Oligomerization of Biomass Cracking Gas to Gasoline Distillates over Amorphous Silica-alumina†

doi:10.7503/cjcu20160309

Abstract

Abstract:

The oligomerization performances of biomass cracking gas over amorphous silica-alumina(ASA) were investigated in a fixed bed in the region of 100—320 ℃ and 2.0—4.0 MPa. NH₃-TPD, Py-IR, TG, SEM, BET and XRD were used to characterize the surface structures, acidity properties and carbon deposition of catalysts. The results showed that there were different degrees of acid amount loss and carbon deposition for ASA during oligomerization under different reaction conditions. The loss of Lewis acid amount decreased gra-dually with increasing temperature, and reached the minimum at 280 ℃, and then begun to increase with continual increase of temperature. The increase of pressure is beneficial to reduce the Lewis acid loss. The change trend of carbon deposition was consistent with that of Lewis acid loss. During oligomerization, the conversion of light olefins and yield of gasoline range products increased gradually with the increase of temperature and pressure, and reached the maximum at 4.0 MPa and 280 ℃. The conversions of ethylene, propylene and butylene reached 19.2%, 37.3% and 58.7%, respectively. The yield of gasoline range product reached 22.9%(molar fraction), and the selectivity of C⁵⁺olefins reached 73.5%.

Key words: Biomass cracking gas, Riched light olefin, Olefins oligomerization, Amorphous silica-alumina, Fixed-bed reactor

CLC Number:

O643

TrendMD:

ZHANG Qian, DING Mingyue, ZHANG Yulan, LI Yuping, WANG Chenguang, WANG Tiejun, MA Longlong. Oligomerization of Biomass Cracking Gas to Gasoline Distillates over Amorphous Silica-alumina^†[J]. Chem. J. Chinese Universities, 2016, 37(11): 2060.

Figures/Tables 15

Fig.1 Schematic diagram of the catalytic reactor system for the oligomerization of olefin-rich biomass syngas

Table 1 Reaction conditions for ASA catalysis oligomerization of olefin-rich biomass syngas*

Run No.	t/℃	p/MPa
R1	100	4.0
R2	200	4.0
R3	240	4.0
R4	280	4.0
R5	320	4.0
R6	280	2.0
R7	280	3.0

Fig.2 SEM images of the ASA with different magnifications

Table 2 Physical and chemical characteristics of ASA before and after different reactions

Catalyst	S_BET/ (m²·g^-1)	Average pore diameter/nm	Pore volume/ (cm³·g^-1)
ASA(Fresh)	467.2	4.33	0.73
ASA-R1	279.9	4.31	0.37
ASA-R2	330.8	3.83	0.43
ASA-R3	307.4	3.81	0.44
ASA-R4	320.9	4.32	0.49
ASA-R5	249.1	3.81	0.35
ASA-R6	361.1	4.29	0.55
ASA-R7	335.1	4.32	0.52

Fig.3 XRD patterns of ASA before and after different reactionsa. ASA-fresh; b. ASA-R1; c. ASA-R2; d. ASA-R3;e. ASA-R4; f. ASA-R5; g. ASA-R6; h. ASA-R7.

Fig.4 NH3-TPD profiles of the ASA catalyst

Table 3 NH3-TPD data of ASA catalyst

Sample	Acid amount/(μmol·g^-1)			T-peak/℃
Sample	Weak acid	Strong acid	Total acid	LT-peak	HT-peak
ASA	77.29	530.34	607.63	230	500

Fig.5 IR spectra of ASA under different conditions a. ASA-fresh; b. ASA-R1; c. ASA-R2; d. ASA-R3; e. ASA-R4; f. ASA-R5; g. ASA-R6; h. ASA-R7.

Table 4 Py-IR data of ASA catalyst

Catalyst	Content of Brönsted acid/ (mmol·g^-1)	Content of Lewis acid/ (mmol·g^-1)	Catalyst	Content of Brönsted acid/ (mmol·g^-1)	Content of Lewis acid/ (mmol·g^-1)
ASA-fresh	0.0304	0.1047	ASA-R4	0.0168	0.0536
ASA-R1	0.0212	0.0612	ASA-R5	0.0244	0.0345
ASA-R2	0.0156	0.0429	ASA-R6	0.0227	0.0478
ASA-R3	0.0199	0.0510	ASA-R7	0.0234	0.0418

Fig.6 TG(A) and DTG(B) analysis curves of catalyst deposited with carbona. ASA-fresh; b. ASA-R1; c. ASA-R2; d. ASA-R3; e. ASA-R4; f. ASA-R5; g. ASA-R6; h. ASA-R7.

Fig.7 TG coke mass loss ratio(histogram) and the loss of mesopore volume ratio(●), loss of Lewis acid site ratio(▲) in different reaction conditions

Fig.8 Carbon conversion of olefin oligomerization under different reaction conditions a. C2H4; b. C3H6; c. C4H8. (A) 4.0 MPa, 100—320 ℃; (B) 2.0—4.0 MPa, 280 ℃.

Fig.9 Effects of reaction temperature on space-time yield(A) and product distribution(B) of olefin oligomerization with 4.0 MPa

Run No.	Carbon yield of liquid(%)	Product distribution(%, mass fraction)
Run No.	Carbon yield of liquid(%)	C₅	C₆	C₇	C₈	C₉	C₁₀	$C 11 +$
R1	2.14	1.30	0.99	39.81	1.08	1.27	51.56	3.99
R2	7.94	5.03	8.61	47.99	7.96	4.09	22.20	4.12
R3	17.56	5.07	13.89	49.92	12.33	4.71	12.23	1.86
R4	22.91	4.21	16.17	56.12	13.46	1.41	6.80	1.83
R5	20.16	5.73	18.65	55.61	8.61	4.46	4.47	2.17

Run No.	Carbon yield of liquid(%)	Product distribution(%, mass fraction)
Run No.	Carbon yield of liquid(%)	C₅	C₆	C₇	C₈	C₉	C₁₀	$C 11 +$
R1	2.14	1.30	0.99	39.81	1.08	1.27	51.56	3.99
R2	7.94	5.03	8.61	47.99	7.96	4.09	22.20	4.12
R3	17.56	5.07	13.89	49.92	12.33	4.71	12.23	1.86
R4	22.91	4.21	16.17	56.12	13.46	1.41	6.80	1.83
R5	20.16	5.73	18.65	55.61	8.61	4.46	4.47	2.17

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