CN107694607A - 一种低co2选择性co加氢制烯烃的核壳催化剂及其制备方法 - Google Patents
一种低co2选择性co加氢制烯烃的核壳催化剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种具有核壳结构和疏水功能的金属氧化物催化剂,用于CO加氢制乙烯、丙烯、丁烯的高选择性生成,同时有效降低CO2选择性。本发明以水热合成的方法将二氧化硅包覆在金属氧化物活性组分中,形成核壳结构,金属氧化物为核,二氧化硅为壳层。选用二氧化硅作为有机基团改性的桥梁,借助于二氧化硅表面Si‑OH与有机硅烷试剂发生的硅烷化反应,实现了疏水基团的嫁接。制备的铁基催化剂保留了其高活性优势,还增添了有机基团的疏水性能、削弱了空间位阻,对制备烯烃作用显著。有机基团的疏水性对抑制WGS反应起到了很好的效果,CO2生成量明显降低。本发明制备方法简单,重复性好,对环境友好,反应寿命长,具有潜在的经济价值。
Description
技术领域
本发明涉及低CO2选择性的费托反应催化剂及其制备方法,具体涉及一种具有核壳结构和疏水功能的金属氧化物催化剂,用于CO加氢制乙烯、丙烯、丁烯的高选择性生成,同时有效降低CO2选择性。
背景技术
低碳烯烃是费托F-T合成的主要初级产物,也是重要的化工基础原料,用途十分广泛。典型的费托合成反应中,初级产物烯烃容易引发二次加氢反应,且产物选择性受到Anderson-Schulz-Flory(A-S-F)分布的限制,导致烃类产物分布宽、烯烃选择性较低、CH4和CO2等副产物选择性较高。
铁基催化剂廉价易得,具有良好的催化活性,被广泛应用于一氧化碳加氢反应中,但是面临着烯烃二次加氢反应严重、CO2选择性较高的难题。涂军令等基于溶剂热合成体系,制备的Fe3O4微球和纳米片催化剂,CO2选择性分别为36.61%和36.40%。位建等分别采用一步合成法和常规共沉淀法制备的Fe/ SiO2催化剂,CO2选择性均达到40%。Bang Gu等比较了负载在几种类型的碳材料以及SiO2上的Fe催化剂的催化性能,其所有的催化剂CO2选择性都达到40%以上。总之,由于铁系催化剂具有较强的水煤气变换反应(WGS)活性,CO2选择性居高不下。
因此,抑制初级烯烃二次反应和WGS反应活性,是提高烯烃选择性、降低CO2选择性、调控产物分布的关键性技术。
发明内容
本发明针对现有技术中存在的缺点提供一种有机基团改性的Fe基核壳催化剂,旨在抑制初级烯烃二次加氢反应和水煤气变换反应WGS,从而提高烯烃选择性、有效降低CO2生成、调控出附加值高的产物分布。
本发明的催化剂结合了催化剂磁子状形貌、中孔结构、金属氧化物的活性相控制及助剂的表面改性,将溶剂本身的亲疏水基团直接嫁接到铁基催化剂的表面,开发出了一种亲疏水性基团改性的铁基核壳催化剂。
本发明以水热合成的方法将二氧化硅包覆在金属氧化物活性组分中,形成核壳结构,金属氧化物为核,二氧化硅为壳层。本发明选用二氧化硅作为有机基团改性的桥梁,借助于二氧化硅表面Si-OH与有机硅烷试剂发生的硅烷化反应,实现了疏水基团的嫁接。制备的铁基催化剂保留了其高活性优势,还增添了有机基团(例如甲基、羟基等)的疏水性能、削弱了空间位阻,对制备线性α-烯烃作用显著。
本发明催化剂的制备方法,选用的水热合成法得到了纳米-微米级颗粒的金属氧化物Fe2O3或Fe3O4,作为催化剂铁核;在超声手段下提高分散度、氧化物溶解性,在悬浮液中引入硅源进行包覆,由配比调节形成的二氧化硅壳层厚度,形貌上呈现出双层结构;利用Stöber法将有机基团改性二氧化硅,进而使得难以关联的铁核携带上了疏水性有机基团。有机基团的疏水性对抑制WGS反应起到了很好的效果。制备方法简单,重复性好,对环境友好,反应寿命长,具有潜在的经济价值。
