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CN116135303B - 乙烯催化降解催化剂及其制备方法和应用 - Google Patents

乙烯催化降解催化剂及其制备方法和应用 Download PDF

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CN116135303B
CN116135303B CN202111356393.6A CN202111356393A CN116135303B CN 116135303 B CN116135303 B CN 116135303B CN 202111356393 A CN202111356393 A CN 202111356393A CN 116135303 B CN116135303 B CN 116135303B
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temperature
hydrogenation
catalyst
time
ethylene
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CN116135303A (zh
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李歌
王宝冬
彭胜攀
马子然
马静
王红妍
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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Priority to CN202111356393.6A priority Critical patent/CN116135303B/zh
Priority to EP21964570.2A priority patent/EP4434619A4/en
Priority to PCT/CN2021/136019 priority patent/WO2023087425A1/zh
Priority to AU2021474825A priority patent/AU2021474825B2/en
Priority to JP2024529233A priority patent/JP2024541397A/ja
Priority to US17/559,673 priority patent/US11813591B2/en
Publication of CN116135303A publication Critical patent/CN116135303A/zh
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Abstract

本发明涉及乙烯催化降解技术领域,公开了一种乙烯催化降解催化剂及其制备方法和应用。所述催化剂包含:TiO2晶体和助剂;其中,所述TiO2晶体的晶型为锐钛矿型,且所述TiO2晶体的表面覆盖有TiO2无序层,所述无序层含有表面羟基。所述乙烯催化降解催化剂在300‑450℃时乙烯降解效率达到50%以上,最高达到90%,相比现有催化剂,可以无任何过渡金属或贵金属为活性组分。

Description

乙烯催化降解催化剂及其制备方法和应用
技术领域
本发明涉及乙烯催化降解技术领域,具体涉及一种乙烯催化降解催化剂及其制备方法和应用。
背景技术
挥发性有机物(以下简称VOCs)是形成PM2.5和O3的重要前体物,为进一步改善空气质量,需加强煤化工等VOCs重点排放行业的综合治理。当前VOCs处理技术主要分为三类:吸附回收技术、燃烧技术、吸附浓缩+燃烧技术,其中燃烧技术用于无回收价值VOCs的治理。例如,煤化工行业挥发性有机物主要来源于煤气化工艺、低温甲醇洗尾气等,具有VOCs种类繁多、回收价值低、风量大等特点,燃烧技术可将VOCs氧化成无害的CO2和H2O排放。
