多级孔纳米SAPO-34分子筛制备及甲醇制烯烃性能研究

doi:10.19964/j.issn.1006-4990.2023-0183

Abstract

Abstract:

In order to shorten the crystallization time of SAPO-34 molecular sieve at high temperature and improve its life and selectivity in MTO reaction，triethylamine and tetraethyl ammonium hydroxide were used as double templates to rapidly prepare nano-sized SAPO-34 molecular sieve with a particle size of 300~500 nm by step crystallization method.At the same time，the surfactant cetyltrimethyl ammonium bromide（CTAB） was added to further modify the molecular sieve，and the multiporous SAPO-34 molecular sieve（C-ST1T2） was obtained.The physicochemical properties of all the samples were characterized and applied to the catalytic reaction of methanol to olefin.The catalytic performance under certain conditions was investigated.The characterization results showed that the crystallization time of nano-sized SAPO-34 molecular sieve could be shortened by step crystallization.After modification by CTAB，SAPO-34 molecular sieve with multistage pore structure and moderate acid strength was obtained.The catalytic performance test showed that the methanol conversion rate of C-ST1T2 could reach 100%，and the catalytic life could reach 690 min，which was significantly improved compared with the molecular sieve synthesized by single template agent.Meanwhile，the selectivity of low carbon olefin was stable at more than 89%.The results showed that the multistage pore modification of molecular sieve using CTAB was beneficial to further improve the MTO reaction performance of molecular sieve.

Key words: SAPO-34, nano molecular sieves, step-by-step crystallization, MTO reaction

CLC Number:

O643.3

CHEN Xu, YANG Gang, LI Haitao. Study on preparation of multistage pore nano-SAPO-34 molecular sieves and its methanol to olefin performance[J]. Inorganic Chemicals Industry, 2024, 56(1): 134-140.

Figures/Tables 10

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References 22

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样品	BET比表面积/（m²·g^–1）			孔容/（cm³·g^–1）
样品	S_BET	S_micro	S_ext	V_total	V_micro	V_meso
ST1	427.10	350.66	76.44	0.30	0.18	0.12
ST2	455.77	413.70	42.07	0.25	0.21	0.04
ST1T2	480.47	460.08	20.39	0.25	0.24	0.01
C-ST1T2	458.33	345.94	112.39	0.37	0.19	0.18

样品	XRF元素分析/%
样品	w（Al）	w（Si）	w（P）
ST1	21.93	5.68	18.81
ST2	25.08	3.44	18.43
ST1T2	21.58	5.20	20.47
C-ST1T2	21.89	4.44	20.52

样品	弱酸量（110~130 ℃）/%	强酸量（250~270 ℃）/%
ST1	2.87	97.13
ST2	1.63	98.37
ST1T2	2.23	97.77
C-ST1T2	5.01	94.99

样品	反应时间/min	产品选择性^*/%				甲醇转化率/%
样品	反应时间/min	C₂⁼	C₃⁼	C₄⁺	C₂⁼+C₃⁼	甲醇转化率/%
ST1	240	50.8	35.8	13.4	86.6	100
ST2	400	52.2	38.3	9.5	90.5	100
ST1T2	570	50.1	39.0	10.9	89.1	100
C-ST1T2	690	59.1	30.7	10.2	89.8	100

[1]	JI Chao,WU Luming,LI Bin,ZANG Jiazhong,YU Haibin. Research progress on modification of SAPO-34 as catalyst for methanol to olefins [J]. Inorganic Chemicals Industry, 2022, 54(7): 1-9.
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[3]	SHI Kai,ZHAO Xu,ZHANG Hongzhi,REN Yixuan,LI Xiaofeng. Study on synthesis of SAPO-34 molecular sieve by silicon-modified pseudo-boehmite [J]. Inorganic Chemicals Industry, 2022, 54(10): 149-154.
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[5]	ZHANG Yao-Ri, PEI Ren-Yan, HUO Zhi-Ping, YU Hai-Bin. Ionothermal synthesis of SAPO-34 molecular sieves in-situ on kaolin microspheres [J]. INORGANICCHEMICALSINDUSTRY, 2015, 47(4): 75-.

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Inorganic Acid-Base-Salt Committee of CIESC

Study on preparation of multistage pore nano-SAPO-34 molecular sieves and its methanol to olefin performance

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