兼具加氢和脱硫活性的富含Niδ+非晶态NiP@γ-Al2O3催化剂的构筑及其用于石油树脂加氢的性能研究

doi:10.11949/0438-1157.20240106

摘要/Abstract

摘要：

C₉石油树脂（C9PR）是由乙烯裂解副产物C₉馏分聚合而成的热塑性树脂，经加氢改性后可以制得色度浅、抗氧化稳定性高、相容性好的高附加值氢化石油树脂（HC9PR）。但C9PR分子量大、空间位阻高且原料中含有硫化物等杂质易使催化剂中毒失活，因此加氢难度极大。为了同时实现C9PR的加氢和脱杂，采用化学还原法结合球磨法制备了非晶态NiP@γ-Al₂O₃催化剂。表征结果显示，该催化剂具有较大的比表面积、富含Ni^δ+活性物种、较多的活性位数量，并对C=C键具有较强的吸附能力。对其进行C9PR加氢性能评价，结果显示非晶态NiP@γ-Al₂O₃催化剂表现出优异的加氢活性（加氢度98.35%）和脱硫活性（硫含量从122.8 μg/g降低至8 μg/g），明显优于利用程序升温还原法结合球磨法制备的不同晶型磷化镍催化剂。此外，经过连续100 h的反应，该催化剂仍能保持较高的加氢度，表明其具有良好的稳定性。

关键词: 石油树脂, 非晶态磷化镍, 加氢, 脱硫, 球磨法

Abstract:

C₉ petroleum resin (C9PR) is a thermoplastic resin polymerized from the C₉ fraction of ethylene cracking byproduct, which can be hydrogenated to produce high value-added hydrogenated C₉ petroleum resin (HC9PR) with light color, high antioxiant stability and good compatibility. However, C9PR has high molecular weight, high steric hindrance and impurities such as sulfide in the raw material which are easy to poison and deactivate the catalyst, making hydrogenation extremely difficult. Herein, in order to achieve simultaneous hydrogenation and desulfurization of C9PR, we have successfully prepared the amorphous NiP@γ-Al₂O₃ catalyst by using chemical reduction method combined with ball milling method. The results showed that the catalyst has large specific surface area, high-content Ni^δ+ active species, high number of active sites and strong adsorption capacity for C=C bond. The obtained amorphous NiP@γ-Al₂O₃ catalyst showed an enhanced hydrogenation activity (hydrogenation degree of 98.35%) and desulfurization activity (sulfur content reduced from 122.8 μg/g to 8 μg/g) for C9PR hydrogenation, which is obviously superior to different crystalline nickel phosphide catalysts (the nickel phosphide was prepared by temperature programmed reduction method and loaded on γ-alumina carrier by ball milling). In addition, the amorphous NiP@γ-Al₂O₃ catalyst exhibited high hydrogenation degree after 100 h of continuous reaction, indicating that the catalyst had good stability.

Key words: petroleum resin, amorphous NiP, hydrogenation, desulfurization, ball milling

中图分类号:

TQ 326.8

胡德政, 王榕, 王世栋, 杨文菲, 张宏伟, 袁珮. 兼具加氢和脱硫活性的富含Ni^δ+非晶态NiP@γ-Al₂O₃催化剂的构筑及其用于石油树脂加氢的性能研究[J]. 化工学报, DOI: 10.11949/0438-1157.20240106.

Dezheng HU, Rong WANG, Shidong WANG, Wenfei YANG, Hongwei ZHANG, Pei YUAN. Construction of amorphous NiP@γ-Al₂O₃ catalyst rich in Ni^δ+ for petroleum resin hydrogenation with enhanced hydrogenation and desulfurization activity[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240106.

