小麦B淀粉浆超低酸水解及其动力学

doi:10.3969/j.issn.1673-5854.2024.02.003

摘要/Abstract

摘要：

小麦B淀粉浆是小麦加工过程产生的一种副产物，将其高值化利用能够促进小麦深加工技术的发展。本研究针对小麦B淀粉浆原料特点，提出了一种超低酸水解糖化工艺路线，考察了超低酸浓度、水解温度和水解时间对水解液中葡萄糖相对质量（DE）值的影响规律，并采用响应面法优化了超低酸水解工艺条件，进一步建立了B淀粉浆的超低酸水解动力学。研究结果显示：B淀粉浆在硫酸质量分数为0.07%，水解温度166℃，水解时间66 min的优化条件下水解，水解液中葡萄糖DE值达到88.58%。动力学结果显示B淀粉浆超低酸水解过程符合一级反应动力学模型，活化能和指前因子分别为75.118 kJ/mol和1.429×10⁷ min^-1。

关键词: B淀粉, 超低酸, 糖化, 动力学

Abstract:

Wheat B starch slurry is the by-product of wheat processing, and its high value utilization can promote the development of wheat deep processing technology. According to the characteristics of wheat B starch slurry, an extremely low acid hydrolysis process was proposed in this study. The effects of extremely low acid concentration, hydrolysis temperature, and hydrolysis time on the dextrose equivalent(DE) values of saccharification were investigated, and the response surface methodology was then used to optimize the conditions of hydrolysis process. Under the optimum conditions of sulfuric acid concentration of 0.07%, hydrolysis temperature of 166℃ and hydrolysis time of 66 minutes, the DE value of B starch slurry saccharification reached 88.58%. Furthermore, the kinetics of extremely low acid hydrolysis of B starch slurry was established. The kinetics results showed that the hydrolysis process followed the first-order reaction kinetics model, and the activation energy and pre-exponential factor were 75.118 kJ/mol and 1.429×10⁷ min^-1, respectively.

Key words: B starch, extremely low acid, saccharification, kinetic

中图分类号:

TQ35
TS236

张欢欢, 杨蕊楠, 阎振丽, 赵子高, 常春. 小麦B淀粉浆超低酸水解及其动力学[J]. 生物质化学工程, 2024, 58(2): 22-30.

Huanhuan ZHANG, Ruinan YANG, Zhenli YAN, Zigao ZHAO, Chun CHANG. Hydrolysis and Kinetics of Wheat B Starch Slurry with Extremely Low Acid[J]. Biomass Chemical Engineering, 2024, 58(2): 22-30.

