K/MgFeZn-HTLcs催化CO加氢制低碳烯烃性能研究

马丽萍; 张建利; 马清祥; 范素兵; 赵天生

K/MgFeZn-HTLcs催化CO加氢制低碳烯烃性能研究

宁夏大学化学化工学院省部共建天然气转化国家重点实验室培育基地, 宁夏银川 750021

基金项目:

宁夏自然科学基金 NZ13010

详细信息

通讯作者:
E-mail: zhaots@nxu.edu.cn.

中图分类号: O643.36
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出版历程
- 收稿日期: 2015-10-21
- 修回日期: 2016-01-15
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-04-30

Direct synthesis of light olefins from CO hydrogenation over K/MgFeZn-HTLcs catalysts

State Key Laboratory Cultivation Base of Natural Gas Conversion, Ningxia University, Yinchuan 750021, China

More Information

Corresponding author: E-mail: zhangjl@nxu.edu.cn,

摘要

摘要: 以MgFeZn-HTLcs为前驱体,制备了不同Mg/Fe/Zn物质的量配比、K改性的K/MgFeZn-HTLcs催化剂,用于CO加氢直接制低碳烯烃反应。采用N₂吸附-脱附、SEM、TG、XRD、XPS、H₂-TPR等手段对催化剂进行了表征。结果表明,MgFeZn-HTLcs前驱体具有典型的层状结构,孔径分布均一;经焙烧、K改性后仍具有一定的层状结构,但比表面积显著减小,平均孔径增大;新鲜催化剂物相以金属氧化物和铁酸盐为主,反应后K/MgFeZn-HTLcs催化剂主要以Fe₅C₂、MgCO₃和ZnO相存在,K/2Fe-1Zn催化剂主要物相为ZnFe₂O₄。在CO加氢反应中,K/MgFeZn-HTLcs催化剂具有较高的C_2-4⁼烯烃选择性和较低的C₅⁺含量,与K/2Fe-1Zn催化剂相比,产物分布明显改善;K/2Mg-2Fe-1Zn催化剂上O/P比值达5.15,C_2-4⁼含量占总烃质量的48.56%。
- 费托合成 /
- K/MgFeZn-HTLcs催化剂 /
- CO加氢 /
- 低碳烯烃
Abstract: A series of K promoted K/MgFeZn-HTLcs catalysts with different Mg/Fe/Zn molar ratios were prepared by means of precipitation method and impregnation method for the direct synthesis of light olefins from CO hydrogenation. The samples were characterized by N₂ adsorption-desorption SEM, TG, XRD, XPS and H₂-TPR measurements. The results showed that the MgFeZn-HTLcs catalyst precursors have typical lamellar structure, larger specific surface area and average pore diameter compared with Fe/Zn catalyst. The BET surface area and the average pore diameter decreased after calcination and K promotion. The bulk composition of the calcined samples was mainly metal oxide and ferrite. Fe₅C₂, MgCO₃ and ZnO were formed in K/MgFeZn-HTLcs catalysts after reaction. However, the main phase in K/2Fe-1Zn catalyst was stabilized in ZnFe₂O₄. During CO hydrogenation, the prepared samples showed high C_2-4⁼ selectivity and low C₅⁺ weight fraction compared with that of K/2Fe-1Zn sample. The product distribution was greatly improved. Over the sample K/2Mg-2Fe-1Zn, an olefin to paraffin ratio of 5.15 and the C_2-4⁼ weight olefin content of 48.56% could be obtained.
- Fischer-Tropsch synthesis /
- K/MgFeZn-HTLcs catalyst /
- CO hydrogenation /
- light olefins

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图 1 催化剂的孔径分布

Figure 1 Pore size distribution of the catalysts

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图 2 焙烧前后催化剂的SEM照片

Figure 2 SEM images of the samples before and after calcination

(a),(c): before calcination； (b),(d): after calcination

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图 3 2Mg-1Fe-1Zn的热重分析曲线

Figure 3 Thermogravimetric curves of 2Mg-1Fe-1Zn sample

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图 4 催化剂的XRD谱图

Figure 4 XRD patterns of the catalyst samples

(a): before calcination; (b): after calcination; (c): after reaction

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图 5 催化剂的XPS谱图

Figure 5 XPS spectra of the catalyst samples

>(a): Fe 2p; (b): Mg 2p; (c): Zn 2p
a: K/4Mg-1Fe-1Zn; b: K/3Mg-1Fe-2Zn; c: K/2Mg-1Fe-2Zn; d: K/3Mg-2Fe-1Zn; e: K/2Mg-2Fe-1Zn; f: K/2Mg-1Fe-1Zn