图/表 18

图1 非晶态NiP、Ni2P、Ni12P5和Ni3P(a)及对应催化剂(b)的XRD谱图

Fig. 1 XRD patterns of amorphous NiP, Ni2P, Ni12P5 and Ni3P (a), and the corresponding catalysts (b)

图2 γ-Al2O3、非晶态NiP@γ-Al2O3、不同晶型催化剂N2吸附-脱附等温曲线和孔径分布

Fig. 2 N2 adsorption-desorption curves and pore size distributions of γ-Al2O3, amorphous NiP@γ-Al2O3 and different crystalline catalysts

表1 γ-Al2O3载体、非晶态NiP@γ-Al2O3和不同晶型催化剂的织构性质

Table 1 Textural properties of γ-Al2O3， amorphous NiP@γ-Al2O3 and different crystalline catalysts

Sample	BET surface area /（m²·g^-1）	Pore volume /（cm³·g^-1）	Pore diameter /nm
γ-Al₂O₃	320	0.88	15.8
非晶态NiP@γ-Al₂O₃	255	0.47	6.9
Ni₂P@γ-Al₂O₃	241	0.53	6.3
Ni₁₂P₅@γ-Al₂O₃	214	0.45	9.3
Ni₃P@γ-Al₂O₃	213	0.65	10.9

图3 非晶态NiP@γ-Al2O3和不同晶型磷化镍催化剂的Ni 2p和P 2p XPS谱图

Fig. 3 Ni 2p XPS spectra and P 2p XPS spectra of amorphous NiP@γ-Al2O3 and different crystalline catalysts

表2 非晶态NiP@γ-Al2O3，Ni2P@γ-Al2O3，Ni12P5@γ-Al2O3和Ni3P@γ-Al2O3催化剂的性质表征结果

Table 2 Properties of amorphous NiP@γ-Al2O3， Ni2P@γ-Al2O3， Ni12P5@γ-Al2O3 and Ni3P@γ-Al2O3 catalysts.

Sample	Ni species^a			P species^a		CO uptakes^b/（μmol·g^-1）	C₂H₄-TPD peak area^c
Sample	Ni^δ+/%	Ni²⁺/%	Satellite/%	P^δ-/%	P-O/%	CO uptakes^b/（μmol·g^-1）	C₂H₄-TPD peak area^c
非晶态NiP@γ-Al₂O₃	36.51	37.44	26.06	58.44	41.56	21.67	1.00
Ni₂P@γ-Al₂O₃	12.06	45.76	42.17	47.15	52.85	11.43	0.69
Ni₁₂P₅@γ-Al₂O₃	9.92	50.42	39.66	46.64	53.36	6.92	0.62
Ni₃P@γ-Al₂O₃	16.44	48.47	35.09	56.85	43.15	16.42	0.89

图4 非晶态NiP@γ-Al2O3，Ni2P@γ-Al2O3，Ni12P5@γ-Al2O3和Ni3P@γ-Al2O3催化剂的乙烯-TPD图

Fig. 4 C2H4-TPD profiles of amorphous NiP@γ-Al2O3, Ni2P@γ-Al2O3, Ni12P5@γ-Al2O3 and Ni3P@γ-Al2O3 catalysts.

表3 C9PR和HC9PR的溴值、Gardner色度、硫含量及加氢度数据

Table 3 The bromine value， Gardner color， sulfur content and hydrogenation degree of raw C9PR and HC9PR products

Sample	溴值/(g·(100g)^-1)	色度	硫含量/(μg/g)	加氢度/%
C9PR	5.06	5.6#	122.80	--
Blank	3.65	4.3#	102.80	27.86
非晶态NiP@γ-Al₂O₃	0.08	0.3#	8.0	98.35
Ni₂P@γ-Al₂O₃	0.63	0.7#	28.60	87.58
Ni₁₂P₅@γ-Al₂O₃	0.94	2.7#	28.53	81.37
Ni₃P@γ-Al₂O₃	0.30	1.0#	28.02	94.05

图5 C9PR原料和HC9PR产物的FT-IR谱图和UV-Vis谱图

Fig. 5 FT-IR spectra and UV-Vis spectra of C9PR and HC9PR

图6 加氢度随Niδ+含量和CO吸附量变化趋势

Fig. 6 Trend of hydrogenation degree with Niδ+ content and CO uptakes

图7 不同负载量的非晶态NiP@γ-Al2O3的XRD谱图

Fig.7 XRD patterns of amorphous NiP@γ-Al2O3 with different loading volumes

表4 C9PR与HC9PR的物性参数

Table 4 Characteristic of raw C9PR and HC9PR products

Sample	溴值/(g·(100g)^-1)	色度	硫含量/(μg/g)	加氢度/%
C9PR	5.06	5.6#	122.80	--
10% 非晶态NiP@γ-Al₂O₃	0.12	0.8#	25.0	97.65
20% 非晶态NiP@γ-Al₂O₃	0.08	0.3#	8.0	98.35
30% 非晶态NiP@γ-Al₂O₃	0.02	0.2#	0	99.10

