CN118184878A - Polyacrylamide for improving recovery ratio as well as preparation method and application thereof - Google Patents
Polyacrylamide for improving recovery ratio as well as preparation method and application thereof Download PDFInfo
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 58
- 238000011084 recovery Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 18
- RMXLHIUHKIVPAB-OWOJBTEDSA-N (e)-1,4-dibromobut-2-ene Chemical compound BrC\C=C\CBr RMXLHIUHKIVPAB-OWOJBTEDSA-N 0.000 claims abstract description 15
- JZINNAKNHHQBOS-AATRIKPKSA-N 3-methylcinnamic acid Chemical compound CC1=CC=CC(\C=C\C(O)=O)=C1 JZINNAKNHHQBOS-AATRIKPKSA-N 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- HTYRTGGIOAMLRR-UHFFFAOYSA-N 5-amino-4-hydroxybenzene-1,3-disulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=CC(S(O)(=O)=O)=C1O HTYRTGGIOAMLRR-UHFFFAOYSA-N 0.000 claims abstract description 12
- DBGROTRFYBSUTR-UHFFFAOYSA-N [4-(trifluoromethoxy)phenyl]methanamine Chemical compound NCC1=CC=C(OC(F)(F)F)C=C1 DBGROTRFYBSUTR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims abstract description 12
- 235000019796 monopotassium phosphate Nutrition 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 135
- 239000000243 solution Substances 0.000 claims description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 239000011259 mixed solution Substances 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 11
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 8
- 238000010008 shearing Methods 0.000 abstract description 7
- 230000001603 reducing effect Effects 0.000 abstract description 6
- 238000004321 preservation Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract 1
- 238000010010 raising Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 14
- 238000006073 displacement reaction Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000008398 formation water Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of petroleum exploitation, and particularly relates to polyacrylamide for improving recovery ratio as well as a preparation method and application thereof. The preparation method comprises the following steps: adding 5-amino-4-hydroxy-1, 3-benzene disulfonic acid, methanol and 1, 4-dibromo-2-butene into a first reactor, heating, carrying out heat preservation reaction, adding 4- (trifluoromethoxy) benzyl amine, heating, carrying out heat preservation reaction, carrying out reduced pressure distillation, adding deionized water, cooling, filtering and drying to obtain a functional monomer; adding acrylamide, functional monomers, 3-methyl cinnamic acid, potassium dihydrogen phosphate and deionized water into a second reactor, and stirring to obtain a mixture solution; dropwise adding an initiator into the second reactor, stirring, heating, raising the temperature, carrying out heat preservation reaction, and reducing the temperature; granulating to obtain the polyacrylamide for improving the recovery ratio of the product. The invention has the characteristics of simple synthesis process, high viscosity, strong shearing resistance and good viscosity reduction effect.
Description
Technical Field
The invention belongs to the technical field of petroleum exploitation, and particularly relates to polyacrylamide for improving recovery ratio as well as a preparation method and application thereof.
Background
Along with the large-scale exploitation and consumption of conventional oil and gas reservoirs, compact sandstone gas, coal bed gas, shale gas and other low-permeability and ultra-low-permeability deep high-temperature unconventional oil and gas resources need to be developed and utilized.
Tertiary oil recovery is one of the main measures to improve crude oil recovery, and polymer flooding plays an important role. The most commonly used displacement polymers are mainly polyacrylamides.
Polyacrylamide is a linear water-soluble polymer and is one of the most widely used varieties of water-soluble polymer compounds. In water, hydrogen bond is easy to form with water, the water-soluble polymer has large hydrodynamic volume after hydration.
Polyacrylamide flooding agent is widely applied in the aspect of oil field production increase, but the polyacrylamide is easy to hydrolyze in formation water and is sensitive to some ions in the formation water, so that the viscosity of a polymer can be quickly reduced, and polymer molecular chains of the polymer solution can be deformed and broken after the polymer solution is subjected to strong shearing in pores of a reservoir, so that the viscosity of the polymer solution is quickly reduced, the polymer solution can flow along large pore channels of the reservoir, and the sweep coefficient of the flooding polymer is reduced.
