CN107185516B - 一种树突状含钼介孔硅球材料的制备方法及应用 - Google Patents
一种树突状含钼介孔硅球材料的制备方法及应用 Download PDFInfo
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- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 55
- 239000011733 molybdenum Substances 0.000 title claims abstract description 55
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- 239000000463 material Substances 0.000 title claims abstract description 53
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
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- 238000001354 calcination Methods 0.000 claims abstract description 9
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 9
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 9
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本发明属于多相催化剂领域,涉及一种树突状含钼介孔硅球的制备方法以及其在燃油脱硫中的应用。制备过程中包括将采用油水两相分层反应的自集成法,并持续搅拌混合反应物,然后将反应物离心,所得白色固体依次醇洗,干燥,研磨,煅烧处理后,得到含钼介孔硅球材料。本发明工艺简单,在合成过程中以十六烷基氯化铵(CTAC)为模板剂,钼酸钠为金属源合成含钼的树突状介孔硅球材料,该材料对燃油中硫化物脱除具有较高持久的催化活性,有效提高油品脱硫率,减少催化剂及氧化剂的用量,降低生产成本,提高油品品质,降低环境污染。
Description
技术领域
本发明属于多相催化剂领域,特指树突状含钼介孔硅球材料的制备方法以及其在燃油脱硫中的应用。
背景技术
近年来,由于汽车工业的飞速发展,世界各国对燃油的需求也越来越大,燃油中的硫化物燃烧所产生的废气带来了严重的环境问题,因此限制燃油的硫含量就显得尤为重要;氧化脱硫技术因具有较高脱硫效率,反应条件温和(常温常压条件下),操作成本低以及工艺流程简单等特点而备受关注;目前的氧化脱硫所涉及的催化剂包括有机酸,离子液体,多金属氧酸盐,金属氧化物和分子筛等。
介孔材料具有较大的比表面积,可调节的孔径和孔型,允许较大体积的分子参与反应等特性,是一种很好的催化剂载体,在这种材料的结构中引入金属催化活性中心,开发出负载型介孔材料催化剂,是一类优良的多相反应催化剂;这类催化剂制备方法主要有两个步骤:(1)先合成金属活性中心;(2)再通过油水两相分层反应的自组装合成二氧化硅载体,再将金属活性中心负载上去。该方法所合成的材料,活性中心往往分散不均匀,且催化活性中心无法有效地进入孔道内,使其在反应中不能被充分利用,影响催化活性;本发明以具有表面活性功能的阳离子和含钼的多酸阴离子匹配形成金属基离子液体,并将其用于一种树突状含钼介孔硅球的可控合成。
发明内容
本发明在于提供一种树突状含钼介孔硅球材料。
本发明还提供了上述树突状含钼介孔硅球材料的制备方法。
