CN108295856B - 粉煤灰提硅残渣制备沼气干式重整双金属催化剂的方法 - Google Patents
粉煤灰提硅残渣制备沼气干式重整双金属催化剂的方法 Download PDFInfo
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Abstract
一种粉煤灰提硅残渣制备沼气干式重整双金属催化剂的方法,先将粉煤灰原样煅烧,与NaOH溶液混合,加入水热反应釜中反应,将反应后产物进行抽滤,得到提硅残渣;提硅残渣与酸溶液混合,将反应后产物进行抽滤,得到滤渣;滤渣用高纯水冲洗,置于高温管式炉中煅烧得到基体,将基体溶解于无水乙醇中形成均一的胶体溶液;将两种可溶性金属盐溶解于醇液中得到金属盐醇溶液,给胶体溶液逐滴加入金属盐醇溶液进行浸渍,加热搅拌至乙醇完全挥发,得到催化剂粉末;得催化剂粉末进行煅烧稳定化,利用压片机对煅烧后的粉末进行压片成型,得到催化剂产品颗粒;本发明所制催化剂能显著降低沼气干式重整的催化成本,具有催化活性高、稳定性强的优点。
Description
技术领域
本发明涉及燃煤发电行业副产物粉煤灰资源化以及催化剂制备技术领域,具体涉及一种粉煤灰提硅残渣制备沼气干式重整双金属催化剂的方法。
背景技术
粉煤灰是从煤燃烧后的烟气中收捕下来的细灰,是燃煤电厂排放的主要固体废物,其含有的重金属(铅、镉、砷等)会随着雨水进入土地及河流,造成水体、土壤的严重污染,对人体和生物造成危害。粉煤灰综合利用途径主要包括:用作井下回填和筑路材料;用作建筑材料,用于生产水泥、混凝土、墙体砖、陶粒等;用于土壤改良及化肥生产。目前已有研究提出对粉煤灰中的二氧化硅进行提取回收,并进一步合成纳米二氧化硅等产品,但对于粉煤灰提硅残渣,尚无较好的利用途径。
沼气是有机废物厌氧发酵产生的气体,主要成分是CH4和CO2,其中CH4占45-75%,CO2占20-55%,这两种温室气体直接排放会加剧温室效应,且存在安全隐患。目前利用沼气作为原料生产合成气的第二代沼气资源化技术受到广泛关注,干式重整技术能够同步利用沼气中的甲烷和二氧化碳两种主要的温室气体来生产合成气,产品纯度高,利于进一步高值化利用,在CO2减排、环境友好性及沼气资源化等方面具有良好的应用前景催化剂在沼气干式重整反应中具有非常关键的作用,基体的选择是影响催化剂活性、稳定性和成本的重要因素。常用的催化剂基体包括SiO2、ZrO2、MgO、TiO2、Al2O3等。然而,商品化的氧化物基体在生产过程中需消耗大量有机模板剂,这提高了催化剂制备成本,一定程度上限制了沼气干式重整技术的大规模应用。
粉煤灰提硅残渣中富含Al2O3、碱金属及碱土金属氧化物,且具有较高的比表面积和较好的高温稳定性,因此,以粉煤灰提硅残渣为基体合成沼气干式重整催化剂能够在保证催化剂活性及稳定性的基础上实现粉煤灰的进一步高值化利用,同时大幅降低催化剂制备成本,利于实现干式重整技术的工业化应用。目前,在国内外尚无文献公开此类技术。
发明内容
为了克服上述现有技术的缺点,本发明的目的在于提供了一种粉煤灰提硅残渣制备沼气干式重整双金属催化剂的方法,为粉煤灰提硅后的残渣进一步高值资源化利用拓宽途径,同时所制催化剂能显著降低沼气干式重整的催化成本,改善催化效果。
为达到上述目的,本发明采用的技术方案是:
一种粉煤灰提硅残渣制备沼气干式重整双金属催化剂的方法,包括以下步骤:
1)将粉煤灰原样在700-900℃下煅烧1-4小时,以去除表面杂质;
2)二氧化硅提取:将步骤1)得到的去除表面杂质的粉煤灰与浓度为4-10mol/L的NaOH溶液以固液比1:2-1:5混合,将混合体系加入水热反应釜中,在60-120℃、搅拌速率200-400rpm条件下反应0.5-1.5小时;将反应后产物进行抽滤,得到提硅残渣;
3)酸液活化:将步骤2)得到的提硅残渣与0.5-2mol/L的酸溶液以固液比1:10-1:20进行混合,在室温下进行机械搅拌,搅拌速率为400-600rpm,搅拌时间0.5-1.5小时;将反应后产物进行抽滤,得到滤渣备用;
