CN116333714B - Boric acid crosslinked thickener - Google Patents
Boric acid crosslinked thickener Download PDFInfo
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- CN116333714B CN116333714B CN202310359116.3A CN202310359116A CN116333714B CN 116333714 B CN116333714 B CN 116333714B CN 202310359116 A CN202310359116 A CN 202310359116A CN 116333714 B CN116333714 B CN 116333714B
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- thickener
- white oil
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- amine oxide
- boric acid
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- 239000002562 thickening agent Substances 0.000 title claims abstract description 74
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000004327 boric acid Substances 0.000 title claims abstract description 44
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 39
- 125000000129 anionic group Chemical group 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 238000012546 transfer Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 21
- -1 dodecyl dihydroxy ethyl Chemical group 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000000230 xanthan gum Substances 0.000 claims description 11
- 229920001285 xanthan gum Polymers 0.000 claims description 11
- 235000010493 xanthan gum Nutrition 0.000 claims description 11
- 229940082509 xanthan gum Drugs 0.000 claims description 11
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 10
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 10
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 10
- 229920000136 polysorbate Polymers 0.000 claims description 10
- 229910000278 bentonite Inorganic materials 0.000 claims description 8
- 229940092782 bentonite Drugs 0.000 claims description 8
- 239000000440 bentonite Substances 0.000 claims description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 8
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 8
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 5
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 5
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 5
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 3
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 3
- 229910000281 calcium bentonite Inorganic materials 0.000 claims description 3
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- 229910000280 sodium bentonite Inorganic materials 0.000 claims description 3
- 229940080314 sodium bentonite Drugs 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N monoethyl amine Natural products CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 4
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011435 rock Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 40
- 239000003921 oil Substances 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 24
- 238000004090 dissolution Methods 0.000 description 23
- 239000002245 particle Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 239000003431 cross linking reagent Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000003444 phase transfer catalyst Substances 0.000 description 8
- 239000013535 sea water Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 239000000779 smoke Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000001246 colloidal dispersion Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- JNGWKQJZIUZUPR-UHFFFAOYSA-N [3-(dodecanoylamino)propyl](hydroxy)dimethylammonium Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)[O-] JNGWKQJZIUZUPR-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229940026210 lauramidopropylamine oxide Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QKQSRIKBWKJGHW-UHFFFAOYSA-N morpholine;prop-2-enoic acid Chemical compound OC(=O)C=C.C1COCCN1 QKQSRIKBWKJGHW-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
- C09K8/64—Oil-based compositions
-
- 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
- C09K8/605—Compositions for stimulating production by acting on the underground formation containing biocides
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Colloid Chemistry (AREA)
Abstract
The invention discloses a boric acid crosslinked thickener. The thickener comprises the following components in parts by weight: 40-50 parts of white oil, 50-60 parts of anionic Polyacrylamide (PAM) powder, 2-5 parts of phase transfer auxiliary agent, 2-7 parts of thickener and 0.1-1.0 part of boric acid; the thickener provided by the invention is a single component and is simple to use, and the solution obtained by dissolving the thickener in water has high viscosity and is used for fracturing, rock stratum seam making and other purposes of oil and gas fields.
Description
Technical Field
The invention particularly relates to the technical field of oil and gas field development, in particular to a boric acid crosslinked thickener, which is suitable for the technical field of fracturing of low-permeability reservoirs of oil and gas fields.
Background
The thickener is a main component of the fracturing fluid, can obviously increase the viscosity of the system after being dissolved in water, is favorable for carrying more sand grains or ceramsite, and increases the pressurizing effect of the fracturing fluid. The industrially synthesized high molecular weight anionic Polyacrylamide (PAM) has wide source and high yield. Meanwhile, PAM solutions have high chemical stability and storage stability.