本发明的另一个目的在于提供了上述材料的应用,并有着优异的催化性能。
为实现上述实验目的,制备方法包括,首先合成含钼离子液体,随后采用油水两相分层反应的自组装法,加入合成所需的原料,离心后取沉淀,醇洗,干燥,最后进行煅烧后,得到一种树突状含钼介孔硅球材料。
一种树突状含钼介孔硅球材料的制备方法,包括如下步骤:
(1)金属源前驱体[C4mim]4Mo10O32的制备:
在圆底烧瓶中加入钼酸钠,水,煮沸5-15min,加入稀释的盐酸溶液搅拌后加入模板剂[C4mim]Cl;静置沉淀,洗涤,干燥,制得[C4mim]4Mo10O32;
(2)在圆底烧瓶中加入步骤(1)制备的金属源[C4mim]4Mo10O32,十六烷基三甲基氯化铵溶液,三乙基胺,H2O,搅拌溶解30-120min,超声1-3h;
(3)在步骤(2)所得溶液中逐滴加入TEOS,不断搅拌,持续反应12-24h;所得产物离心,醇洗2次并于50-100℃干燥,得到白色固体;
(4)将白色固体研磨成粉末,然后置于马弗炉中程序升温至煅烧温度,煅烧结束后,得到含高分散性树突状含钼介孔二氧化硅材料。
步骤(1)中,所述盐酸溶液的浓度为3mol/L;所述干燥温度为80~120℃;
所述钼酸钠,水,盐酸溶液,模板剂[C4mim]Cl的用量比为:4.7g:40mL:13.4mL:1.36g。
步骤(2)中,所述十六烷基三甲基氯化铵溶液的浓度为15wt%;所述搅拌的速度为600-1000r/min。
步骤(3)中,所述搅拌的速度为120-180r/min。
所述金属源[C4mim]4Mo10O32,十六烷基三甲基氯化铵溶液,三乙基胺,H2O,TEOS的用量比为:0.04~0.1g:25mL:0.18mL:36mL:20mL。
步骤(4)中,所述程序升温的速率为2-5℃/min;所述煅烧温度为400-700℃,煅烧时间为3-6h。
本发明所述方法制备的得到树突状含钼介孔硅球材料,比表面积为450~850m2/g,具有介孔结构,孔容为0.7~1.5cm3/g,孔径为6.3~10.9nm;
所述的树突状含钼介孔硅球材料在催化氧化脱除油品中含硫化合物方面的应用,例如4,6-二甲基二苯并噻吩(4,6-DMDBT)的氧化反应,该反应过程可用下式表示:
本发明的树突状含钼介孔硅球材料对脱除油品中硫化物显示出较高的催化活性,其优良活性主要归因于下列因素:
(1)树突状含钼介孔硅球材料具有介孔结构,孔径分布均一,比表面积较大,这些特点首先保证了催化剂金属活性位点的高度均匀分散,其次保证了含硫化合物与活性中心的充分接触。
(2)该树突状含钼介孔硅球材料中的钼物种颗粒较小(6-10nm),具有较高的活性。
该高分散性树突状含钼介孔二氧化硅材料对油品中的不同含硫底物均有较高的脱除率,对芳香族硫化物:二苯并噻吩(DBT),苯并噻吩(BT),4,6-二甲基二苯并噻吩(4,6-DMDBT),4-甲基苯并噻吩(4-MDBT)在70min内脱硫率分别可达到94.5%,80.4%,100%和85.5%,其中4,6-DMDBT在40min即可达到100%。
本发明的有益效果为:
(1)本发明制备的树突状含钼介孔硅球材料在合成步骤中利用功能化离子液体同时作为模板剂和金属源,简化了合成过程,降低合成成本,为合成负载型介孔硅球材料提供了新思路;
(2)该材料具有介孔结构,较大比表面积,活性位高分散,催化活性高等优点,可克服现有技术中的不足,能实现催化活性位点的高分散性,使含硫底物与活性中心的充分接触,最终实现深度脱除燃油中含硫化合物的目标。
附图说明
图1为实例1为所得树突状含钼介孔硅球材料的红外光谱图;
图2为实例1所得树突状含钼介孔硅球材料的X射线衍射图;
图3为实例1所得树突状含钼介孔硅球材料的N2吸附-脱附等温线图;
图4实例1所得树突状含钼介孔硅球材料对不同Mo/Si摩尔比的脱除率;
