發(fā)布時(shí)間：2018-06-25 14:39

  本文選題：高泥化煤泥水 + 疏水聚團(tuán)沉降��； 參考：《安徽理工大學(xué)》2017年博士論文

【摘要】：煤泥水是一種選煤廠濕法洗煤產(chǎn)生的工業(yè)廢水,它的沉降澄清是選煤工藝流程中的關(guān)鍵環(huán)節(jié)之一。然而,由于采煤機(jī)械化程度加大及原煤煤質(zhì)變差,導(dǎo)致大量高泥化煤泥水的產(chǎn)生,高泥化煤泥水具有粒度細(xì)、粘土礦物含量高及顆粒表面電負(fù)性強(qiáng)等特點(diǎn),嚴(yán)重加大了煤泥水處理的難度。本文以淮南礦區(qū)高泥化煤泥水及煤泥水中主要微細(xì)顆粒煤和高嶺石為研究對(duì)象,采用試驗(yàn)和量子化學(xué)/分子動(dòng)力學(xué)模擬相結(jié)合的方法,對(duì)疏水改性劑作用下高泥化煤泥水中微細(xì)顆粒疏水聚團(tuán)特性及機(jī)理進(jìn)行了深入研究,為高泥化煤泥水沉降澄清的新技術(shù)開(kāi)發(fā)及新藥劑設(shè)計(jì)提供理論基礎(chǔ)。煤泥水中微細(xì)顆粒疏水聚團(tuán)特性研究表明,陽(yáng)離子胺/按鹽類(lèi)疏水改性劑能夠通過(guò)靜電引力作用自發(fā)吸附在荷負(fù)電的微細(xì)煤泥礦物顆粒表面,改善顆粒表面疏水性,降低顆粒表面電負(fù)性,促進(jìn)顆粒在疏水引力作用下形成疏水聚團(tuán),進(jìn)而促進(jìn)微細(xì)煤泥礦物顆粒的疏水聚團(tuán)沉降。疏水改性劑作用下單一煤聚團(tuán)沉降效果弱于單一高嶺石的聚團(tuán)沉降效果。藥劑種類(lèi)及藥劑用量、動(dòng)能輸入、礦漿濃度和礦漿pH是影響微細(xì)煤泥礦物顆粒疏水聚團(tuán)沉降效果的主要影響因素。藥劑種類(lèi)和藥劑用量主要通過(guò)控制微細(xì)顆粒形成疏水聚團(tuán)的尺寸大小,影響其疏水聚團(tuán)沉降效果;合適的動(dòng)能輸入和礦漿濃度有利于微細(xì)煤泥礦物顆粒的疏水聚團(tuán)沉降;微細(xì)煤泥礦物顆粒疏水聚團(tuán)沉降的最佳礦漿pH為弱堿性。D和L煤泥水的最佳疏水聚團(tuán)沉降條件為:1831用量3000g/t、攪拌強(qiáng)度750r/min及攪拌時(shí)間10min,該條件下兩煤泥水的沉降速度和透光率分別可達(dá)0.83 cm/min、78.6%及1.31 cm/min、62.4%。同時(shí),混凝劑與疏水改性劑復(fù)配使用,不僅能減少各藥劑的用量,還能顯著提高高泥化煤泥水的疏水聚團(tuán)沉降效果�；炷齽┡c1831的最佳復(fù)配用量為:絮凝劑APAM 40 g/t、凝聚劑CaCl_2 10000 g/t時(shí)及1831 1500 g/t,此條件下煤泥水的初始沉降速度達(dá)0.97 cm/min,透光率達(dá)84.1%。煤表面吸附的DFT模擬研究表明,水分子主要通過(guò)與煤表面不同含氧官能團(tuán)形成氫鍵吸附到煤表面,且在不同煤含氧結(jié)構(gòu)表面吸附的穩(wěn)定性大小為-COOH-C=OPh-OH-O-;不同甲基胺/銨陽(yáng)離子主要通過(guò)與煤表面不同含氧官能團(tuán)形成N-H...O或C-H...O氫鍵吸附到煤表面,且在不同煤含氧結(jié)構(gòu)表面吸附的穩(wěn)定性大小為-C=O-COOH-O-Ph-OH;水及不同甲基胺/銨陽(yáng)離子在煤含氧結(jié)構(gòu)表面吸附的穩(wěn)定性大小為:H_2OCH_6N~+_C2H_8N~+C_3H_(10)N~+C_4H_(12)N~+,即水溶液環(huán)境中甲基胺/銨陽(yáng)離子在煤含氧結(jié)構(gòu)表面的吸附狀態(tài)不穩(wěn)定。高嶺石表面吸附的DFT研究表明,水分子主要通過(guò)氫鍵吸附在高嶺石(001)面和(001)面,單個(gè)水分子在高嶺石(001)面不同位置的吸附能為-72.12～-19.23 kJ/moL小于其在高嶺石(001)面不同位置的吸附能-19.23～-5.77 kJ/moL,即水分子更容易吸附在高嶺石(001)面;不同甲基胺/銨陽(yáng)離子主要通過(guò)靜電作用和氫鍵吸附在高嶺石(001)面和(001)面,且更容易吸附在高嶺石(001)面;不同甲基胺/銨陽(yáng)離子在高嶺石(001)面最佳吸附位為H3位,吸附能(按伯胺陽(yáng)離子、仲胺陽(yáng)離子、叔胺陽(yáng)離子及季銨陽(yáng)離子順序,下同)分別為-125.385、-126.154、-128.654 及-109.711 kJ/mol,在高嶺石(001)面最佳吸附位都為 H1位,吸附能分別為-140.961、-136.154、-138.558 及-115.961 kJ/mol;不同十二烷基胺/銨陽(yáng)離子在高嶺石(001)面不同穴位吸附穩(wěn)定性為H3H2H1,在高嶺石(001)面不同穴位吸附穩(wěn)定性為H1H2H3;不同碳鏈長(zhǎng)度的季銨陽(yáng)離子在高嶺石(001)面及(001)面吸附穩(wěn)定性隨著季銨鹽碳鏈長(zhǎng)度的增加而減小。不同煤含氧結(jié)構(gòu)單元主要通過(guò)形成氫鍵及苯環(huán)與表面間的作用吸附在高嶺石(001)面和(001)面,且吸附平衡后煤含氧結(jié)構(gòu)中的苯環(huán)近似平行于高嶺石(001)面和(001)面;不同煤含氧結(jié)構(gòu)單元在高嶺石在高嶺石(001)面及(001)面吸附穩(wěn)定性大小分別為-COOHPh-OH-C=O-O-和-COOH-C=O-O-Ph-OH,且煤含氧結(jié)構(gòu)更容易吸附在高嶺石(001)面。煙煤表面吸附的MD模擬研究表明,隨著水層水分子數(shù)從200增加至1600,煙煤表面對(duì)水分子的界面效應(yīng)逐漸減小,水分子逐漸遠(yuǎn)離表面,且水分子間排列的有序度不斷減小。十二烷基伯胺陽(yáng)離子和十八烷基三甲基氯化銨陽(yáng)離子在煙煤/水界面處吸附平衡后,其碳鏈都發(fā)生嚴(yán)重扭轉(zhuǎn)現(xiàn)象,且大部分陽(yáng)離子極性頭基朝向溶液,對(duì)煙煤表面疏水改性效果不理想。高嶺石表面吸附的MD模擬研究表明,隨著水覆蓋率從2/3 ML不斷增大到8/3 ML,高嶺石表面對(duì)水分子的束縛力逐漸減小,界面處的氫鍵作用逐漸減弱,且水分子逐漸形成多個(gè)水分子層;相同水覆蓋率時(shí),高嶺石(001)面對(duì)水分子的界面效應(yīng)弱于高嶺石(001)面對(duì)水分子的界面效應(yīng)。十二烷基伯胺陽(yáng)離子和十八烷基三甲基氯化銨陽(yáng)離子在高嶺石/水界面處吸附平衡后,陽(yáng)離子主要以極性頭基吸附在高嶺石表面,非極性碳鏈朝向溶液,并發(fā)生一定程度扭轉(zhuǎn),不同陽(yáng)離子碳鏈通過(guò)疏水締合作用吸引到一起使表面疏水化。煙煤大分子在高嶺石(001)面及(001)面動(dòng)力學(xué)平衡后,煙煤分子中部分苯環(huán)結(jié)構(gòu)近似平行與高嶺石表面,這一結(jié)果進(jìn)一步說(shuō)明,煤與高嶺石顆粒間的相互作用,除了煤分子中含氧官能團(tuán)與高嶺石表面的氫鍵作用外,煤分子中活性較強(qiáng)的苯環(huán)與高嶺石表面也存在較強(qiáng)的作用,即微細(xì)煤與高嶺石間的相互作用機(jī)制主要是氫鍵作用和煤結(jié)構(gòu)中苯環(huán)與高嶺石表面間作用的綜合作用。陽(yáng)離子胺/銨鹽類(lèi)疏水改性劑對(duì)煤泥顆粒的疏水聚團(tuán)作用機(jī)理主要是"吸附電中和"和疏水引力綜合作用的結(jié)果。陽(yáng)離子胺/銨鹽類(lèi)疏水改性劑作用下高泥化煤泥水中微細(xì)粒礦物疏水聚團(tuán)沉降的作用機(jī)理,主要是疏水改性劑陽(yáng)離子通過(guò)靜電引力和氫鍵作用吸附在微細(xì)煤泥礦物顆粒表面,對(duì)顆粒表面進(jìn)行疏水改性:一方面弱化煤泥顆粒間水化斥力,提高煤泥顆粒間疏水引力;另一方面,降低煤泥礦物顆粒表面電負(fù)性,壓縮顆粒表面雙電層,降低顆粒間靜電斥力,進(jìn)而實(shí)現(xiàn)煤泥顆粒的疏水聚團(tuán)沉降。
