived oxides with a(Cu+Mg)/Al mole ratio of 3 and varied Cu/Mg mole ratio(from 0.07 to 0.30) were prepared by co-precipitation and calcination methods, then they were introduced to the hydrogenation of furfural in aqueous-phase. Effects of Cu/Mg mole ratio, reaction temperature, initial hydrogen pressure, reaction time and catalyst amount on the conversion rate of furfural as well as the selectivity toward desired product cyclopentanol were systematically investigated. The conversion of furfural over calcined hydrotalcite catalyst with a Cu/Mg mole ratio of 0.2 was up to 98.5% when the reaction was carried out under 140 ?C and the initial hydrogen pressure of 4 MPa for 10 h, while the selectivity toward cyclopentanol was up to 94.8%. The catalysts were characterized by XRD and SEM. XRD diffraction of all the samples showed characteristic pattern of hydrotalcite with varied peak intensity as a result of different Cu content. The catalytic activity was improved gradually with the increase of Cu component in the hydrotalcite.

Influence of the preparation method on the catalytic activity of Mg-Al hydrotalcites as solid base catalysts

Mg-Al hydrotalcites were synthesized using different preparation methods(a co-precipitation method, a urea method, and a simple one) to analyze their effect on the catalytic activity of these solid base catalysts. The method strongly affected the structure of their layers(e.g., the growth and stacking of the layers, and the type of intercalated anions) and, accordingly, their catalytic activity. The Mg-Al hydrotalcite prepared by co-precipitation showed the best catalytic performance in the isomerization of glucose into fructose, due to the small crystallite size and sand rose morphology enhancing the exposure of surface active sites to reactants.

Preparation, Characterization of Hydrotalcites and the Catalytic Properties in Synthesis of o-Phenylphenol over Pt/CHT

Mg/Al mixed oxides with molar ratios of 2_6 of Mg to Al used as supports for platinum catalysts were obtained by the thermal decomposition method. The effect of the composition of the mixed oxides on the physicochemical properties was studied by TPD, nitrogen sorption, XRD and TG-DTA characterization methods. The synthesis of o-phenylphenol(OPP) from a dimer(obtained from cyclohexanone condensation) was investigated over Pt/CHT catalysts and compared with those over Pt/MgO and Pt/Al 2O 3 catalysts. These catalysts show a high activity and selectivity for OPP, with a conversion reaching 93.8% and a selectivity reaching 87.9% in some experiments. For Pt/CHTx catalysts, the calcined hydrotalcites exhibited strong base sites, which were necessary to catalyze the synthesis of OPP.

“Intelligent” reforming catalysts:Trace noble metal-doped Ni/Mg(Al)O derived from hydrotalcites

Trace amounts of noble metal-doped Ni/Mg（AI）O catalysts were pre- pared starting from Mg-Al hydrotalcites （HTs） and tested in daily start-up and shut-down （DSS） operation of steam reforming （SR） of methane or partial oxidation （PO） of propane. Although Ni/Mg（Al）O catalysts prepared from Mg（Ni）-Al HT exhibited high and stable activity in stationary SR, PO and dry reforming of methane and propane, the Ni/Mg（Al）O catalysts were drastically deactivated due to Ni oxidation by steam as purge gas when they were applied in DSS SR of methane. Such deactivation was effectively suppressed by doping trace amounts of noble metal on the catalysts by using a ＂memory effect＂ of HTs. Moreover, the noble metal-doped Ni/Mg（Al）O catalysts exhibited ＂intelligent＂ catalytic behaviors, i.e., self-activation and self-regenerative activity, leading to high and sustainable activity during DSS operation. Pt was the most effective among noble metals tested. The self-activation occurred by the reduction of Ni2＋ in Mg（Ni,Al）O periclase to Ni^0 assisted by hydrogen spillover from Pt （or Pt-Ni alloy）. The self-regenerative activity was accomplished by self-redispersion of active Ni^0 particles due to a reversible reductionoxidation movement of Ni between the outside and the inside of the Mg（Al）O periclase crystal; surface Ni^0 was oxidized to Ni2＋ by steam and incorporated into Mg（Ni2＋,Al）O periclase, whereas the Ni2＋ in the periclase was reduced to Ni^0 by the hydrogen spillover and appeared as the fine Ni^0 particles on the catalyst surface. Further a ＂green＂ preparation of the Pt/Ni/[Mg3.sAl]O catalysts was accomplished starting from commercial Mg3.5-AI HT by calcination, followed by sequential impregnation of Ni and Pt.

