本文選題：煤 + 氯化��； 參考：《太原理工大學》2017年碩士論文

【摘要】：纖維素是一種廉價易得、儲量豐富的可再生資源,是由D-葡萄糖單體彼此通過β-1,4糖苷鍵連接而成的線性高分子化合物。纖維素傳統(tǒng)的水解方法主要是液體酸和酶水解,但其造成的設備腐蝕、產(chǎn)物不易分離、價格昂貴都限制了它的應用。為了克服上述存在的問題,近些年來碳基固體酸被用于纖維素的高效水解。將大分子煤與碳基固體酸的結(jié)構(gòu)對比不難發(fā)現(xiàn),煤中除沒有-SO_3H外,具備了碳基固體酸所有的結(jié)構(gòu)特征,這意味著煤具有制備碳基固體酸的基因優(yōu)勢。我們以煤為原料,試圖在傳統(tǒng)碳基固體酸上引入電負性較強的氯原子,制備出氯功能化煤基固體酸,打破纖維素羥基之間的氫鍵,促進纖維素水解。實驗主要改變煤種的粘結(jié)性、氯化方法、氯化劑以及三氯乙酸比例等變量制備煤基固體酸并將其應用到纖維素水解。通過掃描電鏡(SEM)、拉曼光譜(Raman spectrum)、比表面積(BET)、X射線衍射(XRD)、紅外光譜(FT-IR)、X射線電子能譜(XPS)等手段來分析煤基固體酸的結(jié)構(gòu)和表面元素含量,通過測定酸性基團密度、纖維二糖吸附量和還原糖得率來考察煤基固體酸的催化性能。探究了催化劑結(jié)構(gòu)、表面活性官能團在纖維素水解過程中的作用機理,實現(xiàn)不同活性官能團之間的有效整合。將四種粘結(jié)性不同的煤作為碳源,通過和三氯乙酸共炭化-磺化的方法制備出四種煤基固體酸,探索碳源的原料組成—催化劑結(jié)構(gòu)—纖維素水解性能之間的構(gòu)效關系。結(jié)果發(fā)現(xiàn),高粘結(jié)性煤制備煤基固體酸的芳香碳片層在空間的排列更加不規(guī)整,無序度更大,有更多的缺陷位,芳香碳片層邊緣負載更多的-COOH基團,總酸密度較大,吸附能力和水解活性也較大。以粘結(jié)性較大的交口肥煤(JKFM)為碳源,采用三種不同的氯化方法制備出三種不同的煤基固體酸。結(jié)果發(fā)現(xiàn),氯以共價鍵的形式直接連在煤基固體酸芳香碳片層的邊緣,催化劑中的S主要以氧化態(tài)(-C-SO_x-)磺酸基團和非氧化態(tài)(C-S-C)噻吩硫的形式存在。共炭化—磺化制備煤基固體酸(SH-SO_3H)的芳香碳片層在空間的排列更加規(guī)整,芳環(huán)縮合程度更大,-SO_3H基團密度較低,但催化劑SH-SO_3H表面氯基團密度最多,吸附能力、水解活性和催化劑的重復利用性最好。以粘結(jié)性較大的交口肥煤為碳源,選擇三種不同的氯化劑采用共炭化—磺化的方法制備出三種煤基固體酸。結(jié)果發(fā)現(xiàn),交口肥煤和不同氯化劑在共炭化時發(fā)生相互作用,在芳香碳片層的邊緣負載了共價鍵氯基團,而且在催化劑表面碳、氧、硫、氯四種元素分布地非常均勻。氯化后制備的煤基固體酸芳香碳片層在空間的排列更加規(guī)整,芳香度變大,芳香片層直徑變大,氯化劑的不同對固體酸表面負載氯基團的含量影響很大,其中以三氯乙酸為氯化劑制備的煤基固體酸芳香碳片層上氯的負載量最大,催化劑的吸附能力和水解性能最好�？疾炝寺然瘎┎煌壤龑γ夯腆w酸結(jié)構(gòu)和性能的影響。結(jié)果發(fā)現(xiàn),氯化劑的添加量不同對制備固體酸表面活性官能團的負載量有很大影響。隨著三氯乙酸比例的增大,-Cl基團密度增大,而-SO_3H基團密度下降,-COOH基團密度略有增加,-OH密度變化很小。固體酸對纖維二糖的吸附量與-Cl基團密度變化趨勢一致,說明催化劑表面負載氯基團的存在有利于提高吸附能力。
[Abstract]:Cellulose is a cheap and readily available and abundant renewable resource. It is a linear polymer composed of D- glucose monomers connected to each other through the glucoside bond of beta -1,4. The traditional hydrolysis method of cellulose is mainly liquid acid and enzyme hydrolysis, but the equipment corrosion, the product is not easy to separate, and the price is expensive to limit its application. In order to overcome the above problems, carbon based solid acids have been used in the efficient hydrolysis of cellulose in recent years. Comparing the structure of large molecular coal with carbon based solid acids, it is not difficult to find that the coal has all the structural characteristics of carbon based solid acids in addition to -SO_3H, which means that coal has the genetic advantage of preparing carbon based solid acids. As raw materials, it is intended to introduce a strong electronegative chlorine atom on the traditional carbon based solid acid, to prepare the chlorinated functionalized coal based solid acids, break the hydrogen bonds between the hydroxyl groups of the cellulose and promote the hydrolysis of cellulose. The experiment mainly changes the adhesion of coal, the chlorination method, the chlorination agent and the proportion of three chloroacetic acid are used to prepare the coal based solid acids and should be used for the preparation of coal based solid acids. Using scanning electron microscopy (SEM), Raman spectroscopy (Raman spectrum), specific surface area (BET), X ray diffraction (XRD), infrared spectroscopy (FT-IR), X ray electron spectroscopy (XPS), and other means to analyze the structure and surface element content of coal based solid acids, by measuring the density of acid group, the adsorption amount of fiber two sugar and the yield of reducing sugar The catalytic properties of coal based solid acids are investigated. The mechanism of the catalyst structure, the action mechanism of the surface active functional groups in the hydrolysis of cellulose and the effective integration of