CN107115887A - 一种用于裂解重芳烃的催化剂制备方法 - Google Patents
一种用于裂解重芳烃的催化剂制备方法 Download PDFInfo
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Abstract
一种用于裂解重芳烃的催化剂制备方法，由以下步骤组成：将拟薄水铝石粉末、沸石分子筛粉末、胶溶剂以及助挤剂混合、干燥、焙烧得到成型载体；取设定量的去离子水，加入设定量极性较强的水溶性溶剂，然后将计量好的Pt或Pd中的至少一种金属盐的加入上述混合溶剂中制得浸渍液；再将成型载体加入浸渍液中并蒸发，然后将蒸发后的浸渍物焙烧即得到裂解重芳烃的催化剂。其优点为：采用引入强极性的有机溶剂，并占据催化剂载体上的强极性位，从而避免贵金属在催化剂载体上的聚集并提高贵金属在催化剂上的分散度和加氢活性。以乙烯裂解重芳烃为原料进行轻质化反应时，高活性贵金属催化剂可以将二烯烃类物质迅速加氢饱和，从而避免聚合结焦反应的发生。
Description
技术领域
本发明涉及一种催化剂制作技术，尤其指一种用于裂解重芳烃的催化剂制备方法。
背景技术
乙烯裂解重芳烃是乙烯装置的副产物，产量约占乙烯生产能力的15％左右，随着乙烯工业的快速发展，乙烯裂解重芳烃的产量也日趋增大，提高乙烯裂解重芳烃的综合利用率已成为乙烯装置降本增效的必要措施。但目前由于缺乏相关技术等原因，国内绝大多数乙烯装置将裂解重芳烃作为燃料直接烧掉，乙烯裂解重芳烃资源的化工利用率很低。如何开发该高附加值资源，加快其综合利用是目前各大石化企业面临的迫切问题。
专利公开号为CN 99113580使用镍和铋改性Beta沸石为催化剂，以甲苯、C9芳烃、C10芳烃混合物为原料，其中C10+芳烃含量5％，总转化率为47％，苯和二甲苯选择性为88％，并没有公开原料中C10芳烃的转化情况。UOP公司在专利No.8481443中公开了一种重芳烃轻质化方法，以贵金属铂为活性组分，以ZSM-5、ZSM-11等分子筛为载体，处理C10重芳烃。在铂的载量为0.115％时，二甲苯收率14％，C10重芳烃转化率48％，产物中含有10％气体轻烃。
上述重芳烃处理技术，均存在以下问题：(1)重芳烃原料组成要求严格，C10 +重芳烃在处理原料中比例较低，很多技术对C10 +重芳烃含量高的原料无法处理；(2)在处理C10 +芳烃含量较高原料时，存在催化剂加氢能力不足、重芳烃转化率低的问题；乙烯裂解重芳烃中含有大量的烯烃和二烯烃，对于加氢能力不足的催化剂，容易导致结焦失活，所以上述制备方法均有待于改进。
发明内容
本发明所要解决的技术问题是针对上述现有技术现状而提供一种用于乙烯裂解重芳烃的催化剂制备方法，该方法制备的催化剂具有重芳烃转化率高、稳定性好的特点。
本发明解决上述技术问题所采用的技术方案为：本发明用于裂解重芳烃的催化剂制备方法，其特征在于：由以下步骤组成：
一、将拟薄水铝石粉末、沸石分子筛粉末、胶溶剂以及助挤剂混合、捏合，直至成型，然后将成型的混合物干燥、焙烧得到成型载体；
二、取设定量的去离子水，加入设定量极性较强的水溶性溶剂，然后将计量好的Pt或Pd中的至少一种金属盐加入上述混合溶剂中，搅拌均匀后制得浸渍液；
三、取步骤一中的成型载体加入浸渍液中，成型载体与浸渍液的体积比为1:1～10，然后将加入有成型载体的浸渍液置于压力为0.1KPa～常压中进行蒸发，蒸发温度为20～100℃，蒸发时间为1～10小时；
四、将蒸发后的浸渍物置于温度为350～550℃下焙烧3～10小时，即得到裂解重芳烃的催化剂。
作为改进，所述的胶溶剂可优选为硝酸水溶液。
作为改进，所述助挤剂可优选为甲基纤维素、田菁粉中的一种。
作为改进，所述极性较强的水溶性溶剂可选择为甲醇、乙醇、乙二醇、丙醇、异丙醇、正丁醇以及异丁醇中的一种或多种。
作为改进，所述水溶性溶剂的加入量可选择为去离子水的0.1～10％，所述百分比为重量百分比。
作为改进，所述Pt金属盐可优选为氯铂酸、氯铂酸铵、硝酸铂一种或多种；所述Pd金属盐为氯钯酸、二氯化钯、四氯钯酸钠以及二氯四氨合钯中的一种或多种。
作为改进，所述步骤三中，所述蒸发可优选在旋转蒸发仪上蒸发脱除水分和溶剂。
再改进，所述裂解重芳烃可选择为乙烯裂解副产物中碳原子数大于等于9且终馏点不大于350℃的单/多环芳烃。
再改进，所述裂解重芳烃可优选为乙烯裂解副产物中C9 +重芳烃或C10 +重芳烃。
作为改进，所述催化剂比表面积为200～400m2/g，所述催化剂的孔体积为0.30～0.60ml/g；所述Pt或Pd或者Pt与Pd混合物加入量占催化剂质量的0.05～0.3％；所述沸石分子筛粉末可优选为HY或USY分子筛粉末，所述HY或USY分子筛粉末加入量占催化剂质量的5～40％，所述百分比为重量百分比。
