本文選題：吸附 + 脫附��； 參考：《華南理工大學(xué)》2015年博士論文

【摘要】：降焦減害是我國(guó)卷煙工業(yè)未來(lái)技術(shù)發(fā)展的重點(diǎn)工作。本文以研究降低煙氣CO濃度和運(yùn)用多孔材料實(shí)現(xiàn)致香成分緩釋增香為潛在的應(yīng)用背景,研究新型固體多孔材料及其吸附CO性能和香料化合物的吸附和緩釋性能,主要涉及研制及改性活性炭、分子篩和MOFs等三類材料及研究其對(duì)CO的吸附性能;研究改性活性炭和無(wú)機(jī)多孔材料及其對(duì)不同官能團(tuán)香料化合物的吸附和緩釋性能。本課題屬于化學(xué)工程、材料工程和表面科學(xué)交叉的研究領(lǐng)域,具有重要的科學(xué)研究?jī)r(jià)值和實(shí)際意義。本文系統(tǒng)地研究了活性炭、分子篩和MOFs等三類材料對(duì)CO的動(dòng)態(tài)吸附性能。采用固定床吸附技術(shù)測(cè)定了CO在不同種類吸附材料上的吸附透過(guò)曲線,分析了吸附材料孔隙結(jié)構(gòu)和表面性質(zhì)對(duì)CO吸附性能的影響。結(jié)果表明:在模擬煙氣CO濃度的動(dòng)態(tài)條件下,傳統(tǒng)活性炭分子篩材料對(duì)CO的吸附容量較低,均低于3 mL/g;而三種MOFs材料對(duì)CO吸附性能明顯優(yōu)于傳統(tǒng)吸附材料,特別是MOF-74(Ni)對(duì)CO的動(dòng)態(tài)吸附容量可達(dá)45.6 mL/g,遠(yuǎn)遠(yuǎn)高于其他材料。這是由于MOF-74(Ni)具有較高的不飽和金屬活性位密度,其骨架上的Ni能與CO分子形成π鍵絡(luò)合,能極大提高其對(duì)CO的吸附能力。本文應(yīng)用Cu(I)鹽和Ag(I)鹽對(duì)β分子篩進(jìn)行改性,并研究了它們對(duì)CO的吸附性能。結(jié)果表明:負(fù)載量為0.1 g/g的Ag(I)@β分子篩對(duì)CO的最大的工作吸附量可達(dá)9.5mL/g;負(fù)載量為0.4 g/g的Cu(I)@β分子篩對(duì)CO的最大工作吸附容量可達(dá)27.1 mL/g,是相同條件下原始β分子篩吸附容量的14倍。同時(shí),本文也采用了IAST模型對(duì)材料CO選擇性吸附性能進(jìn)行模擬,計(jì)算結(jié)果顯示:0.4Cu(I)@β分子篩對(duì)CO/CO2和CO/N2均具有良好的吸附選擇性;在10 KPa以內(nèi),該材料對(duì)CO/N2和CO/CO2的吸附選擇性分別高達(dá)到1600-5200和120-270;在20-100 KPa條件下,對(duì)CO/N2和CO/CO2的吸附選擇性仍能達(dá)到500-1200和8-31。本文采用分子自發(fā)單層分散技術(shù)制備了CuCl@AC吸附劑,并進(jìn)行了表征和CO吸附性能測(cè)定。結(jié)果表明:1.2CuCl@AC對(duì)CO的動(dòng)態(tài)吸附量能達(dá)到14.4 m L/g,約是原始活性炭6.7倍;CO在1.2CuCl@AC和原始活性炭上的等量吸附熱分別為43.4-56.7kJ/mol和約22.0 kJ/mol左右,說(shuō)明活性炭改性后對(duì)CO的吸附結(jié)合力大大增強(qiáng);1.2CuCl@AC對(duì)CO/CO2/N2混合體系均具有良好的選擇吸附性;應(yīng)用試驗(yàn)結(jié)果表明:將兩種CuCl@ACs樣品運(yùn)用于實(shí)際卷煙產(chǎn)品中,能大幅度地降低卷煙主流煙氣中的CO、HCN、NNK、NH3、B[a]P、苯酚、巴豆醛等七種關(guān)鍵有害成分,其中煙氣中HCN含量的降幅分別高達(dá)79.72%和85.64%,能使卷煙危害性指數(shù)H值降低了57.42%-61.72%,具有廣泛的應(yīng)用前景。本文提出應(yīng)用程序升溫脫附(TPD)技術(shù)研究不同官能團(tuán)香料化合物與多孔材料表面之間的相互作用力,分別測(cè)定了γ-壬內(nèi)酯、大馬酮、乙基香蘭素、乙基麥芽酚、和乙酸乙酯以及β-苯乙醇等香料化合物在多種吸附材料上的TPD曲線并估算脫附活化能,討論了香料化合物性質(zhì)與多孔材料之間吸附力強(qiáng)弱的關(guān)系。研究表明:五種香料化合物在活性炭上的脫附活化能隨著分子動(dòng)力學(xué)直徑的增大而增大,表明來(lái)自孔壁吸附勢(shì)力場(chǎng)對(duì)香料化合物吸附結(jié)合力起主導(dǎo)作用;五種香料化合物在MCM-41上的脫附活化能大小順序?yàn)?大馬酮乙基香蘭素乙基麥芽酚乙酸乙酯γ-壬內(nèi)酯;β苯乙醇在五種材料上的脫附活化能的大小順序依次為:XF活性炭MCM-41A型硅膠SBA-15B型硅膠,β苯乙醇在其中的四種非碳多孔材料上的脫附活化能是隨著它們表面的酸性基團(tuán)濃度增加而增大。由于活性炭表面存在共扼大?鍵可與β-苯乙醇的苯環(huán)發(fā)生?-?強(qiáng)吸附作用,因此β-苯乙醇在XF活性炭上的脫附活化能最大。本文提出一種采用碳化改性活性炭的方法,在不同的溫度下對(duì)YK和SY1活性炭進(jìn)碳化改性,研究了改性條件對(duì)材料的孔隙結(jié)構(gòu)和表面化學(xué)的影響以及對(duì)香料物質(zhì)吸附和脫附的影響。結(jié)果表明:碳化改性可有效改變活性炭表面酸性基團(tuán)含量以及組成,它既能夠不影響活性炭對(duì)兩種香料化合物的吸附儲(chǔ)存量,又能削弱活性炭表面對(duì)兩種香料化合物的吸附結(jié)合力。例如,兩種香料化合物在YK-300上的脫附活化能,分別比改性前下降了38.16%和30.75%,這對(duì)于指導(dǎo)香料緩釋材料的研制和應(yīng)用具有重要意義。
