CN100584454C - 含有水铁矿和铝的费托合成催化剂 - Google Patents
含有水铁矿和铝的费托合成催化剂 Download PDFInfo
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Abstract
本发明涉及一种铁基费托合成催化剂组合物,其中主铁相是水铁矿,其中催化剂组合物包括作为结构助催化剂的氧化铝。本发明涉及一种制备该催化剂的方法。在主铁相为水铁矿的铁基催化剂组合物中使用氧化铝作为结构助催化剂可增加催化剂的活性和选择性1.5~3倍。
Description
背景技术
本发明涉及铁基催化剂,特别是涉及铁基催化剂及其在合成气(CO+H2)转化为醇和烯烃中的用途。
国际专利出版No.WO 01/89689公开了铁基费托合成催化剂组合物,其中铁相是水铁矿。催化剂组合物包括可选自Mn或Cr或其混合物的天然助催化剂及可选自Mn、Zn、Cu和碱金属或碱土金属的化学助催化剂。催化剂最好被负载于难熔氧化物载体上例如硅石。根据说明书,催化剂组合物可生产大量的高级链烷烃、烯烃和醇。
本发明的一个目的是提供改进的铁基催化剂,其可增加活性及对醇和烯烃的选择性。
发明内容
根据本发明的第一方面,提供一种铁基催化剂组合物,其中主要的铁相是水铁矿,其中催化剂组合物包括作为结构助催化剂的铝。
所述“铁基”是指Fe构成至少30%(质量)的组合物。术语“主要相是水铁矿”是指至少75%的铁相是水铁矿,其通过使用Cu Kα辐射的X-光衍射进行确定。优选的催化剂组合物表现出类似水铁矿的超精细相互作用的参数,其通过穆氏鲍尔吸收谱(MAS)进行测定。
“结构助催化剂”是一种化学物种/元素,其有助于稳定催化剂的水铁矿相。
“化学助催化剂”是一种化学物种/元素,其可改变产物的选择和催化剂的活性。
有利的是,铁基催化剂组合物也包括Mn。
优选,铁基催化剂组合物也包括选自Zn、Mg、Cu、Ru、Pd、Rh和/或碱金属或碱土金属例如K、Na或Li的一种或多种化学助催化剂。
有利的是,氧化铝占催化剂组合物质量的5%~20%。
通常,催化剂组合物含有以质量计的35%~60%的Fe、1%~25%的Mn、1%~15%的Zn、1%~25%的Cu和0.1%~3%的K2O。
催化剂不必与粘合剂结合,其表面积为150~300m2/g,及孔体积为0.1~0.5cm3/g。
根据本发明的第二方面,提供一种制备铁基催化剂前体的方法,其中主铁相是水铁矿,及其中催化剂组合物包括铝,其中氧化铝通过共沉淀法利被铁相所包夹。
通常制备铁基催化剂前体的方法包括如下的步骤,其中前体中主铁相为水铁矿,及催化剂组合物包括氧化铝:
1、在极性溶剂中制备一种溶液,所述的溶液含有Fe和Al离子;
2、将沉淀剂通常为碱性溶液加入到所述的溶液中以形成催化剂沉淀,其中主铁相是水铁矿;
3、洗涤沉淀;
4、干燥,通常喷雾干燥洗涤的沉淀;及
5、焙烧干燥的沉淀。
另外,Al离子可在步骤2中利用沉淀剂被包夹。
第一溶液可以通过将铁盐例如硝酸铁、氧化铝盐例如硝酸铝溶解在极性溶剂中形成。
有利的是,结构助催化剂离子例如Mn、Cu、Zn、Cd、Ni、Co及化学助催化剂例如Zn、Mg、Cu、Cr、Ru、Pd、Rh或/和碱金属或碱土金属例如K、Na和Li被包含在第一溶液中。
通常,第一溶液包括硝酸铁、硝酸锰、硝酸铝、硝酸铜和硝酸锌。
优选的碱是KOH,但是也可以使用NaOH、Na2(CO)3和K2(CO)3。
在本发明的另一个实施方式中,制备铁基催化剂前体的方法包括如下的步骤,其中前体中主铁相为水铁矿,及催化剂组合物包括氧化铝:
1、在极性溶剂中制备一种溶液,所述的溶液含有Fe和Al离子;
2、将沉淀剂通常为碱性溶液加入到所述的溶液中以形成催化剂沉淀,其中主铁相是水铁矿;
3、洗涤沉淀;
4、干燥,通常喷雾干燥洗涤的沉淀;
5、焙烧干燥的沉淀;及
6、进一步用碱金属或碱土金属浸渍焙烧的沉淀。
另外,Al离子可在步骤2中利用沉淀剂被包夹。
焙烧的沉淀物可用所需要量的碱金属或碱土金属例如K、Na和Li进行进一步浸渍。
根据本发明的第三方面,提供一种通过使H2和CO在基本上如上所述催化剂的存在下进行反应,选择生产高级链烷烃、醇和烯烃的方法。本发明一个优选实施方式中提供选择生产直链链烷烃、醇和烯烃烃的方法。
发明的详细描述