疏水改性的有机基团选用氟化物、或者碳氢化合物;经过疏水改性的催化剂,将其应用于费托合成反应,由于催化剂表面具有较强的疏水能力,反应过程中生成的水会及时的离开催化剂表面,抑制了H2O的吸附,进而抑制了水煤气变换反应(WGS);在CO加氢反应中,通过改变H2/CO比在一定程度上也会降低二次加氢的能力,CO2选择性明显降低的同时伴随烯烃选择性提高。
本发明通过以下技术方案实现:
制备的催化剂通式为A%-B@C-X,其中A为助剂,是钾、镧、镁、锌元素的一种,起修饰作用,占催化剂总量的0.1~10%;
B@C-X是催化剂起催化作用的中心成分,B、C、X间相互作用,催化剂为核壳结构,以B为核心,C-X为壳层, C-X包覆在B周围,壳层中的C由内向外摩尔密度逐渐降低,壳层厚度在5-20nm之间;
B代表金属氧化物,为Fe2O3、Fe3O4的一种或两种,占催化剂总量的40~90%; C代表SiO2,X代表甲基,C-X代表疏水基团,为SiO2-(CH3)n结构,n为1~3,甲基修饰二氧化硅,二氧化硅担载金属氧化物,助剂调节金属表面碱性和电子空穴,协同抑制烯烃二次加氢和水煤气变换反应。
催化剂的制备方法包括如下步骤:
(1)水热法合成B:首先依次向硝酸铁或者氯化铁溶液中添加无水乙酸钠和十六烷基三甲基溴化铵、乙二胺,搅拌均匀转至高压釜中,于200~300℃下加热8~12 h;洗涤至中性,在100 ℃下过夜干燥,制得B;
(2)制备B@C:将B溶解于乙醇中,超声处理,取悬浮液;向悬浮液滴入四乙氧基硅烷,搅拌1-3h后,依次加入氨水、去离子水,继续搅拌1-5h;得固体,洗涤、干燥,得B@C;
(3)制备B@C-X:将B@C浸于甲苯溶液中,添加三甲基氯硅烷、二甲基二乙氧基硅烷、甲基三乙氧基硅烷的一种,超声振荡1-2 h后,于110℃下真空干燥,制得B@C-X;
(4)制备A%-B@C-X:以传统助剂引入方法,即浸渍法、机械混合法、原位水热法的其中一种方法,按Fe/A摩尔比10~25/0.1-5引入助剂钾、镧、镁、锌元素的一种。
本发明催化剂为中孔结构、磁子状形貌。本发明催化剂应用于合成气制备低碳烯烃反应,采用固定床做催化活性评价,反应条件为H2/CO=2,280 ~350℃、1~2 MPa,1000~4000h-1。
催化剂在经红外测试,其在554 cm-1和486 cm-1处存在吸收峰,在3400cm-1处存在O-H伸缩振动的宽峰;在1300 cm-1存在甲基振动峰。
附图说明
图1是Fe2O3@SiO2催化剂的 SEM图。
图2是Fe2O3@SiO2-(CH3)3催化剂的 SEM图。
图3是Fe2O3@SiO2催化剂的 TEM图。
具体实施方式
催化剂制备:
(1)水热法合成Fe2O3
将6.0 g FeCl3·6H2O溶解在90 mL去离子水中,得到红棕色溶液;在搅拌下加入6.0 g无水乙酸钠和3.0 g十六烷基三甲基溴化铵(CTAB),然后加入21.0 mL乙二胺溶液剧烈搅拌;将搅拌均匀的混合液转移到高压釜中,在200 ℃下加热10 h;所得红褐色固体用去离子水反复洗涤至中性,在100 ℃下过夜干燥,制得样品表示为:Fe2O3。
(2)Stöber法制备Fe2O3@SiO2
将0.5 g Fe2O3粉末溶解在300 mL乙醇中,超声波处理120 min得到均匀的悬浮液;向上述悬浮液中加入1.0 mL四乙氧基硅烷,搅拌3 h;然后依次加入5.0 mL氨水和20 mL去离子水,继续剧烈搅拌4 h;所得红褐色固体用乙醇洗涤,在100 ℃下过夜干燥,样品经过压片、过筛(20-40目)后备用,于氮气气氛下焙烧,将粉末在管式炉中以2 ℃/min的升温速率在350 ℃ 下焙烧4 h,管式炉中氮气流速是50 mL/min;焙烧后样品压片过筛至20-40目,作为对比样,样品表示为:Fe2O3@SiO2。
(3)疏水基团改性的Fe2O3@SiO2-X催化剂
取4 g Fe2O3@SiO2粉末放入干燥洁净的锥形瓶中,向其中加入2mL三甲基氯硅烷(TMCS),16 mL甲苯,超声振荡2 h;所得溶液在110℃下真空干燥,制得样品表示为:Fe2O3@SiO2-(CH3)3。
