CN116102677B - Temperature-resistant acid thickener, and preparation method and application thereof - Google Patents
Temperature-resistant acid thickener, and preparation method and application thereof Download PDFInfo
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- CN116102677B CN116102677B CN202310353554.9A CN202310353554A CN116102677B CN 116102677 B CN116102677 B CN 116102677B CN 202310353554 A CN202310353554 A CN 202310353554A CN 116102677 B CN116102677 B CN 116102677B
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- 239000002253 acid Substances 0.000 title claims abstract description 109
- 239000002562 thickening agent Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 29
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 26
- IGVNJALYNQVQIT-UHFFFAOYSA-N tert-butyl 2-bromo-2-methylpropanoate Chemical compound CC(C)(C)OC(=O)C(C)(C)Br IGVNJALYNQVQIT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 31
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000084 colloidal system Substances 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 15
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 6
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 6
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical group C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 5
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 claims description 5
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- CRGOPMLUWCMMCK-UHFFFAOYSA-M benzyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)CC1=CC=CC=C1 CRGOPMLUWCMMCK-UHFFFAOYSA-M 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- NFUDTVOYLQNLPF-UHFFFAOYSA-M trimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCCC[N+](C)(C)C NFUDTVOYLQNLPF-UHFFFAOYSA-M 0.000 claims description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims 2
- 238000010008 shearing Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 35
- 239000000243 solution Substances 0.000 description 28
- 230000001376 precipitating effect Effects 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000843 powder Substances 0.000 description 12
- XSHISXQEKIKSGC-UHFFFAOYSA-N 2-aminoethyl 2-methylprop-2-enoate;hydron;chloride Chemical group Cl.CC(=C)C(=O)OCCN XSHISXQEKIKSGC-UHFFFAOYSA-N 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000000034 method Methods 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 3
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 3
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 3
- JPZYXGPCHFZBHO-UHFFFAOYSA-N 1-aminopentadecane Chemical compound CCCCCCCCCCCCCCCN JPZYXGPCHFZBHO-UHFFFAOYSA-N 0.000 description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 2
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- KVFFVDVAFFSIIL-UHFFFAOYSA-M dimethyl-(3-methyl-2-oxobut-3-enyl)-propylazanium;chloride Chemical compound [Cl-].CCC[N+](C)(C)CC(=O)C(C)=C KVFFVDVAFFSIIL-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000012688 inverse emulsion polymerization Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 methacryloylpropyl trimethylammonium ammonium chloride Chemical compound 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OIFLLGNCLZLPAF-UHFFFAOYSA-M trimethyl-(5-methyl-4-oxohex-5-enyl)azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)CCC[N+](C)(C)C OIFLLGNCLZLPAF-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/725—Compositions containing polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a temperature-resistant acid thickener and a preparation method and application thereof, wherein the acid thickener comprises, by weight, 50-100 parts of acrylamide monomers, 150-300 parts of ammonium chloride monomers, 10-20 parts of long-chain alkylamines, 20-150 parts of functional monomers, 10-15 parts of tert-butyl 2-bromoisobutyrate, 0.1-1 part of chain extenders, 0.2-0.5 part of initiators and 300-450 parts of water. According to the invention, the functional monomer with two carbon-carbon double bonds is introduced, the functional monomer and the acrylamide monomer containing the carbon-carbon double bonds generate a primary chain with free double bonds through copolymerization, the free double bonds are further polymerized to generate a branching effect and form a star-shaped branched polymer, and when the star-shaped branched polymer is subjected to high-speed shearing and high-temperature degradation, a large number of branching points exist, chain breakage can be generated to form a shorter linear molecular chain, and a secondary branching structure, so that the polymer has better temperature resistance and shearing resistance.
Description
Technical Field
The invention relates to the technical field of oil and gas field exploitation, in particular to a temperature-resistant acid thickener, a preparation method and application thereof.
Background
Acidification is an oil and gas well production increasing technology applied earlier, and the main principle is that acid liquor is utilized to erode acid-soluble pollutants and minerals in the stratum, and acid erosion reaction products are discharged out of the stratum along with residual acid or oil and gas.
In the acid fracturing reformation of a reservoir, the acid thickener is mainly used as an acid corrosion inhibitor to delay the reaction speed of acid rock, so that the aim of deep penetration is fulfilled, the safe and efficient construction of acid fracturing is ensured, and the basic requirements of compatibility with the reservoir and low damage are met. The good acid thickener has the characteristics of strong adhesion performance, good temperature resistance and the like.
