Kinetics and Thermodynamics of Hydrolytic Depolymerization of Polyamide Waste at Various Temperature and Autogenious Pressure by High-Pressure Autoclave

Hydrolytic depolymerization of polyamide waste in water was studied using 0.5 L high pressure autoclave at temperatures of 235, 240, 245, 250 °C and at autogenious pressure 480, 500, 520, and 600 psi (pound per square inch).The reaction rate constant, energy of activation, enthalpy of activation, entropy of activation and equilibrium constant were calculated from the experimental data obtained. The maximum depolymerization (59.2%) of polyamide waste into monomer caprolactum was obtained at 250 °C and 600 psi pressure. The reaction rate constant was obtained on basis of measurement of amine value and residual weight. The depolymerization reaction was found to be pseudo first order with reaction rate constant of the order of 10⁻³ min⁻¹. The enthalpy, entropy and free energy of activation were recorded as 85.75, −0.1354 and 156.59 kJ mol⁻¹ respectively at the experimental conditions for maximum depolymerization of polyamide waste. The thermodynamic equilibrium constant for this hydrolysis reaction was found to be 2.3 × 10⁻¹⁶.     

Supercritical methanol for polyethylene terephthalate depolymerization: observation using simulator

To apply PET depolymerization in supercritical methanol to commercial recycling, the benefits of supercritical methanol usage in PET depolymerization was investigated from the viewpoint of the reaction rate and energy demands. PET was depolymerized in a batch reactor at 573 K in supercritical methanol under 14.7 MPa and in vapor methanol under 0.98 MPa in our previous work. The main products of both reactions were the PET monomers of dimethyl terephthalate (DMT) and ethylene glycol (EG). The rate of PET depolymerization in supercritical methanol was faster than that of PET depolymerization in vapor methanol. This indicates supercritical fluid is beneficial in reducing reaction time without the use of a catalyst. We depicted the simple process flow of PET depolymerization in supercritical methanol and in vapor methanol, and by simulation evaluated the total heat demand of each process. In this simulation, bis-hydroxyethyl terephthalate (BHET) was used as a model component of PET. The total heat demand of PET depolymerization in supercritical methanol was 2.35 x 10(6)kJ/kmol Produced-DMT. That of PET depolymerization in vapor methanol was 2.84 x 10(6)kJ/kmol Produced-DMT. The smaller total heat demand of PET depolymerization in supercritical methanol clearly reveals the advantage of using supercritical fluid in terms of energy savings.     

Hydrolysis of <Emphasis Type="Italic">Sasa senanensis</Emphasis> culm with dilute sulfuric acid for production of a fermentable substrate

To prepare a substrate for microbial conversion of xylose into xylitol, the culm of Sasa senanensis was hydrolyzed with dilute sulfuric acid. When the reaction temperature was fixed at 121°C, an optimum yield of xylose was obtained by treatment with 2% sulfuric acid for 1 h. An increase in the sulfuric acid concentration or a prolonged reaction time resulted in a decrease in the xylose yield. A fermentable substrate with a relatively high xylose concentration (36.7 g l⁻¹) was obtained by hydrolysis with 2% sulfuric acid with a liquid-to-solid ratio of 5 g g⁻¹. During hydrolysis at elevated temperatures, certain undesired byproducts were also generated, such as degradation products of solubilized sugars and lignin, which are potential inhibitors of microbial metabolism. These compounds were, however, successfully removed from the hydrolysate by treatment with activated char.     

Nickel recovery from spent nickel catalyst.

A process for nickel recovery from a spent catalyst of definite composition has been developed using the hydro-metallurgical route. The processing steps includes direct sulphuric acid leaching followed by separation of iron as well as silica and other impurities. For a 152 microm particle size catalyst, extraction of about 98% nickel was achieved at 363 K in 2 h using a sulphuric acid concentration (v/v) of 8% and a pulp density of 10%. The dissolution of nickel followed diffusion-controlled leaching kinetics. Increase in temperature and sulphuric acid concentration resulted in increase in the nickel recovery. The activation energy for nickel dissolution was calculated to be 62.8 kJ mol(-1). Finally, nickel was recovered as value-added products such as sulphide and oxalate with overall recovery of 90 and 88% of nickel, respectively.     

