磷酸酯胶凝剂的合成及油基压裂液性能评价

探讨了油基压裂液胶凝剂磷酸酯的合成条件 ,进而对配制的压裂液性能进行了评价。实验结果表明 ,用所合成的磷酸酯胶凝剂配制的柴油基压裂液具有较快的交联速度、良好的耐温性能和耐温耐剪切性能以及快速破胶等综合性能 ,可用于强水敏性、低压低渗透地层的压裂改造。     

Microwave-Assisted Synthesis and Characterization of Stearic Acid Sucrose Ester: A Bio-Based Surfactant

Sugar esters of fatty acids are bio-based surfactants that were synthesized by transesterification of table sugar (sucrose) with stearic acid methyl ester (SAME) in high yield and purity using an optimized microwave-assisted method. The maximum surfactant product yield of 88.2% was obtained by combining reactants with potassium methoxide and irradiating the mixture with microwaves to achieve an ideal reaction temperature of 132 °C over 21 min. The synthetic procedure described herein minimized undesirable sugar pyrolysis as evidenced by retention of white color characteristic of a pure bio-based surfactant product. The experiment implemented Box–Behnken design for response surface methodology to refine reaction parameters for optimal product yield. The following parameters were augmented: the irradiation time, the mole ratio of catalyst to sucrose, and temperature.     

Optimization of the Microencapsulation of Lemon Myrtle Oil Using Response Surface Methodology

Response surface methodology (RSM) was applied to study the effects of types of wall materials (modified starch + maltodextrin and whey protein concentrate + maltodextrin), feed concentration, oil concentration, and outlet air temperature on oil retention and surface oil content of the encapsulated powder. The results revealed that the oil retention was significantly (P < 0.05) affected by the constant term of types of wall materials and the linear term of feed concentration but seemed to be almost independent (P > 0.05) of experimental range of oil concentration and outlet air temperature. The types of wall materials, oil load, and outlet air temperature showed a significant (P < 0.05) influence on surface oil content. The types of wall materials (Hi-Cap and WPC) also influenced significantly the oil retention and surface oil content. Based on the limited range of experimental conditions used in this work, it was not possible to choose the wall materials that can give both high oil retention and low surface oil content. Disregarding the effect of wall material, an optimum response was obtained at 40% of feed concentration (w/w), 18% of oil concentration, and 65°C of outlet air temperature.     

Supercritical CO2 Extraction Optimization of Onion Oil Using Response Surface Methodology

Response surface methodology was employed to optimize the conditions of supercritical CO₂ extraction of the oil from freeze‐dried onion powder. The effects of pressure, temperature and extraction time on the yield of oil were investigated. The maximum extraction yield of 4.69 ± 0.04 g/kg dry basis was achieved at a pressure of 20.6 MPa, a temperature of 40.6 °C, a time of 260 min, a CO₂ flow rate of 22 L h^–1, and an entrainer ratio of 0.1 mL absolute ethanol per gram dry basis. The chemical composition of the oil was analyzed by gas chromatography‐mass spectrometry. The most representative compounds of the essential oil were organosulfur‐containing compounds and, among these, the main constituents were methyl 5‐methylfuryl sulfide (18.30 %), methyl 3,4‐dimethyl‐2‐thienyl disulfide (11.75 %) and 1‐propenyl propyl disulfide (9.72 %).     

Analysis and Optimization of Ultrasound-Assisted Alkaline Palm Oil Transesterification by RSM and ANN-GA

