FTO反应铁基催化剂电子和结构助剂研究进展

doi:10.19964/j.issn.1006-4990.2022-0170

无机盐工业 ›› 2023, Vol. 55 ›› Issue (3): 36-46.doi: 10.19964/j.issn.1006-4990.2022-0170

FTO反应铁基催化剂电子和结构助剂研究进展

温媛¹(), 周晨亮¹(), 张强², 于林飞¹, 赫文秀¹, 刘全生³

1.内蒙古科技大学化学与化工学院，内蒙古自治区煤化工与煤炭综合利用重点实验室，内蒙古包头 014010
2.包头市环润环保投资有限责任公司，内蒙古包头 014010
3.内蒙古工业大学化工学院，内蒙古自治区低阶碳质资源高值功能化利用重点实验室，内蒙古呼和浩特 010051

收稿日期:2022-04-07 出版日期:2023-03-10 发布日期:2023-03-17
通讯作者: 周晨亮，博士，副教授，主要研究方向为费托合成、合成气直接制低碳烯烃；E-mail:627063044@qq.com。
作者简介:温媛（1995— ），女，硕士研究生，主要研究方向为费托合成、合成气直接制低碳烯烃；E-mail:1334094622@qq.com。
基金资助:
内蒙古自治区自然科学基金项目(2020MS02024)

Research progress of electronic and structure promoters of iron-based catalysts for FTO reaction

WEN Yuan¹(), ZHOU Chenliang¹(), ZHANG Qiang², YU Linfei¹, HE Wenxiu¹, LIU Quansheng³

1. Inner Mongolia Key Laboratory of Coal Chemical Industry and Comprehensive Utilization，School of Chemistry and Chemical Engineering，Inner Mongolia University of Science & Technology，Baotou 014010，China
2. Baotou Huanrun;Environmental Protection Investment Co.，Ltd，Baotou 014010，China
3. Inner Mongolia Key Laboratory of;High-Value Function Utilization of Low Rank Carbon Resource，Department of Chemical Engineering，Inner Mongolia University of Technology，Hohhot 010051，China

Received:2022-04-07 Online:2023-03-10 Published:2023-03-17

摘要/Abstract

摘要：

合成气直接制烯烃（FTO）具有生产工艺简单、生产成本低廉等优点，近年来成为中国制烯烃的重要研究方向。铁基催化剂由于成本低、甲烷选择性低、链增长能力弱而备受关注。然而单一的铁基催化剂无法满足工业生产的需求，需要加入助剂提高催化剂的反应性能。综述了电子助剂（碱金属、碱土金属、过渡金属、稀土金属）和结构助剂（二氧化硅、三氧化二铝、二氧化锆等）的电子作用、结构作用对催化剂活性组分的还原、碳化的影响，分析了助剂负载量对催化剂反应性能的影响。指出电子助剂可以促进铁的碳化，增加催化剂的活性和低碳烯烃选择性；结构助剂可以有效提高催化剂晶体的分散性，增加催化剂比表面积，促进催化剂对低碳烯烃选择性。最后指出，助剂的负载量、协同作用及其相关的作用机理都有不足之处，应及时研究以促进FTO反应工业化进程。

关键词: FTO, 铁基催化剂, 低碳烯烃, 电子助剂, 结构助剂

Abstract:

The direct synthesis of light olefins from syngas（FTO） has become an important research direction in China in recent years due to its simple production process and low production cost.Iron-based catalysts have attracted much attention due to their low cost, low methane selectivity and weak chain growth ability.However, a single iron-based catalyst cannot meet the needs of industrial production, and additives need to be added to improve the reaction performance of the catalysts.The effects of electronic additives（alkali metal, alkaline earth metal, transition metal, rare earth metal） and structural additives（SiO₂, Al₂O₃, ZrO₂） on the reduction and carbonization of active components of the catalyst were reviewed.The influence of the loading amount of additives on the reaction performance of the catalyst was analyzed.It was pointed out that electronic additives could promote the carbonization of iron, increase the activity of the catalyst and the selectivity of low olefins.Structural additives could effectively improve the dispersion of catalyst crystal, increase the specific surface area, and promote the selectivity of low carbon olefins.Finally, it was pointed out that the loading capacity, synergistic effect and related action mechanism of additives had shortcomings, and timely research was needed to promote the industrialization process of FTO reaction.

