CN114989350A - Method for preparing polyacrylamide nano-microspheres by photo-initiation - Google Patents
Method for preparing polyacrylamide nano-microspheres by photo-initiation Download PDFInfo
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 64
- 239000004005 microsphere Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- 230000001678 irradiating effect Effects 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 34
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 18
- 239000012498 ultrapure water Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004530 micro-emulsion Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 2
- 229960004488 linolenic acid Drugs 0.000 claims description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 2
- 239000002077 nanosphere Substances 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000003999 initiator Substances 0.000 abstract description 5
- 238000005303 weighing Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000010779 crude oil Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000012688 inverse emulsion polymerization Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
-
- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a method for preparing polyacrylamide nano microspheres by photoinitiation, which is characterized by comprising the following steps: (1) uniformly mixing the oil phase and the emulsifier according to the mass ratio of 2-5:1, and weighing a solution A; (2) mixing a cross-linking agent and deionized water according to the mass ratio of 1: 10000-; (3) according to the mass ratio of 1.5-2.5: 1 adding the solution A into the solution B, and uniformly stirring; (4) transferring to a three-well flask, introducing nitrogen for 25-35min, adding 1-2 ‰ of photoinitiator, dissolving, sealing at 0-20 deg.C, irradiating with low-pressure ultraviolet lamp, controlling temperature before 20 deg.C at 0.06-0.15 deg.C/min after 20 deg.C, and controlling temperature at 27-28 deg.C for 1 hr; after the temperature is not increased any more, continuously reacting for 0.5 h; (5) extracting and purifying the reaction solution by using acetone or ethanol with the volume of 1.5-2 times of the reaction solution for 10-20h to obtain white solid, and crushing the white solid. The invention has the advantages that: the method adopts photo-initiation, the polymerization reaction temperature is random, the reaction is easy to control, the operation is convenient, and no initiator residue exists, so that the method is safe and environment-friendly.
Description
Technical Field
The invention belongs to the field of polymer synthesis, and relates to a method for preparing polyacrylamide nano microspheres by photo-initiation.
Technical Field
Polyacrylamide (PAM) is a linear high molecular polymer with the chemical formula of (C) 3 H 5 NO) n . The product is hard glass state solid at normal temperature, and the product comprises glue solution, latex, white powder, semitransparent beads, flakes and the like. The thermal stability is good. The polyacrylamide is used as a lubricant, a suspending agent, a clay stabilizer, an oil displacement agent, a fluid loss agent and a thickening agent, is widely applied to well drilling, acidification, fracturing, water plugging, well cementation, secondary oil recovery and tertiary oil recovery, and is an extremely important oilfield chemical.
The polyacrylamide is prepared by taking an acrylamide aqueous solution as a raw material, carrying out polymerization reaction under the action of an initiator, cutting, granulating, drying and crushing polyacrylamide rubber blocks generated after the reaction is finished, and finally preparing a polyacrylamide product. The polymerization process is classified into the following according to the state of the monomers in the medium: aqueous solution polymerization, inverse emulsion polymerization, inverse microemulsion polymerization, precipitation polymerization, inverse suspension polymerization, solid state polymerization, and the like.
The prior polyacrylamide microspheres are mostly produced by adopting an inverse emulsion polymerization process, the process has high selection requirement on an emulsifier, more raw materials, unstable polymerization process and higher control requirement on temperature, and the prepared microspheres have larger particle size and lower production efficiency.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides a method for preparing polyacrylamide nano microspheres by photoinitiation.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing polyacrylamide nano-microspheres by photoinitiation is characterized by comprising the following steps:
(1) uniformly mixing the oil phase and the emulsifier according to the mass ratio of 2-5:1 to obtain a solution A;
(2) mixing a cross-linking agent and deionized water according to the mass ratio of 1: 10000-;
(3) according to the mass ratio of the solution A to the solution B of 1.5-2.5: 1, adding the solution A into the solution B, and uniformly stirring to obtain semitransparent reverse microemulsion;
(4) transferring the reverse microemulsion into a three-well flask, introducing nitrogen to remove oxygen for 25-35min, adding a photoinitiator with the mass of 1-2 per mill of the semitransparent reverse microemulsion, stirring until the mixture is completely dissolved, sealing at 10-20 ℃, irradiating and reacting by using a low-pressure ultraviolet lamp, controlling the polymerization temperature rise process by controlling the illumination intensity, taking no temperature control measure before 20 ℃, controlling the temperature rise at 0.06-0.15 ℃ per minute after 20 ℃, and controlling the temperature for 1h at 27-28 ℃; after the polymerization is completed and the temperature is not raised any more, continuously reacting for 0.5h to obtain semitransparent liquid containing the polyacrylamide nano microspheres;
(5) extracting and purifying the semitransparent liquid with acetone or ethanol with the volume of 1.5-2 times of the semitransparent liquid for 10-20h to obtain white solid, and crushing to obtain the polyacrylamide nano microspheres.
