基于Aspen Plus的甲烷联合重整制合成气过程热力学计算

doi:10.16085/j.issn.1000-6613.2023-2118

化工进展 ›› 2024, Vol. 43 ›› Issue (5): 2890-2900.DOI: 10.16085/j.issn.1000-6613.2023-2118

• 集成耦合与优化 • 上一篇

基于Aspen Plus的甲烷联合重整制合成气过程热力学计算

庞淑馨¹(), 王昊², 王健宇³, 朱卡克¹(), 刘志成⁴()

^1.华东理工大学化学工程联合国家重点实验室，上海 200237
^2.中石化齐鲁分公司研究院，山东淄博 255400
^3.国防科技大学气象海洋学院，湖南长沙 410005
^4.中石化（上海）石油化工研究院，绿色化工与工业催化国家重点实验室，上海 201208

收稿日期:2023-12-01 修回日期:2024-02-14 出版日期:2024-05-15 发布日期:2024-06-15
通讯作者: 朱卡克,刘志成
作者简介:庞淑馨（1999—），女，硕士研究生，研究方向为催化反应工程。E-mail：Y82210036@ecust.edu.cn。
基金资助:
国家自然科学基金(U1663221);中国石油化工股份有限公司项目(222215)

Thermodynamic calculation of methane combined reforming to synthesis gas process based on Aspen Plus

PANG Shuxin¹(), WANG Hao², WANG Jianyu³, ZHU Kake¹(), LIU Zhicheng⁴()

^1.State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
^2.Research Institute of Qilu Branch Co. , Sinopec, Zibo 255400, Shandong, China
^3.College of Meteorology and Oceanography, National University of Defense Technology, Changsha 410005, Hunan, China
^4.State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Sinopec Shanghai Research Institute of Petrochemical Technology, Shanghai 201208, China

Received:2023-12-01 Revised:2024-02-14 Online:2024-05-15 Published:2024-06-15
Contact: ZHU Kake, LIU Zhicheng

摘要/Abstract

摘要：

甲烷联合重整产物合成气的组成受热力学平衡控制，反应中积炭反应也受操作条件的影响，因此，计算反应条件（原料组成、温度、压力）对产物组成和积炭形成的影响，进行定量热力学分析是工艺设计所需要的。本文使用Aspen Plus软件中的RGibbs模块，建立甲烷联合重整热力学反应模型，采用吉布斯自由能最小化法，考虑所有相关反应的进料组成、温度和压力对平衡反应混合物组成和积炭的影响。首先，设定化学计量比 CH₄∶（CO₂+H₂O）=1∶1进料，调控CO₂、H₂O相对进料比例，结果发现：CO₂/CH₄比增加时，CH₄和CO₂转化率升高，但积炭量也相应增加，H₂/CO比减小；CH₄和CO₂的平衡转化率随温度升高而升高，且随着温度升高趋于极限，可通过调节温度从而调控H₂/CO比达到所需生产要求。然后，研究了压力对反应平衡的影响，结果表明CH₄和CO₂的热力学平衡转化率随压力升高而降低，积炭量增加。最后，结合进料比、温度和压力的影响，针对合成气制下游化学产品的不同需求以及特定氢碳比精准调控，模拟计算出合适的反应进料比例，为将来实际生产调控提供了理论计算依据。

关键词: 热力学, Aspen Plus, 甲烷联合重整, 吉布斯自由能, 二氧化碳, 天然气

Abstract:

