Densities and Viscosities of the Ionic Liquid [C4mim][PF6]＋ N,N-dimethylformamide Binary Mixtures at 293.15 K to 318.15 K

Viscosities and densities for 1-butyl-3-methylimidazolium hexafluorophosphate （[C4mim][PF6]） and N, N-dimethylformamide （DMF） binary mixtures have been measured at the temperature range from 293.15 K to 318.15 K. It is shown that the viscosities and densities decrease monotonously with temperature and the content of DMF. Various correlation methods including Arrhenius-like equation, Sedclon et al.＇s equation, Redlich-Kister equation with four parameters, and other empirical equations were applied to evaluate these experimental data. A model based on an equation of state Ior estimating the viscosity of mixtures containing ionic liquids were proposed by coupling with the excess Gibbs free energy model of viscosity, which can synchronously calculate the viscosity and the molar volume. The results show that the model gives a deviation of 8.29% for the viscosity, and a deviation of 1.05% for the molar volume when only one temperature-independent adjustable parameter is adopted. The correlation accuracy is further improved when two parameters or one temperature-dependent parameter is used.

Effects of Coagulation and Ozonation Pretreatments on Biochemical Treatment of Fluid Catalytic Cracking Wastewater

Fluid catalytic cracking (FCC) salty wastewaters, containing quaternary ammonium compounds (QACs), are very difficult to treat by biochemical process. Anoxic/oxic (A/O) biochemical system, based on nitrification and denitrification reactions, was used to assess their possible biodegradation. Because of the negative effects of high salt concentration (3%), heavy metals and toxic organic matter on microorganisms’ activities, some techniques consisting of dilution, coagulation and flocculation, and ozonation pretreatments, were gradually tested to evaluate chemical oxygen demand (COD), ammonia-nitrogen (ammonia-N) and total nitrogen (TN) removal rates. In this process of FCC wastewater, starting with university-domesticated sludge, the ammonia-N and TN removal rates were worst. However, when using domesticated SBR’s sludge and operating with five-fold daily diluted influent (thus reducing salt concentration), the ammonia-N removal reached about 57% while the TN removal rate was less than 37% meaning an amelioration of the nitrification process. However, by reducing the dilution factors, these results were inflected after some days of operation, with ammonia-N removal decreasing and TN barely removed meaning a poor nitrification. Even by reducing heavy metals concentration with coagulation/flocculation process, the results never changed. Thereafter, by using ozonation pre-treatment to degrade the detected organic matter of di-tert-butylphenol and certain isoparaffins, COD, ammonia-N and TN removal rates reached 92%, 62% and 61%, respectively. These results showed that the activities of the microorganisms were increased, thus indicating a net denitrification and nitrification reactions improvement.

瞬时NH_(4)^(+)-N冲击对SBR系统污染物去除的影响

探究了瞬时NH_(4)^(+)-N冲击对SBR系统污染物去除效果的影响,在反应运行的第19、33、45天,通过提高单周期瞬时NH_(4)^(+)-N质量浓度至41.05、60.02、80.15 mg/L,对SBR系统进行冲击。结果表明,进水NH4+-N质量浓度从41.05 mg/L增加到80.15 mg/L时,COD、TP、NH_(4)^(+)-N去除效果没有明显变化,TN出水质量浓度从10.25 mg/L增加到21.49 mg/L,TN的出水变高主要受碳源不足的影响。三次瞬时NH4+-N冲击负荷下,NH4+-N降解速率基本不变。三次瞬时NH_(4)^(+)-N冲击负荷下,SBR系统中EPS总量对比常负荷运行时,均有所提高,且PN的含量在增加,PS的含量先升高后降低。而PN和PS含量的变化,在一定程度上会对活性污泥的絮凝造成影响,导致活性污泥粒径逐渐减少。系统在受到瞬时NH_(4)^(+)-N冲击后,TN出水会有所提高,但是经过一个周期的运行便可以恢复。

He^+离子辐照后Hastelloy N合金的耐腐蚀性研究

高温、辐照以及强腐蚀所引起的Hastelloy N合金的失效问题是影响熔盐堆(Molten Salt Reactor,MSR)结构材料使用寿命中的关键问题。在常温下用4.5 MeV的He+离子辐照Hastelloy N合金,吸收剂量分别为:1×1015 He+·cm-2、5×1015He+·cm-2、1×1016 He+·cm-2,采用浸入法在700°C熔融氟化盐(FLiNaK)中进行300 h腐蚀试验,研究辐照剂量对合金耐腐蚀性的影响。利用扫描电子显微(Scanning Electron microscope,SEM)、同步辐射微束X射线荧光分析(Microbeam X-ray fluorescence,μ-XRF)对腐蚀后的样品进行分析测试。结果表明,随着辐照剂量的增大,合金的耐腐蚀性逐渐减弱。μ-XRF结果表明:Hastelloy N合金在熔融氟化盐中的腐蚀主要表现为合金中Cr元素的流失。

