CN109233895B - 一种液化石油气氧化脱硫剂的制备方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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Abstract
本发明公开了一种液化石油气氧化脱硫剂的制备方法,涉及石油化工技术领域。本发明脱硫剂的制备包括硅胶的活化、硅胶的改性、硅胶的负载;α‑羟基酸和硅烷偶联剂可以提升硅胶对液化石油气的亲和能力以及对极性物质的吸附能力;在助剂的催化作用下,负载在硅胶上的氧化剂能快速、高效的将液化石油气中的含硫物质氧化成极性氧化物,从而被硅胶吸附;本发明采用改性硅胶作为脱硫剂,不涉及有机溶剂,操作简单、环保、除硫效果显著,同时吸附后的硅胶可循环使用,成本低,适合工业化生产。
Description
技术领域:
本发明涉及石油化工技术领域,具体涉及一种液化石油气氧化脱硫剂的制备方法。
背景技术:
石油炼制过程中来自催化裂化、延迟焦化等装置的液化石油气,含有大量硫化物,除H2S外,还含有各种形态的硫,如CH3SH、C2H5SH、CH3SCH3等,其中主要为CH3SH。硫化物臭味较大,而且具有很强的腐蚀性,作为燃料燃烧时,硫化物会产生SOX排入大气,形成酸雨,对环境造成严重污染。
液化石油气产品硫含量一般限制在343mg/m3以下,液化石油气脱硫精制主要采用加氢精制方法,该方法要求使用催化剂、氢气、高温高压,并且对设备要求严格,限制了小规模炼厂的使用。Merox抽提氧化法则首先通过MDEA(N-甲基二乙醇胺)抽提塔脱除H2S,再用10%NaOH溶液脱除残余H2S,然后用溶解了磺化酞菁钴催化剂的碱液脱除硫醇,碱液再生循环使用。该工艺的缺点是酞菁钴催化剂容易失活,需频繁更换催化剂,过程中使用了苛性碱加重了环保压力,后来该技术经过改进,用氨水代替苛性碱,但相应地增加气体装置,而且由于氨水碱性弱,有些有机硫化物难于完全脱除。上述技术的氧化脱硫选择性及脱硫深度仍可以进一步提高。
发明内容:
本发明所要解决的技术问题在于提供一种环保无溶剂、操作简单、除硫效果显著的液化石油气脱硫剂的制备方法。
本发明所要解决的技术问题采用以下的技术方案来实现:
一种液化石油气氧化脱硫剂的制备方法,包括以下步骤:
(1)硅胶的活化:将硝酸加入到硅胶中,加热回流5h,冷却后用蒸馏水洗至中性,密封放置,再用6N盐酸于室温浸泡24h,再用蒸馏水洗至中性,再将处理过的硅胶至于马沸炉中120℃干燥10h,得到活化硅胶;
(2)硅胶的改性:将活化硅胶加入到无水乙醇中,加热至回流状态,保温搅拌10-30min,然后添加α-羟基酸和硅烷偶联剂,回流搅拌0.5-2h,自然冷却至室温,过滤,所得硅胶加入碳酸钠搅拌均匀后,密封于0-5℃静置0.5-2h,即得到改性硅胶;
(3)硅胶的负载:将改性后的硅胶加入到去离子水中,加入助剂、高氯酸钠、次氯酸钾和氧化铜,回流搅拌0.5-4h,冷却至30-35℃过滤,所得固体送入100-110℃烘干箱中,干燥至恒重,即得到催化剂。
所述硅胶、硝酸、α-羟基酸、硅烷偶联剂、助剂、高氯酸钠、次氯酸钾、氧化铜的质量比为30-40:30-40:5-10:5-10:1-5:1-5:1-3:1-3。
所述助剂的制备方法为:将聚天门冬氨酸加入到去离子水中,40℃搅拌10-20min,然后加入聚乙烯醇和钛酸四乙酯,加热至回流状态,保温搅拌0.5-2h,然后加入蓖麻油70-75℃搅拌30-50min,趁热过滤,所得固体用去离子水洗去杂质,50℃真空干燥至恒重。