The thickener used in China generally has the problem of poor temperature resistance and salt resistance, and in order to solve the technical problems, the following technical schemes are proposed in the prior art, as described in references 1 and 2.
Reference 1: chinese patent document with publication number CN 113563505B
Reference 1 describes a temperature-resistant acid-resistant salt-resistant acid thickener and a preparation method thereof, and belongs to the technical field of oil and gas field exploitation. The method comprises the following steps: (1) Dissolving a nonionic water-soluble monomer and a cationic monomer in water to obtain a first mixed solution; (2) Dissolving a salt-resistant monomer, a temperature-resistant monomer, a hydrophobic monomer, a penetrating agent and a cosolvent in the first mixed solution to obtain a second mixed solution; (3) Dissolving a chain extender in the second mixed solution to obtain a third mixed solution; (4) Introducing nitrogen into the third mixed solution to remove oxygen, and then sequentially adding an azo initiator, a complexing agent, a molecular weight regulator and a redox initiator to initiate polymerization reaction to obtain polymerized gel; (5) And drying the polymerized gel, and grinding to obtain the temperature-resistant acid-resistant salt-resistant acid thickener. The acid thickener prepared by the invention has the characteristics of strong viscosity increasing capability, small shearing influence, stable acid resistance, good temperature resistance, small secondary damage to stratum and the like.
Reference 2: chinese patent document with publication number CN 114085315A
Reference 2 describes a high-temperature-resistant emulsion type acid thickener and a preparation method thereof, belongs to the technical field of oil and gas field exploitation, and solves the technical problems that the powder type acid thickener and the conventional emulsion type acid thickener cannot meet the construction requirements of acidification and acid fracturing of a deep well reservoir at a high temperature of 200-220 ℃ at the present stage. By adopting the method of inverse emulsion polymerization, two cationic monomers are introduced in the polymerization process, so that the prepared high-temperature emulsion type acid thickener has excellent acid solubility, can be quickly thickened and thickened after being dissolved in acid, and is convenient and quick to construct on site. By introducing the rigid molecular group, the temperature resistance of the acid thickener is improved, and the acid thickener can exert good acidification effect in a reservoir at 200-220 ℃ and is suitable for acidification of a high-temperature deep well and field construction of acid fracturing.
The acid thickener having high temperature resistance is described in references 1 and 2, however, the technical method capable of improving the temperature resistance and the shear resistance of the acid thickener is not limited to the above two, and based on this, the applicant has proposed an acid thickener different from the prior art, which also has excellent temperature resistance and shear resistance.
Disclosure of Invention
The invention aims to provide an acid thickener with a technical thought different from that of the prior art, which has excellent temperature resistance and shearing resistance and delayed crosslinking effect, and simultaneously provides a preparation method of the acid thickener and application of the acid thickener in preparing an oil-gas well modified thickening acid.
The invention solves the technical problems, and adopts the following technical scheme: the temperature-resistant acid thickener comprises, by weight, 50-100 parts of acrylamide monomers, 150-300 parts of ammonium chloride monomers, 10-20 parts of long-chain alkylamines, 20-150 parts of functional monomers, 10-15 parts of tert-butyl 2-bromoisobutyrate, 0.1-1 part of chain extenders, 0.2-0.5 part of initiators and 300-450 parts of water.
As a further optimization of the temperature-resistant acid thickener: the acrylamide monomer is acrylamide, methacrylamide, N-dimethylacrylamide, N-methylenebisacrylamide or N-methylolacrylamide.
As a further optimization of the temperature-resistant acid thickener: the ammonium chloride monomer is methacryloyloxyethyl ammonium chloride, diallyl dimethyl ammonium chloride, methacryloyloxyethyl dimethyl benzyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride or methacryloylpropyl trimethyl ammonium chloride.
As a further optimization of the temperature-resistant acid thickener: the functional monomer is divinylbenzene or triethylene glycol dimethacrylate.
As a further optimization of the temperature-resistant acid thickener: the chain extender is polyethylene glycol dimethacrylate or polypropylene glycol diacrylate.
As a further optimization of the temperature-resistant acid thickener: the initiator is azo initiator or ammonium persulfate.
As a further optimization of the temperature-resistant acid thickener: the long-chain alkylamine is long-chain alkane with amino at the chain end, and the structural general formula is C nH2n+1-NH2, wherein n is a positive integer in 11-16.
