CN117025195A - Resistance-reducing retarded acid and application thereof - Google Patents
Resistance-reducing retarded acid and application thereof Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 79
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003463 adsorbent Substances 0.000 claims abstract description 22
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 14
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 13
- 239000002562 thickening agent Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 8
- 230000020477 pH reduction Effects 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- -1 carbonate hydrocarbon Chemical class 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 3
- 230000035699 permeability Effects 0.000 claims description 3
- 229940126214 compound 3 Drugs 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000011435 rock Substances 0.000 abstract description 19
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 11
- 230000036632 reaction speed Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 230000000979 retarding effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical class OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 230000035515 penetration Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- GZOWLNNGTRYBDH-UHFFFAOYSA-N 2,3,4,5-tetrafluoro-6-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoronon-1-enoxy)benzenesulfonic acid Chemical compound FC=1C(=C(C(=C(C=1F)F)F)S(=O)(=O)O)OC(=C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F GZOWLNNGTRYBDH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- SHGAZHPCJJPHSC-YCNIQYBTSA-N all-trans-retinoic acid Chemical compound OC(=O)\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C SHGAZHPCJJPHSC-YCNIQYBTSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229930002330 retinoic acid Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229960001727 tretinoin Drugs 0.000 description 1
- 238000009736 wetting Methods 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
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
- E21B43/27—Methods for stimulating production by forming crevices or fractures by use of eroding chemicals, e.g. acids
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a resistance-reducing retarded acid and application thereof, wherein the resistance-reducing retarded acid comprises the following components in percentage by weight: 5-20% of hydrochloric acid, 0.1-0.8% of thickening agent and 2-5% of active adsorbent; 5-30% of complex acid and the balance of water; the complex acid comprises polybasic acid and sulfonic acid, and condensate of polybasic acid and sulfonic acid with amine and aldehyde respectively; the resistance-reducing retarded acid has the advantages of low viscosity, low acid-rock reaction speed and low interfacial tension, and can be used for low-permeability carbonate rock oil-gas reservoirs under higher temperature conditions.
Description
Technical Field
The invention relates to the technical field of oil gas chemicals, in particular to resistance-reducing retarded acid and application thereof.
Background
In the conventional acidification, the acid rock reaction rate is high, and the penetration distance of the acid is short, so that the damage of the near-wellbore zone can be eliminated only; and the single acid liquor is even in etching and low in flow conductivity. The deep acidizing of the stratum can be performed by using the retarded acid technology, and meanwhile, groove-shaped non-uniform etching artificial cracks are formed by means of the difference of acid rock reaction speeds of different acid liquids, so that the action depth and the diversion capability of acid fracturing are further improved. The novel retarded acid system consists of a permeation component, retarded acid and other components. The organic acid contained in the novel retarded acid system is a multi-element organic acid, and can generate a plurality of H after ionization in aqueous solution + The primary ionization degree is low, the step-by-step ionization can be carried out under different external environment conditions after the water enters the stratum, and the H is slowly released + Reacts with carbonate and can maintain a lower pH for a longer period of time. Compared with strong acid such as hydrochloric acid, the reaction rate of the acid rock is lower, the acidification distance can be increased to a certain extent, and the aim of retarding is fulfilled. The retarder molecules are introduced into the drag-reducing retarder acid system, and can be carbonateThe surface of the rock forms an adsorption layer to weaken H + The diffusion speed to the surface of the carbonate rock is improved, and the retarding effect of the acid liquor is improved. The penetrating component can obviously reduce the interfacial tension and wetting angle of the system, improve the permeability of the system, fully exert the retarding performance of the system, and act on deep stratum to achieve the purpose of deep acidification.
