镍催化剂上HDPE热解挥发物的氧化蒸汽重整: 载体和助剂的影响

doi:10.1016/S1872-2067(24)60222-6

摘要/Abstract

摘要：

在由锥形喷射床反应器和流化床反应器组成的两步反应体系中进行了高密度聚乙烯(HDPE)热解和在线氧化蒸汽重整(P-OSR)反应. 将550 °C连续塑料热解形成的挥发物在线送入700 °C的氧化蒸汽重整步骤(时空3.12 g-cat min g-HDPE^-1, 当量比 = 0.2, 蒸汽/塑料比(S/P) = 3). 考察了镍基重整催化剂载体(Al₂O₃, ZrO₂和SiO₂)和助剂(CeO₂和La₂O₃)对HDPE热解挥发物转化和生成H₂的影响. 采用湿浸渍法制备催化剂, 并通过N₂吸附-解吸、X射线荧光、程序升温还原和X射线粉末衍射对其进行了表征. 通过焦炭程序升温氧化、透射电镜和氮气吸附-解吸对催化剂上积炭及其失活性能进行了初步研究. 所考察的载体中以ZrO₂的性能最佳, 转化率和H₂产量分别为92.2%和12.8wt%. 虽然添加了二种助剂的催化剂上转化率接近(约90%), 但产氢性能差异显著. 由于La₂O₃能够增强催化剂表面上水的吸附, 因此Ni/La₂O₃-Al₂O₃催化剂上产氢量(12.1 wt%)高于CeO₂促进催化剂的.

关键词: 塑料, 热解, 氧化蒸汽重整, Ni催化剂, 氢气

Abstract:

High density polyethylene (HDPE) pyrolysis and in-line oxidative steam reforming was carried out in a two-step reaction system consisting of a conical spouted bed reactor and a fluidized bed reactor. Continuous plastic pyrolysis was conducted at 550 °C and the volatiles formed were fed in-line to the oxidative steam reforming step (space-time 3.12 g_cat min g_HDPE^-1; ER = 0.2 and steam/plastic = 3) operating at 700 °C. The influence Ni based reforming catalyst support (Al₂O₃, ZrO₂, SiO₂) and promoter (CeO₂, La₂O₃) have on HDPE pyrolysis volatiles conversion and H₂ production was assessed. The catalysts were prepared by the wet impregnation and they were characterized by means of N₂ adsorption-desorption, X-ray fluorescence, temperature-programmed reduction and X-ray powder diffraction. A preliminary study on coke deposition and the deterioration of catalysts properties was carried out, by analyzing the tested catalysts through temperature programmed oxidation of coke, transmission electron microscopy, and N₂ adsorption-desorption. Among the supports tested, ZrO₂ showed the best performance, attaining conversion and H₂ production values of 92.2% and 12.8 wt%, respectively. Concerning promoted catalysts, they led to similar conversion values (around 90%), but significant differences were observed in H₂ production. Thus, higher H₂ productions were obtained on the Ni/La₂O₃-Al₂O₃ catalyst (12.1 wt%) than on CeO₂ promoted catalysts due to La₂O₃ capability for enhancing water adsorption on the catalyst surface.

Key words: Plastic, Pyrolysis, Oxidative steam reforming, Ni catalyst, Hydrogen

Mayra Alejandra Suarez, Laura Santamaria, Gartzen Lopez, Enara Fernandez, Martin Olazar, Maider Amutio, Maite Artetxe. 镍催化剂上HDPE热解挥发物的氧化蒸汽重整: 载体和助剂的影响[J]. 催化学报, 2025, 69: 149-162.

Mayra Alejandra Suarez, Laura Santamaria, Gartzen Lopez, Enara Fernandez, Martin Olazar, Maider Amutio, Maite Artetxe. Oxidative steam reforming of HDPE pyrolysis volatiles on Ni catalysts: Effect of the support (Al₂O₃, ZrO₂, SiO₂) and promoter (CeO₂, La₂O₃) on the catalyst performance[J]. Chinese Journal of Catalysis, 2025, 69: 149-162.

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https://www.cjcatal.com/CN/Y2025/V69/I2/149

图/表 14

Table 1 The textural properties, Ni content and metal dispersion of the catalysts.

