有机-无机复合型固体酸催化剂的制备及其催化甘油乙酸甲酯酯交换反应

doi:10.1016/S1872-2067(21)63811-1

催化学报 ›› 2021, Vol. 42 ›› Issue (10): 1772-1781.DOI: 10.1016/S1872-2067(21)63811-1

有机-无机复合型固体酸催化剂的制备及其催化甘油乙酸甲酯酯交换反应

姜媛媛^a, 周茹茹^a, 赵怀远^a, 叶柏镛^a, 龙奕华^b, 王正宝^b, 侯昭胤^a^,^c()

^a浙江大学化学系生物质化工教育部重点实验室, 浙江杭州310028
^b浙江大学化学工程与生物工程学院, 浙江杭州310027
^c浙江大学化学系化学前瞻技术研究中心, 浙江杭州310028

收稿日期:2021-01-29 接受日期:2021-03-12 出版日期:2021-10-18 发布日期:2021-06-20
通讯作者: 侯昭胤
作者简介:*电话/传真: (0571)88273283; 电子信箱:zyhou@zju.edu.cn
第一联系人：
^†共同第一作者.
基金资助:
国家自然科学基金(21773206);国家自然科学基金(21473155);浙江省自然科学基金(LZ12B03001)

A highly active and stable organic-inorganic combined solid acid for the transesterification of glycerol under mild conditions

Yuanyuan Jiang^a, Ruru Zhou^a, Huaiyuan Zhao^a, Boyong Ye^a, Yihua Long^b, Zhengbao Wang^b, Zhaoyin Hou^a^,^c()

^aKey Laboratory of Biomass Chemical Engineering of Ministry of Education, Department of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, China
^bZhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
^cCenter of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, China

Received:2021-01-29 Accepted:2021-03-12 Online:2021-10-18 Published:2021-06-20
Contact: Zhaoyin Hou
About author:First author contact:
^†Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21773206);National Natural Science Foundation of China(21473155);Natural Science Foundation of Zhejiang Province(LZ12B03001)

摘要/Abstract

摘要：

酸性催化剂在传统的炼化工艺和最近的生物炼制技术中均起着十分重要的作用. 相较于传统的液体酸, 固体酸催化剂由于具有易分离、可重复使用、无腐蚀性和环保等优点而引起了广泛的研究兴趣. 在过去的几十年中, 研究者们成功研制出多种不同类型的固体酸, 如沸石、杂多酸、金属氧化物和磺化的碳基材料等. 但是, 传统的固体酸仍存在一些不足, 如酸中心类型和酸强度不确定、表面酸位点分布不均以及活性位点易流失、稳定性较差等.
甘油是生物柴油生产过程中的主要副产物. 据统计, 2022年全球生物柴油的年产量将达到1410亿升, 这意味着甘油的产量也将增加. 因此, 将过剩的甘油催化转化制备高附加值产品具有重要的意义. 甘油在酸催化的作用下可以制备得到丙酮缩甘油、甘油酯、丙烯醛和甘油醚等高附加值产品. 其中, 乙酸甘油酯(包括单乙酸甘油酯(MAG)、二乙酸甘油酯(DAG)和三乙酸甘油酯)在工业中具有广泛的应用, 它们既可用于医药、食品和化妆品行业, 又可作为燃料添加剂改善生物柴油的性能. 目前乙酸甘油酯的主要合成路径为甘油与乙酸或乙酸酐酯化法, 但乙酸和乙酸酐对反应设备有腐蚀性, 限制了其在工业上的大规模应用. 乙酸甲酯是聚乙烯醇生产过程中的主要副产物, 具有来源广泛、安全、无味、易分离(沸点低)等优点, 因此, 以乙酸甲酯为乙酰化试剂与甘油进行酯交换反应制备乙酸甘油酯这一新的合成路径引起了关注. 然而固体酸催化剂在该反应中的应用鲜有文献报道.
对羟基苯磺酸(PSA)是一种有机液体强酸, 可用于缩醛化、酯化、酯交换等酸催化反应中, 但它不可分离、无法重复使用而且对环境污染严重. 因此, 本文采用一锅法, 将均相PSA固载在经硅烷偶联剂KH560改性的磷酸锆载体(K-ZrP)上, 制备得到一系列不同PSA含量的无机-有机复合型固体酸催化剂(PSA/K-ZrP-x). 通过X射线衍射、红外光谱、固体核磁共振碳谱(¹³C SSNMR)表征方法研究了催化剂的精细结构, 吡啶吸附红外(Py-IR)光谱结果表明催化剂的酸性中心主要是布朗斯特酸, 通过热重、X射线光电子能谱表征结果计算催化剂中活性组分([H⁺], S)的整体与表面含量, 结果表明PSA/K-ZrP-2中PSA的含量已饱和, 且PSA在K-ZrP载体表面分散均匀, 从而增加了表面酸位点的可接触性, 通过氮气吸脱附和扫描电镜研究了PSA/K-ZrP-x的形成过程, 线扫描元素分析表明PSA/K-ZrP-2具有蒲公英状结构. 以甘油乙酸甲酯酯交换反应为模型反应, 考察了所制备催化剂的活性, 结果表明PSA/K-ZrP-2催化剂的稳定性明显高于H₃PW₁₂O₄₀, Amberlyst-45, HBEA和HZSM-5等常见的商业化固体酸和AlCl₃, FeCl₃等路易斯酸. 在2.2%[H⁺]含量的PSA/K-ZrP-2催化剂作用下, 10 mmol甘油与100 mmol乙酸甲酯于100 ºC反应4 h, 甘油转化率可达81.3%, MAG和DAG的选择性之和达97.7%. 在反应初期(0.17 h), 该催化剂的比活性可达24028.2 mg-glycerol/g-cat/h, 且五次循环使用后活性无明显降低. 结合本文表征结果, 偶联剂KH560可增强对羟基苯磺酸和磷酸锆之间的相互作用, 从而提高催化剂的稳定性. 同时, 该催化剂在甘油与其它酯类的酯交换反应中也表现出优异的反应活性, 表明PSA/K-ZrP-2固体酸催化剂具有较好的普适性.