催化燃烧是燃烧技术中的重要手段之一,其中,催化燃烧技术的关键节点包括VOCs氧化催化剂设计与制备。VOCs氧化催化剂一般由载体和活性组分(贵金属)两部分组成。乙烯是常见的煤化工VOCs气体,商业催化氧化乙烯的催化剂主要是Pt/γ-Al2O3催化剂。但活性组分贵金属价格昂贵且供货周期长,基本依赖于国外进口。此外商业Pt/γ-Al2O3催化剂还存在热稳定性差、抗中毒能力差等缺点。
综上所述,开发低成本、抗中毒、稳定的新型环保催化剂以有效减少VOCs大气污染物势在必行。
发明内容
本发明的目的是为了克服现有乙烯催化降解催化剂均需要以贵金属为活性组分的问题,提供一种乙烯催化降解催化剂及其制备方法和应用,该乙烯催化降解催化剂可实现较高的乙烯催化活性。
本发明的发明人在研究过程中发现,当用于乙烯催化降解的催化剂组成中包含K2O和Na2O,以及锐钛矿型的TiO2晶体,且TiO2晶体的表面覆盖有含有表面羟基、Ti3+的TiO2无序层时,能够实现很好的乙烯催化降解成为CO2和H2O,无需催化剂中含有贵金属作为活性组分,因而得到本发明。
为了实现上述目的,本发明第一方面提供了一种乙烯催化降解催化剂,其中,所述催化剂包含:TiO2晶体和助剂;其中,所述TiO2晶体的晶型为锐钛矿型,且所述TiO2晶体的表面覆盖有TiO2无序层,所述无序层含有表面羟基。
本发明第二方面提供了一种乙烯催化降解催化剂的制备方法,其中,该方法包括:
(1)将钛源粉末与酸进行混合,得到的混合料进行焙烧;
(2)将所述焙烧得到的产物进行水浸,然后进行固液分离,得到含Ti滤液;
(3)将所述滤液进行水解和陈化,得到含助剂元素的偏钛酸胶体,所述助剂元素含有Na和K;
(4)将所述偏钛酸胶体进行水洗、干燥和煅烧,得到纳米TiO2粉体;
(5)将所述纳米TiO2粉体进行氢化,得到乙烯催化降解催化剂;
其中,钛源粉末选自含有Na2O和K2O的废SCR脱硝催化剂。
本发明第三方面提供了一种由前述所述的方法制备得到的乙烯催化降解催化剂。
本发明第四方面提供了一种前述所述的乙烯催化降解催化剂在乙烯降解中的应用。
通过上述技术方案,本发明具有如下的有益效果:
(1)本发明的乙烯催化降解催化剂的制备方法采用含有Na2O和K2O助剂的废SCR催化剂为原料,能够合理利用硫酸法制备得到的锐钛矿型TiO2上含有的元素,为氢化TiO2提供酸性位。另外,制备得到的TiO2晶体构筑缺陷,可以合理调控其氧化还原性。
(2)本发明的乙烯催化降解催化剂不需要使用过渡金属或贵金属为活性组分,从而无需处理乙烯催化降解过程中催化剂中毒和老化的问题,且催化剂失活后容易再生。
附图说明
图1为本发明的乙烯催化降解催化剂的制备方法的工艺流程示意图;
图2为本发明实施例1制得乙烯催化降解催化剂与TiO2粉末的外观对比图;
图3为本发明实施例1制得乙烯催化降解催化剂与TiO2粉末的X射线衍射对比图;
图4为本发明实施例1制得乙烯催化降解催化剂的氮气吸附-脱附等温线对比图;
图5为本发明实施例1制得乙烯催化降解催化剂与纯纳米TiO2的EPR对比图;
图6为本发明实施例1制得乙烯催化降解催化剂的TEM图;
图7为本发明实施例1制得乙烯催化降解催化剂的温度与乙烯转化率关系图。
附图标记说明
1、TiO2粉末 2、乙烯催化降解催化剂
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
本发明第一方面提供了一种乙烯催化降解催化剂,其中,所述催化剂包含:TiO2晶体和助剂;其中,所述TiO2晶体的晶型为锐钛矿型,且所述TiO2晶体的表面覆盖有TiO2无序层,所述无序层含有表面羟基。
本发明提供的用于乙烯催化降解的催化剂,含有具有特定结构的TiO2晶体以及助剂,没有贵金属作为活性组分,能够实现更好的乙烯催化降解效果。
在本发明的一些实施方式中,优选地,基于所述催化剂的总重量,所述催化剂中,TiO2的含量为99.9-99.99wt%。
在本发明的一些实施方式中,所述催化剂中还含有的助剂,能够有利于促进提高乙烯催化降解的技术效果。优选地,所述助剂包含K2O和Na2O,基于所含催化剂的总重量,所述催化剂中,K2O的含量为0.002-0.006wt%,Na2O的含量为0.006-0.098wt%。
