CN103450056A - Mahogany petroleum sulfonate preparation method for oil exploitation - Google Patents
Mahogany petroleum sulfonate preparation method for oil exploitation Download PDFInfo
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- CN103450056A CN103450056A CN2013103481386A CN201310348138A CN103450056A CN 103450056 A CN103450056 A CN 103450056A CN 2013103481386 A CN2013103481386 A CN 2013103481386A CN 201310348138 A CN201310348138 A CN 201310348138A CN 103450056 A CN103450056 A CN 103450056A
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Abstract
The invention discloses a high-performance mahogany petroleum sulfonate preparation method for enhanced oil recovery in oil exploitation. A mahogany petroleum sulfonate product is prepared from mahogany petroleum sulfonate as well as crude distillate oil on a distillate fraction of 240-590 DEG C, liquid SO3, NH3H2O and dichloroethane or dichloromethane through sulfonating in a rotary packed bed sulfonation reactor, neutralizing by a homogenizing pump and other chemical reactions, as well as carrying out settling separation, film falling and desolventizing processes. The macro-molecule oil soluble mahogany petroleum sulfonate product is prepared from un-sulfonated oil from settling separation and distillate oil at different proportions through repeated sulfonation and neutralization processes. The mahogany petroleum sulfonate product is high in sulfonating rate and high in performance. The invention provides a mahogany petroleum sulfonate product which is high in recovery rate and wide in application as well as a preparation technology of the mahogany petroleum sulfonate product. The mahogany petroleum sulfonate product is a preferred surfactant for chemical displacement of reservoir oil, which is for enhanced oil recovery in oil exploitation.
Description
Technical field
The invention belongs to the organic chemical industry field, be specifically related to a kind of oil wide fraction section distillate, SO of utilizing
3the liquid phase process for sulfonation prepares oil production and improves sulfonated petro-leum for recovery ratio (being called for short HPPS) and preparation method thereof.
background technology
why recovery ratio is low for water flooding, mainly that development late stage crude oil is present in oil reservoir hyposmosis interval with oil droplet and discontinuous oil film, because the interfacial tension that has 30-50mN/m between profit is capillary force action, crude oil can not flow out ground in the lump with water.Recovery ratio=swept volume * displacement efficiency, according to this theory, increase swept volume (polymer flooding) thereby the mechanism of tertiary oil recovery chemical flooding is exactly the viscosity that improves injection liquid, by adding tensio-active agent, improves displacement efficiency.The sulfonated petro-leum of our development is exactly by reducing profit circle tension force, making it reach 10
-3the ultra low interfacial tension that mN/m is even lower, realization improves the purpose of displacement efficiency.For the agent for improving oilfield recovery of exploitation middle and later periods, the use of sulfonated petro-leum has huge technology and economic implications.
Tradition Sulfonates anion surfactant, generally using dodecylbenzene, heavy alkyl benzene, polycyclic aromatic hydrocarbons as being sulfonated thing, adopts to take the liquid phase autoclave sulfonation that the vitriol oil is sulphonating agent, or with SO
3gas phase membrane type process for sulfonation preparation for sulphonating agent.It mainly exists raw material sources extensive not, complicated process of preparation, and the product chemical structure is single, and application performance is extremely undesirable, the problem that product price is high.
Summary of the invention
the technical problem solved:the invention provides the preparation method of a kind of oil production with sulfonated petro-leum, preparation-obtained sulfonate can effectively improve oil recovery.
technical scheme:high-performance sulfonated petro-leum preparation method for oil production, raw material is: the crude oil fractions of 240 ℃ ~ 590 ℃ of cut sections oil (mixture, precise temp is determined by the test of the true boiling point of crude oil distillation apparatus) and halohydrocarbon are by 1:(0.1 ~ 1) mass ratio be mixed into the A component; Sulphur trioxide and halohydrocarbon are with 1:(2 ~ 4) mass ratio be mixed into the B component; Ammoniacal liquor is the C component; Described halohydrocarbon is ethylene dichloride or methylene dichloride; By the A component with the B component with 1:(0.1 ~ 2) mass ratio mix and add the rotating packed bed sulfonation reactor, 0 ℃ ~ 60 ℃ of temperature, effluent is the intermediate mahogany acid continuously, by mahogany acid aging reaction 4 hours in the aging reaction device, again by the mahogany acid after aging with the C component with 1:(0.1 ~ 2) mass ratio mix and add the homogeneous neutralization reactor, temperature 60 C ~ 120 ℃, effluent is the sulfonated petro-leum crude product continuously; The sulfonated petro-leum crude product enters under 60 ℃ ~ 90 ℃ conditions of slurry tank sedimentation 8 hours; Slurry tank bottom water is emitted and flowed into pond aftertreatment to be accumulated; Slurry tank middle part material is entered continuously under 70 ℃ ~ 120 ℃ conditions of falling-film evaporator and sloughs halohydrocarbon, and effluent is the mahogany acid product salt continuously.