The quality of the polyacrylamide determines the effect of improving the recovery ratio to a considerable extent, and a plurality of scientific researchers aim at structurally modifying the polyacrylamide to ensure that the polyacrylamide has obvious tackifying effect, shearing resistance and high activity, so that the viscosity of displacement fluid can be effectively increased, the sweep efficiency is improved, and the sweep volume is increased.
CN105542073B discloses a preparation method of polyacrylamide for polymer flooding oil extraction, belonging to the technical field of high polymer. The steps are as follows: uniformly mixing a cationic monomer, acrylamide, trimethylol methylamine, a surfactant and water, and then introducing nitrogen into the mixed solution; adding an initiator, heating, maintaining the reaction, cooling, adding hydroxyethyl acrylate and dimethylchlorosilane into the mixture, adjusting the pH value of a reaction system, heating, maintaining the reaction, taking out the obtained gelatinous product after the reaction is finished, and obtaining a polyacrylamide product through cutting, drying, granulating and screening. According to the invention, the monomer reaction sequence of the modified polyacrylamide in polymerization is regulated, a cationic monomer and acrylamide are partially polymerized, and then the polymerization reaction is continuously carried out by hydroxyethyl acrylate and dimethylchlorosilane. However, the viscosity of the polymer oil-displacing agent is only about 30mPa.s at a concentration of 1500mg/L, and the viscosity of the polymer oil-displacing agent is low.
CN104448129B discloses a high-temperature resistant hydrolysis copolymer for oil field, a preparation method and application thereof in oil extraction, which mainly solves the problem of poor hydrolysis stability of polyacrylamide under the condition of high temperature and high mineralization in the prior art. However, the molecular structure of the invention has no surfactant unit, only plays a role in oil displacement of common polymers, and has no functions of reducing the interfacial tension of oil and water and reducing the viscosity of crude oil.
Disclosure of Invention
The invention provides polyacrylamide for improving recovery ratio and a preparation method and application thereof aiming at the defects of the prior art. The invention has the characteristics of simple synthesis process, high viscosity, strong shearing resistance and good viscosity reduction effect.
In order to achieve the above object, one of the objects of the present invention is to disclose a polyacrylamide for improving recovery efficiency, wherein the molecular structural formula of the polyacrylamide is as follows:
Wherein:
m＝50000-500000；
n＝10000-200000；
p＝5000-100000。
preferably, the polyacrylamide has a viscosity average molecular weight of 25000000-30000000.
Another object of the present invention is to provide a method for preparing polyacrylamide for enhanced oil recovery, the method comprising:
(1) Adding 5-amino-4-hydroxy-1, 3-benzene disulfonic acid, methanol and 1, 4-dibromo-2-butene into a first reactor, introducing nitrogen, replacing air in the reactor, adjusting the pH value to 8-9 by using sodium hydroxide solution, heating to 40-50 ℃, keeping the temperature for reaction for 20-30min, keeping the pH value to 6-7 by using sodium hydroxide solution, adding 4- (trifluoromethoxy) benzyl amine, heating to 40-50 ℃, keeping the temperature for reaction for 30-60min, keeping the pH value to 6-7 by using sodium hydroxide solution, distilling off part of methanol under reduced pressure, adding deionized water, adjusting the pH value to 1-2 by using hydrochloric acid, cooling to below 10 ℃, filtering and drying to obtain a functional monomer;
(2) Introducing nitrogen into the second reactor, adding acrylamide, functional monomers, 3-methyl cinnamic acid, potassium dihydrogen phosphate and deionized water, stirring to obtain a mixture solution, and regulating the pH value to 7-8 by using a sodium hydroxide solution;
(3) Dropwise adding an initiator into the second reactor, gradually increasing the viscosity of the liquid in the reactor, continuously stirring for 10-20min, heating to 50-60 ℃, keeping the temperature for 30-60min for reaction, adjusting the pH to 7-7.5 by using a sodium hydroxide solution, and cooling to below 40 ℃;
(4) Granulating the mixed solution to obtain the polyacrylamide for improving the recovery ratio of the product.
In the present invention, it is preferable that the 5-amino-4-hydroxy-1, 3-benzenedisulfonic acid, 4- (trifluoromethoxy) benzylamine, be used in an amount of 0.8 to 1.2 parts by mole, respectively, based on 1 part by mole of 1, 4-dibromo-2-butene in step (1).
