CN118496433A - Oilfield flooding stabilizer and preparation method thereof - Google Patents
Oilfield flooding stabilizer and preparation method thereof Download PDFInfo
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- CN118496433A CN118496433A CN202410962477.1A CN202410962477A CN118496433A CN 118496433 A CN118496433 A CN 118496433A CN 202410962477 A CN202410962477 A CN 202410962477A CN 118496433 A CN118496433 A CN 118496433A
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 35
- -1 hydrocarbon halide Chemical class 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000001105 regulatory effect Effects 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000007599 discharging Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 125000002015 acyclic group Chemical group 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 239000003607 modifier Substances 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229920000858 Cyclodextrin Polymers 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002332 oil field water Substances 0.000 claims description 18
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 17
- 238000002347 injection Methods 0.000 claims description 17
- 239000007924 injection Substances 0.000 claims description 17
- GDFCSMCGLZFNFY-UHFFFAOYSA-N Dimethylaminopropyl Methacrylamide Chemical compound CN(C)CCCNC(=O)C(C)=C GDFCSMCGLZFNFY-UHFFFAOYSA-N 0.000 claims description 14
- 239000001116 FEMA 4028 Substances 0.000 claims description 14
- 229960004853 betadex Drugs 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000003495 polar organic solvent Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000004927 clay Substances 0.000 abstract description 46
- 230000002579 anti-swelling effect Effects 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003129 oil well Substances 0.000 abstract description 3
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- 125000002091 cationic group Chemical group 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000003405 preventing effect Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000002734 clay mineral Substances 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
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- 229940080345 gamma-cyclodextrin Drugs 0.000 description 3
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
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- 150000003254 radicals Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- ODLHGICHYURWBS-LKONHMLTSA-N trappsol cyclo Chemical compound CC(O)COC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)COCC(O)C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1COCC(C)O ODLHGICHYURWBS-LKONHMLTSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical group CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 2
- 229910018512 Al—OH Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 241000316887 Saissetia oleae Species 0.000 description 2
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- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 230000003311 flocculating effect Effects 0.000 description 2
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
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- LXEKPEMOWBOYRF-QDBORUFSSA-N AAPH Chemical compound Cl.Cl.NC(=N)C(C)(C)\N=N\C(C)(C)C(N)=N LXEKPEMOWBOYRF-QDBORUFSSA-N 0.000 description 1
- QGZKDVFQNNGYKY-OUBTZVSYSA-N Ammonia-15N Chemical compound [15NH3] QGZKDVFQNNGYKY-OUBTZVSYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical class OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
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Landscapes
- Polyethers (AREA)
Abstract
The invention belongs to the technical field of oil well water treatment, and particularly relates to an oilfield flooding stabilizer and a preparation method thereof. The method comprises the following steps: 1) Taking an acyclic monoamine ice bath, dropwise adding hydrocarbon halide under the condition of low temperature, uniformly mixing, heating to react after the dropwise adding is finished, and rectifying, filtering and cleaning to obtain a prepolymer; 2) Uniformly mixing the monomers, dispersing the prepolymer in a solvent, keeping stirring, uniformly adding the monomers, regulating the pH value by alkali liquor, discharging oxygen, sealing, and adding an initiator to perform thermal reaction to obtain gel; 3) Breaking the gel and uniformly mixing the gel, the modifier and the solvent to obtain the stabilizer. The stabilizer prepared by the invention has the advantages of high grafting rate, low preparation cost, environmental friendliness and the like, and the oilfield flooding stabilizer prepared by using a small amount of the stabilizer can effectively stabilize stratum clay, improve the problem that sandstone reservoirs are easily damaged, ensure stable oilfield production, and has good anti-swelling performance and washability.
Description
Technical Field
The invention belongs to the technical field of oil well water treatment, and particularly relates to an oilfield flooding stabilizer and a preparation method thereof.
Background
The demand of China for energy sources is increasing, wherein crude oil has higher external dependence and more than 70% of crude oil is imported. To solve the problem, china is greatly developing oil field exploitation, wherein oil field water flooding exploitation is a common exploitation mode. Among them, hydraulic fracturing is a key technology, however, after water molecules are absorbed by a water sensitive oil reservoir, hydration and expansion of clay minerals occur in two stages, namely a surface hydration and expansion stage and a permeation hydration and expansion stage.
Because the surface layer of the clay crystal face has polar silicon oxygen bonds and hydrogen oxygen bonds to absorb polar water molecules, the hydration energy of the surface of the crystalline water-containing layered silicate mineral rich in the stratum clay plays a main role. The clay can adsorb four layers of water molecules, about 10 a, at most during surface hydration. When the clay surface hydrates such that the distance between the crystalline layers exceeds 10 a, the surface hydration energy greatly weakens the hydration effect. When clay is in low-mineralization aqueous solution, the cation concentration between the surface of clay mineral and the crystal layer is higher than that of the oil reservoir layer, and osmotic pressure difference is generated between the surface aqueous solution and the oil reservoir layer solution among the clay mineral layers to cause concentration diffusion, so that water molecules diffuse to the crystal layer and crystal face of the clay mineral, and the cations originally adsorbed on the surface of the clay are diffused to the bulk aqueous solution to form a diffusion double layer. The action of the repulsive force of the diffusion double electric layers further weakens the binding force of the clay crystal layer, greatly increases the clay crystal distance and forms hydration expansion. The volume increase of clay caused by osmotic expansion is much larger than that of surface hydration expansion, and the two effects simultaneously cause the problems of irreversible expansion and migration, pore canal closing, oil layer permeability reduction and the like, thus seriously affecting the recovery rate of crude oil.