Described slurry tank top material (unsulfonated oil), with the A component with 1:(1 ~ 3) mass ratio mix, enter above-mentioned reaction process process, obtain mahogany acid product salt (macromole oil soluble sulfonated petro-leum).
The present invention can use falling-film evaporator to deviate from solvent under 70 ℃ ~ 120 ℃ conditions.
Described desolvation is used rectifying tower refining, and purity reaches the 99.5%wt recycling.
beneficial effect:the preparation method of sulfonated petro-leum for oil production provided by the invention, raw material sources are extensive, and technique is simple, and energy consumption is lower than existing technical scheme, and preparation-obtained sulfonate active matter content is higher, can make oil water interfacial tension be reduced to 10 by 25-50mN/m
-3mN/m, even lower, displacement efficiency is high, raising oil recovery by a larger margin.
The accompanying drawing explanation
Fig. 1 is high-performance sulfonated petro-leum preparation technology schematic diagram.
Embodiment
Above-mentioned embodiment does not limit technical scheme of the present invention in any form, and every employing is equal to replaces or technical scheme that the mode of equivalent transformation obtains all drops on protection scope of the present invention.
The main technique equipment rotating packed bed model related in the present invention is super Hai Qi Science and Technology Ltd. in HG-RPB50HH(Beijing), solvent distillation tower model is that ZZF1.0-600/18670-250 (Wuxi Dongsheng landification equipment company limited), falling-film evaporator model are GM0.66-120/1000-1.2 (Wuxi Dongsheng landification equipment company limited).
embodiment 1:
High-performance sulfonated petro-leum preparation method for oil production, raw material is: the crude oil fractions oil (mixture) of 240 ℃ ~ 590 ℃ of cut sections and halohydrocarbon are mixed into the A component by the mass ratio of 1:0.1; Sulphur trioxide and halohydrocarbon are mixed into the B component with the mass ratio of 1:2; Ammoniacal liquor is the C component; Described halohydrocarbon is methylene dichloride; A component and B component are mixed and add the rotating packed bed sulfonation reactor with the mass ratio of 1:0.2,0 ℃ of temperature, effluent is the intermediate mahogany acid continuously, by mahogany acid aging reaction 4 hours in the aging reaction device, again the mahogany acid after aging and C component are mixed and add the homogeneous neutralization reactor with the mass ratio of 1:0.5, temperature 60 C, effluent is the sulfonated petro-leum crude product continuously; The sulfonated petro-leum crude product enters under 60 ℃ of conditions of slurry tank sedimentation 8 hours; Slurry tank bottom water is emitted and flowed into pond aftertreatment to be accumulated; Slurry tank middle part material is entered continuously under 70 ℃ of conditions of falling-film evaporator and sloughs halohydrocarbon, and effluent is the mahogany acid product salt continuously.Slurry tank top material, mix with the mass ratio of A component with 1:1, enters above-mentioned reaction process process, obtains the mahogany acid product salt.It is refining that the halohydrocarbon of deviating from by falling-film evaporator enters the solvent distillation tower, and purity reaches the 99.5%wt recycling.