在本发明的一些实施方式中,所述催化剂还可以具有有利于乙烯催化降解反应的孔结构。优选地,所述催化剂的比表面积为80-120m2/g,孔体积为0.2-0.8cm3/g,孔径为8-13nm。
在本发明的一些实施方式中,优选地,所述TiO2无序层的厚度为1.8-3nm。所述催化剂中TiO2晶体形成的结构缺陷可以在所述TiO2晶体的表面形成所述TiO2无序层,且能够含有表面羟基。
在本发明的一些实施方式中,优选地,所述TiO2无序层中,Ti3+占钛元素的摩尔百分数为2.15%-10.37%,优选为5.15%-8.66%。本发明中所述TiO2晶体含有上述缺陷且缺陷的量以Ti3+计,当在上述范围内时可以控制所述催化剂与上述助剂有更合适的匹配,表现出更好的乙烯催化降解反应的催化活性。Ti3+的量可以通过X射线光电子能谱分析方法测定。
本发明中,所述表面羟基为羟基与Ti3+相连接,可以表示为Ti-OH。
本发明中,所述乙烯催化降解催化剂的外观为土黄色,形貌为球形。
本发明第二方面提供了一种乙烯催化降解催化剂的制备方法,如图1所示,其中,该方法包括:
(1)将钛源粉末与酸进行混合,得到的混合料进行焙烧;
(2)将所述焙烧得到的产物进行水浸,然后进行固液分离,得到含Ti滤液;
(3)将所述滤液进行水解和陈化,得到含助剂元素的偏钛酸胶体,所述助剂元素含有Na和K;
(4)将所述偏钛酸胶体进行水洗、干燥和煅烧,得到纳米TiO2粉体;
(5)将所述纳米TiO2粉体进行氢化,得到乙烯催化降解催化剂;
其中,钛源粉末选自含有Na2O和K2O的废SCR脱硝催化剂。
在本发明的一些实施方式中,步骤(1)和(2)可以用于主要提取Ti元素,并得到可溶的含Ti化合物,也能够提取Na元素和K元素。优选地,所述酸为浓硫酸;优选地,所述酸的浓度为85-92wt%,优选为88-91wt%。满足提取Ti元素为主的有益元素的要求。
在本发明的一些实施方式中,优选地,所述混合的条件包括:温度为20-30℃,时间为2-6h;优选,温度为22-28℃,时间为3-5h。
在本发明的一些实施方式中,优选地,所述钛源粉末与所述酸的质量比为1:(1.5-2)。其中,所述钛源粉末中,还可以含有助剂,优选含有Na2O和K2O,更优选基于所述钛源粉末的总量,K2O的含量为0.1-0.3wt%,Na2O的含量为0.2-0.8wt%,能够保证提供最终获得的乙烯催化降解催化剂含有限定量的Na2O和K2O,以进一步促进提高乙烯催化降解的催化活性。
在本发明的一些实施方式中,优选地,焙烧温度为150-300℃,焙烧时间为30-90min。
在本发明的一些实施方式中,优选地,所述钛源粉末的平均粒径为10-1000μm,优选为50-200μm。以上条件可以促进更有效提取Ti、Na、K元素,得到可溶的含Ti化合物。
在本发明的一些实施方式中,步骤(2)可以实现溶出Ti元素,还可以溶出助剂元素,如Na和K。优选地,所述水浸的条件包括:温度为60-120℃,时间为60-180min;优选,温度为80-100℃,时间为80-120min。
在本发明的一些实施方式中,优选地,所述产物与所述水浸中使用的水的质量比为1:(2-6),优选为1:(3-5)。
在本发明的一些实施方式中,步骤(3)可以主要用于实现沉淀Ti。优选地,水解温度为80-110℃,优选为85-105℃;水解时间为2-5h,优选为2.5-4h。
在本发明的一些实施方式中,水解后还进行陈化处理,优选地,陈化时间为15-30h,优选为16-26h;陈化温度为10-50℃,优选为20-35℃。
本发明中,将陈化后的物料抽滤分离,水洗,得到含助剂元素的偏钛酸胶体。
在本发明的一些实施方式中,步骤(4)实施可以对偏钛酸胶体进行净化,例如可以用于除杂和除去水分。所述水洗用于除去所述偏钛酸胶体中的杂质,过程包括将所述偏钛酸胶体与水混合、搅拌,并过滤除去滤液。可以进行多次水洗和过滤。优选地,干燥温度为65-95℃,干燥时间为60-120min。
