CN102690641B - Sulfonate surfactant and preparation method thereof - Google Patents
Sulfonate surfactant and preparation method thereof Download PDFInfo
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- CN102690641B CN102690641B CN201210192550.9A CN201210192550A CN102690641B CN 102690641 B CN102690641 B CN 102690641B CN 201210192550 A CN201210192550 A CN 201210192550A CN 102690641 B CN102690641 B CN 102690641B
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- sulfosalt surfactant
- hyperbranched polymer
- sulfonate surfactant
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Abstract
The invention relates to a sulfonate surfactant which is an anionic-nonionic surfactant. The structural formula is as shown in the specification, wherein R1 is H or aryl or long-chain alkyl. The preparation method of the sulfonate surfactant comprises the following steps: synthesizing an AB2 type monomer to synthesize a hydroxyl-terminated hyperbranched polymer; and then modifying the terminal part of the hydroxyl-terminated hyperbranched polymer and introducing sulfonic groups to synthesize the hyperbranched sulfonate surfactant. The sulfonate surfactant has good water solubility, emulsibility, wettability and foaming properties, and has high surfactivity and temperature and salt resistance properties. When the sulfonate surfactant is complexed with polyacrylamide and Na2CO3 to form a ternary composite oil-displacing agent, the oil-water interfacial tension can be reduced to 10<-3> mN/m, thereby greatly improving the oil-displacing effect.
Description
Technical field
The present invention relates to a kind of tensio-active agent, be specifically related to a kind of sulfosalt surfactant; The invention still further relates to the preparation method of this sulfosalt surfactant.
Background technology
Along with the intensification of In Oil Field Exploration And Development degree, major part has entered high water-cut stage mining phase, and water ratio reaches more than 90%, and exploitation difficulty progressively strengthens, and crude production rate successively decreases year by year.For secondary oil recovery, fail extraction irreducible oil and surplus oil, carrying out tertiary oil recovery is the important method that improves recovery ratio, and tensio-active agent occupies critical role in chemical flooding, no matter tensio-active agent is as host or as the auxiliary agent displacement of reservoir oil, to increasing substantially recovery ratio, all plays immeasurable effect.Wherein, sulfosalt surfactant is widely used in tertiary oil recovery, as the alkylaryl sulfonate surfactants such as ORS series, B～100 series have been obtained progress in many field tests district in the world, but due to sulfosalt surfactant temperature tolerance and salt resistance poor, be still difficult to meet the needs in oil field.Along with development and the popularization of ASP ternary composite driving technology, the impact of the geologic condition that recovered the oil, stratum is darker, and the saltness of local water can be relatively high, and temperature also can be higher, and the tensio-active agent of anionic is easily and divalent cation (Ca in local water
2+, Mg
2+deng) precipitate, produce mass spectrum separation phenomenon, work as Ca
2+, Mg
2+while surpassing 300 μ g/g, just lose oil displacement efficiency, and some field tests show in recent years, highly basic can damage stratum.For this reason, work out the attention that the low alkali oil-displacing agent of weak base that has high effective surface active and salt tolerant resistance to elevated temperatures concurrently is subject to domestic and international researchist.
Summary of the invention
The object of the present invention is to provide the low alkali sulfosalt surfactant of a kind of weak base, solve the poor problem of existing sulfosalt surfactant salt tolerant heat resistance.
Another object of the present invention is to provide the preparation method of described sulfosalt surfactant.
The object of the present invention is achieved like this, and a kind of sulfosalt surfactant is a kind of negatively charged ion～nonionogenic tenside, and structural formula is:
Wherein, R
1for H or aryl or chain alkyl.
Another object of the present invention is achieved in that the preparation method of described sulfosalt surfactant, first uses AB
2type monomer is prepared Hyperbranched Polymer with Terminal Hydroxyl, then in the end of described Hyperbranched Polymer with Terminal Hydroxyl, introduces sulfonic group and generates the hyperbranched tensio-active agent of sulfonate.
Described AB
2type monomer reacts with TriMethylolPropane(TMP) and generates Hyperbranched Polymer with Terminal Hydroxyl.
Described AB
2type monomer reacts under catalyst action with TriMethylolPropane(TMP) and generates Hyperbranched Polymer with Terminal Hydroxyl HBP, described AB
2the mol ratio of type monomer and TriMethylolPropane(TMP) is 6～3:1, and described catalyzer is tosic acid, and temperature of reaction is 80～130 ℃, and the reaction times is 4～8h.
Described Hyperbranched Polymer with Terminal Hydroxyl and fat or aromatic series olefin(e) acid or acyl chloride reaction obtain intermediate I, and described intermediate I is reacted with sulphonating agent and generated hyperbranched sulfosalt surfactant.
The mol ratio of described sulphonating agent and intermediate I is 3～1:1, used catalyst is Sodium Nitrite, and its quality is 1%～5% of described sulphonating agent and intermediate I total mass, and temperature of reaction is 50～80 ℃, reaction times 4～8h, described sulphonating agent is S-WAT and sodium bisulfite.
Described AB
2monomer is obtained in methyl acrylate reaction by diethanolamine.