[Abstract]:Coal mud water is a kind of industrial waste water produced by wet coal washing in coal preparation plant. Its settlement clarification is one of the key links in the process of coal preparation. However, due to the increasing mechanization of coal mining and the poor quality of the raw coal and coal, a large number of highly muddy coal mud water is produced. The high muddy coal mud has fine grain size, high clay mineral content and particle surface. In this paper, the high muddy coal mud water and the main fine particle coal and kaolinite in the coal mud water in Huainan mining area are studied in this paper. The hydrophobicity of fine particles in high mud slime water under the action of hydrophobic modifier is used by the method of combining the experiment with the quantum chemistry / molecular dynamics simulation. The characteristics and mechanism of agglomeration are studied in depth, which provide a theoretical basis for the new technology development and new drug design for high mud water settlement clarification. The study of the hydrophobic agglomeration characteristics of the fine particles in the slime water shows that the cationic amines / salt hydrophobic modifiers can be adsorbed spontaneously in the micro slime minerals in the negative electricity by electrostatic force. The surface of the particle can improve the hydrophobicity of the surface of the particles, reduce the electronegativity on the surface of the particles, promote the formation of hydrophobic agglomeration of particles under the action of hydrophobic gravitation, and then promote the hydrophobic agglomeration settlement of the fine slime mineral particles. The effect of the settlement of single coal agglomeration under the action of hydrophobic modifier is weaker than the aggregation settlement effect of single kaolinite. The amount, kinetic energy input, pulp concentration and pulp pH are the main factors affecting the hydrophobic agglomeration effect of the fine slime mineral particles. The kinds of agents and the dosage of the medicament mainly form the size of the hydrophobic agglomeration by controlling the fine particles, and affect the effect of the hydrophobic agglomeration settlement, and the appropriate kinetic energy input and pulp concentration are beneficial to the fine particles. The best slurry pH for the hydrophobic agglomeration of the fine slime mineral particles is the best hydrophobic agglomeration condition of the weak alkaline.D and L coal mud water, which is 1831 3000g/t, the stirring strength 750r/min and the stirring time 10min, and the sedimentation rate and transmittance of the two coal mud water can reach 0.83 cm/min, 78 respectively under this condition. .6% and 1.31 cm/min, 62.4%. simultaneously, the mixture of coagulant and hydrophobic modifier can not only reduce the dosage of various agents, but also significantly improve the hydrophobic agglomeration effect of high mud coal mud water. The optimum compound dosage of coagulant and 1831 is flocculant APAM 40 g/t, coagulant CaCl_2 10000 g/t and 18311500 g/t, under this condition coal mud water The