CN110876924A - 一种碳五原料脱硫吸附剂及其制备方法和应用 - Google Patents
一种碳五原料脱硫吸附剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于石油化工技术领域,具体涉及一种碳五原料脱硫吸附剂及其制备方法和应用。所述吸附剂由以下重量百分数的组分组成:Fe2O32.0%~10.0%;优选3.0%~8.0%;ZnO5.0%~20.0%;优选8.0%~15.0%;干胶20.0%~60.0%;优选20.0%~50.0%;余量为13X分子筛。本发明制备的吸附剂,稳定性好,对碳五中的硫的吸附性能优异;其制备方法,安全、环保、简便,制备过程使用浸渍法活性组分分散均匀,不易流失。本发明吸附剂适用于固定床连续工艺,在温度为40℃~60℃,操作压力为0.1~0.5MPa,空速为0.5h‑1~3h‑1的条件下,能将碳五中的硫化物吸附至2ppm以下。
Description
技术领域
本发明属于石油化工技术领域,具体涉及一种碳五原料脱硫吸附剂及其制备方法和应用。
背景技术
碳五馏分是石油烃高温裂解制乙烯过程的副产物,裂解碳五组成复杂,约含有20多种化合物,其中含量较大的异戊二烯、环戊二烯和间戊二烯。它们的化学性质活泼,都是非常宝贵的基本有机化工原料。裂解碳五的利用已成为充分利用石油资源和提高乙烯生产经济效益的一个重要方面。由于硫化物对碳五馏分加氢过程中的催化剂具有严重的毒害作用,因此开发脱硫剂具有重要意义。
专利CN103182291公开了一种裂解碳五馏分油深度脱硫吸附剂的制法及用途,采用拟薄水铝石粉体添加粘结剂和助挤剂制备载体,然后浸渍锌铜钾钠钙等金属,后焙烧制得吸附剂,其活性金属分两次浸渍,制备过程复杂,所需要的活性金属较多,稳定性难以保证。
专利CN1261533C公开了一种汽油吸附脱硫方法,利用吸附剂进行吸附脱硫,所述的吸附剂载体是二氧化硅、氧化铝、硅酸铝、硅藻土、沸石、氧化锆中的一种或几种,所述的活性金属为钴、钼、镍、钨、锌、铁、钒、铬、铜、钙、钾中的一种或几种。可以将汽油中的硫化物降低到500ppm以下。
专利CN101481627公开了一种烃油脱硫吸附剂及其应用方法,所述的烃油脱硫吸附剂含有分子筛和具有吸附脱硫功能的金属氧化物,所述分子筛的硅铝原子比为50-750,分子筛与具有吸附脱硫功能用的金属氧化物的重量比为45-98:2-55。利用此方法制备的吸附剂不能将硫含量降低到10ppm以下。
发明内容
针对现有技术的不足,本发明的目的是提供一种碳五原料脱硫吸附剂,稳定性好,对碳五中的硫的吸附性能优异;本发明还提供其制备方法和应用,安全、环保、简便。
本发明所述的碳五原料脱硫吸附剂,由以下重量百分数的组分组成:
优选地,所述的碳五原料脱硫吸附剂,由以下重量百分数的组分组成:
本发明的吸附剂适用于碳五脱硫。
本发明所述的碳五原料脱硫吸附剂的制备方法,步骤如下:
1)3X分子筛和干胶混合均匀,滚成球,750℃~850℃下焙烧3~8h;
2)配制浸渍液:浸渍液中含有Zn(NO3)2和Fe(NO3)3;
3)将步骤1)焙烧后的球在浸渍液中静置12个小时;
4)烘干,450℃~550℃下焙烧2~6h,得碳五原料脱硫吸附剂。
步骤4)中,所述的烘干温度为110℃。
本发明所述的碳五原料脱硫吸附剂的应用,采用固定床反应器,将碳五原料脱硫吸附剂设置在固定床反应器中的吸附剂床层,使含硫化物的碳五通过吸附剂床层进行吸附。
所述的吸附,操作压力为0.1~0.5MPa,操作温度为40℃~60℃。
所述的含硫化物的碳五通过吸附剂床层的空速为0.5h-1~3h-1。
本发明制备的碳五原料脱硫吸附剂的技术指标如下:
综上所述,本发明的有益效果如下:
1、本发明制备的吸附剂,稳定性好,对碳五中的硫的吸附性能优异;吸附脱硫是一种价廉而有效的新技术,具有投资少,条件缓和,设备空间小、成本低、适用于深度脱硫的优点。
2、本发明的制备方法,安全、环保、简便,制备过程使用浸渍法活性组分分散均匀,不易流失。
