CN116496769A - Solid acid blocking removing liquid system capable of complexing iron ions and preparation method thereof - Google Patents
Solid acid blocking removing liquid system capable of complexing iron ions and preparation method thereof Download PDFInfo
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- 239000011973 solid acid Substances 0.000 title claims abstract description 162
- -1 iron ions Chemical class 0.000 title claims abstract description 51
- 230000000903 blocking effect Effects 0.000 title claims abstract description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000000536 complexating effect Effects 0.000 title claims abstract description 9
- 239000007788 liquid Substances 0.000 title abstract description 59
- 230000007797 corrosion Effects 0.000 claims abstract description 69
- 238000005260 corrosion Methods 0.000 claims abstract description 69
- 239000004927 clay Substances 0.000 claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000003112 inhibitor Substances 0.000 claims abstract description 34
- 239000003381 stabilizer Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 20
- 230000000149 penetrating effect Effects 0.000 claims abstract description 20
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 10
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001103 potassium chloride Substances 0.000 claims abstract description 10
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 10
- HCFPRFJJTHMING-UHFFFAOYSA-N ethane-1,2-diamine;hydron;chloride Chemical compound [Cl-].NCC[NH3+] HCFPRFJJTHMING-UHFFFAOYSA-N 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 5
- 150000002462 imidazolines Chemical class 0.000 claims abstract description 3
- 125000003406 indolizinyl group Chemical class C=1(C=CN2C=CC=CC12)* 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 75
- 238000003756 stirring Methods 0.000 claims description 10
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 9
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 8
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 8
- 229940120146 EDTMP Drugs 0.000 claims description 7
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 7
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002981 blocking agent Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002357 osmotic agent Substances 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 abstract description 16
- 230000002579 anti-swelling effect Effects 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 8
- 239000003129 oil well Substances 0.000 abstract description 2
- 239000004579 marble Substances 0.000 description 36
- 239000002253 acid Substances 0.000 description 23
- 230000006378 damage Effects 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000012752 auxiliary agent Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- 230000036571 hydration Effects 0.000 description 10
- 238000006703 hydration reaction Methods 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 230000000087 stabilizing effect Effects 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- HOBCFUWDNJPFHB-UHFFFAOYSA-N indolizine Chemical compound C1=CC=CN2C=CC=C21 HOBCFUWDNJPFHB-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 3
- 208000027418 Wounds and injury Diseases 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 208000014674 injury Diseases 0.000 description 3
- 229960003330 pentetic acid Drugs 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
- 150000002478 indolizines Chemical class 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000599 controlled substance Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
Classifications
-
- 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
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention relates to the technical field of acidification in the exploration and development process of oil and gas fields, in particular to a solid acidolysis plugging liquid system capable of complexing iron ions and a preparation method thereof. The solid acid blocking removing liquid system comprises 8-20wt% of solid acid blocking removing agent, 0.1-1.0wt% of penetrating agent, 0.3-1.0wt% of corrosion inhibitor, 0.8-2.0wt% of clay stabilizer and the balance of water. The penetrating agent is one or more of dodecyl betaine, OP-10, OE-35 and fatty alcohol polyoxyethylene ether; the corrosion inhibitor is one or two of aldehyde ketone amine condensate, indolizine derivative, imidazoline derivative and thiourea; the clay stabilizer is one or two of potassium chloride, ethylenediamine hydrochloride, ammonium chloride and polyacrylamide. The solid acid plugging removing liquid system provided by the invention has low surface tension, the surface tension is lower than 29mN/m, and the surface tension is lower than 2mN/m; the solid acid plugging removing liquid system provided by the invention has excellent clay anti-swelling performance, and the anti-swelling rate is more than 90%. Therefore, the method can be widely applied to the acidification blocking removal of the oil well.
Description
Technical Field
The invention relates to the technical field of acidification in the exploration and development process of oil and gas fields, in particular to a solid acidolysis plugging liquid system capable of complexing iron ions and a preparation method thereof.
Background
During the processes of drilling, completion, oil extraction and well repair, external fluid and solid particles invade into a reservoir, a series of reservoir blockages are easily caused, and the yield is reduced or even stopped. Therefore, various blockage relieving and yield increasing technologies are provided for reservoir blockage, and the method has very important significance.
