A kind of iron ion stabilizer and its synthesis method and application

Abstract

The present invention belongs to the field of oil production technology, and in particular to a kind of iron ion stabilizer and its synthesis method and application. The synthesis method is as follows: melamine and water are added to the reactor, beating, bromodibutyric acid is added, room temperature reaction is 1-2h, and pH 7-8 is maintained with sodium hydroxide during the reaction; 2-bromoethyl sodium sulfonate is added to the above-mentioned mixed solution, 40-50 DEG C of reaction is 2-4h, and pH 7-8 is maintained with sodium hydroxide during the reaction; 2-bromoethyl phosphoric acid is added to the above-mentioned mixed solution, 60-70 DEG C of reaction is 6-12h, and pH 8-9 is maintained with sodium hydroxide during the reaction; Hydrochloric acid is added, pH 2-3 is adjusted, the temperature is lowered to less than 10 DEG C, solid is precipitated, filtered, and dried to obtain product iron ion stabilizer. The iron ion stabilizer of the present invention has the advantages of good effect and high temperature resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of petroleum extraction, and in particular relates to an iron ion stabilizer and a synthesis method and application thereof. Background Art

[0002] With the continuous development of oil production technology and the increasing difficulty of oil field development, acidizing operation has become an important measure to increase production and injection. Its principle is to use the chemical dissolution of acid to dissolve rock minerals and blockages in the formation, dredge the pore throat channels of the formation, so as to restore and improve the permeability of the formation, reduce the resistance of oil flowing into the well or the resistance of water injection, so as to achieve the purpose of increasing oil well production and water well injection.

[0003] However, during the acidizing process in oil and water well acid treatment operations, the acid usually comes into contact with metal materials such as ground equipment, downhole tools, and pipes. After entering the formation, it reacts with iron compounds in the rock to produce a large amount of iron ions. As the acid continues to react with the formation rock, the effective concentration of the acid gradually decreases and the pH value increases. In this case, iron hydroxide precipitation may occur, thereby blocking the formation.

[0004] In order to prevent iron precipitation when the acid becomes residual acid, iron ion stabilizers are often added to the acid in acidizing technology to prevent the formation of gel-like iron hydroxide precipitation when the acid becomes residual acid, thereby preventing damage to the oil and gas layers and improving the acidizing treatment effect.

[0005] CN103992782A discloses an acidified corrosion inhibitor and a preparation method thereof, the preparation method comprising the following steps: (1) uniformly mixing an initiator, a catalyst and a halogenated epoxypropane, and causing a ring-opening polymerization reaction at 20°C to 40°C; (2) adding a quinoline derivative to the reaction product obtained in step (1) and mixing them uniformly, condensing and refluxing at 120°C to 180°C for 8h to 10h, causing a quaternization reaction, and obtaining the acidified corrosion inhibitor. The mass ratio of the initiator, the catalyst, the halogenated epoxypropane and 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, etc. However, although the invention can reduce the corrosion of acid to iron metal, it has poor stabilization effect on the generated ferrous ions and ferric ions.

[0006] CN105295887A discloses an excellent iron ion stabilizer for acidification operation and a preparation method thereof. +The concentration continues to decrease, and the pH value continues to increase, so that the iron originally existing in an ionic state begins to precipitate, blocking the oil and gas seepage channels in the formation, causing secondary pollution, and leading to a reduction in recovery rate. Therefore, an iron ion stabilizer needs to be added to make the iron always exist in the residual acid in a soluble state. The technical scheme of the present invention is: sodium isoascorbate, NTA, citric acid, EDTA disodium salt and water are added to the container in proportion, and the mass fraction of each component is: sodium isoascorbate 5% to 16%, NTA 1% to 3%, citric acid 2% to 5%, EDTA disodium salt 2% to 5%, and the balance is water; control a certain temperature and stir to completely dissolve it, cool to room temperature, transfer to a volumetric flask and make up to volume, and obtain the iron ion stabilizer. The iron ion stabilizer has both chelating ability and reducing ability, strong iron stabilizing ability, and low production cost. Under 80°C, the invention's ability to stabilize iron ions is reduced to 30mg / ml, and it is difficult to stabilize iron ions to meet actual production needs. Summary of the invention

[0007] The present invention aims at the deficiencies of the above-mentioned prior art and provides an iron ion stabilizer and a synthesis method and application thereof. The iron ion stabilizer of the present invention has the advantages of good effect and high temperature resistance.

