CN108504345A - Based on fatty alcohol and the synthesis of polyethers " bull list tail " type both sexes oil displacement agent and application study - Google Patents
Based on fatty alcohol and the synthesis of polyethers " bull list tail " type both sexes oil displacement agent and application study Download PDFInfo
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- CN108504345A CN108504345A CN201710109914.5A CN201710109914A CN108504345A CN 108504345 A CN108504345 A CN 108504345A CN 201710109914 A CN201710109914 A CN 201710109914A CN 108504345 A CN108504345 A CN 108504345A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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Abstract
The present invention provides a kind of preparation method of efficient fatty alcohol " bull list tail " type both sexes displacement of reservoir oil type surfactant used for tertiary oil recovery, this method is with fatty alcohol (ten alcohol, lauryl alcohol, tetradecyl alchohol) polyethers (Dodecyl Polyoxyethylene Ether, tetradecyl alchohol polyoxyethylene ether, hexadecanol polyoxyethylene ether) cis-butenedioic anhydride, sodium acrylate, tarine sodium etc. for raw material, by esterification, fatty alcohol " bull list tail " type both sexes displacement of reservoir oil type surfactant is made in the reactions such as Michael's addition.Such new type amphoteric surfactant used for tertiary oil recovery is connected with bull list tail, has a kind of higher novel surfactant of more traditional conventional surfactants performance.There are three advantages for such surfactant tool, first, synthesis step is simple；Second is that reaction yield is higher；Third, properties of product are superior.
Description
Technical field
The present invention relates to the chemical flooding novel surfactant preparation methods for improving oil deposil erude petroleum recovery ratio, if specifically
Traditional surfactant oil displacement is connected into fatty alcohol for dry modern classical chemical reaction and polyethers " bull list tail " type both sexes are driven
Finish surfactant.
Technical background
In national strategy resource, oil one of most important resource at last.Its economy national to one and society are steady
Fixed development all has a very important significance.But tellurian petroleum resources are not inexhaustible.With people
To the continuous exploration and development of oil, not only so that limited resources are fewer and fewer, while also adding the difficulty of oil exploitation.
Therefore, the key subjects that recovery ratio has become oil exploitation research are improved, surfactant recovers the oil due to its is cost-effective three
The most attention of people is obtained in secondary oil recovery research.The technology that strata pressure is kept using water filling, make the recovery ratio of oil from
15%~20% is increased to 30% or more.Interfacial tension between grease is about 30mN/m, drives the required pressure difference to be
9806.7Kpa, and difference between reservoir pre ssure and injection pressure is only 196.1Kpa~392.3Kpa, much smaller than driving pressure difference, therefore, depending merely on increase pressure difference is
It is very difficult.The Residual oil remained in after water drive in rock gap still has 50%~60% or more, these Residual oils are with oil droplet and oil
The form of block is trapped in rock gap and blind hole, or is adsorbed by the rock surface of lipophilic group in the form of oil film.And it utilizes
Surfactant reduces interfacial tension, and improving the characteristic of capillary number, to displace this portion of residual oil be feasible and effectively method,
Therefore, surfactant flooding technology is considered as that can improve recovery ratio, applied widely and most with prospects by a relatively large margin
Technology.The surfactant oil displacement developed both at home and abroad at present is anionic sulphonate (petroleum sulfonate, benzene sulfonamide
Hydrochlorate lignosulfonates) and carboxylic acid type (petroleum carboxylate, natural carboxylates), sulfate type etc.) and non-ionic surface
Activating agent.Since the sixties, surfactant flooding technology develops quickly.As tertiary oil recovery technology continues to develop, table
Face activating agent is widely used in oil field, and when using and evaluating certain surfactant, we pay special attention to surface work
Surface-active, krafft point (Krafft points) and the water solubility of property agent.In tertiary oil recovery it is most widely used be it is cloudy from
Subtype and nonionic surface active agent, however such surfactant is not particularly suited for high temperature and high salt oil deposit condition, so nothing
Method meets the exploitation to high temperature and high salt oil deposit.For containing only there are one hydrophilic and a lipophilic group molecular composition surface-actives
For agent, it is also difficult to a kind of surfactant that above-mentioned performance is all more satisfactory is found, moreover, with the development of the times, surface
Activating agent field also makes rapid progress, and from the point of view of molecular structure development trend, present one-component surfactant molecular structure is not
It is single hydrophilic group or single lipophilic group traditional structure again, but includes the complicated molecule knot of multiple hydrophilic groups or lipophilic group
Structure, " bull list tail " type surfactant are exactly the novel surfactant containing multiple hydrophilic radicals of a kind of function admirable,
For the surfactant of " bull list tail " type, These characteristics can be provided simultaneously with, therefore are referred to as novel surface activity
Agent has great potentiality in surfactant flooding.In order to further enhance the oil displacement efficiency of surfactant, improve former
The recovery ratio of oil, a kind of relatively good novel surfactant of exploitation just seem important.With the day of oilfield exploitation degree
Deeply, used surfactant has been unable to meet the requirement of " harshness " oil reservoir to benefit now, therefore, exploitation novel surface activity
Agent is just very necessary, and " bull list tail " type surfactant with its remarkable performance by the growing interest of people.
