CN1113857C - Nonionic surface active agent for tertiary oil recovery and productive method thereof - Google Patents
Nonionic surface active agent for tertiary oil recovery and productive method thereof Download PDFInfo
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- CN1113857C CN1113857C CN98113886A CN98113886A CN1113857C CN 1113857 C CN1113857 C CN 1113857C CN 98113886 A CN98113886 A CN 98113886A CN 98113886 A CN98113886 A CN 98113886A CN 1113857 C CN1113857 C CN 1113857C
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- diethanolamine
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- nonionogenic tenside
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Abstract
The present invention relates to a preparation method of non-ionic surfactant, which is suitable for tertiary oil recovery. An improved one-step method is adopted, fatty acid and diethanolamine are directly generated into the non-ionic surfactant of fatty acid alkanol acylamide under the action of a catalyst and a cocatalyst. The surfactant has the advantages of stable property and innocuity, and can be chronically stored and protected from light and air. A ternary compound system composed of the non-ionic surfactant, alkali and polymers can form ultralow interfacial tension (10<-3>mN/m order of magnitude) with crude oil within the range of wider formation water salinity and wider surfactant concentration and alkali concentration, and can be used for the tertiary oil recovery, and the crude oil recovery ratio is enhanced. The present invention solves the problems of complicated existing preparation process of fatty acid alcohol amide, limited raw material source, etc.
Description
Technical field: the present invention relates to a kind of nonionogenic tenside and production method thereof that is used for tertiary oil recovery.
Background technology: ternary composite driving is a tertiary oil recovery technology that grows up the external eighties, be characterized in utilizing between tensio-active agent, alkali and polymkeric substance and act synergistically, reduce expensive dosage of surfactant, with inexpensive alkali part substitution tables surface-active agent.The adding of polymkeric substance helps reducing the mobility of three-component compound system, thereby enlarges swept volume.Three-component compound system can be given full play to the advantage of various chemical agents, reduces the cost of chemical flooding significantly, increases substantially oil recovery factor.Most widely used tensio-active agent is a sulfonated petro-leum in the ternary composite driving both at home and abroad, it is the byproduct of purifying white oil, it is cheap, development along with petroleum industry, the demand of sulfonated petro-leum is increasing, the synthetic petroleum sulfonate product is increasing, and the price of sulfonated petro-leum price and nonionogenic tenside is more or less the same.Some geographic crude oil belong to paraffinic base, and aromaticity content is few, and produce sulfonated petro-leum and exist the raw material problem, in addition, synthetic petroleum sulfonate complex process, unstable product quality, SO
3Bring huge difficulty for production mahogany acid salt tensio-active agent to problems such as equipment and environmental pollutions.Seek other tensio-active agent that part substituted or substituted fully Sulfonates, be the development target of efficient and cheap oil-displacing agent always.At present, relevant nonionogenic tenside is a lot of as the report of oil-displacing agent, carried out many field tests as USSR (Union of Soviet Socialist Republics) with OP-7, OP-10 etc., but effect is bad.With nonionogenic tenside preparation three-component compound system such as the external Tritonx-100 that uses, the OP-10 that China's Shengli Oil Field is used etc.Fatty acid alkyl amide type nonionogenic tenside is used for tertiary oil recovery yet there are no report, the synthetic method of fatty acid alkyl amide type nonionogenic tenside mainly contains following several: a kind of is direct method, lipid acid mixes with diethanolamine, and one step of heating finishes; Also have a kind of two step method, relatively typically disclose a kind of method of carrying out in two steps for No. 3024260 as United States Patent (USP), the first step: lipid acid and diethanolamine be reaction earlier, generates amino ester and carboxylic acid amide esters; Second step: dose basic catalyst, unreacted diethanolamine and amino ester and acid amides fat react, and produce fatty acid alkyl amide; Other has No. 49903, a Japanese Patent Publication that aforesaid method has been done further improvement, the first step, lipid acid reacts less than 0.7 with the mol ratio of diethanolamine, second step, dose basic catalyst and remaining diethanolamine, diethanolamine and amino ester and acid amides fat react, produce fatty acid alkyl amide, the fatty acid alcohol acid amides that its purity of product that this method is produced and fatty acid methyl ester and diethanolamine reaction make is suitable, its quality is better than the former, but also exist complex technical process, the problem that raw material sources are limited.