3、本发明吸附剂适用于固定床连续工艺,在温度为40℃~60℃,操作压力为0.1~0.5MPa,空速为0.5h-1~3h-1的条件下,能将碳五中的硫化物吸附至2ppm以下。
附图说明
图1是本发明固定床评价装置结构示意图;
图中:1、原料罐,2、原料计量泵,3、固定床反应器,4、水浴入口,5、水浴出口,6、取样口,7、反应压控,8、冷凝器,9、收集罐,10、放空,11、热偶管。
具体实施方式
下面结合实施例对本发明做进一步说明。
实施例中采用的原料除特殊说明外,均为市购。
实施例1
所述的碳五原料脱硫吸附剂A的制备方法,步骤如下:
将50g粉状干胶和35g粉状13X分子筛混合后滚成球,直径为Φ1.8~2.5mm,在马弗炉中750℃条件下焙烧3h,然后配置含Fe2O35.0g,ZnO15g的浸渍液进行改性,然后静置12个小时,然后再110℃下烘干,450℃下焙烧2h,所得吸附剂即为负载有一定量金属活性组分的脱硫吸附剂。
其活性组分及载体成分在所制备吸附剂中所占的质量百分含量的具体情况见表1,吸附剂的物理性能指标如孔容、比表面及强度情况见表2。
将所得的吸附剂A粉碎至20~40目,取40ml置于Φ25×2.5mm的固定床反应器中,取含硫约30ppm的碳五,在温度为40℃,操作压力0.2MPa,液体空速(LHSV)为2h-1的条件下,通过吸附剂床层,产品取样分析。硫化物含量采用带火焰光度检测器的气相色谱仪进行分析。色谱柱为毛细管柱,分析条件:柱箱:80℃;气化室250℃;检测器250℃;载气(N2):15ml/min;H2:40ml/min;空气:400ml/min;进样体积0.3微升。微量硫含量均用此方法进行分析测量。结果表明硫化物在产物碳五中未检出。
实施例2
所述的碳五原料脱硫吸附剂B的制备方法,步骤如下:
将39g粉状干胶和50g粉状13X分子筛混合后滚成球,直径为Φ1.8~2.5mm,在马弗炉中800℃条件下焙烧5h,然后配置含Fe2O33.0g,ZnO 8g的浸渍液进行改性,然后静置12个小时,然后再110℃下烘干,500℃下焙烧4h,所得吸附剂即为负载有一定量金属活性组分的脱硫吸附剂。
其活性组分及载体成分在所制备吸附剂中所占的质量百分含量的具体情况见表1,吸附剂的物理性能指标如孔容、比表面及强度情况见表2。
将所得的吸附剂B粉碎至20~40目,取40ml置于Φ25×2.5mm的固定床反应器中,取含硫化物约30ppm的碳五,在温度为40℃,操作压力0.2MPa,液体空速(LHSV)为0.5h-1的条件下,通过吸附剂床层,产品取样分析。硫化物含量采用带火焰光度检测器的气相色谱仪进行分析。色谱柱为毛细管柱,分析条件:柱箱:80℃;气化室250℃;检测器250℃;载气(N2):15ml/min;H2:40ml/min;空气:400ml/min;进样体积0.3微升。微量硫化物含量均用此方法进行分析测量。结果表明硫化物在产物碳五中含量为1ppm。
实施例3
所述的碳五原料脱硫吸附剂C的制备方法,步骤如下:
将45g粉状干胶和40g粉状13X分子筛混合后滚成球,直径为Φ1.8~2.5mm,在马弗炉中750℃条件下焙烧5h,然后配置含Fe2O310.0g,ZnO 5.0g的浸渍液进行改性,然后静置12个小时,然后再110℃下烘干,520℃下焙烧3h,所得吸附剂即为负载有一定量金属活性组分的脱硫吸附剂。
其活性组分及载体成分在所制备吸附剂中所占的质量百分含量的具体情况见表1,吸附剂的物理性能指标如孔容、比表面及强度情况见表2。
将所得的吸附剂C粉碎至20~40目,取40ml置于Φ25×2.5mm的固定床反应器中,取含硫化物约30ppm的碳五,在温度为40℃,操作压力0.1MPa,液体空速(LHSV)为2h-1的条件下,通过吸附剂床层,产品取样分析。硫化物含量采用带火化室250℃;检测器250℃;载气(N2):15ml/min;H2:40ml/min;空气:400ml/min;进样体积0.3微升。微量硫化物含量均用此方法进行分析测量。结果表明硫化物在产物甲基进样体积0.3微升。微量硫化物含量均用此方法进行分析测量。结果表明硫化物在产物碳五中未检出。
