CN115975107A - Anionic polyacrylamide emulsion and preparation method thereof - Google Patents
Anionic polyacrylamide emulsion and preparation method thereof Download PDFInfo
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- CN115975107A CN115975107A CN202310240694.5A CN202310240694A CN115975107A CN 115975107 A CN115975107 A CN 115975107A CN 202310240694 A CN202310240694 A CN 202310240694A CN 115975107 A CN115975107 A CN 115975107A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 47
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 44
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000004945 emulsification Methods 0.000 title description 2
- 239000002904 solvent Substances 0.000 claims abstract description 50
- 238000003756 stirring Methods 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 239000003999 initiator Substances 0.000 claims abstract description 36
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010992 reflux Methods 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 16
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims abstract description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 15
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000004090 dissolution Methods 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- -1 5, 6-dimethyl decyl Chemical group 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012530 fluid Substances 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of fracturing fluids, and particularly relates to an anionic polyacrylamide emulsion and a preparation method thereof. The preparation method comprises the following steps: adding acrylamide, p-alkylstyrene, alpha-alkenyl sodium sulfonate and 2-acrylamide-2-methylpropanesulfonic acid into a three-neck flask, adding a first solvent, adding a first initiator after complete dissolution, stirring for reaction, and then cooling to obtain a mixture; and adding ammonia water into the mixture to adjust the pH, then adding an emulsifier, simultaneously dissolving a second initiator into a second solvent, putting into a constant-pressure dropping funnel, after finishing dropping, heating to the reflux temperature of the second solvent, continuing to react, and then cooling to obtain the anionic polyacrylamide emulsion. The polyacrylamide emulsion has the characteristics of low cost and strong adaptability; meanwhile, the polyacrylamide emulsion is simple and convenient to construct, does not need to be prepared in advance, can be prepared and used on site, and can avoid the problem of high cost caused by reagent waste.
Description
Technical Field
The invention belongs to the technical field of fracturing fluids, and particularly relates to an anionic polyacrylamide emulsion and a preparation method thereof.
Background
With the continuous development of oil fields with high economic benefit and the increasing scarcity of high-quality crude oil, the demand of the oil fields in various regions of the world is continuously increased, drilling engineering teams in various oil field regions gradually approach low-permeability and ultra-low-permeability oil and gas fields, and even heavy oil and marginal oil reservoirs become the objects of attention of the oil fields. The low-permeability oil and gas fields known globally have huge areas and considerable reserve resources. However, to efficiently utilize such oil fields, it is necessary to clearly identify difficulties in terms of high capital investment, low return on results, and high technical means requirements. Therefore, how to efficiently and effectively exploit the low-permeability oil field, optimize the reconstruction means of tertiary exploitation, improve the single-day crude oil yield and reduce the capital investment is an important aspect which needs to be treated urgently at present. In the process, hydraulic fracturing is inevitably an important technical means for exploiting oil and gas, and becomes an important process for realizing economic benefit maximization.
The hydraulic fracturing technology, as an important means for reservoir transformation, is gradually becoming a key factor for improving the yield of oil and gas fields. With the development of conventional oil and gas resources stepping in the middle and later stages, people are more and more attentively oriented to low-permeability, ultra-low-permeability and strong-water-sensitivity reservoir exploitation.
Development and Performance evaluation of high temperature emulsified fracturing fluid [ J]Marine oil, 2014, 34 (3): 76-80, liuyi, liujing, liliangchuan and the like prepare a main agent of an emulsion fracturing system, and further develop a system formula, wherein the base fluid comprises: 0.5-0.55% of guanidine gum, small cation clay stabilizer, demulsifying flowback agent and Na 2 CO 3 + NaOH, mixing the initial system and diesel oil according to a ratio of 9. The application in the field is carried out in the strong water-sensitive stratum of the Jidong oil field, and the final result shows that: the permeability damage rate of the rock core is reduced by about 30 percentThe damage rate is lower than 20%. The existing thickening agent generally has the problems of low viscosity and poor sand carrying effect.
