如何实现HDPE装置H2/C2H4比值的稳定性

根据HDPE装置反应釜中H2／C2H4比值的重要性，对出现的H2／C2H4比值在开车时不稳定性进行分析、讨论，并通过修改程序等技术改进，提高了H2／C2H4比值的稳定性。     

Quantum mechanic study on cyclic molecul formation from ethynyl radical （C2H） and ethyne （C2H2）

The first cyclic molecule formation reactions from ethyne （C2H2）, initiated by ethynyl radical （C2H）, were studied by theoretical quantum mechanic. The study included the competition reaction between structure re-arrangement for the favourable ring-closure mechanism and ethyne addition in each step. The analysis was done by evaluating the energy difference of activation （AE）, entalphy （AH）, Gibbs （AG） of the optimized stable and transition molecules. The reaction temperatures were set at normal （T = 298 K） and combustion （T = 1200 K） condition.     

C2H2三聚体离子=苯

许多年来，物理化学家一直希望观察到的一个现象是，在气相条件下生成离子化的乙炔聚集态物质时，乙炔三聚体的离子（C2H2）^3＋能够形成新的共价键，从而得到苯的阳离子（C6H6）^＋。如今，美国弗吉尼亚公立大学的研究人员已经提供了这一过程的最充分证据。他们根据离子活动性和解离数据，结合理论计算确认“（C6H6）^＋在结构上与苯相同、稳定性与苯相同、离解行为与苯相同，因此它一定是苯!”由离子态的乙炔生成苯阳离子可能是科学家已经通过光谱望远镜从太空中观察到的多环芳烃的生成过程中的第一步。     

Dissociation behavior of （CH4 ＋ C2H4） hydrate in the presence of sodium dodecyl sulfate

Separation of a mixture of CH4+C2H4 gas by forming hydrate in ethylene production has become of interest,and the dissociation behavior of(CH4+C2H4) hydrate is of great importance for this process. The hydrate formation rate could be increased by adding a small amount of sodium dodecyl sulfate(SDS) into water. In this work,the kinetic data of CH4(18.5 mol%) +C2H4(81.5 mol%) hydrate decomposition in the presence of 1000 mg·L-1 SDS at different temperatures and pressures were measured with the depressurizing m...     

固体酸SnCl4·5H2O/C催化合成谷氨酸月桂醇酯表面活性剂

以谷氨酸和月桂醇为原料 ,用固体酸SnCl4·H2 O/C为催化剂合成谷氨酸月桂醇酯表面活性剂 ,探讨了反应温度、反应时间、物料配比和催化剂用量对合成反应的影响 ,结果表明该类催化剂催化效果良好 ,月桂醇转化率可达 97 9%。     

Ce4+与H2O2对FCC汽油氧化脱硫比较研究

This article describes two kinds of model oil samples made of a benzothiophene/octane mixture and a 2-me- thylthiophene/octane mixture. Furthermore, this paper investigates the oxidative desulfurization selectivity and reaction efficiency when Ce4+ compound and H2O2 having identical electron equivalent weight were used as oxidants. The test re- sults showed that the two kinds of oxidants were more effective to remove benzothiophene in the model oil samples. For oxidative desulfurization of 2-methylthiophene, Ce4+ compound was obviously superior than H2O2. This paper by means of quantum chemistry analyses elaborates the complex formed between Ce4+ species and 2-methylthiophene and FT-IR spec- trograms of model oil samples before and after oxidation by Ce4+ compound and H2O2, respectively. The results demonstrat- ed that Ce4+ compound could remove sulfur compounds not only through oxidation reaction but also through complexation reaction.     

