CN111939971A - 一种增产丙烯催化裂化助剂的制备方法 - Google Patents
一种增产丙烯催化裂化助剂的制备方法 Download PDFInfo
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- B01J29/405—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract
本发明属于催化裂化助剂制备技术领域,公开一种增产丙烯催化裂化助剂的制备方法,包括:(1)将高岭土、硅藻土、添加剂加入去离子水搅拌混合,喷雾干燥成微球,焙烧得焙烧微球;(2)将焙烧微球、白炭黑、氧化铝、水玻璃、氢氧化钠、晶种和去离子水投入晶化反应釜中水热晶化,过滤干燥得到ZSM‑5分子筛;(3)将ZSM‑5分子筛进行2‑5次盐酸交换,过滤、焙烧,得HZSM‑5分子筛;(4)将HZSM‑5分子筛经改性剂进行混合改性,过滤,干燥,焙烧得增产丙烯催化裂化助剂。本发明制备的增产丙烯助剂用于催化裂化过程,能够有效地提高丙烯收率和丙烯选择性。
Description
技术领域
本发明属于催化裂化助剂制备技术领域,涉及一种增产丙烯催化裂化助剂的制备方法。
背景技术
丙烯是是仅次于乙烯的重要化工基本原料,随着国民经济的发展,市场对丙烯的需求越来越旺盛,需求缺口越来越大。近年全球需求年增长率已超过6.3%,增长速度大大超过乙烯。虽然66%的丙烯主要来自蒸汽裂解制乙烯的联产,但受到原料成本,处理能力,投资规模等的限制;而催化裂化工艺(FCCU)副产32%左右的丙烯,同时可以以重质油为原料,通过深度裂解多产丙烯。
在催化裂化过程中采用加入助催化剂的方式增产丙烯,具有操作简便、反应灵活、对整个过程影响小的优点被广泛采用。现有技术所公开的增产丙烯的催化裂化催化剂或助剂,由于只注重对常规ZSM-5分子筛的改性,没有关注在裂化反应过程中的裂化产物的二次转化,虽然能有效地增加低碳烯烃的产率,提高催化裂化汽油的辛烷值,但在催化裂化反应过程中对于丙烯的选择性并不高,液化气中丙烯浓度的增幅有限。
发明内容
本发明要解决的技术问题是克服上述缺陷,提供一种丙烯选择性高、收率高、成本低廉的增产丙烯催化裂化助剂的制备方法。
为了解决上述技术问题,本发明的技术方案为:
一种增产丙烯催化裂化助剂的制备方法,包括如下步骤:
(1)将高岭土、硅藻土、添加剂混和成固体混合物,加入去离子水放入反应器中,以每分钟200~300的转速搅拌1~2小时,水浴温度为50~80℃,喷雾干燥成微球,微球在900~1100℃下焙烧0.5~5小时,得焙烧微球;
(2)将步骤(1)得到的焙烧微球、白炭黑、氧化铝、水玻璃、氢氧化钠、晶种和去离子水投入晶化反应釜中,用酸将浆液终点pH值调至11~12,在150~190℃下水热晶化30~90h,过滤除去母液后,滤料水洗,过滤,干燥得到ZSM-5分子筛;
(3)将步骤(2)得到的ZSM-5分子筛进行2~5次盐酸交换,室温下交换10~30min,过滤、水洗、过滤后,交换产物在水汽550~650℃下焙烧0.5~3小时,得HZSM-5分子筛;
(4)将步骤(3)得到的HZSM-5分子筛经稀土、磷、镁、锌中两种或两种以上元素的混合改性,室温下改性10~30min,过滤除去母液后,水洗滤料,过滤,干燥,550~650℃下焙烧0.5~3小时,制得增产丙烯催化裂化助剂。
优选的,步骤(1)所述高岭土加入量为固体混合物总重的10~30%。
优选的,步骤(1)所述添加剂包括硅酸钠、氢氧化钠、磷酸盐、碳酸盐、高分子聚合物、玉米粉等中的一种或多种。