From the practical application point of view, the higher the viscosity of the thickener solution, the more sand or haydite is carried, the higher the pressure is generated, and the fracturing and seam making of the rock layer are facilitated. There are two general strategies for increasing the viscosity of thickener solutions: 1) The PAM molecular structure is modified by copolymerization. By means of copolymerization with acrylamide, a rigid hydrophilic monomer (such as sodium styrene sulfonate, morpholine acrylate and the like) is introduced into a PAM molecular chain, so that the strength of the molecular chain in the aqueous solution is increased, and the viscosity of the aqueous solution of the PAM copolymer is improved. 2) The colloidal dispersion gel (intramolecular cross-linking with metal ions) and the aggregation gel (intermolecular cross-linking with metal ions) of PAM are obtained by using the way of coordination between high-valence metal ions (chromium, zirconium, titanium, aluminum and the like) and carboxyl groups of PAM, and the obtained high-viscosity thickener solution is applied to crude oil exploitation. Because of the difference of the reactivity ratios of the comonomers, the copolymerization reaction formula and the corresponding process conditions need to be frequently adjusted according to the structure and the dosage of the comonomers, and the technical threshold for research and development and production is high and the difficulty is high. Compared with the copolymerization modification strategy, the method for adding the crosslinking agent after determining the type and the dosage of the crosslinking agent (high-valence metal ions) is simple and practical.
The mechanism of adopting high-valence metal ions as PAM cross-linking agents is that high-valence positive ions (such as Zr 4+、Cr3+、Al3+、Fe3+、Ti4+ and the like) are subjected to hydration, hydrolysis, hydroxyl bridging, coordination and other reactions in water in sequence. The method has the advantages that the method truly plays a role in that high-valence metal ions and carboxylic acid groups in PAM molecular chains undergo a coordination reaction (the last reaction step), the same metal ions can coordinate with a plurality of carboxylic acid groups, so that the crosslinking reaction in or among PAM molecules is counteracted, the viscosity of a thickener aqueous solution is obviously improved, and the purposes of sand carrying and pressurization are achieved. According to literature reports (Wang Jian, zhao Fulin, mechanism of crosslinking of high-valence metal ions with polyacrylamide, university of petroleum journal (natural science edition), 1992, 16, 32-39), crosslinking of high-valence metal ions with PAM is generally under low pH conditions (i.e., medium, strong acidic conditions). That is, the coordination between the carboxyl groups and the high valence ions in PAM can be achieved only by adjusting the aqueous solution of the thickener to an acidic condition. The aqueous solution of the thickener is pre-adjusted to low pH conditions, requiring the addition of a large amount of acid to the system. This has several disadvantages: 1) A large amount of acid is additionally added, so that material waste is caused; 2) The pH value of the system is low, the acidity is strong, and metal pipelines, drilling equipment and the like are corroded; 3) High-valence metal ions have high price and certain toxicity.
Disclosure of Invention
In order to solve the problems, the invention provides a boric acid crosslinked thickener. The invention takes boric acid (monobasic weak acid) as an external cross-linking agent of a thickener system, and after the boric acid is dissolved in water, the boric acid can produce stable complex with polyhydroxy compound, and the water-soluble polyhydroxy compound is cross-linked, so that the viscosity of the thickener aqueous solution is improved, the sand carrying performance of the thickener aqueous solution is improved, and the fracturing effect is improved.
In order to achieve the above object, the technical scheme of the present invention is as follows:
The boric acid crosslinked thickener comprises the following components in parts by weight:
wherein the thickener is at least one of hydroxymethyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose, xanthan gum, calcium bentonite, sodium bentonite and organic bentonite;
The thickener is prepared by the following method and comprises the following steps:
(1) Sequentially mixing white oil and a thickening agent, then adding a phase transfer auxiliary agent and anionic Polyacrylamide (PAM), sequentially dispersing in the white oil under stirring and at the temperature of between room temperature and 90 ℃ to prepare a mixed solution, and then cooling the mixed solution to the room temperature;
(2) Stirring and adding boric acid at room temperature, mixing, filtering, and packaging to obtain thickener.
Preferably, the anionic Polyacrylamide (PAM) is selected from one or more of the polymers (I) - (V),
And the average diameter of the anionic Polyacrylamide (PAM) is 80-120 mu m, the molecular weight is 1.5X10 7g/mol-2.8×107 g/mol, a, o and p are positive integers not less than 1, and m is n=1.5-3:1.
Preferably, the kinematic viscosity of the white oil is 2-18mm 2/s (40 ℃), and the white oil is at least one of white oil No. 3, white oil No. 5, white oil No. 7, white oil No.10 and white oil No. 15.