Design analysis and its application of M out of N in reactor protection system

The reliability and availability of the reactor protection system （RPS） can be improved by using M out of N judg- ment system. By analyzing two quantitative indicators, the rate of refusal to operate and mal-operation rate, a strict math- ematical formula and an approximate calculation are stated. The differences of a series of judgment systems are discussed on condition that the unsafe failure probability and the security failure probability are both 0.1. Based on given parameters （A, B,P, Q）： A is upper limit of the refusal rate for the RPS, B is upper limit of the real-operation rate, P and Q are basic protection unit rates corresponding to refusal rate and mal-operation rate, respectively. According to these parameters, the values of N and M can be solved.

The Isobaric Vapor-Liquid Equilibrium of Butanone-DMF and Toluene-DMF at Reduced Pressures

The isobaric vapor-liquid equilibrium data of butanone(1)-N, N-dimethylformamide (DMF)(2) at 100.92kPa, 93.32kPa, and 79.99kPa and of toluene(1)-DMF(2) at 100.92kPa were measured using a modified Rose-Williams still. The above data met the thermodynamic consistency test and were correlated with the Wilson,NRTL, and UNIQUAC equations. These data can be used in the analysis and design of the process that involves separating DMF from butanone and toluene in the leather synthesis industry.

球形Ziegler-Natta催化剂在中石化环管聚丙烯工艺装置的应用

在中国石化茂名分公司国产第二代环管聚丙烯工艺装置上,采用国产球形Ziegler-Natta催化剂(催化剂1)生产了PPH-T03、N-Z30S和PPR-M55-S三种牌号聚丙烯。研究了球形催化剂在生产三种牌号聚丙烯时的催化剂效率和氢调性,同时分析了各牌号聚丙烯的粉料粒径及产品质量,并将其与另一个国产球形催化剂(催化剂2)进行了对比分析。实验结果表明,与催化剂2相比,两种催化剂生产的聚丙烯在产品质量上相当,但催化剂1的氢调性更加优异,更有利于装置生产高熔融指数产品。

The Isobaric Vapor-Liquid Equilibrium of Butanone-DMF and Toluene-DMF at Reduced Pressures

The isobaric vapor-liquid equilibrium data of butanone1-N, N-dimethylformamide DMF2 at 100.92kPa, 93.32kPa, and 79.99kPa and of toluene1-DMF2 at 100.92kPa were measured using a modified Rose–Williams still. The above data met the thermodynamic consistency test and were correlated with the Wilson, NRTL, and UNIQUAC equations. These data can be used in the analysis and design of the process that involves separating DMF from butanone and toluene in the leather synthesis industry.

Nitrite Accumulation during the Denitrification Process in SBR for the Treatment of Pre-treated Landfill Leachate

The nitrite accumulation in the denitrification process is investigated with sequencing batch reactor （SBR） treating pre-treated landfill leachate in anoxic/anaerobic up-flow anaerobic sludge bed I（UASB）. Nitrite accumulates obviously at different initial nitrate concentrations （64.9,54.8,49.3 and 29.5 mg·L^-1 ） and low temperatures, and the two break points on the oxidation-reduction potential （ORP） profile indicate the completion of nitrate and nitrite reduction. Usually, the nitrate reduction rate is used as the sole parameter to characterize the denitrification rate, and nitrite is not even measured. For accuracy, the total oxidized nitrogen （nitrate ＋ nitrite） is used as a measure, though details characterizing the process may be overlooked. Additionally, batch tests are conducted to investigate the effects of C/N ratios and types of carbon sources on the nitrite accumulation during the denitrification. It is observed that carbon source is sufficient for the reduction of nitrate to nitrite, but for further reduction of nitrite to nitrogen gas, is deficient when C/N is below the theoretical critical level of 3.75 based on the stoichiometry of denitrification. Five carbon sources used in this work, except for glucose, may cause the nitrite accumulation. From experimental results and cited literature, it is concluded that Alcaligene species may be contained in the SBR activated-sludge system.

Creep damage characterization of UNS N10003 alloy based on a numerical simulation using the Norton creep law and Kachanov–Rabotnov creep damage model

The calculation of inelastic creep damage is important for the structural integrity evaluation of the elevated temperature structure in a thorium molten salt reactor(TMSR). However, a creep damage theory model and numerical simulation method have not been proposed for the key materials(UNS N10003 alloy) in the TMSR. In this study, creep damage characterization of UNS N10003 alloy is investigated using the Norton creep law and Kachanov–Rabotnov(K–R) creep damage model. First, the creep experimental data of the UNS N10003 alloy at 650 °C were adopted to fit the material constants of the two models. Then, the creep damage behavior of the UNS N10003 alloy was analyzed and discussed under uniaxial and multi-axial stress states. The results indicated that the K–R creep damage model is more suitable for the UNS N10003 alloy than the Norton model. Finally, the numerical simulation method was developed by a user-defined UMAT subroutine and subsequently verified through a finite element analysis(FEA). The FEA results were in agreement with the theoretical solutions. This study provides an effective method for the inelastic creep damage analysis of the elevated temperature structure in the TMSR.