图8 C9PR原料和HC9PR产物的FT-IR谱图和UV-Vis谱图

Fig. 8 FT-IR spectra and UV-Vis spectra of C9PR and HC9PR

图9 不同反应条件对30% 非晶态NiP@γ-Al2O3催化剂的C9PR加氢性能的影响 (加氢反应条件固定，考察单一变量：温度220 °C、压力5 MPa、液时空速 1.5 h-1、氢脂比 600:1)

Fig. 9 Effect of different reaction conditions on the C9PR hydrogenation performance of 30% amorphous NiP@γ-Al2O3 catalyst (hydrogenation reaction conditions were fixed and a single variable was examined: temperature of 220 °C, pressure of 5 MPa, LHSV of 1.5 h-1, VRHO of 600:1)

图10 30% 非晶态NiP@γ-Al2O3催化剂用于C9PR的加氢稳定性测试

Fig. 10 Stability of the 30% amorphous NiP@γ-Al2O3 catalysts for C9PR hydrogenation

图11 反应前后30% 非晶态NiP@γ-Al2O3催化剂的XRD谱图和Ni 2p XPS谱图

Fig. 11 XRD patterns and Ni 2p XPS spectra of fresh and spent NiP@γ-Al2O3 catalysts

表5 反应前后NiP@γ-Al2O3催化剂中的各物种组成占比

Table 5 Elemental composition ratio of fresh and spent NiP@γ-Al2O3 catalysts.

Sample	Ni⁰/%	Ni^δ+/%	Ni²⁺/%	Satellite/%	P^δ-/%	P-O/%
Fresh NiP@γ-Al₂O₃	-	39.96	34.26	25.78	53.68	46.32
Spent NiP@γ-Al₂O₃	4.58	23.89	36.87	34.66	40.53	59.47

图12 反应前后30% 非晶态NiP@γ-Al2O3催化剂的N2吸附-脱附等温曲线和孔径分布

Fig.12 N2 adsorption-desorption curves and pore size distributions of fresh and spent NiP@γ-Al2O3 catalysts

