CN106179470A - 一种催化裂化提高汽油辛烷值助剂的制备方法 - Google Patents
一种催化裂化提高汽油辛烷值助剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种催化裂化提高汽油辛烷值助剂的制备方法,制备步骤如下:(1)ZSM‑5分子筛与水打浆,控制固含量35‑45wt%,加入一定比例的改性剂,搅拌均匀。(2)向步骤(1)中的浆液中加入一定比例的拟薄水铝石,并用酸液调节其pH值范围1.8‑2.3。(3)将一定浓度的拟薄水铝石浆液加入到一定浓度的磷酸溶液中,控制反应温度50‑65℃,反应时间>5h。(4)向步骤(3)浆液中加入一定量的水,再加入高岭土,搅拌均匀。(5)将步骤(2)中浆液加入步骤(4)的浆液中,搅拌均匀。(6)喷雾干燥,即得标题物。经工业试验证明,加入本发明助剂占系统藏量3‑10wt%,研究法辛烷值可提高1‑3个单位,丙烯产率提高1‑4百分点。
Description
技术领域:本发明属于催化剂技术领域,具体涉及一种催化裂化提高汽油辛烷值助剂的制备方法。
技术背景:
汽油在气缸中正常燃烧时火焰传播速度为10-20m/s,在爆震燃烧时可达1500-2000m/s,后者会使气缸温度剧升,汽油燃烧不完全,机器强烈震动,从而使输出功率下降,机件受损。因此,汽油辛烷值是衡量车用汽油的一项重要指标,在我国轻质油品的获得主要是通过催化裂化装置,但FCC汽油的辛烷值偏低,无法生产出高标号汽油。
为了追求较高的汽油辛烷值,炼油厂的催化裂化装置现在一般采取高温短接触的操作条件和超稳分子筛催化剂。另外一种方法采用具有高硅分子筛ZSM-5的催化裂化助剂来提高汽油辛烷值,已有大量专利报道。
如USP4929337采用Ga改性的ZSM-5分子筛作为芳构化的活性组分,择型裂化/芳构化组分使烷烃和烯烃裂化/芳构化,择型芳构化组分把烷烃和烯烃转化成芳烃。
USP4867863介绍了一种重油催化裂化提高汽油辛烷值的方法,所用催化剂含0.5-5%的HZSM-5分子筛,采用这种催化剂可以提高汽油的辛烷值。
CN100395311C公开了一种石油烃类裂化催化剂,包括25-50wt%的锌和稀土改性的Y型沸石,20-50wt%的粘土和20-50wt%的无机氧化物,所述的锌和稀土改性的Y型沸石中的锌含量以氧化锌计为0.5-10wt%,稀土含量以氧化稀土计为0.5-5.0wt%,该催化剂用于石油烃类裂化反应,具有较高的重油裂化能力,焦炭产率高,轻油产率高,在保持汽油组分有较高辛烷值的条件下使其烯烃含量降低。
一般的ZSM-5助剂在几次循环反应后,活性会迅速下降,水热稳定性不够理想,选择性变差,因此需要对ZSM-5进行改性。
在分子筛中引入新元素的方法很多。例如,离子交换法、浸渍法和如CN1057408A中介绍的高温处理法等,采用不同的方法,新引入的元素离子在分子筛中所处的位置不同,因此作用不同。本发明改性分子筛是用浸渍法制备的,浸渍法简单易行。浸渍过的分子筛或催化剂经干燥焙烧后,改性元素就沉积并结合在分子筛上,起到调节分子筛改性的作用。
磷铝胶中的有效成分为磷酸二氢铝,作为粘结剂可以制备出强度优良的催化剂。磷酸二氢铝理论配比为P2O5/Al2O3=3:1(摩尔比)。制备时的实际配比均高于该值。过量的磷酸可以与分子筛结合,磷可以改善ZSM-5分子筛的水热稳定性,但是其磷的比例不宜过高,超过一定值后会对分子筛的孔道产生影响,堵塞孔道多聚态的磷亦失去其活性,因此,降低磷铝胶的用量,不仅降低了生产成本,也能提高催化剂反应性能。
目前,普通方法制备的助剂无裂化活性,加入比例超过5%后,影响产品分布,重油升高,高附加值、轻收组分减少,另外使用过量的磷铝胶,导致分子筛孔道被堵,活性、选择性降低,而且磷元素进入FCC粉尘,回收粉尘对零部件产生不利影响。
在常规催化裂化的反应条件下,向催化裂化装置中加入少量本发明所提供的助剂,即可以促进催化汽油中烯烃的裂化反应、氢转移反应、芳构化反应及烃类的异构化反应。因此本发明与现有技术相比,不仅可降低催化汽油中烯烃含量而且可以提高汽油辛烷值,并可适量增加低碳烯烃的产率。
经工业试验证明,加入本发明助剂占系统藏量3-10wt%,研究法辛烷值可提高1-3个单位,丙烯产率提高1-4百分点。
发明内容:
本发明的目的是提供一种既能提高汽油辛烷值,又能改善产品分布的助剂的制备方法。
