AlCl_(3)modified Pd/Al_(2)O_(3)catalyst for enhanced anthraquinone hydrogenation

Anthraquinone hydrogenation to produce H_(2)O_(2) is an economically interesting reaction with great industrial importance.Here,we report a series of Pd/xAl catalysts with different AlCl_(3) contents by a conventional stepwise impregnation method.The optimal Pd/1.0Al catalyst exhibits a higher performance toward anthraquinone hydrogenation with 8.3 g·L^(-1)hydrogenation efficiency,99.5%selectivity and good stability,obviously superior to that of Pd/Al_(2)O_(3) catalyst(5.2 g·L^(-1)and 97.2%).Detailed characterization demonstrates that AlCl_(3) can be grafted on the γ-Al_(2)O_(3) support to obtain a modified support with abundant surface weak acid and Lewis acid,which can adsorb and activate anthraquinone.Meanwhile,its steric hindrance could isolate and disperse active metals to form more active sites.The synergies between metal sites and acid sites promotes the anthraquinone hydrogenation.Furthermore,the good stability after grafting AlCl_(3) could attribute to the enhanced metal-support interaction inhibiting metal particles agglomeration and leaching.

离子排斥色谱用于厌氧消化处理的水中脂肪族羧酸的分析(英文)

The analysis of seven aliphatic carboxylic acids(formic,acetic,propionic,iso-butyric,n-butyric,iso-valeric and n-valeric acid) in anaerobic digestion process waters for biogas production was examined by ion-exclusion chromatography with dilute acidic eluents(benzoic acid,perfluorobutyric acid(PFBA) and sulfuric acid) and non-suppressed conductivity/ultraviolet(UV) detection.The columns used were a styrene/divinylbenzene-based strongly acidic cation-exchange resin column(TSKgel SCX) and a polymethacrylate-based weakly acidic cation-exchange resin column(TSKgel Super IC-A/C).Good separation was performed on the TSKgel SCX in shorter retention times.For the TSKgel Super IC-A/C,peak shape of the acids was sharp and symmetrical in spite of longer retention times.In addition,the mutual separation of the acids was good except for iso-and n-butyric acids.The better separation and good detection was achieved by using the two columns(TSKgel SCX and TSKgel Super IC-A/C connected in series),lower concentrations of PFBA and sulfuric acid as eluents,non-suppressed conductivity detection and UV detection at 210 nm.This analysis was applied to anaerobic digestion process waters.The chromatograms with conductivity detection were relatively simpler compared with those of UV detection.The use of two columns with different selectivities for the aliphatic carboxylic acids and the two detection modes was effective for the determination and identification of the analytes in anaerobic digestion process waters containing complex matrices.

Response surface methodology for optimizing adsorption performance of gel-type weak acid resin for Eu(Ⅲ)

The conditions relating to enhanced adsorption procedure of earth element europium（Eu） onto gel-type weak acid resin（110-H） in aqueous solution were optimized by means of the response surface methodology（RSM）, which proved that 110-H owned satisfactory adsorption capacity（346.85 mg/g） in optimum conditions, belonging to one of the high adsorption capacity materials. Then, the adsorption and desorption behaviors were investigated by batch studies. The adsorption performance showed high agreement with the Lagergren-first-order model and Langmuir isotherm with thermodynamic adsorption parameters of ΔH= 36.1 k J/mol and ΔS=200 J/（mol·K）. Desorption study revealed that 110-H could be effectively eluted by a low concentration of HCl solution（0.1 mol/L） to regenerate and reuse. Finally, the 110-H and Eu（III） loaded 110-H were characterized by IR spectroscopy and scanning electron microscope（SEM） to analyze the mechanism of adsorption, which proved to be chemisorbed.

