磷改性ZSM-5分子筛对4-杂氧庚二醇水解性能研究

doi:10.19964/j.issn.1006-4990.2024-0365

Abstract

Abstract:

4-hexoheptanediol is an impurity in the production process of propylene glycol.It can be hydrolyzed to 1，3-propanediol through a catalytic hydrolysis reaction，thereby increasing the yield of propylene glycol.A phosphorus-modified ZSM-5 zeolite was prepared as a hydrolysis catalyst using the equal volume impregnation method.The structure，acidity，and the form of phosphorus in the zeolite of the catalyst samples were characterized by X-ray diffraction，³¹P solid-state NMR，and X-ray photoelectron spectroscopy respectively.The effect of phosphorus modification on its catalytic hydrolysis performance was studied through evaluation.The results showed that phosphorus modification significantly reduced the acid density of the ZSM-5 zeolite，and the trends of change for strong acid centers and weak acid centers were different.As the phosphorus content increased，the interaction between phosphorus and framework aluminum was gradually strengthened.When the phosphorus content was increased to more than 4%（mas fraction，the same below），the degree of phosphate polymerization was increased significantly.The proportion of P₂O₅ species on the surface of the ZSM-5 zeolite was firstly increased and then decreased with the increase in phosphorus loading.With the increase in phosphorus content in the ZSM-5 zeolite，the conversion rate of 4-hexoheptanediol was increased，while the selectivity of propylene glycol was firstly increased and then decreased.The optimal hydrolysis performance was achieved when the phosphorus loading was between 2% and 4%，and the phosphorus loading improved the hydrolysis stability of 4-hexoheptanediol on the ZSM-5 zeolite.

Key words: hydrolysis, ZSM-5 zeolite, phosphorus-modified, 4-hexoheptanediol

CLC Number:

TQ223.1

YANG Yuwang, LI Xiaoyun, LU Yanfei, WU Tongxu, CAI Qi, ZHOU Peng, ZHOU Jinghui, YAN Shuo, SUN Yanmin. Study on hydrolysis performance of 4-oxaheptanediol over phosphorus-modified ZSM-5 zeolite[J]. Inorganic Chemicals Industry, 2025, 57(11): 123-129.

Figures/Tables 13

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样品	w（SiO₂）/ %	w（Al₂O₃）/ %	相对结晶度/%	硅铝比
Z-P-0	85.86	14.14	93	10.30
Z-P-1	84.70	14.30	90	10.05
Z-P-2	83.99	14.01	88	10.17
Z-P-4	82.09	13.91	85	10.01
Z-P-6	80.53	13.47	79	10.15
Z-P-8	78.77	13.23	75	10.10

样品	总比表面积/ （m²·g^-1）	微孔比表面积/ （m²·g^-1）	介孔比表面积/ （m²·g^-1）	总孔体积/ （cm³·g^-1）	微孔孔体积/ （cm³·g^-1）	介孔孔体积/ （cm³·g^-1）	平均孔径/ nm
Z-P-0	236.96	110.17	126.79	0.196	0.060	0.136	3.31
Z-P-1	224.95	108.83	116.12	0.179	0.058	0.121	3.18
Z-P-2	216.91	103.72	113.19	0.168	0.056	0.112	3.11
Z-P-4	215.75	104.28	111.47	0.161	0.060	0.101	2.98
Z-P-6	206.56	103.93	102.63	0.152	0.056	0.096	2.94
Z-P-8	181.95	99.08	82.87	0.118	0.063	0.055	2.59

编号	弱酸脱附温度/℃	强酸脱附温度/℃	弱酸密度/ （mmol·g^-1）	强酸密度/ （mmol·g^-1）	总酸密度/ （mmol·g^-1）	弱酸比例/ %	强酸比例/ %
Z-P-0	189.1	395.6	0.321	0.061	0.382	84.0	16.0
Z-P-1	186.9	389.5	0.273	0.063	0.336	81.2	18.8
Z-P-2	182.7	382.8	0.266	0.065	0.331	80.4	19.6
Z-P-4	183.3	385.6	0.255	0.066	0.321	79.4	20.6
Z-P-6	184.0	383.3	0.252	0.063	0.315	80.0	20.0
Z-P-8	185.5	392.3	0.246	0.062	0.308	79.9	20.1

化学位移/10^-6	Z-P-1	Z-P-2	Z-P-4	Z-P-6	Z-P-8
0	85.8	81.1	94.3	46.4	156.4
-6	102.2	138.3	125.9	145.9	193.7
-12	256.5	250.6	294.2	306.7	455.6
-18	278.9	324.2	333.4	331.9	461.8
-24	632.6	674.1	644.5	783.6	907.7
-32	328.7	444.3	473.8	538.2	821.5
-40	81.7	103.3	128.1	179.8	196.8
-46	88.7	96.8	135.2	198.6	249.1

催化剂	4-杂氧庚二醇转化率/%	1，3-丙二醇选择性/%	1，3-丙二醇收率/%
Z-P-0	75.51	60.28	45.52
Z-P-1	82.34	62.32	51.31
Z-P-2	83.15	63.44	52.75
Z-P-4	85.63	65.56	56.14
Z-P-6	87.94	58.28	51.25
Z-P-8	89.25	52.72	47.05

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on hydrolysis performance of 4-oxaheptanediol over phosphorus-modified ZSM-5 zeolite

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