在本发明的一些实施方式中,优选地,煅烧温度为450-700℃,煅烧时间为2-8h,升温速率为5-10℃/min。优选情况下,在温度为500-600℃,升温速率为5-7℃/min的条件下进行焙烧5-6h,效果更好。
本发明中,经煅烧后,得到的纳米TiO2粉体的晶型为锐钛矿型。
优选地,所述纳米TiO2粉体中还含有助剂,例如Na2O和K2O,分散在所述纳米TiO2粉体中。
在本发明的一些实施方式中,在步骤(5)中,将所述纳米TiO2粉体进行表面氢化还原,氢化后可以生成缺陷结构。优选地,所述氢化的条件包括:氢化温度为400-550℃,氢化升温速率为5-10℃/min,氢化时间为2-12h,氢气浓度为90-100体积%,氢气流量为100-300mL/min。在设定流量的氢气存在下,将所述TiO2粉末从室温开始,以氢化升温速率加热至氢化温度,然后恒温进行氢化。优选地,在常压下,100体积%H2气氛下,在温度为420-460℃条件下氢化4-12h,氢气流量为100-150mL/min,效果更好。
本发明第三方面提供了一种由前述所述的方法制备得到的乙烯催化降解催化剂。
优选地,由前述所述的方法制备得到的乙烯催化降解催化剂中,包含:TiO2晶体和助剂;基于所含催化剂的总重量,K2O的含量为0.002-0.006wt%,Na2O的含量为0.006-0.098wt%。所述TiO2晶体的晶型为锐钛矿型,TiO2的含量为99.9-99.99wt%,所述TiO2晶体的表面覆盖有TiO2无序层。所述TiO2无序层的厚度为1.8-3nm;所述TiO2无序层中,Ti3+占钛元素的摩尔百分数为2.15%-10.37%,优选为5.15%-8.66%。所述催化剂的比表面积为80-120m2/g,孔体积为0.2-0.8cm3/g,孔径为8-13nm。
本发明第四方面提供了一种前述所述的乙烯催化降解催化剂在乙烯降解中的应用。
根据本发明,具体地,该应用包括:将含有乙烯的有机挥发性气体与本发明的乙烯催化降解催化剂接触进行乙烯催化降解反应。
根据本发明,所述应用在温度可以为100-500℃的温度条件下进行。
根据本发明,有机挥发性气体中,乙烯的体积浓度可以为10-1000ppm。
根据本发明,有机挥发性气体的体积空速为4000-40000h-1
以下将通过实施例对本发明进行详细描述。
以下实施例和对比例中:
(1)制得的乙烯催化降解催化剂的晶体结构通过XRD分析测得,使用德国Bruker公司的D8 ADVANCE,测试扫描速率为0.5°/min至5°/min。
(2)制得的乙烯催化降解催化剂的孔结构和介孔孔径通过N2吸附方法测定,使用美国Micromeritics公司的ASAP 2020物理吸附仪,吸附介质为N2
(3)制得的乙烯催化降解催化剂的形貌通过TEM测定,使用日本JEOL公司的型号为JEM ARM 200F透射电子显微镜。
(4)电子顺磁共振图(EPR)分析使用电子顺磁共振波谱仪。
(5)钛源粉末为废SCR催化剂,平均粒径为74μm,化学组成采用XRF荧光分析方法(RIPP 117-90标准方法)测定,结果如表1所示。制得催化剂组成含量也采用XRF荧光分析方法测定。
表1
实施例1
(1)按照废SCR催化剂(粒径120μm):浓硫酸(90wt%)的质量比为1:1.8进行混合,得到混合料;在180℃下进行焙烧1h。
(2)将焙烧的产物与水按照质量比为1:4进行水浸,温度为100℃,时间为100min,然后,进行固液分离,得到含Ti滤液;
(3)将滤液依次进行水解和陈化,水解条件为水解温度100℃,水解时间3h;陈化条件为陈化温度25℃,陈化时间20h;得到固相产物经分析为含助剂的偏钛酸胶体,助剂含有Na2O和K2O;
(4)将偏钛酸胶体进行水洗,分离得到的固体在80℃烘干60min,最后在马弗炉中以7℃/min的升温速率在500℃下煅烧6h,得到纳米TiO2粉体,分析纳米TiO2粉体的颗粒粒径约为30nm,且分析纳米TiO2粉体的晶型为锐钛矿型;
(5)将纳米TiO2粉体在管式炉中进行氢化,压力为0.1MPa,氢气浓度为100体积%,氢气流量为120mL/min,氢化升温速率为10℃/min,达到氢化温度为420℃,保温氢化时间为12h,然后降至室温,得到乙烯催化降解催化剂,记为T-1。
