噻吩硫化物的硝化产物用于模型油中DBT的高效吸附

doi:10.11949/0438-1157.20191262

摘要/Abstract

摘要：

吸附是柴油深度脱硫的一种有效方法，其关键是高效吸附剂的研究。以活性炭负载的苯并噻吩(BT)、二苯并噻吩(DBT)、DBTO₂、4,6-二甲基DBT(DMDBT)为原料，通过混酸硝化/氧化反应制备了四种炭载吸附剂(NBT/C、NDBT/C、NDBTO₂/C和NDMDBT/C)，表征了产品的组成和结构，并考察了其吸附脱硫性能。结果表明，吸附剂NDBTO₂/C与DBT之间具有较强的络合作用，可形成转荷络合物。NDBTO₂/C的吸附等温线符合Langmuir方程，其对模型油中DBT、BT和DMDBT的饱和吸附量分别为87.4、10.6和8.3 mg S·g^–1，对实际柴油中DBT的吸附量也高达37.2 mg S·g^–1。吸附剂可用甲苯/甲醇溶液洗涤再生，循环使用4次后，其吸附性能仍保持在95%左右。本研究为氧化脱硫或吸附脱硫过程中得到的噻吩硫化物混合物的综合利用提供了有益启示。

关键词: 吸附剂, 分离, 配合物, 电荷转移, 燃料油脱硫, 硝化二苯并噻吩砜

Abstract:

Adsorption is an effective method for deep desulfurizaton of diesel, and the key is the research of high-efficiency adsorbents. In this paper, four activated carbon supported adsorbents (NBT/C, NDBT/C, NDBTO₂/C and NDMDBT/C) were prepared by nitrifying the corresponding carbon loaded benzothiophene (BT), dibenzothiophene (DBT), dibenzothiophone (DBTO₂) and 4,6-dimethyldibenzothiophene(DMDBT) with mixed acids of H₂SO₄ and HNO₃, their composition and structure were characterized, and their adsorptive desulfurization performance were studied. The results show that there exists a strong interaction between NDBTO₂ and DBT, forming a charge transfer complex. The adsorption isotherms of NDBTO₂/C follow the Langmuir equation, with its saturated adsorbance being 87.4, 10.6 and 8.3 mg S·g^–1, respectively for BT, DBT and DMDBT in model oils, and 37.2 mg S·g^–1 for DBT in real diesel. The used adsorbents can be regenerated easily by toluene/methanol washing, and 95% adsorptivity can be remained after four recycles. This study provides useful inspiration for the comprehensive utilization of thiophene sulfide mixtures obtained during oxidative desulfurization or adsorption desulfurization.

Key words: adsorbent, separation, complexes, charge transfer, fuel oil desulfurization, nitrified dibenzothiophene sulfone

中图分类号:

TQ 028.3

孙瑞阳, 陆颖舟, 孟洪, 李春喜. 噻吩硫化物的硝化产物用于模型油中DBT的高效吸附[J]. 化工学报, 2020, 71(5): 2256-2264.

Ruiyang SUN, Yingzhou LU, Hong MENG, Chunxi LI. Efficient adsorption of DBT from model oil by the nitrified thiophenic sulfides via complexation thereof[J]. CIESC Journal, 2020, 71(5): 2256-2264.

图/表 7

表1 吸附剂样品的XPS分析结果

Table 1 XPS analysis results for all adsorbents/%

	O	N	C	S
NBT/C	26.11	7.54	62.95	3.40
NDBT/C	25.36	14.85	51.82	7.96
NDBTO₂/C	35.21	8.03	49.35	7.42
NDMDBT/C	24.45	7.71	65.61	2.24
NDBTO₂	24.88	14.61	51.43	9.09

图1 NDBTO2/C的XPS C谱图和拟合结果

Fig.1 C XPS spectrum and fitting curve of NDBTO2/C

图2 吸附剂的红外光谱和XRD分析图

Fig.2 IR and XPS spectrum of adsorbents

图3 NDBTO2/C吸附过程中电荷转移络合物的UV-vis分析

Fig.3 UV-vis analysis for charge transfer complexes in NDBTO2/C adsorption

图4 吸附剂对模型油中不同噻吩硫的吸附量实验条件：W/M=100, C0=1000 μg·g–1, 25℃, 2 d

Fig.4 Adsorbance of adsorbents for different thiophenic S-compounds in model oils

