稀酸氯盐体系转化竹浆制备5-氯甲基糠醛的研究

doi:10.3969/j.issn.1673-5854.2023.05.002

Abstract

Abstract:

5-Chloromethylfurfural(CMF) was a biobased platform compound that had received considerable attention in recent years. The traditional CMF preparation process required a concentrated hydrochloric acid system, and its high corrosivity remained as a challenge to its scale-up production. To solve this problem, a reaction system based on acidic CaCl₂ solution was established, and the influence of reaction conditions, material concentration and other parameters on the preparation of CMF from bamboo biomass in this system was studied. The results showed that saturated or nearly saturated chloride ion in the water phase could effectively inhibit the hydrolysis of CMF to HMF, thereby improving the stability of CMF in the system, and thus reducing the conversion of unstable intermediate products(i.e., HMF) to humins under acidic conditions. CaCl₂ had excellent catalytic performance in the system, and the highest CMF yield of 59.2% was obtained. 1, 2-Trichloroethane, 1, 3-dichloropropane, 1, 2, 3-trichloropropane and other solvents with higher boiling point had the potential to replace extractant of 1, 2-dichloroethane(DCE). The effects of different pretreatment conditions on CMF yield of bamboo pulp were further studied, and the optimal hydrolysis chlorination conditions were: initial bamboo pulp mass concentration of 16 g/mL, 8 g of H₂O, 1.33 mol/L of HCl, 5.33-6.66 mol/L of CaCl₂, 130 ℃, 1 h and 25 mL of DCE. Under these conditions, the CMF yield was 59.2%, and bamboo pulp samples pretreated by NaHSO₃ or Cooking with Active Oxygen and Solid Alkali(CAOSA) method were more better for CMF preparation than those of treated with traditional alkali methods. The acidic CaCl₂ phase could be recycled and then reused after supplementing a certain amount of HCl. The conversion of bamboo pulp to CMF was scaled up by 15 times and provided the CMF yield of 51.8%. The CMF crude product had good stability in dichloroethane solution, and there was no significant deterioration after 4-12 days of storage.

Key words: biomass, bamboo pulp, CaCl₂, 5-chloromethylfurfural

CLC Number:

TQ35

Guitong NONG, Weiwei HAO, Zheng LI, Xing TANG, Hongcai ZHOU, Lu LIN. Conversion of Bamboo Pulp to 5-Chloromethylfurfural in a Diluted HCl-chloride System[J]. Biomass Chemical Engineering, 2023, 57(5): 8-16.