所述聚天门冬氨酸、聚乙烯醇、钛酸四乙酯、蓖麻油的质量比为5-10:5-10:00.5-0.1:1-3。
所述聚乙烯醇的分子量为20000-50000,醇解度为78%。
α-羟基酸和硅烷偶联剂可以通过化学键连接在硅胶上,提升了硅胶对液化石油气的亲和能力以及对极性物质的吸附能力,同时通过助剂的催化作用能将高氯酸钠、次氯酸钾和氧化铜高效的负载在硅胶上,进而可以把液化石油气中的含硫醚转化成砜或亚砜类物质,把硫醇转化成磺酸,把H2S转化成SO42-,生成的极性氧化产物被硅胶所吸附,从而达到深度脱硫的目的,吸附后的硅胶通过高温活化,即可重新使用。该脱硫过程不涉及反应溶剂,高效环保,所得液化石油气纯度高。
脱硫反应在10-30℃进行,反应时间为2-5h,硫化物被氧化成砜和亚砜类物质,通过分离得到脱硫液化石油气。上述液化石油气的体积以液体体积计。反应控制在使液化石油气为液相的压力下进行,氧化脱硫后可以采用减压气化的方式分离脱硫液化石油气,也可以通过静止分层的方式分离脱硫液化石油气。
本发明的有益效果是:
(1)α-羟基酸和硅烷偶联剂可以通过化学键连接在硅胶上,提升了硅胶对液化石油气的亲和能力以及对极性物质的吸附能力;同时对于液化石油气中的水分和无机杂质也有很强的吸收效果;
(2)在助剂的催化作用下,负载在硅胶上的氧化剂能快速、高效的将液化石油气中的含硫物质氧化成极性氧化物,从而被硅胶吸附;
(3)本发明采用改性硅胶作为脱硫剂,不涉及有机溶剂,操作简单、环保、除硫效果显著,同时吸附后的硅胶可通过高温活化继续使用,成本低,适合工业化生产。
具体实施方式:
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施例,进一步阐述本发明。
实施例1
脱硫剂的制备:
(1)硅胶的活化:将30份硝酸加入到30份硅胶中,加热回流5h,冷却后用蒸馏水洗至中性,密封放置,再用6N盐酸于室温浸泡24h,再用蒸馏水洗至中性,再将处理过的硅胶至于马沸炉中120℃干燥10h,得到活化硅胶;
(2)硅胶的改性:将活化硅胶加入到无水乙醇中,加热至回流状态,保温搅拌10-30min,然后添加6份乙醇酸和6份硅烷偶联剂,回流搅拌2h,自然冷却至室温,过滤,所得硅胶加入硅胶质量3%的碳酸钠搅拌均匀后,密封于3℃静置2h,即得到改性硅胶;
(3)硅胶的负载:将改性后的硅胶加入到去离子水中,加入4份助剂、3份高氯酸钠、2份次氯酸钾和1份氧化铜,回流搅拌0.5-4h,冷却至30-35℃过滤,所得固体送入100-110℃烘干箱中,干燥至恒重,即得到催化剂。
助剂的制备:将6份聚天门冬氨酸加入到去离子水中,40℃搅拌10min,然后加入6份聚乙烯醇和00.8份钛酸四乙酯,加热至回流状态,保温搅拌1h,然后加入2份蓖麻油70℃搅拌30min,趁热过滤,所得固体用去离子水洗去杂质,50℃真空干燥至恒重。
实施例2
脱硫剂的制备:
(1)硅胶的活化:将35份硝酸加入到35份硅胶中,加热回流5h,冷却后用蒸馏水洗至中性,密封放置,再用6N盐酸于室温浸泡24h,再用蒸馏水洗至中性,再将处理过的硅胶至于马沸炉中120℃干燥10h,得到活化硅胶;
(2)硅胶的改性:将活化硅胶加入到无水乙醇中,加热至回流状态,保温搅拌10-30min,然后添加6份乙醇酸和6份硅烷偶联剂,回流搅拌2h,自然冷却至室温,过滤,所得硅胶加入硅胶质量3%的碳酸钠搅拌均匀后,密封于3℃静置2h,即得到改性硅胶;
(3)硅胶的负载:将改性后的硅胶加入到去离子水中,加入4份助剂、3份高氯酸钠、2份次氯酸钾和1份氧化铜,回流搅拌0.5-4h,冷却至30-35℃过滤,所得固体送入100-110℃烘干箱中,干燥至恒重,即得到催化剂。
