CN116212940A - 一种焦炭、干气选择性优异的催化裂化催化剂的制备方法 - Google Patents
一种焦炭、干气选择性优异的催化裂化催化剂的制备方法 Download PDFInfo
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 20
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/08—Halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
本发明提供了一种焦炭、干气选择性优异的催化裂化催化剂的制备方法,通过对高岭土焙烧改性扩孔,在合适位置采用合适的方法添加金属钝化活性成分,使得制备出的催化剂具有合适的孔径、孔分布和酸性酸量,并能有效减少有害金属的毒害作用,具有明显的焦炭、干气选择性优势。
Description
技术领域
本发明涉及一种焦炭、干气选择性优异的催化裂化催化剂的制备方法,属于催化剂制备领域。
背景技术
我国承诺在2030年前,煤炭、石油、天然气等化石能源燃烧活动和工业生产过程以及土地利用变化与林业等活动产生的温室气体排放(也包括因使用外购的电力和热力等所导致的温室气体排放)不再增长,达到峰值。
炼油行业,如何应对呢?普遍的思路是降低炼油的加工吨油能耗,先进的炼油能耗低于50千克标准油/吨原油,国内都是60-70千克标准油/吨原油;改变炼油厂的燃料结构,毕竟,炼油厂碳排放33%是来自炼油厂的燃料燃烧;尽量在炼油厂复杂性和装置数量上找到平衡点,越是复杂的炼油厂,碳排放越高。一个简单型的炼油厂,0.2吨碳/吨原油,复杂型的炼油厂,达到0.4吨碳/吨原油。小型炼油厂,要转型或者产能合并;大型炼油厂,燃料结构必须改变;炼油工艺,必须简单并可操作性强,力争用简单的工艺,生产出复杂的产品。炼油要向低加工能耗、大的装置规模、清洁的燃料结构(甚至电加热工艺介质)、相对简单工艺、化工型转变。
催化裂化装置是炼油厂主要的CO2排放源之一。从降低催化裂化装置CO2排放、提高装置效益的角度出发,降低催化裂化碳排放最经济、最便捷、最有效的方法是开发降低焦炭产率为目标的新型催化裂化催化剂或催化助剂,目前主要通过超稳Y型分子筛技术和制备具有良好孔结构和酸性分布的催化剂载体材料来实现。
降低焦炭产率的分子筛技术主要集中于超稳Y型分子筛的制备研究,如CN200810102243.0,CN101537366A等。而在载体方面,需要提高反应物、生产物的扩散效率,减少过裂化,同时调变酸性类型,提高酸性中心的反应选择性-合成具有高孔体积、大孔径、较高B/L酸比值的材料是主要研究方向。
CN03147975.8公开了一种中孔硅铝材料具有拟薄水铝石的物相结构,以氧化物重量计的无水化学表达式为:(0-0.3)Na2O·(40-90)Al2O3·(10-60)SiO2,其比表面积为200~400m2/g,孔体积为0.5~2.0ml/g,平均孔径为8~20nm,最可几孔径为5~15nm。
CN201110251792.6公开了一种酸性硅铝催化材料,具有拟薄水铝石晶相结构;以氧化物重量计,其无水化学表达式为:(0~0.2)Na2O·(44~46)SiO2·(54~56)Al2O3,孔体积为0.5~1.0ml/g,平均孔径为8~15nm,该催化材料200℃测得的吡啶红外B酸与L酸的比例为0.130~0.150。
CN201110251761.0公开了一种中孔酸性硅铝催化材料,具有拟薄水铝石晶相结构,孔体积为1.0~2.0ml/g,平均孔径为8~20nm,该催化材料在200℃条件下测得的吡啶红外B酸与L酸的比例为0.060~0.085。
CN201210409663.X公开了一种含硅氧化铝干胶的制备方法,制备的含硅氧化铝干胶经500℃~950℃焙烧2~6小时,所得含硅氧化铝的性质如下:孔体积为0.55~1.10ml/g,孔分布如下:孔直径在10nm~50nm的孔的孔体积占总孔体积的30%~80%,B酸/L酸0.110~0.251。