Preferably, the phase conversion aid is at least one of decane-dihydroxyethyl amine oxide, dodecyl-dihydroxyethyl amine oxide, tetradecyl-dihydroxyethyl amine oxide, hexadecyl-dihydroxyethyl amine oxide, octadecyl-dihydroxyethyl amine oxide, dodecylpropyl amine oxide, tetradecyl-amidopropyl amine oxide, hexadecyl-amidopropyl amine oxide, octadecyl-amidopropyl amine oxide, isomeric tridecyl polyoxyethylene ether, octadecyl-trimethyl ammonium chloride, hexadecyl-trimethyl ammonium chloride, tetradecyl-trimethyl ammonium chloride, dodecyl-trimethyl ammonium chloride, tween 20, tween 40, tween 65, tween 80, tween 81 or tween 85.
The invention provides a boric acid crosslinked thickener, wherein in the process of dissolving the thickener in water, electron-deficient boron atoms in boric acid can be matched with hydroxyl groups of four polyhydroxy compounds to generate four boron-oxygen bonds, the water-soluble polyhydroxy compounds are crosslinked to obtain an aggregated gel of the polyhydroxy compounds, hydrated PAM molecular chains are inserted between three-dimensional networks of the aggregated gel, the aggregated gel network has a certain reinforcing effect on the hydrated PAM molecular chains, the local collapse of the PAM molecular chains can be effectively inhibited, the apparent viscosity of PAM aqueous solution is further increased, the sand carrying and pressurizing effects of the thickener are improved, and the fracturing construction requirements are met.
Advantageous effects
(1) Boric acid is matched with polyhydroxy compound and crosslinked to obtain high-viscosity thickener aqueous solution. Unlike the mechanism of conventional high-valence metal ion cross-linking PAM molecular chains, the coordination process of boron atoms and polyhydroxy compounds does not need to be carried out in a specific pH value environment. The coordination reaction of boron atoms and hydroxyl groups has loose reaction conditions and better atom economy;
(2) Boric acid is an extremely weak inorganic acid with small corrosion to equipment, low price and low toxicity, and is an environment-friendly product;
(3) The components are single. Unlike traditional high valence ion crosslinking agent, it is unnecessary to package the thickener and crosslinking agent separately, and the construction process is simple;
(4) Boric acid is an antiseptic and disinfectant, and can be used as a cross-linking agent of polyhydroxy compound, so that the viscosity of the thickener aqueous solution can be improved, biological spoilage of the thickener such as cellulose, xanthan gum and the like can be prevented, and the storage and use stability of the thickener can be maintained.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof.
Example 1
Boric acid crosslinked thickener, which is prepared by the following method:
(1) 40 parts of No. 10 white oil and 2 parts of hydroxymethyl cellulose are sequentially added into a reaction kettle, and 5 parts of tetradecyldihydroxyethyl amine oxide serving as a phase transfer catalyst and 50 parts (average particle diameter 80 mu m, average molecular weight 2.8X10 7 g/mol) of PAM powder (I) are dispersed into the No. 10 white oil under stirring and at the temperature of between room temperature and 90 ℃. Then, the mixture is cooled to room temperature;
(2) At room temperature under stirring, 0.1 part of boric acid was added, stirred for 30 minutes, and filtered to obtain a thickener.
Comparative example 1
40 Parts of No. 10 white oil and 2 parts of hydroxymethyl cellulose are sequentially added into a reaction kettle, and 5 parts of tetradecyldihydroxyethyl amine oxide serving as a phase transfer catalyst and 50 parts (average particle diameter 80 mu m, average molecular weight 2.8X10 7 g/mol) of PAM powder (I) are dispersed into the No. 10 white oil under stirring and at the temperature of between room temperature and 90 ℃. Then, the mixture was cooled to room temperature, filtered and packaged.
Performance test of example 1 and comparative example 1
5.00G of the product of example 1 and comparative example 1, respectively, was added to 495.00g of seawater (about 121℃east longitude and 37℃North latitude, in particular) at room temperature under stirring. The apparent viscosities of the thickener solutions at 2min, 5min and 10min were measured with a six-speed viscometer (the rotational speed of the rotor is 100 rpm), and the measurement results are shown in Table 1.
