CN110560103B - 一种多孔纳米羟基磷灰石负载纳米金催化剂的制备方法及其用途 - Google Patents
一种多孔纳米羟基磷灰石负载纳米金催化剂的制备方法及其用途 Download PDFInfo
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Abstract
本发明属于纳米催化技术领域,公开了一种多孔纳米羟基磷灰石负载纳米金催化剂的制备方法及该催化剂催化氧化1,2‑丙二醇制取乳酸的用途。本发明的技术方案为:采用化学沉淀还原法,把纳米金负载在多孔羟基磷灰石上,形成更多的催化活性中心,制取的纳米金负载羟基磷灰石催化剂所用的还原剂为85%的水合肼。催化氧化1,2‑丙二醇的反应过程为配置一定浓度的1,2‑丙二醇的水溶液,加入一定量的氢氧化钠,再加入一定量的催化剂,然后检查反应器的气密性。用氮气吹扫,排除空气;再迅速升温,在即将到达反应温度时,通入氧气;调节转速为500r/min。反应结束后,用气相色谱仪测反应后1,2‑丙二醇的转化率;加酸酸化以后用高效液相色谱测各种产物的选择性。
Description
技术领域
本发明属于纳米催化领域,涉及一种多孔纳米羟基磷灰石负载纳米金催化剂的制备方法及催化氧化1,2-丙二醇制备乳酸的用途。
背景技术
乳酸是碳水化合物生物催化过程中产生的,是功能性聚合物和可降解塑料的基本原料之一,在工业领域有着广泛的应用。乳酸制备方法有生物制备法和化学制备法。生物制备法主要是利用糖类碳水化合物发酵技术制备。但该法反应速率低,耗水量大,工业分离的成本较大。而且反应过程中会产生大量生物污泥,造成一定的环境污染。化学法制备乳酸有采用乙腈和氨氯酸反应再用硫酸水解的方法制备乳酸,但该方法对环境污染较大,不适合长期大规模生产。另一种化学生产方法是用生物可再生的甘油、1,2-丙二醇等有机质生物原料在催化剂的催化下氧化反应生成乳酸。这种方法对环境不会造成环境污染,生产成本较低,是一种经济环境友好型方法。
1,2-丙二醇是生物质可再生能源的副产物之一,是一种无毒、廉价、高需求的化学品。1,2-丙二醇很容易通过甘油解反应或碳酸二甲醋联产丙二醇反应中获得,传统的1,2-丙二醇生产工艺还有酯交换法、环氧丙烷直接水合法、1,2-二氯丙烷法、丙烯催化氧化法四类。因此,1,2-丙二醇可再生而且成本较低,是生产乳酸很好原料。1,2-丙二醇在催化剂的作用下可以氧化成醛、羧酸等,乳酸是1,2-丙二醇的重要的下游化工产品之一。
1,2-丙二醇氧化制取乳酸主要的催化剂有Cu、Au、Ag、Ni、Pt、Pd等单金属催化剂,但是单金属催化剂受制于其形貌和粒径的影响,催化效果不稳定,双金属CuAu、 AuPd、CuPd等催化剂的乳酸选择性不是很高,会有许多副产物的产生。
发明内容
针对现有技术存在的问题,本发明制备了一种多孔纳米羟基磷灰石负载纳米金单金属催化剂,并用于选择催化氧化1,2-丙二醇制取乳酸。该催化剂用量少,高活性,并具有良好的使用稳定性。
本发明的技术方案如下:
一种多孔纳米羟基磷灰石负载纳米金催化剂的制备方法,包括如下步骤:
(1)多孔纳米羟基磷灰石HAP的制备:
按比例将Ca(NO3)2溶液和H3PO4溶液混合,然后置于30-40℃恒温水浴锅中保持温度恒定,反应过程中使用氨水溶液调整反应溶液体系的pH,并保持pH不变;然后加入造孔剂,搅拌4-6h后,将溶液转移到聚四氟乙烯的水热釜中,水热反应结束后,将所得溶液进行抽滤,用蒸馏水洗涤直到滤液的电导率低于2mS/m,恒温箱中干燥,得到白色粉末即是多孔纳米羟基磷灰石HAP;Ca10(PO4)6(OH)2,英文名为Hydroxyapatite,简写为HAP;
