CN105562114B - 一种高比表面积硅基整体式载体的制备方法 - Google Patents
一种高比表面积硅基整体式载体的制备方法 Download PDFInfo
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Abstract
本发明属于催化以及吸附材料制备领域，具体地，涉及一种具有高比表面积的硅基整体式载体制备方法。硅基整体式载体制备方法，包含以下步骤：步骤一、配置硅溶胶前体；步骤二、溶胶前体pH调节；步骤三、投入整体式底材；步骤四、整体式底材的干燥；步骤五、整体式底材的焙烧；步骤六、选择性重复操作。该制备方法可以得到高比表面积、微观上纳米孔道的整体式底材，同时整个制备方法无须昂贵设备、原料无(低)毒、环境友好、操作安全、成本较低，便于大规模生产。
Description
技术领域
本发明属于催化以及吸附材料制备领域，具体地，涉及一种具有高比表面积的硅基整体式载体制备方法。
背景技术
在工业催化、能源化工、环境催化等领域中，为了增加固体催化剂与反应物、吸附质(术语：底物)之间的接触面积，提高固体催化剂自身的表面积是最常用的方式。为此，将活性组分负载到具有高比表面积的多孔性物质上是制作固体催化剂的常见方法。常见的高比表面积固体物质多为颗粒状，如活性炭，分子筛、多孔性氧化铝等。整体式催化剂与颗粒状催化剂比起来具有一些明显的优点，例如其填装与回收比较方便，用于固定床反应器中压降较小等。
整体式催化剂通常的制备方法是将具有活性组分的小颗粒附着于一个的整体式底材，如堇青石、蜂窝状陶瓷等材料上。其总比表面积往往不高。开发新的整体式催化剂制备方法，或者开发新的整体式载体的制备方法，是该领域技术人员的重要课题。
对于吸附材料领域，固体吸附剂是最常见的吸附剂形式。为了增加吸附剂的吸附能力，增加吸附剂的表面积也是重要的手段。整体式吸附剂于整体式催化剂类似，同样也具有便于与吸附质体系分离的优点；其材料特征、技术需求上与整体式催化剂类似。
对于整体式催化剂而言，提高催化剂的比表面积、提高活性金属组分的分散度，同时降低材料与操作成本是该领域技术人员始终关注的几个问题。专利CN1846855A公开了一种整体催化剂的涂渍方法。该专利将含糖醇的聚合物或聚合单元涂在整体底材表面，而后用浸渍法(该文称为早期湿润法)将金属组分引入整体底材表面。该方法可以得到具有较高比表面积的整体式催化剂，所适用的金属类型涵盖多种金属。该方法制备过程相对繁琐，涉及多种溶液配制、且要使用一些具有腐蚀性(如HNO3)或污染性(如吡咯)物质。
专利CN1411391A公开了一种由金属微纤维与催化剂颗粒组成的整体式催化剂制备方法。金属微纤维被烧结成三维网状结构，束缚了催化剂颗粒。该催化剂具有高稳定性、优良导热性、使用寿命长等优点。然而其基质限定于金属微纤，可能会限制该方法的拓展应用。该专利没有公开相关的表面积等数据。
从原理上看，常用的整体式催化剂或吸附剂可以由整体式载体与活性组分两部分构成。首先应得到整体式载体，而后将活性组分分散于载体上。整体式载体的空间结构特征基本上决定了后续的整体式催化剂或吸附剂的空间结构特征。因此开发具有高比表面积的整体式载体的制备方法，同时要求该方法操作简单、原料环境友好、成本较低，具有重要的研究意义与实用价值，这也是整体式催化剂或吸附剂领域的技术需求。
发明内容
为克服现有技术存在的问题，本发明提供一种具有高比表面积的硅基整体式载体制备方法，该方法可以得到高比表面积、微观上具备纳米级孔道的整体式载体，同时整个制备方法无须昂贵设备、原料无(低)毒、环境友好、操作安全、成本较低。
本发明实现上述目的的技术路线是：利用具有大量微米至毫米级级孔道的整体式底材，在其上通过化学反应原位附着多孔性硅基化合物，从而极大提高原整体式底材的比表面积。
实现上述技术路线的技术方案是：
步骤一、配置硅溶胶前体；具体方法如下：
将正硅酸酯：水：醇按照摩尔比1：m：n的比例混合，其中m的取值在0.1-20范围内，n的取值在0.2-15范围内；其中正硅酸酯指的是正硅酸甲酯、正硅酸乙酯、正硅酸丙酯三者中的一个，或者它们的任意比例混合物；其中醇指的是甲醇、乙醇、1-丙醇、2-丙醇中的一个，或者它们的任意比例混合物；