从加氢脱硫（HDS）循环气中脱除H2S和C1—C4组分

简要介绍了炼油厂生产低硫燃料过程中处理循环氢气物流中的H2 S和轻质烃的几种方法 ,并通过实验对比论述非水溶型硫回收技术可降低氢气损失、增大轻质烃脱除率的优越性     

Vapor-hydrate phases equilibrium of (CH_4 C_2H_6) and (CH_4 C_2H_4) systems

Separation of the(C1 C2)hydrocarbon system is of importance in natural gas processing and ethylene production.However it is the bottleneck because of its high refrigeration energy consumption, and needs to be urgently addressed.The technology of separating gas mixtures by forming hydrate could be used to separate(C 1 C 2 )gas mixtures at around 0°C and has attracted increasing attention worldwide.In this paper,investigation of vapor-hydrate two-phase equilibrium was carried out for(C 1 C 2 )systems with and without tetrahydrofuran(THF).The compositions of vapor and hydrate phases under phase equilibrium were studied with model algorithm when structure I and structure II hydrates coexisted for the(methane ethane)system.The average deviation between the modeled and actual mole fractions of ethane in hydrate and vapor phases was 0.55%,and that of ethylene was 5.7%when THF was not added.The average deviation of the mole fraction of ethane in vapor phase was 11.46%and ethylene was 7.38%when THF was added.The test results showed that the proposed algorithm is practicable.     

Computation of equilibrium hydrate formation temperature for CO2 and hydrocarbon gases containing CO2 in the presence of an alcohol, electrolytes and their mixtures

This work presents the applicability of a unified model to predict the CO₂-rich gas and pure CO₂ hydrate formation conditions in aqueous solutions containing glycerol, methanol, ethylene glycol, electrolytes and their mixtures. A water activity model is introduced that combines the effect of the soluble gases, an alcohol and electrolytes. Then this model is used together with the model of Holder et al. [Holder, G.D., Corbin, G., Papadopoulos, K.D., 1980. Thermodynamic and molecular properties of gas hydrates from mixtures containing methane, argon and krypton. Ind. Eng. Chem. Fundam. 19 (3) 282] to predict CO₂-rich gas and CO₂ hydrate formation conditions. The predictions are in excellent agreement with experimental data.     

NH3作为CO2置换CH4水合物促进剂的分子动力学模拟研究

针对天然气水合物开采中CO₂置换面临的渗透性差、置换效率低的问题,采用分子动力学模拟方法,将对水合物相具有强穿透能力的NH₃作为促进剂,分别模拟了CO₂单组分和CO₂/NH₃混合组分置换水合物过程。结果表明:在模拟设定的温度压力范围内,245 K和255 K条件下,NH₃对CO₂置换水合物过程起到正向促进作用,而当温度升高至265 K时,则会对置换过程起到抑制作用;温度相同时,升高压力可以提高置换效率,但不会改变NH₃对置换过程的促进/抑制作用。该研究结果可为提高CO₂置换法的置换效率提供新的思路。      

Prediction of density and viscosity of ternary systems [C_2q]Br＋[C_4q]Br＋H_2O, [C_2q]Br＋[C_6q]Br ＋H_2O, and [C_4q]Br＋[C_6q]Br＋H_2O at different temperatures using their binary subsystems data

The simple equations for prediction of the density and viscosity of mixed electrolyte solutions were extended to the related properties of mixed ionic liquid solutions. The density and viscosity were measured for ternary solutions [C2q]Br(N-ethylquinolinium bromide)+[C4q]Br (N-butylquinolinium bromide)+H2O, [C2q]Br+[C6q]Br(N-hexylquinolinium bromide)+H2O, and [C4q]Br+[C6q]Br+H2O and their binary subsystems [C2q]Br+H2O, [C4q]Br+H2O, and [C6q]Br+H2O at 15, 20 and 25 °C, respectively. The results were used to test the predictability of the extended equations. The comparison results show that these simple equations can be used to predict the density and viscosity of the mixed ionic liquid solutions from the properties of their binary subsystems of equal ionic strength.     

炼油厂燃料气中C_(3)+及H_(2)优化回收利用北大核心CSCD

目的回收利用炼厂燃料气中的C_(3)+及H_(2),提高经济效益。方法通过对不同来源的燃料气分析对比,找出其中富H_(2)、高C_(3)+燃料气。优化H_(2)利用及回收流程,增加脱氢膜面积,提高H_(2)回收量。利用催化装置和焦化装置的吸收稳定系统回收燃料气中的C_(3)+。结果技改总投资320万元,可回收C_(3)+1.23×10^(4) t/a,增效3000万元/年;H_(2)回收量可增加1050×10^(4) m^(3)/a,降低制氢成本1200万元/年。结论该方案充分利用炼厂现有吸收稳定系统及现有脱氢系统扩容,具有投资少、效益好、见效快的优点,对玉门炼化总厂高质量发展具有重要意义。     