The present invention has following beneficial effect:
1, the present invention passes through AB
2type monomer synthesizes Hyperbranched Polymer with Terminal Hydroxyl, then in the modification of Hyperbranched Polymer with Terminal Hydroxyl terminal portion, introduces sulfonic group, has improved the characteristics such as water-soluble, the emulsification of hyperbranched polymer, moistening and foaming.
2, due to the increase of hyperbranched polymer along with algebraically, its shape approximation is in spherical, and there is cavity inside, and end group mostly is hydrophilic group, from the chain link of the outside branching of core, mostly is oleophilic group, and they are enclosed in intramolecule by end group, forms an oleophylic " cave ".The present invention, in conjunction with the oleophylic " cave " of hyperbranched polymer molecule inside, nonionic and two kinds of hydrophilic radicals of negatively charged ion are designed in a molecular structure simultaneously, thereby the surfactant oil displacement making has high surface and temperature resistant antisalt performance concurrently.
3, sulfonate surfactant of the present invention and polyacrylamide, Na
2cO
3composite formation ternary composite driving finish, makes oil water interfacial tension be down to 10
-3mN/m, has increased substantially oil displacement efficiency.
Accompanying drawing explanation
Fig. 1 is the infrared absorption spectrum of the embodiment of the present invention 1 hyperbranched sulfosalt surfactant;
Fig. 2 is the hyperbranched sulfosalt surfactant surface tension figure of the embodiment of the present invention 1 different concns;
The oil water interfacial tension of the ternary composite driving finish that Fig. 3 contains the embodiment of the present invention 1 hyperbranched sulfosalt surfactant is curve over time.
Embodiment
Wherein, R
1for H.
Fig. 1 is this sulfosalt surfactant infrared spectra.
The preparation method of this sulfosalt surfactant, in acid used, the total number of carbon atoms is 10～18, concrete preparation process is as follows:
Step 1: (1) is first dissolved in a certain amount of methyl alcohol by 1mol diethanolamine, drips 2mol methyl acrylate, stirs 4h at 35 ℃, and under 0.08MPa, vacuum filtration 1h, obtains AB
2monomer;
(2) the catalyzer tosic acid that is 2% by TriMethylolPropane(TMP) and massfraction stirs at 115 ℃, according to AB
2the ratio that monomer and TriMethylolPropane(TMP) mol ratio are 2:1 drips AB
2monomer, reacts 1h at 100 ℃, proceeds to 120 ℃ of backspins of Rotary Evaporators and steams 1h, obtains Hyperbranched Polymer with Terminal Hydroxyl.
Step 2: the mixed in molar ratio that step 1 gained Hyperbranched Polymer with Terminal Hydroxyl and undecylenic acid are pressed to 1:4, stirring reaction 3h at 90 ℃, then steams 1h at 0.01MPa backspin, then washes with water, and filtrate is revolved to steam except anhydrating and is obtained intermediate I.
Step 3: take methyl alcohol as solvent, sulphonating agent is S-WAT and sodium bisulfite and its mol ratio 2:1, the mol ratio of sulphonating agent and intermediate I is 2:1, catalyzer is that Sodium Nitrite and its add-on are 3% of sulphonating agent and intermediate I total mass, under 95 ℃ of conditions, react 4h, with resin anion(R.A), remove sulphonating agent and catalyzer, with HCl, pH is adjusted to 7, add ethanol, remove by filter the NaCl of generation, at 80 ℃, vacuumize except desolventizing, obtain yellow solid superbrnaching end-hydroxy sulfosalt surfactant SHBP～1, infrared spectrogram as shown in Figure 1, wherein 1045, 1181cm～1 is sulfonic charateristic avsorption band.
The performance characterization of hyperbranched sulfosalt surfactant SHBP～1: SHBP～1 of preparation different concns, at room temperature measure surface tension (γ～ρ curve), obtain its critical bundle concentration c mc that waters, at the critical bundle concentration lower surface tension force that waters, can reach 27.5mN/m, result as shown in Figure 2.Because this tensio-active agent has nonionic and anionic hydrophilic base concurrently, there is anti-salt property, at 20 ℃, adopt direct observational method to observe the solvability of cmc lower surface promoting agent in different inorganic salt, NaCl mass concentration is greater than 4 * 10
4after mg/L, start to occur insolubles, CaCl
2mass concentration is greater than 3 * 10
4after mg/L, will start to occur insolubles, MgCl
2mass concentration is greater than 3.5 * 10
4after mg/L, start to occur insolubles, result shows that this tensio-active agent has good salt resistance.
The application of hyperbranched sulfosalt surfactant SHBP～1: hyperbranched sulfosalt surfactant SHBP～1 and Sodium dodecylbenzene sulfonate is composite, and wherein the molar fraction of hyperbranched sulfosalt surfactant SHBP～1 is 0.8.By composite tensio-active agent, 1000mg/L polyacrylamide and 0.4%Na
2cO
3be re-dubbed ternary composite driving finish, measure the oil water interfacial tension that extends crude oil at 50 ℃, balance oil water interfacial tension can reach ultra low interfacial tension 10
-3mN/m, as shown in Figure 3.
