CN1231280A - 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
- Publication number
- CN1231280A CN1231280A CN 98113886 CN98113886A CN1231280A CN 1231280 A CN1231280 A CN 1231280A CN 98113886 CN98113886 CN 98113886 CN 98113886 A CN98113886 A CN 98113886A CN 1231280 A CN1231280 A CN 1231280A
- Authority
- CN
- China
- Prior art keywords
- oil
- fatty acid
- diethanolamine
- reaction
- promotor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The preparation method of nonionic surfactant for tertiary oil recovery is characterized by that it adopts improved one-step method and uses fatty acid and diethanolamine to directly produce the fatty acid alkylolamide type nonionic surfactant under the action of catalyst and catalyst promoter. This surfactant is non-toxic and stable in properties, and can be stored for a long period. The three-component composite system formed from said surfactant, alkali and polymer can form ultralow interfacial tension (10(-3)mN/m order of magnetude) with crude oil in the range of wider mineralized levevls of stratigraphic water, wider activator concentrations and alkali concentrations, can be used for tertiary oil recovery and raise the crude oil recovery efficiency.
Description
The present invention relates to a kind of nonionogenic tenside and production method thereof that is used for tertiary oil recovery.
Ternary composite driving is a tertiary oil recovery technology that grows up the external eighties, is characterized in utilizing between tensio-active agent, alkali and polymkeric substance acting synergistically, and reduces 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, cheap, development along with petroleum industry, the demand of sulfonated petro-leum increases, 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 OP-10 that uses with Tritonx-100, China's Shengli Oil Field 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 so several: a kind of is direct method, lipid acid mixes with diethanolamine, and one step of heating finishes; Also has a kind of two step method, typically as United States Patent (USP) a kind of method of carrying out is in two steps disclosed for No. 3024260 relatively, the first step lipid acid and diethanolamine be reaction earlier, generate amino ester and carboxylic acid amide esters, second step was dosed 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 was dosed 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.
Task of the present invention is: overcome the deficiencies in the prior art, 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: produce fatty acid alkyl amide and adopt improved single stage method: 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, 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.Among the present invention, the weight ratio of lipid acid and diethanolamine is 1: 0.5～1: 1.5, the ratio 0.05～2: 100 (weight) of catalyzer and reaction mixture.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.
Embodiments of the invention 1; 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, and the products obtained therefrom quality is the same with lab scale with performance.
Another embodiment of the present invention adds 250 gram Palmiticacid, 200 gram diethanolamine, 0.5 gram sodium hydroxide and 3 ml methanol in 500 milliliters the four-hole bottle, reacts 5 hours in 160 ℃ under protection of nitrogen gas, and 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 property.
Production equipment of the present invention is one to 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 grams are added by acid, 200 gram diethanolamine in 500 milliliters the four-hole bottle, reacted 6 hours in 160 ℃ under protection of nitrogen gas, add 0.5 gram sodium hydroxide again and continue heating four hours, it the results are shown in subordinate list 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; in 80 ℃; in 50 ℃ of heating 4 hours, it the results are shown in subordinate list 1 after carrying out 1 hour separating methanol under the decompression of 400mmHg.
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; react in 150 ℃ under protection of nitrogen gas, distillate 16 ml waters, 130 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 subordinate list 1.
The performance analysis of table 1 different methods obtain fatty acid alkylolamide
| 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 (* 10mN/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 in heterogeneous body physical model displacement of reservoir oil result relatively
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 by ability, is a kind of good chemical oil displacement agent.
NOS (nonionogenic tenside) consumption is to the influence of oil displacement efficiency
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%.After the experiment, cut the core section and observe discovery, it is fine that each layer of entrance drives, and low permeability layer only is driven to about l/5, and middle low permeability layer is all involved.The pressure reduction maximum value is respectively 4atm and 7atm in the oil displacement process, and oil droplet is described, oil film is started forms oily wall.Minimum moisture dropping to below 40%.