Preparation of biochar catalyst with saccharide and lignocellulose residues of corncob degradation for corncob hydrolysis into furfural

This paper presented a novel process for production of furfural by hydrothermal degradation of corncob over biochar catalyst, in which it was prepared with the recycling degradation solution and lignocellulosic solid residues. The biochar catalyst was papered by lignocellulose residues and concentrated saccharide solution, and then impregnated in 0.5 mol/L sulphuric acid at room temperature for 24 h assisted by the ultrasonic vibration. In the system of recycling, 8.8 % lignocellulose residues and 100 % concentrated saccharide solution from corncob hydrolysis have been recycled. Hydrolysis of corncob was carried out at 180 °C for duration of 170 min over the biochar catalyst. The experimental results have shown that the furfural yield of up to 37.75 % and overall corncob conversion rate of 62.00 % could be achieved under optimum operating conditions for the catalysts preparation and the corncob hydrolysis. It is believed that the acid density of 4.27 mmol/g of biochar catalyst makes the SO₃H groups cleave β-1,4 glycosidic linkages effectively and hydrolyze the cellulose and hemicellulose to water-soluble sugars, as well as to facilitate dehydration of xylose to give the product of furfural.     

利用盐泥制取轻质氧化镁

采用二氧化碳法提取盐泥中的镁,研究了使之转化为轻质氧化镁的影响因素以及主要反应的动力学性质。实验确定的最佳条件为固液比1∶15、二氧化碳通入时间90min、水解温度90℃、水解时间25min,在此条件下,盐泥中镁的总提取率为75%;采用微分法求得氢氧化镁与二氧化碳反应的反应级数和活化能分别为1.7和68.1kJ/mol。     

已二酸生产副产物——混合二元酸的综合利用

采用一水合硫酸氢钠作为催化剂,催化己二酸生产副产物——混合二元酸与甲醇反应合成混合二元酸二甲酯。优化工艺条件为：混合二元酸加入量0．1mol,无水甲醇加入量0．5mol,一水合硫酸氢钠加入量4．0g,环己烷加入量20mL,反应时间1．5h。合成混合二元酸二甲酯的酯化反应收率大于97％。经气相色谱检测,产物中酯的质量分数为98．91％。一水合硫酸氢钠可重复使用3次。     

铜基多相催化剂催化氧气氧化降解水中水合肼

制备了3种铜基多相催化剂,用于催化氧气氧化降解水中水合肼。实验结果表明:三组分催化剂c-CuZnCr比单组分催化剂CuO(c-Cu)和双组分催化剂c-CuZn具有更好的催化性能;在200 mL浓度0.04 mol/L的水合肼水溶液中投加23 mg c-CuZnCr,常温常压下反应360 min,水合肼的降解率达99.96%;c-CuZnCr在使用中稳定性好,循环使用5次未见活性降低。表征结果显示,三组分催化剂具有最大的比表面积,因而表现出最高的催化活性。动力学研究结果表明,c-CuZnCr催化的反应活化能为32.73 kJ/mol,与水合肼浓度和氧气压力相关的反应级数分别为0.97和0.78。     

用化肥废催化剂制备硫酸铝钾

研究了以含铝、钴的化肥废催化剂为原料制备硫酸铝钾(明矾)的方法。确定了最佳工艺条件:化肥废催化剂粒度为300目、硫酸浓度为9 mol／L、浸取时间为30 min、用K2CO3调滤液pH至1-2。在该条件下制备的KAl(SO4)2·12H2O产品纯度为98.2％,达到日本工业标准(JIS K1473-1970)工业级纯度。     

Decomposition of mixed plastics consisting of polypropylene and polyethylene terephthalate into oils over titania/silica catalysts

The catalytic decomposition of mixed plastics consisting of polypropylene (PP) and polyethylene terephthalate (PET) has been investigated over titania/silica catalysts at 698 K. The yield of oil produced was about 70%, and the large amounts of C₁₈₊ hydrocarbons this contained was from the aromatics in PET. Gas was also produced, including C₃–C₅ hydrocarbons. The carbon-number fractions in the oil was influenced by the PET/(PP + PET) ratios and the catalyst weight. The titania/silica catalysts could be used repeatedly, and after they had been fouled, could be regenerated. From the Fourier Transform Infrared (FT–IR) spectroscopic data of adsorbed pyridine on the catalyst surface, most of the acid sites of the titania/silica catalysts were found to be Lewis sites where the hydride abstracted from PP pyrolysates react with PET pyrolysates to form oil and gas. Received: July 19, 2000 / Accepted: October 20, 2000     

Sorption of strontium on bentonite

Sorption of Sr on bentonite was studied using the batch technique. Distribution coefficients (K_d) were determined as a function of contact time, pH, sorbent and sorbate concentration and temperature. The data were interpreted in terms of Freundlich, Langmuir and Dubinin-Radushkevich isotherms. Thermodynamic parameters for the sorption system were determined at three different temperatures. The positive value of the heat of sorption, ΔH° = 30.62 kJ/mol at 298 K, shows that the sorption of strontium on bentonite is endothermic. The negative value of the free energy of sorption, ΔG° = −10.69 kJ/mol at 298 K, shows the spontaneity of the reaction. ΔG° becomes more negative with increasing temperature, which shows that the sorption process is more favorable at higher temperatures. The mean free energy for sorption, E 9 kJ/mol, suggests that ion exchange is the predominant mode of sorption in the Sr concentration range studied, i.e. 0.01 – 0.3 mol/dm³. The presence of complementary cations depresses the sorption of strontium on bentonite in the order Ca²⁺>Mg²⁺>K⁺>Na⁺. Some organic complexing agents and natural ligands also affect the sorption of strontium. The desorption studies with ground water at low strontium loadings on bentonite show that about 90% of Sr is irreversibly sorbed on the bentonite.     

