CN115318275A - 一种催化裂化烟气处理三效助剂的制备方法 - Google Patents
一种催化裂化烟气处理三效助剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种催化裂化烟气处理三效助剂的制备方法，将拟薄水铝石先酸化处理，然后与含有氯化镁、氯化铈、草酸钒的混合溶液混合。将混合溶液与碱溶液反应，反应结束后升温晶化，造粒成球、焙烧，得到类水滑石型催化裂化三效助剂。该助剂具有较好的耐磨损性能，能够满足催化裂化装置的使用要求，同时具有较好的脱硫、脱硝和助燃效果。
Description
技术领域：
本发明涉及一种催化裂化烟气处理三效助剂的制备方法，属于催化裂化助剂领域。
背景技术：
催化裂化是石油炼制的重要二次加工工艺，在带来经济效益的同时也带来了SOx、NOx以及CO的大量排放，腐蚀设备、污染环境。相比于采用操作成本较高的烟气洗涤法来脱除SOx、NOx，使用助剂要比烟气洗涤更具优越性，助剂在FCC催化剂再生过程中捕获再生烟气中的SOx和NOx，在减少SOx和NOx排放的同时，也降低了再生烟气的酸露点，从而减少了对再生器的腐蚀。
专利CN109453783A公开了一种催化裂化再生烟气脱硫催化剂的制备方法，首先将镁盐、铝盐制备成镁铝尖晶石，然后将镁盐、铝盐、锰盐制备成类水滑石；在将两者与粘结剂混合制备成烟气脱硫剂。该助剂具有较高的SOx脱除率和较好的再生性能。
专利CN110124684公开了一种高效低温脱硝催化剂的制备方法，首先将Co和Al共沉淀，形成类水滑石载体，然后负责氧化锰，该脱硝助剂在150～350℃范围内的脱硝效率超过90％以上，具有较好的稳定性以及抗硫性。
专利CN1411908公开了一种在富氧完全燃烧式再生系统使用的助燃CO、脱除NOX和增加轻质油收率的三效助剂，其特征是氧化铝负载铜铝-铈铝复合氧化物。
专利CN106190430A公开了一种脱硫脱硝助燃剂的制备方法。由菜籽饼、炭铵、酸化煤矸石、硝酸钠、高锰酸钾、硫酸铝等多种原材料制备。能够使得燃烧后的烟气中SO2及氮氧化物(NOx)的脱除率均达到80％以上，烟尘能降低70％以上，清焦、缓蚀的效果均能达到90％以上。
专利CN108048157A公开了一种除硫脱硝助燃剂，主要由碳酰二胺、次氯酸钾、二氧化钛、铁粉、氧化钙等多种原材料复合加工制成。具有除硫、除硝、固碳等多种功能。
通过对现有专利检索发现，目前利用助剂来脱除FCC再生烟气中的SOx、NOx和CO，也存在一些问题；(1)助剂功能单一，要脱除再生烟气中的SOx、NOx和CO需要同时加入脱SOx剂、脱NOx剂和CO助燃剂，需要助剂品种多、加注量大，很大程度上稀释了主剂的效果：(2)多种主剂之间可能会相互干扰，一种助剂的使用可能会导致另一种排放物的增加。因此开发一种能同时降低催化裂化再生烟气多种污染物的多效助剂对降低FCC再生烟气污染物排放、减少助剂种类和用量具有重要意义。
发明内容：
为解决现有催化裂化烟气处理面临的问题，本发明旨在提供一种催化裂化烟气处理三效助剂的制备方法，采用的技术路线如下：
(1)将拟薄水铝石按照一定的固含量打浆，加盐酸酸化，备用；
(2)将氯化镁、氯化铈、草酸钒溶液按照一定比例混合均匀，将步骤(1)中酸化好的拟薄水铝石按照一定比例加入到镁铈钒的混合溶液中，记为混合溶液A；
(3)将步骤(2)混合溶液A与含有OH-、CO3 2-的阴离子混合溶液B以一定的速率反应，调节溶液的pH，反应结束后，升温晶化一段时间。