The acid-based blocking removal is the earliest blocking removal technology with obvious yield increasing effect, and HCl is used for increasing the yield of an oil well as early as 1895 American Standard Petroleum company, so that a good effect is obtained. As the conventional acid liquor has strong corrosiveness to pipeline equipment and high acid-rock reaction rate, various retarded acids such as foamed acid, gelled acid, emulsified acid, autogenous acid and the like are developed, and good effects are obtained. However, the current blocking removal technology is mainly a traditional liquid acidification blocking removal technology, such as hydrochloric acid, nitric acid and the like, and the acid liquid has a plurality of problems in the use process: (1) Hydrochloric acid and nitric acid are controlled medicines, and have great danger in the transportation and storage processes, so that the application range of the hydrochloric acid and nitric acid is limited; (2) The acid liquor has single function, multiple additives are needed to be added, and most of the additives are toxic and harmful substances and have far away requirements on current environmental protection and safety; (3) After the acidification operation, a large amount of metal cations (such as iron ions and the like) are generated, so that precipitation is easy to occur, secondary damage is caused to the stratum, and the acidification effect is reduced.
In order to solve the problems, researchers develop a series of solid acid removal systems, but the system performance differences are obvious, and the defects of complex preparation conditions, low corrosion efficiency, complex construction liquid preparation, poor performance of preventing a large amount of iron ions and the like exist. For example, the patent similar to the patent of the invention has a solid acid for removing blocking and promoting dissolution, a preparation method and an application thereof (CN 111088004A), wherein the patent uses glycolide-lactide copolymer, adipic acid, hydrolyzed polymaleic anhydride, polyvinyl alcohol, polyethylene oxide and plasticizer to prepare the solid acid for removing blocking and promoting dissolution, the preparation temperature of the solid acid reaches 150 ℃, the preparation difficulty is high, and meanwhile, the dissolution rate of the solid acid is slower, the operation period is long, and the subsequent construction is influenced; the patent discloses a solid acid blocking remover and a method for removing stratum blocking (CN 111621276A), which introduces a solid acid system which is divided into a pre-solution and a main treatment solution for construction, the construction mode is complex, citric acid is used as an iron ion stabilizer, and calcium citrate precipitation is easy to generate if a large amount of calcium ions are encountered in the operation process, so that secondary damage is caused to the stratum.
Disclosure of Invention
In view of the above problems, the invention provides a solid acid plugging liquid system capable of complexing iron ions and a preparation method thereof, and the solid acid plugging liquid system is suitable for stratum environment with the temperature of 20-80 ℃, can effectively erode carbonate stratum and has stronger capability of complexing iron ions, and prevents iron ions from precipitating; has low surface interfacial tension and excellent clay anti-swelling property.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
the invention provides a solid de-blocking agent capable of complexing iron ions, which comprises the following components in parts by mass:
50-90% of organic sulfonic acid;
5-30% of organic phosphonic acid;
5-30% of aminocarboxylic compounds.
Preferably, the organic sulfonic acid is one or more of methyl sulfonic acid, ethyl sulfonic acid, 1-propyl sulfonic acid and sulfamic acid; more preferably, the organic sulfonic acid is methylsulfonic acid or sulfamic acid.
Preferably, the organic phosphonic acid is one or more of diethylenetriamine penta-methylene phosphonic acid, amino-methylene phosphonic acid and ethylenediamine tetra-methylene phosphonic acid; more preferably, the organic phosphonic acid is selected from diethylenetriamine pentamethylenephosphonic acid or ethylenediamine tetramethylenephosphonic acid.
Preferably, the aminocarboxylic compound is one or more of diethyl triamine pentaacetic acid, nitrilotriacetic acid and ethylenediamine tetrapropionic acid; more preferably, the aminocarboxylic compound is diethyl triamine pentaacetic acid or nitrilotriacetic acid.
On the other hand, the invention also provides a solid acid plugging liquid system based on the solid acid plugging agent, wherein the solid acid plugging liquid system comprises the following components in parts by mass:
preferably, the penetrating agent is one or more of dodecyl betaine, OP-10, OE-35 and fatty alcohol-polyoxyethylene ether; more preferably, the osmotic agent is dodecyl betaine or OP-10.
