Co-Pt/HAP的制备及其催化1，2-丙二醇氨化反应

doi:10.11949/0438-1157.20241406

摘要/Abstract

摘要：

为克服工业上氨与二卤丙烷反应合成1，2-丙二胺工艺的缺点，制备一系列负载型Co基催化剂，对其催化1，2-丙二醇氨化合成1，2-丙二胺反应性能进行研究。采用H₂-TPR、TEM、ICP-MS等方法对催化剂进行了表征，重点考察了载体、第二金属组分、金属负载量等的影响。结果表明，以兼具酸-碱活性位点的羟基磷灰石（HAP）为载体制备的15Co-1.05Pt/HAP催化效果最佳，1，2-丙二醇转化率为68.5%，1，2-丙二胺选择性为27.0%，伯胺总选择性达到95.2%。催化剂中Pt与Co之间存在明显相互作用，Co-Pt纳米颗粒以合金的形式存在；Pt的引入不仅可以促进氧化钴的还原，而且使金属平均粒径更小，从而有效提高了钴基催化剂的性能。利用气相色谱-质谱联用技术对1，2-丙二醇氨化反应体系进行了定性分析，结合设计实验确定了Co-Pt/HAP催化1，2-丙二醇氨化的主要反应路径。

关键词: 1, 2-丙二胺, 1, 2-丙二醇, 催化剂, 催化氨化, 多相反应, 催化作用, 反应路径

Abstract:

To overcome the shortcomings of the industrial production of 1,2-propanediamine by dihalopropane and ammonia, a series of supported Co-based catalysts were prepared to catalyze the synthesis of 1,2-propanediamine by 1,2-propanediol amination. The effects of support, second metal component and metal loading amount on their catalytic performance were investigated particularly on the basis of catalyst characterization by H₂-TPR, TEM and ICP-MS. The results show that the 15Co-1.05Pt/HAP prepared with hydroxyapatite (HAP) as a carrier with both acid and base active sites has the best catalytic effect, with a 1,2-propylene glycol conversion rate of 68.5%, a 1,2-propylene diamine selectivity of 27.0%, and a total selectivity of primary amines of 95.2%. There is an obvious interaction between metal Pt and Co in the catalyst, and further Co-Pt nanoparticles exist in the form of alloy. The introduction of Pt can promote the reduction of cobalt oxide and make the average metal particle size smaller, thereby effectively improving the catalytic performance of Co-based catalysts. Qualitative analysis for 1,2-propanediol amination reaction system was performed by gas chromatography-mass spectrometry (GC-MS). The reaction pathway of 1,2-propanediol amination catalyzed by Co-Pt/HAP was determined with the help of designed experiments.

Key words: 1,2-propanediamine, 1,2-propanediol, catalyst, catalytic amination, multiphase reaction, catalysis, reaction pathway

中图分类号:

TQ 032.4

赵世颖, 左志帅, 贺梦颖, 安华良, 赵新强, 王延吉. Co-Pt/HAP的制备及其催化1，2-丙二醇氨化反应[J]. 化工学报, 2025, 76(7): 3305-3315.

Shiying ZHAO, Zhishuai ZUO, Mengying HE, Hualiang AN, Xinqiang ZHAO, Yanji WANG. Preparation of Co-Pt/HAP catalyst and its catalytic performance for 1,2-propanediol amination[J]. CIESC Journal, 2025, 76(7): 3305-3315.

图/表 15

表1 载体对Co基催化剂的催化性能的影响

Table 1 Effect of supports on the catalytic performance of Co-based catalysts

Catalyst	X_1,2-PDO/%	Selectivity/%
Catalyst	X_1,2-PDO/%	1A2A	2A1H	1A2H	PIP	Primary amine
Co/SiO₂	2.7	0	0	0	0	0
Co/MgO	32.6	3.1	87.6	3.6	3.1	94.3
Co/HAP	37.8	9.8	81.6	3.5	4.9	94.9
Co/MgAlO _x	34.4	0.3	82.3	10.7	3.4	93.3
Co/Nb₂O₅	3.2	0	0	0	0	0

表2 NH3/CO2-TPD测定的负载型Co基催化剂酸碱性质

Table 2 Acid and base properties of various supported Co-based catalysts measured by NH3/CO2-TPD

Catalyst	Acid amount/(μmol·g^-1)				Base amount/(μmol·g^-1)
Catalyst	Weak (<250℃)	Medium (250—400℃)	Strong (>400℃)	Total	Weak (<250℃)	Medium (250—400℃)	Strong (>400℃)	Total
Co/SiO₂	42.6	57.4	34.4	134.4	29.5	25.9	10.9	66.4
Co/MgO	87.4	223.3	72.1	382.8	400.3	360.2	96.4	856.9
Co/HAP	160.0	222.1	74.9	456.9	398.1	295.3	73.8	767.1
Co/MgAlO _x	399.6	383.5	139.6	922.7	252.8	224.1	83.1	560.1
Co/Nb₂O₅	18.7	21.8	6.2	46.7	13.9	14.1	6.6	34.5