广义上将,本发明涉及一种用于在费托合成条件下(压力为20~100巴(2~10MPa),200~310℃的低温下)使合成气转化为链烷烃、烯烃,更特别的高产率地转化为直链醇直到包括洗涤剂醇的催化剂组合物,及其这样的转化方法。
本发明优选实施方式的催化剂组合物是铁基催化剂,其主相是水铁矿并包括结构助催化剂氧化铝。
现在令人惊奇地发现在主铁相为水铁矿的铁基催化剂组合物中使用氧化铝作为结构助催化剂可增加催化剂的活性1.5~3倍(与WO01/89689中描述的催化剂相比)。
也优选催化剂组合物包括作为结构助催化剂的Mn,选自Mg和Zn的化学助催化剂。本发明优选的催化剂组合物包括氧化铝、Mn、Zn、Cu和K。
典型的本发明组合物包括以质量计的35%~65%的Fe、1%~25%的Mn、1%~15%的Zn、1%~25%的Cu、0.1%~3%的K2O及5%~20%的Al2O3。
本发明的催化剂组合物可通过如下步骤制备:制备含硝酸铁(Fe(NO3)3·9H2O)、硝酸锰(Mn(NO3)3·4H2O),硝酸锌(Zn(NO3)3·6H2O)、硝酸铜(Cu(NO3)3·3H2O)、硝酸钾(KNO3)和硝酸铝(Al(NO3)3·9H2O)的第一酸性溶液,将溶液加热到75℃。第二碱性溶液含有以质量计25%的KOH,在45℃下下然后被加入溶液中。调节将第二溶液加入到第一溶液中的加入速度要使pH值保持约为8,温度约为70℃。将第二溶液加入第一溶液中后引起形成沉淀,所述的沉淀是本发明的催化剂组合物。过滤该沉淀并洗涤,滤饼然后被再淤浆化并在入口温度为260℃及出口温度为120℃下进行喷雾干燥。之后,在450℃下焙烧得到的催化剂16小时,筛分为38~150μm的粒度。
尽管上述描述的制备方法是优选的方法,但可以通过将硝酸铝加入到第二碱性溶液中利用共沉淀包夹氧化铝,或通过将含有硝酸铝或氢氧化铝的溶液与淤浆化的沉淀混合,并喷雾干燥和焙烧得到的混合物,从而将氧化铝加入到洗涤的沉淀中。也可以其他的方式加入钾,例如在组合物焙烧后浸渍。在实施例中描述了这些另外的方法。
所谓的本发明催化剂组合物是铁基的,主铁相是水铁矿,催化剂的的表面积为150-300m2/g,孔体积为0.1-0.5,典型地为0.3m3/g。
尽管可以将上述的催化剂结合到耐高温的金属氧化物上,但不必这样做。因此,由于消除了粘合剂添加阶段因而简化了制备阶段。
本发明实施方式的费托合成工艺可以利用如上所述本发明的铁基催化剂组合物,在含有碳链长度为C10~C120例如来自使用Fe或Co基催化剂的淤浆床反应器工艺中得到的蜡的粗合成链烷烃或蜡液体中进行。如上所述的铁基催化剂组合物然后被悬浮于淤浆介质中,催化剂的装填量为淤浆重量的10%~40%。搅拌淤浆并使纯H2、CO或富H2/CO混合物连续流过介质约20小时从而进行调节。另外,可以在大气压下使用H2、CO或H2/CO调节催化剂(还原和碳化)。之后,使合成气连续流过已调节过的淤浆。合成气进料的组成通常包括H2和CO,H2和CO的摩尔比为约5∶1~约1∶5,优选为约1∶1~2∶1。进料合成气也可包括约1~25体积%的CO2、N2和/或CH4。在整个调节过程和合成过程中,反应器在200~310℃的温度,优选为220~250℃,最优选为约240℃及10~100巴压力下进行操作。
与以前结合有SO2的WO 01/89689中描述的那些催化剂相比,费托合成活性提高了1.5~3倍。对烯烃和醇的产率提高了1.5~3倍,选择性提高了1.5~2倍。本发明催化剂另外的优点是增加了约1.5~2倍的C6+醇和烯烃馏分。根据优选的方法制备催化剂组合物也具有经济和环境的优势,因为铝和所有其他元素共沉淀减少了制备过程中金属的损失。
实施例1
含有1787g Fe(NO3)3·9H2O、400g Mn(NO3)3·4H2O、345g AI(NO3)3··9H2O;69g Cu(NO3)3·3H2O和143g Zn(NO3)3·6H2O的4200ml水溶液加热到75℃,与保持在45℃的含有25%(质量)KOH的第二溶液混合。调节这些溶液的加入速度要使沉淀的pH为~8,温度为~70℃。过滤沉淀,用水彻底洗涤直到电导率为2.0mSv。滤饼然后被再淤浆化,并在入口温度260℃及出口温度120℃下进行喷雾干燥。之后得到的催化剂在450℃下焙烧16小时,最后筛分为38~150μm的颗粒,之后进行表征和测试。本发明第一催化剂的组成列于表1中。
表1
