渣油加氢反应样品中含铁和含钙化合物溶解性能研究

王现元; 张涛; 张龙力; 赵愉生; 边钰清; 杨朝合

doi:10.1016/S1872-5813(21)60053-1

渣油加氢反应样品中含铁和含钙化合物溶解性能研究

doi: 10.1016/S1872-5813(21)60053-1

1.
中国石油大学（华东）理学院，山东青岛 266580
2.
中国石油石油化工研究院，北京 102206
3.
中国石油大学（华东）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（21576292）资助

详细信息

作者简介:
王现元：1044097546@qq.com

通讯作者:
Tel: 0532-86983374, E-mail: llzhang@upc.edu.cn

中图分类号: TE622.1
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出版历程
- 收稿日期: 2020-12-22
- 修回日期: 2021-02-02
- 网络出版日期: 2021-03-30
- 刊出日期: 2021-06-30

Study of the dissolution performance of ferrum and calcium compounds in residue hydrogenation reaction samples

1.
College of Science, China University of Petroleum (East China), Qingdao 266580, China
2.
China Petroleum and Petrochemical Research Institute, Beijing 102206, China
3.
State Key Laboratory of Heavy Oil, China University of Petroleum (East China), Qingdao 266580, China

Funds: The project was supported by the National Natural Science Foundation of China (21576292)

More Information

Corresponding author: Tel: 0532-86983374, E-mail: llzhang@upc.edu.cn

摘要

摘要: 以某原油及其对应的减压渣油、加氢原料和加氢产品为研究对象，通过柱色谱分离法和溶剂抽提法，对油样中铁和钙化合物在组分中的含量、分布以及存在形态进行了研究。研究结果表明，柱色谱分离过程中，油样中的含铁或钙的化合物在色谱柱上产生吸附，损失了58%的铁化合物和76%的钙化合物；溶剂抽提法能够有效减少组分中金属元素的损失。原油中97%以上的铁和钙分布在减压渣油馏分中，减压渣油中60%−90%的铁和钙分布在胶质、沥青质组分中。渣油加氢反应过程中，铁、钙化合物主要是从胶质中得到脱除，整体脱除率接近30%，铁化合物更易结合在沥青质中而难以脱除。原油经过常减压蒸馏后，油溶性铁相对分布由95.6%降低为64.7%，水溶性铁相对分布由4.4%升高为35.3%。经过加氢反应后，38%左右的油溶性铁在反应中转化为水溶性铁，30%左右的油溶性钙在反应中转化为水溶性钙。
- 渣油加氢 /
- 铁化合物 /
- 钙化合物 /
- 分布 /
- 存在形态
Abstract: The content, distribution and forms of the ferrum or calcium compounds in a crude oil, the corresponding vacuum residue (VR), hydrogenation feedstock and hydrogenation products were studied. The separation method was studied by column chromatography and solvent extraction method. This work indicated that in the process of column chromatographic separation, some ferrum or calcium compounds in the oil samples were irreversibly adsorbed on the chromatographic column, resulting in the loss of 58% of the ferrum compounds and 76% of calcium compounds. The solvent extraction method could effectively reduce the loss of the metal components and was suitable for the study of the content of metal elements. More than 97% of the ferrum or calcium compounds were distributed in the VR fraction. The 60% to 90% of the ferrum or calcium compounds were distributed in the resin and asphaltene components. During the hydrogenation reaction, the ferrum or calcium compounds in vacuum residue were mainly removed from the resin components, and the overall removal ratio was close to 30%. The ferrum compounds prefered to bond in the asphaltene components and were difficult to remove. Through the process of atmospheric distillation and vacuum distillation of the crude oil, the relative distribution of the oil-soluble ferrum compounds decreased from 95.6% to 64.7%, and the relative distribution of the water-soluble ferrum compounds increased from 4.4% to 35.3%. Through the process of the hydrogenation reaction, 38% of the oil-soluble ferrum compounds were converted into the water-soluble ferrum compounds and 30% of the oil-soluble calcium compounds were converted into the water-soluble calcium compounds in the reaction.
- residue hydrogenation /
- ferrum compounds /
- calcium compounds /
- distribution /
- forms

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FIG. 720. FIG. 720.