Further, dissolving polyacrylamide nano microspheres in ultrapure water, placing the ultrapure water in a water bath kettle at 40-45 ℃, and adding nano Fe with the mass of 3-5 times that of the polyacrylamide nano microspheres into the ultrapure water 3 O 4 Washing the particles and 0.5-1% of ammonium persulfate for 3-5 times, drying for 3-5h, and crushing to obtain the magnetic polyacrylamide nano microspheres.
Further, the oil phase in the step (1) is one or more of white oil, diesel oil, aviation kerosene, gasoline and cyclohexane.
Further, the emulsifier in the step (1) is one or more of organic acids, Span series and Tween series.
Further, the organic acid is oleic acid, linolenic acid, petroleum carboxylic acid, lauric acid and the like.
Further, in the step (2), the cross-linking agent is one or more of methylene bisacrylamide, polyethylene glycol diacrylate and divinyl benzene.
Further, in the step (2), the polymerization monomer is one or more of acrylic acid, acrylamide and acryloyloxyethyl trimethyl ammonium chloride, and the prepared polyacrylamide nano microsphere is cationic, anionic, nonionic or amphoteric.
Further, in the step (4), the photoinitiator is one or more of V50 (2, 2 '-azobisisobutylamidine dihydrochloride), 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, diaryliodonium salt I-250, triarylsulfonium salt photoinitiator I-160, 2-hydroxy-2-methyl-1-phenyl acetone and 1-hydroxycyclohexyl phenyl ketone.
The invention adopts photo-initiation acrylamide reverse phase polymerization, the polymerization reaction can be initiated by ultraviolet light or directly by light, or initiated under the condition of a photoinitiator, the polymerization reaction can be initiated under the condition of lower temperature, the reaction process can be controlled by controlling the light intensity, the reaction can be slowed down or stopped at any time, the control is easy, and the cross-linked polymer chain transfer reaction caused by high temperature is avoided.
The photoinitiator used in the polymerization reaction has low dosage, no initiator residue, no toxicity and no harm and high initiation efficiency; the prepared nano-microsphere has the advantages of stable system, good water solubility and uniform particle size distribution, and overcomes the defect that the crosslinking strength is difficult to control. The prepared polyacrylamide nano-microspheres are used for oil extraction in oil fields, after the polyacrylamide nano-microspheres are injected into stratums, the superior deep profile control and flooding performance is shown due to the super-strong water absorption performance of the polyacrylamide nano-microspheres, and the nano-microspheres block water flow channels in pores, so that the sweep coefficient of injected water in oil layers is increased, and the recovery ratio is improved. It can also be used in combination with a surfactant to produce a lipophilic surfactant of low interfacial tension, thereby improving the efficiency of oil washing.
Meanwhile, ammonium persulfate can be used as an initiator in the preparation process, and the nano Fe is added 3 O 4 The particles are compounded on the polyacrylamide to enable the polyacrylamide to have magnetism, the treatment effect is obvious when the particles are used for treating oily wastewater, the solid-liquid separation speed is accelerated under the condition of an external magnetic field, and the nano-scale particles have good macroscopic quantum tunneling effect and can well improve the flocculation efficiency when in use.
Compared with the prior art, the invention has the following beneficial effects:
1. photo-initiation is adopted, the polymerization reaction temperature is random, the reaction is easy to control, the operation is convenient, no initiator residue exists, and the method is safe and environment-friendly;
2. the prepared polyacrylamide nano microspheres have good water solubility and good stability, can directly act on oil extraction operation, can improve water injection wave and volume, increase the oil washing efficiency of water injection and improve the recovery ratio; proper surfactant is added into polyacrylamide microsphere to produce lipophilic surfactant with low interface tension and thus raised oil washing efficiency.
3. During the preparation process, polyacrylamide can be modified to have magnetism, and the polyacrylamide can be used for treating oily wastewater to accelerate the solid-liquid separation under the condition of an external magnetic field.