4)将步骤3)所得滤渣用高纯水冲洗,在真空烘箱中维持80-110℃干燥2-4小时;再将滤渣置于高温管式炉中,在600-800℃条件下煅烧2-6小时,期间连续通入20-40ml/min的氮气以带走脱附的水及杂质,得到基体;
5)催化剂合成:将两种可溶性金属盐溶解于醇液中得到金属盐醇溶液,两种金属摩尔比为1:5-5:1;
将步骤4)所得基体溶解于无水乙醇中,金属盐中金属总质量占金属与基体总质量的2.5%-20%,并利用超声清洗器促进固液混合,形成均一的胶体溶液;
将胶体溶液在40-60℃温度下进行磁力搅拌,搅拌速度为400-700r/min,同时逐滴加入金属盐醇溶液进行浸渍,加热搅拌至乙醇完全挥发,得到催化剂粉末;
6)催化剂成型:将步骤5)所得催化剂粉末进行煅烧稳定化,置于高温管式炉中,在700-900℃条件下煅烧3-6小时,期间连续通入20-40ml/min的氮气进行保护;利用压片机对煅烧后的粉末进行压片成型,并破碎筛分,得到20-100目的催化剂产品颗粒。
所述的步骤3)中的酸溶液包括但不限于硝酸、盐酸、硫酸和醋酸。
所述的步骤5)中两种可溶性金属盐包括但不限于镍、铁、钴、铜的硝酸盐及卤化物。
所述的步骤5)中醇液包括但不限于乙醇、正丙醇、异丙醇、正丁醇和异丁醇。
本发明的优点在于:
1.以燃煤发电行业副产物粉煤灰提硅残渣为原料合成催化剂,为大宗工业固体废物粉煤灰的有效消纳和高值化利用拓宽了途径,是一种绿色经济的化学反应途径。
2.与商品化的催化剂基体相比,粉煤灰价格低廉,能够大幅降低催化剂的制备成本,利于推动沼气干式重整生产合成气技术的工业化应用。
3.本发明生产的催化剂颗粒具有催化活性高、稳定性强的优点。
附图说明
图1为本发明的流程图。
具体实施方式
下面结合附图和实施例对本发明进行更详尽的描述,但不受这些实施例的限定。
实施例1,参照图1,一种粉煤灰提硅残渣制备沼气干式重整双金属催化剂的方法,包括以下步骤:
1)将粉煤灰原样在空气气氛下800℃煅烧2小时,以去除表面杂质;
2)将步骤1)得到的去除表面杂质的粉煤灰与浓度为5mol/L的NaOH溶液以固液比1:2混合,将混合体系加入水热反应釜中,在110℃、搅拌速率300rpm条件下反应0.5小时;将反应后产物进行抽滤,得到滤渣备用;
3)将步骤2)得到的提硅残渣与2mol/L的硝酸溶液以固液比1:20进行混合,在室温下进行机械搅拌,搅拌速率为500rpm,搅拌时间1.5小时;将反应后产物进行抽滤,得到滤渣备用;
4)将步骤3)所得滤渣用高纯水冲洗,在真空烘箱中维持105℃干燥2小时;再将滤渣置于高温管式炉中,在800℃条件下煅烧4小时,期间连续通入30ml/min的氮气以带走脱附的水及杂质,得到基体;
5)将0.7434g分析纯Ni(NO3)2·6H2O固体及1.0822g分析纯Fe(NO3)3·9H2O固体溶解于30ml左右无水乙醇中得到镍盐醇溶液;
将步骤4)所得基体2.6996g溶解于50ml无水乙醇中,并利用超声清洗器促进固液混合,形成均一的胶体溶液;
将胶体溶液在50℃温度下进行磁力搅拌,搅拌速度为600r/min,同时逐滴加入镍盐醇溶液进行浸渍;加热搅拌至乙醇完全挥发,得到催化剂粉末;
6)将步骤5)所得催化剂粉末置于高温管式炉中,在800℃条件下煅烧4小时,期间连续通入30ml/min的氮气进行保护;利用压片机对煅烧后的粉末进行压片成型,并破碎筛分,得到20-100目的催化剂产品颗粒。
实施例2,参照图1,一种粉煤灰提硅残渣制备沼气干式重整双金属催化剂的方法,包括以下步骤:
1)将粉煤灰原样在空气气氛下800℃煅烧2小时,以去除表面杂质;
2)将步骤1)得到的去除表面杂质的粉煤灰与浓度为5mol/L的NaOH溶液以固液比1:4混合,将混合体系加入水热反应釜中,在110℃、搅拌速率300rpm条件下反应1小时;将反应后产物进行抽滤,得到提硅残渣;
3)将步骤2)得到的提硅残渣与2mol/L的硝酸溶液以固液比1:10进行混合,在室温下进行机械搅拌,搅拌速率为400rpm,搅拌时间1小时;将反应后产物进行抽滤,得到滤渣备用;