The product synthetic gas compositions in methane combined reforming are governed by thermodynamic equilibrium and the relevant coke deposition reactions are also dependent on operation conditions. Hence, quantitative thermodynamic analysis of the influences of operation conditions (feedstock composition, temperature, pressure) on product compositions and coke formation reactions are desirable for process design. In this contribution, the RGibbs reactor in Aspen Plus software was used to calculate Gibbs free energies at varied temperatures, the influence of feeding compositions, temperature and pressure on the compositions of equilibrated reaction mixtures by taking into consideration all relevant reactions. Both methane and carbon dioxide conversions increased as a consequence of temperature increase or pressure decrease, as reflected by the endothermic nature of the volume expansion reaction. When stoichiometric feed [CH₄∶(CO₂+H₂O)=1∶1] was adopted, the influence of different conditions on the composition of reaction products was explored by changing the reaction temperature, pressure and feed composition and the equilibrium conversion of CH₄ and CO₂increased with increasing temperature and tended to the limit with increasing temperature for all stoichiometric ratios. Meanwhile, methane conversion increased and the carbon deposition increased with increasing carbon dioxide to methane ratios, while methane conversion elevation and suppression of carbon deposition could be achieved by increasing the proportion of steam, even under pressurized operations. The H₂/CO ratios in the product syngas could be manipulated to meet the required low concentrations for unconverted methane. With respect to specified downstream use of syngas, to generated methanol, ethanal, acetic acid and Fischer-Tropsch synthesis, the optimized operation conditions was identified. These calculations provided a thermodynamic basis for selection of bi-reforming conditions, process and catalyst design.

Key words: thermodynamics, Aspen Plus, methane combined reforming, Gibbs free energy, carbon dioxide, natural gas

中图分类号:

TE64

庞淑馨, 王昊, 王健宇, 朱卡克, 刘志成. 基于Aspen Plus的甲烷联合重整制合成气过程热力学计算[J]. 化工进展, 2024, 43(5): 2890-2900.

PANG Shuxin, WANG Hao, WANG Jianyu, ZHU Kake, LIU Zhicheng. Thermodynamic calculation of methane combined reforming to synthesis gas process based on Aspen Plus[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2890-2900.