助剂的制备:将6份聚天门冬氨酸加入到去离子水中,40℃搅拌10min,然后加入6份聚乙烯醇和00.8份钛酸四乙酯,加热至回流状态,保温搅拌1h,然后加入2份蓖麻油70℃搅拌30min,趁热过滤,所得固体用去离子水洗去杂质,50℃真空干燥至恒重。
对照例1
脱硫剂的制备:
(1)硅胶的活化:将30份硝酸加入到30份硅胶中,加热回流5h,冷却后用蒸馏水洗至中性,密封放置,再用6N盐酸于室温浸泡24h,再用蒸馏水洗至中性,再将处理过的硅胶至于马沸炉中120℃干燥10h,得到活化硅胶;
(2)硅胶的改性:将活化硅胶加入到无水乙醇中,加热至回流状态,保温搅拌10-30min,然后添加6份硅烷偶联剂,回流搅拌2h,自然冷却至室温,过滤,所得硅胶加入硅胶质量3%的碳酸钠搅拌均匀后,密封于3℃静置2h,即得到改性硅胶;
(3)硅胶的负载:将改性后的硅胶加入到去离子水中,加入4份助剂、3份高氯酸钠、2份次氯酸钾和1份氧化铜,回流搅拌0.5-4h,冷却至30-35℃过滤,所得固体送入100-110℃烘干箱中,干燥至恒重,即得到催化剂。
助剂的制备:将6份聚天门冬氨酸加入到去离子水中,40℃搅拌10min,然后加入6份聚乙烯醇和00.8份钛酸四乙酯,加热至回流状态,保温搅拌1h,然后加入2份蓖麻油70℃搅拌30min,趁热过滤,所得固体用去离子水洗去杂质,50℃真空干燥至恒重。
对照例2
脱硫剂的制备:
(1)硅胶的活化:将30份硝酸加入到30份硅胶中,加热回流5h,冷却后用蒸馏水洗至中性,密封放置,再用6N盐酸于室温浸泡24h,再用蒸馏水洗至中性,再将处理过的硅胶至于马沸炉中120℃干燥10h,得到活化硅胶;
(2)硅胶的改性:将活化硅胶加入到无水乙醇中,加热至回流状态,保温搅拌10-30min,然后添加6份乙醇酸,回流搅拌2h,自然冷却至室温,过滤,所得硅胶加入硅胶质量3%的碳酸钠搅拌均匀后,密封于3℃静置2h,即得到改性硅胶;
(3)硅胶的负载:将改性后的硅胶加入到去离子水中,加入4份助剂、3份高氯酸钠、2份次氯酸钾和1份氧化铜,回流搅拌0.5-4h,冷却至30-35℃过滤,所得固体送入100-110℃烘干箱中,干燥至恒重,即得到催化剂。
助剂的制备:将6份聚天门冬氨酸加入到去离子水中,40℃搅拌10min,然后加入6份聚乙烯醇和00.8份钛酸四乙酯,加热至回流状态,保温搅拌1h,然后加入2份蓖麻油70℃搅拌30min,趁热过滤,所得固体用去离子水洗去杂质,50℃真空干燥至恒重。
对照例3
脱硫剂的制备:
(1)硅胶的活化:将30份硝酸加入到30份硅胶中,加热回流5h,冷却后用蒸馏水洗至中性,密封放置,再用6N盐酸于室温浸泡24h,再用蒸馏水洗至中性,再将处理过的硅胶至于马沸炉中120℃干燥10h,得到活化硅胶;
(2)硅胶的改性:将活化硅胶加入到无水乙醇中,加热至回流状态,保温搅拌10-30min,然后添加6份乙醇酸和6份硅烷偶联剂,回流搅拌2h,自然冷却至室温,过滤,所得硅胶加入硅胶质量3%的碳酸钠搅拌均匀后,密封于3℃静置2h,即得到改性硅胶;
(3)硅胶的负载:将改性后的硅胶加入到去离子水中,加入4份助剂、3份高氯酸钠、2份次氯酸钾和1份氧化铜,回流搅拌0.5-4h,冷却至30-35℃过滤,所得固体送入100-110℃烘干箱中,干燥至恒重,即得到催化剂。
助剂的制备:将6份聚天门冬氨酸加入到去离子水中,40℃搅拌10min,然后加入6份聚乙烯醇和00.8份钛酸四乙酯,加热至回流状态,保温搅拌1h,然后70℃搅拌30min,趁热过滤,所得固体用去离子水洗去杂质,50℃真空干燥至恒重。
对照例4