Preferably, the corrosion inhibitor is one or two of aldehyde ketone amine condensate, indolizine derivative, imidazoline derivative and thiourea; more preferably, the corrosion inhibitor is aldehyde ketone amine condensate or indolizine derivative.
Preferably, the clay stabilizer is one or two of potassium chloride, ethylenediamine hydrochloride, ammonium chloride and polyacrylamide; more preferably, the clay stabilizer is potassium chloride or ethylenediamine hydrochloride.
The third object of the invention is to provide a preparation method of the solid acid plugging solution system, which comprises the following specific steps:
(1) Firstly, organic sulfonic acid and organic phosphonic acid are taken and uniformly mixed; secondly, adding an aminocarboxylic compound into the mixture, and uniformly stirring to obtain a solid acid blocking remover;
(2) Adding the solid acid blocking remover into water, and stirring and adding until the solid acid blocking remover is completely dissolved; secondly, adding a penetrating agent, and stirring until the penetrating agent is completely dissolved to obtain a mixed solution;
(3) Adding a corrosion inhibitor into the mixed solution, uniformly stirring, adding a clay stabilizer, and stirring until the clay stabilizer is completely dissolved to obtain a solid acid-plugging solution system.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The solid acid plugging liquid system provided by the invention is suitable for stratum environment with the temperature of 20-80 ℃, and can effectively erode carbonate stratum;
(2) The solid acid plugging removing liquid system provided by the invention has stronger capability of complexing iron ions, prevents iron ions from precipitating, has lower corrosion rate on N80 steel sheets, and has the corrosion rate lower than 1.5 g/(hMm) 2 )；
(3) The solid acid plugging removing liquid system provided by the invention has low surface tension, the surface tension is lower than 29mN/m, and the surface tension is lower than 2mN/m;
(4) The solid acid plugging removing liquid system provided by the invention has excellent clay anti-swelling performance, and the anti-swelling rate is more than 90%.
The invention overcomes the defects of high safety risk and the like of liquid acid in the transportation and storage processes, and avoids the need of special equipment for the controlled chemicals of hydrochloric acid and nitric acid in the transportation process; meanwhile, the risks of equipment corrosion and personnel safety caused by strong corrosive acid liquid such as hydrochloric acid, nitric acid, earth acid and the like are reduced in the on-site liquid preparation process.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present invention more readily apparent.
Drawings
FIG. 1 shows the dissolution rates of marble at 20-80deg.C for the solid acid plugging solution system prepared in example 11 of the present invention.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. While exemplary embodiments of the present application are shown, it should be understood that the present application may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
Example 1
The embodiment provides a solid acid plugging removing liquid system, wherein the main agent is a solid acid plugging removing agent, and the auxiliary agent is: the components of the penetrating agent, the corrosion inhibitor and the clay stabilizer are as follows in percentage by weight:
solid acid blocking remover: 50% sulfamic acid +30% diethylenetriamine pentamethylene phosphonic acid +20% ethylenediamine tetraacetic acid;
solid acid plugging liquid system: 20% of solid acid blocking remover, 0.5% of dodecyl betaine, 0.3% of aldehyde ketone amine corrosion inhibitor, 0.8% of potassium chloride and 78.4% of water;
the solid acid plugging solution system prepared by the preparation method of the invention is used for measuring the corrosion rate (for marble), surface interfacial tension, corrosion rate and iron ion stabilizing capacity of the solid acid plugging solution system at 60 ℃ according to the method in the technical requirement of Q/SH1020 2744-2019 acid plugging solution, and evaluating the clay anti-swelling rate of the solid acid plugging solution system after complete reaction with marble according to the method in the performance evaluation method of clay stabilizer for SY/T5971-2016 oil and gas field fracturing acidification and water injection, and the experimental results are shown in table 1.
TABLE 1 Properties of the solid acid plugging System in example 1
As shown in Table 1, the solid acid plugging solution system has good corrosion performance on marble, effectively reduces surface tension and interfacial tension, reduces corrosiveness of the system on N80 steel sheets, effectively stabilizes iron ions in the solution, reduces hydration expansion of clay, and prevents secondary damage to stratum, and all indexes meet standard requirements.