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图 6 催化剂的H₂-TPR谱图

Figure 6 H₂-TPR profiles of the catalysts

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表 1 催化剂织构性质

Table 1 Textural properties of the catalysts

Catalyst	BET surface area A/(m²·g^-1 )	Pore volume v/(cm³·g^-1 )	Average pore size d /nm
2Mg-2Fe-1Zn	160.76	0.35	8.64
K/2Mg-1Fe-1Zn	59.29	0.17	11.41
K/2Mg-2Fe-1Zn	52.10	0.17	12.93
K/3Mg-2Fe-1Zn	50.27	0.15	12.17
K/2Mg-1Fe-2Zn	46.16	0.12	10.65
K/3Mg-1Fe-2Zn	43.97	0.14	12.76
K/4Mg-1Fe-1Zn	71.63	0.19	10.79
K/2Fe-1Zn	49.22	0.12	9.97

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表 2 不同催化剂的表面组成

Table 2 Surface composition of different samples

Sample	Surface atom content w_mol/%^a
Sample	Mg	Fe	Zn	K	O	C	Mg/Fe	Fe/Zn	Fe/K
K/2Mg-1Fe-1Zn^b	18.45	3.34	5.34	0.16	52.90	19.82	5.52	0.63	20.88
K/2Mg-2Fe-1Zn^b	19.62	4.46	4.02	0.52	53.50	17.89	4.40	1.11	8.58
K/3Mg-2Fe-1Zn^b	15.55	3.42	2.84	0.44	47.44	30.31	4.55	1.20	7.77
K/2Mg-1Fe-2Zn^b	15.68	3.80	8.64	0.26	49.70	21.92	4.13	0.44	14.62
K/3Mg-1Fe-2Zn^b	19.75	3.24	5.48	0.20	52.94	18.39	6.10	0.59	16.20
K/4Mg-1Fe-1Zn^b	21.93	3.51	3.69	0.17	53.66	17.05	6.25	0.95	20.65
K/2Mg-1Fe-1Zn^c	0.34	0.22	0.67	-	5.49	93.29	1.55	0.33	-
K/2Mg-2Fe-1Zn^c	0.22	0.14	0.36	-	7.90	91.38	1.57	0.39	-
K/3Mg-2Fe-1Zn^c	0.51	0.15	0.65	0.16	7.42	91.12	3.40	0.23	0.94
K/2Mg-1Fe-2Zn^c	3.34	2.23	9.22	0.65	35.80	48.76	1.50	0.24	3.43
K/3Mg-1Fe-2Zn^c	0.52	0.19	0.73	0.03	12.31	86.22	2.74	0.26	6.33
K/4Mg-1Fe-1Zn^c	2.49	0.38	1.20	-	17.66	78.27	6.55	0.32	-
^a: calculated from the peak area of XPS spectra; ^b: fresh samples; ^c: used samples

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表 3 催化剂的反应性能

Table 3 Catalytic performance of the catalysts

Catalyst	CO conv. x/%	Selectivity s/%		Product w/%				O/P
Catalyst	CO conv. x/%	CH₄	CO₂	CH₄	C_2-4⁼	C_2-4⁰	C₅⁺	O/P
K/2Mg-1Fe-1Zn	86.48	11.33	34.21	28.39	48.16	10.44	13.01	4.61
K/2Mg-2Fe-1Zn	86.98	11.56	29.99	28.08	48.56	9.43	13.93	5.15
K/3Mg-2Fe-1Zn	86.68	15.45	25.09	23.06	46.87	8.77	21.30	5.34
K/2Mg-1Fe-2Zn	85.72	13.93	31.19	22.80	43.82	11.88	21.49	3.69
K/3Mg-1Fe-2Zn	74.15	21.49	15.99	32.28	45.51	10.46	11.76	4.35
K/4Mg-1Fe-1Zn	68.11	27.14	10.97	33.74	44.44	11.02	10.80	4.03
K/2Fe-1Zn	90.93	13.95	30.69	22.86	39.05	8.27	29.81	4.72
reaction conditions: H₂/CO(volume ratio)=2,GHSV=1000h^-1,t=320℃,p=1.5MPa

