Catalytic Performance of Micro-/micro-mesoporous H-ZSM-5 Zeolites for Alkylation of Toluene with Methanol†

doi:10.7503/cjcu20170083

Abstract

Abstract:

The effects of acid or alkali treatments as well as acid-alkali treatment on the physicochemical properties and catalytic performances in the alkylation of toluene with methanol over H-ZSM-5 zeolites with different Si/Al ratios were investigated. The zeolites before and after the treatment were characterized by XRD, NH₃-TPD, BET and TEM. The results indicated that the acid and alkali treatment had the great effects on the acidity and pore structure of the zeolites, which can directly influence the catalytic activities of the zeolites. Acid treatment can greatly influence the acidity and catalytic activities of H-ZSM-5 with lower Si/Al ratios, while alkali treatment only had the great effects on H-ZSM-5 with higher Si/Al ratios. The combination of acid and alkali treatment can adjust the acidity and pore structures of the zeolites simultaneously, and then enhance the catalytic activity in the alkylation of toluene with methanol.

Key words: Acid treatment, Alkali treatment, Desilication, Mesopore, Alkylation of toluene with methanol

CLC Number:

O643

TrendMD:

ZHAO Li, YU Dongni, DAI Weili, WU Guangjun, LI Landong, GUAN Naijia. Catalytic Performance of Micro-/micro-mesoporous H-ZSM-5 Zeolites for Alkylation of Toluene with Methanol^†[J]. Chem. J. Chinese Universities, 2017, 38(10): 1834.

Figures/Tables 7

References 19

[1]	Tsai T. C., Liu S. B., Wang I., Appl. Catal. A: Gen., 1999, 181(2), 355—398
[2]	Vermeiren W., Gilson J. P., Topics in Catalysis,2009, 52(9), 1131—1161
[3]	Ahn J. H., Kolvenbach R., Al-Khattaf S. S., Jentysa A., Lercher J. A., Chem. Commun., 2013, 49(90), 10584—10586
[4]	Young L. B., Butter S. A., Kaeding W. W., J. Catal., 1982, 76(2), 418—432
[5]	Kaeding W. W., Chu C., Young L. B., Weinstein B., Butter S. A., J. Catal., 1981, 67(1), 159—174
[6]	Hibino T., Niwa M., Murakami Y., J. Catal., 1991, 128(2), 551—558
[7]	Kim J. H., Ishida A., Okajima M., Niwa. M., J. Catal., 1996, 161(1), 387—392
[8]	Serrano D. P., Pizarro P., Chem. Soc. Rev., 2013, 42(9), 4004—4035
[9]	Mikkelsen Ø., Rønning P. O., Kolboe S., Micro. Meso. Mater., 2000, 40(1), 95—113
[10]	Karger J., Freude D., Chemical Engineering & Technology,2002, 25(8), 769
[11]	Kim J. H., Kunieda T., Niwa M., J. Catal., 1998, 173(2), 433—439
[12]	Perez-Ramirez J., Christensen C. H., Egeblad K., Christensen C. H., Groene J. C., Chem. Soc. Rev., 2008, 37(11), 2530—2542
[13]	Fan W., Snyder M. A., Kumar S., Lee P. S., Yoo W. C., McCormick A. V., Lee Penn R., Stein A., Tsapatsis M., Nature Materials,2008, 7, 984—991
[14]	Madsen C., Jacobsen C. J. H.,Chem. Commun., 1999, 673—674
[15]	Jacobsen C. H. J., Madsen C., Houzvicka J., Schmidt I. Carlsson A., J. Am. Chem. Soc., 2000, 122, 7116—7117
[16]	ParkD. H., Kim S. S., Wang H., Pinnavaia T. J., Papapetrou M. C., Lappas A. A., Triantafyllidis K. S., Angew. Chem. Int. Ed., 2009, 48, 7645—7648
[17]	Groen J. C., Moulijn J. A., Pérez-Ramírez J., J. Mater. Chem., 2006, 16(22), 2121—2131
[18]	Zhang R. Z., Wang C., Xing P., Wen S. B., Wang J., Zhao L. F., Li Y. P., Chem. J. Chinese Universities,2015, 36(4), 725—732
	(张瑞珍, 王翠, 邢普, 温少波, 王剑, 赵亮富, 李玉平. 高等学校化学学报, 2015, 36(4), 725—732)
[19]	Groen J. C., Jansen J. C., Moulijn J. A., Perez-Ramırez J., J. Phys. Chem. B,2004, 108(35), 13062—13065