In addition, the pipeline is easy to be blocked, the water body is easy to form black scale, the components of the black scale comprise ferrous sulfide (more than 90 wt percent), calcium carbonate, ferric carbonate and the like, and the content of hydrogen sulfide at the primary outlet of sewage exceeds 250 mg/L. The iron ions are mainly derived from corrosion products, and in the presence of hydrogen sulfide from a scale-like composition, the iron ions are mainly present in the form of ferrous ions. FeS has a very small solubility product at room temperature and is likely to form a precipitate. In order to prolong the stable existence time of ferrous ions, the pH value is regulated by using acid or acid complexing agent in the field, the sewage quantity is large, the required acid or acid complexing agent quantity is large, the cost is high, and meanwhile, the corrosion to a pipeline can be aggravated due to low pH value. As can be seen, the use of acidic stabilizers is not ideal.
In view of the above, in order to achieve stable production and yield increase of oil fields, development of an alkaline oilfield flooding stabilizer is needed.
Disclosure of Invention
The invention provides an oilfield water injection stabilizer and a preparation method thereof, and aims to solve the problems that the recovery efficiency of crude oil is unstable, the scaling of a pipeline is serious, the using amount of the stabilizer is large, and the acidic stabilizer has a better partial using effect but high cost and has pipeline corrosion phenomenon.
The invention aims at: 1. the wettability of the stabilizer to oil is reduced, and the relative permeability coefficient of water molecules to the stabilizer is reduced.
2. The anti-expansion performance and the water washing resistance of the stabilizer are enhanced.
3. Solves the problem of high content of free iron ions in reinjection water, and enhances the scale and corrosion inhibition of the stabilizer on the transportation pipeline.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
A method of preparing an oilfield water injection stabilizer, the method comprising: 1) And taking an acyclic monoamine ice bath, dropwise adding hydrocarbon halide under the condition of low temperature, uniformly mixing, heating to react after the dropwise adding is finished, and rectifying, filtering and cleaning to obtain the prepolymer.
2) And uniformly mixing the monomers, dispersing the prepolymer in a solvent, keeping stirring, uniformly adding the monomers, regulating the pH value of the system by alkali liquor, discharging oxygen, sealing, and adding an initiator to perform thermal reaction to obtain the gel.
3) Crushing the gel to obtain carrier particles, and uniformly mixing the carrier particles, the modifier and the solvent to obtain a stabilizer; the monomers in step 2) are acrylamide, N- [3- (dimethylamino) propyl ] methacrylamide and hydroxybutyl propyl-beta-cyclodextrin.
Preferably, the acyclic monoamine of step 1) is trimethylamine.
The ice bath in the step 1) is kept at a constant temperature of 5-10 min under the condition of 0-2 ℃.
The low temperature condition in the step 1) is 3-5 ℃.
Preferably, the hydrocarbon halide in the step 1) is epichlorohydrin, and the dosage of the hydrocarbon halide is 0.35-0.45 mL/mL of acyclic monoamine.
The temperature rising reaction in the step 1) is carried out at 55-60 ℃ for 1.5-2 h.
Preferably, the monomers of step 2) are acrylamide, N- [3- (dimethylamino) propyl ] methacrylamide, hydroxybutyl propyl-. Beta. -cyclodextrin according to 1: (1.7-2): (4.2-5.7) preparing the following components in percentage by mass; the amount of the monomer is 2-2.4 g/g prepolymer.
Preferably, the solvent in step 2) is water in an amount of 5 to 15 mL/g prepolymer.
The alkali liquor in the step 2) is ammonia water, the concentration of the alkali liquor is 0.5-1.5 mol/L, and the pH value of the system is regulated to 7.3-7.5.
And step 2), the oxygen discharge is carried out by introducing 10-15 min of nitrogen.
The initiator in the step 2) is azobisisobutylamin hydrochloride, and the dosage of the initiator is 0.001-0.002 g/g prepolymer.
Preferably, the thermal reaction in the step 2) is carried out at a constant temperature of 6-7 h at 60-65 ℃.
Preferably, the modifier in step 3) is trans-1, 2-cyclohexanediamine tetraacetic acid.
The solvent in the step 3) is a polar organic solvent.
The polar organic solvent comprises ethanol.
Preferably, step 3) the carrier particles, modifier, solvent are mixed according to 1: (0.5-0.6): (3-8) in mass ratio.
An oilfield flooding stabilizer.
The invention provides a water-soluble intermediate (prepolymer) for chelating small molecules such as clay, minerals and the like, which is modified with hydrophobic monomer acrylamide and rigid monomer N- [3- (dimethylamino) propyl ] methacrylamide, and the obtained carrier has a special structure with hydrophilic molecular shell and hydrophobic cavity, and can be rapidly dispersed in water to include clay.
