CN117263828A - Novel salt-resistant polymer for oil displacement and preparation method thereof - Google Patents
Novel salt-resistant polymer for oil displacement and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 76
- 150000003839 salts Chemical class 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000011549 displacement method Methods 0.000 title description 2
- 238000006073 displacement reaction Methods 0.000 claims abstract description 59
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims description 50
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 31
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 29
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- -1 lauroyl diphenylmethane Chemical compound 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 20
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- 229960002523 mercuric chloride Drugs 0.000 claims description 10
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 claims description 10
- 238000010898 silica gel chromatography Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical group ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 230000005526 G1 to G0 transition Effects 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 239000003921 oil Substances 0.000 abstract description 51
- 230000000694 effects Effects 0.000 abstract description 7
- 239000004094 surface-active agent Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 239000010779 crude oil Substances 0.000 abstract description 3
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 2
- 238000006277 sulfonation reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 8
- 230000009471 action Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
- C07C309/32—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings containing at least two non-condensed six-membered aromatic rings in the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/08—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with halogenosulfonic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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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
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a novel salt-resistant polymer for oil displacement and a preparation method thereof, wherein the novel salt-resistant polymer for oil displacement takes diphenylmethane as a raw material, and is prepared according to the sequence of Friedel-crafts acylation reaction, criemens reduction, sulfonation and neutralization reaction; the polymer prepared by the invention is an anionic gemini surfactant, has two hydrophobic groups and two hydrophilic groups in the molecular structure, has very high surface activity, can effectively inhibit electrostatic repulsive force formed between ions at a specific temperature, greatly inhibits an electric double layer, ensures that a single electric layer is more compact, and is more beneficial to reducing interfacial tension (IFT) between crude oil and water, thereby improving oil recovery ratio (EOR); meanwhile, the preparation method of the novel salt-resistant polymer for oil displacement is simple, and large-scale production can be realized.
Description
Technical Field
The invention belongs to the technical field of organic high molecular compounds, and particularly relates to a novel salt-resistant polymer for oil displacement and a preparation method thereof.
Background
Chemical flooding is one of the technologies for improving oil recovery ratio (EOR) in petroleum production, and the chemical flooding technology, especially surfactant-polymer (SP) flooding technology, can effectively reduce the water content and increase the petroleum yield. The mechanism of chemical flooding to increase EOR is to increase the capillary number by lowering the interfacial tension (IFT) between crude oil and water, while sulfonate (PS) is typically used in combination with different types of surfactants to produce polymers with high flooding properties in order to achieve ultra low IFT.
Combined surfactant systems find widespread use in reservoirs at low temperatures and low salinity, however, with the development of the petroleum industry, future SP flooding technologies have to face more challenging reservoir conditions at high temperatures and high salinity; under severe reservoir conditions, the SP flooding performance will be affected, and therefore, it is necessary to develop a novel heat and salt resistant polymer for flooding.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel salt-resistant polymer for oil displacement and a preparation method thereof, so as to solve the problem that the existing polymer for oil displacement is poor in heat resistance and salt resistance.
The invention takes diphenylmethane as a raw material, and prepares a novel salt-resistant polymer for oil displacement according to the sequence of Friedel-crafts acylation reaction, cremanion reduction, sulfonation and neutralization reaction; the polymer is an anionic gemini surfactant, has two hydrophobic groups and two hydrophilic groups in the molecular structure, and has high surface activity; meanwhile, at a specific temperature, the novel salt-resistant polymer for oil displacement can effectively inhibit electrostatic repulsive force formed between ions, greatly inhibit an electric double layer, enable a single electric layer to be more compact, and be more beneficial to reducing interfacial tension (IFT) between crude oil and water, so that oil recovery rate (EOR) is improved.
Meanwhile, the preparation method of the novel salt-resistant polymer for oil displacement is simple, and large-scale production can be realized.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a novel salt-resistant polymer for oil displacement, which comprises the following components in parts by weight: 10-15 parts of diphenylmethane, 20-30 parts of nitromethane, 20-30 parts of anhydrous aluminum chloride, 25-30 parts of lauroyl chloride, 8-12 parts of mercuric chloride, 35 parts of zinc powder, 50 parts of chloroform and 12 parts of chlorosulfonic acid.
