Effects of  LAT on chemical structure and enzymatic hydrolysis of crop straw

ZHAO Xiangjun; LI Cong; PENG Hehuan; ZHAO Chao; MA Zhongqing

doi:10.11833/j.issn.2095-0756.20190575

Volume 37 Issue 5

Oct. 2020

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ZHAO Xiangjun, LI Cong, PENG Hehuan, ZHAO Chao, MA Zhongqing. Effects of LAT on chemical structure and enzymatic hydrolysis of crop straw[J]. Journal of Zhejiang A&F University, 2020, 37(5): 898-906. doi: 10.11833/j.issn.2095-0756.20190575

Citation:

ZHAO Xiangjun, LI Cong, PENG Hehuan, ZHAO Chao, MA Zhongqing. Effects of LAT on chemical structure and enzymatic hydrolysis of crop straw[J]. Journal of Zhejiang A&F University, 2020, 37(5): 898-906. doi: 10.11833/j.issn.2095-0756.20190575

Effects of LAT on chemical structure and enzymatic hydrolysis of crop straw

doi: 10.11833/j.issn.2095-0756.20190575

Zhejiang Provincial Collaborative Innovation Center for Bamboo Resources and High-Efficiency Utilization, School of Engineering, Zhejiang A&F University, Hangzhou 311300, Zhejiang, China

Received Date: 2019-10-08
Rev Recd Date: 2020-02-22

Available Online: 2020-10-10

Publish Date: 2020-08-20

Abstract

Objective This study aims to investigate the effects of liquid ammonia treatment (LAT) pretreatment on the hydrolysis resistance of biomass and the enzymatic hydrolysis rate of lignocellulosic biomass. Method Four different types of lignocelluloses biomass, namely wheat straw (Triticum aestivum), alfalfa (Lotus corniculatus), sorghum straw (Sorghum bicolor), and their mixture (mass ratio 1∶1∶1), were pretreated by LAT method, and the effect of LAT on their chemical structure changes was studied by using thermo gravimetric analysis (TGA), Fourier transform infrared spectrometer (FTIR), X-ray diffractometer (XRD), and scanning electron microscope (SEM). Then, the effect of pretreatment temperature and enzymatic hydrolysis time on the enzymatic hydrolysis conversion rates of glucan and xylan in the four raw materials was investigated. Result LAT had a significant effect on the chemical structure of biomass materials. After this pretreatment, the relative content of glucan, xylan, and arabinan in four types of lignocelluloses biomass slightly decreased. The relative content of O and H decreased because some functional groups containing O and H dropped off. The crystallinity decreased slightly, while the surface pore structure significantly increased, and the availability of enzymes in the chemical structure of biomass increased. The optimum pretreatment temperature of wheat straw and mixture was 90 ℃, while that of alfalfa and sorghum straw was 110 ℃. The enzymatic hydrolysis rates of glucan and xylan increased with the increase of enzymatic hydrolysis time. Among the four types of lignocelluloses biomass, the highest enzymatic hydrolysis rate of glucan obtained at the optimal enzymatic hydrolysis condition was wheat straw, followed by the mixture, sorghum straw, and alfalfa. The enzymatic hydrolysis rate of xylan ranging from large to small was sorghum straw, wheat straw, the mixture, and alfalfa. Conclusion LAT can improve the enzymatic hydrolysis efficiency of lignocellulosic biomass, especially that of wheat straw and sorghum straw. [Ch, 8 fig. 2 tab. 24 ref.]
- wheat straw,
- alfalfa,
- sorghum straw,
- liquid ammonia treatment,
- enzymatic hydrolysis,
- cellulose ethanol