Figures/Tables 11

Fig.1

Table 1

Table 2

Table 3

Fig.2

Table 4

Table 5

Table 6

Table 7

Fig.3

Fig.4

References 19

1	卢思, 王琼, 李浔, 等.5-羟甲基糠醛制备及其应用研究进展[J].林产化学与工业,2019,39(1):13-22.
2	BRASHOLZ M , VON KAENEL K , HORNUNG C H , et al.Highly efficient dehydration of carbohydrates to 5-(chloromethyl) furfural(CMF), 5-(hydroxymethyl) furfural(HMF) and levulinic acid by biphasic continuous flow processing[J].Green Chemistry,2011,13(5):1114-1117. doi: 10.1039/c1gc15107j
3	王帅, 唐兴, 孙勇, 等.5-氯甲基糠醛水解制备5-羟甲基糠醛的工艺优化及反应动力学研究[J].林产化学与工业,2022,42,65-74.
4	CHEN B, FENG Y, HUANG R, et al. Efficient synthesis of the liquid fuel 2, 5-dimethylfuran from biomass derived 5-(chloromethyl) furfural at room temperature[J/OL]. Applied Catalysis B: Environmental, 2022, 318: 121842[2022-11-10]. https://doi.org/10.1016/j.apcatb.2022.121842.
5	CHEN B , FENG Y , MA S , et al.One-pot synthesis of 2, 5-bis(hydroxymethyl) furan from biomass derived 5-(chloromethyl) furfural in high yield[J].Journal of Energy Chemistry,2023,76(1):421-428.
6	VICENTE A I, COELHO J A, SIMEONOV S P, et al. Oxidation of 5-chloromethylfurfural(CMF) to 2, 5-diformylfuran(DFF)[J/OL]. Molecules, 2017, 22(2): 329[2022-11-10]. https://doi.org/10.3390/molecules22020329.
7	SASKA J , LI Z , OTSUKI A L , et al.Butenolide derivatives of biobased furans: Sustainable synthetic dyes[J].Angewandte Chemie International Edition in English,2019,131(48):17293-17296.
8	FENTON H J H , GOSTLING M .LXXXV.—Derivatives of methylfurfural[J].Journal of Chemical Society Transactions,1901,79,807-816. doi: 10.1039/CT9017900807
9	MASCAL M , NIKITIN E B .Direct, high-yield conversion of cellulose into biofuel[J].Angewandte Chemie International Edition in English,2008,47,7924-7926. doi: 10.1002/anie.200801594
10	MASCAL M , NIKITIN E B .Dramatic advancements in the saccharide to 5-(chloromethyl)furfural conversion reaction[J].ChemSusChem,2009,2(9):859-861. doi: 10.1002/cssc.200900136
11	WU F , YANG R , YANG F .Metal chlorides as effective catalysts for the one-pot conversion of lignocellulose into 5-chloromethylfurfural(5-CMF)[J].BioResources,2015,10(2):3293-3301.
12	GAO W , LI Y , XIANG Z , et al.Efficient one-pot synthesis of 5-chloromethylfurfural(CMF) from carbohydrates in mild biphasic systems[J].Molecules,2014,19(1):7675-7685.
13	BREEDEN S , CLARK J , FARMER T , et al.Microwave heating for rapid conversion of sugars and polysaccharides to 5-chloromethyl furfural[J].Green Chemistry,2013,15,72-75. doi: 10.1039/C2GC36290B
14	陈泽智, 陈迁, 杨金兰, 等.以蔗渣为原料制备生物汽油中间体5-氯甲基糠醛[J].农业工程学报,2012,28(24):214-219.
15	ZUO M , LI Z , JIANG Y , et al.Green catalytic conversion of bio-based sugars to 5-chloromethyl furfural in deep eutectic solvent catalyzed by metal chlorides[J].RSC Advances,2016,6(40):33492-33492. doi: 10.1039/C6RA90032A
16	CHEN B , LI Z , FENG Y , et al.Green process for 5-(chloromethyl) furfural production from biomass in three-constituent deep eutectic solvent[J].ChemSusChem,2021,14(3):847-851. doi: 10.1002/cssc.202002631
17	JIANG Y , ZENG X , LUQUE R , et al.Cooking with active oxygen and solid alkali: A promising alternative approach for lignocellulosic biorefineries[J].ChemSusChem,2017,10(20):3982-3993. doi: 10.1002/cssc.201700906
18	KUMARI N , OLESEN J K , PEDEREN C M , et al.Synthesis of 5-bromomethylfurfural from cellulose as a potential intermediate for biofuel[J].European Journal of Organic Chemistry,2011,(7):1266-1270.
19	BREDIHHIN A , MAEORG U , VARES L .Evaluation of carbohydrates and lignocellulosic biomass from different wood species as raw material for the synthesis of 5-bromomethyfurfural[J].Carbohyd Research,2013,375(1):63-67.

氯盐种类 chlorides type	H⁺浓度/(mol·L^-1) H⁺ concentration	Cl^-浓度/(mol·L^-1) Cl^- concentration	CMF得率/% CMF yield
无none	0	0	0
无(仅盐酸) none(HCl only)	3.0	3.0	0
CaCl₂	3.0	11.64	15.4
MgCl₂	3.0	11.64	28.1
AlCl₃	3.0	11.64	33.5
AlCl₃	3.0	10.91	33.6
AlCl₃	3.0	10.19	18.8
AlCl₃	3.0	8.73	9.7

