CN114733558A - 一种用于原油直接裂解制低碳烯烃催化剂的制备方法 - Google Patents
一种用于原油直接裂解制低碳烯烃催化剂的制备方法 Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 44
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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Abstract
本发明公开了一种用于原油直接裂解制低碳烯烃催化剂的制备方法，以核壳ZSM‑5分子筛为活性组分，核为低硅铝比ZSM‑5，壳为高硅铝比ZSM‑5，该催化剂活性组分比例高，可以实现预裂化与裂解的接力反应，能够获得更高的低碳烯烃收率。
Description
技术领域
本发明涉及催化剂技术领域，具体涉及一种原油直接裂解制低碳烯烃催化剂的制备方法。
背景技术
低碳烯烃通常指碳四及碳四以下的不饱和碳氢化合物的总称，包括乙烯、丙烯、丁烯等，是不可或缺的化工原料，尤其是随我国经济的发展这些有机化工原料的需求量逐年增长，而产量不能满足日益增长的需求，因此有效提高低碳烯烃产量成为研发的热点之一。
目前，生产低碳烯烃的主要方式有蒸汽裂解、催化裂化丙烷脱氢、MTO催化重整等，生产过程中均存在较高的CO2排放问题，在碳中和战略目标影响下其发展收到极大的限制，而随着新能源汽车的推广，成品油的生产收益逐年递减，如何实现炼油厂利益最大化成为迫切的需求，而催化裂解制低碳烯烃所需温度相对较低，能耗低、原料适用性广，是未来生产低碳烯烃的重要途径。
原油四组分是指饱和分、芳香分、胶质和沥青质，包含有沸点超过590℃的高分子量非挥发性组分，而催化剂性质决定裂解性能以及产物分布，石油裂解催化剂的活性组分主要是ZSM-5分子筛，其孔口直径约为0.53nm，重油大分子难以进入ZSM-5孔道进行反应，较大的反应产物也不易从孔道中扩散出去。此外，反应过程中ZSM-5存在水热稳定性差、易积碳失活的问题。
针对以上问题学者们开展了大量研究，发现可以通过调控催化剂的孔径制备多级孔结构的分子筛催化剂或将ZSM-5与大孔结构的Y分子筛复配改善其性能。
专利CN103708496A公开了一种HZSM-5@silicalite-1核壳结构分子筛及其制备方法与应用。该方法是以HZSM-5分子筛为核，以全硅silicalite-1分子筛为壳，形成的壳层均匀致密，厚度为10～70nm。该发明制备的HZSM-5@silicalite-1核壳结构分子筛用于溴甲烷甲基化甲苯制备对二甲苯时具有优越的催化活性，对位选择性和稳定性。
专利CN108658093A公开一种多级孔ZSM-5分子筛的制备方法，该方法是通过在硅源、铝源、有机结构导向剂和去离子水的合成体系中，添加适量阳离子型表面活性剂十六烷基三甲基溴化铵作为软模板剂，充分搅拌混合均匀形成分子筛合成溶胶凝胶，然后将上述凝胶烘干得到干胶，再利用干胶转化法制备多级孔ZSM-5分子筛。
专利CN108745410B公开一种含磷的多级孔ZSM-5/Y复合分子筛的制备方法，该方法是将碱、有机模板剂和去离子水混合成为溶液，再加入NaY分子筛，加入硅源和硼源，得到混合溶胶晶化，回收晶化产品后脱除模板剂，得到NaZSM-5/Y复合分子筛；然后在铵盐溶液中进行铵离子交换脱除Na离子，得到NH4-ZSM-5/Y复合分子筛；再脱除骨架中硼元素，用磷化物浸渍，得到含磷的ZSM-5/Y复合分子筛。
专利CN113385223A公开一种直接催化裂解原油增产低碳烯烃的催化剂及其制备方法，该方法制备的催化剂包含5-20％Y型分子筛，20-50％的磷和锆改性ZSM-5分子筛，10-40％载体，5-25％粘结剂，该催化剂的特点在于以磷和锆共改性ZSM-5分子筛调控催化剂酸量和催化剂孔道分布，利于反应物在催化剂的扩散和目标产物的生成。该催化剂用于原油直接催化裂解过程中能抑制二次反应的发生、提高产物中低碳烯烃的收率。