In the present invention, preferably, in the step (1), the mass ratio of the methanol to the 1, 4-dibromo-2-butene is 10-15:1.
In the present invention, preferably, in the step (1), the partial methanol is 1/2 to 2/3 of the total methanol mass.
In the present invention, preferably, in the step (1), the mass ratio of the deionized water to the 1, 4-dibromo-2-butene is 15-20:1.
In the present invention, preferably, in the step (2), the molar ratio of the functional monomer, 3-methyl cinnamic acid to acrylamide is 0.2 to 0.4:0.1-0.2:1.
In the present invention, preferably, in the step (2), the mass ratio of the potassium dihydrogen phosphate, deionized water and acrylamide is 0.1-0.2:6-8:1.
In the present invention, preferably, in the step (3), the initiator is a mixed solution of persulfate and sodium bisulfite, wherein the concentration of persulfate is 8-10wt%, the concentration of sodium bisulfite is 3-4wt%, and the weight ratio of the initiator to acrylamide is 0.2-0.4:1.
Preferably, the persulfate is one of potassium persulfate, ammonium persulfate and sodium persulfate.
The reaction equation for synthesizing the polyacrylamide for improving the recovery ratio is as follows:
The polyacrylamide for improving the recovery ratio is a ternary high polymer taking acrylamide, a functional monomer and 3-methyl cinnamic acid as monomers. Acrylamide is the main body; the functional monomer introduces lipophilic hydrophilic groups such as trifluoromethoxy and two sulfonic groups, and the like, so that the surface activity of the polyacrylamide is enhanced; the benzyl and carboxyl in the 3-methyl cinnamic acid further strengthen the hydrophilic and lipophilic properties, and can greatly improve the oil displacement performance. The benzene ring structure is introduced into the functional monomer and the 3-methyl cinnamic acid, so that the shearing resistance is further enhanced, the water shutoff and profile control capability is improved, and the oil displacement capability can be further improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The polyacrylamide for improving the recovery ratio has higher viscosity, and the concentration viscosity of 1500mg/L is not lower than 60 mPa.s;
(2) The polyacrylamide for improving the recovery ratio has stronger shearing resistance, and the viscosity retention rate is not lower than 95% after shearing for 2 hours under the conditions of 50 ℃ and 170S -;
(3) The polyacrylamide for improving the recovery ratio has a good crude oil viscosity reduction effect, and the viscosity reduction rate of the crude oil with 5500 mPa.s is more than 98.4% when the concentration of the polyacrylamide is 1500 mg/L.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The technical scheme of the invention is further described below by combining specific embodiments.
Example 1
(1) Preparation of functional monomers: adding 0.08mol of 5-amino-4-hydroxy-1, 3-benzene disulfonic acid, 214g of methanol and 0.1mol of 1, 4-dibromo-2-butene into a first reactor, introducing nitrogen, replacing air in the reactor, adjusting the pH value to 8-9 by using sodium hydroxide solution, heating to 40 ℃, keeping the temperature for 20min, keeping the pH value to 6-7 by using sodium hydroxide solution, adding 0.08mol of 4- (trifluoromethoxy) benzyl amine, heating to 40 ℃, keeping the temperature for 30min, keeping the pH value to 6-7 by using sodium hydroxide solution, distilling off 107g of methanol under reduced pressure, adding 321g of deionized water, adjusting the pH value to 1-2 by using hydrochloric acid, cooling to below 10 ℃, filtering and drying to obtain the functional monomer.
(2) The second reactor was purged with nitrogen, and 0.5mol of acrylamide, 0.1mol of a functional monomer, 0.1mol of 3-methyl cinnamic acid, 3.6g of potassium dihydrogen phosphate, 213g of deionized water were added and stirred to obtain a mixture solution, and the pH was adjusted to 7-8 with a sodium hydroxide solution.
(3) 7.1G of initiator, namely 8wt% of potassium persulfate and 3wt% of sodium bisulphite mixed solution, is dropwise added into the second reactor, the viscosity of the liquid in the reactor is gradually increased, stirring is continued for 10min, heating is carried out to 50 ℃, the temperature is kept for 30min for reaction, the pH is regulated to 7-7.5 by sodium hydroxide solution, and the temperature is reduced to below 40 ℃.
