CN101455950B - Sulphonate surfactant preparation method and use thereof - Google Patents
Sulphonate surfactant preparation method and use thereof Download PDFInfo
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- CN101455950B CN101455950B CN2007101792652A CN200710179265A CN101455950B CN 101455950 B CN101455950 B CN 101455950B CN 2007101792652 A CN2007101792652 A CN 2007101792652A CN 200710179265 A CN200710179265 A CN 200710179265A CN 101455950 B CN101455950 B CN 101455950B
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- alkylbenzene
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Abstract
The present invention relates to a preparation method of a sulphonate surface active agent. The preparation method comprises: mixing and preheating refinery distillate oil and alkylbenzene to 50 DEG C; introducing the mixed gas of sulfur trioxide and air, and controlling the concentration of sulfur trioxide between 0.03 and 0.08g/L and the flux at 600L/h; carrying out reaction at 40 to 70 DEG C till the acid value of product reaches 120 to 160mgKOH/g; and neutralizing the product by 20 to 40 percent alkali solution till the pH value reaches 8 to 10 to obtain a product. Refinery distillate oil and alkylbenzene are mixed in the weight ratio of 5:5 to 8:2 as raw oil; and the sulphonate surface active agent, Na2CO3 and water are compounded as a tertiary oil extraction oil-displacing agent. The oil-displacing agent comprises compositions by mass percentage: 0.5 percent of sulphonate surface active agent, 0.4 to 2.0 percent of Na2CO3, and the balance being water; in addition, crude product yield is150 percent and the content of active matter is 25 to 30 percent. The preparation method has simple preparation process and low cost, and the interfacial tension of crude oil reaches 5*10<-3>mN/m.
Description
Technical field
The present invention relates to a kind of the oil recovery with the Preparation method and use of sulfosalt surfactant.
Background technology
Sulfosalt surfactant is a kind of surfactant oil displacement commonly used, and it is a raw material with the fraction oil of petroleum mainly, and therefore characteristics such as have that the source is wide, compatibility is good, good water solubility, stability are strong are subjected to the common concern of industry relevant department.But different petroleum sulfonates,, sulfonating agent raw materials used and sulfonation condition difference because of it, the ability that different crude oils is reduced interfacial tension is also different, and its application is restricted.
Patent CN01110282.9, CN01129677.1, CN98101774.6, CN99107580.3 provide a kind of method that adopts aryl crude oil fractions oil to prepare petroleum sulfonate as sulfonating agent for raw material, sulfur trioxide respectively, there is following problem in these methods: 1. will be through oversulfonate, neutralization, extraction, technical process such as concentrate, complicated process of preparation; 2. need to adopt alkane to extract; 3. preparation process produces acid sludge; 4. product cost height.Patent CN02125840.6 adopts multipole sulfonation method to prepare petroleum sulfonate with sulfur trioxide, but its raw material and sulfonating agent all need to dilute with organic solvent, and neutralization back redistillation goes out solvent, makes complex process, has increased cost.
It is that raw material, sulfur trioxide are the method that sulfonating agent prepares heavy alkylbenzene sulfonate with the heavy alkyl benzene that patent CN01136653.2 provides a kind of, and its preparation needs through oversulfonate, neutralization, extraction, technology such as concentrates, complex process, cost height.Patent CN01144907.1, CN02144084.0, CN200410034873.0 are raw material, are that sulfonating agent prepares alkylbenzenesulfonate with the oleum with heavy alkyl benzene or linear alkylbenzene (LAB) respectively, course of reaction produces a large amount of spent acid, sulfonated products need be through undue sour PROCESS FOR TREATMENT, and the oleic acid slag generates.
The present invention is that raw material, sulfur trioxide are that sulfonating agent prepares sulfosalt surfactant with the miscella of fraction oil of petroleum and alkylbenzene, and technology is simple, and no acid sludge does not need extract and separate.
Summary of the invention
The object of the present invention is to provide a kind of have active high, adaptability is good, cost is low, be suitable for recovering the oil and use sulfosalt surfactant, a kind of do not have a method that acid sludge, technology simply prepare above-mentioned sulfosalt surfactant; A purpose is to provide above-mentioned sulfosalt surfactant as the application of oil displacement agent in tertiary oil recovery again.