步骤二、溶胶前体pH调节；具体方法如下：
对步骤一所述混合液缓慢加入氨水，直到溶液的pH值处于8.0–10.5的范围内，之后静置1min–30h；
步骤三、投入整体式底材；具体方法如下：
将一个质量在1-300g范围内的整体式底材浸入步骤二所述的溶胶前体液中，浸入时间为5min–30h，之后将整体式底材取出；
步骤四、整体式底材的干燥；具体方法如下：
采用自然晾干、阳光晒干、热气吹干、干燥器内晾干、抽真空晾干、红外灯烘干、加热烘干等方法单独或者组合使用，对步骤三所述整体式底材进行干燥，直到整体式底材上观察不到液体流动或滴下；
步骤五、整体式底材的焙烧；具体方法如下：
将步骤四所述整体式底材放入马弗炉中焙烧，焙烧温度在200–800℃范围内，焙烧时间为20min–24h；当炉内温度高于150℃时，要求温度变化速率不超过4℃/min；从马弗炉中取出的产品为硅基整体式载体；
步骤六、选择性重复操作；具体方法如下：
将上述步骤一至步骤五的流程称为一次循环操作；重复这种循环操作，重复次数在0–15次范围内；对于任意一次重复循环操作，其特征在于，将该次循环操作中步骤三的“整体式底材”，替换成其上一次循环操作中步骤五从马弗炉中取出的硅基整体式载体产品；对于任意一次重复循环操作，其具体的操作工艺参数可以与其上一次循环操作相同，也可以不同，只要在上述步骤一至步骤五的限定范围内即可。
制备过程完毕。所制备的产品为硅基整体式载体产品，其比表面积与作为原材料的整体式底材相比有20–300倍的提高；附着于整体式底材底材上的硅基物质微观上具有大量纳米尺度的孔洞(孔洞尺寸在3–15nm)。
其中步骤三所述的“整体式底材”是本领域的一个术语，其特征在于：它是一种具有大量延伸性孔道的块体，每平方厘米的块体表面上具有的孔数目在20–2000个范围内，孔截面的平均直径在10微米–1毫米范围内；载体的材质为无机材质，包含但不限于陶瓷、耐火材料、砂芯片、堇青石、无机碳材料、粘土、氧化镁、氧化铝、氧化硅、硅铝酸盐、氧化锆、氧化镧、氧化铈、氧化钛、氧化锰、玻璃、氧化铁、不锈钢、铁、镍、锌等材料之一，或上述材料以任意比例混合得到的材料。
其中步骤二所述的其中氨水指的是含NH3质量百分数大于3％的水溶液。
其中“比表面积”指的是用催化、界面化学领域中普遍使用的Brunauer-Emmett-Teller方法测定得到的BET比表面积，可通过低温N2的吸脱附曲线的测定得到；此类吸脱附曲线还可以得到固体物质所含的孔洞大小以及分布情况等信息。
与现有的技术相比，本发明的积极效果如下：
(1)、可方便地将原有不具备高比表面积的整体式底材，转化为高比表面积的整体式载体，同时保留原有底材的机械性质，为后续的使用提供便利。
(2)、制备过程简单，操作成本低，不含有难以处理的化学物质，方便大规模生产。
(3)、所得到的底材具有大量纳米级别的孔道，为后续的使用提供结构基础。
具体实施方式
实施例一
步骤一、配置硅溶胶前体；具体方法如下：
将正硅酸酯：水：醇按照摩尔比1：12：4.5；其中正硅酸酯指的是正硅酸乙酯；其中醇指的是乙醇；
步骤二、溶胶前体pH调节；具体方法如下：
对步骤一所述混合液缓慢加入氨水，直到溶液的pH值为9.6，之后静置3h；
步骤三、投入整体式底材；具体方法如下：
将一个质量为31.1g的整体式底材浸入步骤二所述的溶胶前体液中，浸入时间为5h，之后将整体式底材取出；
步骤四、整体式底材的干燥；具体方法如下：
将步骤三所述整体式底材放在红外灯下干燥，直到整体式底材上观察不到液体滴下；
步骤五、整体式底材的焙烧；具体方法如下：
将步骤四所述整体式底材放入马弗炉中焙烧，焙烧温度为450℃，焙烧时间为20h；当炉内温度高于150℃时，炉内温度变化速率低于4℃/min；从马弗炉中取出的产品为硅基整体式载体的1代产品；
步骤六、选择性重复操作；具体方法如下：
将上述步骤一至步骤五的流程称为一次循环操作；重复这种循环操作，重复次数为2次；对于任意一次重复循环操作，其特征在于，将该次循环操作中步骤三的“整体式底材”，替换成其上一次循环操作中步骤五从马弗炉中取出的硅基整体式载体产品；每一次重复循环操作的具体操作工艺参数，都与第一次循环操作相同。
制备过程完毕。所制备的产品为硅基整体式载体，其BET比表面积与作为原材料之一的整体式底材相比提高32.1倍；N2的吸脱附曲线表明该产品具有大量3-5nm的孔道。