图5为实例1所得树突状含钼介孔硅球材料对不同含硫底物的脱除率。
具体实施方式
下面结合附图及具体实施例对本发明的内容进一步说明,但是本发明的保护范围不限于此。
实施例1
一种树突状含钼介孔硅球材料的制备方法,包括下列步骤:
1)在150mL圆底烧瓶中加入4.6938g钼酸钠,40mL水并煮沸5min;向混合液加入稀释的13.4mL/3M盐酸,搅拌后加入1.3625g[C4mim]Cl,静置沉淀,洗涤,干燥,备用;
2)在150mL的圆底烧瓶中加入含钼源的0.0906g[C4mim]4Mo10O32,25mL十六烷基三甲基氯化铵溶液(15wt%),0.18mL TEA,36mL H2O,搅拌溶解30min,超声1h;逐滴加入20mLTEOS于上述溶液中,不断搅拌,持续反应12h;所得产物离心,乙醇洗两次于50℃下干燥8h,干燥后用研钵研成粉体,将粉体至于程序升温管式炉中以2℃/min的速率升温至400℃,保持3h,得到树突状含钼介孔硅球材料。
树突状含钼介孔硅球材料的红外光谱图如图1所示,X射线衍射如图2所示,N2吸附-脱附等温线图如图3所示。
用BET法测定上诉实施例1得到高分散性树突状含钼介孔二氧化硅材料,比表面积为858.8m2/g,孔容为1.55cm3/g,孔径为6.94nm。所制得的高分散性树突状含钼介孔二氧化硅材料具有介孔结构,孔径分布均一,具有较大比表面积,钼物种高度分散。
实施例2
一种树突状含钼介孔硅球材料的制备方法,包括下列步骤:
1)在150mL圆底烧瓶中加入4.6938g钼酸钠,40mL水并煮沸10min;向混合液加入稀释的13.4mL/3M盐酸,搅拌后加入1.3625g[C4mim]Cl,静置沉淀,洗涤,干燥,备用;
2)在150mL的圆底烧瓶中加入含钼源的0.1811g[C4mim]4Mo10O32,25mL十六烷基三甲基氯化铵溶液(15wt%),0.18mL TEA,36mL H2O,搅拌溶解60min,超声1h;逐滴加入20mLTEOS于上述溶液中,不断搅拌,持续反应24h;所得产物离心,乙醇洗两次于80℃下干燥8h,干燥后用研钵研成粉体,将粉体至于程序升温管式炉中以2℃/min的速率升温至500℃,保持4h,得到树突状含钼介孔硅球材料。
实施例3
一种树突状含钼介孔硅球材料的制备方法,包括下列步骤:
1)在150mL圆底烧瓶中加入4.6938g钼酸钠,40mL水并煮沸15min;向混合液加入稀释的13.4mL/3M盐酸,搅拌后加入1.3625g[C4mim]Cl,静置沉淀,洗涤,干燥,备用;
2)在150ml的圆底烧瓶中加入含钼源的0.0604g[C4mim]4Mo10O32,25mL十六烷基三甲基氯化铵溶液(15wt%),0.18mL TEA,36mL H2O,搅拌溶解90min,超声2h;逐滴加入20mLTEOS于上述溶液中,不断搅拌,持续反应18h;所得产物离心,乙醇洗两次于100℃下干燥8h,干燥后用研钵研成粉体,将粉体至于程序升温管式炉中以2℃/min的速率升温至600℃,保持6h,得到树突状含钼介孔硅球材料。
实施例4
一种树突状含钼介孔硅球材料的制备方法,包括下列步骤:
1)在150mL圆底烧瓶中加入4.6938g钼酸钠,40mL水并煮沸15min;向混合液加入稀释的13.4mL/3M盐酸,搅拌后加入1.3625g[C4mim]Cl,静置沉淀,洗涤,干燥,备用;
2)在150mL的圆底烧瓶中加入含钼源的0.0453g[C4mim]4Mo10O32,25mL十六烷基三甲基氯化铵溶液(15wt%),0.18mL TEA,36mL H2O,搅拌溶解30min,超声1h;逐滴加入20mLTEOS于上述溶液中,不断搅拌,持续反应24h;所得产物离心,乙醇洗两次于80℃下干燥8h,干燥后用研钵研成粉体,将粉体至于程序升温管式炉中以2℃/min的速率升温至700℃,保持3h,得到树突状含钼介孔二氧化硅材料。