优选的,步骤(2)所述白炭黑的加入量为步骤(2)固体总重1~10%;所述氧化铝的加入量为步骤(2)固体总重1~10%。
优选的,步骤(2)所述晶种为ZSM-5、Y型、X型分子筛中的任意一种。
优选的,步骤(2)所述晶种的加入量为步骤(2)固体总重1~10%。
与现有技术相比本发明的有益效果是:
(1)本发明助剂的制备过程中采用了混合组元为主要原料,添加添加剂与混合组元相互作用,有效调节助剂的孔道,丰富了助剂内部的中大孔结构,特别是大孔比列,阻止了孔道的堆积。
(2)本发明助剂中ZSM-5分子筛的活性组分通过原位合成配方得到有效控制,调节了分子筛和基质组分的分配比例,有效调节助剂的反应活性。
(3)本发明提供的增产丙烯助剂用于催化裂化过程,能够有效地提高丙烯收率和丙烯选择性。
(4)本发明增产丙烯催化裂化助剂的制备方法简单,成本低廉,具有更好的社会效益和经济效益。
附图说明
图1(a)为实施例2合成ZSM-5的XRD图
图1(b)为实施例3合成ZSM-5的XRD图
具体实施方式
以下对本发明专利的原理和特征进行描述,所举实例只用于解释本发明专利,并非用于限定本发明专利的范围。
实施例1
一种增产丙烯催化裂化助剂的制备方法,包括如下步骤:
(1)将300g高岭土、700g硅藻土和1700mL去离子水放入反应器中,加入10g硅酸钠,在200rpm的转速下,搅拌2小时,控制水浴温度为50℃,使浆液混合均匀,喷雾干燥成微球,微球在900℃下焙烧5小时,得焙烧微球;
(2)将89g焙烧微球、5g白炭黑、5g氧化铝、403mL水玻璃、42mL氢氧化钠、1g Y型分子筛和995mL去离子水投入晶化反应釜中,用硫酸将浆液终点pH调至11~12,在150℃下水热晶化90h,过滤除去母液后,滤料水洗,过滤,干燥得到ZSM-5分子筛;经X-射线衍射测定,含48%的ZSM-5分子筛;
(3)将步骤(2)得到的ZSM-5分子筛80g、240mL去离子水,加入盐酸控制pH=2.5,室温下交换10min,过滤、水洗、过滤后,交换产物在100%水汽、550℃下焙烧3小时,以上步骤重复一次,得HZSM-5分子筛;
(4)将步骤(3)得到的70g HZSM-5分子筛、LaCl3溶液17mL、氯化锌7g、135mL去离子水加入到反应釜中进行改性,室温下交换10min,过滤除去母液后,水洗滤料,过滤,干燥,550℃下焙烧3小时,制得增产丙烯催化裂化助剂。
经检测助剂的比表面185m2/g,堆比0.66g/ml。
实施例2
一种增产丙烯催化裂化助剂的制备方法,包括如下步骤:
(1)将200g高岭土、800g硅藻土和1600mL去离子水放入反应器中,加入10g磷酸钠,在250rpm的转速下,搅拌1.5小时,控制水浴温度为60℃,使浆液混合均匀,喷雾干燥成微球,微球在1000℃下焙烧1小时,得焙烧微球;
(2)将84g焙烧微球、5g白炭黑、10g氧化铝、394mL水玻璃、39mL氢氧化钠、1gX型分子筛和1113mL去离子水投入晶化反应釜中,用硫酸将浆液终点pH调至11~12,在160℃下水热晶化82h,过滤除去母液后,滤料水洗,过滤,干燥得到ZSM-5分子筛;经X-射线衍射测定,含43%的ZSM-5分子筛;
(3)将步骤(2)得到的ZSM-5分子筛80g、240mL去离子水,加入盐酸控制pH=2.0,室温下交换20min,过滤、水洗、过滤后,交换产物在100%水汽、600℃下焙烧2小时,以上步骤重复一次,得HZSM-5分子筛;
