催化裂化油浆中烯烃分布研究

郭爱军; 郑文林; 焦守辉; 陈坤; 刘贺; 王宗贤; 王子豪

催化裂化油浆中烯烃分布研究

中国石油大学(华东) 化学工程学院重质油国家重点实验室, 山东青岛 266580

基金项目:

国家自然科学基金 21776313

山东省重点研发计划 2017GGX70108

重质油国家重点实验室项目 SLKZZ-2017011

详细信息

中图分类号: TE65
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出版历程
- 收稿日期: 2017-12-19
- 修回日期: 2018-02-01
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-04-10

Study on olefin distribution of catalytic cracking slurry

State Key Laboratory of Heavy Oil, College of Chemical Engineering, China University of Petroleum(East China), Qingdao 266580, China

Funds:

the National Natural Science Foundation of China 21776313

the Provincial Key Research and Development Plan of Shandong 2017GGX70108

the State Key Laboratory of Heavy Oil Processing SLKZZ-2017011

More Information

Corresponding author: GUO Ai-jun, Tel: 0532-86980607, Fax: 0532-86981787, E-mail: ajguo@upc.edu.cn

摘要

摘要: 以某催化裂化油浆为原料，通过二烯值和溴价分析方法测定了其四组分和五个馏分中共轭烯烃（双键）和烯烃（双键）的含量；同时结合紫外光谱法、核磁共振氢谱法（¹H-NMR）对其四组分和五个馏分中的烯烃类型和含量进行了表征和测定。结果表明，催化裂化油浆中的确存在烯烃（双键）和共轭烯烃（双键），其烯烃（双键）和共轭烯烃（双键）的含量高达21%和6%，四组分中的共轭烯烃（双键）含量依次增多，五个馏分中共轭烯烃（双键）的含量在5%左右，且四组分和五个馏分中烯烃（双键）的含量均呈现先减小后增大的趋势。同时，不同组分和不同馏分之间正构α-烯烃和内烯烃的含量也存在差异。
- 催化裂化油浆 /
- 二烯值 /
- 溴价 /
- 核磁共振 /
- 烯烃类型与分布
Abstract: The content of conjugated olefins (double bonds) and olefins (double bonds) in four fractions and five fractions of a FCC slurry was determined by the diene number and bromine number analysis method. UV and ¹H-NMR were used to characterize and determine the type and content of olefins in the four fractions and five fractions. The results confirm that the olefin (double bond) and conjugated olefin (double bond) exist in FCC slurry, the contents of olefin (double bond) and conjugated olefin (double bond) are as high as 21% and 6%, the content of conjugated olefin (double bond) in the four components increased in turn, the content of conjugated olefin (double bond) in the five fractions was about 5%, and the content of olefin (double bond) in four components and five fractions all showed a trend of decreasing first and then increasing. At the same time, there are also differences in the content of normal alpha-olefins and internal olefins between different components and different fractions.
- FCC slurry /
- diene value /
- bromine number /
- ¹H-NMR /
- olefin type and distribution