Summary of the invention: task of the present invention is to overcome the deficiencies in the prior art, and it is short to design a kind of operational path, and raw material sources are extensive, and price is low, nonionogenic tenside that is used for tertiary oil recovery and production method thereof that purity is high.Task of the present invention realizes as follows: its core is to produce the production method of fatty acid alkyl amide, it adopts improved single stage method, and lipid acid and diethanolamine directly generate fatty acid alkyl amide type nonionogenic tenside under the effect of catalyzer, promotor; Its temperature of reaction is between 60～200 ℃, reaction times is between 2～20 hours, wherein lipid acid is industrial synthetic fatty acid, and it is the lipid acid that is obtained by butter, lard, sheep oil, Oleum Cocois, plam oil, Viscotrol C, peanut oil, soybean oil, Semen Maydis oil, Rice pollard oil hydrolysis; The purity of diethanolamine is greater than 85%; Used catalyzer is sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, salt of wormwood, yellow soda ash or their mixture; Promotor is methyl alcohol, ethanol, Virahol, butanols.The weight ratio of lipid acid and diethanolamine is 1 among the present invention: (0.5～1.5), the ratio of catalyzer and reaction mixture are (0.05～2): 100 (weight).The ratio of promotor and reaction mixture is (0.05～3): 100 (weight).The promoting agent stable performance that the present invention produced, quality are better than existing like product, and required starting material source is wide, and cheap, technology is simple, and is energy-conservation, so production cost is low.Because producing three-component compound system that fatty acid alkyl amide, alkali and polymkeric substance constitute, method of the present invention can in the surfactant concentration of the formation water salinity of broad, broad and alkali concn scope, form ultra low interfacial tension (10 with crude oil
-3The mN/m order of magnitude), this nonionogenic tenside has than advantage such as anion surfactant (as sulfonated petro-leum) heatproof, anti-salt and low interfacial tension window be wide; Nonionogenic tenside of the present invention and anion active agent are composite, can significantly improve the ability of the anti-polyvalent cation of system, and this nonionogenic tenside can be separately and alkali, polymkeric substance constitute ternary composite oil-displacing system, also can with the composite use of anion active agent, therefore of many uses.
Embodiment one: adopt improved single stage method; oleic acid 500 grams are mixed with diethanolamine 500 grams; adding 5 milliliters of catalyzer sodium hydroxide 1 grams, promotor ethanol again, to add volume be in 2 liters the four-hole bottle; under protection of nitrogen gas, reacted 6 hours in 160 ℃; it the results are shown in subordinate list; should react and amplify 1000 times, the products obtained therefrom quality is the same with lab scale with performance.
Embodiment two: 250 gram Palmiticacid, 200 gram diethanolamine, 0.5 gram sodium hydroxide and 3 ml methanol are added in 500 milliliters the four-hole bottle, reacted 5 hours in 160 ℃ under protection of nitrogen gas, it the results are shown in Table 1.Should react and amplify 1000 times, the quality of products obtained therefrom is the same with lab scale with performance.Produce production equipment that the fatty acid alcohol acid amides adopted and be and one have agitator, have reflux condensing tube; with thermal oil (or) heating tank reactor; feed nitrogen protection in the reaction process; with thermopair measured reaction temperature, take by weighing raw fatty acid and diethanolamine by metering, add appropriate amount of catalysts and promotor; begin to stir; be heated to assigned temperature and pick up counting, stop heating after the reaction times, cooling gets product.Method of the present invention and following each prior art compare: 1, direct method: 250 gram oleic acid, 200 are restrained in the four-hole bottle of 500 milliliters of diethanolamine addings; under protection of nitrogen gas, reacted 6 hours in 160 ℃; add 0.5 gram sodium hydroxide again and continue heating four hours, it the results are shown in Table 1.2, No. 3024260 methods of United States Patent (USP); 250 gram oleic acid, 200 are restrained in the four-hole bottle of 500 milliliters of diethanolamine addings; under protection of nitrogen gas, react in 150 ℃; distillate 16 ml waters; the 8 ml methanol solution that will dissolve 5 gram sodium hydroxide are then filled out in the flask; under 80 ℃ of decompressions, carry out 1 hour separating methanol at 400mmHg; in 50 ℃ of heating 4 hours, it the results are shown in Table 1 then.3, the method for Japanese Patent Publication-49903 is reacted; 250 gram oleic acid, 70 are restrained in the four-hole bottle of 500 milliliters of diethanolamine addings; under protection of nitrogen gas, react in 150 ℃; distillate 16 ml waters; the 130 gram diethanolamine that will dissolve 1.5 gram sodium hydroxide are then dosed in the flask; in 50 ℃ of heating 4 hours, it the results are shown in Table 1.