Synthesis and Characterization of Chitosan-Grafted-Poly(2-Hydroxyaniline) Microstructures for Water Decontamination

Chitosan as a biopolymer, biodegradable, safe, non-toxic and widely abundant in nature was grafted with poly(2-hydroxyaniline) (P2-HA) through aqueous chemical oxidative copolymerization using ammonium persulphate in acetic acid medium. The grafting conditions were studied by varying grafting parameters. The effect of oxidant, 2-hydroxyaniline (2-HA) and acetic acid concentrations on the rate of copolymerization was studied. The synthesized graft characterized using UV–Vis, FTIR, TGA, XRD, and scanning electron microscope and compared with chitosan and P2-HA. The grafting enhances the thermal properties of chitosan. The effect of temperature on the rate of grafting copolymerization reaction was studied. The apparent activation energy (Ea) of the copolymerization reaction found to be 21.1116 kJ/mol. Also, ΔH^* and ΔS^*, were calculated and found to 22.8630 kJ/mol and ?109.4290 J/mol K respectively. The mechanism of the grafting copolymerization reaction discussed. Chitosan, P2-HA and chitosan-graft-P2-HA used for the removal of Cr, Fe, Mn, Cu and Zn divalent ions from a contaminated water samples. The adsorption isotherm parameters are given.     

Chemical Recycling of Polyamide Waste at Various Temperatures and Pressures Using High Pressure Autoclave Technique

Chemical recycling of polyamide waste in water was studied using 0.5 L high pressure autoclave at temperatures of 150, 200, 210, 220,230 and 240 °C and at various pressures of 100, 200, 300, 400, 500, 600 and 700 psi (pound per square inch). Viscosity average molecular weight of the polyamide waste sample was determined by Ostwald method and recorded as 1.928 × 10³. The reaction was found to be first order with velocity constant in order of 10⁻² min⁻¹. The velocity constant and percent conversion of depolymerization reaction at 240 °C and 700 psi pressure were recorded as 2.936 × 10⁻² min⁻¹ and 99.99% respectively. The velocity constant was obtained on the basis of measurement of amine value. Kinetic and thermodynamic parameters such as energy of activation, frequency factor, enthalpy of activation were found to be 10.6 kJ mole⁻¹, 0.3719 min⁻¹ and 6.3 kJ mole⁻¹ respectively, at the optimum conditions for maximum depolymerization of polyamide waste.     

二壬基萘磺酸反胶团萃取模拟废水中的铅

以二壬基萘磺酸（DNNSA）反胶团煤油溶液萃取模拟含铅废水中的铅。在萃取前水相中铅离子浓度为3×10-4 mol/L、DNNSA浓度为0.010 mol/L、油水比为1∶20、模拟含铅废水pH为6、萃取温度为303 K、萃取时间为40 min的条件下,萃取后水相中铅离子浓度为0.845×10-4 mol/L,有机相中铅离子浓度为4.517×10-3 mol/L,铅萃取率为71.83%。DNNSA反胶团萃取铅离子萃取容量为1 188.62 mg/g,热力学焓变为2.595 kJ/mol。     

Methanolysis and Hydrolysis of Polycarbonate Under Moderate Conditions

Alkali-catalyzed methanolysis and hydrolysis of polycarbonate (PC) in a solvent in which PC can substantially dissolve such as N-methyl-2-pyrrolidone, 1,4-dioxane, tetrahydrofuran and so on were studied. Reaction conditions were optimized for the purpose of recycling PC in the form of bisphenol A and carbon carbonate. The results showed that both the methanolysis and hydrolysis of PC could take place under moderate conditions. Under the conditions of reaction temperature 40 °C, m(PC):m(MeOH) = 1:1, m(PC):m(NaOH) = 50:1, reaction time 35 min and using tetrahydrofuran as solvent, the methanolysis conversion of PC was almost 100% and the yield of bisphenol A was over 95%. Moreover, under the conditions of reaction temperature 100 °C, m(PC):m(H₂O) = 1:0.7, m(PC):m(NaOH) = 10:1, reaction time 8 h and using 1,4-dioxane as solvent, the hydrolysis conversion of PC was almost 100% and the yield of bisphenol A was over 94%.     