Detailed Description
A method for preparing polyacrylamide nano-microspheres by photoinitiation comprises the following specific implementation steps:
example 1
(1) 519.4g of aviation kerosene, 90.1g of lauric acid, 54.28g of Span80 and 36.78g of Tween60 are mixed and then uniformly mixed to obtain solution A;
(2) mixing 25.2g of acrylic acid, 0.01g of polyethylene glycol diacrylate and 145g of water, adding 199g of acrylamide, uniformly stirring, then adding 1.85g of ammonium sulfate solid until the ammonium sulfate solid is completely dissolved, and adjusting the pH value to 3.0 by using a sulfuric acid solution with the mass concentration of 50% for later use, namely obtaining a solution B;
(3) 700.56g of the solution A is added into 371g of the solution B, and the solution B is stirred evenly to obtain semitransparent reverse microemulsion;
(4) transferring the reverse microemulsion into a three-well flask, introducing nitrogen to remove oxygen for 30min, adding 1.1g of photoinitiator V50, stirring until the mixture is completely dissolved, sealing at 10 ℃, irradiating and reacting by using a low-pressure ultraviolet lamp, controlling the polymerization temperature rise process by controlling the illumination intensity, taking no temperature control measures before 20 ℃, controlling the temperature after 20 ℃ and controlling the temperature at 0.06-0.15 ℃ per minute and controlling the temperature at 27-28 ℃ for 1 h; after the polymerization is completed and the temperature is not raised any more, continuously reacting for 0.5h to obtain semitransparent liquid containing the polyacrylamide nano microspheres;
(5) extracting 20g of semitransparent liquid with 500g of acetone, purifying for 10h to obtain white solid, and crushing to obtain the polyacrylamide nano microspheres.
The prepared polyacrylamide nano microsphere system is prepared into 200g of 0.5% aqueous solution by using ultrapure water, 0.2g of NaOH is added, and the mixture is fully and uniformly stirred to prepare the profile control and flooding system used in the experiment.
Dissolving 5g of the polyacrylamide nano microspheres in ultrapure water, placing the ultrapure water in a water bath kettle at 40 ℃, and adding 15g of nano Fe into the ultrapure water 3 O 4 And washing the particles and 0.025g of ammonium persulfate for 5 times, drying at 120 ℃ for 4h, and crushing to obtain the magnetic polyacrylamide nano microspheres.
The invention uses Malvern particle size analyzer to detect, the result Z-Average (d.nm) = 115.5;
the method comprises the steps of measuring the interfacial tension between the crude oil and the profile control and flooding system by a TX-500C type droplet interfacial tension meter in the morning, taking a crude oil sample (the viscosity is 1320mPa & s when measured at 50 ℃), and measuring at 70 ℃, wherein the interfacial tension between the profile control and flooding system and the crude oil is reduced to 10 -3 And compared with the commercially available polyacrylamide emulsion profile control and flooding products, the profile control and flooding system has obvious effect of reducing interfacial tension, thereby improving the recovery ratio.
The magnetic polyacrylamide nano microspheres are prepared into 200mg/L dispersed suspension solution through a dispersing agent (a dispersing agent A obtained from chemical industry Co., Ltd., Tianrun, Anhui), the dispersed suspension solution is added into an oily sewage treatment device to be treated, and test results show that the flocculation time is 3min20s, the turbidity of treated supernatant is reduced by 89.52%, and the oil content is reduced by 79.25%.
Example 2
(1) 363.58g of white oil, 63.07g of oleic acid, 37.996g of Span80 and 37.996g of Tween80 are mixed and uniformly mixed to obtain solution A;
(2) mixing 17.64g of acryloyloxyethyltrimethyl ammonium chloride, 0.007g of methylene-bisacrylamide and 101.5g of water, adding 139.3g of acrylamide, stirring uniformly, then adding 1.295g of ammonium sulfate solid until the ammonium sulfate solid is completely dissolved, and adjusting the pH to 3.5 by using a sulfuric acid solution with the mass concentration of 48% for later use to obtain a solution B;
(3) 502.64g of the solution A is added into 259.74g of the solution B, and the mixture is stirred evenly to obtain semitransparent reverse microemulsion;
(4) transferring the reverse microemulsion into a three-well flask, introducing nitrogen to remove oxygen for 33min, adding 0.8g of photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, stirring until the mixture is completely dissolved, sealing at 15 ℃, carrying out irradiation reaction by using a low-pressure ultraviolet lamp, controlling the polymerization temperature rise process by controlling the illumination intensity, adopting no temperature control measure before 20 ℃, controlling the temperature rise at 0.06-0.15 ℃ per minute after 20 ℃, and controlling the temperature for 1h at 27-28 ℃; after the polymerization is completed and the temperature is not raised any more, continuously reacting for 0.5h to obtain semitransparent liquid containing the polyacrylamide nano microspheres;
(5) extracting 20g of semitransparent liquid with 500g of acetone, purifying for 15h to obtain white solid, and crushing to obtain the polyacrylamide nano microspheres.