The preparation method of the temperature-resistant acid thickener comprises the following steps:
s1, taking an acrylamide monomer, an ammonium chloride monomer, a functional monomer, long-chain alkylamine, a chain extender, an initiator and water according to the proportion of the raw materials for standby;
S2, adding long-chain alkylamine, partial acrylamide monomer, functional monomer and tert-butyl 2-bromoisobutyrate into tetrahydrofuran solvent, uniformly mixing, introducing nitrogen to remove oxygen, slowly heating to 60 ℃ to react for 0.5-1h, adding ammonium chloride monomer, chain extender, water and residual acrylamide monomer, continuously introducing nitrogen to remove oxygen, continuously heating to 80-90 ℃ and adding initiator to react for 2-8h to obtain polymer colloid;
and S3, granulating the polymer colloid to obtain the acid thickener.
The preparation method of the temperature-resistant acid thickener is further optimized: the slow temperature rise to 60 ℃ is specifically as follows: heating to 60 ℃ within 30-60 min.
The application of the temperature-resistant acid thickener or the temperature-resistant acid thickener prepared by the method in preparing the oil-gas well modified thickener is provided.
The invention has the following beneficial effects: according to the invention, the functional monomer with two carbon-carbon double bonds is introduced, the functional monomer and the acrylamide monomer containing the carbon-carbon double bonds generate a primary chain with free double bonds through copolymerization, the free double bonds are further polymerized to generate a branching effect and form a star-shaped branched polymer, and when the star-shaped branched polymer is subjected to high-speed shearing and high-temperature degradation, a large number of branching points exist, chain breakage can be generated to form a shorter linear molecular chain, and a secondary branching structure, so that the polymer has better temperature resistance and shearing resistance. Meanwhile, long-chain alkylamine is introduced, long-chain groups of the long-chain alkylamine can form interpenetration with a branched polymerization structure in the polymerization process, so that a secondary branched structure with a more stable structure can be formed after chain breakage of the polymer at high temperature and high-speed shearing, and the temperature resistance and the shearing resistance of the polymer are further improved.
Description of the embodiments
For a better understanding of the present invention, the following examples are set forth to illustrate, but are not to be construed as limiting the invention.
The temperature-resistant acid thickener comprises, by weight, 50-100 parts of acrylamide monomers, 150-300 parts of ammonium chloride monomers, 10-20 parts of long-chain alkylamines, 20-150 parts of functional monomers, 10-15 parts of tert-butyl 2-bromoisobutyrate, 0.1-1 part of chain extenders, 0.2-0.5 part of initiators and 300-450 parts of water.
The acrylamide monomer is acrylamide, methacrylamide, N-dimethylacrylamide, N-methylenebisacrylamide or N-methylolacrylamide.
The ammonium chloride monomer is methacryloxyethyl ammonium chloride, diallyl dimethyl ammonium chloride, methacryloxyethyl dimethyl benzyl ammonium chloride, methacryloxyethyl trimethyl ammonium chloride or methacryloxypropyl trimethyl ammonium chloride.
The functional monomer is divinylbenzene or triethylene glycol dimethacrylate; the chain extender is polyethylene glycol dimethacrylate or polypropylene glycol diacrylate; the initiator is azo initiator or ammonium persulfate.
The long-chain alkylamine is a long-chain alkane with an amino group at the chain end, and the structural general formula is C nH2n+1-NH2, wherein n is a positive integer in 11-16.
The preparation method of the temperature-resistant acid thickener comprises the following steps:
S1, taking an acrylamide monomer, an ammonium chloride monomer, a functional monomer, long-chain alkylamine, a chain extender, an initiator and water according to the proportion of the raw materials for standby.
S2, adding long-chain alkylamine, partial acrylamide monomer (1/5-1/2), functional monomer and tert-butyl 2-bromoisobutyrate into tetrahydrofuran solvent, uniformly mixing, introducing nitrogen to remove oxygen, heating to 60 ℃ within 30-60min, reacting for 0.5-1h, then adding ammonium chloride monomer, chain extender, water and residual acrylamide monomer, continuously introducing nitrogen to remove oxygen, continuously heating to 80-90 ℃ and adding initiator to react for 2-8h, thus obtaining polymer colloid.
And S3, granulating the polymer colloid to obtain the acid thickener.