相同的制备方法,分别用二甲基二乙氧基硅烷(DMDES)和甲基三乙氧基硅烷(MTES)处理Fe2O3@SiO2,制得样品分别表示为: Fe2O3@SiO2-(CH3)2和Fe2O3@SiO2-CH3。
(4)疏水基团浓度增大的改性Fe2O3@SiO2-X催化剂
取4 g Fe2O3@SiO2粉末放入干燥洁净的锥形瓶中,向其中加入4mL三甲基氯硅烷(TMCS),16 mL甲苯,超声振荡2 h;所得溶液在110℃下真空干燥,制得样品表示为:Fe2O3@SiO2-(CH3)3-2。
(5)机械混合K改性K%-Fe2O3@SiO2-X催化剂
称取一定量疏水基团改性的Fe2O3@SiO2-X粉末,按Fe/K摩尔比10/1机械混合K2CO3,压片粉粹至20-40目即得催化剂,记为: K%-Fe2O3@SiO2- (CH3)n{ n=1,2,3}。
催化剂表征
经红外测试,催化剂样品在 554和486 cm-1处出现了较强的吸收峰,归属于Fe2O3晶体中的Fe-O键振动吸收峰。纯Fe2O3样品在2852.02和2921.76 cm-1处的吸收峰分别归属于CTAB中的C-CH2对称伸缩振动和不对称伸缩振动,表明水热法合成的Fe2O3表面有大量表面活性剂CTAB。对于Fe2O3@SiO2催化剂,在3401cm-1处的宽峰归属于表面吸附水的O-H伸缩振动;在1384 cm-1处的峰归属于是CH3的C-H键振动,这个峰可能来源于Si-OC2H5的不完全水解和缩聚;1130 cm-1处的吸收峰是由于SiO2骨架的Si-O-Si键振动引起的;939cm-1处的峰是由于Si-OH的伸缩振动引起的,表明Fe2O3@SiO2催化剂具有一定的亲水性。
对于Fe2O3@SiO2-(CH3)n{ n=1,2,3}催化剂,除观察到以上吸收峰外,还观察到Si-OH的对称伸缩振动峰强度减弱,表明催化剂表面硅羟基浓度减少;在1300 cm-1左右甲基的振动峰强度随着甲基数目的增多不断增强,说明催化剂甲基有效嫁接到了SiO2表面,催化剂疏水性增强。
图1为Fe2O3@SiO2催化剂的SEM图。图1显示,Fe2O3@SiO2催化剂为大小比较均匀的磁子状,磁子的平均长度和宽度分别为1.6um和450nm,催化剂表面光滑。图2为Fe2O3@SiO2-(CH3)3催化剂的SEM图。由图2 显示Fe2O3@SiO2-(CH3)3催化剂的表面凹凸不平,可能原因是TMCS和SiO2完全反应,导致SiO2壳层被破坏。
图3是Fe2O3@SiO2催化剂的TEM图。由图3可以清晰的看到Fe2O3@SiO2催化剂为明显且完整的核壳结构,Fe2O3表面均匀包覆了一层薄薄的SiO2壳层,壳层厚度约为15nm。
催化活性
表1为催化剂的CO加氢催化性能。由表1可以看出,经甲基修饰后的Fe2O3@SiO2催化剂,烯烃选择性明显提高。Fe2O3@SiO2-(CH3)3催化剂的C2 =-C4 =占总烃重量分布的44.55%,O/P值为3.18,CO2选择性低至13.08%;增大甲基浓度制备的Fe2O3@SiO2-(CH3)3-2催化剂其C2 =-C4 =占总烃重量分布的43.87%,O/P值为3.52,CO2选择性仅占12.20%。钾改性后的催化剂表现出很好的催化活性,C2 =-C4 =占总烃重量分布的46.52%,O/P值为4.22。
分析产物分布改变的原因是三个甲基改性的催化剂,其表面的疏水能力较强,反应过程中生成的水会及时的离开催化剂表面,抑制了H2O的吸附,进而抑制了水煤气变换反应(WGS),通过改变H2/CO比一定程度上降低了二次加氢的能力,因此CO2选择性明显降低的同时O/P值增加。经测试,催化剂在150h内运行稳定。
表1 催化剂CO加氢反应活性
Reaction conditions: H2/CO=2, 320 ºC, 1.5MPa, 3000 h-1.
