限域型催化剂Ni@S2对甲烷干重整反应性能影响

doi:10.19964/j.issn.1006-4990.2024-0242

Abstract

Abstract:

The dry reforming reaction（DRM） of methane can rationally utilize two greenhouse gases of CO₂ and CH₄ to produce environmentally friendly and clean fuels of CO and H₂.However，the nickel-based catalysts used in this process are susceptible to carbon accumulation and sintering at high temperatures，which makes it difficult to satisfy the demands of industrial production.Based on this，domain-limited Ni@S2（Silicalite-2） catalysts were prepared by the grinding crystallization method.The results showed that the domain-limited Ni@S2 catalyst exhibited an olivine-like crystal structure with a large specific surface area and a narrow pore size distribution，and the NiO nanoparticles were uniformly dispersed in the Silicalite-2 skeleton，with an average NiO grain size of about 4.63 nm.After the dry reforming reaction at 700 ℃ for 6 h［F_in=40 mL/min，V（CH₄）:V（CO₂）:V（Ar）=44:44:12］，compared with the loaded catalyst 10Ni/SiO₂，the confined 10Ni@S2 catalysts exhibited excellent catalytic activity and carbon deposition resistance，the instantaneous conversion of CH₄ was increased from 65.51% to 91.91%，the instantaneous conversion of CO₂ was increased from 71.89% to 91.14%，and the carbon deposition rate was decreased from 16.30% to 1.20%.The excellent catalytic performance and stability of the catalyst were due to the limited domain structure，which avoided the sintering of the active component，reduced the particle size of NiO，and improved the interaction between the metal and the support.This study opened up a new direction for the preparation of low cost and high stability nickel-based catalysts.

Key words: grinding crystallization method, drm reaction, Silicate-2 zeolite, confined catalyst, carbon deposition

CLC Number:

O643.3

ZHU Jicheng, YANG Qixin, LIANG Haoquan, WANG Zengkun, OUYANG Fugui, DI Jing, GAI Xikun. Effect of confined catalyst Ni@S2 on performance of methane dry reforming reaction[J]. Inorganic Chemicals Industry, 2025, 57(2): 138-146.

