CN107243342B - 一种负载型催化剂及其制备方法和应用 - Google Patents
一种负载型催化剂及其制备方法和应用 Download PDFInfo
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- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
本发明公开了一种负载型催化剂及其制备方法和应用,属于催化剂领域。本发明通过离子交换,使主催化活性组分与载体相结合,由于主催化活性组分与载体之间通过静电作用力相结合,结合稳定,不易流失;主催化活性组分为镍、铁、钴、钌及其氧化物中的一种或几种;用转化为钙型阳离子吸附剂制备成载体,钙的存在有利于焙烧过程中的孔道保持,在高温处理时不易烧结,从而使催化剂拥有较高的比表面积。所得负载型催化剂的活性成分分散性好,催化剂机械强度高,性能稳定,能有效提高水热法降解有机物的降解率和反应效率。
Description
技术领域
本发明属于催化剂领域,更具体地说,涉及一种负载型催化剂及其制备方法和应用。
背景技术
有机废弃物的水热解技术就是以亚、超临界水为介质,对有机物进行热解,使大分子有机物、碳氢化合物的分子键断裂,转变成小分子物质的过程。水热气化应用较多的是生物质的方面中,但水热解技术在处理有机废弃物方面有很多优势,对发展分布式能源具有重要作用,潜在利用前景广阔。而催化剂在水热气化中的作用很重要,它能够加快反应速率,提高目标产物的产率,目前使用的水热催化剂主要分三类:碳类催化剂、金属类催化剂和碱类催化剂。就目前来说,金属类催化剂催化效果好,但单金属类催化剂存在易中毒失活,且无法重复利用等问题,而制备负载型催化剂是一种有效的解决方法。
现有负载型金属催化剂一般选用活性炭、壳聚糖、多孔陶粒、活性氧化铝、二氧化硅、沸石或粘土等为载体,负载的活性组分包括过渡金属(如镍、铁、钴等)和贵金属(如钌、铂、钯等)。如,中国专利“一种Ni/Ag/Cu/硅藻土复合催化剂的制备及其应用”(公告号CN103623841B)公开了一种以硝酸铜、硝酸银、硝酸镍为原料,硅藻土为载体,通过浸渍、干燥、焙烧、还原的步骤制备不同负载量的Ni/Ag/Cu/硅藻土复合负载型催化剂的方法。但浸渍法由于活性组分与载体间主要为非特异性吸附作用,结合力较弱,使活性组分易流失,并且活性组分在载体表面难以分布均匀,易形成局部团聚,影响催化活性。
专利“生物质气化炉催化剂及生产方法”(公告号CN1686606A)公开了一种生物质气化炉催化剂及其生产方法,所述催化剂由凹凸棒石粘土、高铝矾土、氧化铁、氧化镁、氧化钙和无烟煤组成,经配料、搅拌、磨粉、造粒、烘干、筛分检测和包装为成品,其中焦油裂解率在75%以上。该方法采用简单的机械混合制备催化剂,各组分之间的相互作用较弱,容易造成活性金属的烧结,引起催化剂失活。
专利号CN201410768421.9的专利(公告号CN104549292A)公开了一种以块状金属镍靶为原料;将二氧化硅固体粉末分散于去离子水中;将镍靶材置于上述溶液中,在磁力搅拌及电动平移台辅助作用下采用纳秒聚焦脉冲激光烧蚀靶材,制得镍/二氧化硅悬浮液;再将该悬浮液抽滤、干燥后制得镍/二氧化硅粉末状负载型催化剂的制备方法。该方法催化剂稳定性较高,但存在合成装置要求高,不利于推广的缺点。
离子交换剂作为催化剂的载体已有很多应用,如专利“贵金属负载型烷基芳烃异构化催化剂”(公开号CN1149002A),将沸石与氧化铝先混合成型、制成载体,然后用铵离子将沸石中的钠离子交换至一定交换度,再用铂金属进行浸渍而制成催化剂,用于芳烃异构化过程制取对位产物,具有良好的异构化活性、选择性和活性稳定性。但离子交换剂往往在高温下极易烧结,不能用于水热法的高温高压环境。
