同步溶胀-担载催化剂对烟煤-重油共炼的影响

以Fe(NO3)3和Na2S分别作为催化剂前体和原位硫化剂,在20℃下分别用水、甲醇(M)、N-N二甲基甲酰胺(DMF)和二甲亚砜(DMSO)对神华烟煤溶胀12 h,同步溶胀-担载催化剂后的烟煤脱除溶剂后与轮古常渣(LGAR)和杜84超稠油(Du84)在2∶1油煤质量比,8 MPa冷氢压,420℃,1 h的条件下进行加氢共处理.结果表明,神华烟煤经过溶胀处理后与两种重油共处理的液化率都明显提高,煤的转化率明显增大;三种有机溶胀剂相比,DMF同步溶胀促进液化效果最好,其次为DMSO,甲醇最差.两种配油相比,Du84比LGAR更适合煤-重油共处理.XRD分析表明,同步溶胀-担载法制备的溶胀煤载铁催化剂以非晶态和高分散的状态存在于溶胀煤表面,在共处理中催化剂最终转化为Fe1-xS.在煤-重油共处理中,经DMF同步溶胀-担载的催化剂失活,结晶相对不明显.     

神华煤在有机溶剂中溶胀动力学的研究

研究了不同温度( 4 0℃～1 2 0℃)下神华煤在有机溶剂N,N-二甲基甲酰胺、四氢萘和循环油中的溶胀动力学.结果表明:随温度升高,神华煤在有机溶剂中的溶胀速率在增大,但在极性溶剂N,N-二甲基甲酰胺中的溶胀速率远大于在非极性溶剂四氢萘中的溶胀速率;神华煤的溶胀行为符合一级反应动力学方程;神华煤在三种溶剂中的活化能均小于1 0 k J/mol,表明在溶胀过程中,其速度由溶剂分子在煤中的扩散所控制.     

几种煤的溶胀动力学研究

测定了不同溶胀时间下胜利煤、H煤和神华煤在九江循环溶剂中的的溶胀度,研究了这三种煤在常压下溶胀动力学行为,胜利煤、神华煤和H煤的平衡溶胀度(溶胀4 h)分别为1.068,1.054和1.162,胜利煤和神华煤约35 min达到溶胀平衡,H煤约20 min即达到溶胀平衡,开发了一种新的溶胀动力学模型--吸附溶胀动力学模型,按二级动力学方程对煤粒的溶胀行为进行描述,并利用文献查得的Suuberg法动力学方程分析可知,胜利煤、H煤和神华煤在九江溶剂中的扩散主要是Case-Ⅱ扩散,经比较可知,吸附溶胀法较Suuberg法能更好地描述煤的溶胀行为.     

煤溶胀前后溶解度参数变化研究

选择6种性质不同的溶剂作为溶胀剂,对烟煤进行了溶胀预处理。对溶胀前后煤样进行了形貌分析、红外分析及溶解度参数测定,并考察了直接加氢液化效果。结果表明,溶剂溶胀预处理未破坏煤大分子结构,而煤的微观形貌变得疏松。所选6种溶剂中,N,N-二甲基甲酰胺(DMF)与煤二者之间的溶解度参数差值最小,DMF对煤溶胀效果也最好,溶胀度达1.71。同时,6种溶胀煤中,经DMF溶胀煤样(C_(DMF))的溶解度参数值最低,直接液化性能最好。相比于原煤(C_R),C_(DMF)的溶解度参数降低了2.73%,气产率降低了89.71%,液产率和转化率分别提高了27.48%和5.35%。     

超声波辐射溶胀对煤炭直接液化性能的影响

为探讨超声波辐射溶胀在煤炭直接液化过程中的积极作用,以吡啶为溶胀剂对神华煤进行了超声波辐射条件下的溶剂溶胀处理,通过对溶胀过程中不同溶胀时间煤样的溶胀度与质量损失情况测定以及超声波辐射溶胀煤与自然溶胀煤的液化实验比较,发现超声辐射有助于煤的溶胀作用,煤液化转化率提高了3%~4%.实验表明,超声溶胀能够进一步提高煤催化加氢直接液化的反应性能.     

