改性壳聚糖用于平衡剂脱钒的再生工艺研究

石油炼制与化工 ›› 2019, Vol. 50 ›› Issue (9): 47-52.

改性壳聚糖用于平衡剂脱钒的再生工艺研究

刘伟志¹,耿桐¹,任满年²,曹发海¹

1. 华东理工大学化学工程系
2. 中国石化洛阳分公司

收稿日期:2019-02-01 修回日期:2019-03-22 出版日期:2019-09-12 发布日期:2019-09-25
通讯作者: 曹发海 E-mail:fhcao@ecust.edu.cn
基金资助:

MODIFIED CHITOSAN FOR VANADIUM REMOVAL FROM SPENT FCC CATALYST

Received:2019-02-01 Revised:2019-03-22 Online:2019-09-12 Published:2019-09-25
Contact: hai faCao E-mail:fhcao@ecust.edu.cn
Supported by:

摘要/Abstract

摘要： 催化裂化（FCC）催化剂在使用过程中会因金属沉积等因素作用而中毒失活，传统的废催化剂填埋处理不仅会引起生态污染，还会增加生产成本，寻找一种有效的FCC催化剂再生方法已成为业界所关注的热点问题。本文采用壳聚糖与CS2为原料,通过亲核加成反应合成了改性壳聚糖-二硫代氨基甲酸盐(DTC-CTS)并将其用于脱除FCC平衡剂上的金属钒，从而达到平衡剂再生的目的。探究了工艺条件对DTC-CTS脱钒效果的影响，结果表明，当反应温度为125℃、反应时间为4.5 h 时，钒的脱除率达到54.9%，DTC-CTS对平衡剂表现出良好的脱钒效果。采用XRD、BET及SEM等表征方法对再生前后平衡剂的结构进行表征，并采用ACE评价装置考察其微反活性，结果表明，再生后的催化剂保留了Y型分子筛的晶体结构，比表面积和孔体积增大，微观形貌改善，微反活性提高5百分点。

关键词: 改性壳聚糖, 脱钒, 催化裂化, 平衡剂再生

Abstract: Fluid catalytic cracking (FCC) catalysts are poisoned and deactivated due to metal deposition during operation. Traditional landfill treatment not only causes ecological pollution, but also increases production costs. Therefore, finding an effective regeneration method has become a hot issue in the industry. Dithiocarbamates (DTC-CTS) was synthesized by modified chitosan made by nucleophilic addition reaction using chitosan and CS2 as raw materials. The DTC-CTS was used to remove vanadium from spent FCC catalyst to achieve the purpose of regeneration. The technological conditions of vanadium removal using DTC-CTS were further investigated. It was found that at 125℃ and the reaction time of 4.5h, the vanadium removal ratio reached the maximum (54.9%), which indicates that DTC-CTS has a good removal efficiency on vanadium from the equilibrium catalyst. The structure of FCC equilibrium catalyst before and after regeneration was determined by XRD、BET and SEM techniques. The results showed that the crystal structure of Y zeolite was retained in the regenerated catalyst, and the specific surface area and pore volume of the catalyst were increased. The MAT activity was increased by 5 percentage points.

Key words: modified chitosan, vanadium removal, catalytic cracking, equilibrium catalyst regeneration

中图分类号:

刘伟志耿桐任满年曹发海. 改性壳聚糖用于平衡剂脱钒的再生工艺研究[J]. 石油炼制与化工, 2019, 50(9): 47-52.

参考文献

[1] Yuan Chengyuan, Tan Zhengguo, Pan Zhishuang. Research on Catalytic Cracking Performance Improvement of Waste FCC Catalyst by Magnesium Modification [J]. China Petroleum Processing & Petrochemical Technology, 2018, 2(6) : 48-55.
[2]JAERAS S. Rapid methods of determining the metals resistance of cracking catalysts[J]. Appl Catal, 2016 2 (4-5):207-218.
[3]Wormsbecher R F, Peters A W, Maselli J M, et al. Vanadium poisoning of cracking catalysts[J]. Journal of Catalysis, 2016,100:130-137.
[4]卢国俭, 刘培, 朱英杰等. 废FCC催化剂复活再生及结构变化研究[J]稀有金属, 2016,12:1240-1248.
[5]王东, 洪林, 林时等.催化裂化催化剂的磁分离及再生回用技术的发展[J].环境保护科学, 2001(04):18-19+22.
[6]Yoo J.S. Metal recovery and rejuvenation of metal-loaded spent catalysts[J].Catalysis Today.1998,44(1):27-46.
[7]Cho S I,Jung K S, Woo S I. Regeneration of catalyst irreversibly deactivated by Ni,Fe,and V contained in heavy oil[J].Applied Catalysis B;Environmenta1,2001,33:249-261。
[8] Alves N M，Mano J F. Chitosan derivatives obtained by chemical modifications for biomedical and environmental applications[J]. International Journal of Biological Macromolecules,2017,43(5):401-414.
[9]尚秀丽, 风林, 德强.改性壳聚糖对废水中镍离子的吸附研究[J].化工新型材料,2016,7(44),199-201.
[10] Kai Yang,Gang Wang,Xuemin Chen.Treatment of Wastewater Containing Cu2+ Using a Novel Macromolecular Heavy Metal Chelating Flocculant Xanthated Chitosan[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects,2018,1:20-16
[11] Song, QP,Wang, CX,Zhang, Z. Adsorption of Cu(II) and Ni(II) using a Novel Xanthated Carboxymethyl Chitosan[J]. Separation Science and Technolog,2015,49(8):1235-1243.
[12]赖水秀, 清峰, 岳平.不同结构DTC用于重金属废水处理试验研究[J].浙江大学学报, 2014,41(1):67-73.
[13] Etim UJ,Xu B,Bai P. Role of nickel on vanadium poisoned FCC catalyst: A study of physiochemical properties[J].Journal of Energy Chemistry,16,25(4):667-676.
[14] Ubong J.Etim, Rooh Ullah, Faze Subhan. Vanadium contamination of FCC catalyst: Understanding the destruction and passivation mechanisms[J].AppliedCatalysis A:General,2018(2):108-117.
[15]Fanghua Wu,Dongfang Wu. Attrition resistances and mechanisms of three types of FCC catalysts[J].Powder Technology,2017,305:289-296.