CN112237940A - 一种增产柴油催化裂化助剂的制备方法 - Google Patents
一种增产柴油催化裂化助剂的制备方法 Download PDFInfo
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Abstract
本发明属于催化裂化助剂制备技术领域,公开一种增产柴油催化裂化助剂的制备方法,包括:(1)将高岭土、海泡石、白炭黑、添加剂混合成固体混合物,加水打浆,喷雾干燥成微球,焙烧;(2)将焙烧微球与硅酸钠、碱液、导向剂、细粉混合投入晶化反应釜中,水热晶化8‑36h,过滤,干燥得到含有微孔分子筛的复合材料;(3)将复合材料进行酸交换和铵盐交换,过滤水洗,水汽条件下焙烧得HY分子筛;(4)将HY分子筛经改性剂进行混合改性,过滤干燥,焙烧得增产柴油催化裂化助剂。本发明制备的增产柴油催化裂化助剂,调节了微孔分子筛和介孔组分的分配比例,有效调节助剂的反应活性,在增产柴油助剂的同时,降低焦炭产率。
Description
技术领域
本发明属于催化裂化助剂制备技术领域,涉及一种增产柴油催化裂化助剂的制备方法。
背景技术
催化裂化是石油炼制过程中的重要环节之一,是在热和催化剂的作用下使重质油发生裂化反应,转变为裂化气、汽油和柴油等的过程,其中汽油收率和柴油收率之和称为轻质油收率,轻质油收率与液化气收率之和称为总液收,炼油厂所追求的催化裂化产品的分布应该是尽可能高的轻质油收率或总液收,以达到最大的经济效益。然而催化裂化过程中会产生大量的二氧化碳,催化裂化产生的二氧化碳排放居炼油工业的首位,占炼厂二氧化碳排放的15-20%,最高达到30%。因此,降低炼厂二氧化碳排放首先必须降低催化裂化二氧化碳排放。催化裂化二氧化碳排放主要是在催化剂再生烧焦过程中产生的,因此,降低催化裂化二氧化碳排放必须降低催化裂化的焦炭产率。
目前催化裂化的改进主要是从催化剂入手,常用方法是对催化剂的基质组分进行改性或增加分子筛的二级孔,但是采用这种方法常导致深度裂化,产品结构由重燃料油向低沸点产品转化,并且使气体和焦炭产率明显升高催化裂化过程的改进除了从催化剂改进入手外,还可以选择采用有着辅助作用的催化裂化助剂,催化剂助剂使用简便,无需更换催化裂化催化剂,用量小,见效快。然而目前催化裂化助剂普遍存在着附加值高的产品增收效果不明显,抗焦阻垢能力差、仍需添加金属钝化剂等缺陷。
发明内容
本发明要解决的技术问题是克服上述缺陷,提供一种焦炭产率低、方法简单、成本低廉的增产柴油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:
一种增产柴油催化裂化助剂的制备方法,包括如下步骤:
(1)将高岭土、海泡石、白炭黑、添加剂混合成固体混合物,加水打浆,喷雾干燥成微球,微球在700~1000℃下焙烧0.5~5小时,得焙烧微球;
(2)将步骤(1)得到的焙烧微球与硅酸钠、碱液、导向剂、细粉混合投入晶化反应釜中,在95~120℃下水热晶化8~36h,过滤除去母液后,滤料水洗,过滤,干燥得到含有微孔分子筛的复合材料;
(3)将步骤(2)得到的复合材料进行2~5次酸交换和铵盐交换,室温下交换10~120min,过滤、水洗、过滤后,交换产物在60~100%水汽、450~650℃下焙烧0.5~3小时,得HY分子筛;
(4)将步骤(3)得到的HY分子筛经改性剂进行混合改性,室温下改性 10~120min,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,制得增产柴油催化裂化助剂。
优选的,步骤(1)所述高岭土加入量为固体混合物总重的30~60%,所述海泡石加入量为固体混合物总重10~50%,所述白炭黑加入量为固体混合物总重 5~20%。
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、氧化铝、铝溶胶、拟薄水铝石、氢氧化铝、高分子聚合物、玉米粉等中的一种或多种。
优选的,步骤(1)所述添加剂加入量为固体混合物总重1~10%。
优选的,步骤(2)所述细粉为原位生产过程产生的细粉,所述细粉的平均中位径小于5μm,所述细粉的加入量为焙烧微球总量的1~5%。
优选的,步骤(2)所述复合材料中包括微孔分子筛和改性介孔组分,其中所述微孔分子筛含量为总量的20~30%,改性介孔组分含量为总量的40~60%。
优选的,步骤(4)所述改性剂为稀土与磷、镁、锌中一种或两种以上元素组成的改性剂。
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,有效调节助剂的北部孔道的分布,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)本发明制备的增产柴油催化裂化助剂的微孔分子筛的活性组分通过原位合成配方得到有效控制,调节了微孔分子筛和介孔组分的分配比例,有效调节助剂的反应活性,在增产柴油助剂的同时,降低焦炭产率。