图/表 10

参考文献 32

1	USMAN Muhammad, WAN DAUD W M A, ABBAS Hazzim F. Dry reforming of methane: Influence of process parameters—A review[J]. Renewable and Sustainable Energy Reviews, 2015, 45: 710-744.
2	TANG Pei, ZHU Qingjun, WU Zhaoxuan, et al. Methane activation: The past and future[J]. Energy & Environmental Science, 2014, 7(8): 2580-2591.
3	SCHULZ Hans. Short history and present trends of Fischer-Tropsch synthesis[J]. Applied Catalysis A: General, 1999, 186(1/2): 3-12.
4	Mark E DRY. The Fischer-Tropsch process: 1950—2000[J]. Catalysis Today, 2002, 71(3/4): 227-241.
5	OLAH George A, GOEPPERT Alain, CZAUN Miklos, et al. Bi-reforming of methane from any source with steam and carbon dioxide exclusively to metgas (CO-2H₂) for methanol and hydrocarbon synthesis[J]. Journal of the American Chemical Society, 2013, 135(2): 648-650.
6	CHOUDHARY Vasant R, MAMMAN Ajit S. Simultaneous oxidative conversion and CO₂ or steam reforming of methane to syngas over CoO-NiO-MgO catalyst[J]. Journal of Chemical Technology & Biotechnology, 1998, 73(4): 345-350.
7	HEGARTY M E S, O’CONNOR A M, ROSS J R H. Syngas production from natural gas using ZrO₂-supported metals[J]. Catalysis Today, 1998, 42(3): 225-232.
8	CHOUDHARY Vasant R, RAJPUT Amarjeet M. Simultaneous carbon dioxide and steam reforming of methane to syngas over NiO-CaO catalyst[J]. Industrial & Engineering Chemistry Research, 1996, 35(11): 3934-3939.
9	SANTOS Bruno A V, LOUREIRO José M, RIBEIRO Ana M, et al. Methanol production by bi-reforming[J]. The Canadian Journal of Chemical Engineering, 2015, 93(3): 510-526.
10	CHOUDHARY Vasant R, MONDAL Kartick C. CO₂ reforming of methane combined with steam reforming or partial oxidation of methane to syngas over NdCoO₃ perovskite-type mixed metal-oxide catalyst[J]. Applied Energy, 2006, 83(9): 1024-1032.
11	NORONHA F B, SHAMSI A, TAYLOR C, et al. Catalytic performance of Pt/ZrO₂ and Pt/Ce-ZrO₂ catalysts on CO₂ reforming of CH₄ coupled with steam reforming or under high pressure[J]. Catalysis Letters, 2003, 90(1): 13-21.
12	AMIN Nor Aishah Saidina, Tung Chun YAW. Thermodynamic equilibrium analysis of combined carbon dioxide reforming with partial oxidation of methane to syngas[J]. International Journal of Hydrogen Energy, 2007, 32(12): 1789-1798.
13	LI Yunhua, WANG Yaquan, ZHANG Xiangwen, et al. Thermodynamic analysis of autothermal steam and CO₂ reforming of methane[J]. International Journal of Hydrogen Energy, 2008, 33(10): 2507-2514.
14	SONG Chunshan, PAN Wei. Tri-reforming of methane: A novel concept for catalytic production of industrially useful synthesis gas with desired H₂/CO ratios[J]. Catalysis Today, 2004, 98(4): 463-484.
15	ZHU J, ZHANG D, KING K D. Reforming of CH₄ by partial oxidation: Thermodynamic and kinetic analyses[J]. Fuel, 2001, 80(7): 899-905.
16	陈亚男, 胡科峰, 潘牧. C-H-O三元热力学图在甲烷重整积炭研究中的研究进展[J]. 化工进展, 2015, 34(S1): 60-65.
	CHEN Yanan, HU Kefeng, PAN Mu. Progress about thermodynamic analysis of carbon deposition in methane reforming with C-H-O triangular diagrams[J]. Chemical Industry and Engineering Progress, 2015, 34(S1): 60-65.
17	YANG Yu, LIU Jing, SHEN Weifeng, et al. High-efficiency utilization of CO₂ in the methanol production by a novel parallel-series system combining steam and dry methane reforming[J]. Energy, 2018, 158: 820-829.
18	CHEN Chong, JIN Yuqi, YAN Jianhua, et al. Simulation of municipal solid waste gasification in two different types of fixed bed reactors[J]. Fuel, 2013, 103: 58-63.
19	HARDING S T, FLOUDAS C A. Phase stability with cubic equations of state: Global optimization approach[J]. AIChE Journal, 2000, 46(7): 1422-1440.
20	Smith J M, Van N H C, Abbott M M. Introduction to chemical engineering thermodynamics[M]. 6th ed. Boston: McGraw-Hill, 2001
21	NOURELDIN Mohamed M B, ELBASHIR Nimir O, EL-HALWAGI Mahmoud M. Optimization and selection of reforming approaches for syngas generation from natural/shale gas[J]. Industrial & Engineering Chemistry Research, 2014, 53(5): 1841-1855.
22	PENG Dingyu, ROBINSON Donald B. A new two-constant equation of state[J]. Industrial & Engineering Chemistry Fundamentals, 1976, 15(1): 59-64.
23	JABBOUR Karam. Tuning combined steam and dry reforming of methane for “metgas” production: A thermodynamic approach and state-of-the-art catalysts[J]. Journal of Energy Chemistry, 2020, 48: 54-91.
24	CUNHA A F, MATA T M, CAETANO N S, et al. Catalytic bi-reforming of methane for carbon dioxide ennoblement[J]. Energy Reports, 2020, 6: 74-79.
25	WITTICH Knut, Michael KRÄMER, BOTTKE Nils, et al. Catalytic dry reforming of methane: Insights from model systems[J]. ChemCatChem, 2020, 12(8): 2130-2147.
26	NEMATOLLAHI Behzad, REZAEI Mehran, LAY Ebrahim Nemati, et al. Thermodynamic analysis of combined reforming process using Gibbs energy minimization method: In view of solid carbon formation[J]. Journal of Natural Gas Chemistry, 2012, 21(6): 694-702.
27	THEOFANIDIS Stavros Alexandros, GALVITA Vladimir V, POELMAN Hilde, et al. Enhanced carbon-resistant dry reforming Fe-Ni catalyst: Role of Fe[J]. ACS Catalysis, 2015, 5(5): 3028-3039.
28	SEPEHRI Soodeh, REZAEI Mehran. Ce promoting effect on the activity and coke formation of Ni catalysts supported on mesoporous nanocrystalline γ-Al₂O₃ in autothermal reforming of methane[J]. International Journal of Hydrogen Energy, 2017, 42(16): 11130-11138.
29	HAGHIGHI Mohammad, SUN Zhi-Qiang, WU Jin-Hu, et al. On the reaction mechanism of CO₂ reforming of methane over a bed of coal char[J]. Proceedings of the Combustion Institute, 2007, 31(2): 1983-1990.
30	DEROUANE E G. Combinatorial catalysis and high throughput catalyst design and testing[M]. Dordrecht: Kluwer Academic Publishers, 2000.
31	PAKHARE Devendra, SPIVEY James. A review of dry (CO₂) reforming of methane over noble metal catalysts[J]. Chemical Society Reviews, 2014, 43(22): 7813-7837.
32	Jens ROSTRUP-NIELSEN, CHRISTIANSEN Lars J. Concepts in syngas manufacture[M]. London: Imperial College Press, 2011.