郑金玉等通过成胶、陈化等工艺成功制备出一种具有拟薄水铝石结构的无序介孔硅铝材料(JSA),该材料具有较高的比表面积和孔体积,比表面积达300m2/g以上,孔体积大于0.7cm3/g,可几孔径在6~7nm,同时含有L酸中心和B酸中心,但L酸数量明显高于B酸中心。
存在的不足:(1)放大了介孔基质的扩散优势,认为只要扩散快,就不会有过度裂化,或者有一部分考虑基质的酸性和酸量,很少考虑到金属中毒对焦炭和干气选择性的影响更大;(2)自制的介孔基质不易酸化和粘结,需要更多的粘结剂或者提高成胶酸铝比才能保证磨损性能,而过多的粘结剂会堵塞分子筛孔道,过高的酸铝比加上过多的铝溶胶引入大量的氯离子,催化剂焙烧或加入FCC装置时,氯离子释放处理对设备腐蚀严重。
发明内容:
为了解决以上技术存在的不足,本发明提供了一种焦炭、干气选择性优异的催化裂化催化剂的制备方法,其具体步骤如下:
(1)高岭土打浆时加入一定比例的氯化镁、氯化稀土,搅拌均匀;
(2)将上述浆液干燥,饱和浸渍有机锌,焙烧处理;
(3)焙烧料加水打浆,添加一定比例的多水高岭土,加入复合酸,反应一段时间,继续加入一定比例的拟薄水铝石,整个过程需采取措施控制温升;
(4)向上述浆液中加入一定比例的REUSY分子筛、铝溶胶,喷雾造粒;
(5)喷雾后颗粒进入焙烧炉时,采用气相法引入氯化锑,与颗粒充分接触,焙烧完毕进行过滤洗涤和干燥,即得标题物。
步骤(1)中氯化镁的加入量以Mg0计为高岭土干基的(0.3-0.8)wt%,氯化稀土的加入量以RE2O3计为高岭土干基的(0.5-1.2)wt%;
步骤(2)中有机锌的加入量以ZnO计为高岭土干基的(0.6-0.9)wt%,可以是葡萄糖酸锌、柠檬酸锌或甘氨酸锌;
步骤(3)中复合酸的加入量为多水高岭土干基的(8-15)wt%,拟薄水铝石的加入量以Al2O3计为多水高岭土干基的(5-12)wt%;
步骤(4)中REUSY分子筛加入量为标题物干基的(30-43)wt%,铝溶胶的加入量以Al2O3计为标题物干基的(2-6)wt%;
步骤(5)中氯化锑加入量为标题物干基的(0.08-0.25)wt%,氯化锑应先升温到230℃,以气态的方式通过喷嘴进入焙烧炉炉头与喷雾塔底下来的催化剂颗粒充分接触。
高岭土与多水高岭土干基比例为(0.6-2.5):1。
本发明的有益之处:
(1)高岭土焙烧成偏土后使用复合酸改性,可以产生适当的扩孔作用,多水高岭土被复合酸处理,其管状的片层结构伸展开,一部分活性氧化铝还可以跟复合酸形成具有粘结性能的物质,有利于降低外加含氯粘结剂的添加比例;
(2)添加了一定比例的碱土金属、氧化稀土、锌、锑等元素,可以钝化钒、镍、铁等金属,这些金属都会引起焦炭、干气产率的增加;
(3)使用可溶性可用于食品添加的有机锌,避免制备时其他种类锌对工人和环境的毒害,采用有机锌饱和浸渍,使得锌最终主要负载在颗粒表面,因为毒害金属基本上都是沉积在颗粒表面。
(4)氯化锑在223.5℃以上气化,采用气相沉淀的方法,避免毒性较大的锑与人的接触,其与喷雾塔底落下的低温催化剂颗粒接触,液化后吸附在颗粒表面,随后被分解固定在催化剂颗粒表面。
具体实施方式:
下面进一步用实施例说明本发明,但本发明并不仅限于这些例子。
实施例中所用原材料规格如下:
以下材料均取自青岛惠城环保科技集团股份有限公司生产车间。
高岭土:干基75wt%;
氯化镁溶液:5wt%,以MgO计;
氯化稀土溶液:20.3wt%,以RE2O3计
有机锌溶液:3.2-4.2wt%,以ZnO计;
多水高岭土:干基63.5wt%;
复合酸:浓度35%;
拟薄水铝石:干基65wt%;
REUSY分子筛:灼减15wt%;
铝溶胶:21.2%,以Al2O3计;
实施例1:
(1)1333g高岭土加水打浆,加入氯化镁80g、氯化稀土54.2g,搅拌均匀;
(2)将上述浆液干燥,饱和浸渍有机锌200g(3.25%),焙烧处理;