Further, the novel salt-resistant polymer for oil displacement is prepared from C 12 -DSDM (3 a) and 15% sodium hydroxide solution are mixed and extracted.
Further, the C 12 The preparation process of the DSDM (3 a) comprises the following steps:
s1, 50 parts by weight of chloroform and 20 parts by weight of 4, 4-di-linear chain alkylated diphenyl methane (2 a) are mixed, 12 parts by weight of chlorosulfonic acid is added, and the mixture is stirred for 6 hours at 25 ℃ to obtain a mixed solution.
S2, transferring the mixed solution obtained in the step S1 into a rotary evaporator, evaporating and refluxing for 4 hours, and extracting to obtain C 12 -DSDM(3a)。
Further, in the extraction process, the extractant is carbon tetrachloride.
Further, the preparation process of the 4, 4-di-linear alkylated diphenylmethane (2 a) comprises the following steps:
s1, adding 70 parts by weight of water, 4 parts by weight of hydrochloric acid and 8-12 parts by weight of mercuric chloride into a round bottom flask equipped with a magnetic stirring device, and stirring for 3 hours at 25 ℃ to obtain a mixture A.
S2, adding 35 parts by weight of zinc powder into the mixture A obtained in the step S1, stirring for 0.5h, and filtering to remove insoluble substances to obtain a mixture B.
S3, mixing the mixture B obtained in the step S2 with 28 parts by weight of 4, 4-linear lauroyl diphenylmethane (1 a), adding 100 parts by weight of hydrochloric acid, heating to 85 ℃, condensing and refluxing for 8 hours, purifying and eluting by silica gel chromatography, and extracting to obtain 4, 4-di-linear alkylated diphenylmethane (2 a).
Further, the stationary phase in the silica gel chromatography is 200-300 mesh silica gel particles, the eluent is a mixture of benzene and ethyl acetate, and the volume ratio of benzene to ethyl acetate is 180:1.
further, the preparation process of the 4, 4-linear lauroyl diphenylmethane (1 a) comprises the following steps:
s1, adding 10-15 parts by weight of diphenylmethane and 20-30 parts by weight of nitromethane into a three-neck round bottom flask provided with a mechanical stirrer, a dropping funnel and a condenser reflux, then turning on the stirrer, putting the flask into an ice-water bath, and stirring for 0.5h to obtain a homogeneous mixed solution A.
S2, adding 20-30 parts by weight of anhydrous aluminum chloride into the homogeneous mixed solution A obtained in the step S1, and continuing stirring until the anhydrous aluminum chloride is completely dissolved to obtain a homogeneous mixed solution B.
S3, adding 25-30 parts by weight of lauroyl chloride into the homogeneous mixed solution B obtained in the step S2, continuously stirring for 20 minutes after all lauroyl chloride is added, then keeping the reaction temperature at 25 ℃, and continuously stirring for 24 hours to obtain a homogeneous mixed solution C.
S4, heating the homogeneous mixed solution C obtained in the step S3 to 70 ℃, continuously heating for 6 hours, then transferring into an ice-water bath, cooling to 0 ℃, taking out the product, washing with deionized water for three times, and then washing with ethanol for three times to obtain the 4, 4-linear lauroyl diphenylmethane (1 a).
Further, the lauroyl chloride is added into the three-necked round bottom flask at a constant speed within 0.5h, and the addition is completed completely within 0.5 h.
Further, the preparation process of the novel salt-resistant polymer for oil displacement comprises the following steps:
s1, 18 parts by weight of C 12 DSDM (3 a) is mixed with 100 parts of water and then the pH is adjusted to 9 using 15% strength sodium hydroxide solution to give a mixed solution.
