Al-modified yolk-shell silica particle-supported NiMo catalysts for ultradeep hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene:Efficient accessibility of active sites and suitable acidity

Yolk-shell SiO2 particles(YP)with center-radial meso-channels were fabricated through a simple and effective method.Al-containing YP-supported NiMo catalysts with different Al amounts(NiMo/AYP-x,x=Si/Al molar proportion)were prepared and dibenzothiophene(DBT)and 4,6-dimethyl-dibenzothiophene(4,6-DMDBT)were employed as the probes to evaluate the hydrodesulfurization(HDS)catalytic performance.The as-prepared AYP-x carriers and corresponding catalysts were characterized by some advanced characterizations to obtain deeper correlations between physicochemical properties and the HDS performance.The average pore sizes of series AYP-x supports are above 6.0 nm,which favors the mass transfer of organic sulfides.The cavity between the yolk and the shell is beneficial for the enrichment of S-containing compounds and the accessibility between reactants and active metals.Aluminum embedded into the silica framework could facilitate the formation of Lewis(L)and Brønsted(B)acid sites and adjust the metal-support interaction(MSI).Among all the as-synthesized catalysts,NiMo/AYP-20 catalyst shows the highest HDS activities.The improved HDS activity of NiMo/AYP-20 catalyst is attributed to the perfect combination of excellent structural properties of the yolk-shell mesoporous silica,enhanced acidity,moderate MSI,and good accessibility/dispersion of active components.

Combined Promoting Effects of Specific Organic Functional Groups and Alumina Surface Characteristics for the Design of a Highly Efficient NiMo/Al_(2)O_(3) Hydrodesulfurization Catalyst

To prepare a highly efficient NiMo/Al_(2)O_(3) hydrodesulfurization catalyst,the combined effects of specific organic functional groups and alumina surface characteristics were investigated.First,the correlation between the surface characteristics of four different alumina and the existing Mo species states was established.It was found that the Mo equilibrium adsorption capacity can be used as a specific descriptor to quantitatively evaluate the changes in surface characteristics of different alumina.A lower Mo equilibrium adsorption capacity for alumina means weaker metal-support interaction and the loaded Mo species are easier to transform into MoS2.However,the Mo-O-Al bonds still exist at the metal-support interface.The introduction of cationic surfactant hecadecyl trimethyl ammonium bromide(CTAB)can further improve Mo species dispersion through electrostatic attraction with Mo anions and interaction of its alkyl chain with the alumina surface;meanwhile,the introduction of ethylenediamine tetraacetic acid(EDTA)can complex with Ni ions to enhance the Ni-promoting effect on Mo.Therefore,the NiMo catalyst designed using alumina with lower Mo equilibrium adsorption capacity and the simultaneous addition of EDTA and CTAB exhibits the highest hydrodesulfurization activity for 4,6-dimethyl dibenzothiophene because of its proper metal-support interaction and more well-dispersed Ni-Mo-S active phases.

不育男性精子HDS与精子DFI、精子形态的相关性及其对IVF结局的影响

目的:探讨男性不育患者精子高可染性指数(HDS)与精子DNA碎片指数(DFI)、精子畸形的相关性及其对体外受精(IVF)结局的影响,评估精子HDS的临床价值。方法:采用流式细胞仪辅助的精子染色质结构分析法(SCSA)检测322个仅因女方输卵管因素行IVF助孕周期的不育男性精子DFI、HDS,根据精子HDS值进行分组,比较各组精液常规参数、精子畸形率、精子DFI以及IVF受精率、卵裂率、优胚率及妊娠结局的差异。结果:322例不育男性中精子HDS值0~<5%、5~<10%、10~<15%、15~<20%、≥20%分别为119例(36.96%)、117例(36.34%)、50例(15.53%)、23例(7.14%)、13例(4.03%),随着精子HDS升高、精子浓度、精子活率、精子前向运动率下降,但无统计学差异(P>0.05),精子DFI、精子畸形率与精子HDS呈正相关(r=0.236,r=0.203);IVF受精率、优胚率、妊娠率随着HDS增高而下降,但无统计学差异(P>0.05);当HDS>10%时,早期流产率显著升高。结论:精子HDS可能是导致精子DFI、精子畸形的风险指标,HDS可作为IVF早期流产的预测指标。