Key words: Fischer-Tropschto olefins, iron-based catalysts, light olefin, electronic promoter, structural promoter

中图分类号:

O643.36

温媛, 周晨亮, 张强, 于林飞, 赫文秀, 刘全生. FTO反应铁基催化剂电子和结构助剂研究进展[J]. 无机盐工业, 2023, 55(3): 36-46.

WEN Yuan, ZHOU Chenliang, ZHANG Qiang, YU Linfei, HE Wenxiu, LIU Quansheng. Research progress of electronic and structure promoters of iron-based catalysts for FTO reaction[J]. Inorganic Chemicals Industry, 2023, 55(3): 36-46.

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参考文献 72

1	CHENG Kang， VIRGINIE M， ORDOMSKY V V，et al.Pore size effects in high-temperature Fischer-Tropsch synthesis over supported iron catalysts[J].Journal of Catalysis，2015，328:139-150.
2	CENTI G， ALESSANDRA QUADRELLI E， PERATHONER S.Catalysis for CO₂ conversion:A key technology for rapid introduction of renewable energy in the value chain of chemical industries[J].Energy & Environmental Science，2013，6（6）:1711-1731.
3	DIERCKS R， ARNDT J D， FREYER S，et al.Raw material changes in the chemical industry[J].Chemical Engineering & Technology，2008，31（5）:631-637.
4	ZHANG Zhengpai， ZHANG Jun， WANG Xu，et al.Promotional effects of multiwalled carbon nanotubes on iron catalysts for Fisch-er-Tropsch to olefins[J].Journal of Catalysis，2018，365:71-85.
5	TIAN Peng， WEI Yingxu， YE Mao，et al.Methanol to olefins （MTO）:From fundamentals to commercialization[J].ACS Catalysis，2015，5（3）:1922-1938.
6	WU Xinqiang， XU Shutao， ZHANG Wenna，et al.Direct mechanism of the first carbon-carbon bond formation in the methanol-to-hydrocarbons process[J].Angewandte Chemie，2017，56（31）:9039-9043.
7	YANG Miao， FAN Dong， WEI Yingxu，et al.Recent progress in methanol-to-olefins（MTO） catalysts[J].Advanced Materials，2019，31（50）.Doi:10.1002/adma.201902181.
8	ZHOU Wei， CHENG Kang， KANG Jincan，et al.New horizon in C1 chemistry:Breaking the selectivity limitation in transformation of syngas and hydrogenation of CO₂ into hydrocarbon chemicals and fuels[J].Chemical Society Reviews，2019，48（12）:3193-3228.
9	HUANG Jian， QIAN Weixin， ZHANG Haitao，et al.In situ investigation on co-phase evolution and its performance for Fischer-Tropsch synthesis over Nb-promoted cobalt catalysts[J].Catalysis Science & Technology，2017，7（23）:5530-5539.
10	LI Zhengjia， LIN Tiejun， YU Fei，et al.Mechanism of the Mn promoter via CoMn spinel for morphology control:Formation of Co₂C nanoprisms for Fischer-Tropsch to olefins reaction[J].ACS Catalysis，2017，7（12）:8023-8032.
11	RAUSCH A K， SCHUBERT L， HENKEL R，et al.Enhanced olefin production in Fischer-Tropsch synthesis using ammonia containing synthesis gas feeds[J].Catalysis Today，2016，275:94-99.
12	BAE J S， HONG S Y， PARK J C，et al.Eco-friendly prepared iron-ore-based catalysts for Fischer-Tropsch synthesis[J].Applied Catalysis B:Environmental，2019，244:576-582.
13	段建国，王亚雄，刘全生，等.费托合成铁基催化剂关键影响因素研究进展[J].无机盐工业，2017，49（11）:1-7.
	DUAN Jianguo， WANG Yaxiong， LIU Quansheng，et al.Research advance in key influencing factors of iron-based catalyst for Fischer-Tropsch synthesis[J].Inorganic Chemicals Industry，2017，49（11）:1-7.