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图 1 溶剂抽提法分三组分流程图

Figure 1 Three-components flow chart of solvent extraction

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图 2 各形态铁、钙的含量测定流程图

Figure 2 Flow chart for determination of ferrum and calcium content of various forms

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图 3 加氢系列油样A的组分含量

Figure 3 Variations of the components content of hydrogenated oil sample A

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图 4 渣油中铁、钙化合物的主要形态

Figure 4 Main forms of ferrum and calcium compounds in residue oil

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表 1 加氢系列油样A的基础物性参数

Table 1 Basic properties of hydrogenated oil sample A

Analysis item	Crude oil	Vacuum residue	Hydrogenation feedstock	Hydrogenation products
Density(20 ℃)/(g·cm⁻³)	0.85	0.96	0.95	0.93
CSP*/(g·g⁻¹)	3.10	4.28	3.36	3.03
Acid value/(mg·g⁻¹)	0.26	0.32	0.42	0.03
Molecular weight/(g·mol⁻¹)	$ {\rm{9}}{{.31 \times 1}}{{\rm{0}}^{\rm{2}}}$	$ {\rm{1}}{{.98 \times 1}}{{\rm{0}}^{\rm{3}}}$	$ {\rm{1}}{\rm{.21 \times 1}}{{\rm{0}}^{\rm{3}}} $	$ {\rm{9}}{\rm{.58 \times 1}}{{\rm{0}}^{\rm{2}}}$
Dipole moment/Debye	2.80	4.90	4.00	2.40
C/%	85.5	86.3	86.2	87.0
H/%	13.1	12.5	12.2	12.8
N/%	0.18	0.43	0.37	0.24
S/%	0.77	1.34	1.08	0.61
V/(μg·g⁻¹)	15.6	39.1	33.7	6.60
Ni/(μg·g⁻¹)	6.1	22.1	17.2	4.00
Fe/(μg·g⁻¹)	34.2	112	82.4	72.7
Ca/(μg·g⁻¹)	10.8	61.2	43.1	32.1
*: Drops of diffusion method

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表 2 实验试剂一览表

Table 2 List of experiment reagents

Reagent	Specification	Manufacturer
Petroleum ether （60−90 ℃）	analytic reagent	Shanghai Woke Biotechnology Co., Ltd
Methylbenzene	analytic reagent	Sinopharm Chemical Reagent Co., Ltd
N-eptane	analytic reagent	Xilong Chemical Co., Ltd
Cyclohexane	analytic reagent	Sinopharm Chemical Reagent Co., Ltd
Acetone	analytic reagent	Tianjin Fuyu Fine Chemicals Co., Ltd
Hydrochloric acid	guaranteed reagent	Sinopharm Chemical Reagent Co., Ltd

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表 3 实验仪器一览表

Table 3 List of experiment equipments

Instrument name	Type	Manufacturer
Automatic rapid crude oil distillation apparatus	SDM-06A	Beijing Opwiye Technology Co., Ltd
AAS	controAA700	Jena Analytical Instruments Ag
Steam pressure penetrator	K700	Knauer
CHSN elemental analyzer	VARIO EL Ⅲ	German Company Elementar
Automatic acid value tester	SY-3000A	Taizhou Jiangyan Analysis Instrument Factory

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表 4 A原油中金属铁和钙随馏程的分布

Table 4 Distribution of the metal ferreum and calcium with distillation range in crude oil A

Sample	Fraction content w/%	Fe content/ (μg·g⁻¹)	Relative distribution /%	Ca content/ (μg·g⁻¹)	Relative distribution /%
Crude oil	100	34.2	100	10.8	100
Gasoline fraction	28.1	0.22	0.18	0.01	0.03
Diesel fraction	20.7	0.53	0.32	0.01	0.02
Vacuum gas oil	27.6	2.60	2.10	0.31	0.79
Vacuum residure	23.6	112	97.4	61.2	99.16

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表 5 不同分离方法所得组分中铁和钙的含量

Table 5 Contents of the ferrum and calcium compounds in the components obtained by different separation methods