North China oil-gas separation company high-temperature low-permeability carbonate oil-gas reservoir, poor reservoir connectivity, large seepage resistance, high temperature and high closing pressure, and acid liquor with low acid rock reaction rate, high temperature resistance and good permeation effect is needed to realize deep penetration. The acid liquor system widely used at present realizes the retarding effect mostly through two ways, one is to reduce H by increasing the viscosity of the acid liquor represented by conventional thickening acid + The diffusion speed to the surface of the rock stratum is increased, so that the purpose of retarding the acid liquor system is achieved. However, the acid liquor system has high viscosity and high friction resistance, which causes difficulty in pumping, and has high interfacial tension and seepage resistance, so that the multi-directional etching communication of cracks is difficult to realize. The other is to isolate the acid liquid from the rock surface by emulsification or foaming, so as to realize retarding effect. Although the acid liquor has lower viscosity and is favorable for deep penetration, the acid liquor is limited by the influence of additives such as foaming agents or emulsifying agents, and the like, so that the acid liquor has obviously insufficient temperature resistance and cannot be applied to a high-temperature reservoir.
Therefore, the present field needs to design a retarded acid with low viscosity, slow acid rock reaction speed and low interfacial tension, and the retarded acid is introduced into a high-temperature low-permeability carbonate rock oil-gas reservoir to meet the requirement of being used under the condition of higher temperature.
Disclosure of Invention
The invention provides a resistance-reducing retarded acid and application thereof, and at least solves the defect that retarded acid in the prior art cannot meet the requirement of a high-temperature low-permeability carbonate oil-gas reservoir.
In order to achieve the above object, the present invention is as follows:
the composition of the drag-reducing retarded acid comprises the following components in percentage by weight: 5 to 20 percent of hydrochloric acid, 0.1 to 0.8 percent of thickening agent and 2 to 5 percent of active adsorbent; 5-30% of complex acid and the balance of water; the complex acid comprises polybasic acid and sulfonic acid, and condensate of polybasic acid and sulfonic acid with amine and aldehyde respectively.
Further, the active adsorbent comprises the following components in percentage by weight: fluorocarbon activator: 0.1 to 0.5 percent of Mannich base 10 to 25 percent, propynyl epoxy compound 3 to 15 percent and the balance of methanol.
Further, the complex acid is obtained by reacting excessive polybasic acid and sulfonic acid with ethylenediamine and formaldehyde at 85-90 ℃ for 6-8 h.
Further, the polyacid is phosphoric acid.
Still further, the condensate has the structural formula (I):
wherein R is taken fromThe condensate accounts for 2-10% of the total amount of the resistance-reducing retarded acid according to the mass ratio.
Further, the thickening agent is at least one of polyacrylamide and derivatives thereof, and carboxymethyl cellulose and derivatives thereof.
Preferably, the molecular weight of the thickener is 5000-200000.
The invention also provides application of the drag reducing and retarding acid in sandstone reservoir acidification, and the drag reducing and retarding acid has the advantages of low viscosity, low acid-rock reaction speed and low interfacial tension, is introduced into a high-temperature low-permeability carbonate rock oil-gas reservoir, and can be used under a higher temperature condition.
Further, the sandstone reservoir is a low permeability carbonate hydrocarbon reservoir.
Further, the acidification process temperature is above 160 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the drag-reducing retarded acid obtained by the compound acid and the active adsorbent has the advantages of low viscosity, slow reaction speed of acid rock and low interfacial tension, is introduced into a high-temperature low-permeability carbonate rock oil-gas reservoir, and can be used under the condition of higher temperature.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with preferred embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In one embodiment, a drag reducing retarder is provided, comprising the following components in percentage by weight: 5-20% of hydrochloric acid, 0.1-0.8% of thickening agent and 2-5% of active adsorbent; 5-30% of complex acid and the balance of water; the complex acid comprises polybasic acid and sulfonic acid, and condensate of polybasic acid and sulfonic acid with amine and aldehyde respectively. The active adsorbent comprises the following components in percentage by weight: fluorocarbon activator: 0.1-0.5%, 10-25% of Mannich base, 3-15% of propynyl epoxy compound and the balance of methanol. The Mannich base group is used as an adsorption main agent; the fluorocarbon active agent has the functions of dispersion and adsorption; the propargyl alcohol epoxide acts as a potentiator. The complex acid comprises polybasic acid, sulfonic acid and condensate of the polybasic acid and the sulfonic acid, and is obtained by reacting excessive polybasic acid, sulfonic acid, ethylenediamine and formaldehyde for 6-8 hours at 85-90 ℃. The complex acid satisfies the multi-stage ionization H + On the other hand, the condensation product has slow release performance, and the comprehensive performance of the drag reducing retarded acid is improved.