TABLE 1 apparent viscosity at various dissolution times for example 1 and comparative example 1
As can be seen from table 1, the viscosity of the thickener solution of example 1 tended to increase with increasing dissolution time. If the solution is dissolved for 2min, the apparent viscosity of the solution is 30 mPas, when the solution is dissolved for 5min, the viscosity of the solution is 32 mPas, and when the solution is dissolved for 10min, the viscosity of the solution is 37 mPas. The longer the dissolution time of the thickener solution, the higher the apparent viscosity, which means that boric acid has crosslinked the hydroxymethyl cellulose molecules to form colloidal dispersion gel and aggregation gel, and the viscosity of the thickener solution is improved. Comparative example 1 the thickener solution viscosity was not very related to dissolution time. At dissolution times of 2min, 5min and 10min, the viscosity of the solution was 31 mPas, 33 mPas and 34 mPas, respectively. Comparative example 1 shows that PAM powder and hydroxymethyl cellulose have completed the dissolution process at a dissolution time of 5 minutes.
Example 2
Boric acid crosslinked thickener, which is prepared by the following method:
(1) Adding 20 parts of white oil No. 3, 15 parts of white oil No. 5, 15 parts of white oil No. 15, 2 parts of hydroxypropyl methylcellulose, 2 parts of hydroxyethyl cellulose and 3 parts of organic bentonite in sequence into a reaction kettle, adding 2 parts of tetradecyl dihydroxyethyl amine oxide serving as a phase transfer catalyst and 50 parts of PAM (II) powder (average particle diameter of 120 mu m, average molecular weight of 1.5X10 7 g/mol) under the conditions of stirring and room temperature, and stirring for 60 minutes;
(2) 1 part of boric acid is added under the condition of stirring at room temperature, stirring is carried out for 30 minutes, and the thickener is obtained after filtration.
Comparative example 2
Adding 20 parts of white oil No. 3, 15 parts of white oil No. 5, 15 parts of white oil No. 15, 2 parts of hydroxypropyl methylcellulose, 2 parts of hydroxyethyl cellulose and 3 parts of organic bentonite in sequence into a reaction kettle, adding 2 parts of tetradecyl dihydroxyethyl amine oxide serving as a phase transfer catalyst and 50 parts of PAM (II) powder (average particle diameter of 120 mu m, average molecular weight of 1.5X10 7 g/mol) under the conditions of stirring and room temperature, and stirring for 60 minutes; filtering and packaging;
performance test of example 2 and comparative example 2
5.00G of the product of example 2 and comparative example 2 was added to 495.00g of seawater (smoke table east coast yellow sea area, specifically around 121 east longitude and 37 ° north latitude) at room temperature with stirring. The apparent viscosities of the thickener solutions at 2min, 5min and 10min were measured with a six-speed viscometer (the rotational speed of the rotor is 100 rpm), and the measurement results are shown in Table 2.
TABLE 2 apparent viscosity of the two thickeners at different dissolution times
From the experimental data in table 2, it can be seen that the viscosity of the aqueous solution of example 2 increases gradually with the dissolution time. At dissolution times of 2min, 5min and 10min, the viscosity of the solution was 31 mPas, 37 mPas and 41 mPas, respectively. Whereas the viscosities of the solutions of comparative example 2 at dissolution times of 2min, 5min and 10min were 31 mPas, 34 mPas and 35 mPas, respectively. Illustrating that boric acid and hydroxyl groups of hydroxyethyl cellulose in the thickener solution obtained in example 2 undergo a coordination reaction to form colloidal dispersion gel and aggregation gel, and the viscosity of the thickener solution is improved. In contrast, in the water dissolution process of the thickener of comparative example 2, only PAM powder and hydroxyethyl cellulose were dissolved. Therefore, when the dissolution time exceeds 5 minutes, the apparent viscosity of the solution is not changed significantly any more. Meanwhile, as can be seen from the results of example 2 and comparative example 2, the coordination crosslinking reaction of boric acid and hydroxyethyl cellulose can be performed without additionally adjusting the pH value of the system after boric acid is added, and the viscosity of the solution is improved.