1) preparation of sulfosalt surfactant: required raw material are refinery's distillate, alkylbenzene, sulfur trioxide, aqueous slkali, air;
Concrete grammar is:
1. in reactor, add refinery's distillate and alkylbenzene, mix, and be preheating to 50 ℃;
2. under agitation feed sulfur trioxide and air gas mixture in feedstock oil, control sulfur trioxide concentration is 0.03～0.08g/L, and flow is 600L/h;
3. react to the product acid number at 50～60 ℃ and reach 120～160mgKOH/g;
4. it is 8～10 that above-mentioned product is neutralized to pH with 20～40% aqueous slkalis, promptly gets the sulfosalt surfactant product;
Used refinery's distillate is the vacuum distillate that normal four lines, vacuum 1st side cut, second line of distillation are rich in 200～500 ℃ of the distillate of aromatic hydrocarbons or refineries, and refinery's distillate and alkylbenzene are 5: 5～8: 2 by weight.
Used sulfur trioxide can be produced by sulfur burning, also can be produced by the air purge oleum.
Used aqueous slkali can be NaOH, potassium hydroxide, ammoniacal liquor.
2) sulfosalt surfactant is as the application of oil displacement agent.
Sulfosalt surfactant, Na
2CO
3Composite as the tertiary oil recovery oil displacement agent with water, sulfosalt surfactant is 0.5% by mass percentage, Na
2CO
3Be 0.4～2.0%, surplus is a water.
The present invention has following characteristics:
1. preparation technology of the present invention is simple: at present, petroleum sulfonate synthetic and produce generally will be through oversulfonate, neutralization, extraction, technical process such as concentrate, and the present invention does not have extract and separate, process such as concentrates, preparation technology is simple.
2. preparation method of the present invention does not have the acid sludge accessory substance: at present, all can produce a large amount of acid sludges in the preparation process of petroleum sulfonate, these acid sludges do not have value and the processing that goes out of use, and not only cause waste of material, environment have been caused pollution yet.The present invention gets preparation process does not have the acid sludge generation, does not need acid sludge treatment process process.
3. sulfosalt surfactant cost of the present invention is low: because preparation technology is simple, do not need to extract, distill concentration with solvent, and no acid sludge, thus reduced the cost of product.
4. sulfosalt surfactant product yield height of the present invention: the present invention has good production repeatability, and thick product yield is about 150%, and active matter content reaches 25%～30%.
5. sulfosalt surfactant of the present invention is suitable for and weak base Na
2CO
3Composite use.
6. sulfosalt surfactant activity of the present invention is high, adaptability is good: sulfonate/Na of the present invention
2CO
3The interfacial tension of a plurality of block crude oil in compound system and Kelamayi reaches 5 * 10
-3MN/m, the scope of application is wider.
The specific embodiment
Embodiment 1:
The preparation of sulfosalt surfactant of the present invention
Prepare raw material: the vacuum distillate that oil plant is 200～500 ℃, Nanjing alkylbenzene factory heavy alkyl benzene, oleum, 40% sodium hydrate aqueous solution.
Nanjing alkylbenzene factory heavy alkyl benzene decompression flow process is 344.5 ℃～510.0 ℃, and the physico-chemical property of the vacuum distillate that oil plant is 200～500 ℃ sees Table 1.
The physico-chemical property of the vacuum distillate that table 1 oil plant is 200～500 ℃
| Project | Density (20 ℃), mg/m 3 | Saturated hydrocarbons, % | Aromatic hydrocarbons, % | Gum asphalt, % |
| Numerical value | 0.9112 | 68.014 | 28.67 | 3.19 |
Concrete grammar is:
1. the vacuum distillate and the heavy alkyl benzene 100g that add 200～500 ℃ in reactor by weight 7: 3 ratio mix, and are preheating to 50 ℃;
2. use air to purge oleum, obtain San Yanghualiu air gas mixture with certain flow through super-dry;
3. under agitation feed sulfur trioxide/air gas mixture in feedstock oil, control sulfur trioxide concentration is 0.05g/L, and flow is 600L/h;
4. react to the product acid number at 50 ℃ and reach 120mgKOH/g;
5. it is 8～10 that above-mentioned product is neutralized to pH with the 40%NaOH aqueous solution, promptly gets thick product.