The technical scheme of the invention is that trimethylamine and epichlorohydrin are adopted to prepare a nitrogenous positive ion active intermediate, the trimethylamine and the epichlorohydrin are prepolymerized in a free radical and ring-opening polymerization mode, the prepolymer acts as a cross-linking agent, and the obtained prepolymer has the characteristics of low shearing dilution rate, strong lubricity, good water solubility and the like. Through orthogonal experiments, the usage amount of trimethylamine and epichlorohydrin is found to obviously influence the anti-expansion performance of the stabilizer, and the trimethylamine and epichlorohydrin are prepared in a certain mass ratio, so that the conversion rate of the product can be improved. With the increase of the consumption of the epichlorohydrin, the anti-expansion rate of the stabilizer is increased and then reduced. At the same time of epoxy chloropropane ring opening, long chains are connected to form tree-shaped and net-shaped macromolecules, and at the same time, the cationic groups generated by the reaction are increased, which is favorable for flocculating mineral micromolecules and settling flocculates. However, a large amount of epichlorohydrin results in a low basicity of the reactant medium, resulting in a low conversion of the product, and at the same time, long chains are bridged and entangled, making it difficult for the prepolymer to be uniformly dispersed in water, and the anti-swelling property is lowered. In addition, the reaction of amine and epoxy group is nucleophilic substitution reaction and exothermic reaction, the low temperature is unfavorable for activating reactant molecules, and can not provide enough energy to overcome intermolecular steric hindrance, and the reaction is slow; and too high a temperature prevents the reaction from proceeding forward, resulting in a problem of low conversion of the target active. In order to ensure higher conversion rate of the active intermediate, the invention strictly controls the reactant dosage, the thermal reaction temperature and the thermal reaction time condition. Under certain reaction conditions with equivalent trimethylamine and epichlorohydrin consumption, the product conversion rate is higher.
Further, the use of hydroxybutyl propyl-beta-cyclodextrin can increase the radius of gyration of the polymer, i.e., the molecular chain is in a state of unfolding, slowing down the intramolecular association. In the invention, the dosage of the hydroxybutyl propyl-beta-cyclodextrin is relatively more, the hydrophobic chain segments are more included, the degree of destruction of intramolecular association is high, compared with the gamma-cyclodextrin compound, the particle size of the stabilizer is smaller, the infiltration speed is faster after the stabilizer is put into an oil sample, and the viscosity increasing effect is stronger when the stabilizer with the same dosage is put into the oil sample. In addition, the present invention avoids the use of α -cyclodextrin compounds in view of economic efficiency.
The invention is modified based on a special structure with large cavity inner diameter of cyclodextrin compound. Through a series of experiments, the hydrophobic chain is connected in the inner cavity of the hydroxybutyl propyl-beta-cyclodextrin, a dynamic network structure capable of reversible physical crosslinking is formed through association, the relative permeability coefficient of water molecules to the stabilizer is also reduced, and the stabilizer is ensured to be capable of long-term inclusion of clay and mineral micromolecules. Meanwhile, the N- [3- (dimethylamino) propyl ] methacrylamide provides a rigid structure, so that the supportability of the stabilizer is enhanced, shrinkage and collapse of the space of the chelated mineral micromolecule are avoided, and the temperature resistance of the chelated mineral micromolecule is improved. With the increase of the amount of acrylamide and N- [3- (dimethylamino) propyl ] methacrylamide monomers, the association structure is more and more dense, and the association strength is increased. However, excessive acrylamide can cause surface modification of the prepolymer, and when the product is put into an oil sample, the wetting effect is poor, and long mixing time is required, so that the applicability of the product is affected. And the network structure is overlapped layer by layer, so that the modification of the hydroxypropyl-beta-cyclodextrin is influenced.
When the pH of the system is alkaline, the anti-expansion rate is firstly increased and then decreased. The variability negative charge of the clay particles is changed by the influence of a strong alkaline stabilizer, the strong alkaline matters dissociate hydrogen ions (clay-Al-OH+OH - - & gt clay-Al-O -+H2 O), and meanwhile, broken bonds generated by breaking of silica bonds in clay silica tetrahedra and alumina bonds in alumina octahedra exist on the surface of the clay, so that the clay particles accumulate negative charges, and the anti-expansion rate decline trend is larger. In addition, if NaOH alkali liquor is added to adjust the pH value of the system, partial hydrolysis of the hydrophobic chain segment can be caused, when the degree of hydrolysis is too high, negative electricity on the high polymer chain is excessively accumulated, and mutual repulsion of stabilizer molecules and suspended particles can be caused, so that the capability of the stabilizer for chelating mineral micromolecules is reduced. Therefore, the invention adopts ammonia water and controls the pH of the system to be weak alkaline.
The invention adopts the azo diisobutylamidine hydrochloride (AAPH) water-soluble azo initiator, and two cationic groups and nitrogen are released after the azo diisobutylamidine hydrochloride is decomposed, so that the azo diisobutylamidine hydrochloride can be used for replacing the initiator such as a persulfate system, and is suitable for synthesizing high molecular cationic polymers. Under the protection of nitrogen, azo diisobutylamidine hydrochloride is used for initiating the polymerization of prepolymer and monomer, and the intrinsic viscosity of the system is increased and then reduced along with the increase of the use amount of an initiator. An amount of initiator is added, the number of free radicals increases, the polymerization rate of the monomer increases, the polymer viscosity increases, and the increase in the number of free radicals leads to an increase in chain termination, resulting in a decrease in the molecular weight of the product. Likewise, during the initiation reaction, the temperature is raised to favor polymer dissolution. However, too high a temperature is detrimental to the hydrophobic and rigid segments to the hydroxypropyl-beta-cyclodextrin. In addition, in the reaction process, the nitrogen positive ions on the long chain have the function of pushing electrons, so that the electron cloud density of the carbon-carbon double bonds is increased, the attack of cationic active species is facilitated, the electron cloud of carbon cation dispersion is stabilized, and side reactions are reduced.