Invention content
The technical assignment of the present invention is insufficient for above-mentioned surfactant oil displacement performance, provides a kind of oil displacement efficiency
It is good, " the bull list tail " for being applied to the efficient displacement of reservoir oil used for tertiary oil recovery less than 1*10-2MN/m interfacial tensions can be formed with crude oil
Type single dose.
The present invention is applied to single oil displacement agent used for tertiary oil recovery, and synthetic method includes mainly following components：
(1) preparation of monoesters：Corresponding fatty alcohol (ten alcohol, lauryl alcohol, tetradecyl alchohol) is added in maleic anhydride and is returned
Stream, return time are 3 hours, ensure that reaction system cannot have water, the corresponding monoesters of gained (ten monoesters, 12 monoesters, 14 lists
Ester).
(2) bull carboxylic acid sodium-sodium sulfonate intermediateIt prepares：Claim to obtain 25.11g
(0.2mol) tarine is mixed with 8.11g (0.2mol) sodium hydroxide, is completely dissolved after the stirring of 24.10g distilled water is added,
PH value of solution=10-11.Claim 14.43g (0.1mol) acrylic acid is mixed with 8.15g (0.2mol) sodium hydroxide, be added 26.15g
It is completely dissolved after being stirred after distilled water, pH value of solution=7.It is colourless transparent liquid, pH value of solution=10-11 after the two mixing.Mixed
The liquid of conjunction pours into heating water bath in three-necked flask and is stirred at reflux four hours, obtains intermediate
(3) at salt：Monoesters and (2) bull carboxylic acid sodium-sodium sulfonate intermediate is made in (1) step, it is anti-to carry out Michael's addition
It should be to get final product.
(1) preparation of α, β unsaturated fatty acid：Take the tetradecyl alchohol polyoxyethylene ether of the amount of certain substance in three-necked flask
In, it is passed through nitrogen protective gas 15min.Magnetic agitation is heated to 60 DEG C of stabilizations, and the maleic anhydride of the amount of same substance is added, reaction
90 DEG C of stabilizations are warming up to after 10min.Corresponding α, β unsaturated fatty acids is made in reflux 70min.
(2) preparation of N, N- dipropionic acid tarine trisodium：
1. weighing 0.1mol tarines and 0.1mol sodium hydroxides in a 250ml beakers, 13ml distilled water is added
Dissolving is complete, then covers beaker mouth with preservative film.
2. weighing 0.2mol acrylic acid with 0.2mol sodium hydroxides in a 250ml beakers, addition 26ml distills water dissolution
(heat release is violent in course of dissolution, pays attention to safeguard procedures) completely
3. by step 1. and 2. in product be uniformly mixed and pour into three-necked flask, be inserted into thermometer, open magnetic force heating
Agitating device is warming up to 90 DEG C of condensing reflux 9h, obtains intermediate monomer N, N- dipropionic acid tarine trisodium.
(3) preparation of " bull list tail " type amphoteric surfactant intermediate monomer：By α obtained, β unsaturated fatty acids with
N, N- dipropionic acid tarine trisodium in than being added in three-necked flask for 1.2: 1 ratio, be heated to reflux 16h obtain it is " more
The single tail of head " type amphoteric surfactant intermediate monomer.
(4) at salt：Monomer obtained by step (3) is subjected to acid-base titration into salt with sodium hydroxide solution, finally obtains " bull
Single tail " type amphoteric surfactant.
The present invention is applied to the oil displacement agent of tertiary oil recovery, has the advantages that following protrusion in synthesis and application：
(1) one is that synthesis step is simple.Involved raw material is that market is commercially available common industrial chemicals, is related to
Reaction is also the classical reaction of organic synthesis.One step esterification and two step Michael addition reactions.This just promotes to be easy real
Existing industrialized production.
(2) second is that reaction yield is higher, the esterification of maleic acid monoester can reach 95% in three hour yields, two steps
The gross production rate of Michael addition reaction reaches 80% or more.
