CN117430634A - Iron ion stabilizer for acidizing and fracturing and preparation method thereof - Google Patents
Iron ion stabilizer for acidizing and fracturing and preparation method thereof Download PDFInfo
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- CN117430634A CN117430634A CN202311401691.1A CN202311401691A CN117430634A CN 117430634 A CN117430634 A CN 117430634A CN 202311401691 A CN202311401691 A CN 202311401691A CN 117430634 A CN117430634 A CN 117430634A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 75
- 239000003381 stabilizer Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 111
- -1 iron ion Chemical class 0.000 claims abstract description 72
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000012360 testing method Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 230000001105 regulatory effect Effects 0.000 claims abstract description 20
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 18
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- WKBWYLXFNPONGU-UHFFFAOYSA-N [bromo(phosphono)methyl]phosphonic acid Chemical compound OP(O)(=O)C(Br)P(O)(O)=O WKBWYLXFNPONGU-UHFFFAOYSA-N 0.000 claims abstract description 14
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims abstract description 14
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 230000001376 precipitating effect Effects 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 8
- 230000000087 stabilizing effect Effects 0.000 abstract description 15
- 239000003208 petroleum Substances 0.000 abstract description 3
- 230000020477 pH reduction Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910021646 siderite Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
- C07F9/6521—Six-membered rings
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of petroleum exploitation, and particularly relates to an iron ion stabilizer for acid fracturing and a preparation method thereof. The preparation method comprises the following steps: adding melamine, ethanol and sodium chloroacetate into a reactor, stirring and dissolving, adding sodium hydroxide solution, adjusting pH to 9-10, heating to 60-65 ℃, preserving heat and reacting for 1-2h, testing pH at intervals during the reaction, and adjusting pH to 8-8.5 if the pH is lower than 8, so as to obtain a mixed solution; adding bromomethylene diphosphonic acid into the mixed solution, regulating the pH to 9-10, heating and refluxing for 2-4h, testing the pH at random during the reaction, and regulating the pH to 8-8.5 if the pH is lower than 8; cooling, adding toluene, cooling to below 10 ℃, precipitating solid, filtering, and drying to obtain the product iron ion stabilizer. The iron ion stabilizer has the advantages of good iron ion stabilizing effect and high temperature resistance.
Description
Technical Field
The invention belongs to the technical field of petroleum exploitation, and particularly relates to an iron ion stabilizer for acid fracturing and a preparation method thereof.
Background
With the continuous development of oil extraction technology and the increase of the development difficulty of oil fields, the acidizing operation becomes an important measure for stabilizing the production and increasing the production of oil and gas wells and stabilizing the injection and increasing the injection of water injection wells. The principle is that acid liquor is utilized to remove pollution near the bottom of a production well and a water injection well, the permeability of the stratum is recovered or the rock cementing agent of the stratum is eroded to improve the permeability of the stratum, and a fluid seepage channel is dredged, so that the productivity of the well is recovered and improved.
However, in the acid treatment operation of the oil-water well in the acidification process, the acid liquid is usually contacted with metal substances such as construction equipment, downhole tools, pipe columns and the like,after entering the stratum, the mixture reacts with iron-containing minerals and clay minerals (such as siderite, hematite, magnetite, pyrite, chlorite, etc.) in the stratum to make the solution contain Fe 3+ And Fe (Fe) 2+ When the pH value is raised and reaches a certain value, ferric hydroxide precipitation is generated, and a newly opened flow pore canal through acidification construction is seriously blocked. In addition, the iron ions can also enhance the stability of residual acid emulsion, and bring difficulty to acid discharge; the generation of acid sludge is aggravated, and new damage is brought to the oil layer.
In order to prevent secondary precipitation of iron from blocking an oil gas seepage channel in a stratum to reduce recovery ratio, an iron ion stabilizer is added into acid liquor in an acidification technology to prevent gelatinous ferric hydroxide precipitation from generating when the acid liquor becomes residual acid, and damage to an oil gas layer is prevented, so that an acidification treatment effect is improved.
CN104109530a discloses an iron ion stabilizer for acidification and a preparation method thereof, wherein the iron ion stabilizer comprises the following components in parts by weight: 2-3 parts of chelating agent, 1-2 parts of reducing agent and 1-2 parts of pH buffering agent. The iron ion stabilizer for acidification of the invention mainly comprises chelating agent, reducing agent and pH buffer agent, wherein the chelating agent, the reducing agent and the pH buffer agent are mutually matched to coordinate, so that the iron ion stabilizer has chelating effect and reducing capability, and can maximally stabilize iron ions in the acidification process; meanwhile, the dosage of each component is small, the acidification cost is reduced, the addition amount of metal ions in the formula is small, no additional damage is generated to the reservoir, the production and use costs are low, and the method is suitable for popularization and application. However, the invention is only obtained by compounding conventional iron ions, the effect is only tens of mg/ml, and the iron ion stabilizing capability is low.