图5 不同因素对NDBTO2/C吸附能力的影响

Fig.5 Adsorption capacity of NDBTO2/Cin different conditions

表2 多种吸附剂的吸附脱硫效果比较

Table 2 Adsorption capacity of various adsorbents for BT, DBT and DMDBT

吸附剂	溶剂	含硫溶质	C_e/(μg·g^–1)	$Q e$ /(mg S·g^–1)	S-分配系数	文献
HCuY	n-decane	BT 2-MBT 5-MBT	102	2.4^①	23.5	[12]
HNiY			97	2.5^①	25.8
HZnY			131	2.3^①	17.6
HCeYIE-1			111	8.0^①	72.1
KCeYIE-1			219	5.8^①	26.5
KCeY-IE-2			79	12.9^①	163.3
PS	n-hexane	DBT		65^③		[14]
PC				54^③
BX				53^③
BP				47^③
BPS				82^③
SIFSIX-1-Cu(1)	n-octane	DBT	200	22.5^②	112.5	[19]
SIFSIX-1-Cu(1)		BT	200	18.7^②	93.5
SIFSIX-1-Cu(2)		DBT	200	17.8^②	89
SIFSIX-1-Cu(2)		DBT	600	33.8^②	56.3
SIFSIX-1-Cu(3)		DBT	200	15.0^②	75
SIFSIX-1-Cu(3)		DBT	600	29.2^②	48.7
C300	2,2,4-trimethylpentane	DBT	200	10.8^②	54	[32]
C300			600	23.5^②	39.2
A100			200	7.5^②	37.5
A100			600	25.8^②	43
ACMB-1	n-hexadecane n-decane	BT DBT MDBT DMDBT	50	6.6^①	132	[34]
ACMB-1			200	21.2^②	106
ACC			50	4.4^①	88
ACC			200	10.5^②	52.5
ACNU			50	2.7^①	54
ACNU			200	6.8^②	34
Cu⁺(0)	n-octane	BT	200	25.5^②	127.5	[35]
Cu⁺(M)	n-octane	BT	200	34.5^②	172.5	[35]
UMCM-152	2,2,4-trimethylpentane	DBT	600	31.8^②	53	[36]
UMCM-153	2,2,4-trimethylpentane	DBT	600	73.5	122.5	[36]
NDBTO₂/C	n-octane	BT	184	3.2	17.4	this work
		DMDBT	170	3.3	19.4
		DBT	186	47.8	257
			598	87.4	146.2
				97.8^③

表2 多种吸附剂的吸附脱硫效果比较

Table 2 Adsorption capacity of various adsorbents for BT, DBT and DMDBT

吸附剂	溶剂	含硫溶质	C_e/(μg·g^–1)	$Q e$ /(mg S·g^–1)	S-分配系数	文献
HCuY	n-decane	BT 2-MBT 5-MBT	102	2.4^①	23.5	[12]
HNiY			97	2.5^①	25.8
HZnY			131	2.3^①	17.6
HCeYIE-1			111	8.0^①	72.1
KCeYIE-1			219	5.8^①	26.5
KCeY-IE-2			79	12.9^①	163.3
PS	n-hexane	DBT		65^③		[14]
PC				54^③
BX				53^③
BP				47^③
BPS				82^③
SIFSIX-1-Cu(1)	n-octane	DBT	200	22.5^②	112.5	[19]
SIFSIX-1-Cu(1)		BT	200	18.7^②	93.5
SIFSIX-1-Cu(2)		DBT	200	17.8^②	89
SIFSIX-1-Cu(2)		DBT	600	33.8^②	56.3
SIFSIX-1-Cu(3)		DBT	200	15.0^②	75
SIFSIX-1-Cu(3)		DBT	600	29.2^②	48.7
C300	2,2,4-trimethylpentane	DBT	200	10.8^②	54	[32]
C300			600	23.5^②	39.2
A100			200	7.5^②	37.5
A100			600	25.8^②	43
ACMB-1	n-hexadecane n-decane	BT DBT MDBT DMDBT	50	6.6^①	132	[34]
ACMB-1			200	21.2^②	106
ACC			50	4.4^①	88
ACC			200	10.5^②	52.5
ACNU			50	2.7^①	54
ACNU			200	6.8^②	34
Cu⁺(0)	n-octane	BT	200	25.5^②	127.5	[35]
Cu⁺(M)	n-octane	BT	200	34.5^②	172.5	[35]
UMCM-152	2,2,4-trimethylpentane	DBT	600	31.8^②	53	[36]
UMCM-153	2,2,4-trimethylpentane	DBT	600	73.5	122.5	[36]
NDBTO₂/C	n-octane	BT	184	3.2	17.4	this work
		DMDBT	170	3.3	19.4
		DBT	186	47.8	257
			598	87.4	146.2
				97.8^③

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