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Cs、In掺杂Ni/MgAl(O)催化剂的甲烷二氧化碳干重整反应抗积炭性能研究
Study on coke resistance performances of Cs, In doped Ni/MgAl(O) catalysts in dry reforming reaction of methane and carbon dioxide
- 低碳化学与化工 2025, 50(12): 11-20.
- 作者机构：
1.华东理工大学 化学工程联合国家重点实验室，上海 200237
2.中石化（上海）石油化工研究院 绿色化工与工业催化国家重点实验室，上海 201208
3.中石化齐鲁分公司研究院，山东 淄博 255400
- 作者简介：
袁亨源（2001—），硕士研究生，研究方向为催化反应工程，E-mail：Y82220068@mail.ecust.edu.cn。
刘志成（1975—），博士，教授级高级工程师，研究方向为催化反应工程，E-mail：liuzc.sshy@sinopec.com；
朱卡克（1975—），博士，教授，研究方向为催化反应工程，E-mail：kakezhu@ecust.edu.cn。
- 基金信息：国家自然科学基金(22250005;U1663221);中国石油化工股份有限公司资助项目(222215)
DOI：10.12434/j.issn.2097-2547.20250087
中图分类号： TE64;TQ426收稿：2025-03-06，
修回：2025-04-15，
纸质出版：2025-12-25
- 稿件说明：
移动端阅览
袁亨源,王昊,刘小梁等.Cs、In掺杂Ni/MgAl(O)催化剂的甲烷二氧化碳干重整反应抗积炭性能研究[J].低碳化学与化工,2025,50(12):11-20.
YUAN Hengyuan,WANG Hao,LIU Xiaoliang,et al.Study on coke resistance performances of Cs, In doped Ni/MgAl(O) catalysts in dry reforming reaction of methane and carbon dioxide[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(12):11-20.
袁亨源,王昊,刘小梁等.Cs、In掺杂Ni/MgAl(O)催化剂的甲烷二氧化碳干重整反应抗积炭性能研究[J].低碳化学与化工,2025,50(12):11-20. DOI： 10.12434/j.issn.2097-2547.20250087.
YUAN Hengyuan,WANG Hao,LIU Xiaoliang,et al.Study on coke resistance performances of Cs, In doped Ni/MgAl(O) catalysts in dry reforming reaction of methane and carbon dioxide[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(12):11-20. DOI： 10.12434/j.issn.2097-2547.20250087.
摘要
甲烷二氧化碳干重整（DRM）是一种有应用前景的“碳中和”工业催化过程，但该过程存在催化剂易积炭失活的问题。目前针对DRM催化剂的研究主要集中在对活性金属的单因素调控，而对载体和活性金属协同调控的研究相对较少。以Ni/MgAl
2
O
4
催化剂为基础，采用共沉淀法制备了一系列Ni质量分数均为2%的Ni基催化剂及Cs、In掺杂Ni基催化剂。结合XRD、H
2
-TPR和CO
2
-TPD等多种表征方法，研究了
n
(MgO):
n
(Al
2
O
3
)及Cs、In掺杂对催化剂结构和DRM反应催化性能的影响，并分析了催化剂的抗积炭机理。结果表明，在温度为1073 K、压力为0.1 MPa、
V
(CO
2
):
V
(CH
4
)为1:1和空速为72000 mL/(g·h)的条件下反应120 h，
n
(Cs):
n
(In):
n
(Ni) = 1:1:5、
n
(MgO):
n
(Al
2
O
3
) = 3:1的催化剂（Cs
0.2
In
0.2
-Ni/MAN-3）表现出最优的催化性能及抗积炭性能，其CH
4
转化率和CO
2
转化率分别为76.3%和79.5%，TG失重（质量分数）为2.0%。
Abstract
Dry reforming of methane and carbon dioxide (DRM) is a promising “carbon-neutral” industrial catalytic process. However
the process suffers from the problem of catalyst deactivation due to coke deposition. Current researches on DRM catalysts primarily focus on single-factor regulation of active metals
while studies on the synergistic regulation between supports and active metals remain relatively limited. Based on the Ni/MgAl
2
O
4
catalyst
a series of Ni-based catalysts and Cs
In doped Ni-based catalysts with the constant Ni mass fraction of 2% were prepared by co-precipitation method
. Combining with various characterization techniques such as XRD
H
2
-TPR
and CO
2
-TPD
the effects of
n
(MgO):
n
(Al
2
O
3
) as well as Cs
In doping on catalyst structures and DRM catalytic performances were investigated
and the anti-coking mechanism of catalysts was analyzed. The results indicate that after reaction for 120 h under the conditions of temperature of 1073 K
pressure of 0.1 MPa
V
(CO
2
):
V
(CH
4
) of 1:1 and space velocity of 72000 mL/(g·h)
the catalyst with
n
(Cs):
n
(In):
n
(Ni) of 1:1:5 and
n
(MgO):
n
(Al
2
O
3
) of 3:1 (Cs
0.2
In
0.2
-Ni/MAN-3) exhibits optimal catalytic and coke resistance performances
while its CH
4
conversion rate and CO
2
conversion rate are 76.3% and 79.5%
respectively
and the TG weight loss (mass fraction) is 2.0%.