The yield of product, mean molecule quantity and active matter content see Table 2.
Embodiment 2:
With normal four line distillates, the preparation method is the 160mgKOH/g except that control product acid number wherein with embodiment 1, and all the other are with embodiment 1.
The yield of product, mean molecule quantity and active matter content see Table 2.
Embodiment 3:
With normal four lines, vacuum 1st side cut and second line of distillation mixed fraction oil, the preparation method is with embodiment 1, and wherein except that the sulfonic acid that uses 40%KOH aqueous solution neutralization reaction to generate, all the other are with embodiment 1.
Embodiment 4:
With the refinery is the vacuum 1st side cut distillate, and the preparation method is with embodiment 1, and wherein in using 20% ammonia spirit and the sulfonic acid that generates, all the other are with embodiment 1.
Embodiment 5:
Sulfosalt surfactant of the present invention is as the application of oil displacement agent
The sulfosalt surfactant of embodiment 1 and embodiment 2 is formulated as sulfonate concentration 0.5%, Na respectively
2CO
3The compound system aqueous solution of concentration 0.6%, the interfacial tension of itself and Karamay oilfield crude oil reaches 10
-3MN/m (seeing Table 3).
Embodiment 6:
Sulfosalt surfactant of the present invention is as the application of oil displacement agent
Sulfosalt surfactant and Na with embodiment 1
2CO
3Be formulated as sulfonate concentration 0.5% aqueous solution, work as Na
2CO
3Concentration was at 0.4%～2.0% o'clock, and the interfacial tension of compound system and Karamay oilfield different blocks crude oil all can reach 10
-3MN/m (seeing Table 4).
Table 2 sulfonate yield, mean molecule quantity and active matter content
| Thick product yield | Active matter content | Mineral oil content | Inorganic salt content | Mean molecule quantity | |
| Embodiment 1 | 150％ | 30.54％ | 30.24％ | 6.83％ | 479.50 |
| Embodiment 2 | 165％ | 28.19％ | 31.53％ | 9.14％ | 484.26 |
Table 3 sulfonate/Na
2CO
3The interfacial tension of compound system and Kelamayi crude oil
| Interfacial tension (* 10 -3mN/m) | ||||||
| 1min | 10min | 20min | 30min | 40min | 50min | |
| Embodiment 1 | 3.58 | 1.32 | 1.17 | 0.822 | 0.751 | 0.751 |
| Embodiment 2 | 3.50 | 1.50 | 0.711 | 0.790 | 0.831 | 0.868 |
Table 4 sulfonate/Na
2CO
3The interfacial tension of compound system and Kelamayi different blocks crude oil
| Na 2CO 3Concentration (%) | Interfacial tension (* 10 -3mN/m) | |||
| Yi Zhong district crude oil | Liu Zhong district crude oil | Color southern crude oil | Seven Sector East crude oil | |
| 0.4 | 2.07 | 16.4 | ||
| 0.6 | 1.78 | 5.88 | 84.0 | 12.4 |
| 0.8 | 1.08 | 5.91 | 5.48 | 2.39 |
| 1.2 | 5.38 | 4.80 | 4.04 | 0.96 |
| 1.6 | 4.20 | 0.526 | 1.08 | |
| 2.0 | 7.18 | 2.91 | 2.82 | |
Claims (4)
1. the preparation method of a sulfosalt surfactant, it is characterized in that: required raw material are refinery's distillate, alkylbenzene, sulfur trioxide, aqueous slkali and air;
Concrete preparation method is:
1. in reactor, add refinery's distillate and alkylbenzene, mix, and be preheating to 50 ℃;
2. under agitation feed sulfur trioxide and air gas mixture in refinery's distillate and alkylbenzene, control sulfur trioxide concentration is 0.03～0.08g/L, and flow is 600L/h;
3. react to the product acid number at 40 ℃～70 ℃ and reach 120～160mgKOH/g;
4. to be neutralized to pH with 20～40% aqueous slkalis be 8～10 to product, promptly gets the sulfosalt surfactant product;
Refinery's distillate and alkylbenzene are 5: 5～8: 2 by weight;
Used refinery's distillate is the vacuum distillate that normal four lines, vacuum 1st side cut, second line of distillation are rich in 200～500 ℃ of the distillate of aromatic hydrocarbons or refineries.