initial sedimentation rate is 0.97 cm/min. The DFT simulation study on the adsorption of 84.1%. on coal surface shows that water molecules mainly form hydrogen bonds with different oxygen containing functional groups on the coal surface to adsorb to the coal surface, and the stability of the adsorption on the surface of different coal containing oxygen structure is -COOH-C= OPh-OH-O-, and the different methyl amine / ammonium cation is mainly passed through. The hydrogen bonds of N-H... O or C-H... O are adsorbed on coal surface with different oxygen functional groups on coal surface, and the stability of adsorption on the surface of different coal containing oxygen is -C=O-COOH-O-Ph-OH. The stability of water and different methyl amine / ammonium cation adsorption on the surface of coal containing oxygen is H_2OCH_6N~+_C2H_8N~+C_3H_ (10) N~+C_4H_ (12) N~+, that is water solubility. The adsorption state of methyl amine / ammonium cation on the surface of coal containing oxygen is unstable in liquid environment. DFT study on the adsorption of kaolinite surface shows that water molecules are adsorbed mainly on kaolinite (001) and (001) surfaces through hydrogen bonds, and the adsorption energy of single water molecules at different positions of kaolinite (001) is -72.12 to -19.23 kJ/moL less than that of kaolinite (001) The adsorption energy of different positions can be -19.23 ~ -5.77 kJ/moL, that is, water molecules are more easily adsorbed on kaolinite (001). Different methylamine / ammonium ions are adsorbed on kaolinite (001) and (001) surface mainly by electrostatic and hydrogen bonds, and are more easily adsorbed on kaolinite (001). The best adsorption sites of different methyl amine / ammonium cation on kaolinite (001) surface For H3 position, the adsorption energy (according to the order of primary amine cation, secondary amine cation, tertiary amine cation and quaternary ammonium cation, the same below) is -125.385, -126.154, -128.654 and -109.711 kJ/mol respectively. The best adsorption sites for kaolinite (001) are H1 sites, and the adsorption energy is -140.961, -136.154, -138.558 and -115.961 kJ/mol, and different twelve alkyl amines / ammonium positive. The adsorption stability of different acupoints on kaolinite (001) surface is H3H2H1, and the adsorption stability is H1H2H3 at different acupoints on kaolinite (001). The adsorption stability of quaternary ammonium cation on kaolinite (001) surface and (001) surface decreases with the increase of the length of quaternary ammonium salt carbon chain. The interaction between the benzene ring and the surface is adsorbed on the kaolinite (001) and (001) surfaces, and the benzene ring in the oxygen containing structure is approximately parallel to the kaolinite (001) and (001) surfaces after the adsorption equilibrium. The adsorption stability of different coal containing oxygen structural units in kaolinite (001) and (001) surfaces is -COOHPh-OH-C=O-O- and -COOH-C=O-O-Ph-OH, respectively. The oxygen containing structure is more easily adsorbed on the kaolinite (001) surface. The MD simulation study on the surface adsorption of bituminous coal shows that the interfacial effect of water molecules on the surface of the bituminous coal gradually decreases with the number of water molecules from 200 to 1600, and the water molecules are gradually far away from the surface, and the