(4)晶化结束后过滤，将滤饼洗涤至中性，重新打浆、喷雾造粒，焙烧，得到标题物。
本发明提供的制备方法所述步骤(1)中，拟薄水铝石以Al2O3计固含量为5～15wt％，盐酸与拟薄水铝石(以Al2O3计)的质量比为0.03～0.10:1。
本发明提供的制备方法所述步步骤(2)中，氯化镁的加入量以MgO计，占混合溶液A干基固含量的20％～40wt％；氯化铈的加入量以CeO2计，占混合溶液A干基固含量的20％～40wt％；草酸钒的加入量以V2O5计，占混合溶液A干基固含量的1％～3wt％。
本发明提供的制备方法所述步骤(2)中，拟薄水铝石的加入量以Al2O3计，占混合溶液A干基固含量的20％～40wt％。
本发明提供的制备方法所述步骤(3)中，调节浆液pH为9～11，反应温度为50～70℃，晶化温度为70～100℃，晶化时间为6～24h。
本发明提供的制备方法所述步骤(4)中，滤饼洗涤至中性，胶体打浆干基固含量≥10wt％。
本发明提供的制备方法所述步骤(4)中，焙烧温度为450～650℃，焙烧1～3h。
与现有技术相比，本发明的创新点或优势有以下几点：
(1)助剂中的活性组分MgO能够在再生器中吸收SO2生成稳定的硫酸盐。CeO2可以与CO反应形成Ce2O3，而Ce2O3又可以与NO反应形成N2，起到了助燃和脱硝的作用，而且产生的CeO2还可以促进SO2的氧化，避免了富氧状态下NOX的生成。
(2)以酸化的拟薄水铝石为部分载体，另一部分Al可以参与反应形成镁铝铈钒型类水滑石，同时在成型过程中控制胶体固含量和焙烧方式，具有更好的耐磨损性能，能够满足催化裂化装置的使用要求。
具体实施方式：
以下对本发明的具体实施进行详细说明，应当理解的是此处所描述的内容是对本发明的说明而不是限制。
本实施例中所用原料的数据如下：
拟薄水铝石：以Al2O3计，Al2O3＝63.5wt％；
氯化镁：以MgO计，MgO＝13.2wt％；
硫酸铝：以Al2O3计，Al2O3＝7.5w％；
氯化铈：以CeO2计，CeO2＝22.5wt％；
草酸钒：以V2O5计，V2O5＝4.5wt％；
盐酸：以HCl计，HCl＝14.5wt％
氢氧化钠：以NaOH计，NaOH＝20.5wt％；
碳酸钠：以Na2CO3计，Na2CO3＝30.5wt％；
实施例1:
(1)取30份拟薄水铝石加水按照14wt％固含量打浆，加盐酸酸化，盐酸与拟薄水铝石的质量比为0.05:1；
(2)取40份氯化镁、28份氯化铈、2份草酸钒溶液混合均匀，将步骤(1)中酸化好的拟薄水铝石按照一定比例加入到镁铈钒的混合溶液中，记为混合溶液A；
(3)将步骤(2)混合溶液A与含有NaOH、Na2CO3的混合溶液B以一定的速率反应，调节溶液的pH为10～10.5，反应温度为60℃，反应结束后升温到80℃，晶化时间为12h。
(4)晶化结束后过滤，将滤饼洗涤至中性；滤饼重新加水打浆，打浆固含量为10wt％，喷雾造粒；焙烧，焙烧温度为600℃，焙烧时间为2h，得到实施例1。
实施例2:
(1)取35份拟薄水铝石加水按照10wt％固含量打浆，加盐酸酸化，盐酸与拟薄水铝石的质量比为0.07:1；
(2)取30份氯化镁、32份氯化铈、3份草酸钒溶液混合均匀，将步骤(1)中酸化好的拟薄水铝石按照一定比例加入到镁铈钒的混合溶液中，记为混合溶液A；
(3)将步骤(2)混合溶液A与含有NaOH、Na2CO3的混合溶液B以一定的速率反应，调节溶液的pH为10～10.5，反应温度为70℃，反应结束后升温到90℃，晶化时间为8h。