Catalyst	n(Si)/ n(Al)^*	S_BET/ (m²·g^-1)	S_micro/ (m²·g^-1)	S_meso/ (m²·g^-1)	S_int/ (m²·g^-1)	S_ext/ (m²·g^-1)	V_total/ (cm³·g^-1)	V_micro/ (cm³·g^-1)	V_meso/ (cm³·g^-1)
H-ZSM-5-25	12.5	292.0	194.7	97.3	238.9	53.1	0.20	0.13	0.07
DA-ZSM-5-25	40.2	391.2	265.5	125.7	323.6	67.6	0.30	0.18	0.12
DS-ZSM-5-25	7.3	336.8	222.6	114.2	260.6	76.2	0.25	0.10	0.15
DS-DA-ZSM-5-25	24.1	425.5	220.4	205.1	295.8	129.7	0.36	0.15	0.21
H-ZSM-5-47	24.0	274.9	182.3	92.6	222.1	52.8	0.22	0.12	0.10
DA-ZSM-5-47	50.6	386.2	264.8	121.4	277.1	109.1	0.32	0.17	0.15
DS-ZSM-5-47	9.3	341.1	201.9	139.2	219.1	122	0.35	0.16	0.19
DS-DA- ZSM-5-47	30.1	516.0	295.3	220.7	335.4	180.6	0.51	0.15	0.36
H-ZSM-5-148	72.8	324.4	216.3	108.1	265.7	58.7	0.24	0.15	0.09
DA-ZSM-5-148	90.4	336.5	213.2	123.3	260.9	75.6	0.28	0.17	0.11
DS-ZSM-5-148	30.5	362.6	219.2	143.4	273	89.6	0.30	0.14	0.16
DS-DA-ZSM-5-148	80.2	436.0	234.4	201.6	315.6	120.4	0.32	0.15	0.17
H-ZSM-5-220	108.5	330.5	220.3	110.2	274.4	56.1	0.24	0.14	0.10
DA-ZSM-5-220	120.3	356.9	220.2	136.7	276.9	80.0	0.27	0.16	0.11
DS-ZSM-5-220	55.4	374.5	222.2	152.3	278.8	95.7	0.31	0.15	0.16
DS-DA-ZSM-5-220	145.1	474.3	250.9	223.4	329.2	145.1	0.41	0.15	0.26

Catalyst	n(Si)/ n(Al)^*	S_BET/ (m²·g^-1)	S_micro/ (m²·g^-1)	S_meso/ (m²·g^-1)	S_int/ (m²·g^-1)	S_ext/ (m²·g^-1)	V_total/ (cm³·g^-1)	V_micro/ (cm³·g^-1)	V_meso/ (cm³·g^-1)
H-ZSM-5-25	12.5	292.0	194.7	97.3	238.9	53.1	0.20	0.13	0.07
DA-ZSM-5-25	40.2	391.2	265.5	125.7	323.6	67.6	0.30	0.18	0.12
DS-ZSM-5-25	7.3	336.8	222.6	114.2	260.6	76.2	0.25	0.10	0.15
DS-DA-ZSM-5-25	24.1	425.5	220.4	205.1	295.8	129.7	0.36	0.15	0.21
H-ZSM-5-47	24.0	274.9	182.3	92.6	222.1	52.8	0.22	0.12	0.10
DA-ZSM-5-47	50.6	386.2	264.8	121.4	277.1	109.1	0.32	0.17	0.15
DS-ZSM-5-47	9.3	341.1	201.9	139.2	219.1	122	0.35	0.16	0.19
DS-DA- ZSM-5-47	30.1	516.0	295.3	220.7	335.4	180.6	0.51	0.15	0.36
H-ZSM-5-148	72.8	324.4	216.3	108.1	265.7	58.7	0.24	0.15	0.09
DA-ZSM-5-148	90.4	336.5	213.2	123.3	260.9	75.6	0.28	0.17	0.11
DS-ZSM-5-148	30.5	362.6	219.2	143.4	273	89.6	0.30	0.14	0.16
DS-DA-ZSM-5-148	80.2	436.0	234.4	201.6	315.6	120.4	0.32	0.15	0.17
H-ZSM-5-220	108.5	330.5	220.3	110.2	274.4	56.1	0.24	0.14	0.10
DA-ZSM-5-220	120.3	356.9	220.2	136.7	276.9	80.0	0.27	0.16	0.11
DS-ZSM-5-220	55.4	374.5	222.2	152.3	278.8	95.7	0.31	0.15	0.16
DS-DA-ZSM-5-220	145.1	474.3	250.9	223.4	329.2	145.1	0.41	0.15	0.26