氯盐 chlorides	Cl^-浓度/(mol·L^-1) concentration of Cl^-	CMF得率/%¹⁾ CMF yield
LiCl	15.30	59.60
CaCl₂	12.70	57.90
MnCl₂	10.00	8.72
FeCl₂	9.45	7.90
CuCl₂	10.40	2.36
CoCl₂	9.45	13.90
MgCl₂	9.45	57.00
NiCl₂	8.73	30.40
AlCl₃	8.73	50.90
KCl	5.09	6.24
NaCl	5.09	10.10
BaCl₂	5.09	5.98
无盐酸without HCl	2.00	0

萃取剂 extractants	沸点/℃ boiling point	CMF得率/% CMF yield
1, 2-二氯乙烷DCE	83.5	59.2
1, 1, 1-三氯乙烷1, 1, 1-trichloroethane	74	54.4
1, 1, 2-三氯乙烷1, 1, 2-trichloroethane	114	58.9
1, 1, 2, 2-四氯乙烷1, 1, 2, 2-tetrachloroethane	146.4	30.6
1, 3-二氯丙烷1, 3-dichloropropane	125	57.9
1, 2, 3-三氯丙烷1, 2, 3-trichloropropane	156	60.9
1, 4-二氯丁烷1, 4-dichlorobutane	161~163	50.3
乙酸乙酯ethyl acetate	77	22.3
环己烷cyclohexane	80.7	16.5
甲基异丁基酮MIBK	115.8	26.5
氯苯chlorobenzene	132	14.7
二甲苯xylenes	137~140	35.7

萃取剂 extractants	竹浆/g bamboo pulp	底物质量分数/% substrate mass fraction	底物质量浓度/(g·mL^-1) substrate mass concentration	CMF质量/g m_CMF	CMF得率/% CMF yield
1, 1, 2-三氯乙烷 1, 1, 2-trichloroethane	1	5.72	8.28	0.396 4	58.90
	2	11.46	16.56	0.609 6	36.20
	2*	11.46	16.56	0.170 5	10.10
1, 2, 3-三氯丙烷	1	5.73	8.28	0.410 1	60.90
1, 2, 3-trichloropropane	2	11.46	16.56	0.433 3	32.20

预处理方法¹⁾ pretreatment method	CMF质量/g m_CMF	CMF得率/% CMF yield
无none	0.101 1	26.8
无none(140 ℃)	0.139 4	34.3
5% NaOH	0.170 2	30.5
10% NaOH	0.220 2	41.6
10% CaO	0.167 7	33.4
NaHSO₃	0.345 1	52.5
CAOSA	0.422 0	56.0

Conversion of Bamboo Pulp to 5-Chloromethylfurfural in a Diluted HCl-chloride System

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 11

References 19

Related Articles 15

Recommended Articles

Metrics

Comments

底物 substrate	底物质量浓度/(g·mL^-1) substrate mass concentration	反应条件reaction conditions		CMF质量/g m_CMF	CMF得率/% CMF yield
底物 substrate	底物质量浓度/(g·mL^-1) substrate mass concentration	温度temp./℃	时间time/h	CMF质量/g m_CMF	CMF得率/% CMF yield
竹浆bamboo pulp	9.93	130	1	5.81	57.4
竹浆bamboo pulp	16.6	120	1	8.72	51.8
纤维素粉cellulose powder	22.5	130	1	13.84	38.5

放置时间/d duration time	处理方法 treatment method	样品1 sample 1		样品2 sample 2		CMF浓度变化/% CMF concentration change
放置时间/d duration time	处理方法 treatment method	c_CMF/ (mg·g^-1)	质量分数/% mass fraction	c_CMF/ (mg·g^-1)	质量分数/% mass fraction	CMF浓度变化/% CMF concentration change
1		4.417		5.247
4	未处理untreated	4.428	0.26	5.432	3.52	1.89
4	除酸、除水acid and water removed	4.335	-1.85	5.356	2.08	0.12
12	未处理untreated	4.322	-2.15	5.275	0.53	-0.81
12	除酸、除水acid and water removed	4.428	0.24	5.413	3.16	1.70

