铝基废催化剂载体的回收与再生制备

doi:10.16085/j.issn.1000-6613.2024-0504

化工进展 ›› 2024, Vol. 43 ›› Issue (S1): 640-649.DOI: 10.16085/j.issn.1000-6613.2024-0504

铝基废催化剂载体的回收与再生制备

李琳¹^,²(), 黄国勇¹^,²(), 徐盛明²^,³, 郁丰善¹^,⁴, 翁雅青⁵, 曹才放⁶, 温嘉玮¹(), 王春霞¹, 王俊莲⁷, 顾斌涛⁵, 张袁华², 刘斌⁸, 王才平⁹, 潘剑明⁸, 徐泽良⁴, 王翀⁹, 王珂²

^1.中国石油大学（北京）新能源与材料学院，北京 102249
^2.江西耐华环保科技有限公司，江西上饶 334000
^3.清华大学核能与新能源研究院，北京 100084
^4.江西省君鑫贵金属科技材料有限公司，江西上饶 335500
^5.江西省科学院，江西南昌 330096
^6.江西理工大学，江西赣州 341000
^7.北京科技大学土木与资源工程学院，北京 100083
^8.浙江微通催化新材料有限公司，浙江丽水 323300
^9.横峰县凯怡实业有限公司，江西上饶 334300

收稿日期:2024-03-27 修回日期:2024-06-12 出版日期:2024-11-20 发布日期:2024-12-06
通讯作者: 黄国勇,温嘉玮
作者简介:李琳（1999—），女，硕士研究生，研究方向为铝资源回收及再生利用。E-mail：lilin03211999@163.com。
基金资助:
国家重点研发计划(2021YFC2901100);国家自然科学基金(52274307);中国石油大学科学基金(2462021QNX2010);重油加工国家重点实验室(HON-KFKT2022-10)

Recovery and regeneration preparation of aluminum-based spent catalyst support

LI Lin¹^,²(), HUANG Guoyong¹^,²(), XU Shengming²^,³, YU Fengshan¹^,⁴, WENG Yaqing⁵, CAO Caifang⁶, WEN Jiawei¹(), WANG Chunxia¹, WANG Junlian⁷, GU Bintao⁵, ZHANG Yuanhua², LIU Bin⁸, WANG Caiping⁹, PAN Jianming⁸, XU Zeliang⁴, WANG Chong⁹, WANG Ke²

^1.College of New Energy and Materials, China University of Petroleum, Beijing 102249, China
^2.Jiangxi Naihua Environmental Protection Technology Co. , Ltd. , Shangrao 334000, Jiangxi, China
^3.Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China
^4.Jiangxi Province Junxin Precious Metal Technology Materials Co. , Ltd. , Shangrao 335500, Jiangxi, China
^5.Jiangxi Academy of Sciences, Nanchang 330096, Jiangxi, China
^6.Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi, China
^7.College of Civil and Resource Engineering, University of Science and Technology Beijing, Beijing 100083, China
^8.Zhejiang Micro General New Catalytic materials Co. , Ltd. , Lishui 323300, Zhejiang, China
^9.Hengfeng Kaiyi Industrial Co. , Ltd. , Shangrao 334300, Jiangxi, China

Received:2024-03-27 Revised:2024-06-12 Online:2024-11-20 Published:2024-12-06
Contact: HUANG Guoyong, WEN Jiawei

摘要/Abstract

摘要：

铝基催化剂是石油精炼行业中需求量最大、用途最广的催化剂。将报废无法继续使用的铝基废催化剂载体回收再生，可大幅度地提高工业催化过程的综合经济效益。本研究工作通过“钠化焙烧-弱碱性浸出”将用于轻质油催化重整工艺的废Pt-Sn/Al₂O₃催化剂中的铝元素回收得到NaAlO₂溶液，并采用反沉淀法将NaAlO₂制备成具有高比表面积、大孔体积的介孔γ-Al₂O₃。通过改变焙烧温度、原料质量比、浸出pH等参数，研究铝浸出率的影响规律，在焙烧温度为450℃、质量比为1.2、浸出pH为8.5的条件下，铝的浸出率高达99.9%，效果最佳。将回收的NaAlO₂溶液制备为介孔γ-Al₂O₃，利用X射线粉末衍射仪（XRD）、Brunner-Emmet-Teller（BET）、粒度分析仪等对制备的样品进行表征。结果表明，在焙烧温度为500℃、老化时间为12h、反应pH为10的条件下，合成的介孔氧化铝比表面积为284.19m²/g，孔体积为0.47cm³/g，平均孔径为6.65nm，且其孔径分布均一、颗粒均匀程度良好，所得再生γ-Al₂O₃的比表面积、粒径等均满足《氧化铝》（GB/T24487—2022），样品纯度可达99.9%。

