Progress on solketal synthesis catalyzed by porous materials

doi:10.16085/j.issn.1000-6613.2022-0759

Abstract

Abstract:

Solketal is an emerging derivative in biodiesel industry with high value added, which can be used as high-performance plasticizer and gasoline and diesel enhancer. Solketal exhibits several advantages such as low toxicity and degradability. However, efficient and green synthesis of solketal is still a major challenge. The reaction mechanism of acetone to glycerol and the catalyst structure-activity relationship have been critically reviewed. The reaction mechanism of glycerol acetalization mainly includes BAS, LAS, BAS-LAS synergistic and base-acid synergism. Regulation methods of catalysts involves loading metal oxides on the porous materials, treating catalysts with acids/salts and surfactant. Studying the inhibition of catalyst deactivation due to hydration polarization is necessary to improve the anti-salt and anti-impurity ability of catalysts in the future, which could provide ideas for the development of low-carbon green synthesis process of acetone glycerol and its derivatives in the future.

Key words: catalysis, catalyst, biodiesel, solketal, porous materials

摘要：

丙酮缩甘油是生物柴油行业新兴的高附加值衍生物，可以用作高性能增塑剂和汽柴油增强剂，具有低毒和可降解等诸多优点。如何高效实现丙酮缩甘油的高效和绿色合成一直是本行业需要解决的重大关键难题。本文从反应合成机理和多孔材料催化剂表面理化性质调控两个角度，详细分析了丙酮缩甘油反应过程机理和催化剂构效关系研究进展，生成丙酮缩甘油的反应机理主要包括BAS、LAS、BAS-LAS协同和酸碱协同催化反应机理，催化剂性能调控方法主要为负载金属氧化物、酸/盐改性和表面活性剂处理。未来该领域仍须在抑制催化剂水合极化失活方面进一步研究，提高催化剂抗盐抗杂性能，为未来丙酮缩甘油及其衍生物的低碳绿色合成工艺开发提供思路。

关键词: 催化, 催化剂, 生物柴油, 丙酮缩甘油, 多孔材料

CLC Number:

TQ152

JIN Xin, LI Yushan, XIE Qingqing, WANG Mengyu, XIA Xingfan, YANG Chaohe. Progress on solketal synthesis catalyzed by porous materials[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 731-743.

金鑫, 李玉姗, 解青青, 王梦雨, 夏星帆, 杨朝合. 多孔材料催化丙酮缩甘油合成研究进展[J]. 化工进展, 2023, 42(2): 731-743.

Figures/Tables 17

反应温度（Si/Al=90）/℃	初始反应速率/Con^1/2·min^-1	反应级数	Si/Al比（25℃下）	初始反应速率/Con^1/2·min^-1	反应级数
25	0.7415	1/2	30	0.6320	1/2
50	4.436 $\times$ 10³	-2.5	90	0.7415	1/2
60	1.3256 $\times$ 10²	-1.3	160	0.6500	1/2

反应温度（Si/Al=90）/℃	初始反应速率/Con^1/2·min^-1	反应级数	Si/Al比（25℃下）	初始反应速率/Con^1/2·min^-1	反应级数
25	0.7415	1/2	30	0.6320	1/2
50	4.436 $\times$ 10³	-2.5	90	0.7415	1/2
60	1.3256 $\times$ 10²	-1.3	160	0.6500	1/2

分子筛	初始反应速率/Con^1/2·min^-1	反应级数
MCM-41	0.5766	0.1
磺化MCM-41	3.9 $\times$ 10²	-1

分子筛	初始反应速率/Con^1/2·min^-1	反应级数
MCM-41	0.5766	0.1
磺化MCM-41	3.9 $\times$ 10²	-1

PL速率方程	ER速率方程	LHHW速率方程
PL1　 $r = k_{1} \cdot C_{c a t} \cdot C_{G l y} \cdot C_{A c} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}$	ER1　 $r = \frac{k_{1} \cdot C_{c a t} \cdot C_{G l y} \cdot C_{A c} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{1 + k_{w} \cdot C_{w}}$	LHHW1　 $r = \frac{k_{1} \cdot C_{c a t} \cdot C_{G l y} \cdot C_{A c} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{(1 + k_{w} \cdot C_{w})^{2}}$
PL2　 $r = k_{1} \cdot C_{c a t} \cdot C_{G l y} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}$	ER2　 $r = \frac{k_{1} \cdot C_{c a t} \cdot C_{G l y} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{1 + k_{w} \cdot C_{w}}$	LHHW2　 $r = \frac{k_{1} \cdot C_{c a t} \cdot C_{G l y} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{(1 + k_{w} \cdot C_{w})^{2}}$
PL3　 $r = k_{1} \cdot C_{c a t} \cdot C_{A c} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}$	ER3　 $r = \frac{k_{1} \cdot C_{c a t} \cdot C_{A c} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{1 + k_{w} \cdot C_{w}}$	LHHW3　 $r = \frac{k_{1} \cdot C_{c a t} \cdot C_{A c} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{(1 + k_{w} \cdot C_{w})^{2}}$
PL4　 $r = k_{1} \cdot C_{c a t} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}$	ER4　 $r = \frac{k_{1} \cdot C_{c a t} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{1 + k_{w} \cdot C_{w}}$	LHHW4　 $r = \frac{k_{1} \cdot C_{c a t} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{(1 + k_{w} \cdot C_{w})^{2}}$

