CN114505069A - 低温脱除煤气中羰基硫的水解催化剂及其制备方法 - Google Patents
低温脱除煤气中羰基硫的水解催化剂及其制备方法 Download PDFInfo
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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Abstract
本发明公开了低温脱除煤气中羰基硫的水解催化剂及其制备方法,所述方法为将载体加入到马弗炉中进行煅烧,再与活性组分混合后进行研磨,放入管式炉中焙烧,并通氮气进行保护,得到的负载活性组分的载体放在烧杯中加入助剂和水进行浸渍,浸渍后取出放入烘箱中烘干,烘干后的产物与改性剂混合研磨,N2气氛下再将其放入管式炉中焙烧,得到低温脱除煤气中羰基硫的水解催化剂。本发明通过采用限定方法得到的低温脱除煤气中羰基硫的水解催化剂,具有优异的脱硫效率,在130℃下,连续运行100h,脱除效率高达95%以上。
Description
技术领域
本发明涉及煤气脱硫净化技术领域,具体涉及一种低温脱除煤气中羰基硫的水解催化剂及其制备方法。
背景技术
随着碳中和以及碳达峰的发展要求,低碳排放成为关注的热点问题,钢铁行业作为二氧化碳来源的主要行业之一,影响着碳达峰目标的实现,煤气是钢厂中的主要燃料之一,由于工艺不同,可分为三类:焦炉煤气(氢气(55%-60%)和甲烷(23%-27%),一氧化碳(5%-8%)、C2以上不饱和烃(2%-4%)、二氧化碳(1.5%-3%)、氧气(0.3%-0.8%))、氮气(3%-7%));高炉煤气(主要为二氧化碳6-12%、一氧化碳28-33%、氢气1-4%、氮气55-60%、烃类0.2-0.5%);转炉煤气(一氧化碳60%-80%,二氧化碳15-20%,以及氮、氢和微量氧)。此外,三种煤气中都含有少量的硫化氢、羰基硫、二硫化碳、噻吩、硫醚、硫醇等。其中,羰基硫:60mg/m3-250mg/m3,2019年4月,生态环境部《关于推进实施钢铁行业超低排放的意见》(环大气[2019]35号)正式公布实施,首次明确提出要“加强源头控制,高炉煤气、焦炉煤气应实施精脱硫”。目前煤气主要是通过煤气管网输送到各个车间,作为燃料提供热能,煤气燃烧时,其中的羰基硫会和氧气发生反应,生成二氧化硫和二氧化碳,2COS+3O2=2SO2+2CO2,因此需要在各车间添加脱硫塔脱除二氧化硫,但该方法占地面积大、成本高。因此,开发一种羰基硫低温水解催化剂进行前端处理,在煤气输送到各个车间前,集中脱除羰基硫,使煤气燃烧后生成的SO2直接达到排放标准,无需进一步的处理,具有非常重要的意义。H2O分子的活化是COS催化水解的关键步骤,可以通过催化剂的缺陷进行调控。氧空位作为一种内在缺陷,可以通过电子转移降低反应的能垒,从而显着提高催化效率。当在材料中引入过渡金属,可以发现过渡金属原子可以获得电子,产生更多的空轨道。这些空轨道将接受H2O分子中氧原子的孤对电子,从而促进H2O的活化。目前的羰基硫水解催化剂存在转化率差、易失活的问题,主要原因是由于水解过程中生成的硫酸盐和硫单质沉积在催化剂的表面,导致碱性活性位点减少。
发明内容
针对现有技术中存在的上述问题,本发明的目的是提供一种低温反应、转化率高、稳定性好的水解催化剂及其制备方法,有效解决了现有技术中水解催化剂反应温度高、耐硫性差等问题。
本发明限定了低温脱除煤气中羰基硫的水解催化剂的制备方法,其特征在于将载体加入到马弗炉中进行煅烧,再与活性组分混合后进行研磨,放入管式炉中焙烧,并通氮气进行保护,得到的负载活性组分的载体放在烧杯中加入助剂和水进行浸渍,浸渍后取出放入烘箱中烘干,烘干后的产物与改性剂混合研磨,N2气氛下再将其放入管式炉中焙烧,得到低温脱除煤气中羰基硫的水解催化剂。
进一步地,本发明限定了载体为CeO2,在马弗炉中的焙烧温度为300℃-600℃,焙烧时间2~7小时,制备得到含有氧空缺的CeO2载体。
进一步地,本发明限定了载体与活性组分在管式炉中于200℃~700℃下保温焙烧1~6小时。
进一步地,本发明限定了加改性剂后在管式炉中于100℃~500℃下保温焙烧1~6小时。