4.数据小结。
(1)与Fe2O3@SiO2催化剂相比,Fe2O3@SiO2-(CH3)3催化剂CO2选择性由40.27%降低至9.68%,C2 =-C4 =选择性由21.80%提高至43.87%,经钾改性后,催化活性更好。
(2)在催化剂中加入碱金属助剂K并进行疏水集团改性,可以将K助剂提高低碳烯烃选择性的优势和甲基抑制WGS变换反应活性、降低CO2选择性的优势相结合,高选择性的生成低碳烯烃的同时降低CO2选择性。
(3)Fe2O3@SiO2-(CH3)3催化剂表面疏水能力较强,对H2O的吸附能力减弱,能有效的抑制WGS反应的活性,因此在提高低碳烯烃选择性的同时能有效的降低CO2选择性。
Claims (4)
1.一种低CO2选择性CO加氢制烯烃的核壳催化剂及其制备方法,其特征在于:所述催化剂通式为A%-B@C-X,其中A为助剂,是钾、镧、镁、锌元素的一种,起修饰作用,占催化剂总量的0.1~10%;
B@C-X是催化剂起催化作用的中心成分,B、C、X间相互作用,催化剂为核壳结构,以B为核心,C-X为壳层, C-X包覆在B周围,壳层中的C由内向外摩尔密度逐渐降低,壳层厚度在5-20nm之间;
B代表金属氧化物,为Fe2O3、Fe3O4的一种或两种,占催化剂总量的40~90%; C代表SiO2,X代表甲基,C-X代表疏水基团,为SiO2-(CH3)n结构,n为1~3,甲基修饰二氧化硅,二氧化硅担载金属氧化物,助剂调节金属表面碱性和电子空穴,协同抑制烯烃二次加氢和水煤气变换反应。
2.根据权利要求1所述的一种低CO2选择性CO加氢制烯烃的核壳催化剂及其制备方法,其特征在于所述催化剂的制备方法包括如下步骤:
(1)水热法合成B:首先依次向硝酸铁或者氯化铁溶液中添加无水乙酸钠和十六烷基三甲基溴化铵、乙二胺,搅拌均匀转至高压釜中,于200~300℃下加热8~12 h;洗涤至中性,在100 ℃下过夜干燥,制得B;
(2)制备B@C:将B溶解于乙醇中,超声处理,取悬浮液;向悬浮液滴入四乙氧基硅烷,搅拌1-3h后,依次加入氨水、去离子水,继续搅拌1-5h;得固体,洗涤、干燥,然后于氮气或氩气气氛下焙烧,焙烧温度200-350 ℃,焙烧2-4h,得B@C;
(3)制备B@C-X:将B@C浸于甲苯溶液中,添加三甲基氯硅烷、二甲基二乙氧基硅烷、甲基三乙氧基硅烷的一种,超声振荡1-2 h后,于110℃下真空干燥,制得B@C-X;
(4)制备A%-B@C-X:以传统助剂引入方法,即浸渍法、机械混合法、原位水热法的其中一种方法,按Fe/A摩尔比10~25/0.1-5引入助剂钾、镧、镁、锌元素的一种。
3.根据权利要求1所述的一种低CO2选择性CO加氢制烯烃的核壳催化剂及其制备方法,其特征在于所述催化剂为中孔结构、磁子状形貌。
4.根据权利要求1所述的一种低CO2选择性CO加氢制烯烃的核壳催化剂及其制备方法,其特征在于所述催化剂应用于合成气制备低碳烯烃反应,反应条件为H2/CO=1~2,280 ~350℃、1~2 MPa,1000~4000h-1。
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