(4) Granulating the mixed solution to obtain the polyacrylamide for improving the recovery ratio of the product.
Example 2
(1) Preparation of functional monomers: adding 0.12mol of 5-amino-4-hydroxy-1, 3-benzene disulfonic acid, 318g of methanol and 0.1mol of 1, 4-dibromo-2-butene into a first reactor, introducing nitrogen, replacing air in the reactor, adjusting pH to 8-9 by using sodium hydroxide solution, heating to 50 ℃, keeping the temperature for 30min, keeping pH to 6-7 by using sodium hydroxide solution, adding 0.12mol of 4- (trifluoromethoxy) benzyl amine, heating to 50 ℃, keeping the temperature for 60min, keeping pH to 6-7 by using sodium hydroxide solution, distilling 212g of methanol under reduced pressure, adding 363g of deionized water, adjusting pH to 1-2 by using hydrochloric acid, reducing the temperature to below 10 ℃, filtering and drying to obtain the functional monomer.
(2) The second reactor was purged with nitrogen, and 0.5mol of acrylamide, 0.12mol of a functional monomer, 0.09mol of 3-methyl cinnamic acid, 4g of potassium dihydrogen phosphate, and 215g of deionized water were added and stirred to obtain a mixture solution, and the pH was adjusted to 7-8 with a sodium hydroxide solution.
(3) And (3) dropwise adding 8.5g of an initiator into the second reactor, wherein the initiator is a mixed solution of 9wt% of potassium persulfate and 4wt% of sodium bisulphite, the viscosity of the liquid in the reactor is gradually increased, stirring is continued for 20min, heating to 60 ℃, preserving heat and reacting for 60min, regulating the pH to 7-7.5 by using a sodium hydroxide solution, and cooling to below 40 ℃.
(4) Granulating the mixed solution to obtain the polyacrylamide for improving the recovery ratio of the product.
Example 3
(1) Preparation of functional monomers: adding 0.085mol of 5-amino-4-hydroxy-1, 3-benzene disulfonic acid, 243g of methanol and 0.1mol of 1, 4-dibromo-2-butene into a first reactor, introducing nitrogen, replacing air in the reactor, adjusting the pH to 8-9 by using sodium hydroxide solution, heating to 40 ℃, preserving the temperature for 25min, maintaining the pH to 6-7 by using sodium hydroxide solution during the reaction, adding 0.09mol of 4- (trifluoromethoxy) benzyl amine, heating to 45 ℃, preserving the temperature for 50min, maintaining the pH to 6-7 by using sodium hydroxide solution during the reaction, distilling 128g of methanol under reduced pressure, adding 418g of deionized water, adjusting the pH to 1-2 by using hydrochloric acid, reducing the temperature to below 10 ℃, filtering and drying to obtain the functional monomer.
(2) The second reactor was purged with nitrogen, and 0.5mol of acrylamide, 0.14mol of a functional monomer, 0.08mol of 3-methyl cinnamic acid, 4.5g of potassium dihydrogen phosphate, and 240g of deionized water were added and stirred to obtain a mixture solution, and the pH was adjusted to 7-8 with a sodium hydroxide solution.
(3) 14.2G of initiator, namely 8wt% of potassium persulfate and 3wt% of sodium bisulphite mixed solution, is dropwise added into the second reactor, the viscosity of the liquid in the reactor is gradually increased, stirring is continued for 15min, heating is carried out to 55 ℃, the temperature is kept for 40min, the pH is regulated to 7-7.5 by sodium hydroxide solution, and the temperature is reduced to below 40 ℃.
(4) Granulating the mixed solution to obtain the polyacrylamide for improving the recovery ratio of the product.
Example 4
(1) Preparation of functional monomers: adding 0.11mol of 5-amino-4-hydroxy-1, 3-benzene disulfonic acid, 300g of methanol and 0.1mol of 1, 4-dibromo-2-butene into a first reactor, introducing nitrogen, replacing air in the reactor, adjusting the pH to 8-9 by using a sodium hydroxide solution, heating to 40 ℃, keeping the temperature for 28min, keeping the pH to 6-7 by using the sodium hydroxide solution, adding 0.095mol of 4- (trifluoromethoxy) benzyl amine, heating to 46 ℃, keeping the temperature for 40min, keeping the pH to 6-7 by using the sodium hydroxide solution, distilling 188g of methanol under reduced pressure, adding 403g of deionized water, adjusting the pH to 1-2 by using hydrochloric acid, cooling to below 10 ℃, filtering and drying to obtain a functional monomer.
