基于一種硫磷復配體系土壤復合重金屬化學固定技術(shù)研究
發(fā)布時間：2019-06-12 01:02
【摘要】：隨著近期國家《土壤環(huán)境保護和污染治理行動計劃》的發(fā)布實施,土壤污染問題日益引起人們的關(guān)注。重金屬土壤污染具有污染范圍廣、持續(xù)時間長、不易被發(fā)現(xiàn)、無法被生物降解等特點,并可能通過食物鏈在生物體內(nèi)富集,最終引起重金屬污染事故。由于化學固定技術(shù)具有成本低廉、操作方便、效果迅速等特點且施工經(jīng)驗較多,被廣泛應用于重金屬污染土壤治理中。化學固定修復技術(shù)的關(guān)鍵在于選擇綜合性能優(yōu)良的固定劑,而含硫試劑和含磷試劑對多種重金屬具有優(yōu)良的固定效果,因此硫、磷試劑的開發(fā)具有廣闊的應用前景和市場。本課題以土壤中鉛(Pt)、鎘(Cd)、汞(Hg)、銅(Cu)、鋅(Zn)為固定目標,選擇硫脲-羥基磷酸鈣復配體系作為固定劑,通過均勻設計實驗方法安排實驗,通過改變硫脲用量、羥基磷酸鈣用量、氫氧化鈉用量、固定時間和土壤含水率篩選出最佳固定條件并得到該污染土壤體系下重金屬固定率與固定條件的穩(wěn)定關(guān)系模型。得到的主要結(jié)果如下:(1)通過控制變量法研究了水溶液中硫脲、羥基磷酸鈣、氫氧化鈉對重金屬離子固定率的影響。硫脲用量達到與重金屬摩爾比為1.5時,對水溶液中鉛(Pb)、鎘(Cd)、汞(Hg)、銅(Cu)、鋅(Zn)均有良好的固定效果;當氫氧化鈉用量足以提供硫脲水解所需要的堿基時,增加氫氧化鈉使用量對提高重金屬離子去除率效果不明顯;如若過量時,反而不利于重金屬離子的去除;羥基磷酸鈣對(Pb)、鎘(Cd)、銅(Cu)、鋅(Zn)表現(xiàn)出良好的去除效果,對汞(Hg)也有一定的去除效果;經(jīng)過SEM分析反應前后的羥基磷酸鈣形貌,結(jié)合硫脲-羥基磷酸鈣復配體系水溶液中去除重金屬離子實驗,發(fā)現(xiàn)羥基磷酸鈣對重金屬離子有很強的吸附能力,形成大基團,可使固定劑發(fā)揮最大的固定能力,并延長固定有效期。(2)研究了硫脲-羥基磷酸鈣復配體系對復合重金屬污染土壤的化學固定。均勻設計實驗組中鉛(Pb)、鎘(Cd)、汞(Hg)、銅(Cu)和鋅(Zn)最大固定率分別為99.58%、91.42%、96.36%、99.51%和94.66%。分析得各重金屬固定率與固定條件不成線性關(guān)系,對鉛(Pb)、鎘(Cd)、汞(Hg)、銅(Cu)和鋅(Zn)固定率與固定條件分別建模,得到了通過穩(wěn)定性檢驗的模型。其中鉛(Pt)、汞(Hg)和銅(Cu)模型的預報最優(yōu)值大于1,這在實驗中是不可能發(fā)生的;而鎘(Cd)和鋅(Zn)模型的預報最優(yōu)值分別為0.9893和0.9972,遠大于均勻設計實驗組重金屬最大固定率,由此可以對其模型進行修整。另外,鉛(Pb)、鎘(Cd)、汞(Hg)、銅(Cu)和鋅(Zn)的預報最優(yōu)固定條件之間存在差異,這表明對重金屬固定率進行歸一化處理是非常必要的。(3)完成了重金屬固定率的歸一化處理、建模,得到了通過檢驗的穩(wěn)定模型和最佳固定條件。采用了 1965年系統(tǒng)科學家札德(L.A.zadeh)提出的模糊集合概念,通過隸屬度計算,將重金屬固定率轉(zhuǎn)化為子集,結(jié)合“專家權(quán)”和“客觀權(quán)”,選擇了鎘(Cd)、銅(Cu)、汞(Hg)、鉛(Pb)和鋅(Zn)的權(quán)重系數(shù)分別為0.05、0.3、0.3、0.05和0.3,完成了重金屬固定率的歸一化處理得到其綜合評分集。通過對綜合評分集與固定條件建模,得到通過檢驗的穩(wěn)定模型,預報最優(yōu)綜合評分集為Y=1.1001,需要注意的是在這里Y1是可能的。因為我們在各子集隸屬度計算時,把實測最大點值定義為1,模型優(yōu)化值完全有可能超過樣本的實測好點值。將預報最優(yōu)固定條件進行實驗驗證,得到鎘(Cd)、銅(Cu)、汞(Hg)、鉛(Pt)和鋅(Zn)的固定率分別為90.91%、99.51%、96.36%、98.76%和93.36%,經(jīng)過計算綜合評分集Y=0.9783,預報相對偏差為12.4%。將補充實驗與U10(108)實驗數(shù)據(jù)一起建模,對模型進行修整,得到預報最優(yōu)Y=1.0277,將預報最優(yōu)固定條件進行驗證實驗,得到鎘(Cd)、銅(Cu)、汞(Hg)、鉛(Pt)和鋅(Zn)的固定率分別為 91.42%、93.26%、93.01%、99.58%和 91.37%,經(jīng)過計算綜合評分集 Y=0.9541,預報相對偏差為8.0%,模型的最大值預報偏差得到較大改善,已經(jīng)能被土壤修復專業(yè)工程技術(shù)研究所接受。
[Abstract]:With the implementation of the recent National Action Plan for Environmental Protection and Pollution Control, the problem of soil pollution has attracted more and more attention. The heavy metal soil pollution has the characteristics of wide pollution range, long duration, is not easy to be found, can not be degraded, and the like, can be enriched in the living body through the food chain, and finally causes heavy metal pollution accidents. Because the chemical fixing technology has the characteristics of low cost, convenient operation, rapid effect and the like, and the construction experience is more, the chemical fixing technology is widely applied to the soil treatment of heavy metal pollution. The key to the chemical fixed repair technology is to select a fixing agent with excellent comprehensive performance, and the sulfur-containing reagent and the phosphorus-containing reagent have excellent fixing effect on a plurality of heavy metals, so that the development of the sulfur and the phosphorus reagent has a wide application prospect and a market. In this paper, the fixed target of lead (Pt), carbon (Cd), mercury (Hg), copper (Cu) and zinc (Zn) in the soil was chosen as the fixed target. The experiment was carried out by the method of uniform design. The optimal fixation conditions were selected from the amount of sodium hydroxide, the fixed time and the water content of the soil, and a stable relationship model of the fixation rate and the fixed conditions of the heavy metals in the contaminated