脱硫剂的制备:
(1)硅胶的活化:将30份硝酸加入到30份硅胶中,加热回流5h,冷却后用蒸馏水洗至中性,密封放置,再用6N盐酸于室温浸泡24h,再用蒸馏水洗至中性,再将处理过的硅胶至于马沸炉中120℃干燥10h,得到活化硅胶;
(2)硅胶的改性:将活化硅胶加入到无水乙醇中,加热至回流状态,保温搅拌10-30min,然后添加6份乙醇酸和6份硅烷偶联剂,回流搅拌2h,自然冷却至室温,过滤,所得硅胶加入硅胶质量3%的碳酸钠搅拌均匀后,密封于3℃静置2h,即得到改性硅胶;
(3)硅胶的负载:将改性后的硅胶加入到去离子水中,加入3份高氯酸钠、2份次氯酸钾和1份氧化铜,回流搅拌0.5-4h,冷却至30-35℃过滤,所得固体送入100-110℃烘干箱中,干燥至恒重,即得到催化剂。
实施例3
以实施例1为基础,设置不添加乙醇酸的对照例1、不添加硅烷偶联剂的对照例2、不添加蓖麻油的对照例3、不添加助剂的对照例4。
利用实施例1-2、对照例1-4进行液化石油气的脱硫,并对相关数据进行检测,结果如表1所示。
脱硫方法:在500毫升不锈钢密闭容器中,事先加入脱硫剂,在加压状态下注入硫含量1120mg/m3液化石油气100毫升(以液相体积计),容器密闭好后,在20℃下振荡反应4小时,减压放出精制脱硫后的液化石油气,液化石油气脱硫率超过90%。
表1液化石油气脱硫性能的测试
组别 | 脱硫剂质量,g | 脱硫后的硫含量,mg/m<sup>3</sup> | 脱硫率,% |
实施例1 | 10 | 29 | 97.4 |
实施例2 | 15 | 27 | 97.6 |
对照例1 | 10 | 49 | 95.6 |
对照例2 | 10 | 48 | 95.7 |
对照例3 | 10 | 35 | 96.9 |
对照例4 | 10 | 61 | 94.5 |
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (2)
1.一种液化石油气氧化脱硫剂的制备方法,其特征在于,包括以下步骤:
(1)硅胶的活化:将硝酸加入到硅胶中,加热回流5h,冷却后用蒸馏水洗至中性,密封放置,再用6N盐酸于室温浸泡24h,再用蒸馏水洗至中性,再将处理过的硅胶至于马沸炉中120℃干燥10h,得到活化硅胶;
(2)硅胶的改性:将活化硅胶加入到无水乙醇中,加热至回流状态,保温搅拌10-30min,然后添加α-羟基酸和硅烷偶联剂,回流搅拌0.5-2h,自然冷却至室温,过滤,所得硅胶加入碳酸钠搅拌均匀后,密封于0-5℃静置0.5-2h,即得到改性硅胶;
(3)硅胶的负载:将改性后的硅胶加入到去离子水中,加入助剂、高氯酸钠、次氯酸钾和氧化铜,回流搅拌0.5-4h,冷却至30-35℃过滤,所得固体送入100-110℃烘干箱中,干燥至恒重,即得到催化剂;
所述助剂的制备方法为:将聚天门冬氨酸加入到去离子水中,40℃搅拌10-20min,然后加入聚乙烯醇和钛酸四乙酯,加热至回流状态,保温搅拌0.5-2h,然后加入蓖麻油70-75℃搅拌30-50min,趁热过滤,所得固体用去离子水洗去杂质,50℃真空干燥至恒重;其中,聚天门冬氨酸、聚乙烯醇、钛酸四乙酯、蓖麻油的质量比为5-10:5-10:0.5-0.1:1-3。
2.根据权利要求1所述的液化石油气氧化脱硫剂的制备方法,其特征在于:所述硅胶、硝酸、α-羟基酸、硅烷偶联剂、助剂、高氯酸钠、次氯酸钾、氧化铜的质量比为30-40:30-40:5-10:5-10:1-5:1-5:1-3:1-3。
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