In this study, the effects of ultrasound irradiation on transesterification process and characteristics of the synthesized biodiesel were investigated. The study was divided into two parts. In the first part, response surface methodology (RSM) and Central Composite Design (CCD) were employed to design experiments, develop the regression model, and evaluate individual and interactive impacts of five independent operational variables. The obtained results were then predicted by an optimized artificial neural network-genetic algorithm (ANN-GA) algorithm. The estimated results were compared with the experimental results. In the second part of the work, the impact of ultrasound irradiation on the main characteristics of the synthesized biodiesel was investigated. The analysis of the operating conditions indicated that reaction temperature and MeOH:oil molar ratio were the most important variables on reaction yield. The experimental results showed that there was a change in the main properties of the synthesized palm oil biodiesel with the density changed by about 0.3 kg/m³, viscosity by 0.12 mm²/s, pour/cloud point by 1–2°C, and flash point by 5°C, depending on different combinations of operational parameters. Besides, the numerical optimization technique was employed to optimize process variables in order to obtain the maximum FAME content (reaction yield) along with the best properties using both RSM and ANN-GA techniques. The maximum reaction yields of 95.2% and 95.1% were predicted by the RSM and ANN-GA models, respectively, at the optimum conditions. The conditions predicted by RSM and ANN-GA proved to be feasible for modeling and optimizing transesterfication yield with an accuracy of 99.18% and 99.14% and biodiesel properties of 98.61% and 98.28%, respectively.     

油基改性腐植酸降滤失剂的制备及性能评价

采用腐植酸与改性剂进行反应,制备用于油基钻井液的抗高温降滤失剂。通过多组单因素实验考察了改性剂种类、反应配比、反应温度、反应时间对产品的影响,结果表明最佳改性产品的制备条件为:腐植酸与N2改性剂的质量比11∶4,温度180℃,时间8 h;产物的红外谱图证实改性反应成功。室内评价该油基降滤失剂的适宜加量为3%,150℃高温高压滤失量为13 mL,综合性能优于沥青类降滤失剂。     

Dimerization of 2-Ethylhexylphosphonic Acid Mono-2-ethylhexyl Ester (HEH[EHP]) as Determined by NMR Spectrometry

ABSTRACT

The aggregation state of extractant molecules is an important consideration in characterizing or modeling solvent extraction systems used in hydrometallurgy. For example, previously reported efforts to measure organic-phase dimerization constants have required the presence of an additional phase, either aqueous phase or gas phase. NMR spectroscopy can be used to probe organic-phase inter-molecular interactions without requiring the presence of an additional phase, making it possible to study the simplest organic system, that contain only extractant and diluent. In this report, the dimerization of 2-ethylhexylphosphonic acid mono-2-ethylhexl ester (HEH[EHP]) in n-dodecane and in toluene was investigated by two different NMR-based methods: chemical shifts and Diffusion Ordered SpectroscopY (DOSY). The chemical-shift analysis requires monitoring the chemical shift of the acidic proton as the concentration of HEH[EHP] changes. DOSY is a 2D NMR technique used to probe the size of molecules. The size of diffusing species was related back to the average aggregate molecular weight via a calibration curve. Because the DOSY method had not been used in this manner before, a validation of the method using the interaction constant between HDEHP and CMPO was performed. After this validation, DOSY was applied to HEH[EHP] dimerization. DOSY results demonstrated that the chemical shift of the acidic proton was the peak most affected by the dimerization state of the HEH[EHP]. All other peaks, including that of ³¹P, were affected more significantly by the changing dielectric constant of the solution. The dimerization constants determined were significantly lower than those reported in prior literature, possibly due to the effect of water in the literature values.     

响应面法优化Aspergillus oryzae Cs007产酯水解酶发酵条件

对米曲霉菌株Aspergillus oryzae Cs007产酯水解酶发酵条件进行了研究。首先通过单因子实验确定最佳碳源为橄榄油、最佳氮源为蛋白胨、最佳表面活性剂为阿拉伯胶;再利用Plackett-Burman设计筛选出具有显著效应的3个因素：蛋白胨、KH2PO4、阿拉伯胶;然后通过最陡爬坡实验和响应面法（RSM）分析确定了显著因素的最优水平;最后通过单因子实验确定最佳摇床转速和培养时间。优化后的产酶条件为：橄榄油1%（体积分数）,蛋白胨1.76%（质量浓度）,KH2PO40.11%（质量浓度）,MgSO40.05%（质量浓度）,NaCl 0.05%（质量浓度）,阿拉伯胶0.37%（质量浓度）,起始pH值5,培养温度30℃,摇床转速200r.min-1,培养时间48h。优化条件下所产酯水解酶酶活达6.49U.mL-1,比初始酶活2.8U.mL-1提高了1.32倍。     