MgFe hydrotalcites-derived layered structure iron molybdenum sulfide catalysts for eugenol hydrodeoxygenation to produce phenolic chemicals

Hydrodeoxygenation（HDO） is an effective alternative to produce value-added chemicals and liquid fuels by removing oxygen from lignin-derived compounds. Sulfide catalysts have been proved to have good activity for the HDO and particularly high selectivity to phenolic products. Herein, we presented a novel way to prepare the layered structure sulfide catalysts（MgFeMo-S） derived from MgFe hydrotalcites via the intercalation of Mo in consideration of the memory effect of the calcined hydrotalcite. By varying the Mg/Fe mole ratio, a series of MgFeMo-S catalysts were successfully prepared and characterized by nitrogen adsorption/desorption isotherms, X-ray diffraction（XRD）, transmission electron microscopy（TEM）,and inductively coupled plasma optical emission spectrometer（ICP-OES）. The characterization results indicated that the MgFeMo-S catalyst has retained the unique layered structure, which can facilitate uniform dispersion of the MoS2 species on both the surface and interlayer of the catalysts. For the HDO of eugenol, the Mg1Fe2Mo-S catalysts exhibited the best HDO activity among all the catalysts due to its higher active metal contents and larger pore size. The HDO conversion was 99.6% and the yield of phenolics was 63.7%, under 5 MPa initial H2 pressure（measured at RT） at 300 ℃ for 3 h. More importantly,MoS2 species deposited on the interlayer galleries in the MgFeMo-S catalysts resulted in dramatically superior HDO activity to MoS2/Mg1Fe2-S catalyst. Based on the mechanism investigation for eugenol, the HDO reaction route of eugenol under sulfide catalytic system has been proposed for the first time. Further applicability of the catalyst on HDO of more lignin-derived compounds was operated, which showed good HDO activity and selectivity to produce aromatic products.

Structural Analysis of Magnesium-Aluminium Hydrotalcites Modified with Iron III Obtained by Hydroxide Precipitation Method

Hydrotalcite-type anionic clays are a group of important materials used in adsorption processes, mainly for organic pollutants removal due the layered double hydroxide structure. The layer-interlayer interactions provide a structural memory even after dehydration and dehydroxylation process, since a very stable interlayer anions are part of material composition, like the carbonate one. A limited numbers of trivalent modifier cations can replace the aluminium cation due the ionic radii mismatch or oxidation state restrictions. Transition metal cations can replace the aluminium one in octahedral site of hydroxide lamellas in order to improve the adsorptive behaviors. In this work, we have investigate three compositions of carbonated magnesium-aluminium hydrotalcite with dif-ferent iron (III) contents through the co-precipitation method at pH 11 and aging step at 60°C for 6 hours. Thermal analysis was performed aiming the determination of the hydration water and hydroxyl amounts in dried precipitate samples, taking in account the results obtained for X-ray diffractometry, infrared spectroscopy, and nitrogen adsorption-desorption characterization for several thermally treated samples. All of synthesized samples showed high surface areas, even for high temperature of thermal treatment. The co-substitution with iron (III) reduced the temperature of dehydration and dehydroxylation process, but the co-substitution at 5 mol% provides other desirables characteristics, like a more amount of rhombohedral HDL phase and higher porosity, even after the thermal treatment at 500°C for 4 hours. This result makes that composition very applicable as a reusable adsorbent material in order to removal several types of micro-pollutant compounds in aqueous media.

Efficient Removal of Phosphate from Aqueous Solutions Using Corundum-hollow-spheres Supported Caclined Hydrotalcite Porous Thin Films

Phosphate was removed from aqueous environment by corundum-hollow-spheres supported caclined hydrotalcite (cHT) thin films. Mg-Al-CO3 hydrotalcite (HT) thin films were deposited on corundumhollow-sphere substrates by hydrothermal homogeneous precipitation at 120℃for 30-240 min and cHT thin films were obtained by annealing of the HT thin films at 500℃for 180 min. Their crystal phase, morphology and microstructure were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).The results show that homogeneous, well-crystallized and hierarchical flower-like thin films were deposited firmly on the surface of the corundum. The mechanism of nucleation and growth of the HT thin films was fitted well with the anion coordination polyhedron growth unit model. To determine the absorption of phosphate by this adsorbent, different bed depth (10-30 cm) and flow rate (1.0-3.0 m L/min) were examined by column experiments. The highest removal efficiency of phosphate amounted to 98.5%under optimum condition (pH=7.2). The adsorption capacity increased as the bed depth increased and decreased as the flow rate increased.