The prepared polyacrylamide nano microsphere system is prepared into 200g of 0.5% aqueous solution by using ultrapure water, 0.2g of NaOH is added, and the mixture is fully and uniformly stirred to prepare the profile control and flooding system used in the experiment.
Dissolving 5g of the polyacrylamide nano microspheres in ultrapure water, placing the ultrapure water in a water bath kettle at the temperature of 45 ℃, and adding 15g of nano Fe into the ultrapure water 3 O 4 And washing the particles and 0.025g of ammonium persulfate for 4 times, drying for 4 hours at 120 ℃, and crushing to obtain the magnetic polyacrylamide nano microspheres.
The invention uses Malvern particle size analyzer to detect, the result Z-Average (d.nm) = 244.3;
the method comprises the steps of measuring the interfacial tension between the crude oil and the profile control and flooding system in the morning by a TX-500C type drop interfacial tension meter, taking a crude oil sample (the viscosity is 1320mPa & s when measured at 50 ℃), and measuring at 70 ℃, wherein the interfacial tension between the profile control and flooding system and the crude oil is reduced to 10 -3 Compared with the commercially available polyacrylamide emulsion profile control and flooding products, the profile control and flooding system has obvious effect of reducing interfacial tension, thereby improving the recovery ratio.
The magnetic polyacrylamide nano-microspheres are prepared into 150mg/L dispersed suspension solution by a dispersant (a product dispersant A of chemical industry Co., Ltd., Anhui Tianrun), the dispersed suspension solution is added into an oily sewage treatment device to be treated, and test results show that the flocculation time is 3min7s, the turbidity of the treated supernatant is reduced by 91.22%, and the oil content is reduced by 83.21%.
Example 3
(1) 327.2g of diesel oil, 44.14g of petroleum carboxylic acid, 34.20g of Span80 and 34.20g of Tween60 are mixed and uniformly mixed to obtain solution A;
(2) 0.0068g of methylene bisacrylamide and 91.35g of water are mixed, 125.37g of acrylamide is added, the mixture is stirred uniformly, 1.16g of ammonium sulfate solid is added until the ammonium sulfate solid is completely dissolved, and then sulfuric acid solution with mass concentration of 54% is used for adjusting the pH value to 3.3 for standby, namely solution B;
(3) 439.74g of the solution A is added into 217.88g of the solution B, and the mixture is stirred evenly to obtain semitransparent reverse microemulsion;
(4) transferring the reverse microemulsion into a three-well flask, introducing nitrogen to remove oxygen for 28min, adding 0.7g of photoinitiator V50 and 0.1g of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, stirring until the materials are completely dissolved, sealing at 20 ℃, carrying out irradiation reaction by using a low-pressure ultraviolet lamp, controlling the polymerization temperature rise process by controlling the illumination intensity, adopting no temperature control measure before 20 ℃, controlling the temperature rise at 0.06-0.15 ℃ per minute after 20 ℃, and controlling the temperature at 27-28 ℃ for 1 h; after the polymerization is completed and the temperature is not raised any more, continuously reacting for 0.5h to obtain semitransparent liquid containing the polyacrylamide nano microspheres;
(5) extracting 20g of semitransparent liquid with 600g of ethanol, purifying for 20h to obtain white solid, and crushing to obtain the polyacrylamide nano microspheres.
And preparing 200g of 0.5% aqueous solution of the prepared polyacrylamide nano microsphere system by using ultrapure water, adding 0.2g of NaOH, and fully and uniformly stirring to obtain the profile control and flooding system for experiments.
Dissolving 5g of the polyacrylamide nano microspheres in ultrapure water, placing the ultrapure water in a water bath kettle at the temperature of 43 ℃, and adding 15g of nano Fe into the ultrapure water 3 O 4 And washing the particles and 0.025g of ammonium persulfate for 3 times, drying for 4 hours at 120 ℃, and crushing to obtain the magnetic polyacrylamide nano microspheres.
The invention uses Malvern particle size analyzer to detect, the result Z-Average (d.nm) = 123.4;
the method comprises the steps of measuring the interfacial tension between the crude oil and the profile control and flooding system by a TX-500C type droplet interfacial tension meter in the morning, taking a crude oil sample (the viscosity is 1320mPa & s when measured at 50 ℃), and measuring at 70 ℃, wherein the interfacial tension between the profile control and flooding system and the crude oil is reduced to 10 -3 Compared with the commercially available polyacrylamide emulsion profile control and flooding products, the profile control and flooding system has obvious effect of reducing interfacial tension, thereby improving the recovery ratio.
