丙烯酸十八酯-苯乙烯共聚物对含蜡原油改性效果与分子动力学模拟

合成了单体配比不同的丙烯酸十八酯-苯乙烯共聚物(OAS)降凝剂,采用实验与分子动力学模拟相结合的方法对降凝剂的性能进行评价.实验结果表明,OAS降凝剂的降凝减黏性能随丙烯酸十八酯比例的增加呈现出先增大后减小的趋势.在2000 mg/kg加剂量下,苯乙烯与丙烯酸十八酯摩尔比为1:3的降凝剂OAS-4能使含蜡原油凝点降低4...     

Synthesis of cyclohexanone-alcohol hemiketals and evaluation as flow improver for waxy crude oil

In this paper, four novel cyclohexanone-alcohol hemiketals (KL-1, KL-2, KL-3, KL-4) as waxy crude oil flow improver have been prepared by cyclohexanone and 1-pentanol, 1-Hexanol, 1-heptanol, 1-octanol. Evaluation results demonstrate the hemiketal compounds have obvious effect on the viscosity and pour point of Henan crude oil. DSC analysis showed that waxing point and waxing peak decreased to a certain degree in 0.05% hemiketal solutions. Wax crystal morphology analysis indicated the four hemiketals played a role of nucleation in the process of waxy crude oil decoagulation, and in that way acts as waxy crude oil flow improver.     

BEM系列原油流动性改进剂的研制

通过对EVA的醋酸乙烯含量、熔融指数对含蜡原油的降凝影响的研究 ,探讨EVA对含蜡原油的最佳加入量以及不同的结构表面活性剂对原油降凝剂抗重复加热和抗剪切能力的作用 ,BEM降凝平均相对分子质量与含蜡原油蜡碳数分布之间的关系等。研制的BEM降凝剂广泛用于鲁宁线、中洛线等多条管输管道     

共聚型原油流动改进剂AMSA的合成与评价

针对中原原油中高含蜡量的特点，以丙烯酸十八酯(ODA)、顺丁烯二酸酐(MA)、苯乙烯(St)和丙烯腈(AN)4种单体为原料，采用自由基溶液聚合反应合成了原油流动改进剂AMSA。最佳合成条件：n(ODA)：n(MA)：n(St)：n(AN)=16：1：1：3，引发剂为偶氮二异丁腈(AIBN)，用量1．2％(质量分数)；聚合温度85℃；聚合时间7h。在中原原油中加入质量分数为0．1％的AMSA可以使原油的凝固点降低14℃，25℃粘度下降92．9％，屈服值下降96．4％。     

前南高蜡原油降凝剂的研究

文章选择了几种不同的单体进行聚合反应,得到了两种三元聚合物,并分别和EVA进行复配。依次考察了两种复配型降凝剂在不同加剂量和不同温度下对前南原油的降凝效果。实验结果表明:在加剂温度为70℃时,AMS-EVA复配降凝剂的最佳加剂量为0.03%,可使前南原油凝点降低9℃;AVS-EVA复配降凝剂的最佳加剂量为0.1%,可使前南原油凝点降低10℃。这两种复配型降凝剂均可以降低前南原油的黏度,改善其低温流变性。     

Investigating the synergistic effect between oil soluble surfactants and styrene–maleic anhydride copolymers to enhance the flow properties of waxy crude oil

Styrene–maleic anhydride (SMA) copolymer is prepared and then reacted with octadecyl alcohol SMASA, hexadecylamine SMACA, benzyl alcohol SMABA, and aniline SMAAn to obtain four copolymers. Three oil soluble surfactants are prepared by esterification of mono-, di-, and triethanolamine with oleic acid MEAO, DEAO, and TEAO. The structure of the prepared copolymers is characterized using spectroscopic techniques such as infra-red (FTIR), ¹H nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC). The prepared copolymers are evaluated individually as flow improvers then mixed with surfactants. From the results, it is found that the copolymer with aliphatic side chain SMACA exhibited the maximum pour point depression (ΔPP = 21°C at 1,500 ppm), whereas the rest copolymers SMASA, SMABA, and SMAAn exhibited the same pour point depression ΔPP = 18°C at 1,500 ppm. Moreover, the blend (B4) between SMACA and TEAO exhibited the maximum pour point depression ΔPP = 27°C.     