HTML全文

图 1 催化裂化油浆四组分的二烯值和溴价

Figure 1 Diene value and bromine number of the four components of FCC slurry

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图 2 催化裂化油浆五个馏分的二烯值和溴价

Figure 2 Diene value and bromine number of five fractions of FCC slurry

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图 3 催化裂化油浆四组分的紫外光谱谱图

Figure 3 UV-vis spectra of the four components of FCC slurry

a: saturates; b: aromatics; c: resins; d: asphaltenes

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图 4 催化裂化油浆五个馏分的紫外光谱谱图

Figure 4 UV-vis spectra of the five fractions of FCC slurry

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图 5 催化裂化油浆四组分的核磁共振氢谱图

Figure 5 ¹H-NMR spectra of four components of FCC slurry

a: saturates; b: aromatics; c: resins; d: asphaltenes

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图 6 催化裂化油浆五个馏分的核磁共振氢谱谱图

Figure 6 ¹H-NMR spectra of five fractions of FCC slurry

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表 1 催化裂化油浆的主要物理及化学性质

Table 1 Main physical and chemical properties of FCC slurry

Quantity analyzed	Result
Density ρ₂₀ /(g·cm^-3)	0.9773
Viscosity η₈₀/(mPa·s)	98.60
Viscosity η₁₀₀ /(mPa·s)	50.10
Carbon residue w/%	10.76
Ash w/%	0.1601
Relative molecular mass	593.10
C w/%	87.79
H w/%	11.25
S w/%	0.41
N w/%	0.31
H/C(atomic ratio)	1.527
Saturates w/%	44.64
Aromatics w/%	35.23
Resins w/%	19.49
n-C₇ Asphaltenes w/%	0.64
Bromine number/(g (Br)/100 g)	5.70
Diene value /(g (I₂)/100 g)	2.64

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表 2 催化裂化油浆的馏程分布

Table 2 Distillation distribution of FCC slurry

Code	Distillated boiling rang t/℃	Value w/%
A	350-400	5.19
B	400-440	1.89
C	440-470	10.24
D	470-500	12.68
E	> 500	70.01

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表 3 催化裂化油浆四个组分烯烃(双键)的含量

Table 3 Olefin (double bond) content in four components of FCC slurry

Type	Saturates	Aromatics	Resins	Asphaltenes	Slurry(calculated)⁴
Olefinic compound¹/%	31.03	9.80	17.84	56.66	21.14
Conjugated olefinic compound²/%	0.00	9.49	11.20	35.67	5.75
Ratio³/%	0.00	96.84	62.78	62.95	27.20
Average molecular weight	380.02	624.13	997.06	2003.11	593.10
¹: olefinic compound(%)=(bromine number×average molecular weight of the sample)/(2×79.90)；²: conjugated olefinic compound(%)=(diene value×average molecular weight of the sample)/253.80；³: ratio=conjugated olefinic compound(%)/olefinic compound(%)；⁴: olefinic compound or conjugated olefinic compound in slurry(%)=∑content of the olefinic compound or conjugated olefinic compound in each component×the content of each component of the slurry in Table 1 and Table 2

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表 4 催化裂化油浆五个馏分烯烃(双键)的含量

Table 4 Olefin (double bond) content in five fractions of FCC slurry

Type	A	B	C	D	E	Slurry (calculated)⁴
Olefinic compound¹/%	22.42	15.81	13.01	8.96	25.15	21.54
Conjugated olefinic compound²/%	2.60	5.42	4.69	3.34	7.11	6.12
Ratio³/%	11.60	34.28	36.05	37.28	28.27	28.41
Average molecular weight	298.02	323.08	364.12	402.03	710.10	593.10
reaction conditions: see Table 3

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表 5 ¹H-NMR测得的催化裂化油浆四组分的烯氢类型与分布

Table 5 Type and distribution of hydrogenation of the four components of FCC slurry by ¹H-NMR

Hydrogen type	Chemical shift δ^[9]	Hydrogen molar percentage/%
Hydrogen type	Chemical shift δ^[9]	saturates	aromatics	resins	asphaltenes
-CR=CH₂	4.5-4.7	8.29	29.52	10.49	19.38
-CH=CH₂	4.7-5.0	18.13	29.44	15.38	23.26
-CR=CH-	5.0-5.2	22.48	16.09	18.52	17.80
-CH=CH-	5.2-5.5	51.10	24.95	55.61	39.56

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表 6 ¹H-NMR测得的催化裂化油浆五个馏分的烯氢类型与分布

Table 6 Type and distribution of hydrogenation of the five fractions of FCC slurry by ¹H-NMR

Hydrogen type	Chemical shift δ^[9]	Hydrogen mole percentage/%
Hydrogen type	Chemical shift δ^[9]	A	B	C	D	E
-CR=CH₂	4.5-4.7	25.31	9.54	13.29	34.64	23.84
-CH=CH₂	4.7-5.0	25.93	20.30	22.60	22.50	33.64
-CR=CH-	5.0-5.2	17.46	21.12	18.96	11.89	19.16
-CH=CH-	5.2-5.5	31.30	49.04	45.15	30.97	23.36

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