CN111111771A - 一种催化裂化废催化剂的回收利用方法及应用 - Google Patents
一种催化裂化废催化剂的回收利用方法及应用 Download PDFInfo
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Abstract
一种催化裂化废催化剂的回收利用方法及应用，1)用水配置亚铁盐溶液，其中亚铁离子的浓度为0.01mol/L～1mol/L，向配置好的亚铁盐溶液中加入一定质量的催化裂化废催化剂并均匀搅拌，形成溶液A；2)向上述溶液A中通入过量的空气或者氧气，加入碱溶液并搅拌均匀，通过加入碱溶液的含量控制反应过程pH值在4.0～7.0，反应0.4～5h，反应温度为10～60摄氏度；所述碱溶液为含有氢氧根离子的强碱或者弱碱；3)反应结束后出料，脱水并干燥，得到活性组分为α‑FeOOH的负载型催化剂。该方法生产制备方式简单，成本低廉，环境污染小且易于工业化，能够实现资源的有效循环利用。
Description
技术领域
本发明涉及工业废弃催化剂回收利用技术领域，特别涉及一种催化裂化废催化剂的回收利用方法及应用。
背景技术
世界原油开采到今天，原油中高分子的沥青、胶质；金属污染物和硫、氮、氧等化合物含量的上升导致的重质化越来越严重，进而引发全球范围内的裂化催化剂需求量的大幅度增加。我国作为催化裂化能力世界第二位的大国，对催化裂化催化剂的需求同样增长迅速。催化裂化装置中会有部分自然损耗的催化裂化催化剂，还会有大量活性或选择性降低导致必须定期卸出的废催化剂，造成巨大的经济损失，同时废催化剂中毒后含有一定量的钒、镍和锡等有毒重金属，导致废催化剂成为有毒的固体废料
目前废催化剂的再利用主要有三种：(1)直接作为其他工艺的催化剂使用，国外专门针对金属含量较高的渣油炼制的RFCC装置较少，占全部FCC装置的比重不高，因此FCC装置中排出的废催化剂可直接供RFCC装置使用；(2)作为铺路材料再次利用，这一点国外曾有相关的一些报导，另外，也有报导将废催化剂混合到到沥青中使用，但国内未见这一方面的研究报导；(3)作为水泥的代替原料再利用，理论上，采用废催化剂作为生产水泥的原料具有极大的可行性，但一般水泥厂的规模较大，对原料的需求量较大，虽然FCC装置中卸出的废催化剂总量不小，但相比水泥厂的需求量还是明显不足，难以做到连续生产，实际应用上存在一定困难。因此，如何有效回收再利用催化裂化废催化剂，是当前亟需解决的问题。
发明内容
为了克服上述现有技术的不足，本发明的目的在于提供一种催化裂化废催化剂的回收利用方法及应用，以催化裂化废催化剂为载体，纳米级α-FeOOH为活性组分，通过共沉淀法合成负载型α-FeOOH催化剂，应用于煤液化反应，活性好且脱硫性能强。该方法生产制备方式简单，成本低廉，环境污染小且易于工业化，能够实现资源的有效循环利用。
为了实现上述目的，本发明采用的技术方案是：
一种催化裂化废催化剂的回收利用方法，包括以下步骤；
1)用水配置亚铁盐溶液，其中亚铁离子的浓度为0.01mol/L～1mol/L，向配置好的亚铁盐溶液中加入待合成催化剂的50wt％-97wt％的催化裂化废催化剂并均匀搅拌，形成溶液A；
2)向上述溶液A中通入过量的空气或者氧气，加入碱溶液并搅拌均匀，通过加入碱溶液的含量控制反应过程pH值在4.0～7.0，反应0.4～5h，反应温度为10～60摄氏度；所述碱溶液为含有氢氧根离子的强碱或者弱碱；
3)反应结束后出料，脱水并干燥，得到活性组分为α-FeOOH的负载型催化剂。
所述的催化裂化废催化剂为石油化工催化剂裂化工艺排出的废催化剂，其粒径为0～50μm，α-FeOOH负载量为1％～50％；负载型α-FeOOH催化剂比表面积为10～1000m2/g。