(4)将步骤(3)得到的70g HZSM-5分子筛、LaCl3溶液30mL、硫酸镁10g、400mL去离子水加入到反应釜中进行改性,室温下交换30min,过滤除去母液后,水洗滤料,过滤,干燥,600℃下焙烧1小时,制得增产丙烯催化裂化助剂。
经检测助剂的比表面167m2/g,堆比0.67g/ml。
实施例3
一种增产丙烯催化裂化助剂的制备方法,包括如下步骤:
(1)将100g高岭土、900g硅藻土和1500mL去离子水放入反应器中,加入10g碳酸铵,在300rpm的转速下,搅拌1小时,控制水浴温度为80℃,使浆液混合均匀,喷雾干燥成微球,微球在950℃下焙烧4小时,得焙烧微球;
(2)将100g焙烧微球、1g白炭黑、1g氧化铝、450mL水玻璃、50mL氢氧化钠、1gZSM-5和1200mL去离子水投入晶化反应釜中,用硫酸将浆液终点pH调至11~12,在170℃下水热晶化68h,过滤除去母液后,滤料水洗,过滤,干燥得到ZSM-5分子筛;经X-射线衍射测定,含61%的ZSM-5分子筛;
(3)将步骤(2)得到的ZSM-5分子筛80g、240mL去离子水,加入盐酸控制pH=2.5,室温下交换60min,过滤、水洗、过滤后,交换产物在100%水汽、650℃下焙烧1.5小时,以上步骤重复一次,得HZSM-5分子筛;
(4)将步骤(3)得到的70g HZSM-5分子筛、LaCl3溶液25mL、磷酸10g、140mL去离子水加入到反应釜中进行改性,室温下交换30min,过滤除去母液后,水洗滤料,过滤,干燥,600℃下焙烧2小时,制得增产丙烯催化裂化助剂。
经检测助剂的比表面236m2/g,堆比0.68g/ml。
实施例4
一种增产丙烯催化裂化助剂的制备方法,包括如下步骤:
(1)将100g高岭土、900g硅藻土和1500mL去离子水放入反应器中,加入10g玉米粉,在300rpm的转速下,搅拌1小时,控制水浴温度为70℃,使浆液混合均匀,喷雾干燥成微球,微球在1100℃下焙烧0.5小时,得焙烧微球;
(2)将84g焙烧微球、10g白炭黑、5g氧化铝、466mL水玻璃、50mL氢氧化钠、1gZSM-5和1010mL去离子水投入晶化反应釜中,用硫酸将浆液终点pH调至11~12,在190℃下水热晶化30h,过滤除去母液后,滤料水洗,过滤,干燥得到ZSM-5分子筛;经X-射线衍射测定,含65%的ZSM-5分子筛;
(3)将步骤(2)得到的ZSM-5分子筛80g、240mL去离子水,加入盐酸控制pH=2.0,室温下交换30min,过滤、水洗、过滤后,交换产物在100%水汽、650℃下焙烧0.5小时,以上步骤重复一次,得HZSM-5分子筛;
(4)将步骤(3)得到的70g HZSM-5分子筛、LaCl3溶液33mL、硫酸锌10g、150mL去离子水加入到反应釜中进行改性,室温下交换30min,过滤除去母液后,水洗滤料,过滤,干燥,650℃下焙烧0.5小时,制得增产丙烯催化裂化助剂。
经检测助剂的比表面251m2/g,堆比0.69g/ml。
其中,X-射线衍射测定方法:采用日本理学Rigaku-D-MaxrA 12kW型X射线衍射仪(XRD)进行样品的物相分析,测试条件:Cu靶,波长λ=1.54056nm,管电压40kV,管电流40mA,发散狭缝和散射狭缝扫描速度为8°/min。
比表面测试方法:产品在美国Micromeritics ASAP 2020型自动吸附仪上测定比表面积和孔结构,在77K下测定吸脱附等温线。在测量之前,需要将样品在623K下脱气12h。比表面积使用BET公式计算,利用BJH法计算孔隙参数、孔体积等。
反应活性及选择性检测