关键词
Keywords
references
HUANG L N , LI D Y , TIAN D , et al . Optimization of Ni-based catalysts for dry reforming of methane via alloy design: A review [J ] . Energy & Fuels , 2022 , 36 ( 10 ): 5102 - 5151 .
NEMATOLLAHI B , REZAEI M , KHAJENOORI M . Combined dry reforming and partial oxidation of methane to synthesis gas on noble metal catalysts [J ] . International Journal of Hydrogen Energy , 2011 , 36 ( 4 ): 2969 - 2978 .
BARAMA S , DUPEYRAT-BATIOT C , CAPRON M , et al . Catalytic properties of Rh, Ni, Pd and Ce supported on Al-pillared montmorillonites in dry reforming of methane [J ] . Catalysis Today , 2009 , 141 ( 3/4 ): 385 - 392 .
WHANG H S , CHOI M S , LIM J , et al . Enhanced activity and durability of Ru catalyst dispersed on zirconia for dry reforming of methane [J ] . Catalysis Today , 2017 , 293 : 122 - 128 .
KEHRES J , JAKOBSEN J G , ANDREASEN J W , et al . Dynamical properties of a Ru/MgAl 2 O 4 catalyst during reduction and dry methane reforming [J ] . Journal of Physical Chemistry C , 2012 , 116 ( 40 ): 21407 - 21415 .
ZHANG J C , GE B H , LIU T F , et al . Robust ruthenium-saving catalyst for high-temperature carbon dioxide reforming of methane [J ] . ACS Catalysis , 2020 , 10 ( 1 ): 783 - 791 .
CLARIDGE J B , YORK A P E , BRUNGS A J , et al . New catalysts for the conversion of methane to synthesis gas: Molybdenum and tungsten carbide [J ] . Journal of Catalysis , 1998 , 180 ( 1 ): 85 - 100 .
YORK A P E , CLARIDGE J B , BRUNGS A J , et al . Molybdenum and tungsten carbides as catalysts for the conversion of methane to synthesis gas using stoichiometric feedstocks [J ] . Chemical Communications , 1997 , ( 1 ): 39 - 40 .
MARQUART W , RASEALE S , PRIETO G , et al . CO 2 reduction over Mo 2 C-based catalysts [J ] . ACS Catalysis , 2021 , 11 ( 3 ): 1624 - 1639 .
ZHANG X , LIU Y , ZHANG M T , et al . Synergy between β -Mo 2 C nanorods and non-thermal plasma for selective CO 2 reduction to CO [J ] . Chem , 2020 , 6 ( 12 ): 3312 - 3328 .
HORLYCK J , LAWREY C , LOVELL E C , et al . Elucidating the impact of Ni and Co loading on the selectivity of bimetallic NiCo catalysts for dry reforming of methane [J ] . Chemical Engineering Journal , 2018 , 352 : 572 - 580 .
KIM D K , STÖEWE K , MÜELLER F , et al . Mechanistic study of the unusual catalytic properties of a new Ni-Ce mixed oxide for the CO 2 reforming of methane [J ] . Journal of Catalysis , 2007 , 247 ( 1 ): 101 - 111 .
SUN Y H , ZHANG G J , XU Y , et al . Dry reforming of methane over Co-Ce-M/AC-N catalyst: Effect of promoters (Ca and Mg) and preparation method on catalytic activity and stability [J ] . International Journal of Hydrogen Energy , 2019 , 44 ( 41 ): 22972 - 22982 .
LI H C , HAO C , TIAN J Q , et al . Ultra-durable Ni-Ir/MgAl 2 O 4 catalysts for dry reforming of methane enabled by dynamic balance between carbon deposition and elimination [J ] . Chem Catalysis , 2022 , 2 ( 7 ): 1748 - 1763 .