Kinetics of (TBAF + CO2) semi-clathrate hydrate formation in the presence and absence of SDS

In this communication, the impacts of adding SDS (sodium dodecyl sulfate), TBAF (tetra-n-butylammonium fluoride) and the mixture of SDS + TBAF on the main kinetic parameters of CO₂ hydrate formation (induction time, the quantity and rate of gas uptake, and storage capacity) were investigated. The tests were performed under stirring conditions at T = 5 ℃ and P = 3.8 MPa in a 169 cm³ batch reactor. The results show that adding SDS with a concentration of 400 ppm, TBAF with a concentration of 1–5 wt%, and the mixture of SDS + TBAF, would increase the storage capacity of CO₂ hydrate and the quantity of gas uptake, and decrease the induction time of hydrate formation process. The addition of 5 wt% of TBAF and 400 ppm of SDS would increase the CO₂ hydrate storage capacity by 86.1% and 81.6%, respectively, compared to pure water. Investigation of the impact of SDS, TBAF and their mixture on the rate of gas uptake indicates that the mixture of SDS + TBAF does not have a significant effect on the rate of gas uptake during hydrate formation process.     

高压下乙炔水合物的形成与分解实验研究

气体水合物是水和气体在高压低温下形成的一种笼形结晶化合物,具有强大的储气能力。关于水合物的形成、性质特征及能源利用、储存方面的研究日益受到重视,进行水合物研究的实验装置和测试技术也在不断发展,目前多数研究侧重于甲烷、二氧化碳等气体的水合物,对乙炔气体水合物的详细研究未见相关报道。文章基于自行设计的水合物合成及原位观测装置,采用化学反应生成气体的方法提供乙炔气源,在此基础上对乙炔水舍物合成的条件进行讨论,得出了乙炔形成与分解规律的初步结果,可为进一步研究乙炔水合物及应用于乙炔气体的储运等提供参考。     

Thermodynamic modeling of equilibrium conditions of CH4/CO2/N2 clathrate hydrate in presence of aqueous solution of sodium chloride inhibitor

In this work, the effect of sodium chloride (NaCl) on thermodynamic properties of CH₄+CO₂+N₂ hydrate formation and equilibrium condition has been studied. The three-phase (hydrate–liquid–gas) equilibrium calculation has been carried out using the Peng–Robinson equation of state (PR EoS) and Universal Quasi Chemical (UNIQUAC) activity coefficient models. The PR EoS coupled with classic mixing rule is applied for the vapor phase. The calculations of the gas hydrate formation pressures are performed in the absence and presence of sodium chloride inhibitor for the gas hydrate systems. The Chen–Guo model has been used for the hydrate phase and the UNIQUAC activity coefficient is applied for non-ideality of the liquid phase. To obtain higher accuracy, the solubility of the gases in the aqueous phase is also taken into account using pressure corrected Henry's law. Finally, the stepwise procedure has been followed to obtain the results and compared with the experimental results. The addition of 2% (by volume) sodium chloride to water results in large shifts in phase equilibrium boundary to increase pressure for the same temperature condition.     

一种新型CO_2置换CH_4水合物的开采方法

天然气水合物储量巨大,是未来极具开发潜力的清洁能源。CO_2置换法兼具能源开采与温室气体封存的双重功效,但通常CO_2对CH_4的置换速率非常低。为此,结合抑制剂存在条件下CH_4水合物和CO_2水合物具有不同的热力学稳定性这一特点,提出并通过实验证实了一种可用于开采天然气水合物的新方法,它将CO_2置换法与注热力学抑制剂的工艺相结合,实现了CH_4水合物分解过程的加速。通过岩心驱替实验,对比考察了两类3种常见CH_4水合物热力学抑制剂(甲醇、氯化钠和氯化镁)的作用效果。实验结果表明:在甲醇溶液作用下,CH_4水合物分解速率高达0.011 94 mol/h,远高于电解质盐溶液的作用效果(分别为0.000 86 mol/h和0.001 41 mol/h)。选择甲醇溶液作为水合物分解加速剂,通过前期注入甲醇溶液段塞、后期连续注入CO_2的方式,使得CH_4水合物分解率超过92%,且实现了CO_2气体以水合物形式的封存固定,最终CO_2水合物的生成量占到初始甲烷水合物总量的16%~27%。