(3)本发明增产柴油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。
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
一种增产柴油催化裂化助剂的制备方法,包括如下步骤:
(1)将633g高岭土、359g海泡石、53g白炭黑混合打浆,加入10g硅酸钠,加水制成固含量38%的浆液,喷雾干燥成微球,微球在700℃下焙烧5小时,得焙烧微球;
(2)将500g焙烧微球、253mL硅酸钠、278mL碱液、138mL导向剂、120mL 水、5g细粉投入晶化反应釜中,在95℃下水热晶化36h,过滤除去母液后,滤料水洗,过滤,干燥得到合成含有微孔分子筛的复合材料;经X-射线衍射测定,含29%的NaY沸石,比表面为311m2/g,孔体积为0.35g/l;
(3)将步骤(2)得到的复合材料300g、氯化铵30g、水900mL,加入盐酸控制pH=3.0,室温下交换10min,过滤、水洗、过滤后,交换产物在60%水汽、450℃下焙烧3小时,以上步骤重复2次,得HY分子筛;
(4)将步骤(3)得到的HY分子筛、LaCl3溶液50mL、氯化镁10g、水 750mL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,制得增产柴油催化裂化助剂。
实施例2
一种增产柴油催化裂化助剂的制备方法,包括如下步骤:
(1)将317g高岭土、528g海泡石、105g白炭黑混合打浆,加入35g磷酸钠、35g氢氧化铝、35g玉米粉,加水制成固含量38%的浆液,喷雾干燥成微球,微球在900℃下焙烧2小时,得焙烧微球;
(2)将360g焙烧微球、175mL硅酸钠、195mL碱液、97mL导向剂、18g 细粉投入晶化反应釜中,在110℃下水热晶化15h,过滤除去母液后,滤料水洗,过滤,干燥得到合成含有微孔分子筛的复合材料;经X-射线衍射测定,含21%的NaY沸石,比表面为223m2/g,孔体积为0.32g/l;
(3)将步骤(2)得到的复合材料300g、氯化铵45g、水900mL,加入盐酸控制pH=3.2,室温下交换80min,过滤、水洗、过滤后,交换产物在80%水汽、500℃下焙烧1小时,以上步骤重复一次,得HY分子筛;
(4)将步骤(3)得到的HY分子筛、LaCl3溶液40mL、氯化锌6g、水750mL 加入到反应釜中进行改性,室温下交换60min,过滤除去母液后,水洗滤料,过滤,干燥,600℃下焙烧2小时,制得增产柴油催化裂化助剂。
实施例3
一种增产柴油催化裂化助剂的制备方法,包括如下步骤:
(1)将400g高岭土、480g海泡石、115g白炭黑混合打浆,加入40g碳酸铵,20g氢氧化钠,加水制成固含量38%的浆液,喷雾干燥成微球,微球在850℃下焙烧3小时,得焙烧微球;
(2)将730g焙烧微球、511mL硅酸钠、450mL碱液、200mL导向剂、185mL 水、21g细粉投入晶化反应釜中,在100℃下水热晶化20h,过滤除去母液后,滤料水洗,过滤,干燥得到合成含有微孔分子筛的复合材料;经X-射线衍射测定,含25%的NaY沸石,比表面为257m2/g,孔体积为0.33g/l;
(3)将步骤(2)得到的复合材料300g、氯化铵90g、水900mL,加入盐酸控制pH=3.0,室温下交换30min,过滤、水洗、过滤后,交换产物在100%水汽、550℃下焙烧1.5小时,以上步骤重复一次,得HY分子筛;
(4)将步骤(3)得到的HY分子筛、LaCl3溶液45mL、氯化锌10g、水 750mL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,制得增产柴油催化裂化助剂。
实施例4
一种增产柴油催化裂化助剂的制备方法,包括如下步骤:
(1)将633g高岭土、105g海泡石、211g白炭黑混合打浆,加入55g氧化铝、50g高分子聚合物,加水制成固含量38%的浆液,喷雾干燥成微球,微球在 1000℃下焙烧0.5小时,得焙烧微球;
(2)将600g焙烧微球、278mL硅酸钠、360mL碱液、163mL导向剂、24g 细粉投入晶化反应釜中,在120℃下水热晶化8h,过滤除去母液后,滤料水洗,过滤,干燥得到合成含有微孔分子筛的复合材料;经X-射线衍射测定,含27%的NaY沸石,比表面为271m2/g,孔体积为0.37g/l;
(3)将步骤(2)得到的复合材料300g、氯化铵45g、水900mL,加入盐酸控制pH=3.0,室温下交换120min,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HY分子筛;
