石油中镍、钒的研究进展

对石油中镍、钒的研究状况进行了评述.讨论了石油中镍、钒的存在形式及其在化工生产中的毒害作用;对石油镍、钒的脱除、卟啉镍和卟啉钒的分离提纯以及鉴定方法进行了详细阐述.     

低品位碱预处理红土镍矿加压浸出过程

研究了低品位碱预处理红土镍矿在混合酸介质中的加压浸出过程.褐铁型红土镍矿经碱预处理改性后,铁主要以非晶态铁氧化物形态存在,而镍主要以氧化镍形态吸附于非晶态铁氧化物表面.由实验确定的改性红土镍矿加压浸出优化工艺条件为:浸出温度458K、保温时间60min、浸出体系初始酸度2.44mol/L、液固比2mL/g、搅拌转速500r/min.上述工艺具有良好的稳定性,镍与钴浸出率分别保持在95%和80%左右,浸出渣含镍和钴分别低至约0.028%和0.007%,而杂质铁浸出率低至1%左右,有价金属镍、钴与杂质铁分离性能良好.经加压浸出,改性红土镍矿中的铁最终以赤铁矿形式水解沉淀入渣,且浸出渣含铁矿物中几乎不含镍,浸出渣中的铁可进一步回收利用.     

改性糠醛渣对废水中镍离子的吸附性能

研究了改性糠醛渣对镍离子的吸附性能。结果表明,改性糠醛渣对废水中镍离子的吸附在30 min达到平衡;在50 mL含20 mg/L的镍离子废水中,加入改性糠醛渣0.02 g时,对废水中镍离子的吸附量达到19mg/g左右;平衡吸附量与平衡浓度之间的关系符合Freundlich和Langmuir等温吸附方程所描述的规律。     

球形聚合物刷对卟啉镍的脱除规律研究

以八乙基镍卟啉（OEP-Ni）为模型物，探究聚乙烯基咪唑刷（PVIm@SiO₂）、聚乙烯基吡咯烷酮刷（PVP@SiO₂）和聚丙烯酸刷（PAA@SiO₂）对OEP-Ni的脱除差异性。结果表明，当脱镍温度为110℃、时间为3 h、脱镍剂质量分数为6 000μg/g时，PVIm@SiO₂、PVP@SiO₂和PAA@SiO₂对OEP-Ni的脱除率分别为28.9%、15.7%和9.8%;同时，3种聚合物刷对模拟原油的脱除率分别为9.9%、6.8%和5.8%。DFT计算结果表明，3种单体对镍的螯合能力为乙烯基咪唑（VIm）>乙烯基吡咯烷酮（VP）>丙烯酸（AA）,与聚合物刷对OEP-Ni的脱除效果一致。以四苯基镍卟啉（TPP-Ni）为模型物，研究PVIm@SiO₂、PAA@SiO₂和5%醋酸溶液对TPP-Ni的脱除效果，结果表明，PVIm@SiO₂和PAA@SiO₂对T...     

污泥焚烧渣处理含镍废水的模拟实验

污泥焚烧渣具有较大的表面积,对镍离子有一定的吸附能力.本文研究了吸附时间、镍离子初始浓度、废水pH和城市污泥焚烧渣投加量对废水中镍离子吸附率的影响.结果表明,当镍离子初始质量浓度为30 mg/L,废水pH为7.0,吸附时间为6 h,城市污泥焚烧渣投加量为10 g/L时,吸附效果最佳.     