different active functional groups are realized. Four kinds of coal with different cohesiveness are used as carbon sources to prepare four kinds of coal based solid acids by CO carbonization and sulfonation of three chloroacetic acid and explore carbon. The structure effect relationship between the raw material of the source - the structure of the catalyst - the hydrolysis property of cellulose has been found. The results show that the arrangement of aromatic carbon layers of coal based solid acids in high bond coal is more irregular in space, with greater disorder degree, more defect positions, more -COOH groups on the edge of the aromatic carbon layer, and the total acid density is larger, and the adsorption energy is higher. The force and hydrolysis activity are also large. Three different coal based solid acids are prepared by three different chlorination methods with three different chlorination methods. The results show that chlorine is directly linked to the edge of the aromatic carbon layer of coal based solid acid in the form of covalent bond, and the S in the catalyst is mainly oxidized by the -C-SO_x- sulfonic acid group. The form of non oxidative state (C-S-C) thiophene sulphur exists. The aromatic carbon lamelles of CO carbonization and sulfonation of coal based solid acid (SH-SO_3H) are more orderly in the arrangement of the space, the degree of aromatic ring condensation is greater, the density of the -SO_3H group is lower, but the density of the chloride Group on the surface of the catalyst SH-SO_3H is the most, the adsorption capacity, the hydrolysis activity and the reutilization of the catalyst are the most. Three kinds of coal based solid acids were prepared by three different kinds of chlorination agents using CO carbonization and sulfonation. The results showed that the interaction between the mixed coal and the different chlorination agents in the carbonization was negatively loaded with the covalent chloride group on the edge of the aromatic carbon layer, and the surface of the catalyst was on the surface of the catalyst. The four elements of carbon, oxygen, sulfur and chlorine are very evenly distributed. The arrangement of the coal based solid acid aromatic carbon lamellae after chlorination is more regular, the aromatic degree becomes larger, the diameter of the aromatic layer is larger, the different chlorination agents have a great influence on the content of the chlorine groups on the surface of the solid acid, and the coal based solid acid prepared with the chloroacetic acid as the chlorination agent is three chloroacetic acid. The load of chlorine on the aromatic carbon layer is the largest, the adsorption capacity and the hydrolysis performance of the catalyst are the best. The effects of the different proportion of the chlorination agent on the structure and properties of the coal based solid acid are investigated. The results show that the addition of the chlorination agent has a great influence on the load of the solid acid surface active functional group. With the increase of the proportion of three chloroacetic acid, The density of -Cl group increased, the density of -SO_3H group decreased, the density of -COOH group increased slightly, and the density of -OH changed little. The adsorption capacity of solid acid on fiber two sugar was the same as that of -Cl group density, indicating that the presence of the chlorine group on the surface of the catalyst was beneficial to the improvement of the adsorption energy.
【學位授予單位】：太原理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TQ530;TQ352.78

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