Embodiment 2, a kind of sulfosalt surfactant and preparation method thereof, and referring to embodiment 1, as different from Example 1, and in step 2, the mixed in molar ratio that step 1 gained Hyperbranched Polymer with Terminal Hydroxyl and cinnamyl chloride are pressed to 1:4.
Embodiment 3, a kind of sulfosalt surfactant and preparation method thereof, and referring to embodiment 1, as different from Example 1, step 2: the mixed in molar ratio that step 1 gained Hyperbranched Polymer with Terminal Hydroxyl and oleic acid are pressed to 1:4.
Embodiment 4～6, a kind of sulfosalt surfactant and preparation method thereof, and referring to embodiment 1, the processing condition different from embodiment 1 and relevant data are in Table 1.
The processing condition of table 1 embodiment 4～6 and relevant data
Embodiment 7-9, a kind of sulfosalt surfactant and preparation method thereof, wherein R
1for aryl, referring to embodiment 1, the processing condition different from embodiment 1 and relevant data are in Table 2.
The processing condition of table 2 embodiment 7～9 and relevant data
Embodiment 10-12, a kind of sulfosalt surfactant and preparation method thereof, referring to embodiment 1, the processing condition different from embodiment 1 and relevant data are in Table 3.
The processing condition of table 3 embodiment 10～12 and relevant data
Claims (5)
1. a sulfosalt surfactant, is characterized in that: be a kind of nonionic～aniorfic surfactant, its structural formula is:
Wherein, R
1for H or aryl or chain alkyl.
2. the preparation method of sulfosalt surfactant as claimed in claim 1, is characterized in that: first use AB
2type monomer is prepared Hyperbranched Polymer with Terminal Hydroxyl, and described Hyperbranched Polymer with Terminal Hydroxyl and fat or aromatic series olefin(e) acid or acyl chloride reaction obtain intermediate I, and described intermediate I is reacted with sulphonating agent and generated hyperbranched sulfosalt surfactant; The mol ratio of described sulphonating agent and intermediate I is 3～1:1, used catalyst is that Sodium Nitrite and its quality are 1%～5% of described sulphonating agent and intermediate I total mass, temperature of reaction is 50～80 ℃, reaction times 4～8h, and described sulphonating agent is S-WAT and sodium bisulfite.
3. the preparation method of sulfosalt surfactant as claimed in claim 2, is characterized in that: described AB
2type monomer reacts with TriMethylolPropane(TMP) and generates Hyperbranched Polymer with Terminal Hydroxyl.
4. the preparation method of sulfosalt surfactant as claimed in claim 3, is characterized in that: described AB
2type monomer reacts under catalyst action with TriMethylolPropane(TMP) and generates Hyperbranched Polymer with Terminal Hydroxyl, described AB
2the mol ratio of type monomer and TriMethylolPropane(TMP) is 6～3:1, and described catalyzer is tosic acid, and temperature of reaction is 80～130 ℃, and the reaction times is 4～8h.
5. the preparation method of the sulfosalt surfactant as described in claim 2～4 any one, is characterized in that: described AB
2monomer is reacted and obtains with methyl acrylate by diethanolamine.
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| CN103111229B (en) * | 2013-03-08 | 2014-11-05 | 山东大学 | Gemini type fluorocarbon surfactant containing sulfonic group and preparation method thereof |
| CN104232046B (en) * | 2013-06-17 | 2017-02-15 | 中国石油化工股份有限公司 | Surface active agent composition for chemical displacement of reservoir oil and preparation method and application thereof |
| CN107973730B (en) * | 2016-10-25 | 2020-04-24 | 中国科学院化学研究所 | Oligo polyanion sulfonate surfactant, preparation method and application thereof |
| CN108251094B (en) * | 2016-12-28 | 2020-09-04 | 中国石油天然气股份有限公司 | Sand carrying liquid and preparation method and application thereof |
| CN108384021A (en) * | 2018-03-19 | 2018-08-10 | 济南大学 | A kind of synthesis and its application of hyperbranched surfactant |
| CN108384023B (en) * | 2018-03-19 | 2020-10-30 | 济南大学 | Preparation and application of hyperbranched animal protein foaming agent |
| CN110639426A (en) * | 2019-10-10 | 2020-01-03 | 太原理工大学 | Branched alkyl sulfonate surfactant and preparation process thereof |
| CN112174611B (en) * | 2020-10-09 | 2022-08-26 | 丰城市复建高科有限公司 | Regenerated building material and preparation method thereof |
| CN112341076A (en) * | 2020-10-09 | 2021-02-09 | 韩昌龙 | Fair-faced concrete and preparation method thereof |
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Effective date of registration: 20170511 Address after: 528042 room 22, block 68, 801 Rainbow Road, Chancheng District, Guangdong, Foshan Patentee after: Foshan City, Hao Qi Chemical Development Co. Ltd Address before: 710021 Shaanxi city of Xi'an province Beijiao Weiyang University Park Patentee before: Shaanxi University of Science and Technology |
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