得到的乙烯催化降解催化剂,进行XRD分析,乙烯催化降解催化剂包含晶型为锐钛矿型的TiO2晶体,从图6的TEM图可以看出,催化剂具有2.74nm厚度的无序层,其中Ti3+的摩尔百分数为6.73%。催化剂还含有Na2O、K2O,组成见表2。
图2为实施例1制得乙烯催化降解催化剂与TiO2粉末的外观对比图;从图中能够看出:TiO2粉末为白色粉末,而本发明的乙烯催化降解催化剂的外观为土黄色,形貌为球形。
图3为实施例1制得乙烯催化降解催化剂X射线衍射对比图,从图3可以看出:本发明的乙烯催化降解催化剂的所有的衍射峰均与TiO2粉末的衍射峰吻合,无杂质出现,此结果与文献报道的介孔TiO2的XRD谱相一致;另外,乙烯催化降解催化剂的XRD衍射峰明显变宽且变低,说明微晶的尺寸与结构发生了较小的改变,这是因为氢化还原的过程中产生了三价钛和氧空位。
图4为实施例1制得乙烯催化降解催化剂的氮气吸附-脱附等温线对比图;其中,两个曲线一个是吸附曲线,一个是脱附曲线,图4表明本发明的乙烯催化降解催化剂为朗格缪尔IV型,属于典型的介孔物质吸附曲线,即随着吸附分压的提高,出现了一个大的滞后环。另外,吸附等温线中吸附量陡增点所对应的相对压力p/p0值标示样品的孔径大小,从图4中的孔径分布图可看出:本发明的乙烯催化降解催化剂具有高度有序的介孔结构、均一的孔径分布和规整的孔道。
图5为实施例1制得乙烯催化降解催化剂与TiO2粉末的EPR对比图;在g值<2处信号峰为氧空位(VO *)Ti3+的信号峰;从图5可以看出,1表示TiO2粉末,2表示本发明的乙烯催化降解催化剂,氢化后生成了较多的(VO *)Ti3+的信号峰,说明氢化使材料表面生成了较多的氧空位,更有利于脱硝反应的进行。
图6为实施例1制得乙烯催化降解催化剂的TEM图;从图6中(中部下方,多处标记虚线和箭头)能够看出:TiO2晶核的边缘像被刻蚀一样,生成了薄的一层无序层,进一步表明TiO2被成功的氢化。
图7为实施例1制得乙烯催化降解催化剂的反应活性图;从图7中能够看出:在325-500℃时,乙烯催化降解催化剂的乙烯降解活性>50%;450℃后乙烯催化降解催化剂的乙烯降解活性>90%。
实施例2
(1)按照废SCR催化剂(粒径50μm):浓硫酸(88wt%)的质量比为1:1.5进行混合,得到混合料;在150℃下进行焙烧0.5h。
(2)将焙烧的产物与水按照质量比为1:3进行水浸,温度为90℃,时间为80min,然后,进行固液分离,得到含Ti滤液;
(3)将滤液依次进行水解和陈化,水解条件为水解温度85℃,水解时间2.5h;陈化条件为陈化时间16h,陈化温度20℃;得到固相产物经分析为含助剂的偏钛酸胶体,助剂含有Na2O和K2O;
(4)将偏钛酸胶体进行水洗,分离得到的固体在95℃烘干120min,最后在马弗炉中以5℃/min的升温速率在600℃下煅烧5h,得到纳米TiO2粉体,分析纳米TiO2粉体的颗粒粒径约为20nm,且分析纳米TiO2粉体的晶型为锐钛矿型;
(5)将纳米TiO2粉体在管式炉中进行氢化,压力为0.1MPa,氢气浓度为100体积%,氢气流量为100mL/min,氢化升温速率为5℃/min,达到氢化温度为430℃,保温氢化时间为4h,然后降至室温,得到乙烯催化降解催化剂,记为T-2。
将T-2进行分析,结果如表2所示。进行外观、XRD、氮气吸附-脱附等温线、EPR、TEM的比对,得到的照片或曲线或谱图的结果与实施例1获得的相似。
实施例3
(1)按照废SCR催化剂(粒径200μm):浓硫酸(91wt%)的质量比为1:2进行混合,得到混合料;在300℃下进行焙烧1.5h。
(2)将焙烧的产物与水按照质量比为1:5进行水浸,温度为80℃,时间为120min,然后,进行固液分离,得到含Ti滤液;
(3)将滤液依次进行水解和陈化,水解条件为水解温度105℃,水解时间4h;陈化条件为陈化时间26h,陈化温度35℃;得到固相产物经分析为含助剂的偏钛酸胶体,助剂含有Na2O和K2O;