红土镍矿硝酸加压浸出工艺

采用硝酸介质加压浸出处理红土镍矿,考察了初始硝酸浓度、浸出温度、保温时间和液固比对有价组分浸出率的影响,确定了该工艺的可行性。得到优化工艺条件为初始硝酸浓度330 kg/t,浸出温度190℃,保温时间60 min,液固比1.5:1~1.7:1 mL/g。最优工艺条件下,镍、钴的浸出率均大于85%,镁浸出率为80%,铝的浸出率大于60%,铁的浸出率低于1%,产出了含铁55%的富铁渣。对浸出液采用氧化镁梯级沉淀的方法,控制温度85℃、pH?3.0,可除掉95%的铁;控制pH=4.0~4.3,可除掉99%以上的铝,原矿中约90%以上的钪随铝进入渣相,得到含钪近1000 g/t的铝钪富集物;调节pH=7.5~8.0,溶液中的镍钴沉淀完全,得到含镍24.8%和含钴2.3%的氢氧化镍钴渣,实现了镍、钴与铁、铝高效分离和富集。梯级沉淀后的硝酸镁溶液蒸发结晶,在500℃下煅烧,得到轻质氧化镁;回收热分解产生的氮氧化物气体再生硝酸,常压下再生率达92%以上,实现了红土镍矿中有价组分的高效分离和浸出介质的循环利用。     

镍渣基泡沫玻璃的制备及其性能研究

以镍渣和废玻璃作为主要原料,使用Na2CO3为发泡剂,采用模具装填法来烧制泡沫玻璃.研究了镍渣的掺量、发泡剂掺量、发泡温度和发泡时间对泡沫玻璃的气孔结构和相关力学性能的影响.研究表明:镍渣掺量减少,Na2CO3掺量增加和发泡温度的升高,均会降低泡沫玻璃的体积密度,提高样品的平均气孔直径;镍渣掺量对泡沫玻璃的组成成分和晶体种类没有明显的影响;以20%镍渣和80%玻璃粉为主料,5%~7%Na2CO3为发泡剂,在发泡温度870 ℃下保温60 min,可以制备出气孔率为85.14%,体积密度为0.3715 g/cm3,抗折强度为2.062 MPa,平均气孔直径在3.13 mm的镍渣基泡沫玻璃.     

ICP-MS测定镍精矿中贵金属金、铂、钯含量

镍精矿含有的贵金属金、铂、钯具有重要的价值,由于含量低,传统测量方法必须经过分离富集,存在预处理速度慢,过程繁琐,处理费用高等问题。本文采用不经预分离富集,利用电感耦合等离子体质谱法(ICP-M)直接测定镍精矿中的金、铂、钯。考察了矿样分析方法,测定条件的选择,Ni、Fe、Cu等基体元素的干扰及消除,测定方法的精密度和准确度等。在所测镍精矿样品中测得金的含量为0.7~1.2μg/g、铂的含量为1.0~2.0μg/g和钯的含量为1.0~2.0μg/g,结果与试金富集法一致。方法精密度均小于5%。     

溶剂极性对沙棘渣提取物组成及体外降血糖、降血脂活性的影响

为探讨溶剂极性对沙棘渣提取物组成及体外降糖降脂活性影响，以沙棘果渣和籽渣为原料，采用不同极性溶剂经超声波辅助提取，评价沙棘渣中活性成分含量及其体外降血糖和降血脂能力，结合超高效液相色谱串联四极杆静电场轨道阱高分辨质谱(UPLC-Q-Orbitrap HRMS)对沙棘渣中活性成分进行鉴定。结果表明，溶剂极性对多酚类化合物的提取效率、降血糖、降血脂能力有显著影响，其中60%乙醇提取物具有最高的粗提物得率，果渣的60%乙醇提取物中总酚含量（11.08 mg/g）、总黄酮含量（6.49 mg/g）和原花青素含量（6.18 mg/g）最高。籽渣的80%乙醇提取物中总酚含量（25.70 mg/g）最高，丙酮提取物中总黄酮含量（14.23 mg/g）、原花青素含量（16.87 mg/g）最高。沙棘果渣和籽渣丙酮提取物具有最好的α-葡萄糖苷酶与α-淀粉酶活性抑制能力。籽渣80%乙醇提取物、果渣60%乙醇提取物具有最好的甘氨胆酸钠和牛磺胆酸钠结合能力。原花青素是籽渣提取物体外降血脂、降血糖活性主要贡献者。果渣提取物中的总多酚与降血脂能力显著相关。从沙棘渣提取物中共鉴定出37种化合物，主要为黄酮和萜类成分。沙棘籽渣提取物具有很强的体外降血糖、降血脂活性，有望用于特膳食品和功能性食品基料的研发。     