Disclosure of Invention
The invention provides an anionic polyacrylamide emulsion and a preparation method thereof aiming at the defects of the prior art, and the polyacrylamide emulsion has the characteristics of simple preparation process, low cost and strong adaptability; meanwhile, the polyacrylamide emulsion is simple and convenient to construct, does not need to be prepared in advance, can be prepared and used on site, and can avoid the problem of high cost caused by reagent waste.
Accordingly, in order to achieve the above objects, in one aspect, the present invention discloses an anionic polyacrylamide emulsion having the following formula:
wherein:
a is an integer from 100000 to 450000;
b is an integer of 2000 to 225000;
c is an integer of 100 to 90000;
d is an integer of 100 to 90000;
x is an integer of 1 to 8;
r is C 1 ~C 16 Long chain alkyl or branched alkyl.
On the other hand, the invention provides a preparation method of the anionic polyacrylamide emulsion, which comprises the following steps:
adding acrylamide, p-alkylstyrene, alpha-alkenyl sodium sulfonate and 2-acrylamide-2-methylpropanesulfonic acid into a three-neck flask with a stirring device and a condensation pipe, adding a first solvent, stirring for 10-30min under the condition of stirring speed of 300-500rpm, adding a first initiator after complete dissolution, adjusting the temperature to be the reflux temperature of the first solvent, continuously stirring for reaction for 4-6 h, and then cooling to obtain a mixture;
adding ammonia water into the mixture to adjust the pH value to 9-10, then adding an emulsifier, adjusting the stirring speed to 10000-50000rpm, simultaneously dissolving a second initiator into a second solvent, putting the second initiator into a constant-pressure dropping funnel, dropping the initiator at the speed of 10-60 drops/min, after the dropping is finished, heating to the reflux temperature of the second solvent, continuing to react for 2-6h, and then cooling to obtain the anionic polyacrylamide emulsion.
The polyacrylamide emulsion provided by the invention belongs to an anionic polymer, the monomer used by the polymer is mainly acrylamide, and the selected functional monomers belong to monomers which are easy to copolymerize, so that the polymer has a large molecular weight and a high viscosity; benzene ring rigid groups introduced into the molecules can inhibit molecular curling, have the effect of resisting high temperature and high salt and can further improve the apparent viscosity of the molecules; in addition, double hydrophobic groups are introduced into molecules, the hydrophobic association effect is stronger through the bridging effect of hydrogen bonds among the molecules, the apparent viscosity of the polymer aqueous solution is further enhanced, and the interaction of the triple mechanisms enables the developed anionic polyacrylamide emulsion to have excellent tackifying property at a lower concentration.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the anionic polyacrylamide emulsion has the characteristics of simple preparation process, low cost and strong adaptability;
the anionic polyacrylamide emulsion has obvious thickening effect, and the apparent viscosity of the anionic polyacrylamide emulsion at 1.0wt% concentration is more than or equal to 300mPa & s under the conditions that the mineralization degree is 20000mg/L and the temperature is 50 ℃;
the anionic polyacrylamide emulsion has the advantages of simple construction, no need of advanced preparation effect, realization of the ready-to-use preparation, and avoidance of the problem of high cost caused by reagent waste.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, an anionic polyacrylamide emulsion is disclosed, the formula of the anionic polyacrylamide emulsion is as follows:
wherein:
a is an integer of 100000 to 450000, more preferably an integer of 150000 to 300000;
b is an integer of 2000 to 225000, more preferably an integer of 10000 to 50000;
c is an integer of 100 to 90000, more preferably an integer of 5000 to 15000;
d is an integer of 100 to 90000, more preferably an integer of 1000 to 20000;
x is an integer of 1 to 8; more preferably, x is 2 or 3;
r is C 1 ~C 16 Long chain alkyl or branched alkyl of (a); more preferably, R is C 10 ~C 16 A branched alkyl group of (a); more preferably, R is 5, 6-dimethyldecyl, having the formula:
in a second aspect, the present invention provides a preparation method of the above anionic polyacrylamide emulsion, wherein the preparation method comprises:
(1) Adding acrylamide, p-alkylstyrene, alpha-alkenyl sodium sulfonate and 2-acrylamide-2-methylpropanesulfonic acid into a three-neck flask with a stirring device and a condensation pipe, adding a first solvent, stirring for 10-30min under the condition of stirring speed of 300-500rpm, adding a first initiator after complete dissolution, adjusting the temperature to be the reflux temperature of the first solvent, continuously stirring for reaction for 4-6 h, and then cooling to obtain a mixture;
(2) Adding ammonia water into the mixture to adjust the pH value to 9-10, then adding an emulsifier, adjusting the stirring speed to 10000-50000rpm, simultaneously dissolving a second initiator into a second solvent, putting the second initiator into a constant-pressure dropping funnel, dropping the initiator at the speed of 10-60 drops/min, after the dropping is finished, heating to the reflux temperature of the second solvent, continuing to react for 2-6h, and then cooling to obtain the anionic polyacrylamide emulsion.
