稠油污水混凝除硅效果及作用機(jī)理探討
發(fā)布時(shí)間：2018-08-03 13:19
【摘要】：稠油污水成分復(fù)雜且又有回用熱采鍋爐的高水質(zhì)需求,因此處理難度很高,其中硅含量的去除更是一個難點(diǎn)。稠油熱力開采過程中,高溫蒸汽及冷凝液會與地層巖石反應(yīng),脫除其中的硅并帶入到采出液中,最終進(jìn)入稠油污水。國標(biāo)中要求處理后稠油污水回用鍋爐前其中硅含量應(yīng)低于50mg/L,這樣才能保證鍋爐長期運(yùn)行下不產(chǎn)生硅垢�；瘜W(xué)混凝除硅是稠油污水除硅的主要方法,很多金屬氧化物或氫氧化物都有良好的除硅效果,但它們的具體除硅機(jī)制卻并不明朗,一方面是因?yàn)樗械墓杷嵊卸喾N形態(tài),另一方面則是因?yàn)檫@些除硅藥劑在水中的水解成分也較為復(fù)雜。本文介紹了稠油含硅污水中硅的來源、混凝處理技術(shù)及相關(guān)理論的研究進(jìn)展。以遼河稠油污水和實(shí)驗(yàn)室模擬污水為主要研究對象,結(jié)合前人的研究成果建立起污水中各形態(tài)硅酸的分析方法,包括單硅酸(Sia)、低聚硅酸(Sib)、高聚硅酸(Sic)和不溶硅酸等,考察了水中的硅酸在溫度、pH和鹽等影響下的形態(tài)變化與轉(zhuǎn)化規(guī)律。應(yīng)用多種鈣類、鎂類及鋁類等混凝劑,研究其加量和成分等對不同硅酸形態(tài)去除效果的影響,分析各類除硅劑的有效作用成分,總結(jié)了混凝除硅過程中的主要作用機(jī)理。實(shí)驗(yàn)結(jié)果表明:溫度較高時(shí)有利于污水中的Sic向Sia變化,且溫度越高平衡后Sia含量越高;酸性條件會抑制Sia的形成,而堿性條件下則會促進(jìn)其它形態(tài)的可溶硅酸向單硅酸轉(zhuǎn)化;Mg2+、Al3+、Fe3+等陽離子能顯著影響溶液中可溶硅酸的含量,主要是以沉降去除為主,其中Al3+表現(xiàn)最好,Ca2+則有一定的抑制Sia聚合的作用,而Cl-、HCO3-、NO3-、SO42-等離子則無明顯作用。由于污水中高含HCO3-,鈣類除硅劑的效果不如鎂類,而同等條件下強(qiáng)堿復(fù)合MgCl2效果最好,在pH=12時(shí),800mg/L加量下,除硅率達(dá)到91.89%,反應(yīng)后總硅含量降低到38.4mg/L;其次是MgO顆粒,最差是Mg(OH)2顆粒,對MgO的粒徑考察發(fā)現(xiàn)粒徑越小除硅效果越好,但分析除硅過程中的硅酸形態(tài)表明,鈣類和鎂類除硅劑主要直接去除的是水中的Sia,它們很可能是通過在水中形成的表面水化層對單硅酸的吸附來達(dá)到除硅作用;Al2(SO4)3在加量為6mmol/L時(shí)能將稠油污水中的總硅降低到50mg/L以下,聚合氯化鋁(市售)在加量為4mmol/L時(shí)即可達(dá)到同等效果;pH值會影響硫酸鋁的水解形態(tài),pH=5時(shí)Al2(SO4)3表現(xiàn)出最優(yōu)的除硅效果,其中對Sic的去除效果要優(yōu)于Sia;新制備的Al(OH)3對污水中Sia的去除效果優(yōu)于對Sic;對比實(shí)驗(yàn)室制備的不同鋁形態(tài)分布的PAC10、PAC22及PAC25的除硅效果可見,單核鋁(Ala)含量高的PAC10對含硅污水處理后,污水中殘余的Sic更少,膠溶鋁(Alc)含量高的PAC25處理后污水中殘余的Sia更少,即Ala對Sic、Alc對Sia分別有針對性的去除效果;吸附-改性理論可以解釋硅鋁之間的相互作用,在硅鋁高聚物的氧化物或氫氧化物表面形成的硅鋁酸鹽位或固溶體覆蓋層降低了原物質(zhì)的溶解度,從而導(dǎo)致其更容易在污水混凝過程中沉降去除。
[Abstract]:Heavy oil sewage is complex and has high water quality demand for reusing heat recovery boiler. Therefore, it is difficult to treat the silicon content. In the process of heavy oil thermal recovery, the high temperature steam and condensate will react with the formation rock, remove the silicon and lead into the extraction liquid, and eventually enter the heavy oil sewage. The national standard is required. The silicon content of the treated heavy oil sewage boiler should be lower than 50mg/L, so as to ensure that the boiler does not produce silicon scale in the long run. Chemical coagulation removal of silicon is the main method of heavy oil sewage removal of silicon. Many metal oxides and hydroxides have good silicon removal effect, but their specific silicon removal mechanism is not clear, on the one hand Because of the various forms of silicic acid in water, on the other hand, the hydrolysis components of these chemicals in water are also more complex. This paper introduces the source of silicon in heavy oil and silicon polluted water, the technology of coagulation treatment and the research progress of related theories. The analytical methods of silicic acid in various forms of sewage were established, including monosilic acid (Sia), oligosilicate acid (Sib), high Polysilic acid (Sic) and insoluble silicic acid. The morphological changes and transformation laws of silicic acid in water were investigated under the influence of temperature, pH and salt. The additives, such as calcium, magnesium and aluminum, were used to study the amount and composition of the acid. The effect of different silicic acid on the removal efficiency of silicon removal agent is analyzed. The main mechanism of action in the process of coagulation removal is summarized. The experimental results show that when the temperature is high, the Sic changes to the Sia in the sewage, and the higher the temperature is, the higher the Sia content is, the acidic condition will inhibit the formation of Sia and the alkaline condition. Mg2+, Al3+, Fe3+ and other cations can significantly affect the content of soluble silicic acid in the solution, mainly by settlement removal, of which Al3+ is the best, Ca2+ has a certain effect on the inhibition of Sia polymerization, while Cl-, HCO3-, NO3-, SO42- plasma has no obvious effect. The effect of HCO3-, calcium desilication agent is not as good as that of magnesium, and the effect of strong alkali compound MgCl2 is the best under the same condition. Under 800mg/L addition, the removal of silicon content is 91.89%, the total silicon content is reduced to 38.4mg/L after the reaction; the second is MgO particles, the worst is Mg (OH) 2 particles, and the smaller the particle diameter of MgO is, the better the silicon removal efficiency is, but the analysis of silicon removal is analyzed. The form of silicic acid in the process indicates that calcium and magnesium desilication agents mainly remove Sia in water. They are likely to be desilicate by adsorption of monosilicate by the surface hydration layer formed in water. Al2 (SO4) 3 can reduce the total silicon in thick oil to below 50mg/L when adding amount of 6mmol/L and polymerized aluminum chloride (market). The same effect can be achieved when adding the amount of 4mmol/L; the pH value will affect the hydrolysis of aluminum sulfate, and Al2 (SO4) 3 shows the best effect on the removal of silicon at pH=5, and the removal effect of Sic is better than that of Sia; the new Al (OH) 3 is superior to Sic in the removal of Sia in the sewage. The desilication effect of C25 shows that the PAC10 with high Ala content has less residual Sic in the wastewater after the treatment of silicon containing sewage, and the residual Sia in sewage is less in the wastewater after PAC25 treatment with high Alc content, that is, Ala pairs Sic, Alc to Sia respectively, and adsorption modification theory can explain the interaction between silicon and aluminum, in silicon The aluminate or solid solution covering layer formed on the oxide or hydroxide surface of the aluminum polymer reduces the solubility of the raw material, which makes it easier to settle down in the process of sewage coagulation.