Example 1]
The preparation method of the temperature-resistant acid thickener comprises the following steps:
S1, taking the following raw materials in parts by weight for standby: 100g of acrylamide, 200g of methacryloxyethyl ammonium chloride, 15g of hexadecylamine, 100g of divinylbenzene, 10g of tert-butyl 2-bromoisobutyrate, 0.5g of polyethylene glycol dimethacrylate, 0.5g of ammonium persulfate and 400g of water.
S2, adding hexadecylamine, 40g acrylamide, divinylbenzene and tert-butyl 2-bromoisobutyrate into tetrahydrofuran solvent, uniformly mixing, introducing nitrogen to remove oxygen, heating to 60 ℃ within 50min, reacting for 50min, then adding methacryloyloxyethyl ammonium chloride, polyethylene glycol dimethacrylate, water and the rest acrylamide, continuously introducing nitrogen to remove oxygen, continuously heating to 85 ℃ and adding ammonium persulfate to react for 6h to obtain the polymer colloid.
S3, precipitating the polymer colloid with absolute ethyl alcohol, filtering, dissolving with a small amount of water, precipitating with ethanol, repeatedly precipitating for 3 times, soaking the precipitated polymer in absolute ethyl alcohol to harden, grinding, and vacuum drying for 48 hours to obtain the acid thickener powder.
Example 2]
The preparation method of the temperature-resistant acid thickener comprises the following steps:
S1, taking the following raw materials in parts by weight for standby: 80g of methacrylamide, 300g of diallyl dimethyl ammonium chloride, 20g of dodecylamine, 50g of triethylene glycol dimethacrylate, 15g of tert-butyl 2-bromoisobutyrate, 1g of polypropylene glycol diacrylate, 0.2g of azobisisobutyronitrile and 350g of water.
S2, adding dodecylamine, 30g of methacrylamide, triethylene glycol dimethacrylate and tert-butyl 2-bromoisobutyrate into tetrahydrofuran solvent, uniformly mixing, introducing nitrogen to remove oxygen, heating to 60 ℃ within 30min, reacting for 0.5h, then adding diallyl dimethyl ammonium chloride, polypropylene glycol diacrylate, water and the rest of methacrylamide, continuously introducing nitrogen to remove oxygen, continuously heating to 80 ℃ and adding azobisisobutyronitrile to react for 2-8h, thus obtaining the polymer colloid.
S3, precipitating the polymer colloid with absolute ethyl alcohol, filtering, dissolving with a small amount of water, precipitating with ethanol, repeatedly precipitating for 3 times, soaking the precipitated polymer in absolute ethyl alcohol to harden, grinding, and vacuum drying for 48 hours to obtain the acid thickener powder.
Example 3]
The preparation method of the temperature-resistant acid thickener comprises the following steps:
S1, taking the following raw materials in parts by weight for standby: 50g of N, N-dimethylacrylamide, 150g of methacryloxyethyl dimethyl benzyl ammonium chloride, 10g of tetradecylamine, 20g of divinylbenzene, 12g of tert-butyl 2-bromoisobutyrate, 0.8g of polyethylene glycol dimethacrylate, 0.5g of ammonium persulfate and 300-450g of water.
S2, adding tetradecylamine, 20g of N, N-dimethylacrylamide, divinylbenzene and tert-butyl 2-bromoisobutyrate into tetrahydrofuran solvent, uniformly mixing, introducing nitrogen to remove oxygen, heating to 60 ℃ within 60min, reacting for 1h, then adding methacryloyloxyethyl dimethyl benzyl ammonium chloride, polyethylene glycol dimethacrylate, water and the rest of N, N-dimethylacrylamide, continuously introducing nitrogen to remove oxygen, continuously heating to 90 ℃ and adding ammonium persulfate to react for 2-8h to obtain polymer colloid;
s3, precipitating the polymer colloid with absolute ethyl alcohol, filtering, dissolving with a small amount of water, precipitating with ethanol, repeatedly precipitating for 3 times, soaking the precipitated polymer in absolute ethyl alcohol to harden, grinding, and vacuum drying for 48 hours to obtain the acid thickener powder.
Example 4]
The preparation method of the temperature-resistant acid thickener comprises the following steps:
S1, taking the following raw materials in parts by weight for standby: 100g of N, N-methylene bisacrylamide, 200g of methacryloyloxyethyl trimethyl ammonium chloride, 15g of undecylamine, 100g of triethylene glycol dimethacrylate, 10g of tert-butyl 2-bromoisobutyrate, 0.5g of polyethylene glycol dimethacrylate, 0.5g of ammonium persulfate and 400g of water.