Support	Ni⁰ content (wt%)	S_BET (m² g^-1)	V_pore (cm³ g^-1)	d_pore (Å)	d_M XRD^a (nm)	Ni dispersion^b (%)
Al₂O₃	—	87	0.38	173	—	—
SiO₂	—	703	0.14	45	—	—
ZrO₂	—	97	0.34	110	—	—
Supported catalyst
Ni/Al₂O₃ (commercial)	11.34	19	0.04	122	25	3.9
Ni/SiO₂	9.55	429	0.12	53	11	8.8
Ni/ZrO₂	9.51	34	0.31	322	25	3.9
Promoted catalyst
Ni/CeO₂-Al₂O₃	8.15	66	0.36	181	18	5.4
Ni/La₂O₃-Al₂O₃	8.10	52	0.39	214	20	4.9
Ni/CeO₂-ZrO₂	6.57	29	0.15	197	32	3.0

Fig. 1. TPR profiles of Ni based supported catalysts (a) and promoted catalysts (b).

Fig. 2. XRD patterns of supported catalysts after the reduction step. Crystalline phases: () Ni0, () CaO(Al2O3)2, () CaAl2O4, () CaAl12O19, () Al2O3 and () Monoclinic ZrO2.

Fig. 3. XRD patterns of promoted catalysts after the reduction step. Crystalline phases: () Ni0, () Monoclinic ZrO2, () Tetragonal ZrO2, () Al2O3, () CeAlO3 and () CeO2.

Fig. 4. Performance of supported catalysts (conversion and H2 production) in the oxidative steam reforming of HDPE pyrolysis volatiles. Reaction conditions: 700 °C, space time 3.12 gcat min gHDPE-1.

Fig. 5. Individual product yields obtained in the oxidative steam reforming of HDPE pyrolysis volatiles on the supported catalysts. Reaction conditions: 700 °C, space time 3.12 gcat min gHDPE-1.

Fig. 6. TPO profiles of the coke deposited on the supported catalysts.

Table 2 Textural prope rties, coke amount and deposition rate of used supported catalysts.

Supported catalyst	Textural properties (fresh/tested)			Coke deposition
Supported catalyst	S_BET (m² g^-1)	V_pore (cm³ g^-1)	d_pore (Å)	C_c (wt%)	t (min)	r_c (mg_coke g_cat^-1 g_HDPE^-1)
Ni/Al₂O₃ (commercial)	19/17	0.04/0.03	122/140	1.95	30	0.65
Ni/SiO₂	429/305	0.12/0.11	53/55	0.77	30	0.26
Ni/ZrO₂	34/28	0.31/0.2	322/257	1.92	30	0.64

Fig. 7. TEM images of Ni/Al2O3 (a), Ni/SiO2 (b) and Ni/ZrO2 (c) used catalysts.

Fig. 8. Effect of promoted catalysts on the conversion and H2 production in the oxidative steam reforming of HDPE pyrolysis volatiles. Reaction conditions: 700 °C, space time 3.12 gcat min gHDPE-1.

Fig. 9. Effect of promoted catalysts on the yields of the individual products obtained in the oxidative steam reforming of HDPE pyrolysis volatiles. Reaction conditions: 700 °C, space time 3.12 gcat min gHDPE-1.

Fig. 10. TPO profiles of the coke deposited on the promoted catalysts.

Table 3 Textural properties, coke amount and deposition rate of used promoted catalysts.

Promoted catalyst	Textural properties (fresh/tested)			Coke deposition
Promoted catalyst	S_BET (m² g^-1)	V_pore (cm³ g^-1)	d_pore (Å)	C_c (wt%)	t (min)	r_c (mg_coke g_cat^-1 g_HDPE^-1)
Ni/CeO₂-Al₂O₃	66/57	0.36/0.22	181/155	1.07	30	0.36
Ni/La₂O₃-Al₂O₃	52/32	0.39/0.20	214/175	1.83	30	0.61
Ni/CeO₂-ZrO₂	29/18	0.15/0.08	197/180	1.20	30	0.40

Fig. 11. TEM images of Ni/CeO2-Al2O3 (a), Ni/La2O3-Al2O3 (b) and Ni/CeO2-ZrO2 (c) used catalysts.

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