碳中和目标驱动下合成燃料技术的发展

doi:10.16085/j.issn.1000-6613.2023-1692

摘要/Abstract

摘要：

全球主要发达国家和地区均制定了实现碳中和的规划路线，我国也提出了“双碳”目标。鉴于节能改造、提升效率、用能优化等措施对炼化企业减少碳排放要求的不断提高，炼化企业实现低碳、零碳发展必须从原料构成、原始加工技术的角度出发，开发新的碳循环经济技术和零碳合成燃料技术。基于此，本文综述了国内外由捕集/储存CO₂与可再生H₂（绿氢）制碳氢燃料（e-Fuels）技术和由生物质制合成燃料（SNG）技术的反应机理、技术路线、催化剂、技术经济性和碳减排潜力等方面的研究进展和发展趋势，分析了未来炼化企业实现碳中和发展的技术发展路径，为炼厂转型发展提供了借鉴。

关键词: 碳中和, 合成燃料, 炼化企业, CO₂循环经济, 零碳技术

Abstract:

The main developed countries and regions in the world have formulated the planning route to achieve carbon neutrality, and China has also put forward the "Double carbon" target. In view of the weakening effect of energy-saving retrofit, efficiency improvement and energy optimization on the reduction of carbon emissions by refining and petrochemical enterprises, in order to realize low-carbon and zero-carbon development, the refining and chemical enterprises must develop new carbon cycle economy technology and zero-carbon synthetic fuel technology from the perspective of raw material composition and original processing technology. Based on this, the reaction mechanism, technology route, catalyst, technical economy and carbon emission reduction potential of the technologies of carbon capture/storage and renewable H₂ to e-Fuels and biomass to SNG at home and abroad are reviewed, and the technological development path of carbon neutrality development in the future refining and chemical enterprises is analyzed, which provide reference for the transformation and development of refineries.

Key words: carbon neutrality, synthesis fuel, refining enterprises, CO₂circular economy, zero-carbon technology

中图分类号:

韩恒文, 韩伟, 程薇. 碳中和目标驱动下合成燃料技术的发展[J]. 化工进展, 2024, 43(10): 5457-5466.

HAN Hengwen, HAN Wei, CHENG Wei. Development trend of synthetic fuel technology driven by carbon neutrality[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5457-5466.

图/表 6

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项目	工艺1^[12]	工艺2^[14]	工艺3^[15]	工艺4^[16]	工艺5^[13]
温度/℃	200	250	266	260	250
压力/MPa	3.0	3.0	3.0	5.0	5.0
催化剂	Pd/CuO-ZnO-Al₂O₃-ZrO₂/HZSM-5	CuO-TiO₂-ZrO₂/HZSM-5	CuO-ZnO/Al₂O₃	6CuO-3ZnO-Al₂O₃/HZSM-5	CuZr-Pd/HZSM-5
n(CO₂)∶n(H₂)	1∶3.3	1∶3	1∶3	1∶3	1∶3
产品选择性/%
DME	73.56	47.5	32.4	75	51.8
CO	13.05	39.2	33.58	20	33.9
CH₄	0.1	—	—	—	0.2
MeOH	13.29	13.0	33.98	5	14.1

项目	工艺1^[12]	工艺2^[14]	工艺3^[15]	工艺4^[16]	工艺5^[13]
温度/℃	200	250	266	260	250
压力/MPa	3.0	3.0	3.0	5.0	5.0
催化剂	Pd/CuO-ZnO-Al₂O₃-ZrO₂/HZSM-5	CuO-TiO₂-ZrO₂/HZSM-5	CuO-ZnO/Al₂O₃	6CuO-3ZnO-Al₂O₃/HZSM-5	CuZr-Pd/HZSM-5
n(CO₂)∶n(H₂)	1∶3.3	1∶3	1∶3	1∶3	1∶3
产品选择性/%
DME	73.56	47.5	32.4	75	51.8
CO	13.05	39.2	33.58	20	33.9
CH₄	0.1	—	—	—	0.2
MeOH	13.29	13.0	33.98	5	14.1

项目	蒸汽气化^[53]	SER工艺^[53]	CO₂气化^[52]
φ(干基)/%
CO	21.2	8.6	40
CO₂	21.5	5.6	40
H₂	48	69.5	15
CH₄	8.8	14	5
C _x H _y	0.5	2.3	0
φ(H₂O)/%	32	41	7
气化温度/℃	797	629	>840
床层材料	石灰石	石灰石	橄榄石
气化效率/%	84	73	73

项目	蒸汽气化^[53]	SER工艺^[53]	CO₂气化^[52]
φ(干基)/%
CO	21.2	8.6	40
CO₂	21.5	5.6	40
H₂	48	69.5	15
CH₄	8.8	14	5
C _x H _y	0.5	2.3	0
φ(H₂O)/%	32	41	7
气化温度/℃	797	629	>840
床层材料	石灰石	石灰石	橄榄石
气化效率/%	84	73	73

工艺	反应器段数	操作温度/℃	原料分流数	一反控温方法	循环气温度/℃	催化剂参数（型号、适用温度、状态）	应用企业
Davy	4	250~620	2	部分二反产品气循环	150~155	CRG-S2（250~700℃）/氧化态或预还原态	大唐克旗/阜新、伊利新天
Topsoe	5	250~675	2	部分一反产品气循环并添加部分蒸汽	180~210	MCR-2X（250~700℃）、PK-7R （250~400℃）/氧化态	新疆庆华
Topsoe	4	250~650	2	部分二反产品气循环	190~210	MCR-2X（250~700℃）、PK-7R （250~400℃）/氧化态	内蒙古汇能韩国浦项光阳
Lurgi	3	230~650	1或2	部分二反产品气循环	60~150	G1-85（230~510℃）G1-86（230~650℃）/氧化态	工业化推广
大唐化工	4	240~650	4	部分二反产品气循环	170~190	DTC-M1S（250~700℃）、DTC-M1C（250~700℃）/预还原态	大唐克旗