胜利煤的溶胀行为及溶胀煤的特性分析

为了考察溶胀作用对液化油煤浆黏度变化的影响作用,参照煤直接液化工艺条件,在四氢萘(THN)、N,N-二甲基甲酰胺(DMF)、液化起始溶剂(STA)和液化循环溶剂(REC)等不同有机溶剂中对胜利煤进行了溶胀行为研究。采用扫描电镜、孔隙比表面积分析仪、红外光谱仪等手段,研究了不同条件下胜利溶胀煤的表面性质变化。结果表明,胜利煤在极性溶剂N,N-二甲基甲酰胺中的溶胀度要大于在非极性溶剂四氢萘、起始溶剂和循环溶剂中的溶胀度;随着温度的升高,胜利煤的溶胀速率增大。溶胀后的胜利煤呈松散的云状结构,煤的形貌发生了一定程度变化;溶胀煤的孔径增大,比表面积减小。     

采用位移传感器测量煤的溶胀行为研究

根据溶胀测量原理,采用位移传感器,可以对煤的溶胀过程进行在线监测.测量获得了L1褐煤和B3烟煤在9种溶剂(4种非极性溶剂、4种极性溶剂和蒸馏水)中的溶胀等温线,溶胀等温线对时间求导得到溶胀速率曲线.同时考察了另外4种煤样(2种褐煤和2种烟煤)在N-甲基吡咯烷酮(NMP)中的溶胀曲线.结果表明,采用位移传感器可以在线监测煤样的溶胀过程.L1褐煤在4种非极性溶剂中没有显著溶胀,在4种极性溶剂中溶胀显著,尤其在NMP中溶胀比最大,在蒸馏水中也有显著溶胀.B3烟煤在4种非极性溶剂中除正己烷外均有显著溶胀,在极性溶剂NMP中溶胀比最大,在蒸馏水中也有显著溶胀.由溶胀速率曲线可知,在溶胀初始时刻,L1褐煤和B3烟煤在乙腈和乙醇中溶胀速率最快,两种煤样在二硫化碳中溶胀速率较快.在NMP中,3种烟煤均呈现较大溶胀比,3种褐煤的溶胀行为差异较大,其中1种褐煤的溶胀比显著高于另外2种褐煤的溶胀比,与烟煤的溶胀比相近.     

煤溶胀影响因素及溶胀技术的应用

以煤溶胀机理、溶胀动力学等为基础,综述了溶剂性质、煤阶、氧化、温度、预处理、溶胀时间、水分、煤粉粒度等对煤溶胀的影响。结果发现:溶剂的供电子数目(EDN)、溶剂碱性、溶剂类型对煤的溶胀有不同的影响。煤阶对煤的溶胀影响较大,表现在随着C的增多,溶胀度也在增大,但当C含量大于85%时,溶胀度急剧降低。氧化煤易于溶胀。升高温度和预处理均有利于煤的溶胀。煤粉粒度越小溶胀度越好。脱除煤中的矿物质后有利于提高煤的溶胀度,但增加幅度不大。最后详细介绍了煤溶胀技术在研究煤分子结构、煤热解、煤液化方面的应用。     