S2, transferring the mixed solution obtained in the step S1 into a rotary evaporator, evaporating and refluxing for 6 hours, and drying the product at 70 ℃ for 12 hours after extraction to finally obtain the novel salt-resistant polymer for oil displacement.
Further, the diphenyl methane is of industrial grade, the purities of nitromethane, lauroyl chloride and chloroform are all 99.5%, and the chlorosulfonic acid, anhydrous aluminum chloride, mercury chloride and zinc powder are all of analytical grade.
Compared with the prior art, the invention has the following beneficial effects:
(1) The novel salt-resistant polymer for oil displacement provided by the invention is a gemini surfactant, and has two hydrophobic groups and two hydrophilic groups in the molecular structure, so that the novel salt-resistant polymer has good surface activity and excellent interfacial activity; gemini surfactants have better temperature and salt resistance than traditional anionic, cationic and nonionic surfactants.
(2) The novel salt-resistant polymer for oil displacement provided by the invention can generate more stable and smaller emulsion liquid drops in the adsorption process, effectively reduces the influence of diffusion relaxation on the elasticity of a water/oil interface, and ensures that the oil displacement polymer has higher stability.
(3) The novel salt-resistant polymer for oil displacement provided by the invention has good hydrophobicity and strong hydrophobic interaction, and the molecular arrangement at the interface is more orderly and compact, so that the oil displacement polymer has excellent interface activity; meanwhile, due to hydrophilic groups in the structure, the novel salt-resistant polymer for oil displacement provided by the invention also has good compatibility, can be well compatible with other polymers, and is beneficial to application in the field of chemical oil displacement.
(4) The novel salt-resistant polymer for oil displacement provided by the invention has the advantages of simple preparation method, simple and easily obtained raw materials, low cost and capability of realizing mass production
Drawings
FIG. 1 is a synthetic route diagram of a novel anti-salt polymer for oil displacement provided by the invention;
FIG. 2 is a mass spectrum characterization diagram of the novel salt-resistant polymer for oil displacement provided by the invention;
FIG. 3 is an infrared spectrum of a novel anti-salt polymer for oil displacement provided in example 1;
fig. 4 is an atomic force microscope image of a novel salt-resistant polymer for oil displacement provided in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following preferred examples, but the present invention is not limited to the following examples.
The chemical reagents involved in the invention are purchased commercially and can be used without purification unless otherwise specified.
Example 1
The invention provides a novel salt-resistant polymer for oil displacement and a preparation method thereof, which specifically comprises the following steps:
the novel salt-resistant polymer for oil displacement comprises the following components in parts by weight: 15 parts of diphenylmethane, 30 parts of nitromethane, 30 parts of anhydrous aluminum chloride, 30 parts of lauroyl chloride, 12 parts of mercuric chloride, 35 parts of zinc powder, 50 parts of chloroform and 12 parts of chlorosulfonic acid.
Wherein, the novel salt-resistant polymer for oil displacement is prepared from C 12 -DSDM (3 a) and 15% sodium hydroxide solution are mixed and extracted.
Wherein C is 12 The preparation process of the DSDM (3 a) comprises the following steps:
s1, 50 parts by weight of chloroform and 20 parts by weight of 4, 4-di-linear chain alkylated diphenyl methane (2 a) are mixed, 12 parts by weight of chlorosulfonic acid is added, and the mixture is stirred for 6 hours at 25 ℃ to obtain a mixed solution.
S2, transferring the mixed solution obtained in the step S1 into a rotary evaporator, evaporating and refluxing for 4 hours, and extracting to obtain C 12 -DSDM(3a)。
Wherein in the extraction process, the extractant is carbon tetrachloride.
Wherein, the preparation process of the 4, 4-di-linear chain alkylated diphenyl methane (2 a) comprises the following steps:
s1, adding 70 parts by weight of water, 4 parts by weight of hydrochloric acid and 12 parts by weight of mercuric chloride into a round-bottom flask equipped with a magnetic stirring device, and stirring at 25 ℃ for 3 hours to obtain a mixture A.