The invention utilizes the coordination effect of nitrogen positive ion long chain and transition metal ion to synergize the trans-1, 2-cyclohexanediamine tetraacetic acid, thereby enhancing the scale inhibition and corrosion inhibition of the stabilizer. When the lone pair electrons enter the empty orbit of the metal ion to form coordination bonds, and meanwhile, the trans-1, 2-cyclohexanediamine tetraacetic acid promotes the stabilizer to complex divalent ions, and a stable complex with a complex ring structure is formed on the surface of the clay, so that the space energy is the lowest, and the stable existence of the complex is ensured. Not only inhibit the generation of ferric sulfide, but also enhance the stability of stratum clay. The synergistic trans-1, 2-cyclohexanediamine tetraacetic acid, the stabilizer particles weaken the shielding of Na + on the negative charge of the molecular chain of the stabilizer particles, so that the effective molecular volume of the stabilizer in an oil sample is increased, and the viscosity of the system is increased.
The positively charged quaternary nitrogen molecules of the stabilizer are adsorbed on the negatively charged clay particles, electrostatic attraction is generated between opposite charges, and further electrostatic neutralization is generated, so that the electric charge quantity of the clay surface is obviously reduced, electrostatic repulsion between the clay particles is reduced, and the swelling of the clay particles is inhibited. It is evident that the preparation of the stabilizer with a higher cationicity is advantageous for increasing the density of positive charges of the polymer molecules, and the electrostatic effect of neutralizing the negative charges on the surface of the clay particles is stronger, i.e. the bonding strength is high. The method has the advantages that a large amount of clay particles and mineral micromolecules are gathered into a whole, contact with a water-oil mixture is reduced, hydration expansion is inhibited, meanwhile, the whole aggregate has high bonding strength, is difficult to be washed and dispersed by water, and is dispersed and moved, so that a long-acting and irreversible expansion preventing effect is achieved. Meanwhile, interlayer hydration cations of the stabilizer are easy to exchange, double-layer diffusion is inhibited, and as the molecular structure contains a large number of quaternary nitrogen groups and the affinity between the cationic groups is greater than that with water molecules, the water molecules are difficult to permeate into clay and mineral crystals, so that hydration expansion of the clay is inhibited. According to the principle, the total positive charge density is increased, the absolute value of the surface potential of the clay is reduced, the thickness of the double electric layers of the clay is compressed, and the clay is stabilized through the adsorption and bridging action of the polymer, so that the molecules of the stabilizer are tightly combined with the clay.
The beneficial effects of the invention are as follows: (1) The stabilizer prepared by the invention has the advantages of high grafting rate, low preparation cost, environmental friendliness and the like, and is suitable for large-scale application in oil fields.
(2) The water-oil mixture has poor wetting effect on the stabilizer-clay combination, and the oilfield flooding stabilizer prepared by using a small amount of the water-oil mixture can effectively stabilize stratum clay, improve the problem that sandstone reservoirs are easily damaged, and ensure stable oilfield production.
(3) The stabilizer prepared by the invention has good anti-expansion performance and washability.
(4) The stabilizer has good scale and corrosion inhibition, prolongs the service life of the pipeline, reduces the pollution to oil reservoirs, and improves the quality and efficiency of oil fields.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
The raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art unless specifically stated otherwise; the methods used in the examples of the present invention are those known to those skilled in the art unless specifically stated otherwise.
Example 1: a method of preparing an oilfield water injection stabilizer, the method comprising: 1) 10 mL trimethylamine is taken, kept at a constant temperature of 5min at 0 ℃, 3.5 mL epichlorohydrin is added dropwise at 5 ℃ to be uniformly mixed, after the dripping is finished, the reaction is carried out at 55 ℃ for 2h, and the prepolymer is obtained after the filtration and the washing with saturated saline and the washing with saturated sodium bicarbonate solution.
2) According to 1:1.9:4.2 mixing acrylamide, N- [3- (dimethylamino) propyl ] methacrylamide and hydroxybutyl propyl-beta-cyclodextrin uniformly to obtain mixed monomers, adding 10mL water and 2 g mixed monomers into the prepolymer according to each gram of prepolymer under the condition of maintaining stirring, adding ammonia water with the concentration of 1 mol/L, regulating the pH value of the system to 7.5, introducing nitrogen to 15 min, discharging oxygen, sealing, adding 0.001 g azo diisobutyl hydrochloride into each gram of prepolymer, and keeping the temperature at 65 ℃ to 6 h to obtain gel.
3) Mechanically crushing the gel, and sieving with a 500-mesh sieve to obtain carrier particles with the particle size of 25 mu m according to the following formula 1:0.5: and 5, preparing carrier particles, trans-1, 2-cyclohexanediamine tetraacetic acid and ethanol according to the mass ratio, and uniformly mixing to obtain the stabilizer.
The performance of the stabilizer prepared in this example was measured as follows.
1. Expansion resistance: and adding 1 wt% of stabilizer into the oil sample, uniformly mixing, and calculating the expansion resistance of the stabilizer by adopting a centrifugal method according to SY/T5971-2016 standard to evaluate the expansion resistance of the stabilizer.
The calculation formula is as follows: wherein alpha is the expansion preventing rate of the stabilizer, and V 0、V1、V2 represents the volume of stratum clay in an oil sample, the stabilizer and a test solution (water for experiments) respectively.
