Co/La-Ga-O复合氧化物用于催化二氧化碳加氢制乙醇

郑晋楠; 安康; 王嘉明; 李晶; 刘源

Co/La-Ga-O复合氧化物用于催化二氧化碳加氢制乙醇

郑晋楠^{1, 2},
安康^{1, 2},
王嘉明^{1, 2},
李晶^{1, 2},
刘源^{1, 2, ,}

1.
天津大学化学工程学院天津市应用催化科学与工程重点实验室, 天津 300072
2.
天津化学化工协同创新中心, 天津 300072

基金项目:

国家自然科学基金 21872101

国家自然科学基金 21576192

详细信息

中图分类号: O643.38
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- 被引次数: 0
出版历程
- 收稿日期: 2019-02-26
- 修回日期: 2019-03-27
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-06-10

Direct synthesis of ethanol via CO₂ hydrogenation over the Co/La-Ga-O composite oxide catalyst

ZHENG Jin-nan^{1, 2},
AN Kang^{1, 2},
WANG Jia-ming^{1, 2},
LI Jing^{1, 2},
LIU Yuan^{1, 2
, ,}

1.
School of Chemical Engineering, Tianjin University Tianjin Key Laboratory of Applied Catalysis Science and Technology, Tianjin 300072, China
2.
Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Tianjin 300072, China

Funds:

the National Natural Science Foundation of China 21872101

the National Natural Science Foundation of China 21576192

More Information

Corresponding author: LIU Yuan, E-mail: yuanliu@tju.edu.cn

摘要

摘要: 以LaCo_1-xGa_xO₃为前驱体，还原后得到的Co/La₂O₃-La₄Ga₂O₉复合氧化物催化剂，用于CO₂加氢直接制乙醇。通过XRD、XPS、TPD和TEM等技术对催化剂结构进行了表征，采用微型固定床反应器在230-290℃、3 MPa、空速（GHSV）为3000 mL/（g_cat·h）和H₂/CO₂进料物质的量比为3.0的条件下，考察了该Co/La-Ga-O复合氧化物用于CO₂加氢制乙醇的催化性能。结果显示，该Co/La-Ga-O复合氧化物催化剂对生成乙醇具有很高的选择性。与LaCoO₃相比，Ga的掺杂可抑制甲烷的形成，促进醇类（特别是乙醇）的生成。当Co/Ga比为7：3时，还原后的LaCo_1-xGa_xO₃催化剂体现出最好的催化性能，CO₂转化率为9.8%，总醇选择性达到74.7%，其中，液相产物中的乙醇质量分数可达到88.1%。基于实验结果推测，该催化剂上Co⁰和Co^δ+的协同作用促使CO₂选择性加氢生成乙醇。
- 二氧化碳加氢 /
- 乙醇合成 /
- 钙钛矿型氧化物 /
- 钴 /
- 镓
Abstract: A new Co/La₂O₃-La₄Ga₂O₉ catalyst was prepared by reducing LaCo_1-xGa_xO₃ perovskite and used in the direct synthesis of ethanol from CO₂ hydrogenation. The composite catalyst was characterized by XRD, XPS, TPD and TEM and its catalytic performance in CO₂ hydrogenation was investigated in a micro fixed-bed reactor operated at 230-290℃, 3 MPa, gas hourly space velocity (GHSV) of 3000 mL/(g_cat·h) and H₂/CO₂ molar ratio of 3.0. The results indicate that the Co/La-Ga-O composite oxide catalyst exhibits high selectivity to ethanol in CO₂ hydrogenation. In comparison with the LaCoO₃ catalyst, the incorporation of Ga dopant can inhibit the formation of CH₄ and then promote the production of alcohols, especially ethanol. With a Co/Ga atomic ratio of 7:3, the Co/La-Ga-O composite oxide catalyst displays the best performance in CO₂ hydrogenation, with a CO₂ conversion of 9.8%, a selectivity of 74.7% to total alcohols and ethanol content of 88.1% (mass ratio) in the alcohols mixture. On the basis of the experimental results, it is speculated that the synergistic effect of surface Co⁰ and Co^δ+ may contribute to the excellent performance of the Co/La₂O₃-La₄Ga₂O₉ catalyst in CO₂ hydrogenation to ethanol.
- carbon dioxide hydrogenation /
- ethanol synthesis /
- perovskite-type oxide /
- cobalt /
- gallium

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图 1 LaCo_1-xGa_xO₃样品(x=0、0.2、0.3、0.4和0.5)的XRD谱图

Figure 1 XRD patterns of the LaCo_1-xGa_xO₃ samples (x=0, 0.2, 0.3, 0.4 and 0.5)

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图 2 LaCoO₃(a)和LaCo_0.7Ga_0.3O₃ (b)样品煅烧后、还原后和反应后的XRD谱图