[0008] One of the purposes of the present invention is to disclose a method for synthesizing an iron ion stabilizer, and the specific steps of the synthetic method are as follows:

[0009] (1) Add melamine and water into a reactor, beat the mixture, add dibromobutyric acid, and react at room temperature for 1-2 hours. During the reaction, use sodium hydroxide to maintain the pH at 7-8.

[0010] (2) Add sodium 2-bromoethylsulfonate to the above mixture, react at 40-50°C for 2-4 hours, and use sodium hydroxide to maintain the pH at 7-8 during the reaction;

[0011] (3) Add 2-bromoethylphosphoric acid to the above mixture, react at 60-70°C for 6-12 hours, and use sodium hydroxide to maintain the pH at 8-9 during the reaction;

[0012] (4) Add hydrochloric acid to adjust the pH to 2-3, cool to below 10°C, precipitate solid, filter, and dry to obtain the product iron ion stabilizer.

[0013] In the present invention, preferably, based on 1 mole of melamine, the amounts of dibromobutyric acid, sodium 2-bromoethylsulfonate and 2-bromoethylphosphoric acid are 0.8-1.2 mole, 0.8-1.2 mole and 0.8-1.2 mole, respectively.

[0014] In the present invention, preferably, the weight ratio of water to melamine in step (1) is 20-30:1.

[0015] The iron ion stabilizer synthesis reaction equation of the present invention is as follows:

[0016]

[0017]

[0018]

[0019] Another object of the present invention is to disclose an iron ion stabilizer, the molecular structure of the iron ion stabilizer is as follows:

[0020] .

[0021] The third object of the present invention is to disclose the application of the above iron ion stabilizer in oil field acid fracturing.

[0022] The iron ion stabilizer of the present invention contains three functional groups for stabilizing iron ions, including one carboxylic acid functional group, one sulfonic acid functional group and one phosphoric acid functional group. These functional groups all have a chelating effect and can chelate iron ions, thereby greatly reducing free iron ions. The sodium salt molecules of the present invention have strong polarity and high solubility in water, so the present invention will not settle out of the water after chelating the iron ions. The present invention contains a plurality of nitrogen atoms, and the nitrogen atoms have lone pairs of electrons, which can form coordination bonds with iron ions, thereby further reducing free iron ions.

[0023] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0024] (1) The iron ion stabilizer of the present invention has a strong ability to stabilize iron ions, reaching 160 mg / g or above at room temperature;

[0025] (2) The iron ion stabilizer of the present invention has strong temperature resistance. After being kept at 220°C for 4 hours, the iron ion stabilization capacity is still maintained at 150 mg / g or above. DETAILED DESCRIPTION

[0026] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0027] The present invention will be further described below with reference to specific embodiments.

[0028] In the present invention, the devices or equipment used are all conventional devices or equipment known in the art and are commercially available.

[0029] In the following examples and comparative examples, unless otherwise specified, all reagents used were commercially available chemically pure reagents.

[0030] Example 1

[0031] (1) Add 0.1 mol of melamine and 252 g of water into a reactor, slurry, add 0.08 mol of dibromobutyric acid, and react at room temperature for 1 hour. During the reaction, use sodium hydroxide to maintain the pH at 7-8;

[0032] (2) Add 0.08 mol of sodium 2-bromoethylsulfonate to the above mixture and react at 40°C for 2 h. During the reaction, use sodium hydroxide to maintain the pH at 7-8.

[0033] (3) Add 0.12 mol of 2-bromoethylphosphoric acid to the above mixture and react at 60°C for 6 h. During the reaction, use sodium hydroxide to maintain the pH at 8-9.

[0034] (4) Add hydrochloric acid to adjust the pH to 2-3, cool to below 10°C, precipitate solid, filter, and dry to obtain the product iron ion stabilizer.