所述的催化裂化废催化剂可作为煤油共炼、煤直接液化、重劣质油轻质化、煤焦油加氢催化剂的原料载体，通过共沉淀法负载α-FeOOH于催化裂化废催化剂，制备新型煤油共炼、煤直接液化、重劣质油轻质化、煤焦油加氢催化剂。
α-FeOOH的负载型催化剂应用于煤油共炼、煤直接液化、重劣质油轻质化、煤焦油加氢时，添加量为反应原料的0.1～3wt％。
各项条件是：反应温度：＞440摄氏度；反应压力：＞16MPa；煤的加入量：＜50wt％。
本发明的有益效果：
1)本发明提供了一种催化裂化废催化剂回收再利用的新方法，创造性的将催化裂化废催化剂作为载体制备负载型α-FeOOH催化剂，扩大了催化裂化废催化剂回收再利用的应用领域，减少了催化裂化废催化剂的处理成本，具有较好的经济效益和环境效益。
2)本发明以催化裂化废催化剂作为载体制备的负载型α-FeOOH催化剂，在煤液化反应中活性好且脱硫性能强，综合性能优异。
3)本发明提供的催化裂化废催化剂回收再利用方法具有生产制备方式简单，成本低廉，环境污染小且易于工业化的优点，能够实现资源的有效循环利用。
附图说明
图1为本发明实施例1中负载型α-FeOOH催化剂的x射线衍射图谱(XRD)。
图2为本发明实施例2中负载型α-FeOOH催化剂的放大35000倍扫描电镜(SEM)照片。
具体实施方式
下面结合附图对本发明作进一步详细说明。
本发明首先提出一种催化裂化废催化剂的利用方法，采用催化裂化废催化剂为载体，纳米级α-FeOOH为活性组分，通过共沉淀法合成负载型α-FeOOH催化剂。
进一步的，以上负载型α-FeOOH催化剂负载量为1％～50％；比表面积为10～1000m2/g。
本发明还提供了上述负载型α-FeOOH催化剂的制备方法，包括以下步骤：
1)用水配置亚铁盐溶液，其中亚铁离子的浓度为0.01mol/L～1mol/L，向配置好的亚铁盐溶液中加入待合成催化剂的50wt％-97wt％的催化裂化废催化剂并均匀搅拌，形成溶液A；
2)向上述溶液A中通入过量的空气或者氧气，加入碱溶液并搅拌均匀，通过加入碱溶液的含量控制反应过程pH值在4.5～7.0，反应0.4～5h，反应温度为10～60摄氏度；所述碱溶液为含有氢氧根离子的强碱或者弱碱；
3)反应结束后出料，、脱水并干燥，得到活性组分为α-FeOOH的负载型催化剂。
本发明还提供了一种上述负载型α-FeOOH催化剂的应用，用于煤液化反应时，添加量为反应原料的0.1～3wt％。
以下通过具体实施例进一步详细说明本发明。除非特别说明，被发明实施例所用的原料均可通过常规市购买，或根据本领域的常规方法制备得到，所用设备为实验室常用设备。除非另有定义或说明，本文中所使用的专业用语与本领域技术熟练人员所熟悉的意义相同。
实施例1
用去离子水配置成浓度为0.027mol/L的硫酸亚铁溶液，并向该溶液中加入5.6g催化裂化废催化剂；向上述溶液中通入流量为1m3/h的空气，同时逐渐加入浓度为1mol/L的氨水溶液，溶液pH维持在6～7，反应1.5h，反应温度为40摄氏度。随后出料、抽滤并在80摄氏度的恒温干燥箱中干燥，得到以Fe计算负载量为9wt％的本发明负载型α-FeOOH催化剂，该催化剂的SEM照片如图所示。
实施例2
将实施例1得到的负载型α-FeOOH催化剂应用于煤液化反应中，以催化裂化油浆和杭来湾煤作为原料。反应条件为：反应温度455摄氏度；反应氢气初始压力：9MPa；催化剂加入量：1wt％(反应原料)；煤加入量：20wt％；硫化剂：硫粉；反应时间：1h。反应结果及煤液化相关指标如下表所示：
图1为实施例1中负载型α-FeOOH催化剂的x射线衍射图谱(XRD)。可以看出，在18°、21°、26°、33°、35°、37°、40°、41°、53°、59°等处出现了明显的α-FeOOH特征衍射峰；在5°、15°等处出现了催化裂化催化剂的特征衍射峰。