embodiment 2:
High-performance sulfonated petro-leum preparation method for oil production, raw material is: the crude oil fractions oil (mixture) of 240 ℃ ~ 590 ℃ of cut sections and halohydrocarbon are mixed into the A component by the mass ratio of 1:0.6; Sulphur trioxide and halohydrocarbon are mixed into the B component with the mass ratio of 1:3; Ammoniacal liquor is the C component; Described halohydrocarbon is ethylene dichloride; A component and B component are mixed and add the rotating packed bed sulfonation reactor with the mass ratio of 1:1,20 ℃ of temperature, effluent is the intermediate mahogany acid continuously, by mahogany acid aging reaction 4 hours in the aging reaction device, again the mahogany acid after aging and C component are mixed and add the homogeneous neutralization reactor with the mass ratio of 1:1,80 ℃ of temperature, effluent is the sulfonated petro-leum crude product continuously; The sulfonated petro-leum crude product enters under 70 ℃ of conditions of slurry tank sedimentation 8 hours; Slurry tank bottom water is emitted and flowed into pond aftertreatment to be accumulated; Slurry tank middle part material is entered continuously under 90 ℃ of conditions of falling-film evaporator and sloughs halohydrocarbon, and effluent is the mahogany acid product salt continuously.Slurry tank top material, mix with the mass ratio of A component with 1:2, enters above-mentioned reaction process process, obtains the mahogany acid product salt.It is refining that the halohydrocarbon of deviating from by falling-film evaporator enters the solvent distillation tower, and purity reaches the 99.5%wt recycling.Embodiment 2 products of take are detected object:
Table 1, high-performance sulfonated petro-leum performance test data
Table 2, high-performance sulfonated petro-leum and the contrast of similar products at home and abroad application performance
---reduce oil water interfacial tension (mN m
-1)
embodiment 3:
High-performance sulfonated petro-leum preparation method for oil production, raw material is: the crude oil fractions oil (mixture) of 240 ℃ ~ 590 ℃ of cut sections and halohydrocarbon are mixed into the A component by the mass ratio of 1:1; Sulphur trioxide and halohydrocarbon are mixed into the B component with the mass ratio of 1:4; Ammoniacal liquor is the C component; Described halohydrocarbon is ethylene dichloride; A component and B component are mixed and add the rotating packed bed sulfonation reactor with the mass ratio of 1:2, temperature 60 C, effluent is the intermediate mahogany acid continuously, by mahogany acid aging reaction 4 hours in the aging reaction device, again the mahogany acid after aging and C component are mixed and add the homogeneous neutralization reactor with the mass ratio of 1:2,120 ℃ of temperature, effluent is the sulfonated petro-leum crude product continuously; The sulfonated petro-leum crude product enters under 90 ℃ of conditions of slurry tank sedimentation 8 hours; Slurry tank bottom water is emitted and flowed into pond aftertreatment to be accumulated; Slurry tank middle part material is entered continuously under 120 ℃ of conditions of falling-film evaporator and sloughs halohydrocarbon, and effluent is the mahogany acid product salt continuously.Slurry tank top material, mix with the mass ratio of A component with 1:3, enters above-mentioned reaction process process, obtains the mahogany acid product salt.It is refining that the halohydrocarbon of deviating from by falling-film evaporator enters the solvent distillation tower, and purity reaches the 99.5%wt recycling.
Claims (4)
1. high-performance sulfonated petro-leum preparation method for oil production is characterized in that raw material is: the crude oil fractions oil of 240 ℃ ~ 590 ℃ of cut sections with halohydrocarbon by 1:(0.1 ~ 1) mass ratio be mixed into the A component; Sulphur trioxide and halohydrocarbon are with 1:(2 ~ 4) mass ratio be mixed into the B component; Ammoniacal liquor is the C component; Described halohydrocarbon is ethylene dichloride or methylene dichloride; By the A component with the B component with 1:(0.1 ~ 2) mass ratio mix and add the rotating packed bed sulfonation reactor, 0 ℃ ~ 60 ℃ of temperature, effluent is the intermediate mahogany acid continuously, by mahogany acid aging reaction 4 hours in the aging reaction device, again by the mahogany acid after aging with the C component with 1:(0.1 ~ 2) mass ratio mix and add the homogeneous neutralization reactor, temperature 60 C ~ 120 ℃, effluent is the sulfonated petro-leum crude product continuously; The sulfonated petro-leum crude product enters under 60 ℃ ~ 90 ℃ conditions of slurry tank sedimentation 8 hours; Slurry tank bottom water is emitted and flowed into pond aftertreatment to be accumulated; Slurry tank middle part material is entered continuously under 70 ℃ ~ 120 ℃ conditions of falling-film evaporator and sloughs halohydrocarbon, and effluent is the mahogany acid product salt continuously.