[0035] Example 2

[0036] (1) Add 0.1 mol of melamine and 289 g of water into a reactor, slurry, add 0.12 mol of dibromobutyric acid, and react at room temperature for 2 h. During the reaction, use sodium hydroxide to maintain the pH at 7-8;

[0037] (2) Add 0.09 mol of sodium 2-bromoethylsulfonate to the above mixture and react at 45°C for 3 h. During the reaction, use sodium hydroxide to maintain the pH at 7-8.

[0038] (3) Add 0.08 mol of 2-bromoethylphosphoric acid to the above mixture and react at 70°C for 8 h. During the reaction, use sodium hydroxide to maintain the pH at 8-9.

[0039] (4) Add hydrochloric acid to adjust the pH to 2-3, cool to below 10°C, precipitate solid, filter, and dry to obtain the product iron ion stabilizer.

[0040] Example 3

[0041] (1) Add 0.1 mol of melamine and 314 g of water into a reactor, slurry, add 0.09 mol of dibromobutyric acid, and react at room temperature for 2 h. During the reaction, use sodium hydroxide to maintain the pH at 7-8;

[0042] (2) Add 0.12 mol of sodium 2-bromoethylsulfonate to the above mixture and react at 50°C for 4 h. During the reaction, use sodium hydroxide to maintain the pH at 7-8.

[0043] (3) Add 0.085 mol 2-bromoethylphosphoric acid to the above mixture and react at 65°C for 12 h. During the reaction, use sodium hydroxide to maintain the pH at 8-9.

[0044] (4) Add hydrochloric acid to adjust the pH to 2-3, cool to below 10°C, precipitate solid, filter, and dry to obtain the product iron ion stabilizer.

[0045] Example 4

[0046] (1) Add 0.1 mol of melamine and 378 g of water into a reactor, slurry, add 0.11 mol of dibromobutyric acid, and react at room temperature for 1 hour. During the reaction, use sodium hydroxide to maintain the pH at 7-8;

[0047] (2) Add 0.085 mol of sodium 2-bromoethylsulfonate to the above mixture and react at 42°C for 3 h. During the reaction, use sodium hydroxide to maintain the pH at 7-8.

[0048] (3) Add 0.115 mol of 2-bromoethylphosphoric acid to the above mixture and react at 62°C for 10 h. During the reaction, use sodium hydroxide to maintain the pH at 8-9.

[0049] (4) Add hydrochloric acid to adjust the pH to 2-3, cool to below 10°C, precipitate solid, filter, and dry to obtain the product iron ion stabilizer.

[0050] Example 5

[0051] (1) Add 0.1 mol of melamine and 352 g of water into a reactor, slurry, add 0.11 mol of dibromobutyric acid, and react at room temperature for 1.5 h. During the reaction, use sodium hydroxide to maintain the pH at 7-8;

[0052] (2) Add 0.09 mol of sodium 2-bromoethylsulfonate to the above mixture and react at 43°C for 2 h. During the reaction, use sodium hydroxide to maintain the pH at 7-8.

[0053] (3) Add 0.1 mol of 2-bromoethylphosphoric acid to the above mixture and react at 67°C for 9 h. During the reaction, use sodium hydroxide to maintain the pH at 8-9.

[0054] (4) Add hydrochloric acid to adjust the pH to 2-3, cool to below 10°C, precipitate solid, filter, and dry to obtain the product iron ion stabilizer.

[0055] Example 6

[0056] (1) Add 0.1 mol of melamine and 333 g of water into a reactor, slurry, add 0.095 mol of dibromobutyric acid, and react at room temperature for 2 h. During the reaction, use sodium hydroxide to maintain the pH at 7-8;

[0057] (2) Add 0.11 mol of sodium 2-bromoethylsulfonate to the above mixture and react at 46°C for 3 h. During the reaction, use sodium hydroxide to maintain the pH at 7-8.

[0058] (3) Add 0.09 mol 2-bromoethylphosphoric acid to the above mixture and react at 68°C for 10 h. During the reaction, use sodium hydroxide to maintain the pH at 8-9.

[0059] (4) Add hydrochloric acid to adjust the pH to 2-3, cool to below 10°C, precipitate solid, filter, and dry to obtain the product iron ion stabilizer.