表6 反应前后30% 非晶态NiP@γ-Al2O3催化剂的织构性质

Table 6 Textural properties of fresh and spent NiP@γ-Al2O3 catalysts

Sample

BET surface area

/（m²·g^-1）

Pore volume /（cm³·g^-1）

参考文献 37

1	Jiang M, Wei X J, Chen X P, et al. C9 petroleum resin hydrogenation over a PEG1000-modified nickel catalyst supported on a recyclable fluid catalytic cracking catalyst residue[J]. ACS Omega, 2020, 5(32): 20291-20298.
2	Zhang W G, Qiu L, Liu J P, et al. Modification mechanism of C9 petroleum resin and its influence on SBS modified asphalt[J]. Construction and Building Materials, 2021, 306: 124740.
3	何志山, 韦小杰, 陈小鹏, 等. β-环糊精修饰Ni/SFCC强化C₉石油树脂催化加氢性能[J]. 石油炼制与化工, 2020, 51(6): 62-71.
	He Z S, Wei X J, Chen X P, et al. β-cyclodextrin modified Ni/SFCC to enhance catalytic hydrogenation of C₉ petroleum resin[J]. Petroleum Processing and Petrochemicals, 2020, 51(6): 62-71.
4	俞陆军, 江大好, 徐娇, 等. C₉石油树脂显色原因及其加氢改性的研究[J]. 石油化工, 2012, 41(10): 1181-1185.
	Yu L J, Jiang D H, Xu J, et al. Color cause and hydrogenation modification of C₉ petroleum resin[J]. Petrochemical Technology, 2012, 41(10): 1181-1185.
5	Yu Lujun; Jiang Dahao; Xu Jiao; Ma Lei; Li Xiaonian. Two-stage hydrogenation modification of C₉ petroleum resin over NiWS/γ-Al₂O₃ and PdRu/γ-Al₂O₃ catalysts in series[J]. China Petroleum Processing & Petrochemical Technology, 2012, 14(3): 83-89.
6	Suwaid M A, Varfolomeev M A, Al-muntaser A A, et al. In-situ catalytic upgrading of heavy oil using oil-soluble transition metal-based catalysts[J]. Fuel, 2020, 281: 118753.
7	Sae-Ma N, Praserthdam P, Panpranot J, et al. Color improvment of C₉hydrocarbon resin by hydrogenation over 2% Pd/γ-alumina catalyst: Effect of degree of aromatic rings hydrogenation[J]. Journal of Applied Polymer Science, 2010, 117(5): 2862-2869.
8	Petrukhina N N, Korchagina S A, Khan O I, et al. Hydrogenation of polymeric petroleum resins in the presence of unsupported sulfide catalysts synthesized from water-soluble precursors[J]. Petroleum Chemistry, 2018, 58(14): 1192-1197.
9	Petrukhina N N, Zakharyan E M, Korchagina S A, et al. Hydrogenation of petroleum resins in the presence of supported sulfide catalysts[J]. Petroleum Chemistry, 2018, 58(1): 48-55.
10	Wu C H, Chen X P, Tang L Q, et al. Rationally constructing a nano MOF-derived Ni and CQD embedded N-doped carbon nanosphere for the hydrogenation of petroleum resin at low temperature[J]. ACS Applied Materials & Interfaces, 2021, 13(9): 10855-10869.
11	Liu Q H, Yang J T, Zhang H W, et al. Tuning the properties of Ni-based catalyst via La incorporation for efficient hydrogenation of petroleum resin[J]. Chinese Journal of Chemical Engineering, 2022, 45: 41-50.
12	Oyama S T, Wang X, Lee Y K, et al. Effect of phosphorus content in nickel phosphide catalysts studied by XAFS and other techniques[J]. Journal of Catalysis, 2002, 210(1): 207-217.
13	Zhao H Y, Oyama S T, Freund H J, et al. Nature of active sites in Ni₂P hydrotreating catalysts as probed by iron substitution[J]. Applied Catalysis B: Environmental, 2015, 164: 204-216.
14	Oyama S T, Wang X, Lee Y K, et al. Active phase of Ni₂P/SiO₂in hydroprocessing reactions[J]. Journal of Catalysis, 2004, 221(2): 263-273.
15	Jiang L, Feng F, Jiang D H, et al. Highly active and stable Ni₂P/SiO₂ catalyst for hydrogenation of C₉ petroleum resin[J]. China Petroleum Processing & Petrochemical Technology, 2016, 18(1): 36-43.
16	Wang R, Sun H M, Liang M X, et al. Flower-like nickel phosphide catalyst for petroleum resin hydrogenation with enhanced catalytic activity, hydrodesulfurization ability and stability[J]. Chemical Engineering Science, 2022, 264: 118180.
17	Yang W F, Wu S Z, Hu C J, et al. In-situ synthesis of Ni₂P/Al₂O₃ catalyst with liquid-phase phosphidation for enhancing hydrogenation and desulfurization performance in C9 petroleum resin[J]. Chemical Engineering Science, 2024, 286: 119648.
18	Moreau L M, Ha D H, Zhang H T, et al. Defining Crystalline/Amorphous phases of nanoparticles through X-ray absorption spectroscopy and X-ray diffraction: the case of nickel phosphide[J]. Chemistry of Materials, 2013, 25(12): 2394-2403.