Table 2 ternary composite driving in heterogeneous body physical model displacement of reservoir oil result relatively
| Core number | The variation coefficient | Rate of permeation Kg | Rate of permeation Kw | The porosity station | 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 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 in heterogeneous body physical model displacement of reservoir oil result relatively
| Core number | The variation coefficient | Rate of permeation Kg | Rate of permeation Kw | Porosity % | Initial oil saturation % | Water drive | 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: the former speed oil 1m/d of the two factory's II-1 of recovering the oil
Z44: ternary system slug: NOS0.4%; NaOH1.2%; HPAM1200mg/L injects 0.3PV; 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 formation water salinity, broad structure surfactant concentration and the alkali concn scope of broad
-3The mN/m order of magnitude), can be used for tertiary oil recovery, improve oil recovery factor.
Claims (3)
1, a kind of production method of producing fatty acid alkyl amide, it is characterized in that: adopt 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 ℃, and the reaction times is between 2-20 hour; Used lipid acid is industrial synthetic fatty acid, 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, the ratio 0.05～2: 100 of catalyzer and reaction mixture, and the ratio of promotor and reaction mixture is 0.05～3: 100.
2, the production method of fatty acid alkyl amide as claimed in claim 1; it is characterized in that: the production equipment that is adopted is one to have agitator and have reflux condensing tube; with thermal oil (or) heating still or reactor; feed nitrogen protection in the reaction process; take by weighing raw fatty acid and diethanolamine with thermopair measured reaction temperature 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 a kind of usefulness such as claim 1,2 described methods productions, it is characterized in that: the three-component compound system that this nonionogenic tenside, alkali and polymkeric substance constitute 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
-3MN/m), can be used for tertiary oil recovery and improve recovery ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113886A CN1113857C (en) | 1998-04-03 | 1998-04-03 | Nonionic surface active agent for tertiary oil recovery and productive method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113886A CN1113857C (en) | 1998-04-03 | 1998-04-03 | Nonionic surface active agent for tertiary oil recovery and productive method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1231280A true CN1231280A (en) | 1999-10-13 |
| CN1113857C CN1113857C (en) | 2003-07-09 |
Family
ID=5223581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98113886A Expired - Fee Related CN1113857C (en) | 1998-04-03 | 1998-04-03 | Nonionic surface active agent for tertiary oil recovery and productive method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1113857C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101435331A (en) * | 2008-12-05 | 2009-05-20 | 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 |
| CN101230303B (en) * | 2007-01-23 | 2011-04-20 | 许建平 | Preparing wire rope surface grease by using rice bran oil as basic material |
| CN101148617B (en) * | 2006-09-21 | 2012-02-29 | 雅富顿公司 | Alkanolamides and their use as fuel additives |
| CN103242816A (en) * | 2013-05-08 | 2013-08-14 | 山东大学 | Preparation method of low-permeability reservoir oil-displacing agent |
| CN105985761A (en) * | 2015-02-12 | 2016-10-05 | 中国科学院理化技术研究所 | Crude oil emulsifier and application thereof |
| CN106433781A (en) * | 2016-09-09 | 2017-02-22 | 徐文忠 | High-temperature corrosion inhibitor for oilfield exploitation and petroleum refining process and preparation method of high-temperature corrosion inhibitor |
| CN106479257A (en) * | 2016-10-25 | 2017-03-08 | 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035635C (en) * | 1993-03-23 | 1997-08-13 | 中国石化辽阳石油化纤公司 | Oil well paraffin cleaning agent |
| US6022834A (en) * | 1996-05-24 | 2000-02-08 | Oil Chem Technologies, Inc. | Alkaline surfactant polymer flooding composition and process |
-
1998
- 1998-04-03 CN CN98113886A patent/CN1113857C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148617B (en) * | 2006-09-21 | 2012-02-29 | 雅富顿公司 | 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 |
| CN101435331A (en) * | 2008-12-05 | 2009-05-20 | 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 |