关键词: 固体酸, 对羟基苯磺酸, 磷酸锆, 甘油, 酯交换

Abstract:

S olid acid catalyst plays a crucial role in the petroleum refinery industry and bio-refinery technology. In this work, p-phenolsulfonic acid (PSA) was successfully grafted onto the surface of KH560-modified zirconium phosphate (K-ZrP) in a facile routine. The structure and property of this organic-inorganic combined solid acid PSA/K-ZrP-x were characterized via XRD, FTIR, ¹³C solid-state NMR, TG, N₂ adsorption-desorption, SEM, pyridine-adsorption FTIR and XPS technologies. The characterization results showed that KH560 can bond with ZrP and promote the grafting of PSA on the surface of K-ZrP via the condensation reaction between its epoxy ring and the phenolic hydroxyl group in PSA. Consequently, PSA/K-ZrP-2 exhibited excellent performance and stability in the transesterification between glycerol and methyl acetate among the tested H₃PW₁₂O₄₀, Amberlyst-45, HBEA, HZSM-5, ZrP, AlCl₃ and FeCl₃ catalysts. The calculated conversion of glycerol reached 81.3% with a 97.9% selectivity for monoacetin (MAG) and diacetin (DAG) with a 2.2% dosage of [H⁺] at 100 °C for 4 h. The highest specific activity of PSA/K-ZrP-2 reached 24028.2 mg-glycerol/g-cat/h in a short reaction time (at 0.17 h), and it could be recycled five times without obvious deactivation.

Key words: Solid acid catalyst, p-Phenolsulfonic acid, Zirconium phosphate, Glycerol, Transesterification

姜媛媛, 周茹茹, 赵怀远, 叶柏镛, 龙奕华, 王正宝, 侯昭胤. 有机-无机复合型固体酸催化剂的制备及其催化甘油乙酸甲酯酯交换反应[J]. 催化学报, 2021, 42(10): 1772-1781.

Yuanyuan Jiang, Ruru Zhou, Huaiyuan Zhao, Boyong Ye, Yihua Long, Zhengbao Wang, Zhaoyin Hou. A highly active and stable organic-inorganic combined solid acid for the transesterification of glycerol under mild conditions[J]. Chinese Journal of Catalysis, 2021, 42(10): 1772-1781.

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图/表 17

Scheme 1. Transesterification of glycerol with methyl acetate.

Scheme 2. Synthesis routine of PSA/K-ZrP-2.

Fig. 1. XRD patterns of ZrP, K-ZrP and PSA/K-ZrP-2.

Fig. 2. FTIR spectra of ZrP, K-ZrP and PSA/K-ZrP-2.

Fig. 3. 13C solid-state NMR spectrum of PSA/K-ZrP-2.

Fig. 4. Thermal analysis curves of PSA/K-ZrP-2.

Table 1 Properties of ZrP, K-ZrP and PSA/K-ZrP-x.