Figure 2 XRD patterns of the fresh, reduced and spent LaCoO₃ (a) and LaCo_0.7Ga_0.3O₃ (b) samples

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图 3 LaCo_1-xGa_xO₃样品(x=0，0.2，0.3，0.4和0.5)的H₂-TPR谱图

Figure 3 H₂-TPR profiles of the LaCo_1-xGa_xO₃ samples (x=0, 0.2, 0.3, 0.4 and 0.5)

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图 4 还原后的LaCoO₃(■)、LaCo_0.8Ga_0.2O₃(●)、LaCo_0.7Ga_0.3O₃(▲)以及LaCo_0.7Ga_0.3O₃反应100 h后(▶)、LaCo_0.6Ga_0.4O₃(▼)和LaCo_0.5Ga_0.5O₃(◆)样品的N₂吸附-脱附等温线(a)和BJH孔径分布曲线(b)

Figure 4 N₂ adsorption-desorption isotherms (a) and BJH pore size distribution (b) of the reduced LaCoO₃ (■), LaCo_0.8Ga_0.2O₃ (●), LaCo_0.7Ga_0.3O₃ (▲) and LaCo_0.7Ga_0.3O₃ after reaction for 100 h(▶), LaCo_0.6Ga_0.4O₃ (▼) and LaCo_0.5Ga_0.5O₃ (◆) samples

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图 5 还原后的LaCo_1-xGa_xO₃样品的CO₂-TPD谱图

Figure 5 CO₂-TPD profiles of the reduced LaCo_1-xGa_xO₃ samples

a: x=0; b: x=0.2, c: x=0.3, d: x=0.4; e: x=0.5

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图 6 反应后的LaCoO₃(a)，LaCo_0.7Ga_0.3O₃(b)和还原后LaCo_0.7Ga_0.3O₃(b′)样品的XPS谱图

Figure 6 XPS spectra of the used LaCoO₃ (a), LaCo_0.7Ga_0.30₃ (b) and reduced LaCo_0.7Ga_0.30₃ (b′) samples

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图 7 还原后((a)和(a′))以及反应100 h后((b)、(b′)和(b″))的LaCo_0.7Ga_0.30₃样品的TEM照片

Figure 7 TEM images of LaCo_0.7Ga_0.30₃ samples after reduction ((a) and (a′)) and after 100 h reaction test ((b), (b′) and (b″))

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图 8 LaCo_0.7Ga_0.3O₃样品反应48 h(a)、100 h(b)和LaCoO₃样品反应48 h(c)的TG曲线

Figure 8 TG curves of the spent LaCo_0.7Ga_0.3O₃ catalysts after reaction for 48 h (a) and 100 h (b) and the used LaCoO₃ catalyst after reaction for 48 h (c)

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图 9 还原后的LaCoO₃(■)、LaCo_0.8Ga_0.2O₃(●)、LaCo_0.7Ga_0.3O₃(▲)、LaCo_0.6Ga_0.4O₃(▼)、LaCo_0.5Ga_0.5O₃(◆)样品的CO₂转化率(a)、总醇选择性(b)和乙醇分布(c)随反应温度的变化

Figure 9 CO₂ conversion (a), selectivity to alcohols (b), and ethanol distribution (c) as function of reaction temperature on the reduced LaCoO₃ (■), LaCo_0.8Ga_0.2O₃ (●), LaCo_0.7Ga_0.3O₃ (▲), LaCo_0.6Ga_0.4O₃ (▼) and LaCo_0.5Ga_0.5O₃ (◆) catalysts

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图 10 还原后LaCo_0.7Ga_0.3O₃样品的液相分布随反应时间(h)的变化

Figure 10 Distribution of ROH products with the time on steam for CO₂ hydrogenation over the reduced LaCo_0.7Ga_0.3O₃ catalyst

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表 1 LaCo_1-xGa_xO₃样品(x=0、0.2、0.3、0.4和0.5)的元素组成、晶粒粒径、耗氢量以及还原度计算

Table 1 Elemental analysis, crystal sizes, hydrogen consumptions and reducibility degree of Coⁿ⁺ in the LaCo_1-xGa_xO₃ samples (x=0, 0.2, 0.3, 0.4 and 0.5)