实施例5
三种树突状含钼介孔硅球材料的制备方法,包括下列步骤:
1)将实施例1(2)所得到的样品80℃下干燥8h,干燥后用研钵研成粉体,将粉体至于程序升温管式炉中以2℃/min的速率分别升温至450℃,550℃,650℃并保持6h,得到树突状含钼介孔硅球材料。
实施例6
将实施例1所得到的树突状含钼介孔硅球材料(Mo@SiO2)用于催化氧化脱除油品中含硫化合物,具体过程如下,在一个带有回流冷凝管的自制双颈套瓶中加入0.01gMo@SiO2,33μL TBHP(30%),5mL硫含量为500ppm的模拟油,使用加热控温磁力搅拌器设定在60℃下进行水浴加热搅拌反应。
以4,6—DMDBT为例,反应式为:
表1.不同条件下合成的树突状含钼介孔硅球材料(Mo@SiO2)对氧化4,6-DMDBT催化活性表
表1不同材料的脱硫活性图
对不同含硫底物的催化活性结果如图5,可以看出高分散性树突状含钼介孔二氧化硅材料(Mo@SiO2)在较少的催化剂及TBHP用量情况下对不同含硫底物均有较高的脱除效率。
Claims (8)
1.一种树突状含钼介孔硅球材料的制备方法,其特征在于,采用油水包融法,包括如下步骤:
(1)金属源前驱体[C4mim]4Mo10O32的制备:
在圆底烧瓶中加入钼酸钠,水,煮沸5-15min,加入稀释的盐酸溶液搅拌后加入模板剂[C4mim]Cl;静置沉淀,洗涤,干燥,制得[C4mim]4Mo10O32;
(2)在圆底烧瓶中加入步骤(1)制备的金属源[C4mim]4Mo10O32,十六烷基三甲基氯化铵溶液,三乙基胺,H2O,搅拌溶解30-120min,超声1-3h;
(3)在步骤(2)所得溶液中逐滴加入TEOS,不断搅拌,持续反应12-24h;所得产物离心,醇洗2次并于50-100℃干燥8h,得到白色固体;
(4)将白色固体研磨成粉末,然后置于马弗炉中程序升温至煅烧温度,煅烧结束后,得到含高分散性树突状含钼介孔硅球材料。
2.根据权利要求1所述的一种树突状含钼介孔硅球材料的制备方法,其特征在于,步骤(1)中,所述盐酸溶液的浓度为3mol/L;所述干燥温度为80~120℃;
所述钼酸钠,水,盐酸溶液,模板剂[C4mim]Cl的用量比为:4.7g:40mL:13.4mL:1.36g。
3.根据权利要求1所述的一种树突状含钼介孔硅球材料的制备方法,其特征在于,步骤(2)中,所述十六烷基三甲基氯化铵溶液的浓度为15wt%;所述搅拌的速度为600-1000r/min。
4.根据权利要求1所述的一种树突状含钼介孔硅球材料的制备方法,其特征在于,步骤(3)中,所述搅拌的速度为120-180r/min。
5.根据权利要求1所述的一种树突状含钼介孔硅球材料的制备方法,其特征在于,步骤(3)中,所述金属源[C4mim]4Mo10O32,十六烷基三甲基氯化铵溶液,三乙基胺,H2O,TEOS的用量比为:0.04~0.1g:25mL:0.18mL:36mL:20mL。
6.根据权利要求1所述的一种树突状含钼介孔硅球材料的制备方法,其特征在于,步骤(4)中,所述程序升温的速率为2-5℃/min;所述煅烧温度为400-700℃,煅烧时间为3-6h。
7.一种树突状含钼介孔硅球材料,其特征在于,是通过权利要求1~6任一项所述制备方法得到的,比表面积为450~850m2/g,具有介孔结构,孔容为0.7~1.5cm3/g,孔径为6.4~10.9nm。
8.将权利要求7所述的树突状含钼介孔硅球材料应用于催化氧化脱除燃油中芳香族硫化物和脂肪族硫化物。
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