图/表 11

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参考文献 31

1	ZHANG B , ZHAO K , SU C Y , et al. Comparing the multi-scale structure, physicochemical properties and digestibility of wheat A- and B-starch with repeated versus continuous heat-moisture treatment[J]. International Journal of Biological Macromolecules, 2020, 163, 519- 528. doi: 10.1016/j.ijbiomac.2020.07.002
2	ZHANG K, LU Q Y. Physicochemical properties of A- and B-type granules of wheat starch and effects on the quality of wheat-based noodle[J/OL]. International Journal of Food Engineering, 2017, 13(7): 20160437[2023-05-20]. https://doi.org/10.1515/ijfe-2016-0437.
3	BANGAR S P, ASHOGBON A O, SINGH A, et al. Enzymatic modification of starch: A green approach for starch applications[J/OL]. Carbohydrate Polymers, 2022, 287: 119265[2023-05-20]. https://doi.org/10.1016/j.carbpol.2022.119265.
4	吴桂玲, 李文浩, 郭洪梅, 等. 脱脂脱蛋白处理对小麦A、B淀粉理化性质的影响[J]. 现代食品科技, 2015, 31 (10): 227- 233.
5	SHANG J Y , LI L M , ZHAO B , et al. Comparative studies on physicochemical properties of total, A- and B-type starch from soft and hard wheat varieties[J]. International Journal of Biological Macromolecules, 2020, 154, 714- 723. doi: 10.1016/j.ijbiomac.2020.03.150
6	ZAINI N A B M , CHATZIFRAGKOU A , CHARALAMPOPOULOS D . Alkaline fractionation and enzymatic saccharification of wheat dried distillers grains with solubles(DDGS)[J]. Food and Bioproducts Processing, 2019, 118, 103- 113. doi: 10.1016/j.fbp.2019.09.006
7	刘云艳. 复合酶法小麦淀粉制糖工艺探索[J]. 发酵科技通讯, 2013, 42 (1): 20- 21.
8	LI H T, YU W M, DHITAL S, et al. Starch branching enzymes contributing to amylose and amylopectin fine structure in wheat[J/OL]. Carbohydrate Polymers, 2019, 224: 115185[2023-05-20]. https://doi.org/10.1016/j.carbpol.2019.115185.
9	高洪芳, 施志斌. 淀粉超低酸水解反应葡萄糖产率的探究[J]. 化学教学, 2018, (8): 69- 73.
10	亢潘潘, 胡秋林. 酸-酶联用液化法制备小麦淀粉麦芽糖浆的工艺研究[J]. 武汉工业学院学报, 2012, 31 (1): 8- 12.
11	YU Z P , DU Y L , SHANG X N , et al. Enhancing fermentable sugar yield from cassava residue using a two-step dilute ultra-low acid pretreatment process[J]. Industrial Crops and Products, 2018, 124, 555- 562. doi: 10.1016/j.indcrop.2018.08.029
12	HU X , LIEVENS C , LARCHER A , et al. Reaction pathways of glucose during esterification: Effects of reaction parameters on the formation of humin type polymers[J]. Bioresource Technology, 2011, 102 (21): 10104- 10113. doi: 10.1016/j.biortech.2011.08.040
13	ŚWIĄTEK K , GAAG S , KLIER A , et al. Acid hydrolysis of lignocellulosic biomass: Sugars and furfurals formation[J]. Catalysts, 2020, 10 (4): 437. doi: 10.3390/catal10040437
14	ZHAO S B , WANG Z H , CHANG C , et al. Enhanced production of levulinic acid/ester from furfural residue via pretreatment and two-stage alcoholysis[J]. Biomass Conversion and Biorefinery, 2023, 13 (4): 2933- 2946. doi: 10.1007/s13399-021-01307-1
15	TANG Z , SU J H . Direct conversion of cellulose to 5-hydroxymethylfurfural(HMF) using an efficient and inexpensive boehmite catalyst[J]. Carbohydrate Research, 2019, 481, 52- 59. doi: 10.1016/j.carres.2019.06.010
16	WANG K , YANG H Y , CHEN Q , et al. Influence of delignification efficiency with alkaline peroxide on the digestibility of furfural residues for bioethanol production[J]. Bioresource Technology, 2013, 146, 208- 214. doi: 10.1016/j.biortech.2013.07.008
17	孙岩, 严亲清, 周婉哲, 等. 糠醛渣超低酸水解制取乙酰丙酸的工艺条件研究[J]. 化学工程师, 2019, 33 (11): 5- 8.
18	WANG J H, CUI H Y, WANG J G, et al. Kinetic insight into glucose conversion to 5-hydroxymethyl furfural and levulinic acid in LiCl₃H₂O without additional catalyst[J/OL]. Chemical Engineering Journal, 2021, 415: 128922[2023-05-20]. https://doi.org/10.1016/j.cej.2021.128922.
19	CHEN W B , HU H W , CAI Q J , et al. Synergistic effects of furfural and sulfuric acid on the decomposition of levulinic acid[J]. Energy Fuels, 2020, 34 (2): 2238- 2245. doi: 10.1021/acs.energyfuels.9b03971
20	SHIVARAJU V K, VALLAYIL APPUKUTTAN S, SUNNY K. The influence of bound water on the FTIR characteristics of starch and starch nanocrystals obtained from selected natural sources[J/OL]. Die Stärke, 2019, 71(5/6): 1700026[2023-05-20]. https://doi.org/10.1002/star.201700026.
21	LI M N , XIE Y , CHEN H Q , et al. Effects of heat-moisture treatment after citric acid esterification on structural properties and digestibility of wheat starch, A- and B-type starch granules[J]. Food Chemistry, 2019, 272, 523- 529. doi: 10.1016/j.foodchem.2018.08.079
22	LI P , DU Z J , CHANG C , et al. Efficient catalytic conversion of waste peanut shells into liquid biofuel: An artificial intelligence approach[J]. Energy & Fuels, 2020, 34 (2): 1791- 1801.
23	陈佩, 张晓, 赵冰, 等. 糯小麦淀粉形态及内部结构的研究[J]. 食品工业科技, 2015, 36 (1): 70- 72.
24	ZHANG B , LI X , LIU J , et al. Supramolecular structure of A- and B-type granules of wheat starch[J]. Food Hydrocolloids, 2013, 31 (1): 68- 73. doi: 10.1016/j.foodhyd.2012.10.006
25	AMARAWEERA S M , GUNATHILAKE C , GUNAWARDENE O H P , et al. Preparation and characterization of biodegradable cassava starch thin films for potential food packaging applications[J]. Cellulose, 2021, 28 (16): 10531- 10548. doi: 10.1007/s10570-021-04199-6
26	CHEN P , XIE F W , ZHAO L , et al. Effect of acid hydrolysis on the multi-scale structure change of starch with different amylose content[J]. Food Hydrocolloids, 2017, 69, 359- 368. doi: 10.1016/j.foodhyd.2017.03.003
27	ADEWUMI C N, EKPO E I, ACHUGASIM O, et al. Substrate concentration: A more serious consideration than the amount of 5-hydroxyme-thylfurfural in acid-catalyzed hydrolysis during bioethanol production from starch biomass[J/OL]. Heliyon, 2022, 8(12): 12047[2023-05-20]. https://doi.org/10.1016/j.heliyon.2022.e12047.
28	UMRIGAR V , CHAKRABORTY M , PARIKH P . Esterification and ketalization of levulinic acid with desilicated zeolite β and pseudo-homogeneous model for reaction kinetics[J]. International Journal of Chemical Kinetics, 2019, 51 (4): 299- 308. doi: 10.1002/kin.21253
29	LI C, HU Y M. Effects of acid hydrolysis on the evolution of starch fine molecular structures and gelatinization properties[J/OL]. Food Chemistry, 2021, 353: 129449[2023-05-20]. https://doi.org/10.1016/j.foodchem.2021.129449.
30	WEI W Q , WU S B . Experimental and kinetic study of glucose conversion to levulinic acid catalyzed by synergy of Lewis and Brønsted acids[J]. Chemical Engineering Journal, 2017, 307, 389- 398. doi: 10.1016/j.cej.2016.08.099
31	CRAPSE J, PAPPIREDDI N, GUPTA M, et al. Evaluating the Arrhenius equation for developmental processes[J/OL]. Molecular Systems Biology, 2021, 17(8): 9895[2023-05-20]. https://doi.org/10.15252/msb.20209895.