Example 2
The embodiment provides a solid acid plugging removing liquid system, wherein the main agent is a solid acid plugging removing agent, and the auxiliary agent is: the components of the penetrating agent, the corrosion inhibitor and the clay stabilizer are as follows in percentage by weight:
solid acid blocking remover: 50% sulfamic acid +20% ethylenediamine tetramethylene phosphonic acid +30% nitrilotriacetic acid;
solid acid plugging liquid system: 20% of solid acid blocking remover, 0.2% of OP-10, 0.3% of dodecyl betaine, 0.3% of indolizine corrosion inhibitor, 1.5% of polyacrylamide and 77.7% of water;
the solid acid plugging solution system prepared by the preparation method of the invention is used for measuring the corrosion rate (for marble), surface interfacial tension, corrosion rate and iron ion stabilizing capacity of the solid acid plugging solution system at 60 ℃ according to the method in the technical requirement of Q/SH1020 2744-2019 acid plugging solution, and evaluating the clay anti-swelling rate of the solid acid plugging solution system after complete reaction with marble according to the method in the performance evaluation method of clay stabilizer for SY/T5971-2016 oil and gas field fracturing acidification and water injection, and the experimental results are shown in Table 2.
TABLE 2 Properties of the solid acid plugging System in example 2
As shown in Table 2, the solid acid plugging solution system has good corrosion performance on marble, effectively reduces surface tension and interfacial tension, reduces corrosiveness of the system on N80 steel sheets, effectively stabilizes iron ions in the solution, reduces hydration expansion of clay, and prevents secondary damage to stratum, and all indexes meet standard requirements.
Example 3
The embodiment provides a solid acid plugging removing liquid system, wherein the main agent is a solid acid plugging removing agent, and the auxiliary agent is: the components of the penetrating agent, the corrosion inhibitor and the clay stabilizer are as follows in percentage by weight:
solid acid blocking remover: 60% sulfamic acid +20% aminotrimethylene phosphonic acid +20% diethyl triamine pentaacetic acid;
solid acid plugging liquid system: 18.0% of solid acid blocking remover, 0.3% of fatty alcohol polyoxyethylene ether, 0.2% of dodecyl betaine, 1.0% of aldehyde ketone amine corrosion inhibitor, 2.0% of ethylenediamine hydrochloride and 78.5% of water;
the solid acid plugging solution system prepared by the preparation method of the invention is used for measuring the corrosion rate (for marble), surface interfacial tension, corrosion rate and iron ion stabilizing capacity of the solid acid plugging solution system at 60 ℃ according to the method in the technical requirement of Q/SH1020 2744-2019 acid plugging solution, and evaluating the clay anti-swelling rate of the solid acid plugging solution system after complete reaction with marble according to the method in the performance evaluation method of clay stabilizer for SY/T5971-2016 oil and gas field fracturing acidification and water injection, and the experimental results are shown in Table 3.
TABLE 3 Properties of the solid acid plugging System in example 3
As shown in Table 3, the solid acid plugging solution system has good corrosion performance on marble, effectively reduces surface tension and interfacial tension, reduces corrosiveness of the system on N80 steel sheets, effectively stabilizes iron ions in the solution, reduces hydration expansion of clay, and prevents secondary damage to stratum, and all indexes meet standard requirements.
Example 4
The embodiment provides a solid acid plugging removing liquid system, wherein the main agent is a solid acid plugging removing agent, and the auxiliary agent is: the components of the penetrating agent, the corrosion inhibitor and the clay stabilizer are as follows in percentage by weight:
solid acid blocking remover: 60% methylsulfonic acid +25% diethylenetriamine pentamethylene phosphonic acid +15% nitrilotriacetic acid;
solid acid plugging liquid system: 18% of solid acid blocking remover, 0.8% of OE-35, 0.5% of thiourea corrosion inhibitor, 1.5% of ethylenediamine hydrochloride and 79.2% of water;
the solid acid plugging solution system prepared by the preparation method of the invention is used for measuring the corrosion rate (for marble), surface interfacial tension, corrosion rate and iron ion stabilizing capacity of the solid acid plugging solution system at 60 ℃ according to the method in the technical requirement of Q/SH1020 2744-2019 acid plugging solution, and evaluating the clay anti-swelling rate of the solid acid plugging solution system after complete reaction with marble according to the method in the performance evaluation method of clay stabilizer for SY/T5971-2016 oil and gas field fracturing acidification and water injection, and the experimental results are shown in table 4.