In a preferred embodiment, the polyacid may be selected from organic or inorganic acids above the usual diacids, preferably phosphoric acid. Taking phosphoric acid as an example, the product produced in the reaction process of the phosphoric acid, ethylenediamine and formaldehyde has the structure shown in the formula (I):
wherein the substituents R are taken fromThe condensate of the structure of the formula (I) accounts for 2-10wt% of the total amount of the resistance-reducing retarder acid. The condensate of the structure of formula (I) aids in the uniform dispersion of the organic acid solution in the formation.
In a preferred embodiment, H is reduced to meet the viscosity of the acid solution + The thickening agent is at least one of polyacrylamide and derivatives thereof, and carboxymethyl cellulose and derivatives thereof; preferably, the molecular weight of the thickener is 5000-200000.
In the above examples, the fluorocarbon surfactant means that all or part of hydrogen atoms in hydrocarbon chains of the hydrocarbon surfactant are replaced with fluorine atoms, that is, fluorocarbon chains replace hydrocarbon chains, so that the nonpolar groups in the surfactant have not only hydrophobic properties but also unique oleophobic properties. The Mannich base is a common modified amine epoxy curing agent, is generally prepared by Mannich reaction of formaldehyde, phenolic active hydrogen and amine active hydrogen, has excellent epoxy curing activity, contains a heat-resistant rigid phenolic aldehyde skeleton structure in a molecular structure, and can remarkably improve the heat deformation temperature of a cured product, so that the cured product has excellent heat resistance and corrosion resistance. The propiolic epoxide is condensate of propiolic alcohol and epoxy compounds such as ethylene oxide or propylene oxide, and is widely used in petroleum exploitation industry as a key effective component of an efficient acidification corrosion inhibitor under high temperature and high pressure and high concentration hydrochloric acid in an oil-gas well.
In preferred embodiments, the fluorocarbon surfactant includes, but is not limited to, one or more of sodium perfluorononenoxybenzenesulfonate, fluorocarbon surfactants FS-10, FS-50; the propynyl alcohol epoxide compounds include, but are not limited to, one or more of ethylene oxide propynyl alcohol, propylene oxide propynyl alcohol.
In another embodiment, the preparation method of the drag reducing retarded acid is provided, and the preparation method is obtained by sequentially adding metered hydrochloric acid, a thickening agent, an active adsorbent, a compound acid and the balance of water and fully stirring.
The following is a preferred embodiment for explaining the technical scheme provided by the invention and verifying the technical effects thereof. Unless otherwise specified, the starting materials used in the following examples were all commercially available standard chemicals.
Example 1
The composition of the drag-reducing retarded acid is 100% of the total mass ratio: 15% of hydrochloric acid, 0.5% of polyacrylamide and 3% of active adsorbent; 5% of phosphoric acid, 5% of methylsulfonic acid, 10% of a polymer with a structure of formula (I) and the balance of water. The active adsorbent comprises the following components in percentage by mass of 100 percent: 0.5% of perfluor nonenoxybenzenesulfonic acid sodium, 10% of Mannich base, 10% of propylene oxide alkynol and the balance of methanol.
Example 2
The composition of the drag-reducing retarded acid is 100% of the total mass ratio: 5% of hydrochloric acid, 0.3% of carboxymethyl cellulose and 2% of active adsorbent; 15% of phosphoric acid, 7% of methylsulfonic acid, 8% of a polymer with a structure of formula (I) and the balance of water. The active adsorbent comprises the following components in percentage by mass of 100 percent: fluorocarbon surfactant FS-10.3%, mannich base 15%, oxirane propargyl alcohol 5% and the balance of methanol.