表3 负载型双金属催化剂的催化性能

Table 3 Catalytic performance of various supported bimetallic catalysts

Catalyst	X_1,2-PDO/%	Selectivity/%
Catalyst	X_1,2-PDO/%	1A2A	2A1H	1A2H	PIP	Primary amine
Co/HAP	41.6	12.6	78.4	2.8	5.6	93.8
Co-Fe/HAP	33.8	7.3	77.1	2.4	6.7	86.8
Co-Ni/HAP	39.8	18.0	63.2	4.2	11.3	85.4
Co-Cu/HAP	37.7	8.8	65.3	2.6	17.1	76.7
Co-Ru/HAP	44.6	16.0	64.0	2.7	9.5	82.7
Co-Pt/HAP	63.9	18.9	62.4	2.3	14.5	83.6
Co-Pd/HAP	19.9	0.2	72.2	4.1	9.7	76.5

图1 Co-M/HAP催化剂的XRD谱图

Fig.1 XRD patterns of Co-M/HAP catalysts

图2 Co/HAP与Co-M/HAP催化剂的H2-TPR曲线

Fig.2 H2-TPR curves of Co/HAP and Co-M/HAP catalysts

表4 Co与Pt质量比对Co-Pt/HAP催化性能的影响

Table 4 Effect of mass ratio of Co to Pt on catalytic performance of Co-Pt/HAP

Catalyst	X_1,2-PDO/%	Selectivity/%
Catalyst	X_1,2-PDO/%	1A2A	2A1H	1A2H	PIP	Primary amine
Co/HAP	41.6	12.6	78.4	2.8	5.6	93.8
10Co-0.1Pt/HAP	59.5	15.7	64.7	2.8	15.3	83.2
10Co-0.3Pt/HAP	62.1	16.9	62.5	2.6	14.7	82.0
10Co-0.5Pt/HAP	63.9	18.9	62.4	2.3	14.5	83.6
10Co-0.7Pt/HAP	66.3	24.1	62.1	2.7	9.5	88.9
10Co-1Pt/HAP	67.6	19.3	57.1	2.3	14.3	78.7

图3 Pt/HAP与不同Pt负载量Co-Pt/HAP催化剂的H2-TPR曲线

Fig. 3 H2-TPR curves of Pt/HAP and Co-Pt/HAP catalysts with different Pt loading amount

表5 金属总负载量对Co-Pt/HAP催化性能的影响

Table 5 Effect of metal loading amount on the catalytic performance of Co-Pt/HAP

Catalyst	X_1,2-PDO/%	Selectivity/%
Catalyst	X_1,2-PDO/%	1A2A	2A1H	1A2H	PIP	Primary amine
5Co-0.35Pt/HAP	63.7	19.5	55.4	2.5	10.3	77.4
10Co-0.7Pt/HAP	66.3	24.1	62.1	2.7	9.5	88.9
15Co-1.05Pt/HAP	68.5	27.0	65.0	3.2	3.9	95.2
20Co-1.4Pt/HAP	70.8	25.0	62.9	3.0	9.0	90.9

表6 不同金属负载量Co-Pt/HAP催化剂的织构性质

Table 6 Textural properties of Co-Pt/HAP catalysts with different metal loading amount

Catalyst	Specific surface area/(m²·g^-1)	Pore volume/(cm³·g^-1)	Average pore size/nm
5Co-0.35Pt/HAP	138.1	0.47	11.8
10Co-0.7Pt/HAP	125.7	0.41	11.6
15Co-1.05Pt/HAP	113.1	0.34	11.2
20Co-1.4Pt/HAP	100.0	0.23	8.6

表7 HAP负载金属催化剂上的1，2-丙二醇氨化反应性能

Table 7 Performance of 1，2-propanediol amination reaction over various HAP supported metal catalysts

Catalyst	X_1,2-PDO/%	Selectivity/%
Catalyst	X_1,2-PDO/%	1A2A	2A1H	1A2H	PIP	Primary amine
HAP	0.6	0	0	0	0	0
15Co/HAP	48.4	21.2	69.4	2.8	6.0	93.4
1.05Pt/HAP	5.0	0	24.9	0	0	24.9
15Co-1.05Pt/HAP	68.5	27.0	65.0	3.2	3.9	95.2
15Co/HAP与 1.05Pt/HAP物理混合	55.8	19.9	71.8	2.6	5.3	94.3

图4 15Co/HAP催化剂的TEM和HRTEM图像

Fig. 4 TEM and HRTEM images of the 15Co/HAP catalyst

图5 1.05Pt/HAP催化剂的TEM和HRTEM图像

Fig. 5 TEM and HRTEM images of the 1.05Pt/HAP catalyst

图6 15Co-1.05Pt/HAP催化剂的TEM[（a），（b）]、HRTEM（c）、HAADF-STEM 和EDS（d）照片

Fig. 6 TEM [(a), (b)], HRTEM (c), HAADF-STEM and EDS-mapping (d) of 15Co-1.05Pt/HAP catalysts

图7 反应物和产物浓度随反应时间的变化图（a）和局部放大图（b）

Fig. 7 Changes in the concentration of reactants and products versus reaction time (a) and local enlargement (b)

表8 15Co-1.05Pt/HAP对不同中间产物氨化反应的催化性能

Table 8 The catalytic performance of 15Co-1.05Pt/HAP on the amination of different intermediates

Raw material	X/%	Yield/%		Selectivity/%
Raw material	X/%	1A2A	2,5-DMP	1A2A	2,5-DMP
2A1H	34.5	21.9	12.4	63.6	34.1
1A2H	91.6	73.1	16.4	79.8	17.9

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