电渗析处理电镀镍回收液的实验研究

采用电渗析法对电镀镍回收液进行分离浓缩实验。实验表明,选用BJT离子交换膜,在溶液Ni2+初始浓度为2 g/L、电压值为7.5 V、浓缩室和淡化室流量均为8 L/h时,Ni2+浓缩到8.39 g/L,有机物的相对去除率达46.46%。电渗析法能实现镍回收液中镍离子与杂质的分离,达到净化回收液和浓缩镍离子的目的。     

Interaction of vanadium and nickel porphyrins with catalysts, relevance to catalytic demetallisation

The binding of vanadium and nickel porphyrins to γ-Al₂O₃, SiO₂-Al₂O₃ MoO₃/Al₂O₃, NiO/Al₂O₃, and to Co- and Ni-Mo/Al₂O₃ catalysts in their oxide and sulfide forms, and their subsequent decomposition reactions when heated in nitrogen or exposed to hydrogen and thiophene in catalytic hydrodesulfurisation, have been studied by electron spin resonance. We wished to discover which part of the porphyrin molecule became bound to the catalyst and to which surface sites. Our main conclusions are that the porphyrins are bound to the catalyst by a donor-acceptor interaction,, the delocalised π-system of the porphyrin ring being the electron donor, and the Bronsted and/or Lewis acid function of the catalyst being the acceptor. Depending on the conditions, oxidation or hydrogenation of the porphyrin ring at the meso carbons is the initial stage in the decomposition of the bound porphyrins.     

Porphyrin derivatives for telomere binding and telomerase inhibition

The capacity of G-quadruplex ligands to stabilize four-stranded DNA makes them able to inhibit telomerase, which is involved in tumour cell proliferation. A series of cationic metalloporphyrin derivatives was prepared by making variations on a meso-tetrakis(4-N-methyl-pyridiniumyl)porphyrin skeleton (TMPyP). The DNA binding properties of nickel(II) and manganese(III) porphyrins were studied by surface plasmon resonance, and the capacity of the nickel porphyrins to inhibit telomerase was tested in a TRAP assay. The nature of the metal influences the kinetics (the process is faster for Ni than for Mn) and the mode of interaction (stacking or external binding). The chemical alterations did not lead to increased telomerase inhibition. The best selectivity for G-quadruplex DNA was observed for Mn-TMPyP, which has a tenfold preference for quadruplex over duplex.     

Hydrotreatment catalyst poisoning by vanadium and nickel porphyrin: ESR and NMR

Hydrotreatment catalysts (NiMo) are poisoned by vanadyl and nickel porphyrins. Their HDS activities are correlated to the nature and the structure of the poison, analyzed by EPR, Metal Solid NMR and High Resolution TPR on the active sulphided surfaces.     

化学沉淀法回收化学镀镍废水中镍的研究

采用化学沉淀法从化学镀镍废水中回收镍,通过实验优化了NaOH处理含镍废水的工艺参数,并对沉渣镍盐进行了处理.结果表明,化学沉淀法处理化学镀镍废水的最佳工艺参数为:H2O2 30 mL/L,NaOH 15.67 g/L,絮凝剂聚丙烯酰胺4g/L.用硫酸处理沉淀物后镍的回收率可达97.25％.     

Separation and identification of petroporphyrins extracted from the oil shales of Tarfaya: geochemical study

Vanadyl and nickel porphyrins were isolated from the oil shales of Tarfaya (Morocco) by extraction followed by column chromatography. The ratios and characteristics of these porphyrin complexes were essentially obtained on the basis of UV-visible and mass spectrometry data. Geochemical information could be drawn from these data. The nature and the contents of the metals coordinated and non-coordinated to porphyrin systems were also determined in this study.     