Sulfonated-polysulfone membrane surface modification by employing methacrylic acid through UV-grafting: Optimization through response surface methodology approach

Membrane surface modification through UV-grafting method was studied and optimized using response surface methodology (RSM) approach. Sulfonated-polysulfone (SPS) membrane was modified through grafting process by employing methacrylic acid (MAA) monomer solution under the exposure of UV light. The parameters used were the concentration of MAA in the range of 0–6 wt% and UV activation time of 0–50 min. The optimized parameters from RSM were 2.61 wt% of MAA and 21.10 min of UV activation time. The optimized water permeability obtained was 8.75 L m⁻² h⁻¹ bar⁻¹, while the rejection percentages for humic acid, NaCl and MgSO₄ solution were 95.0%, 65.7% and 48.3%, respectively.     

响应面法优化产低温脂肪酶工程菌Cl02的发酵条件

目的采用响应面法优化产低温脂肪酶工程菌Cl02的发酵条件。方法通过单因素试验考察培养基中酵母氮源含量、pH值、甘油含量和甲醇含量对酶活的影响,确定产酶的主要影响条件,在此基础上,根据Box-Benheken中心组合试验设计原理,采用三因素三水平的响应面分析法,综合考察各因子对低温脂肪酶酶活的影响,建立低温脂肪酶酶活的二次回归模型。结果培养基中酵母氮源含量、pH值和甲醇含量对酶活的影响显著。最适产低温脂肪酶条件为:酵母氮源含量7.3 g/L、pH 6.0、甲醇含量9.1 g/L,在此条件下,低温脂肪酶酶活可达42.25 IU/ml,比优化前(28.0 IU/ml)提高了50.9%。结论利用响应面法优化的发酵条件可显著提高工程菌的产酶能力,为规模化生产低温脂肪酶奠定了基础。     

Response Surface Optimization of the Critical Media Components for the Production of Surfactin

Optimization of the fermentation media for maximization of surfactin production was carried out. The carbon source (glucose), the nitrogen source (ammonium nitrate) and the mineral salts ferrous and manganous sulphates were the critical components of the medium optimized. A 2⁴ full factorial central composite experimental design followed by multi-stage Monte-Carlo optimization was used in the design of experiments and in the analysis of results. This procedure limited the number of actual experiments performed while allowing for possible interactions between the four components. The optimum values for the tested variables for the maximal production of surfactin were (in g dm⁻³): glucose = 36·5; NH₄NO₃ = 4·5; FeSO₄ = 4×10⁻³ and MnSO₄ = 27·5 ×10⁻². Relative surfactant concentrations were expressed as the reciprocal of the critical micelle concentration (CMC⁻¹) and the maximum predicted yield of surfactin in terms of CMC⁻¹ was 45·5. © 1997 SCI.     

Experiment research on mix design and early mechanical performance of alkali-activated slag using response surface methodology (RSM)

To enhance the quality of alkali-activated slag (AAS) materials, scientific and efficient mix design method is preferred. This paper presents an optimization of AAS materials using Response Surface Methodology (RSM). Three factors related to early strength such as modulus (n), concentration of alkali activator (CAA) and liquid–solid ratio (LSR) were investigated. Specimens with different mix ratios were prepared based on RSM design. The early mechanical performance was assessed, after 2 or 3 h of curing. Then response surface models were established and the effect law of each factor was systemically analyzed. The result shows that both n and CAA have a significant effect on the early strength, while LSR affects slightly. By adjusting the mix design parameters, the early performance of AAS can be effectively improved. This study verifies that RSM is efficient in the preparation of AAS and it can control the early strength of AAS accurately.     