元素 | 催化剂1 |
Fe[%] | 42.9 |
Cu[/100gFe] | 8.3 |
Mn[/100gFe] | 32.6 |
Zn[100gFe] | 12.6 |
K<sub>2</sub>O[/100gFe] | 0.64 |
Al<sub>2</sub>O<sub>3</sub>[/100gFe] | 15.7 |
实施例2
用与实施例1相同的方法制备本发明的第二催化剂,不同之处在于该实施例的目的是在洗涤期间除去所有的K2O。焙烧后K2O的含量为0.16g/100g Fe。利用淤浆浸渍方法,催化剂浸渍到所需要的K2O含量为1.00g/100g Fe。
0.2612g的KNO3溶解于10ml的蒸馏水并与60ml的甲醇混合。混合物然后加入到含有30g催化剂的烧瓶中,在65℃及800mmHg~50mmHg下在旋转蒸发仪中进行加热。干燥的催化剂在450℃下焙烧16小时。本发明的第二催化剂的组成列于表2。
表2
元素 | 催化剂2 |
Fe[%] | 38.8 |
Cu[/100gFe] | 6.8 |
Mn[/100gFe] | 27.5 |
Zn[100gFe] | 11.5 |
K<sub>2</sub>O[/100gFe] | 1.04 |
Al<sub>2</sub>O<sub>3</sub>[/100gFe] | 29.7 |
实施例3
与实施例1列出的相同方法制备催化剂3。焙烧后K2O含量为5.3g/100g Fe。通过用稀释的HNO3洗涤催化剂除去多余的K2O。
100ml的蒸馏水加入到30g催化剂中并彻底进行混合。稀释的HNO3(1∶3稀释55.5M)逐滴加入直到pH为~5.5。倾去溶剂使用甲醇在旋转蒸发仪中干燥湿的催化剂。本发明催化剂3的组成列于表3
表3
元素 | 催化剂3 |
Fe[%] | 34.5 |
Cu[/100gFe] | 6.8 |
Mn[/100gFe] | 36.1 |
Zn[100gFe] | 10.7 |
K<sub>2</sub>O[/100gFe] | 0.59 |
Al<sub>2</sub>O<sub>3</sub>[/100gFe] | 30.7 |
实施例4~6
通过连续制备的方法制备催化剂4~6。金属溶液(Fe、Zn、Mn和Cu的硝酸盐)加热到70℃,KOH溶液的温度保持在~45℃。调节这些溶液的加入速度要使沉淀的pH为~8,温度为~70℃。沉淀后过滤沉淀,用水洗涤直到电导率为2.0mSv。然后将沉淀分为不同的批次,如实施例4~6描述研究Al的加入。
实施例4
在第一个方法中,硝酸铝与如第二部分描述制备的淤浆混合。该步骤称为粘合剂加入阶段。在将硝酸铝与铁的淤浆混合后,将淤浆喷雾干燥并如实施例1一样进行焙烧。催化剂最后的组成列于表4中。
表4
元素 | 催化剂4 |
Fe[%] | 52.1 |
Cu[/100gFe] | 7.5 |
Mn[/100gFe] | 11.2 |
Zn[100gFe] | 10.9 |
K<sub>2</sub>O[/100gFe] | 1.19 |
Al<sub>2</sub>O<sub>3</sub>[/100gFe] | 12.3 |
实施例5
氢氧化铝与洗涤的铁淤浆进行混合以得到希望的氧化铝含量。随后进行喷雾干燥和焙烧。第5催化剂最后的组成列于表5中。
表5
元素 | 催化剂5 |
Fe[%] | 51.4 |
Cu[/100gFe] | 8.5 |
Mn[/100gFe] | 12.2 |
Zn[100gFe] | 11.9 |
K<sub>2</sub>O[/100gFe] | 1.68 |
Al<sub>2</sub>O<sub>3</sub>[/100gFe] | 13.4 |
表6
列出与WO 01/89689制备的催化剂相比,本发明实施例1~4催化剂的性能。
实施例7
用共沉淀Al(NO3)3·9H2O和其他的金属硝酸盐制备催化剂7和8,不同之处在于在催化剂9和10中,AI(NO3)3·9H2O在喷雾干燥前加入催化剂淤浆中。
表7
列出了共沉淀硝酸铝可减少其他金属的损失
Claims (5)
1.一种铁基费托合成催化剂组合物,其中铁占该催化剂组合物的至少30质量%,其中主铁相是水铁矿,即至少75%的铁相是水铁矿,其中催化剂组合物包括作为结构助催化剂的占催化剂组合物5质量%~20质量%的氧化铝,也包括Mn。