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参考文献(33)

[1]	TORRES GALVIS H M, DE JONG K P. Catalysts for production of lower olefins from synthesis gas: A review[J]. ACS Catal, 2013, 3(9): 2130-2149. doi: 10.1021/cs4003436
[2]	FU T J, JIANG Y H, LV J, LI Z H. Effect of carbon support on Fischer-Tropsch synthesis activity and product distribution over Co-based catalysts[J]. Fuel Process Technol, 2013, 110(6): 141-149.
[3]	HADNADEV-KOSTIĈ M S, VULIĈT J, MARINKOVIĈ-NEDUĈIN R P, NIKOLIĈA D, JOVIĈ B. Mg-Fe-mixed oxides derived from layered double hydroxides: A study of the surface properties[J]. J Serb Chem Soc, 2011, 76(12): 1661-1671. doi: 10.2298/JSC110429149H
[4]	董丽, 杨学萍. 合成气直接制低碳烯烃技术发展前景[J]. 石油化工, 2012, 4(10): 1201-1206. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG201210019.htm DONG Li, YANG Xue-ping. New advances in direct production of light olefins from syngas[J]. Petrochem Technol, 2012, 4(10): 1201-1206. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG201210019.htm
[5]	LIU Y, TENG B T, GUO X H, LI Y, CHANG J, TIAN L, HAO X, WANG Y, XIANG H W, XU Y Y, LI Y W. Effect of reaction conditions on the catalytic performance of Fe-Mn catalyst for Fischer-Tropsch synthesis[J]. J Mol Catal A: Chem, 2007, 272(1/2): 182-190. http://d.scholar.cnki.net/detail/SJES_U/SJES13011300654452
[6]	YANG C, ZHAO H B, HOU Y L, MA D. Fe₅C₂ Nanoparticles: A facile bromide-induced synthesis and as an active phase for Fischer-Tropsch synthesis[J]. J Am Chem Soc, 2012, 134(38): 15814-15821. doi: 10.1021/ja305048p
[7]	WANG C F, PAN X L, BAO X H. Direct production of light olefins from syngas over a carbon nanotube confined iron catalyst[J]. Chin Sci Bull, 2010, 55(12): 1117-1119. doi: 10.1007/s11434-010-0076-8
[8]	王虎林, 杨勇, 王洪, 相宏伟, 李永旺. Zn对沉淀铁催化剂结构及其F-T合成性能的影响[J]. 燃料化学学报, 2012, 40(1): 59-67. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1267.shtml# WANG Hu-lin, YANG Yong, WANG Hong, XIANG Hong-wei, LI Yong-wang. Effects of Zn promoter on the structure and Fischer-Tropsch performance of iron catalyst[J]. J Fuel Chem Technol, 2012, 40(1): 59-67. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1267.shtml#
[9]	TORRES GALVIS H M, BITTER J H, DAVIDIAN T, RUITENBEEK M, DUGULAN A I, DE JONG K P. Iron particle size effects for direct production of lower olefins from synthesis gas[J]. J Am Chem Soc, 2012, 134(39): 16207-16215. doi: 10.1021/ja304958u
[10]	ZHANG J L, FAN S B, ZHAO T S, LI W H, SUN Y H. Carbon modified Fe-Mn-K catalyst for the synthesis of light olefins from CO hydrogenation[J]. React Kinet Mech Cat, 2011, 102(2): 437-445. doi: 10.1007/s11144-010-0275-y
[11]	汪根存, 张侃, 刘平, 惠海涛, 李文怀, 谭猗生. Fe-Mn催化剂浆态床合成低碳烯烃的反应性能[J]. 石油化工, 2012, 41(11): 1234-1238. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG201211004.htm WANG Gen-cun, ZHANG Kan, LIU Ping, HUI Hai-tao, LI Wen-hua, TAN Yi-sheng. Performance of Fe-Mn catalyst for preparation of light olefins in slurry bed reactor[J]. Petrochem Technol, 2012, 41(11): 1234-1238. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG201211004.htm