Figures/Tables 14

Fig.1

Fig.2

Fig.3

Table 1

Fig.4

Fig.5

Fig.6

Fig.7

Fig.8

Fig.9

Table 2

Fig.10

Fig.11

Fig.12

References 28

1	CHEN Siyuan， LIU Jiangfeng， ZHANG Qi，et al.A critical review on deployment planning and risk analysis of carbon capture，utilization，and storage（CCUS） toward carbon neutrality［J］.Renewable and Sustainable Energy Reviews，2022，167：112537.
2	ABBASI K R， HUSSAIN K， RADULESCU M，et al.Does natural resources depletion and economic growth achieve the carbon neutrality target of the UK？A way forward towards sustainable development［J］.Resources Policy，2021，74：102341.
3	YANG Songxi， YANG Jian， SHI Shuo，et al.The rising impact of urbanization-caused CO₂ emissions on terrestrial vegetation［J］.Ecological Indicators，2023，148：110079.
4	WANG Fang， HARINDINTWALI J D， YUAN Zhizhang，et al.Technologies and perspectives for achieving carbon neutrality［J］.The Innovation，2021，2（4）：100180.
5	SOVACOOL B K， BAZILIAN M D， KIM J，et al.Six bold steps towards net-zero industry［J］.Energy Research & Social Science，2023，99：103067.
6	LA PAROLA V， LIOTTA L F， PANTALEO G，et al.CO₂ reforming of CH₄ over Ni supported on SiO₂ modified by TiO₂ and ZrO₂：Effect of the support synthesis procedure［J］.Applied Catalysis A：General，2022，642：118704.
7	GUHAROY U， REINA T R， LIU Jian，et al.A theoretical overview on the prevention of coking in dry reforming of methane using non-precious transition metal catalysts［J］.Journal of CO2 Utilization，2021，53：101728.
8	GONZÁLEZ-CASTAÑO M， LE SACHÉ E， BERRY C，et al.Nickel phosphide catalysts as efficient systems for CO₂ upgrading via dry reforming of methane［J］.Catalysts，2021，11（4）：446.
9	LI Jianwei， LI Jun， ZHU Qingshan.Carbon deposition and catalytic deactivation during CO₂ reforming of CH₄ over Co/MgO catalyst［J］.Chinese Journal of Chemical Engineering，2018，26（11）：2344-2350.
10	胡明亮，周微，李滨，等.协同效应催化甲烷二氧化碳重整研究进展［J］.无机盐工业，2024，56（1）：23-32.
	HU Mingliang， ZHOU Wei， LI Bin，et al.Research progress of synergistic effect catalytic reforming of methane and carbon dioxide［J］.Inorganic Chemicals Industry，2024，56（1）：23-32.
11	ZHANG Qiulin， WANG Mingzhi， ZHANG Tengfei，et al.A stable Ni/SBA-15 catalyst prepared by the ammonia evaporation method for dry reforming of methane［J］.RSC Advances，2015，5（114）：94016-94024.
12	SETIABUDI H D， CHONG C C， ABED S M，et al.Comparative study of Ni-Ce loading method：Beneficial effect of ultrasonic-assisted impregnation method in CO₂ reforming of CH₄ over Ni-Ce/SBA-15［J］.Journal of Environmental Chemical Engineering，2018，6（1）：745-753.
13	WANG Luhui， LIU Hui， YE Han，et al.Vacuum thermal treated Ni-CeO₂/SBA-15 catalyst for CO₂ methanation［J］.Nanomaterials，2018，8（10）：759.
14	WANG Chengtao， ZHANG Jian， QIN Gangqiang，et al.Direct conversion of syngas to ethanol within zeolite crystals［J］.Chem，2020，6（3）：646-657.
15	WANG Chengtao， WANG Liang， ZHANG Jian，et al.Product selectivity controlled by zeolite crystals in biomass hydrogenation over a palladium catalyst［J］.Journal of the American Chemical Society，2016，138（25）：7880-7883.
16	狄璐，王卫国，陈珏先，等.过渡金属负载Silicalite-1分子筛的制备及其催化糠醛加氢性能研究［J］.无机盐工业，2024，56（4）：125-132.
	DI Lu， WANG Weiguo， CHEN Juexian，et al.Study on preparation of transition metal-supported Silicalite-1 zeolite catalyst and its catalytic performance for furfural hydrogenation［J］.Inorganic Chemicals Industry，2024，56（4）：125-132.
17	DENG Min， MA Jun， LIU Yuantong，et al.Pd nanoparticles confined in pure Silicalite-2 zeolite with enhanced catalytic performance for the dehydrogenation of formic acid at room temperatu- re［J］.Fuel，2023，333：126466.
18	WANG Jiyang， FU Yu， KONG Wenbo，et al.Design of a carbon-resistant Ni@S-2 reforming catalyst：Controllable Ni nanoparticles sandwiched in a peasecod-like structure［J］.Applied Catalysis B：Environmental，2021，282：119546.
19	ZHANG Yidan， LI Shuqing， FU Yu，et al.Local coordination environment triggers key Ni-O-Si copolymerization on silicalite-2 for dry reforming of methane［J］.Applied Catalysis B：Environment and Energy，2024，350：123903.
20	盖希坤，杨丹，朱继成，等.嵌入型Ni@S1催化剂的制备及其CH₄-CO₂重整反应性能［J］.洁净煤技术，2022，28（5）：71-80.
	GAI Xikun， YANG Dan， ZHU Jicheng，et al.Preparation and performance of embedded type Ni@S1 catalyst for CH₄-CO₂ reforming reaction［J］.Clean Coal Technology，2022，28（5）：71-80.
21	WANG Yi， MI Jinxing， WU Zhongshuai.Recent status and challenging perspective of high entropy oxides for chemical cataly- sis［J］.Chem Catalysis，2022，2（7）：1624-1656.
22	TORREZ-HERRERA J J， KORILI S A， GIL A.Recent progress in the application of Ni-based catalysts for the dry reforming of methane［J］.Catalysis Reviews，2023，65（4）：1300-1357.
23	GAI Xikun， YANG Dan， TANG Ruiyuan，et al.Preparation of Ni-Co/SiO₂ catalyst by ammonia reflux impregnation and its CH₄-CO₂ reforming reaction performance［J］.Fuel，2022，316：123337.
24	LV Hongwei， GUO Wenxin， CHEN Min，et al.Rational construction of thermally stable single atom catalysts：From atomic structure to practical applications［J］.Chinese Journal of Catalysis，2022，43（1）：71-91.
25	刘国东.ZnO改性纳米Silicalite-1沸石表面酸性及催化性能的研究［D］.大连：大连理工大学，2019.
	LIU Guodong.Study on surface acidity and catalytic performance of nano-Silicalite-1 zeolite modified by ZnO［D］.Dalian：Dalian University of Technology，2019.
26	ALHASSAN A M， HUSSAIN I， TAIALLA O A，et al.Advances in catalytic dry reforming of methane（DRM）：Emerging trends，current challenges，and future perspectives［J］.Journal of Cleaner Production，2023，423：138638.
27	MOVASATI A， ALAVI S M， MAZLOOM G.Dry reforming of methane over CeO₂-ZnAl₂O₄ supported Ni and Ni-Co nano-catalysts［J］.Fuel，2019，236：1254-1262.
28	LU Peng， RISWAN M， CHANG Xiaoning，et al.Hydrogenation of CO₂ to light olefins on ZZ/MnSAPO-34@Si-2：Effect of silicalite-2 seeds on the acidity and catalytic activity［J］.Fuel，2022，330：125470.