降凝剂对高蜡稠油的改性效果及机理研究

实验研究了工业品原油降凝剂WHP改善含蜡56.9%、其中96.6%为正构烷烃的胜利郑王庄稠油流动性的效果。WHP含乙烯/醋酸乙烯/乙烯醇嵌段聚醚三元共聚物30%-35%。在60℃将WHP加入稠油中,测定其凝点和32℃、0-42.6 s^-1范围5个剪切速率下的黏度,均随WHP加量的增加（50-300 mg/L）而降低,200 mg/L为最佳加量,在该加量下0.32 s^-1黏度由34.16 Pa·s降至79.2 mPa·s,凝点（℃）、屈服值（Pa）、稠度系数（Pa·s^n）分别由49.0、32.42、31.57降至39.5、0.1297、0.02142,流型指数由0.1176升至0.9790。由黏温曲线求出,加入200mg/L WHP使该稠油析蜡点由65℃降至58℃,反常点由70℃降至50℃。根据空白和加剂原油扫描电镜照片显示的蜡晶形态,利用共晶机理分析讨论了WHP这种高分子表面活性剂的降凝、降黏、改善流动性的作用。图3表3参5。     

管输原油降凝剂的研究进展

总结了石蜡结晶机理及其影响因素,并对国内外含蜡原油降凝剂的发展过程、作用机理、常用降凝剂的种类以及影响降凝剂作用效果的各种因素进行了介绍;指出了降凝剂在研究和应用中存在的问题,对降凝技术的发展进行了客观评价和展望。     

聚合物型原油降凝剂的作用机理及应用

介绍了聚合物原油降凝剂的种类、作用机理、筛选和评价方法及其在国内外的应用     

用于高含蜡原油的双聚合物降凝剂的研制

通过在有机溶剂中进行的引发聚合 ,由摩尔比 2∶3∶3的马来酸酐、丙烯酸十八酯、醋酸乙烯酯合成了共聚物降凝剂A ,由摩尔比 1∶2∶3的苯乙烯、马来酸酐、丙烯酸十八酯合成了共聚物降凝剂B。A和B均为质量分数 30 %的溶液。简介了合成方法。A +B组合实验和组合物加量实验结果表明 ,对于密度 86 8.9kg m3、含蜡量 2 6 .6 %的辽河曙光原油 ,质量比 3∶1的A +B的降凝降粘效果最好 ,加入量为 0 .5 %时原油凝点由 2 9℃降至 2 1℃ ,80℃、15 0s- 1下的粘度由 2 0 0 0mPa·s降至 95 0mPa·s,降粘率达 5 2 .5 % ;对于密度 886 .7kg m3、含蜡量 18.9%的吉林新民渣油(原油减压蒸馏釜底残液 ) ,质量比 1∶2的A +B的降凝降粘效果最好 ,加入量为 0 .4 %时渣油凝点由 13℃降至 1.0℃ ,80℃、15 0s- 1 下的粘度由 95 0mPa·s降至 2 6 0mPa·s,降粘率达 72 .6 %。降凝剂A +B加量增大时 ,原油和渣油的凝点、粘度均降低。表 3参 8。     

原油降凝降粘剂的合成与性能评价

以十八醇和丙烯酸为原料,在不加带水剂的条件下合成了丙烯酸十八酯（ODA）,其合成条件为：十八醇108g,n（十八醇）：n（丙烯酸）=1．0：1．2,对甲苯磺酸1．0％（催化剂,以醇酸总质量计）,对苯二酚0．7％（阻聚剂,以醇酸总质量计）,反应温度135℃,反应时间6h。然后再用实验合成的丙烯酸十八酯、顺丁烯二酸酐（MA）和醋酸乙烯酯（VA）3种单体为原料,采用自由基溶液聚合反应合成了原油降凝剂AMV。通过实验确定了最佳合成条件：nODA：nMA：nVA=8：1：1,引发剂为偶氮二异丁腈（AIBN）,用量0．5％（w））;聚合温度90℃;聚合时间6h。在原油中加入质量分数为0．5％的AMV可以使原油的凝固点降低10℃。50℃时的粘度由148．2mPa·s下降到40mPa·s,降粘率迭73％。     

热处理作用对含蜡原油流变性的影响

热处理技术是改善含蜡原油低温流动性的一种主要方法,以BH油田含蜡原油为例,通过一系列热处理试验对含蜡原油进行了流变性能研究,对实验数据进行了理论分析,并结合现场应用情况验证了试验结论的正确性。分析结果表明：温度是影响热处理效果的主要因素,中温段（50～60℃）的热处理会对含蜡原油的凝点产生恶化效果;高温段（70～95℃）的热处理可以大幅降低含蜡原油的凝点。冷却速度对含蜡原油热处理效果的影响至关重要,当冷却速度较小（0．5～1．0℃／min）时,油样热处理效果较好;冷却速度太快（1．2～1．5％／min）,将使热处理效果变差。剪切速率对热处理效果有一定影响,通常在较低速率的剪切作用下,原油热处理效果较好,随着剪切速率的增加,原油热处理效果变差。热处理后油样的稳定性对热处理效果的影响也不可忽视。     

添加流动性改进剂改善原油低温流动性能的研究

以烯烃，脂肪酸烯基酯和烯基酰胺或烯基磺酸盐为主要原料，合成了能降低含蜡原油凝点的流动性改进剂Ｈ８９－２。综合评定了流动性改进剂Ｈ８９－２对改善青海原油流动性能的效果。确定了流动性改进剂Ｈ８９－２的最佳添加量。     