(2) The second reactor was purged with nitrogen, and 0.5mol of acrylamide, 0.15mol of a functional monomer, 0.07mol of 3-methyl cinnamic acid, 5g of potassium dihydrogen phosphate, and 252g of deionized water were added and stirred to obtain a mixture solution, and the pH was adjusted to 7-8 with a sodium hydroxide solution.
(3) And (3) dropwise adding 10.3g of an initiator into the second reactor, wherein the initiator is a mixed solution of 10wt% of sodium persulfate and 4wt% of sodium bisulphite, the viscosity of the liquid in the reactor is gradually increased, stirring is continued for 12min, heating to 58 ℃, reacting for 40min while keeping the temperature, regulating the pH to 7-7.5 by using a sodium hydroxide solution, and cooling to below 40 ℃.
(4) Granulating the mixed solution to obtain the polyacrylamide for improving the recovery ratio of the product.
Example 5
(1) Preparation of functional monomers: adding 0.095mol of 5-amino-4-hydroxy-1, 3-benzene disulfonic acid, 252g of methanol and 0.1mol of 1, 4-dibromo-2-butene into a first reactor, introducing nitrogen, replacing air in the reactor, adjusting pH to 8-9 by using sodium hydroxide solution, heating to 50 ℃, keeping the temperature for 22min, keeping pH to 6-7 by using sodium hydroxide solution, adding 0.11mol of 4- (trifluoromethoxy) benzyl amine, heating to 48 ℃, keeping the temperature for 38min, keeping pH to 6-7 by using sodium hydroxide solution, distilling 143g of methanol under reduced pressure, adding 424g of deionized water, adjusting pH to 1-2 by using hydrochloric acid, cooling to below 10 ℃, filtering and drying to obtain functional monomers.
(2) The second reactor was purged with nitrogen, and 0.5mol of acrylamide, 0.17mol of a functional monomer, 0.06mol of 3-methyl cinnamic acid, 5.5g of potassium dihydrogen phosphate, and 228g of deionized water were added and stirred to obtain a mixture solution, and the pH was adjusted to 7-8 with a sodium hydroxide solution.
(3) 12.4G of initiator, which is a mixed solution of 9wt% sodium persulfate and 3.5wt% sodium bisulfite, is dripped into the second reactor, the viscosity of the liquid in the reactor is gradually increased, stirring is continued for 15min, heating is carried out to 58 ℃, the temperature is kept for 55min, the pH is regulated to 7-7.5 by sodium hydroxide solution, and the temperature is reduced to below 40 ℃.
(4) Granulating the mixed solution to obtain the polyacrylamide for improving the recovery ratio of the product.
Example 6
(1) Preparation of functional monomers: adding 0.105mol of 5-amino-4-hydroxy-1, 3-benzene disulfonic acid, 280g of methanol and 0.1mol of 1, 4-dibromo-2-butene into a first reactor, introducing nitrogen, replacing air in the reactor, adjusting the pH to 8-9 by using sodium hydroxide solution, heating to 44 ℃, keeping the temperature for 24min, keeping the pH to 6-7 by using sodium hydroxide solution, adding 0.1mol of 4- (trifluoromethoxy) benzyl amine, heating to 44 ℃, keeping the temperature for 34min, keeping the pH to 6-7 by using sodium hydroxide solution, distilling off 168g of methanol under reduced pressure, adding 376g of deionized water, adjusting the pH to 1-2 by using hydrochloric acid, cooling to below 10 ℃, filtering and drying to obtain the functional monomer.
(2) The second reactor was purged with nitrogen, and 0.5mol of acrylamide, 0.19mol of a functional monomer, 0.06mol of 3-methyl cinnamic acid, 6.4g of potassium dihydrogen phosphate, 235g of deionized water were added and stirred to obtain a mixture solution, and the pH was adjusted to 7-8 with a sodium hydroxide solution.