[12]	位健, 马现刚, 方传艳, 葛庆杰, 徐恒泳. Fe/SiO₂纳米复合物上合成气制低碳烯烃催化性能研究[J]. 燃料化学学报, 2014, 42(7): 827-832. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1300.shtml# WEI Jian, MA Xian-gang, FANG Chuan-yan, GE Qing-jie, XU Heng-yong. Iron-silica nanocomposites as a catalyst for the selective conversion of syngas to light olefins[J]. J Fuel Chem Technol, 2014, 42(7): 827-832. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1300.shtml#
[13]	ZHANG Y L, MA L L, WANG T J, LI X J. Synthesis of Ag promoted porous Fe₃O₄ microspheres with tunable pore size as catalysts for Fischer-Tropsch production of lower olefins[J]. Catal Commun, 2015, 64: 32-36. doi: 10.1016/j.catcom.2015.01.033
[14]	WANG G C, ZHANG K, LIU P, HUI H T, TAN Y S. Synthesis of light olefins from syngas over Fe-Mn-V-K catalysts in the slurry phase[J]. J Ind Eng Chem, 2013, 19(3): 961-965. doi: 10.1016/j.jiec.2012.11.017
[15]	ZHANG Q H, KANG J C, WANG Y. Development of novel catalysts for Fischer-Tropsch synthesis: Tuning the product selectivity[J]. ChemCatChem, 2010, 2(9): 1030-1058. doi: 10.1002/cctc.201000071
[16]	徐龙伢, 王清遐, 蔡光宇, 陈国权. 担体对Fe-MnO催化剂上乙烯二次反应的影响[J]. 燃料化学学报, 1993, 21(2): 121-126. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX199302001.htm XU Long-ya, WANG Qing-xia, CAI Guang-yu, CHEN Guo-quan. Effect of support on secondary reactions of ethylene over supported Fe-MnO catalyst[J]. J Fuel Chem Technol, 1993, 21(2): 121-126. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX199302001.htm
[17]	TSAI Y T, MO X H, CAMPOS A, GOODWIN JR J G, SPIVEY J J. Hydrotalcite supported Co catalysts for CO hydrogenation[J]. Appl Catal A: Gen, 2011, 396(1/2): 91-100. http://www.academia.edu/811228/Hydrotalcite_supported_Co_catalysts_for_CO_hydrogenation
[18]	高鹏, 李枫, 赵宁, 王慧, 魏伟, 孙予罕. 以类水滑石为前驱体的Cu/Zn/Al/(Zr)/(Y)催化剂制备及其催化CO₂加氢合成甲醇的性能[J]. 物理化学学报, 2014, 30(6): 1155-1162. GAO Peng, LI Feng, ZHAO Ning, WANG Hui, WEI Wei, SUN Yu-han. Preparation of Cu/Zn/Al/(Zr)/(Y) catalysts from hydrotalcite-like precursors and their catalytic performance for the hydrogenation of CO₂ to methanol[J]. Acta Phys-Chim Sin, 2014, 30(6): 1155-1162.
[19]	DI FRONZO A, PIROLA C, COMAZZI A, GALLI F, BIANCHI C L, DI MICHELE A, VIVANI R, NOCCHETTI M, BASTIANINI M, BOFFITO D C. Co-based hydrotalcites as new catalysts for the Fischer-Tropsch synthesis process[J]. Fuel, 2014, 119(3): 62-69. https://www.researchgate.net/publication/259505166_Co-based_hydrotalcites_as_new_catalysts_for_the_Fischer-Tropsch_synthesis_process
[20]	DíEZ V K, APESTEGUÍA C R, DI COSIMO J I. Effect of the chemical composition on the catalytic performance of Mg_yAlO_x catalysts for alcohol elimination reactions[J]. J Catal, 2003, 215(2): 220-233. doi: 10.1016/S0021-9517(03)00010-1
[21]	徐龙伢, 王清遐, 杨力, 蔡光宇, 王开立. 碱土金属氧化物担载Fe-MnO催化剂的CO加氢反应制低碳烯烃性能[J]. 燃料化学学报, 1995, 23(2): 125-130. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX502.002.htm XU Long-ya, WANG Qing-xia, YANG Li, CAI Guang-yu, WANG Kai-li. Performance of IIA metal oxide supported Fe-MnO catalyst for production of light alkenes via syngas[J]. J Fuel Chem Technol, 1995, 23(2): 125-130. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX502.002.htm
