CN112569947B - 一种形貌可控的均匀棒状结构铁/石墨烯催化剂及其制备方法和应用 - Google Patents
一种形貌可控的均匀棒状结构铁/石墨烯催化剂及其制备方法和应用 Download PDFInfo
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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Abstract
本发明公开了一种形貌可控的均匀棒状结构铁/石墨烯催化剂及其制备方法和应用。包括以下重量份数的原料制备而成:(a)3‑90份铁元素或其氧化物或氢氧化物;(b)0.05‑10份选自钾和钠元素中的一种元素或其氧化物;(c)15‑90份石墨烯。本发明基于石墨烯材料制备大尺寸规整形貌的催化剂,该催化剂具有CO转化率高、产物中长链α‑烯烃选择性高的优点。将该催化剂用于合成气制取长链α‑烯烃,解决了合成气制取长链α‑烯烃技术中产物中目标产品选择性低、而低碳烯烃选择性高的问题。
Description
技术领域
本发明涉及一种形貌可控的均匀棒状结构铁/石墨烯催化剂及其制备方法和应用,属于材料化学和工业催化技术领域。
背景技术
长链α-烯烃是指不饱和键位于链烃端位的碳五以上的烯烃。由于分子中含有活性位(烯键),α-烯烃容易接入各种官能团,衍化成醇、酸、酯等化合物,广泛应用于表面活性剂、共聚单体、润滑油等精细化学品生产。三聚α-烯烃就是著名的PAO润滑油基础油。1-己烯是重要的聚乙烯共聚单体,用于烯烃共聚,可提升聚烯烃的品质。
国外α-烯烃总生产能力约为212万吨,国内缺乏生产长链α-烯烃的能力,1-己烯产能几万吨,而1-辛烯和其它碳数α-烯烃几乎完全依赖进口。随着我国润滑油及洗涤剂等行业对原料的要求逐渐提高,长链α-烯烃的市场前景非常看好。
长链α-烯烃生产工艺有长链烷烃脱氢、乙烯齐聚和煤化工副产品分离三种。现行洗涤剂原料就由C14-C18烷烃脱氢制得。润滑油基础油所用α-烯烃从石蜡裂解而来。由于裂解或脱氢工艺产生内烯烃、低碳烃等非目标产物,产品质量差,缺乏经济竞争力,在国外已逐渐被淘汰。乙烯齐聚得到产品质量好、碳数分布窄,是国外普遍采用的工艺。但是,该工艺为国外公司垄断,国内仍在研发阶段。另一条生产路线是费托合成。费托合成反应机理决定,其本身会产生可观的α-烯烃,特别是,如果采用合适催化剂和反应器,α-烯烃的生成量是相当可观的。由于是一步直接得到,且原料为廉价的合成气而非乙烯,所以该生产工艺在成本上有较大优势。比如,Sasol从费托合成产物中分离1-辛烯、1-己烯。该装置可以调整几种烯烃的比例,其1-己烯的产量超过10万吨/年。这些产品取得了良好的经济效益。
发明内容
本发明旨在提供一种形貌可控的均匀棒状结构铁/石墨烯催化剂及其制备方法,基于石墨烯材料制备大尺寸规整形貌的催化剂,该催化剂具有CO转化率高、产物中长链α-烯烃选择性高的优点。将该催化剂用于合成气制取长链α-烯烃,解决了合成气制取长链α-烯烃技术中产物中目标产品选择性低、而低碳烯烃选择性高的问题。
本发明制备了形貌规整、尺寸较大的羟基氧化铁和/或氧化铁物相,在保持烯烃选择性的前提下,促进长链烃的生成,实现长链α-烯烃的定向合成。如图1和表1所示,实施案例1中催化剂中铁呈现宽为30nm,长为100-200nm的棒状结构,合成α-烯烃产物中α-烯烃的选择性为67.5%。对比案例1中,催化剂中铁为20-40nm的球状,α-烯烃的选择性为55.2%,且反应稳定性较差。以上结果进一步证实了一定尺寸的铁微晶物相,可以优选生成长链α-烯烃。
本发明提供了一种形貌可控的均匀棒状结构铁/石墨烯催化剂,包括以下重量份数的组分:
(a)3-90份铁元素或其氧化物或氢氧化物;
(b)0.05-10份选自钾和钠元素中的一种元素或其氧化物;
(c)15-90份石墨烯。
上述技术方案中,所述铁为氢氧化铁,或为α-FeOOH与Fe2O3的混合相,含量的范围为20-50份。
