本文關(guān)鍵詞：基于生物質(zhì)精煉的杜仲全組分結(jié)構(gòu)解析及其解離機(jī)制研究　出處：《西北農(nóng)林科技大學(xué)》2016年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 生物質(zhì)精煉 杜仲 結(jié)構(gòu)解析 解離機(jī)制

【摘要】：杜仲(Eucommia ulmoides Oliver,EU)單科單屬單種,為中國(guó)特有的經(jīng)濟(jì)樹(shù)種,在中國(guó)的種植面積占世界資源總量的95%以上。杜仲?gòu)臈U、葉、皮到果實(shí),渾身都是寶,尤其是可以提取作為國(guó)家戰(zhàn)略資源的杜仲橡膠,其研究和生產(chǎn)實(shí)際意義重大。由于杜仲產(chǎn)業(yè)的特殊性,目前依然有一些難題亟需攻克,首先是如何低成本的獲取杜仲資源作為產(chǎn)業(yè)化發(fā)展的基礎(chǔ);再者是如何基于生物質(zhì)精煉的杜仲全組分高效提取分離和產(chǎn)品開(kāi)發(fā);最后是如何闡明杜仲全組分在高值化提取分離過(guò)程中的解離機(jī)制成為杜仲產(chǎn)業(yè)化方面的難題之一。上述問(wèn)題的解決不僅對(duì)于杜仲資源配置方面的研究具有重要的推動(dòng)作用,而且涉及到健康食品、保健品以及其他相關(guān)產(chǎn)品的大規(guī)模開(kāi)發(fā)和利用提供重要的理論基礎(chǔ)。本文從杜仲資源培育模式的生理特征和次級(jí)代謝產(chǎn)物積累規(guī)律的關(guān)系出發(fā),分析了杜仲葉林栽培模式和喬林栽培模式初級(jí)代謝和次級(jí)代謝之間規(guī)律,闡明的兩種栽培模式的物質(zhì)積累差異性原因。此外,針對(duì)杜仲資源方面的不同器官,提出了幾種基于生物精煉的杜仲資源高效清潔提取分離及利用的方法,并對(duì)這些處理過(guò)程中解離機(jī)制進(jìn)行了深入的探討。系統(tǒng)的研究杜仲葉林栽培模式和傳統(tǒng)喬林栽培模式下形態(tài)特征與生理生態(tài)特性的差異,對(duì)促進(jìn)我國(guó)杜仲高效栽培模式與技術(shù)創(chuàng)新及可持續(xù)利用具有重要意義。以葉林栽培模式和喬林栽培模式的杜仲樹(shù)為材料,檢測(cè)了杜仲樹(shù)生長(zhǎng)期內(nèi)形態(tài)特征、光合生理、化學(xué)成分和生物量動(dòng)態(tài)變化規(guī)律,系統(tǒng)探討了栽培模式對(duì)其生長(zhǎng)與生理特征的影響。結(jié)果表明:不同測(cè)定時(shí)期,喬林栽培模式下杜仲葉片的最大凈光合速率(Pnmax)和水分利用效率(WUE)顯著低于葉林栽培模式;除10月中旬外,杜仲喬林栽培模式的葉片光響應(yīng)曲線的表觀量子效率(AQE)均顯著低于葉林栽培模式;兩種栽培模式的杜仲葉片暗呼吸速率(Rd)和光補(bǔ)償點(diǎn)(LCP)均隨生育期的延續(xù)呈降低的變化趨勢(shì);杜仲喬林栽培模式的株高、地徑和胸徑均顯著高于葉林模式,但其葉片面積呈相反趨勢(shì);10月中旬時(shí),喬林栽培模式的莖、皮和葉生物量干重均顯著低于葉林栽培模式。綜合所述,在杜仲葉林栽培模式下除株高、地徑和胸徑等形態(tài)特征外,葉面積、光合能力、生物量累積等生理生態(tài)特性方面較傳統(tǒng)喬林栽培模式均具有明顯的優(yōu)勢(shì)。利用杜仲樹(shù)皮(喬林和葉林)以及杜仲樹(shù)葉為原料,將杜仲葉和樹(shù)皮先后用熱水提取、堿處理、酶水解的多步集成處理,獲得杜仲浸膏、杜仲水溶性多糖、堿提多糖和杜仲膠。研究結(jié)果表明,杜仲葉中提取出浸膏的生物活性成分主要由綠原酸、槲皮素、京尼平甙、桃葉珊瑚甙組成,而杜仲樹(shù)皮中提取出浸膏的生物活性成分主要由京尼平苷酸、京尼平苷、桃葉珊瑚苷組成。此外,從樹(shù)皮和樹(shù)葉提取出的水溶性多糖主要由葡萄糖組成,而堿提多糖主要由阿拉伯糖組成。另外,從樹(shù)皮中分離得到的杜仲膠比樹(shù)葉中的杜仲膠具有較高的分子量和較窄的分子量分布。通過(guò)分析可知集成的多步處理是一種環(huán)境友好型的方法,有利于杜仲資源在產(chǎn)業(yè)化過(guò)程中產(chǎn)品的升級(jí)和產(chǎn)值的增大,有效的降低了成本,提高了杜仲產(chǎn)品的市場(chǎng)競(jìng)爭(zhēng)力。杜仲木材生物量比樹(shù)皮和樹(shù)葉高,對(duì)于杜仲木材的基礎(chǔ)研究意義重大。本研究利用杜仲木材為原料,主要探索了杜仲木材經(jīng)過(guò)自水解和有機(jī)溶劑脫木素協(xié)同處理的過(guò)程中木質(zhì)素的結(jié)構(gòu)變化對(duì)于木材酶水解效率的影響。通過(guò)自水解預(yù)處理可以降解半纖維素,從而分離出低聚木糖,隨后的有機(jī)溶劑脫木素過(guò)程,可以獲得高純度的木質(zhì)素和富含纖維素的基質(zhì)。研究結(jié)果表明,與磨木素相比,經(jīng)過(guò)協(xié)同預(yù)處理后的木質(zhì)素具有較低的分子量、窄的分散度、較高的酚羥基含量和高的S/G值。利用核磁共振對(duì)于所得的木質(zhì)素的結(jié)構(gòu)進(jìn)行了表征發(fā)現(xiàn),經(jīng)過(guò)協(xié)同預(yù)處理后,所得的木質(zhì)素的β-O-4鍵斷裂的比較嚴(yán)重,形成了對(duì)苯基乙烯的結(jié)果單元,同時(shí)也發(fā)現(xiàn)在有機(jī)溶劑脫木素過(guò)程中,木質(zhì)素的β-β結(jié)構(gòu)單元降解不是非常嚴(yán)重。此外,對(duì)于富含纖維素的基質(zhì)經(jīng)過(guò)酶水解處理。結(jié)果發(fā)現(xiàn),經(jīng)過(guò)協(xié)同預(yù)處理的基質(zhì)經(jīng)過(guò)酶水解其葡萄糖得率達(dá)到了89.3%,該結(jié)果分別是有機(jī)溶劑預(yù)處理基質(zhì)的1.0倍,自水解基質(zhì)的1.3倍,杜仲木材的3.8倍。該協(xié)同過(guò)程,不但獲得了高純度的木質(zhì)素,同時(shí)也為杜仲木材生物乙醇的高值化利用提供了新的途徑。