Supercritical water oxidation of landfill leachate

In this paper, ammonia as an important ingredient in landfill leachate was mainly studied. Based on Peng-Robinson formulations and Gibbs free energy minimization method, the estimation of equilibrium composition and thermodynamic analysis for supercritical water oxidation of ammonia (SCWO) was made. As equilibrium is reached, ammonia could be totally oxidized in SCW. N(2) is the main product, and the formation of NO(2) and NO could be neglected. The investigation on SCWO of landfill leachate was conducted in a batch reactor at temperature of 380-500 °C, reaction time of 50-300s and pressure of 25 MPa. The effect of reaction parameters such as oxidant equivalent ratio, reaction time and temperature were investigated. The results showed that COD and NH(3) conversion improved as temperature, reaction time and oxygen excess increased. Compared to organics, NH(3) is a refractory compound in supercritical water. The conversion of COD and NH(3) were higher in the presence of MnO(2) than that without catalyst. The interaction between reaction temperature and time was analyzed by using response surface method (RSM) and the results showed that its influence on the NH(3) conversion was relatively insignificant in the case without catalyst. A global power-law rate expression was regressed from experimental data to estimate the reaction rate of NH(3). The activation energy with and without catalyst for NH(3) oxidation were 107.07 ± 8.57 kJ/mol and 83.22 ± 15.62 kJ/mol, respectively.     

Depolymerization of Waste PET with Phosphoric Acid–Modified Silica Gel Under Microwave Irradiation

Chemical recycling of waste poly(ethylene terephthalate) (PET) using phosphoric acid–modified silica gel as a solid catalyst is reported. Advantageously, microwave irradiation was used to progress the depolymerization of PET. In this study, depolymerization of PET with a small amount of water is suggested as a suitable method. The depolymerized product, terephthalic acid was obtained and assigned by ¹H NMR and FT-IR spectroscopy. Finally, over 90 % conversion to terephthalic acid was achieved when waste plastic bottles were treated with the method. This results confirm the importance of the microwave power technique as a promising recycling method for plastic bottles made from PET, resulting in monomer recovery in addition to substantial energy saving.     

废聚碳酸酯水解法制双酚A

以1,4-二氧六环为溶剂、NaOH为催化剂,采用废聚碳酸酯(PC)常压水解法制双酚A(BPA).对反应影响因素进行了研究.实验结果表明,在反应温度为100℃、反应时间为8h、m(NaOH):m(水+溶剂)=1:33、m(溶剂):m(PC)=4:1、m(水):m(PC)=1:1的最佳反应条件下,PC水解率大于98%,BPA收率大于95%.     

Sonophotocatalytic Degradation of Chitosan in the Presence of Fe(III)/H2O2 System

The degradation of chitosan by means of ultrasound irradiation and its combination with homogeneous photocatalysis (photo-Fenton) was investigated. Emphasis was given on the effect of additive on degradation rate constants. 24 kHz of ultrasound irradiation was provided by a sonicator, while an ultraviolet source of 16 W was used for UV irradiation. To increase the efficiency of degradation process, degradation system was combined with Fe(III) (2.5 × 10⁻⁴mol/L) and H₂O₂ (0.020–0.118 mol/L) in the presence of UV irradiation and the rate of degradation process change from 1.873 × 10⁻⁹−6.083 × 10⁻⁹ mol^1.7 L s⁻¹. Photo-Fenton process led to complete chitosan degradation in 60 min with the rate increasing with increasing catalyst loading. Sonophotocatalysis in the presence of Fe(III)/H₂O₂ was always faster than the respective individual processes. A synergistic effect between ultrasound and ultraviolet irradiation in the presence of Fenton reagent was calculated. The degraded chitosans were characterized by X-ray diffraction (XRD), gel permeation chromatography (GPC) and Fourier transform infrared (FT-IR) spectroscopy and average molecular weight of ultrasonicated chitosan was determined by measurements of intrinsic viscosity of samples. The results show that the total degree of deacetylation (DD) of chitosan change, partially after degradation and the decrease of molecular weight led to transformation of crystal structure. A negative order for the dependence of the reaction rate on total molar concentration of chitosan solution within the degradation process was suggested. Results of this study indicate that the presence of catalyst in the reaction medium can be utilized to reduce molecular weight of chitosan while maintaining the power of irradiated ultrasound and degree of deacetylation.     

废聚苯乙烯硝化氧化制对硝基苯甲酸

研究了用聚苯乙烯废料为原料,经过硝化氧化制造具有高附加值的精细化工产品－对硝基苯甲酸。探讨了影响对硝基苯甲酸产率的因素,如硝酸的浓度和用量,压力,反应时间及催化剂用量等。结果表明,在优化条件下对硝基苯甲酸产率达５２％,产品纯度为９９％。