Intermolecular Acid-Base-Pairs Containing Poly(p-Terphenyl-co-lsatin Piperidinium)for High Temperature Proton Exchange Membrane Fuel Cells

How to optimize and regulate the distribution of phosphoric acid in matrix,and pursuing the improved electrochemical performance and service lifetime of high temperature proton exchange membrane(HT-PEMs)fuel cell are significant challenges.Herein,bifunctional poly(p-terphenyl-co-isatin piperidinium)copolymer with tethered phosphonic acid(t-PA)and intrinsic tertiary amine base groups are firstly prepared and investigated as HT-PEMs.The distinctive architecture of the copolymer provides a well-designed platform for rapid proton transport.Protons not only transports through the hydrogen bond network formed by the adsorbed free phosphoric acid(f-PA)anchored by the tertiary amine base groups,but also rely upon the proton channel constructed by the ionic cluster formed by the t-PA aggregation.Thorough the design of the structure,the bifunctional copolymers with lower PA uptake level(<100%)display prominent proton conductivities and peak power densities(99 mS cm^(-1),812 mW cm^(-2)at 160℃),along with lower PA leaching and higher voltage stability,which is a top leading result in disclosed literature.The results demonstrate that the design of intermolecular acid-base-pairs can improve the proton conductivity without sacrificing the intrinsic chemical stability or mechanical property of the thin membrane,realizing win-win demands between the mechanical robustness and electrochemical properties of HT-PEMs.

Mechanical properties and damage constitutive model of sandstone after acid corrosion and high temperature treatments

Aiming at the problem of temperature-mechanics-chemical(T-M-C)action encountered by rocks in underground engineering,sandstone was selected as the sample for acid corrosion treatment at pH 1,3,5 and 7,the acid corrosion treated samples were then subjected to high-temperature experiments at 25,300,600,and 900℃,and triaxial compression experiments were conducted in the laboratory.The experimental results show that the superposition of chemical damage and thermal damage has a significant impact on the quality,wave velocity,porosity and compression failure characteristics of the rock.Based on the Lemaitre strain equivalent hypothesis theory,the damage degree of rock material was described by introducing damage variables,and the spatial mobilized plane(SMP)criterion was adopted.The damage constitutive model can well reflect the stress-strain characteristics of the rock triaxial compression process,which verified the rationality and reliability of the model parameters.The experiment and constitutive model analyzed the change law of mechanical properties of rock after chemical corrosion and high temperature thermal damage,which had certain practical significance for rock engineering construction.

High Temperature During Rice Grain Filling Enhances Aspartate Metabolism in Grains and Results in Accumulation of AspartateFamily Amino Acids and Protein Components

Global warming causes the exacerbation of rice growing environment, which seriously affects rice growth and reproduction, and finally results in the decrease of rice yield and quality. We investigated the activities of aspartate metabolism enzymes in grains, and the contents of Aspartate-family amino acids and protein components to further understand the effects of high temperature （HT） on rice nutritional quality during rice grain filling. Under HT, the average activities of aspartate aminotransferase （AAT） and aspartokinase （AK） in grains significantly increased, the amino acid contents of aspartate （Asp）, lysine （Lys）, threonine （Thr）, methionine （Met） and isoleucine （lie） and the protein contents of albumin, globulin, prolamin and glutelin also significantly increased. The results indicated that HT enhanced Asp metabolism during rice grain filling and the enhancement of Asp metabolism might play an important role in the increase of Asp-family amino acids and protein components in grains. In case of the partial appraisal of the change of Asp-family amino acids and protein components under HT, we introduced eight indicators （amino acid or protein content, ratio of amino acid or protein, amino acid or protein content per grain and amino acid or protein content per panicle） to estimate the effects of HT. It is suggested that HT during rice grain filling was benefit for the accumulation of Asp-family amino acids and protein components. Combined with the improvement of Asp-family amino acid ratio in grains under HT, it is suggested that HT during grain filling may improve the rice nutritional quality. However, the yields of parts of Asp-family amino acids and protein components were decreased under HT during rice grain filling.

Leaching behavior of metals from limonitic laterite ore by high pressure acid leaching

The leaching behavior of metals from a nickeliferous limonitic laterite ore was investigated by high pressure acid leaching process for the extraction of nickel and cobalt.The effects of sulfuric acid added,leaching temperature,leaching time and liquid/solid（L/S） ratio on metals extraction were examined.More than 97% Ni,96% Co,93% Mn,95% Mg and less than 1% Fe are extracted under optimum conditions.Analysis of the high pressure acid leaching residue by chemical and XRD analysis indicates that the residual iron and sulfur are mainly present in phases of hematite and alunite,respectively.The high pressure leaching process provides a simple and efficient way for the high recovery of nickel and cobalt from laterite ore,leaving residue as a suitable iron resource.