本发明提供了一种形貌可控的均匀棒状结构铁/石墨烯催化剂的制备方法,包括以下步骤:
(1)用Hummer法制备氧化石墨,洗涤,超声得到氧化石墨烯的均匀溶液;
(2)将含铁盐的溶液加入到氧化石墨烯水溶液中,并搅拌均匀,得到物料A;
(3)将物料A进行超声,并在此过程中加入碱液,调节pH值为8.0-12.0,得到物料B;
(4)将物料B移入水热釜中,进行水热处理;
(5)水热反应结束后,用大量的去离子水和乙醇的混合溶液洗涤,并离心,然后在烘箱中干燥催化剂,得到定制形貌的Fe/石墨烯催化剂;
(6)将所得的Fe/石墨烯催化剂破碎、筛分,并在一定保护气氛下进行热处理焙烧,冷却后得到所需的催化剂。
本发明中,铁盐为硝酸铁、氯化铁、氯化亚铁、草酸铁、柠檬酸铁铵、亚硫酸铁、醋酸铁、乙酰丙酮铁中的一种,或其中的几种,优选硝酸铁、硫酸亚铁或乙酰丙酮铁。
本发明中,碱液包括但不限于氨水、NaOH、KOH、Na2CO3、K2CO3中的一种,或其中的几种,优选KOH或NaOH。碱液需在超声的过程中缓慢加入。
本发明步骤(2)中,氧化石墨烯水溶液中氧化石墨烯与去离子水的质量比为1:800-2000,优选1:800-1200。
本发明步骤(4)中,水热的温度为120-240℃,优选150-220℃。
本发明步骤(5)中,洗涤液中去离子水与乙醇的质量为1:1-1:20,优选1:1-1:5。
本发明步骤(5)中,干燥箱温度最优为40-80℃,优选60-80℃。
本发明步骤(6)中,热处理的气氛包括但不限于H2、Ar、CO+H2、空气中的一种,优选Ar或H2。热处理的温度为200-800℃,优选350-650℃。热处理的时间为4-16小时,优选6-10小时。
本发明提供了上述形貌可控的均匀棒状结构铁/石墨烯催化剂在合成气直接制取α-烯烃中的应用。
催化剂用于合成气制α-烯烃的反应条件为:温度240-340℃,反应压力0.5MPa-5.0MPa,合成气中H2与CO体积比为0.67-3.0,空速为3-50L/gcat/h。反应温度优选260-320℃,反应压力优选2.0-4.0MPa,合成气中H2与CO体积比优选为1:1.5.其中,空速最高可达到50L/gcat/h,α-烯烃的选择性不低于65%。
采用本发明催化剂,α-烯烃在碳氢化合物中的选择性可达到65%,催化剂可连续稳定运行3000小时。
本发明的有益效果:
(1)本发明基于石墨烯材料制备大尺寸规整形貌的催化剂,该催化剂具有CO转化率高、产物中长链α-烯烃选择性高的优点;将该催化剂用于合成气制取长链α-烯烃,解决了合成气制取长链α-烯烃技术中产物中目标产品选择性低、而低碳烯烃选择性高的问题。
(2)按照国内聚乙烯产量1200万吨,聚丙烯产量1200万吨的规模计算,α-烯烃添加量按10%计,国内作为共聚单体的α-烯烃的市场容量为240万吨/年;我国年生产洗涤剂850万吨,按照表面活性剂用量30%估算,表面活性剂的需求量为255万吨/年;考虑到合成表面活性剂份额占80%以上,合成表面活性剂的用量约200万吨左右;国内PAO基础油主要由Exxon-Mobil和BP-AMOCO占据,二者占国内市场的67%。国内PAO基础油使用滞后,预测销售量约50万吨/年;按照1.8万元/吨的售价计算,则10万吨示范厂的产值达到18亿。国内α-烯烃的市场约500万吨/年,如果一半采用了此技术,则将形成一个年产值900亿的新兴产业。国际石油巨头一直对我国封锁乙烯制α-烯烃的技术,α-烯烃完全依赖进口,这限制了聚烯烃、PAO等产业的升级。本发明提供的合成气制α-烯烃方法可以打破国际垄断,避免受制于人。
附图说明
图1为实施例1和对比例1所制备的形貌可控的均匀棒状结构铁/石墨烯催化剂的TEM图;图2为实施例1和实施例3所制备的形貌可控的均匀棒状结构铁/石墨烯催化剂的XRD图;图3为所制备的形貌可控的均匀棒状结构铁/石墨烯催化剂的反应稳定性图;
图4为合成α-烯烃的产物色谱图。
具体实施方式