实施例4
所述的碳五原料脱硫吸附剂D的制备方法,步骤如下:
将50g粉状干胶和42g粉状13X分子筛混合后滚成球,直径为Φ1.8~2.5mm,在马弗炉中800℃条件下焙烧5h,然后配置含Fe2O38.0g,ZnO 10.0g的浸渍液进行改性,然后静置12个小时,然后再110℃下烘干,550℃下焙烧2h,所得吸附剂即为负载有一定量金属活性组分的脱硫吸附剂。
其活性组分及载体成分在所制备吸附剂中所占的质量百分含量的具体情况见表1,吸附剂的物理性能指标如孔容、比表面及强度情况见表2。
将所得的吸附剂D粉碎至20~40目,取40ml置于Φ25×2.5mm的固定床反应器中,取含硫化物约30ppm的碳五,在温度为60℃,操作压力0.5MPa,液体空速(LHSV)为1h-1的条件下,通过吸附剂床层,产品取样分析。硫化物含量采用带火焰光度检测器的气相色谱仪进行分析。色谱柱为毛细管柱,分析条件:柱箱:80℃;气化室250℃;检测器250℃;载气(N2):15ml/min;H2:40ml/min;空气:400ml/min;进样体积0.3微升。微量硫化物含量均用此方法进行分析测量。结果表明硫化物在产物碳五中未检出。
实施例5
所述的碳五原料脱硫吸附剂E的制备方法,步骤如下:
将30g粉状干胶和48g粉状13X分子筛混合后滚成球,直径为Φ1.8~2.5mm,在马弗炉中750℃条件下焙烧3h,然后配置含Fe2O34.0g,ZnO 18.0g的浸渍液进行改性,然后静置12个小时,然后再110℃下烘干,450℃下焙烧6h,所得吸附剂即为负载有一定量金属活性组分的脱硫吸附剂。
其活性组分及载体成分在所制备吸附剂中所占的质量百分含量的具体情况见表1,吸附剂的物理性能指标如孔容、比表面及强度情况见表2。
将所得的吸附剂E粉碎至20~40目,取40ml置于Φ25×2.5mm的固定床反应器中,取含硫化物约30ppm的碳五,在温度为40℃,操作压力0.2MPa,液体空速(LHSV)为2h-1的条件下,通过吸附剂床层,产品取样分析。硫化物含量采用带火焰光度检测器的气相色谱仪进行分析。色谱柱为毛细管柱,分析条件:柱箱:80℃;气化室250℃;检测器250℃;载气(N2):15ml/min;H2:40ml/min;空气:400ml/min;进样体积0.3微升。微量硫化物含量均用此方法进行分析测量。结果表明硫化物在产物碳五中含量为1.8ppm。
实施例6
所述的碳五原料脱硫吸附剂F的制备方法,步骤如下:
将30g粉状干胶和45g粉状13X分子筛混合后滚成球,直径为Φ1.8~2.5mm,在马弗炉中850℃条件下焙烧4h,然后配置含Fe2O310.0g,ZnO15.0g的浸渍液进行改性,然后静置12个小时,然后再110℃下烘干,500℃下焙烧5h,所得吸附剂即为负载有一定量金属活性组分的脱硫吸附剂。
其活性组分及载体成分在所制备吸附剂中所占的质量百分含量的具体情况见表1,吸附剂的物理性能指标如孔容、比表面及强度情况见表2。
将所得的吸附剂F粉碎至20~40目,取40ml置于Φ25×2.5mm的固定床反应器中,取含硫化物约30ppm的碳五,在温度为50℃,操作压力0.1MPa,液体空速(LHSV)为0.5h-1的条件下,通过吸附剂床层,产品取样分析。硫化物含量采用带火焰光度检测器的气相色谱仪进行分析。色谱柱为毛细管柱,分析条件:柱箱:80℃;气化室250℃;检测器250℃;载气(N2):15ml/min;H2:40ml/min;空气:400ml/min;进样体积0.3微升。微量硫化物含量均用此方法进行分析测量。结果表明硫化物在产物碳五中未检出。
实施例7
所述的碳五原料脱硫吸附剂G的制备方法,步骤如下:
