Cu-Fe-MgO/AlPO<sub>4</sub>-5对甲醇水蒸气重整制氢的催化性能研究

巢磊; 武丹丹; 李工

Cu-Fe-MgO/AlPO₄-5对甲醇水蒸气重整制氢的催化性能研究

常州大学石油化工学院, 江苏常州 213164

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中图分类号: O643
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出版历程
- 收稿日期: 2017-04-24
- 修回日期: 2017-06-27
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-09-10

Study on catalytic properties of Cu-Fe-MgO/AlPO₄-5 for hydrogen production from steam reforming of methanol

School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China

More Information

Corresponding author: LI Gong, E-mail:ligong136@126.com

摘要

摘要: 以AlPO₄-5分子筛为载体，采用浸渍法制备Cu-Fe-MgO/AlPO₄-5催化剂，用于催化甲醇和水蒸气重整反应制氢气。采用XRD、N₂吸附-脱附、H₂-TPR、CO₂-TPD和NH₃-TPD等对催化剂进行表征。结果表明，加入Fe可以明显提高甲醇的转化率，但副产物二甲醚的选择性也增加，添加MgO对降低二甲醚具有明显的作用，但不能提高甲醇的转化率。AlPO₄-5负载Cu、Fe和MgO的质量分数分别为15%、6%和1%时具有较高的催化活性，在反应温度300℃、水醇物质的量比为1.1：1和质量空速2.51 h^-1的条件下，对甲醇的转化率为93.08%，二氧化碳和氢气的选择性分别为95.80%和96.93%，对副产物一氧化碳和二甲醚的选择性分别为1.70%和2.51%。表征结果表明，Cu-Fe-MgO/AlPO₄-5同时含有弱酸弱碱和强酸强碱中心，适量的MgO增加了强碱中心的量，降低弱酸中心的强度，但对强酸中心影响不大。
- AlPO₄-5分子筛 /
- Cu-Fe-MgO/AlPO₄-5 /
- 催化反应 /
- 甲醇水蒸气重整 /
- 氢气
Abstract: Cu-Fe-MgO/AlPO₄-5 catalysts were prepared by impregnation method using AlPO₄-5 molecular sieve as support to produce hydrogen through steam reforming of methanol. The catalysts were characterized by XRD, N₂ adsorption-desorption, H₂-TPR, CO₂-TPD and NH₃-TPD. The reaction results indicated that the addition of Fe could significantly increase the conversion of methanol, but the selectivity of dimethyl ether was also increased. The addition of MgO had obvious effects on the reduction of dimethyl ether formation, but the conversion of methanol could not be improved. The catalyst with Cu, Fe and MgO loadings of 15%, 6% and 1%, respectively showed a higher catalytic activity. Under the reaction conditions of 300℃, 1.1:1 of molar ratio of water to alcohol and 2.51 h^-1 of mass space velocity, the conversion of methanol was 93.08%, the selectivity of carbon dioxide and hydrogen were 95.80% and 96.93% respectively and the selectivity of by-products of carbon monoxide and dimethyl ether were 1.70% and 2.51% respectively. According to the characterization results, Cu-Fe-MgO/AlPO₄-5 contains weak acid and base sites, strong acid and base sites. It can be concluded that appropriate amount of MgO increases the amount of strong basic sites, reduces the strength of weak acidic sites, but had little effects on strong acidic sites.
- AlPO₄-5 molecular sieve /
- Cu-Fe-MgO/AlPO₄-5 /
- catalytic reaction /
- methanol steam reforming /
- hydrogen

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图 1 H₂O/CH₃OH物质的量比对催化活性的影响

Figure 1 Effect of H₂O/CH₃OH molar ratio on catalytic performance

a: s_CO; b: s_CH₃OCH₃; c: x_CH₃OH; d: s_CO₂; e: s_H₂

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图 2 质量空速对催化活性的影响

Figure 2 Effect of WHSV on catalytic performance

a: s_CO; b: s_CH₃OCH₃; c: x_CH₃OH; d: s_CO₂; e: s_H₂

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图 3 反应时间对催化剂活性的影响

Figure 3 Effect of reaction time on catalytic performance

a: s_CO; b: s_CH₃OCH₃; c: x_CH₃OH; d: s_CO₂; e: s_H₂

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图 4 催化剂的XRD谱图

Figure 4 XRD patterns of the catalysts

a: AlPO₄-5; b: Cu(15)/AlPO₄-5; c: Cu(15)-Fe(6)/AlPO₄-5; d: Cu(15)-Fe(6)-MgO(1)/AlPO₄-5