soil system was obtained. The main results are as follows: (1) The influence of the sulfur content, the calcium phosphate and the sodium hydroxide on the fixation rate of the heavy metal ions is studied by the control variable method. When the molar ratio of the sulfur to the heavy metal reaches 1.5, the lead (Pb), the sulfur (Cd), the mercury (Hg), the copper (Cu) and the zinc (Zn) in the aqueous solution have good fixing effect; when the amount of the sodium hydroxide is sufficient to provide the base required for the hydrolysis of the sulfur, the increase of the use amount of the sodium hydroxide is not obvious to the improvement of the removal rate of the heavy metal ions; if the excessive amount of the sodium hydroxide is not beneficial to the removal of heavy metal ions, the hydroxyl calcium phosphate pair (Pb), the carbon disulfide (Cd), the copper (Cu) and the zinc (Zn) show good removal effect, the effect of the removal of the mercury (hg) also has a certain removal effect; the morphology of the hydroxyl calcium phosphate before and after the reaction is analyzed by the sem, the heavy metal ion experiment is removed in the aqueous solution of the thiophene-hydroxyl calcium phosphate compound system, and the hydroxyl calcium phosphate is found to have strong adsorption capacity on the heavy metal ions and form a large group, The fixing agent can be used for the maximum fixing capacity, and the fixed shelf life can be prolonged. (2) The chemical fixation of the composite heavy metal contaminated soil was studied. The maximum fixed rates of lead (Pb), Hg (Cd), mercury (Hg), copper (Cu) and zinc (Zn) in the experimental group were 99.58%, 91.42%, 96.36%, 99.51% and 94.66%, respectively. The relationship between the fixed rate of the heavy metals and the fixed conditions was analyzed, and the fixed rate and the fixed conditions of the lead (Pb), the carbon (Cd), the mercury (Hg), the copper (Cu) and the zinc (Zn) were respectively modeled, and the model of the stability test was obtained. The optimum value of the prediction of lead (Pt), mercury (Hg) and copper (Cu) model is more than 1, which is not likely to occur in the experiment, and the optimum value of the prediction of the (Cd) and Zn (Zn) model is 0.9893 and 0.9972, which is much larger than that of the heavy metal in the experimental group. So that the model can be trimmed. In addition, there is a difference between the optimal fixation conditions for the prediction of lead (Pb), Hg (Cd), mercury (Hg), copper (Cu) and zinc (Zn), which indicates that the normalization of the fixation rate of heavy metals is necessary. (3) The normalized treatment and modeling of the heavy metal fixation rate were completed, and the stability model and the optimal fixation condition were obtained. The concept of fuzzy set, which was proposed by the system scientist in 1965 (L.A.zadeh), was adopted, and the fixed rate of heavy metal was converted into a sub-set by the degree of membership, combined with the "the right of experts" and the "objective right", and the carbon (Cd), copper (Cu), and mercury (Hg) were selected. The weight coefficients of lead (Pb) and zinc (Zn) were 0.05, 0.3, 0.3, 0.05 and 0.3, respectively. By modeling the integrated score set and the fixed condition, the stable model of the test is obtained, the best comprehensive score set is Y = 1.1001, and it is important to note that Y1 is possible here. As we calculate the membership degree of each subset, the measured maximum point value is defined as 1, and the model optimization value is completely possible to