TABLE 4 Properties of the solid acid plugging System in example 4
As shown in Table 4, the solid acid plugging solution system has good corrosion performance on marble, effectively reduces surface tension and interfacial tension, reduces corrosiveness of the system on N80 steel sheets, effectively stabilizes iron ions in the solution, reduces hydration expansion of clay, and prevents secondary damage to stratum, and all indexes meet standard requirements.
Example 5
The embodiment provides a solid acid plugging removing liquid system, wherein the main agent is a solid acid plugging removing agent, and the auxiliary agent is: the components of the penetrating agent, the corrosion inhibitor and the clay stabilizer are as follows in percentage by weight:
solid acid blocking remover: 70% of methylsulfonic acid, 10% of aminotrimethylene phosphonic acid and 20% of ethylenediamine tetrapropionic acid;
solid acid plugging liquid system: 15% of solid acid blocking remover, 1.0% of dodecyl betaine, 0.7% of thiourea corrosion inhibitor, 2.0% of polyacrylamide and 81.3% of water;
the solid acid plugging solution system prepared by the preparation method of the invention is used for measuring the corrosion rate (for marble), surface interfacial tension, corrosion rate and iron ion stabilizing capacity of the solid acid plugging solution system at 60 ℃ according to the method in the technical requirement of Q/SH1020 2744-2019 acid plugging solution, and evaluating the clay anti-swelling rate of the solid acid plugging solution system after complete reaction with marble according to the method in the performance evaluation method of clay stabilizer for SY/T5971-2016 oil and gas field fracturing acidification and water injection, and the experimental results are shown in Table 5.
TABLE 5 Properties of the solid acid plugging System in example 5
As shown in Table 5, the solid acid plugging solution system has good corrosion performance on marble, effectively reduces surface tension and interfacial tension, reduces corrosiveness of the system on N80 steel sheets, effectively stabilizes iron ions in the solution, reduces hydration expansion of clay, and prevents secondary damage to stratum, and all indexes meet standard requirements.
Example 6
The embodiment provides a solid acid plugging removing liquid system, wherein the main agent is a solid acid plugging removing agent, and the auxiliary agent is: the components of the penetrating agent, the corrosion inhibitor and the clay stabilizer are as follows in percentage by weight:
solid acid blocking remover: 70% of methylsulfonic acid +20% of ethylenediamine tetramethylene phosphonic acid +10% of diethylenetriamine pentaacetic acid;
solid acid plugging liquid system: 15% of solid acid blocking remover, 0.6% of OP-10, 0.4% of fatty alcohol polyoxyethylene ether, 1.0% of indolizine corrosion inhibitor, 0.5% of potassium chloride, 0.5% of ethylenediamine hydrochloride and 80% of water;
the solid acid plugging solution system prepared by the preparation method of the invention is used for measuring the corrosion rate (for marble), surface interfacial tension, corrosion rate and iron ion stabilizing capacity of the solid acid plugging solution system at 60 ℃ according to the method in the technical requirement of Q/SH1020 2744-2019 acid plugging solution, and evaluating the clay anti-swelling rate of the solid acid plugging solution system after complete reaction with marble according to the method in the performance evaluation method of clay stabilizer for SY/T5971-2016 oil and gas field fracturing acidification and water injection, and the experimental results are shown in Table 6.
TABLE 6 Properties of the solid acid plugging System in example 6
As shown in Table 6, the solid acid plugging solution system has good corrosion performance on marble, effectively reduces surface tension and interfacial tension, reduces corrosiveness of the system on N80 steel sheets, effectively stabilizes iron ions in the solution, reduces hydration expansion of clay, and prevents secondary damage to stratum, and all indexes meet standard requirements.