14	CHENG Kang， ORDOMSKY V V， LEGRAS B，et al.Sodium-promoted iron catalysts prepared on different supports for high temperature Fischer-Tropsch synthesis[J].Applied Catalysis A:General，2015，502:204-214.
15	WEI Yuxue， ZHANG Chenghua， LIU Xi，et al.Enhanced Fischer-Tropsch performances of graphene oxide-supported iron catalysts via argon pretreatment[J].Catalysis Science & Technology，2018，8（4）:1113-1125.
16	CANO L A， GARCIA BLANCO A A， LENER G，et al.Effect of the support and promoters in Fischer-Tropsch synthesis using sup-ported Fe catalysts[J].Catalysis Today，2017，282:204-213.
17	LI Jifan， CHENG Xiaofan， ZHANG Chenghua，et al.Effects of alkali on iron-based catalysts for Fischer-Tropsch synthesis:CO chemisorptions study[J].Journal of Molecular Catalysis A:Che- mical，2015，396:174-180.
18	MA Zhunzhun， QIAN Weixin， ZHANG Haitao，et al.High-temperature Fischer-Tropsch synthesis over the Li-promoted FeMnMgO_x catalysts[J].Fuel，2022，319.Doi:10.1016/j.fuel.2022.123613.
19	CHEN Qinyuan， QIAN Weixin， ZHANG Haitao，et al.Effect of Li promoter on FeMn/CNTs for light olefins from syngas[J].Catalysis Communications，2019，124:92-96.
20	WU Xian， QIAN Weixin， MA Hongfang，et al.Li-decorated Fe-Mn nanocatalyst for high-temperature Fischer-Tropsch synthesis of light olefins[J].Fuel，2019，257.Doi:10.1016/j.fuel.2019. 116101.
21	XIE Jingxiu， YANG Jia， DUGULAN A I，et al.Size and promoter effects in supported iron Fischer-Tropsch catalysts:Insights from experiment and theory[J].ACS Catalysis，2016，6（5）:3147-3157.
22	ZHANG Hewei， ZHANG Haitao， QIAN Weixin，et al.Sodium modified Fe-Mn microsphere catalyst for Fischer-Tropsch synthesis of light olefins[J].Catalysis Today，2022，388-389:199-207.
23	LI Jiangbing， MA Hongfang， ZHANG Haitao，et al.Sodium promoter on iron-based catalyst for direct catalytic synthesis of light alkenes from syngas[J].Fuel Processing Technology，2014，125:119-124.
24	TORRES GALVIS H M， BITTER J H， KHARE C B，et al.Supported iron nanoparticles as catalysts for sustainable production of lower olefins[J].Science，2012，335（6070）:835-838.
25	DAS S K， MOHANTY P， MAJHI S，et al.CO-hydrogenation over silica supported iron based catalysts:Influence of potassium loading[J].Applied Energy，2013，111:267-276.
26	CHENG Yi， LIN Jun， XU Ke，et al.Fischer-Tropsch synthesis to lower olefins over potassium-promoted reduced graphene oxide supported iron catalysts[J].ACS Catalysis，2016，6（1）:389-399.
27	NGANTSOUE-HOC W， ZHANG Yongqing， O′BRIEN R J，et al.Fischer-Tropsch synthesis:Activity and selectivity for group I alkali promoted iron-based catalysts[J].Applied Catalysis A:General，2002，236（1/2）:77-89.
28	RIBEIRO M C， JACOBS G， DAVIS B H，et al.Fischer–Tropsch synthesis:An in-situ TPR-EXAFS/XANES investigation of the influence of group I alkali promoters on the local atomic and electronic structure of carburized iron/silica catalysts[J].The Journal of Physical Chemistry C，2010，114（17）:7895-7903.
29	XIONG Haifeng， MOTCHELAHO M A， MOYO M，et al.Effect of group I alkali metal promoters on Fe/CNT catalysts in Fischer-Tropsch synthesis[J].Fuel，2015，150:687-696.