现有技术制备的负载型催化剂,存在其催化剂活性成分成分易流失,并且活性成分在载体上的分散性难以调控的问题,影响催化剂的使用效果和使用寿命。而采用离子交换剂作为催化剂载体时,虽然载体和活性成分结合力相对较强,但制成的催化剂在高温高压环境下极易烧结,引起催化剂失活。
发明内容
1.要解决的问题
针对现有的负载型催化剂存在活性成分成分易流失、活性成分的分散性不易调控以及易烧结等问题,本发明提供一种负载型催化剂及其制备方法和应用,本发明的催化剂具有高分散度、大比表面积、高强度、耐高温高压等优点,可用于水热法降解有机废弃物,转化率高,使用寿命长。
2.技术方案
为了解决上述问题,本发明所采用的技术方案如下:
一种负载型催化剂,载体上负载有主催化活性成分,所述的载体为钙型阳离子交换剂;所述的主催化活性成分为镍、铁、钴、钌及其氧化物中的一种或几种,负载量为0.5~20%(质量分数)。
进一步地,所述的负载型催化剂还含有CaO,CaO的质量是催化剂总质量的0.5%~2.0%;所述的主催化活性组分与所述的载体之间通过静电作用力相结合。
进一步地,所述的负载型催化剂的比表面积为300~1000m2/g。
上述的一种负载型催化剂在水热法催化降解有机废弃物领域中的应用,反应温度在700~900℃,反应压力23~30MPa,反应时间60~90min,有机物转化率大于95%。
一种负载型催化剂的制备方法,主要包括如下的步骤:
(1)将阳离子交换剂用Ca2+溶液处理为钙型,形成钙型阳离子交换剂;
(2)将步骤(1)制得的钙型阳离子交换剂用主催化活性成分的前体的乙醇溶液或氨水溶液进行离子交换,反应温度为60~70℃;
(3)步骤(2)的产物烘干后在N2保护下升温至500~900℃;
(4)通入活化气体活化2~8h;
(5)在N2保护下冷却至室温;
(6)将步骤(5)得到的产物在沸水中处理30~90min;
(7)烘干,即得负载型催化剂。
进一步地,步骤(1)中的阳离子交换剂为大孔阳离子交换树脂。
进一步地,步骤(1)中,所述用Ca2+溶液处理的过程为按碱、水、酸、水、碱的顺序通过装填有载体的离子交换柱,其中,所述碱为氢氧化钙或碳酸钙的饱和溶液,所述酸为5~10%的盐酸。
进一步地,步骤(2)中的主催化活性成分的前体为乙酸镍、乙酸铁、乙酸钴、乙酸钌及其水合物中的一种或几种,用量为所用阳离子交换剂的质量的1~50%。
进一步地,步骤(3)中的升温速度为5~15℃/min。
进一步地,步骤(4)中的活化方法为通入水蒸汽或空气或H2/Ar混合气,其中混合气的混合比例为H2:Ar=1:(3~5)(体积比)。
3.有益效果
相比于现有技术,本发明的有益效果为:
(1)本发明主催化活性组分与载体通过离子交换过程结合,主催化活性组分与载体之间通过静电作用力相结合,结合稳定,不易流失;
(2)本发明用转化为钙型阳离子交换剂制备成载体,钙的存在有利于焙烧过程中的孔道保持,在高温处理时不易烧结,从而使催化剂拥有较高的比表面积;
(3)本发明采用氨水或乙醇制备主催化活性成分的前体的溶液,促使主催化活性成分主要以阳离子形态存在,以离子交换的形式键联在载体上,避免其在载体上的吸附,从而保证主催化活性成分的高分散度,获得高催化活性;
(4)本发明采用乙酸盐为主催化活性组分的前体,避免了制备过程中产生NOx、SO2、H2S、HCl等污染物质;
(5)本发明制得的催化剂耐高温高压,在水热解法处理有机废弃物的高温高压环境中性能稳定,使用寿命长;
(6)本发明在主催化活性成分进行催化反应的同时,氧化钙成分可以吸收体系中的CO2,促进氢气的产生。
附图说明
图1为本发明实施例6中得到的催化剂的SEM剖面和表面图;
图2为本发明实施例6中得到的催化剂使用后的SEM剖面和表面图;
图3是本发明实施例所述的水热反应过程示意图。