The fatty acid alkyl amide performance analysis that table 1 makes with different methods:
| Example 1 | Example 2 | Comparison example 1 | Comparison example 2 | Comparison example 3 | |
| The water-soluble foaming of amine value ester group surely steep the ability interfacial tension (* 10mM/m) | 203 no fine very strong 2.56 | 171 no fine very strong 4.98 | 230 have an insolubles extreme difference 101 very greatly | 217 have insolubles general 52 more greatly | 207 slightly fine better 13.1 |
Ternary composite driving compares in heterogeneous body physical model displacement of reservoir oil result, and table 2 has been listed two ternary system prescriptions and oil displacement experiment result.The interfacial tension of system and crude oil all reaches 10
-3The order of magnitude, the viscosity of compound system are also very close, and crude oil is oil extraction No.1 Factory crude oil.The chemical flooding recovery ratio of NOS three-component compound system is 21.5%, and the chemical flooding recovery ratio of ORS three-component compound system is 19.8%.This result shows that nonionogenic tenside NOS has stronger washing oil ability, is a kind of good chemical oil displacement agent.NOS (nonionogenic tenside) consumption is to the influence of oil displacement efficiency, and table 3 is respectively 0.4% and the 0.6% o'clock displacement of reservoir oil result of compound system on the heterogeneous body physical model for the NOS consumption.With the increase of NOS consumption, the chemical flooding recovery ratio increases.The combination flooding recovery ratio is respectively 17.1% and 20.0%.Experiment back is cut the core section and is observed and find that it is fine that each layer of entrance drives, and it is about 1/5 that low permeability layer only is driven to, and middle low permeability layer is all involved.The pressure reduction maximum value is respectively 4atm and 7atm in the oil displacement process, illustrates that oil droplet, oil film are started the oily wall of formation.Minimum moisture dropping to below 40%.
Table 2 ternary composite driving compares in heterogeneous body physical model displacement of reservoir oil result:
| Core number | The variation coefficient | Rate of permeation Kg | Rate of permeation Kw | Porosity % | Initial oil saturation % | Waterflood recovery efficiency factor % | The combination flooding recovery ratio | Overall recovery factor % | The remarks ternary system |
| J21 | 0.65 | 828 | 703 | 18.9 | 70.1 | 30.1 | 21.5 | 51.6 | NOS |
| Z31 | 0.65 | 999 | 788 | 20.5 | 71.0 | 31.8 | 19.8 | 51.5 | ORS |
Crude oil: oil extraction No.1 Factory gas-free oil, speed are 1m/d.J21: ternary system slug: NOS0.6%; NaOH1.2%, 1275A1200mg/L injects 0.3PV; Protection slug 0.283PV (600mg/L, 1275A).Z31: ternary system slug: ORS0.6%; NaOH1.2%, 1275A1200mg/L injects 0.3PV; Protection slug 0.283PV (600mg/L, 1275A).
Table 3 ternary composite driving compares in heterogeneous body physical model displacement of reservoir oil result:
| Core number | The variation coefficient | Rate of permeation Kg | Rate of permeation Kw | Porosity % | Initial oil saturation % | Water drive | The combination flooding recovery ratio | Overall recovery factor % | Remarks NOS % | |
| The PV number | Recovery ratio % | |||||||||
| Z44 | 0.65 | 805 | 820 | 21.5 | 71.4 | 2.49 | 27.4 | 17.1 | 44.5 | 0.4 |
| Z45 | 0.65 | 739 | 650 | 20.8 | 70.0 | 2.71 | 23.9 | 20.0 | 43.9 | 0.6 |
Crude oil: two II-1 of the factory crude oil that recover the oil, speed is 1m/d.Z44: ternary system slug: NOS0.4%; NaOH1.2%; HPAM1200mg/L injects 03PV; Protection slug 0.283PV.Z45: ternary system slug: ORS0.6%; NaOH1.2%; HPAM1200mg/L injects 0.3PV; Protection slug 0.283PV.The three-component compound system that nonionogenic tenside, alkali and the polymkeric substance of being produced by method of the present invention constitutes can form ultra low interfacial tension (10 with crude oil in the surfactant concentration of the formation water salinity of broad, broad and alkali concn scope
-3The mN/m order of magnitude), can be used for tertiary oil recovery, improve oil recovery factor.