(4)晶化结束后过滤，将滤饼洗涤至中性；滤饼重新加水打浆，打浆固含量为12wt％，喷雾造粒；焙烧，焙烧温度为650℃，焙烧时间为2h，得到实施例2。
实施例3:
(1)取40份拟薄水铝石加水按照12wt％固含量打浆，加盐酸酸化，盐酸与拟薄水铝石的质量比为0.1:1；
(2)取30份氯化镁、27份氯化铈、3份草酸钒溶液混合均匀，将步骤(1)中酸化好的拟薄水铝石按照一定比例加入到镁铈钒的混合溶液中，记为混合溶液A；
(3)将步骤(2)混合溶液A与含有NaOH、Na2CO3的混合溶液B以一定的速率反应，调节溶液的pH为9.5～10，反应温度为60℃，反应结束后升温到80℃，晶化时间为12h。
(4)晶化结束后过滤，将滤饼洗涤至中性；滤饼重新加水打浆，打浆固含量为12wt％，喷雾造粒；焙烧，焙烧温度为600℃，焙烧时间为2h，得到实施例3。
三效助剂的性能评价试验是在我公司自主搭建的提升管催化裂化试验装置上进行的。该装置是高低并列式催化裂化催化剂评价装置，能够模拟工业催化裂化装置进行反应—再生连续运转，可对催化剂循环量实现有效的自动控制，原料油可以是常减压的馏分油、常压渣油、减压渣油、蜡油等，且与工业提升管催化裂化装置工况十分接近，是研究催化裂化催化剂和工艺的重要设备。取FCC平衡剂作为对比样，分别添加3％藏量的实施例助剂，通过烟气分析仪检测再生器烟气流量计后SOX、NO、CO含量。三效助剂对SOX、NO、CO的脱除效率见下表1；可以发现实施例助剂对SOX、NO、CO均具有较好的脱除效果。
表1三效助剂对SOX、NO、CO的脱除效率
Claims (7)
1.一种催化裂化烟气处理三效助剂的制备方法，其具体步骤如下:
(1)将拟薄水铝石按照一定的固含量打浆，加盐酸酸化，备用。
(2)将氯化镁、氯化铈、草酸钒溶液按照一定比例混合均匀，将步骤(1)中酸化好的拟薄水铝石按照一定比例加入到镁铈钒的混合溶液中，记为混合溶液A。
(3)将步骤(2)中混合溶液A与含有OH-、CO2 3-的阴离子混合溶液B以一定的速率反应，调节溶液的pH，反应结束后，升温晶化一段时间。
(4)晶化结束后过滤，将滤饼洗涤至中性，重新打浆、喷雾造粒，焙烧，得到标题物。
2.根据权利要求1所述制备方法，其特征在于：步骤(1)中拟薄水铝石以Al2O3计固含量为5～15wt％，盐酸与拟薄水铝石(以Al2O3计)的质量比为0.03～0.10:1。
3.根据权利要求1所述制备方法，其特征在于：步骤(2)中，氯化镁的加入量以MgO计，占混合溶液A干基固含量的20％～40wt％；氯化铈的加入量以CeO2计，占混合溶液A干基固含量的20％～40wt％；草酸钒的加入量以V2O5计，占混合溶液A干基固含量的1％～3wt％。
4.根据权利要求1所述制备方法，其特征在于：步骤(2)中拟薄水铝石的加入量以Al2O3计，占混合溶液A干基固含量的20％～40wt％。
5.根据权利要求1所述制备方法，其特征在于：步骤(3)中，调节浆液pH为9～11，反应温度为50～70℃，晶化温度为70～100℃，晶化时间为6～24h。
6.根据权利要求1所述制备方法，其特征在于：步骤(4)中，滤饼洗涤至中性，打浆胶体固含量≥10wt％。
7.根据权利要求1所述制备方法，其特征在于：步骤(4)中，焙烧温度为450～650℃，焙烧1～3h。
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