CN112642443A - 一种失活加氢精制催化剂的再生方法 - Google Patents
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Abstract
本发明公开了一种失活加氢精制催化剂的再生方法,包括:将失活加氢催化剂与酸性有机试剂、有机分散剂混合,依次采用干馏、烧炭处理对失活加氢催化剂进行再生;再生后的加氢催化剂降温至80℃~120℃,将其浸渍在络合剂溶液中;所述的络合剂溶液由柠檬酸、环己二胺四乙酸和磷酸铵配制而成的络合剂溶液;经过步骤(2)浸渍处理的加氢催化剂在130℃~220℃下处理1h~15h,获得活性恢复的加氢催化剂。所述的加氢精制催化剂为KF‑848催化剂。本发明将失活加氢催化剂的再生和活性恢复结合,使二类活性中心加氢催化剂的活性得到恢复,相比单一络合剂,本发明复合络合剂处理催化剂,使得再生催化剂具有更高的加氢脱硫、脱氮活性。
Description
技术领域
本发明涉及一种失活加氢精制催化剂的再生方法。
背景技术
石油和化学工业是当代社会最基本、最大的三大支柱产业之一(还有能源和材料、信息),它与能源和材料工业关系密切。石油化学工业的发展离不开催化剂,许多重要的石油化工过程,若不用催化剂,其化学反应速度非常慢,或根本无法进行工业生产。据估计,现代燃料工业和化学工业的生产,有80%以上采用催化过程。
由于世界上几乎每个炼厂都有加氢装置,加氢过程必须得使用大量各种各样的催化剂。加氢催化剂在使用前活性金属组分为氧化态,氧化态催化剂在工业使用前,其活性金属需转化为硫化态才具有较高的催化活性。随着催化剂长时间的运转,加氢催化剂存在着失活现象。加氢催化剂的失活机理分中毒、结焦及烧结三类。结焦是在催化剂表面形成炭质,覆盖在活性中心上,大量的结焦导致孔堵塞,阻止反应物分子进入孔内活性中心;碱性氮诸如吡啶类化合物化学吸附在酸性中心上,不仅使催化剂失去活性而且堵塞孔口及内孔道;烧结则使催化剂结构发生变化而丧失活性中心,对于加氢催化剂是指金属聚集或晶体变大。结焦和杂质化学吸附造成的酸碱中和均属于暂时性中毒,在这种情况下,失活是可逆的,可以再生,对于比较昂贵的催化剂来说,三五年更换一次显然是不合适的,因此炼化企业纷纷选择再生的方式来降低加工成本,这就为催化剂的再生提供了广阔的市场。目前,我国各种加氢装置的总加工能力已达6000万t/年,其中加氢裂化(包括渣油加氢裂化)的加工能力也高达1800万t/年。如果满负荷开工,每年需要再生的催化剂约1500-2000t,因此提高催化剂再生规模是当务之急。
催化剂再生有两种方式,一是催化剂器内再生,即催化剂在原装置反应器内进行。发达国家常不采用这种再生方式,而是采用另外一种再生方式—催化剂器外再生,即把催化剂卸出,在另外的专用设备中去再生和预处理。这样不仅可延长加氢装置的开工周期,而且还可通过催化剂过筛,降低床层压降;器外再生还可以做到精心操作,减少催化剂活性损失,可以对催化剂再生、预处理产生的污染集中处理。
申请人在中国专利申请CN 109465036 A公开了一种加氢催化剂活性恢复方法,对以氧化铝为载体,以Mo-Ni为活性组分,以柠檬酸为有机助剂,以MoO3计Mo的含量为24%,以NiO计Ni的含量为3.0%,柠檬酸的含量为3%的失活加氢催化剂F-4进行再生,能有效恢复催化剂的活性,催化剂活性也有一定的提高。但是申请人将该加氢催化剂活性恢复方法(实施例1-实施例4)用于失活KF-848催化剂的再生,按照CN106475114A实施例1的方法进行KF-848再生催化剂活性评价,精制油硫含量和氮含量均偏高。因此,亟需改进加氢催化剂活性恢复方法。