Example 3
Boric acid crosslinked thickener, which is prepared by the following method:
(1) 20 parts of No. 3 white oil, 25 parts of No. 15 white oil, 3 parts of xanthan gum, 1 part of calcium montmorillonite and 1 part of organic bentonite are sequentially added into a reaction kettle, 2.5 parts of phase transfer catalyst lauramidopropyl amine oxide and 60 parts of polymer (IV) powder (average particle diameter is 85 mu m, average molecular weight is 1.5X10 7 g/mol) are added into the reaction kettle under stirring and 50 ℃, and stirring is carried out for 60 minutes. Then slowly cooling to room temperature;
(2) Under the condition of room temperature and stirring, 0.6 part of boric acid cross-linking agent is added, stirred for 30 minutes, filtered and packaged.
Comparative example 3
20 Parts of No. 3 white oil, 25 parts of No. 15 white oil, 3 parts of xanthan gum, 1 part of calcium montmorillonite and 1 part of organic bentonite are sequentially added into a reaction kettle, 2.5 parts of phase transfer catalyst lauramidopropyl amine oxide and 60 parts of polymer (IV) powder (average particle diameter is 85 mu m, average molecular weight is 1.5X10 7 g/mol) are added into the reaction kettle under stirring and 50 ℃, and stirring is carried out for 60 minutes. Then, the mixed solution is slowly cooled to room temperature, filtered and packaged.
Performance test of example 3 and comparative example 3:
5.00g of the product of example 3 and comparative example 3 was added to 495.00g of seawater (smoke table east coast yellow sea area, specifically around 121 east longitude and 37 ° north latitude) at room temperature with stirring. The apparent viscosities of the thickener solutions at 2min, 5min and 10min were measured with a six-speed viscometer (the rotational speed of the rotor is 100 rpm), and the measurement results are shown in Table 3.
TABLE 3 apparent viscosity of the two thickeners at different dissolution times
From the experimental data in Table 3, it can be seen that the viscosity of the aqueous solution of example 3 increases gradually with the dissolution time. At dissolution times of 2min, 5min and 10min, the viscosity of the solution was 33 mPas, 42 mPas and 47 mPas, respectively. Whereas the viscosities of the solutions of comparative example 3 at dissolution times of 2min, 5min and 10min were 33 mPas, 35 mPas and 36 mPas, respectively. The viscosity of both thickener solutions was greater than that of examples 1 and 2 and comparative examples 1 and 2, because in example 3 and comparative example 3, the mass percent of PAM powder added was greater (60 parts of powder was used). For example 3, the increasing viscosity of the thickener solution was dependent primarily on coordination, crosslinking of the boric acid with the hydroxyl groups of the xanthan gum building block. In contrast, in the system of comparative example 3, only the dissolution process of PAM powder was performed, and no coordination crosslinking reaction occurred, so that the solution viscosity did not show a tendency to increase stepwise.
Example 4
Boric acid crosslinked thickener, which is prepared by the following method:
(1) 30 parts of No. 7 white oil, 15 parts of No. 10 white oil, 3 parts of hydroxymethyl cellulose, 0.5 part of xanthan gum, 0.5 part of hydroxymethyl cellulose and 1 part of sodium bentonite are sequentially added into a reaction kettle, 3.5 parts of octadecyl trimethyl ammonium chloride serving as a phase transfer catalyst and 60 parts of polymer (III) powder (average particle diameter of 80 mu m, average molecular weight of 2.1X10 7 g/mol) are added under stirring at 80 ℃ and stirred for 60 minutes. Then, cooling the mixed solution to room temperature;
(2) At room temperature under stirring, 0.8 part of boric acid was added, stirred for 30 minutes, and filtered to obtain a thickener.
5.00G of the product of example 4 was added to 495.00g of seawater (a smoke table of the east coast yellow sea area, specifically 121% east longitude and 37% north latitude) at room temperature with stirring, and the apparent viscosities of the thickener solutions were measured with a six-speed viscometer (the rotational speed of the rotor is 100 rpm) for 2min, 5min and 10min, respectively: 31mpa.s, 40mpa.s and 48mpa.s.