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图 5 催化剂的SEM照片

Figure 5 SEM micrographs of the catalyst samples

(a): AlPO₄-5; (b): Cu(15)-Fe(6)-MgO(1)/AlPO₄-5

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图 6 催化剂的H₂-TPR谱图

Figure 6 H₂-TPR profiles of the catalysts

a: Fe(6)/AlPO₄-5; b: Cu(15)/AlPO₄-5; c: Cu(15)-Fe(6)/AlPO₄-5;d: Cu(15)-Fe(6)-MgO(1)/AlPO₄-5

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图 7 催化剂的CO₂-TPD谱图

Figure 7 CO₂-TPD profiles of the catalysts

a: AlPO₄-5; b: Cu(15)/AlPO₄-5; c: Fe(6)/AlPO₄-5; d: Cu(15)-Fe(6)/AlPO₄-5; e: Cu(15)-Fe(6)-MgO(1)/AlPO₄-5

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图 8 催化剂的NH₃-TPD谱图

Figure 8 NH₃-TPD profiles of the catalysts

a: AlPO₄-5; b: Cu(15)/AlPO₄-5; c: Fe(6)/AlPO₄-5; d: Cu(15)-Fe(6)/AlPO₄-5; e: Cu(15)-Fe(6)-MgO(1)/AlPO₄-5

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表 1 铜负载量对催化活性的影响

Table 1 Effect of Cu content on catalytic activity

Catalyst	t/℃	x_CH₃OH/%	s_CO₂/%	s_H₂/%	s_CO/%	s_{CH₃ OCH₃} /%
Cu(5)/AlPO₄-5	260	16.44	87.76	89.92	3.23	9.01
	280	24.61	90.64	92.33	2.54	6.82
	300	42.88	88.84	90.34	2.25	8.91
	315	51.31	89.78	91.16	2.08	8.14
Cu(10)/AlPO₄-5	260	20.87	95.44	97.01	2.35	2.21
	280	26.41	92.51	93.60	1.63	5.86
	300	44.14	91.07	92.42	2.02	6.91
	315	52.33	90.49	91.99	2.25	7.26
Cu(15)/AlPO₄-5	260	23.44	95.93	97.01	1.63	2.44
	280	34.65	94.44	95.49	1.58	3.99
	300	55.16	92.16	93.42	1.88	5.96
	315	60.64	91.13	92.34	1.81	7.06
Cu(20)/AlPO₄-5	260	26.25	96.91	98.18	1.90	1.19
	280	35.45	96.31	96.95	0.96	2.73
	300	50.00	94.91	96.00	1.63	3.46
	315	55.26	93.30	94.55	2.39	4.32
reaction conditions：WHSV=3.52 h^-1, H₂O/CH₃OH(molar ratio)=1.1:1

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表 2 铁负载量对催化活性的影响

Table 2 Effect of Fe content on catalytic activity

Catalyst	t/℃	x_CH₃OH/%	s_CO₂/%	s_H₂/%	s_CO/%	s_{CH₃ OCH₃} /%
Cu(15)-Fe(2)/AlPO₄-5	260	37.73	89.50	91.14	2.46	8.04
	280	52.89	89.25	90.17	1.38	9.37
	300	67.65	90.43	91.39	1.45	8.12
	315	72.13	87.83	89.68	2.78	9.39
Cu(15)-Fe(5)/AlPO₄-5	260	35.54	89.04	90.67	2.44	8.52
	280	75.31	91.43	92.55	1.68	6.89
	300	89.54	91.74	92.96	1.84	6.42
	315	87.39	86.39	89.12	4.09	9.52
Cu(15)-Fe(7.5)/AlPO₄-5	260	41.41	92.14	93.03	1.33	6.53
	280	64.48	91.43	92.25	1.23	7.34
	300	85.75	92.09	93.03	1.41	6.49
	315	89.25	87.64	90.49	4.27	8.09
Cu(15)-Fe(10)/AlPO₄-5	260	38.25	93.18	94.33	1.72	5.10
	280	62.59	90.62	91.60	1.48	7.90
	300	76.27	88.22	89.18	1.44	10.34
	315	84.06	86.13	87.61	2.21	11.66
reaction conditions：WHSV=3.52 h^-1, H₂O/CH₃OH(molar ratio)=1.1:1