KIM S M , ABDALA P M , MARGOSSIAN T , et al . Cooperativity and dynamics increase the performance of NiFe dry reforming catalysts [J ] . Journal of the American Chemical Society , 2017 , 139 ( 5 ): 1937 - 1949 .
FAKEEHA A H , AL-FATESH A S A , ABASAEED A E . Modification of alumina support with TiO 2 -P25 in CO 2 reforming of CH 4 [J ] . Journal of Industrial and Engineering Chemistry , 2012 , 18 ( 1 ): 212 - 217 .
LI B T , LI L Y , TOMISHIGE K C , et al . Modification of silica supported nickel catalysts with lanthanum for stability improvement in methane reforming with CO 2 [J ] . International Journal of Hydrogen Energy , 2022 , 47 ( 89 ): 37792 - 37810 .
LV X Y , CHEN J F , TAN Y S , et al . A highly dispersed nickel supported catalyst for dry reforming of methane [J ] . Catalysis Communications , 2012 , 20 : 6 - 11 .
ANDRAOS S , ABBAS-GHALEB R , CHLALA D , et al . Production of hydrogen by methane dry reforming over ruthenium-nickel based catalysts deposited on Al 2 O 3 , MgAl 2 O 4 , and YSZ [J ] . International Journal of Hydrogen Energy , 2019 , 44 ( 47 ): 25706 - 25716 .
GUO J J , LOU H , ZHAO H , et al . Dry reforming of methane over nickel catalysts supported on magnesium aluminate spinels [J ] . Applied Catalysis A: General , 2004 , 273 ( 1 ): 75 - 82 .
MARGOSSIAN T , LARMIER K , KIM S M , et al . Molecularly tailored nickel precursor and support yield a stable methane dry reforming catalyst with superior metal utilization [J ] . Journal of the American Chemical Society , 2017 , 139 ( 20 ): 6919 - 6927 .
MEDEIROS R L B A , MACEDO H P , MELO V R M , et al . Ni supported on Fe-doped MgAl 2 O 4 for dry reforming of methane: Use of factorial design to optimize H 2 yield [J ] . International Journal of Hydrogen Energy , 2016 , 41 ( 32 ): 14047 - 14057 .
SADYKOV V A , EREMEEV N F , SADOVSKAYA E , et al . Approaches to the design of efficient and stable catalysts for biofuel reforming into syngas: Doping the mesoporous MgAl 2 O 4 support with transition metal cations [J ] . Dalton Transactions , 2023 , 52 ( 25 ): 8756 - 8769 .
ALABI W O , ADESANMI B M , WANG H , et al . Correlation of MgO loading to spinel inversion, octahedral site occupancy, site generation and performance of bimetal Co-Ni catalyst for dry reforming of CH 4 [J ] . International Journal of Hydrogen Energy , 2024 , 51 : 1087 - 1098 .
ALABI W O , SULAIMAN K O , WANG H , et al . Effect of spinel inversion and metal-support interaction on the site activity of Mg-Al-O x supported Co catalyst for CO 2 reforming of CH 4 [J ] . Journal of CO 2 Utilization , 2020 , 37 : 180 - 187 .
ALABI W O , WANG H , ADESANMI B M , et al . Support composition effect on the structures, metallic sites formation, and performance of Ni-Co-Mg-Al-O composite for CO 2 reforming of CH 4 [J ] . Journal of CO 2 Utilization , 2021 , 43 : 101355 - 101364 .
LONGO A , THEOFANIDIS S A , CAVALLARI C , et al . What makes Fe-modified MgAl 2 O 4 an active catalyst support? Insight from X-ray Raman scattering [J ] . ACS Catalysis , 2020 , 10 ( 12 ): 6613 - 6622 .
ZHANG P H , YAO J T , ZHU Y A , et al . Cs-promoted Co particles on yttria-stabilized zirconia as coke-tolerance methane dry reforming catalyst under elevated pressure [J ] . Chemnanomat , 2025 , 11 ( 1 ): e202400460 .
HALLSTEDT B . Thermodynamic assessment of the system MgO-Al 2 O 3 [J ] . Journal of the American Ceramic Society , 1992 , 75 ( 6 ): 1497 - 1507 .
KHANI Y , KAMYAR N , BAHADORAN F , et al . MAl 2 O 4 (M: Mg, Ni, and Co) as unique support for Ni active metal to form a catalyst for renewable biohydrogen and syngas production from glycerol reforming over a microchannel reactor [J ] . Fuel , 2023 , 332 : 126119 - 126133 .