下面通过实施例来进一步说明本发明,但不局限于以下实施例。
实施例1:
以Hummer法制备氧化石墨,经洗涤、超声后得到均匀的棕色氧化石墨烯溶液。取一定量的氧化石墨溶液(含碳量0.5g),在搅拌中加入30ml溶解有3.40g九水合硝酸铁的水溶液,搅拌30分钟后,在超声处理下缓慢加入50ml溶解有KOH的溶液,调节pH值至9,继续超声30分钟,再搅拌30分钟。将上述悬浮液移入水热釜中,在150℃条件下,保持5个小时,再降至室温。以乙醇和水混合溶液洗涤数次,在60℃下干燥4小时,即得到形貌可控的均匀棒状结构的铁/石墨烯催化剂。经ICP测定该催化剂中铁的含量为38wt%,钾含量为0.05wt%。
实施例2
以Hummer法制备氧化石墨,经洗涤、超声后得到均匀的棕色氧化石墨烯溶液。取一定量的氧化石墨溶液(含碳量0.5g),在搅拌中加入30ml溶解有3.40g九水合硝酸铁的水溶液,搅拌30分钟后,在超声处理下缓慢加入50ml溶解有KOH和NaOH的溶液,调节pH值至9,继续超声30分钟,再搅拌30分钟。将上述悬浮液移入水热釜中,在180℃条件下,保持5个小时,再降至室温。以乙醇和水混合溶液洗涤数次,在60℃下干燥4小时,即得到含K、Na的形貌可控的均匀棒状结构的铁/石墨烯催化剂。经ICP测定该催化剂中铁的含量为40wt%,K含量为0.1wt%,NaOH含量为0.07wt%。
实施例3
以Hummer法制备氧化石墨,经洗涤、超声后得到均匀的棕色氧化石墨烯溶液。取一定量的氧化石墨溶液(含碳量0.5g),在搅拌中加入30ml溶解有3.40g九水合硝酸铁的水溶液,搅拌30分钟后,在超声处理下缓慢加入50ml溶解有NaOH的溶液,调节pH值至9,继续超声30分钟,再搅拌30分钟。将上述悬浮液移入水热釜中,在180℃条件下,保持5个小时,再降至室温。以乙醇和水混合溶液洗涤数次,在60℃下干燥4小时,即得到含K、Na的形貌可控的均匀棒状结构的铁/石墨烯催化剂。经ICP测定该催化剂中铁的含量为37wt%,钠含量为0.01wt%。
对比例1
以Hummer法制备氧化石墨,经洗涤、超声后得到均匀的棕色氧化石墨烯液。用水合肼将氧化石墨烯还原,得到黑色还原氧化石墨烯的溶液。取一定量的上述还原氧化石墨烯溶液(含碳量0.5g),在搅拌中加入30ml溶解有3.40g九水合硝酸铁的水溶液,搅拌30分钟后,在超声处理下缓慢加入氨水,调节pH值至9,继续超声30分钟,再搅拌30分钟。将上述悬浮液移入水热釜中,在180℃条件下,保持5个小时,再降至室温。以乙醇和水混合溶液洗涤数次,在60℃下干燥4小时,即得到铁/石墨烯催化剂。经ICP测定该催化剂中铁的含量为38wt%。
对比例2
将3.40g九水合硝酸铁溶解于去离子水中,搅拌30分钟后,在超声处理下缓慢加入50ml溶解有KOH的溶液(nKOH : nNaOH= 1 : 1),调节pH值至9,继续超声30分钟,再搅拌30分钟,离心分离液固两相。以乙醇和水混合溶液将所得固体离心、洗涤数次,在60℃下干燥4小时,即得到纳米铁催化剂。经ICP测定该催化剂中铁的含量为40wt%,K含量为0.1wt%。
对比例3
取0.5g膨胀石墨,用H2O2将其进行回流处理,然后分散在300ml的蒸馏水中,在搅拌中加入30ml溶解有3.40g九水合硝酸铁的水溶液,搅拌30分钟后,在超声处理下缓慢加入含NaOH的溶液,调节pH值至9,继续超声30分钟,再搅拌30分钟。将上述悬浮液移入水热釜中,在180℃下,保持5个小时,再降至室温。以乙醇和水混合溶液洗涤数次,在60℃下干燥4小时,即得到铁/膨胀石墨催化剂。经ICP测定该催化剂中铁的含量为38wt%,钾含量为0.1wt%,钠含量为0.07wt%。
反应性能评价步骤如下:本发明实施例1-3所得催化剂的合成气直接制取α-烯烃的反应结果:
将实施例1~3干燥后的催化剂经破碎、过筛,取60-80目的颗粒,与石英砂均匀混合后装入不锈钢反应器中,通入H2在550℃下原位还原8个小时。还原完成后,待反应器降至室温,通入CO+H2。反应条件为:温度280℃,压力2.0MPa,原料气中H2与CO的体积比为2.15,催化剂的装量为1g。反应结果列于表1。
