本文選題：木質(zhì)素 + 馬尾松��； 參考：《中南林業(yè)科技大學(xué)》2017年碩士論文

【摘要】：目前,工業(yè)木質(zhì)素的利用率還不到10%,其中絕大部分作為廢物排放,既浪費(fèi)資源又污染環(huán)境。故本課題希望能通過對屬于針葉材的馬尾松和屬于闊葉材的楊木用不同提取方法提取出不同種類木質(zhì)素(酸不溶木素、堿木素、磨木木素),然后在不同條件下對三種不同種類木質(zhì)素進(jìn)行熱重分析以及熱裂解和催化熱裂解,能得到不同種類木質(zhì)素的熱解特性,選擇出合適的條件(溫度、催化劑等),在木質(zhì)素?zé)峤庵心芴岣邿峤猱a(chǎn)物中單一酚組分的含量,降低分離成本,同時探索木質(zhì)素?zé)峤鈾C(jī)理,為木質(zhì)素資源化利用奠定基礎(chǔ)。通過對馬尾松、楊木不同種類木質(zhì)素?zé)嶂胤治?得知木質(zhì)素?zé)峤庵饕A段即揮發(fā)份析出階段,不同種類木質(zhì)素?zé)峤獾谋碛^活化能主要集中在39-55KJ/mol。以馬尾松酸不溶木素、堿木素、磨木木素為原料,通過Py-GC-MS聯(lián)用分析技術(shù),分析500℃條件下熱裂解產(chǎn)物的結(jié)構(gòu)和含量。磨木木素裂解產(chǎn)物中總酚相對含量高達(dá)62.3%,其中愈創(chuàng)木酚為9.75%、4-甲基-2-甲氧基苯酚為8.56%。堿木素的熱裂解產(chǎn)物中總酚的相對含量為44.86%,其中愈創(chuàng)木酚為7.76%,而酸不溶木素裂解產(chǎn)物中總酚相對含量僅為16.25%,無一酚類組分相對含量超過5%。熱裂解溫度從400℃升高到700℃的過程中,馬尾松磨木木素的裂解產(chǎn)物中,總酚的相對含量從59.78%升高到62.31%再升高到65.72%再下降到45.54%。愈創(chuàng)木酚等部分愈創(chuàng)木酚類化合物相對含量隨著溫度升高呈現(xiàn)先增后減的趨勢,而4-乙烯基-2-甲氧基苯酚等的相對含量則隨著溫度的升高而不斷下降。而鄰苯二酚類化合物的相對含量則隨熱裂解溫度的升高而增加,不含甲氧基的烷基酚類化合物的相對含量均比較低,也呈現(xiàn)隨溫度升高而略有升高的趨勢。熱裂解產(chǎn)物中還存在部分含有愈創(chuàng)木酚基本結(jié)構(gòu)的醛酮類化合物隨著溫度的升高相對含量呈下降趨勢。以楊木酸不溶木素、堿木素、磨木木素為原料,在500℃條件下進(jìn)行裂解分析。磨木木素裂解產(chǎn)物中總酚相對含量達(dá)到54.28%,2-甲氧基-3-甲基苯酚(5.44%)等多種化合物的相對含量均超過5%。堿木素的熱裂解產(chǎn)物中總酚的相對含量為48.96%,2-甲氧基苯酚(5.7%)等部分化合物的相對含量都超過5%,而酸不溶木素裂解產(chǎn)物中總酚相對含量僅為37.65%,只有二氧化硫(6.44%)等四種化合物的相對含量也都超過5%。以楊木磨木木素為原料,分析不同溫度條件下熱裂解產(chǎn)物的結(jié)構(gòu)和含量。熱裂解溫度從400℃升高到700℃的過程中,總酚的相對含量從31.44%升高到54.28%再下降到42.85%再下降到25.16%。對于主要酚類組分,愈創(chuàng)木酚等酚類化合物相對含量隨著溫度升高呈現(xiàn)先增后減的趨勢,而2-甲氧基-4-乙烯基苯酚等化合物的相對含量則隨著溫度的升高而不斷下降。以工業(yè)堿木素為原料,分析不同溫度、不同催化劑條件下裂解產(chǎn)物的結(jié)構(gòu)和含量,熱裂解溫度從400℃升高到700℃的過程中,總酚相對含量從51.86%升高到54.37%再升高到55.08%再下將到40.86%。愈創(chuàng)木酚(2-甲氧基苯酚)的相對含量從400℃時相對含量6.69%升高到500℃時的9.78%再下降到600℃時的7.07%再到700℃時的5.40%;4-丙烯基-2-甲氧基苯酚的相對含量從400℃時相對含量8.41%下降到500℃時的5.30%再下降到600℃時的5.28%再下降到700℃時的 4.67%。以馬尾松磨木木素為原料,分別加入Na型分子篩ZSM-5(硅鋁比25、50)、H型分子篩HZSM-5(硅鋁比25、50、130)、鈦硅型分子篩Ts-1六種分子篩催化劑進(jìn)行催化裂解。六種催化劑對大部分酚類化合物的生成均有抑制作用,其中H型HZSM型和Ts-1型催化劑影響最明顯。但也有部分物質(zhì)如3-甲基苯酚、愈創(chuàng)木酚、4-乙基-2-甲氧基苯酚、3,4-二甲氧基甲苯等在Na型分子篩(硅鋁比25)催化作用下相對含量均出現(xiàn)升高,其中3,4-二甲氧基甲苯的相對含量甚至升高了40%左右。在TiO2、ZSM-5分子篩Na型-25兩種催化劑作用下,工業(yè)堿木素裂解產(chǎn)物的總酚含量均存在一定的下降,從54.37%分別下降到50.13%和48.94%。愈創(chuàng)木酚在Na型-25的作用下含量有明顯提高,從9.78%升高到11.28%,但在TiO2的作用下,相對含量從9.78%下降至9.15%;鄰苯二酚的相對含量在兩種催化劑作用下均略有下降,從12.42%分別下降至12.11%和12.19%。
[Abstract]:At present, the utilization of industrial lignin is less than 10%, most of which are used as waste, not only to waste resources but also to pollute the environment. Therefore, we hope to extract different lignin (acid insoluble lignin, alkali lignin and milkwood lignin) by different extraction methods for Pinus massoniana and broadleaf wood. Thermogravimetric analysis and pyrolysis and catalytic pyrolysis of three different kinds of lignin under different conditions can obtain the pyrolysis characteristics of different kinds of lignin. The suitable conditions (temperature, catalyst, etc.) can be selected. In lignin pyrolysis, the content of single phenolic components in the pyrolysis products can be increased, the separation cost is reduced, and wood is explored at the same time. The mechanism of lignin pyrolysis is the foundation for the utilization of lignin. Through the analysis of the thermogravimetric analysis of different lignin of Masson Pine and poplar wood, it is found that the main stage of lignin pyrolysis is volatilization phase, and the apparent activation energy of different lignin pyrolysis is mainly concentrated in 39-55KJ/mol. with Masson Pine acid insoluble lignin, alkali lignin and lignin. The structure and content of pyrolysis products at 500 C were analyzed by Py-GC-MS combined analysis technology. The relative content of total phenol in the products of lignin cracking was 62.3%, of which guaiacol was 9.75% and 4- methyl -2- methoxy phenol was 8.56%. alkali lignin, the relative content of total phenol was 44.86%, and guaiacol was 7.7. 