超声波辐射下溶胀改善煤液化性能的研究

以山东兖州局的北宿煤 ( BS)、兴隆庄煤 ( XLZ)、枣庄局的柴里煤 ( CL)等为研究用煤 ,首先在自然条件下使用吡啶溶剂进行原煤样的溶胀 ,然后利用超声波仪 ,在 40 k Hz和 5 0 0 W辐射功率和室温的条件下 ,进行超声波辐射作用下的吡啶溶剂溶胀 .经过对脱除溶剂后溶胀煤的加氢液化实验、低温干馏焦油产率测定、挥发分产率测定及体积溶胀率的测定 ,结果表明该三种原煤具有良好的可溶胀性能 ,溶胀煤均具有良好的加氢液化性能 .在 H2 冷态压力 8.2 MPa,40 0℃ ,Fe SO4·7H2 O和升华 S作催化剂、反应 1 .5 h的液化实验条件下 ,自然溶胀煤的液化油产率比原煤增加 1 2%～ 2 5 % ,北宿溶胀煤的液化油产率达到 69.76% .辐射溶胀后的溶胀煤与自然溶胀煤比较 ,在如上所述同样的液化条件下 ,兴隆庄煤的液化油产率增加了 2 2 % ,并且煤的总转化率也增加了 .实验数据表明 ,对于以提高煤加氢液化反应活性为目的的研究 ,当超声波辐射的频率和功率一定时 ,辐射时间对于改善煤样加氢液化的性能存在着最适宜值 ,这一最适宜值与煤的变质程度有直接关系 .     

鑫源煤在有机溶剂中的溶胀特性研究

对不同溶胀时间、不同溶剂、矿物质、预处理和金属无机盐等实验条件下鑫源低阶烟煤的溶胀行为和溶胀动力学进行了研究.结果表明,随着时间的延长,溶胀率逐渐增大,48 h溶胀基本达到平衡,溶胀特征是典型的slow-climbing-type溶胀;煤在混合溶剂中的溶胀率大于单一溶剂中的溶胀率,在极性溶剂中的溶胀率大于非极性溶剂中的溶胀率;脱除矿质元素后,煤溶胀率增大;溶胀、酸洗和碱洗使煤溶胀率增大,烘干使煤溶胀率减小;溶胀动力学表明,该煤的溶胀行为符合一级反应动力学方程,在THN和吡啶溶剂中的表观活化能均小于20 kJ/mol,这与煤中范德华力的破坏相对应,溶胀机制是由Case-Ⅱ扩散控制的.     

Polyelectrolyte swelling of polyamidobenzimidazole

Conclusions An extreme character of the swelling of PABI fibres in DMAc-water mixtures has been detected. The maximum is observed in the region of a 10% water content.The peculiarity in swelling has been explained by the manifestation of a polyelectrolyte nature of the polymer.Translated from Khimicheskie Volokna, No. 5, pp. 34–35, September–October, 1987.     

Gas-induced swelling in coal

Dilatometric studies were carried out on three coal samples in various gaseous environments. The carbon contents of the three samples were 65.8%, 78.3% and 83.8% d.a.f., respectively. The sample with the lowest carbon content has shown the maximum length increase (0.5%) on exposure to a CO₂ atmosphere. This corresponds to a volume increase of 1.31%. Volume increases of the order of 9% are necessary to account for the surface areas usually found by CO₂ adsorption on coal (200–250 m² g⁻¹). However, the dilatomeric studies have generally not reached equilibrium even after 280 h of exposure to CO₂. The 1.31% volume increase value is thus probably a lower limit, a higher value should be obtained at equilibrium.     

Cyclic swelling of clays

Changes in free swelling and swelling pressure of different types of clays in response to varying cycles of wetting and drying have been studied. It can be shown that cyclic tests lead to a gradual destruction of the durable contacts in the clay structure and their transformation into less durable ones. At the same time, a reconstruction of the structure of the clays takes place, manifested by the destruction of large micro-aggregates and by disorientation of structural elements. All these phenomena result in great swelling with increase in the number of wetting cycles. Between cycles 3 and 20 the expansibility is at its maximum and may be 1.3–10 times as much as that after one wetting cycle. Cyclic swelling leads to an overall equilibrium in the system, when the internal energy of the clay is minimal and the bound water content is at its maximum. Clay in this state exhibits its maximum moisture uptake (W′_s), the meaning of which is of thermodynamic character and depends neither on the initial soil density and moisture, nor on the scheme of cyclic tests adopted.     