发明内容
本发明的目的在于针对现有技术的不足,本发明提供一种失活加氢催化剂的再生方法,该方法采用“浸渍+高温烘干”的组合方法对失活加氢催化剂进行再生。
本发明的目的是通过以下技术方案实现的:
一种失活加氢精制催化剂的再生方法,包括以下步骤:
步骤(1)、将失活加氢催化剂与酸性有机试剂、有机分散剂混合,依次采用干馏、烧炭处理对失活加氢催化剂进行再生;
步骤(2)、再生后的加氢催化剂降温至80℃~120℃,将其浸渍在络合剂溶液中;所述的络合剂溶液由柠檬酸、环己二胺四乙酸和磷酸铵配制而成的络合剂溶液;
步骤(3)、经过步骤(2)浸渍处理的加氢催化剂在130℃~220℃下处理1h~15h,获得活性恢复的加氢催化剂。
所述的加氢精制催化剂为KF-848催化剂,KF-848催化剂是以Ni-Mo为活性金属、以氧化铝为载体的加氢催化剂,同时具有加氢脱氮活性,可以用来生产硫质量分数为10~50μg/g的低硫含量柴油。
步骤(1)中,所述的酸性有机试剂一般为巯基乙酸、巯基丙酸、二甲基亚砜、氨基壬酸、氨基乙酸、柠檬酸、乙二醇、丙三醇、四甘醇中的一种或几种;优选为柠檬酸。
所述的酸性有机试剂的用量一般为失活加氢精制催化剂重量的1%~3%。
所述的有机分散剂一般为棕榈油、豆油中的至少一种。
所述的有机分散剂用量为失活加氢精制催化剂重量的5%~20%。
所述的干馏为在氮气气氛下的热处理,加热处理条件为在150~200℃下处理3~6小时。
所述的烧炭处理采用控制烧炭温度和氧气含量的阶段性再生方法,首先浅度烧炭250℃~280℃,恒温3h~6h,控制氧气含量(体积分数)不超过10%;然后烧炭升至350℃~380℃,恒温2h~4h,控制氧气含量在15%~21%;最后深度烧炭450℃~550℃,恒温4h~8h,控制氧气含量在25%~30%。
步骤(2)中,所述的络合剂溶液是由柠檬酸、环己二胺四乙酸、磷酸铵和水按照质量比为3.5~5:0.1~0.5:1~3:50配制而成的。
所述的络合剂用量为失活加氢精制催化剂重量的4%~5%。
步骤(3)中,经过浸渍处理的加氢精制催化剂在空气气氛、贫氧空气气氛、惰性气体气氛或水蒸汽气氛等条件下130℃~220℃下处理1~15小时。
和现有技术相比,本发明的有益效果:
1、本发明先通过酸性有机试剂浸渍失活加氢精制催化剂,使失活加氢精制催化剂中的碱性大分子团与酸性中心吸附作用力减弱,并起到络合剂作用,对形成二类活性中心的活性金属形成保护;同时,烧炭前的干馏,很好的脱除分散剂和残留的烃类物质,避免再生过程中的急剧放热现象。
2、本发明通过有机分散剂浸渍失活精制加氢催化剂,与加氢精制催化剂微孔道中残留的烃类物质达到相似相容的作用,避免残留在加氢精制催化剂孔道内的烃类物质向加氢精制催化剂金属活性中心扩散形成屏蔽层,确保酸性有机试剂扩散到孔道内部的金属活性中心,更有利于孔道内部的加氢精制催化剂的二类活性中心活性恢复。
3、将烧炭再生过程分为三阶段,能够很好的控制烧炭过程:较多小分子团的含碳化合物在低温低氧的浅度烧炭过程中脱除;较少大分子团且难烧掉的含碳化合物在高温高氧含量的过程中脱除;通过控制不同阶段的氧含量,能让烧除物充分脱除,同时还能避免在再生过程中的急剧放热现象,避免金属聚集。
