CN113976132B - 一种废旧塑料热裂解用碱性催化剂的制备方法 - Google Patents
一种废旧塑料热裂解用碱性催化剂的制备方法 Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/8472—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明公开了一种废旧塑料热裂解用碱性催化剂的制备方法,利用催化裂化装置卸下的平衡剂,进行扩孔、重构处理形成了适宜的孔径分布,为大分子提供了畅通的反应场所,再使用碱性金属进行反应和交换,形成分散的碱性中心,将大分子活化成碳负离子再进行β位断裂,可以减少焦炭的产生,提高使用周期。
Description
技术领域
本发明涉及一种废旧塑料热裂解用碱性催化剂的制备方法,属于碱性催化剂的范畴。
背景技术
塑料制品方便了人民的生活,但随着使用量的增加,导致大量的旧塑料的产生,如何处理成为难题。目前市面上有各种处理塑料的方法。
其中废塑料热解主要包括热裂解法、催化热裂解法、热裂解-催化改质法,并且有不同的工艺。
通常所用的催化剂有固体硅酸铝、分子筛等,但在反应过程中大量的焦炭沉积于催化剂表面使其失活,而且反应温度>650℃,对催化剂的稳定性提出了更高得要求。
固体碱催化剂作为环境友好催化剂应用于废旧塑料催化热裂解工艺中有其优势,其分类有单组分金属氧化物、碱金属改性分子筛、载体负载碱金属离子。
钙基固体碱催化活性中心具有极强的供电子能力,近年来研究较多,但粉未状的氧化钙催化剂存在比表面小、易吸收空气中CO2致失活等特点。
另外我国每年废FCC催化剂在10万吨以上,近年来划为危险废物,其再生处理主要采用磁分离技术和化学分离技术。磁分离利用Ni、Fe等金属的磁性以达到去除污染重的催化剂的目的,分离出污染较轻的催化剂用于平衡剂。该工艺电耗高、粉尘污染重、收率低。化学法主要使用酸浸,脱除部分金属,但程度不易控制。
发明内容
针对以上存在的现状,本发明提供了一种新的制备方法,所制备的碱性催化剂充分利用废平衡剂原有空间结构,又将活性组分通过酸碱反应和离子交换分散在废平衡剂孔道内外壁上,可以方便与塑料油气大分子接触反应,选择性好,使用周期长。
为了实现上述目的,本发明采用了以下技术方案:
(1)将催化裂化废平衡剂用水打浆,加入氟硅酸溶液,氟硅酸的加入量以氧化硅计与催化裂化废平衡剂干基的质量比为(0.096-0.325):1,调节pH值至2.0-2.8,常温反应60分钟后进行过滤洗涤;
(2)滤饼重新加水打浆,分批加入氢氧化钙固体,加入时间不低于3个小时,其加入量以氧化钙计与催化裂化废平衡剂干基的质量比为(0.36-0.64):1,控制浆液温度30-40℃;
(3)将上述浆液过滤,淋洗BaCl2溶液,BaCl2的加入量以BaO计与催化裂化废平衡剂干基的质量比为(0.12-0.45):1,闪蒸干燥后进行焙烧,焙烧温度为750-900℃,时间1-2小时,即得催化剂。
本发明具有以下特点及优势:
(1)保持催化剂的原有孔道和结构,并进行了适当的孔道清理与结构重构,使其作为进一步处理的基础。
(2)FCC催化剂再生温度>680℃,其40%为高岭土,在此温度下,高岭土进行脱羟基反应后形成了偏高岭土,其中的氧化铝组分得到活化。
Al2O3+Ca(OH)2→Ca(AlO2)2+H2O
而且高岭土在原有颗粒上均匀分布,布满催化剂的内外孔道壁上,能够提供有效的扩散通道。
(3)焙烧的过程,一是可以稳固结构,二是使活性V、Ni等金属得以固化,减少其脱氢性能。
具体实施方式
下面用具体实施方式对本发明作进一步详细说明。
本发明可用到的原材料的规格如下:
FCC废平衡剂:比表面105m2/g,V 4196ppm,Ni 3945ppm,灼减4.5wt%;
Ca(OH)2:以CaO计, 75.7wt%;
氟硅酸:以SiO2计, 90.5g/L;
BaCl2:以BaO计,5.15wt %。
实施例1:
(1)取FCC废平衡剂1570克,加水5182克进行打浆,加入3248mL的氟硅酸,用盐酸调pH值至2.75左右,反应60分钟后进行过滤水洗;
(2)将滤饼重新打浆,分批加入713克氢氧化钙,时间不少于3小时;
(3)过滤,洗涤,淋洗3495克BaCl2溶液,滤饼闪蒸干燥后在750℃焙烧2小时,样品标记为B-cat-1。
