CN114471518B - 一种常温cos水解剂及其制备方法和应用 - Google Patents
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种常温COS水解剂及其制备方法和应用,主要解决现有技术中常温水解活性低,脱除精度不够,COS处理量低,换剂频繁的问题。本发明提供的常温COS水解剂,以水解剂质量为基准,包括:a)0.01%~25%碱金属;b)0.01%~25%过渡金属;c)50%~99.98%的氧化铝;水解剂碱中心≥0.6mmol/g。所述水解剂孔容大于0.5cm3/g。该水解剂具有较多的碱中心和较大的孔容,常温下COS水解率≥99%,COS处理量达到470mg/g以上,可以实现常温对COS的精度脱除,可用于天然气、合成气、轻质气液态烃类等脱除COS。
Description
技术领域
本发明涉及一种常温COS水解剂及其制备方法和应用。
背景技术
在以天然气、煤、石油等为原料制取的气体中,都会有二硫化碳(CS2)、羰基硫(COS)等有机硫和硫化氢(H2S)等无机硫并存。目前脱除有机硫的方法可分为湿法和干法两种。湿法主要包括有机胺类溶剂吸收剂和液态催化水解转化法。湿法的投资及操作费用高、动力消耗大、操作复杂,而且远达不到精脱硫要求。干法主要有加氢转化法、氧化法、吸附法和水解法等。加氢转化法存在一定的副反应。氧化法虽然脱硫效率高,但是投资费用较高,且氧化法会将黄磷尾气中CO氧化,吸附法主要用于高精度H2S的脱除,其反应温度较高,且会有副反应的发生。较其它方法相比,水解法所需能耗明显降低,而且低温催化水解过程可有效避免副产物的产生,是目前脱除COS的主要方法。水解法脱除COS和CS2的过程是:COS在催化剂上和H2O发生水解反应生成产物H2S,然后H2S在后续工段脱硫剂上被脱除。
CN102600850B公开了一种同时脱除羰基硫和二硫化碳活性炭基催化剂的制备方法,该方法以微波活性炭为载体,碱性物质和金属氧化物为活性组分制备得到能同时脱除羰基硫和二硫化碳活性炭基催化剂;该催化剂可以在温度30~90℃下将气体中的COS和CS2同时脱除,同时脱除其副产物,该方法流程简单,操作方便,运行费用低,COS和CS2脱除效率高,COS和CS2的转化率均大于90%。但是,该催化剂的水解温度较高,一方面在使用过程中增加能耗;另一方面在碳载体存在的情况下,容易造成积碳现象,堵塞催化剂孔道,影响催化剂活性。
CN101559379A公开了一种水解催化剂的制备方法,该催化剂的载体为活性炭,活性组分为碱性物质和金属氧化物。可以在温度30~100℃下将气体中的COS脱除,并将水解产生的H2S一并除去。其具体组成是:以活性炭(AC)为载体,采用溶胶-凝胶法负载活性金属Fe和Cu(Fe2O3的负载量为5%且n(Fe):n(Cu)=5:1),于400℃下焙烧3h,超声浸渍5%KOH,干燥后得到。上述催化剂存在的不足是无法实现CS2的精度脱除。
CN110102302A公开了一种羰基硫净化用催化剂及其制备方法,该催化剂包括多孔载体、活性组分和碱金属。可以在还原气氛下,100~200℃的环境下实现对羰基硫的催化净化。该专利发明的催化剂使用温度较高,一般在100℃以上,不能满足低温使用要求,且无法实现羰基硫的精度脱除。
CN108970611A公开了一种天然气有机硫水解催化剂及其制备方法,该催化剂以氧化铝、氧化钛、白炭黑三种组分作为载体,以钠盐和铈盐作为活性组分。制备的催化剂比表面积大于300m2/g、孔容0.45ml/g,活性稳定性好,有机硫水解率≥99%。该专利发明添加了氧化钛作为载体,制作成本较高,且反应温度在60℃,不能满足低温使用要求且无法实现有机硫的精度脱除。
上述催化剂以活性炭、氧化铝和/或氧化钛为载体,添加部分活性组分脱除有机硫,其不足之处在于:(1)脱硫组分单一,水解活性较低,不能实现精度脱除。(2)水解反应温度较高,能耗高,无法实现常温脱除。
发明内容