Biodegradation of coffee pulp tannin by Penicillium verrucosum for production of tannase,statistical optimization and its application

Coffee pulp is a primary by-product produced during coffee processing and represents 30% of the coffee fruit on a dry-weight basis. A novel potential tannin degrading fungi was isolated from coffee by-products. Among the various fungi isolated, Penicillium sp. CFR303 was found to be potent with 66.5 ± 0.9% tannin degradation. The potent tannin degrader was identified as Penicillium verrucosum using internal transcribed spacer's (ITS) −5.8S rDNA analysis. Solid state fermentation was carried out on coffee pulp as a sole carbon source and yielded 28.173 ± 1.4 U/gds of tannase. Further, 3.93 fold increase in tannase production (115.995 U/gds) was achieved using central composite rotatable design, a statistical approach. Model validations showed excellent agreement between the experimental results and the predicted responses with a confidence level of 95%. Coffee pulp accounts to 8–10% tannin content and the present study demonstrates coffee pulp as an excellent substrate for production of value added products. Aonla and pomegranate juice were treated with partially purified tannase and the degradation of tannins was evident by changes in the physicochemical parameters of the juice. Thus, the present investigation signifies utilization of coffee pulp for production of tannase as value addition and its potential application in the food industry.     

Intensification of biodiesel production from vegetable oils using ultrasonic-assisted process: Optimization and kinetic

Intensification of biodiesel production process using low frequency ultrasonic irradiation (20 kHz, 200 W) is elucidated in this study. Effects of five process variables in an ultrasonic-assisted reactor catalyzed by SrO through transesterification of vegetable oils are investigated. RSM was employed and the optimum conditions were at an ultrasonic pulse on of 9 s followed by 2 s of pulse off within a reaction time of 30.7 min. The optimum ultrasonic power was found to be 130 W using an oil amount of 52 g (R² = 0.97). The model was applicable to different types of oil with errors less than 10%. FFA content was responsible for the different yields obtained with different oils. Three steps of the transesterification process were measured to obtain the kinetic study. The results revealed that the reaction followed a second-order kinetic. The activation energies varied between 70.63 kJ/mol and 136.93 kJ/mol showing relatively high coefficient of determinations.     

Optimization of process conditions using response surface methodology for the microwave-assisted transesterification of Jatropha oil with KOH impregnated CaO as catalyst

A transesterification reaction of Jatropha curcas oil with methanol in the presence of KOH impregnated CaO catalyst was performed in a simple continuous process. The process variables such as methanol/oil molar ratio (X₁), amount of catalyst (X₂) and total reaction time (X₃) were optimized through response surface methodology, using the Box–Behnken model. Within the range of the selected operating conditions, the optimal ratio of methanol to oil, amount of catalyst and total reaction time were found to be 8.42, 3.17% and 67.9 min, respectively. The results showed that the amount of catalyst and total reaction time have significant effects on the transesterification reaction. For the product to be accepted as a biodiesel fuel, its purity must be above 96.5% of alkyl esters. Based on the optimum condition, the predicted biodiesel conversion was 97.6% while the actual experimental value was 97.1%. The above mentioned results demonstrated that the response surface methodology (RSM) based on Box–Behnken model can well predict the optimum condition for the biodiesel production.     

A comparative study on the performance of different advanced oxidation processes (UV/O3/H2O2) treating linear alkyl benzene (LAB) production plant's wastewater

A detailed investigation on photooxidation of linear alkyl benzene (LAB) industrial wastewater is presented in this study. The process analysis was performed by varying four significant independent variables including two numerical factors (initial pH (3–11) and initial H₂O₂ concentration (0–20 mM)) and two categorical factors (UV irradiation and ozonation). The experiments were conducted based on a central composite design (CCD) and analyzed using response surface methodology (RSM). To assess the process performance, two parameters viz. TCOD removal efficiency and BOD₅/COD were measured throughout the experiments. A maximum reduction in TCOD was 58, 53, 51, and 49%, respectively for UV/H₂O₂/O₃, H₂O₂/O₃, UV/O₃ and UV/H₂O₂ processes at the optimum conditions (initial pH of 7, initial H₂O₂ concentration of 100 mM, and reaction time of 180 min). A considerable increase in BOD₅/COD ratio was obtained in the combined processes (0.46, 0.51, 0.53, and 0.55 for UV/H₂O₂, UV/O₃, H₂O₂/O₃ and UV/H₂O₂/O₃, respectively) compared to the single oxidant process (0.35). The results showed that mineralization of the LAB industrial wastewater in neutral pH is more favored than in acidic and basic pH. Gas chromatography–mass spectrometry (GC–MS) was applied to show the fate of organic compounds. In conclusion, the photooxidation process (UV/H₂O₂/O₃, H₂O₂/O₃, UV/O₃ and UV/H₂O₂) could be an appropriate pretreatment method prior to a biological treatment process.     

