NiMoRe/HZSM-5催化剂的制备及其催化脂肪酸甲酯加氢脱氧

doi:10.3969/j.issn.0253-2417.2024.02.016

Abstract

Abstract:

A 5 kg NiMoRe/HZSM-5 catalyst was prepared by impregnation method, and the physicochemical properties of the catalyst were analyzed using characterization techniques such as X-ray diffraction(XRD), scanning electron microscopy(SEM), and inductively coupled plasma optical emission spectrometry(ICP-OES). The optimal conditions for the catalyst in the hydrogenation deoxygenation reaction of stearic acid methyl ester were explored. The research results showed that, compared to three commercial catalysts, the metal nickel in NiMoRe/HZSM-5 had smaller and more uniformly dispersed particles, a larger BET specific surface area(S_BET) of 239.1 m²/g, and exhibited better catalytic activity. Under the optimal reaction conditions of 260 ℃, catalyst dosage of 0.3 g, reaction time of 4 hours, and initial H₂ pressure of 3 MPa, both the raw material conversion rate and alkane selectivity were 100%. The catalyst demonstrated good stability, with a high raw material conversion rate of 96.1% even after the 5th cycle, and the ratio of hydrogenation deoxygenation(HDO) reaction to decarboxylation/decarbonylation(DCO) reaction decreased from 1.2 to 0.56. After scaling up the hydrogenation deoxygenation reaction of fatty acid methyl ester under solvent-free conditions using the NiMoRe/HZSM-5 catalyst, a pilot-scale evaluation was conducted on 25 kg of fatty acid methyl ester in a 2.8 L fixed bed reactor. After 15 cycles, the fatty acid methyl ester achieved a conversion rate of 98%.

Key words: fatty acid methyl ester, pilot plant test, hydrodeoxygenation, hydrocarbon based biodiesel

CLC Number:

TQ35

Xiaobo GUO, Wenduo JIANG, Wenbiao HOU, Ping ZHAO, Junming XU, Peng LIU. Preparation of NiMoRe/HZSM-5 Catalyst for Hydrodeoxygenation of Fatty Acid Methyl Ester[J]. Chemistry and Industry of Forest Products, 2024, 44(2): 119-126.

Figures/Tables 10

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催化剂 catalyst	金属元素质量分数metal mass fraction/%			S_BET/ (m²·g^-1)	V_total/ (cm³·g^-1)	D_BJH/nm
催化剂 catalyst	Ni	Mo	Re	S_BET/ (m²·g^-1)	V_total/ (cm³·g^-1)	D_BJH/nm
NiMoRe/HZSM-5	8.2	6.4	2.0	239.1	0.12	3.7
NiMo-1	26.8	6.4		130.4	0.20	12.7
NiMo-2	24.2	6.4		116.1	0.52	17.2
硫化态Ni sulfide state Ni	10.5			78.7	0.27	13.9

催化剂 catalyst	转化率/% conversion	选择性selectivity/%		S_HDO/DCO/%
催化剂 catalyst	转化率/% conversion	w_C₁₇	w_C₁₈	S_HDO/DCO/%
NiMoRe/HZSM-5	100	45.46	54.54	1.19
NiMo-1	99.98	73.65	26.35	0.32
NiMo-2	15.22	97.91	2.09	0.02
硫化态Ni sulfide state Ni	50.25	93.20	1.33	0.01

FAME用量/g FAME dosage	补氢次数 number of hydrogenation	压力/MPa press	时间/h time	C15~C18选择性/% C15-C18 selectivity	转化率/% conversion
500	1	4.5	3.0	77.98	30.38
	2	4.5	3.0
	3	6.0	3.0	85.15	99.46
	4	6.0	3.0	84.52	99.46
	5	6.0	3.0	79.46	100
1 000	1	6.0	6.0	37.56	22.42
	2	6.0	3.0	58.21	39.32
	3	6.0	6.0	55.58	71.41
	4	6.0	6.0	62.52	93.04
	5	6.0	6.0	68.92	98.59
	6	6.0	6.0	79.86	100

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Preparation of NiMoRe/HZSM-5 Catalyst for Hydrodeoxygenation of Fatty Acid Methyl Ester

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