废FCC催化剂在LPG吸附脱硫中的资源化利用

doi:10.16085/j.issn.1000-6613.2021-0331

摘要/Abstract

摘要：

金属污染是导致流化催化裂化（FCC）催化剂失活的重要因素，充分利用沉积的重金属是废FCC催化剂资源化的关键。本文将废FCC催化剂引入到轻质油品吸附脱硫领域，以脱除液化石油气（LPG）中的二甲基二硫醚作为考核目标，验证了废FCC催化剂作为脱硫剂的可行性。除去废FCC催化剂表面积炭后，其脱硫性能得到明显改善，在常温、质量空速为4.0h^-1的条件下，LPG中硫化物质量分数从382mg/m³脱除至40mg/m³。镧、铁、镍、钒、钙、锑6种金属在新鲜催化剂和焙烧后废催化剂上的总质量分数从10.2%升高至46.6%，6种金属按照对应含量分别固载在新鲜催化剂上，脱硫效果较未改性新鲜催化剂均有明显提升。验证实验表明，导致FCC催化剂失活的金属具有较高脱硫活性，废FCC催化剂作为轻质油品脱硫剂具备工业前景。

关键词: 分子筛, 失活, 吸附, 脱硫

Abstract:

Metal contamination is an important factor leading to the deactivation of fluidized bed catalytic cracking (FCC) catalyst, and making full use of the deposited heavy metals is the key to utilization the spent FCC catalyst. In this paper, the waste FCC catalyst was proposed for the adsorption desulfurization of light oil. The removal of dimethyl disulfide in LPG was taken as the target to test the feasibility of using the spent FCC catalyst as desulfurizer. After removing the deposited carbon on the spent FCC catalyst surface, the desulfurization performance was improved obviously. Under the conditions of normal temperature and mass space velocity of 4.0h^-1, the sulfide mass fraction in LPG was reduced from 382mg/m³ to 40mg/m³. The total mass fraction of lanthanum, iron, nickel, vanadium, calcium and antimony was increased from 10.2% in fresh catalyst to 46.6% in the calcined spent catalyst. The desulfurization ability was significantly improved after immobilizing the six metals on fresh catalyst separately. Results showed that the metals which lead to the deactivation of FCC catalyst had high desulfurization activity, and the utilization of spent FCC catalyst in LPG adsorption desulfurization has a good industrial application prospect.

Key words: molecular sieves, deactivation, adsorption, desulfurization

中图分类号:

TQ424.2

黄朝晖, 刘乃旺. 废FCC催化剂在LPG吸附脱硫中的资源化利用[J]. 化工进展, 2022, 41(1): 453-460.

HUANG Zhaohui, LIU Naiwang. Resource utilization of spent FCC catalysts in LPG adsorption desulfurization[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 453-460.

图/表 9

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名称	质量分数/%	硫含量/mg?m^-3
烷烃	77.5
正丁烷	24.1
异丁烷	14.2
丙烷	39.2
烯烃	14.2
丙烯	3.9
丁烯	10.3
其他	8.3
合计	100
硫化物		383.12
羰基硫		7.32
二硫化碳		0.67
二甲基二硫醚		360.63
甲硫醇		10.66
乙硫醇		3.42
硫化氢		0.42

名称	质量分数/%	硫含量/mg?m^-3
烷烃	77.5
正丁烷	24.1
异丁烷	14.2
丙烷	39.2
烯烃	14.2
丙烯	3.9
丁烯	10.3
其他	8.3
合计	100
硫化物		383.12
羰基硫		7.32
二硫化碳		0.67
二甲基二硫醚		360.63
甲硫醇		10.66
乙硫醇		3.42
硫化氢		0.42

样品	BET比表面积/m²?g^-1	总孔容/cm³?g^-1	BJH孔径/nm
FC	194	0.122	7.78
WC	116	0.147	9.17
WC-C	119	0.189	8.03

样品	BET比表面积/m²?g^-1	总孔容/cm³?g^-1	BJH孔径/nm
FC	194	0.122	7.78
WC	116	0.147	9.17
WC-C	119	0.189	8.03

吸附剂	T	T_L	T_B	S_L	S_B	W_L	W_B	W_L/W_B
FC	300.1	50.1	250	12.2	76.6	37.9	173.5	0.22
WC	24.6	18.4	6.2	8.3	0	11.1	8.3	1.34
WC-C	35.6	14.8	20.9	3.5	13.6	11.3	7.3	1.54