Adsorption behavior and mechanism of D113 resin for lanthanum

The sorption properties of macroporous weak acid resin （D113） for La^3＋ ion were studied by chemical analysis and IR spectra. Experimental results indicate that the D113 resin has a good adsorption ability for La^3＋ at pH = 6.0 in the HAc-NaAc medium. The statically saturated adsorption capacity is 273.3 mg/g. Separation coefficients of βLa^3＋/Ce^3＋, βLa^3＋/Gd^3＋, βLa^3＋/Er^3＋, and βLa^3＋/Y^3＋ are 2.29, 3.64, 4.27, and 0.627, respectively. The apparent activation energy of adsorption, Ea is 18.4 kJ/mol, the thermodynamics parameters AH, AS, and AG of sorption are 4.53 kJ/mol, 61.8 J/（mol·K）, -13.9 kJ/mol, respectively. The adsorption behavior of D113 for La^3＋ obeys the Freundlich isotherm. La^3＋adsorbed on resin can be eluted by 2.0 mol/L HCl quantitatively.

A Kinetic Spectrophotometric Method for the Determination of Iron (Ⅲ) in Water Samples

A new kinetic spectrophotometric method has been developed for the determination of iron （Ⅲ）. The method is based on the catalytic effect of iron （Ⅲ） on the oxidation of weak acid brilliant blue dye （RAWL） by KIO4 in acid medium. The advantages of the proposed method are that it is sensitive, accurate, rapid, inexpensive, can be operated under room temperature and has a large determination concentration range compared to other techniques. The obtained optimum conditions are： pH 3.15, RAWL （200 mgL^-1） 5.00mL, Potassium periodate solution （0.01 molL^-1） 0.30mL, phenanthroline （0.02 molL^-1） 1.00mL, reaction temperature 25℃ and reaction time 7 min. With this method iron could quantitively be determined in the range 0.00-0.02 mgL^-1, the detection limit being 4.10 × 10^10gmL^-1. The relative standard deviations （RSD） in five replicate determinations for 3 μgL^-1and 5 μgL^-1 iron （Ⅲ） are 3.1% and 1.9%, respectively. The method has been applied to the determination of iron （Ⅲ） in tap water samples and seawater samples （from the South China Sea）, the recovery rates being 98.0% and 100.5%, respectively.

Determination of Trace Copper (Ⅱ) in Water Samples by Kinetic-spectrophotometry

A new kinetic-spectrophotometric method is proposed for the determination of copper (Ⅱ). The method is based on the catalytic effect of copper (Ⅱ) on the oxidation of weak acid brilliant blue dye (RAWL) by hydrogen peroxide. The copper (Ⅱ) can be determined spectrophotometrically by measuring the decrease of absorbance of RAWL at λ = 626 nm using the fix-time method. The optimum reaction conditions are as follows: pH 7.20, buffer solution NaOH-KH2PO4, RAWL (200 mg L-1) 5.00 mL, H2O2 (30%) 0.50 mL, reaction temperature 80℃ and reaction time 20 min. The linear range of this method is between 0 μg L-1 and 12 μg L-1 and the limit of detection is 0.011 μg L-1, the relative standard deviation (RSD) in five replicate determinations for 2 and 8 μg L-1 copper (Ⅱ) are 3.2% and 2.3%, respectively. Twenty ions do not interfere in the determination of copper (Ⅱ). The method has been applied satisfactorily to the determination of copper (Ⅱ) in freshwater samples (tap water and Yellow River water from Lijin, Shandong, China) and seawater samples (from the South China Sea), the recovery rates are 98.0%, 102.5% and 96.0%, respectively.