19	Li X Z, Wu K L, Ye Y, et al. Gas-assisted growth of boron-doped nickel nanotube arrays: rapid synthesis, growth mechanisms, tunable magnetic properties, and super-efficient reduction of 4-nitrophenol[J]. Nanoscale, 2013, 5(9): 3648-3653.
20	Bastakoti B P, Munkaila S, Guragain S. Micelles template for the synthesis of hollow nickel phosphate nanospheres[J]. Materials Letters, 2019, 251: 34-36.
21	Chen Y D, Li C M, Zhou J Y, et al. Metal phosphides derived from hydrotalcite precursors toward the selective hydrogenation of phenylacetylene[J]. ACS Catalysis, 2015, 5(10): 5756-5765.
22	Gan Y, Wang C, Chen X, et al. High conductivity Ni₁₂P₅ nanowires as high-rate electrode material for battery-supercapacitor hybrid devices[J]. Chemical Engineering Journal, 2020, 392: 123661.
23	Laursen A, Wexler R B, Whitaker M J, et al. Climbing the volcano of electrocatalytic activity while avoiding catalyst corrosion: Ni₃P, a hydrogen evolution electrocatalyst stable in both acid and alkali[J]. ACS Catalysis, 2018, 8(5): 4408-4419.
24	Wang F, Ma J Z, He G Z, et al. Nanosize effect of Al₂O₃ in Ag/Al₂O₃ catalyst for the selective catalytic oxidation of ammonia[J]. ACS Catalysis, 2018, 8(4): 2670-2682.
25	Feng J T, Lin Y J, Evans D G, et al. Enhanced metal dispersion and hydrodechlorination properties of a Ni/Al₂O₃ catalyst derived from layered double hydroxides[J]. Journal of Catalysis, 2009, 266(2): 351-358.
26	Du W C, Zheng L P, Li X W, et al. Plate-like Ni–Mg–Al layered double hydroxide synthesized via a solvent-free approach and its application in hydrogenolysis of D-sorbitol[J]. Applied Clay Science, 2016, 123: 166-172.
27	Liu T, Li A R, Wang C B, et al. Interfacial electron transfer of Ni₂P-NiP₂ polymorphs inducing enhanced electrochemical properties[J]. Advanced Materials, 2018, 30(46): e1803590.
28	Xu J, Yang N J, Yu S Y, et al. Ultra-high energy density supercapacitors using a nickel phosphide/nickel/titanium carbide nanocomposite capacitor electrode[J]. Nanoscale, 2020, 12(25): 13618-13625.
29	Wang Z K, Wang S Y, Ma L X, et al. Water-induced formation of Ni₂P-Ni₁₂P₅ interfaces with superior electrocatalytic activity toward hydrogen evolution reaction[J]. Small, 2021, 17(6): 2006770.
30	Fu H Q, Zhang L, Wang C W, et al. 1D/1D hierarchical nickel sulfide/phosphide nanostructures for electrocatalytic water oxidation[J]. ACS Energy Letters, 2018, 3(9): 2021-2029.
31	Li S L, Ma R G, Hu J C, et al. Coordination environment tuning of nickel sites by oxyanions to optimize methanol electro-oxidation activity[J]. Nature Communications, 2022, 13(1): 2916.
32	Ihsan-Ul-Haq M, Huang H, Cui J, et al. Chemical interactions between red P and functional groups in NiP₃/CNT composite anodes for enhanced sodium storage[J]. Journal of Materials Chemistry A, 2018, 6(41): 20184-20194.
33	Ge X H, Dou M Y, Cao Y Q, et al. Mechanism driven design of trimer Ni₁Sb₂ site delivering superior hydrogenation selectivity to ethylene[J]. Nature Communications, 2022, 13: 5534.
34	Shimura K, Yoshida S, Oikawa H, et al. Impacts of Ni-loading method on the structure and the catalytic activity of NiO/SiO₂-Al₂O₃ for ethylene oligomerization[J]. Catalysts, 2023, 13(9): 1303.
35	Sun H M, Yang J T, Zhang H W, et al. Hierarchical flower-like NiCu/SiO₂ bimetallic catalysts with enhanced catalytic activity and stability for petroleum resin hydrogenation[J]. Industrial & Engineering Chemistry Research, 2021, 60(15): 5432-5442.
36	Chen D, Wang L L, Chen X P, et al. A Ni-based catalyst with polyvinyl pyrrolidone as a dispersant supported in a pretreated fluid catalytic cracking catalyst residue for C9 petroleum resin (C9 PR) hydrogenation[J]. Royal Society Open Science, 2018, 5(5): 172052.
37	Bai Z X, Chen X, Li C, et al. Preparation of supported palladium catalyst from hydrotalcite-like compound for dicyclopentadiene resin hydrogenation[J]. Molecular Catalysis, 2020, 484: 110728.

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兼具加氢和脱硫活性的富含Ni^δ+非晶态NiP@γ-Al₂O₃催化剂的构筑及其用于石油树脂加氢的性能研究

Construction of amorphous NiP@γ-Al₂O₃ catalyst rich in Ni^δ+ for petroleum resin hydrogenation with enhanced hydrogenation and desulfurization activity

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