4、本发明将再生后的催化剂浸渍在复合络合剂溶液进行处理,络合剂和活性金属发生相互作用,从而改变了浸渍液和催化剂的物化性质,减弱了活性金属和载体间的相互作用,并使硫化过程发生改变,使活性相的结构和形态发生变化,最终形成更多的活性中心,提高了催化剂的加氢活性。具体表现为:柠檬酸与金属物种形成的络合物有助于调节Ni与Mo物种的硫化速率,同时,在硫化过程中部分柠檬酸转化为碳物种保留在催化剂上,这些碳物种的存在一方面可修饰载体表面,促进金属物种硫化,另一方面有利于形成尺寸较小的高活性NiMoSⅡ类活性相;环己二胺四乙酸和磷酸铵可协同降低活性金属和载体间的相互作用,有利于形成更多的二类活性相,同时又恢复催化剂的比表面积和孔容。相比单一络合剂,本发明复合络合剂处理催化剂,使得再生催化剂具有更高的加氢脱硫、脱氮活性。
5、本发明将失活加氢催化剂的再生和活性恢复结合,使二类活性中心加氢催化剂的活性得到恢复,甚至优于新鲜剂,同时还降低了能耗,减少生产成本,缩短生产周期。
具体实施方式
下面通过具体实施方式对本发明的技术方案作进一步说明。
实施例1
取失活KF-848催化剂200克,浸渍于2克柠檬酸与40克豆油的混合有机溶液中。在氮气气氛中,180℃下干馏4小时。再进行烧炭处理:升至260℃,恒温3h,控制氧气含量(体积分数)在8%;再升至350℃,恒温4h,控制氧气含量在15%~20%;再升至470℃,恒温6h,控制氧气含量在25%~30%。烧炭结束后,降温至130℃。经过烧炭处理后的加氢催化剂KF-848浸渍在复合络合剂溶液(由8g柠檬酸、0.1g环己二胺四乙酸、1g磷酸铵和50g水配制而成)中,在空气气氛下升温至180℃时,恒温4小时,降至室温,获得活性恢复的加氢催化剂KF-848。
表1、实施例1中KF-848催化剂指标对比情况
实施例2
取失活KF-848催化剂200克,浸渍于2.6克柠檬酸与40克豆油的混合有机溶液中。在氮气气氛中,190℃下干馏4小时。再进行烧炭处理:升至260℃,恒温3h,控制氧气含量在8%;再升至360℃,恒温4h,控制氧气含量在15%~20%;再升至490℃,恒温6h,控制氧气含量在25%~30%。烧炭结束后,降温至130℃。经过烧炭处理后的加氢催化剂KF-848浸渍在络合剂溶液(由7g柠檬酸、0.1g环己二胺四乙酸、1.5g磷酸铵和50g水配制而成)中,在空气气氛下升温至200℃时,恒温4小时,降至室温,获得活性恢复的加氢催化剂KF-848。
实施例3
取失活KF-848催化剂200克,浸渍于6克柠檬酸与36克棕榈油的混合有机溶液中。在氮气气氛中,180℃下干馏3小时。再进行烧炭处理:升至260℃,恒温3h,控制氧气含量在8%;再升至350℃,恒温4h,控制氧气含量在15%~20%;再升至470℃,恒温6h,控制氧气含量在25%~30%。烧炭结束后,降温至130℃。经过烧炭处理后的加氢催化剂KF-848浸渍降在络合剂溶液(由6g柠檬酸、0.1g环己二胺四乙酸、2g磷酸铵和50g水配制而成)中,在空气气氛下升温至210℃时,恒温4小时,降至室温,获得活性恢复的加氢催化剂KF-848。
对比例1
取失活KF-848催化剂200克,浸渍于2克柠檬酸与40克豆油的混合有机溶液中。在氮气气氛中,180℃下干馏4小时。再进行烧炭处理:升至260℃,恒温3h,控制氧气含量(体积分数)在8%;再升至350℃,恒温4h,控制氧气含量在15%~20%;再升至470℃,恒温6h,控制氧气含量在25%~30%。烧炭结束后,降温至130℃。经过烧炭处理后的加氢催化剂KF-848浸渍在络合剂溶液(由8g柠檬酸和50g水配制而成)中,在空气气氛下升温至180℃时,恒温4小时,降至室温,获得活性恢复的加氢催化剂KF-848。
分别取实施例1、对比例1再生催化剂KF-848以及新鲜加氢精制催化剂KF-848,由抚顺石油化工研究院通过两个工艺条件对催化剂进行了活性评价,详细内容如下。
所用的原料油性质见表2。
