CN109289695A - A kind of carboxylic acid surfactant and its preparation method and application - Google Patents
A kind of carboxylic acid surfactant and its preparation method and application Download PDFInfo
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- CN109289695A CN109289695A CN201811123709.5A CN201811123709A CN109289695A CN 109289695 A CN109289695 A CN 109289695A CN 201811123709 A CN201811123709 A CN 201811123709A CN 109289695 A CN109289695 A CN 109289695A
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- carboxylic acid
- acid surfactant
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- allyl
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- C—CHEMISTRY; METALLURGY
- 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
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/28—Organic compounds not containing metal atoms containing sulfur as the only hetero atom, e.g. mercaptans, or sulfur and oxygen as the only hetero atoms
Abstract
The present invention relates to a kind of carboxylic acid surfactants and its preparation method and application; the preparation of carboxylic acid surfactant is the following steps are included: under conditions of heating, stirring and inert gas shielding; in allyl sulphonic acid sodium solution; allyl polyglycol and maleic anhydride monomer mixed solution are dropped evenly on one side, drops evenly initiator ammonium persulfate solution on one side, after being added dropwise to complete; insulation reaction is for a period of time; it is cooling, pH value is then neutralized to 7, obtains carboxylic acid surfactant.Carboxylic acid surfactant is added carboxylic acid surfactant and is dehydrated with desanding in application, in ageing oil.The present invention is separated the fine sand in ageing oil by chemically reacting, and the sand isolated can be with water to water treatment system, and with treated the production direct outlet of water, post-processing is relatively easy, and treated that ageing oil is aqueous few, reaches outer defeated requirement.
Description
Technical field
The invention belongs to technical field of oilfield chemistry, and in particular to a kind of carboxylic acid surfactant and preparation method thereof and answer
With.
Background technique
In offshore oilfield production process, it may result in down-hole sand control apparatus failure due to exploiting for a long time, make the original of extraction
Contain sand or clay in oil, the presence of this sand can seriously affect the separating effect of grease, and intractable crude oil is in storage tank borough chief
Between save, just will become intractable ageing oil containing sand.The conventional method of oilfield treatments ageing oil is Mechanical Method at present --- rotation
Stream centrifugal process the sand in crude oil is removed by the density contrast of crude oil and sand, the disadvantages of the method are as follows the treating capacity of equipment it is small,
Desanding efficiency is low, and the oil-sand post-processing isolated is relatively difficult.
Summary of the invention
The object of the present invention is to provide a kind of carboxylic acid surfactants and its preparation method and application.The present invention is using chemistry
Desanding method adds a small amount of chemical agent in ageing oil, separates the fine sand in ageing oil by chemically reacting, isolates
Sand can post-process relatively easy with water to water treatment system, with treated the production direct outlet of water, and that treated is old
Carburetion is aqueous few, reaches outer defeated requirement.
To solve the above problems, the present invention adopts the following technical scheme:
A kind of carboxylic acid surfactant, characterized in that structural formula is as follows:
Wherein: n 6-7；A is 56-58, b 163-245, c 83-139.
The present invention also provides the preparation methods of carboxylic acid surfactant, comprising the following steps: in heating, stirring and inertia
Under conditions of gas shield, in allyl sulphonic acid sodium solution, allyl polyglycol and maleic anhydride list are dropped evenly on one side
Body mixed solution, drops evenly initiator ammonium persulfate solution on one side, and after being added dropwise to complete, insulation reaction is for a period of time, cooling, so
PH value is neutralized afterwards to 7, obtains carboxylic acid surfactant.
Further, the additional amount of each substance is as follows: allyl polyglycol monomer: allyl polyglycol: maleic acid
Acid anhydride: Sodium Allyl Sulfonate: the mass ratio of ammonium persulfate are as follows: 1:1:0.8~1.2:0.6~1.0:0.06~0.12.
Further, the allyl sulphonic acid sodium solution, ammonium persulfate solution concentration be the aqueous solution of 20wt%；Alkene
Propyl polyethylene glycol and maleic anhydride monomer mixed solution are the allyl polyglycol aqueous solution of 20wt% and the horse of 20wt%
Take the mixed liquor of anhydride monomers aqueous solution.
Further, the heating temperature is 85 DEG C；The stirring rate is 150r/min, and the inert gas is nitrogen
Gas.
Further, the time dropped evenly is 4h, and the time of the insulation reaction is 3 hours.
Further, using in 40% NaOH solution and pH value is to 7.
Further, configured allyl sulphonic acid sodium water solution is placed in four-hole boiling flask, installs thermometer, stirring
Device, condensing unit, dropping funel, nitrogen protection device are stirred continuously and are warming up to 85 DEG C, allyl polyglycol is added dropwise on one side
With maleic anhydride monomer mixed solution, initiator ammonium persulfate solution is added dropwise on one side.
