合成气直接转化制低碳烯烃催化剂设计及反应条件优化

田育峰; 王浩; 董梅; 秦张峰; 樊卫斌; 王建国

合成气直接转化制低碳烯烃催化剂设计及反应条件优化

田育峰^{1, 2},
王浩^1, ,,
董梅¹,
秦张峰¹,
樊卫斌¹,
王建国¹

1.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001
2.
中国科学院大学, 北京 100049

基金项目:

国家自然科学基金 21773281

山西省回国留学人员科研项目 2014-102

详细信息

中图分类号: O643.36
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- 被引次数: 0
出版历程
- 收稿日期: 2018-03-12
- 修回日期: 2018-04-17
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-06-10

Design of the catalysts for direct conversion of syngas to light olefins and optimization of the reaction conditions

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds:

the National Natural Science Foundation of China 21773281

Shanxi Scholarship Council of China 2014-102

More Information

Corresponding author: WANG Hao, Tel: (0351) 4046239，E-mail: wanghao@sxicc.ac.cn

摘要

摘要: 采用水热法合成了相同粒径、不同硅铝比的ZSM-5分子筛，并通过浸渍法将Fe基（Fe-Cu-K）催化剂负载于ZSM-5上，系统考察了分子筛硅铝比变化对合成气制烯烃（FTO）反应的影响。结果表明，反应条件、分子筛酸性对CO转化率和低碳烯烃选择性有显著影响。当ZSM-5分子筛硅铝比为50时负载型催化剂有着最高的CO转化率（84.71%）和低碳烯烃选择性（32.08%）。H₂-TPR结果表明，硅铝比为50的Z50/FeCuK中Fe物相的还原度最高。原位漫反射红外光谱（DRIFTS）、热重差热分析（TG-DTA）、X射线粉末衍射（XRD）等结果表明，Z50/FeCuK催化剂表面吸附的碳酸盐和烃类吸附物种最多，且其反应后形成了较多的FeC_x晶相。最后对反应条件进行了优化，结果表明，温度为310 ℃，H₂/CO（volume ratio）=2和压力为1.0 MPa时FTO的催化性能最优。
- ZSM-5分子筛 /
- 酸性 /
- FTO /
- CO加氢
Abstract: ZSM-5 catalysts with same particle size and different Si/Al molar ratio were synthesized successfully by hydrothermal synthesis method, and then, Fe-Cu-K-containing ZSM-5 samples were prepared via aqueous incipient wetness impregnation. The effect of Si/Al molar ratio on the FTO reaction was systematically investigated. The results indicated that the conversion of CO and selectivity to light olefins strongly depended on the reaction conditions and the acidic properties of the zeolite. The ZSM-5/FeCuK catalyst with a Si/Al molar ratio of 50 possessed the highest CO conversion (84.71%) and selectivity to light olefins (32.08%) compared with others. H₂-TPR results showed that the reduction of Fe phase in Z50/FeCuK was the highest. With the combination of DRIFTS, TG-DTA and XRD techniques, it was found that there were more carbonate and hydrocarbon species adsorbed on the surface of Z50/FeCuK and more FeC_x phases were formed after reaction compared with the other catalysts. Finally, the reaction conditions were optimized and the results showed that the catalyst had the best performance at 310 ℃, H₂/CO(volume ratio)=2 and 1.0 MPa.
- ZSM-5 molecular sieve /
- acidic property /
- FTO /
- CO hydrogenation

HTML全文

图 1 ZSM-5及ZSM-5/FeCuK催化剂的XRD谱图

Figure 1 XRD patterns of ZSM-5 (a) and ZSM-5/FeCuK (b) catalysts with different molar ratio of Si/Al

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图 2 不同硅铝比ZSM-5及负载FeCuK催化剂的SEM照片

Figure 2 SEM images of ZSM-5 and supported FeCuK catalysts with different molar ratio of Si/Al