4)将步骤3)所得滤渣用高纯水冲洗,在真空烘箱中维持105℃干燥2小时;再将滤渣置于高温管式炉中,在750℃条件下煅烧4小时,期间连续通入30ml/min的氮气以带走脱附的水及杂质,得到基体;
5)将1.1152g分析纯Ni(NO3)2·6H2O固体及1.1096g分析纯Co(NO3)2·6H2O固体溶解于50ml无水乙醇中得到镍盐醇溶液;
将步骤4)所得基体4.0512g溶解于50ml无水乙醇中,并利用超声清洗器促进固液混合,形成均一的胶体溶液;
将胶体溶液在60℃温度下进行磁力搅拌,搅拌速度为500r/min,同时逐滴加入镍盐醇溶液进行浸渍;加热搅拌至乙醇完全挥发,得到催化剂粉末;
6)将步骤5)所得催化剂粉末置于高温管式炉中,在800℃条件下煅烧4小时,期间连续通入30ml/min的氮气进行保护;利用压片机对煅烧后的粉末进行压片成型,并破碎筛分,得到20-100目的催化剂产品颗粒。
实施例3:与实施例1区别在于步骤2)中NaOH溶液浓度为8mol/L,其它步骤与实施例1相同。
实施例4:与实施例1区别在于步骤3)中硝酸溶液浓度为1mol/L,其它步骤与实施例1相同。
实施例5:与实施例1区别在于步骤4)中煅烧温度为700℃,其它步骤与实施例1相同。
实施例6:与实施例1区别在于步骤4)中煅烧时间为2小时,其它步骤与实施例1相同。
实施例1-实施例4的催化剂产品颗粒的比表面积、CH4转化率、CO2转化率如表1所示,从表1中能够看出,本发明生产的催化剂颗粒具有催化活性高、稳定性强的优点。
表1
Claims (4)
1.一种粉煤灰提硅残渣制备沼气干式重整双金属催化剂的方法,其特征在于,包括以下步骤:
1)将粉煤灰原样在700-900℃下煅烧1-4小时,以去除表面杂质;
2)二氧化硅提取:将步骤1)得到的去除表面杂质的粉煤灰与浓度为4-10mol/L的NaOH溶液以固液比1:2-1:5混合,将混合体系加入水热反应釜中,在60-120℃、搅拌速率200-400rpm条件下反应0.5-1.5小时;将反应后产物进行抽滤,得到提硅残渣;
3)酸液活化:将步骤2)得到的提硅残渣与0.5-2mol/L的酸溶液以固液比1:10-1:20进行混合,在室温下进行机械搅拌,搅拌速率为400-600rpm,搅拌时间0.5-1.5小时;将反应后产物进行抽滤,得到滤渣备用;
4)将步骤3)所得滤渣用高纯水冲洗,在真空烘箱中维持80-110℃干燥2-4小时;再将滤渣置于高温管式炉中,在600-800℃条件下煅烧2-6小时,期间连续通入20-40ml/min的氮气以带走脱附的水及杂质,得到基体;
5)催化剂合成:将两种可溶性金属盐溶解于醇液中得到金属盐醇溶液,两种金属摩尔比为1:5-5:1;
将步骤4)所得基体溶解于无水乙醇中,金属盐中金属总质量占金属与基体总质量的2.5%-20%,并利用超声清洗器促进固液混合,形成均一的胶体溶液;
将胶体溶液在40-60℃温度下进行磁力搅拌,搅拌速度为400-700r/min,同时逐滴加入金属盐醇溶液进行浸渍,加热搅拌至乙醇完全挥发,得到催化剂粉末;
6)催化剂成型:将步骤5)所得催化剂粉末进行煅烧稳定化,置于高温管式炉中,在700-900℃条件下煅烧3-6小时,期间连续通入20-40ml/min的氮气进行保护;利用压片机对煅烧后的粉末进行压片成型,并破碎筛分,得到20-100目的催化剂产品颗粒。
2.根据权利要求1所述的一种粉煤灰提硅残渣制备沼气干式重整双金属催化剂的方法,其特征在于:所述的步骤3)中的酸溶液包括但不限于硝酸、盐酸、硫酸和醋酸。
3.根据权利要求1所述的一种粉煤灰提硅残渣制备沼气干式重整双金属催化剂的方法,其特征在于:所述的步骤5)中两种可溶性金属盐包括镍、铁、钴、铜的硝酸盐及卤化物。
4.根据权利要求1所述的一种粉煤灰提硅残渣制备沼气干式重整双金属催化剂的方法,其特征在于:所述的步骤5)中醇液包括但不限于乙醇、正丙醇、异丙醇、正丁醇和异丁醇。
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