从表1可以看出,本发明提出的方法制备的形貌可控的均匀棒状结构铁/石墨烯催化剂表现出优异的合成气直接制取长链α-烯烃反应稳定性。
表1 形貌可控的均匀棒状结构的铁/石墨烯催化剂及对比催化剂在合成气直接制取α-烯烃反应中的催化剂性能
Claims (7)
1.一种形貌可控的均匀棒状结构铁/石墨烯催化剂,其特征在于:包括以下重量份数的组分:
(a)20-50份的α-FeOOH与Fe2O3的混合相;
(b)0.05-10份选自钾和钠元素中的一种元素或其氧化物;
(c)15-90份石墨烯;
所述的形貌可控的均匀棒状结构铁/石墨烯催化剂的制备方法,包括以下步骤:
(1)用Hummer法制备氧化石墨,洗涤,超声得到氧化石墨烯的均匀溶液;
(2)将铁盐的溶液加入到氧化石墨烯水溶液中,并搅拌均匀,得到物料A;
(3)将物料A进行超声,并在此过程中加入碱液,调节pH值为8.0-12.0,得到物料B;碱液包括NaOH、KOH、Na2CO3、K2CO3中的一种,或其中的几种;碱液需在超声的过程中缓慢加入;
(4)将物料B移入水热釜中,进行水热处理;
(5)水热反应结束后,用大量的去离子水和乙醇的混合溶液洗涤,并离心,然后在烘箱中干燥催化剂,得到定制形貌的Fe/石墨烯催化剂;
(6)将所得的Fe/石墨烯催化剂破碎、筛分,并在保护气氛下进行热处理焙烧,冷却后得到所需的催化剂。
2.根据权利要求1所述的形貌可控的均匀棒状结构铁/石墨烯催化剂,其特征在于:所述铁盐为硝酸铁、氯化铁、氯化亚铁、草酸铁、柠檬酸铁铵、亚硫酸铁、醋酸铁、乙酰丙酮铁中的一种,或其中的几种。
3.根据权利要求1所述的形貌可控的均匀棒状结构铁/石墨烯催化剂的制备方法,其特征在于:步骤(2)中,氧化石墨烯水溶液中,氧化石墨烯与去离子水的质量比为1:800-2000。
4.根据权利要求1所述的形貌可控的均匀棒状结构铁/石墨烯催化剂的制备方法,其特征在于:步骤(4)中,水热的温度为120-240℃,洗涤液中去离子水与乙醇的质量为1:1-1:20。
5.根据权利要求1所述的形貌可控的均匀棒状结构铁/石墨烯催化剂的制备方法,其特征在于:步骤(5)中,干燥箱温度为40-80℃。
6.根据权利要求1所述的形貌可控的均匀棒状结构铁/石墨烯催化剂的制备方法,其特征在于:步骤(6)中,热处理的气氛包括H2、Ar、CO+H2、空气中的一种;热处理的温度为200-800℃;热处理的时间为4-16小时。
7.一种权利要求1所述的形貌可控的均匀棒状结构铁/石墨烯催化剂在合成气直接制取α-烯烃中的应用,其特征在于:
催化剂用于合成气制α-烯烃的反应条件为:小型固定床反应器催化剂的装填量为3ml,温度240-340℃,反应压力0.5MPa-5.0MPa,合成气中H2与CO体积比为0.67-3.0,空速为3-50L•g-1cat•h-1;α-烯烃在碳氢化合物中的选择性能达到65%,催化剂能连续稳定运行3000小时。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103949262A (zh) * | 2014-04-21 | 2014-07-30 | 武汉凯迪工程技术研究总院有限公司 | 一种用于合成气生产α-烯烃的结构化铁基催化剂及制备方法和应用 |
CN105964263A (zh) * | 2016-05-14 | 2016-09-28 | 复旦大学 | 石墨烯负载的高效铁基费托合成制低碳烯烃催化剂及其制备方法 |
CN107051461A (zh) * | 2017-05-02 | 2017-08-18 | 江南大学 | 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 |