[Abstract]:In order to study the potential application background of reducing the concentration of CO and using porous materials to realize the sustained release of incense by using porous materials, this paper studies the absorption and release properties of new solid porous materials and their adsorbed CO properties and perfumery compounds, mainly involving the development and modification. Three kinds of materials, such as activated carbon, molecular sieve and MOFs, and their adsorption properties to CO, and the adsorption and release properties of modified activated carbon and inorganic porous materials and their functional group perfume compounds. This subject belongs to the research field of chemical engineering, material engineering and surface science, which has important scientific research value and practice. The dynamic adsorption properties of three kinds of materials, such as activated carbon, molecular sieve and MOFs, were systematically studied in this paper. The adsorption transmission curves of CO on different kinds of adsorbents were measured by fixed bed adsorption technology. The effects of pore structure and surface properties of the adsorbents on the adsorption energy of CO were analyzed. The results showed that the CO concentration of CO in the flue gas was simulated. Under the dynamic conditions, the adsorption capacity of the traditional activated carbon molecular sieve material to CO is lower than 3 mL/g, and the adsorption properties of the three MOFs materials are obviously superior to the traditional adsorbents, especially the dynamic adsorption capacity of MOF-74 (Ni) to CO is up to 45.6 mL/g, which is much higher than that of the other materials. This is due to the high unsaturated gold of MOF-74 (Ni). At the active site density, the Ni on the skeleton can form a pion bond with the CO molecule, which can greatly improve its adsorption capacity to CO. In this paper, Cu (I) salt and Ag (I) salt were used to modify the beta molecular sieve, and their adsorption properties to CO were studied. The results showed that the maximum working adsorption capacity of Ag (I) @ beta molecular sieve with a load of 0.1 g/g can reach the maximum capacity of the CO. /g; the maximum working adsorption capacity of Cu (I) @ beta molecular sieve with a load of 0.4 g/g to CO is up to 27.1 mL/g, which is 14 times the adsorption capacity of the original beta molecular sieve under the same condition. At the same time, the IAST model is used to simulate the selective adsorption performance of the material CO. The results show that 0.4Cu (I) @ beta molecular sieve is good for CO/CO2 and CO/N2. Under 10 KPa, the adsorption selectivity of the material to CO/N2 and CO/CO2 is up to 1600-5200 and 120-270, respectively, and the adsorption selectivity for CO/N2 and CO/CO2 can still reach 500-1200 and 8-31. under 20-100 KPa conditions and CuCl@AC adsorbents are prepared by molecular spontaneous monolayer dispersion technique, and the characterization and CO adsorption are carried out. The results show that the dynamic adsorption capacity of 1.2CuCl@AC to CO can reach 14.4 m L/g, about 6.7 times the original activated carbon, and the equal adsorption heat of CO on 1.2CuCl@AC and original activated carbon is 43.4-56.7kJ/mol and about 22 kJ/mol respectively, indicating that the adsorption binding force of activated carbon on CO is greatly enhanced; 1.2CuCl@AC to CO/CO2/N2 mixing. The experimental results show that