2. Washing resistance: adding 1 wt% of stabilizer into the oil sample, mixing uniformly, pouring out supernatant of the centrifuge tube, re-injecting water to 10 mL, shaking uniformly, standing for 2h, and centrifuging for 15 min. And (3) washing for 3 times, measuring the volume V 3 of stratum clay in the centrifuge tube after the 3 rd washing, and calculating the expansion resistance to evaluate the water washing resistance of the stabilizer.
The calculation formula is as follows: Wherein alpha is the expansion preventing rate of the stabilizer, and V 0、V2、V3 respectively represents the volume of the stratum clay in the oil sample and the test liquid (the water for experiments) and the volume of the stratum clay in the centrifuge tube after water washing.
3. Soil content measurement: adding 1 wt% of stabilizer into the oil sample, uniformly mixing, standing for 240: 240 h, and measuring the iron content, suspended solid content and turbidity in the oil sample.
4. Temperature resistance: adding 1 wt% of stabilizer into the oil sample, uniformly mixing, standing for 2: 2h, testing the anti-expansion rate of the oil sample with the same concentration at 35, 55, 75 and 95 ℃, and measuring the anti-expansion rate by adopting the same method for detecting the expansion performance of the formula 1.
The results are as follows.
The expansion resistance of the following table is expressed as the result of temperature resistance test, i.e., expansion resistance under different temperature conditions.
The oil sample in the oil well was further sampled, and 1 wt% of a commercially available stabilizer was added thereto, and the measurement of the swelling preventing property, the washing resistance and the dirt content were carried out as described above, with the following results.
The oilfield flooding stabilizer is used for protecting a reservoir of an oil reservoir, fixing clay particles for a long time, and reducing reservoir damage in the process of multiple flooding development. According to the invention, the stabilizer branched chain has higher cationic degree through a sodium tetraphenylboron titration method. The invention adds 0.3 wt percent, 0.5 wt percent, 0.8 wt percent, 1 wt percent, 1.3 wt percent and 1.5 wt percent (the proportion of the stabilizer to the total amount of the oil sample) of the stabilizer into the oil sample, and the expansion preventing rate increases along with the increase of the dosage of the stabilizer. When the concentration of the clay stabilizer is increased from 0.8 wt% to 1 wt%, the expansion-preventing rate increases most rapidly, the dosage of the stabilizer is further increased, and the expansion-preventing rate increases less. According to a relation diagram of the anti-expansion rate and the stabilizer dosage, the economic benefit and the anti-expansion effect are comprehensively considered, and the stabilizer dosage is determined to be 1 wt% of the oil sample. And when a certain amount of stabilizer is added, the higher the viscosity of the oil sample is, the better the anti-swelling effect is.
According to the results in the table, the stabilizer has excellent anti-swelling properties, and after 3 water washes, the anti-swelling rate overall remains at a higher level, indicating that the stabilizer has excellent water wash resistance. The oil sample suspension is obviously reduced by the treatment of the stabilizing agent, and the turbidity change is small and the water quality is stable by standing. Compared with the oil sample which is not treated by the stabilizer, the oil sample has less dirt observed by naked eyes, which indicates that the stabilizer has certain descaling performance. As the temperature increases, the anti-swelling effect gradually decreases, as the high temperature exacerbates the hydration swelling of the clay. And when the temperature is increased to 95 ℃, the anti-expansion rate of the stabilizer still exceeds 90%, which shows that the stabilizer has good temperature resistance.
Example 2: a method of preparing an oilfield water injection stabilizer, the method comprising: 10 mL trimethylamine is taken, the temperature is kept at 5min at 0 ℃, then 4.0 mL epichlorohydrin is added dropwise at 5 ℃ to be uniformly mixed, after the dripping is finished, the reaction is carried out at 55 ℃ for 2h, the prepolymer is obtained after the filtration and the washing with saturated saline solution and the washing with saturated sodium bicarbonate solution.
2) According to 1:1.9:4.2 mixing acrylamide, N- [3- (dimethylamino) propyl ] methacrylamide and hydroxybutyl propyl-beta-cyclodextrin uniformly to obtain mixed monomers, adding 10mL water and 2 g mixed monomers into the prepolymer according to each gram of prepolymer under the condition of maintaining stirring, adding ammonia water with the concentration of 1 mol/L, regulating the pH value of the system to 7.5, introducing nitrogen to 15 min, discharging oxygen, sealing, adding 0.001 g azo diisobutyl hydrochloride into each gram of prepolymer, and keeping the temperature at 65 ℃ to 6 h to obtain gel.
3) Mechanically crushing the gel, and sieving with a 500-mesh sieve to obtain carrier particles with the particle size of 25 mu m according to the following formula 1:0.5: and 5, preparing carrier particles, trans-1, 2-cyclohexanediamine tetraacetic acid and ethanol according to the mass ratio, and uniformly mixing to obtain the stabilizer.
The stabilizer prepared in this example was subjected to the performance test as in example 1, and the results were as follows.
The expansion resistance of the following table is expressed as the result of temperature resistance test, i.e., expansion resistance under different temperature conditions.
Through a plurality of orthogonal experiments, the usage amount of trimethylamine and epichlorohydrin is found to obviously influence the anti-expansion performance of the stabilizer. At the same time of epoxy chloropropane ring opening, long chains are connected to form tree-shaped and net-shaped macromolecules, and at the same time, the cationic groups generated by the reaction are increased, which is favorable for flocculating mineral micromolecules and settling flocculates. The stabilizer of this example showed an increase in expansion resistance compared to example 1.