(4)将偏钛酸胶体进行水洗,分离得到的固体在65℃烘干100min,最后在马弗炉中以6℃/min的升温速率在550℃下煅烧5h,得到纳米TiO2粉体,分析纳米TiO2粉体的颗粒粒径约为40nm,且分析纳米TiO2粉体的晶型为锐钛矿型;
(5)将纳米TiO2粉体在管式炉中进行氢化,压力为0.1MPa,氢气浓度为100体积%,氢气流量为150mL/min,氢化升温速率为8℃/min,达到氢化温度为460℃,保温氢化时间为9h,然后降至室温,得到乙烯催化降解催化剂,记为T-3。
将T-3进行分析,结果如表2所示。进行外观、XRD、氮气吸附-脱附等温线、EPR、TEM的比对,得到的照片或曲线或谱图的结果与实施例1获得的相似。
实施例4
按照实施例1的方法,不同的是,“氢化温度为400℃”替换“氢化温度为420℃”。制备得到的乙烯催化降解催化剂记为T-4。
将T-4进行分析,结果如表2所示。进行外观、XRD、氮气吸附-脱附等温线、EPR、TEM的比对,得到的照片或曲线或谱图的结果与实施例1获得的相似。
实施例5
按照实施例1的方法,不同的是,“氢化时间为2h”替换“氢化时间为12h”。制备得到的乙烯催化降解催化剂记为T-5。
将T-5进行分析,结果如表2所示。进行外观、XRD、氮气吸附-脱附等温线、EPR、TEM的比对,得到的照片或曲线或谱图的结果与实施例1获得的相似。
对比例1
采用商业购买的TiO2,该催化剂的参数如表2所示。
对比例2
按照实施例1的方法,不同的是,“氢气浓度为50体积%”替换“氢气浓度为100体积%”。得到的催化剂的参数如表2所示。
对比例3
按照实施例1的方法,不同的是,“氢化时间0.5h”替换“氢化时间为12h”,“氢化温度200℃”替换“氢化温度为420℃”。得到的催化剂的参数如表2所示。
表2
通过表2的结果可以看出,对比例1采用没有杂质的TiO2氢化,对比例2采用浓度不高的氢气氢化,对比例3采用氢化时间和氢化温度都不在本发明所限定的范围之内的条件进行氢化;结果,实施例1-5中采用本发明的制备方法,获得的乙烯催化降解催化剂具有特定的无序层厚度和Ti3+占钛元素的摩尔百分数。
应用例
将实施例1-5和对比例1-3制备的催化剂应用于乙烯催化降解反应中,其中,进行催化氧化分解有机挥发性气体中,乙烯体积浓度为700ppm,其他气体含量O2 10v%,N2为平衡气,总流量为1000mL/min;有机挥发性气体的体积空速为100000h-1,结果如表3所示。
其中,降解效率%=(入口乙烯浓度-出口乙烯浓度)/入口乙烯浓度×100%。
表3
通过表3的结果可以看出,采用对比例1未经过氢化的二氧化钛,对乙烯无降解效率,对比例2和3中的氢化时间、温度以及氢气浓度不在范围内,得到的催化剂不具有本发明的催化剂的结构,乙烯催化降解效果相比实施例1-5按照本发明的提供催化剂较差。另外,将对比例1的二氧化钛按照实施例1中步骤(4)的条件煅烧,得到锐钛矿型晶体,并按实施例1中步骤(5)的方法进行氢化,但得到的催化剂不含有助剂K2O和Na2O,也不能具有本发明限定的厚度的无序层和Ti3+的摩尔百分数,不能获得好的乙烯催化降解效果。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。

Claims (19)

1.一种乙烯催化降解催化剂,其特征在于,所述催化剂包含:TiO2晶体和助剂;
其中,所述TiO2晶体的晶型为锐钛矿型,且所述TiO2晶体的表面覆盖有TiO2无序层,所述无序层含有表面羟基;所述助剂为K2O和Na2O;
其中,所述TiO2无序层中,Ti3+占钛元素的摩尔百分数为5.15%-8.66%;
其中,所述TiO2无序层的厚度为1.8-3 nm;
基于所述催化剂的总重量,所述催化剂中,TiO2的含量为99.9-99.99wt%,K2O的含量为0.002-0.006wt%,Na2O的含量为0.006-0.098wt%。
2.一种权利要求1所述的乙烯催化降解催化剂的制备方法,其特征在于,该方法包括:
(1)将钛源粉末与酸进行混合,得到的混合料进行焙烧;
(2)将所述焙烧得到的产物进行水浸,然后进行固液分离,得到含Ti滤液;
