Kinetics of Hydrolysis of Chloride Salts in Model Crude Oil

Abstract

Chloride salts are difficult to remove from heavy crude oils and bitumens. In the presence of steam, the chloride salts form hydrochloric acid, causing significant corrosion in the downstream equipment. The rate and the extent of the hydrolysis reactions for magnesium, calcium, and sodium chloride salts were measured by contacting with flowing steam at 100°C to 350°C. The extent of hydrolysis was controlled by salt cations and by the external particle area. The non-volatile products of the reactions were metal hydroxychlorides. Intraparticle reaction of the water limited the rate of hydrolysis, therefore, the water of hydration was most reactive.     

Inhibition and Promotion of Hydrolysis of Chloride Salts in Model Crude Oil and Heavy Oil

Abstract

The interactions of chloride salts with naphthenic acid and inhibitors during exposure to steam at 100–350°C were investigated in order to understand the release of hydrochloric acid in crude units. Naphthenic acid promoted the release of chlorine from calcium and sodium chlorides by a factor of up to 30 times, forming metal naphthenates in solution. Mitigation of the hydrolysis reactions was achieved with the use of chemical additives in both a model oil and in a Canadian heavy oil.     

催化水解醋酸甲酯的动力学

采用G—6104型阳离子交换树脂为催化剂,于间歇搅拌反应釜中测得了消除外扩散影响的醋酸甲酯水解反应速率数据,归纳得到了实验条件下阳离子交换树脂催化水解醋酸甲脂的动力学方程式。结果表明反应过程控制步骤是吸附在催化剂表面的醋酸甲酯同未吸附的水发生表面反应。催化剂用量和水酯摩尔比为醋酸甲酯水解率的重要影响因素。     

阳离子交换树脂催化水解乙酸甲酯的动力学研究

在间歇搅拌釜反应器中测定了G-6104型阳离子交换树脂催化水解乙酸甲酯的反应动力学；测得了消除外扩散影响的水解反应速率数据，归纳得到了实验条件下的动力学模型方程。研究表明，控制步骤是吸附在催化剂表面的乙酸甲酯与未吸附的水所发生的表面反应。实验还测定了反应温度、催化剂用量和水酯比对乙酸甲酯水解率的影响。     

乙醇酸甲酯水解制备乙醇酸的反应动力学

在无外加催化剂的条件下对乙醇酸甲酯水解制备乙醇酸的反应动力学进行了研究,分别考察了搅拌转速、初始水酯的物质的量比和温度对反应速率的影响。基于均相模型,通过实验数据的回归得到了指前因子与活化能。研究发现用活度代替物质的量分数进行反应动力学拟合效果更好,其中各组分的活度系数用UNIFAC法估算.通过范特霍夫方程估算得到该反应的标准反应焓约为16.12kJ/mol。     

氯化钕配合物催化4-乙烯吡啶聚合反应动力学研究

研究了氯化钕配合物催化４－乙烯吡啶聚合反应动力学，通过考察反应时间、催化剂浓度和温度对聚合反应的影响，建立了该体系动力学方程，并求取出反应级数为１，表观活化能约为４８．８６ｋＪ／ｍｏｌ。     

玉米秸秆的水解糖化研究

In this paper three methods(dilute acid pretreatment, aqueous ammonia/dilute acid pretreatment and alkaline pretreatment) were used to study the hydrolysis of corn stover and characteristics of each method were compared. The results showed that the lignin removal rate was 71.8% when the corn stover was treated with a caustic soda solution containing 1.5% of NaOH, at a temperature of 75 ℃ for 90 min with an initial solid-liquid ratio of 1:8(w/v). Hydrolysis yield of the NaOH pretreated sample reached 78.5%, which was much higher than other control groups. These results are useful for evaluation of pretreatment technologies, and identification of key factors that limit cellulose hydrolysis, and can also serve as a basis for designing and screening appropriate pretreatment technologies.     