反应压力/bar	零积炭对应的CO₂∶H₂O∶CH₄进料比	出口CH₄低于7%对应的反应温度/℃	（H₂/CO）/mol·mol^-1	CH₄转化率/%
1	0.4∶0.6∶1	975	2.64	91.53
5	0.4∶0.6∶1	975	1.83	91.53
10	0.3∶0.7∶1	940	2.05	80.60
15	0.3∶0.7∶1	955	2.73	76.65
20	0.4∶0.6∶1	985	1.77	76.56
25	0.3∶0.7∶1	1010	2.02	76.32
30	0.4∶0.6∶1	1030	1.76	76.26

反应压力/bar	零积炭对应的CO₂∶H₂O∶CH₄进料比	出口CH₄低于7%对应的反应温度/℃	（H₂/CO）/mol·mol^-1	CH₄转化率/%
1	0.4∶0.6∶1	975	2.64	91.53
5	0.4∶0.6∶1	975	1.83	91.53
10	0.3∶0.7∶1	940	2.05	80.60
15	0.3∶0.7∶1	955	2.73	76.65
20	0.4∶0.6∶1	985	1.77	76.56
25	0.3∶0.7∶1	1010	2.02	76.32
30	0.4∶0.6∶1	1030	1.76	76.26

下游产品	下游产品所需合成气条件		计算合适上游制合成气反应条件
下游产品	氢碳比^①	反应压力/bar	反应温度/℃	进料比CO₂∶H₂O∶CH₄	CH₄转化率/%	H₂O转化率%	CO₂转化率/%
甲醇	2.1	35	840	0.2∶2.8∶1	69.10	37.70	—
	2.1	35	890	0.2∶1.8∶1	69.00	41.47	—
	2.1	35	960	0.2∶1.1∶1	69.27	56.33	—
乙醛	1.5	50	850	2∶2.8∶1	74.72	—	22.64
	1.5	50	900	1.8∶2.8∶1	84.78	—	28.13
	1.5	50	1000	1.8∶3.4∶1	97.23	—	32.27
高碳醇	1.0	30	900	1.6∶1∶1	82.86	—	51.27
高温费-托合成	2.1	2	900	1∶2.6∶1	88.04	—	25.49

下游产品	下游产品所需合成气条件		计算合适上游制合成气反应条件
下游产品	氢碳比^①	反应压力/bar	反应温度/℃	进料比CO₂∶H₂O∶CH₄	CH₄转化率/%	H₂O转化率%	CO₂转化率/%
甲醇	2.1	35	840	0.2∶2.8∶1	69.10	37.70	—
	2.1	35	890	0.2∶1.8∶1	69.00	41.47	—
	2.1	35	960	0.2∶1.1∶1	69.27	56.33	—
乙醛	1.5	50	850	2∶2.8∶1	74.72	—	22.64
	1.5	50	900	1.8∶2.8∶1	84.78	—	28.13
	1.5	50	1000	1.8∶3.4∶1	97.23	—	32.27
高碳醇	1.0	30	900	1.6∶1∶1	82.86	—	51.27
高温费-托合成	2.1	2	900	1∶2.6∶1	88.04	—	25.49