本发明所要解决的技术问题是现有技术中常温水解活性低,COS不易脱除的问题,提供一种常温COS水解剂及其制备方法。该水解剂具有较大的孔容,可以减少硫的堵塞,减缓水解剂失活,提高COS处理量。
为解决上述技术问题,本发明第一方面在于提供一种常温COS水解剂,以水解剂质量为基准,包括:a)0.01%~25%碱金属;b)0.01%~25%过渡金属;c)50%~99.98%的氧化铝;水解剂碱中心≥0.6mmol/g,优选为0.6~1.8mmol/g。
上述技术方案中,水解剂孔容大于0.5cm3/g,优选为0.55~1.5cm3/g。
上述技术方案中,碱金属选自K或Na中一种或多种,优选的碱金属的质量含量为0.5%~20%,更优选为1%~15%。
上述技术方案中,过渡金属选自Cu、Zn、Ni或Co中一种或多种,优选过渡金属质量含量为0.5%~20%,更优选为1%~15%。
本发明第二方面在于提供一种水解剂的制备方法,包括:
1)配制粘结剂水溶液;
2)向步骤1)的粘结剂水溶液中并流加入偏铝酸钠以及过渡金属硝酸盐溶液进行反应,反应过程调整pH=6~8,得到沉淀物,将沉淀物干燥,得到水解剂前驱体;
3)将步骤2)得到的水解剂前驱体成型、熟化、干燥、焙烧,得到成型后水解剂前驱体;
4)将上述步骤3)成型后水解剂前驱体置于碱金属溶液中浸渍,烘干,得到水解剂。
上述技术方案中,制备过程优选在共沉淀反应器中进行。步骤1)中所述粘结剂优选为聚丙烯酸、纤维素钠中的至少一种。粘结剂水溶液中粘结剂的含量为0.1wt%~1.5wt%。
上述技术方案中,步骤2)中偏铝酸钠溶液的浓度为0.5mol/L~1.5mol/L。优选的过渡金属盐溶液为Cu(NO3)2、Zn(NO3)2、Ni(NO3)2、Co(NO3)2溶液中的一种或多种。其可以采用任何适宜的浓度,其加入量可根据产物中的实际需求计算所得。步骤2)中优选采用硝酸溶液调整pH值。步骤2)中所述反应的反应温度为40~90℃,反应时间为0.5~3h。
上述技术方案中,步骤3)中所述成型优选滚球成型,成型后粒径优选为3-5mm;所述熟化,优选在空气中熟化。干燥为在50℃~110℃干燥。焙烧为300℃-500℃焙烧6~8小时。
上述技术方案中,步骤4)浸渍过程中水解剂前驱体与碱溶液的固液体积比为1:0.8~1:1.3。步骤4)中所述碱金属含量为5wt%~20wt%。优选的碱性溶液为KOH、Na2CO3、NaHCO3或K2CO3溶液中的一种或多种。步骤4)中烘干温度为50℃~150℃。
本发明第三方面在于提供一种所述水解剂在天然气、合成气、轻质气液态烃类脱除COS中的应用。
本发明所述水解剂,在共沉淀过程中将过渡金属直接引入,过渡金属更加分散;同时负载碱性金属,水解剂具有更多的碱性中心,具有更高的水解活性。水解剂具有较大的孔容,可以减少硫的堵塞,减缓水解剂失活,提高硫容量。
本发明所述水解剂可用于天然气、合成气、轻质气液态烃类中COS的脱除。常温下COS水解率≥99%,COS处理量达到470mg/g以上,可以实现常温对COS的精度脱除。
具体实施方式
下面结合具体实施例对本发明做进一步的阐述,但应当理解本发明的保护范围并不受具体实施方式的限制。
【实施例1】
在共沉淀反应器中加入400ml蒸馏水,加入聚丙烯酸0.5g,搅拌均匀。以10ml/min速度加入浓度为0.5mol/L的偏铝酸钠溶液,同时滴加0.5mol/L硝酸溶液和0.035mol/L硝酸锌溶液,保持pH=7,在50℃,反应1小时得沉淀物。将沉淀物洗涤干燥,得到水解剂前驱体。将上述前驱体置于滚球机中,喷洒2.5%硝酸溶液,转动滚球成型,直到原料形成3-5mm的小球,将球形颗粒筛分,得到大小均匀的,直径均为3-5mm的小球;将小球在空气中熟化,80℃干燥,500℃焙烧6小时。
取上述小球100g(体积约为50ml),在50g 7%KOH溶液中浸渍,100℃烘干制得水解剂。水解剂孔容0.55cm3/g,碱中心0.6mmol/g。水解剂的组成为:5wt%碱金属,2.5wt%过渡金属,92.5wt%氧化铝。