S2, adding 35 parts by weight of zinc powder into the mixture A obtained in the step S1, stirring for 0.5h, and filtering to remove insoluble substances to obtain a mixture B.
S3, mixing the mixture B obtained in the step S2 with 28 parts by weight of 4, 4-linear lauroyl diphenylmethane (1 a), adding 100 parts by weight of hydrochloric acid, heating to 85 ℃, condensing and refluxing for 8 hours, purifying and eluting by silica gel chromatography, and extracting to obtain 4, 4-di-linear alkylated diphenylmethane (2 a).
Wherein, the stationary phase in the silica gel chromatography is silica gel particles with 200-300 meshes, the eluent is a mixture of benzene and ethyl acetate, and the volume ratio of benzene to ethyl acetate is 180:1.
wherein, the preparation process of the 4, 4-linear lauroyl diphenylmethane (1 a) comprises the following steps:
s1, adding 15 parts by weight of diphenylmethane and 30 parts by weight of nitromethane into a three-neck round-bottom flask provided with a mechanical stirrer, a dropping funnel and a condenser reflux, then turning on the stirrer, putting the flask into an ice-water bath, and stirring for 0.5h to obtain a homogeneous mixed solution A.
S2, adding 30 parts by weight of anhydrous aluminum chloride into the homogeneous mixed solution A obtained in the step S1, and continuing stirring until the anhydrous aluminum chloride is completely dissolved, so as to obtain a homogeneous mixed solution B.
S3, adding 30 parts by weight of lauroyl chloride into the homogeneous mixed solution B obtained in the step S2, continuously stirring for 20 minutes after all lauroyl chloride is added, and then keeping the reaction temperature at 25 ℃ and continuously stirring for 24 hours to obtain a homogeneous mixed solution C.
S4, heating the homogeneous mixed solution C obtained in the step S3 to 70 ℃, continuously heating for 6 hours, then transferring into an ice-water bath, cooling to 0 ℃, taking out the product, washing with deionized water for three times, and then washing with ethanol for three times to obtain the 4, 4-linear lauroyl diphenylmethane (1 a).
Wherein lauroyl chloride is added into the three-necked round bottom flask at a constant speed within 0.5h, and the dripping is completed within 0.5 h.
Wherein, the preparation process of the novel salt-resistant polymer for oil displacement comprises the following steps:
s1, 18 parts by weight of C 12 DSDM (3 a) is mixed with 100 parts of water and then the pH is adjusted to 9 using 15% strength sodium hydroxide solution to give a mixed solution.
S2, transferring the mixed solution obtained in the step S1 into a rotary evaporator, evaporating and refluxing for 6 hours, and drying the product at 70 ℃ for 12 hours after extraction to finally obtain the novel salt-resistant polymer for oil displacement.
The diphenyl methane is of industrial grade, the purities of nitromethane, lauroyl chloride and chloroform are all 99.5%, and chlorosulfonic acid, anhydrous aluminum chloride, mercury chloride and zinc powder are all of analytical grade.
Example 2
The invention provides a novel salt-resistant polymer for oil displacement and a preparation method thereof, which specifically comprises the following steps:
the novel salt-resistant polymer for oil displacement comprises the following components in parts by weight: 10 parts of diphenylmethane, 20 parts of nitromethane, 20 parts of anhydrous aluminum chloride, 25 parts of lauroyl chloride, 8 parts of mercuric chloride, 35 parts of zinc powder, 50 parts of chloroform and 12 parts of chlorosulfonic acid.
Wherein, the novel salt-resistant polymer for oil displacement is prepared from C 12 -DSDM (3 a) and 15% sodium hydroxide solution are mixed and extracted.
Wherein C is 12 The preparation process of the DSDM (3 a) comprises the following steps:
s1, 50 parts by weight of chloroform and 20 parts by weight of 4, 4-di-linear chain alkylated diphenyl methane (2 a) are mixed, 12 parts by weight of chlorosulfonic acid is added, and the mixture is stirred for 6 hours at 25 ℃ to obtain a mixed solution.