与现有技术相比，本发明具有以下优点：本发明在制备催化剂过程中引入强极性的有机溶剂，该有机溶剂能够占据催化剂载体上的强极性位，从而避免贵金属在催化剂载体上的聚集并提高贵金属在催化剂上的分散度和加氢活性。因此，以乙烯裂解重芳烃为原料进行轻质化反应时，高活性贵金属催化剂可以将二烯烃类物质迅速加氢饱和，从而避免聚合结焦反应的发生。因此，本发明方法制备的催化剂可以在临氢条件下处理裂解重芳烃原料，能够将裂解重芳烃转化为BTX芳烃或者高辛烷值汽油，既具有较高的裂解重芳烃转化率，又具有较好的稳定性。BTX是对苯、甲苯、二甲苯的简称。
具体实施方式
以下结合实施例对本发明作进一步详细描述。
本实施例的用于裂解重芳烃的催化剂制备方法，由以下步骤组成：
一、将拟薄水铝石粉末、沸石分子筛粉末、胶溶剂以及助挤剂混合、捏合，直至成型，然后将成型的混合物干燥、焙烧得到成型载体；
二、取设定量的去离子水，加入设定量极性较强的水溶性溶剂，然后将计量好的Pt或Pd中的至少一种金属盐加入上述混合溶剂中，搅拌均匀后制得浸渍液；
三、取步骤一中的成型载体加入浸渍液中，成型载体与浸渍液的体积比为1:1～10，然后将加入有成型载体的浸渍液置于压力为0.1KPa～常压中进行蒸发，蒸发温度为20～100℃，蒸发时间为1～10小时；
四、将蒸发后的浸渍物置于温度为350～550℃下焙烧3～10小时，即得到裂解重芳烃的催化剂。
本实施例中采用的胶溶剂优选为硝酸水溶液。所述助挤剂为甲基纤维素、田菁粉中的一种。极性较强的水溶性溶剂为甲醇、乙醇、乙二醇、丙醇、异丙醇、正丁醇以及异丁醇中的一种或多种。水溶性溶剂的加入量为去离子水的0.1～10％，所述百分比为重量百分比。Pt金属盐为氯铂酸、氯铂酸铵、硝酸铂一种或多种；Pd金属盐为氯钯酸、二氯化钯、四氯钯酸钠以及二氯四氨合钯中的一种或多种。步骤三中，蒸发在旋转蒸发仪上蒸发脱除水分和溶剂。裂解重芳烃为乙烯裂解副产物中碳原子数大于等于9且终馏点不大于350℃的单/多环芳烃。裂解重芳烃为乙烯裂解副产物中C9 +重芳烃或C10 +重芳烃。
上述催化剂比表面积为200～400m2/g，所述催化剂的孔体积为0.30～0.60ml/g；所述Pt或Pd或者Pt与Pd混合物加入量占催化剂质量的0.05～0.3％；所述沸石分子筛粉末为HY或USY分子筛粉末，所述HY或USY分子筛粉末加入量占催化剂质量的5～40％，所述百分比为重量百分比。HY或USY分子筛粉末是公知技术，在网上均能找到。
下面通过具体实施例对本发明的技术方案及技术效果进行进一步描述，
实施例1
(1)载体制备
称取市售拟薄水铝石粉末100g，USY分子筛(硅铝比为15)30g，田菁粉3g，硝酸(65％)4g以及100ml去离子水，充分混合、捏合成可塑状后挤三叶草条状(Φ1.5mm)。湿条在110℃干燥4h，550℃焙烧4h，得到成型载体。硝酸65％，是指硝酸的浓度，即指硝酸溶液中含有重量百分比为65％的硝酸。
(2)催化剂制备
取去离子水200ml，然后加入10ml甲醇，混合均匀后加入0.32g氯铂酸，搅拌溶解后得到浸渍液。然后取步骤(1)中的成型载体100ml加入到上述浸渍液中，接着在旋转蒸发仪上蒸发脱除水分和溶剂，蒸发温度为80℃，压力为0.5KPa，蒸发5h后载体表面基本无水分，500℃下焙烧5h，得到裂解重芳烃轻质化催化剂A1，评价结果见表2。
实施例2
催化剂制备方法及过程同实施例1，只是将步骤(2)中甲醇改为乙醇，最后制得裂解重芳烃轻质化催化剂B，评价结果见表2。
实施例3
催化剂制备方法及过程同实施例1，只是将步骤(2)甲醇的量改为5ml，最后制得裂解重芳烃轻质化催化剂A2，评价结果见表2。
实施例4
催化剂制备方法及过程同实施例1，只是步骤(2)中不加入极性溶剂甲醇，最后制得裂解重芳烃轻质化催化剂A3，评价结果见表2。
根据所述催化剂的制备方法，其特征在于：所述催化剂在裂解C10 +重芳烃轻质化反应过程中的用途：
将10g催化剂装入固定床反应器，进行预处理，活化条件为：温度250～400℃，升温速率为5～10℃/min，在250℃保持1～4h，在400℃保持1～4h，氮气(或者氢气)流速为30～220mL/min。活化结束后降低床层温度至200～320℃，进行C10 +重芳烃加氢反应，反应条件为：温度300～450℃，压力为1.5～5MPa，重时空速为0.8～3h-1，氢烃体积比为500～1000。反应稳定24h后，连续定期取样分析，用气相色谱仪分析液体产物组成，并计算得到重芳烃转化率。所述h是指小时。
C10 +重芳烃转化率的定义为：
C10 +重芳烃转化率＝(进料中C10 +重芳烃的质量-产物中C10 +重芳烃质量)/进料中C10 +重芳烃的质量×100％；
表1C10 +裂解重芳烃原料组成