S2, adding undecylamine, 40g of N, N-methylene bisacrylamide, triethylene glycol dimethacrylate and tert-butyl 2-bromoisobutyrate into tetrahydrofuran solvent, uniformly mixing, introducing nitrogen to remove oxygen, heating to 60 ℃ within 50min, reacting for 50min, then adding methacryloyloxyethyl trimethyl ammonium chloride, polyethylene glycol dimethacrylate, water and the rest of N, N-methylene bisacrylamide, continuously introducing nitrogen to remove oxygen, continuously heating to 85 ℃ and adding ammonium persulfate to react for 6h to obtain polymer colloid.
S3, precipitating the polymer colloid with absolute ethyl alcohol, filtering, dissolving with a small amount of water, precipitating with ethanol, repeatedly precipitating for 3 times, soaking the precipitated polymer in absolute ethyl alcohol to harden, grinding, and vacuum drying for 48 hours to obtain the acid thickener powder.
Example 5 ]
The preparation method of the temperature-resistant acid thickener comprises the following steps:
s1, taking the following raw materials in parts by weight for standby: 50g of N-methylolacrylamide, 150g of methacryloyl propyl trimethyl ammonium chloride, 10g of pentadecyl amine, 20g of divinylbenzene, 12g of tert-butyl 2-bromoisobutyrate, 0.8g of polyethylene glycol dimethacrylate, 0.5g of ammonium persulfate and 300-450g of water.
S2, adding pentadecylamine, 20g of N-methylolacrylamide, divinylbenzene and tert-butyl 2-bromoisobutyrate into a tetrahydrofuran solvent, uniformly mixing, introducing nitrogen to remove oxygen, heating to 60 ℃ within 60min, reacting for 1h, then adding methacryloylpropyl trimethylammonium ammonium chloride, polyethylene glycol dimethacrylate, water and the rest N-methylolacrylamide, continuously introducing nitrogen to remove oxygen, continuously heating to 90 ℃ and adding ammonium persulfate to react for 2-8h to obtain polymer colloid;
s3, precipitating the polymer colloid with absolute ethyl alcohol, filtering, dissolving with a small amount of water, precipitating with ethanol, repeatedly precipitating for 3 times, soaking the precipitated polymer in absolute ethyl alcohol to harden, grinding, and vacuum drying for 48 hours to obtain the acid thickener powder.
< Examples 6 to 10>
3G of the acid thickener powder prepared in the example 1-5 is added into 100g of hydrochloric acid with the concentration of 20% and stirred until the thickener powder is dissolved, and then the thickener acid <6-10> is prepared.
Comparative example 1]
An acid thickener is prepared by the following steps:
S1, taking the following raw materials in parts by weight for standby: 100g of acrylamide, 200g of methacryloyloxyethyl ammonium chloride, 15g of hexadecylamine, 0.5g of polyethylene glycol dimethacrylate, 0.5g of ammonium persulfate and 400g of water.
S2, adding hexadecylamine and acrylamide into tetrahydrofuran solvent, uniformly mixing, then adding methacryloyloxyethyl ammonium chloride, polyethylene glycol dimethacrylate and water, introducing nitrogen for deoxidization, continuously heating to 85 ℃ and adding ammonium persulfate for reaction for 6 hours to obtain polymer colloid.
S3, precipitating the polymer colloid with absolute ethyl alcohol, filtering, dissolving with a small amount of water, precipitating with ethanol, repeatedly precipitating for 3 times, soaking the precipitated polymer in absolute ethyl alcohol to harden, grinding, and vacuum drying for 48 hours to obtain the acid thickener powder.
3G of the prepared acid thickener powder is added into 100g of hydrochloric acid with the concentration of 20 percent, and the mixture is stirred until the solution is dissolved, thus obtaining the thickener acid.
Comparative example 2]
An acid thickener is prepared by the following steps:
S1, taking the following raw materials in parts by weight for standby: 100g of acrylamide, 200g of methacryloyloxyethyl ammonium chloride, 100g of divinylbenzene, 10g of tert-butyl 2-bromoisobutyrate, 0.5g of polyethylene glycol dimethacrylate, 0.5g of ammonium persulfate and 400g of water.