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表 3 氧化镁含量对催化活性的影响

Table 3 Effect of MgO content on catalytic activity

Catalyst	t/℃	x_CH₃OH/%	s_CO₂/%	s_H₂/%	s_CO/%	s_{CH₃ OCH₃} /%
Cu(15)-Fe(5)-MgO(0.5)/AlPO₄-5	260	48.66	94.91	96.30	2.08	3.00
	280	74.84	96.05	96.95	1.34	2.60
	300	78.88	93.51	94.67	1.74	4.75
	315	82.11	90.29	92.37	3.11	6.59
Cu(15)-Fe(5)-MgO(1)/AlPO₄-5	260	40.55	96.80	97.84	1.55	1.64
	280	71.46	94.75	95.18	1.64	3.61
	300	87.70	93.83	95.40	1.99	4.18
	315	89.43	90.04	91.36	2.35	7.62
Cu(15)-Fe(5)-MgO(2)/AlPO₄-5	260	27.14	96.34	97.70	2.05	1.61
	280	44.58	95.77	96.86	1.63	2.60
	300	61.78	94.85	95.94	1.64	3.51
	315	70.94	94.05	95.49	2.16	3.79
Cu(15)-Fe(5)-MgO(4)/AlPO₄-5	260	37.88	97.88	99.05	1.76	0.36
	280	63.79	97.29	98.48	1.78	0.92
	300	72.49	95.72	97.06	2.00	2.27
	315	74.69	95.21	96.67	2.19	2.60
reaction conditions：WHSV=3.52 h^-1, H₂O/CH₃OH(molar ratio)=1.1:1

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表 4 L₉(3⁴) Cu-Fe-MgO/AlPO₄-5催化甲醇水蒸气重整制氢反应的正交实验

Table 4 Orthogonal experiment and analysis table of hydrogen production by steam reforming of methanol over Cu-Fe-MgO/AlPO₄-5 catalyst

Program					Index
Number	A t/℃	B Cu/%	C Fe/%	D MgO/%	x_CH₃OH /%	s_CO₂/%
1	1(280)	1(12)	3(7)	2(2)	61.43	95.95
2	2(300)	1(12)	1(3)	1(1)	88.89	93.77
3	3(310)	1(12)	2(5)	3(3)	69.67	91.07
4	1(280)	2(15)	2(5)	1(1)	71.46	94.75
5	2(300)	2(15)	3(7)	3(3)	76.40	95.11
6	3(310)	2(15)	1(3)	2(2)	77.10	93.36
7	1(280)	3(17)	1(3)	3(3)	40.76	97.83
8	2(300)	3(17)	2(5)	2(2)	82.74	95.92
9	3(310)	3(17)	3(7)	1(1)	91.54	92.42
K_A1, K_B1	173.65，288.53	219.99，280.79	206.76，284.96	251.89，280.94	total=659.99	total=850.18
K_A2, K_B2	248.03，284.80	224.97，283.22	223.87，281.74	221.28，285.23
K_A3, K_B3	238.32，276.85	215.04，286.17	229.37，283.48	186.83，284.01
k_A1, k_B1	57.88，96.18	73.33，93.60	68.92，94.99	83.96，93.65
k_A2, k_B2	82.68，94.93	74.99，94.41	74.62，93.91	73.76，95.08
k_A3, k_B3	79.44，92.28	71.68，95.39	76.46，94.49	62.28，94.67
R_A, R_B	24.80，3.90	3.31，1.79	7.54，1.08	21.68，1.43
reaction conditions：WHSV=3.52 h^-1; H₂O/CH₃OH(molar ratio)=1.1:1; the subscript of K and k, A and B were defined as the index of methanol conversion and CO₂ selectivity

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表 5 反应温度对催化活性的影响

Table 5 Effect of temperature on catalytic activity

Catalyst	t/℃	x_CH₃OH/%	s_CO₂/%	s_H₂/%	s_CO/%	s_CH₃OCH₃/%
Cu(15)-Fe(6)-MgO(1)/AlPO₄-5	260	65.58	96.21	95.89	1.02	2.77
	280	79.17	96.40	97.16	1.14	2.47
	300	93.08	95.80	96.93	1.70	2.51
	315	96.18	94.48	95.91	2.15	3.37
reaction conditions：m_cat=0.7 g, WHSV=2.51 h^-1，H₂O/CH₃OH(molar ratio)=1.1:1