Measurement of Trace Manganese(Ⅱ) by the Catalytic Kinetic Spectrophotometric Method

A new kinetic spectrophotometric method is developed for the measurement of manganese(Ⅱ) in water. The method is based on the catalytic effect of manganese(Ⅱ) with the oxidation of weak acid brilliant blue dye(RAWL) by KIO4 using the Nitrilo triacetic acid(NTA) as an activation reagent. The optimum conditions obtained are 40 mgL-1 RAWL,1×10-4molL-1 KIO4,2×10-4 molL-1 Nitrilo triacetic acid(NTA),pH = 5.8,the reaction time of 3.00 min and the temperature of 20.0 ℃. Under the optimum conditions,the proposed method allows the measurement of manganese(Ⅱ) in a range of 0-50.0 ng mL-1 and with a detection limit of down to 0.158 ng mL-1. The recovery efficiency in measuring the standard manganese(Ⅱ) solution is in a range of 98.5%-102%,and the RSD is in a range of 0.76%-1.25%. The new method has been successfully applied to the measurement of manganese(Ⅱ) in both fresh water and seawater samples with satisfying results. Moreover,few cations and anions interfere with the measurement of manganese(Ⅱ). Compared with other kinetic catalytic methods and instrumental methods,the proposed method shows fairly good selectivity and sensitivity,low cost,cheapness,low detection limit and rapidity. It can be applied on boats easily.

Preparation of Diphenyl Oxalate from Transesterification of Dimethyl Oxalate with Phenol over TS-1 Catalyst

Diphenyl oxalate was synthesized from transesterification of dimethyl oxalate with phenol over TS-1 ( 2.5 wt% Ti ) catalyst. TS-1 catalyst, as a heterogeneous catalyst, showed excellent selectivity of diphenyl oxalate and methylphenyl oxalate compared with other homogeneous catalysts. Lewis acid sites on TS-1 catalyst were the active sites for transesterification of dimethyl oxalate with phenol. The high selectivity was closely related to the weak acid sites over TS-1.

Adsorption of Pb^(2+) on macroporous weak acid adsorbent resin from aqueous solutions: Batch and column studies

The adsorption properties of a novel macroporous weak acid resin （D152） for Pb^2＋ were investigated with chemical methods. The optimal adsorption condition of D152 resin for Pb^2＋ is at pH 6.00 in HAc-NaAc medium. The statically saturated adsorption capacity is 527 mg/g at 298 K. Pb^2＋ adsorbed on D152 resin can be eluted with 0.05 mol/L HCI quantitatively. The adsorption rate constants determined under various temperatures are k288 n=2.22×10-5 s^-1, k298 K=2.51 × 10^-5 s^-1, and k308 K= 2.95 × 10^-5 s^-1, respectively. The apparent activation energy, Ea is 10.5 kJ/mol, and the adsorption parameters of thermodynamics are ΔH^Θ=13.3 kJ/mol, ΔS^Θ=119 J/（mol·K）, and ΔG^Θ298 K =-22.2 kJ/mol, respectively. The adsorption behavior of D152 resin for Pb^2＋ follows Langmuir model.

Sorption Behaviour and Mechanism of Lanthanum (Ⅲ) on HD-2 Resin

La(Ⅲ) was quantitatively adsorbed by macroporous weak acid resin (HD-2) in the medium of pH=6.16. The statically saturated sorption capacity is 231 mg·g -1(resin). 3.0 mol·L -1 HCl can be used as an eluant. The elution percentage is 100%. The sorption rate constant is k_ 298=3.04×10 -5 s -1. The apparent sorption activation energy of HD-2 for La(Ⅲ) is 31.2 kJ·mol -1. The sorption behavior of HD-2 for La(Ⅲ) obeys the Freundlich isotherm. The adsorption parameters of thermodynamic are ΔH=9.56 kJ·mol -1, ΔS=35.7 J·mol -1·K -1, ΔG=-1.08 kJ·mol -1, respectively.

Laboratory Research on Tahe AR Fluid Coking on Weak Acid Catalysts

Fluid coking on micro-spherical particles with acid sites on them could produce more light oils from Tahe AR.The conversion rate could increase by about 20% on the catalyst B compared to that obtained on the catalyst A and the light oil yield could increase by about 12%.The yield of gasoline and diesel was more than 50% from Tahe AR over the catalyst B.Tests on acidity of the catalyst B by pyridine FT-IR spectrometry showed that the total acid content and the ratio of weak acid number to total acid number were higher than other catalysts.