Example 7
The embodiment provides a solid acid plugging removing liquid system, wherein the main agent is a solid acid plugging removing agent, and the auxiliary agent is: the components of the penetrating agent, the corrosion inhibitor and the clay stabilizer are as follows in percentage by weight:
solid acid blocking remover: 80% methylsulfonic acid +10% diethylenetriamine pentamethylene phosphonic acid +10% nitrilotriacetic acid;
solid acid plugging liquid system: 12% of solid acid blocking remover, 0.2% of OE-35, 0.5% of imidazoline corrosion inhibitor, 1.0% of ammonium chloride and 86.3% of water;
the solid acid plugging solution system prepared by the preparation method of the invention is used for measuring the corrosion rate (for marble), surface interfacial tension, corrosion rate and iron ion stabilizing capacity of the solid acid plugging solution system at 60 ℃ according to the method in the technical requirement of Q/SH1020 2744-2019 acid plugging solution, and evaluating the clay anti-swelling rate of the solid acid plugging solution system after complete reaction with marble according to the method in the performance evaluation method of clay stabilizer for SY/T5971-2016 oil and gas field fracturing acidification and water injection, and the experimental results are shown in Table 7.
TABLE 7 Properties of the solid acid plugging System in example 7
As shown in Table 7, the solid acid plugging solution system has good corrosion performance on marble, effectively reduces surface tension and interfacial tension, reduces corrosiveness of the system on N80 steel sheets, effectively stabilizes iron ions in the solution, reduces hydration expansion of clay, and prevents secondary damage to stratum, and all indexes meet standard requirements.
Example 8
The embodiment provides a solid acid plugging removing liquid system, wherein the main agent is a solid acid plugging removing agent, and the auxiliary agent is: the components of the penetrating agent, the corrosion inhibitor and the clay stabilizer are as follows in percentage by weight:
solid acid blocking remover: 80% of ethylsulfonic acid +15% of aminotrimethylene phosphonic acid and 5% of ethylenediamine tetrapropionic acid;
solid acid plugging liquid system: 12% of solid acid blocking remover, 0.1% of OE-35, 0.1% of fatty alcohol polyoxyethylene ether, 0.3% of aldehyde ketone amine corrosion inhibitor, 0.3% of thiourea corrosion inhibitor, 0.8% of polyacrylamide and 86.4% of water;
the solid acid plugging solution system prepared by the preparation method of the invention is used for measuring the corrosion rate (for marble), surface interfacial tension, corrosion rate and iron ion stabilizing capacity of the solid acid plugging solution system at 60 ℃ according to the method in the technical requirement of Q/SH1020 2744-2019 acid plugging solution, and evaluating the clay anti-swelling rate of the solid acid plugging solution system after complete reaction with marble according to the method in the performance evaluation method of clay stabilizer for SY/T5971-2016 oil and gas field fracturing acidification and water injection, and the experimental results are shown in Table 8.
TABLE 8 Properties of the solid acid blocking liquid System in example 8
As shown in Table 8, the solid acid plugging solution system has good corrosion performance on marble, effectively reduces surface tension and interfacial tension, reduces corrosiveness of the system on N80 steel sheets, effectively stabilizes iron ions in the solution, reduces hydration expansion of clay, and prevents secondary damage to stratum, and all indexes meet standard requirements.
Example 9
The embodiment provides a solid acid plugging removing liquid system, wherein the main agent is a solid acid plugging removing agent, and the auxiliary agent is: the components of the penetrating agent, the corrosion inhibitor and the clay stabilizer are as follows in percentage by weight:
solid acid blocking remover: 80% of ethylsulfonic acid +5% of ethylenediamine tetramethylene phosphonic acid +15% of diethylenetriamine pentaacetic acid;
solid acid plugging liquid system: 12% of solid acid blocking remover, 0.6% of fatty alcohol polyoxyethylene ether, 0.4% of dodecyl betaine, 0.5% of aldehyde ketone amine corrosion inhibitor, 0.5% of indolizine corrosion inhibitor, 0.8% of potassium chloride, 0.8% of polyacrylamide and 84.4% of water;
the solid acid plugging solution system prepared by the preparation method of the invention is used for measuring the corrosion rate (for marble), surface interfacial tension, corrosion rate and iron ion stabilizing capacity of the solid acid plugging solution system at 60 ℃ according to the method in the technical requirement of Q/SH1020 2744-2019 acid plugging solution, and evaluating the clay anti-swelling rate of the solid acid plugging solution system after complete reaction with marble according to the method in the performance evaluation method of clay stabilizer for SY/T5971-2016 oil and gas field fracturing acidification and water injection, and the experimental results are shown in Table 9.