Example 5
Boric acid crosslinked thickener, which is prepared by the following method:
(1) 10 parts of No. 3 white oil, 20 parts of No. 7 white oil, 15 parts of No. 15 white oil, 3 parts of hydroxypropyl methyl cellulose, 1 part of calcium bentonite and 0.5 part of organic bentonite are sequentially added into a reaction kettle, 2 parts of Tween 20 serving as a phase transfer catalyst, 1.5 parts of hexadecylaminopropyl amine oxide and 60 parts of polymer (V) powder (average particle diameter of 110 mu m, average molecular weight of 2.4X10 7 g/mol) are added under stirring and 60 ℃ conditions, and stirring is carried out for 30 minutes. Then, slowly cooling the mixed solution to room temperature;
(2) 0.5 part of boric acid is added under stirring at room temperature, stirred for 30 minutes, filtered and packaged.
5.00G of the product of example 5 was added to 495.00g of seawater (a smoke table of the east coast yellow sea area, specifically 121% east longitude and 37% north latitude) at room temperature with stirring, and the apparent viscosities of the thickener solutions were measured with a six-speed viscometer (the rotational speed of the rotor is 100 rpm) for 2min, 5min and 10min, respectively: 29mPa.s,39mPa.s and 45mPa.s.
Example 6
Boric acid crosslinked thickener, which is prepared by the following method:
(1) Sequentially adding 30 parts of No. 5 white oil, 10 parts of No. 10 white oil and 10 parts of No. 15 white oil into a reaction kettle, and adding 4 parts of hydroxyethyl cellulose, 2 parts of xanthan gum and 1 part of sodium montmorillonite under the condition of stirring at 50 ℃; adding 1 part of Tween 65, 1 part of dodecyl dihydroxyethyl amine oxide and 1 part of dodecyl trimethyl ammonium chloride, mixing together 30 parts of polymer (II) powder (average particle diameter 120 μm, average molecular weight 1.5X10 7 g/mol) and 30 parts of polymer (III) powder (average particle diameter 110 μm, average molecular weight 2.1X10 7 g/mol), stirring at 50deg.C for 40 min, and cooling the mixture to room temperature;
(2) 1.0 part of boric acid is added under stirring at room temperature, stirred for 30 minutes, and filtered to obtain the thickening agent.
Comparative example 4
Sequentially adding 30 parts of No. 5 white oil, 10 parts of No. 10 white oil and 10 parts of No. 15 white oil into a reaction kettle, and adding 4 parts of hydroxyethyl cellulose, 2 parts of xanthan gum and 1 part of sodium montmorillonite under the condition of stirring at 50 ℃; 1 part of Tween 65, 1 part of dodecyldihydroxyethyl amine oxide and 1 part of dodecyltrimethyl ammonium chloride were added, 30 parts of polymer (II) powder (average particle diameter: 120 μm, average molecular weight: 1.5X10- 7 g/mol) and 30 parts of polymer (III) powder (average particle diameter: 110 μm, average molecular weight: 2.1X10- 7 g/mol) were mixed together, and after stirring at 50℃for 40 minutes, the mixture was cooled to room temperature, filtered and packaged.
Performance test of example 6 and comparative example 4:
5.00g of the product of example 6 and comparative example 4 was added to 495.00g of seawater (smoke table east coast yellow sea area, specifically around 121 east longitude and 37 north latitude) at room temperature with stirring. The apparent viscosities of the thickener solutions at 2min, 5min and 10min were measured with a six-speed viscometer (the rotational speed of the rotor is 100 rpm), and the measurement results are shown in Table 4.
TABLE 4 apparent viscosity of the two thickeners at different dissolution times
From the experimental data in Table 4, it can be seen that the viscosity of the aqueous solution of example 6 increases gradually with the dissolution time. At dissolution times of 2min, 5min and 10min, the viscosity of the solution was 32 mPas, 46 mPas and 51 mPas, respectively. Whereas the viscosities of the solutions of comparative example 4 at dissolution times of 2min, 5min and 10min were 33 mPas, 36 mPas and 35 mPas, respectively. For example 6, the increasing viscosity of the thickener solution over time of stirring is mainly the contribution of coordination, crosslinking of boric acid with the hydroxyl groups in the xanthan gum building block. In contrast, in comparative example 4, since only the dissolution process of PAM powder was performed and no coordination crosslinking reaction occurred, the solution viscosity did not show a tendency to increase stepwise.