采用ACE评价产品的反应活性及选择性。主剂和实施例1-4制备的助剂均经过800℃、17小时、100%水蒸汽老化,然后以5%的助剂用量与主剂混合进行评价,分为对照组和实验组,其中对照组为主剂,实验组分别是主剂添加5%的实施例1-4制备的助剂,分别为实验组1-4。具体评价结果见表1。
从表上数据可以看出,添加本发明制备的增产丙烯助剂均表现出增产丙烯能力强、焦炭选择性好的特点。
以上为本发明较佳实施例,只适用于帮助理解本发明实施例的原理;同时,对于本领域的一般技术人员,依据本实施例,在具体实施方式以及应用范围上均会有改变之处,综上所述,本说明书内容不应理解为对本发明的限制。对于本领域技术人员而言,显然本发明专利不限于上述示范性实施例的细节,而且在不背离本发明专利的精神或基本特征的情况下,能够以其它的具体形式实现本发明专利。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明专利的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明专利内,不应将权利要求中的任何附图标记视为限制所涉及的权利要求。
以上所述仅为本发明专利的较佳实施例,并不用以限制本发明专利,凡在本发明专利的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明专利的保护范围之内。
Claims (7)
1.一种增产丙烯催化裂化助剂的制备方法,其特征在于:包括如下步骤:
(1)将高岭土、硅藻土、添加剂混和成固体混合物,加入去离子水放入反应器中,以每分钟200~300的转速搅拌1~2小时,水浴温度为50~80℃,喷雾干燥成微球,微球在900~1100℃下焙烧0.5~5小时,得焙烧微球;
(2)将步骤(1)得到的焙烧微球、白炭黑、氧化铝、水玻璃、氢氧化钠、晶种和去离子水投入晶化反应釜中,用酸将浆液终点pH值调至11~12,在150~190℃下水热晶化30~90h,过滤除去母液后,滤料水洗,过滤,干燥得到ZSM-5分子筛;
(3)将步骤(2)得到的ZSM-5分子筛进行2~5次盐酸交换,室温下交换10~30min,过滤、水洗、过滤后,交换产物在水汽550~650℃下焙烧0.5~3小时,得HZSM-5分子筛;
(4)将步骤(3)得到的HZSM-5分子筛经稀土、磷、镁、锌中两种或两种以上元素的混合改性,室温下改性10~30min,过滤除去母液后,水洗滤料,过滤,干燥,550~650℃下焙烧0.5~3小时,制得增产丙烯催化裂化助剂。
2.根据权利要求1所述的增产丙烯催化裂化助剂的制备方法,其特征在于:步骤(1)所述高岭土加入量为固体混合物总重的10~30%。
3.根据权利要求1所述的增产丙烯催化裂化助剂的制备方法,其特征在于:步骤(1)所述添加剂包括硅酸钠、氢氧化钠、磷酸盐、碳酸盐、高分子聚合物、玉米粉等中的一种或多种。
4.根据权利要求1所述的增产丙烯催化裂化助剂的制备方法,其特征在于:步骤(2)所述白炭黑的加入量为步骤(2)固体总重1~10%。
5.根据权利要求1所述的增产丙烯催化裂化助剂的制备方法,其特征在于:步骤(2)所述氧化铝的加入量为步骤(2)固体总重1~10%。
6.根据权利要求1所述的增产丙烯催化裂化助剂的制备方法,其特征在于:步骤(2)所述晶种为ZSM-5、Y型、X型分子筛中的任意一种。
7.根据权利要求1所述的增产丙烯催化裂化助剂的制备方法,其特征在于:步骤(2)所述晶种的加入量为步骤(2)固体总重1~10%。
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