【學(xué)位授予單位】：東北石油大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：X741
本文編號：2161866
[Abstract]:Heavy oil sewage is complex and has high water quality demand for reusing heat recovery boiler. Therefore, it is difficult to treat the silicon content. In the process of heavy oil thermal recovery, the high temperature steam and condensate will react with the formation rock, remove the silicon and lead into the extraction liquid, and eventually enter the heavy oil sewage. The national standard is required. The silicon content of the treated heavy oil sewage boiler should be lower than 50mg/L, so as to ensure that the boiler does not produce silicon scale in the long run. Chemical coagulation removal of silicon is the main method of heavy oil sewage removal of silicon. Many metal oxides and hydroxides have good silicon removal effect, but their specific silicon removal mechanism is not clear, on the one hand Because of the various forms of silicic acid in water, on the other hand, the hydrolysis components of these chemicals in water are also more complex. This paper introduces the source of silicon in heavy oil and silicon polluted water, the technology of coagulation treatment and the research progress of related theories. The analytical methods of silicic acid in various forms of sewage were established, including monosilic acid (Sia), oligosilicate acid (Sib), high Polysilic acid (Sic) and insoluble silicic acid. The morphological changes and transformation laws of silicic acid in water were investigated under the influence of temperature, pH and salt. The additives, such as calcium, magnesium and aluminum, were used to study the amount and composition of the acid. The effect of different silicic acid on the removal efficiency of silicon removal agent is analyzed. The main mechanism of action in the process of coagulation removal is summarized. The experimental results show that when the temperature is high, the Sic changes to the Sia in the sewage, and the higher the temperature is, the higher the Sia content is, the acidic condition will inhibit the formation of Sia and the alkaline condition. Mg2+, Al3+, Fe3+ and other cations can significantly affect the content of soluble silicic acid in the solution, mainly by settlement removal, of which Al3+ is the best, Ca2+ has a certain effect on the inhibition of Sia polymerization, while Cl-, HCO3-, NO3-, SO42- plasma has no obvious effect. The effect of HCO3-, calcium desilication agent is not as good as that of magnesium, and the effect of strong alkali compound MgCl2 is the best under the same condition. Under 800mg/L addition, the removal of silicon content is 91.89%, the total silicon content is reduced to 38.4mg/L after the reaction; the second is MgO particles, the worst is Mg (OH) 2 particles, and the smaller the particle diameter of MgO is, the better the silicon removal efficiency is, but the analysis of silicon removal is analyzed. The form of silicic acid in the process indicates that calcium and magnesium desilication agents mainly remove Sia in water. They are likely to be desilicate by adsorption of monosilicate by the surface hydration layer formed in water. Al2 (SO4) 3 can reduce the total silicon in thick oil to below 50mg/L when adding amount of 6mmol/L and polymerized aluminum chloride (market). The same effect can be achieved when adding the amount of 4mmol/L; the pH value will affect the hydrolysis of aluminum sulfate, and Al2 (SO4) 3 shows the best effect on the removal of silicon at pH=5, and the removal effect of Sic is better than that of Sia; the new Al (OH) 3 is superior to Sic in the removal of Sia in the sewage. The desilication effect of C25 shows that the PAC10 with high Ala content has less residual Sic in the wastewater after the treatment of silicon containing sewage, and the residual Sia in sewage is less in the wastewater after PAC25 treatment with high Alc content, that is, Ala pairs Sic, Alc to Sia respectively, and adsorption modification theory can explain the interaction between silicon and aluminum, in silicon The aluminate or solid solution covering layer formed on the oxide or hydroxide surface of the aluminum polymer reduces the solubility of the raw material, which makes it easier to settle down in the process of sewage coagulation.
【學(xué)位授予單位】：東北石油大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：X741
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