30	LI Jifan， ZHANG Chenghua， CHENG Xiaofan，et al.Effects of alkaline-earth metals on the structure，adsorption and catalytic behavior of iron-based Fischer-Tropsch synthesis catalysts[J].Applied Catalysis A:General，2013，464/465:10-19.
31	徐龙伢，王清遐，杨力，等.碱土金属氧化物担载Fe－MnO催化剂的CO加氢反应制低碳烯烃性能[J].燃料化学学报，1995，23（2）:125-130.
	XU Longya， WANG Qingxia， YANG Li，et al.Performance of iia metal oxide supported fe-mno catalyst for production of light alkenes syngas[J].Journal of Fuel Chemistry and Technology，1995，23（2）:125-130.
32	YANG Jun， SUN Yuchuan， TANG Yu，et al.Effect of magnesium promoter on iron-based catalyst for Fischer-Tropsch synthesis[J].Journal of Molecular Catalysis A:Chemical，2006，245（1/2）:26-36.
33	LUO Mingsheng， DAVIS B H.Fischer-Tropsch synthesis:Group II alkali-earth metal promoted catalysts[J].Applied Catalysis A:General，2003，246（1）:171-181.
34	CHUN D H， RHIM G B， YOUN M H，et al.Brief review of precipitated iron-based catalysts for low-temperature Fischer-Trops-ch synthesis[J].Topics in Catalysis，2020，63（9）:793-809.
35	CHUN D H， PARK J C， RHIM G B，et al.Nanocrystalline ferrihy-drite-based catalysts for Fischer-Tropsch synthesis:Part I.reduction and carburization behavior[J].Journal of Nanoscience and Nanotechnology，2016，16（2）:1660-1664.
36	周晨亮，温媛，赫文秀，等.FTO反应Fe基催化剂活化与活性相研究进展[J].精细化工，2022，39（1）:17-23.
	ZHOU Chenliang， WEN Yuan， HE Wenxiu，et al.Research progress of iron-based catalysts for FTO reaction on activation manner and active phases[J].Fine Chemicals，2022，39（1）:17-23.
37	NASSER A H， EL-BERY H M， ELNAGGAR H，et al.Selective conversion of syngas to olefins via novel Cu-promoted Fe/RGO and Fe-Mn/RGO Fischer-Tropsch catalysts:Fixed-bed reactor vs slurry-bed reactor[J].ACS Omega，2021，6（46）:31099-31111.
38	SUN Xiaodong， LIU Xingwu， LIU Jinjia，et al.Elucidation of the influence of Cu promoter on carburization prior to iron-based Fis-cher-Tropsch synthesis:An in situ X-ray diffraction study[J].ChemCatChem，2019，11（2）:715-723.
39	DE SMIT E， DE GROOT F M F， BLUME R，et al.The role of Cu on the reduction behavior and surface properties of Fe-based Fischer-Tropsch catalysts[J].Physical Chemistry Chemical Phy- sics，2010，12（3）:667-680.
40	CHONCO Z H， FERREIRA A， LODYA L，et al.Comparing silver and copper as promoters in Fe-based Fischer-Tropsch catalysts using delafossite as a model compound[J].Journal of Catalysis，2013，307:283-294.
41	CHONCO Z H， LODYA L， CLAEYS M，et al.Copper ferrites:A model for investigating the role of copper in the dynamic iron-based Fischer-Tropsch catalyst[J].Journal of Catalysis，2013，308:363-373.
42	PENDYALA V R R， JACOBS G， GNANAMANI M K，et al.Selectivity control of Cu promoted iron-based Fischer-Tropsch catalyst by tuning the oxidation state of Cu to mimic K[J].Applied Catalysis A:General，2015，495:45-53.
43	LI Tingzhen， WANG Hulin， YANG Yong，et al.Effect of manganese on the catalytic performance of an iron-manganese bimetallic catalyst for light olefin synthesis[J].Journal of Energy Chemistry，2013，22（4）:624-632.
