介孔碳负载Ni催化剂催化顺酐加氢反应研究

doi:10.11949/0438-1157.20241148

摘要/Abstract

摘要：

丁二酸酐（SA）是合成可降解塑料聚丁二酸丁二醇酯（PBS）的原料，开展顺酐（MA）加氢制备SA催化剂的研究具有重要的应用价值。为解决MA低温加氢转化率低且容易失活的问题，本文以介孔碳为载体制备了系列不同镍含量的yNi/MC催化剂并进行表征和催化性能评价。由于介孔碳具有较大的比表面积和孔容，故适量提高金属Ni负载量［40%（质量）］可以增加金属Ni位点，有利于提高MA催化加氢反应的活性。在低负载量情况下，适当增加氢气的弱吸附位点有利于提高MA催化加氢的活性；而Ni的负载量高于20%（质量）之后，H₂吸附解离能力相对较强，而C=C键的桥式吸附成为反应活性的提升关键。研究表明，40%（质量）镍负载量的40Ni/MC催化剂经500℃还原后，在较低的温度（60℃）和较高的质量空速（8.3 h^-1）条件下可实现100%的SA选择性和80.1%的MA转化率，并在5次循环套用中表现出较佳的稳定性。而且，当反应温度提高至90℃时，MA转化率和SA选择性均接近100%。当采用固定床反应体系评价时，可达到150 h后依旧保持100%的MA转化率和SA选择性。因此，所制备的介孔碳负载镍催化剂在MA加氢领域显示了良好的工业应用前景。

关键词: 顺酐, 丁二酸酐, 镍, 介孔碳, 加氢, 催化剂, 载体

Abstract:

Succinic anhydride (SA) is the raw material for synthesizing biodegradable plastic-polybutylene succinate (PBS). The research on the preparation of SA catalyst by hydrogenation of maleic anhydride (MA) has important application value. In order to solve the problem of low activity and easy deactivation of the catalyst in maleic anhydride hydrogenation at low temperature, a series of yNi/MC catalysts with different nickel content were prepared by using a kind of mesoporous carbon as the carrier and their properties were characterized and evaluated. Due to the large specific surface area and pore volume of mesoporous carbon, an appropriate Ni loading [40% (mass)] can increase the number of metal nickel site, which is conducive to the high activity in the hydrogenation of maleic. When the Ni loading is relatively lower, increasing the number of active site for weak adsorption of hydrogen is beneficial for improving its catalytic activity in MA hydrogenation. When the load of Ni is higher than 20% (mass), the adsorption and dissociation capacity of H₂ is greatly enhanced so that the bridge adsorption of C=C bond on the catalyst surface becomes the bottleneck problem for further boosting the reaction activity. This work demonstrated that the 40Ni/MC catalyst with 40% (mass) Ni loading reduced at 500℃ had a remarkable performance, achieving 100% selectivity towards succinic anhydride and 80.1% conversion of maleic anhydride at a low temperature of 60℃ and high WHSV of 8.3 h^-1. Furthermore, this catalyst displayed superior stability during the five successive recycling operations. In addition, when the reaction temperature was increased to 90℃, both the conversion and selectivity are close to 100%. When the fixed bed reaction system was used for evaluation, 100% MA conversion and SA selectivity could be maintained after 150 h. Therefore, the as-prepared mesoporous carbon-supported Ni catalyst exhibited a prospective future in maleic anhydride hydrogenation from the viewpoint of industrial application.

Key words: maleic anhydride, succinic anhydride, nickel, mesoporous carbon, hydrogenation, catalyst, support

中图分类号:

O 643.38

周琳, 叶斌, 孙心怡, 孔令鑫, 徐艳, 赵玉军. 介孔碳负载Ni催化剂催化顺酐加氢反应研究[J]. 化工学报, 2024, 75(11): 4264-4273.

Lin ZHOU, Bin YE, Xinyi SUN, Lingxin KONG, Yan XU, Yujun ZHAO. Study on the catalytic hydrogenation of maleic anhydride by mesoporous carbon-supported Ni catalyst[J]. CIESC Journal, 2024, 75(11): 4264-4273.