Separation method	Component	Component content w/%	Ca content/(μg·g⁻¹)	Recovery ratio/%	Fe content/(μg·g⁻¹)	Recovery ratio/%
Column chromatography	saturated + aromatic	73.7	2.33	2.81	4.75	3.13
	resin	24.2	N	N	147	31.8
	asphaltene	2.1	596	20.4	376	7.05
	metal recovery rate/%			23.2		41.9
Solvent extraction	saturation + aromatic	73.1	11.1	13.3	42.7	27.9
	resin	24.7	151	60.9	244	53.8
	asphaltene	2.20	856	30.8	781	15.3
	metal recovery ratioe/%			105		97.0
N: the value was not detected by the instrument

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表 6 金属铁在加氢系列油样A组分中的分布变化

Table 6 Distribution variations of the metallic ferrum compounds in components of hydrogenated oil sample A

Sample	Oil (Saturated+ Aromatic)			Resin		Asphaltene
Sample	total Fe content/(μg·g⁻¹)	Fe content/ (μg·g⁻¹)	relative distribution/%	Fe content/ (μg·g⁻¹)	relative distribution/%	Fe content/ (μg·g⁻¹)	relative distribution/%
Crude oil	34.2	20.1	58.3	372	37.2	669	4.50
Vacuum residue	112	42.7	28.8	244	55.5	781	15.7
Hydrogenation feedstock	82.4	20.4	19.0	271	60.5	812	20.5
Hydrogenation products	72.7	21.9	26.2	239	44.7	992	29.1

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表 7 金属钙在加氢系列油样A组分中的分布变化

Table 7 Distribution variations of the metallic calcium compounds in component of hydrogenated oil sample A

Sample	Saturated + Aromatic			Resin		Asphaltene
Sample	total Ca content/(μg·g⁻¹)	Ca content/ (μg·g⁻¹)	relative distribution/%	Ca content/ (μg·g⁻¹)	relative distribution/%	Ca content/ (μg·g⁻¹)	relative distribution/%
Crude oil	10.8	4.17	37.9	170	53.4	424	8.70
Vacuum residue	61.2	11.1	12.7	151	58.1	856	29.2
Hydrogenation feedstock	43.1	13.4	24.2	112	48.6	555	27.2
Hydrogenation products	32.1	15.7	38.0	89.0	33.6	479	28.4

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表 8 加氢系列油样A中铁化合物的溶解性能

Table 8 Dissolution performance of the ferrum compounds in hydrogenated oil sample A

Sample	Total Fe	Oil-soluble Fe		Water-soluble Fe		Petroleum acid Fe		Porphyrin Fe and non-porphyrin Fe
Sample	content/ (μg·g⁻¹)	content/ (μg·g⁻¹)	relative distribution/%	content/ (μg·g⁻¹)	relative distribution/%	content/ (μg·g⁻¹)	relative distribution/%	content/ (μg·g⁻¹)	relative distribution/%
Crude oil	34.2	32.7	95.6	1.50	4.40	19.7	57.5	13.1	38.2
Vacuum residue	112	72.4	64.7	39.6	35.3	44.4	39.6	28.1	25.0
Hydrogenation feedstock	82.4	66.7	81.0	15.7	19.0	25.5	30.9	41.3	50.1
Hydrogenation products	72.7	31.4	43.2	41.3	56.8	6.60	9.10	24.8	34.1

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表 9 加氢系列油样A中钙化合物的溶解性能

Table 9 Dissolution performance of the calcium compounds in hydrogenated oil sample A

Sample	Total Ca	Oil-soluble calcium		Water-soluble calcium
Sample	content/(μg·g⁻¹)	content/(μg·g⁻¹)	relative distribution/%	content/(μg·g⁻¹)	relative distribution/%
Crude oil	10.8	6.70	62.0	4.10	38.0
Vacuum residue	61.2	58.6	95.7	2.60	4.30
Hydrogenation feedstock	43.1	31.3	72.7	11.8	27.3
Hydrogenation products	32.1	10.0	31.1	22.1	68.9

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