Example 3: a method of preparing an oilfield water injection stabilizer, the method comprising: 1) 10 mL trimethylamine is taken, kept at a constant temperature of 5min at 0 ℃, then 4.5 mL epichlorohydrin is added dropwise at 5 ℃ to be uniformly mixed, after the dripping is finished, the reaction is carried out at 55 ℃ for 2h, and the prepolymer is obtained after the filtration and the washing with saturated saline and the washing with saturated sodium bicarbonate solution.
2) According to 1:1.9:4.2 mixing acrylamide, N- [3- (dimethylamino) propyl ] methacrylamide and hydroxybutyl propyl-beta-cyclodextrin uniformly to obtain mixed monomers, adding 10mL water and 2 g mixed monomers into the prepolymer according to each gram of prepolymer under the condition of maintaining stirring, adding ammonia water with the concentration of 1 mol/L, regulating the pH value of the system to 7.5, introducing nitrogen to 15 min, discharging oxygen, sealing, adding 0.001 g azo diisobutyl hydrochloride into each gram of prepolymer, and keeping the temperature at 65 ℃ to 6 h to obtain gel.
3) Mechanically crushing the gel, and sieving with a 500-mesh sieve to obtain carrier particles with the particle size of 25 mu m according to the following formula 1:0.5: and 5, preparing carrier particles, trans-1, 2-cyclohexanediamine tetraacetic acid and ethanol according to the mass ratio, and uniformly mixing to obtain the stabilizer.
The stabilizer prepared in this example was subjected to the performance test as in example 1, and the results were as follows.
The expansion resistance of the following table is expressed as the result of temperature resistance test, i.e., expansion resistance under different temperature conditions.
The high amount of epichlorohydrin results in lower basicity of the reactant medium and thus lower conversion of the product, and at the same time, bridging and entanglement between long chains makes it difficult for the prepolymer to be uniformly dispersed in water, and the anti-swelling property is lowered. In summary, the amounts of trimethylamine and epichlorohydrin should be controlled.
Comparative example 1: a method of preparing an oilfield water injection stabilizer, the method comprising: 1) 10 mL trimethylamine is taken, the temperature is kept at 5min at 0 ℃, then 4.0 mL epichlorohydrin is added dropwise at 5 ℃ to be uniformly mixed, after the dripping is finished, the reaction is carried out at 55 ℃ for 2h, the prepolymer is obtained after the filtration and the washing with saturated saline solution and the washing with saturated sodium bicarbonate solution.
2) According to 1:1.9:4.2 mixing acrylamide, N- [3- (dimethylamino) propyl ] methacrylamide and gamma-cyclodextrin uniformly to obtain mixed monomers, adding 10 mL water and 2 g mixed monomers into the prepolymer according to each gram of prepolymer in a stirring state, adding 1 mol/L ammonia water, regulating the pH value of the system to 7.5, introducing nitrogen 15 min, discharging oxygen, sealing, adding 0.001 g azobisisobutyronitrile hydrochloride according to each gram of prepolymer, and keeping the temperature at 65 ℃ for 6 h to obtain gel.
3) Mechanically crushing the gel, and sieving with a 500-mesh sieve to obtain carrier particles with the particle size of 25 mu m according to the following formula 1:0.5: and 5, preparing carrier particles, trans-1, 2-cyclohexanediamine tetraacetic acid and ethanol according to the mass ratio, and uniformly mixing to obtain the stabilizer.
The stabilizer prepared in this example was subjected to the performance test as in example 1, and the results were as follows.
The expansion resistance of the following table is expressed as the result of temperature resistance test, i.e., expansion resistance under different temperature conditions.
The stabilizer prepared by adopting the gamma-cyclodextrin in the example has larger particle size, the stabilizer with the same dosage is added into the oil sample, the tackifying effect is inferior to that of the stabilizer prepared in the example 2, and the infiltration speed is slower after the oil sample is added. Because the polymer has larger intra-molecular association, the polymer molecular chain of the example is twisted and interpenetrated, the effective inclusion space is reduced, and the descaling capability of the stabilizer is obviously deteriorated.
Comparative example 2: a method of preparing an oilfield water injection stabilizer, the method comprising: 1) 10 mL trimethylamine is taken, the temperature is kept at 5min at 0 ℃, then 4.0 mL epichlorohydrin is added dropwise at 5 ℃ to be uniformly mixed, after the dripping is finished, the reaction is carried out at 55 ℃ for 2h, the prepolymer is obtained after the filtration and the washing with saturated saline solution and the washing with saturated sodium bicarbonate solution.
2) According to 1:4.2, uniformly mixing acrylamide and hydroxybutyl propyl-beta-cyclodextrin to obtain a mixed monomer, adding 10 mL water and 2 g mixed monomer into the prepolymer according to each gram of prepolymer under the condition of keeping stirring, adding ammonia water with the concentration of 1mol/L, adjusting the pH value of the system to 7.5, introducing nitrogen to 15 min, discharging oxygen, sealing, adding 0.001 g azobisisobutyronium hydrochloride into each gram of prepolymer, and keeping the temperature at 65 ℃ for 6 h to obtain gel.
3) Mechanically crushing the gel, and sieving with a 500-mesh sieve to obtain carrier particles with the particle size of 25 mu m according to the following formula 1:0.5: and 5, preparing carrier particles, trans-1, 2-cyclohexanediamine tetraacetic acid and ethanol according to the mass ratio, and uniformly mixing to obtain the stabilizer.
The stabilizer prepared in this example was subjected to the performance test as in example 1, and the results were as follows.
The expansion resistance of the following table is expressed as the result of temperature resistance test, i.e., expansion resistance under different temperature conditions.