S2, transferring the mixed solution obtained in the step S1 into a rotary evaporatorEvaporating and refluxing for 4h, and extracting to obtain C 12 -DSDM(3a)。
Wherein in the extraction process, the extractant is carbon tetrachloride.
Wherein, the preparation process of the 4, 4-di-linear chain alkylated diphenyl methane (2 a) comprises the following steps:
s1, adding 70 parts by weight of water, 4 parts by weight of hydrochloric acid and 8 parts by weight of mercuric chloride into a round-bottom flask equipped with a magnetic stirring device, and stirring at 25 ℃ for 3 hours to obtain a mixture A.
S2, adding 35 parts by weight of zinc powder into the mixture A obtained in the step S1, stirring for 0.5h, and filtering to remove insoluble substances to obtain a mixture B.
S3, mixing the mixture B obtained in the step S2 with 28 parts by weight of 4, 4-linear lauroyl diphenylmethane (1 a), adding 100 parts by weight of hydrochloric acid, heating to 85 ℃, condensing and refluxing for 8 hours, purifying and eluting by silica gel chromatography, and extracting to obtain 4, 4-di-linear alkylated diphenylmethane (2 a).
Wherein, the stationary phase in the silica gel chromatography is silica gel particles with 200-300 meshes, the eluent is a mixture of benzene and ethyl acetate, and the volume ratio of benzene to ethyl acetate is 180:1.
wherein, the preparation process of the 4, 4-linear lauroyl diphenylmethane (1 a) comprises the following steps:
s1, adding 10 parts by weight of diphenylmethane and 20 parts by weight of nitromethane into a three-neck round-bottom flask provided with a mechanical stirrer, a dropping funnel and a condenser reflux, then turning on the stirrer, putting the flask into an ice-water bath, and stirring for 0.5h to obtain a homogeneous mixed solution A.
S2, adding 20 parts by weight of anhydrous aluminum chloride into the homogeneous mixed solution A obtained in the step S1, and continuing stirring until the anhydrous aluminum chloride is completely dissolved, so as to obtain a homogeneous mixed solution B.
S3, adding 25 parts by weight of lauroyl chloride into the homogeneous mixed solution B obtained in the step S2, continuously stirring for 20 minutes after all lauroyl chloride is added, and then keeping the reaction temperature at 25 ℃ and continuously stirring for 24 hours to obtain a homogeneous mixed solution C.
S4, heating the homogeneous mixed solution C obtained in the step S3 to 70 ℃, continuously heating for 6 hours, then transferring into an ice-water bath, cooling to 0 ℃, taking out the product, washing with deionized water for three times, and then washing with ethanol for three times to obtain the 4, 4-linear lauroyl diphenylmethane (1 a).
Wherein lauroyl chloride is added into the three-necked round bottom flask at a constant speed within 0.5h, and the dripping is completed within 0.5 h.
Wherein, the preparation process of the novel salt-resistant polymer for oil displacement comprises the following steps:
s1, 18 parts by weight of C 12 DSDM (3 a) is mixed with 100 parts of water and then the pH is adjusted to 9 using 15% strength sodium hydroxide solution to give a mixed solution.
S2, transferring the mixed solution obtained in the step S1 into a rotary evaporator, evaporating and refluxing for 6 hours, and drying the product at 70 ℃ for 12 hours after extraction to finally obtain the novel salt-resistant polymer for oil displacement.
The diphenyl methane is of industrial grade, the purities of nitromethane, lauroyl chloride and chloroform are all 99.5%, and chlorosulfonic acid, anhydrous aluminum chloride, mercury chloride and zinc powder are all of analytical grade.
Example 3
The invention provides a novel salt-resistant polymer for oil displacement and a preparation method thereof, which specifically comprises the following steps:
the novel salt-resistant polymer for oil displacement comprises the following components in parts by weight: 12 parts of diphenylmethane, 25 parts of nitromethane, 25 parts of anhydrous aluminum chloride, 27 parts of lauroyl chloride, 10 parts of mercuric chloride, 35 parts of zinc powder, 50 parts of chloroform and 12 parts of chlorosulfonic acid.