表2、原料油的性质
原料油 | |
密度(20℃),g.cm<sup>-3</sup> | 0.8598 |
链烷烃 | 42.8 |
环烷烃 | 29.5 |
芳烃 | 27.7 |
馏程(IBP/EBP),℃ | 188/376 |
碳/氢,% | 86.45/12.75 |
硫,μg.g<sup>-1</sup> | 14687 |
氮,μg.g<sup>-1</sup> | 359 |
表3、实施例1再生KF-848催化剂活性指标
表4、新鲜加氢精制催化剂KF-848活性指标
表5、对比例1再生KF-848催化剂活性指标
通过实施例1再生KF-848催化剂和新鲜催化剂比较可知,失活加氢催化剂KF-848经本发明加氢催化剂活性恢复方法处理后能有效恢复催化剂的活性,达到新鲜催化剂活性水平;且与使用单一络合剂相比,本发明使用复合络合剂得到的再生催化剂具有更高的加氢脱硫、脱氮活性。
Claims (8)
1.一种失活加氢精制催化剂的再生方法,其特征在于包括以下步骤:
步骤(1)、将失活加氢催化剂与酸性有机试剂、有机分散剂混合,依次采用干馏、烧炭处理对失活加氢催化剂进行再生;
步骤(2)、再生后的加氢催化剂降温至80℃~120℃,将其浸渍在络合剂溶液中;所述的络合剂溶液由柠檬酸、环己二胺四乙酸和磷酸铵配制而成的络合剂溶液;
步骤(3)、经过步骤(2)浸渍处理的加氢催化剂在130℃~220℃下处理1h~15h,获得活性恢复的加氢催化剂。
2.根据权利要求1所述的失活加氢精制催化剂的再生方法,其特征在于所述的加氢精制催化剂为KF-848催化剂。
3.根据权利要求1所述的失活加氢精制催化剂的再生方法,其特征在于步骤(1)中,所述的酸性有机试剂为巯基乙酸、巯基丙酸、二甲基亚砜、氨基壬酸、氨基乙酸、柠檬酸、乙二醇、丙三醇、四甘醇中的一种或几种;所述的有机分散剂为棕榈油、豆油中的至少一种。
4.根据权利要求1所述的失活加氢精制催化剂的再生方法,其特征在于步骤(1)中,所述的酸性有机试剂的用量为失活加氢精制催化剂重量的1%~3%;所述的有机分散剂用量为失活加氢精制催化剂重量的5%~20%。
5.根据权利要求1所述的失活加氢精制催化剂的再生方法,其特征在于步骤(1)中,所述的干馏为在氮气气氛下的热处理,加热处理条件为在150~200℃下处理3~6小时。
6.根据权利要求1所述的失活加氢精制催化剂的再生方法,其特征在于步骤(1)中,所述的烧炭处理采用控制烧炭温度和氧气含量的阶段性再生方法,首先浅度烧炭250℃~280℃,恒温3h~6h,控制氧气含量(体积分数)不超过10%;然后烧炭升至350℃~380℃,恒温2h~4h,控制氧气含量在15%~21%;最后深度烧炭450℃~550℃,恒温4h~8h,控制氧气含量在25%~30%。
7.根据权利要求1所述的失活加氢精制催化剂的再生方法,其特征在于步骤(2)中,所述的络合剂溶液是由柠檬酸、环己二胺四乙酸、磷酸铵和水按照质量比为3.5~5:0.1~0.5:1~3:50配制而成的。
8.根据权利要求1所述的失活加氢精制催化剂的再生方法,其特征在于步骤(2)中,所述的络合剂用量为失活加氢精制催化剂重量的4%~5%。
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CN111250100B (zh) * | 2020-02-25 | 2023-08-25 | 山东科技大学 | 一种合成气耐硫变换脱氧催化剂及其制备方法 |
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