橡胶与沥青溶胀模型的建立与溶胀参数的确定

以Crank扩散模型为基础,建立了描述橡胶与沥青溶胀过程的数理方程,提出溶胀系数和最终溶胀量2个溶胀参数,且通过多因子方差分析考察了橡胶种类、温度、沥青标号对最终溶胀量的影响程度。结果表明,通过模型可计算得出溶胀系数和最终溶胀量;橡胶种类对最终溶胀量的影响最大,温度的影响次之,沥青标号的影响最小;斜交轮胎比子午线轮胎具有更好的溶胀能力,提高温度和沥青标号有助于加速橡胶与沥青的溶胀。     

Interferometric measurement of inhomogeneous swelling

Differential thermal contraction between matrix and fiber materials in composites and between adhesive and adherend materials in adhesive joints occurs during cooling from the resin cure temperature and gives rise to non-uniform internal stress fields. Resin swelling associated with water uptake during service gives rise to inhomogeneous stress, the magnitude and distribution of which is the subject of the present investigation. Thin layers of cured epoxy resin have been allowed to absorb water at their edges only, and the swelling normal to these layer planes has been measured by studying optical interference patterns. The stresses resulting from inhomogeneous swelling, a few tens of bars, are of similar magnitude to those resulting from inhomogeneous shrinkage during cooling from resin cure temperatures.     

On activated seed swelling technique

The activated seed swelling technique is one of the promising methods in synthesis of micron‐sized monodispersed polymer particles. However, there are some parameters (eg the interference of acetone residue on particle swelling) that make this method difficult to carry out and even lead to a broad particle‐size distribution. Here, these parameters are studied and how to control them is discussed. The polydisperse seed swelling appeared at lower concentration of acetone and with incomplete evaporation of acetone from the system. The monodisperse swelling and larger particle sizes were achieved at higher concentration of acetone and longer evaporation time using a vacuum pump. These results suggest that the particle size and particle‐size distribution in the activated seed swelling technique can be controlled by the carrier (acetone) and the hydrophobe concentration in aqueous medium before and after the swelling process. Copyright © 2005 Society of Chemical Industry     

Fiber-jet swelling during chemical-fiber formation

Swelling of the jet during the formation of chemical fibers by the wet method is studied. The swelling of a jet is investigated in the shear regime during extrusion of the spinning solution through a capillary with free efflux and with stretching of a freshly formed jet in the spinning bath. It is shown that the magnitude of the swelling is determined by the viscoelastic properties of the polymer system (equilibrium relaxation time and power-law exponent) and by the conditions of extrusion of the polymer system through a capillary. Relations for determining the magnitude of the swelling and the equilibrium relaxation time are presented.     

Nonisothermal annual die swelling analysis

The effects of thermal properties of Newtonian liquids on annular die swelling were studied numerically using a finite element method. Fluid viscosity was assumed to be a decreasing exponential in temperature, with a proportionality constant, β, which was assumed to be a material property. Three swelling ratios were found as functions of constant β, Peclet number (Pe), Nusselt number (Nu), and a viscous heat dissipation. The fluid behavior was remarkably different when the viscous heat dissipation was involved or excluded. Explanations are presented for these differences.     

The swelling of Nigma fibres

Conclusions -- It has been found that the primary swelling of fibres prepared from solutions of cellulose curpimonium complex has an extremal dependency on the composition of the aqueous—organic precipitation bath.-- The character of the dependence of the swelling of the finished CuC and HC fibres on composition of the mixed precipitant indicates a structural memory of the fibre during the transition CuAC CuC HC.-- The extremal character of the temperature dependence of swelling of HC fibres in a solvent + precipitant mixture is probably brought about by several oppositely directed processes, including complex formation, change in solubility, ionization, etc.Translated from Khimicheskie Volokna, No. 1, pp. 56–58, January–February, 1991.