Wherein, the novel salt-resistant polymer for oil displacement is prepared from C 12 -DSDM (3 a) and 15% sodium hydroxide solution are mixed and extracted.
Wherein C is 12 The preparation process of the DSDM (3 a) comprises the following steps:
s1, 50 parts by weight of chloroform and 20 parts by weight of 4, 4-di-linear chain alkylated diphenyl methane (2 a) are mixed, 12 parts by weight of chlorosulfonic acid is added, and the mixture is stirred for 6 hours at 25 ℃ to obtain a mixed solution.
S2, transferring the mixed solution obtained in the step S1 into a rotary evaporator, evaporating and refluxing for 4 hours, and extracting to obtain C 12 -DSDM(3a)。
Wherein in the extraction process, the extractant is carbon tetrachloride.
Wherein, the preparation process of the 4, 4-di-linear chain alkylated diphenyl methane (2 a) comprises the following steps:
s1, adding 70 parts by weight of water, 4 parts by weight of hydrochloric acid and 10 parts by weight of mercuric chloride into a round-bottom flask equipped with a magnetic stirring device, and stirring at 25 ℃ for 3 hours to obtain a mixture A.
S2, adding 35 parts by weight of zinc powder into the mixture A obtained in the step S1, stirring for 0.5h, and filtering to remove insoluble substances to obtain a mixture B.
S3, mixing the mixture B obtained in the step S2 with 28 parts by weight of 4, 4-linear lauroyl diphenylmethane (1 a), adding 100 parts by weight of hydrochloric acid, heating to 85 ℃, condensing and refluxing for 8 hours, purifying and eluting by silica gel chromatography, and extracting to obtain 4, 4-di-linear alkylated diphenylmethane (2 a).
Wherein, the stationary phase in the silica gel chromatography is silica gel particles with 200-300 meshes, the eluent is a mixture of benzene and ethyl acetate, and the volume ratio of benzene to ethyl acetate is 180:1.
wherein, the preparation process of the 4, 4-linear lauroyl diphenylmethane (1 a) comprises the following steps:
s1, adding 12 parts by weight of diphenylmethane and 25 parts by weight of nitromethane into a three-neck round-bottom flask provided with a mechanical stirrer, a dropping funnel and a condenser reflux, then turning on the stirrer, putting the flask into an ice-water bath, and stirring for 0.5h to obtain a homogeneous mixed solution A.
S2, adding 25 parts by weight of anhydrous aluminum chloride into the homogeneous mixed solution A obtained in the step S1, and continuing stirring until the anhydrous aluminum chloride is completely dissolved to obtain a homogeneous mixed solution B.
S3, adding 27 parts by weight of lauroyl chloride into the homogeneous mixed solution B obtained in the step S2, continuously stirring for 20 minutes after all lauroyl chloride is added, and then keeping the reaction temperature at 25 ℃ and continuously stirring for 24 hours to obtain a homogeneous mixed solution C.
S4, heating the homogeneous mixed solution C obtained in the step S3 to 70 ℃, continuously heating for 6 hours, then transferring into an ice-water bath, cooling to 0 ℃, taking out the product, washing with deionized water for three times, and then washing with ethanol for three times to obtain the 4, 4-linear lauroyl diphenylmethane (1 a).
Wherein lauroyl chloride is added into the three-necked round bottom flask at a constant speed within 0.5h, and the dripping is completed within 0.5 h.
Wherein, the preparation process of the novel salt-resistant polymer for oil displacement comprises the following steps:
s1, 18 parts by weight of C 12 DSDM (3 a) is mixed with 100 parts of water and then the pH is adjusted to 9 using 15% strength sodium hydroxide solution to give a mixed solution.
S2, transferring the mixed solution obtained in the step S1 into a rotary evaporator, evaporating and refluxing for 6 hours, and drying the product at 70 ℃ for 12 hours after extraction to finally obtain the novel salt-resistant polymer for oil displacement.