Sample	Surface area (m²/g)	PSA content^a (wt%)	Bulk S content^b (%)	Surface S content^c (%)	[H⁺] content^d (mmol/g_-cat)	Acid density ^e (mmol/m²)
ZrP	43.6	—	—	—	1.300 ^f	0.0298
K-ZrP	13.9	—	—	—	—	—
PSA/K-ZrP-0.2	6.3	3.1	0.4	—	0.188	0.0298
PSA/K-ZrP-1	3.8	16.2	2.2	—	0.938	0.247
PSA/K-ZrP-2	2.1	38.2	4.8	5.6	2.190	1.043
PSA/K-ZrP-3	1.7	45.2	5.3	5.4	2.594	1.526

Fig. 5. N2 adsorption-desorption isotherms of ZrP, K-ZrP and PSA/K-ZrP-2.

Fig. 6. SEM images of ZrP (a), K-ZrP (b), PSA/K-ZrP-2 (c) and line-EDS of PSA/K-ZrP-2.

Table 2 Transesterification of glycerol with methyl acetate over PSA/K-ZrP-x a.

Catalyst	Conversion (%)	Specific activity^b (mg-glycerol/g-cat/h)	Product selectivity (%)			Carbon balance ^c
Catalyst	Conversion (%)	Specific activity^b (mg-glycerol/g-cat/h)	MAG	DAG	TAG	Carbon balance ^c
ZrP	0 1.4	32.2	100	0	0	99.5
K-ZrP	0.7	16.1	100	0	0	99.5
PSA/K-ZrP-0.2	44.9	1032.7	96.1	3.9	0	99.0
PSA/K-ZrP-1	67.9	1561.7	71.8	27.3	0.9	98.5
PSA/K-ZrP-2	81.3	1869.9	63.8	34.1	2.1	98.3
PSA/K-ZrP-3	80.9	1860.7	65.8	32.5	1.7	98.0
PSA	85.4	1964.2	61.9	34.8	3.3	97.5

Table 3 Transesterification of glycerol with methyl acetate over acid catalysts a.

Catalyst	Conversion (%)	Specific activity (mg-glycerol/g-cat/h) ^b	Product selectivity (%)			Carbon balance ^c
Catalyst	Conversion (%)	Specific activity (mg-glycerol/g-cat/h) ^b	MAG	DAG	TAG	Carbon balance ^c
Amberlyst-45	86.6	1991.8	59.5	37.3	3.2	99.0
H₃PW₁₂O₄₀	82.5	1897.5	68.9	28.3	2.8	97.8
HBEA ^d	51.3	1179.9	79.1	19.9	1.0	99.3
HZSM-5 ^d	1.8	41.4	100	0	0	99.3
PSA/K-ZrP-2	81.3	1869.9	63.8	34.1	2.1	98.3
AlCl₃	40.1	922.3	92.0	7.9	0.1	98.5
FeCl₃	18.2	418.6	100	0	0	98.5

Fig. 7. Recycle usage of PSA/K-ZrP-2. Reaction conditions: 10 mmol glycerol, 100 mmol methyl acetate, initial 0.1 g catalyst, 100 °C, 0.5 h, 1 MPa N2.

Fig. 8. Transesterification of glycerol at varied temperature over PSA/K-ZrP-2. Reaction conditions: 10 mmol glycerol, 100 mmol methyl acetate, 0.1 g catalyst, 4 h, 1 MPa N2.

Fig. 9. Transesterification of glycerol with different molar ratios of methyl acetate/glycerol in feed. Reaction conditions: 10 mmol glycerol, 0.1 g catalyst, 100 °C, 4 h, 1 MPa N2.

Fig. 10. Transesterification of glycerol with methyl acetate with different dosages of PSA/K-ZrP-2. Reaction conditions: 10 mmol glycerol, 100 mmol methyl acetate, 100 °C, 4 h, 1 MPa N2.

Fig. 11. Time course of transesterification of glycerol with methyl acetate. Reaction conditions: 10 mmol glycerol, 100 mmol methyl acetate, 0.1 g catalyst, 100 °C, 1 MPa N2.

Table 4 Transesterification of glycerol with different esters over PSA/K-ZrP-2 a.

Entry	Esters	Temperature, time	Conv. (%)	Product selectivity (%)
Entry	Esters	Temperature, time	Conv. (%)	MG	DG	TG
1		100 °C, 4 h	75.6	88.5	10.5	1.0
2		100 °C, 4 h	83.3	54.0	43.0	3.0
3		100 °C, 4 h	90.2	27.4	54.9	17.6
4		120 °C, 4 h	80.5	61.3	36.7	2.0
5		120 °C, 6 h	81.9	54.5	42.3	3.2

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有机-无机复合型固体酸催化剂的制备及其催化甘油乙酸甲酯酯交换反应

A highly active and stable organic-inorganic combined solid acid for the transesterification of glycerol under mild conditions

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