当前原油直接催化裂解的研究鲜有报道，该技术存在原油组成复杂，轻重组分同时裂解困难，催化剂稳定性差且低碳烯烃收率低的诸多问题，但该方向的研究必将成为热点。
发明内容
针对现有技术存在的一些问题，本发明的目的是提供一种催化剂的制备方法，该催化剂中的活性组分是具有核壳结构，核为低硅铝比ZSM-5，壳为高硅铝比ZSM-5，该催化剂与原油接触，外部高硅铝比ZSM-5主要起汽化作用并实现链初步断裂。原料经热裂解、催化预裂解后形成较小分子产物，通过催化剂颗粒内部较大的孔道扩散进入内部与低硅铝比ZSM-5接触，实现进一步的裂解形成了大量的低碳烯烃产物，并且外部的高硅铝比ZSM-5能够控制原油的裂解深度，避免大量焦炭产生及堵塞催化剂的扩散通道。粘结成分采用硅溶胶，避免铝基粘结剂L酸过的缺点，减少不必要的非选择性氢转移反应，提高低碳烯烃产率与选择性。
本发明所述制备方法其步骤具体如下：
1、硅溶胶与ZSM-5分子筛混合打浆，喷雾造粒、焙烧，获得的颗粒物记作A；
2、将模板剂和活性剂加入硫酸铝溶液中混合均匀，将该浆液记作B；
3、将A用水打浆，水玻璃与B并流加入浆液A中，混合均匀后升温晶化；
4、晶化完毕，将浆液过滤、洗涤、干燥后获得标题物。
步骤(1)中ZSM-5分子筛的硅铝比为38-60，以氧化硅计的硅溶胶与ZSM-5分子筛的质量比为0.1-0.25:1；焙烧温度600-800℃，焙烧时间2-6小时。
步骤(2)中的活性剂为二甘醇胺。
步骤(3)中各物料加入比例以摩尔计：A:水玻璃：硫酸铝：模板剂：H2O：活性剂＝1.11-1.39:169-212:1:1.49-2.98:400-600:0.15-0.30，其中A中所含的ZSM-5与后生成的高硅铝比ZSM-5的质量比为0.4-0.5:1。
步骤(3)中的晶化温度为150-220℃，晶化时间4-72小时。
步骤(4)中洗涤液中应含有硫酸铵，标题物中的氧化钠应小于0.1wt％。
具体实施方式：
下面将结合实施例对本发明进一步说明，需要说明的是以下所述的实施例仅仅是本发明的一部分实施例，并不意味着是对本发明范围的限制。
实施例1
(1)将硅溶胶与ZSM-5分子筛按照质量比1:10进行称重，其中ZSM-5分子筛硅铝比为38，将两者进行充分搅拌均匀后用喷雾成型，然后经650℃焙烧后得到产物记作A；
(2)将模板剂、活性剂和硫酸铝按照摩尔比1.5:0.15:1进行称重并倒入搅拌桶中充分搅拌均匀，得到产物记作B；
(3)将A用水打浆，并将水玻璃和B并流加入A的浆液中，混合均匀后升温晶化，其中各原料组分的配比为：A:水玻璃：硫酸铝：模板剂：H2O：活性剂＝1.2:200:1:1.5:400:0.15；
(4)晶化完毕后，将浆液过滤、洗涤、干燥后得到目标产物CAT-1。
实施例2
(1)将硅溶胶与ZSM-5分子筛按照质量比1:10进行称重，其中ZSM-5分子筛硅铝比为38，将两者进行充分搅拌均匀后用喷雾成型，然后经650℃焙烧后得到产物记作A；
(2)将模板剂、活性剂和硫酸铝按照摩尔比1.5:0.3:1进行称重并倒入搅拌桶中充分搅拌均匀，得到产物记作B；
(3)将A用水打浆，并将水玻璃和B并流加入A的浆液中，混合均匀后升温晶化，其中各原料组分的配比为：A:水玻璃：硫酸铝：模板剂：H2O：活性剂＝1.2:200:1:1.5:400:0.3；
(4)晶化完毕后，将浆液过滤、洗涤、干燥后得到目标产物CAT-2。
实施例3
(1)将硅溶胶与ZSM-5分子筛按照质量比1:10进行称重，其中ZSM-5分子筛硅铝比为38，将两者进行充分搅拌均匀后用喷雾成型，然后经650℃焙烧后得到产物记作A；
(2)将模板剂、活性剂和硫酸铝按照摩尔比2.5:0.3:1进行称重并倒入搅拌桶中充分搅拌均匀，得到产物记作B；