Claims (3)
1, the production method that is used for the nonionogenic tenside of tertiary oil recovery, its core is the production method of fatty acid alcohol acid amides, it is characterized in that it adopts improved single stage method, lipid acid and diethanolamine directly generate fatty acid alkyl amide type nonionogenic tenside under the effect of catalyzer, promotor; Wherein temperature of reaction is between 30～200 ℃, reaction times is between 2～20 hours, used lipid acid is industrial synthetic fatty acid, and it is the lipid acid that is obtained by butter, lard, sheep oil, Oleum Cocois, plam oil, Viscotrol C, peanut oil, soybean oil, Semen Maydis oil, Rice pollard oil hydrolysis; The purity of the diethanolamine that is adopted is greater than 85%; Used catalyzer is sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, salt of wormwood, yellow soda ash or their mixture; Promotor is methyl alcohol, ethanol, Virahol, butanols; The weight ratio of lipid acid and diethanolamine is 1: 0.5～1.5, and the ratio of catalyzer and reaction mixture is 0.05～2: 100, and the ratio of promotor and reaction mixture is 0.05～3: 100.
2, the production method that is used for the nonionogenic tenside of tertiary oil recovery according to claim 1; it is characterized in that producing production equipment that the fatty acid alcohol acid amides adopted and be and one have agitator, have reflux condensing tube; tank reactor with heat-conducting oil heating; feed nitrogen protection in the reaction process; with thermopair measured reaction temperature; take by weighing raw fatty acid and diethanolamine by metering; add appropriate amount of catalysts and promotor; begin to stir; being heated to assigned temperature picks up counting; stop heating after the reaction times, cooling gets product.
3, the nonionogenic tenside of method production according to claim 1 and 2, it is characterized in that the three-component compound system that this nonionogenic tenside, alkali and polymkeric substance constitute, can in the surfactant concentration of the formation water salinity of broad, broad and alkali concn scope, form ultra low interfacial tension, can be used for tertiary oil recovery with crude oil.
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| CN98113886A CN1113857C (en) | 1998-04-03 | 1998-04-03 | Nonionic surface active agent for tertiary oil recovery and productive method thereof |
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| CN98113886A CN1113857C (en) | 1998-04-03 | 1998-04-03 | Nonionic surface active agent for tertiary oil recovery and productive method thereof |
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| CN1113857C true CN1113857C (en) | 2003-07-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8444720B2 (en) * | 2006-09-21 | 2013-05-21 | Afton Chemical Corporation | Alkanolamides and their use as fuel additives |
| CN101230303B (en) * | 2007-01-23 | 2011-04-20 | 许建平 | Preparing wire rope surface grease by using rice bran oil as basic material |
| CN101435331B (en) * | 2008-12-05 | 2013-03-13 | 中国石化股份胜利油田分公司地质科学研究院 | Method for making cracking rock core |
| CN103242816B (en) * | 2013-05-08 | 2016-01-06 | 山东大学 | A kind of preparation method of low-permeability oil deposit oil-displacing agent |
| CN105985761B (en) * | 2015-02-12 | 2019-02-15 | 中国科学院理化技术研究所 | A kind of crude oil emulsifying agent and application |
| CN106433781B (en) * | 2016-09-09 | 2018-10-02 | 徐文忠 | High-temperature corrosion inhibitor and preparation method thereof for oilfield exploitation and petroleum refining process |
| CN106479257B (en) * | 2016-10-25 | 2019-07-02 | 广东富行洗涤剂科技有限公司 | A kind of deinking agent |
| CN107382762A (en) * | 2017-07-18 | 2017-11-24 | 钟千里 | A kind of synthetic method of fatty diglycollic amide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076002A (en) * | 1993-03-23 | 1993-09-08 | 中国石化辽阳石油化纤公司 | A kind of well wax clearing agent for oil of the usefulness of recovering the oil |
| CN1171292A (en) * | 1996-05-24 | 1998-01-28 | 徐松南 | Compound surfactant for teriary oil producation and appliction thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076002A (en) * | 1993-03-23 | 1993-09-08 | 中国石化辽阳石油化纤公司 | A kind of well wax clearing agent for oil of the usefulness of recovering the oil |
| CN1171292A (en) * | 1996-05-24 | 1998-01-28 | 徐松南 | Compound surfactant for teriary oil producation and appliction thereof |
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