镀层结构对压延铜箔表面颜色的影响

采取无氰电镀技术使压延铜箔表面黑化,镀液配方为:硫酸镍40~60 g/L,柠檬酸钠20~30 g/L,硼酸30~50 g/L,硫酸铵5~15 g/L,表面活性添加剂5~15 g/L。从扫描电镜(SEM)和透射电镜(TEM)对镀层表面与横截面形貌的观察发现,晶粒间距和晶粒高度对镀层颜色有决定性影响。当晶粒间距超过0.7μm,同时晶粒高度超过0.8μm时,镀层会变黑。能谱(EDS)分析证实黑化镀层表面不含有任何硫化物,说明镀层并非物质致黑,而是由于形成了“光陷阱”结构而发黑。     

Nickel and Lanthanum Hydroxide Nanocomposites with Much Improved Electrochemical Performance for Supercapacitors

By developing a facile low temperature hydrothermal process, we demonstrate the direct growth of nickel and lanthanum hydroxide nanocomposites on Ni‐foam substrate. The hydroxide nanocomposites thus derived show much enhanced overall electrochemical capacitance and improved stability of the alpha nickel hydroxide phase in alkaline solution. By adjusting the initial molar ratio between nickel and lanthanum nitrates from 1:0 to 1:2, the electrochemical behavior, such as specific capacitance, shows a dramatic change, while the nickel hydroxide phase evolves from beta nickel hydroxides (1:0) to alpha nickel hydroxide (1:2). Lanthanum hydroxide is not expected to contribute to the pseudocapacitance as it only shows a capacitance of <10 F/g. The specific capacitance is increased from 970 F/g (Ni:La = 1:0) to 1874 F/g (Ni: La = 1:2) at the discharging current of 1 A/g. At high discharging currents (e.g. 10 A/g), the Ni:La = 1:2 sample can retain a capacitance of 1055 F/g. An excellent cycling performance is demonstrated for the Ni:La = 1:2 nanocomposite sample upon 2000 cycles at the discharging current density of 2 A/g, where the stability of alpha nickel hydroxide in the alkaline solution is improved. The low temperature hydrothermal method compares favorably to other previously documented preparation processes, such as chemical coprecipitation and electrochemical deposition, for lanthanum‐doped nickel hydroxides, where the specific capacitance is typically less than 1000 F/g (1 A/g).     

铝材表面化学镀镍技术

在常规铝材化学镀镍工艺基础上，提出一种在酸性化学镀镍前增加一道碱性化学预镀镍工艺的铝材表面化学镀镍新技术。介绍了其预镀镍的工艺流程与操作要点。研制了一种中等浓度的含镍、铁的多元合金浸锌液，并通过正交实验得出了浸锌最佳方案，确定了碱性化学预镀镍的最佳配方：25g／L硫酸镍，25g/L次磷酸钠，30g／L柠檬酸三钠，10g／L焦磷酸钠，10-15mL／L三乙醇胺，30g/L氯化铵。弯曲试验表明，镀镍层与铝基体结合强度很高；镀镍层SEM照片显示，镀镍层晶粒尺寸大小均匀，各晶粒间结合紧密，孔隙率低，耐腐蚀能力强。     

石油中卟啉化合物的研究进展

介绍了原油中卟啉化合物的结构及其物理和化学性质。讨论了镍和矾在原油中的存在形态,以及对石油后续加工造成的危害。阐述了石油中镍和矾的脱除方法。     

一种化学退镍剂的研制

以防染盐(间硝基苯磺酸钠)为氧化剂,研制了一种新型的化学退镍剂。通过正交实验获得了退镍剂的最佳配方为:80 g/L的防染盐,37.5 g/L的单乙醇胺,30 g/L的甘氨酸,4.5 g/L的硫代硫酸钠和0.03 g/L的十二烷基硫酸钠。讨论了退镍剂中各组分的作用。研究了温度对化学镀镍层和电镀镍层的退镍速度的影响,并通过XRD图解释了两者退镍速度的差异。