| CN103242816A (en) * | 2013-05-08 | 2013-08-14 | 山东大学 | Preparation method of low-permeability reservoir oil-displacing agent |
| CN105985761A (en) * | 2015-02-12 | 2016-10-05 | 中国科学院理化技术研究所 | Crude oil emulsifier and application thereof |
| CN105985761B (en) * | 2015-02-12 | 2019-02-15 | 中国科学院理化技术研究所 | Crude oil emulsifier and application thereof |
| CN106433781A (en) * | 2016-09-09 | 2017-02-22 | 徐文忠 | High-temperature corrosion inhibitor for oilfield exploitation and petroleum refining process and preparation method of high-temperature corrosion inhibitor |
| 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 |
| CN106479257A (en) * | 2016-10-25 | 2017-03-08 | 广东富行洗涤剂科技有限公司 | A kind of deinking agent |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1113857C (en) | 2003-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110791273B (en) | Gas well foam scrubbing agent composition, preparation method and application thereof | |
| CN1231280A (en) | Nonionic surface active agent for tertiary oil recovery and productive method thereof | |
| CN114105835B (en) | Anionic nonionic gemini surfactant as well as preparation method and application thereof | |
| CN101279938A (en) | Alkyl phenol sulfonic polyethenoxy ether sodium monosulfosuccinates and preparation thereof | |
| CN101279936B (en) | Alkyl phenol sulfonic polyoxyethylene ether sulfate and preparation thereof | |
| CN104231257A (en) | Aryl alkyl alcohol-polypropylene oxide-polyoxyethylene block copolymer as well as preparation method and application of block polymer | |
| CN105670590A (en) | Ternary composite system and surfactant suitable for high-temperature hypersalinity oil reservoir and preparation method of ternary composite system and surfactant | |
| CN107814755B (en) | Anionic gemini surfactant and preparation method thereof | |
| CN100434500C (en) | Guerbet anionic surfactant and preparation method and application thereof | |
| CN110746955B (en) | Gemini surfactant for oil displacement, binary composite system, preparation method and application thereof | |
| CN1100080C (en) | Process for preparing surfactant from lignosulfonates | |
| CN101735790A (en) | Preparation method of compound ion head double-tail surface active agent for oil displacement | |
| CN101891656A (en) | Preparation method of anionic surface active agent for binary displacement oil | |
| CN106146562B (en) | A kind of production method of phosphorous nitride methyl oleate green lubrication additive | |
| CN103421175B (en) | N, N '-bis-fatty acyl hydroxyethyl aliphatic diamine polyethenoxy ether carboxylate or sulfonate and preparation method thereof | |
| CN1035176C (en) | Preparation of polyoxyalkylene-alpha, omega-dicarboxylic acids | |
| CN101280182A (en) | Surfactant composition and use thereof | |
| CN114350383A (en) | Novel fatty alcohol ether carboxylic acid surfactant and preparation method thereof | |
| CN114315661A (en) | Aralkyl alcohol polyoxypropylene ether sulfate and preparation and application thereof | |
| CN113429954A (en) | Oil-displacing surfactant system, and preparation method and application thereof | |
| CN114479810B (en) | Surfactant composition, preparation method and application thereof | |
| CN103420818B (en) | Polyformaldehyde dimethyl ether preparation method | |
| CN111004142A (en) | Synthetic method of surfactant | |
| CN113930228B (en) | Oil washing agent composition containing anionic-nonionic surfactant and preparation method thereof | |
| RU2812536C1 (en) | Surfactant and method of its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: DAQING OIL FIELD CO., LTD. Free format text: FORMER OWNER: NONE |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT INVENTOR; FROM: KANG WANLI; DAN XILIN; LI JUNGANG; TO: KANG WANLI; DAN XILIN; LI JUNGANG; DONG XIGUI; QI BAOYAN; ZUO LONGQING; GENG ZIYUN Effective date: 20021121 |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20021121 Address after: Heilongjiang Province, Daqing City Ranghulu District 163453 Address after: 151400 anda Daqing Petroleum Institute, Heilongjiang Applicant after: Daqing Petroleum College Co-applicant after: Daqing Oil Field Co., Ltd. Inventor after: Kang Wanli Inventor after: single Greek Inventor after: Li Jungang Inventor after: Dong Xigui Inventor after: Qi Baoyan Inventor after: Zuo Longqing Inventor after: Geng Ziyun Address before: 151400 anda Daqing Petroleum Institute, Heilongjiang Applicant before: Daqing Petroleum College Inventor before: Kang Wanli Inventor before: Dan Xilin Inventor before: Li Jungang |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20030709 Termination date: 20100403 |