[0060] Example 7

[0061] (1) Add 0.1 mol of melamine and 352 g of water into a reactor, slurry, add 0.1 mol of dibromobutyric acid, and react at room temperature for 1 hour. During the reaction, use sodium hydroxide to maintain the pH at 7-8;

[0062] (2) Add 0.1 mol of sodium 2-bromoethylsulfonate to the above mixture and react at 48°C for 2 h. During the reaction, use sodium hydroxide to maintain the pH at 7-8.

[0063] (3) Add 0.105 mol of 2-bromoethylphosphoric acid to the above mixture and react at 65°C for 9 h. During the reaction, use sodium hydroxide to maintain the pH at 8-9.

[0064] (4) Add hydrochloric acid to adjust the pH to 2-3, cool to below 10°C, precipitate solid, filter, and dry to obtain the product iron ion stabilizer.

[0065] Example 8

[0066] The iron ion stabilizer of the present invention (Examples 1-7) was tested for its iron ion stabilizing ability N1, N2, and N3 at room temperature, 160°C, and 220°C. The test method was based on SY / T 6571-2012 "Performance Evaluation Method of Iron Ion Stabilizer for Acidification". The iron ion stabilizer of Jinan Quanxing New Materials Co., Ltd. was used for comparative experiments. The test results are shown in Table 1.

[0067] Table 1 Test results of the ability to stabilize iron ions at room temperature, 160°C, and 220°C

[0068]

[0069] From Table 1 we can see that:

[0070] (1) The iron ion stabilizer of the present invention (Examples 1-7) has an iron ion stabilizing capacity of 160 mg / g or more at room temperature, and the highest is 170 mg / g; while the iron ion stabilizer of the comparative example Jinan Quanxing New Materials Co., Ltd. has an iron ion stabilizing capacity of 70 mg / g, which is significantly lower than that of the present invention;

[0071] (2) The iron ion stabilizer of the present invention (Examples 1-7) has an iron ion stabilizing capacity of 158 mg / g or more at 160°C, with the highest reaching 168 mg / g; while the iron ion stabilizer of the comparative example Jinan Quanxing New Materials Co., Ltd. has an iron ion stabilizing capacity of 67 mg / g, which is significantly lower than that of the present invention;

[0072] (3) The iron ion stabilizer of the present invention (Examples 1-7) has an iron ion stabilizing capacity of 150 mg / g or more at 220°C, with the highest reaching 155 mg / g; while the iron ion stabilizer of the comparative example Jinan Quanxing New Materials Co., Ltd. has an iron ion stabilizing capacity of 60 mg / g, which is significantly lower than that of the present invention.

[0073] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for synthesizing an iron ion stabilizer, characterized in that: The specific steps of the synthetic method are as follows: (1) Add melamine and water into a reactor, beat the mixture, add dibromobutyric acid, and react at room temperature for 1-2 hours. During the reaction, use sodium hydroxide to maintain the pH at 7-8. The weight ratio of water to melamine is 20-30:

1. (2) Add sodium 2-bromoethylsulfonate to the above mixture, react at 40-50°C for 2-4 hours, and use sodium hydroxide to maintain the pH at 7-8 during the reaction; (3) Add 2-bromoethylphosphoric acid to the above mixture, react at 60-70°C for 6-12 hours, and use sodium hydroxide to maintain the pH at 8-9 during the reaction; (4) Add hydrochloric acid to adjust the pH to 2-3, cool to below 10°C, precipitate solid, filter, and dry to obtain the product iron ion stabilizer; Based on 1 mole of melamine, the amounts of dibromobutyric acid, sodium 2-bromoethylsulfonate, and 2-bromoethylphosphoric acid are 0.8-1.2 mole, 0.8-1.2 mole, and 0.8-1.2 mole, respectively; The molecular structure of the iron ion stabilizer is as follows: 。 2. The iron ion stabilizer prepared by the synthesis method according to claim 1, characterized in that: The molecular structure of the iron ion stabilizer is as follows: 。 3. Use of the iron ion stabilizer according to claim 2 in oil field acid fracturing.

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