取5g水解剂,常温常压下,空速1000h-1,入口COS的1000ppm,COS转化率大于99%,COS处理量480mg/g。
【实施例2】
在共沉淀反应器中加入400ml蒸馏水,加入聚丙烯酸5g,搅拌均匀。以10ml/min速度加入浓度为0.5mol/L的偏铝酸钠溶液,同时滴加0.5mol/L硝酸溶液和0.10mol/L硝酸钴溶液,保持pH=7,在90℃,反应0.5小时得沉淀物,将沉淀物洗涤干燥,得到水解剂前驱体。将上述前驱体置于滚球机中,喷洒2.5%硝酸溶液,转动滚球成型,直到原料形成3-5mm的小球,将球形颗粒筛分,得到大小均匀的,直径均为3-5mm的小球;将小球在空气中熟化,80℃干燥,500℃焙烧6小时。
取上述小球100g(体积约为50ml)在60g 15%NaOH溶液中浸渍,50℃烘干制得水解剂。水解剂孔容0.75cm3/g,碱中心1.6mmol/g。水解剂的组成为:10wt%碱金属,5wt%过渡金属,85wt%氧化铝。
取5g水解剂,常温常压下,空速1000h-1,入口COS的1000ppm,COS转化率大于99%,COS处理量490mg/g。
【实施例3】
在共沉淀反应器中加入400ml蒸馏水,加入聚丙烯酸2.5g,搅拌均匀。以10ml/min速度加入浓度为1.0mol/L的偏铝酸钠溶液,同时滴加0.5mol/L硝酸溶液和0.15mol/L硝酸铜溶液,保持pH=8,在60℃,反应2小时得沉淀物,将沉淀物洗涤干燥,得到水解剂前驱体。将上述前驱体置于滚球机中,喷洒2.5%硝酸溶液,转动滚球成型,直到原料形成3-5mm的小球,将球形颗粒筛分,得到大小均匀的,直径均为3-5mm的小球;将小球在空气中熟化,60℃干燥,500℃焙烧6小时。
取上述小球100g(体积约为50ml),在40g 1%NaHCO3溶液中浸渍,150℃烘干制得水解剂。水解剂孔容1.2cm3/g,碱中心1.0mmol/g。水解剂的组成为:2wt%碱金属,15wt%过渡金属,83wt%氧化铝。
取5g水解剂,常温常压下,空速1000h-1,入口COS的1000ppm,COS转化率大于99%,COS处理量470mg/g。
【实施例4】
在共沉淀反应器中加入400ml蒸馏水,加入纤维素钠0.5g,搅拌均匀。以10ml/min速度加入浓度为1.5mol/L的偏铝酸钠溶液,同时滴加0.5mol/L硝酸溶液和0.035mol/L硝酸镍溶液,保持pH=6,在50℃,反应1小时得沉淀物,将沉淀物洗涤干燥,得到水解剂前驱体。将上述前驱体置于滚球机中,喷洒2.5%硝酸溶液,转动滚球成型,直到原料形成3-5mm的小球,将球形颗粒筛分,得到大小均匀的,直径均为3-5mm的小球;将小球在空气中熟化,100℃干燥,300℃焙烧8小时。
上述小球在100g(体积约为50ml)在50g 7%Na2CO3溶液中浸渍,80℃烘干制得水解剂。水解剂孔容0.58cm3/g,碱中心0.65mmol/g。水解剂的组成为:5wt%碱金属,2.5wt%过渡金属,92.5wt%氧化铝。
取5g水解剂,常温常压下,空速1000h-1,入口COS的1000ppm,COS转化率大于99%,COS处理量485mg/g。
【比较例1】
取常规氧化铝小球100g(体积约为50ml),加入50g 10%硝酸锌溶液,浸渍过夜,120℃烘干,500℃焙烧。上述小球在50g 7%KOH溶液中浸渍,110℃烘干制得水解剂。水解剂孔容0.4cm3/g,碱中心0.4mmol/g。
取5g水解剂,常温常压下,空速1000h-1,入口COS的1000ppm,COS转化率99%,COS处理量100mg/g。
【比较例2】
在共沉淀反应器中加入400ml蒸馏水,加入聚丙烯酸0.5g,搅拌均匀。以10ml/min速度加入浓度为0.5mol/L的偏铝酸钠溶液,同时滴加0.5mol/L硝酸溶液反应,保持pH=7,在50℃,反应1小时得沉淀物,将沉淀物洗涤干燥,得到水解剂前驱体。将上述前驱体置于滚球机中,喷洒2.5%硝酸溶液,转动滚球成型,直到原料形成3-5mm的小球,将球形颗粒筛分,得到大小均匀的,直径均为3-5mm的小球;将小球在空气中熟化,80℃干燥,500℃焙烧。
