天然气水合物生成条件的测定和计算

利用全透明蓝宝石水合物静力学实验装置,测定了4种塔里木油田天然气在纯水中的水合物生成条件.将Chen-Guo 水合物模型应用于天然气水合物生成条件的计算,实验测定的4种天然气水合物生成条件的计算结果和实验结果符合得很好.     

气体水合物平衡生成条件的测定及预测

建立了一套气体水合物实验测定装置，采用该装置在温度２６２．６－２８５．２Ｋ范围内分别测定了甲烷，二氧化碳和一种合成天然气在纯水、电解质水溶液以甲醇水溶液中水合物的平衡生成压力，共计９个体系，７８个数据点。     

天然气水合物热力学模型研究

天然气作为一种清洁型能源,全球需求量逐年增大,开采量也不断攀升。而对于运输天然气主要方式的管道运输来说,天然气在适宜的条件下,容易在管道生成天然气水合物,造成管线、阀门等设备堵塞,影响输送。通过查阅大量的国内外文献,对天然气水合物的产生条件进行简单分析,并且对天然气水合物生成预测模型进行总结整理,有助于数学求解与应用。     

含极性抑制剂体系中水合物生成条件的研究

应用两步水合物热力学模型,结合基于局部组成概念的混合规则,将水合物生成条件预测成功地扩展应用于含极性抑制剂体系,计算结果较理想,大量检验结果表明,单流体混合规则不能很好地描述极性体系。同时可以看出,极性体系相对平衡计算的准确性对水合物生成条件预测有很大的影响。     

甲烷+氨水体系水合物生成条件实验测定及计算

甲烷在氨水体系中生成水合物的实验数据对于开发水合法回收合成氨驰放气工艺以及操作条件的确定具有重要意义。本文测定了氨摩尔分数为1.018、3.171、5.278氨水溶液中甲烷气体水合物的生成条件。结果表明：氨的加入对甲烷水合物的生成起着明显抑制作用,而且随着氨浓度的增加,生成压力越高。采用Chen-Guo模型对甲烷在氨水中生成水合物的数据进行了计算,得到了较为满意的计算结果,平均误差为2.71%,说明Chen-Guo模型能够较好地预测该类体系的水合物的生成条件。     

页岩气集输过程水合物生成条件预测方法研究

页岩气与集输过程中携带或产生的游离水,在适当温度和压力条件下将会生成天然气水合物。水合物一旦生成,可能会堵塞集输管线或损坏生产设备,严重影响集输系统的安全运行。通过酸性气体图、平衡常数法、波诺马列夫法和回归公式法预测页岩I区块天然气水合物生成条件,为预防页岩气集输过程中生成水合物提供理论指导和技术支持。     

CSM模型与CPA状态方程预测高压水合物生成条件

传统的统计热力学模型假设天然气水合物为理想固体溶液,同时忽略了极性水分子之间的氢键缔合作用,在预测高压条件下的水合物生成条件时偏差较大。针对这一问题,提出了基于CSM模型与CPA状态方程计算高压天然气水合物生成条件的新方法。基于该方法计算的5种高压天然气水合物生成条件与实验数据的对比表明:当水合物生成压力低于20 MPa时,水合物生成压力计算值与实验值之间的平均相对偏差范围为0.59%—5.24%;当压力范围为20—69.84 MPa时,计算值的平均相对偏差范围为0.79%—6.76%,显著优于CSM模型结合SRK状态方程的计算结果。预测高压条件天然气水合物生成条件时,需要同时考虑水合物溶液的非理想性和水分子之间氢键缔合作用。     

水合物法分离合成气实验研究

分别测定了煤气化合成气在纯水以及两种不同浓度(6%(mol)和5%(mol)的四氢呋喃(THF)水溶液中的水合物生成条件,实验结果表明THF的加入可以大大降低合成气生成水合物的压力,使合成气能够在较低的压力下通过生成水合物的方法得到分离,同时也为该分离方法应用于实际工业装置提供了可行性。研究还成功地将Chen-Guo水合物热力学模型应用到含有一氧化碳气体的水合物生成条件的预测,并对合成气在纯水中不同温度下生成水合物的压力进行了计算,与本次实验值比较,得到平均误差为8.64%,肯定了实验结果的准确性。在此基础上,选定在5%(mol)THF水溶液中,气液比为100:1,反应压力为5MPa(绝)的条件下,分别进行反应温度为279.15K、281.15K、283.15K、284.15K和285.15K的水合物法分离合成气实验,提浓其中的氢气和一氧化碳。实验结果表明,284.15K时,氢气的回收率达到79.8%,氢气和一氧化碳的总回收率为76.0%,分离后二者总的体积百分含量由原料气中的88%提高到93%,分离效果较为满意。     