PL速率方程	ER速率方程	LHHW速率方程
PL1　 $r = k_{1} \cdot C_{c a t} \cdot C_{G l y} \cdot C_{A c} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}$	ER1　 $r = \frac{k_{1} \cdot C_{c a t} \cdot C_{G l y} \cdot C_{A c} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{1 + k_{w} \cdot C_{w}}$	LHHW1　 $r = \frac{k_{1} \cdot C_{c a t} \cdot C_{G l y} \cdot C_{A c} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{(1 + k_{w} \cdot C_{w})^{2}}$
PL2　 $r = k_{1} \cdot C_{c a t} \cdot C_{G l y} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}$	ER2　 $r = \frac{k_{1} \cdot C_{c a t} \cdot C_{G l y} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{1 + k_{w} \cdot C_{w}}$	LHHW2　 $r = \frac{k_{1} \cdot C_{c a t} \cdot C_{G l y} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{(1 + k_{w} \cdot C_{w})^{2}}$
PL3　 $r = k_{1} \cdot C_{c a t} \cdot C_{A c} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}$	ER3　 $r = \frac{k_{1} \cdot C_{c a t} \cdot C_{A c} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{1 + k_{w} \cdot C_{w}}$	LHHW3　 $r = \frac{k_{1} \cdot C_{c a t} \cdot C_{A c} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{(1 + k_{w} \cdot C_{w})^{2}}$
PL4　 $r = k_{1} \cdot C_{c a t} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}$	ER4　 $r = \frac{k_{1} \cdot C_{c a t} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{1 + k_{w} \cdot C_{w}}$	LHHW4　 $r = \frac{k_{1} \cdot C_{c a t} - k_{2} \cdot C_{c a t} \cdot C_{s k} \cdot C_{w}}{(1 + k_{w} \cdot C_{w})^{2}}$

催化剂	温度/℃	溶剂	转化率/%	选择性/%	参考文献
OTS-HY	30	—	89	95	[30]
HUSY-W₂₀	40	—	100	97.87	[19]
Sil-F	70	—	65.8	63.9	[11]
5%V-Si-ITQ-6	60	—	100	99	[21]
HUSY-Nb₅	40	—	66	98	[31]
MIL-100-V	70	5mL乙腈	85.4	97.7	[16]
MIL-100-Al	70	5mL乙腈	44.2	94.3	[16]
MIL-100-Fe	70	5mL乙腈	19.5	86.1	[16]
MIL-100-Cr	70	5mL乙腈	4.2	77.5	[16]
Cu-Mor	RT	—	95	98	[23]
Zn-Mor	RT	—	90	81	[23]
Ni-Mor	RT	—	93	88	[23]
Co-Mor	RT	—	87	73	[23]
Fe-Mor	RT	—	88	84	[23]
MFI-CA	70	—	81	99	[40]
BEA-CA	70	—	82	99	[40]
Mor-CA	70	—	79	98	[40]
PDSA-BEA	30	—	80	100	[41]
pTSA-BEA	30	—	82	90	[41]
H-Beta	RT	—	86	98.5	[15]
Sn-TUD-1	80	10mmol叔丁醇	44	99	[38]
Zr-TUD-1	80	10mmol叔丁醇	46	99	[38]
Hf-TUD-1	80	10mmol叔丁醇	52	99	[38]
Ga-MCM-41	25	15mL乙腈	75	95	[14]
XS-Ga-MCM-41	80	1.8g叔丁醇	28	99	[33]
TFAl-MCM-41	25	15mL乙腈	97	97	[24]
OS-MCM-22	40	—	81	95	[37]
Nb-SBA-16	50	—	86	96	[32]
ZrMo-KIT-6	50	—	85.8	97.8	[18]
Nb-MCF	40	—	48	99	[39]
Ta-MCF	40	—	74	99	[39]
Mo-MCF	40	—	48	99	[39]
MP-MCF	40	—	83	99	[39]
CS-MCF	40	—	87	99	[39]
TFAl-MCM-41	30	—	92		[34]
Sn-TUD-1	80	10mmol叔丁醇	44	99	[38]
Zr-TUD-1	80	10mmol叔丁醇	46	99	[38]
Hf-TUD-1	80	10mmol叔丁醇	52	99	[38]
MoPO-SBA-15	RT	—	100	98	[49]
Pr-SBA-15	70	—	79	—	[42]
Ar-SBA-15	70	—	82	—	[42]
1M-MM	50	—	57	97.4	[47]
HSCS	70	—	80	98	[43]
SO₃H-Cel		—	80	95	[44]
C-HSO₃	50	—	80	99.5	[45]
5%Ni–1%Zr/AC	45	—	82	74	[35]

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