图/表 17

图 1 MA加氢制SA的反应网络

Fig.1 Reaction routes of continuous production of succinic anhydride by hydrogenation of maleic anhydride

表1 反应温度和氢气压力对MA加氢性能的影响

Table 1 Effect of reaction temperature and hydrogen pressure on the hydrogenation performance of maleic anhydride

催化剂	反应温度/℃	氢气压力/MPa	MA 转化率/%	SA 选择性/%
40Ni/MC	30	1	20.8	100.0
	60	1	80.1	100.0
	90	1	100.0	100.0
	60	2	86.9	100.0
	60	3	89.1	100.0
	60	4	96.5	100.0

图2 还原温度对催化活性的影响

Fig.2 Effect of reduction temperature on catalytic activity

图3 10Ni/MC催化剂不同还原温度下XPS谱图

Fig.3 XPS spectra of 10Ni/MC catalyst at different reduction temperatures

表 2 ICP-OES测得不同镍负载量催化剂的实际镍含量

Table 2 The real Ni loadings of the catalysts from the results of ICP-OES

理论镍负载量/%（质量）	ICP-OES测定镍负载量/%（质量）
10	9.9
20	20.4
30	29.8
40	39.4
50	50.2

图 4 不同镍负载量催化剂评价结果

Fig.4 Performances of catalysts with different nickel loadings

图 5 （a）还原前催化剂的XRD谱图;（b）不同还原温度下的10Ni/MC催化剂的XRD谱图

Fig.5 (a) XRD pattern of the catalyst before reduction; (b) XRD pattern of the 10Ni/MC catalyst at different reduction temperatures

图6 不同负载量Ni/MC催化剂TEM图像

Fig.6 TEM images of catalysts with different nickel loadings (a) 10Ni/MC; (b) 20Ni/MC; (c) 30Ni/MC; (d) 40Ni/MC; (e) 50Ni/MC; (f) average particle size of yNi/MC catalysts

图7 不同负载量的Ni/MC催化剂的N2吸脱附曲线（a）和孔径分布曲线（b）

Fig.7 N2 adsorption-desorption isotherms （a） and pore size distribution curves （b） of yNi/MC catalysts

表 3 不同镍负载量的介孔碳催化剂物理结构特征

Table 3 Textural properties of Ni/MC catalysts with different content of Ni

Catalyst	S_BET^①/ （m²/g）	V_pore^①/ （cm³/g）	D_pore^①/nm	Metal dispersion^②/%
MC	974	3.4	11.8	—
10Ni/MC	905	1.8	8.2	7.5
20Ni/MC	825	1.6	8.3	6.8
30Ni/MC	718	1.5	8.5	5.5
40Ni/MC	654	1.4	8.8	4.3
50Ni/MC	560	1.2	8.9	3.7

表4 不同镍负载量催化剂的H2-TPR曲线拟合结果

Table 4 H2-TPR curve fitting results of catalysts with different nickel loads

Catalyst	Temperature/℃		Peak area×10³
Catalyst	α	β	α	β
MC	—	491.9	—	102.9
10Ni/MC	246.2	492.7	3.5	134.1
20Ni/MC	234.3	500.9	10.5	158.4
30Ni/MC	243.0	495.6	19.7	196.2
40Ni/MC	223.7	492.3	23.0	228.7
50Ni/MC	213.4	494.0	17.9	254.7

图8 催化剂的H2-TPR谱图

Fig.8 H2-TPR profiles of different types of catalysts

图9 催化剂的C2H4-TPD谱图

Fig.9 C2H4-TPD profiles of catalysts

表 5 不同镍负载量催化剂的C2H4-TPD曲线拟合结果

Table 5 C2H4-TPD curve fitting results of catalysts with different nickel loads

Catalyst	Temperature/℃			Peak area
Catalyst	α	β	γ	α	β	γ
20Ni/MC	112.6	259.1	377.8	8.5	13.5	15.5
30Ni/MC	114.3	263.1	378.0	14.4	27.8	34.3
40Ni/MC	114.4	263.2	382.2	21.6	26.8	30.9
50Ni/MC	116.7	271.8	378.5	20.3	41.3	63.4

表 6 不同镍负载量催化剂的H2-TPD曲线拟合结果

Table 6 H2-TPD curve fitting results of catalysts with different nickel loads

Catalyst	Temperature/℃		Peak area
Catalyst	α	β	α	β
MC	111.8	472.6	—	—
10Ni/MC	93.3	475.0	240.8	2694.5
20Ni/MC	127.7	484.2	489.6	2502.6
30Ni/MC	126.4	504.4	509.1	3090.5
40Ni/MC	114.9	494.6	534.8	3701.3
50Ni/MC	114.2	521.1	519.8	3852.4

图10 催化剂的H2-TPD谱图

Fig.10 H2-TPD profiles of catalysts

图 11 （a）40Ni/MC催化剂在间歇反应釜中的循环套用性能；（b）40Ni/MC催化剂在固定床反应器中的性能

Fig.11 (a) Performances of 40Ni/MC catalyst in batch kettle reactor (reaction conditions: 60℃, 1 MPa, WHSV 8.3 h-1); (b) Performances of 40Ni/MC catalyst in fixed bed reactor (reaction conditions: 60℃, 1 MPa, WHSV 2 h-1, H2/MA=20)

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