进一步地,本发明限定了活性组分选自Cu、Co、Ni中的至少一种,活性组分的分前驱体为Cu、Co、Ni对应的氯化物、硝酸盐或硫酸盐。
进一步地,本发明限定了活性组分前驱体选自硝酸铜、硝酸钴、硝酸镍中的至少一种。
进一步地,本发明限定了助剂包括氯化钾、氯化钠、氢氧化钾、氢氧化钠中的至少一种。
进一步地,本发明限定了改性剂选自MoS2、尿素或三聚氰胺。
进一步地,本发明限定了以重量份计,各原料的投料份数为:活性组分5~20份、助剂20~60份、改性剂2-15份、载体50-300份、水30~80份。
更进一步地,本发明还限定了由限定制备方法得到的低温脱除煤气中羰基硫的水解催化剂。
通过采用上述技术,与现有技术相比,本发明的有益效果如下:
1)本发明采用CeO2载体,在限定的条件下焙烧得到含有氧空缺的CeO2,通过EPR检测发现在g=2.001处出现对称峰,对应于氧空位中的未配对电子,证明其含有氧空缺存在时,脱硫率更高;而且以含有氧空缺的CeO2作为载体能降低脱硫反应的反应温度,从而实现低温水解催化羰基硫,同时在载体上引入活性组分能增加催化剂的活性位点,增强对酸性气体的水解;
2)本发明通过在负载活性组分的载体上浸渍碱金属盐,增加催化剂表面的含氧官能团,如羟基等,进而使酸性气体更易吸附在催化剂的表面,易于下一步的水解催化;
3)本发明提供的低温水解催化剂,将MoS2作为改性剂,解决了传统催化剂耐硫性差的问题,增强了载体和活性组分之间的相互作用,提高了水解效率;本发明所得的该水解催化剂在固定床反应器或移动床反应器中使用,即使在低温下也具有较高的脱硫效率,且连续运行100h,脱除效率仍高达95%,可以满足固定床反应器或移动床反应器连续稳定性运行;
4)本发明提供的低温水解催化剂,脱硫率高、反应条件温和,可在低温下进行水解,克服现有水解催化剂反应温度高、耐硫性差等问题,且其转化率高、稳定性好,能在固定床反应器循环使用多次,脱硫率仍在95%以上。
附图说明
图1为实施例1和实施例16的EPR图;
图2为实施例1催化剂的SEM图;
图3为实施例1催化剂的吸附等温线图;
图4为实施例1催化剂的孔径分布图;
图5为实施例1与对比例的COS转化率;
图6为实施例1的COS转化稳定性实验。
具体实施方式
下面将结合本发明实施例,对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
一种低温脱除煤气中羰基硫的水解催化剂,以重量份数记,其原料如下:活性组分硝酸钴12.5g、助剂氯化钾40g、改性剂MoS28g、载体CeO2160g,水50g;其制备方法如下:
将160gCeO2加入到马弗炉中在450℃下煅烧3h,煅烧后的CeO2与12.5g硝酸钴进行研磨,放入管式炉中在450℃下焙烧4h,通氮气进行保护,将负载后的CeO2放在烧杯中加入40g氯化钾和50g的水进行浸渍5h,浸渍后放入烘箱中在80℃下放置24h进行烘干,烘干后将其与8gMoS2混合研磨,然后再将其放入管式炉中300℃焙烧3.5h,得到低温脱除煤气中羰基硫的水解催化剂。
实施例2
一种低温脱除煤气中羰基硫的水解催化剂,以重量份数记,其原料如下:活性组分硝酸铜5g、助剂氯化钠20g、改性剂MoS2 2g、载体CeO250g,水30g;其制备方法如下:
将50CeO2加入到马弗炉中在300℃下煅烧2h,煅烧后的CeO2与5g硝酸铜进行研磨,放入管式炉中在500℃下焙烧3h,通氮气进行保护,将负载后的CeO2放在烧杯中加入20g氯化钠和30g的水进行浸渍5h,浸渍后放入烘箱中在80℃下放置24h进行烘干,烘干后将其与2gMoS2混合研磨,然后再将其放入管式炉中100℃焙烧1h,得到所述的低温脱除煤气中羰基硫的水解催化剂。
实施例3
一种低温脱除煤气中羰基硫的水解催化剂,以重量份数记,其原料如下:活性组分硝酸镍20g、助剂氢氧化钠60g、改性剂MoS215g、载体CeO2300g,水80g;其制备方法如下:
将300CeO2加入到马弗炉中在600℃下煅烧7h,煅烧后的CeO2与20g硝酸镍进行研磨,放入管式炉中在700℃下焙烧6h,通氮气进行保护,将负载后的CeO2放在烧杯中加入60g氢氧化钠和80g的水进行浸渍5h,浸渍后放入烘箱中在80℃下放置24h进行烘干,烘干后将其与15gMoS2混合研磨,然后再将其放入管式炉中500℃焙烧6h,得到所述的低温脱除煤气中羰基硫的水解催化剂。
实施例4
一种低温脱除煤气中羰基硫的水解催化剂,以重量份数记,其原料如下:活性组分硝酸钴7g、助剂氢氧化钾30g、改性剂MoS24g、载体CeO275g,水40g;其制备方法如下:
将75CeO2加入到马弗炉中在350℃下煅烧2.5h,煅烧后的CeO2与7g硝酸钴进行研磨,放入管式炉中在350℃下焙烧2h,通氮气进行保护,将负载后的CeO2放在烧杯中加入30g氢氧化钾和40g的水进行浸渍5h,浸渍后放入烘箱中在80℃下放置24h进行烘干,烘干后将其与4gMoS2混合研磨,然后再将其放入管式炉中200℃焙烧2h,得到所述的低温脱除煤气中羰基硫的水解催化剂。
实施例5
一种低温脱除煤气中羰基硫的水解催化剂,以重量份数记,其原料如下:活性组分硝酸钴15g、助剂氢氧化钾50g、改性剂MoS212g、载体CeO2250g,水60g;其制备方法如下:
将250CeO2加入到马弗炉中在550℃下煅烧6h,煅烧后的CeO2与15g硝酸钴进行研磨,放入管式炉中在600℃下焙烧5h,通氮气进行保护,将负载后的CeO2放在烧杯中加入50g氢氧化钾和60g的水进行浸渍5h,浸渍后放入烘箱中在80℃下放置24h进行烘干,烘干后将其与12gMoS2混合研磨,然后再将其放入管式炉中450℃焙烧5h,得到所述的低温脱除煤气中羰基硫的水解催化剂。
实施例6-15反应过程如实施例1,其反应原料及条件如表1所示
对比例1
根据CN113441124A实施例3制备得到催化剂C。将0.2626g(1.09mmol)三水合硝酸铜和3.6378g(12.50mmol)六水合硝酸钴加入到80mL乙二醇,300r/min搅拌1小时至完全溶解,然后向溶液中加入1.1g(27.5mmol)氢氧化钠,600r/min剧烈搅拌1小时后,加入0.5g聚乙烯吡咯烷酮(PVP)和0.5g草酸充分搅拌1小时,将混合后的溶液转移至聚四氟乙烯内衬中,置于高压釜反应装置中,180℃下反应18小时。待反应结束后冷却至室温,然后用乙醇和去离子水进行离心洗涤至上清液pH为中性,再将沉淀于烘箱中80-100℃下干燥12小时至恒重,经研磨后,将得到的固体粉末在空气气氛下350℃煅烧3小时,然后机械压片成型,过筛(40-60目),制得Cu/Co3O4催化剂,记为催化剂C。
对比例2
根据CN113578329A实施例2制备得到催化剂K3Fe5/TiAl。催化剂原料为:四氯化钛6.044mL、氨水、硝酸铝41.2643g、硝酸铁3.6172g、碳酸钾0.5316g。催化剂制备方法包括:首先,将钛-铝复合氧化物载体经煅烧以去除杂质后备用;其次,将钛-铝复合氧化物载体溶于50mL去离子水中,加入硝酸铁、碳酸钾;先在25℃磁力搅拌下以45r/s均匀搅拌2h,再升温至85℃以45r/s继续搅拌浸渍,待水分蒸干后,于105℃在烘箱中干燥12h,取出后研磨,在马弗炉中500℃煅烧5h,即可制得组分质量分数为K3Fe5/TiAl水解催化剂。
对比例3
购买四川绵阳某公司羰基硫水解催化剂。
实验例
对实施例1-22和对比例1-3中的低温水解催化剂的水解转化率进行检测,羰基硫标气采购于杭州民星气体公司,标气组分为:高炉煤气COS:300mg/m3、CO:25%、CO2:15%,其余为氮气;焦炉煤气COS:300mg/m3、H2:57%、CH4:25%、CO:8%、CO2:3%,其余为氮气;转炉煤气COS:300mg/m3、CO:60%、CO2:15%,其余为氮气。通过气相色谱进行在线检测,每间隔1小时检测一次。在固定床中进行检测,固定床装填0.2g催化剂,反应温度为50-150℃,温度间隔20℃,反应中水蒸气温度为50℃,空速为6000h-1。其中,实施例1-20为高炉煤气,实施例21为焦炉煤气,实施例22为转炉煤气,对比例1-3为高炉煤气。
η=[(C0-Ci)/C0]*100%
式中:η——COS转化率,%;
C0——COS进口浓度,mg/m3;
Ci——COS出口浓度(i=1,2,3…),mg/m3;
