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

摘要/Abstract

摘要：

5-氯甲基糠醛(CMF)是近年来受到广泛关注的生物质基平台化合物。传统CMF制备在浓盐酸体系中进行, 浓盐酸的高腐蚀性对其放大生产带来了挑战。为解决此问题, 构建了一种基于酸性CaCl₂溶液的反应系统, 研究了反应条件、物料浓度等参数对竹浆在该体系中制备CMF的影响, 研究结果表明: 水相中饱和或者近饱和的氯离子可有效抑制CMF水解为HMF从而提高体系中CMF的稳定性, 减少了酸性条件下不稳定中间产物HMF向腐殖质的转化; CaCl₂在体系中具有极佳的催化性能, 取得了最高59.2%的CMF产率, 1, 1, 2-三氯乙烷、1, 3-二氯丙烷、1, 2, 3-三氯丙烷等较高沸点溶剂均具有取代萃取剂1, 2-二氯乙烷(DCE)的潜力。实验进一步研究了竹浆原料的不同预处理条件对其制备的CMF产率的影响, 结果表明: 水解氯代反应较优工艺即竹浆初始质量浓度16 g/mL, 8 g H₂O, 1.33 mol/L HCl, 5.33~6.66 mol/L CaCl₂, 25 mL DCE, 反应温度130 ℃, 反应时间1 h, 此条件下CMF得率为59.2%。NaHSO₃或固体碱活性氧蒸者(CAOSA)处理所得竹浆更适于制备CMF。稀酸氯盐水相循环性能的实验结果表明: 通过补充一定量的盐酸可使本体系具有循环使用能力。对竹浆制备CMF的反应进行15倍放大实验, 取得了51.8%的CMF产率, CMF粗产品在DCE溶液中具有良好的稳定性, 经过4~12 d存放没有明显变质。

关键词: 生物质, 竹浆, 氯化钙, 5-氯甲基糠醛

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

中图分类号:

TQ35

农贵彤, 郝唯唯, 李铮, 唐兴, 周宏才, 林鹿. 稀酸氯盐体系转化竹浆制备5-氯甲基糠醛的研究[J]. 生物质化学工程, 2023, 57(5): 8-16.

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.

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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