2. the preparation method of a kind of sulfosalt surfactant according to claim 1 is characterized in that: used sulfur trioxide is to be produced or produced by the air purge oleum by sulfur burning.
3. the preparation method of a kind of sulfosalt surfactant according to claim 1, it is characterized in that: used aqueous slkali is NaOH, potassium hydroxide or ammoniacal liquor.
4. the purposes of the sulfosalt surfactant of preparation method's preparation according to claim 1 is characterized in that: sulfosalt surfactant, Na
2CO
3Composite as the tertiary oil recovery oil displacement agent with water, sulfosalt surfactant is 0.5% by mass percentage, Na
2CO
3Be 0.4～2.0%, surplus is a water.
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| CN101455950B true CN101455950B (en) | 2011-09-07 |
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|---|---|---|---|---|
| CN101811999B (en) * | 2010-04-01 | 2012-11-28 | 中国日用化学工业研究院 | Method for preparing sulfonates of components of different groups of petroleum distillate |
| CN107803276B (en) * | 2016-09-08 | 2019-10-11 | 中国石油天然气股份有限公司 | The preparation method of sulfonate flotation agent |
| CN114539102B (en) * | 2020-11-26 | 2024-03-26 | 中国石油天然气股份有限公司 | Process for preparing petroleum sulfonate |
Citations (7)
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|---|---|---|---|---|
| WO1999042206A1 (en) * | 1998-02-18 | 1999-08-26 | The Procter & Gamble Company | Surfactants for structuring non-aqueous liquid compositions |
| US6087529A (en) * | 1996-03-12 | 2000-07-11 | Exxon Chemical Patents Inc. | Process for the stabilization of alkylbenzenesulphonates |
| CN1272393A (en) * | 1999-04-30 | 2000-11-08 | 大庆石油管理局 | Alkyl benzene sulfonate surfactant, its preparation method and application in tertiary oil recovery |
| CN1275431A (en) * | 1999-05-27 | 2000-12-06 | 大庆石油管理局 | Petroleum sulfonate surfactant for oil field, its preparation process and use in tertiary oil recovery |
| CN1327979A (en) * | 2001-06-27 | 2001-12-26 | 秦立君 | Process for preparing petroleum sulfonate used in oil field |
| CN1426833A (en) * | 2001-12-21 | 2003-07-02 | 大庆油田有限责任公司 | Alkyl phenyl sulfonate surfactant, its preparation and application in tertiary oil extraction |
| CN1683064A (en) * | 2004-04-16 | 2005-10-19 | 大庆油田有限责任公司 | Alkyl benzene sulfonate surfactant and preparing method and use |
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2007
- 2007-12-12 CN CN2007101792652A patent/CN101455950B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6087529A (en) * | 1996-03-12 | 2000-07-11 | Exxon Chemical Patents Inc. | Process for the stabilization of alkylbenzenesulphonates |
| WO1999042206A1 (en) * | 1998-02-18 | 1999-08-26 | The Procter & Gamble Company | Surfactants for structuring non-aqueous liquid compositions |
| CN1272393A (en) * | 1999-04-30 | 2000-11-08 | 大庆石油管理局 | Alkyl benzene sulfonate surfactant, its preparation method and application in tertiary oil recovery |
| CN1275431A (en) * | 1999-05-27 | 2000-12-06 | 大庆石油管理局 | Petroleum sulfonate surfactant for oil field, its preparation process and use in tertiary oil recovery |
| CN1327979A (en) * | 2001-06-27 | 2001-12-26 | 秦立君 | Process for preparing petroleum sulfonate used in oil field |
| CN1426833A (en) * | 2001-12-21 | 2003-07-02 | 大庆油田有限责任公司 | Alkyl phenyl sulfonate surfactant, its preparation and application in tertiary oil extraction |
| CN1683064A (en) * | 2004-04-16 | 2005-10-19 | 大庆油田有限责任公司 | Alkyl benzene sulfonate surfactant and preparing method and use |
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