将取上述小球100g(体积约为50ml),加入50g 10%硝酸锌溶液,浸渍过夜,120℃烘干,500℃焙烧。
上述小球在50g 7%KOH溶液中浸渍,50℃-150℃烘干制得水解剂。水解剂孔容0.55cm3/g,碱中心0.6mmol/g。
取5g水解剂,常温常压下,空速1000h-1,入口COS的1000ppm,COS转化率大于99%,COS处理量300mg/g。
Claims (15)
1.一种常温COS水解剂,其特征在于,以水解剂质量为基准,包括:a)0.01%~25%碱金属;b)0.01%~25%过渡金属;c)50~99.98%的氧化铝;水解剂碱中心≥0.6 mmol/g;
所述过渡金属选自Cu、Zn、Ni或Co中的一种或多种;
所述水解剂孔容大于0.5 cm3/g;
所述水解剂的制备方法,包括如下步骤:
1)配制粘结剂水溶液;
2)向步骤1)的粘结剂水溶液中并流加入偏铝酸钠以及过渡金属硝酸盐溶液进行反应,反应过程调整pH=6~8,得到沉淀物,将沉淀物干燥,得到水解剂前驱体;
3)将步骤2)得到的水解剂前驱体成型、熟化、干燥、焙烧,得到成型后水解剂前驱体;
4)将上述步骤3)成型后水解剂前驱体置于碱金属溶液中浸渍,烘干,得到水解剂。
2.根据权利要求1所述的水解剂,其特征在于,水解剂碱中心为0.6~1.8 mmol/g。
3.根据权利要求1所述的水解剂,其特征在于,所述水解剂孔容为0.55~1.5 cm3/g。
4.根据权利要求1所述的水解剂,其特征在于,所述碱金属选自K或Na中一种或多种,碱金属的质量含量为0.5%~20%。
5.根据权利要求4所述的水解剂,其特征在于,所述碱金属的质量含量为1%~15%。
6.根据权利要求1所述的水解剂,其特征在于,过渡金属质量含量为0.5 % ~ 20 %。
7.根据权利要求1所述的水解剂,其特征在于,过渡金属质量含量为1 %~15 %。
8.一种权利要求1-7任一项所述水解剂的制备方法,其特征在于,包括如下步骤:
1)配制粘结剂水溶液;
2)向步骤1)的粘结剂水溶液中并流加入偏铝酸钠以及过渡金属硝酸盐溶液进行反应,反应过程调整pH=6~8,得到沉淀物,将沉淀物干燥,得到水解剂前驱体;
3)将步骤2)得到的水解剂前驱体成型、熟化、干燥、焙烧,得到成型后水解剂前驱体;
4)将上述步骤3)成型后水解剂前驱体置于碱金属溶液中浸渍,烘干,得到水解剂。
9.根据权利要求8所述的制备方法,其特征在于,步骤1)中所述粘结剂为聚丙烯酸、纤维素钠中的至少一种,粘结剂水溶液中粘结剂的含量为0.1 wt%~1.5 wt%。
10.根据权利要求8所述的制备方法,其特征在于,步骤2)中偏铝酸钠溶液的浓度为0.5mol/L~1.5mol/L。
11.根据权利要求8所述的制备方法,其特征在于,步骤2)中过渡金属盐溶液为Cu(NO3)2、Zn(NO3)2、Ni(NO3)2、Co(NO3)2溶液中的一种或多种。
12.根据权利要求8所述的制备方法,其特征在于,步骤2)中所述反应的反应温度为 40~90℃,反应时间为0.5~3h。
13.根据权利要求8所述的制备方法,其特征在于,步骤4)浸渍过程中水解剂前驱体与碱金属溶液的固液体积比为1:0.8 ~ 1:1.3。
14.根据权利要求8所述的制备方法,其特征在于,步骤4)中所述碱金属含量为5 wt%~20 wt%,碱金属溶液为KOH、Na2CO3、NaHCO3或K2CO3溶液中的一种或多种。
15.一种权利要求1-7中任一项所述水解剂或权利要求8-14中任一项制备方法所制备的水解剂在天然气、合成气、轻质气液态烃类脱除COS中的应用。
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