Mo<sub>2</sub>N/Zr-MCM-41新型催化剂的制备、表征及其麻疯树油加氢脱氧的催化性能

谭启航; 曹阳; 李进

Mo₂N/Zr-MCM-41新型催化剂的制备、表征及其麻疯树油加氢脱氧的催化性能

谭启航¹,
曹阳^{1, 2},
李进^1, ,

1.
海南大学南海海洋资源利用国家重点实验室材料与化工学院, 海南海口 570228
2.
琼台师范学院, 海南海口 571127

基金项目:

海南省重点 ZDYF2018134

详细信息

中图分类号: O643.361
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- 被引次数: 0
出版历程
- 收稿日期: 2018-07-17
- 修回日期: 2018-09-15
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-11-10

Preparation and characterization of Mo₂N/Zr-MCM-41 catalyst and its performance in hydrodeoxygenation of Jatropha curcas oil

TAN Qi-hang¹,
CAO Yang^{1, 2},
LI Jin^{1
, ,}

1.
State Key Laboratory of Marine Resource Utilization in South China Sea, College of Materials and Chemical Engineering, Hainan University, Haikou 570228, China
2.
Qiongtai Normal University, Haikou 571127, China

Funds:

the Hainan Provincial Key Projects ZDYF2018134

More Information

Corresponding author: LI Jin, Tel:15607608499, E-mail:316800681@qq.com

摘要

摘要: 采用水热法合成载体MCM-41与不同初始n（Si）/n（Zr）的Zr-MCM-41，由（NH₄）₆Mo₇O₂₄与载体经过共浸渍、高温焙烧、氨气程序升温氮化制备了Mo₂N/Zr-MCM-41新型加氢脱氧催化剂。采用XRD、BET、XPS、TEM以及吡啶红外等手段对催化剂进行了表征，并采用高压反应釜评价了不同n（Si）/n（Zr）的Mo₂N/Zr-MCM-41催化麻疯树油加氢脱氧反应的性能。结果表明，Zr改性后的载体与纯硅MCM-41同样具有良好的孔道结构，且L酸、B酸酸值提高。Mo₂N作为活性组分体现出了优异的加氢脱氧性能，在反应温度350℃、氢气分压3.0 MPa条件下催化的产品油组成主要为直链烷烃与芳香族化合物，占产品组分的90%（质量分数）以上；不同n（Si）/n（Zr）的新型催化剂脱氧率可高达100%；芳香族化合物含量高于直链烷烃，最高可占组成的72.09%（质量分数），主要以单环、双环芳香烃为主，碳链长度分布在C_8-16；直链烷烃碳链长度分布在C_8-17。通过Mo₂N/Zr-MCM-41催化后的麻疯树油经分馏处理后可制备生物燃料。
- Mo₂N/Zr-MCM-41 /
- 加氢脱氧 /
- 麻疯树油 /
- 异构化
Abstract: MCM-41 and Zr-MCM-41 with different initial n(Si)/n(Zr) ratios were synthesized by hydrothermal method. Mo₂N/Zr-MCM-41 hydrodeoxygenation catalysts were prepared by (NH₄)₆Mo₇O₂₄ carrier co-impregnation, calaination, temperature programing and nitridation, and characterized by XRD, XPS, TEM and Py-FTIR methods. The catalytic performance of Mo₂N/Zr-MCM-41 in hydrodeoxygenation of Jatropha curcas oil was evaluated in a high pressure reactor. The results indicate that Zr modified carrier has the same pore structure as pure silicon MCM-41, and the value of L acid and B acid increases. As the active component, the Mo₂N has an excellent HDO performance. Under the reaction temperature of 350℃ and the hydrogen pressure of 3.0 MPa, the catalyzed product oil is mainly composed of straight chain alkanes and aromatic compounds, accounting for more than 90% of the product components. The deoxygenation rates of the new catalysts with different n(Si)/n(Zr) ratios are all above 98%, and the content of aromatic compounds is higher than that of straight chain alkanes, which accounts for 72.09% of the total composition. The aromatic compounds are mainly single ring and bicyclic aromatic hydrocarbons with the length of carbon chain of C_8-16. After the leprosy oils catalyzed by Mo₂N/Zr-MCM-41 are fractionated, it can be prepared to be biofuels.
- Mo₂N/Zr-MCM-41 /
- hydrodeoxygenation /
- Jatropha oil /
- isomerization