(2)采用化学还原法制备Au/HAP催化剂:
将步骤(1)制备的HAP超声分散于聚乙烯醇乙醇溶液中,为溶液A;
将氯金酸溶解于聚乙烯醇乙醇溶液中,为溶液B;
将溶液A和溶液B混合,搅拌,为保持HAP的表面电负性特性,用NaOH乙醇溶液逐步调节反应液的pH,让金离子(Au+)有效吸附在羟基磷灰石表面,继续搅拌,再逐滴加入水合肼的乙醇溶液进行还原反应,恒温搅拌,反应结束后,用水和乙醇溶液离心洗涤,即可得到多孔纳米羟基磷灰石负载纳米金催化剂,即Au/HAP催化剂。
高金含量催化剂制备通过采用低金含量Au/HAP催化剂为载体,重复以上实验过程。
步骤(1)中,Ca(NO3)2溶液和H3PO4溶液的摩尔浓度比为1:0.6-1.8,体积比为1:1。
所述氨水的质量百分浓度为25%,反应溶液体系的pH为8-10。
所述造孔剂为乙二胺四乙酸二钠,添加量为制取的多孔纳米羟基磷灰石理论质量的 5-10%。
所述水热反应温度的为40-120℃,反应时间为12-24h;恒温箱中干燥的温度为100-120℃。
步骤(2)中,溶液A中,HAP和聚乙烯醇乙醇溶液的用量比为1g:20mL;溶液B中,氯金酸和聚乙烯醇乙醇溶液的用量比为0.01~0.1g:20mL;溶液A和溶液B的体积比为1:1,其中,聚乙烯醇乙醇溶液中,聚乙烯醇的质量为乙醇溶液总质量为5%。
NaOH乙醇溶液的浓度为1mol/L,调节反应液的pH为6-8。
水合肼的物质的量为氯金酸物质的量的5-10倍;
所述还原反应的时间为2-4h。
将本发明制备的Au/HAP催化剂用于在低温常压下催化氧化1,2-丙二醇制备乳酸的用途。使用方法为:在密闭不锈钢反应釜中,按比例加入1,2-丙二醇,NaOH,Au/HAP 催化剂和水,用N2吹扫反应釜排空里面的空气,然后在常压的环境下持续通入氮气,然后在100-200rpm的搅拌速度下,加热反应釜达到指定反应温度后,停止通入氮气,釜内持续通入纯O2,并调节500-600rpm的搅拌速度,开始催化1,2一丙二醇氧化反应,反应结束后,接通冷却水开始冷却至室温,然后取出产物进行分析。
其中,NaOH与1,2-丙二醇的浓度比为0.5-4:1;Au/HAP催化剂质量与1,2-丙二醇的质量比为0.025-0.3:1;
通入氧气的流速为100-150ml/min;催化反应温度为40-80℃,反应时间为1-4h。
本发明的有益效果为:
(1)本发明采用单金属负载型催化剂既能弥补单金属催化剂的转化率不高的问题,又能有效地提高乳酸的选择性,是一种有工业运用前景的催化剂。
(2)本发明采用羟基磷灰石作为载体,以纳米金为载体,在60℃下,4h的转化率高达96.8%,乳酸选择性达到92.1%。
具体实施方式
以下为本发明的较佳实施例,能够更好地理解本发明,但本发明的实施例不限于此,同时其所示数据不代表对本发明特征范围的限制。
实施例1:
步骤1:HAP的制备,反应条件的优选:
先将1mol/L的Ca(NO3)2溶液和0.6mol/L的H3PO4溶液等体积混合加入三口烧瓶中,并将三口烧瓶置于30℃恒温水浴锅中保持温度恒定。反应过程中使用25%的氨水溶液调整反应溶液体系的pH值至8,并且整个反应过程都要保持pH值为8。反应过程加入 0.05g乙二胺四乙酸二钠,溶液搅拌反应4h之后将其转移到聚四氟乙烯的反应釜中,并放入80℃的恒温箱中反应24h。反应结束后,将所得溶液进行抽滤,用蒸馏水洗涤直到滤液的电导率低于2mS/m。最后在120℃恒温箱中干燥得到白色粉末即是纳米羟基磷灰石(HAP)。
分别改变Ca(NO3)2和H3PO4的浓度比,溶液体系的pH的值和水浴反应温度和时间,造孔剂的添加量以及水热反应的温度和时间等制备参数制备了不同样品,对制备的纳米羟基磷灰石进行表征分析,所得样品1~样品11的详细数据列于表1。