S2, adding 40g of acrylamide, divinylbenzene and tert-butyl 2-bromoisobutyrate into a tetrahydrofuran solvent, uniformly mixing, introducing nitrogen to remove oxygen, heating to 60 ℃ within 50min, reacting for 50min, then adding methacryloyloxyethyl ammonium chloride, polyethylene glycol dimethacrylate, water and the rest of acrylamide, continuously introducing nitrogen to remove oxygen, continuously heating to 85 ℃ and adding ammonium persulfate to react for 6h to obtain the polymer colloid.
S3, precipitating the polymer colloid with absolute ethyl alcohol, filtering, dissolving with a small amount of water, precipitating with ethanol, repeatedly precipitating for 3 times, soaking the precipitated polymer in absolute ethyl alcohol to harden, grinding, and vacuum drying for 48 hours to obtain the acid thickener powder.
3G of the prepared acid thickener powder is added into 100g of hydrochloric acid with the concentration of 20 percent, and the mixture is stirred until the solution is dissolved, thus obtaining the thickener acid.
< Temperature resistance Property >
Taking the acid solution prepared in the embodiment <5-10>, testing the apparent viscosity (mu 0) under the shearing condition 180S -1 at room temperature, then placing the acid solution in an oil bath, heating the acid solution to 120 ℃ at the constant temperature of 120 ℃ for 3 hours, cooling the acid solution to room temperature after the heating is finished, testing the apparent viscosity (mu 1) under the shearing condition 180S -1, then placing the acid solution in the oil bath, heating the acid solution to 160 ℃ at the constant temperature of 160 ℃ for 3 hours, cooling the acid solution to room temperature after the heating is finished, and testing the apparent viscosity (mu 2) under the shearing condition 180S -1. The apparent viscosity decrease rate of the acid solution was then calculated (decrease rate% = (μ 1-μ2）/μ1), the results are shown in the following table:
as can be seen from the above table, the acid solutions in examples 6 to 10 had an apparent viscosity decrease rate of about 16% after heating at 120℃for 3 hours, whereas the acid solution in comparative example 1 had an apparent viscosity decrease rate of 23.5% after heating at 120℃for 3 hours, whereas the acid solution in comparative example 2 had an apparent viscosity decrease rate of 27.5% after heating at 120℃for 3 hours. The acid solutions of examples 6 to 10 had an apparent viscosity decrease of about 20% after heating at 160℃for 3 hours, the acid solution of comparative example 1 had an apparent viscosity decrease of 25% after heating at 160℃for 3 hours, and the acid solution of comparative example 2 had an apparent viscosity decrease of 31.2% after heating at 160℃for 3 hours. The applicant believes that this is due to the fact that the absence of the functional monomer added to comparative example 1 results in poor temperature resistance of the final acid thickener, whereas the acid temperature resistance of comparative example 1 is superior to that of comparative example 2, since the introduction of long chain alkylamine has a weaker effect on temperature resistance than the introduction of the functional monomer.
< Shear resistance >
The acid solution prepared in the example <5-10> was heated to 160 ℃ in an oil bath and subjected to continuous shearing (2 h) under shearing conditions 180S -1, during which the apparent viscosity of the acid solution was measured every 30min, with the results shown in the following table:
As can be seen from the above table, the acid solution in examples 6 to 10 has an apparent viscosity value of about 71mpa S after shearing at 180S -1 for 30min, whereas the acid solution in comparative example 1 has an apparent viscosity value of 59.4mpa S after shearing at 180S -1 for 30min, whereas the acid solution in comparative example 2 has a lower viscosity value (50.7 mpa S) than comparative example 1 after shearing at 180S -1 for 30min after shearing at 180S -1 for 30 min. After continuing to shear for 120min, the apparent viscosity value of the acid solution in examples 6-10 was reduced to about 41mpa s, while the apparent viscosity value of the acid solution in comparative example 1 was reduced to 33.2mpa s after shearing for 120min, and the apparent viscosity value of the acid solution in comparative example 2 was reduced to 20.4mpa s after shearing for 120min, thus it was seen that the acid solution in comparative examples 1-2 had significantly lower shear resistance than the acid solution in examples 6-10, and that the acid solution in comparative example 2 had significantly lower shear resistance than the acid solution in comparative example 1. The applicant believes that this is due to the fact that the absence of the functional monomer added to comparative example 1 results in poor shear resistance of the final acid thickener, whereas the acid of comparative example 1 has better shear resistance than comparative example 2, since the introduction of long chain alkylamine has a weaker impact on the shear resistance than the introduction of the functional monomer.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (4)