TABLE 9 Properties of the solid acid plugging System in example 9
As shown in Table 9, the solid acid plugging solution system has good corrosion performance on marble, effectively reduces surface tension and interfacial tension, reduces corrosiveness of the system on N80 steel sheets, effectively stabilizes iron ions in the solution, reduces hydration expansion of clay, and prevents secondary damage to stratum, and all indexes meet standard requirements.
Example 10
The embodiment provides a solid acid plugging removing liquid system, wherein the main agent is a solid acid plugging removing agent, and the auxiliary agent is: the components of the penetrating agent, the corrosion inhibitor and the clay stabilizer are as follows in percentage by weight:
solid acid blocking remover: 90% 1-propylsulfonic acid+5% diethylenetriamine pentamethylene phosphonic acid+5% nitrilotriacetic acid;
solid acid plugging liquid system: 8% of solid acid blocking remover, 0.1% of OP-10, 0.1% of OE-35, 0.7% of indolizine corrosion inhibitor, 1.0% of ammonium chloride and 90.1% of water;
the solid acid plugging solution system prepared by the preparation method of the invention is used for measuring the corrosion rate (for marble), surface interfacial tension, corrosion rate and iron ion stabilizing capacity of the solid acid plugging solution system at 60 ℃ according to the method in the technical requirement of Q/SH1020 2744-2019 acid plugging solution, and evaluating the clay anti-swelling rate of the solid acid plugging solution system after complete reaction with marble according to the method in the performance evaluation method of clay stabilizer for SY/T5971-2016 oil and gas field fracturing acidification and water injection, and the experimental results are shown in Table 10.
TABLE 10 Properties of the solid acid plugging System in example 10
As shown in Table 10, the solid acid plugging solution system has good corrosion performance on marble, effectively reduces surface tension and interfacial tension, reduces corrosiveness of the system on N80 steel sheets, effectively stabilizes iron ions in the solution, reduces hydration expansion of clay, and prevents secondary damage to stratum, and all indexes meet standard requirements.
Example 11
The embodiment provides a solid acid plugging removing liquid system, wherein the main agent is a solid acid plugging removing agent, and the auxiliary agent is: the components of the penetrating agent, the corrosion inhibitor and the clay stabilizer are as follows in percentage by weight:
solid acid blocking remover: 80% 1-propylsulfonic acid+5% aminotrimethylene phosphonic acid+15% ethylenediamine tetrapropionic acid;
solid acid plugging liquid system: 18% of solid acid blocking remover, 0.5% of OP-10, 0.5% of imidazoline corrosion inhibitor, 0.8% of potassium chloride and 80.2% of water;
the solid acid plugging solution system prepared by the preparation method of the invention is tested according to the method in the technical requirement of Q/SH1020 2744-2019 acid plugging solution, the corrosion rate (for marble) of the solid acid plugging solution system in different time periods of 20-80 ℃ is measured, and the experimental result is shown in figure 1.
As can be seen from fig. 1, as the reaction temperature increases, the dissolution rate of the deblocking liquid system for marble increases gradually, and finally the dissolution rate of the deblocking liquid system for marble increases, which means that the temperature can promote the dissolution of the deblocking liquid system for marble.
Example 12
The embodiment provides a solid acid plugging removing liquid system, wherein the main agent is a solid acid plugging removing agent, and the auxiliary agent is: the components of the penetrating agent, the corrosion inhibitor and the clay stabilizer are as follows in percentage by weight:
solid acid blocking remover: 80% sulfamic acid +5% diethylenetriamine penta-methylene phosphonic acid +15% diethylenetriamine pentaacetic acid;
solid acid plugging liquid system: 18% of solid acid blocking remover, 0.5% of OP-10, 0.5% of thiourea corrosion inhibitor, 0.8% of potassium chloride and 80.2% of water;
according to the solid acid plugging liquid system prepared by the preparation method, excessive marble is added into the solid acid plugging liquid system, after the reaction is finished, solid acid plugging liquid residual liquid is obtained, the harmfulness of the residual liquid to a rock core is evaluated by referring to a method in SY/T5107-2016 water-based fracturing liquid evaluation method, and the experimental results are shown in Table 11.