44	LIU Yi， CHEN Jianfeng， BAO Jun，et al.Manganese-modified Fe₃O₄ microsphere catalyst with effective active phase of forming light olefins from syngas[J].ACS Catalysis，2015，5（6）:3905-3909.
45	ZHANG Yulan， MA Longlong， WANG Tiejun，et al.MnO₂ coated Fe₂O₃ spindles designed for production of C₅₊ hydrocarbons in Fischer-Tropsch synthesis[J].Fuel，2016，177:197-205.
46	王虎林，杨勇，王洪，等.Zn对沉淀铁催化剂结构及其F-T合成性能的影响[J].燃料化学学报，2012，40（1）:59-67.
	WANG Hulin， YANG Yong， WANG Hong，et al.Effects of Zn promoter on the structure and Fischer-Tropsch performance of iron catalyst[J].Journal of Fuel Chemistry and Technology，2012，40（1）:59-67.
47	GAO Xinhua， ZHANG Jianli， CHEN Ning，et al.Effects of zinc on Fe-based catalysts during the synthesis of light olefins from the Fischer-Tropsch process[J].Chinese Journal of Catalysis，2016，37（4）:510-516.
48	WANG Gencun， ZHANG Kan， LIU Ping，et al.Synthesis of light olefins from syngas over Fe-Mn-V-K catalysts in the slurry phase[J].Journal of Industrial and Engineering Chemistry，2013，19（3）:961-965.
49	WANG Hulin， YANG Yong， XU Jian，et al.Study of bimetallic interactions and promoter effects of FeZn，FeMn and FeCr Fischer-Tropsch synthesis catalysts[J].Journal of Molecular Catalysis A:Chemical，2010，326（1/2）:29-40.
50	HORÁČEK J.Fischer-Tropsch synthesis，the effect of promoters，catalyst support，and reaction conditions selection[J].Monatshe-shefte Für Chemie-Chemical Monthly，2020，151（5）:649-675.
51	孙永仕，吴宝山，李永旺.Cu、Ni、Ru、Pt对费托合成Fe催化剂的助剂作用研究[J].燃料化学学报，2015，43（7）:829-838.
	SUN Yongshi， WU Baoshan， LI Yongwang.Promoting effects of Cu，Ni，Ru and Pt on Fe-based catalysts in Fischer-Tropsch[J].Journal of Fuel Chemistry and Technology，2015，43（7）:829-838.
52	HAN Zhonghao， QIAN Weixin， ZHANG Haitao，et al.Effect of rare-earth promoters on precipitated iron-based catalysts for Fis-cher-Tropsch synthesis[J].Industrial & Engineering Chemistry Research，2020，59（33）:14598-14605.
53	XU Dandan， ZHANG Haitao， MA Hongfang，et al.Effect of Ce promoter on Rh-Fe/TiO₂ catalysts for ethanol synthesis from syngas[J].Catalysis Communications，2017，98:90-93.
54	ZAMANI Y， BAKAVOLI M， RAHIMIZADEH M，et al.Synergetic effect of La and Ba promoters on nanostructured iron catalyst in Fischer-Tropsch synthesis[J].Chinese Journal of Catalysis，2012，33（7/8）:1119-1124.
55	HAN Wenfeng， WANG Lingyu， LI Zhi，et al.γ-Fe₂O₃ as the precursor of iron based catalyst prepared by solid-state reaction at room temperature for Fischer-Tropsch to olefins[J].Applied Catalysis A:General，2019，572:158-167.
56	MCCUE A J， ANDERSON J A.Sulfur as a catalyst promoter or selectivity modifier in heterogeneous catalysis[J].Catalysis Science & Technology，2014，4（2）:272-294.
57	TORRES GALVIS H M， KOEKEN A C J， BITTER J H，et al.Effects of sodium and sulfur on catalytic performance of supported iron catalysts for the Fischer-Tropsch synthesis of lower olefins[J].Journal of Catalysis，2013，303:22-30.
58	ZHOU Xiangping， JI Jian， WANG Di，et al.Hierarchical structured α-Al₂O₃ supported S-promoted Fe catalysts for direct conversion of syngas to lower olefins[J].Chemical Communications，2015，51（42）:8853-8856.