According to the results in the table, the stabilizer of the example has better expansion resistance, but the temperature resistance is obviously reduced, and the reduction trend is larger. The reason is that the method does not adopt a rigid structure monomer, the consumption of the acrylamide and the hydroxybutyl propyl-beta-cyclodextrin monomer is relatively increased, the association structure is more and more dense, the association strength is increased, but the effective inclusion structure is unstable, and the space of the chelated mineral micromolecule is contracted and collapsed.
Comparative example 3: a method of preparing an oilfield water injection stabilizer, the method comprising: 1) 10 mL trimethylamine is taken, the temperature is kept at 5min at 0 ℃, then 4.0 mL epichlorohydrin is added dropwise at 5 ℃ to be uniformly mixed, after the dripping is finished, the reaction is carried out at 55 ℃ for 2h, the prepolymer is obtained after the filtration and the washing with saturated saline solution and the washing with saturated sodium bicarbonate solution.
2) According to 2:1.9:4.2 mixing acrylamide, N- [3- (dimethylamino) propyl ] methacrylamide and hydroxybutyl propyl-beta-cyclodextrin uniformly to obtain mixed monomers, adding 10mL water and 2 g mixed monomers into the prepolymer according to each gram of prepolymer under the condition of maintaining stirring, adding ammonia water with the concentration of 1 mol/L, regulating the pH value of the system to 7.5, introducing nitrogen to 15 min, discharging oxygen, sealing, adding 0.001 g azo diisobutyl hydrochloride into each gram of prepolymer, and keeping the temperature at 65 ℃ to 6 h to obtain gel.
3) Mechanically crushing the gel, and sieving with a 500-mesh sieve to obtain carrier particles with the particle size of 25 mu m according to the following formula 1:0.5: and 5, preparing carrier particles, trans-1, 2-cyclohexanediamine tetraacetic acid and ethanol according to the mass ratio, and uniformly mixing to obtain the stabilizer.
The stabilizer prepared in this example was subjected to the performance test as in example 1, and the results were as follows.
The expansion resistance of the following table is expressed as the result of temperature resistance test, i.e., expansion resistance under different temperature conditions.
According to the results in the table, the stabilizer of the example has poor anti-expansion performance and poor descaling performance. In the case of using a large amount of acrylamide, when the polymer cavity is modified and the balance is left, the polymer cavity is subjected to surface hydrophobic modification, and when the product is put into an oil sample, the infiltration time is required to exceed 2h, so that the applicability of the stabilizer is poor. The reticular structure layers in the polymer micromolecules are overlapped, and the modification effect of the hydroxypropyl-beta-cyclodextrin is poor.
Comparative example 4: a method of preparing an oilfield water injection stabilizer, the method comprising: 1) 10 mL trimethylamine is taken, the temperature is kept at 5min at 0 ℃, then 4.0 mL epichlorohydrin is added dropwise at 5 ℃ to be uniformly mixed, after the dripping is finished, the reaction is carried out at 55 ℃ for 2h, the prepolymer is obtained after the filtration and the washing with saturated saline solution and the washing with saturated sodium bicarbonate solution.
2) According to 1:1.9:4.2 mixing acrylamide, N- [3- (dimethylamino) propyl ] methacrylamide and hydroxybutyl propyl-beta-cyclodextrin uniformly to obtain mixed monomers, adding 10 mL water and 2g mixed monomers into the prepolymer according to each gram of prepolymer under the condition of maintaining stirring, adding ammonia water with the concentration of 1 mol/L, regulating the pH value of the system to 10, introducing nitrogen to 15min, discharging oxygen, sealing, adding 0.001 g azo diisobutyl hydrochloride into each gram of prepolymer, and maintaining the temperature to 6 h at 65 ℃ to obtain gel.
3) Mechanically crushing the gel, and sieving with a 500-mesh sieve to obtain carrier particles with the particle size of 25 mu m according to the following formula 1:0.5: and 5, preparing carrier particles, trans-1, 2-cyclohexanediamine tetraacetic acid and ethanol according to the mass ratio, and uniformly mixing to obtain the stabilizer.
The above preparation was comparative example (4-1), and this example (4-1) was labeled as the above preparation.
The stabilizer prepared in this example (4-1) was subjected to the performance test as in example 1, and the results were as follows.
The expansion resistance of the following table is expressed as the result of temperature resistance test, i.e., expansion resistance under different temperature conditions.
The variability negative charge of the clay particles is changed by the influence of a strong alkaline stabilizer, the strong alkaline matters dissociate hydrogen ions (clay-Al-OH+OH - - & gt clay-Al-O -+H2 O), and meanwhile, broken bonds generated by breaking of silica bonds in clay silica tetrahedra and alumina bonds in alumina octahedra exist on the surface of the clay, so that the clay particles accumulate negative charges, and the anti-expansion rate decline trend is larger.
Only the aqueous ammonia used in this example (4-1) was adjusted to NaOH alkali solution and labeled as comparative example (4-2), and the stabilizer was prepared under the same conditions as in comparative example (4-1) except that the other preparation parameters were the same, and the stabilizer prepared in comparative example (4-2) was subjected to the same measurement of the swelling preventing property, water washing resisting property, and soil content as in example 1, with the following results.