In the present invention, it is preferable that the molar ratio of acrylamide, p-alkylstyrene, sodium α -alkenyl sulfonate and 2-acrylamide-2-methylpropanesulfonic acid is 1:0.02 to 0.5:0.001 to 0.2:0.001 to 0.2; more preferably, the molar ratio of acrylamide, p-alkylstyrene, sodium alpha-alkenyl sulfonate and 2-acrylamide-2-methylpropanesulfonic acid is 1:0.08 to 0.15:0.05 to 0.1:0.05 to 0.1.
In the invention, in the step (1), the first solvent is preferably one of N, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide, and the amount of the first solvent is 2 to 8 times of the mass of acrylamide.
Preferably, in the step (1), the first initiator is azobisisobutyronitrile, and the amount of the first initiator is 0.1 to 0.5% of the mass of the acrylamide.
In the invention, preferably, in the step (2), the emulsifier is one of sodium dodecyl benzene sulfonate and polyoxyethylene ether surfactant, and the dosage of the emulsifier is 0.3 to 2 percent of the mass of the acrylamide.
Preferably, in the step (2), the second initiator is one of persulfate and sulfite, and the dosage of the second initiator is 0.05 to 0.5 percent of the mass of the acrylamide.
Preferably, in the step (2), the second solvent is deionized water, and the using amount of the second solvent is 10 to 15 times of the mass of the acrylamide.
The synthesis reaction equation of the anionic polyacrylamide emulsion is as follows:
it should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.
The present invention will be further described with reference to specific examples.
In the present invention, the apparatus or equipment used is a conventional apparatus or equipment known in the art, and is commercially available.
In the following examples and comparative examples, the reagents used are all chemically pure reagents from commercial sources, unless otherwise specified.
Example 1 (1) 1mol of acrylamide, 0.02mol of p-alkylstyrene, 0.001mol of sodium alpha-olefin sulfonate and 0.001mol of 2-acrylamide-2-methylpropanesulfonic acid are added into a three-neck flask with a stirring device and a condensation tube, 142g of a first solvent N, N-dimethylformamide is added, stirring is carried out for 10min at the stirring speed of 300rpm, after complete dissolution, 0.07g of a first initiator azobisisobutyronitrile is added, the temperature is adjusted to the reflux temperature of the first solvent, stirring reaction is carried out for 4h, and then cooling is carried out to obtain a mixture;
(2) Adding ammonia water into the mixture to adjust the pH value to 9-10, then adding 0.213g of emulsifier sodium dodecyl benzene sulfonate, adjusting the stirring speed to 10000rpm, simultaneously dissolving 0.036g of second initiator persulfate into 710g of second solvent deionized water, putting the mixture into a constant-pressure dropping funnel, dropwise adding the mixture at a speed of 10 drops/min, after the dropwise adding is completed, heating to the reflux temperature of the second solvent, continuing to react for 2 hours, and then cooling to obtain the anionic polyacrylamide emulsion A 1 。
Example 2 (1) 1mol of acrylamide, 0.05mol of p-alkylstyrene, 0.005mol of sodium alpha-olefin sulfonate and 0.005mol of 2-acrylamide-2-methylpropanesulfonic acid are added into a three-neck flask with a stirring device and a condenser, 205g of first solvent N-methylpyrrolidone is added, stirring is carried out for 15min under the condition of a stirring speed of 350rpm, 0.15g of first initiator azobisisobutyronitrile is added after complete dissolution, the temperature is adjusted to be the reflux temperature of the first solvent, stirring reaction is carried out for 5h, and then cooling is carried out to obtain a mixture;
(2) Adding ammonia water into the mixture to adjust the pH value to 9-10, then adding 0.38g of emulsifier sodium dodecyl benzene sulfonate, adjusting the stirring speed to 30000rpm, simultaneously dissolving 0.062g of second initiator persulfate into 790g of second solvent deionized water, putting the mixture into a constant-pressure dropping funnel, dropwise adding the mixture at a speed of 20 drops/min, after the dropwise adding is completed, heating to the reflux temperature of the second solvent, continuing to react for 3 hours, and then cooling to obtain the anionic polyacrylamide emulsion A 2 。
