CN110229268A - A kind of pH response type thick oil emulsifier and preparation method thereof - Google Patents
A kind of pH response type thick oil emulsifier and preparation method thereof Download PDFInfo
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- CN110229268A CN110229268A CN201910606874.4A CN201910606874A CN110229268A CN 110229268 A CN110229268 A CN 110229268A CN 201910606874 A CN201910606874 A CN 201910606874A CN 110229268 A CN110229268 A CN 110229268A
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
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- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a kind of pH response type thick oil emulsifiers and preparation method thereof, belong to reducing thick oil viscosity technical field in oil exploitation.Its technical solution is: hydrophilic monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and pH response type monomer methacrylic acid diethylaminoethyl are added in flask with molar ratio 1:1~9, total monomer is 10~30%, logical nitrogen 30min, 0.1~0.5% initiator is added, 4~8h is reacted at being 50~70 DEG C in temperature, pH response type thick oil emulsifier is made.The thick oil emulsifier has preferable surface-active in alkaline condition, and reducing thick oil viscosity rate reaches 90% or more；It adjusts under lotion pH to acid condition, emulsifier loses surface-active, and viscous oil emulsion is demulsified automatically.The thinner overcomes the difficult problem of thick-oil emulsified adhesive-reducing post-processing, has many advantages, such as that preparation is simple, raw material is cheap and easily-available and viscosity break ratio is high, has broad application prospects in reducing thick oil viscosity field.
Description
Technical field
The present invention relates to a kind of pH response type thick oil emulsifiers and preparation method thereof.
Background technique
China's viscous crude is resourceful.According to statistics, China successively has found a viscous crude field more than 70 in 12 basins, establishes
5 great development production districts, yield have accounted for the 10% of national petroleum total output, and viscous crude positive performer in China's energy resource structure is more next
More important role.But viscous crude molecular structure is complicated, heavy constituent content is high, and viscosity is big, defeated brings to the exploitation sum aggregate of viscous crude
The difficulty that arrives very much.
For a long time, mainly use that heating, viscosity reducing collection is defeated, thin oil blending visbreaking collection is defeated, reducing viscosity by emulsifying collection is defeated to viscous crude both at home and abroad
And the modes such as oil-soluble viscosity reducer collection is defeated.Heating, viscosity reducing fuel consumption is big, at high cost；Thin oil blending visbreaking is not only by thin oil source
Limitation, and mix viscous crude thin oil according to viscous crude calculation of price, it is low in economic efficiency；Thick-oil emulsified adhesive-reducing collection is defeated to be gone out
Now post-processing (as being dehydrated) problem, and it is not suitable for low water-bearing crude oil；Oil-soluble viscosity reducer viscosity break ratio is not high, cannot individually make
With.Stimuli responsive type surfactant is to cause the variation of surfactant molecule structure in aqueous solution by certain method,
To make corresponding surface tension appearance significantly change, correspondingly, certain macro surface properties of system change.It is logical
Say popularly, be exactly people can adjust according to their own needs make it have or do not have surface active function, this change
It can regulate and control.Nonionic surfactant is traditional temperature response type surfactant, as the temperature rises, it is non-from
The hydrophily of sub- surfactant gradually decreases until disappearing, and surface-active reduces, and temperature restores to the original state again after reducing.
PH response type thick oil emulsifier is exactly a kind of emulsifier that surface-active changes with pH, by the variation of pH come real
Existing emulsified viscous oil and demulsification.Can be with effective solution reducing thick oil viscosity the problem of, and post-processing (demulsification) is convenient, operation letter
It is single, it is easy to control.Thinner viscosity reducing effect is good, and dosage is few, at low cost.
Summary of the invention
That the purpose of the present invention is to provide a kind of viscosity reducing effects is good, post-processing is easy, simple process and low-cost
PH response type thick oil emulsifier and preparation method thereof for heavy oil pipeline conveying.
To achieve the goals above, the present invention provides following technical scheme.
The emulsifier includes two kinds of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and diethylaminoethyl base ethyl ester
Monomer, structural formula are as follows:
Wherein m and n is monomer mole ratio, and m is 10%~90%, n=1-m.
Emulsifier preparation includes following synthesis step: by hydrophilic monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride
With pH response type monomer methacrylic acid diethylaminoethyl with molar ratio 1:1~9 be added flask in, total monomer be 10~
30%, lead to nitrogen 30min, 0.1~0.5% initiator is added, reacts 4~8h at being 50~70 DEG C in temperature, pH is made and rings
Answer type thick oil emulsifier.The diethylaminoethyl base ethyl ester is a kind of pH response type monomer, under alkaline normal condition
It is a kind of lipophilic monomer, is oil-soluble；It is protonated in acid condition tertiary amine and becomes hydrophilic, it is variable with hydrophily
Property.
The MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is hydrophilic monomer, and diethylaminoethyl base ethyl ester is
Oleophylic monomer, emulsifying under alkaline condition agent surface-active with higher；In acid condition, diethylaminoethyl base
Ethyl ester is protonated, and emulsifier loses surface-active.
Under alkaline condition, the emulsifier and viscous crude, water can form stable lotion；The pH of viscous oil emulsion is adjusted to
Acidity, emulsifier lose surface-active, and viscous oil emulsion is demulsified automatically.
Beneficial effects of the present invention:
1. pH response type thick oil emulsifier prepared by the present invention has raw material sources extensive, low in cost, preparation process
Simply, there is good surfactant, reducing thick oil viscosity rate reaches 90% or more, meets the requirement of heavy oil pipeline conveying.
2. pH response type thick oil emulsifier prepared by the present invention has pH responsiveness, have under alkaline condition good
Surface-active and reducing viscosity by emulsifying performance can be demulsified automatically when the pH of lotion is adjusted to acidity, solve thick-oil emulsified adhesive-reducing
Post-process difficult problem.
Specific embodiment
In order to better understand the present invention, below by specific embodiment, the present invention is further described, but the present invention
Content be not limited solely to the following examples.
Embodiment one
18g diethylaminoethyl base ethyl ester, 2g methylacryoyloxyethyl trimethyl chlorine are added in 250mL flask
Change ammonium, be made into the aqueous solution that monomer gross mass concentration is 20%, leads to nitrogen 30min, the initiation of monomer gross mass 0.5% is added
Agent obtains thick oil emulsifier in 70 DEG C of reaction 8h.
Viscous crude (50 DEG C of viscosity 30000mPa.s) 50g is taken, the heavy crude thinner in 2g embodiment one is dissolved in 50mL distilled water
In, then viscous crude is added in emulsifier under agitation, it is 241mPa.s that its viscosity is surveyed at 50 DEG C, and viscosity break ratio is
Syneresis rate is 10% after 99.26%, 2h.However emulsion pH is adjusted to 5~6 with HCl, emulsion is demulsified rapidly layering,
0.5h syneresis rate reaches 80% or more.
Embodiment two
16g diethylaminoethyl base ethyl ester, 4g methylacryoyloxyethyl trimethyl chlorine are added in 250mL flask
Change ammonium, be made into the aqueous solution that monomer gross mass concentration is 20%, leads to nitrogen 30min, the initiation of monomer gross mass 0.5% is added
Agent reacts 8h at 70 DEG C, obtains thick oil emulsifier.
Viscous crude (50 DEG C of viscosity 30000mPa.s) 50g is taken, the heavy crude thinner in 3g embodiment one is dissolved in 50mL distilled water
In, then viscous crude is added in emulsifier under agitation, it is 113mPa.s that its viscosity is surveyed at 50 DEG C, and viscosity break ratio is
Syneresis rate is 11% after 99.65%, 2h.However emulsion pH is adjusted to 5~6 with HCl, emulsion is demulsified rapidly layering,
0.5h syneresis rate reaches 80% or more.
Embodiment three
14g diethylaminoethyl base ethyl ester, 6g methylacryoyloxyethyl trimethyl chlorine are added in 250mL flask
Change ammonium, be made into the aqueous solution that monomer gross mass concentration is 20%, leads to nitrogen 30min, the initiation of monomer gross mass 0.5% is added
Agent reacts 8h at 70 DEG C, obtains thick oil emulsifier.
Viscous crude (50 DEG C of viscosity 30000mPa.s) 50g is taken, the heavy crude thinner in 4g embodiment one is dissolved in 50mL distilled water
In, then viscous crude is added in emulsifier under agitation, it is 74mPas that its viscosity is surveyed at 50 DEG C, and viscosity break ratio is
Syneresis rate is 3% after 99.77%, 2h.However emulsion pH is adjusted to 5~6 with HCl, emulsion is demulsified rapidly layering, 0.5h
Syneresis rate reaches 80% or more.
Example IV
12g diethylaminoethyl base ethyl ester, 8g methylacryoyloxyethyl trimethyl chlorine are added in 250mL flask
Change ammonium, be made into the aqueous solution that monomer gross mass concentration is 20%, leads to nitrogen 30min, the initiation of monomer gross mass 0.5% is added
Agent reacts 8h at 70 DEG C, obtains thick oil emulsifier.