[1]	高凡翔, 刘阳, 张贵泉, 秦锋, 姚建涛, 金辉, 师进文. 燃煤烟气湿法协同脱硫脱碳技术研究进展[J]. 化工进展, 2024, 43(5): 2324-2342.
[2]	江安迪, 丁雪兴, 王世鹏, 丁俊华, 力宁. 超临界CO₂干气密封热动力学性能研究进展[J]. 化工进展, 2024, 43(5): 2354-2369.
[3]	冯勇强, 王洁茹, 王超娴, 李芳, 苏婉婷, 孙宇, 赵彬然. γ-Al₂O₃负载的Ni、Fe、Cu对介质阻挡放电等离子体转化CO₂/CH₄的影响[J]. 化工进展, 2024, 43(5): 2705-2713.
[4]	解仲凯, 施伟东. 电荷极化光催化剂光转化二氧化碳制多碳化学品的研究进展[J]. 化工进展, 2024, 43(5): 2714-2722.
[5]	周运桃, 王洪星, 李新刚, 崔丽凤. CeO₂载体在CO₂加氢制甲醇中的应用和研究进展[J]. 化工进展, 2024, 43(5): 2723-2738.
[6]	苗诒贺, 王耀祖, 刘雨杭, 朱炫灿, 李佳, 于立军. 添加剂改性固态胺吸附剂用于碳捕集的研究进展[J]. 化工进展, 2024, 43(5): 2739-2759.
[7]	黄澎, 邹颖, 王宝焕, 王逍妍, 赵勇, 梁鑫, 胡迪. 二氧化碳电催化还原反应制合成气催化剂研究进展[J]. 化工进展, 2024, 43(5): 2760-2775.
[8]	周秋明, 牛丛丛, 吕帅帅, 李红伟, 文富利, 徐润, 李明丰. 通过产物转化分离推动CO₂加氢制甲醇过程的研究进展[J]. 化工进展, 2024, 43(5): 2776-2785.
[9]	卢欣欣, 蔡东仁, 詹国武. 基于固体前体构建集成催化剂及CO₂加氢研究进展[J]. 化工进展, 2024, 43(5): 2786-2802.
[10]	武西宁, 张宁, 秦佳敏, 徐龙, 魏朝阳, 马晓迅. 低冷量下强化CO₂吸收的甲醇基纳米流体性能[J]. 化工进展, 2024, 43(5): 2811-2822.
[11]	李海鹏, 吴桐, 王琪, 郜时旺, 王晓龙, 李旭, 高新华, 年佩, 魏逸彬. 透水NaA分子筛膜强化的CO₂加氢高效制甲醇[J]. 化工进展, 2024, 43(5): 2834-2842.
[12]	王东亮, 李婧玮, 孟文亮, 杨勇, 周怀荣, 范宗良. 二氧化碳加氢制甲醇过程碳氢利用率的影响因素与工艺优化分析[J]. 化工进展, 2024, 43(5): 2843-2850.
[13]	李晶莹, 马龙飞, 潘一搏, 卢山, 张红娟, 徐龙, 马晓迅. 焦炉煤气脱碳法及甲烷化法制液化天然气的生命周期环境影响分析[J]. 化工进展, 2024, 43(5): 2872-2879.
[14]	王德斌, 林梦雨, 杨雪, 董殿权. 锌掺杂型钛系铯离子筛的制备及其吸附性能[J]. 化工进展, 2024, 43(4): 1953-1961.
[15]	廖昌建, 张可伟, 王晶, 曾翔宇, 金平, 刘志禹. 直接空气捕集二氧化碳技术研究进展[J]. 化工进展, 2024, 43(4): 2031-2048.

基于Aspen Plus的甲烷联合重整制合成气过程热力学计算

Thermodynamic calculation of methane combined reforming to synthesis gas process based on Aspen Plus

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 32

相关文章 15

编辑推荐

Metrics

本文评价