Study on the Determination of Trace Ni(II) by the Catalytic Kinetic Spectrophotometric Method

A new kinetic spectrophotometric method has been developed for the determination of trace Ni （Ⅱ in natural water. The method is based on the catalytic effect of Ni （Ⅱ） on the oxidation of weak acid brilliant blue dye （RAWL） by KIO4 in acid medium. The concentration of nickel （Ⅱ） can be determined spectrophotometrically by measuring the decrease of absorbance of RAWL at λ = 626 nm using the fix-time method. The influencing factors are investigated by the orthogonal experimental design. The obtained optimum analytical conditions are： pH = 2.00, CRAWL = 5.00×10^-5 mol·L^-1, c KlO4 = 2.00× 10^-5 mol·L^-1, the reaction time t= 10min and the temperature T = 25 ℃. Under the optimum conditions, the developed method allows the measurement of Ni （Ⅱ） in a range of 0 - 40.0ngmL1. The standard deviation of eleven independent measurements of blank reaction is S = 3.08× 10^-3 and the limit of detection is 2.20ng·mL^-1. The relative standard deviations （RSDs） in six replicate determinations of 5 ngmL-1 and 8 ngmL1 Ni （Ⅱ） are 2.87% and 1.11%, respectively. Moreover, the experiments show few cations and anions can interfere with the measurement of Ni （Ⅱ）. The recovery efficiencies of this method are in a range of 97.0%-102.5% in freshwater samples. But there is a decreasing effect, which is about 0.2 times the added Ni （Ⅱ） in seawater medium. After reasonable calibration this processing method is used for the determination of Ni （Ⅱ） in seawater samples successfully. The results show this developed method has high accuracy and precision, high sensitivity, large range of linearity and high speed. The method can, therefore, be employed at room temperature.

QUANTITATIVE ANALYSIS OF VERY WEAK ACID AND BASE BY pH-FIXED TITRATION METHOD

pH-fixed titration method for the determination of weak acids and bases has been studied in this paper.It is not necessary to know the ionization constant of weak acid or base and the concentration of titrant. This method had been applied to determine phenol,4-aminoantipyrine and glycine,whose ionization constants range from 10^(-10)to 10^(-12).The results were satisfactory.

New Method for the Determination of Ionization Constants of Polyprotic Weak Acid

A new method for the determination of ionization constants of polyprotic weak acids is presented. Based on dissociation equilibrium,mass balance and charge balance, the mathematic model is established and the non linear least squares Gauss Newton method is applied to numerically solve the model equations. In order to get the concentration of hydrogen ion, the Debye Hückel equation is used to calculate its activity coefficient. The ionization constants of H 2SO 3 and H 2C 2O 4 obtained by this method are in good agreement with the literature values.

DIRECT TITRATION OF VERY WEAK ACIDS(BASES)IN AQUEOUS SOLUTION WITH STRONG BASES(ACIDS)USING VISUAL END-POINT INDICATION WITHOUT INDICATOR

This paper reports a new method of titration for very weak acids and bases using the appearance of incisions on oscillopolarogram to indicate the end-point.This method has the advantages of rapidity,simplicity,no indicator needed as well as good precision.

Adsorption behavior of benzenesulfonic acid by novel weakly basic anion exchange resins