High Temperature at Grain-filling Stage Affects Nitrogen Metabolism Enzyme Activities in Grains and Grain Nutritional Quality in Rice

Rice plants would more frequently suffer from high temperature (HT) stress at the grain-filling stage in future. A japonica rice variety Koshihikari and an indica rice variety IR72 were used to study the effect of high temperature on dynamic changes of glutamine synthetase (GS) activity, glutamate synthase (GOGAT) activity, glutamic oxalo-acetic transminase (GOT) activity, glutamate pyruvate transminase (GPT) activity in grains and grain nutritional quality at the grain-filling stage. Under HT, the activities of GOGAT, GOT, GPT and soluble protein content in grains significantly increased, whereas GS activity significantly decreased at the grain-filling stage. In addition to the increase of protein and amino acids contents, it was suggested that GOGAT, GOT and GPT in grains played important roles in nitrogen metabolism at the grain-filling stage. Since the decrease of GS activity in grains did not influence the accumulations of amino acids and protein, it is implied that GS might not be the key enzyme in regulating glutamine content in grains.

Sulfuric acid leaching of high iron-bearing zinc calcine

Sulfuric acid leaching of high iron-bearing zinc calcine was investigated to assess the effects of sulfuric acid concentration, liquid-to-solid ratio, leaching time, leaching temperature, and the stirring speed on the leaching rates of zinc and iron. The results showed that the sulfuric acid concentration, liquid-to-solid ratio, leaching time, and leaching temperature strongly influenced the leaching of zinc and iron, whereas stirring speed had little influence. Zinc was mainly leached and the leaching rate of iron was low when the sulfuric acid concentration was less than 100 g/L. At sulfuric acid concentrations higher than 100 g/L, the leaching rate of iron increased quickly with increasing sulfuric acid concentration. This behavior is attributed to iron-bearing minerals such as zinc ferrite in zinc calcine dissolving at high temperatures and high sulfuric acid concentrations but not at low temperatures and low sulfuric acid concentrations.

Enhanced Acid/Base Catalysis in High Temperature Liquid Water

Two novel and environmentally benign solvent systems, organic acids-ennchea high temperature liquid water （HTLW） and NH3-enriched HTLW, were developed, which can enhance the reaction rate of acid/base-catalyzed organic reactions in HTLW. We investigated the decomposition of fructose in organic acids-enriched HTLW, hydrolysis of cinnamaldehyde and aldol condensation of phenylaldehyde with acetaldehyde in NH3-enriched HTLW. The experimental results demonstrated that organic acids-enriched or NH3-enriched HTLW can greatly accelerate acid/base-catalyzed organic reactions in HTLW.

The Combined Effects of High Temperature and Carbon Monoxide on Heat Stress Response

In this study,we have examined the effects of exposure to high temperature, carbon inonoxideor a combination of both conditions in a model system,the rat and in industrial workers.In the rat liver, HSP70 mRNA and HSP70 synthesis were measured by dot hybridization and western blot. The results showed that after a heat stress HSP70 mRNA and its product, HSP70 increased significantly and there was a synergism in the combined effects of high temperature and carbon monoxide exposure on the induction of HSP70 mRNA and HSP70 synthesis. Heat played a major role in this induction. The presence of antibodies to human HSP27, HSP60, HSP70,HSC73, HSP89 αand β in workers exposed to heat, carbon monoxide was also measured by western blot using purified HSPs as antigens. Plasma free amino acids were measured in the saine group of workers. The incidence of antibodies to HSP27 and HSP70 Was significantly higher in the workers working in an environment with extreme heat, and high carbon monoxide ernission than in a control group. The carbon monoxide exposed group showed the highest incidence of antibodies to HSPs. Although our previous results indicated that workers had an insufficient protein intake,plasma free amino acids tended to increase, especially in methionine and tryptophan two kinds of amino acids which are absent from the main stress protein, HSP70.These results suggest that the major problems that these workers may face are how to facilitate the use of plasma free amino acids and reduce the inhibition of synthesis of normal proteins when they are exposed to occupational harmful factors.These resultsalso add new information on the measurement of HSPs as a potential biomonitor to assess whether organisms are experiencing metabolic stress within their environment.