CN103992782a discloses an acidizing corrosion inhibitor and a preparation method thereof, the preparation method comprises the following steps: (1) Uniformly mixing an initiator, a catalyst and halogenated epoxypropane, and performing ring-opening polymerization at 20-40 ℃; (2) Adding quinoline derivatives into the reaction product in the step (1), uniformly mixing, condensing and refluxing for 8-10 hours at 120-180 ℃ and carrying out quaternization reaction to obtain the acidizing corrosion inhibition agentAnd (3) an agent. The mass ratio of the initiator to the catalyst to the halogenated epoxypropane to the quinoline derivative is 2-4:1-2:50-100:10-30. The corrosion inhibitor provided by the invention has the characteristics of good water solubility, small dosage, good corrosion inhibition effect and the like. But the invention can reduce the corrosion of acid liquor to iron metal, and the generated Fe 3+ And Fe (Fe) 2+ There is no stabilizing effect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the iron ion stabilizer for acidizing and fracturing and the preparation method thereof.
The invention discloses an iron ion stabilizer for acid fracturing, which has the following molecular structural formula:
the invention further discloses a preparation method of the iron ion stabilizer for acidizing and fracturing, which comprises the following specific steps:
(1) Adding melamine, ethanol and sodium chloroacetate into a reactor, stirring and dissolving, adding sodium hydroxide solution, adjusting pH to 9-10, heating to 60-65 ℃, preserving heat and reacting for 1-2h, testing pH at intervals during the reaction, and adjusting pH to 8-8.5 by sodium hydroxide if the pH is lower than 8, so as to obtain a mixed solution;
(2) Adding bromomethylene diphosphonic acid into the mixed solution, regulating the pH to 9-10 by using sodium hydroxide solution, heating and refluxing for 2-4 hours, testing the pH at random during the reaction, and regulating the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8;
(3) Cooling, adding toluene, cooling to below 10 ℃, precipitating solid, filtering, and drying to obtain the product iron ion stabilizer.
In the present invention, preferably, the molar ratio of sodium chloroacetate, bromomethylenediphosphonic acid to melamine is 2.5 to 3.5:2.5-3.5:1, a step of; more preferably, the molar ratio of sodium chloroacetate, bromomethylenediphosphonic acid to melamine is 2.7-3.3:2.7-3.3:1.
in the present invention, preferably, the weight ratio of the ethanol to the melamine in the step (1) is 30 to 40:1.
in the present invention, preferably, the weight ratio of toluene to melamine in step (3) is 45 to 60:1.
the synthesis reaction equation of the iron ion stabilizer for acidizing and fracturing is as follows:
the iron ion stabilizer for acid fracturing of the invention has the following action principle based on three aspects:
(1) The iron ion stabilizer disclosed by the invention contains 3 carboxylic acid functional groups, has a chelating effect, can chelate iron ions, and can greatly reduce free iron ions, so that the possibility of the iron ions settling out of a solution is reduced;
(2) The iron ion stabilizer contains 6 phosphoric acid functional groups, has a chelating effect, can chelate iron ions, can greatly reduce free iron ions, has strong molecular polarity and high solubility in water, and therefore cannot be settled out of the water after chelating the iron ions;
(3) The iron ion stabilizer disclosed by the invention contains 6 tertiary amine functional groups, and a nitrogen atom has a lone pair electron, so that a coordination bond can be formed with iron ions, and free iron ions are further reduced.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The iron ion stabilizer has strong capability of stabilizing iron ions, and the maximum normal temperature can reach 159mg/g;
(2) The iron ion stabilizing agent has strong temperature resistance, and the iron ion stabilizing capability is reduced slightly after the iron ion stabilizing agent is kept at 200 ℃ for 4 hours, and the maximum iron ion stabilizing capability is still kept at 156mg/g.
Detailed Description
The invention will be further illustrated with reference to specific examples:
example 1
(1) Adding 20mmol of melamine, 75.6g of ethanol and 50mmol of sodium chloroacetate into a reactor, stirring for dissolution, adding a sodium hydroxide solution, adjusting the pH to 9-10, heating to 60 ℃, preserving heat for reaction for 2 hours, testing the pH at intervals during the reaction, and adjusting the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8 to obtain a mixed solution;
(2) Adding 52mmol of bromomethylene diphosphonic acid into the mixed solution, regulating the pH to 9-10 by using sodium hydroxide solution, heating and refluxing for 2h, testing the pH at random during the reaction, and regulating the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8;
(3) Cooling, adding 113.4g of toluene, cooling to below 10 ℃, precipitating solid, filtering, and drying to obtain the product of the iron ion stabilizer.