The diphenyl methane is of industrial grade, the purities of nitromethane, lauroyl chloride and chloroform are all 99.5%, and chlorosulfonic acid, anhydrous aluminum chloride, mercury chloride and zinc powder are all of analytical grade.
Performance testing
The prepared novel salt-resistant polymer for oil displacement is subjected to surface property test.
Using a commercial product from GermanyCompany K20 type axisymmetric drop shape analysis tensiometer measures critical micelle concentration, surface tension and Γmax values of polymer at different salinity and temperature, infrared spectrum of polymer is measured by Nicoletis type 5 Fourier transform infrared spectrometer purchased from thermo Fisher scientific company of U.S.A., surface morphology of polymer is observed by NX7 type atomic force microscope purchased from PSIA company of U.S.A., and molecular structure of polymer is observed by B from SwitzerlandThe ruker company's Avance II 400MHz nuclear magnetic resonance spectrometer.
The data shown in the table above shows that the critical micelle concentration and the surface tension of the prepared novel salt-resistant polymer for oil displacement reach 1.452mmol/L and 38.49Mn/m respectively at 298K, which shows that the polymer has very high surface activity, and meanwhile, the surface tension and Γmax of the polymer change less along with the change of salinity and temperature, which shows that the polymer has quite stability in a high-salt high-temperature environment, and meanwhile, the flocculation effect generated by the combined action of Brownian aggregation and sedimentation aggregation is beneficial to increasing the capillary number.
FIGS. 1 and 2 show the preparation route and nuclear magnetic resonance spectrum of a novel salt-resistant polymer for oil displacement, respectively, and illustrate the molecular structure of the polymer in detail; FIG. 3 shows an infrared spectrum with a wavelength of 3386.4cm –1 Where the O-H group is subjected to stretching vibration, the wavelength is 2925.52854.2cm- 1 At which are characteristic peaks for-CH-groups, wavelengths 1207.2 and 624.8cm –1 respectively-SO 3 The asymmetric expansion vibration peak and the out-of-plane bending vibration peak of the group correspond to the molecular structure of the polymer in the nuclear magnetic resonance spectrogram well as the result of the infrared spectrogram; the atomic force microscope picture shown in fig. 4 shows that the prepared novel salt-resistant polymer emulsion for oil displacement has good dispersibility and uniform particle size.
The characterization result shows that the novel salt-resistant polymer for oil displacement has good application value under various salinity and temperature, stable physical properties and good uniformity, and can improve chemical oil displacement performance under high-salt and high-temperature environments.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The invention and its embodiments have been described above with no limitation, and the actual construction is not limited to the embodiments of the invention as shown in the drawings. In summary, if one of ordinary skill in the art is informed by this disclosure, a structural manner and an embodiment similar to the technical solution should not be creatively devised without departing from the gist of the present invention.
Claims (10)
1. The novel salt-resistant polymer for oil displacement is characterized by comprising the following components in parts by weight: 10-15 parts of diphenylmethane, 20-30 parts of nitromethane, 20-30 parts of anhydrous aluminum chloride, 25-30 parts of lauroyl chloride, 8-12 parts of mercuric chloride, 35 parts of zinc powder, 50 parts of chloroform and 12 parts of chlorosulfonic acid.
2. The novel salt-resistant polymer for oil displacement according to claim 1, which is characterized in that: the novel salt-resistant polymer for oil displacement is prepared from C 12 -DSDM (3 a) and 15% sodium hydroxide solution are mixed and extracted.
3. The novel salt-resistant polymer for oil displacement according to claim 2, wherein the polymer C 12 Preparation of DSDM (3 a)The method comprises the following steps:
s1, mixing 50 parts by weight of chloroform with 20 parts by weight of 4, 4-di-linear chain alkylated diphenyl methane (2 a), adding 12 parts by weight of chlorosulfonic acid, and stirring at 25 ℃ for 6 hours to obtain a mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a rotary evaporator, evaporating and refluxing for 4 hours, and extracting to obtain C 12 -DSDM(3a)。
4. A novel salt-resistant polymer for oil displacement according to claim 3, characterized in that: in the extraction process, the extractant is carbon tetrachloride.