Correlations Between the Pour Point/Gel Point and the Amount of Precipitated Wax for Waxy Crudes

Abstract:

The amount of precipitated wax is one of the key factors that governs the flow properties of waxy crudes. Experimental results of 24 crudes have shown that approximately 2 wt% precipitated wax is sufficient to cause a virgin waxy crude gelling. Accordingly, a correlation between the pour point and the temperature at which 2 wt% of wax has precipitated out from a crude oil; i.e., T _c (2 wt%), and a correlation between the gel point and T _c (2 wt%) have been developed. The proposed correlation of the pour point is in accordance with the correlation developed by Letoffe et al. (1995) Letoffe, J. M., Claudy, P., Kok, M. V., Garcin, M. and Vollet, J. L. 1995. Fuel, 74(6): 810–817. [CSA][CROSSREF][Crossref] , [Google Scholar] on the basis of 14 crudes from eight countries. The development of the gel point correlation and further verification of the pour point correlation indicate that there is a relationship between the gelling of virgin waxy crudes and the amount of precipitated wax. According to these correlations and the amount of precipitated wax, which can be determined only with a little sample by thermodynamic models or Differential Scanning Calorimetry (DSC) experiment, the gel point and pour point of virgin waxy crude can be predicted even if the oil sample is very limited. Heat treatment and chemical treatment can greatly improve flow behavior of waxy crudes, and more precipitated wax is present when the beneficiated (thermally beneficiated or PPD-beneficiated) crude oils gel. Experimental results showed that approximately two or three times the amount of precipitated wax presents at the gelling temperature when the oils were in their beneficiated (thermally beneficiated or PPD-beneficiated) conditions.     

H89-2原油流动性改进剂的研究

应用流动性改进剂(化学添加剂)可改善原油的低温流动性能.本文以烯烃、脂肪酸烯基酯和烯基酰胺或烯基磺酸盐为主要原料,在含有自由基引发剂的溶液中,在温度55～85℃,压力5～9MPa,聚合3～8h合成了能降低原油凝点的流动性改进剂H89-2(三元共聚物).综合评定了H89-2改善青海原油低温流动性能的效果,在原油中加入15×10^-5H89-2,可使凝点从31.5℃降至12℃;表观粘度(20℃)从5158.9mPa·s降至79.2mPa·s;屈服值从73.6Pa降至0Pa.探讨了H89-2的降凝作用机理.因为H89-2既含有适度的烷烃碳链,又含有两种极性不同的极性基因,所以对原油的适应性较强.     

聚合物/微纳米复合含蜡原油降凝剂的研究进展

含蜡原油中蜡分子的结晶析出会使原油的低温流变性显著恶化,降低原油管输的安全性和经济性.添加少量的聚合物型降凝剂能够改变蜡分子的结晶习性,改善原油的宏观流动性.加降凝剂原油的凝点越低、低温黏度越小,意味着输送的能耗越低、安全性越高,因此人们对原油降凝剂的降凝降黏效果追求是无止境的.利用不同的微纳米颗粒,研制高效的聚合物/...     

苯乙烯-马来酸酐-丙烯酸十八烷基酯三元共聚物的合成及其降凝性能

合成了用作降凝剂的苯乙烯－马来酸酐－丙烯酸十八烷基酯三元共聚物。研究表明,当苯乙烯、马来酸酐、丙烯酸十八烷基酯三种单体摩尔比为1∶3∶3,原油预热温度为60℃,三元共聚物在江汉原油中加量为300mg/L时,此三元共聚物可使江汉原油的凝固点为28℃降到13℃。它是一种新型的原油降凝剂。     

Synthesis and characterization of polymeric additives based on α-Olefin as pour point depressant for Egyptian waxy crude oil

Several strategies have been utilized to minimize the problems that causes losses of billions of dollars per year to the petroleum industry. Octadecene (OD) copolymerizes with styrene (S) at variable ratios of 1:1, 1:2, and its copolymers were obtained from alkylation by Friedel-Craft followed by esterification and amidation. Infrared spectra (IR), gel permeation chromatography (GPC), and nuclear magnetic resonance (NMR) spectroscopy were performed to characterize the end products. Waxy crude oil (Blank PPT = 27°C) from NQ7 well, Qarun Petroleum Company, Western Desert, Egypt, was studied, and the results indicate that crude oil treated with the prepared copolymers at dosage 2,000 ppm depresses PPT to 6°C and enhances the paraffin inhibition (PI) to 80% compared with blank. Good results are obtained by using the highest molecular weight copolymer compared with others.     

原油流动性改进剂的制备及应用

以烯烃、烯烃基脂肪酸酯和烯属不饱和酰胺或烯属烃磺酸盐为主要原料，合成了含蜡原油降凝剂H89－2（三元共聚物）。综合评定了H89－2改善青海原油流动性能的效果。阐明了确定降凝剂最佳添加量的原则。