CN106881121B - 一种磷掺杂碳材料加氢催化剂、其制备方法及其用途 - Google Patents
一种磷掺杂碳材料加氢催化剂、其制备方法及其用途 Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种加氢催化剂,其为磷掺杂多孔碳材料,其比表面积为700cm2/g以上,所述磷占总质量的1.4~10%;所述催化剂中的一部分磷元素在X射线光电子能谱中在132.5eV处呈现特征峰。本发明还公开了所述加氢催化剂的制备方法及用于含取代基的硝基芳烃的选择性加氢反应中的用途。
Description
技术领域
本发明属于催化剂领域,具体涉及一种磷掺杂碳材料加氢催化剂、其制备方法及其在催化硝基芳烃类物质选择性加氢用途。
背景技术
在油品精炼和加工、以及精细大宗化学品生产中,多相催化加氢是最重要的合成转化手段之一,而硝基芳烃化合物加氢制取芳胺类化合物的反应尤其重要。因为苯胺作为一种常见的有机物,用途广泛,是一种重要的精细化学品和有机合成中间体。在染料工业中用于制造多种染料,如靛蓝、酸性媒介BS等;在农药工业中用于制备多种类型杀虫剂、杀菌剂,如除草醚、DDV等;在医药行业中用于生产磺胺类药物;同时在香料、塑料、清漆、胶片等生产中作为中间体也起到了较为重要的作用,故需求量较大,应用前景非常广阔。
目前苯胺的生产工艺主要有如下几种,分别是硝基苯铁还愿法、硝基苯催化加氢法和苯酚氨化法,其它的还包括水合肼还原法、电化学还原法和光化学还原法。硝基苯铁粉还原法对环境不友好,会产生大量的四氧化三铁,同时严重腐蚀设备,操作维护费用也比较高。苯酚氨化法理论产率能达到99%,同时生产方法简单、三废少,缺点是和直接加氢相比工艺成本比较高。水合肼还原法、电化学还原法和光化学还原法目前处于实验室研究阶段,主要由于三种途径条件要求苛刻,工业上很难达到实施标准。硝基苯催化加氢法因其反应温度低,生产能力大而被广泛应用于工业生产过程中,占苯胺总生产的85%以上。
目前工业上利用硝基苯直接催化加氢制苯胺所用的催化剂主要有两类,一类是以铂钯等贵金属为活性组分的催化剂,这类催化剂由于贵金属昂贵的价格和有限的资源限制了该类催化剂的广泛使用;另一类是镍等过渡金属为活性组分的催化剂,该类催化剂在使用过程中会产生像苯基羟胺、亚硝基苯、偶氮苯、氧化偶氮苯等中间产物,降低目标产物的选择。
专利CN104418756A、CN103349983A和CN1803761等采用负载型贵金属催化剂,在液相体系中使氯代硝基苯进行选择性加氢生成氯代苯胺。反应条件温和,过程清洁,没有产生副产物,反应温度从原来的200℃降到了100℃左右;专利CN104475136A通过将膨润土加入到可溶性镍盐的水溶液中,制备出了非晶态的Ni-P合金插层的膨润土催化剂,用于硝基苯加氢;专利CN105413693A将制备的Fe3O4纳米颗粒与水溶性的钴盐超声混合、以还原的方式得到Co-Fe3O4复合物,用于对氯硝基苯加氢反应。
通过对以上研究分析来看,目前在硝基苯催化加氢领域,所用的催化剂几乎都是以金属元素的单质为主要活性组分的;而负载型贵金属催化剂,由于贵金属昂贵的价格和有限的资源严重限制了这类催化剂在工业上的广泛应用;同时要保证金属催化剂有较高的选择性,就必须严格控制金属颗粒尺寸和一些其他的特性,制备工艺存在很大的挑战,这也同样限制了金属催化剂的使用。例如专利CN1803761制备的负载型钯催化剂,虽然极大地降低了反应温度,但是所用的溶剂为超临界二氧化碳,实用性有待解决;再如专利CN103349983A制备的负载型铂催化剂,反应体系所用还原剂为甲酸、甲酸钠、水合肼和硼氢化钠,甲酸及甲酸钠在反应过程中会对反应釜造成一定的腐蚀,而水合肼和硼氢化钠的使用存在一定的危险性,在应用该成果前要解决这些问题。而新兴的以非贵金属为活性组分的催化剂大多数还处于实验室研究阶段,催化剂制备工艺相对苛刻。例如专利CN105413693A在反应体系中选用水合肼为还原剂,在适用性上存在一定问题。
发明内容
针对以上金属催化剂存在的一些问题,本专利制备出了一种磷掺杂的多孔碳材料作为硝基苯及其衍生物的选择性加氢催化剂;该催化剂在温和的反应条件下实现了对硝基芳烃类化合物(包括多种邻、间、对位含取代基的硝基苯)良好的催化活性和对硝基的选择性。此外,本发明的催化剂在经过数次循环反应之后,仍保持着较好的活性。
本发明第一方面涉及一种加氢催化剂,其为磷掺杂多孔碳材料,其比表面积为700cm2/g以上,所述磷占总质量的1.4~10%。
优选地,所述催化剂中的一部分磷元素在X射线光电子能谱中在132.5eV处呈现特征峰。
本发明第二方面涉及所述的加氢催化剂的制备方法,包括如下步骤:
(1)将含磷有机物在160~200℃下加热预聚16~24h,反应结束后降至室温,得到有机物聚合物;
(2)将步骤(1)得到的有机物聚合物在惰性气氛下进行热解,热解温度为700~1000℃,热解时间为1~3小时,反应结束后降至室温;