基于LS-SVM的天然气水合物生成条件预测模型建立

在天然气管线内生成的水合物会严重影响天然气的开采、运输,因而天然气水合物的预测方法和防治措施备受重视。针对天然气水合物生成条件,考虑天然气组分对水合物生成的影响,为简化计算、提高预测精度,引入一种能够很好解决复杂物理问题的最小二乘支持向量机(LS-SVM),并且通过Matlab语言编程,建立了一种包含CH4浓度、CO2浓度、H2S浓度以及水合物生成温度为输入,水合物生成压强为输出的天然气水合物生成条件预测模型,同时将实验数据作为最小二乘支持向量机训练数据并进行预测分析。结果表明,该预测模型不仅拥有较高的预测精度,而且方法简单、可行,为天然气水合物生成条件预测提供了一种新的解决方法。     

水合物分解和生成的动力学模型

水合物的动力学研究一般分为分解动力学和生成动力学,其动力学模型可以划分为宏观模型和微观模型。本文对水合物分解、生成的主流动力学模型进行介绍,包括Jamaluddin模型、Goel模型、Komai模型、Englezos模型、Bergeron—Servio模型。最后,提出建立一个分解和生成双过程统一的动力学模型设想。     

流动体系中的水合物成核诱导期研究

The appearance of turbidity due to large numbers of critical size hydrate nuclei may significantly affect the outgoing light intensity and the flow resistance in the pipe loop. The induction period of hydrate formation was determined by analyzing the experimental data——either based on the shading ratio data of laser detector or based on the pressure drop data of the flow system. The induction period of CC12F2 (R12) in pure water and that of CH4 in (tetrahydrofuran ＋ water) systems were then measured with the above two methods. Experimental data show that the induction period depends on the driving force exponentially. Flow rate also has a significant influence on the hydrate nucleation. A new induction period model taking the driving force and liquid flow rate into account was proposed. And it is successfully applied to the calculation of the induction period, which is in good agreement with the experimental data obtained in this study.     

进口甲烷再燃烧对煤粉燃烧以及NOx生成影响的数值模拟

A full two-fluid model of reacting gas-particle flows and coal combustion is used to simulate coal combustion with and without inlet natural gas added in the inlet. The simulation results for the case without natural gas burning is in fair agreement with the experimental results reported in references. The simulation results of different natural gas adding positions indicate that the natural gas burning can form lean oxygen combustion enviroment at the combustor inlet region and the NOx concentration is reduced. The same result can be obtained from chemical equilibrium analysis.     

PSRK模型的修正混合规则及其应用于聚合物溶液汽液平衡的预测

To extend the PSRK (predictive Soave-Redlich-Kwong equation of state) model to vapor-liquid equilibria of polymer solutions, a new EOS-gE mixing rule is applied in which the term ∑xiln(b/bi) in the PSRK mixing rule for the parameter a, and the combinatorial part in the original universal functional activity coefficient (UNIFAC) model are cancelled. To take into account the free volume contribution to the excess Gibbs energy in polymer solution, a quadratic mixing rule for the cross co-volume bij with an exponent equals to 1/2 is applied [bij^1/2=1/2(bi1/2 bj1/2)]. The literature reported Soave-Redlich-Kwong equation of state (SRK EOS) parameters of i3 - 2- pure polymer are employed. The PSRK model with the modified mixing rule is used to predict the vapor-liquid equilibrium (VLE) of 37 solvent-polymer systems over a large range of temperature and pressure with satisfactory results.     

评估混合气在PDMS膜中渗透性能的操作模型

An operational model is developed to evaluate and predict the permeation performance of mixed gas through poly（dimethylsiloxane） （PDMS） membranes by combining the ideal gas permeation model with the experimental analysis of the mixed gas transport character. This model is tested using the binary and ternary mixed gas with various compositions through the PDMS membranes, and the predicted data of the permeation flux and the compositions of the permeated gas are in good agreement with the experimental ones, which indicates that the operational model is applicable for the evaluation of the permeation performance of mixed gas through PDMS membranes.     

空间质量作用模型预测小分子离子交换平衡

The steric mass-action (SMA) model has been widely reported in the literature for ion-exchange and metal-affinity interaction adsorption equilibrium of biomacromolecules. In this paper, the usefulness of SMA model is analyzed for describing micromolecule ion-exchange equilibrium onto cation exchangers, CM Sephadex C-25 and Streamline SP. Batch adsorption experiments with ephedrine hydrochloride as a model adsorbate are carried out to determine the model parameters, that is, steric factor, characteristic charge and equilibrium constant. The result shows that the SMA model parameters of micromolecule cannot be obtained using the nonlinear least-square fitting method as protein‘s due to the remarkable difference between the molecular mass and dimension of micromolecule and protein. It is considered that the small size of the adsorbates dealt with in this study justifies the neglect of steric hindrances arising from adsorbate bulkiness. Thus, the three-parameter SMA model is reduced to two-parameter one (i.e., steric factor is equal to zero) for describing micromolecule ion-exchange equilibrium. It is found that the equilibrium constant for CM Sephadex C-25 increases with increasing ionic strength, while the equilibrium constant for Streamline SP shows an opposite trend. This is probably due to the remarkable difference between the physicalpro perties of the two adsorbents. Then, the relationship between the equilibrium constant and ionic strength is described by an expression. The computer simulations show that, the theoretical model with the correlation is promising in the prediction of micromolecule adsorption decrease with increasing ionic strength in a wide range of salt concentration.     