(3) three be that properties of product are superior, in terms of oil displacement efficiency, has higher interfacial activity, the equal energy of oil water interfacial tension
Reach 1.0*10-2MN/m.
Specific implementation mode
Below by embodiment, the present invention is further elaborated, and the purpose is to can be best understood from present disclosure.
Embodiment 1：
It takes 0.5mol fatty alcohols to be reacted with maleic anhydride and produces corresponding monoesters ethanesulfonic acid, acrylic acid and sodium hydroxide mixing
Add distillation water dissolution, carries out Michael addition reaction and generate bull carboxylic acid sodium-sodium sulfonate, finally by the monoesters of generation and bull carboxylic
End product is obtained by the reaction in sour sodium-sodium sulfonate.Parallel 3 experiments, gross production rate is on 95%.
Embodiment 2：
(1) the product solution configuration of positive ten alcohol reaction：Take positive ten alcohol oil displacement surfactant 0.6g, the NaCl solid of preparation
1.00g, then measure distilled water 99.40ml with graduated cylinder.Stirring can be such that solute is completely dissolved under room temperature.
(2) the product solution configuration of lauryl alcohol reaction：Take positive ten alcohol oil displacement surfactant 0.6g, the NaCl solid of preparation
1.00g, then measure distilled water 99.40ml with graduated cylinder.Stirring cannot be such that solute is completely dissolved under room temperature, and solution is heated to 32 DEG C
When be completely dissolved.
The crude oil that sticks together respectively with Gudong Crude Oil, victory makees interfacial tension determination experiment.Measure interfacial tension and can reach 1~
3×10-2mM/m.The solution concentration of experimental configuration is the aqueous solution of 6 ‰, salinity 10000mg/L (NaCl content 10g/L).
Claims (6)
1. a kind of new and effective both sexes displacement of reservoir oil type surfactant used for tertiary oil recovery --- fatty alcohol and polyethers " bull list tail " type
Both sexes displacement of reservoir oil type synthesis of surfactant new method, fatty alcohol (ten alcohol, lauryl alcohol, tetradecyl alchohol) polyethers (lauryl alcohol polyoxyethylene
Ether, tetradecyl alchohol polyoxyethylene ether, hexadecanol polyoxyethylene ether) cis-butenedioic anhydride, sodium acrylate, tarine sodium etc. is raw material, passes through
Esterification, the reactions such as Michael's addition generate fatty alcohol " bull list tail " type both sexes displacement of reservoir oil type series of surfactants, special
Sign is：Such new type amphoteric surfactant used for tertiary oil recovery is connected with bull list tail, is had more traditional common
A kind of higher novel surfactant of surfactant properties.There are three advantages for such surfactant tool, first, synthesis step
It is rapid simple；Second is that reaction yield is higher；Third, properties of product are superior.
2. according to the method described in claim 1, the synthesis step of fatty alcohol " bull list tail " type both sexes oil displacement agent is as follows：
(1) preparation of monoesters：Corresponding fatty alcohol (ten alcohol, lauryl alcohol, tetradecyl alchohol) is added in maleic anhydride and is flowed back, is returned
It is 3 hours to flow the time, ensures that reaction system cannot have water, the corresponding monoesters of gained (ten monoesters, 12 monoesters, 14 monoesters).
(2) bull carboxylic acid sodium-sodium sulfonate intermediateIt prepares：Claim to obtain 25.11g (0.2mol) amino second sulphur
Acid is mixed with 8.11g (0.2mol) sodium hydroxide, is completely dissolved after the stirring of 24.10g distilled water is added, pH value of solution=10-11.Claim
14.43g (0.1mol) acrylic acid is obtained to mix with 8.15g (0.2mol) sodium hydroxide, it is complete after being stirred after addition 26.15g distilled water
Fully dissolved, pH value of solution=7.It is colourless transparent liquid, pH value of solution=10-11 after the two mixing.Mixed liquid is poured into three mouthfuls
Heating water bath is stirred at reflux four hours in flask, obtains intermediate
(3) at salt：Monoesters and (2) bull carboxylic acid sodium-sodium sulfonate intermediate is made in (1) step, carries out Michael addition reaction, i.e.,
Obtain final product.
3. according to the method described in claim 1, the synthesis step of aliphatic alcohol polyether " bull list tail " type both sexes oil displacement agent is as follows：
(1) preparation of α, β unsaturated fatty acid：It takes the tetradecyl alchohol polyoxyethylene ether of the amount of certain substance in three-necked flask, leads to
Enter nitrogen protective gas 15min.Magnetic agitation is heated to 60 DEG C of stabilizations, and the maleic anhydride of the amount of same substance is added, and reacts 10min
After be warming up to 90 DEG C of stabilizations.Corresponding α, β unsaturated fatty acids is made in reflux 70min.