常温羰基硫水解催化剂的研究进展

综述了常温羰基硫（COS）水解催化剂的失活原因及提高催化性能的主要方法,指出探索催化剂的现场再生方法、开发活性炭基载体及与有机醇胺脱硫体系的结合将是这一领域未来的发展方向     

加拿大油砂沥青喷雾造粒溶剂体系的选择

以正戊烷+正己烷、正戊烷+环戊烷2个系列混合物作为溶剂,采用溶剂沉淀法从加拿大油砂沥青中得到沥青质,通过对沥青质SARA族组成、元素组成、平均分子结构、分子片层堆积结构的测定,考察了溶剂混合比例对所得沥青质性质的影响。结果表明,随着正己烷或环戊烷掺入比例的增加,沥青质的收率显著降低,软化点明显提高;正戊烷+环戊烷混合溶剂更适宜作为加拿大油砂沥青喷雾造粒的溶剂体系,正戊烷中加入少量的环戊烷就能达到沥青喷雾造粒的要求。在正戊烷中掺入体积分数10%的环戊烷,可将脱油沥青收率降低4百分点,软化点相应升高10~12℃,从而生产出外观形态良好的沥青粉,可以作为加拿大油砂沥青喷雾造粒的溶剂体系。     

FeO_x/HZSM－5催化剂上苯与氯苄苄基化反应动力学及催化剂的表征

采用浸渍法制备了不同Fe负载量的FeOx/HZSM-5催化剂,用于催化苯与氯苄苄基化反应。考察了FeOx/HZSM-5催化剂的催化性能并得到了反应动力学参数。采用XRD、N2等温吸附-脱附和UV-Vis等手段对FeOx/HZSM-5催化剂进行了表征。实验结果表明,Fe负载量(质量分数)为8.0%的8.0-FeOx/HZSM-5催化剂对苯与氯苄苄基化反应有较好的催化性能;Fe负载量影响FeOx/HZSM-5催化剂上铁物种的结构和性质,当Fe负载量小于等于5.0%时,FeOx/HZSM-5催化剂上铁物种主要是"分立"的Fe3+物种;当Fe负载量大于等于8.0%时,催化剂上铁物种主要是"分立"的Fe3+物种和少量超细Fe2O3,由于"分立"的Fe3+物种和超细Fe2O3协同作用,使8.0-FeOx/HZSM-5催化剂的性能较佳。     

国内外COS水解技术研究状况

羰基硫 (COS)催化水解是从气体中间接脱除COS的主要过程 ,本文从催化剂活性组分与载体、催化水解反应机理和催化剂中毒失活三个方面介绍了国内外COS催化水解技术研究发展状况 ,COS水解催化剂产品开发及有关COS水解技术的专利 ,并指出多组分混合或添加抗中毒助剂制备高活性、高稳定性和耐硫中毒COS水解催化剂是未来这一领域的发展方向。     

常温COS水解催化剂的失活与再生

对常温COS水解催化剂的失活与再生进行了研究。采用XRD、压汞、微反 -色谱等多种物理测试方法对失活催化剂进行表征 ,结果表明 ,导致催化剂失活的原因主要是硫沉积使催化剂孔道堵塞 ,影响了内扩散。失活催化剂经5 5 0℃焙烧、浸渍再生剂再生 ,其活性可以恢复到新鲜催化剂的 90 %以上     

The Preparation and Characterization of Some Novel Quaternary Iminium Salts Based on Schiff-base as a Corrosion Inhibitor

Abstract

Novel quaternary iminium compounds, namely, N-(4-methoxybenzylidene)-N-benzyldodecyliminium chloride (I_a), N-(4-methoxybenzylidene)-N-benzylhexadecyl iminium chloride (I_b), N-(4-methoxybenzylidene)-N-benzyloctadecyliminium chloride (I_c), and N-benzylidene-N-benzyldodecyliminium chloride, were prepared. The surface properties such as surface and interfacial tension, foaming, and emulsifying power of these surfactants were investigated. The surface parameters including critical micelle concentration (CMC), maximum surface excess (Γ_max), minimum surface area (A_min), efficiency (PC₂₀), and effectiveness (π_CMC) were calculated. Free energy of micellization (ΔG°_mic) and adsorption (ΔG°_ads) were calculated.     

泡沫衰变的动力学方程

论述了泡沫的衰变机理，用搅拌法测定了不同表面活性剂的泡沫衰变过程。根据测得数据，得出5种表面活性剂的发泡能力及泡沫稳定性次序为：SDS〉ABS〉AES〉OP〉AS，得出了产生的泡沫体积随时间的变化关系，并总结出了各表面活性剂的泡沫衰变的动力学方程。     

Development of method for monitoring of chloride release in the oil refining processes

During oil refining, equipments are constantly exposed to the action of compounds such as salts, leading corrosion problems and to decrease in equipment service life. Soon, the growing search for productivity increasingly demand more strategies to monitor the processes and minimize costs. This article contributes to the methodology development to study the chlorides released during the oil distillation, in a similar process that occurs in refineries, enabling predict and minimize damage. Oils were evaluated with respect to chloride release during each stage of oil heating. Salinity mass balance were obtained as well as their respective chloride release percentage to each oil.     