Table 11 experimental data on the injury of the gel breaking liquid to the core
| Core type | Permeability before damage/mD | Post-injury permeability/mD | Injury rate |
| Carbonate rock | 0.0186 | 0.0162 | 12.90％ |
The damage data of the plugging removal liquid residual liquid is 12.90 percent through experiments, which is far lower than the technical requirement that the core matrix permeability damage is less than 30 percent in SY/T6376-2008 fracturing liquid general technical condition, the performance characteristics of low damage are shown, and the method is favorable for improving the yield of reservoirs.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art can easily think about variations, substitutions and improvements within the technical scope of the present invention, and the scope of the present invention is intended to be covered by the present invention.
In the description provided herein, numerous specific details are set forth. However, it is understood that embodiments of the present application may be practiced without these specific details. In some instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.
Claims (15)
1. The solid acid blocking remover capable of complexing iron ions is characterized by comprising the following components in parts by mass:
50-90% of organic sulfonic acid;
5-30% of organic phosphonic acid;
5-30% of aminocarboxylic compounds.
2. The solid acid blocking remover according to claim 1, wherein the organic sulfonic acid is one or more of methyl sulfonic acid, ethyl sulfonic acid, 1-propyl sulfonic acid and sulfamic acid.
3. The solid acid blocking agent according to claim 2, wherein the organic sulfonic acid is methylsulfonic acid or sulfamic acid.
4. The solid acid blocking remover according to claim 1, wherein the organic phosphonic acid is one or more of diethylenetriamine penta-methylene phosphonic acid, amino-methylene phosphonic acid and ethylenediamine tetra-methylene phosphonic acid.
5. The solid acid blocking remover according to claim 4, wherein the organic phosphonic acid is diethylenetriamine penta-methylene phosphonic acid or ethylenediamine tetra-methylene phosphonic acid.
6. The solid acid blocking remover according to claim 1, wherein the aminocarboxylic compound is one or more of diethyl triamine pentaacetic acid, nitrilotriacetic acid and ethylenediamine tetraacetic acid.
7. The solid acid plugging agent according to claim 6, wherein the aminocarboxylic compound is diethyl triamine pentaacetic acid or nitrilotriacetic acid.
8. A solid acid plugging solution system comprising the solid acid plugging agent according to any one of claims 1 to 7, wherein the solid acid plugging solution system comprises the following components in mass percent:
9. the solid acid plugging removal system of claim 8, wherein the penetrating agent is one or more of dodecyl betaine, OP-10, OE-35, and fatty alcohol polyoxyethylene ether.
10. The solid acid plugging system of claim 9, wherein the osmotic agent is dodecyl betaine or OP-10.
11. The solid acid plugging solution system according to claim 8, wherein the corrosion inhibitor is one or two of aldehyde ketone amine condensate, indolizine derivative, imidazoline derivative and thiourea.
12. The solid acid plugging solution system according to claim 11, wherein the corrosion inhibitor is an aldehyde ketone amine condensate or an indolizine derivative.
13. The solid acid plugging solution system according to claim 8, wherein the clay stabilizer is one or two of potassium chloride, ethylenediamine hydrochloride, ammonium chloride and polyacrylamide.
14. The solid acid plugging removal system of claim 13, wherein the clay stabilizer is potassium chloride or ethylenediamine hydrochloride.
15. The method for preparing a solid acid plugging solution system according to any one of claims 8 to 14, wherein the preparation method comprises the following specific steps:
(1) Firstly, organic sulfonic acid and organic phosphonic acid are taken and uniformly mixed; secondly, adding an aminocarboxylic compound into the mixture, and uniformly stirring to obtain a solid acid blocking remover;
(2) Adding the solid acid blocking remover into water, and stirring and adding until the solid acid blocking remover is completely dissolved; secondly, adding a penetrating agent, and stirring until the penetrating agent is completely dissolved to obtain a mixed solution;
(3) Adding a corrosion inhibitor into the mixed solution, uniformly stirring, adding a clay stabilizer, and stirring until the clay stabilizer is completely dissolved to obtain a solid acid-plugging solution system.
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