利用杜仲葉林枝木為原料,探索蒸汽爆破和堿性過(guò)氧化氫預(yù)協(xié)同處理的過(guò)程中,木質(zhì)素結(jié)構(gòu)的變化對(duì)于木材酶水解效率的影響。蒸汽爆破預(yù)處理破壞了木質(zhì)纖維素的結(jié)構(gòu),隨后的堿性過(guò)氧化氫預(yù)處理過(guò)程分離得到了高純度的木質(zhì)素和富含纖維素的基質(zhì)。研究結(jié)果表明,與蒸汽爆破磨木素相比,經(jīng)過(guò)協(xié)同預(yù)處理后的木質(zhì)素具有低的分子量、窄的分散度、低含量的酚羥基值和低的S/G值。利用核磁共振對(duì)于所得的木質(zhì)素的結(jié)構(gòu)進(jìn)行了表征發(fā)現(xiàn),與蒸汽爆破磨木素相比,堿性過(guò)氧化氫處理過(guò)程中輕微的對(duì)于木質(zhì)素的成分和結(jié)構(gòu)單元有所影響,表現(xiàn)在經(jīng)過(guò)堿性過(guò)氧化氫處理后,所得的木質(zhì)素結(jié)構(gòu)單元中β-O-4、β-β和β-5含量較高。此外,經(jīng)過(guò)協(xié)同預(yù)處理的殘?jiān)淦咸烟堑寐侍岣叩?1.69%,這是因?yàn)閰f(xié)同預(yù)處理過(guò)程中可以分離大量的木質(zhì)素和半纖維素,促使獲得了高結(jié)晶度和比表面積的富含纖維素的基質(zhì)。協(xié)同預(yù)處理的過(guò)程是一個(gè)環(huán)境友好型的預(yù)處理過(guò)程,獲得了高純度的木質(zhì)素和富含纖維素基質(zhì)的同時(shí),為杜仲木材轉(zhuǎn)化為生物材料和生物乙醇提供了有效的途徑。基于生物精煉的杜仲木材自水解預(yù)處理和炭活化后處理的協(xié)同處理過(guò)程,經(jīng)過(guò)不同條件的自水解預(yù)處理可以獲得低聚木糖(XOS,1.5-34.4%)和半纖維素的降解產(chǎn)物,后續(xù)炭活化過(guò)程生產(chǎn)的高性能活性炭和少量的不可冷凝氣體。結(jié)果表明,在基于100 kg杜仲木材的基礎(chǔ)上,自水解預(yù)處理的最佳條件(170℃,1h),隨后炭活化(50%H3PO4,550℃,120 min)自水解基質(zhì)的協(xié)同處理過(guò)程,可以得到10.37 kg低聚木糖,1.39 kg半纖維素的降解產(chǎn)物,17.29 kg來(lái)自半纖維素的其他產(chǎn)品和40.72 kg活性炭(SBET 1534.06 m2/g)。其中,在所有活性炭樣品中AC170-1.0的比表面積為最高。同時(shí),從最佳綜合過(guò)程中產(chǎn)生的不可冷凝氣體(29.14 kg)比從直接炭活化處理(68.84 kg)產(chǎn)量顯著降低。此外,通過(guò)催化甲烷分解制氫實(shí)驗(yàn)表明最佳活性炭樣品(AC170-1.0)具有較好的催化活性和較高穩(wěn)定性。總體而言,基于生物精煉的綜合過(guò)程同時(shí)獲得品質(zhì)較優(yōu)的低聚木糖和高性能活性炭,這有效的提高了杜仲木材的熱解產(chǎn)業(yè)的附加值和工業(yè)應(yīng)用前景。
[Abstract]:(Eucommia ulmoides Oliver, Eucommia EU) a single species, for China unique economic species in Chinese planting area accounted for more than 95% of the total world resources. From eucommia leaf, fruit bar, skin, whole body is a treasure, especially can be extracted as Eucommia rubber and the national strategic resources, and its research the actual production of great significance. Because of the particularity of Eucommia industry, at present there are still some problems need to be overcome, the first is based on how low cost acquisition of Eucommia resources as the industrial development; and how biomass refining Du Zhongquan components and product development based on efficient extraction and separation; and finally how to clarify Du Zhongquan components in high value the extraction and dissociation mechanism of the separation process has become one of the difficult problems of the industrialization. To solve these problems not only for the study of Eucommia resources allocation role is important, but Related to health food, provide an important theoretical basis for large-scale development and utilization of health care products and other related products. From the perspective of relationship resource cultivation mode of Eucommia ulmoides physiological characteristics and secondary metabolite accumulation, analyzes the regularity between forest cultivation mode and cultivation of Eucommia ulmoides