根据数据分析结果发现,随着乙二胺四乙酸二钠添加量的增加,载体的孔径和孔容在逐渐增大,比表面积在减小。纳米羟基磷灰石颗粒的孔径,孔容和比表面积随着硝酸钙与磷酸摩尔浓度比的增大而随之减小。水热温度升高,导致纳米颗粒的孔径,孔容和比表面积先增大再减小。水热时间延长,有利于提高纳米羟基磷灰石颗粒的孔径,孔容和比表面积。样品6为最佳样品。
步骤2:Au/HAP催化剂的制备,制备条件的优选
称取1g羟基磷灰石(样品6)通过超声分散于20mL5%聚乙烯乙醇醇溶液中,再将0.0211g氯金酸(HAuCl4·3H2O)溶解于20mL的5%聚乙烯醇乙醇溶液中,超声溶解,将两种溶液混合倒入三颈烧瓶中,保温30℃,搅拌15min,再用配置的1mol/L的氢氧化钠乙醇溶液逐步调高pH为6,再保温搅拌30min,然后再滴加85%的水合肼溶液,缓慢滴加5到8滴,再保温搅拌4h。反应结束后,将反应产物分别用水和乙醇洗涤,然后离心干燥。得到1%Au-HAP催化剂备用。催化剂中纳米Au颗粒的平均粒径约为7nm。
优化催化剂制备条件,分别改变溶液浓度、pH值,反应时间,对制备的1%Au-HAP催化剂进行表征分析,结果列于表2。分析结果显示,随着水合肼浓度的提高,制备的催化剂中Au纳米粒径在也随之增大。改变溶液的pH值对制备的Au纳米颗粒的尺寸影响不大;随着反应时间的延长,Au纳米颗粒的平均粒径随之减小。将不同条件下制备 1%Au-HAP催化剂进行催化活性分析,结果表明,Au纳米颗粒的尺寸对其催化活性有较大影响。催化剂1为最佳反应条件下制备的催化剂。
步骤3:催化剂中Au负载量的优选
在实施例2中催化剂1的制备条件下,分别制备了不同负载量的Au/HAP催化剂,并进行了催化氧化1,2-丙二醇的催化活性测试,结果列于表3。
根据催化活性数据结果分析发现,与单一Au纳米催化剂相比,负载型Au/HAP催化剂的催化活性均优于单一纳米Au催化剂。并且,随着催化剂中Au纳米颗粒的负载量的增加,1,2-丙二醇的转化率和乳酸选择性也随之提高。
步骤4:Au/HAP催化剂催化氧化1,2-丙二醇制备乳酸,催化条件的优选
以实施例3中样品10%Au/HAP为模型催化剂,进行催化氧化1,2-丙二醇的活性测试。具体催化反应过程如下所示:取1.5218g 1,2-丙二醇加入200mL容量瓶中,定容。在一个密闭的反应釜中加入所配置好浓度的1,2-丙二醇,加入1.6g氢氧化钠,加入 0.07609g催化剂。组装好仪器后,通入100ml/min的氮气,除去反应釜中的空气,持续通入氮气然后通入高纯氧气,流速为150ml/min。缓慢升温至40-80℃,保温下反应 1-4h,搅拌速率为500r/min;反应结束后,将反应物料冷却至室温。通过气相色谱和高效液相色谱对反应物料组成进行检测分析。
为了优化催化反应条件,分别改变氧气流速,氢氧化钠浓度,催化剂用量,反应温度,反应时间等工艺参数进行Au/HAP催化剂催化1,2-丙二醇的催化活性测试,分析结果列于表4。
研究结果显示,随着反应温度的升高,1,2-丙二醇的转化率随之升高,但是,当温度升至80℃时,1,2-丙二醇的转化率达到了100%,但是乳酸的选择性降至71.2%;氢氧化钠的浓度和催化剂的用量与1,2-丙二醇的转化率成正比与乳酸的选择性成反比;反应时间过短不利于转化率和乳酸的选择性;氧气流速对反应的影响很小,可忽略。本专利中最佳反应条件:NaOH浓度为0.2mol/L的,催化剂用量为0.0762g,氧气流速为 100ml/min,反应温度为60℃,反应时间为4h。
本发明所制备的Au/HAP具有负载量少,催化活性好,乳酸选择高、成本低等优点,具有很大的工业应用前景。