具体实施方式
下面结合具体实施例对本发明进一步进行描述。
实施例1
取D001大孔阳离子交换树脂,(1)用3倍体积的饱和氢氧化钙和5%的稀盐酸,按碱、水、酸、水、碱的顺序洗涤,(2)在60℃下加入含5%乙酸钌的乙醇溶液进行离子交换,乙酸钌和树脂的质量比为1:100,(3)产物干燥后在N2保护下,在管式炉中以5℃/min的速度升温至500℃后,(4)通入水蒸汽活化8h,(5)在N2保护下冷却至室温,(6)产物在沸水中处理90min,(7)于100℃干燥,所得负载型催化剂记为催化剂(Ⅰ)。以质量计,催化剂(Ⅰ)中钌含量为0.5%,CaO含量为2%,催化剂比表面积为352m2/g。
实施例2
取D061大孔阳离子交换树脂,(1)用3倍体积的饱和碳酸钙和5%的稀盐酸,按碱、水、酸、水、碱的顺序洗涤,(2)在70℃下加入含15%的乙酸镍的氨溶液进行离子交换,乙酸镍和树脂的质量比为1:2,(3)产物干燥后在N2保护下,在管式炉中进行升温,升温速度为10℃/min,至900℃,(4)通入空气活化6h,(5)在N2保护下冷却至室温,(6)产物在沸水中处理30min,(7)于110℃干燥,所得负载型催化剂记为催化剂(Ⅱ)。以质量计,催化剂(Ⅱ)中氧化镍含量为18.7%,CaO含量为0.5%,催化剂比表面积为916m2/g。
实施例3
取D152大孔阳离子交换树脂,(1)用3倍体积的饱和氢氧化钙和5%的稀盐酸,按碱、水、酸、水、碱的顺序洗涤,(2)在70℃下加入含10%的乙酸钴的乙醇溶液进行离子交换,乙酸钴和树脂的质量比为1:10,(3)产物干燥后在N2保护下,在管式炉中进行升温,升温速度为8℃/min,至700℃,(4)通入H2/Ar混合气活化2h,其中混合气的混合比例为H2:Ar=1:4(体积),(5)在N2保护下冷却至室温,(6)产物在沸水中处理60min,(7)于110℃干燥,所得负载型催化剂记为催化剂(Ⅲ)。以质量计,催化剂(Ⅲ)中钴含量为1.6%,CaO含量为1%,催化剂比表面积为472m2/g。
实施例4
取D113大孔阳离子交换树脂,(1)用3倍体积的饱和碳酸钙和10%的稀盐酸,按碱、水、酸、水、碱的顺序洗涤,(2)在60℃下加入含10%的水合乙酸铁溶液进行离子交换,水合乙酸铁和树脂的质量比为1:5,(3)产物干燥后在N2保护下,在管式炉中进行升温,升温速度为15℃/min,至600℃,(4)通入H2/Ar混合气活化5h,其中混合气的混合比例为H2:Ar=1:5(体积),(5)在N2保护下冷却至室温,(6)产物在沸水中处理45min,(7)于110℃干燥,所得负载型催化剂记为催化剂(Ⅳ)。以质量计,催化剂(Ⅳ)中氧化铁含量为7.6%,CaO含量为1.5%,催化剂比表面积为300m2/g。
实施例5
取江苏南大环保科技有限公司生产的ND-77型大孔阳离子交换树脂,(1)用3倍体积的饱和氢氧化钙和10%的稀盐酸,按碱、水、酸、水、碱的顺序洗涤,(2)在60℃下加入含10%的水合乙酸镍溶液进行离子交换,水合乙酸镍和树脂的质量比为1:3,(3)产物干燥后在N2保护下,在管式炉中进行升温,升温速度为15℃/min,至600℃,(4)通入H2/Ar混合气活化5h,其中混合气的混合比例为H2:Ar=1:5(体积),(5)在N2保护下冷却至室温,(6)产物在沸水中处理30min,(7)于110℃干燥,所得负载型催化剂记为催化剂(Ⅴ)。以质量计,催化剂(Ⅴ)中氧化镍含量为20.0%,CaO含量为0.5%,催化剂比表面积为1000m2/g。
实施例6