CN107570155A (zh) * | 2017-08-28 | 2018-01-12 | 中科合成油技术有限公司 | 多孔氧化铁/氧化石墨烯纳米复合材料在催化费托合成中的应用 |
CN111111723A (zh) * | 2020-02-06 | 2020-05-08 | 江南大学 | 一种铁基费托催化剂及其制备方法与应用 |
-
2020
- 2020-12-29 CN CN202011590546.9A patent/CN112569947B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103949262A (zh) * | 2014-04-21 | 2014-07-30 | 武汉凯迪工程技术研究总院有限公司 | 一种用于合成气生产α-烯烃的结构化铁基催化剂及制备方法和应用 |
CN105964263A (zh) * | 2016-05-14 | 2016-09-28 | 复旦大学 | 石墨烯负载的高效铁基费托合成制低碳烯烃催化剂及其制备方法 |
CN107051461A (zh) * | 2017-05-02 | 2017-08-18 | 江南大学 | 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 |
CN107570155A (zh) * | 2017-08-28 | 2018-01-12 | 中科合成油技术有限公司 | 多孔氧化铁/氧化石墨烯纳米复合材料在催化费托合成中的应用 |
CN111111723A (zh) * | 2020-02-06 | 2020-05-08 | 江南大学 | 一种铁基费托催化剂及其制备方法与应用 |
Non-Patent Citations (6)
Title |
---|
Iron oxide/oxyhydroxide decorated graphene oxides for oxygen reduction reaction catalysis:a comparison study;Xiangqian Liu et al.;《RSC Advances》;20160316;29848-29854 * |
K2CO3溶液处理对费托合成熔铁催化剂性能的影响;孙桃梅等;《天然气化工(C1 化学与化工)》;20141231;第39卷;48-52 * |
Mesoporous Iron Oxide Nanoparticle-Decorated Graphene Oxide Catalysts for Fischer−Tropsch Synthesis;Yuxue Wei et al.;《ACS Appl. Nano Mater.》;20200610;第3卷;7182页摘要、7183页2.1部分 * |
Porous Graphene-Confined Fe−K as Highly Efficient Catalyst for CO2 Direct Hydrogenation to Light Olefins;Tijun Wu et al.;《ACS Appl. Mater. Interfaces》;20180629;第10卷;23439-23443 * |
Synthesis and influence of alkaline concentration on α-FeOOH nanorods shapes;ZHANG ENLEI et al.;《Bull. Mater. Sci.》;20140731;第37卷;761页第2部分 * |
Yuxue Wei et al..Mesoporous Iron Oxide Nanoparticle-Decorated Graphene Oxide Catalysts for Fischer−Tropsch Synthesis.《ACS Appl. Nano Mater.》.2020,第3卷 * |
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