煤矸石浸渣制备白炭黑工艺优化及性能分析

为实现煤矸石固废的资源化高效综合利用,以煤矸石浸取Al、Fe、Ti等元素后的浸渣为原料,利用煤矸石浸渣-硫酸钠干法制备出水玻璃,然后采用碳化法制备白炭黑产品。借助邻苯二甲酸二丁酯(DBP)测定产品的吸油值,并通过比表面积测定(BET)、X射线衍射分析(XRD)、红外光谱分析(FTIR)、扫描电镜(SEM)以及热重-差热分析(TG-DSC)等对白炭黑进行了结构表征与性能测试;考察了水玻璃质量分数、反应温度、Na2CO3质量浓度、CO2通入速率对白炭黑DBP吸油值和比表面积的影响,在单因素实验基础上以比表面积为主要指标,利用正交实验设计与响应曲面法联合设计优化了制备工艺。结果表明:在水玻璃质量分数为10%、反应温度为77℃、CO2通入速率为147 mL/min、Na2CO3质量浓度为3 g/L条件下,实验结果与响应曲面预测结果基本吻合,制得比表面积为267.33 m2/g、DBP吸油值为2.77 mL/g的白炭黑产品。产品性能分析表明,所制白炭黑为由非晶态物质组成的无定形态产品,产品中基本无杂质出现,纯度较高,微观形貌较好,符合HG/T3061—2009中A类产品的要求。     

Optimization of process variables for supercritical fluid extraction of ergothioneine and polyphenols from Pleurotus ostreatus and correlation to free-radical scavenging activity

Supercritical carbon dioxide extraction was employed to extract antioxidants from Pleurotus ostreatus. The response surface methodology was employed to determine the optimal conditions for extraction of ergothioneine and polyphenols. The ergothioneine concentration in the mushroom extract was quantified and characterized using high pressure liquid chromatography (HPLC) followed by tandem mass spectrometry (MS/MS). The optimized values of responses were obtained at a pressure of 21 MPa, a temperature of 48 °C and a co-solvent amount of 133 ml, yielding an ergothioneine content of 1.35 mg/g dw, total phenol content of 5.48 mg GAE/g dw, and IC50 for DPPH radical scavenging capacity of 0.008 mg/ml. A higher desirability value of 0.98 for model demonstrated that response surface methodology can be successfully applied for optimizing supercritical carbon dioxide extraction of antioxidants from P. ostreatus. A good correlation was found between DPPH radical scavenging capacity and ergothioneine (R² = 0.94) as well as with polyphenols (R² = 0.95).     

响应曲面优化法合成聚丙烯酰胺类共聚物

采用响应曲面优化法(Response surface methodology)以丙烯酰胺(AM)和二甲基二烯丙基氯化铵(DMDAAC)为共聚单体,通过自由基聚合对聚丙烯酰胺类共聚物(PDA)进行制备研究。探讨了3个主要因子单体摩尔比、聚合体系p H、引发剂用量的最佳水平及各自变量间的交互作用对PDA得率的影响,通过该法设计得到了最佳优化条件:单体摩尔比n(AM)∶n(DMDAAC)=2.5∶1,聚合体系p H6.00,引发剂用量为单体总质量的1.00%。在模型提供的最优水平下PDA得率89.807%,与预测值91.6944%相吻合,表明所选模型准确、可靠。该方法为聚丙烯酰胺类共聚物的合成及应用提供了依据。