(3) And (3) dropwise adding 10.1g of an initiator into the second reactor, wherein the initiator is a mixed solution of 8wt% of ammonium persulfate and 3.5wt% of sodium bisulfite, the viscosity of the liquid in the reactor is gradually increased, stirring is continued for 18min, heating to 56 ℃, preserving heat and reacting for 40min, regulating the pH to 7-7.5 by using a sodium hydroxide solution, and cooling to below 40 ℃.
(4) Granulating the mixed solution to obtain the polyacrylamide for improving the recovery ratio of the product.
Example 7
(1) Preparation of functional monomers: adding 0.1mol of 5-amino-4-hydroxy-1, 3-benzene disulfonic acid, 260g of methanol and 0.1mol of 1, 4-dibromo-2-butene into a first reactor, introducing nitrogen, replacing air in the reactor, adjusting the pH to 8-9 by using sodium hydroxide solution, heating to 50 ℃, keeping the temperature for 20min, keeping the pH to 6-7 by using sodium hydroxide solution, adding 0.105mol of 4- (trifluoromethoxy) benzyl amine, heating to 45 ℃, keeping the temperature for 60min, keeping the pH to 6-7 by using sodium hydroxide solution, distilling off 150g of methanol under reduced pressure, adding 358g of deionized water, adjusting the pH to 1-2 by using hydrochloric acid, cooling to below 10 ℃, filtering and drying to obtain the functional monomer.
(2) The second reactor was purged with nitrogen, and 0.5mol of acrylamide, 0.2mol of a functional monomer, 0.05mol of 3-methyl cinnamic acid, 7.1g of potassium dihydrogen phosphate, 244g of deionized water were added and stirred to obtain a mixture solution, and the pH was adjusted to 7-8 with a sodium hydroxide solution.
(3) 11.1G of initiator, namely 9wt% ammonium persulfate and 3wt% sodium bisulphite mixed solution, is dropwise added into the second reactor, the viscosity of the liquid in the reactor is gradually increased, the stirring is continued for 15min, the heating temperature is increased to 55 ℃, the heat preservation reaction is carried out for 42min, the pH value is regulated to 7-7.5 by sodium hydroxide solution, and the temperature is reduced to below 40 ℃.
(4) Granulating the mixed solution to obtain the polyacrylamide for improving the recovery ratio of the product.
Example 8 apparent viscosity test
The polyacrylamide for enhanced recovery of the present invention (examples 1 to 7) was prepared as a 1500mg/L concentration solution with tap water, and the apparent viscosity/. Mu. 0 was measured with a Hark rheometer at 50 ℃. PAM for oil displacement by the Ministry of victory petrochemical Co was used as a comparative sample, and the test results are shown in Table 1.
As can be seen from table 1: the apparent viscosity of the polyacrylamide for improving recovery ratio (examples 1-7) is not lower than 60mPa.s and reaches 70mPa.s at the concentration of 1500mg/L (example 2); whereas the apparent viscosity of PAM for displacement of reservoir oil of comparative example victory petrochemical Co., ltd is 40mPa.s, which is significantly lower than that of the present invention.
Example 9 shear resistance test
The sample in example 8 was continuously sheared at 50℃for 2 hours under 170S -, and the apparent viscosity/. Mu. 1 was measured to calculate the viscosity retention/. Eta. 1. PAM for oil displacement by the Ministry of victory petrochemical Co was used as a comparative sample, and the test results are shown in Table 1.
As can be seen from table 1: the polyacrylamide for improving the recovery ratio (examples 1-7) is continuously sheared for 2 hours at 50 ℃ and 170S -, and the viscosity retention rate is not lower than 95% and reaches 97.1% at most (examples 2 and 3); and the viscosity retention rate of PAM for oil displacement of comparative victory petrochemical Co., ltd is 77.5%, which is obviously lower than that of the present invention.
EXAMPLE 10 determination of viscosity reducing Effect
The sample of example 8 was preheated to 50℃and dehydrated crude oil (preheated to 50℃with a viscosity of 5500 mPa.s) at a station associated with the victory oilfield in a weight ratio of 1:1, fully stirring, testing the viscosity mu 2, and calculating the viscosity reduction rate eta 2. PAM for oil displacement by the Ministry of victory petrochemical Co was used as a comparative sample, and the test results are shown in Table 1.