5. The novel salt-resistant polymer for oil displacement according to claim 4, wherein the preparation process of the 4, 4-di-linear alkylated diphenylmethane (2 a) comprises the following steps:
s1, adding 70 parts by weight of water, 4 parts by weight of hydrochloric acid and 8-12 parts by weight of mercuric chloride into a round-bottom flask equipped with a magnetic stirring device, and stirring for 3 hours at 25 ℃ to obtain a mixture A;
s2, adding 35 parts by weight of zinc powder into the mixture A obtained in the step S1, stirring for 0.5h, and then filtering to remove insoluble substances to obtain a mixture B;
s3, mixing the mixture B obtained in the step S2 with 28 parts by weight of 4, 4-linear lauroyl diphenylmethane (1 a), adding 100 parts by weight of hydrochloric acid, heating to 85 ℃, condensing and refluxing for 8 hours, purifying and eluting by silica gel chromatography, and extracting to obtain 4, 4-di-linear alkylated diphenylmethane (2 a).
6. The novel salt-resistant polymer for oil displacement according to claim 5, which is characterized in that: the stationary phase in the silica gel chromatography is 200-300 meshes of silica gel particles, the eluent is a mixture of benzene and ethyl acetate, and the volume ratio of benzene to ethyl acetate is 180:1.
7. the novel salt-resistant polymer for oil displacement according to claim 4, wherein the preparation process of the 4, 4-linear lauroyl diphenylmethane (1 a) comprises the following steps:
s1, adding 10-15 parts by weight of diphenylmethane and 20-30 parts by weight of nitromethane into a three-neck round bottom flask provided with a mechanical stirrer, a dropping funnel and a condenser reflux device, then opening the stirrer, putting the flask into an ice-water bath, and stirring for 0.5h to obtain a homogeneous mixed solution A;
s2, adding 20-30 parts by weight of anhydrous aluminum chloride into the homogeneous mixed solution A obtained in the step S1, and continuously stirring until the anhydrous aluminum chloride is completely dissolved to obtain a homogeneous mixed solution B;
s3, adding 25-30 parts by weight of lauroyl chloride into the homogeneous mixed solution B obtained in the step S2, continuously stirring for 20 minutes after all lauroyl chloride is added, then keeping the reaction temperature at 25 ℃, and continuously stirring for 24 hours to obtain a homogeneous mixed solution C;
s4, heating the homogeneous mixed solution C obtained in the step S3 to 70 ℃, continuously heating for 6 hours, then transferring into an ice-water bath, cooling to 0 ℃, taking out the product, washing with deionized water for three times, and then washing with ethanol for three times to obtain the 4, 4-linear lauroyl diphenylmethane (1 a).
8. The novel salt-resistant polymer for oil displacement according to claim 7, wherein: the lauroyl chloride is dropwise added into the three-necked round bottom flask at a constant speed within 0.5h, and the dropwise addition is completed within 0.5 h.
9. The novel salt-resistant polymer for oil displacement according to claim 8, wherein the preparation process of the novel salt-resistant polymer for oil displacement comprises the following steps:
s1, 18 parts by weight of C 12 -DSDM (3 a) and 100 parts of water are mixed and then the pH is adjusted to 9 using 15% strength sodium hydroxide solution to obtain a mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a rotary evaporator, evaporating and refluxing for 6 hours, and drying the product at 70 ℃ for 12 hours after extraction to finally obtain the novel salt-resistant polymer for oil displacement.
10. The novel salt-resistant polymer for oil displacement according to claim 1, which is characterized in that: the diphenyl methane is of industrial grade, the purities of nitromethane, lauroyl chloride and chloroform are all 99.5%, and chlorosulfonic acid, anhydrous aluminum chloride, mercury chloride and zinc powder are all of analytical grade.
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