其中步骤三所述的“整体式底材”为砂芯片块体，每平方厘米的块体表面上具有的孔数目约为120个，孔截面的平均直径约为80平方微米。
其中步骤二所述的其中氨水指的是含NH3质量百分数为19％的水溶液。
实施例二
其它同实施例一，区别在于：
步骤六、选择性重复操作；重复次数为5次。
制备过程完毕。所制备的产品为硅基整体式载体，其BET比表面积与作为原材料的整体式底材相比提高47.5倍；N2的吸脱附曲线表明该产品具有大量3-5nm的孔道。
实施例三
其它同实施例一，区别在于：
步骤一、配置硅溶胶前体；使用的正硅酸酯为正硅酸甲酯。
制备过程完毕。所制备的产品为硅基整体式载体，其BET比表面积与作为原材料的整体式底材相比提高51倍；N2的吸脱附曲线表明该产品具有大量3-7nm的孔道。
实施例四
其它同实施例一，区别在于：
步骤五、整体式底材的焙烧；焙烧温度为650℃，焙烧时间为8h。
制备过程完毕。所制备的产品为硅基整体式载体，其BET比表面积与作为原材料的整体式底材相比提高23.2倍；N2的吸脱附曲线表明该产品具有大量5-9nm的孔道。
实施例五
其它同实施例一，区别在于：
步骤三：使用的整体式底材为堇青石；其质量为14.2g。
制备过程完毕。所制备的产品为硅基整体式载体，其BET比表面积与作为原材料之一的整体式底材相比提高66倍；N2的吸脱附曲线表明该产品具有大量3-6nm的孔道。
Claims (3)
1.一种具有高比表面积的硅基整体式载体制备方法，其特征在于，包含以下步骤：
步骤一、配置硅溶胶前体；具体方法如下：
将正硅酸酯：水：醇按照摩尔比1：m：n的比例混合，其中m的取值在0.1-20范围内，n的取值在0.2-15范围内；其中正硅酸酯指的是正硅酸甲酯、正硅酸乙酯、正硅酸丙酯三者中的一个，或者它们的任意比例混合物；其中醇指的是甲醇、乙醇、1-丙醇、2-丙醇中的一个，或者它们的任意比例混合物；
步骤二、溶胶前体pH调节；具体方法如下：
对步骤一所述混合液缓慢加入氨水，直到溶液的pH值处于8.0 –10.5的范围内，之后静置 1 min – 30 h；
其中，氨水指的是含NH3质量百分数大于3%的水溶液；
步骤三、投入整体式底材；具体方法如下：
将一个质量在1 -300g范围内的整体式底材浸入步骤二所述的溶胶前体液中，浸入时间为5 min – 30 h，之后将整体式底材取出；
步骤四、整体式底材的干燥；具体方法如下：
采用自然晾干、阳光晒干、热气吹干、干燥器内晾干、抽真空晾干、红外灯烘干、加热烘干方法单独或者组合使用，对步骤三所述整体式底材进行干燥，直到整体式底材上观察不到液体流动或滴下；
步骤五、整体式底材的焙烧；具体方法如下：
将步骤四所述整体式底材放入马弗炉中焙烧，焙烧温度在200 – 800 oC范围内，焙烧时间为20 min –24 h；当炉内温度高于150 oC时，要求温度变化速率不超过4 oC/min；从马弗炉中取出的产品为硅基整体式载体；
步骤六、选择性重复操作；具体方法如下：
重复上述步骤一至步骤五的流程称为一次循环操作；重复这种循环操作，重复次数在0–15次范围内；对于任意一次重复循环操作，其特征在于，将该次循环操作中步骤三的“整体式底材”，替换成其上一次循环操作中步骤五从马弗炉中取出的硅基整体式载体产品。
2.根据权利要求1所述的一种具有高比表面积的硅基整体式载体制备方法，其特征在于，步骤三所述的整体式底材的特征是：一种具有大量延伸性孔道的块体，每平方厘米的块体表面上具有的孔数目在20 ~ 2000个范围内，孔截面的平均直径在10微米 ~ 1毫米范围内；载体的材质为无机材质，包含陶瓷、耐火材料、砂芯片、堇青石、无机碳材料、粘土、氧化镁、氧化铝、氧化硅、硅铝酸盐、氧化锆、氧化镧、氧化铈、氧化钛、氧化锰、玻璃、氧化铁、不锈钢、铁、镍、锌材料之一，或上述材料以任意比例混合得到的材料。
3.根据权利要求1所述的一种具有高比表面积的硅基整体式载体制备方法，其特征在于，所制备的硅基整体式载体，其比表面积与作为原材料的整体式底材相比有20 ~300倍的提高。
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