Water-induced electrode poisoning and the mitigation strategy for high temperature polymer electrolyte membrane fuel cells

Engineering failure of membrane electrode assembly caused by increasingly fuel poisoning in the high temperature polymer electrolyte membrane fuel cells fed with humidified reformate gases is firstly demonstrated herein this work. Based on the results of the in-situ environmental scanning electron microscope, electrochemical analyses, and limiting current method, a water-induced phosphoric acid invasion model is constructed in the porous electrode to elucidate the failure causations of the hindered hydrogen mass transport and the enhanced carbon monoxide poisoning. To optimize the phosphoric acid distribution under the inevitably humidified circumstance, a facile and effective strategy of constructing acid-proofed electrode is proposed and demonstrates outstanding stability with highly humidified reformate gases as anode fuel. This work discusses a potential defect that was rarely studied previously under practical working circumstance for high temperature polymer electrolyte membrane fuel cells, providing an alternative opinion of electrode design based on the fundamental aspects towards the engineering problems.

Sulfonated polybenzimidazole/amine functionalized titanium dioxide(s PBI/AFT) composite electrolyte membranes for high temperature proton exchange membrane fuel cells usage

The novel sulfonated polybenzimidazole(sPBI)/amine functionalized titanium dioxide(AFT) composite membrane is devised and studied for its capability of the application of high temperature proton exchange membrane fuel cells(HT-PEMFCs),unlike the prior low temperature AFT endeavors.The high temperature compatibility was actualized because of the filling of free volumes in the rigid aromatic matrix of the composite with AFT nanoparticles which inhibited segmental motions of the chains and improved its thermal stability.Besides,amine functionalization of TiO2 enhanced their dispersion character in the sPBI matrix and shortened the interparticle separation gap which finally improved the proton transfer after establishing interconnected pathways and breeding more phosphoric acid(PA) doping.In addition,the appeared assembled clusters of AFT flourished a superior mechanical stability.Thus,the optimized sPBI/AFT(10 wt%) showed 65.3 MPa tensile strength;0.084 S·cm^-1 proton conductivity(at 160℃;in anhydrous conditions),28.6% water uptake and PA doping level of 23 mol per sPBI repeat unit.The maximum power density peak for sPBI/AFT-10 met the figure of0.42 W·cm^-2 at 160℃(in dry conditions) under atmospheric pressure with 1.5 and 2.5 stoichiometric flow rates of H2/air.These results affirmed the probable fitting of sPBI/AFT composite for HT-PEMFC applications.

High Temperature Chemical Reaction of La_2O_3 in H_3BO_3-C System

The high temperature chemical reaction process of La2O3 in H3BO3-C system was studied by means of XRD and TG-DTA.The results showed that dehydration reaction of H3BO3 occurred in the temperature range of 82～390 ℃;La2O3 and B2O3 reacted to form LaB3O6,LaBO3,and B4C in the temperature range of 836～1400℃;at 1450 ℃,B4C and LaBO3 further reacted to form LaB4,and partial LaB4 and B reacted to form LaB6;at 1500 ℃,LaB4 and B reacting into LaB6 was the main reaction,and the content of LaB6 increased with prolonging time.

Research on Experimental and Application for the High Efficient Enrichment of the Low-grade Precious Metal Materials

On the basis of reviewing the progress in the high efficient enrichment from secondary resources of low grade precious metals at home and abroad, a process route of the high efficient enrichment precious metals from secondary resources of low-grade metals by adding iron oxide as the trapping agent, reducing agent, additive, mixing uniformly and grinding, pelletizing, reduction, grinding and separation, and selectively acid leaching iron has been put forward in this paper. The experiments of reduction, grinding and separation, and selectively acid leaching iron were carried out mainly. Under the decided experiment parameters and conditions, iron generated during the reduction can trap precious metals during reduction, high active alloy powders were obtained from the reduced products by grinding and separation, the concentration of precious metals was obtained by acid leaching high active alloy powders. The better enrichment effect was obtained by adopting the technical route of processing. Other low grade noble metal materials and enrichment ratio of precious metals from the materials to acid products was high through acid leaching. This process has the advantages of simple process, environmental-friendly, strong adaptability of raw materials, high concentration ratio, which was regarded as a kind of the general efficient enrichment technology of low grade precious metal materials.