Effect and Mechanism of Rare Earth Hydrotalcite Inhibiting Coal Spontaneous Combustion

A hydrotalcite(layered double hydroxide, LDH) inhibitor which is suitable for the whole process of coal spontaneous combustion and a LDH inhibitor containing rare earth lanthanum elements were prepared. The inhibition effect and mechanism were analyzed by scanning electron microscopy(SEM),X-ray diffraction(XRD), thermal performance analysis, in-situ diffuse reflectance infrared spectroscopy and temperature-programmed experiment. The results have shown that the inhibitor containing lanthanum can play a good inhibitory role in every stage of coal oxidation. During the slow oxidation of coal samples, the inhibitor containing lanthanum ions can slow down the oxidation process of coal and increase the initial temperature of coal spontaneous combustion. At the same time, because the hydroxyl groups in LDHs are connected with-COO-groups on the coal surface through hydrogen bonds, the stability of coal is improved. With the increase of temperature, LDHs can remove interlayer water molecules and reduce the surface temperature of coal. CO release rate of coal samples decreases significantly after adding inhibitor containing lanthanum element, and the maximum inhibition rate of the inhibitor is 58.1%.

Structure and base properties of calcined hydrotalcites

Five hydrotalcites with Mg/Al molar ratio range of 3–15 were prepared. The structure and basicity of Mg-Al mixed oxides (Mg(Al)O) transformed from hydrotalcites were investigated by TPD, XPS, XRD, FT-IR and NMR techniques. The results of elemental analysis and XPS indicate that Al is enriched in the surface regions of Mg(Al)O, and its amount increases with the Mg/Al molar do and the Calcination temperature. 27Al-MAS-NMR results show that Al exists in two chemical environments: tetrahedral aluminium (Al(t)) and octahedral aluminium (Al(o)) in Mg(Al)O. The amount of Al(t) increases with the Mg/Al molar ratio and the calcination temperature. It is assumed that A(t) may be mainly from the surface Al. Temperature-programmed desorption (IPD) of CO2 shows that the number of basic sites of Mg(Al)0 samples increases with the Mg/Al molar ratio, and the maximum number of basic sites is obtained for hydrotalcite calcined at 773 K. Infrared spectra of adsorbed CO2 and B(OCH3)3 reveal that there are two kinds of basic sites: weak basic OH? sites and strong basic O2 sites on the Mg(Al)0 samples, the base strength depends on the Mg/Al molar do and calcination temperature.

N-doped CoAl oxides from hydrotalcites with enhanced oxygen vacancies for excellent low-temperature propane oxidation

A series of nitrogen-doped CoAlO(N-CoAlO)were constructed by a hydrothermal route combined with a controllable NH_(3) treatment strategy.The effects of NH_(3) treatment on the physico-chemical properties and oxidation activities of N-Co AlO catalysts were investigated.In comparison to CoAlO,a smallest content decrease in surface Co^(3+)(serving as active sites)while a largest increased amount of surface Co^(2+)(contributing to oxygen species)are obtained over N-Co AlO/4h among the N-CoAlO catalysts.Meanwhile,a maximum N doping is found over N-CoAlO/4h.As a result,N-CoAlO/4h(under NH_(3) treatment at 400℃ for 4 hr)with rich oxygen vacancies shows optimal catalytic activity,with a T90(the temperature required to reach a 90% conversion of propane)at 266℃.The more oxygen vacancies are caused by the co-operative effects of N doping and suitable reduction of Co^(3+) for NCoAlO/4h,leading to an enhanced oxygen mobility,which in turn promotes C_(3)H_(8) total oxidation activity dominated by Langmuir-Hinshelwood mechanism.Moreover,in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTs)analysis shows that N doping facilities the decomposition of intermediate species(propylene and formate)into CO_(2)over the catalyst surface of N-CoAlO/4h more easily.Our reported design in this work will provide a promising way to develop abundant oxygen vacancies of Co-based catalysts derived from hydrotalcites by a simple NH_(3) treatment.