关键词: 催化剂载体, 弱碱性浸出, 偏铝酸钠, 反沉淀法, 再生, 氧化铝, 理化指标调控

Abstract:

Aluminum-based catalyst is the most demanding and widely used catalyst in petroleum refining industry. The comprehensive economic benefits of industrial catalytic process can be greatly improved by recycling the discarded aluminum-based spent catalyst support that can not be used any more. In this study, the aluminum support from spent Pt-Sn/Al₂O₃ catalyst was recovered by“sodium roasting-weak alkaline leaching”to obtain NaAlO₂ solution, and NaAlO₂ was prepared into mesoporous alumina with high specific surface area and large pore volume by reverse precipitation. By changing the parameters such as roasting temperature, mass ratio of raw materials and leaching pH, the leaching rate of aluminum was optimized. Under the conditions of roasting temperature of 450℃, mass ratio of 1.2 and leaching pH of 8.5, the leaching rate of aluminum could reach 99.9%. Mesoporous alumina was prepared from recovered NaAlO₂ solution, and prepared samples were characterized by X-ray diffraction (XRD), Brunner-Emmet-Teller (BET) and particle size analyzer. The results show that under the conditions of calcination temperature of 500℃, aging time of 12h and reaction pH of 10, the specific surface area of mesoporous alumina synthesized is 284.19m²/g, the pore volume is 0.47cm³/g, and the average pore diameter is 6.65nm. The pore size distribution is uniform and the particle uniformity is good. The specific surface area and particle size of the regenerated alumina meet the national standard of alumina (GB/T24487—2022).

Key words: catalyst support, weak alkaline leaching, NaAlO₂, inverse precipitation method, regeneration, alumina, physical and chemical index regulation

中图分类号:

X789

李琳, 黄国勇, 徐盛明, 郁丰善, 翁雅青, 曹才放, 温嘉玮, 王春霞, 王俊莲, 顾斌涛, 张袁华, 刘斌, 王才平, 潘剑明, 徐泽良, 王翀, 王珂. 铝基废催化剂载体的回收与再生制备[J]. 化工进展, 2024, 43(S1): 640-649.

LI Lin, HUANG Guoyong, XU Shengming, YU Fengshan, WENG Yaqing, CAO Caifang, WEN Jiawei, WANG Chunxia, WANG Junlian, GU Bintao, ZHANG Yuanhua, LIU Bin, WANG Caiping, PAN Jianming, XU Zeliang, WANG Chong, WANG Ke. Recovery and regeneration preparation of aluminum-based spent catalyst support[J]. Chemical Industry and Engineering Progress, 2024, 43(S1): 640-649.

图/表 15

图1 铝基废催化剂中载体的回收与再生制备流程

图2 铝基废催化剂的XRD表征结果

图3 铝基废催化剂的SEM和Mapping

表1 铝基废催化剂的物质组成及质量分数

Al₂O₃	PtO₂	Fe₂O₃	SnO₂	Ga₂O₃	CuO	P₂O₅	SO₃	SiO₂
97.97%	0.35%	0.19%	0.18%	0.17%	0.09%	0.05%	0.04%	0.03%

表2 铝基废催化剂的元素组成及质量分数

Al	Ca	Si	Fe	Sn	Pt	Ce	P
47.40%	0.59%	0.36%	0.32%	0.30%	0.24%	0.20%	0.11%

图4 氧化铝与两种钠源反应的吉布斯自由能变图

图5 不同温度下铝在Al-H2O系统中的Eh-pH图

图6 不同质量比条件下的XRD

图7 不同焙烧、浸出条件下铝的浸出率

图8 在焙烧温度500℃、老化时间为12h时不同反应pH条件下生成的样品XRD、N2吸脱附曲线及孔径分布曲线

图9 不同pH条件下合成的Al2O3的孔体积及平均孔径

图10 不同的反应pH条件下制备的Al2O3的SEM

图11 不同焙烧温度条件下制备pH为10的Al2O3N2吸脱附曲线及孔径分布曲线

图12 不同反应pH条件下制备的Al2O3的粒度分布曲线

表3 氧化铝样品部分理化性质与《氧化铝》（GB/T 24487—2022）对比

理化性质	GB/T 24487—2022	合成样品
比表面积/m²‧g^-1	≥60.00	284.19
粒径	粒径小于45.00μm的含量≤20%	D₇₅=38.84μm

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铝基废催化剂载体的回收与再生制备

Recovery and regeneration preparation of aluminum-based spent catalyst support

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