Preparation of boric acid from low-grade ascharite and recovery of magnesium sulfate

Boric acid and kieserite were prepared from low-grade ascharite by sulfuric acid method.This method results in the recovery of 71.06%and 45.03%for boric acid and kieserite,respectively.Meanwhile,the boric acid was precipitated from the filtrate at low temperature and the solution was recycled without discharging waste liquid in the whole process.The influence of amount of sulfuric acid,mass fraction of sulfuric acid,reaction temperature and reaction time on the leaching rate of boric acid were studied. The results show that the leaching rate of boric acid reaches 93.80%under the following conditions:the amount of sulfuric acid is 85%of theoretical dosage;the mass fraction of sulfuric acid is 25%;reaction temperature is 95℃;and the reaction time is 100 min. Meanwhile,the effects of mass fraction of magnesium sulfate,crystallization temperature and crystallization time on the crystallization of kieserite were investigated and the optimal crystallization conditions are obtained:the mass fraction of magnesium sulfate is 28%;the crystallization temperature is 180℃and the crystallization time is 4h.

Corrosion Rate of Hydrogenation to C110 Casing in High H_2S Environment

The corrosion behavior of C110 bushing at high temperature and high pressure with a high H2S / CO2 was studied, and a basis for the materials selection of sour gas well bushing was provided in H2S, CO2 and saline coexisting environment. Under acidic condiction, hydrogen atoms greatly entered into the material and caused the material properties changed. Weight loss method was used to study the corrosion rate of hydrogen charging samples and original untreated samples in simulated oil field environment. PAR2273 electrochemical workstation was used to examine the electrochemical performance of samples untreated, hydrogen charging after reacting in autoclave. The corrosion product film was observed through SEM. The experimental results show that sample with hydrogen charging has a much more obvious partial corrosion and pitting corrosion than the untreated blank sample even the downhole corrosion speed of bushing is increased after being used for a period of time. Polarization curve shows the corrosion tendency is the same between sample with or without hydrogen charging and corrosion tendency is reduced by corrosion product film. A layer of dense product film formed on the surface of samples provides a certain protective effect to the matrix, but cracked holes which will accelerate partial corrosion of the sample were also observed.

废烟气脱硝催化剂中TiO_(2)资源化回收实验研究

采用高温碱浸和酸洗的方法对废选择性催化还原(SCR)脱硝催化剂进行处理,研究碱浸和酸洗对催化剂各组分的浸出效果,考察温度对催化剂浸出行为的影响规律。结果表明,碱浸温度的提高促进V和W的浸出,210℃时V和W的浸出率分别为82.38%和74.92%。经高温碱浸和酸洗处理后,Al、Ca、Na等杂质的最高浸出率均可达98%以上,回收TiO_(2)的纯度较高,可用于生产新催化剂。高温碱浸会破坏催化剂的结构,有利于后续HCl处理对杂质的去除,除杂效果优于直接酸洗处理。高温碱浸过程中会生成Na_(2)TiO_(3),经HCl反应并水解后会形成新的TiO_(2)颗粒,形成更多的小孔,比表面积增大。

825合金在含单质硫高温高酸性环境中的局部腐蚀行为

在132℃、H_(2)S分压4.8MPa、CO_(2)分压1.6MPa、氯离子质量浓度42750mg·L^(-1)的气田模拟地层水中,通过腐蚀挂片试验研究了825合金在含单质硫(每升地层水中包裹合金的单质硫质量为10g)与不含单质硫条件下的局部腐蚀行为。结果表明:在不含单质硫条件下825合金几乎不发生腐蚀,腐蚀6d时的腐蚀速率仅为0.0077mm·a^(-1);添加单质硫腐蚀3d时腐蚀速率达到0.0552mm·a^(-1),合金发生了严重的局部腐蚀,随腐蚀时间的延长,合金表面局部腐蚀坑面积、腐蚀坑最大深度和腐蚀速率增大。在不含单质硫条件下合金表面腐蚀产物极少,主要为FeCO_(3),在含单质硫条件下,随着腐蚀时间的延长,表面腐蚀产物增多,主要为FeCO_(3)与FeS;单质硫在高温下发生歧化反应产生H^(+)和S^(2-),使825合金表面腐蚀产物膜破裂,从而加剧了局部腐蚀。

船用铸铁耐高温甲酸腐蚀涂层抗高温腐蚀性能研究

为有效预防铸铁材料的腐蚀,提高船舶的安全性,研究船用铸铁耐高温甲酸腐蚀涂层抗高温腐蚀性能。制备纳米Fe粉体材料和添加了纳米Al粉和Cr_(3)C_(2)粉的Fe-Al/Cr_(3)C_(2)复合喷涂粉体材料以及指标甲酸溶液,利用正火态20钢制备铸铁试件M-1和M-2,将甲酸溶液作为腐蚀溶液,在不同高温环境下进行抗高温腐蚀性能测试。试验结果表明,铸铁涂层试件在高温甲酸溶液腐蚀后,涂层表明呈现不同程度凸起,该凸起为Al和Cr氧化物以及Fe氧化物,该氧化物对铸铁材料起到了保护膜作用,因此试件M-2的抗高温腐蚀性能较好;在相同高温甲酸溶液腐蚀环境下,试件M-2的质量损失数值也低于试件M-1,表明添加了纳米Al粉和Cr_(3)C_(2)粉的Fe-Al/Cr_(3)C_(2)复合喷涂粉体材料制备成的铸铁试件M-2抗高温腐蚀能力较强。