(3)将A用水打浆，并将水玻璃和B并流加入A的浆液中，混合均匀后升温晶化，其中各原料组分的配比为：A:水玻璃：硫酸铝：模板剂：H2O：活性剂＝1.2:200:1:2.5:600:0.3；
(4)晶化完毕后，将浆液过滤、洗涤、干燥后得到目标产物CAT-3。
实施例4
(1)将硅溶胶与ZSM-5分子筛按照质量比1:4进行称重，其中ZSM-5分子筛硅铝比为60，将两者进行充分搅拌均匀后用喷雾成型，然后经650℃焙烧后得到产物记作A；
(2)将模板剂、活性剂和硫酸铝按照摩尔比1.5:0.15:1进行称重并倒入搅拌桶中充分搅拌均匀，得到产物记作B；
(3)将A用水打浆，并将水玻璃和B并流加入A的浆液中，混合均匀后升温晶化，其中各原料组分的配比为：A:水玻璃：硫酸铝：模板剂：H2O：活性剂＝1.2:200:1:1.5:400:0.15；
(4)晶化完毕后，将浆液过滤、洗涤、干燥后得到目标产物CAT-4。
实施例5
(1)将硅溶胶与ZSM-5分子筛按照质量比1:4进行称重，其中ZSM-5分子筛硅铝比为60，将两者进行充分搅拌均匀后用喷雾成型，然后经650℃焙烧后得到产物记作A；
(2)将模板剂、活性剂和硫酸铝按照摩尔比2.5:0.3:1进行称重并倒入搅拌桶中充分搅拌均匀，得到产物记作B；
(3)将A用水打浆，并将水玻璃和B并流加入A的浆液中，混合均匀后升温晶化，其中各原料组分的配比为：A:水玻璃：硫酸铝：模板剂：H2O：活性剂＝1.2:200:1:2.5:600:0.3；
(4)晶化完毕后，将浆液过滤、洗涤、干燥后得到目标产物CAT-5。
对比例
(1)先制备一定量的磷铝胶；
(2)称取一定量的磷铝胶、高岭土、水，将三者导入不锈钢桶内进行搅拌均匀；
(3)称取一定量的ZSM-5分子筛浆液，并将分子筛浆液导入步骤(2)中的浆液中进行混合搅拌均匀，搅拌均匀后再加入一定量的硅溶胶再进行搅拌均匀；
(4)将步骤(3)的浆料进行离心喷雾干燥后得到对比剂CAT-0。
制备好的催化剂样品分别置于ACE-AP中进行性能评价，评价前需将催化剂预先进行800℃，100％H2O，17小时的水热老化处理，催化剂装填量12克，反应温度620℃，剂油比20。评价所用原料油的组成如表1所示，ACE评价结果如表2所示。
表1原料油基本性质
表2催化剂评价结果
从上述评价数据可以看出，采用本发明制备的催化剂用于原油制低碳烯烃中低碳烯烃的收率要高于对比剂大约5.9-7.5％，液化气产率也明显高于对比剂5.31-6.34％。
Claims (6)
1.一种用于原油直接裂解制低碳烯烃催化剂的制备方法，其具体步骤如下：
(1)硅溶胶与ZSM-5分子筛混合打浆，喷雾造粒、焙烧，获得的颗粒物记作A；
(2)将模板剂和活性剂加入硫酸铝溶液中混合均匀，将该浆液记作B；
(3)将A用水打浆，水玻璃与B并流加入浆液A中，混合均匀后升温晶化；
(4)晶化完毕，将浆液过滤、洗涤、干燥后获得标题物。
2.根据权利要求1所述的制备方法，其特征在于：步骤(1)中ZSM-5分子筛的硅铝比为38-60，以氧化硅计的硅溶胶与ZSM-5分子筛的质量比为0.1-0.25:1；焙烧温度600-800℃，焙烧时间2-6小时。
3.根据权利要求1所述的制备方法，其特征在于：步骤(2)中的活性剂为二甘醇胺。
4.根据权利要求1所述的制备方法，其特征在于：步骤(3)中各物料加入比例以摩尔计为A:水玻璃：硫酸铝：模板剂：H2O：活性剂＝1.11-1.39:169-212:1:1.49-2.98:400-600:0.15-0.30，其中A中所含的ZSM-5与后生成的高硅铝比ZSM-5的质量比为0.4-0.5:1。
5.根据权利要求1所述的制备方法，其特征在于：步骤(3)中的晶化温度为150-220℃，晶化时间4-72小时。
6.根据权利要求1所述的制备方法，其特征在于：步骤(4)中洗涤液中应含有硫酸铵，洗涤后催化剂中的氧化钠应小于0.1wt％。
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