实施例2:
(1)取FCC废平衡剂1570克,加水6690克进行打浆,加入1740mL的氟硅酸,用盐酸调pH值至2.55左右,反应60分钟后进行过滤水洗;
(2)将滤饼重新打浆,分批加入951克氢氧化钙,时间不少于3小时;
(3)过滤,洗涤,淋洗7572克BaCl2溶液,滤饼闪蒸干燥后在750℃焙烧2小时,样品标记为B-cat-2。
实施例3:
(1)取FCC废平衡剂1570克,加水4320克进行打浆,加入4110mL的氟硅酸,用盐酸调pH值至2.35左右,反应60分钟后进行过滤水洗;
(2)将滤饼重新打浆,分批加入1109克氢氧化钙,时间不少于3小时;
(3)过滤,洗涤,淋洗10776克BaCl2溶液,滤饼闪蒸干燥后在750℃焙烧2小时,样品标记为B-cat-3。
使用聚丙烯塑料颗粒,每次进料2克,在自制的固定床裂解反应装置上进行评价,催化剂加剂量9克,反应温度660℃,产物分布如下:
项目 | B-cat-1 | B-cat-2 | B-cat-3 |
氢气 | 0.52 | 0.48 | 0.66 |
甲烷 | 10.10 | 9.89 | 12.15 |
乙烯 | 22.50 | 22.00 | 25.90 |
乙烷 | 3.90 | 4.09 | 4.11 |
丙烯 | 13.90 | 14.50 | 16.11 |
丙烷 | 0.33 | 0.55 | 1.01 |
丁二烯 | 5.09 | 4.87 | 7.32 |
C5馏分 | 3.90 | 4.01 | 2.15 |
C6~C8芳烃 | 11.30 | 12.15 | 13.33 |
柴油 | 3.3 | 4.2 | 1.8 |
从以上数据可以看出,其产物中乙烯+丙烯+丁烯,芳烃等高附加值产物较多,经济效益可观。
Claims (1)
1.一种废旧塑料热裂解用碱性催化剂的制备方法,具体步骤如下:
(1)将催化裂化废平衡剂用水打浆,加入氟硅酸溶液,氟硅酸的加入量以氧化硅计与催化裂化废平衡剂干基的质量比为(0.096-0.325):1,调节pH值至2.0-2.8,常温反应60分钟后进行过滤洗涤;
(2)滤饼重新加水打浆,分批加入氢氧化钙固体,加入时间不低于3个小时,其加入量以氧化钙计与催化裂化废平衡剂干基的质量比为(0.36-0.64):1,控制浆液温度30-40℃;
(3)将上述浆液过滤,淋洗BaCl2溶液,BaCl2的加入量以BaO计与催化裂化废平衡剂干基的质量比为(0.12-0.45):1,闪蒸干燥后进行焙烧,焙烧温度为750-900℃,时间1-2小时,即得催化剂。
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Citations (3)
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CN103157479A (zh) * | 2011-12-16 | 2013-06-19 | 山东辰昊化工有限公司 | 一种含钒废催化裂化平衡剂的再生方法 |
CN104815704A (zh) * | 2015-04-15 | 2015-08-05 | 中国石油大学(华东) | 一种和氯化稀土交换催化裂化废催化剂复活方法 |
CN105251525A (zh) * | 2015-10-18 | 2016-01-20 | 任丘市华北石油科林环保有限公司 | 一种含钒废催化裂化平衡剂的回收再利用方法 |
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CN103157479A (zh) * | 2011-12-16 | 2013-06-19 | 山东辰昊化工有限公司 | 一种含钒废催化裂化平衡剂的再生方法 |
CN104815704A (zh) * | 2015-04-15 | 2015-08-05 | 中国石油大学(华东) | 一种和氯化稀土交换催化裂化废催化剂复活方法 |
CN105251525A (zh) * | 2015-10-18 | 2016-01-20 | 任丘市华北石油科林环保有限公司 | 一种含钒废催化裂化平衡剂的回收再利用方法 |
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