(4)将步骤(3)得到的HY分子筛、LaCl3溶液30mL、磷酸二氢铵10g、水750mL加入到反应釜中进行改性,室温下交换120min,过滤除去母液后,水洗滤料,过滤,干燥,650℃下焙烧0.5小时,制得增产柴油催化裂化助剂。
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=1.54056 nm,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15%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15%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。
项目 | 对照组 | 实验组1 | 实验组2 | 实验组3 | 实验组4 |
温度/℃ | 500 | 500 | 500 | 500 | 500 |
剂油比 | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 |
干气 | 2.14 | 2.07 | 2.01 | 2.04 | 2.11 |
液化气 | 16.69 | 16.33 | 16.18 | 16.45 | 16.32 |
汽油 | 46.23 | 46.38 | 46.65 | 47.06 | 46.46 |
柴油 | 19.68 | 21.12 | 20.97 | 20.80 | 21.23 |
重油 | 7.09 | 6.47 | 6.35 | 6.13 | 6.21 |
焦碳 | 8.17 | 7.63 | 7.84 | 7.52 | 7.67 |
转化率/m% | 73.23 | 72.41 | 72.68 | 73.07 | 72.56 |
轻收/m% | 65.91 | 67.50 | 67.62 | 67.86 | 67.69 |
从表上数据可以看出,添加本发明制备的增产柴油助剂均表现出增产柴油能力强、焦炭选择性好的特点,尤其是实施例3制备的增产柴油助剂的性能能优。
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。
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)
1.一种增产柴油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、海泡石、白炭黑、添加剂混合成固体混合物,加水打浆,喷雾干燥成微球,微球在700~1000℃下焙烧0.5~5小时,得焙烧微球;
(2)将步骤(1)得到的焙烧微球与硅酸钠、碱液、导向剂、细粉混合投入晶化反应釜中,在95~120℃下水热晶化8~36h,过滤除去母液后,滤料水洗,过滤,干燥得到含有微孔分子筛的复合材料;
(3)将步骤(2)得到的复合材料进行2~5次酸交换和铵盐交换,室温下交换10~120min,过滤、水洗、过滤后,交换产物在60~100%水汽、450~650℃下焙烧0.5~3小时,得HY分子筛;
(4)将步骤(3)得到的HY分子筛经改性剂进行混合改性,室温下改性10~120min,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,制得增产柴油催化裂化助剂。
2.根据权利要求1所述的增产柴油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30~60%,所述海泡石加入量为固体混合物总重10~50%,所述白炭黑加入量为固体混合物总重5~20%。
3.根据权利要求1所述的增产柴油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、氧化铝、铝溶胶、拟薄水铝石、氢氧化铝、高分子聚合物、玉米粉等中的一种或多种。
4.根据权利要求3所述的增产柴油催化裂化助剂的制备方法,其特征在于:步骤(1)所述添加剂加入量为固体混合物总重1~10%。
5.根据权利要求1所述的增产柴油催化裂化助剂的制备方法,其特征在于:步骤(2)所述细粉为催化剂生产过程产生的细粉,所述细粉的平均中位径小于5μm,所述细粉的加入量为焙烧微球总量的1~5%。
6.根据权利要求1所述的增产柴油催化裂化助剂的制备方法,其特征在于:步骤(2)所述复合材料中包括微孔分子筛和改性介孔组分,其中所述微孔分子筛含量为总量的20~30%,改性介孔组分含量为总量的40~60%。
7.根据权利要求1所述的增产柴油催化裂化助剂的制备方法,其特征在于:步骤(4)所述改性剂为稀土与磷、镁、锌中一种或两种以上元素组成的改性剂。
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