59	FEYZI M， KHODAEI M M， SHAHMORADI J.Effect of sulfur on the catalytic performance of Fe-Ni/Al₂O₃ catalysts for light olefins production[J].Journal of the Taiwan Institute of Chemical Engineers，2014，45（2）:452-460.
60	JIANG Feng， ZHANG Min， LIU Bing，et al.Insights into the influence of support and potassium or sulfur promoter on iron-based Fischerâ Tropsch synthesis:Understanding the control of catalytic activity，selectivity to lower olefins，and catalyst deactivation[J].Catalysis Science & Technology，2017，7（5）:1245-1265.
61	PAALANEN P P， WECKHUYSEN B M.Carbon pathways，sodi-um-sulphur promotion and identification of iron carbides in iron-based Fischer-Tropsch synthesis[J].ChemCatChem，2020，12（17）:4202-4223.
62	LIU Yi， CHEN Jianfeng， ZHANG Yi.The effect of pore size or iron particle size on the formation of light olefins in Fischer-Tropsch synthesis[J].RSC Advances，2015，5（37）:29002-29007.
63	SUO Haiyun， WANG Shengguang， ZHANG Chenghua，et al.Chemical and structural effects of silica in iron-based Fischer-Tropsch synthesis catalysts[J].Journal of Catalysis，2012，286:111-123.
64	LIN Quan， CHENG Meng， ZHANG Kui，et al.Development of an iron-based Fischer-Tropsch catalyst with high attrition resistance and stability for industrial application[J].Catalysts，2021，11（8）.Doi:10.3390/catal11080908.
65	AL-DOSSARY M， FIERRO J L G， SPIVEY J J.Cu-promoted Fe₂O₃/MgO-based Fischer-Tropsch catalysts of biomass-derived syngas[J].Industrial & Engineering Chemistry Research，2015，54（3）:911-921.
66	孟庆龙.Fe₂O₃负载MgO反应活性及表面形貌研究[J].工业加热，2022，51（2）:59-63.
	MENG Qinglong.Study on reactivity and surface morphology of Fe₂O₃ supported MgO[J].Industrial Heating，2022，51（2）:59-63.
67	XU Longya， WANG Qingxia， XU Yide，et al.A new supported Fe-MnO catalyst for the production of light olefins from syngas.I.Effect of support on the catalytic performance[J].Catalysis Letters，1994，24（1/2）:177-185.
68	CHOU Weichao， WU Peng， LUO Mingsheng，et al.Effects of Al，Si，Ti，Zr promoters on catalytic performance of iron-based Fisch-er-Tropsch synthesis catalysts[J].Catalysis Letters，2020，150（7）:1993-2002.
69	WAN Haijun， WU Baoshan， XIANG Hongwei，et al.Fischer-Tropsch synthesis:Influence of support incorporation manner on metal dispersion，metal-support interaction，and activities of iron catalysts[J].ACS Catalysis，2012，2（9）:1877-1883.
70	WAN Haijun， WU Baoshan， AN Xia，et al.Effect of Al₂O₃ binder on the precipitated iron-based catalysts for Fischer-Tropsch synthesis[J].Journal of Natural Gas Chemistry，2007，16（2）:130-138.
71	MA Zixuan， ZHOU Chenliang， WANG Danmei，et al.Co-precipi-tated Fe-Zr catalysts for the Fischer-Tropsch synthesis of lower olefins（C₂O~C₄O）:Synergistic effects of Fe and Zr[J].Journal of Catalysis，2019，378:209-219.
72	QING Ming， YANG Yong， WU Baoshan，et al.Effect of the zirconia addition manner on the modification of Fe-SiO₂ interacti- on[J].Catalysis Today，2012，183（1）:79-87.

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