TABLE 1 apparent viscosity, shear resistance, viscosity reduction test results
As can be seen from table 1: the polyacrylamide for improving recovery ratio (examples 1-7) has a viscosity reduction rate of more than 98.4 percent and up to 98.58 percent for crude oil with 5500 mPa.s when the concentration is 1500mg/L (examples 6 and 7); and PAM for oil displacement of comparative victory petrochemical industry Co., ltd is not layered, and the viscosity reduction effect is not obvious.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further. Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. The preparation method of the polyacrylamide for improving the recovery ratio is characterized by comprising the following steps of:
(1) Adding 5-amino-4-hydroxy-1, 3-benzene disulfonic acid, methanol and 1, 4-dibromo-2-butene into a first reactor, introducing nitrogen, replacing air in the reactor, adjusting the pH value to 8-9 by using sodium hydroxide solution, heating to 40-50 ℃, keeping the temperature for reaction for 20-30min, keeping the pH value to 6-7 by using sodium hydroxide solution, adding 4- (trifluoromethoxy) benzyl amine, heating to 40-50 ℃, keeping the temperature for reaction for 30-60min, keeping the pH value to 6-7 by using sodium hydroxide solution, distilling off part of methanol under reduced pressure, adding deionized water, adjusting the pH value to 1-2 by using hydrochloric acid, cooling to below 10 ℃, filtering and drying to obtain a functional monomer;
(2) Introducing nitrogen into the second reactor, adding acrylamide, functional monomers, 3-methyl cinnamic acid, potassium dihydrogen phosphate and deionized water, stirring to obtain a mixture solution, and regulating the pH value to 7-8 by using a sodium hydroxide solution;
(3) Dropwise adding an initiator into the second reactor, gradually increasing the viscosity of the liquid in the reactor, continuously stirring for 10-20min, heating to 50-60 ℃, keeping the temperature for 30-60min for reaction, adjusting the pH to 7-7.5 by using a sodium hydroxide solution, and cooling to below 40 ℃;
(4) Granulating the mixed solution to obtain the polyacrylamide for improving the recovery ratio of the product.
2. The method for producing polyacrylamide for enhanced oil recovery according to claim 1, wherein in the step (1), the 5-amino-4-hydroxy-1, 3-benzenedisulfonic acid and 4- (trifluoromethoxy) benzyl amine are used in an amount of 0.8 to 1.2 parts by mole and 0.8 to 1.2 parts by mole, respectively, based on 1 part by mole of 1, 4-dibromo-2-butene.
3. The method for preparing polyacrylamide for improving recovery efficiency according to claim 1, wherein in the step (1), the mass ratio of the methanol to the 1, 4-dibromo-2-butene is 10-15:1.
4. The method for producing polyacrylamide for enhanced oil recovery according to claim 1, wherein in the step (1), the partial methanol is 1/2 to 2/3 of the total methanol mass.
5. The method for preparing polyacrylamide for improving recovery ratio according to claim 1, wherein in the step (2), the molar ratio of the functional monomer, 3-methyl cinnamic acid and acrylamide is 0.2-0.4:0.1-0.2:1.
6. The method for preparing the polyacrylamide for improving the recovery ratio according to claim 1, wherein in the step (2), the mass ratio of the monopotassium phosphate, the deionized water and the acrylamide is 0.1-0.2:6-8:1.
7. The method for preparing polyacrylamide for improving recovery ratio according to claim 1, wherein in the step (3), the initiator is a mixed solution of persulfate and sodium bisulfite, wherein the concentration of persulfate is 8-10wt%, the concentration of sodium bisulfite is 3-4wt%, and the weight ratio of the initiator to acrylamide is 0.2-0.4:1.
8. The method for preparing polyacrylamide for improving recovery efficiency according to claim 7, wherein the persulfate is one of potassium persulfate, ammonium persulfate and sodium persulfate.
9. The polyacrylamide for improving the recovery ratio is characterized by comprising the following molecular structural formula:
Wherein:
m＝50000-500000；
n＝10000-200000；
p＝5000-100000。
10. the enhanced oil recovery polyacrylamide of claim 9 wherein the polyacrylamide has a viscosity average molecular weight of 25000000-30000000.
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