ZSM系列分子筛是一种高硅、具有三维交叉直通道结构的新型分子筛,它具有亲油、疏水、热稳定高等特点。其很大多数孔径为5.5埃左右,它的催化活性依赖于表面酸性,这些酸中心绝大部分位于分子筛的孔径内。由于特殊的孔道结构和酸中心的共同作用,使其具有特殊的择型催化作用,对酸催化反应来说,不同的反应要求不同的酸中心强度,并且酸中心的强度对反应选择性有直接影响。为了促进理想反应,必须适当调整分子筛酸中心的数量、强度和分布。本发明采用分子筛中引入新元素来达到改性的目的。
本发明引进的新元素是锌,用浸渍法制得的ZnZSM-5沸石,其Zn存在状态可能有三种,以ZnO状态存在;以Zn+状态存在;以Zn(OH)+状态存在。研究表明,Zn在ZnZSM-5沸石中分别以Zn+和Zn(OH)+两种形态存在,因此锌具有脱氢作用,所以可提高芳构化性能,它可使C3-C8的烷烃、环烷烃和烯烃分子芳构化。
本发明的目的是提供一种既能提高汽油辛烷值,又能改善产品分布的助剂的制备方法。
一种催化裂化提高汽油辛烷值助剂的制备方法,包括以下步骤:
(1)ZSM-5分子筛与水打浆,控制固含量35-45wt%,加入一定比例的改性剂,搅拌均匀。
(2)向步骤(1)中的浆液中加入一定比例的拟薄水铝石,并用酸液调节其pH值范围1.8-2.3。
(3)将一定浓度的拟薄水铝石浆液加入到一定浓度的磷酸溶液中,控制反应温度50-65℃,反应时间>5h。
(4)向步骤(3)浆液中加入一定量的水,再加入高岭土,搅拌均匀。
(5)将步骤(2)中浆液加入步骤(4)的浆液中,搅拌均匀。
(6)喷雾干燥,即得标题物。
步骤(1)中所述ZSM-5的硅铝比100-300,氧化钠含量≤0.2wt%。
步骤(1)中所述改性剂为氯化锌、硝酸锌、碳酸锌或硫酸锌中的一种或几种混合,优选硝酸锌,加入比例以氧化锌计其质量比为ZnO/ZSM-5干基=0.01-0.05:1。
步骤(2)中所述拟薄水铝石的加入比例以氧化铝计占所制备成的助剂干基的1-8wt%。
步骤(2)中所述酸液为盐酸、硝酸、磷酸或者硫酸中的一种或几种混合,优选硝酸,其浓度以硝酸计5-10wt%。
步骤(3)中所述拟薄水铝石的浓度以氧化铝计为35-45wt%,磷酸的浓度以磷酸计为55-65wt%,两者比例以氧化物计的质量比为P2O5/Al2O3=3-5:1。
步骤(4)中水的比例使得最终喷雾时浆液的固含量为33-40wt%。
各组分所占比例如下ZSM-5:Al2O3:P2O5:高岭土=30-40:2.2-13:6-15:32-61.8,各组分含量之和满足百分之百。
在常规催化裂化的反应条件下,向催化裂化装置中加入少量本发明所提供的助剂,即可以促进催化汽油中烯烃的裂化反应、氢转移反应、芳构化反应及烃类的异构化反应。因此本发明与现有技术相比,不仅可降低催化汽油中烯烃含量而且可以提高汽油辛烷值,并可适量增加低碳烯烃的产率。
经工业试验证明,加入本发明助剂占系统藏量3-10wt%,研究法辛烷值可提高1-3个单位,丙烯产率提高1-4百分点。
具体实施方式:
为了更好地理解本发明,下面结合实施例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
本发明实施例与对比例中所用的分析测试评价方法:
(1)化学组成:X射线荧光光谱仪,德国布鲁克,S8Tiger 3KW。
(2)磨损指数:鹅颈管法,RIPP。
(3)比表面:氮气吸附仪,美国康塔,NOVA-E。
本发明实施例与对比例中所用原料:制备使用的原料均为市售品,可以商购获得。
(1)高岭土:中国高岭土有限公司,灼减25wt%
(2)拟薄水铝石:中国铝业股份有限公司山东分公司,灼减30wt%
(3)铝溶胶:市售,氧化铝含量22.0wt%
(4)磷酸:以磷酸计75.0wt%
(5)硝酸:分析纯。
(6)ZSM-5分子筛:硅铝比120,灼减10wt%
(7)硝酸锌:市售,Zn(NO3)2.6(H2O)。
实施例1:
(1)777.0克ZSM-5分子筛(硅铝比120)与973.0克水打浆,加入49.0克硝酸锌,搅拌均匀。
(2)向(1)中的浆液中加入171.4克拟薄水铝石,加入硝酸6ml,调节其pH值2.0。
(3)99.0克拟薄水铝石浆液与74.5克水打浆,记作浆液A,75%的磷酸460.5克与70.8克水打浆,记作浆液B,A加入B中,控制反应温度63℃,反应时间5h。
(4)向反应完毕的(3)中的浆液中加入1910.0克水,再加入1120.0克高岭土,搅拌均匀。
(5)将(2)中浆液加入(4)中,搅拌均匀。