The hydrophobic chain segment is partially hydrolyzed under the influence of OH - ions, negative electricity on the high molecular chain is excessively accumulated, and the stabilizer molecules and suspended particles are mutually repelled, so that the capability of the stabilizer for chelating small mineral molecules is reduced. The stabilizer prepared in comparative example (4-2) had poorer anti-swelling properties, particularly significantly reduced descaling properties, than the stabilizer prepared in example (4-1).
Comparative example 5: a method of preparing an oilfield water injection stabilizer, the method comprising: 1) 10 mL trimethylamine is taken, the temperature is kept at 5min at 0 ℃, then 4.0 mL epichlorohydrin is added dropwise at 5 ℃ to be uniformly mixed, after the dripping is finished, the reaction is carried out at 55 ℃ for 2h, the prepolymer is obtained after the filtration and the washing with saturated saline solution and the washing with saturated sodium bicarbonate solution.
2) According to 1:1.9:4.2 mixing acrylamide, N- [3- (dimethylamino) propyl ] methacrylamide and hydroxybutyl propyl-beta-cyclodextrin uniformly to obtain mixed monomers, adding 10mL water and 2 g mixed monomers into the prepolymer according to each gram of prepolymer under the condition of maintaining stirring, adding ammonia water with the concentration of 1 mol/L, regulating the pH value of the system to 7.5, introducing nitrogen to 15 min, discharging oxygen, sealing, adding 0.001 g azobisisobutylmethamide hydrochloride into each gram of prepolymer, obtaining gel at the constant temperature of 6h under the temperature of 65 ℃, mechanically crushing the gel, and sieving with a 500-mesh sieve to obtain the stabilizer with the particle size of 25 mu m.
The stabilizer prepared in this example was subjected to the performance test as in example 1, and the results were as follows.
The expansion resistance of the following table is expressed as the result of temperature resistance test, i.e., expansion resistance under different temperature conditions.
According to the results in the table, the anti-swelling effect of the stabilizer prepared in this example is similar to that of the stabilizer sold in the market, but the scale inhibition and corrosion inhibition are remarkably reduced. The weakening effect of the stabilizer particles against Na + shielding the negative charge of the molecular chain is reduced compared to example 2, and the effective molecular volume in the oil sample is reduced. The effect of complexing mineral small molecules by the stabilizer is poor, the complex formed on the clay surface is easy to disperse, the complex cannot exist stably, and the stability of stratum clay is poor.
Claims (9)
1. A method for preparing an oilfield flooding stabilizer, the method comprising: 1) Taking an acyclic monoamine ice bath, dropwise adding hydrocarbon halide under the condition of low temperature, uniformly mixing, heating to react after the dropwise adding is finished, and rectifying, filtering and cleaning to obtain a prepolymer; 2) Uniformly mixing the monomers, dispersing the prepolymer in a solvent, keeping stirring, uniformly adding the monomers, regulating the pH value of the system by alkali liquor, discharging oxygen, sealing, and adding an initiator to perform thermal reaction to obtain gel; 3) Crushing the gel to obtain carrier particles, and uniformly mixing the carrier particles, the modifier and the solvent to obtain a stabilizer; the monomers in step 2) are acrylamide, N- [3- (dimethylamino) propyl ] methacrylamide and hydroxybutyl propyl-beta-cyclodextrin.
2. The method for preparing an oilfield water injection stabilizer according to claim 1, wherein the acyclic monoamine in step 1) is trimethylamine; the ice bath in the step 1) is kept at a constant temperature of 5-10 min under the condition of 0-2 ℃; the low temperature condition in the step 1) is 3-5 ℃.
3. The method for preparing an oilfield water injection stabilizer according to claim 1 or 2, wherein the hydrocarbon halide in the step 1) is epichlorohydrin, and the dosage of the hydrocarbon halide is 0.35-0.45 mL/mL acyclic monoamine; the temperature rising reaction in the step 1) is carried out at 55-60 ℃ for 1.5-2 h.
4. The method for preparing oilfield water injection stabilizer according to claim 1, wherein in the step 2), acrylamide, N- [3- (dimethylamino) propyl ] methacrylamide, and hydroxybutyl propyl-beta-cyclodextrin are mixed according to the following formula 1: (1.7-2): (4.2-5.7) preparing the following components in percentage by mass; the amount of the monomer is 2-2.4 g/g prepolymer.
5. The method for preparing an oilfield water injection stabilizer according to claim 1, wherein the solvent in the step 2) is water, and the amount of the solvent is 5-15 mL/g prepolymer; step 2) the alkali liquor is ammonia water, the concentration of the alkali liquor is 0.5-1.5 mol/L, and the pH value of the system is regulated to 7.3-7.5; the step 2) of oxygen discharge is to introduce 10 to 15 min of nitrogen; the initiator in the step 2) is azobisisobutylamin hydrochloride, and the dosage of the initiator is 0.001-0.002 g/g prepolymer.
6. The method for preparing a stabilizer for oilfield flooding of claim 1, 4 or 5, wherein the thermal reaction in step 2) is carried out at a constant temperature of 6-7 h at 60-65 ℃.
7. The method for preparing an oilfield water injection stabilizer according to claim 1, wherein the modifier in step 3) is trans-1, 2-cyclohexanediamine tetraacetic acid; step 3) the solvent is a polar organic solvent; the polar organic solvent comprises ethanol.
8. The method for preparing the oilfield water injection stabilizer according to claim 1 or 7, wherein in the step 3), the carrier particles, the modifier and the solvent are mixed according to the following formula 1: (0.5-0.6): (3-8) in mass ratio.
9. An oilfield water injection stabilizer prepared by the process of any one of claims 1 to 8.
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