取江苏南大环保科技有限公司生产的ND-77型大孔阳离子交换树脂,(1)用3倍体积的饱和氢氧化钙和10%的稀盐酸,按碱、水、酸、水、碱的顺序洗涤,(2)在60℃下加入乙酸钌和乙酸镍的混合溶液进行离子交换,乙酸镍和乙酸钌与树脂的质量比分别为1:5和1:50,(3)产物干燥后在N2保护下,在管式炉中进行升温,升温速度为5℃/min,至800℃,(4)通入H2/Ar混合气活化7h,其中混合气的混合比例为H2:Ar=1:3(体积),(5)在N2保护下冷却至室温,(6)产物在沸水中处理90min,(7)于100℃干燥,所得负载型催化剂记为催化剂(Ⅵ)。以质量计,催化剂(Ⅵ)中氧化镍含量为8.2%,氧化钌含量为0.8%,CaO含量为1%,催化剂比表面积为580m2/g。
对比例1采用天然矿物催化剂白云石,于900℃下煅烧4小时后装在密封袋中备用,其组分以质量百分比计,包括29.06%CaO,22.44%MgO,0.38%SiO2,0.20%Fe2O3,0.08%Al2O3。
对比例2采用购买的Cu-Zn-Al催化剂,其组成以质量百分比计,包括30%CuO,35%ZnO,20%Al2O3,5%MnO2,10%ZrO2。
分别将上述催化剂(Ⅰ)~(Ⅵ)以及对比例1和2中的催化剂装入水热反应器中,以某化工厂产生的工业污泥为处理对象,反应过程如图3所示,反应条件和反应结果见下表。
实施例1~6得到的催化剂结构和性能相近,反应前后结构和性能无显著变化,说明催化剂的稳定性良好。
表1实施例1~6中的催化剂及对比例1和2中的催化剂的催化条件和结果对比
Claims (8)
1.一种负载型催化剂,载体上负载有主催化活性成分,其特征在于:所述的载体为钙型阳离子交换剂,该阳离子交换剂为大孔阳离子交换树脂;所述的主催化活性成分为镍、铁、钴、钌及其氧化物中的一种或几种,负载量为0.5~20%,以质量分数计;所述的负载型催化剂还含有CaO,CaO的质量是催化剂总质量的0.5%~2.0%;所述的主催化活性组分与所述的载体之间通过静电作用力相结合。
2.根据权利要求1所述的一种负载型催化剂,其特征在于:所述的负载型催化剂的比表面积为300~1000m2/g。
3.权利要求1~2中任意一项所述的一种负载型催化剂在水热法催化降解有机废弃物领域中的应用,其特征在于:反应温度在700~900℃,反应压力23~30MPa,反应时间60~90min,有机物转化率大于95%。
4.一种负载型催化剂的制备方法,主要包括如下的步骤:
(1)将阳离子交换剂用Ca2+溶液处理为钙型,形成钙型阳离子交换剂,所述的阳离子交换剂为大孔阳离子交换树脂;
(2)将步骤(1)制得的钙型阳离子交换剂用主催化活性成分的前体的乙醇溶液或氨水溶液进行离子交换,反应温度为60~70℃;
(3)步骤(2)的产物烘干后在N2保护下升温至500~900℃;
(4)通入活化气体活化2~8h;
(5)在N2保护下冷却至室温;
(6)将步骤(5)得到的产物在沸水中处理30~90min;
(7)烘干,即得负载型催化剂。
5.根据权利要求4所述的一种负载型催化剂的制备方法,其特征在于:步骤(1)中,所述用Ca2+溶液处理的过程为按碱、水、酸、水、碱的顺序通过装填有载体的离子交换柱,其中,所述碱为氢氧化钙或碳酸钙的饱和溶液,所述酸为5~10%的盐酸。
6.根据权利要求4所述的一种负载型催化剂的制备方法,其特征在于:步骤(2)中,所述的主催化活性成分的前体为乙酸镍、乙酸铁、乙酸钴、乙酸钌及其水合物中的一种或几种,用量为所用阳离子交换剂的质量的1~50%。
7.根据权利要求4所述的一种负载型催化剂的制备方法,其特征在于:步骤(3)中,所述的升温速度为5~15℃/min。
8.根据权利要求4所述的一种负载型催化剂的制备方法,其特征在于:步骤(4)中,所述的活化方法为通入水蒸汽或空气或H2/Ar混合气,其中混合气的混合比例为H2:Ar=1:(3~5)以体积比计。
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