(3)焙烧料加水打浆,添加1575g多水高岭土,加入复合酸314g,反应一段时间,继续加入590g拟薄水铝石,整个过程需采取措施控制温升;
(4)向上述浆液中加入1906gREUSY分子筛、603g铝溶胶,喷雾造粒;
(5)喷雾后颗粒进入焙烧炉时,采用气相法引入氯化锑6.43g,与颗粒充分接触,焙烧完毕进行过滤洗涤和干燥,记做CAT-1。
实施例2:
(1)1333g高岭土加水打浆,加入氯化镁120g、氯化稀土39.4g,搅拌均匀;
(2)将上述浆液干燥,饱和浸渍有机锌200g(3.75%),焙烧处理;
(3)焙烧料加水打浆,添加2362g多水高岭土,加入复合酸600g,反应一段时间,继续加入448g拟薄水铝石,整个过程需采取措施控制温升;
(4)向上述浆液中加入2168gREUSY分子筛、915g铝溶胶,喷雾造粒;
(5)喷雾后颗粒进入焙烧炉时,采用气相法引入氯化锑13.7g,与颗粒充分接触,焙烧完毕进行过滤洗涤和干燥,记做CAT-2。
实施例3:
(1)1333g高岭土加水打浆,加入氯化镁160g、氯化稀土29.6g,搅拌均匀;
(2)将上述浆液干燥,饱和浸渍有机锌200g(4.25%),焙烧处理;
(3)焙烧料加水打浆,添加787g多水高岭土,加入复合酸114g,反应一段时间,继续加入656g拟薄水铝石,整个过程需采取措施控制温升;
(4)向上述浆液中加入1588gREUSY分子筛1005g铝溶胶,喷雾造粒;
(5)喷雾后颗粒进入焙烧炉时,采用气相法引入氯化锑16.8g,与颗粒充分接触,焙烧完毕进行过滤洗涤和干燥,记做CAT-3。
催化剂采用循环污染的方式浸渍铁、镍、钒等金属,对比剂为常规制备相同分子筛含量和活性的配方,进行适当的水热老化处理,使用ACE-AP评价装置进行对比评价。所用原料油的数据见表1,评价数据见表2,表3。
表1原料油性质
表2浸渍铁后评价数据
表3浸渍镍、钒后对比评价数据
从以上对比评价数据可以看出,本发明的催化剂,在较高金属含量下,干气、焦炭选择性均有了明显的改善,相应的轻收和液收也明显有了提高,性能优异。
Claims (7)
1.一种焦炭、干气选择性优异的催化裂化催化剂的制备方法,该方法包括以下步骤:
(1)高岭土打浆时加入一定比例的氯化镁、氯化稀土,搅拌均匀;
(2)将上述浆液干燥,饱和浸渍有机锌,焙烧处理;
(3)焙烧料加水打浆,添加一定比例的多水高岭土,加入复合酸,反应一段时间,继续加入一定比例的拟薄水铝石,整个过程需采取措施控制温升;
(4)向上述浆液中加入一定比例的REUSY分子筛、铝溶胶,喷雾造粒;
(5)喷雾后颗粒进入焙烧炉时,采用气相法引入氯化锑,与颗粒充分接触,焙烧完毕进行过滤洗涤和干燥,即得标题物。
2.根据权利要求书1所述的制备方法,其特征在于步骤(1)中氯化镁的加入量以Mg0计为高岭土干基的(0.3-0.8)wt%,氯化稀土的加入量以RE2O3计为高岭土干基的(0.5-1.2)wt%。
3.根据权利要求书1所述的制备方法,其特征在于步骤(2)中有机锌的加入量以ZnO计为高岭土干基的(0.6-0.9)wt%,有机锌可以是葡萄糖酸锌、柠檬酸锌或甘氨酸锌。
4.根据权利要求书1所述的制备方法,其特征在于步骤(3)中复合酸的加入量为多水高岭土干基的(8-15)wt%,拟薄水铝石的加入量以Al2O3计为多水高岭土干基的(5-12)wt%。
5.根据权利要求书1所述的制备方法,其特征在于步骤(4)中REUSY分子筛加入量为标题物总干基的(30-43)wt%,铝溶胶的加入量以Al2O3计为标题物总干基的(2-6)wt%。
6.根据权利要求书1所述的制备方法,其特征在于步骤(5)中氯化锑加入量为标题物总干基的(0.08-0.25)wt%,氯化锑应先升温到230℃,以气态的方式通过喷嘴进入焙烧炉炉头与喷雾塔底下来的催化剂颗粒充分接触。
7.根据权利要求书1所述的制备方法,其特征在于高岭土与多水高岭土干基比例为(0.6-2.5):1。
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