王玉和 , 刘红梅 , 徐柏庆 . NiO-MgO固溶体的形成对Ni/MgO-AN催化CO 2 重整CH 4 反应活性和稳定性的影响 [J ] . 催化学报 , 2005 , 26 ( 12 ): 1117 - 1121 .
WANG Y H , LIU H M , XU B Q . Effect of formation of NiO-MgO solid solution on activity and stability of Ni/MgO-AN for CO 2 reforming of methane [J ] . Chinese Journal of Catalysis , 2005 , 26 ( 12 ): 1117 - 1121 .
LIN X Y , LI R L , LU M M , et al . Carbon dioxide reforming of methane over Ni catalysts prepared from Ni-Mg-Al layered double hydroxides: Influence of Ni loadings [J ] . Fuel , 2015 , 162 : 271 - 280 .
ZHAN Y Q , HAN J , BAO Z H , et al . Biogas reforming of carbon dioxide to syngas production over Ni-Mg-Al catalysts [J ] . Molecular Catalysis , 2017 , 436 : 248 - 258 .
LI Z W , KATHIRASER Y , ASHOK J , et al . Simultaneous tuning porosity and basicity of nickel@nickel-magnesium phyllosilicate core-shell catalysts for CO 2 reforming of CH 4 [J ] . Langmuir , 2014 , 30 ( 48 ): 14694 - 14705 .
BIAN Z F , SURYAWINATA I Y , KAWI S . Highly carbon resistant multicore-shell catalyst derived from Ni-Mg phyllosilicate nanotubes@silica for dry reforming of methane [J ] . Applied Catalysis B: Environmental , 2016 , 195 : 1 - 8 .
ZENG L , CHENG K , SUN F F , et al . Stable anchoring of single rhodium atoms by indium in zeolite alkane dehydrogenation catalysts [J ] . Science , 2024 , 383 ( 6686 ): 998 - 1004 .
LIU W M , LI L , LIN S X , et al . Confined Ni-In intermetallic alloy nanocatalyst with excellent coking resistance for methane dry reforming [J ] . Journal of Energy Chemistry , 2022 , 65 : 34 - 47 .
STÖCKER M , JENS K J , RIIS T , et al . Characterization of Ni-exchanged montmorillonites by X-ray photoelectron spectroscopy [J ] . Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases , 1988 , ( 6 ): 3901 - 4366 .
HAN J , ZHU Y T , QIN L B , et al . Preparation of Ni-B/MgAl 2 O 4 catalysts for hydrogen production via steam reforming of methane [J ] . International Journal of Hydrogen Energy , 2024 , 78 : 353 - 362 .
YIN X L , SHEN L H , WANG S , et al . Double adjustment of Co and Sr in LaMnO 3+ δ perovskite oxygen carriers for chemical looping steam methane reforming [J ] . Applied Catalysis B-Environmental , 2022 , 301 : 120816 - 120832 .
谢华 , 王烈林 , 罗德礼 , 等 . 烧绿石型富氧相Ce 2 Zr 2 O 8 与缺氧相Nd 2 Zr 2 O 7 的振动光谱及XPS对比研究 [J ] . 光谱学与光谱分析 , 2014 , 34 ( 6 ): 1518 - 1523 .
XIE H , WANG D L , LUO D L , et al . Vibrational spectrum and XPS contrastive studies on pyrochlore-type oxygen-rich Ce 2 Zr 2 O 8 and oxygen-defective Nd 2 Zr 2 O 2 phases [J ] . Spectroscopy and Spectral Analysis , 2014 , 34 ( 6 ): 1518 - 1523 .
DE A K , SINHA I . Synergistic effect of Ni doping and oxygen vacancies on the visible light photocatalytic properties of Ag 2 O nanoparticles [J ] . Journal of Physics and Chemistry of Solids , 2022 , 167 : 110733 - 110742 .
LUAN K R , CAO J P , TANG W , et al . Effect of oxygen vacancy of lignite-char-supported Co catalysts doped with In on efficient dry reforming of methane [J ] . Chemical Engineering Science , 2024 , 290 : 119914 - 119924 .
HORVÁTH A , NÉMETH M , BECK A , et al . Longevity increase of an impregnated Ni/CeO 2 -Al 2 O 3 dry reforming catalyst by indium [J ] . Applied Catalysis A: General , 2024 , 669 : 119495 - 119508 .
BU K K , DENG J , ZHANG X Y , et al . Promotional effects of B-terminated defective edges of Ni/boron nitride catalysts for coking- and sintering-resistant dry reforming of methane [J ] . Applied Catalysis B: Environmental , 2020 , 267 : 118692 - 118703 .
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