Two novel weakly basic anion exchange resins（SZ-1 and SZ-2） were prepared via the reaction of macroporous chloromethylated polystyrene-divinylbenzene（Cl-PS-DVB） beads with dicyclohexylamine and piperidine, respectively. The physicochemical structures of the resulting resins were characterized using Fourier Transform Infrared Spectroscopy and pore size distribution analysis. The adsorption behavior of SZ-1 and SZ-2 for benzenesulfonic acid（BA） was evaluated, and the common commercial weakly basic anion exchanger D301 was also employed for comparison purpose. Adsorption isotherms and influence of solution p H, temperature and coexisting competitive inorganic salts（Na2SO4and Na Cl） on adsorption behavior were investigated and the optimum desorption agent was obtained.Adsorption isotherms of BA were found to be well represented by the Langmuir model.Thermodynamic parameters involving ΔH, ΔG and ΔS were also calculated and the results indicate that adsorption is an exothermic and spontaneous process. Enhanced selectivity of BA sorption over sulfate on the two novel resins was observed by comparison with the commercial anion exchanger D301. The fact that the tested resins loaded with BA can be efficiently regenerated by Na Cl solution indicates the reversible sorption process. From a mechanistic viewpoint, this observation clearly suggests that electrostatic interaction is the predominant adsorption mechanism. Furthermore, results of column tests show that SZ-1possesses a better adsorption property than D301, which reinforces the feasibility of SZ-1for potential industrial application.

Adsorption behavior of ytterbium (Ⅲ) on gel-type weak acid resin

The adsorption and desorption behaviors of Yb（Ⅲ） on gel-type weak acid resin （110） were investigated. The influence of operational conditions such as contact time,initial concentration of Yb（Ⅲ）,initial pH of solution and temperature on the adsorption of Yb（Ⅲ） were also examined. The results showed that the optimal adsorption condition of 110 resin for Yb（Ⅲ） was achieved at pH=5.5 in HAc-NaAc medium. The maximum uptake capacity of Yb（Ⅲ） was 265.8 mg/g at 298 K. Yb（Ⅲ） could be eluted by using 3.0 mol/L HCl solution and the 110 resin could be regenerated and reused. The adsorption of Yb（Ⅲ） followed the Langmuir isotherm,and the correlation coefficients were evaluated. Various thermodynamic parameters such as standard enthalpy change （△H）,standard entropy change （△S） and standard free energy change （△G） were evaluated. The adsorption of Yb（III） on the 110 resin was found to be endothermic in nature. Thomas model was successfully applied to experimental data to predict the breakthrough curves and to determine the characteristics parameters of the column useful for process design. And the resin sample both before and after adsorption was described by IR spectroscopy.

A facile and universal method to achieve liposomal remote loading of non-ionizable drugs with outstanding safety profiles and therapeutic effect

Liposomes have made remarkable achievements as drug delivery vehicles in the clinic.Liposomal products mostly benefited from remote drug loading techniques that succeeded in amphipathic and/or ionizable drugs,but seemed impracticable for nonionizable and poorly water-soluble therapeutic agents,thereby impeding extensive promising drugs to hitchhike liposomal vehicles for disease therapy.In this study,a series of weak acid drug derivatives were designed by a simplistic one step synthesis,which could be remotely loaded into liposomes by p H gradient method.Cabazitaxel(CTX)weak acid derivatives were selected to evaluate regarding its safety profiles,pharmacodynamics,and pharmacokinetics.CTX weak acid derivative liposomes were superior to Jevtanaa in terms of safety profiles,including systemic toxicity,hematological toxicity,and potential central nerve toxicity.Specifically,it was demonstrated that liposomes had capacity to weaken potential toxicity of CTX on cortex and hippocampus neurons.Significant advantages of CTX weak acid derivative-loaded liposomes were achieved in prostate cancer and metastatic cancer therapy resulting from higher safety and elevated tolerated doses.

Removal of Low-concentration Ammonia from Ambient Air by Aluminophosphates

A series of aluminumphosphate materials was prepared and used as adsorbents for the removal of ammonia at low concentrations. The influence of various preparation parameters, including the pH value of sol, calcination temperature and molar ratio of P/A1, on the structure and surface properties as well as adsorption capacity was investigated. The results showed that large amount of P-OH present on the surface of aluminophosphates was suitable for the removal of ammonia. They were the major source of weak Br6nsted acid sites and acted as the main active centers for capturing ammonia.