6%, the relative content of total phenol in the acid insoluble lignin cracking product is only 16.25%, and the relative content of no one phenolic component exceeds the 5%. thermal cracking temperature from 400 to 700. In Mayo Matsumakikiso's pyrolysis products, the relative content of total phenol rises from 59.78% to 62.31% and then rises to 65.72%, and then drops to 45.54%. guaiacol. The relative content of the guaiacols increased first and then decreased with the increase of temperature, while the relative content of 4- vinyl -2- methoxy phenol decreased with the increase of temperature, while the relative content of catechol compounds increased with the increase of thermal cracking temperature, and the alkyl phenolic compounds without methoxy were added. The relative content is low, and there is a tendency to increase slightly with the increase of temperature. In the pyrolysis products, some aldehydes and ketones containing the basic structure of guaiacol also decrease with the increase of the temperature. Yang Musuan insoluble lignin, alkali lignin and milkwood are used as raw materials, and the pyrolysis points are carried out at 500 degrees centigrade. The relative content of 2- methoxy -3- methyl phenol (5.44%) and so on is 54.28%, and the relative content of the total phenol in the pyrolysis products of 5%. alkali lignin is 48.96%, and the relative content of 2- methoxy phenol (5.7%) is more than 5%, and the acid insoluble lignin cracking product The relative content of total phenol is only 37.65%, and the relative content of four compounds, such as sulfur dioxide (6.44%), is also more than 5%.. The structure and content of the pyrolytic products are analyzed under different temperature conditions. The relative content of total phenol is increased from 31.44% to 54.28% in the process of thermal cracking temperature rising from 400 to 700. The relative content of the phenolic compounds, such as guaiacol and other phenolic compounds, increased first and then decreased with the increase of temperature, while the relative content of 2- methoxy -4- vinyl phenol and other compounds decreased with the increase of temperature, while the relative content of 25.16%. methoxy -4- vinyl phenol and other compounds decreased with the increase of temperature. Under the conditions of catalyst, the relative content of total phenol in the process of increasing from 400 to 700 C, the relative content of total phenol increased from 51.86% to 54.37% and then to 55.08%, and the relative content of 40.86%. guaiacol (2- methoxy phenol) decreased from 6.69% to 500 degrees C at 400 C and then 9.78% to 600 centigrade. The relative content of 4- acryl -2- methoxy phenol at the time of 7.07% to 700 C; the relative content of 4- methoxy phenol decreased from 8.41% to 500 C at 500 C and then dropped to 600 degrees C, and then dropped to 600 degrees C, and then dropped to 700 centigrade, with Masson Pine grinding lignin as raw material, adding Na molecular sieve ZSM-5 (Si / Al ratio 25,50), H type molecular sieve HZSM-5 (silicon), respectively. Six kinds of molecular sieves are catalytic cracking. Six kinds of catalysts have inhibitory effect on the formation of most phenolic compounds. The H type HZSM type and Ts-1 type catalyst are most obvious, but there are some substances such as 3- methyl phenol, healing lignan, 4- ethyl -2- methoxy phenol, 3,4- two methoxy. The relative content of toluene was increased under the catalysis of Na type molecular sieves (Si / Al 25), and the relative content of 3,4- two methoxy toluene increased by about 40%. Under the action of TiO2, ZSM-5 molecular sieve Na -25 two catalysts, the total phenolic content of industrial alkali lignin cracking products decreased from 54.37% to 50., respectively. 13% and 48.94%. guaiacol content increased significantly under the action of Na -25, rising from 9.78% to 11.28%, but the relative content of guaiacol decreased from 9.78% to 9.15% under the action of TiO2, and the relative content of catechol decreased slightly under the action of two catalysts, from 12.42% to 12.11% and 12.19%., respectively.

【學(xué)位授予單位】：中南林業(yè)科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O636.2
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本文編號：1816351