图2为实施例1所述催化剂的扫描电镜(SEM)照片，可以看出活性组分α-FeOOH颗粒在催化裂化废催化剂表面排列整齐，均匀分散。
将上述负载型α-FeOOH催化剂应用于煤液化反应中，各项条件是：反应温度：＞440摄氏度；反应压力：＞16MPa；煤的加入量：＜50wt％。
FCC催化剂是一种分子筛催化剂。分子筛材料具有特殊的表面性质，是理想的催化剂载体，负载活性组分α-FeOOH得到的Fe基催化剂应用于煤液化反应时，具有良好的催化活性；还可利用其表面的酸性位点作为脱硫的活性中心，提高反应脱硫率。该催化剂制备方法简单，成本低廉，环境污染小且易于工业化，能够实现资源的有效循环利用。
实施例3
用去离子水配置成浓度为0.01mol/L的硫酸亚铁溶液，并向该溶液中加入5.6g催化裂化废催化剂；向上述溶液中通入流量为1m3/h的空气，同时逐渐加入浓度为1mol/L的氨水溶液，溶液pH维持在6～7，反应1.5h，反应温度为40摄氏度。随后出料、抽滤并在80摄氏度的恒温干燥箱中干燥，得到以Fe计算负载量为3.4wt％的本发明负载型α-FeOOH催化剂。
实施例4
用去离子水配置成浓度为1mol/L的硫酸亚铁溶液，并向该溶液中加入35.6g催化裂化废催化剂；向上述溶液中通入流量为1m3/h的空气，同时逐渐加入浓度为1mol/L的氨水溶液，溶液pH维持在6～7，反应1.5h，反应温度为40摄氏度。随后出料、抽滤并在80摄氏度的恒温干燥箱中干燥，得到以Fe计算负载量为44wt％的本发明负载型α-FeOOH催化剂。
发明人声明，本发明通过上述实施例来说明本发明的详细工艺流程，但本发明并不局限于上述详细工艺流程，即不意味着本发明必须依赖上述详细工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品个原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。
Claims (6)
1.一种催化裂化废催化剂的回收利用方法，其特征在于，包括以下步骤；
1)用水配置亚铁盐溶液，其中亚铁离子的浓度为0.01mol/L～1mol/L，向配置好的亚铁盐溶液中加入催化裂化废催化剂并均匀搅拌，形成溶液A；
2)向上述溶液A中通入过量的空气或者氧气，加入碱溶液并搅拌均匀，通过加入碱溶液的含量控制反应过程pH值在4.0～7.0，反应0.4～5h，反应温度为10～60摄氏度；所述碱溶液为含有氢氧根离子的强碱或者弱碱；
3)反应结束后出料，脱水并干燥，得到活性组分为α-FeOOH的负载型催化剂。
2.根据权利要求1所述的一种催化裂化废催化剂的回收利用方法，其特征在于，所述的催化裂化废催化剂为石油化工催化剂裂化工艺排出的废催化剂，其粒径为0～50μm，活性组分为α-FeOOH的负载型催化剂中α-FeOOH负载量为1％～50％；活性组分为α-FeOOH的负载型催化剂比表面积为10～1000m2/g。
3.根据权利要求1所述的一种催化裂化废催化剂的回收利用方法，其特征在于，所述的催化裂化废催化剂作为煤油共炼、煤直接液化、重劣质油轻质化、煤焦油加氢催化剂的原料载体，通过共沉淀法负载α-FeOOH于催化裂化废催化剂，制备新型煤油共炼、煤直接液化、重劣质油轻质化、煤焦油加氢催化剂。
4.权利要求1制备的活性组分为α-FeOOH的负载型催化剂应用于煤油共炼、煤直接液化、重劣质油轻质化、煤焦油加氢。
5.根据权利要求4所述的应用，其特征在于，活性组分为α-FeOOH的负载型催化剂的添加量为反应原料的0.1～3wt％。
6.根据权利要求4所述的应用，其特征在于，反应中的各项条件是：反应温度：＞440摄氏度；反应压力：＞16MPa；煤的加入量：＜50wt％。
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