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表 6 催化剂的孔结构参数

Table 6 Pore structure parameters of the catalyst

Catalyst	A_BET /(m²·g^-1)	Pore size d/nm
AlPO₄-5	133.3	6.1
Cu/AlPO₄-5	41.4	14.6
Cu-Fe/AlPO₄-5	39.7	13.7
Cu-Fe-MgO/AlPO₄-5	34.3	18.8

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参考文献(23)

[1]	HU J, ZHANG Q, JING YLEE D. Photosynthetic hydrogen production from enzyme-hydrolyzed micro-grinded maize straws[J]. Int J Hydrogen Energy, 2016, 41(46):21665-21669. doi: 10.1016/j.ijhydene.2016.07.029
[2]	LEE Y L, CHI C F, LIAU S Y. CdS/CdSe Co-Sensitized TiO₂ Photoelectrode for efficient hydrogen generation in a Photoelectrochemical Cell[J]. Chem Mater, 2016, 22(3):922-927. doi: 10.1021/cm901762h?src=recsys
[3]	MA Y, LIU B, OUYANG B, LI J. Production of hydrogen from water-gas shift reaction over Ru-[BMIM]BF₄/ZnO catalyst[J]. Int J Hydrogen Energy, 2016, 42(7):4146-4154. http://www.whxb.pku.edu.cn/EN/abstract/abstract27635.shtml
[4]	BARRIOS C E, ALBITER E, JIMENEZ J M G Y, TIZNADO H, ROMOHERRERA J, ZANELLA R. Photocatalytic hydrogen production over titania modified by gold-Metal (palladium, nickel and cobalt) catalysts[J]. Int J Hydrogen Energy, 2016, 41(48):23287-23300. doi: 10.1016/j.ijhydene.2016.09.206
[5]	JIAO Y, ZHANG J, DU Y, LI F, LI C, LU C, LU J, WANG J, CHEN Y. Hydrogen production by catalytic steam reforming of hydrocarbon fuels over Ni/Ce-Al₂O₃, bifunctional catalysts:Effects of SrO addition[J]. Int J Hydrogen Energy, 2016, 41(31):13436-13447. doi: 10.1016/j.ijhydene.2016.05.178
[6]	LU J, LI X, HE S, HAN C, WAN G, LEI Y, CHEN R, LIU P, CHEN K, ZHANG L, LUO Y. Hydrogen production via methanol steam reforming over Ni-based catalysts:Influences of Lanthanum (La) addition and supports[J]. Int J Hydrogen Energy, 2016, 42(7):3647-3657.
[7]	NA Y K, YANG E H, LIM S S, JUNG J S, LEE J S, HONG G H, NOH Y S, LEE K Y, MOON D J. Hydrogen production by steam reforming of methane over mixed Ni/MgAl+CrFe₃O₄, catalysts[J]. Int J Hydrogen Energy, 2015, 40(35):11848-11854. doi: 10.1016/j.ijhydene.2015.06.104
[8]	WANG C, BOUCHER M, MING Y, SALTSBURG H, MARIA F. ZnO-modified zirconia as gold catalyst support for the low-temperature methanol steam reforming reaction[J]. Appl Catal B:Environ, 2014, 154(5):142-152.
[9]	王艳华, 张敬畅, 徐恒泳.甲醇水蒸气重整制氢Pd/ZnO催化剂的研究[J].燃料化学学报, 2005, 33(4):391-395. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract16582.shtml WANG Yan-hua, ZHANG Jing-chang, XU Heng-yong. Study of Pd/ZnO catalyst for hydrogen production from steam reforming of methanol[J]. J Fuel Chem Technol, 2005, 33(4):391-395. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract16582.shtml
[10]	BANESHI J, HAGHIGHI M, JODEIRI N, ABDOUAHIFAR M, AJAMEIN H. Homogeneous precipitation synthesis of CuO-ZrO₂ -CeO₂ -Al₂O₃, nanocatalyst used in hydrogen production via methanol steam reforming for fuel cell applications[J]. Energy Convers Manage, 2014, 87(9):928-937.
[11]	AZENHA C S R, MATEOS-PEDRERO C, QUEIRÓ S, CONCEPTION P, MENDES A.Innovative ZrO₂-supported CuPd catalysts for the selective production of hydrogen from methanol steam reforming[J]. Appl Catal B:Environ, 2017, 203:400-407. doi: 10.1016/j.apcatb.2016.10.041
