Catalytic Properties of Silylated⁃Salicylaldimine Transition Metal Complexes Functionalized Nano⁃silica Catalysts in Ethylene Oligomerization

doi:10.19894/j.issn.1000-0518.210239

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (6): 949-959.DOI: 10.19894/j.issn.1000-0518.210239

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Catalytic Properties of Silylated⁃Salicylaldimine Transition Metal Complexes Functionalized Nano⁃silica Catalysts in Ethylene Oligomerization

Feng LI, Shi-Yu LU, Yu ZHANG, Li-Jun GUO, Xue ZHAI, Cui-Qin LI()

Provincial Key Laboratory of Petroleum and Natural Gas Chemical Engineering，College of Chemistry and Chemical Engineering，Northeast Petroleum University，Daqing 163318，China

Received:2021-05-17 Accepted:2021-08-29 Published:2022-06-01 Online:2022-06-27
Contact: Cui-Qin LI
About author:licuiqin78@163.com
Supported by:
the Natural Science Foundation of Heilongjiang Province(E2018012);Heilongjiang Postdoctoral Research Foundation(16190023)

Abstract

Abstract:

Three kinds of silylated-salicylaldimine transition metal complexes functionalized nano-silica catalysts were prepared with silylated-salicylaldimine transition metal complexes as precursors and with nano-silica as support. Three kinds of heterogeneous catalysts were characterized by elemental analysis， FT-IR， SEM and ICP. The effect of the reaction parameters and the kinds of catalytic active center on the catalytic properties of the three heterogeneous catalysts were investigated with methylaluminoxane （MAO） as the cocatalyst. The results show that when the precatalyst dosage is 7 μmol， the molar ratio of Al/M （M=Cr， Ni， Co） is 500， the reaction temperature is 35 ℃， the reaction pressure is 0.5 MPa and the reaction time is 30 min， the catalytic activities for Si-Schiff-SiO₂-Cr， Si-Schiff-SiO₂-Ni and Si-Schiff-SiO₂-Co in ethylene oligonerization are 1.92×10⁵ g/（mol Cr·h）， 2.17×10⁵ g/（mol Ni·h） and 2.07×10⁵ g/（mol Co·h）， respectively， and the main oligomers are C4 and C6 olefin. Si-Schiff-SiO₂-M has lower catalytic activity and narrower product distribution compared to the corresponding homogeneous catalyst due to the low loading of metal active center and the confinement effect of the support. Si-Schiff-SiO₂-M has the good repeatability and the better thermal stability， and the activity of the recovered catalyst is up to 1.39×10⁵ g/（mol Cr·h）， 1.68×10⁵ g/（mol Ni·h） and 1.42×10⁵ g/（mol Co·h）， respectively after three oligomerization reactions.

Key words: Ethylene oligomerization, Nano-silica, Heterogeneous catalyst, Covalent modification, Silylated-salicylaldimine

CLC Number:

O643.3

Feng LI, Shi-Yu LU, Yu ZHANG, Li-Jun GUO, Xue ZHAI, Cui-Qin LI. Catalytic Properties of Silylated⁃Salicylaldimine Transition Metal Complexes Functionalized Nano⁃silica Catalysts in Ethylene Oligomerization[J]. Chinese Journal of Applied Chemistry, 2022, 39(6): 949-959.

Figures/Tables 11

Table 1 Results of elemental analysis

化合物 Compound	测量值 Measured value/%
化合物 Compound	碳元素 C	氢元素 H	氮元素 N	金属元素 M
Si?Schiff?SiO₂?Cr	14.07	1.59	1.24	2.31
Si?Schiff?SiO₂?Ni	12.85	1.36	1.04	2.18
Si?Schiff?SiO₂?Co	12.62	1.31	0.91	1.92

Fig. 1 FT-IR spectra of three supported complexes

Fig.2 XRD patterns of three supported complexes

Fig.3 SEM images of three supported complexes

Fig. 4 Effect of the dosage of main catalysts on the catalytic propertiesA. Catalytic activity (a. Si?Schiff?SiO2?Cr；b. Si?Schiff?SiO2?Ni；c. Si?Schiff?SiO2?Co) ；B. Selectivity of Si?Schiff?SiO2?Cr；C. Selectivity of Si?Schiff?SiO2?Ni；D. Selectivity of Si?Schiff?SiO2?Co

Fig. 5 Effect of n（Al）/n（M）on the catalytic propertiesA. Catalytic activity (a. Si?Schiff?SiO2?Cr；b. Si?Schiff?SiO2?Ni；c. Si?Schiff?SiO2?Co)； B. Selectivity of Si?Schiff?SiO2?Cr；C. Selectivity of Si?Schiff?SiO2?Ni；D. Selectivity of Si?Schiff?SiO2?Co

Fig.6 Effect of the reaction temperature on the catalytic propertiesA. Catalytic property(a. Si?Schiff?SiO2?Cr；b. Si?Schiff?SiO2?Ni；c. Si?Schiff?SiO2?Co)； B. Selectivity of Si?Schiff?SiO2?Cr；C. Selectivity of Si?Schiff?SiO2?Ni；D. Selectivity of Si?Schiff?SiO2?Co

Fig.7 Effect of the reaction pressure on the catalytic propertiesA. Catalytic activity（a. Si?Schiff?SiO2?Cr；b. Si?Schiff?SiO2?Ni；c. Si?Schiff?SiO2?Co）；B. Selectivity of Si?Schiff?SiO2?Cr；C. Selectivity of Si?Schiff?SiO2?Ni；D. Selectivity of Si?Schiff?SiO2?Co

Table 2 Confinement effect and recycling properties of the three supported complexes

催化剂 Catalyst	活性 10^-5Activity/（g·mol^-1 M·h^-1）	齐聚分布 Gathering distribution/%
催化剂 Catalyst	活性 10^-5Activity/（g·mol^-1 M·h^-1）	C4	C6	C8	C10+
Si?Schiff?Ni	11.18	21.68	42.31	20.12	15.89
Si?Schiff?Co	10.51	16.16	35.14	31.58	17.12
Si?Schiff?Cr	10.26	28.12	50.27	12.92	8.69
SiO₂?S?Schiff?Ni（0）	2.17	56.82	22.40	9.71	11.07
SiO₂?S?Schiff?Ni（1）	2.09	57.06	22.47	8.65	11.82
SiO₂?S?Schiff?Ni（2）	1.96	57.76	22.36	9.61	10.27
SiO₂?S?Schiff?Ni（3）	1.68	56.95	23.15	8.56	11.34
SiO₂?S?Schiff?Co（0）	2.07	30.64	60.04	5.44	3.88
SiO₂?S?Schiff?Co（1）	1.94	33.92	58.61	5.14	2.33
SiO₂?S?Schiff?Co（2）	1.67	34.29	54.19	7.34	4.18
SiO₂?S?Schiff?Co（3）	1.42	35.02	55.62	6.37	2.99
SiO₂?S?Schiff?Cr（0）	1.92	40.64	50.04	5.44	3.88
SiO₂?S?Schiff?Cr（1）	1.76	33.23	52.15	9.14	5.48
SiO₂?S?Schiff?Cr（2）	1.52	35.45	50.11	10.34	4.1
SiO₂?S?Schiff?Cr（3）	1.39	37.12	49.62	10.37	2.89

Fig.8 Proposed mechanisms for ethylene oligomerization

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Catalytic Properties of Silylated⁃Salicylaldimine Transition Metal Complexes Functionalized Nano⁃silica Catalysts in Ethylene Oligomerization

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