将40g粉状干胶和33g粉状13X分子筛混合后滚成球,直径为Φ1.8~2.5mm,在马弗炉中800℃条件下焙烧5h,然后配置含Fe2O37.0g,ZnO20.0g的浸渍液进行改性,然后静置12个小时,然后再110℃下烘干,550℃下焙烧6h,所得吸附剂即为负载有一定量金属活性组分的脱硫吸附剂。
其活性组分及载体成分在所制备吸附剂中所占的质量百分含量的具体情况见表1,吸附剂的物理性能指标如孔容、比表面及强度情况见表2。
将所得的吸附剂G粉碎至20~40目,取40ml置于Φ25×2.5mm的固定床反应器中,取含硫化物约30ppm的碳五,在温度为40℃,操作压力0.5MPa,液体空速(LHSV)为1.5h-1的条件下,通过吸附剂床层,产品取样分析。硫化物含量采用带火焰光度检测器的气相色谱仪进行分析。色谱柱为毛细管柱,分析条件:柱箱:80℃;气化室250℃;检测器250℃;载气(N2):15ml/min;H2:40ml/min;空气:400ml/min;进样体积0.3微升。微量硫化物含量均用此方法进行分析测量。结果表明硫化物在产物碳五中未检出。
对比例
采用专利CN101481627B中提供的吸附剂制备方法制备了吸附剂用于碳五脱硫,将30g粉状干胶和48g粉状13X分子筛混合后滚成球,直径为Φ1.8~2.5mm,在马弗炉中750℃条件下焙烧3h,然后配置含Fe2O34.4g,ZnO 17.6g的浸渍液进行改性,然后静置12个小时,然后再110℃下烘干,450℃下焙烧6h,所得吸附剂即为负载有一定量金属活性组分的脱硫吸附剂。
将所得的吸附剂粉碎至20~40目,取40ml置于Φ25×2.5mm的固定床反应器中,取含硫化物约30ppm的碳五,在温度为40℃,操作压力0.2MPa,液体空速(LHSV)为2h-1的条件下,通过吸附剂床层,产品取样分析。硫化物含量采用带火焰光度检测器的气相色谱仪进行分析。色谱柱为毛细管柱,分析条件:柱箱:80℃;气化室250℃;检测器250℃;载气(N2):15ml/min;H2:40ml/min;空气:400ml/min;进样体积0.3微升。微量硫化物含量均用此方法进行分析测量。结果表明硫化物在产物碳五中含量为23ppm。
采用对比例制备的吸附剂脱硫效果明显差于实施例的脱硫效果。
表1吸附剂组成
表2吸附剂的物理性能
实施例 | 吸附剂编号 | 孔容ml·g<sup>-1</sup> | 比表面m<sup>2</sup>·g<sup>-1</sup> | 强度N/颗 |
1 | A | 0.39 | 120 | 109 |
2 | B | 0.36 | 130 | 111 |
3 | C | 0.37 | 155 | 107 |
4 | D | 0.37 | 170 | 110 |
5 | E | 0.42 | 115 | 97 |
6 | F | 0.44 | 180 | 99 |
7 | G | 0.39 | 167 | 105 |
Claims (7)
3.一种权利要求1或2所述的碳五原料脱硫吸附剂的制备方法,其特征在于:步骤如下:
1)3X分子筛和干胶混合均匀,滚成球,750℃~850℃下焙烧3~8h;
2)配制浸渍液:浸渍液中含有Zn(NO3)2和Fe(NO3)3;
3)将步骤1)焙烧后的球在浸渍液中静置12个小时;
4)烘干,450℃~550℃下焙烧2~6h,得碳五原料脱硫吸附剂。
4.根据权利要求3所述的制备方法,其特征在于:步骤4)中,所述的烘干温度为110℃。
5.一种权利要求1或2所述的碳五原料脱硫吸附剂的应用,其特征在于:采用固定床反应器,将碳五原料脱硫吸附剂设置在固定床反应器中的吸附剂床层,使含硫化物的碳五通过吸附剂床层进行吸附。
6.根据权利要求5所述的应用,其特征在于:所述的吸附,操作压力为0.1~0.5MPa,操作温度为40℃~60℃。
7.根据权利要求5所述的应用,其特征在于:所述的含硫化物的碳五通过吸附剂床层的空速为0.5h-1~3h-1。
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