exceed the measured value of the sample. The optimum fixed conditions were experimentally verified to obtain the fixed rates of Cd, Cu, Hg, lead (Pt) and zinc (Zn) of 90.91%, 99.51%, 96.36%, 98.76% and 93.36%, respectively, and the calculated comprehensive score of Y = 0.9783 and the relative deviation of the forecast was 12.4%. The complementary experiment was modeled with U10 (108) experimental data, and the model was trimmed to obtain the optimal Y = 1.077, and the optimal fixed conditions were tested to obtain the fixed rates of (Cd), copper (Cu), mercury (Hg), lead (Pt) and zinc (Zn) of 91.42%, 93.26% and 93.01%, respectively. 99.58% and 91.37%, the calculated comprehensive score of Y = 0.9541, the relative deviation of the forecast is 8.0%, the maximum forecast deviation of the model is greatly improved, and it can be accepted by the Institute of Engineering and Engineering of the Soil Restoration.
【學位授予單位】：上海應用技術(shù)大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：X53;TQ421
本文編號：2497597
[Abstract]:With the implementation of the recent National Action Plan for Environmental Protection and Pollution Control, the problem of soil pollution has attracted more and more attention. The heavy metal soil pollution has the characteristics of wide pollution range, long duration, is not easy to be found, can not be degraded, and the like, can be enriched in the living body through the food chain, and finally causes heavy metal pollution accidents. Because the chemical fixing technology has the characteristics of low cost, convenient operation, rapid effect and the like, and the construction experience is more, the chemical fixing technology is widely applied to the soil treatment of heavy metal pollution. The key to the chemical fixed repair technology is to select a fixing agent with excellent comprehensive performance, and the sulfur-containing reagent and the phosphorus-containing reagent have excellent fixing effect on a plurality of heavy metals, so that the development of the sulfur and the phosphorus reagent has a wide application prospect and a market. In this paper, the fixed target of lead (Pt), carbon (Cd), mercury (Hg), copper (Cu) and zinc (Zn) in the soil was chosen as the fixed target. The experiment was carried out by the method of uniform design. The optimal fixation conditions were selected from the amount of sodium hydroxide, the fixed time and the water content of the soil, and a stable relationship model of the fixation rate and the fixed conditions of the heavy metals in the contaminated soil system was obtained. The main results are as follows: (1) The influence of the sulfur content, the calcium phosphate and the sodium hydroxide on the fixation rate of the heavy metal ions is studied by the control variable method. When the molar ratio of the sulfur to the heavy metal reaches 1.5, the lead (Pb), the sulfur (Cd), the mercury (Hg), the copper (Cu) and the zinc (Zn) in the aqueous solution have good fixing effect; when the amount of the sodium hydroxide is sufficient to provide the base required for the hydrolysis of the sulfur, the increase of the use amount of the sodium hydroxide is not obvious to the improvement of the removal rate of the heavy metal ions; if the excessive amount of the sodium hydroxide is not beneficial to the removal of heavy metal ions, the hydroxyl calcium phosphate pair (Pb), the carbon disulfide (Cd), the copper (Cu) and the zinc (Zn) show good removal effect, the effect of the removal of the mercury (hg) also has a certain removal effect; the morphology of the hydroxyl calcium phosphate