草酸溶液处理对SAPO-34分子筛物性和催化性能的影响

doi:10.11962/1006-4990.2019-0169

无机盐工业 ›› 2020, Vol. 52 ›› Issue (2): 84-90.doi: 10.11962/1006-4990.2019-0169

草酸溶液处理对SAPO-34分子筛物性和催化性能的影响

邵武俊,刘春燕,贺宁,郭洪臣()

大连理工大学化工学院,催化化学与工程系精细化工国家重点实验室,辽宁大连 116023

收稿日期:2019-08-29 出版日期:2020-02-10 发布日期:2020-02-26
作者简介:邵武俊（1992— ）,男,硕士研究生;E-mail：shaowujun@mail.dlut.edu.cn。

Effect of oxalic acid solution treatment on physiochemical properties and catalytic performance of SAPO-34 molecular sieve

Shao Wujun,Liu Chunyan,He Ning,Guo Hongchen()

State Key Laboratory of Fine Chemicals,Department of Catalytic Chemistry and Engineering,Dalian University of Technology,Dalian 116023,China

Received:2019-08-29 Published:2020-02-10 Online:2020-02-26

摘要/Abstract

摘要：

用XRD、SEM、N₂物理吸附、XRF、ICP-AES以及NH₃-TPD、FT-IR、固体NMR和固定床甲醇制烯烃技术（MTO）反应评价等表征手段,研究了草酸溶液处理对SAPO-34分子筛的改性作用。结果表明,用草酸溶液对SAPO-34分子筛进行后处理可以通过刻蚀骨架在晶体中产生大孔,调变孔道结构,改善微孔扩散性能;选择性地降低分子筛的骨架硅含量,从而降低分子筛的酸强度和酸中心密度。将改性前后的分子筛应用于MTO反应中。评价结果表明,适度的酸处理能够在保证分子筛收率和乙烯、丙烯选择性的前提下,明显提高催化剂的单程寿命。草酸溶液处理是一种值得研究的SAPO-34分子筛后处理改性方法和MTO催化剂制备手段。

关键词: SAPO-34分子筛, 草酸溶液处理, MTO反应

Abstract:

The modification effect of oxalic acid solution treatment on SAPO-34 molecular sieve was studied by means of XRD,SEM,N₂ physisorption,XRF,ICP-AES,NH₃-TPD,FT-IR,solid NMR and fixed-bed methanol to olefins（MTO） reaction performance evaluation.Results showed that,treating SAPO-34 molecular sieve with oxalic acid solution can produce macropores in the crystalsvia skeleton etching,and consequently adjust the pore structure and micropore diffusivity.Meanwhile,the acid treatment can also selectively reduce the framework Si content,and consequently decrease the acid strength and surface acid site concentrationof SAPO-34 molecular sieve.These modification effects of the oxalic acid solution treatment can notably improve the anti-coking deactivation ability of SAPO-34 catalyst in MTO reaction.Therefore,the oxalic acid solution treatment is a method worth studying for the modification of SAPO-34 molecular sieve and the preparation of MTO catalyst.

Key words: SAPO-34 molecular sieve, oxalic acid solution treatment, MTO reaction

中图分类号:

TQ223.121

邵武俊,刘春燕,贺宁,郭洪臣. 草酸溶液处理对SAPO-34分子筛物性和催化性能的影响[J]. 无机盐工业, 2020, 52(2): 84-90.

Shao Wujun,Liu Chunyan,He Ning,Guo Hongchen. Effect of oxalic acid solution treatment on physiochemical properties and catalytic performance of SAPO-34 molecular sieve[J]. Inorganic Chemicals Industry, 2020, 52(2): 84-90.

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参考文献 12

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样品	物质的量组成	n（P）/ n（Al）	n（Si）/ n（Al）	n（Si）/ n（P）	收率/ %
sp34	Al_0.491P_0.459Si_0.050	0.935	0.102	0.109	—
sp34-c-0.01	Al_0.496P_0.457Si_0.047	0.921	0.095	0.103	95
sp34-c-0.03	Al_0.494P_0.459Si_0.047	0.929	0.096	0.102	89
sp34-c-0.05	Al_0.500P_0.455Si_0.045	0.910	0.090	0.099	83
sp34-c-0.07	Al_0.501P_0.456Si_0.043	0.910	0.086	0.094	76
sp34-c-0.11	Al_0.503P_0.455Si_0.042	0.905	0.083	0.092	59
sp34-c-0.15	Al_0.505P_0.455Si_0.040	0.901	0.078	0.088	43

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
sp34	481	459	22	0.24	0.21	0.03
sp34-c-0.01	504	502	2	0.26	0.23	0.03
sp34-c-0.03	474	469	5	0.24	0.21	0.03
sp34-c-0.05	476	475	1	0.24	0.22	0.02
sp34-c-0.07	462	454	8	0.24	0.21	0.03
sp34-c-0.11	472	457	15	0.25	0.21	0.04
sp34-c-0.15	468	445	23	0.25	0.20	0.05

样品	寿命/min	选择性（质量分数计）/%
样品	寿命/min	CH₄	C₂H₄	C₂H₆	C₃H₆	C₃H₈	C₄+C₅+C₆	C₂⁼与C₃⁼选择性之比	C₂⁼+C₃⁼
sp34	153	2.07	54.95	0.39	30.95	0.48	10.74	1.78	85.90
sp34-c-0.01	199	2.51	55.27	0.44	30.41	0.56	10.53	1.81	85.68
sp34-c-0.05	176	2.20	55.46	0.37	30.52	0.45	10.71	1.82	85.98
sp34-c-0.11	153	2.01	53.12	0.35	32.03	0.49	11.70	1.66	85.15

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草酸溶液处理对SAPO-34分子筛物性和催化性能的影响

Effect of oxalic acid solution treatment on physiochemical properties and catalytic performance of SAPO-34 molecular sieve

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草酸溶液处理对SAPO-34分子筛物性和催化性能的影响

Effect of oxalic acid solution treatment on physiochemical properties and catalytic performance of SAPO-34 molecular sieve

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