Example 3 (1) 1mol of acrylamide, 0.1mol of p-alkylstyrene, 0.01mol of sodium alpha-olefin sulfonate and 0.02mol of 2-acrylamide-2-methylpropanesulfonic acid are added into a three-neck flask with a stirring device and a condensation tube, 286g of a first solvent N, N-dimethylacetamide is added, the mixture is stirred for 12min at the stirring speed of 380rpm, 0.18g of a first initiator azobisisobutyronitrile is added after complete dissolution, the temperature is adjusted to the reflux temperature of the first solvent, the mixture is continuously stirred and reacted for 6h, and then the temperature is reduced to obtain a mixture;
(2) Adding ammonia water into the mixture to adjust the pH value to 9-10, then adding 0.52g of emulsifier sodium dodecyl benzene sulfonate, adjusting the stirring speed to 15000rpm, simultaneously dissolving 0.105g of second initiator sulfite into 815g of second solvent deionized water, putting the mixture into a constant-pressure dropping funnel, dropwise adding the mixture at a speed of 50 drops/min, after the dropwise adding is completed, heating to the reflux temperature of the second solvent, continuing to react for 4 hours, and then cooling to obtain the anionic polyacrylamide emulsion A 3 。
Example 4 (1) 1mol of acrylamide, 0.2mol of p-alkylstyrene, 0.05mol of sodium alpha-olefin sulfonate and 0.06mol of 2-acrylamide-2-methylpropanesulfonic acid are added into a three-necked flask with a stirring device and a condensation tube, 353g of a first solvent N, N-dimethylformamide is added, stirring is carried out at a stirring speed of 400rpm for 20min, after complete dissolution, 0.23g of a first initiator azobisisobutyronitrile is added, the temperature is adjusted to the reflux temperature of the first solvent, stirring reaction is carried out continuously for 5h, and then cooling is carried out to obtain a mixture;
(2) Adding ammonia water into the mixture to adjust the pH value to 9-10, then adding 0.75g of emulsifier polyoxyethylene ether surfactant, adjusting the stirring speed to 25000rpm, simultaneously dissolving 0.185g of second initiator persulfate into 867g of second solvent deionized water, putting the mixture into a constant-pressure dropping funnel, dropwise adding the mixture according to the speed of 40 drops/min, after dropwise adding is completed, heating to the reflux temperature of the second solvent, continuing to react for 4 hours, and then cooling to obtain the anionic polyacrylamide emulsion A 4 。
Example 5 (1) 1mol of acrylamide, 0.3mol of p-alkylstyrene, 0.1mol of sodium alpha-olefin sulfonate and 0.12mol of 2-acrylamide-2-methylpropanesulfonic acid are added into a three-neck flask with a stirring device and a condensation tube, 402g of first solvent N-methylpyrrolidone is added, the mixture is stirred for 25min at the stirring speed of 450rpm, 0.28g of first initiator azobisisobutyronitrile is added after complete dissolution, the temperature is adjusted to the reflux temperature of the first solvent, the reaction is continuously stirred for 5h, and then the temperature is reduced to obtain a mixture;
(2) Adding ammonia water into the mixture to adjust the pH value to 9-10, then adding 0.98g of emulsifier sodium dodecyl benzene sulfonate, adjusting the stirring speed to 45000rpm, simultaneously dissolving 0.215g of second initiator sulfite into 926g of second solvent deionized water, putting the mixture into a constant-pressure dropping funnel, dropwise adding the mixture at the speed of 30 drops/min, after the dropwise adding is completed, heating to the reflux temperature of the second solvent, continuing to react for 3 hours, and then cooling to obtain the anionic polyacrylamide emulsion A 5 。