order of the arrangement of water molecules decreases continuously. Twelve alkyl amine amines and eighteen alkanes. After adsorption equilibrium at the bituminous coal / water interface, the carbon chain of the base three methyl ammonium chloride is seriously torsional, and most of the cationic polar heads are directed towards the solution, and the hydrophobic modification effect on the surface of the bituminous coal is not ideal. The MD simulation study on the adsorption of kaolinite surface shows that with the increasing water coverage from 2/3 ML to 8/3 ML, kaolinite The binding force of the surface to water molecules gradually diminished, the hydrogen bond at the interface weakened gradually, and the water molecules gradually formed a number of water molecular layers, and the interface effect of kaolinite (001) facing water molecules was weaker than the interface effect of kaolinite (001) on water molecules. Twelve alkyl primary amine cations and eighteen alkyl three methyl chlorination were found in the same water coverage. After the adsorption equilibrium of ammonium cation at the kaolinite / water interface, the cation mainly adsorbs on the surface of Kaolinite on the polar head base, the non polar carbon chain faces the solution, and turns to a certain extent. The different cation carbon chains are attracted by the hydrophobicity association to make the surface hydrophobicity together. The kinetics of the kaolinite (001) surface and (001) surface dynamics of the coal large molecule After the balance, some of the benzene ring structure in the bituminous coal is approximately parallel to the kaolinite surface. This result further indicates that the interaction between coal and kaolinite particles, besides the hydrogen bond between the oxygen containing functional group and the kaolinite surface in the coal molecules, has a strong effect on the surface of the coal and kaolinite, that is, the surface of the kaolinite. The interaction mechanism between coal and kaolinite is mainly the interaction of hydrogen bond and the interaction between the benzene ring and the kaolinite surface in the coal structure. The mechanism of the hydrophobic polymerization of the cationic amine / ammonium salt hydrophobic modifier to the slime particles is mainly the result of the synthesis of "adsorption electricity neutralization" and the hydrophobic attraction. The hydrophobic modification of cationic amine / ammonium salt type is the result. The mechanism of hydrophobic aggregation settlement of fine particles in slime water under the action of sex agent is mainly that hydrophobic modifier cations are adsorbed on the surface of fine slime mineral particles through electrostatic and hydrogen bonds, and the surface of the particles is modified by hydrophobicity. On the one hand, it weakens the hydration repulsion between the slime particles and improves the hydrophobic attraction between the slime particles. On the other hand, it reduces the surface electronegativity of the slime mineral particles, compresses the double layer of particles on the surface of the particles, reduces the electrostatic repulsion among the particles, and then realizes the hydrophobic agglomeration settlement of the slime particles.
【學(xué)位授予單位】：安徽理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：X752
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本文編號(hào)：2066350