表1不同制备条件下羟基磷灰石的比表面积、孔径和孔容大小
表2不同制备条件下的催化剂粒径大小及催化活性
表3不同组分条件对催化剂Au/HAP催化转化1,2-丙二醇制备乳酸的影响
表4不同反应条件对催化剂10%Au/HAP催化转化1,2-丙二醇制备乳酸的影响
Claims (10)
1.一种多孔纳米羟基磷灰石负载纳米金催化剂的制备方法,其特征在于,包括如下步骤:
(1)多孔纳米羟基磷灰石HAP的制备:
按比例将Ca(NO3)2溶液和H3PO4溶液混合,然后置于30-40℃恒温水浴锅中保持温度恒定,反应过程中使用氨水溶液调整反应溶液体系的pH,并保持pH不变;然后加入造孔剂,搅拌4-6h后,将溶液转移到聚四氟乙烯的水热釜中,水热反应结束后,将所得溶液进行抽滤,用蒸馏水洗涤直到滤液的电导率低于2 mS/m,恒温箱中干燥,得到白色粉末即是多孔纳米羟基磷灰石HAP;
所述造孔剂为乙二胺四乙酸二钠,添加量为制取的多孔纳米羟基磷灰石理论质量的5-10%;
(2)Au/HAP催化剂的制备:
将步骤(1)制备的HAP超声分散于聚乙烯醇乙醇溶液中,为溶液A;
将氯金酸溶解于聚乙烯醇乙醇溶液中,为溶液B;
将溶液A和溶液B混合,搅拌,用NaOH乙醇溶液逐步调节反应液的pH,继续搅拌,再逐滴加入水合肼的乙醇溶液进行还原反应,恒温搅拌,反应结束后,用水和乙醇溶液离心洗涤,即可得到多孔纳米羟基磷灰石负载纳米金催化剂,即Au/HAP催化剂。
2.如权利要求1所述的制备方法,其特征在于,步骤(1)中,Ca(NO3)2溶液和H3PO4溶液的摩尔浓度比为1:0.6-1.8,体积比为1:1。
3.如权利要求1所述的制备方法,其特征在于,步骤(1)中,所述氨水的质量百分浓度为25%,反应溶液体系的pH为8-10。
4.如权利要求1所述的制备方法,其特征在于,步骤(1)中,所述水热反应的 温度为40-120 ℃,反应时间为12-24 h;恒温箱中干燥的温度为100-120℃。
5.如权利要求1所述的制备方法,其特征在于,步骤(2)中,溶液A中,HAP和聚乙烯醇乙醇溶液的用量比为1g:20 mL;溶液B中,氯金酸和聚乙烯醇乙醇溶液的用量比为0.01~0.1g:20 mL;溶液A和溶液B的体积比为1:1,其中,聚乙烯醇乙醇溶液中,聚乙烯醇的质量为乙醇溶液总质量为5%。
6.如权利要求1所述的制备方法,其特征在于,步骤(2)中,NaOH乙醇溶液的浓度为1mol/L,调节反应液的pH为6-8;水合肼的物质的量为氯金酸物质的量的5-10倍。
7.如权利要求1所述的制备方法,其特征在于,步骤(2)中,所述还原反应的时间为2-4h。
8.将权利要求1~7任一项所述制备方法制备的Au/HAP催化剂用于在低温常压下催化氧化1,2-丙二醇制备乳酸的用途。
9.如权利要求8所述的用途,其特征在于,使用方法为:在密闭不锈钢反应釜中,按比例加入1,2-丙二醇,NaOH,Au/HAP催化剂和水,用N2吹扫反应釜排空里面的空气,然后在常压的环境下持续通入氮气,然后在100-200rpm的搅拌速度下,加热反应釜达到指定反应温度后,停止通入氮气,釜内持续通入纯O2,并调节500-600 rpm的搅拌速度,开始催化1,2一丙二醇氧化反应,反应结束后,接通冷却水开始冷却至室温,然后取出产物进行分析。
10.如权利要求9所述的用途,其特征在于,NaOH与1,2-丙二醇的浓度比为0.5-4:1;Au/HAP催化剂质量与1,2-丙二醇的质量比为0.025-0.3:1;
通入氧气的流速为100-150 ml/min;催化反应温度为40-80℃,反应时间为1-4h。
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