The Kinetics of Hydrodesulphurization of Diesel: Pore Diffusion Aspects

Abstract

Indian fuel policy aims at producing ultra-low-sulfur diesel (ULSD) in the near future. A catalyst for meeting such requirements has been developed and the kinetics of this catalytic ultra-deep hydrodesulfurization (UDHDS) process is being looked into. Experiments were carried out in a flow microreactor over a presulfided catalyst and intrinsic parameters were estimated (Ganguly, 2009 Ganguly, S. K. Kinetics of hydrodesulphurization of diesel: Mass transfer aspects. International Conference on Energy and Environment, Enviroenergy 2009. March18–19, Chandigarh, India. pp.258–262.  [Google Scholar], 2010 Ganguly, S. K. Kinetics of hydrodesulphurization of diesel: Pore diffusion effects. International Symposium on Fuels and Lubricants, ISFL2010. March9–12, New Delhi, India.  [Google Scholar]). It was established that the UDHDS process is internal resistance controlled. In the present study we have tried to demonstrate by simulations how we could reduce the internal resistance by increasing the effective pore diffusivity so that the conversion of sulfur can be improved.     

The Mechanism and Kinetics for the Alkylation of Benzene with Ethylene

The paper introduces the mechanism and kinetics of the alkylation of benzene with ethylene to produce ethylbenzene. The alkylation reaction mechanism that takes place in the surface of the ZSM-5 catalyst and the [bmim]Cl/FeCl₃ ionic liquid catalyst is described; at the same time the alkylation reaction kinetics is put forward based on the corresponding mechanism. The method obtained aids in the understanding of the microcosmic process of alkylation for adapting to the necessity of industrialization.     

聚合物驱产出液中聚合物分子量和水解度的准确测定

聚合物分子量和水解度的测定仅限于纯净聚合物溶液,而对于含盐和其它杂质的油井产出液来说,传统的测定方法误差较大,影响了聚合物驱油井产出聚合物浓度的监测及地层聚合物存在形式的研究。采用超滤方法,应用美国微孔切向流超滤系统,消除了盐和其它杂质的影响,得到了较纯净的聚合物溶液,从而准确测定了产出液中聚合物的分子量和水解度。试验结果表明,应用美国微孔切向流超滤系统测得的聚合物分子量和水解度的相对误差均小于2.0%;而不经过美国微孔切向流超滤系统超滤的聚合物溶液,其分子量测定的相对误差在25.0%以上,其水解度误差甚至超过100%,达到104%。此外,采用超滤-沉淀的方法可以准确测定产出液中聚合物的浓度。实验表明,该法可以准确测定聚合物驱油井产出液中聚合物的分子量和水解度,满足现场检测的要求。     

Zn-Ca-Fe氧化物催化水解微晶纤维素

以尿素为沉淀剂制备了一系列复合金属沉淀物,将其在高温条件下煅烧获得一系列复合金属氧化物固体催化剂,并将其用于催化微晶纤维素的水解反应;考察了反应温度、反应时间、搅拌转速、催化剂用量和微晶纤维素用量对反应的影响。实验结果表明,在反应温度160℃、反应时间20 h、搅拌转速400 r/mnin、微晶纤维素2.0 g、Zn-Ca-Fe氧化物0.9 g和H_2O 200 mL的条件下,微晶纤维素的转化率高达42.56%,葡萄糖的收率为69.20%,且微晶纤维素水解液为中性溶液。在相同反应条件下,Zn-Ca-Fe氧化物可重复使用5次,其催化活性无明显降低。     

The Biodegradation Kinetics of Refining Wastewater by Microorganism UBD

Abstract

In order to develop the wastewater treatment technology for the refineries, the authors studied the biodegradation kinetics of the total petroleum hydrocarbon (TPH) in the refining wastewater based on the experiment data through simplifying the Monod equation properly. The biodegradation kinetics equation can be expressed as v = v_max = 0.25 . The microorganism UBD has strong ability for the biodegradation of the refining wastewater. It can be seen from the parameters of the kinetics equation that the TPH in the refining wastewater is not the nondegradation compound for the microorganism UBD.