Example 3
The composition of the drag-reducing retarded acid is 100% of the total mass ratio: 20% of hydrochloric acid, 0.3% of polyacrylamide, 0.5% of carboxymethyl cellulose and 5% of active adsorbent; 2% of phosphoric acid, 2% of methylsulfonic acid, 2% of a polymer of the structure of formula (I), and the balance of water. The active adsorbent comprises the following components in percentage by mass of 100 percent: fluorocarbon surfactant FS-50.2%, mannich base 25%, propylene oxide propargyl alcohol 3% and the balance of methanol.
Example 4
The composition of the drag-reducing retarded acid is 100% of the total mass ratio: 8% of hydrochloric acid, 0.1% of polyacrylamide, 0.5% of carboxymethyl cellulose and 3% of active adsorbent; 10% of phosphoric acid, 8% of methylsulfonic acid, 10% of a polymer with a structure of formula (I) and the balance of water. The active adsorbent comprises the following components in percentage by mass of 100 percent: fluorocarbon surfactant FS-50.5%, mannich base 20%, propylene oxide propargyl alcohol 15% and the balance of methanol.
Comparative example 1
The composition of the drag reducing retarder is different from that of the embodiment 1 in that the compound acid does not contain condensate with the structure of the formula (I), and other components and contents are the same.
Comparative example 2
The composition of the drag-reducing retarded acid is 100% of the total mass ratio: 15% of hydrochloric acid, 0.5% of polyacrylamide and 3% of active adsorbent; 15% of phosphoric acid, 5% of methylsulfonic acid and the balance of water. The active adsorbent comprises the following components in percentage by mass of 100 percent: 0.5% of perfluor nonenoxybenzenesulfonic acid sodium, 10% of Mannich base, 10% of propylene oxide alkynol and the balance of methanol.
Comparative example 3
The composition of the retarder acid is different from that of example 1 in that the retarder acid does not contain phosphoric acid, the proportion of the methanesulfonic acid is 10%, and the other components and the content are the same.
Comparative example 4
The composition of the anti-drag retarder is different from that of example 1 in that the active adsorbent component does not contain Mannich base, and other components and the content are the same.
Comparative example 5
The composition of the drag reducing retarder is different from that of the embodiment 1 in that the active adsorbent component does not contain fluorocarbon surfactant, and other components and the content are the same.
Comparative example 6
The composition of the drag reducing retarder differs from that of example 1 in that the active adsorbent component does not contain a propynyl epoxy compound, and the other components and the content are the same.
Experimental example
1) Measuring the corrosion capacity of the system after 24 hours at 90 ℃; the control group was 20% hydrochloric acid and the results are shown in Table 1.
Table 1: EXAMPLES 1 to 4 comparative results of the corrosion rates of Retinoic acid and 20% hydrochloric acid
| Group of | Corrosion rate% |
| Example 1 | 98.4 |
| Example 2 | 98.2 |
| Example 3 | 98.6 |
| Example 4 | 98.3 |
| Hydrochloric acid | 98.5 |
As can be seen from Table 1, the dissolution rates of the retarder acids of examples 1 to 4 were comparable to those of 20% hydrochloric acid after 24 hours at 90 ℃.
2) Friction resistance performance test
The friction resistances of the different fluids of the examples 1-4, the friction resistances of which are tested under different shear rates in a 1/4' pipeline by using a pipeline friction resistance measuring instrument, and the results show that the friction resistances of the examples 1-4 are gradually increased along with the increase of the shear rate, and the shear rate is 14000s -1 When the resistance is reduced, the resistance can reach 52 percent. And the resistance reduction rate of the comparative examples 1-2 and comparative example 5 is less than 40%.