Example 6 (1) 1mol of acrylamide, 0.4mol of p-alkylstyrene, 0.15mol of sodium alpha-olefin sulfonate and 0.16mol of 2-acrylamide-2-methylpropanesulfonic acid are added into a three-neck flask with a stirring device and a condenser tube, 495g of first solvent N-methylpyrrolidone is added, stirring is carried out for 30min under the condition of a stirring speed of 500rpm, 0.32g of first initiator azobisisobutyronitrile is added after complete dissolution, the temperature is adjusted to the reflux temperature of the first solvent, stirring reaction is carried out for 4h, and then cooling is carried out to obtain a mixture;
(2) Adding ammonia water into the mixture to adjust the pH value to 9-10, then adding 1.21g of emulsifier polyoxyethylene ether surfactant, adjusting the stirring speed to 35000rpm,simultaneously dissolving 0.287g of second initiator sulfite into 978g of second solvent deionized water, adding the solution into a constant-pressure dropping funnel, dropwise adding the solution at the rate of 30 drops/min, heating the solution to the reflux temperature of the second solvent after the dropwise adding is finished, continuously reacting for 5 hours, and then cooling the solution to obtain the anionic polyacrylamide emulsion A 6 。
Example 7 (1) 1mol of acrylamide, 0.5mol of p-alkylstyrene, 0.2mol of sodium alpha-olefin sulfonate and 0.2mol of 2-acrylamide-2-methylpropanesulfonic acid are added into a three-neck flask with a stirring device and a condenser, 568g of a first solvent, N-dimethylacetamide is added, the mixture is stirred for 25min at a stirring speed of 450rpm, after the mixture is completely dissolved, 0.35g of a first initiator, azobisisobutyronitrile, is added, the temperature is adjusted to be the reflux temperature of the first solvent, the mixture is continuously stirred and reacted for 6h, and then the temperature is reduced to obtain a mixture;
(2) Adding ammonia water into the mixture to adjust the pH value to 9-10, then adding 1.42g of emulsifier polyoxyethylene ether surfactant, adjusting the stirring speed to 50000rpm, simultaneously dissolving 0.355g of second initiator sulfite into 1065g of second solvent deionized water, putting the mixture into a constant-pressure dropping funnel, dropwise adding the mixture at the speed of 60 drops/min, after the dropwise adding is completed, heating to the reflux temperature of the second solvent, continuing to react for 6 hours, and then cooling to obtain the anionic polyacrylamide emulsion A 7 。
Example 8 viscosity average molecular weight and apparent viscosity measurement
Experimental selection of A of the invention 1 ~A 8 Comparing the apparent viscosities of the anionic polyacrylamide emulsion and a non-crosslinked clean fracturing fluid CHZJ-2 product produced by Chengdu Jianxiang Shu technology Limited company, wherein the apparent viscosity test method comprises the following steps: the test sample was first diluted to a 1.0wt% solution with brine having a degree of mineralization of 20000mg/L and the dissolution time was recorded, and then the prepared solution was tested for apparent viscosity at 50 ℃ using a haake rheometer. The test results are shown in Table 1.
TABLE 1 comparison of dissolution time and apparent viscosity of anionic polyacrylamide emulsions and commercial products
From the test results, compared with the commercially available emulsion fracturing fluid, the anionic polyacrylamide emulsion disclosed by the invention has higher apparent viscosity, under the condition of a high mineralization degree of 20000mg/L, the apparent viscosity of the anionic polyacrylamide emulsion disclosed by the invention at a concentration of 1% is more than 300mPa & s, and the commercially available product CHZJ-2 also belongs to an emulsion fracturing fluid thickener and belongs to an excellent thickener series in China, but the apparent viscosity of a solution diluted to 1.0wt% by 20000mg/L saline is only 42mPa & s and is far lower than the viscosity of the anionic polyacrylamide emulsion disclosed by the invention, so that the product can have better sand carrying capacity at a lower concentration, has the excellent characteristics of low use cost, reusability and the like, and can meet the field application requirements of various types of fracturing.
