發(fā)布時間：2018-05-31 14:40

  本文選題：嵌段聚醚 + 高穩(wěn)含油污水　； 參考：《西南石油大學》2015年碩士論文

【摘要】：隨著渤海油田聚合物驅(qū)油技術(shù)的實施,相應產(chǎn)生了大量的含聚采出水。采出水由于殘余聚合物的存在,異常穩(wěn)定。目前,處理這種污水較為有效的方法是加入陽離子型聚合物絮凝劑,雖然效果明顯,但分離過程中的絮凝體粘附性很強,易堵塞污水處理設備及管道。通過前期研究發(fā)現(xiàn),用非離子型嵌段聚醚處理這類污水,既能使處理后污水水質(zhì)達標,同時還不會產(chǎn)生大量粘性絮凝體。但其作用機理不夠明確,無法確定影響聚醚處理含聚污水性能的主要因素以及相應的調(diào)控方法,因此藥劑的優(yōu)化及現(xiàn)場應用受到限制。本文針對這一問題,對嵌段聚醚強化高穩(wěn)含油污水破乳過程的機理進行了研究。 本文以SZ36-1CEPK油田生產(chǎn)污水為處理對象,首先測定了污水的基本性質(zhì),其PH=6.8,含油量為4724mg/L,固含量為80mg/L,聚合物濃度為282mg/L,粒徑中值為5.1μm,污水中原油的等效烷烴碳數(shù)為9.2,油水乳化程度高,屬于高穩(wěn)含油污水。 針對這類污水具有凈水性能的嵌段聚醚亞組分EO、PO摩爾比接近0.75。分離的幾種聚醚中,產(chǎn)物中有效組分不超過50%,如果在實際生產(chǎn)中能很好控制產(chǎn)物的EO/PO比值,提高其有效含量,將大大降低產(chǎn)物的使用濃度。具有良好處理效果的嵌段聚醚,起效溫度均大于濁點小于PIT；無處理效果的嵌段聚醚,其濁點或小于30℃(過小)、或大于40℃(過高),在嵌段聚醚分子設計中,可按照使用溫度設計合成起效溫度介于濁點和PIT之間的產(chǎn)物。 嵌段聚醚從水相擴散至界面是自發(fā)過程,該過程是熵驅(qū)動過程,熵變可反映嵌段聚醚分子頂替原界面活性物質(zhì)及改變界面膜緊密度的能力。幾種典型嵌段聚醚中,DMEA1231(以醇胺為起始劑的四嵌段聚醚,分子結(jié)構(gòu)中EO、PO、EO、PO的質(zhì)量比為1：2：3：1)擴散過程的熵變最大,為614J/K·mol,即具有處理效果的嵌段聚醚,擴散過程中熵變相對較大。 宏觀絮凝動力學實驗表明,陽離子型絮凝劑的絮凝速率是嵌段聚醚的3-5倍,對于DMEA1231,其最佳處理條件：溫度在55℃附近,攪拌強度為200rpm。微觀絮凝動力學實驗結(jié)果表明,嵌段聚醚作用下,油滴的聚并速率常數(shù)七明顯大于陽離子絮凝劑,但嵌段聚醚受溫度影響較陽離子絮凝劑大。即與陽離子絮凝劑不同,嵌段聚醚主要是通過油滴聚并實現(xiàn)乳液破乳,對油珠的聚集行為無明顯影響。 Zeta電位測定結(jié)果表明,陽離子絮凝劑能有效破壞乳液雙電層結(jié)構(gòu),通過靜電中和實現(xiàn)除油；而加入嵌段聚醚后,其電性未發(fā)生改變。這證實了陽離子絮凝劑與嵌段聚醚強化污水破乳過程的機理的差異性。嵌段聚醚能有效頂替界面活性物質(zhì),降低油水界面膜強度,從而破壞其穩(wěn)定性。隨著溫度的升高,擴張模量隨溫度的升高呈降低趨勢。55℃時界面擴張模量最低,與相轉(zhuǎn)變溫度和絮凝動力學測定結(jié)果相符。油滴聚并-再聚集過程是嵌段聚醚強化高穩(wěn)含油污水破乳的過程,其中油滴聚并是關(guān)鍵,這一步驟是通過相轉(zhuǎn)變驅(qū)動乳液失穩(wěn)實現(xiàn)。用量升高擴張模量降低；隨著聚合物濃度和分子量的增大,界面擴張模量會隨之增大。 通過DMEA1231相轉(zhuǎn)變溫度測定結(jié)果以及組分分析結(jié)果,引入HLD值(親水親油差異值)理論,對破乳機理進行了宏觀理論描述。計算得到在DMEA1231作用下,溫度為55℃時,乳狀液體系的HLD值為0.886,DMEA1231在其相轉(zhuǎn)變溫度(55℃)附近,會誘導乳液體系發(fā)生相轉(zhuǎn)變,此時乳液穩(wěn)定性較差。
[Abstract]:With the implementation of polymer flooding technology in Bohai oilfield, a large amount of water containing polymining produced water has been produced. The produced water is abnormally stable because of the existence of residual polymer. At present, the more effective method to treat this kind of sewage is to add cationic polymer flocculant, although the effect is obvious, the flocculation of the flocculant is strong and easy to plug in the process of separation. The sewage treatment equipment and pipeline have been found. Through the previous study, it is found that the treatment of this kind of sewage with non-ionic block polyether can not only make the sewage water quality reach the standard after treatment, but also do not produce a large number of viscous flocculates, but its mechanism is not clear enough to determine the main factors affecting the performance of polyether treatment and the corresponding regulation and control. In this paper, the mechanism of the demulsification process of the embedded polyether reinforced high stability oily wastewater was studied in this paper.
In this paper, the basic properties of sewage in SZ36-1CEPK oilfield are measured, and the basic properties of the sewage are measured first, which is PH=6.8, the oil content is 4724mg/L, the solid content is 80mg/L, the concentration of the polymer is 282mg/L, the median diameter is 5.1 u m, the equivalent alkane carbon number of the raw oil in the sewage is 9.2, the oil and water emulsification is high, which belongs to the high stability oily sewage.