3) The indexes such as the retardation rate of the resistance-reducing retarded acid and the high-temperature corrosion speed are measured, and the results are shown in Table 2.
Table 2: results of examples and comparative examples
Note that: the static corrosion speed is the corrosion effect when the static corrosion speed acts on the carbonate rock core for 4 hours at 90 ℃ under normal pressure; the dynamic corrosion speed is the corrosion effect when 60r/min acts on the carbonate rock core for 4 hours under the pressure conditions of 120 ℃ and more than or equal to 8 MPa. The corrosion speed at 160 ℃ is the corrosion effect when 60r/min acts on the carbonate rock core for 4 hours under the pressure conditions of 160 ℃ and more than or equal to 16 MPa.
Discussion: as can be seen from table 2, the resistance-reducing retarded acids obtained in examples 1 to 4 have excellent retarded rate, and the static and dynamic corrosion rates are controlled in a small range, and the corrosion rate is still low at 160 ℃ high temperature, the temperature resistance is strong, and the acid-reducing retarded acid has the remarkable advantage of being used for acidizing a low-permeability carbonate hydrocarbon reservoir at high temperature. When the condensate of the structure of formula (I) is not used in comparative example 1 and when the addition of the condensate is replaced with excessively added phosphoric acid in comparative example 2, the slow release rate is lowered and the high temperature corrosion rate is increased, probably because the non-addition of the condensate is unfavorable for the uniform dispersion of the organic acid liquid in the formation; after a 10% increase in the methylsulfonic acid ratio in comparative example 3, and due to the lack of H for multistage ionization + Leading to a decrease in the slow release rate, the actual sulfonic acid being more acidic than the phosphoric acid, leading to a significant decrease in the rate of the corrosion reaction during penetration of the deep formation. In comparative examples 4 to 6, the sustained release rate was decreased in the absence of the mannich base, the fluorocarbon surfactant, and the propynyl alcohol epoxy compound, respectively, indicating that the coexistence of the three has a synergistic effect in improving the sustained release rate.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The anti-drag retarded acid is characterized by comprising the following components in percentage by weight: 5-20% of hydrochloric acid, 0.1-0.8% of thickening agent and 2-5% of active adsorbent; 5-30% of complex acid and the balance of water; the complex acid comprises polybasic acid and sulfonic acid, and condensate of polybasic acid and sulfonic acid with amine and aldehyde respectively.
2. The resistance-reducing retarder of claim 1, wherein the active adsorbent comprises, in weight percent: fluorocarbon activator: 0.1 to 0.5 percent of Mannich base 10 to 25 percent, propynyl epoxy compound 3 to 15 percent and the balance of methanol.
3. The resistance-reducing retarded acid according to claim 1, wherein the complex acid is obtained by reacting excessive polybasic acid and sulfonic acid with ethylenediamine and formaldehyde at 85-90 ℃ for 6-8 hours.
4. A drag reducing retarded acid according to claim 3 wherein the polyacid is phosphoric acid.
5. The drag reducing retarder of claim 4, wherein the condensate has the structural formula (I):
wherein R is taken fromThe condensate accounts for 2-10% of the total amount of the resistance-reducing retarded acid according to the mass ratio.
6. The drag reducing retarder of claim 1, wherein the thickener is at least one of modified polyacrylamide and derivatives thereof, carboxymethyl cellulose and derivatives thereof.
7. The drag reducing retarder of claim 6, wherein the thickener has a molecular weight of 5000-200000.
8. Use of a drag reducing retarded acid according to any one of claims 1 to 7 in sandstone reservoir acidizing.
9. The use of claim 8, wherein the sandstone reservoir is a low permeability carbonate hydrocarbon reservoir.
10. The use according to claim 8, wherein the acidification process temperature is above 160 ℃.
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| CN117986458A (en) * | 2024-04-02 | 2024-05-07 | 成都劳恩普斯科技有限公司 | High-temperature-resistant deep penetration molecular diaphragm acid copolymer and preparation method thereof |
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