Active phase morphology engineering of NiMo/Al2O3 through La introduction for boosting hydrodesulfurization of 4,6-DMDBT

Herein,we designed and constructed a mesoporous LaAlOx via a solvent evaporation induced self-assembly protocol.The structure and physicochemical property of the corresponding NiMo supported catalyst was analyzed by a set of characterizations,and its catalytic activity was investigated for hydrodesulfurization(HDS)of 4,6-dimethyldibenzothiophene.It has confirmed that the incorporation of La profoundly facilitate the generation of“Type II”NiMoS phase by weakening the interaction of Mo–O–Al leakage and promoting the sulfidation of both Ni and Mo oxides as well as changing the morphology of Ni promoted MoS2 slabs,thereafter boosting the HDS performance substantially.The finding here may contribute to the fundamental understanding of structure-activity in ultra-deep desulfurization and inspire the advancement of highly-efficient HDS catalyst in future.

Highly Active Sulfided NiPMo Hydrodesulfurization Catalyst Prepared from Keggin-type Phosphomolybdic Acid

A highly active sulfided NiPMo/MCM-41(NiPMo-S/M41)hydrodesulfurization(HDS)catalyst was successfully synthesized using Keggin-type phosphomolybdic acid as the phosphorus and molybdenum source and thioacetamide as the sulfur source.The supported catalysts NiPMo/M41,Ni_(2)P-Mo/M41,and Ni_(2)P/M41 were also prepared to investigate the effects of Mo,S,and the Keggin structure on the HDS performance.The HDS activities of NiPMo/M41 and NiPMo-S/M41 toward dibenzothiophene were much higher than that of Ni_(2)P-Mo/M41,demonstrating that the active phases in the Keggin-structured catalysts were significantly superior to the Mo-modified Ni_(2)P phase.The HDS activities of the catalysts followed the order NiPMo-S/M41(96.7%)>NiPMo/M41(89.9%)>Ni_(2)P-Mo/M41(53.5%)>Ni_(2)P/M41(48.9%).For Ni_(2)P/M41,Ni_(2)P-Mo/M41,and NiPMo/M41,cyclohexylbenzene(CHB)was formed in low concentrations(<21.0%),indicating that direct desulfurization was the favored reaction route and that this did not change for Keggin-structured NiPMo/M41.By contrast,the CHB selectivity of NiPMo-S/M41 increased to 44.6%,much higher than that of NiPMo/M41(17.6%),demonstrating that sulfidation enhanced the hydrogenation ability,which was ascribed to a metal-acid synergistic effect.

Tuning active sites in MoS_(2)-based catalysts via H_(2)O_(2)etching to enhance hydrodesulfurization performance

A H_(2)O_(2)etching strategy was adopted to introduce coordinatively unsaturated sites(CUS)on MoS_(2)-based catalysts for dibenzothiophene(DBT)hydrodesulfurization(HDS).The CUS concentrations on MoS_(2) slabs were finely regulated by changing the concentrations of H_(2)O_(2)solution.With the increasing H_(2)O_(2)concentrations(0.1–0.3 mol/L),The CUS concentrations on MoS_(2) slabs increased gradually.However,the high-concentration H_(2)O_(2)etching(0.5 mol/L)increased the MoOxSy and MoO_(3) contents on MoS_(2) slabs compared to etching with the H_(2)O_(2)concentration of 0.3 mol/L,which led to the less CUS concentration in the sulfided Mo–H-0.5 catalyst than in the sulfided Mo–H-0.3 catalyst.A microstructure-activity correlation indicated that the CUS introduced by H_(2)O_(2)etching on MoS_(2) slabs significantly enhanced DBT HDS.Different Co loadings were further introduced into Mo–H-0.3,which had the most CUS concentration,and the corresponding 0.2-CoMo catalyst with the highest CoMoS content(3.853 wt%)exhibited the highest reaction rate constant of 6.95×10^(−6)mol g^(−1)s^(−1)among these CoMo catalysts.