before and after the reaction is analyzed by the sem, the heavy metal ion experiment is removed in the aqueous solution of the thiophene-hydroxyl calcium phosphate compound system, and the hydroxyl calcium phosphate is found to have strong adsorption capacity on the heavy metal ions and form a large group, The fixing agent can be used for the maximum fixing capacity, and the fixed shelf life can be prolonged. (2) The chemical fixation of the composite heavy metal contaminated soil was studied. The maximum fixed rates of lead (Pb), Hg (Cd), mercury (Hg), copper (Cu) and zinc (Zn) in the experimental group were 99.58%, 91.42%, 96.36%, 99.51% and 94.66%, respectively. The relationship between the fixed rate of the heavy metals and the fixed conditions was analyzed, and the fixed rate and the fixed conditions of the lead (Pb), the carbon (Cd), the mercury (Hg), the copper (Cu) and the zinc (Zn) were respectively modeled, and the model of the stability test was obtained. The optimum value of the prediction of lead (Pt), mercury (Hg) and copper (Cu) model is more than 1, which is not likely to occur in the experiment, and the optimum value of the prediction of the (Cd) and Zn (Zn) model is 0.9893 and 0.9972, which is much larger than that of the heavy metal in the experimental group. So that the model can be trimmed. In addition, there is a difference between the optimal fixation conditions for the prediction of lead (Pb), Hg (Cd), mercury (Hg), copper (Cu) and zinc (Zn), which indicates that the normalization of the fixation rate of heavy metals is necessary. (3) The normalized treatment and modeling of the heavy metal fixation rate were completed, and the stability model and the optimal fixation condition were obtained. The concept of fuzzy set, which was proposed by the system scientist in 1965 (L.A.zadeh), was adopted, and the fixed rate of heavy metal was converted into a sub-set by the degree of membership, combined with the "the right of experts" and the "objective right", and the carbon (Cd), copper (Cu), and mercury (Hg) were selected. The weight coefficients of lead (Pb) and zinc (Zn) were 0.05, 0.3, 0.3, 0.05 and 0.3, respectively. By modeling the integrated score set and the fixed condition, the stable model of the test is obtained, the best comprehensive score set is Y = 1.1001, and it is important to note that Y1 is possible here. As we calculate the membership degree of each subset, the measured maximum point value is defined as 1, and the model optimization value is completely possible to exceed the measured value of the sample. The optimum fixed conditions were experimentally verified to obtain the fixed rates of Cd, Cu, Hg, lead (Pt) and zinc (Zn) of 90.91%, 99.51%, 96.36%, 98.76% and 93.36%, respectively, and the calculated comprehensive score of Y = 0.9783 and the relative deviation of the forecast was 12.4%. The complementary experiment was modeled with U10 (108) experimental data, and the model was trimmed to obtain the optimal Y = 1.077, and the optimal fixed conditions were tested to obtain the fixed rates of (Cd), copper (Cu), mercury (Hg), lead (Pt) and zinc (Zn) of 91.42%, 93.26% and 93.01%, respectively. 99.58% and 91.37%, the calculated comprehensive score of Y = 0.9541, the relative deviation of the forecast is 8.0%, the maximum forecast deviation of the model is greatly improved, and it can be accepted by the Institute of Engineering and Engineering of the Soil Restoration.
【學位授予單位】：上海應用技術(shù)大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：X53;TQ421
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