Sample	Co loading/%	Co/Ga^a	Co/Ga^b	Crystal size of Co^{c, d}/nm	H₂ uptake/ (mmol·g^-1)	Co dispersion/%^{c, e}	H₂ consumptions from TPR results^{f, g}		Total theoretic H₂consumptions^g	Reducibility degree of Coⁿ⁺/%
Sample	Co loading/%	Co/Ga^a	Co/Ga^b	Crystal size of Co^{c, d}/nm	H₂ uptake/ (mmol·g^-1)	Co dispersion/%^{c, e}	α	β	Total theoretic H₂consumptions^g	Reducibility degree of Coⁿ⁺/%
x=0	26.6	-	-	18.5	0.104	5.2	0.101	0.204	0.305	100
x=0.2	20.6	4.00	3.97	8.8	0.184	11.5	0.077	0.162	0.242	98.8
x=0.3	17.8	2.33	2.36	7.6(10.5)^h	0.188(0.137)	13.4(9.8)^h	0.068	0.138	0.211	97.6
x=0.4	15.0	1.50	1.50	6.9	0.173	14.4	0.064	0.122	0.180	103.3
x=0.5	12.3	1.00	1.01	7.4	0.136	13.6	0.051	0.108	0.149	106.7
^a: Co/Ga ratio in synthesis system; ^b: Co/Ga ratio in sample measured from ICP; ^c: calculated from the results of H₂-TPD; ^d: the crystal size for catalysts after reduction; ^e: assuming H/Co=1; ^f: experimental H₂ consumptions calculated from TPR results using CuO as the reference material; ^g: the unit is mmol H₂ per 50 mg of catalyst; ^h: crystal size of Co after 100 h stability test in the parentheses

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表 2 还原后LaCo_1-xGa_xO₃样品(x=0、0.2、0.3、0.4和0.5)的物理性质

Table 2 Physical properties of the reduced LaCo_1-xGa_xO₃ samples

Sample	Specific surface area A/(m²·g^-1)	Total pore volume v/(cm³·g^-1)	Average pore size d/nm
x=0	5.6	0.02	4.2
x=0.2	9.6	0.04	27.0
x=0.3	9.4(9.1)^a	0.02(0.03)^a	25.8(24.4)^a
x=0.4	8.8	0.02	8.9
x=0.5	6.5	0.02	6.2
^a: data in the parentheses are for the spent catalyst after 100 h reaction test

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表 3 通过XPS计算所得反应后的LaCo_1-xGa_xO₃样品(x=0和0.3)表面组成

Table 3 Surface atomic ratios calculated by XPS results of the spent LaCo_1-xGa_xO₃ samples (x=0 and 0.3) after reaction

Sample	Atomic ratio/%
Sample	La/Σ[M]^a	Co/Σ[M]^a	Ga/Σ[M]^a
LaCoO₃-used	56.1(50.0)^b	43.9(50.0)^b	-
LaCo_0.7Ga_0.3O₃-used	47.0(50.0)^b	15.5(35.0)^b	37.5(15.0)^b
^a: the atomic ratio of metal M is M/(La+Co+Ga) and the data in the parentheses are theoretical values

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表 4 LaCo_1-xGa_xO₃(x=0、0.2、0.3、0.4和0.5)系列样品在CO₂+H₂的催化转化

Table 4 Reaction results of CO₂ hydrogenation to alcohols over reduced LaCo_1-xGa_xO₃ catalysts (x=0, 0.2, 0.3, 0.4 and 0.5)^a

Sample	CO₂ conversion x/%	Selectivity^b s_{C, mol}/%			Alcohol distribution^c w/%
Sample	CO₂ conversion x/%	CH₄	C₂₊H	ROH	MeOH	EtOH
x=0	30.4	97.8	1.7	0.5	77.0	23.0
x=0.2	10.6	37.4	2.5	60.1	30.2	69.8
x=0.3	9.8	23.1	2.2	74.7	11.9	88.1
x=0.4	8.1	12.2	2.1	85.7	27.5	72.5
x=0.5	4.78	11.1	2.4	86.5	-	-
^a: reaction conditions: 240 ℃, 3 MPa, n(H₂)/n(CO₂) = 3.0, GSHV = 3000 mL/(gcat·h); the data were obtained after 18 h on stream; ^b: product selectivity was based carbon molar quantity, defined as the carbon molar quantity in a carbon-containing product divided by converted carbon moles; C₂₊H represents hydrocarbons exclusive of methane; ^c: alcohol distribution (mass ratio) is the weight fraction of each alcohol in total alcohols

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表 5 Co基催化剂在适当反应条件下的CO₂加氢活性和产物选择性^{[11, 18, 45]}

Table 5 Summary of reaction conditions with CO₂ hydrogenation activity and product selectivity over Co-based catalyst reported in references

Catalyst	H₂/CO₂^a	t/℃	p/MPa	CO₂ con. x/%	Selectivity s_{C, mol}/%
Catalyst	H₂/CO₂^a	t/℃	p/MPa	CO₂ con. x/%	CO	CH₄	C₂₊H	ROH
Pt/Co₃O₄^[11]	3	200	2	22.4	-	77.8	2.3	19.9
Co/SiO₂^[18]	4	360	0.1	44.3	13.5	86.5	-	-
Co-Pt/Al₂O₃^[45]	1	220	1.9	6.8	-	93.1	6.8	-
^a: the mole ratio of H₂ to CO₂

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