[22]	DE SMIT E, WECKHUYSEN B M. The renaissance of iron-based Fischer-Tropsch synthesis: On the multifaceted catalyst deactivation behavior[J]. Chem Soc Rev, 2008, 37(12): 2758-2781. doi: 10.1039/b805427d
[23]	HUO C F, WU B S, GAO P, YANG Y, LI Y W, JIAO H J. The mechanism of potassium promoter: Enhancing the stability of active surfaces[J]. Angew Chem Int Ed, 2011, 50(32): 7403-7406. doi: 10.1002/anie.v50.32
[24]	CAVANI F, TRIFIRÒ F, VACCARI A. Hydrotalcite-type anionic clays: Preparation, properties and applications[J]. Catal Today, 1991, 11(2): 173-301. doi: 10.1016/0920-5861(91)80068-K
[25]	EVANS D G, SLADE R C T. Structural aspects of layered double hydroxides[J]. Struct Bond, 2006, 119: 1-87. doi: 10.1007/430_005
[26]	谢鲜梅. 类水滑石化合物的制备、性能及应用研究[D]. 太原: 太原理工大学, 2006. http://www.cnki.com.cn/Article/CJFDTOTAL-ZJTY201001006.htm XIE Xian-mei. Study on the preparation, performances and application of hydrotalcite-like-compounds[D]. Taiyuan: Taiyuan University of Technology, 2006. http://www.cnki.com.cn/Article/CJFDTOTAL-ZJTY201001006.htm
[27]	TOSHIYUKI H, YASUMASA Y, KATSUNORI K, ATSUMU T. Decarbonation behavior of Mg-A1-CO₃ hydrotalcite-like compounds during heat treatment[J]. Clay Clay Miner, 1995, 43(4): 427-432. doi: 10.1346/CCMN
[28]	VALENTE J S, PRINCE J, MAUBERT A M, LARTUNDO-ROJAS L, ANGEL P D, FERRAT G, HERNANDEZ J G, LOPEZ-SALINAS E. Physicochemical study of nanocapsular layered double hydroxides evolution[J]. J Phys Chem C, 2009, 113(14): 5547-5555. doi: 10.1021/jp810293y
[29]	ZHAO M Q, ZHANG Q, ZHANG W, HUANG J Q, ZHANG Y H, SU D S, WEI F. Embedded high density metal nanoparticles with extraordinary thermal stability derived from guest-host mediated layered double hydroxides[J]. J Am Chem Soc, 2010, 132(42): 14739-14741. doi: 10.1021/ja106421g
[30]	LI P, JIANG E Y, BAI H L. Fabrication of ultrathin epitaxial γ-Fe₂O₃ films by reactive sputtering[J]. J Phys D: Appl Phys, 2011, 44(7): 75003-75007. doi: 10.1088/0022-3727/44/7/075003
[31]	SUO H Y, WANG S G, ZHANG C H, XU J, WU B S, YANG Y, XIANG H W, LI Y W. Chemical and structural effects of silica in iron-based Fischer-Tropsch synthesis catalysts[J]. J Catal, 2012, 286(2): 111-123. https://www.researchgate.net/publication/256737739_Chemical_and_structural_effects_of_silica_in_iron-based_Fischer-Tropsch_synthesis_catalysts
[32]	杨雁南, 钟炳, 彭少逸, 王琴, 陈义龙, 徐斌富. 铁/锌催化剂的物相结构及其还原行为的穆斯堡尔谱研究[J]. 分子催化, 1993, 7(6): 425-431. http://www.cnki.com.cn/Article/CJFDTOTAL-FZCH199306003.htm YANG Yan-nan, ZHONG Bing, PENG Shao-yi, WANG Qin, CHEN Yi-long, XU Bin-fu. A Mossbauer spectrum study on Fe/Zn catalysts for Fischer-Tropsch synthesis[J]. J Mol Catal, 1993, 7(6): 425-431. http://www.cnki.com.cn/Article/CJFDTOTAL-FZCH199306003.htm
[33]	LIU X M, LU G Q, YAN Z F, BELTRAMINI J. Recent advances in catalysts for methanol synthesis via hydrogenation of CO and CO₂[J]. Ind Eng Chem Res, 2003, 42(25): 6518-6530. doi: 10.1021/ie020979s