某锂矿低温熟化—水浸提锂和提纯高纯石英新工艺

皖南低品位热液蚀变型锂矿Li_(2)O含量0.21%,属于新类型锂矿资源,主要矿物成分有长石、石英、白云母、绿泥石,锂主要以晶格形式赋存于锂绿泥石中。新工艺采用-1 mm原矿筛分,+0.425 mm粒级进入磨矿,制备-0.425+0.074 mm合格粒级。脱泥后合格粒级产品经磁选得云母精矿,非磁性物浮选得到长石精矿和石英精矿,长石精矿和云母精矿分别进行提锂,石英精矿进行酸处理提纯得高纯石英。将原矿筛出的-0.074 mm细泥、再磨产生的-0.074 mm细泥、合格粒级搅拌擦洗产生的-0.074 mm细泥,合并为总泥进行后续提锂。试验结果表明:总泥、云母、长石分别采用低温熟化—水浸工艺提锂,累计得Li_(2)O浸出率88.78%,酸浸后石英精矿含SiO_(2)99.942%,Fe 4.38 mg/kg,达到高纯石英低端产品要求,提锂后的长石和云母浸渣产率54.48%,可用于建筑材料。浸出前后样品的XRD和SEM分析表明,硫酸低温熟化破坏了锂绿泥石晶格结构,H+代替锂绿泥石中Li+,将锂释放出来。新工艺降低了磨矿成本,锂浸出率高,兼顾云母、石英、长石的回收,减少了尾矿排放,提高了低品位热液蚀变型锂矿的综合利用水平。

塔里木盆地库车山前超深气井砂垢堵塞成因及靶向解除技术

塔里盆地库车山前超深气田是西气东输主力气源地,具有超高温、超高压、高矿化度、储层裂缝非均质性强等特征,气井生产过程中砂垢堵塞问题突出,据统计最高影响气田产能达800×104 m^(3)/d。为实现超深气井高效解堵,通过气水两相结垢热力学预测模型、裂缝性储层岩石力学实验、井筒内气液固流动模拟等研究,揭示了超深气井砂垢复合堵塞成因,并形成了靶向解堵复产关键技术。研究结果表明:①“高温流动压降结垢、裂缝面破裂出砂”是超深气井出砂结垢的内在机理;②结垢固化松散砂桥形成复合堵塞是气井堵塞减产的主要原因,其中靶向除垢是解堵复产的关键所在;③靶向除垢解堵区域为井筒变径处和井周5 m内基质—裂缝系统,气井堵塞率30%~60%为最佳解堵时机;④非酸性除垢解堵液相比常用的酸性解堵液,在同级别溶垢能力的基础上,腐蚀速率降至0.49 g/(m^(2)·h),可同时满足低腐蚀和高效除垢的技术要求。结论认为,形成的超深气井靶向除垢解堵技术在塔里木盆地库车山前超深气田规模应用159井次,有效率达93.3%,累计增产天然气75.08×10^(8)m^(3),已成为西气东输主力气井快速解堵复产的“冬保良方”,可为国内外同类气田解堵复产提供技术借鉴。

丙烯酸-没食子酸基新型改性转锈剂乳液及耐高温涂料的合成研究

转锈剂具有反应条件温和、高效等优点,因此被广泛应用于金属表面的防锈处理。为解决大型钢材建筑除锈难的问题,本研究以丙烯酸、没食子酸为原料,采用种子乳液聚合法制备了一种新型的转锈剂乳液,并以此为成膜物质。以环氧树脂、多异氰酸酯为主要原料,采用溶胶-凝胶法制备了一种耐高温涂料。结果表明,改性丙烯酸转锈乳液粒径相对均匀,涂覆锈转化涂料的样品腐蚀电位为-0.613 V,比裸钢及附着锈钢的腐蚀电位要低得多,对锈转化有一定的抑制作用。通过一系列单因素实验得出耐高温涂料的最佳制备条件为:研磨时间为50 min、分散时间为60 min、颜基比为3.0、漆膜厚度为300μm、固化剂用量为15%。研究制得的转锈剂乳液稳定性较好,耐腐蚀性能优异,可实现金属设备的防腐蚀要求。