Example 2
(1) Adding 20mmol of melamine, 82.4g of ethanol and 54mmol of sodium chloroacetate into a reactor, stirring for dissolution, adding a sodium hydroxide solution, adjusting the pH to 9-10, heating to 65 ℃, preserving heat for reaction for 1h, testing the pH at intervals during the reaction, and adjusting the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8 to obtain a mixed solution;
(2) Adding 70mmol of bromomethylene diphosphonic acid into the mixed solution, regulating the pH to 9-10 by using sodium hydroxide solution, heating and refluxing for reaction for 4 hours, testing the pH at random during the reaction, and regulating the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8;
(3) Cooling, adding 131.3g of toluene, cooling to below 10 ℃, precipitating solid, filtering and drying to obtain the product of the iron ion stabilizer.
Example 3
(1) Adding 20mmol of melamine, 100.8g of ethanol and 70mmol of sodium chloroacetate into a reactor, stirring for dissolution, adding a sodium hydroxide solution, adjusting the pH to 9-10, heating to 65 ℃, preserving heat for reaction for 1.5h, testing the pH at intervals during the reaction, and adjusting the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8 to obtain a mixed solution;
(2) Adding 66mmol of bromomethylene diphosphonic acid into the mixed solution, regulating the pH to 9-10 by using sodium hydroxide solution, heating and refluxing for 2.5h, testing the pH at random during the reaction, and regulating the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8;
(3) Cooling, adding 151.2g toluene, cooling to below 10 ℃, precipitating solid, filtering, and drying to obtain the product of the iron ion stabilizer.
Example 4
(1) Adding 20mmol of melamine, 96.1g of ethanol and 66mmol of sodium chloroacetate into a reactor, stirring for dissolution, adding a sodium hydroxide solution, adjusting the pH to 9-10, heating to 63 ℃, preserving heat for reaction for 2 hours, testing the pH at intervals during the reaction, and adjusting the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8 to obtain a mixed solution;
(2) Adding 50mmol of bromomethylene diphosphonic acid into the mixed solution, regulating the pH to 9-10 by using sodium hydroxide solution, heating and refluxing for reaction for 3 hours, testing the pH at intervals during the reaction, and regulating the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8;
(3) Cooling, adding 143g toluene, cooling to below 10 ℃, precipitating solid, filtering and drying to obtain the product iron ion stabilizer.
Example 5
(1) Adding 20mmol of melamine, 85.2g of ethanol and 57mmol of sodium chloroacetate into a reactor, stirring for dissolution, adding a sodium hydroxide solution, adjusting the pH to 9-10, heating to 64 ℃, preserving heat for reaction for 1.2h, testing the pH at intervals during the reaction, and adjusting the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8 to obtain a mixed solution;
(2) Adding 64mmol of bromomethylene diphosphonic acid into the mixed solution, regulating the pH to 9-10 by using sodium hydroxide solution, heating and refluxing for reaction for 3.5h, testing the pH at intervals during the reaction, and regulating the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8;
(3) Cooling, adding 132g of toluene, cooling to below 10 ℃, precipitating solid, filtering and drying to obtain the product of the iron ion stabilizer.
Example 6
(1) Adding 20mmol of melamine, 90.4g of ethanol and 63mmol of sodium chloroacetate into a reactor, stirring for dissolution, adding a sodium hydroxide solution, adjusting the pH to 9-10, heating to 62 ℃, preserving heat for reaction for 2 hours, testing the pH at intervals during the reaction, and adjusting the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8 to obtain a mixed solution;
(2) Adding 58mmol of bromomethylene diphosphonic acid into the mixed solution, regulating the pH to 9-10 by using sodium hydroxide solution, heating and refluxing for 2h, testing the pH at random during the reaction, and regulating the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8;
(3) And (3) cooling, namely adding 141.6g of toluene, cooling to below 10 ℃, precipitating solid, filtering and drying to obtain the product of the iron ion stabilizer.
Example 7
(1) Adding 20mmol of melamine, 88.5g of ethanol and 60mmol of sodium chloroacetate into a reactor, stirring for dissolution, adding a sodium hydroxide solution, adjusting the pH to 9-10, heating to 63 ℃, preserving heat for reaction for 1.8 hours, testing the pH at intervals during the reaction, and adjusting the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8 to obtain a mixed solution;
(2) Adding 60mmol of bromomethylene diphosphonic acid into the mixed solution, regulating the pH to 9-10 by using sodium hydroxide solution, heating and refluxing for reaction for 4 hours, testing the pH at intervals during the reaction, and regulating the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8;
(3) Cooling, adding 133g of toluene, cooling to below 10 ℃, precipitating solid, filtering and drying to obtain the product of the iron ion stabilizer.