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沈阳化工大学材料科学与工程学院沈阳 110142

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液氨预处理法(liquid ammonia treatment，LAT)在氨纤维爆破预处理法(ammonia fiber explosion, AFEX)的基础上改进得来，通过提高反应温度、去除爆破工艺，将氨由快速释放转化为慢速释放，从而降低预处理工艺操作难度，具有非常广阔的发展前景^[1]。赵相君等^[2]研究了液氨预处理法和双氧水预处理法对稻草(水稻Oryza sativa)酶解转化率的影响，发现双氧水预处理后的葡聚糖和木聚糖的酶解转化率仅为61.6%和47.8%，显著低于液氨预处理法(88.6%和79.3%)。OLADI等^[3]和ZHAO等^[4]利用响应面法对液氨预处理工艺(温度、氨添加量、反应时间等)进行了优化，当反应温度为170 ℃、氨与原材料质量比为5∶1、载水与原材料质量比为0.8~1.6∶1.0、反应时间为10 min时，芦竹Arundo donax葡聚糖和木聚糖的酶解转化率最高，达到了94.2%和84.4%，总糖回收率高达530.9 g·kg⁻¹。现有文献主要集中于研究LAT预处理工艺对单种生物质原料酶解率的影响^[5-7]，而对多种生物质经预处理后化学结构的变化规律(如微观形貌结构、表面化学官能团、纤维素结晶度等)的研究还鲜有报道。中国是农业生产大国，农业生物质资源丰富^[8]。小麦Triticum aestivum、高粱Sorghum bicolor和苜蓿Lotus corniculatus作为传统且非常有潜力的农作物，具有栽植面积广，产量可观的优势^[9-11]。本研究以麦秸秆、苜蓿草、高粱秸秆及其混合物(质量比为1∶1∶1)为原料，在不同温度条件下开展LAT预处理试验，利用热重分析仪(TGA)、傅里叶变化红外光谱仪(FTIR)、X-射线衍射仪(XRD)、扫描电镜(SEM)等对原料预处理前后的物理化学特性进行表征分析，并利用高效液相色谱(HPLC)对4类原料中葡聚糖/木聚糖的酶解转化率进行对比，探究最理想的LAT预处理温度及预处理前后材性的变化，为LAT预处理工艺设计提供理论依据，也为农作物转化为生物燃料建立基础。

1. 材料与方法

1.1. 材料

麦秸秆取自浙江省杭州市临安区清凉峰镇，苜蓿草和高粱秸秆取材于甘肃省白银市会宁县，混合物由麦秸秆、苜蓿草、高粱秸秆按质量比1∶1∶1混合而成。先将原料烘干至含水率低于15%，再粉碎成粒径为50~100目的粉末。用水分分析仪(MA35，赛多利斯科学仪器有限公司)测试实际含水率，测试后用密封袋密封低温(−20 ℃)保存。纤维素酶(NS50013)和β-葡萄糖苷酶(NS50010)由诺维信公司(中国)提供。

1.2. LAT预处理

称取各生物质原料20 g，加去离子水，使固液质量比达到70%，搅拌均匀并平衡10 min后转移到高压反应釜(GCF-1 L20/350，大连自控设备厂)中，并对反应釜抽真空。将液氨注入称量小钢瓶，使氨与原材料的质量比为1∶1；加热小钢瓶至50 ℃，用以提升氨的压力，再将氨注入反应釜。控制每组样品的反应釜温度在70、90、110、130、150和170 ℃下各反应5 min，反应结束后快速冷却反应釜并释放氨气。取出原料，40 ℃真空烘箱中干燥24 h后测量质量和含水率，计算预处理后原料得率，再将处理后的原料放入−20 ℃的冰箱冷藏备用。

1.3. LAT预处理前后原料的物理化学特性分析

采用元素分析仪(Vario EL Ⅲ，德国 Elementary 公司) 测定预处理前后原料的元素组成；根据国家可再生能源实验室(NREL)标准中的LAP002方法^[12]测定碳水化合物相对含量，根据LAP003方法^[12]测定酸不溶性木质素(Klason木质素)相对含量；采用高效液相色谱(HPLC-1200，美国安捷伦科技有限公司)测定各种单糖质量分数，并计算葡聚糖(纤维素)、木聚糖、阿拉伯聚糖等组分的相对含量；根据GB/T 2677.3−1993《造纸原料灰分的测定》标准测定原料灰分测定原料灰分。

采用热重分析仪(TG209F1，德国耐驰仪器制造有限公司)分析预处理前后的原料的热失重规律。称取10 mg原料放入三氧化二铝坩埚中，以20 ℃·min⁻¹升温速率升至600 ℃；载气为高纯氮气(99.999%)，载气流量为40 mL·min⁻¹，保护气流量为20 mL·min⁻¹。采用傅里叶红外光谱仪(Nicolet 6700，美国尼高力仪器公司)分析预处理前后原料的表面官能团。称取1 mg样品粉末与溴化钾(质量比1∶200)混合研磨均匀并压片，在4 000~500 cm⁻¹波长范围内扫描。采用冷场发射扫描电镜(SEM，SU8010，日本日立公司)观察预处理前后样品微观结构。采用 X 射线衍射仪(XRD-6000，日本岛津公司)分析预处理前后原料的结晶度进行。称取200 mg粉末样品，压片处理后放入样品室，扫描范围为5°~40°，步长为0.05°，扫描速度为5°·min⁻¹。根据公式计算纤维素结晶度I_Cr=(I₀₀₂−I_am)/I₀₀₂×100%。其中，I₀₀₂为结晶峰的衍射强度，I_am为无定形区域衍射强度。