2.如权利要求1的催化剂组合物,其中催化剂组合物也包括选自Zn、Mg、Cu、Ru、Pd、Rh和碱金属或碱土金属的一种或多种化学助催化剂。
3.如权利要求2的催化剂组合物,其中碱金属为K或Na。
4.如权利要求2的催化剂组合物,其中氧化铝占催化剂组合物质量的5%~20%。
5.如权利要求4的催化剂组合物,含有以质量计的35%~60%的Fe、1%~25%的Mn、1%~15%的Zn、1%~25%的Cu和0.1%~3%的K2O。
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CN100594060C (zh) * | 2004-06-24 | 2010-03-17 | 青岛金王应用化学股份有限公司 | 一种用于合成气制取重质蜡的催化剂及其制备方法 |
AU2013242856B2 (en) * | 2007-08-30 | 2016-04-21 | Res Usa, Llc | Strengthened iron catalyst for slurry reactors |
DE102007046160A1 (de) * | 2007-09-27 | 2009-04-02 | Bayer Materialscience Ag | Verfahren zur Herstellung eines Katalysators für die Herstellung von Kohlenstoffnanoröhrchen |
US7964114B2 (en) * | 2007-12-17 | 2011-06-21 | Sud-Chemie Inc. | Iron-based water gas shift catalyst |
CN101559372A (zh) * | 2008-01-23 | 2009-10-21 | 亚申科技研发中心(上海)有限公司 | 用于费托合成的铁/锰催化剂及其制备方法 |
US20110201702A1 (en) * | 2009-08-14 | 2011-08-18 | Sumit Bali | Ultra small synthetic doped ferrihydrite with nanoflake morphology for synthesis of alternative fuels |
CN102304380B (zh) * | 2010-07-23 | 2014-01-29 | 中国科学技术大学 | 一种利用生物质和生物油制生物质基混合液体燃料的方法 |
EP2439185A1 (en) * | 2010-08-20 | 2012-04-11 | Shell Internationale Research Maatschappij B.V. | Process for preparing olefins from synthesis gas using a cobalt and manganese containing catalyst |
CN102371154B (zh) * | 2010-08-23 | 2013-06-05 | 中国石油化工股份有限公司 | 合成轻质烃的铁基催化剂及其制备方法 |
WO2012138415A1 (en) * | 2011-04-04 | 2012-10-11 | Dow Global Technologies Llc | Improved fischer-tropsch process for converting synthesis gas to a lower olefin |
CN107530679B (zh) * | 2015-04-28 | 2021-05-18 | 3M创新有限公司 | 用于呼吸防护的过滤器介质 |
CN105214663B (zh) * | 2015-09-02 | 2018-05-25 | 中国科学院上海高等研究院 | 一种用于低温浆态床费托合成的铁基催化剂及其制备方法和用途 |
CN109092311A (zh) * | 2017-06-21 | 2018-12-28 | 神华集团有限责任公司 | 低温脱硫催化剂和由费托合成铁基催化剂废料制备低温脱硫催化剂的方法 |
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