乙酸选择性加氢制乙醇反应性能研究

田树勋; 程继红; 狄伟; 陈强; 龙俊英; 罗熙; 胡云剑; 孟祥堃; 孙守理; 孙琦

乙酸选择性加氢制乙醇反应性能研究

北京低碳清洁能源研究所, 北京 102209

基金项目:

神华集团科技创新项目 2014-NICF-5

详细信息

通讯作者:
田树勋, Tel: 010-57339367, E-mail: tianshuxun@nicenergy.com

中图分类号: TQ214
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- 被引次数: 0
出版历程
- 收稿日期: 2016-01-05
- 修回日期: 2016-04-01
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-07-10

Study on the selective hydrogenation of acetic acid to ethanol

National Institute of Clean-and-Low Carbon Energy, Beijing 102209, China

Funds:

The project was supported by the Science and Technology Innovation Program of Shenhua Group 2014-NICF-5

More Information

Corresponding author: TIAN Shu-xun, Tel: 010-57339367, E-mail: tianshuxun@nicenergy.com

摘要

摘要: 在固定床反应器上考察了反应温度、反应压力、乙酸(HAC) 液体进料空速、H₂/HAC (总气体空速GHSV或H₂流量) 对乙酸选择性加氢制乙醇反应的影响, 研究了乙酸转化率、产物选择性、乙醇时空收率的变化规律, 验证了自主开发催化剂的稳定性。结果表明, 副产物的选择性受反应条件的影响, 选择合适的反应条件可以抑制乙酸乙酯和丙酮的生成。原料与催化剂床层接触时间小于5 s时, 可以避免发生乙酸加氢分解脱羰反应生成甲烷气相产物, 也避免了乙醇的进一步反应生成乙烷。在反应温度为280 ℃, 反应压力为2.5 MPa, 乙酸进料液时空速为0.72 h^-1, H₂/HAC (mol ratio) 为16的条件下, 乙酸乙酯选择性为6%。900 h长周期实验表明, 自主开发催化剂具有较好的工业应用前景。
- 乙酸选择性加氢 /
- 反应条件 /
- 选择性 /
- 酯化反应 /
- 脱羧酮化反应 /
- 加氢脱羰
Abstract: Effects of temperature, pressure, acetic acid (HAC) feeding rate and H₂/HAC (GHSV or H₂ flow) on the conversion of acetic acid, product selectivities and the productivity of ethanol in selective hydrogenation of acetic acid to ethanol were investigated in a fixed-bed reactor. The good stability of the lab-made catalyst was verified. The results show that the reaction rate of esterification and decarboxylation/ketonization are very fast. Selectivities of ethyl acetate and acetone are affected by the catalyst composition and reaction conditions. The hydrodecarbonylation of acetic acid to methane and the further conversion of ethanol can be avoided when the contact time of the reactants with the catalyst is less than 5 s. Optimum reaction conditions were found at 280 ℃, 2.5 MPa, LHSV=0.72 h^-1, H₂/HAC (mol ratio)=16, under which the selectivity of ethyl acetate could reach 6%.Life time test more than 900 h shows that the lab-made catalyst has a good potential for industrial application.
- selective hydrogenation of acetic acid /
- reaction conditions /
- selectivity /
- esterification /
- decarboxylation/ketonization reaction /
- hydrodecarbonylation

HTML全文

图 1 乙酸加氢制乙醇反应产物全组分色谱分析典型图谱

Figure 1 Typical chromatography spectrumof all products in the FID detector

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图 2 乙酸选择性加氢制乙醇基本反应网络示意图^{[17, 18]}

Figure 2 Schematic diagram of the reactions involved in the conversion of acetic acid

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图 3 乙酸选择性加氢生成乙醇分子演变过程

Figure 3 Evolution course schematic of selective hydrogenation of acetic acid to ethanol

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图 4 反应温度对乙酸转化率和乙醇选择性、副产物产物选择性以及乙醇收率的影响

Figure 4 Effect of temperature on the conversion of HAC and the selectivity of ethanol (a), selectivities of byproducts (b), ethanol yield reaction conditions: LHSV=0.72 h^-1, H₂/HAC (mol ratio)=16:1, 2.5 MPa

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图 5 反应压力对乙酸转化率和乙醇选择性、副产物产物选择性以及乙醇收率的影响

Figure 5 Effect of reaction pressure on the conversion of HAC and the selectivity of ethanol (a), selectivities of byproducts (b), ethanol yield (c) reaction conditions: LHSV=0.72 h^-1, H₂/HAC (mol ratio)=16:1, 280 ℃

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图 6 乙酸液体进料空速对乙酸转化率和乙醇选择性、副产物产物选择性以及乙醇收率的影响

Figure 6 Effect of space time velocity of acetic acid on the conversion of HAC and theselectivity of ethanol (a), selectivities of byproducts (b), ethanol yield (c) reaction conditions: H₂ flow rate=343 sccm, reaction temperature=280 ℃, reaction pressure=2.5 MPa

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图 7 H₂/HAC物质的量比对乙酸转化率和乙醇选择性(a)、副产物产物选择性(b) 以及乙醇收率(c) 的影响

Figure 7 Effect of H₂/HAC mol ratio on the conversion of HAC and the selectivity of ethanol (a), selectivities of byproducts (b), ethanol yield (c) reaction conditions: 280 ℃, 2.5 MPa, LHSV of HAC=0.6 h^-1

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图 8 自主催化剂的稳定性

Figure 8 Life time test of the lab-made catalyst for the hydroconversion of acetic acid reaction conditions: H₂/HAC (mol ratio)=16:1, 280 ℃, 2.5 MPa, LHSV=0.72 h^-1

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表 1 H₂流量转化数据表

Table 1 Conversion data of H₂ flow

H₂/HAC/(mol ratio)	H₂ flow (S.T.P) q_v/(mL·min^-1)	HAC feed q_v/(mL·min^-1)	GHSV (S.T.P)/h^-1	Contact time of the gaseous feed with catalyst t/s
4.7	100	0.05	1 434	32.2
9.4	200	0.05	2 625	17.6
14	300	0.05	3 814	12.1
16.4	350	0.05	4 407	10.5
21	450	0.05	5 597	8.3
28	600	0.05	7 380	6.3
37.4	800	0.05	9 759	4.7
79	1 700	0.05	20 462	2.3

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