Example 7
Boric acid crosslinked thickener, which is prepared by the following method:
(1) 30 parts of No. 3 white oil, 10 parts of No. 5 white oil, 20 parts of No. 15 white oil, 2 parts of hydroxyethyl cellulose, 1 part of hydroxypropyl cellulose, 1 part of xanthan gum and 1 part of organic bentonite are sequentially added into a reaction kettle, 2 parts of Tween-80, 2 parts of tetradecyl trimethyl ammonium chloride and 20 parts of polymer (I) powder (average particle diameter 80 μm, average molecular weight 2.8X10 7 g/mol) and 35 parts of polymer (V) powder (average particle diameter 110 μm, average molecular weight 2.4X10 7 g/mol) are added under stirring at 75 ℃ for 30 minutes. Then, slowly cooling the mixed solution to room temperature;
(2) 0.75 part of boric acid is added under stirring at room temperature, stirred for 30 minutes, filtered and packaged.
5.00G of the product of example 5 was added to 495.00g of seawater (a smoke table of the east coast yellow sea area, specifically 121% east longitude and 37% north latitude) at room temperature with stirring, and the apparent viscosities of the thickener solutions were measured with a six-speed viscometer (the rotational speed of the rotor is 100 rpm) for 2min, 5min and 10min, respectively: 30mPa.s,40mPa.s and 47mPa.s.
The existence of boric acid in the thickener remarkably improves the thickening effect, so that the viscosity of the thickener solution is continuously increased along with the extension of stirring time. Boric acid is used in glass industry to improve heat resistance and transparency of glass product, raise mechanical strength and shorten melting time, and may be used as antiseptic and disinfectant. However, the boric acid is equivalent to a cross-linking agent, and can be matched with water-soluble polyhydroxy compounds (four boron-oxygen bonds are formed) after being dissolved in water, so that the polyhydroxy compounds are cross-linked into a three-dimensional network structure, the viscosity of a thickener solution is improved, and the implementation of sand carrying and fracturing processes is facilitated. Because boric acid is fast in compounding speed with water-soluble polyhydroxy compounds, and the boric acid does not react with high-valence ions such as calcium, magnesium and the like, the boric acid crosslinked thickener shows better salt resistance.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (3)
1. The boric acid crosslinked thickener is characterized by comprising the following components in parts by weight:
wherein the thickener is at least one of hydroxymethyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose, xanthan gum, calcium bentonite, sodium bentonite and organic bentonite;
The anionic polyacrylamide is selected from one or more of polymers (I) - (V),
And the average diameter of the anionic polyacrylamide is 80-120 mu m, the molecular weight is 1.5X10 7g/mol-2.8×107 g/mol, a, o and p are positive integers not less than 1, and m is n=1.5-3:1;
The phase transfer auxiliary agent is at least one of decane-dihydroxy ethyl amine oxide, dodecyl dihydroxy ethyl amine oxide, tetradecyl dihydroxy ethyl amine oxide, hexadecyl dihydroxy ethyl amine oxide, octadecyl dihydroxy ethyl amine oxide, dodecylpropyl amine oxide, tetradecyl amidopropyl amine oxide, hexadecyl amidopropyl amine oxide, octadecyl amidopropyl amine oxide, isomeric tridecyl polyoxyethylene ether, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, tween 20, tween 40, tween 65, tween 80, tween 81 or tween 85;
The thickener is prepared by the following method and comprises the following steps:
(1) Sequentially mixing white oil and a thickening agent, then adding a phase transfer auxiliary agent and anionic polyacrylamide, sequentially dispersing in the white oil under the conditions of stirring and room temperature to 90 ℃ to prepare a mixed solution, and then cooling the mixed solution to room temperature;
(2) Stirring and adding boric acid at room temperature, mixing, filtering, and packaging to obtain thickener.
2. The thickener according to claim 1, wherein the kinematic viscosity of the white oil at 40 ℃ is 2-18mm 2/s.
3. The thickener according to claim 1, wherein the white oil is at least one selected from the group consisting of No. 3 white oil, no. 5 white oil, no. 7 white oil, no. 10 white oil, and No. 15 white oil.
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| CN111706311A (en) * | 2020-07-22 | 2020-09-25 | 青岛大地新能源技术研究院 | Fracturing construction process for liquid self-supporting high-speed channel |
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| CN111706311A (en) * | 2020-07-22 | 2020-09-25 | 青岛大地新能源技术研究院 | Fracturing construction process for liquid self-supporting high-speed channel |
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