(2) preparation of N, N- dipropionic acid tarine trisodium：
1. weighing 0.1mol tarines and 0.1mol sodium hydroxides in a 250ml beakers, 13ml is added and distills water dissolution
Completely, then beaker mouth is covered with preservative film.
2. weighing 0.2mol acrylic acid with 0.2mol sodium hydroxides in a 250ml beakers, addition 26ml distillation water dissolutions are complete
(heat release is violent in course of dissolution, pays attention to safeguard procedures)
3. by step 1. and 2. in product be uniformly mixed and pour into three-necked flask, be inserted into thermometer, open magnetic force heating stirring
Device is warming up to 90 DEG C of condensing reflux 9h, obtains intermediate monomer N, N- dipropionic acid tarine trisodium.
(3) preparation of " bull list tail " type amphoteric surfactant intermediate monomer：By α obtained, β unsaturated fatty acids and N, N-
Dipropionic acid tarine trisodium is heated to reflux 16h and obtains " bull list in than being added in three-necked flask for 1.2: 1 ratio
Tail " type amphoteric surfactant intermediate monomer.
(4) at salt：Monomer obtained by step (3) is subjected to acid-base titration into salt with sodium hydroxide solution, finally obtains " bull list
Tail " type amphoteric surfactant.
4. according to the method described in claim 1, it is characterized in that synthesized product is fatty alcohol and polyethers " bull list tail "
Type both sexes displacement of reservoir oil type surfactant.
5. according to the method described in claim 1, it is characterized in that synthesized fatty alcohol and polyethers " bull list tail " type both sexes
Displacement of reservoir oil type surfactant lipophilic group raw material is ten alcohol, lauryl alcohol, tetradecyl alchohol and Dodecyl Polyoxyethylene Ether, tetradecyl alchohol polyoxy
Vinethene, hexadecanol polyoxyethylene ether.
6. according to the method described in claim 1, it is characterized in that synthesized fatty alcohol " bull list tail " type both sexes displacement of reservoir oil type
Surfactant hydrophilic radical is sulfonic group and carboxylic acid group.
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| CN201710109914.5A CN108504345A (en) | 2017-02-23 | 2017-02-23 | Based on fatty alcohol and the synthesis of polyethers " bull list tail " type both sexes oil displacement agent and application study |
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| CN201710109914.5A CN108504345A (en) | 2017-02-23 | 2017-02-23 | Based on fatty alcohol and the synthesis of polyethers " bull list tail " type both sexes oil displacement agent and application study |
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Citations (7)
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|---|---|---|---|---|
| EP0481668A1 (en) * | 1990-10-15 | 1992-04-22 | Calgon Corporation | Multifunctional scale inhibitors |
| CN1084730C (en) * | 1994-02-22 | 2002-05-15 | 花王株式会社 | Taurine derivatives for use in cleanser compositions |
| US20090247428A1 (en) * | 2006-06-26 | 2009-10-01 | Simon Neil Duncum | Wellbore Fluid |
| EP2154224A1 (en) * | 2008-07-25 | 2010-02-17 | Bp Exploration Operating Company Limited | Method of carrying out a wellbore operation |
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| CN103408469A (en) * | 2013-08-27 | 2013-11-27 | 华鼎鸿基采油技术服务（北京）有限公司 | Preparation method and application of novel polymeric surfactant |
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-
2017
- 2017-02-23 CN CN201710109914.5A patent/CN108504345A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0481668A1 (en) * | 1990-10-15 | 1992-04-22 | Calgon Corporation | Multifunctional scale inhibitors |
| CN1084730C (en) * | 1994-02-22 | 2002-05-15 | 花王株式会社 | Taurine derivatives for use in cleanser compositions |
| US20090247428A1 (en) * | 2006-06-26 | 2009-10-01 | Simon Neil Duncum | Wellbore Fluid |
| US20160052868A1 (en) * | 2008-04-17 | 2016-02-25 | Thomas P. Daly | Biological buffers with wide buffering ranges |
| EP2154224A1 (en) * | 2008-07-25 | 2010-02-17 | Bp Exploration Operating Company Limited | Method of carrying out a wellbore operation |
| CN101912745A (en) * | 2009-10-31 | 2010-12-15 | 任朝华 | Sulfamic acid amphoteric surfactant and synthesis method thereof |
| CN103408469A (en) * | 2013-08-27 | 2013-11-27 | 华鼎鸿基采油技术服务（北京）有限公司 | Preparation method and application of novel polymeric surfactant |
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Application publication date: 20180907 |