分子筛固载化三氯化铁的制备及催化性能研究

摘要/Abstract

摘要：

采用萘与异丙醇的烷基化合成路线,考察了改性分子筛的催化性能以及反应条件对异丙基化反应的影响。以分子筛为载体,采用离子交换法制备了固载FeCl₃的HM（H-SAPO-11、HZSM-5）分子筛催化剂,采用XRD、扫描电镜/X射线能谱仪（SEM/EDS）、BET、FT-IR对催化剂做了表征;在微分反应器上考察了改性分子筛的催化性能和反应条件对萘异丙基化反应的影响。当FeCl₃在HM上的固载量（质量分数,下同）从10%增至50%时,萘的转化率也随之增大。对50%Fe/HM分子筛催化剂,在原料配比为n（萘）∶n（异丙醇）∶n（环己烷）=1∶2∶10、催化剂质量为2 g、质量空速为1 h^-1、反应温度为280 ℃的条件下,萘转化率为61.4%,2,6-DIPN的收率为38.4%,β,β-DIPN选择性为84.6%。

关键词: 沸石分子筛, FeCl₃, 异丙基化, 微分反应器

Abstract:

The alkylation route of naphthalene and isopropanol was used to investigate the effects of catalytic performance and reaction conditions of the modified molecular sieve on the isopropylation reaction.Using molecular sieve as carrier,HM(H-SAPO-11 and HZSM-5) zeolite catalysts supported on FeCl₃ were prepared by ion exchange method.The above catalysts were characterized by means of X-ray diffraction（XRD）,scanning electron microscope/energy dispersion spectrometer (SEM/EDS）,Brunauer-Emmett-Teller（BET）,Fourier transform infrared spectroscopy（FT-IR）.The effects of catalytic properties and reaction conditions of modified molecular sieve on isopropylation of naphthalene were carried out with fixed-bed flow microreactor.The conversion of naphthalene increased substantially with the increase of FeCl₃ on HM loading from 10% to 50%(mass fraction).The ratio of raw materials was[n(naphthalene)∶n(isopropanol)∶n(cyclohexane)=1∶2∶10],the mass of the catalyst was 2 g,the mass space velocity was 1 h^-1,and the reaction temperature was 280 ℃. Under the conditions,for the 50% Fe/HM,the conversion of naphthalene reached 61.4%,the yield of 2,6-DIPN was 38.4% and the selectivity of β,β-DIPN was 84.6%.

Key words: molecular sieves, ferric chloride, isopropylation, fixed-bed flow microreactor

中图分类号:

TQ138.11

刘希东. 分子筛固载化三氯化铁的制备及催化性能研究[J]. 无机盐工业, 2019, 51(5): 87-91.

Liu Xidong. Preparation of molecular sieves immobilized FeCl₃ and its catalytic performance[J]. Inorganic Chemicals Industry, 2019, 51(5): 87-91.

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参考文献 11

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催化剂名称	比表面积/ （m²·g^-1）	平均孔径/ nm	催化剂名称	比表面积/ （m²·g^-1）	平均孔径/ nm
HM	32.64	0.72	SAPO-11	36.86	0.62
Fe/HM10	29.17	0.71	Fe/SAP20	32.29	0.60
Fe/HM20	27.59	0.70	HZSM-5	171.45	0.56
Fe/HM50	28.86	0.71	Fe/HZSM20	169.15	0.55
Fe/HM100	26.84	0.69

催化剂	萘转化率/ %	X（IPN）/%	X（DIPN）/%	n（2,6-DIPN）/ n（DIPN）/%	n（β- IPN)/ n（α-IPN)	n（2,6- DIPN)/ n（2,7-DIPN)	n（β,β-DIPN)/ n（DIPN）/%
HM	23.2	15.3	7.2	43.0	2.80	1.51	77.2
Fe/HM10	36.9	25.5	9.6	42.7	7.80	1.15	84.1
Fe/HM20	36.0	24.4	9.0	41.7	7.70	1.13	83.7
Fe/HM50	47.6	32.2	12.5	41.9	9.10	1.11	84.2
Fe/HM100	36.4	24.3	8.8	42.5	7.30	1.16	84.6
HZSM-5	1.7	0.8	0.2	43.3	2.90	1.33	83.0
Fe/HZSM10	2.5	1.6	0.2	36.8	2.50	1.58	79.2
Fe/HZSM20	4.4	1.9	0.2	35.1	2.60	1.43	77.7
Fe/HZSM50	3.2	2.8	0.1	37.0	2.70	1.34	76.0
Fe/HZSM100	1.8	2.5	0.2	40.4	3.90	1.33	72.6
SAPO-11	7.3	1.8	0.7	42.0	2.80	1.53	71.8
Fe/SAP10	5.2	1.7	0.6	38.8	8.70	1.44	75.2
Fe/SAP20	3.7	1.6	0.6	34.6	12.50	1.15	79.5
Fe/SAP50	2.9	0.6	0.0	0.0	0.90	0.0	0.0
Fe/SAP100	1.5	0.4	0.0	0.0	0.90	0.0	0.0

质量空速/ h^-1	萘转化率/ %	X（IPN）/%	X（DIPN）/%	n（2,6-DIPN）/ n（DIPN）/%	n（β- IPN）/ n（α-IPN）	n（2,6- DIPN）/ n（2,7-DIPN）	n（β,β-DIPN）/ n（DIPN）/%
1	61.4	41.1	17.2	38.4	11.2	1.04	84.6
2	54.7	35.8	17.4	41.3	9.3	1.16	84.0
3	47.6	32.2	12.5	41.9	9.1	1.11	84.2
4	45.3	30.4	12.4	42.7	7.4	1.16	83.6
5	39.6	27.4	11.3	44.0	6.5	1.26	83.6

反应温度/ ℃	萘转化率/ %	X（IPN）/%	X（DIPN）/%	n（2,6-DIPN)/ n（DIPN）/%	n（β-IPN）/ n（α-IPN）	n（2,6- DIPN）/ n（2,7-DIPN）	n（β,β-）/ n（DIPN）/%
200	36.5	25.2	11.0	40.5	2.4	1.47	72.7
230	41.0	24.5	12.8	45.9	3.1	1.64	78.7
250	44.5	25.9	14.8	47.1	5.1	1.60	84.9
280	47.6	32.2	12.5	41.9	9.1	1.11	84.2
300	42.6	32.3	7.5	39.2	10.4	1.02	83.0

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