1. A temperature-resistant acid thickener is characterized in that: the raw materials comprise, by weight, 50-100 parts of acrylamide monomers, 150-300 parts of ammonium chloride monomers, 10-20 parts of long-chain alkylamines, 20-150 parts of functional monomers, 10-15 parts of tert-butyl 2-bromoisobutyrate, 0.1-1 part of chain extenders, 0.2-0.5 part of initiators and 300-450 parts of water; the acrylamide monomer is acrylamide, methacrylamide, N-dimethylacrylamide, N-methylenebisacrylamide or N-methylolacrylamide; the ammonium chloride monomer is diallyl dimethyl ammonium chloride, methacryloxyethyl dimethyl benzyl ammonium chloride, methacryloxyethyl trimethyl ammonium chloride or methacryloxypropyl trimethyl ammonium chloride; the functional monomer is divinylbenzene or diethyleneglycol dimethacrylate, and the chain extender is polyethylene glycol dimethacrylate or polypropylene glycol diacrylate; the long-chain alkylamine is long-chain alkane with an amino group at the chain end, and the structural general formula is C nH2n+1-NH2, wherein n is a positive integer in 11-16;
The preparation method of the temperature-resistant acid thickener comprises the following steps:
s1, taking an acrylamide monomer, an ammonium chloride monomer, a functional monomer, long-chain alkylamine, a chain extender, an initiator and water according to the raw material ratio for standby;
s2, adding long-chain alkylamine, partial acrylamide monomer, functional monomer and tert-butyl 2-bromoisobutyrate into tetrahydrofuran solvent, uniformly mixing, introducing nitrogen to remove oxygen, slowly heating to 60 ℃ to react for 0.5-1h, adding ammonium chloride monomer, chain extender, water and residual acrylamide monomer, continuously introducing nitrogen to remove oxygen, heating to 80-90 ℃ and adding initiator to react for 2-8h to obtain polymer colloid;
and S3, granulating the polymer colloid to obtain the acid thickener.
2. The temperature resistant acid thickener of claim 1, wherein: the initiator is azo initiator or ammonium persulfate.
3. The temperature resistant acid thickener of claim 1, wherein: the slow temperature rise to 60 ℃ is specifically as follows: heating to 60 ℃ within 30-60 min.
4. Use of the temperature-resistant acid thickener according to any of claims 1 to 3 for preparing an oil and gas well modified thickener acid.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454708A (en) * | 2020-03-13 | 2020-07-28 | 山东滨州昱诚化工科技有限公司 | Preparation method of clean thickening agent for fracturing |
| CN112745454A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Thickener for high-temperature deep well acidification and preparation method thereof |
| CN113321764A (en) * | 2021-08-03 | 2021-08-31 | 山东诺尔生物科技有限公司 | Acid liquor thickener and preparation method and application thereof |
| CN113563505A (en) * | 2021-09-26 | 2021-10-29 | 山东诺尔生物科技有限公司 | Temperature-resistant acid-resistant salt-resistant acid thickener and preparation method thereof |
| CN114085315A (en) * | 2021-12-06 | 2022-02-25 | 陕西科技大学 | High-temperature-resistant emulsion type acid liquid thickener and preparation method thereof |
| WO2023005769A1 (en) * | 2021-07-30 | 2023-02-02 | 中国石油化工股份有限公司 | Polymer, thickening agent, and preparation method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745454A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Thickener for high-temperature deep well acidification and preparation method thereof |
| CN111454708A (en) * | 2020-03-13 | 2020-07-28 | 山东滨州昱诚化工科技有限公司 | Preparation method of clean thickening agent for fracturing |
| WO2023005769A1 (en) * | 2021-07-30 | 2023-02-02 | 中国石油化工股份有限公司 | Polymer, thickening agent, and preparation method therefor |
| CN113321764A (en) * | 2021-08-03 | 2021-08-31 | 山东诺尔生物科技有限公司 | Acid liquor thickener and preparation method and application thereof |
| CN113563505A (en) * | 2021-09-26 | 2021-10-29 | 山东诺尔生物科技有限公司 | Temperature-resistant acid-resistant salt-resistant acid thickener and preparation method thereof |
| CN114085315A (en) * | 2021-12-06 | 2022-02-25 | 陕西科技大学 | High-temperature-resistant emulsion type acid liquid thickener and preparation method thereof |
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