Catalyst	Conversion(%)	Product selectivity(%, molar fraction)
Catalyst	Conversion(%)	C1—C5	Benzene	Xylene	C9~	PX
H-ZSM-5-25	27.0	8.2	10.0	63.2	18.6	25.6
DS-ZSM-5-25	29.7	8.0	15.3	62.0	14.7	32.1
DA-ZSM-5-25	40.0	9.4	7.5	63.9	19.2	35.4
DS-DA-ZSM-5-25	41.5	93.0	6.3	62.9	21.5	33.5
H-ZSM-5-47	32.8	9.8	6.0	62.0	22.2	30.5
DS-ZSM-5-47	34.6	7.7	7.0	66.3	19.0	32.6
DA-ZSM-5-47	36.7	10.5	5.7	61.2	22.6	33.4
DS-DA-ZSM-5-47	42.2	7.8	4.4	64.7	23.1	35.1
H-ZSM-5-148	29.7	17.1	1.1	50.5	31.3	32.1
DS-ZSM-5-148	30.3	17.6	1.1	49.5	31.8	38.3
DA-ZSM-5-5-148	30.6	17.9	0.5	52.4	29.2	37.6
DS-DA-ZSM-5-148	31.0	18.7	0.1	56.1	25.1	36.2
H-ZSM-5-220	19.9	12.0	0.7	59.8	27.5	34.7
DS-ZSM-5-220	31.0	4.6	0.0	74.9	20.5	38.4
DA-ZSM-5-220	20.7	11.1	0.8	62.0	26.1	39.6
DS-DA-ZSM-5-220	28.1	5.7	0.6	71.6	22.1	37.9

Catalyst	Conversion(%)	Product selectivity(%, molar fraction)
Catalyst	Conversion(%)	C1—C5	Benzene	Xylene	C9~	PX
H-ZSM-5-25	27.0	8.2	10.0	63.2	18.6	25.6
DS-ZSM-5-25	29.7	8.0	15.3	62.0	14.7	32.1
DA-ZSM-5-25	40.0	9.4	7.5	63.9	19.2	35.4
DS-DA-ZSM-5-25	41.5	93.0	6.3	62.9	21.5	33.5
H-ZSM-5-47	32.8	9.8	6.0	62.0	22.2	30.5
DS-ZSM-5-47	34.6	7.7	7.0	66.3	19.0	32.6
DA-ZSM-5-47	36.7	10.5	5.7	61.2	22.6	33.4
DS-DA-ZSM-5-47	42.2	7.8	4.4	64.7	23.1	35.1
H-ZSM-5-148	29.7	17.1	1.1	50.5	31.3	32.1
DS-ZSM-5-148	30.3	17.6	1.1	49.5	31.8	38.3
DA-ZSM-5-5-148	30.6	17.9	0.5	52.4	29.2	37.6
DS-DA-ZSM-5-148	31.0	18.7	0.1	56.1	25.1	36.2
H-ZSM-5-220	19.9	12.0	0.7	59.8	27.5	34.7
DS-ZSM-5-220	31.0	4.6	0.0	74.9	20.5	38.4
DA-ZSM-5-220	20.7	11.1	0.8	62.0	26.1	39.6
DS-DA-ZSM-5-220	28.1	5.7	0.6	71.6	22.1	37.9