[1]	BI Hongyan, LI Tianya, WANG Zhibo, WANG Qidong, CAO Hongyun, ZHANG Qinqin. Progress on Platform Chemicals Synthesis of Levulinates [J]. Biomass Chemical Engineering, 2023, 57(5): 61-70.
[2]	LIU Yun, LU Yi, ZHANG Yuan, YI Zechuan, YAO Xin. Research Progress on Migration and Transformation of Alkali and Alkaline Earth Metals in Biomass Gasification [J]. Biomass Chemical Engineering, 2023, 57(5): 71-78.
[3]	Hengtao GUO, Xuetao WANG, Lili XING, Haojie LI, Haoshan ZHAI. Research Advance in Biomass Steam Catalytic Reforming for Hydrogen Production [J]. Biomass Chemical Engineering, 2023, 57(4): 60-70.
[4]	Zhenglong XUE, Guanhua WANG, Hao SUN, Yunli ZHAO, Chuanling SI, Hongyu JIA. Research Status and Development Trend of Bio-based Dust Suppressants [J]. Biomass Chemical Engineering, 2023, 57(2): 62-70.
[5]	Mengjie CAI, Jun RAO, Yajie HU, Dan SUN, Feng PENG. Research Progress on Hydrothermal Synthesisand and Application of Biomass Porous Carbon Materials [J]. Biomass Chemical Engineering, 2023, 57(2): 79-88.
[6]	Jianhua WANG, Sisi ZHANG, Yuting ZHUANG, Qiong XU, Dulin YIN. Research Progress on Heterogenous Catalytic Conversion of Furfural to γ-Valerolactone by One-pot Reaction [J]. Biomass Chemical Engineering, 2023, 57(1): 62-72.
[7]	Qin CHENG, Ziyang WU, Yan MA, Jun YE, Weihong TAN. Research Progress on Hydrothermal Liquefaction of Lignocellulosic Fiber [J]. Biomass Chemical Engineering, 2023, 57(1): 84-98.
[8]	Xinyue GAO, Shizhen YUAN, Junjie WENG, Pengbo ZHAO, Chang'an WANG, Defu CHE. Research Progress of NO_x Control Technology in Biomass-fired Boiler [J]. Biomass Chemical Engineering, 2022, 56(6): 51-60.
[9]	Tianhe WANG, Lin LIN, Jing LIU, Qiang ZHANG, Wenbiao XU, Junyou SHI. Research Progress of Heteroatom-doped Biomass-based Carbon Materials [J]. Biomass Chemical Engineering, 2022, 56(6): 71-80.
[10]	Biao MA, Ru LI. Evaluation and Product Analysis of Large-scale Continuous Biomass Carbonization Equipment [J]. Biomass Chemical Engineering, 2022, 56(5): 43-50.
[11]	Lei WANG, Xinyuan BI, Fei YE, Yibei LIU, Min WU, Peng LU. Research Progress of Biomass-based Porous Materials on Thermal Insulation Materials [J]. Biomass Chemical Engineering, 2022, 56(4): 58-66.
[12]	Haohan JIANG, Shuangming LI, Sansan YU. Research Progress on Lignin Depolymerization and Liquid Phase Catalytic Degradation [J]. Biomass Chemical Engineering, 2022, 56(4): 67-76.
[13]	Jurong REN, Yunhong SU, Hao YING, Yunjuan SUN, Wei XU, Hang YIN. Research Progress of Biomass Gasification for Hydrogen-rich Syngas [J]. Biomass Chemical Engineering, 2022, 56(3): 39-46.
[14]	Hao SUN, Yunjuan SUN, Mingzhe MA, Kang SUN, Jianchun JIANG. Development Trend and Strategic Countermeasures of Forestry Resources Gasification, Heat Supply and Power Generation Industry [J]. Biomass Chemical Engineering, 2022, 56(2): 40-48.
[15]	Haodong FAN, Dongwang ZHANG, Bin ZHAO, Man ZHANG, Yan JIN. Summary of Corrosion Characteristics and Inhibition Methods of Biomass Fluidized Bed [J]. Biomass Chemical Engineering, 2022, 56(1): 30-36.