Optimization of dendritic TS-1/Silica micro–mesoporous composites for efficient hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene

A novel composite material(TD)composed of TS-1 microcrystalline and dendritic mesoporous silica nanospheres(DMSNs)was successfully prepared.The TD composite material had open pore structure and large specific surface area,which was conducive to the mass transfer of reactants and products.The Ti element in TS-1 could be used as an electron assistant,and the spillover d-electrons were conducive to the improvement of the sulfidation and dispersion of MoS_(2),thereby forming more type II MoS_(2) active phases.The incorporation of Ti could bring more Brønsted(B)and Lewis(L)acid,which was conducive to the hydrogenation pathway(HYD)selectivity(41.2%)of dibenzothiophene(DBT)hydrodesulfurization(HDS)and isomerization(ISO)route selectivity(21.9%)of 4,6-dimethyldibenzothiophene(4,6-DMDBT)HDS,thus improve the HDS activity of DBT and 4,6-DMDBT.NiMo/TD-70(Aging temperature=70℃)had the best HDS activities of DBT(99.0%)and 4,6-DMDBT(93.7%)due to its large open pore structure,good acidity,suitable metal-support interaction(MSI)and perfect dispersion of the metallic active sites.

负载型MoS_(2)基加氢催化剂活性相的限域构建及其加氢脱硫活性

基于对负载型NiMo加氢脱硫催化剂活性相的结构设计,以具有内径10~30 nm直通孔道的天然埃洛石纳米管(HNT)为载体,利用其“孔道空间限域效应”作为MoS_(2)活性相结构的控制基础,以硫代钼酸铵和硝酸镍为金属前驱物,采用等体积浸渍法一次浸渍工艺,通过改变金属负载量、Ni/Mo(原子比)等工艺条件制备系列双金属NiMo/HNT催化剂。通过X射线衍射(XRD)、比表面积(BET)、高分辨透射电子显微镜(HRTEM-EDS mapping)、X射线光电子能谱仪(XPS)等手段对所得催化剂的结构进行表征,以二苯并噻吩(DBT)为模型化合物对催化剂的脱硫活性进行评价。结果表明:HNT载体的使用可有效控制MoS_(2)活性相尺寸,催化剂中的Mo、Ni金属组分几乎全部集中于载体的孔道内部并呈原生的亲密接触状态,同时Ni、Mo组分具有更高的硫化程度,协同效果更好;NiMo/HNT催化剂的加氢脱硫活性和加氢选择性均显著优于使用氧化铝载体的参比催化剂,其中DBT转化率最高增幅41.6%,反应速率R最大可以提升92%,加氢选择性最大可提升60%。

Al_(2)O_(3)基材作载体制备MoP加氢脱硫催化剂的研究

采用低温燃烧法和溶剂热法分别合成了富含五配位Al^(3+)物种的氧化铈改性Al_(2)O_(3)(Ce-Al_(2)O_(3))和介孔-大孔Al_(2)O_(3)(M-Al_(2)O_(3));通过程序升温还原浸渍法负载的Mo的磷酸盐前驱体制备了MoP催化剂。以二苯并噻吩(DBT)为模型含硫化合物评价了其加氢脱硫(HDS)性能。结果表明,M-Al_(2)O_(3)上制备纯相MoP所需磷酸盐前驱体的P/Mo摩尔比在1~1.2之间。DBT在MoP催化剂上转化率大小为MoP(1)/SiO_(2)>MoP(1)/Ce-Al_(2)O_(3)>MoP(1.2)/M-Al_(2)O_(3)。动力学研究表明,DBT在MoP(1)/Ce-Al_(2)O_(3)和MoP(1.2)/M-Al_(2)O_(3)上的HDS反应活化能几乎相同,显著小于MoP(1)/SiO_(2)上的活化能。在MoP催化剂上,直接脱硫(DDS)路径选择性随温度的增加而增加。在较低的温度下(如280℃),DBT主要通过加氢(HYD)反应路径脱硫;在较高的温度下(如360℃),DDS和HYD两条反应路径并重。