各指标检测结果如表1所示。
由实施例1-20的检测数据可以看出,本发明提供的低温水解催化剂,可用于固定床反应器或移动床反应器中。在低温条件下对高炉煤气中的羰基硫具有较高的转化率。由实施例1和实施例6、7,实施例2和实施例8、9,实施例3和实施例10、11的检测数据可以看出,当所使用的金属盐为硝酸盐时,具有较高的转化效率。此外,由实施例12和13,以及实施例14和15也可以看出,当使用的金属盐为多组分时,含有硝酸盐的情况下,脱硫效率更高,硝酸根的加入会在催化剂表面接枝氨基官能团,提高催化剂的碱性性能,因此较为优选的活性组分为含有硝酸根的过渡金属。由实施例1和实施例16可以看出,当使用氧空缺的二氧化铈作为载体时,具有更高的脱硫效率,此外,由实施例16和实施例17以及实施例1和实施例18可以看出,当载体存在氧空缺时,脱硫效果更高。实施例1和实施例19、20可以看出,当改性剂为MoS2时,脱硫效率更高,这是由于未添加二硫化钼导致催化剂的抗硫性能下降。由实施例1和实施例21、22对比看出,制备得到的催化剂对于高炉煤气、焦炉煤气、转炉煤气均具有优异的脱除效率。实施例1制备得到的催化剂微观形貌如图2所示,实施例1的吸附等温线和孔径分布见图3和图4,实施例1与三个对比例COS转化率的性能图,见图5,实验温度为130℃,实施例1的性能稳定图,见图6。
Claims (10)
1.低温脱除煤气中羰基硫的水解催化剂的制备方法,其特征在于将载体加入到马弗炉中进行煅烧,再与活性组分混合后进行研磨,放入管式炉中焙烧,并通氮气进行保护,得到的负载活性组分的载体放在烧杯中加入助剂和水进行浸渍,浸渍后取出放入烘箱中烘干,烘干后的产物与改性剂混合研磨,N2气氛下再将其放入管式炉中焙烧,得到低温脱除煤气中羰基硫的水解催化剂。
2.根据权利要求1所述的低温脱除煤气中羰基硫的水解催化剂的制备方法,其特征在于载体为CeO2,在马弗炉中的焙烧温度为300℃-600℃,焙烧时间2~7小时,制备得到含有氧空缺的CeO2载体。
3.根据权利要求1所述的低温脱除煤气中羰基硫的水解催化剂的制备方法,其特征在于载体与活性组分在管式炉中于200℃~700℃下保温焙烧1~6小时。
4.根据权利要求1所述的低温脱除煤气中羰基硫的水解催化剂的制备方法,其特征在于加改性剂后在管式炉中于100℃~500℃下保温焙烧1~6小时。
5.根据权利要求1所述的低温脱除煤气中羰基硫的水解催化剂的制备方法,其特征在于活性组分选自Cu、Co、Ni中的至少一种,活性组分的分前驱体为Cu、Co、Ni对应的氯化物、硝酸盐或硫酸盐。
6.根据权利要求1所述的低温脱除煤气中羰基硫的水解催化剂的制备方法,其特征在于活性组分前驱体选自硝酸铜、硝酸钴、硝酸镍中的至少一种。
7.根据权利要求1所述的低温脱除煤气中羰基硫的水解催化剂的制备方法,其特征在于助剂包括氯化钾、氯化钠、氢氧化钾、氢氧化钠中的至少一种。
8.根据权利要求1所述的低温脱除煤气中羰基硫的水解催化剂的制备方法,其特征在于改性剂选自MoS2、尿素或三聚氰胺。
9.根据权利要求1-8任一所述的低温脱除煤气中羰基硫的水解催化剂的制备方法,其特征在于以重量份计,各原料的投料份数为:活性组分5~20份、助剂20~60份、改性剂2-15份、载体50-300份、水30~80份。
10.一种根据权利要求1所述的制备方法得到的低温脱除煤气中羰基硫的水解催化剂。
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CN116099354A (zh) * | 2023-02-10 | 2023-05-12 | 昆明理工大学 | 一种球形氧化铈催化剂在低温催化水解有机污染物中的应用 |
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CN116099354A (zh) * | 2023-02-10 | 2023-05-12 | 昆明理工大学 | 一种球形氧化铈催化剂在低温催化水解有机污染物中的应用 |
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