Graphene oxide/hydrotalcite modified polyethersulfone nanohybrid membrane for the treatment of lead ion from battery industrial effluent

In the present study, polyethersulfone based nanohybrid membranes were effectively fabricated by incorporating graphene oxide(GO) and hydrotalcite(HT) nanosheets into the membrane structure. HT was prepared to overcome the irreversible agglomeration behavior of GO at a high concentration which affects the performance of the membranes. In particular, the shedding of HT in formamide provides a two-dimensional nanosheet with a higher positive charge density to prevent the restacking of GO nanosheets. Here, exfoliated GO and HT with different combinations(1:1, 1:2 and 1:3) were infused in the membrane matrix to treat lead-acid battery effluent effectively. Finally, the hybrid membranes were characterized for hydrophilicity, mechanical strength and pure water flux. In combination with the superior properties of GO and HT, the prepared hybrid membranes can be used as effectively to improve the separation and permeation performance. The phase inversion process eliminated the leaching of nanoparticles from the membrane matrix. The reusability of the hybrid membrane was achieved using0.1 mol·L^(-1)NaOH solution and reused without significant reduction in lead removal efficiency. The cost analysis of the membrane was also estimated from the lab study. Therefore, the present study suggested the selective and sustainable treatment of lead from a real-life effluent.

Mg/Al complex oxides-A new type of solid basic catalyst for epoxidation

Hydrotalcites known as anionic clays are found in nature. Hydrotalcites, hydrotalcite-like compounds, and calcined hydrotalcites (as mixed or complex oxides) as highly active, selective catalysts play an important role in many base/catalyzed reactions. Mg/Al hydrotalcite (MAH) as precursor was used to prepare Mg/Al metal complex oxides (MAO), used as epoxidation catalysts in the current research. In this paper, some primary physical and catalytic properties of MAH and MAO were investigated. The results indicated that the qualified MAH (Mg/Al mol ratio of 3) can be achieved when the suspension was crystallized under 80°C for 16h, and after being filtered, dried at 100 °C for 5h in a oven. MAO was prepared by calcining MAH for 4h in a muffle furnace, and calcination temperature was determined to be 500 °C by a differential scanning calorimeter (DSC). Crystal structure and parameters of MAH and MAO were characterized by X/ray diffraction (XRD), good crystal structure was observed and typical peaks of MAH were detected when 2θ was at 11.5 (003), 23.0 (006), 35.0 (009), and 61.0 (110), respectively. The morphology of calcined precursor, i.e. MAO, was investigated with scanning electron microscopy (SEM);the finer lamellar structure and smaller average size of 3μm was observed. Molding research was performed and confirmed by SEM, the results indicated that the surface bulge and cavity with size of several micrometers were increased, which simultaneously suggested the increasing of specific surface area. The catalytic activity of molding MAO was finally examined by using octanol as starting reagent and ethylene oxide as reactant, and narrower molecular distribution was observed comparing with the traditional catalyst-KOH.

Hydrotalcite的合成与应用

介绍了以碱式碳酸镁、铝酸碱金属盐为原料合成Hydrotalcite的方法,并论述了其作为制酸剂和抗胃脘剂、聚烯烃树脂的中和剂、PVC热稳定剂的应用。

Adsorption removal of thiocyanate from aqueous solution by calcined hydrotalcite

A hydrotalcite with Mg/AI molar ratio 2 was prepared by co-precipitation method and was characterized by XRD, TG/DTA, Zeta potential and BET surface area. The hydrotalcite was calcined at 500℃, with the dehydration from interlayer, the dehydroxilation from the brucite-like layer and the decomposition of carbonate successively, transformed into the mixed oxide type. The removal of thiocyanate from aqueous solution by using the original hydrotalcite and calcined hydrotalcite （HTC-500） was investigated. The results showed that the thiocyanate adsorption capacity of calcined hydrotalcite was much higher than that of the original form. Calcined hydrotalcite was particularly effective at removing thiocyanate, and that the effective range of pH for the thiocyanate removal are between 5.5-10.0. The experimental data of thiocyanate removal fit nicely with Langmuir isotherm, and the saturated adsorption uptake was 96.2 mg SCN-/g HTC-500. The adsorption of thiocyanate by calcined hydrotalcite follows first-order kinetics. And the intercalation to the structure recovery for calcined hydrotalcite. But the presence of additional anions could affect the adsorption behavior of thiocyanate.