The present invention also provides the applications of carboxylic acid surfactant, characterized in that in ageing oil, the carboxylic acid table is added
Face activating agent is dehydrated with desanding.
Further, in ageing oil, the additional amount of the carboxylic acid surfactant is 40ppm.
Inventive principle:
Surfactant desanding principle: a part of polar group such as ester group ,-the OH ,-COO- of carboxylic acid surfactant institute band
It is tightly adsorbed on highly polar fine sand grain surface Deng by interactions such as ionic bond, covalent bond, hydrogen bond, Van der Waals forces,
Remaining polar group-SO3- ,-COO- etc. show extremely strong hydrophily, go out to be conducive to fine sand grain from separation of oil
To enter water phase.Briefly, carboxylic acid water reducer is able to maintain the stability of decentralized system by steric repulsion power.And carboxylic acid table
Face activating agent be mainly in oil clay or silt taken in water phase by chemical bond, and then reach clay in oil removing
Or the effect of silt, the mode of action and action principle of the two be not identical.
Beneficial effect
The present invention uses allyl polyglycol (AEO), maleic anhydride, sodium vinyl sulfonate for polymerized monomer, aqueous solution
Free radical polymerization synthesizes a series of polycarboxylic acids surfactants.Using chemical desanding method, chemical agent is added in ageing oil, is led to
It crosses chemical reaction the sand separation in ageing oil is gone out, the sand isolated can arrive water treatment system, direct outlet, post-processing operation
Simply, treated, and ageing oil moisture content is low, can achieve outer defeated standard.
The preparation process of carboxylic acid surfactant of the invention is simple, production cost is low.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
Take 20g allyl polyglycol, 20g maleic anhydride, 16g Sodium Allyl Sulfonate and 1.8g initiator persulfuric acid
Ammonium is configured to 20% aqueous solution with distilled water respectively；Configured Sodium Allyl Sulfonate is placed on 500ml four-hole boiling flask
In, thermometer, blender, condensing unit, dropping funel, nitrogen protection device are installed, is stirred continuously and is warming up to 85 DEG C, on one side
Allyl polyglycol and maleic anhydride monomer mixed solution is added dropwise, initiator ammonium persulfate solution is added dropwise on one side, drops evenly
4h is dripped off, and keeps the temperature 3h, cooling, in 40% NaOH solution and pH value is to 7, obtains carboxylic acid surfactant CS-01.
Wherein: n ≈ 7；a≈57；b≈204；c≈111
By adjusting allyl polyglycol, maleic anhydride, Sodium Allyl Sulfonate and initiator ammonium persulfate feed intake quality
Ratio synthesizes the carboxylic acid surfactant of different molecular weight and different branched structures:
When the mass ratio of allyl polyglycol, maleic anhydride, Sodium Allyl Sulfonate and initiator ammonium persulfate is
1.0:0.8:1.0:0.06 when, the carboxylic acid surfactant of preparation is CS-02；
Wherein: n ≈ 6；a≈58；b≈163；c≈139
When the mass ratio of allyl polyglycol, maleic anhydride, Sodium Allyl Sulfonate and initiator ammonium persulfate is
1.0:1.2:0.6:0.09 when, the carboxylic acid surfactant of preparation is CS-03；
Wherein: n ≈ 7；a≈57；b≈245；c≈83
When the mass ratio of allyl polyglycol, maleic anhydride, Sodium Allyl Sulfonate and initiator ammonium persulfate is
1.0:1.0:0.6:0.12 when, the carboxylic acid surfactant of preparation is CS-04.
Wherein: n ≈ 7；a≈57；b≈204；c≈83
Embodiment 2:
Ageing oil is carried out from the carboxylic acid surfactant of different branched structures to different molecular weight obtained in embodiment 1 to remove
Sand dehydration experiment, and compared with the blank sample of not adding medicine, experimental temperature is 80 DEG C, tests ageing oil sand content used and is
1.2%, comprehensive water cut 2.5%, experimental result is as follows:
It is learnt by above-mentioned experimental verification, the aging of carboxylic acid surfactant CS-01, CS-02, CS-03, CS-04 of preparation
Oily desanding and dehydrating effect are all fine, and when adding consistency is not less than 30ppm, ageing oil is not less than 87.5% except sand coarse aggregate ratio, experiment
Ageing oil moisture content is not higher than 0.5% afterwards, and ageing oil moisture content is qualified；Under identical medicament filling concentration, the effect of CS-01 is most
Good, when adding consistency is 40ppm, ageing oil is 95.8% except sand coarse aggregate ratio, ageing oil moisture content 0.3% after experiment.
Claims (10)
1. a kind of carboxylic acid surfactant, characterized in that structural formula is as follows:
Wherein: n 6-7；A is 56-58, b 163-245, c 83-139.