(a): Z20; (b): Z20/FeCuK; (c): Z50; (d): Z50/FeCuK; (e): Z100; (f): Z100/FeCuK

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图 3 不同硅铝比ZSM-5及负载FeCuK催化剂的孔径分布

Figure 3 Pore size distribution of ZSM-5 with different molar ratio of Si/Al and supported FeCuK catalysts

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图 4 Z20负载Fe、Cu、FeCuK，Z50负载Fe、Cu、FeCuK和Z100负载

Fe、Cu、FeCuK催化剂的H₂-TPR谱图

Figure 4 H₂-TPR profiles of Z20 supported Fe, Cu, FeCuK catalysts (a), Z50 supported

Fe, Cu, FeCuK catalysts (b) and Z100 supported Fe, Cu, FeCuK catalysts (c)

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图 5 ZSM-5及负载FeCuK催化剂的NH₃-TPD谱图

Figure 5 NH₃-TPD profiles of ZSM-5 (a) and supported FeCuK (b) catalysts

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图 6 ZSM-5及负载FeCuK催化剂的Py-FTIR谱图

Figure 6 Py-FTIR profiles of ZSM-5 (a) and supported FeCuK (b) catalysts

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图 7 不同硅铝比ZSM-5负载FeCuK催化剂的催化活性

Figure 7 Catalytic activity of supported FeCuK catalysts with time on stream

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图 8 原位还原及反应72h后催化剂的XRD谱图

Figure 8 X-ray diffraction patterns of in-situ reduction and used ZSM-5/FeCuK catalysts after reaction of 72h

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图 9 反应72h后催化剂的热重曲线

Figure 9 TG curves of the used catalysts after 72h reaction

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图 10 不同催化剂上原位吸附CO的红外光谱谱图

Figure 10 FT-IR spectra of adsorbed CO over different catalysts

(Ar purging at room temperature ((a), (b), (c)) and changes as temperature increasing ((d), (e), (f)))

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表 1 不同催化剂的物理化学性质和酸碱性质

Table 1 Physicochemical properties and acid-base properties of the catalysts with different molar ratio of Si/Al

Fresh catalyst	Si/Al (molar ratio)^a	A_BET /(m²·g^-1)	v_mic /(m³·g^-1)	v_total /(m³·g^-1)	Acidic site^b /(mmol·g^-1)		Acidic type^c /(mmol·g^-1)		Basic intensity^d/ (mmol·g^-1)
Fresh catalyst	Si/Al (molar ratio)^a	A_BET /(m²·g^-1)	v_mic /(m³·g^-1)	v_total /(m³·g^-1)	strong	weak	Brønsted	Lewis	Basic intensity^d/ (mmol·g^-1)
Z20	17.6	375.68	0.12	0.35	0.34	0.51	0.327	0.151	-
Z20/FeCuK	19.6	200.46	0.06	0.23	-	0.16	-	0.183	0.023
Z50	40.5	342.75	0.13	0.20	0.26	0.19	0.115	0.079	-
Z50/FeCuK	44.8	195.50	0.07	0.14	-	0.09	-	0.163	0.067
Z100	73.4	352.59	0.13	0.20	0.16	0.08	0.003	0.022	-
Z100/FeCuK	77.3	213.81	0.07	0.14	-	0.05	-	0.067	0.079
^a：the result from ICP; ^b：density of acid sites, determined by NH₃-TPD, strong, NH₃ desorbed at 250-500℃; weak, NH₃ desorbed at 120-250℃; ^c：density of acid sites, determined by Py-FTIR; ^d：intensity of surface basic sites, determined by CO₂-TPD, desorbed above 100℃

