CN107051461B - 一种石墨烯修饰的铁基催化剂及其制备与在费托反应中的应用 - Google Patents
一种石墨烯修饰的铁基催化剂及其制备与在费托反应中的应用 Download PDFInfo
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- CN107051461B CN107051461B CN201710300472.2A CN201710300472A CN107051461B CN 107051461 B CN107051461 B CN 107051461B CN 201710300472 A CN201710300472 A CN 201710300472A CN 107051461 B CN107051461 B CN 107051461B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- -1 Graphene modified iron Chemical class 0.000 title claims abstract description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001336 alkenes Chemical class 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 8
- 150000002505 iron Chemical class 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004313 iron ammonium citrate Substances 0.000 claims description 2
- 235000000011 iron ammonium citrate Nutrition 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- ZXQVPEBHZMCRMC-UHFFFAOYSA-R tetraazanium;iron(2+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZXQVPEBHZMCRMC-UHFFFAOYSA-R 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000012692 Fe precursor Substances 0.000 claims 3
- 230000007062 hydrolysis Effects 0.000 claims 2
- 238000006460 hydrolysis reaction Methods 0.000 claims 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims 2
- 238000001556 precipitation Methods 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 7
- 238000002390 rotary evaporation Methods 0.000 abstract description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 2
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 239000012495 reaction gas Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 4
- 229910001950 potassium oxide Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Abstract
本发明公开了一种石墨烯修饰的铁基催化剂及其在费托反应制烯烃中的应用。该催化剂是由质量百分含量为0.01～30％的石墨烯、0～20％助剂和60～99.99％的铁氧化物组成。该催化剂的制备过程是将石墨烯、氧化铁粉末和助剂先后置于水溶液中进行超声、搅拌，再经旋转蒸发、干燥和焙烧制得，制备方法简单。该催化剂在费托反应中表现出非常优异的活性，在很高的反应空速下长时间内保持高CO转化率，90％以上；同时产物中烷烃含量低，烯烷比可达14，具有极高的工业应用价值。
Description
技术领域
本发明属于合成气催化转化技术领域，涉及一种将合成气经费托合成路线直接制取低碳烯烃的石墨烯修饰的铁基催化剂及其制备与应用。
背景技术
低碳烯烃包括乙烯、丙烯和丁烯是重要的化工原料，其主要来源于石脑油的裂解。随着原油资源的减少和环境问题的日益突出，同时页岩气规模性的开发，使得从石油路线获得烯烃受到挑战，也变得不可持续。因此，非石油路线制取低碳烯烃越来越受到重视。合成气直接制低碳烯烃作为生产乙烯和丙烯等低碳烯烃的一条替代技术路线，对于利用我国较为丰富的煤炭资源、缓解对石油资源的依赖，具有重要意义。该工艺无需像间接法工艺那样从合成气经甲醇或二甲醚，进一步制备烯烃，简化工艺流程，操作成本低、大大减少投资。