1.4. 酶水解实验

根据NREL标准中的LAP009^[12]规程进行酶水解实验。称取150 mg葡聚糖当量的原料，用pH 4.8的蒸馏水-柠檬酸钠缓冲溶液溶解得到15 mL酶解液，加入抗生素(四环素和环己酰亚胺)防止菌落滋生。预混合1 h，添加纤维素酶和β-葡萄糖苷酶，放入摇床。酶解温度为50 ℃，摇床转速为150 r·min⁻¹。

酶解24和72 h时取样，酶解液摇匀后用移液枪量取1 mL样品注入离心管，100 ℃下放置20 min，使酶蛋白变性完全失效，−20 ℃下冷却5 min，15 000 r·min⁻¹转速下离心5 min，经0.22 μm聚醚砜膜过滤后注入HPLC分析瓶中，测定酶解液中的单糖相对含量。HPLC采用示差检测器，色谱柱(HPX-87H Ion Exclusion Column，Bio-Rad公司)条件：进样量为15 μL，每个样品运行20 min，柱温为50 ℃，流动相为0.005 mol·L⁻¹稀硫酸，流速为0.5 mL·min⁻¹。

用实际获得的单糖与原料中聚糖理论上可转换的同类单糖之比表示酶解率。计算其中葡聚糖和木聚糖的酶解率d=g×15/m×c×k×1 000×100%。其中：g为HPLC测得的酶解液中葡萄糖或木糖的质量浓度(g·L⁻¹)；m为加入原料的干基质量(g)；c为原料成分分析(酸解法)葡聚糖或木聚糖相对含量(%)；k为葡聚糖或木聚糖分别转化为葡萄糖或木糖的系数，取0.90和0.88。总糖回收量定义为1 000 g干基材料经LAT预处理72 h后酶解所释放的葡聚糖和木聚糖总质量之和。

3. 结论

采用LAT法对麦秸秆、苜蓿草、高粱秸秆以及三者混合物(质量比1∶1∶1)进行预处理，研究预处理温度与葡聚糖和木聚糖酶解转化率的关系，得到结论如下：①LAT预处理对生物质原料的化学结构影响显著。LAT预处理后，原料化学组分中葡聚糖、木聚糖和阿拉伯糖的相对含量下降；元素组分中的氧和氢相对含量下降，碳和氮相对含量上升；结晶度小幅下降，生物质表面孔隙结构增强，使得酶在生物质化学结构上的可及度增加。②麦秸秆和混合物中葡聚糖和木聚糖的酶解率在LAT预处理温度为90 ℃时达到最大值，苜蓿草和高粱秸秆在110 ℃时达到最大值。随着酶解时间延长，4种原料葡聚糖和木聚糖的酶解率均增加；葡聚糖的最大酶解率从大到小依次为麦秸秆、混合物、高粱秸秆、苜蓿草，木聚糖的最大酶解率从大到小依次为高粱秸秆、麦秸秆、混合物、苜蓿草。

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样品	葡聚糖/%	木聚糖/%	阿拉伯聚糖/%	Klason木质素/%	灰分/%	固体得率/%
未处理的麦秸秆	35.54	19.06	3.19	18.92	13.83	100
LAT预处理的麦秸秆	32.86	17.99	3.19	15.34	11.59	99.84
未处理的苜蓿草	27.38	12.88	3.02	21.38	5.90	100
LAT预处理的苜蓿草	25.81	11.53	3.01	20.09	5.04	99.77
未处理的高粱秸秆	37.90	17.63	3.35	13.53	3.67	100
LAT预处理的高粱秸秆	33.72	14.69	3.28	10.35	2.71	98.99
未处理的混合物	33.58	17.23	3.44	16.70	7.89	100
LAT预处理的混合物	30.32	16.81	3.43	13.61	7.22	99.46

样品	碳/%	氢/%	氧/%	氮/%	硫/%	高位热值/(MJ·kg⁻¹)
未处理的麦秸秆	39.06	6.63	53.16	0.79	0.36	20.33
LAT预处理的麦秸秆	39.07	6.49	52.69	1.49	0.27	20.14
未处理的苜蓿草	43.79	7.22	47.47	1.36	0.16	22.24
LAT预处理的苜蓿草	43.87	6.90	46.83	3.10	0.29	21.29
未处理的高粱秸秆	43.53	7.09	48.21	1.01	0.17	22.29
LAT预处理的高粱秸秆	43.57	6.91	46.61	2.74	0.17	21.52
未处理的混合物	42.46	6.93	49.36	1.03	0.22	21.25
LAT预预处理的混合物	41.60	6.58	49.23	2.40	0.19	20.51