来源source	平方和sum of squares	自由度degree of freedom	均方mean square	F值F value	P值P value
模型model	7 074.81	9	786.09	537.2	< 0.000 1
X₁	881.16	1	881.16	602.17	< 0.000 1
X₂	13.24	1	13.24	9.04	0.019 7
X₃	110.48	1	110.48	75.5	< 0.000 1
X₁X₂	0.82	1	0.82	0.56	0.478 8
X₁X₃	181.85	1	181.85	124.27	0.001 1
X₂X₃	2 500	1	2 500	1 710	0.468 2
X₁²	4 947.29	1	4 947.29	3 380.88	< 0.000 1
X₂²	36.16	1	36.16	24.71	0.001 6
X₃²	612.44	1	612.44	418.53	< 0.000 1
残差residual	10.24	7	1.46	0.32	0.813 9
失拟项lack of fit	1.97	3	0.66
净误差pure error	8.28	4	2.07
总残差total	7 085.05	16

温度/℃ temp.	β=0		β=1		β=2
温度/℃ temp.	R²	k/(g·L^-1·min^-1)	R²	k/min^-1	R²	k/(g·L^-1·min)^-1
150	0.967 6	0.005 1±0.000 29	0.996 5	0.007 6±0.000 15	0.915 2	0.017 2±0.001 65
160	0.936 9	0.006 8±0.000 56	0.998 6	0.013 9±0.000 16	0.966 7	0.033 8±0.001 98
170	0.871 9	0.007 2±0.000 87	0.994 2	0.018 7±0.000 45	0.957 9	0.066 1±0.004 62

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