催化剂	^a表面积/ （m²·g^-1）		^b孔体积/ （cm³·g^-1）		孔径/ nm		^c粒径/ nm
催化剂	反应前	反应后	反应前	反应后	反应前	反应后	反应前	反应后
S2	558.30		0.38		5.41
10Ni/SiO₂	230.27	203.48	0.77	0.63	14.20	14.26	9.58	21.3
10Ni/S2	432.34	349.87	0.21	0.13	5.23	2.34	11.32	24.9
5Ni@S2	411.49	405.32	0.13	0.14	3.07	3.07	5.66	5.64
10Ni@S2	397.93	393.63	0.11	0.12	3.49	3.22	4.63	4.72
30Ni@S2	369.44	287.43	0.10	0.11	4.36	1.97	9.34	26.2

催化剂	CH₄转化率/%		CO₂转化率/%		S（H₂）/ S（CO）
催化剂	起始	反应6 h后	起始	反应6 h后	S（H₂）/ S（CO）
10Ni/SiO₂	65.51	63.17	71.89	70.19	0.83
10Ni/S2	84.39	65.40	83.26	68.74	0.91
5Ni@S2	87.26	88.45	90.35	88.45	0.93
10Ni@S2	91.91	91.93	91.14	90.93	0.96
30Ni@S2	90.69	75.44	90.60	76.58	0.91

[1]	LIU Huangfei, ZHANG Li, LIU Tao. Research progress of fast synthesis technologies of zeolites [J]. Inorganic Chemicals Industry, 2025, 57(2): 36-43.
[2]	LUO Chengling, FAN Xiaofan. Research progress of microstructure-regulated catalysts for urea oxidation reactions [J]. Inorganic Chemicals Industry, 2025, 57(2): 26-35.
[3]	FAN Jingxin, LI Bin, HONG Luwei, HONG Meihua, GONG Xin. Research status and prospects of olefin removal catalyst from aromatic reforming oil [J]. Inorganic Chemicals Industry, 2025, 57(2): 14-25.
[4]	LIU Guangming. Study on photocatalytic and mechanical properties of C₃N₅/NH₂-MIL-125（Ti） modified concrete mortar [J]. Inorganic Chemicals Industry, 2025, 57(1): 120-128.
[5]	SUN Qinghao, LI Keyan, GUO Xinwen. Study on photocatalytic benzyl alcohol oxidation coupled with hydrogen production over Pd/ZnIn₂S₄ nanosheets [J]. Inorganic Chemicals Industry, 2025, 57(1): 113-119.
[6]	WANG Yawen, WANG Fangfang, GENG Siyu, JU Jia, CHEN Lei, CHEN Changdong. Study on preparation and photocatalytic performance of SrTiO₃-SrWO₄ [J]. Inorganic Chemicals Industry, 2024, 56(7): 143-149.
[7]	LI Yongheng, MI Xiaotong, ZHANG Peipei. Synthesis of holycrystalline nano-ZSM-5 aggregate and its application in methylation of toluene [J]. Inorganic Chemicals Industry, 2024, 56(5): 135-140.
[8]	LI Jiangpeng, ZHANG Huibin. Synergistic degradation of methylene blue by photo-Fenton and photocatalytic with 3D porous LaFeO₃/CeO₂/SrTiO₃ [J]. Inorganic Chemicals Industry, 2024, 56(5): 141-148.
[9]	WANG Chao, SONG Guoliang, XIAO Han. Industrial application of THFS-2 sulfurized reforming prehydrogenation catalysts [J]. Inorganic Chemicals Industry, 2024, 56(5): 94-100.
[10]	DI Lu, WANG Weiguo, CHEN Juexian, WU Chuanshu. Study on preparation of transition metal-supported Silicalite-1 zeolite catalyst and its catalytic performance for furfural hydrogenation [J]. Inorganic Chemicals Industry, 2024, 56(4): 125-132.
[11]	TANG Bei. Preparation of ZnO/g-C₃N₄ heterojunction photocatalytic material and its degradation of pyridine [J]. Inorganic Chemicals Industry, 2024, 56(4): 133-142.
[12]	ZHU Jinjian, YANG Xiaxia, MU Zhanpeng, SONG Guoliang, LI Zihan, LIU Wei, XU Yan, ZHANG Jingcheng. Effect of different additives on liquid phase selective hydrogenation performance of maleic anhydride over Ni/Al₂O₃ [J]. Inorganic Chemicals Industry, 2024, 56(4): 143-150.
[13]	ZHOU Xuan, LI Mengrui, CHEN Yichen, FAN Huiqiang, WANG Bin, YUAN Gang. Research progress of nickel-based phosphide composites in improving of catalytic water electrolysis for hydrogen evolution performance [J]. Inorganic Chemicals Industry, 2024, 56(4): 8-15.
[14]	HU Mingliang, ZHOU Wei, LI Bin, LAI Xiaoling. Research progress of synergistic effect catalytic reforming of methane and carbon dioxide [J]. Inorganic Chemicals Industry, 2024, 56(1): 23-32.
[15]	CHEN Xu, YANG Gang, LI Haitao. Study on preparation of multistage pore nano-SAPO-34 molecular sieves and its methanol to olefin performance [J]. Inorganic Chemicals Industry, 2024, 56(1): 134-140.

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Effect of confined catalyst Ni@S2 on performance of methane dry reforming reaction

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 14

References 28

Related Articles 15

Metrics

Comments

Recommended 0