合成气直接制低碳烯烃是指合成气(CO和H2)在催化剂作用下，通过费托合成制得碳原子数小于或等于4的烯烃的过程，该过程副产水和CO2。由于费托合成产品分布受Anderson-Schulz-Flory规律(链增长依指数递减的摩尔分布)的限制，且反应的强放热性易导致甲烷和低碳烷烃的生成，并促使生成的烯烃发生二次反应，想要高选择性地得到低碳烯烃较为困难，关键在于高性能催化剂的开发。
尽管也有文献报道将钴基或钌基催化剂用于费托反应制低碳烯烃，但因铁基催化剂其成本低，具有较高的低碳烯烃选择性，成为费托合成直接制低碳烯烃反应首选的活性组分。近来，有较多的文献报道在制备铁基催化剂过程中使用到了碳材料。碳材料不仅能提供所需的稳定性，也有利于铁物种的还原和活化，因而碳材料无论作为载体或助剂都成为近年来的研究热点。石墨烯作为一种新型的碳材料，具有大的比表面积、独特的二维结构、优良的导电和导热性、以及易于进行化学修饰等优点，而被认为是一种理想的催化剂载体或助剂。而目前的大多数研究多将石墨烯添加到铁基催化剂前驱体过程中，制备过程较为复杂，同时催化性能及稳定性改善也不是非常显著。因此需要开发一种能够对铁基催化剂直接采用石墨烯修饰的方法，简化催化剂的制备过程，同时可显著提高催化剂活性、低碳烯烃选择性和稳定性。
发明内容
本发明涉及一种能实现合成气高选择性地制备低碳烯烃，同时可制备高级α-烯烃、活性高、稳定性好和制备方法简单的石墨烯修饰的铁基催化剂及其制备方法。
本发明的催化剂是一种石墨烯修饰的铁基催化剂及其在费托反应制烯烃中的应用。该催化剂是由质量百分含量为0.01～30％的石墨烯、0～20％的助剂和60～99.99％的铁氧化物粉体组成；
本发明的催化剂其特征在于：铁氧化物为四氧化三铁、三氧化二铁、氧化亚铁中的一种或任意几种组合，铁氧化物颗粒尺寸为50～1000nm，优选100～500nm；助剂为K、Na、Mn、Cu、Zn、Mo、Co、S中的一种或任意几种组合；
本发明的催化剂的制备过程其特征以下步骤：(1)10～80℃条件下，将石墨烯分散于水溶液中形成悬浊液，超声分散0.5～5h后搅拌1～24h；(2)根据计量比将铁氧化物粉体加入步骤(1)形成的悬浊液中，并不断搅拌0.5～24h；(3)根据计量比将助剂前驱体加入到步骤(2)形成的悬浊液中，并不断搅拌1～24h；(4)对步骤(3)所得到的溶液旋转蒸发至干，所得固体80～120℃下干燥1～24h，随后在氮气或氦气或氩气中一种气体中250～800℃焙烧1～24h，即得石墨烯修饰的铁基催化剂。
本发明的催化剂中铁元素的氧化物的前躯体为可溶性铁盐，优选氯化物、硝酸盐、醋酸盐、硫酸盐、柠檬酸铁铵、亚铁氰酸铵和铁氰酸铵中一种或两种以上；助剂的前躯体选取含助剂元素的可溶性化合物，优选硝酸盐、碳酸盐、醋酸盐、钼酸盐、硫化物中的一种或两种以上；
与现有技术比较，本发明具有的优点如下：
(1)所制备的催化剂其制备方法简单，一步形成，在反应过程中可有效形成的微小碳化铁活性相，维持其高活性。
(2)所制备的催化剂具有极高的总烯烃选择性和较低甲烷选择性。催化剂的活性极高，可在极高空速下保持催化剂的稳定性。
具体实施方式
本发明技术细节通过下述实施例做详细的说明。需要说明的是所举的实施例，其作用只是进一步说明本发明的技术特征，而不是限定本发明。同时，实施例只是给出了实现此目的的部分条件，并不意味着必须满足这些条件才可以达到此目的。
1.石墨烯修饰的铁基催化剂的制备
实施例1
分别取0.677g氧化石墨烯、3.112g三氧化二铁粉体40℃下先后溶解于水溶液中，并不断搅拌12h；然后85℃下进行旋转蒸发至干，并在105℃干燥24h。随后在氮气氛围中400℃焙烧5h，得石墨烯含量为17.8％，三氧化二铁含量为82.2％的催化剂A。
实施例2
分别取0.325g氧化石墨烯、2.876g三氧化二铁粉体、0.0715g碳酸钾40℃下先后溶解于水溶液中，并不断搅拌12h；然后85℃下进行旋转蒸发至干，并在105℃干燥24h。随后在氮气氛围中400℃焙烧5h，得石墨烯含量为10％，三氧化二铁含量为88.5％和氧化钾含量为1.5％的催化剂B。
实施例3
分别取0.551g氧化石墨烯、4.052g四氧化三铁粉体40℃下先后溶解于水溶液中，并不断搅拌12h；然后85℃下进行旋转蒸发至干，并在105℃干燥24h。随后在氮气氛围中400℃焙烧5h，得石墨烯含量为12％，四氧化三铁含量为88％的催化剂C。
实施例4
分别取0.861g氧化石墨烯、4.001g四氧化三铁粉体和0.435g硝酸钾40℃下先后溶解于水溶液中，并不断搅拌12h；然后85℃下进行旋转蒸发至干，并在105℃干燥24h。随后在氮气氛围中400℃焙烧5h，得石墨烯含量为17％，四氧化三铁含量为79％和氧化钾含量为4％的催化剂D。
2.石墨烯修饰的铁基催化剂在合成气转化中的利用。
将制备好的催化剂在5.5MPa压力下成型、破碎、过筛获取40～60目的样品。取0.15g催化剂置于连续流动的反应器中，反应前催化剂均要采用H2预还原一定时间，然后降温至反应温度进行连续反应。反应气由47.5vol％CO、47.5vol％H2和5vol％Ar组成，其中Ar作为内标气，用来计算CO的转化率。产物经冷阱后常压在线分析，由一台同时配置TCD和FID检测器的气相色谱来分析。
实施例5