视频分布式系统在全国高清气象视频会商系统中的应用

视频分布式系统自21世纪出现以后,经过近二十年的发展,已经成为一个成熟、先进的音视频处理系统,其出色的性能可以弥补全国高清气象视频会商系统以视频矩阵为核心的传统音视频处理系统的不足,因此在新一代全国高清气象视频会商系统中得以应用。视频分布式系统的应用提升了会商系统的稳定性和便捷性,在国省两级视频会商业务中发挥了重要作用。阐述了视频分布式系统的技术特点,分析了视频分布式系统在新一代全国高清气象视频会商系统中的应用。

基于毫米波通信技术的超高清视频传输方法研究

为了提高对超高清视频传输能力,提出基于毫米波通信的超高清视频传输方法。采用多频调制通信组网技术构建超高清视频传输的信道模型,建立超高清视频毫米波通信传输的自适应图像信息交互和采集模型;结合Lyapunov指数谱密度特征分析,实现谱特征分解和信道均衡模型构建;建立视频传输的视景转换和高阶谱特征提取模型;采用毫米波通信技术,实现滤波补偿和反馈增益调节;采用联合自相关的统计特征分析方法,得到动态均衡迭代函数,通过复杂信道环境下的抗干扰抑制和均衡调度,实现对超高清视频的无损传输和编码解码。实验结果表明,该方法进行超高清视频传输的误码率较低,平均为0.058 2,传输时延较低,平均为248.4 ms,峰值信噪比为49 dB。

TiO_2负载非晶态合金NiB催化剂的制备、表征及HDS动力学研究

用等体积浸渍 -还原法制备了负载型的NiB/TiO2 (B/Ni=5∶1摩尔比 )非晶态合金 ,并在相同条件下制备了NiB/Al2 O3 (B/Ni=5∶1摩尔比 )与之对照。用XRD、SEM和TEM等表征方法比较了样品的非晶性质。在脉冲微反 -色谱装置上以噻吩的HDS反应为探针测定了NiB/TiO2 、NiB/Al2 O3 的反应活性 ,进行了动力学研究。结果证明 ,NiB/TiO2 的低温活性远高于NiB/Al2 O3 ,其原因是它的活化能远远小于后者。

FCC汽油选择性HDS催化剂Co-Mo/镁铝尖晶石-Al2O3的研制

采用镁铝尖晶石(MgAl2O4)对γ-Al2O3进行了改性,并以其为载体,以Co-Mo为活性组元,采用等体积浸渍法制备了一系列MgAl2O4含量不同的Co-Mo/MgAl2O4-Al2O3催化剂。以FCC汽油为原料,在高压微反装置上对Co-Mo/MgAl2O4-Al2O3催化剂的加氢脱硫(HDS)活性进行了评价,计算了催化剂的HDS选择性因子。采用低温N2吸附-脱附、XRD、NH3-TPD、Py-IR及TPR手段对镁铝尖晶石改性后载体和相应催化剂进行了表征。结果表明,Co-Mo/MgAl2O4-Al2O3催化剂具有较高的HDS活性和较大的HDS选择性因子。镁铝尖晶石的加入减弱了载体的酸性,减弱了金属与载体的相互作用,提高了催化活性,降低了反应温度,从而使催化剂的HDS选择性因子提高。在MgAl2O4-Al2O3载体中镁铝尖晶石质量分数为50%时,其所制备的Co-Mo/MgAl2O4-Al2O3的HDS选择性因子达到最大值。

负载型纳米TiO_2复合载体催化剂及其HDS活性研究

采用溶胶 -凝胶法在γ-Al2 O3 上制备出负载型纳米 Ti O2 ,负载活性组分 Co和 Mo,对其进行了噻吩 HDS活性评价 ,并与国产工业 HDS催化剂 T2 0 5进行比较 ,并提出负载型纳米 Ti O2 为半球模型 .