Colin model of primary metabolism and secondary metabolism, the reasons for difference in two the cultivation mode of material accumulation. In addition to clarify, in view of the different organs of Eucommia ulmoides resources, put forward several methods of separation and utilization of bio extraction refined Eucommia resources and efficient cleaning based on the dissociation mechanism of these processes is discussed. The difference of forest cultivation pattern system of Eucommia ulmoides and traditional cultivation pattern of Colin the morphological characteristics and physiological and ecological characteristics, to promote China's efficient cultivation mode and technology innovation and sustainable utilization of Eucommia ulmoides out Is of great significance. In forest cultivation mode and forest cultivation mode of Eucommia ulmoides were examined the morphological characteristics of Eucommia ulmoides growth period, photosynthetic physiology, variation of composition and dynamics of biomass chemistry, discusses cultivation pattern on growth and physiological characteristics of it. The result showed that different testing period. Joe forest cultivation mode of Eucommia leaf maximum net photosynthetic rate (Pnmax) and water use efficiency (WUE) was significantly lower than that of forest cultivation mode; in mid October, Joe forest cultivation mode of Eucommia ulmoides Ye Pianguang response curve of the apparent quantum efficiency (AQE) were significantly lower than that of forest cultivation mode; Eucommia ulmoides leaves of two kinds of cultivation patterns the dark respiration rate (Rd) and light compensation point (LCP) with the continuation of growth stages had a decreasing tendency; Joe forest cultivation mode of Eucommia plant height, ground diameter and DBH were significantly higher than those in model, but the leaf area was in the opposite Trend; in mid October, Joe forest cultivation pattern of stem, bark and leaf dry weight were significantly lower than those of Ye Lin. The comprehensive cultivation mode, cultivation mode of Eucommia ulmoides in Ye Lin except plant height, ground diameter and DBH morphological characteristics, leaf area, photosynthetic capacity, biomass accumulation, physiological and ecological characteristics compared with the traditional Qiao Lin cultivation mode has remarkable advantages. The use of Eucommia ulmoides Oliv (Qiao Lin and Ye Lin) and Eucommia ulmoides leaves as raw material, the leaves and bark of Eucommia successively with hot water extraction, alkali treatment, multi step integrated processing of enzymatic hydrolysis, obtain Eucommia extract, Eucommia polysaccharide, alkaliextracted and eucommia glue. The results show that the leaves of Eucommia ulmoides extract bioactive constituents of extract mainly composed of chlorogenic