(3)将所述滤液进行水解和陈化,得到含助剂元素的偏钛酸胶体,所述助剂元素含有Na和K;
(4)将所述偏钛酸胶体进行水洗、干燥和煅烧,得到纳米TiO2粉体;
(5)将所述纳米TiO2粉体进行氢化,得到乙烯催化降解催化剂;
其中,钛源粉末选自含有Na2O和K2O的废SCR脱硝催化剂。
3.根据权利要求2所述的方法,其中,所述酸为浓硫酸;其中,所述酸的浓度为85-92wt%;
和/或,所述混合的条件包括:温度为20-30℃,时间为2-6h;
和/或,所述钛源粉末与所述酸的质量比为1:(1.5-2);
和/或,焙烧温度为150-300℃,焙烧时间为30-90min;
和/或,所述钛源粉末的平均粒径为10-1000 μm。
4.根据权利要求2或3所述的方法,其中,所述水浸的条件包括:温度为60-120℃,时间为60-180min;
和/或,所述产物与所述水浸中使用的水的质量比为1:(2-6)。
5.根据权利要求2或3所述的方法,其中,水解温度为80-110℃;水解时间为2-5h;
和/或,陈化时间为15-30 h;陈化温度为10-50℃。
6.根据权利要求4所述的方法,其中,水解温度为80-110℃;水解时间为2-5h;
和/或,陈化时间为15-30 h;陈化温度为10-50℃。
7.根据权利要求2或3所述的方法,其中,水解温度为85-105℃,水解时间为2.5-4h;
和/或,陈化时间为16-26h;陈化温度为20-35℃。
8.根据权利要求4所述的方法,其中,水解温度为85-105℃,水解时间为2.5-4h;
和/或,陈化时间为16-26h;陈化温度为20-35℃。
9.根据权利要求2、3、6、8中任意一项所述的方法,其中,干燥温度为65-95℃,干燥时间为60-120min;
和/或,煅烧温度为450-700℃,煅烧时间为2-8 h,升温速率为5-10℃/min。
10.根据权利要求4所述的方法,其中,干燥温度为65-95℃,干燥时间为60-120min;
和/或,煅烧温度为450-700℃,煅烧时间为2-8 h,升温速率为5-10℃/min。
11.根据权利要求5所述的方法,其中,干燥温度为65-95℃,干燥时间为60-120min;
和/或,煅烧温度为450-700℃,煅烧时间为2-8 h,升温速率为5-10℃/min。
12.根据权利要求7所述的方法,其中,干燥温度为65-95℃,干燥时间为60-120min;
和/或,煅烧温度为450-700℃,煅烧时间为2-8 h,升温速率为5-10℃/min。
13.根据权利要求2、3、6、8、10-12中任意一项所述的方法,其中,所述氢化的条件包括:氢化温度为400-550℃,氢化升温速率为5-10℃/min,氢化时间为2-12 h,氢气浓度为90-100体积%,氢气流量为100-300 mL/min。
14.根据权利要求4所述的方法,其中,所述氢化的条件包括:氢化温度为400-550℃,氢化升温速率为5-10℃/min,氢化时间为2-12 h,氢气浓度为90-100体积%,氢气流量为100-300 mL/min。
15.根据权利要求5所述的方法,其中,所述氢化的条件包括:氢化温度为400-550℃,氢化升温速率为5-10℃/min,氢化时间为2-12 h,氢气浓度为90-100体积%,氢气流量为100-300 mL/min。
16.根据权利要求7所述的方法,其中,所述氢化的条件包括:氢化温度为400-550℃,氢化升温速率为5-10℃/min,氢化时间为2-12 h,氢气浓度为90-100体积%,氢气流量为100-300 mL/min。
17.根据权利要求9所述的方法,其中,所述氢化的条件包括:氢化温度为400-550℃,氢化升温速率为5-10℃/min,氢化时间为2-12 h,氢气浓度为90-100体积%,氢气流量为100-300 mL/min。
18.一种权利要求3-17中任意一项所述的方法制备得到的乙烯催化降解催化剂。
19.一种权利要求1和18中任意一项所述的催化剂在乙烯催化降解中的应用。
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