(3)将步骤(2)得到的固体,研磨成粉末,用去离子水洗涤后干燥,即得到所述的加氢催化剂。
在本发明第二方面的优选实施方案中,步骤(1)所述的含磷有机物为膦酸或膦酸酯。
优选地,所述为膦酸为1-辛基磷酸;所述膦酸酯为植酸、1-磷酸葡萄糖或三磷酸肌醇中的一种或几种。
在本发明第二方面的优选实施方案中,步骤(2)所述的惰性气氛为氮气气氛。
本发明第三方面涉及所述的加氢催化剂用于含取代基的硝基芳烃的选择性加氢反应中的用途。
本发明的有益效果:
(1)本发明的加氢催化剂对硝基苯类物质具有优异的催化活性和选择性,并且在循环实验中保持很好的耐受性,经过10次循环使用后反应物的转化率维持在85%以上。所涉及的反应体系条件温和,易于工业化;本发明的加氢催化剂不仅用作硝基苯加氢催化剂,还可以用作各种含取代基的硝基芳烃的选择性加氢反应中;
(2)本发明的加氢催化剂制备方法所使用的原材料均廉价易得,多为常见的化工原料和实验药品;且制备工艺操作简单,容易实现工业化。
(3))本发明的加氢催化剂只含C、O、P三种元素,与大多数以金属元素为活性组分的催化剂相比,对环境更加友好,更容易处理。
附图说明
图1为本发明的实施例1制得加氢催化剂的高倍透射电镜效果图;
图2为本发明的实施例1制得加氢催化剂的P2pXPS表征图;
图3为本发明的实施例1制得加氢催化剂的循环10次反应物的转化率的示意图;
具体实施方式
实施例1
按以下步骤制备加氢催化剂:
(1)在烧杯中称取10g植酸水溶液(质量分数50%),放入160℃的烘箱中加热预聚16小时,反应结束后待温度降至室温,得到蓬松的黑色固体,研磨至粉末状待用;
(2)将得到的粉末预聚物放在氮气气氛炉中进行焙烧,温度为600℃下焙烧1小时,温度为900℃焙烧1小时;反应结束后自然降温至室温;
(3)将获得的黑色固体,研磨成黑色粉末,用去离子水洗涤3次,并离心干燥,得到所述的加氢催化剂。
得到的加氢催化剂的高倍透射电镜图(标尺为10nm)如图1所示。由图1可以清楚地看到得到的磷掺杂碳材料的堆积成层的微观结构以及碳材料特征的皱褶,采用氮气吸附-脱附测试得到比表面积为750cm2/g;得到的加氢催化剂的P2p XPS谱图如图2所示,从图2可以看出,磷元素呈现出两种不同的结合状态,在132.5eV和134.4eV处能看到明显的特征峰,这两个峰分别对应于P-C和P-O,P-C的存在直观地说明磷原子已经进入到了材料的碳骨架当中,即说明本发明得到的加氢催化剂为磷掺杂的碳材料。
将得到的加氢催化剂用于硝基苯的加氢反应中,步骤为:在高压反应釜中,加入50mg本发明得到的加氢催化剂,0.5mmol硝基芳烃,5ml无水乙醇,随后密封反应釜,并通入高纯氮气至4MPa,如此操作三次,然后通入高纯氢气至4MPa,也反复操作三次,反应温度为120℃,体系压力为3MPa。结果见表1。
将得到的加氢催化剂用于评价催化剂的循环使用的耐受性,如图3所示,反应条件为:50mg催化剂,0.5mmol硝基苯,5ml无水乙醇,氢气分压为30bar,反应时间为10小时。可以看到,经过10次循环使用后,硝基苯转化率维持在85%以上,催化剂保持着较高的活性,具有较好的工业应用前景。
实例2:具体操作同实例1,不同之处只有是预聚温度为200℃。
实例3:具体操作同实例1,不同的是预聚时间为24h。
实例4:具体操作同实例1,不同的是焙烧温度为700℃。
实例5:具体操作同实例1,不同的是焙烧温度为800℃。
实例6:具体操作同实例1,不同的是焙烧时间为2h。
实例7:具体操作同实例1,不同的是焙烧时间为3h。
实例8:具体操作同实例1,不同的是含磷有机物为1-磷酸葡萄糖。
实例9:具体操作同实例1,不同的是含磷有机物为1-辛基磷酸。
实例10:具体操作同实例1,不同的是含磷有机物为三磷酸肌醇。
实例1至实例10所制备的加氢催化剂的反应条件及用于硝基苯加氢的反应活性见表2。
表1
表2
Claims (3)
1.一种加氢催化剂的制备方法,其特征在于,所述加氢催化剂为磷掺杂多孔碳材料,其比表面积为700cm2/g以上,所述磷占总质量的1.4~10%;所述催化剂中的一部分磷元素在X射线光电子能谱中在132.5eV处呈现特征峰;所述制备方法包括如下步骤:
(1)将含磷有机物在160~200℃下加热预聚16~24h,反应结束后降至室温,得到有机物聚合物;所述含磷有机物为膦酸或膦酸酯;所述膦酸为1-辛基磷酸;所述膦酸酯为植酸、1-磷酸葡萄糖或三磷酸肌醇中的一种或几种;
(2)将步骤(1)得到的有机物聚合物在惰性气氛下进行热解,热解温度为700~1000℃,热解时间为1~3小时,反应结束后降至室温;
(3)将步骤(2)得到的固体,研磨成粉末,用去离子水洗涤后干燥,即得到所述的加氢催化剂。
2.根据权利要求1所述的制备方法,其特征在于,步骤(2)所述的惰性气氛为氮气气氛。
3.一种根据权利要求1所述的制备方法制备的加氢催化剂用于含取代基的硝基芳烃的选择性加氢反应中的用途。
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