the application of the two CuCl@ACs samples to the actual cigarette products can greatly reduce the seven key harmful components, such as CO, HCN, NNK, NH3, B[a]P, phenol, and croton aldehyde in the mainstream cigarette smoke, of which the decrease of HCN content in the smoke is up to 79.72% and 85.64% respectively. The H value of the smoke hazard index has been reduced by 57.42%-61.72% and has a wide application prospect. In this paper, the application of temperature programmed desorption (TPD) technology to study the interaction between different functional groups of aromatic compounds and the surface of porous materials was studied, and the determination of gamma nonylolide, damazone, ethyl vanillin, ethyl maltol, ethyl acetate and beta benzene respectively. The relationship between the properties of the aromatic compounds and the strong and weak adsorbability between the porous materials and the TPD curves on various adsorbents is discussed. The study shows that the activation energy of the five compounds on the activated carbon increases with the increase of the molecular dynamic diameter, indicating the adsorption of the pore wall. The power field plays a leading role in the adsorption and binding of aromatic compounds; the order of activation energy of the five kinds of spice compounds on MCM-41 is: the order of the desorption activation energy of the ethyl vanillin ethyl maltol acetate gamma nonylate, and the sequence of the activation energy of the desorption activation energy of the beta benzol on the five materials in sequence is the XF activated carbon MCM-41A type silica gel SBA-15B type The desorption activation energy of silica gel and beta benzol on four kinds of non carbon porous materials increases with the increase of the acid group concentration on their surface. The activation energy of the desorption activation energy of beta benzol on XF activated carbon is the greatest. A carbonated modified activated carbon was used to modify the carbonization of YK and SY1 activated carbon at different temperatures. The effects of the modification conditions on the pore structure and surface chemistry of the materials and the effect on the adsorption and desorption of the material were studied. The results showed that the carbonation modification could effectively change the content of the acid group on the surface of the activated carbon and the group. As a result, it can not affect the adsorption storage of activated carbon to two kinds of perfume compounds, but also weaken the adsorption binding force of the activated carbon surface to two kinds of perfume compounds. For example, the activation energy of the two spice compounds on YK-300 decreased by 38.16% and 30.75% before the modification, which should be developed for the development of spice sustained-release materials. It is of great significance to use.
【學(xué)位授予單位】：華南理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：TQ424

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本文編號(hào)：2090307