催化剂A置于加压固定床反应器中，在H2氛围中以5℃/min升温至380℃，常压下，空速1000h-1还原10h。随后降温引入反应气体进行反应，反应压力1.0MPa，反应空速20000h-1，反应温度为300，320和340℃，考察反应温度的影响。CO转化率和烯烃选择性结果见表1。
实施例6
催化剂B置于加压固定床反应器中，在H2氛围中以5℃/min升温至380℃，常压下，空速1000h-1还原10h。随后降温引入反应气体进行反应，反应压力1.0MPa，反应温度300℃，反应空速10000h-1，20000和40000h-1，考察反应空速的影响。CO转化率和烯烃选择性结果见表1。
实施例7
催化剂C置于加压固定床反应器中，在H2氛围中以5℃/min升温至380℃，常压下，空速1000h-1还原10h。随后降温引入反应气体进行反应，反应压力1.0MPa，反应空速20000h-1，反应温度340℃，CO转化率和烯烃选择性结果见表1。
实施例8
催化剂D分别置于加压固定床、流化床和浆态床反应器中，均在H2氛围中以5℃/min升温至380℃，常压下，空速1000h-1还原10h。随后降温引入反应气体进行反应，反应压力1.0MPa，反应空速20000h-1，反应温度340℃，CO转化率和烯烃选择性结果见表1。该结果用于比较催化剂在不同反应器中反应结果。
对比例1
分别取3.88g三氧化二铁粉体和0.176g碳酸钾40℃下先后溶解于水溶液中，并不断搅拌12h；然后85℃下进行旋转蒸发至干，并在105℃干燥24h。随后在氮气氛围中400℃焙烧5h，得三氧化二铁含量为97％和氧化钾含量为3％的催化剂E。将该催化剂置于加压固定床反应器中，在H2氛围中以5℃/min升温至380℃，常压下，空速1000h-1还原10h。随后降温引入反应气体进行反应，反应压力1.0MPa，反应空速20000h-1，反应温度为300和340℃，考察反应温度的影响。CO转化率和烯烃选择性结果见表2。
对比例2
分别取0.506g活性炭，4.948四氧化三铁粉体和0.248g碳酸钾40℃下先后溶解于水溶液中，并不断搅拌12h；然后85℃下进行旋转蒸发至干，并在105℃干燥24h。随后在氮气氛围中400℃焙烧5h，得活性炭含量为9％，四氧化三铁含量为89％和氧化钾含量为3％的催化剂F。将该催化剂置于加压固定床和流化床反应器中，在H2氛围中以5℃/min升温至380℃，常压下，空速1000h-1还原10h。随后降温引入反应气体进行反应，反应压力1.0MPa，反应空速20000h-1，反应温度为340℃。CO转化率和烯烃选择性结果见表2。
表1不同催化剂的合成气转化制低碳烯烃的反应性能
反应条件：固定床反应器，1.0MPa，反应100-500h内的平均数据。
*流化床反应器；**浆态床反应器；
表2对比例实验结果
反应条件：固定床反应器，1.0MPa，5-10h内的平均数据。
*流化床反应器。
对比表1和表2中实验结果，可清晰地看出石墨烯修饰的铁基催化剂表现出优异的催化性能，在反应500小时内保持活性稳定；在很高的反应空速仍然表现出很高的CO转化率。即使在没有助剂添加的情况下，产物中烯烃选择性就已接近50％，烯烷比可达13。而没有石墨烯修饰或采用其它碳材料修饰的铁基催化剂，在反应数小时内就快速失去活性，且产物中以烷烃为主。该结果表明石墨烯修饰的铁基催化剂具有极好的工业应用价值。
Claims (7)
1.一种用于费托反应制烯烃的石墨烯修饰的铁基催化剂的制备方法，其特征在于：所述催化剂的制备过程是按照以下步骤进行：
(1)10～80℃条件下，将氧化石墨烯分散于水溶液中形成悬浊液，超声分散0 .5～5h后搅拌1～24h；
(2)根据计量比将铁氧化物粉末加入步骤(1)形成的悬浊液中，并不断搅拌0.5～24h；
(3)根据计量比将助剂前驱体加入到步骤(2)形成的悬浊液中，并不断搅拌1～24h；
(4)对步骤(3)所得到的混合液旋转蒸发至干，所得固体于80～120℃下干燥1～24h，随后在氮气或氦气或氩气中250～800℃焙烧1～24h，即得石墨烯修饰的铁基催化剂；
制得的石墨烯修饰的铁基催化剂由质量百分含量为0.01～30％的氧化石墨烯、0～20％助剂和60～99.99％的铁氧化物组成，所述铁氧化物的颗粒尺寸为50～1000nm，助剂含量不为0，且上述三种组分的含量总和为100%。
2.如权利要求1所述铁基催化剂的制备方法，其特征在于：铁氧化物为四氧化三铁、三氧化二铁、氧化亚铁中的一种或任意几种组合；铁氧化物的形貌为球形或方形；助剂为K、Na、Mn、Cu、Zn、Mo、Co、S中的一种或任意几种组合。
3.如权利要求2所述铁基催化剂的制备方法，其特征在于：所述铁氧化物颗粒尺寸为100～500nm。
4.如权利要求1～3任一所述铁基催化剂的制备方法，其特征在于：铁氧化物的制备方法为水解法、水热法、沉淀法中的一种，铁的前躯体为可溶性铁盐。
5.如权利要求4所述铁基催化剂的制备方法，其特征在于：所述铁的前躯体为氯化物、硝酸盐、醋酸盐、硫酸盐、柠檬酸铁铵、亚铁氰酸铵和铁氰酸铵中一种或两种以上。
6.如权利要求1所述铁基催化剂的制备方法，其特征在于：铁氧化物的制备方法为水解法、水热法、沉淀法中的一种，铁的前躯体为可溶性铁盐；所述助剂前躯体选取含助剂元素的可溶性化合物。
7.如权利要求6所述铁基催化剂的制备方法，其特征在于：所述含助剂元素的可溶性化合物为硝酸盐、碳酸盐、醋酸盐、钼酸盐、硫化物中的一种或两种以上。
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