acid, quercetin, geniposide, aucubin, and Eucommia ulmoides Oliv extract bioactive constituents of extract is mainly composed of geniposidic acid, geniposide, peach Ye Shanhu was formed. In addition, from the bark and leaves of extracting water soluble polysaccharide was composed of glucose, and alkaline polysaccharides mainly composed of Arabia sugar. In addition, the molecular weight of the separation of Eucommia ulmoides gum obtained from the bark is higher than that in the leaves of Du Zhongjiao and a narrow molecular weight distribution through the analysis. Integrated multi step processing method is a kind of environment friendly, is conducive to the increase of Eucommia resources in the industry in the process of the upgrading of products and output, effectively reduce the cost, improve the market competitiveness of the products. The wood of Eucommia eucommia bark and leaf biomass ratio for wood based high, Eucommia research is of great significance. This study uses Eucommia wood as raw material, mainly to explore the Eucommia wood after the structural changes of lignin during self hydrolysis and organic solvent delignification treatment for wood synergistic enzymatic hydrolysis efficiency influence. By self hydrolysis pretreatment can degrade hemicellulose, thereby separating the xylooligosaccharides, lignin removal process of organic solvent followed, can obtain high purity of lignin and cellulose rich matrix. The results show that, compared with the MWL, through the wood quality collaborative after pretreatment with a low molecular weight and narrow dispersion the high content of phenolic hydroxyl group and high S/G value. The use of nuclear magnetic resonance for the wood element structure is characterized by that synergistic pretreatment, beta -O-4 bond breaking the lignin is serious, the formation of the phenyl ethylene unit, also found in organic solvent delignification in the process of beta beta degradation of lignin structural unit is not very serious. In addition, the matrix is rich in cellulose by enzyme hydrolysis treatment. The results showed that after CO matrix pretreatment after enzymatic hydrolysis of the grape Sugar yield reached 89.3%, the results were 1 times of organic solvent pretreatment matrix, since 1.3 times the hydrolysis of substrate, 3.8 times. The collaborative process of Eucommia wood, not only to obtain high purity of lignin, but also for Eucommia wood bio ethanol is a new way to provide high utilization value. The use of Eucommia forest branch wood as raw materials, to explore the steam explosion and alkaline hydrogen peroxide pre co processing process, influence the change of lignin structure for wood hydrolysis efficiency. Steam explosion pretreatment destroyed the structure of lignocellulose pretreatment, separation of alkaline hydrogen