表2不同催化剂的评价结果
从表2中可以看出，采用本发明制备的催化剂在临氢条件下具有高C10 +重芳烃转化率以及轻质C6～C9芳烃收率。但若是催化剂制备过程中未引入强极性的有机溶剂，催化剂初始活性较低，且反应一段时间后(200h)催化剂活性明显下降。
Claims (10)
1.一种用于裂解重芳烃的催化剂制备方法，其特征在于：由以下步骤组成：
一、将拟薄水铝石粉末、沸石分子筛粉末、胶溶剂以及助挤剂混合、捏合，直至成型，然后将成型的混合物干燥、焙烧得到成型载体；
二、取设定量的去离子水，加入设定量极性较强的水溶性溶剂，然后将计量好的Pt或Pd中的至少一种金属盐加入上述混合溶剂中，搅拌均匀后制得浸渍液；
三、取步骤一中的成型载体加入浸渍液中，成型载体与浸渍液的体积比为1:1～10，然后将加入有成型载体的浸渍液置于压力为0.1KPa～常压中进行蒸发，蒸发温度为20～100℃，蒸发时间为1～10小时；
四、将蒸发后的浸渍物置于温度为350～550℃下焙烧3～10小时，即得到裂解重芳烃的催化剂。
2.根据权利要求1所述的催化剂制备方法，其特征在于：所述的胶溶剂为硝酸水溶液。
3.根据权利要求1所述的催化剂制备方法，其特征在于：所述助挤剂为甲基纤维素、田菁粉中的一种。
4.根据权利要求1所述的催化剂制备方法，其特征在于：所述极性较强的水溶性溶剂为甲醇、乙醇、乙二醇、丙醇、异丙醇、正丁醇以及异丁醇中的一种或多种。
5.根据权利要求1所述的催化剂制备方法，其特征在于：所述水溶性溶剂的加入量为去离子水的0.1～10％，所述百分比为重量百分比。
6.根据权利要求1所述的催化剂制备方法，其特征在于：所述Pt金属盐为氯铂酸、氯铂酸铵、硝酸铂一种或多种；所述Pd金属盐为氯钯酸、二氯化钯、四氯钯酸钠以及二氯四氨合钯中的一种或多种。
7.根据权利要求1所述的催化剂制备方法，其特征在于：所述步骤三中，所述蒸发是在旋转蒸发仪上蒸发脱除水分和溶剂。
8.根据权利要求1所述的催化剂制备方法，其特征在于：所述裂解重芳烃为乙烯裂解副产物中碳原子数大于等于9且终馏点不大于350℃的单/多环芳烃。
9.根据权利要求8所述的催化剂制备方法，其特征在于：所述裂解重芳烃为乙烯裂解副产物中C9 +重芳烃或C10 +重芳烃。
10.根据权利要求1所述的催化剂制备方法，其特征在于：所述催化剂比表面积为200～400m2/g，所述催化剂的孔体积为0.30～0.60ml/g；所述Pt或Pd或者Pt与Pd混合物加入量占催化剂质量的0.05～0.3％；所述沸石分子筛粉末为HY或USY分子筛粉末，所述HY或USY分子筛粉末加入量占催化剂质量的5～40％，所述百分比为重量百分比。
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| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 100011 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Applicant after: China Offshore Oil Group Co., Ltd. Applicant after: China National Offshore Oil Corporation Applicant after: CNOOC ZHOUSHAN PETROCHEMICAL CO., LTD. Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant after: CNOOC Huizhou Petrochemical Co., Ltd. Address before: 100011 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Applicant before: China National Offshore Oil Corporation Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC ZHOUSHAN PETROCHEMICAL CO., LTD. Applicant before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant before: CNOOC Huizhou Petrochemical Co., Ltd. |
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| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170901 |