重质油窄馏分的HDS和HDN反应动力学特性

用破碎的工业加氢裂化催化剂 Ni-Mo/Al2 O3 ,在 1 0 0 ml的高压反应釜内 ,对 3种不同渣油的超临界流体萃取分馏的窄馏分进行加氢处理 ,建立了釜式反应器内渣油催化加氢脱硫和加氢脱氮反应的扩散 -反应动力学模型 。

TiO_2负载氮化钼催化剂的HDS活性与反应动力学的研究

在合成出纯相氮化物γ-Mo2 N的基础上 ,制备了以 Ti O2 为载体负载金属氮化物 ( Mo2 N/Ti O2 )的加氢脱硫( HDS)催化剂 ,并对其晶体结构进行了 XRD表征。用不同的预处理条件 ,以脉冲微型反应器和色谱联用的方法 ,研究了 Mo2 N/Ti O2 的 HDS活性及其反应动力学 ,同时制备了以 Al2 O3为载体负载 Mo2 N的催化剂 ( Mo2 N/Al2 O3)

HDS废催化剂碱浸取提钒的动力学研究

用空气焙烧 碱浸取的方法从HDS废催化剂中提取钒 ,研究了分别用Na2 CO3 H2 O、NH4HCO3 H2 O及NH3 ·H2 O浸取焙烧产物中钒的动力学规律。用最小二乘法对实验数据进行非线性回归 ,得到了 3种碱液浸取提钒的动力学方程式。由动力学方程式计算的钒浸取转化率与实验值绝对偏差不超过 6% ,平均偏差小于 3 %。通过比较化学反应与内、外扩散过程阻力的大小 ,证实了在实验条件下 ,浸取过程的控制步骤为化学反应控制。 3种碱液浸取反应的活化能分别为 2 0 .5 0kJ/mol、45 .74kJ/mol和 42 .3

多花水仙HDS基因cDNA全长克隆与序列分析

以‘黄花水仙2号’和‘金盏银台’为材料,水仙各自花瓣的c DNA为模板,采用RT-PCR和RACE技术克隆出2个HDS基因,分别命名为Nt HDSY和Nt HDSJ,测序结果表明,Nt HDSY和Nt HDSJ基因全长分别为2 592 bp和2 599 bp,2个基因均含有1个2 178 bp的开放阅读框(ORF),编码745个氨基酸。同源性分析表明,黄花水仙2号与金盏银台、铁皮石斛、长春花、大豆、葡萄和苹果的相似系数分别为:97.77%、79.29%、75.29%、75.51%、75.02%和74.40%。Real-time PCR分析表明:Nt HDS基因在花瓣和副冠内的表达量在开花过程的花蕾期与盛花期存在明显差异,推测该基因可能与多花水仙香气物质的合成有关。

HDS工艺处理某矿山酸性废水试验研究

通过对高密度泥浆法处理矿山酸性废水的工艺参数试验研究,结果表明HDS法可降低中和药剂使用量高达16.7%,絮凝剂的投加量也适量减少,沉淀室泥水分离的时间仅为8 min,外排中和渣固体物浓度达26.7%,出水水质达标排放。

负载型碳氧化钼催化剂的制备及其二苯并噻吩的HDS活性

通过XRD物相分析和利用小型在线质谱仪,对负载的或体相的氧化钼利用正己烷作为碳源,进行程序升温碳化考察,对所制备的负载型催化剂进行了二苯并噻吩(DBT)加氢脱硫(HDS)活性评价。实验发现,与采用甲烷相比,采用正己烷作为碳源进行碳化可以适当降低碳化所需要的温度,但对于HDS反应来说,并不是碳化越完全催化效果越好。对30%MoO3/-γA l2O3进行碳化时,碳化原料组成为正己烷/氢气=0.025(摩尔比),在620℃碳化1h所得催化剂具有比较好的DBT HDS活性。讨论了制备因素对HDS活性的影响。