Example 8
Testing the iron ion stabilizing Agents of the present invention (examples 1-7) for their ability to stabilize iron ions N at normal temperature, 160℃and 200 ℃ 1 、N 2 、N 3 The evaluation method was carried out with reference to the method in SY/T6571-2012, evaluation method for iron ion stabilizer Performance for acidification.
The Shanxi forest Rayleigh petroleum technology is used for developing the Fe ion stabilizer of the limited company to carry out a comparison experiment.
The test results are shown in Table 1.
TABLE 1 test results of capability of stabilizing iron ions at normal temperature, 160℃and 200 ℃C
| Iron ion stabilizer | N 1 ，mg/g | N 2 ，mg/g | N 3 ，mg/g |
| Example 1 | 142 | 140 | 138 |
| Example 2 | 151 | 147 | 146 |
| Example 3 | 155 | 152 | 150 |
| Example 4 | 150 | 146 | 144 |
| Example 5 | 156 | 154 | 152 |
| Example 6 | 159 | 157 | 155 |
| Example 7 | 159 | 158 | 156 |
| Comparative example | 69 | 58 | 55 |
As can be seen from table 1:
(1) Iron ion stabilizing agent of the present invention (examples 1 to 7) stabilizing iron ion ability N at ordinary temperature 1 142mg/g and above, up to 159mg/g (examples 6 and 7); whereas comparative example Shanxi senrui oil technology development of iron ion stabilizing ability N of iron ion stabilizer of Limited company 1 69mg/g, which is significantly lower than the present invention;
(2) The iron ion stabilizers of the invention (examples 1 to 7) stabilize the iron ion ability N at 160 ℃ 2 All reach 140mg/g and above, up to 158mg/g (example 7); whereas comparative example Shanxi senrui oil technology development of iron ion stabilizing ability N of iron ion stabilizer of Limited company 2 58mg/g, which is significantly lower than the present invention;
(3) Iron ion stabilizers of the invention (examples 1-7) stabilize iron ion capability N at 200 ℃ 3 All reach 138mg/g and above, up to 156mg/g (example 7); whereas comparative example Shanxi senrui oil technology development of iron ion stabilizing ability N of iron ion stabilizer of Limited company 3 55mg/g, which is significantly lower than the present invention.
The iron ion stabilizer has strong iron ion stabilizing capability and strong temperature resistance, and the high temperature has no influence on the iron ion stabilizing capability.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (6)
1. The preparation method of the iron ion stabilizer for the acid fracturing is characterized by comprising the following specific steps of:
(1) Adding melamine, ethanol and sodium chloroacetate into a reactor, stirring and dissolving, adding sodium hydroxide solution, adjusting pH to 9-10, heating to 60-65 ℃, preserving heat and reacting for 1-2h, testing pH at intervals during the reaction, and adjusting pH to 8-8.5 by sodium hydroxide if the pH is lower than 8, so as to obtain a mixed solution;
(2) Adding bromomethylene diphosphonic acid into the mixed solution, regulating the pH to 9-10 by using sodium hydroxide solution, heating and refluxing for 2-4 hours, testing the pH at random during the reaction, and regulating the pH to 8-8.5 by using sodium hydroxide if the pH is lower than 8;
(3) Cooling, adding toluene, cooling to below 10 ℃, precipitating solid, filtering, and drying to obtain the product iron ion stabilizer.
2. The method for preparing the iron ion stabilizer for acidizing and fracturing according to claim 1, wherein the molar ratio of sodium chloroacetate, bromomethylenediphosphonic acid and melamine is 2.5-3.5:2.5-3.5:1.
3. the method for preparing the iron ion stabilizer for acidizing and fracturing according to claim 2, wherein the molar ratio of sodium chloroacetate, bromomethylenediphosphonic acid and melamine is 2.7-3.3:2.7-3.3:1.
4. the method for preparing an iron ion stabilizer for acid fracturing according to claim 1, wherein the weight ratio of the ethanol to the melamine in the step (1) is 30-40:1.
5. the method for preparing an iron ion stabilizer for acid fracturing according to claim 1, wherein the weight ratio of toluene to melamine in the step (3) is 45-60:1.
6. the iron ion stabilizer for the acidizing and fracturing is characterized by comprising the following molecular structural formula:
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311401691.1A CN117430634A (en) | 2023-10-26 | 2023-10-26 | Iron ion stabilizer for acidizing and fracturing and preparation method thereof |
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2023
- 2023-10-26 CN CN202311401691.1A patent/CN117430634A/en active Pending
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