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表 2 不同催化剂的催化性能

Table 2 Catalyst performance of the catalysts

Catalyst	Fe/Cu/K^a	x_CO /%	s_CO₂/%	Selectivity of hydrocarbons s/%				O/(O+P)	Yield to C_2-4⁼ w/%^b
Catalyst	Fe/Cu/K^a	x_CO /%	s_CO₂/%	CH₄	C_2-4⁰	C_2-4⁼	C₅₊	O/(O+P)	Yield to C_2-4⁼ w/%^b
Z20/FeCuK	20.4/3.1/4.9	71.98	42.64	28.72	27.73	13.17	30.38	0.32	5.58
Z50/FeCuK	17.7/3.1/4.9	84.71	46.87	22.83	11.08	32.08	34.01	0.74	13.61
Z100/FeCuK	18.9/3.0/4.7	38.60	45.77	20.08	8.56	20.85	50.50	0.71	4.27
^a：the result from ICP; ^b: CO (mol%) transformed to olefins in the range of C_2-4 hydrocarbons; reaction conditions: 310℃，1.0MPa，H₂/CO(volume ratio)=2，GHSV=4000mL/h; the values were obtained at the steady-state after 48h on stream

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表 3 反应温度对催化剂FTO性能的影响

Table 3 Effect of reaction temperature on the FTO performance of catalysts

Temp.t/℃	x_CO /%	s_CO₂ /%	Selectivity of hydrocarbons s/%				O/(O+P)	Yield to C_2-4⁼ w/%
Temp.t/℃	x_CO /%	s_CO₂ /%	CH₄	C_2-4⁰	C_2-4⁼	C₅₊	O/(O+P)	Yield to C_2-4⁼ w/%
290	58.28	45.19	19.35	10.22	36.01	34.42	0.78	9.66
310	84.71	46.87	22.83	11.08	32.08	34.01	0.74	13.61
330	73.91	48.15	33.68	13.10	33.64	19.58	0.72	12.32
350	58.96	49.13	44.10	13.74	26.54	15.62	0.66	8.36
reaction conditions: 1.0MPa，H₂/CO(volume ratio)=2，GHSV=4000mL/h, the values were obtained at the steady-state after 48h on stream

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表 4 H₂/CO体积比对催化剂FTO性能的影响

Table 4 Effect of different H₂/CO volume ratios on the FTO performance of the catalysts

H₂/CO (volume ratio)	x_CO /%	s_CO₂ /%	Selectivity of hydrocarbons s/%				O/(O+P)	Yield to C_2-4⁼ w/%
H₂/CO (volume ratio)	x_CO /%	s_CO₂ /%	CH₄	C_2-4⁰	C_2-4⁼	C₅₊	O/(O+P)	Yield to C_2-4⁼ w/%
2/1	84.71	46.87	22.83	11.08	32.08	34.01	0.74	13.61
1.5/1	80.08	50.61	22.53	11.06	33.48	32.93	0.75	12.48
1/1	60.19	52.32	22.28	9.79	32.61	35.32	0.77	8.79
1/1.5	38.35	54.43	19.54	7.34	33.91	39.22	0.82	5.54
reaction conditions: 310℃，1.0MPa，GHSV=4000mL/h, the values were obtained at the steady-state after 48h on stream

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表 5 反应压力对催化剂FTO性能的影响

Table 5 Effect of reaction pressure on the FTO performance of the catalysts

Pressure p/MPa	x_CO /%	s_CO₂ /%	Selectivity of hydrocarbons s/%				O/(O+P)	Yield to C_2-4⁼ w/%
Pressure p/MPa	x_CO /%	s_CO₂ /%	CH₄	C_2-4⁰	C_2-4⁼	C₅₊	O/(O+P)	Yield to C_2-4⁼ w/%
0.5	31.47	45.24	34.03	8.46	37.86	19.65	0.82	5.42
1.0	84.71	46.87	22.83	11.08	32.08	34.01	0.74	13.61
1.5	86.77	46.96	22.54	12.09	30.71	34.66	0.72	13.56
2.0	84.83	47.17	22.41	12.53	28.70	36.36	0.70	12.88
reaction conditions: 310℃，H₂/CO(volume ratio)=2，GHSV=4000mL/h, the values were obtained at the steady-state after 48h on stream

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