peroxide and obtained high purity stromatin and wood rich in cellulose. The results show that, compared with the steam explosion pretreatment after CO grinding lignin, the lignin has low molecular weight, narrow dispersion, low content of phenolic hydroxyl value and low S/G value using. The lignin NMR was characterized, compared with the steam explosion of MWL, effect of composition and structure unit for lignin has mild alkaline peroxide treatment process, performance after alkaline peroxide treatment, beta -O-4 lignin structural unit in the beta, beta and beta -5 content high. In addition, after CO pretreatment of glucose residue the rate increased to 91.69%, this is because you can isolate a large number of lignin and hemicellulose synergistic pretreatment process, to get the matrix of high crystallinity and specific surface area rich in cellulose. Synergistic pretreatment process of the pretreatment process is an environment friendly, obtained high purity of lignin and cellulose rich matrix at the same time, it provides an effective way for Eucommia timber into biological materials and bio ethanol based on bio refining. The collaborative process from Eucommia wood hydrolysis pretreatment and activated carbon, through different conditions can be obtained from hydrolysis pretreatment of xylo oligosaccharides (XOS, 1.5-34.4%) and the degradation of hemicellulose, the subsequent activation of high performance activated carbon production process and a small amount of non condensable gas. The results show that based on the based on the 100 kg Eucommia wood, since the optimum conditions of hydrolysis pretreatment (at 170 1H), then activated carbon (50%H3PO4550 C, 120 min) since the coordination process of hydrolysis of the matrix, you can get 10.37 kg xylooligosaccharides, 1.39 kg hemicellulose degradation products, other products from hemicellulose and 17.29 kg 40.72 kg activated carbon (SBET 1534.06 m2/g). Among them, AC170-1.0 in all active carbon in the sample surface area is the highest. At the same time, produced from the best comprehensive in the process of non condensable gas (29.14 kg) than from direct carbon activation Daniel (68.84 kg) significantly decreased the yield. In addition, show that the best activated carbon samples by catalytic decomposition of methane hydrogen production experiment (AC170-1.0) has good catalytic activity and high stability. Overall, comprehensive process of bio refining based on both carbon xylo oligosaccharide and high performance activity of better quality, which can effectively improve the pyrolysis the wood industry of Eucommia added value and the prospect of industrial application.

【學(xué)位授予單位】：西北農(nóng)林科技大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：S567.19
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本文編號(hào)：1417191