Ni-P/rGO复合催化剂的制备、表征及其松香加氢性能研究

doi:10.3969/j.issn.0253-2417.2019.03.008

摘要/Abstract

摘要：

以鳞片石墨为原料，采用改良后的Hummer's法制备了氧化石墨烯（GO）分散液，然后以化学还原法制备非晶态Ni-P/rGO复合催化剂，并以松香加氢为探针反应考察了催化剂制备条件对催化性能的影响，进一步通过正交试验优化了松香加氢反应的工艺条件。结果表明：在Ni元素与GO质量比为6:1、溶液pH值为11、n（P）/n（Ni）为5:1、温度为70℃的优化制备条件下，以及反应时间4.5 h、催化剂用量5%、反应温度200℃和反应压力4.5 MPa的适宜加氢反应条件下，该催化剂对松香加氢具有较高的活性，枞酸型树脂酸转化率达99.37%，且重现性良好，该催化剂重复使用7次仍能保持较高的催化活性。X射线衍射（XRD）、透射电镜（TEM）、X射线光电子能谱（XPS）表征结果表明：非晶态Ni-P/rGO复合催化剂已经成功制备，未与rGO复合的Ni-P粒子颗粒较大且分散性较差，使用7次后复合催化剂中Ni⁰含量相对下降，活性组分流失导致催化活性稍有降低。

关键词: Ni-P, 石墨烯, 催化, 松香

Abstract:

The graphene oxide(GO) dispersion was prepared by the modified Hummer's method using flake graphite as raw material. The amorphous Ni-P/rGO composite catalyst was prepared by chemical reduction method, and the rosin hydrogenation was used as the probe reaction to study the effects of catalyst preparation conditions on the catalytic performance. And the process conditions of rosin hydrogenation were further optimized by orthogonal test. The results showed that the optimum preparation conditions were the mass ratio of Ni element to GO 6:1, the pH value of the solution 11, the ratio of n(P)/n(Ni) 5:1, the temperature 70℃, and the reaction time 4.5 h. The catalyst had a high activity for hydrogenation of rosin under the suitable hydrogenation conditions of 5% catalyst, reaction temperature 200℃ and reaction pressure 4.5 MPa. The conversion of abietic-type resin acid was 99.37%, and the reproducibility was good. The catalyst could maintain high catalytic activity after 7 times repeated using. X-ray diffraction(XRD), transmission electron microscopy(TEM) and X-ray photoelectron spectroscopy(XPS) characterization showed that the amorphous Ni-P/rGO composite catalyst was successfully prepared, and the Ni-P particles without rGO had larger particle size and poor dispersity. The Ni⁰ content in the composite catalyst decreased relatively after 7 times of use, and the loss of active components caused a slight decrease in catalysis.

Key words: Ni-P, graphene, catalysis, rosin

中图分类号:

TQ35
TB333

申晨,王亚明,蒋丽红,郑艳娥,宋爽爽,来倩. Ni-P/rGO复合催化剂的制备、表征及其松香加氢性能研究[J]. 林产化学与工业, 2019, 39(3): 57-64.

Chen SHEN,Yaming WANG,Lihong JIANG,Yan'e ZHENG,Shuangshuang SONG,Qian LAI. Preparation and Characterization of Ni-P/rGO Composite Catalysts and Their Hydrogenation Properties of Rosin[J]. Chemistry and Industry of Forest Products, 2019, 39(3): 57-64.

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序号 No.	A催化剂用量/% catalyst dosage	B反应温度/℃ temperature	C反应压力/MPa pressure	D反应时间/h time	转化率/% conversion rate
1	3	190	3.5	3.5	83.56
2	3	200	4.0	4.0	94.15
3	3	210	4.5	4.5	95.23
4	5	190	4.0	4.5	94.90
5	5	200	4.5	3.5	96.07
6	5	210	3.5	4.0	97.85
7	7	190	4.5	4.0	95.15
8	7	200	3.5	4.5	98.49
9	7	210	4.0	3.5	92.87
k₁	90.980	91.203	93.300	90.833
k₂	96.273	96.237	93.971	95.721
k₃	95.501	95.322	95.483	96.207
R	5.293	5.034	2.183	5.374

反应次数/次 reaction times	产物中枞酸GC含量/% GC content of abietic acid in product	转化率/% conversion rate
1	0.27	99.67
2	0.28	99.66
3	0.44	99.47
4	0.63	99.22
5	0.47	99.42
6	0.24	99.70
7	1.33	98.37

序号 No.	催化剂 catalyst	反应条件 reaction conditions	转化率/% conversion rate	参考文献 reference
1	Ni-P/rGO	200 ℃、4.5 MPa、4.5 h	99.37	本研究this study
2	Ni/Al₂O₃-M_xO_y	200 ℃、4.5 MPa、2 h	98	[20]
3	纳米镍nano nickel	160 ℃、4.0 MPa、1 h	97.3	[21]
4	NiB/MCM-41	180~190 ℃、7~9 MPa、5 h	≥99.44	[22]
5	FAPEPP与钯的配合物comples of FAPEPP and Pd	160 ℃、5.0 MPa、3 h	≥93.74	[23]
6	Ranry Ni	80~170 ℃、4~8 MPa、90 min	99.8	[24]

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