2. the preparation method of carboxylic acid surfactant according to claim 1, characterized in that the following steps are included: adding
Under conditions of heat, stirring and inert gas shielding, in allyl sulphonic acid sodium solution, allyl polyglycol is dropped evenly on one side
With maleic anhydride monomer mixed solution, initiator ammonium persulfate solution is dropped evenly on one side, after being added dropwise to complete, one section of insulation reaction
It is time, cooling, pH value is then neutralized to 7, obtains carboxylic acid surfactant.
3. the preparation method of carboxylic acid surfactant according to claim 2, characterized in that the additional amount of each substance is such as
Under: allyl polyglycol monomer: allyl polyglycol: maleic anhydride: Sodium Allyl Sulfonate: the mass ratio of ammonium persulfate
Are as follows: 1:1:0.8~1.2:0.6~1.0:0.06~0.12.
4. the preparation method of carboxylic acid surfactant according to claim 3, characterized in that the Sodium Allyl Sulfonate is molten
Liquid, ammonium persulfate solution concentration be the aqueous solution of 20wt%；Allyl polyglycol is with maleic anhydride monomer mixed solution
The mixed liquor of the maleic anhydride monomer aqueous solution of the allyl polyglycol aqueous solution and 20wt% of 20wt%.
5. the preparation method of carboxylic acid surfactant according to claim 2, characterized in that the heating temperature is 85
℃；The stirring rate is 150r/min, and the inert gas is nitrogen.
6. the preparation method of carboxylic acid surfactant according to claim 2, characterized in that the time dropped evenly
For 4h, the time of the insulation reaction is 3 hours.
7. the preparation method of carboxylic acid surfactant according to claim 2, characterized in that using 40% NaOH solution
PH value is neutralized to 7.
8. the preparation method of carboxylic acid surfactant according to claim 3, characterized in that by configured allyl sulphur
Acid sodium aqueous solution is placed in four-hole boiling flask, installs thermometer, blender, condensing unit, dropping funel, nitrogen protection device,
It is stirred continuously and is warming up to 85 DEG C, allyl polyglycol and maleic anhydride monomer mixed solution are added dropwise on one side, be added dropwise draw on one side
Send out agent ammonium persulfate solution.
9. the application of carboxylic acid surfactant according to claim 1, characterized in that in ageing oil, the carboxylic is added
Acid surfaces activating agent is dehydrated with desanding.
10. the application of carboxylic acid surfactant according to claim 8, characterized in that in ageing oil, the carboxylic acid table
The additional amount of face activating agent is 40ppm.
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| CN201811123709.5A CN109289695B (en) | 2018-09-26 | 2018-09-26 | Carboxylic acid surfactant and preparation method and application thereof |
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| CN201811123709.5A CN109289695B (en) | 2018-09-26 | 2018-09-26 | Carboxylic acid surfactant and preparation method and application thereof |
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| CN109289695A true CN109289695A (en) | 2019-02-01 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050194292A1 (en) * | 2003-09-22 | 2005-09-08 | Beetge Jan H. | Processing aids for enhanced hydrocarbon recovery from oil sands, oil shale and other petroleum residues |
| CN105542093A (en) * | 2016-03-15 | 2016-05-04 | 苏州市兴邦化学建材有限公司 | Synthesis process of polyether type polycarboxylate water reducers with high water reduction property |
| CN107177367A (en) * | 2017-05-09 | 2017-09-19 | 常州大学 | Oil-sand cavitation process technique |
| CN107664675A (en) * | 2016-07-29 | 2018-02-06 | 中国石油化工股份有限公司 | Based on thickening type emulsification surfactants washing oil rate analysis method |
| CN107859507A (en) * | 2016-09-22 | 2018-03-30 | 中国石油化工股份有限公司 | Improve the method for increasing of oil well single well productivity |
-
2018
- 2018-09-26 CN CN201811123709.5A patent/CN109289695B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050194292A1 (en) * | 2003-09-22 | 2005-09-08 | Beetge Jan H. | Processing aids for enhanced hydrocarbon recovery from oil sands, oil shale and other petroleum residues |
| CN105542093A (en) * | 2016-03-15 | 2016-05-04 | 苏州市兴邦化学建材有限公司 | Synthesis process of polyether type polycarboxylate water reducers with high water reduction property |
| CN107664675A (en) * | 2016-07-29 | 2018-02-06 | 中国石油化工股份有限公司 | Based on thickening type emulsification surfactants washing oil rate analysis method |
| CN107859507A (en) * | 2016-09-22 | 2018-03-30 | 中国石油化工股份有限公司 | Improve the method for increasing of oil well single well productivity |
| CN107177367A (en) * | 2017-05-09 | 2017-09-19 | 常州大学 | Oil-sand cavitation process technique |
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