Effects of hydrotalcite combined with esomeprazole on gastric ulcer healing quality: A clinical observation study

AIM To evaluate the effects of hydrotalcite combined with esomeprazole on gastric ulcer healing quality. METHODS Forty-eight patients diagnosed with gastric ulcer between June 2014 and February 2016 were randomly alloc at e d t o t he c ombinat ion t he r apy gr oup or monotherapy group. The former received hydrotalcite combined with esomeprazole, and the latter received esomeprazole alone, for 8 wk. Twenty-four healthy volunteers were recruited and acted as the healthy control group. Endoscopic ulcer healing was observed using white light endoscopy and narrow band imaging magnifying endoscopy. The composition of collagen fibers, amount of collagen deposition, expression of factor Ⅷ and TGF-β1, and hydroxyproline content were analyzed by Masson staining, immunohistochemistry, immunofluorescent imaging and ELISA. RESULTS Following treatment, changes in the gastric microvascular network were statistically different between the combination therapy group and the monotherapy group(P < 0.05). There were significant differences(P < 0.05) in collagen deposition, expression level of Factor Ⅷ and TGF-β1, and hydroxyproline content in the two treatment groups compared with the healthy control group. These parameters in the combination therapy group were significantly higher than in the monotherapy group(P < 0.05). The ratio of collagen?Ⅰ?to collagen Ⅲ was statistically different among the three groups, and was significantly higher in the combination therapy group than in the monotherapy group(P < 0.05). CONCLUSION Hydrotalcite combined with esomeprazole is superior to esomeprazole alone in improving gastric ulcer healing quality in terms of improving microvascular morphology, degree of structure maturity and function of regenerated mucosa.

Unique catalysis of Ni-Al hydrotalcite derived catalyst in CO_2 methanation: cooperative effect between Ni nanoparticles and a basic support

Ni-Al hydrotalcite derived catalyst （Ni-Al2O3-HT） exhibited a narrow Ni particle-size distribution with an average particle size of 4.0 nm. Methanation of CO2 over this catalyst initiated at 225℃ and reached 82.5% CO2 conversion with 99.5% CH4 selectivity at 350℃, which was much better than its impregnated counterpart. Characterizations by means of CO2 microcalorimetry and 27 Al NMR indicated that large amount of strong basic sites existed on Ni-Al2O3-HT, originated from the formation of Ni-O-Al structure. The existence of strong basic sites facilitated the activation of CO2 and consequently promoted the activity. The combination of highly dispersed Ni with strong basic support led to its unique and high efficiency for this reaction. Keywords

Tuning the base properties of Mg–Al hydrotalcite catalysts using their memory effect

Herein,the relationship between the structure and base properties of Mg–Al hydrotalcite catalysts was comprehensively investigated in relation to heat treatment and rehydration processes,which are well known as memory effects of hydrotalcite.The structure of Mg–Al hydrotalcites changed from layered double hydroxide(LDH)to mixed metal oxide and subsequently to a spinel structure during heat treatment,and it was returned from mixed metal oxide to a LDH structure by rehydration.Based on various characterizations,we successfully proposed a detailed mechanism of memory effect.We also confirmed that the Mg–Al hydrotalcites had weak or strong base sites and that their base properties could be systematically tuned by heat treatment and rehydration.The prepared Mg–Al hydrotalcites were applied to a model reaction,isomerization of glucose to fructose,as base catalysts.Among the catalysts tested,the rehydrated Mg–Al hydrotalcite efficiently produced fructose due to its appropriate base and structure properties.We finally concluded that the base sites of Mg–Al hydrotalcites can be designed as desired by heat treatment and rehydration.Moreover,through systematic design of the base sites of Mg–Al hydrotalcites,these can be promising catalysts for various heterogeneous reactions over base catalysts,giving excellent catalytic performances.

Structural Evolvement of Heating Treatment of Mg/AI-LDH and Preparation of Mineral Mesoporous Materials

Although hydrotalcite, or layered double hydroxides （LDHs）, is not a common mineral, it is an important material that can be easily synthesized in laboratory. In this study, structural evolvement and BET surface area changes of heat treated Mg/AI-LDH is evaluated by XRD, TEM and N2-BET analyses. The results indicate that the magnesium-aluminum LDH with carbonate as interlayer anion, periclase-like oxides was formed at temperatures of 400-800℃. Meanwhile, 2-3 nanometer mesoporous were formed during decomposition of LDH. However, the heat treated samples still preserve the morphology of the original LDH plates. Periclase-like formed from LDH heat treatment may re-hydrolyze and recover the structure of LDH. However, crystallinity of the recovered LDH is lower than that of the original LDH. This heat treatment will result in formation of （Mg, Al）-oxide nano-crystals and nanopores among the nano-crystals. When heating temperature exceeds 1000, the periclase-like （Mg, Al）-oxide is transformed into a composite with periclase （MgO） and spinel phases. The periclase can be re-hydrolyzed and dissolved in HCl solution. After acid treatment, the sample with a high surface area is composed of spinel nano-crystals and nanopores among them. Our results will provide a new and economic way to synthesize mesoporous materials through pathways of phase transformation of precursor materials with different composition.