低C/N比CANON工艺脱氮机制分析

该文在微氧升流反应器中构建颗粒-絮体污泥体系,以乙酸钠作为碳源,探究了C/N对CANON工艺脱氮效率的影响,并分析了低C/N下该工艺的脱氮机制。当C/N=0.75时,TN和NH_(4)^(+)-N去除率达到了最高值92%和95%。而当C/N从0.75增长至1时,TN和NH_(4)^(+)-N去除率分别下降至80%和85%;C/N回调至0.75后,10 d左右反应器性能恢复至91%TN去除率。C/N=0.75时脱氮贡献分析和粒度分布表明AnAOB对NO_(2)^(-)-N的摄取处于优势地位,反应器内主要发生Anammox反应和短程反硝化反应,合适的C/N并不会导致异养菌取代AnAOB的优势地位,且Anammox反应的脱氮贡献在56%~62%之间。

3D ball-type self-assemble CeO_(2) nanostructure produced by facile hydrothermal strategy for catalytic wet air oxidation of N,N-dimethylformamide

CeO_(2)plays an important role in heterogeneous catalysis,and its performance is highly dependent on the oxygen vacancies and surface defects,which can be easily tuned by manipulating the particle dimensions and morphology.In this article,we report a facile strategy to synthesize a new type of CeO_(2)with modified surface property which can improve its ability to active oxygen.The obtained ball-type 3D selfassemble CeO_(2)(M-CeO_(2)) is composed of large amounts of small 1D crystals which are stro ngly connected with each other.Detailed characterizations confirm its morphology,particle size and improved reducibility with abundant fraction of Ce^(3+)and more surface active oxygen when compared with CeO_(2)-nanorods and CeO_(2)-nanocubes.In the catalytic wet air oxidation(CWAO)of N,N-dimethylfo rmamide,the total organic carbon(TOC)and total nitrogen(TN)conversion of M-CeO_(2)at 180℃in 3 h are 68%and 46%,respectively,which are higher than that of CeO_(2)-nanorods and CeO_(2)-nanocubes.Besides,M-CeO_(2) presents the lowest activation energy,which is related to its modified surface property.The good stability with consecutive four reactions of M-CeO_(2)in catalytic reactions suggests its potential application in CWAO processes for industrial wastewater treatment.

改进A^(2)/N双污泥工艺启动条件的研究

针对原有的A^(2)/N双污泥法,以实验室原有的AnOR反应器为基础,增设沉淀池与曝气生物滤塔构建部分一体化双污泥工艺装置,进一步简化处理流程,探究该工艺的启动条件。实验结果表明:最佳的启动条件为进水流量为3 L/h,硝化液回流比110%,维持2/5池内污泥高度,厌氧池ORP在-200 mV左右,缺氧池ORP在-240 mV左右,好氧池DO质量浓度为2~4 mg/L,曝气生物滤塔DO质量浓度为2~3 mg/L,启动期COD、NH_(4)^(+)-N、TN和TP平均去除率分别为97.0%、98.8%、71.6%和65.0%,各项指标基本满足城镇污水处理厂排放标准的污染物排放限值。

Recovery Technology of DMF from Wet Type Polyurethane Synthetic Leather Waste Gas

A new recovery technology is developed to recycle N,N-dimethyl formamide （DMF） in waste gas from wet type polyurethane synthetic leather industry. Given that the concentration of DMF in waste gas was as low as 325.6- 688.3 mg·m^-3, it was necessary to make sure two phases contact adequately and strengthen the mass transfer by increasing contact area and enhancing the turbulence. Therefore, two-stage countercurrent absorption and two-stage fog removing system were introduced into the technology. The top section of the absorption column was filled with structured wire-ripple stainless steel packing BX500, while the lower section with sting-ripple packing CB250Y. Total height of packing material was 6 m. In addition, there were both two-stage fog removing layer and high efficiency liquid distributor at the column top. All the operating parameters, including temperature, pressure, flow rate and liquid position, could be controlled by computers without manual operation, making sure the outlet gas achieved the national emission standard that the DMF concentration should be below 40 mg·m^-3. The whole equipment could recover 237.6 t of DMF each year, with the profit up to CNY 521×10^3.