Claims (10)
1. An anionic polyacrylamide emulsion, wherein the molecular formula of the anionic polyacrylamide emulsion is as follows:
wherein: a is an integer from 100000 to 450000;
b is an integer of 2000 to 225000;
c is an integer of 100 to 90000;
d is an integer of 100 to 90000;
x is an integer of 1 to 8;
r is C 1 ~C 16 Long chain alkyl or branched alkyl.
2. The anionic polyacrylamide emulsion of claim 1 wherein the anionic polyacrylamide emulsion has the formula:
wherein:
a is an integer of 150000 to 300000;
b is an integer of 10000 to 50000;
c is an integer of 5000 to 15000;
d is an integer of 1000 to 20000;
x is 2 or 3;
r is C 10 ~C 16 Branched alkyl groups of (a).
3. The anionic polyacrylamide emulsion of claim 2 wherein said anionic polyacrylamide emulsion has the formula:
wherein:
r is 5, 6-dimethyl decyl and has a structural formula:
4. the method for preparing an anionic polyacrylamide emulsion according to any one of claims 1-3, wherein the method comprises the following steps:
(1) Adding acrylamide, p-alkylstyrene, alpha-alkenyl sodium sulfonate and 2-acrylamide-2-methylpropanesulfonic acid into a three-neck flask with a stirring device and a condensation pipe, adding a first solvent, stirring for 10-30min under the condition of stirring speed of 300-500rpm, adding a first initiator after complete dissolution, adjusting the temperature to be the reflux temperature of the first solvent, continuously stirring for reaction for 4-6 h, and then cooling to obtain a mixture;
(2) Adding ammonia water into the mixture to adjust the pH value to 9-10, then adding an emulsifier, adjusting the stirring speed to 10000-50000rpm, simultaneously dissolving a second initiator into a second solvent, putting the second initiator into a constant-pressure dropping funnel, dropping the initiator at the speed of 10-60 drops/min, after the dropping is finished, heating to the reflux temperature of the second solvent, continuing to react for 2-6h, and then cooling to obtain an anionic polyacrylamide emulsion;
the mol ratio of the acrylamide to the p-alkylstyrene to the alpha-alkenyl sodium sulfonate to the 2-acrylamide-2-methylpropanesulfonic acid is 1:0.02 to 0.5:0.001 to 0.2:0.001 to 0.2.
5. The method according to claim 4, wherein the molar ratio of acrylamide, p-alkylstyrene, sodium alpha-olefin sulfonate and 2-acrylamide-2-methylpropanesulfonic acid is 1:0.08 to 0.15:0.05 to 0.1:0.05 to 0.1.
6. The preparation method according to claim 4, wherein in the step (1), the first solvent is one of N, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide, and the amount of the first solvent is 2 to 8 times of the mass of acrylamide.
7. The preparation method according to claim 4, wherein in the step (1), the first initiator is azobisisobutyronitrile, and the amount of the first initiator is 0.1 to 0.5 percent of the mass of the acrylamide.
8. The preparation method according to claim 4, wherein in the step (2), the emulsifier is one of sodium dodecyl benzene sulfonate and polyoxyethylene ether surfactant, and the dosage of the emulsifier is 0.3-2% of the mass of the acrylamide.
9. The preparation method according to claim 4, wherein in the step (2), the second initiator is one of persulfate and sulfite, and the amount of the second initiator is 0.05 to 0.5 percent of the mass of the acrylamide.
10. The preparation method according to claim 4, wherein in the step (2), the second solvent is deionized water, and the amount of the deionized water is 10 to 15 times of the mass of the acrylamide.
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| US20210122969A1 (en) * | 2019-10-28 | 2021-04-29 | S.P.C.M. Sa | Reverse emulsion for hydraulic fracturation |
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| CN101649024A (en) * | 2009-08-19 | 2010-02-17 | 中国海洋石油总公司 | Preparation method of water-in-water cationic polyacylamide emulsion |
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