2. high-performance sulfonated petro-leum preparation method for oil production according to claim 1, is characterized in that slurry tank top material, with the A component with 1:(1 ~ 3) mass ratio mix, enter above-mentioned reaction process process, obtain the mahogany acid product salt.
3. high-performance sulfonated petro-leum preparation method for oil production according to claim 1, is characterized in that using falling-film evaporator to deviate from solvent under 70 ℃ ~ 120 ℃ conditions.
4. high-performance sulfonated petro-leum preparation method for oil production according to claim 1, is characterized in that desolvation is used rectifying tower refining, and purity reaches the 99.5%wt recycling.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230765A (en) * | 2014-09-01 | 2014-12-24 | 中国石油天然气股份有限公司 | Production method of petroleum sulfonate |
| CN106810475A (en) * | 2015-11-27 | 2017-06-09 | 中国石油天然气股份有限公司 | Method for removing inorganic salt from petroleum sulfonate |
| CN109799300A (en) * | 2019-03-18 | 2019-05-24 | 中国科学院兰州化学物理研究所 | A kind of method of mahogany acid salt content in analysis detection oil sample |
| CN113926590A (en) * | 2021-11-01 | 2022-01-14 | 武汉理工大学 | Flotation reagent and flotation method for separating feldspar from quartz |
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| US4560517A (en) * | 1979-03-22 | 1985-12-24 | Marathon Oil Company | Sulfonation of crude oils with gaseous SO3 to produce petroleum sulfonates |
| CN1203935A (en) * | 1998-05-07 | 1999-01-06 | 深圳市爱博特实业发展有限公司 | Petroleum sulfonate for tertiary oil recovery, and its preparing method and its use |
| CN1445328A (en) * | 2003-04-01 | 2003-10-01 | 中国石化胜利油田有限公司规划设计研究院 | Anionic surface active agent for expelling oil and its preparation method |
| CN101397494A (en) * | 2008-10-10 | 2009-04-01 | 北京工业大学 | Method for preparing surfactants for displacement of oil |
| CN101664656A (en) * | 2009-09-17 | 2010-03-10 | 北京化工大学 | Method for preparing alkyl aryl sulfonate anionic surfactant |
-
2013
- 2013-08-09 CN CN2013103481386A patent/CN103450056A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4560517A (en) * | 1979-03-22 | 1985-12-24 | Marathon Oil Company | Sulfonation of crude oils with gaseous SO3 to produce petroleum sulfonates |
| CN1203935A (en) * | 1998-05-07 | 1999-01-06 | 深圳市爱博特实业发展有限公司 | Petroleum sulfonate for tertiary oil recovery, and its preparing method and its use |
| CN1445328A (en) * | 2003-04-01 | 2003-10-01 | 中国石化胜利油田有限公司规划设计研究院 | Anionic surface active agent for expelling oil and its preparation method |
| CN101397494A (en) * | 2008-10-10 | 2009-04-01 | 北京工业大学 | Method for preparing surfactants for displacement of oil |
| CN101664656A (en) * | 2009-09-17 | 2010-03-10 | 北京化工大学 | Method for preparing alkyl aryl sulfonate anionic surfactant |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230765A (en) * | 2014-09-01 | 2014-12-24 | 中国石油天然气股份有限公司 | Production method of petroleum sulfonate |
| CN106810475A (en) * | 2015-11-27 | 2017-06-09 | 中国石油天然气股份有限公司 | Method for removing inorganic salt from petroleum sulfonate |
| CN106810475B (en) * | 2015-11-27 | 2018-09-04 | 中国石油天然气股份有限公司 | Method for removing inorganic salt from petroleum sulfonate |
| CN109799300A (en) * | 2019-03-18 | 2019-05-24 | 中国科学院兰州化学物理研究所 | A kind of method of mahogany acid salt content in analysis detection oil sample |
| CN113926590A (en) * | 2021-11-01 | 2022-01-14 | 武汉理工大学 | Flotation reagent and flotation method for separating feldspar from quartz |
| CN113926590B (en) * | 2021-11-01 | 2024-05-24 | 武汉理工大学 | Flotation reagent and flotation method for separating feldspar from quartz |
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Application publication date: 20131218 |