N-异丙基丙烯酰胺凝胶在NaCl水溶液中溶胀行为的预测研究

In this paper, a model is presented to correlate and predict the swelling behavior of hydrogels in aqueous solutions of electrolytes. The model is a combination of VERS-model, “phantom network“ theory and “free-volume“ contribution. The VERS-model is used to calculate Gibbs excess energy; “phantom network“ theory to describe the elastic properties of polymer network, and “free-volume“ contribution to account for additional difference in the size of the species. To test the model, a series of N-isopropylacrylamide based hydrogels are synthesized by free radical polymerization in oxygen-free, deionized water at 25~C under nitrogen atmosphere. Then, the degree of swelling of all investigated gels as well as the partition of the solute between the gel phase and the surrounding coexisting liquid phase are measured in aqueous solution of sodium chloride. The model test demonstrates that the swelling behavior correlated and predicted by the model agrees with the experimental data within the experimental uncertainty. The phase transition appeared in the experiment, and the influences of the total mass fraction of polymerizable materials ξgel as well as the mole fraction of the crosslinking agent YCR on the swelling behavior of IPAAm-gels can also be predicted correctly. All these show the potential of such model for correlation and prediction of the swelling behavior of hydrogels in aqueous solutions of electrolytes.     

非牛顿流体中的气泡行为

非牛顿流体广泛存在于各学科领域（如化工、食品和生物医学等）,也与许多工业过程及人类的生命过程密切相关。非牛顿流体中的气泡行为直接影响流体传质、传热及化学过程的快慢。因此,了解和研究非牛顿流体中的气泡行为具有重要意义。本文分别从气泡生成、聚并和破裂3个方面对非牛顿流体中气泡行为的研究进展进行评述。     

低温水相一步合成钛酸钡：颗粒合成研究

The formation of BaTiO3 nanoparticles via the reaction of BaCl2, TiCl4 and NaOH in aqueous solution has been systematically studied. The formation of BaTiO3 from the ionic precursors has been elucidated to be a very rapid process, occurring at temperature higher than 60℃. Furthermore, the particle size could be controlled by the proper selection of the synthesis conditions （e.g. reactant concentration of 0.5-1.0mol.L^-1, temperature of 80- 95℃ and pH ≥ 13）. A two-step precipitation mechanism was proposed. The first stage of the synthesis involved the formation of amorphous Ti-rich gel phase. The second stage of the synthesis was the reaction between the amorphous phase and the solution-based Ba^2＋ ions, which led to the crystallization of BaTiO3. Based on the particle formation mechanism, a novel method, high gravity reactive precipitation, was proposed and used to mass production of BaTiO3 of average particle size of about 60 nm and with narrow particle size distribution. Because it could break up the amorphous Ti-rich gel into small pieces, intensify mass transfer, promote the reaction rate of amorphous Ti-rich gel with Ba^2＋ ions.     

保护裂缝性气藏储层的钻井液技术

理论分析和油田现场钻井实践表明,钻井液中液相及固相颗粒侵入裂缝是造成裂缝性气藏储层伤害的主要因素。本文阐述了裂缝储层损害机理,系统介绍了保护裂缝性储层的钻井液技术。     

Monte Carlo模拟对称型三嵌段共聚高分子的吸附

The adsorption behavior of symmetric triblock copolymers, Am/2BnAm/2, from a nonselective solvent at solid-liquid interface has been studied by Monte Carlo simulations on a simple lattice model. Either segment A or segment B is attractive, while the other is non-attractive to the surface. Influences of the adsorption energy,bulk concentration, chain composition and chain length on the microstructure of adsorbed layers are presented.The results show that the total surface coverage and the adsorption amount increases monotonically as the bulk concentration increases. The larger the adsorption energy and the higher the fraction of adsorbing segments, the higher the total surface coverage is exhibited. The product of surface coverage and the proportion of non-attractive segments are nearly independent of the chain length, and the logarithm of the adsorption amount is a linear function of the reciprocal of the reduced temperature. When the adsorption energy is larger, the adsorption amount exhibits a maximum as the fraction of adsorbing segment increases. The adsorption isotherms of copolymers with different length of non-attractive segments can be mapped onto a single curve under given adsorption energy. The adsorption layer thickness decreases as the adsorption energy and the fraction of adsorbing segments increases, but it increhses as the length of non-attractive segments increases. The tails mainly govern the adsorption layer thickness.