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图 1 不同Zr掺杂的Zr-MCM-41载体的XRD谱图

Figure 1 XRD patterns of Zr-MCM-41 carrier with different zirconium doping

a: 5; b: 10; c: 20; d: 40; e: 80

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图 2 Mo₂N/Zr-MCM-41的XRD谱图

Figure 2 XRD spectrum of Mo₂N/Zr-MCM-41

(a): small-angle XRD of Mo₂N/Zr-MCM-41; (b)-a: wide-angle XRD of Mo₂N/Zr-MCM-41; (b)-b: wide-angle XRD of the carrier

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图 3 Mo₂N/Zr-MCM-41催化剂的XPS谱图

Figure 3 XPS spectra of the Mo₂N/Zr-MCM-41 catalyst

(a): N 1s; (b): Mo 3d

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图 4 Mo₂N/Zr-MCM-41催化剂的TEM照片

Figure 4 TEM image of Mo₂N/Zr-MCM-41 catalyst

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图 5 产品油直链烷烃及芳香族化合物组分含量

Figure 5 Components of linear paraffins and aromatics compounds in the oil generated from HDO of Jatropha curcas oil over the Mo₂N/Zr-MCM -41 catalysts with different n(Si)/n(Zr)

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表 1 不同n(Si)/n(Zr)的Zr-MCM-41载体在150和350 ℃下的L酸和B酸值

Table 1 L acid and B acid values of Zr-MCM-41 carrier with different n(Si)/n(Zr) at 150 and 350 ℃

n(Si)/n(Zr)	Acid density at 150 ℃ /(μmol·g^-1)		Acid density at 350 ℃ /(μmol·g^-1)
n(Si)/n(Zr)	L acid	B acid	L acid	B acid
10	0.32517	0.01313	0.00533	0
20	0.03222	0.00805	0.00508	0.00207
40	0.03136	0.00726	0.00549	0
80	0.00079	0.01140	0	0
MCM-41	0.00076	0.00757	0	0

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表 2 不同n(Si)/n(Zr)催化剂所得的产品油组分含量

Table 2 Product oil component obtained by zeolites with different n(Si)/n(Zr)

n(Si)/n(Zr)	w/%
n(Si)/n(Zr)	linear paraffin	oxy-compound	isoparaffin	cycloparaffin	olefin	aromatic
10	23.22	1.13	0	0.82	2.74	72.09
20	35.71	1.74	0	0	1.92	60.63
40	47.13	0	3.42	0	0.74	48.71
80	35.16	0	5.26	0	3.03	56.55

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表 3 不同n(Si)/n(Zr)催化剂所得的产品油中饱和烷烃具体组分含量

Table 3 Saturated alkanes component in the product oil derived from different n(Si)/n(Zr) catalysts

Sample	w/%
Sample	n(Si)/n(Zr)=10	n(Si)/n(Zr)=20	n(Si)/n(Zr)=40	n(Si)/n(Zr)=80
Nonane	5.11	6.34	6.34	5.50
Decane	4.64	5.83	6.35	6.82
Undecane	4.49	5.72	5.45	5.08
Dodecane	0.60	2.19	3.42	5.53
Tridecane	2.37	3.71	4.04	4.56
Tetradecane	0.35	3.86	4.15	0
Pentadecane	2.83	3.81	8.48	2.36
Hexadecane	0.62	1.11	2.74	5.32
Heptadecane	2.21	3.13	9.56	5.50
Saturated alkanes	23.22	35.71	50.55	40.66

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表 4 产品油中各芳香族化合物含量占芳烃总量百分比

Table 4 Contents of aromatics in product oils as a percentage of total aromatics

n(Si)/n(Zr)	w/%
n(Si)/n(Zr)	monocyclic aromatic	bicyclic aromatic	tricyclic aromatic	tetracyclic aromatic	pentacyclic aromatic
10	54.75	36.18	6.39	2.03	0.65
20	42.65	48.69	5.57	3.09	0.00
40	36.08	49.74	8.69	5.49	0.00
80	31.39	50.28	9.22	8.58	0.52

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