固定床催化合成N,N,N′,N′-四甲基乙二胺的研究

通过自制备的金属负载型催化剂,以二甲胺和乙二醇为原料,在气固固定床反应器中合成了N,N,N′,N′-四甲基乙二胺.以γ-Al2O3为载体,Cu、Ni、Cr、Zn等金属为活性组分,通过浸渍法制备了3种二元金属负载型催化剂:Cu-Ni型、Cu-Zn型、Cu-Cr型.在相同条件下对3种催化剂的催化性能进行了考察,对乙二醇转化率及四甲基乙二胺的选择性进行了分析,结果表明:Cu-Ni型催化剂的催化效果最佳.通过平行实验对反应温度、胺醇的物质的量比及体积空速进行了研究,获得了较优的条件区间范围.根据平行实验结果,采用响应面实验设计方法(DesignEx-pert软件)对反应条件进行了优化,获得了最优的反应条件:以Cu-Ni为活性组分的催化剂进行催化,反应温度为204.81℃,胺醇的物质的量比为5.27,体积空速为0.29h-1,最佳产率可以达到79.84%.

N-氰乙基苯胺的合成工艺研究

利用高压反应釜,在高温下用氯化锌和盐酸催化苯胺与丙烯腈反应,合成N-氰乙基苯胺。考察不同反应条件对反应结果的影响,探究提高N-氰乙基苯胺反应速率的方法,同时探索影响副反应发生的条件,确定最优工艺参数,为连续化放大设计提供参考依据。本研究的最优反应条件:温度为110℃,反应时间为6~8 h,搅拌速率为300 r/min,盐酸用量为苯胺用量的14.4%,氯化锌用量为苯胺用量的11.1%。

A2N2系统反硝化除磷性能的优化及稳定运行

利用按"厌氧/硝化/缺氧/硝化"方式运行的双污泥反硝化除磷系统(A_2N_2),以低C/N值实际生活污水为研究对象,重点研究A^2/O-SBR和N-SBR单元的运行条件优化过程中,各污染物去除的变化规律及系统的脱氮除磷性能.研究结果表明;完全反硝化除磷无好氧吸磷模式不利于反硝化聚磷菌(DPAOs)的生长繁殖,后曝气对保障A_2N_2系统高效稳定的脱氮除磷效果及长期稳定运行必不可少;A^2/O-SBR单元厌氧1.5h,基本完成了可生物降解COD的氧化;N-SBR单元硝化5h,实现了NH4+-N的完全硝化;在A2/O-SBR单元厌氧释磷1.5h,反硝化除磷2h,好氧吸磷0.5h,N-SBR单元一次硝化5h,二次硝化1h的条件下,系统平均出水COD、NH_4^+-N、TN和PO_4^(3-)-P浓度分别为46.2、0.82、13.63、0.3mg/L,满足了同步脱氮除磷的要求.

N-乙烯基己内酰胺的合成工艺及应用研究

叙述了N-乙烯基己内酰胺的国内外研究现状和进展,介绍了它的合成工艺及应用。论述了制取乙烯基己内酰胺的液相法:在氢氧化钾存在下,通过乙炔和己内酰胺发生反应生成。该方法操作简单,易于控制,且为常压反应。

N-苯基碳酰胺酸甲酯的合成

研讨了N-苯基甲酰胺酸甲酯(MPC)的新颖合成,整个合成分为两步完成:①起始原料尿素与苯胺在无溶剂存在下反应合成N,N′-二苯基脲(DPU),通过实验确定最佳工艺条件为:反应温度170℃;n(苯胺)∶n(尿素)=5∶1;反应时间1.5h,N,N′-二苯基脲粗产物经重结晶法纯化,产率可达96.3%;②N,N′-二苯基脲与甲醇在高压反应釜中(氮气保护)无其它溶剂存在下醇解反应合成N-苯基碳酰胺酸甲酯。经过实验优化确定反应工艺条件为:反应温度170℃,n(N,N′-二苯基脲)∶n(甲醇)=1∶10,反应时间4h。粗产物经柱色谱分离提纯,N-苯基碳酰胺酸甲酯的分离产率可达83.7%。所有产物的分子结构经1 H NMR,13C NMR以及IR光谱表征。

Polarization-dependent ultrafast optical nonlinearities of N,N-dimethylformamide at 400 nm

Ultrafast optical nonlinearities of N,N-dimethylformamide(DMF)are studied by using polarized light at 400 nm.Both nonlinear refraction(NLR)and stimulated Rayleigh-wing scattering(SRWS)depend on the polarization state of incident beam,while two-photon absorption(TPA)changes negligibly with polarization state.The polarization dependence of SRWS originates from that of NLR via self-focusing effect.Third-order susceptibility elements of DMF were determined,and a method to distinguish the multi-photon absorption signal from SRWS in Z-scan is provided.These results are helpful for the nonlinear optical research of the novel materials dissolved in DMF.