The magnetic polyacrylamide nano microspheres are prepared into 180mg/L dispersed suspension solution through a dispersant (a product dispersant A of chemical industry Co., Ltd., Tianrun, Anhui), and the dispersed suspension solution is added into an oily sewage treatment device to be treated, and test results show that the flocculation time is 3min35s, the turbidity of the treated supernatant is reduced by 87.69%, and the oil content is reduced by 79.84%.
Claims (8)
1. A method for preparing polyacrylamide nano-microspheres by photoinitiation is characterized by comprising the following steps:
(1) uniformly mixing the oil phase and the emulsifier according to the mass ratio of 2-5:1 to obtain a solution A;
(2) mixing a cross-linking agent and deionized water according to the mass ratio of 1:10000-20000, adding a polymerization monomer which is 1.3-1.6 times of the total mass of the mixed solution, uniformly stirring, adding ammonium sulfate solid accounting for 0.1-2% of the total mass of the mixed solution until the ammonium sulfate solid is completely dissolved, and adjusting the pH value to 3-3.5 by using a sulfuric acid solution with the mass concentration of 45-55% for later use, wherein the solution is called as solution B;
(3) according to the mass ratio of 1.5-2.5: 1, adding the solution A into the solution B, and uniformly stirring to obtain semitransparent reverse microemulsion;
(4) transferring the reverse microemulsion into a three-well flask, introducing nitrogen to remove oxygen for 25-35min, adding a photoinitiator with the mass of 1-2 per mill of the semitransparent reverse microemulsion, stirring until the mixture is completely dissolved, sealing at 10-20 ℃, irradiating and reacting by using a low-pressure ultraviolet lamp, controlling the polymerization temperature rise process by controlling the illumination intensity, taking no temperature control measure before 20 ℃, controlling the temperature rise at 0.06-0.15 ℃ per minute after 20 ℃, and controlling the temperature for 1h at 27-28 ℃; after polymerization is completed and temperature does not rise any more, continuously reacting for 0.5h to obtain semitransparent liquid containing polyacrylamide nano microspheres;
(5) extracting and purifying the semitransparent liquid with acetone or ethanol with the volume of 1.5-2 times of the semitransparent liquid for 10-20h to obtain white solid, and crushing to obtain the polyacrylamide nano microspheres.
2. The method for preparing polyacrylamide nano-microspheres by photoinitiation according to claim 1, wherein: dissolving polyacrylamide nano microspheres in ultrapure water, placing the ultrapure water in a water bath kettle at 40-45 ℃, and adding nano Fe with the mass of 3-5 times that of the polyacrylamide nano microspheres into the ultrapure water 3 O 4 Washing the particles with 0.5-1% ammonium persulfate for 3-5 times, oven drying for 3-5 hr, and pulverizing to obtain magnetic polyacrylamide nanometer micro-particlesA ball.
3. The method for preparing polyacrylamide nano microspheres by photo-initiation according to claim 1, wherein: the oil phase in the step (1) is one or more of white oil, diesel oil, aviation kerosene, gasoline and cyclohexane.
4. The method for preparing polyacrylamide nano-microspheres by photoinitiation according to claim 1, wherein: the emulsifier in the step (1) is one or more of organic acids, Span series and Tween series.
5. The method for preparing polyacrylamide nano-microspheres by photoinitiation according to claim 4, wherein: the organic acid is oleic acid, linolenic acid, petroleum carboxylic acid and lauric acid.
6. The method for preparing polyacrylamide nano-microspheres by photoinitiation according to claim 1, wherein: the cross-linking agent in the step (2) is one or more of methylene bisacrylamide, polyethylene glycol diacrylate and divinyl benzene.
7. The method for preparing polyacrylamide nano microspheres by photo-initiation according to claim 1, wherein: the polymerized monomer in the step (2) is one or more of acrylic acid, acrylamide and acryloyloxyethyl trimethyl ammonium chloride, and the prepared polyacrylamide nano microsphere is cationic, anionic, nonionic or amphoteric.
8. The method for preparing polyacrylamide nanospheres according to any one of claims 1-7, wherein: the photoinitiator in the step (4) is one or more of V50 (2, 2 '-azobisisobutylamidine dihydrochloride), 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, diaryliodonium salt I-250, triarylsulfonium salt photoinitiator I-160, 2-hydroxy-2-methyl-1-phenyl acetone and 1-hydroxycyclohexyl phenyl ketone.
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