[12]	PONGSTABODEE S, MONYANON S, LUENGNARUEMITCHAI A. Hydrogen production via methanol steam reforming over Au/CuO, Au/CeO₂, and Au/CuO-CeO₂, catalysts prepared by deposition-precipitation[J].J Ind Eng Chem, 2012, 18(4):1272-1279. doi: 10.1016/j.jiec.2012.01.021
[13]	DESHMANE V G, ABROKWAH R Y, KUILA D. Synthesis of stable Cu-MCM-41 nanocatalysts for H₂, production with high selectivity via steam reforming of methanol[J]. Int J Hydrogen Energy, 2015, 40(33):10439-10452. doi: 10.1016/j.ijhydene.2015.06.084
[14]	李永红, 任杰, 孙予罕. Fe助剂对Cu/ZrO₂甲醇水蒸气重整制氢催化剂的影响[J].燃料化学学报, 2002, 30(5):429-432. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX200206016.htm LI Yong-hong, REN Jie, SUN Yu-han. Effect of iron on Cu/ZrO₂ catalysts in production of hydrogen from methanol steam reforming[J]. J Fuel Chem Technol, 2002, 30(5):429-432. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX200206016.htm
[15]	NA S, CHU Y, XIN S, WANG Q, YI X, FENG Z, MENG X, LIU X, DENG F, XIAO F. Insights of the Crystallization Process of Molecular Sieve AlPO₄-5 Prepared by Solvent-Free Synthesis[J]. J Am Chem Soc, 2016, 138(19):6171-6176. doi: 10.1021/jacs.6b01200
[16]	XU R, ZHU G, YIN X, WAN X, QIU S. Epitaxial growth of highly-oriented AlPO₄-5 molecular sieve films for microlaser systems[J]. J Mat Chem, 2006, 16(22):2200-2204. doi: 10.1039/b516305f
[17]	STOEGER J A, VEZIRI C M, PALOMINO M, CORMA A, KANELLOPOULOS N K, TSAPATSIS M, KARANIKOLOS G N. On stability and performance of highly c-oriented columnar AlPO₄-5 and CoAPO-5 membranes[J]. Micropor Mesopor Mat, 2012, 147(1):286-294. doi: 10.1016/j.micromeso.2011.06.028
[18]	WEIβÖ, IHLEIN G, SCHVTH F. Synthesis of millimeter-sized perfect AlPO₄-5 crystals[J]. Micropor Mesopor Mat, 2000, 35(99):617-620. https://core.ac.uk/display/14593198
[19]	SHOKRANI R, HAGHIGHI M, JODEIRI N, AJAMEIN H, ABDOLLAHIFAR M. Fuel cell grade hyd-rogen production via methanol steam reforming over CuO/ZnO/Al₂O₃ nanocatalyst with various oxide ratios synthesized viaurea-nitrates combustion method[J]. Int J Hydrogen Energy, 2014, 39(25):13141-13155. doi: 10.1016/j.ijhydene.2014.06.048
[20]	PARK J E, YIM S D, CHANG S K, PARK E D. Steam reforming of methanol over Cu/ZnO/ZrO₂/Al₂O₃ catalyst. Int J Hydrogen Energy[J]. Int J Hydrogen Energy, 2014, 39(22):11517-11527. doi: 10.1016/j.ijhydene.2014.05.130
[21]	黄媛媛, 巢磊, 李工, 丁嘉, 郭剑桥. Cu-ZrO₂-CeO₂/γ-Al₂O₃催化甲醇水蒸气重整制氢反应的性能研究[J].化工进展, 2017, 36(1):216-223. http://www.cnki.com.cn/Article/CJFDTOTAL-TRQH200201000.htm HUANG Yuan-yuan, CHAO Lei, LI Gong, DING Jia, GUO Jian-qiao. Performance of Cu-ZrO₂ -CeO₂/γ-Al₂O₃ catalysts for hydrogen production from steam reforming of methanol[J]. Chem Ind Eng Prog, 2017, 36(1):216-223. http://www.cnki.com.cn/Article/CJFDTOTAL-TRQH200201000.htm
[22]	DONGARE M K, SABDE D P, SHAIKH R A, KAMBLE K R, HEGDE S G. Synthesis, characterization and catalytic properties of ZrAPO-5[J]. Catal Today, 1999, 49(49):267-276. doi: 10.1023%2FA%3A1014176806483.pdf
[23]	徐杰, 王文祥. CuO-Fe₂O₃体系的相互作用[J].催化学报, 1992, 13(6):420-424. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA199206002.htm XU Jie, WANG Wen-xiang. The interaction in CuO-Fe₂O₃ system[J]. Chin J Catal, 1992, 13(6):420-424. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA199206002.htm