For this kind of sewage with water purification capacity of the block polyether subcomponent EO, PO mole ratio close to 0.75. separation of several polyether, the product is not more than 50% of the effective component, if the actual production can well control the product's EO/PO ratio, improve its effective content, will greatly reduce the use of low product concentration. With good treatment effect of block polymerization. The starting temperature of the ether is greater than the cloud point less than PIT, and the untreated block polyether, whose cloud point is less than 30 C (too small), or more than 40 degrees C (too high), can be designed in the block polyether molecular design, and can be designed to synthesize the products with the starting temperature between the cloud point and the PIT according to the use temperature.
The diffusion of block polyether from the water phase to the interface is a spontaneous process. This process is an entropy driven process. The entropy change can reflect the ability of the block polyether molecules to replace the original interface active material and change the tightness of the boundary mask. Several typical block polyether, DMEA1231 (four block polyether with alcohol amine as starting agent, EO, PO, EO, PO in molecular structure) have a mass ratio of 1: 2:3:1) the entropy change of diffusion process is the largest, which is 614J/K? Mol, that is, block polyether with processing effect, and the entropy change is relatively large during diffusion.
The macro flocculation kinetics experiment shows that the flocculating rate of the cationic flocculant is 3-5 times as high as that of the block polyether. For DMEA1231, the optimum treatment condition is that the temperature is near 55, and the stirring intensity is 200rpm. micro flocculation kinetics experimental results show that the coalescence rate constant seven of the oil droplets is obviously greater than the cationic flocculant under the action of the block polyether. However, the block polyether is more affected by the temperature than the cationic flocculant. That is, different from the cationic flocculant, the block polyether is mainly through oil droplets and emulsion demulsification, and has no obvious effect on the aggregation behavior of the oil beads.
The results of Zeta potential determination show that the cationic flocculant can effectively destroy the structure of the double layer of emulsion and realize the deoiling by electrostatic neutralization, but the electrical property of the cationic flocculant is not changed after adding the block polyether. This proves that the mechanism of the cationic flocculant and the block polyether to strengthen the demulsification process is different. The block polyether can effectively replace the interfacial activity. As the temperature rises, the dilatation modulus of the interfacial dilatation modulus is the lowest at.55 C with the increase of temperature, which is consistent with the phase transition temperature and flocculation kinetics. The process of oil droplet aggregation and re aggregation is the process of demulsification of the embedded polyether and high stable oily wastewater. The key is the accumulation of oil droplets. This step is realized by the phase transition driven emulsion instability. As the amount increases, the dilatation modulus decreases. With the increase of polymer concentration and molecular weight, the interfacial dilatation modulus will increase.
Through the results of DMEA1231 phase transition temperature determination and component analysis, the theory of HLD value (hydrophilic difference value) is introduced to describe the mechanism of demulsification. The HLD value of the emulsion system is 0.886 at the temperature of 55, and DMEA1231 will induce the emulsion system near the phase transition temperature (55 degrees C). The phase change occurs, and the stability of the emulsion is poor at this time.
【學位授予單位】：西南石油大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：X741;O631

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