Viscous crude (50 DEG C of viscosity 30000mPa.s) 50g is taken, the heavy crude thinner in 2g embodiment one is dissolved in 50mL distilled water
In, then viscous crude is added in emulsifier under agitation, it is 90mPa.s that its viscosity is surveyed at 50 DEG C, and viscosity break ratio is
Syneresis rate is 4% after 99.72%, 2h.However emulsion pH is adjusted to 5~6 with HCl, emulsion is demulsified rapidly layering, 0.5h
Syneresis rate reaches 80% or more.
Embodiment five
10g diethylaminoethyl base ethyl ester, 10g methylacryoyloxyethyl trimethyl are added in 250mL flask
Ammonium chloride is made into the aqueous solution that monomer gross mass concentration is 20%, leads to nitrogen 30min, the initiation of monomer gross mass 0.5% is added
Agent reacts 8h at 70 DEG C, obtains thick oil emulsifier.
Viscous crude (50 DEG C of viscosity 30000mPa.s) 50g is taken, the heavy crude thinner in 4g embodiment one is dissolved in 50mL distilled water
In, then viscous crude is added in emulsifier under agitation, it is 166mPa.s that its viscosity is surveyed at 50 DEG C, and viscosity break ratio is
Syneresis rate is 14% after 99.49%, 2h.However emulsion pH is adjusted to 5~6 with HCl, emulsion is demulsified rapidly layering,
0.5h syneresis rate reaches 80% or more.
Claims (3)
1. a kind of pH response type thick oil emulsifier, it is characterised in that: the emulsifier includes methylacryoyloxyethyl trimethyl chlorine
Change two kinds of monomers of ammonium and diethylaminoethyl base ethyl ester, structural formula is as follows:
Wherein m and n is monomer molar score, m=0.1~0.9, n=1-m.
2. a kind of pH response type thick oil emulsifier according to claim 1, it is characterised in that preparation method includes following step
It is rapid: by hydrophilic monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and pH response type monomer methacrylic acid diethylin second
Ester is added in flask with molar ratio 1:1~9, and total monomer is 10~30%, leads to nitrogen 30min, is added 0.1~0.5%
Initiator reacts 4~8h at being 50~70 DEG C in temperature, pH response type thick oil emulsifier is made.
3. a kind of pH response type thick oil emulsifier according to claim 1, it is characterised in that: emulsifying under alkaline condition agent tool
There is higher surface-active, stable emulsion can be formed with viscous crude, water；PH is adjusted to acidity, it is living that emulsifier loses surface
Property, viscous oil emulsion can be demulsified automatically.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848864A (en) * | 2020-07-28 | 2020-10-30 | 宁波锋成先进能源材料研究院 | Amphiphilic copolymer and preparation method and application thereof |
| CN113461576A (en) * | 2021-06-23 | 2021-10-01 | 四川大学 | Dynamic covalent bond-based responsive surfactant and preparation method thereof |
| CN115368885A (en) * | 2022-08-23 | 2022-11-22 | 西南石油大学 | Dual-stimulus-response type polymer thickened oil emulsifying viscosity reducer and preparation method thereof |
Citations (2)
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| JP2012176606A (en) * | 2011-02-02 | 2012-09-13 | Fujifilm Corp | Lithographic printing original plate and method for producing the same |
| CN104961856A (en) * | 2015-07-01 | 2015-10-07 | 广东灵捷制造化工有限公司 | High-molecular amphoteric surfactant, preparation method and use |
-
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- 2019-07-06 CN CN201910606874.4A patent/CN110229268A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012176606A (en) * | 2011-02-02 | 2012-09-13 | Fujifilm Corp | Lithographic printing original plate and method for producing the same |
| CN104961856A (en) * | 2015-07-01 | 2015-10-07 | 广东灵捷制造化工有限公司 | High-molecular amphoteric surfactant, preparation method and use |
Non-Patent Citations (1)
| Title |
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| 周占胜等: "新型两性高分子表面活性剂的合成及性能 ", 《广东化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848864A (en) * | 2020-07-28 | 2020-10-30 | 宁波锋成先进能源材料研究院 | Amphiphilic copolymer and preparation method and application thereof |
| CN113461576A (en) * | 2021-06-23 | 2021-10-01 | 四川大学 | Dynamic covalent bond-based responsive surfactant and preparation method thereof |
| CN115368885A (en) * | 2022-08-23 | 2022-11-22 | 西南石油大学 | Dual-stimulus-response type polymer thickened oil emulsifying viscosity reducer and preparation method thereof |
| CN115368885B (en) * | 2022-08-23 | 2023-09-26 | 西南石油大学 | Dual-stimulus response type polymer thickened oil emulsifying viscosity reducer and preparation method thereof |
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Application publication date: 20190913 |