(6)喷雾干燥,即得辛烷值助剂SL-1。
实施例2:
(1)666.0克ZSM-5分子筛(硅铝比120)与834.0克水打浆,加入70克硝酸锌,搅拌均匀。
(2)向(1)中的浆液中加入228.6克拟薄水铝石,加入硝酸9.5ml,调节其pH值1.9。
(3)79.1克拟薄水铝石浆液与59.4克水打浆,记作浆液A,75%的磷酸368.1克与56.7克水打浆,记作浆液B,A加入B中,控制反应温度65℃,反应时间5h。
(4)向反应完毕的(3)中的浆液中加入2030克水,再加入1313克高岭土,搅拌均匀。
(5)将(2)中浆液加入(4)中,搅拌均匀。
(6)喷雾干燥,即得辛烷值助剂SL-2。
对比例1:
(1)145.7克拟薄水铝石浆液与109.3克水打浆,记作浆液A。
75%的磷酸681.0克与105.0克水打浆,记作浆液B。
A加入B中,控制反应温度65℃,反应时间5h。
(2)加入2790.0克水,1104.0克高岭土,777.0克ZSM-5分子筛(硅铝比120),混合均匀喷雾干燥,样品记作DB-1。
对比例2:
(1)2347.0克水、909.0克铝溶胶、987.0克水打浆,打浆时间超过5h。
(2)加入777.0克ZSM-5分子筛(硅铝比120),514.0克拟薄水铝石,然后加入180克13%HCl酸化胶体,喷雾干燥,样品记作DB-2.
分析辛烷值助剂SL-1、SL-2、DB-1、DB-2,实例中助剂的分析结果如下表1
表1辛烷值助剂理化性质分析
催化剂老化:将制备的助剂在800℃、100%水蒸气条件下水热处理17h后备用。
催化剂评价:催化剂的评价在FFB小型固定流化床上进行评价评价。原料油选取采用大庆二重混合原料油,原料性质见表2,主催化剂采用AIC-950(青岛惠城环保科技股份有限公司生产),助剂添加量为总催化剂量8%。反应温度为520℃,剂油比为4.95,催化剂藏量180g,重油空速20h-1,评价结果见表3。
表2原料性质(大庆二重混合原料油)
表3.FFB小型固定流化床评价结果
其中:轻收=汽油+柴油,液收=液化气+汽油+柴制备的助剂油。
从以上数据可以看出在相同加入比例下使用实施例,与对比剂相比,轻收和液收均明显提高,其中轻收最高增加3.35%,液收最高增加1.75%,液化气中的丙烯浓度也大大增高,最高增加4.42wt%,汽油辛烷值也提高2个百分点。
Claims (8)
1.一种催化裂化提高汽油辛烷值助剂的制备方法,包括以下步骤:
(1)ZSM-5分子筛与水打浆,控制固含量35-45wt%,加入一定比例的改性剂,搅拌均匀。
(2)向步骤(1)中的浆液中加入一定比例的拟薄水铝石,并用酸液调节其pH值范围1.8-2.3。
(3)将一定浓度的拟薄水铝石浆液加入到一定浓度的磷酸溶液中,控制反应温度50-65℃,反应时间>5h。
(4)向步骤(3)浆液中加入一定量的水,再加入高岭土,搅拌均匀。
(5)将步骤(2)中浆液加入步骤(4)的浆液中,搅拌均匀。
(6)喷雾干燥,即得标题物。
2.如权利要求1所述的制备方法,其特征是:步骤(1)中所述ZSM-5的硅铝比100-300,氧化钠含量≤0.2wt%。
3.如权利要求1所述的制备方法,其特征是:步骤(1)中所述改性剂为氯化锌、硝酸锌、碳酸锌或硫酸锌中的一种或几种混合,优选硝酸锌,加入比例以氧化锌计其质量比为ZnO/ZSM-5干基=0.01-0.05:1。
4.如权利要求1所述的制备方法,其特征是:步骤(2)中所述拟薄水铝石的加入比例以氧化铝计占所制备成的助剂干基的1-8wt%。
5.如权利要求1所述的制备方法,其特征是:步骤(2)中所述酸液为盐酸、硝酸、磷酸或者硫酸中的一种或几种混合,优选硝酸,其浓度以硝酸计5-10wt%。
6.如权利要求1所述的制备方法,其特征是:步骤(3)中所述拟薄水铝石的浓度以氧化铝计为35-45wt%,磷酸的浓度以磷酸计为55-65wt%,两者比例以氧化物计的质量比为P2O5/Al2O3=3-5:1。
7.如权利要求1所述的制备方法,其特征是:步骤(4)中水的比例使得最终喷雾时浆液的固含量为33-40wt%。
8.如权利要求1所述的制备方法,其特征是:各组分所占比例如下ZSM-5:Al2O3:P2O5:高岭土=30-40:2.2-13:6-15:32-61.8,各组分含量之和满足百分之百。
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