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A kind of viscoelastic surfactant for high temperature self-steering acid, preparation method and application

A surfactant and self-diverting acid technology, which is used in the preparation of carboxylic acid amides, the preparation of organic compounds, the preparation of amino compounds, etc., can solve the problems that VES is difficult to maintain a stable chemical structure, the reaction speed of reservoir rocks is fast, and the dosage is high. Achieve excellent acid thickening performance, facilitate large-scale use, and stabilize chemical structure

Active Publication Date: 2020-01-10
SICHUAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, for a long time, there have been two problems in the conventional acid system: (1) The reaction speed with the reservoir rock is fast, resulting in too short acidizing distance, making it difficult to realize deep acidizing
(2) Due to the heterogeneity of the reservoir, after the acid fluid is injected into the formation, following the principle of least resistance, it preferentially enters the high-permeability area rather than the low-permeability area that needs acid treatment most; moreover, the subsequent injection The acid liquid will flow along the reacted large pores with less resistance, which will over-acidify the high-permeability area, while the medium-low permeability area will not be effectively improved by plugging removal, which will eventually lead to further increase of interlayer heterogeneity (F. Chang, Q. Qu, W. Frenier. A novel self-diverting-acid developed for matrix stimulation of carbonate reservoirs. Paper SPE65033 presented at the SPE International Symposium on Oilfield Chemistry held in Houston, Texas, 13–16 February 2001)
U.S. Patent No. 4,695,389 discloses a VDA system based on N,N-dihydroxyethyl fatty amine acetate surfactant. The initial viscosity of the system is low, but as the acid-rock reaction proceeds, the viscosity of the system increases, making it The increased flow resistance forces the subsequent acid liquid to enter the low-permeability area, which can achieve the purpose of uniform acidification. However, the viscosity of the system is as low as 5 mPa s at 80 °C, which makes it difficult to achieve the function of reducing the acid-rock reaction rate.
U.S. Patent No. 7,119,050 discloses a VDA system based on alkyl betaine amphoteric surfactants. As the acid-rock reaction proceeds, the viscosity first increases and then decreases. Active agent usage as high as 8%, resulting in high operating costs
[0007] (2) Most of the VES used in the current VDA system are cationic and zwitterionic surfactants, especially alkyl betaine amphoteric surfactants, amine oxide amphoteric surfactants, etc. Most of these VES molecular structures contain easily hydrolyzed surfactants. The weak bonds (amide bonds, ester bonds, ether bonds, etc.) of VES are easily broken in high temperature and strong acid environment, so it is difficult for VES to maintain a stable chemical structure during acidification operations, and it is easy to deteriorate and decompose (Z.Y.Zhao, G.C Lv, Y.H.Zhang, S.J.Lian,N.Tian.Performance of EDAB-HCl acid blended system as fracturing fluids in oil fields.Chinese J.Chem.Engin.,2014,22,202)

Method used

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  • A kind of viscoelastic surfactant for high temperature self-steering acid, preparation method and application
  • A kind of viscoelastic surfactant for high temperature self-steering acid, preparation method and application
  • A kind of viscoelastic surfactant for high temperature self-steering acid, preparation method and application

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preparation example Construction

[0046] A kind of preparation method of described viscoelastic surfactant for high temperature self-steering acid, comprises the following steps:

[0047] S1: Add fatty acid and organic amine into the reactor, raise the temperature to 160-170°C and react for 11-13 hours to stop the reaction. During the reaction process, keep the circulating water to cool the organic amine to reflux. After the reaction liquid is cooled to 25-35°C, Pour it into cold acetone solution, stir and filter, wash and filter the solid with acetone for 2 to 3 times, and obtain a white solid intermediate after freeze-drying. Wherein, the molar ratio of organic amine to fatty acid is (1.1-1.5):1.

[0048] The fatty acid is at least one or a combination of saturated or unsaturated alkyl fatty acids with 18 to 28 carbon atoms, and the organic amine includes N,N-dimethylethylenediamine, N,N- Dimethyl-1,3-propanediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethylethylenediamine, N,N-diethyl-1,3 -A combination...

Embodiment 1

[0058] (1) Weigh 16.92g (0.05mol) of cis-docos-13-enoic acid (commonly known as "erucic acid") and 7.66g (0.075mol) of N,N-dimethylpropylenediamine into a three-necked reaction flask, Gradually raise the temperature to 160°C. Stop the reaction after reacting for 11 hours. After the solution is cooled to room temperature, transfer it to an acetone solution, stir and filter, and freeze-dry to obtain a white powder solid, which is N-(cis-docos-9-enyl-amide propyl)-N,N-dimethyl tertiary amine, its structural characterization is shown in the NMR spectrum ( figure 1), the chemical shifts of each proton peak in the compound have been assigned in the spectrum, and the ratio of the integral area of ​​each proton resonance peak is in good agreement with the theoretical value, indicating that the compound has been successfully synthesized.

[0059] (2) Add the obtained N-(cis-docos-9-enyl-amidopropyl)-N,N-dimethyl tertiary amine into a 500mL round bottom flask, add 100mL tetrahydrofuran...

Embodiment 2

[0065] (1) Weigh 14.22g (0.05mol) of octadecanoic acid (commonly known as "stearic acid") and 5.61g (0.055mol) of N,N-dimethylpropylenediamine into a three-necked reaction flask, and gradually heat up to 170°C . After 13 hours of reaction, the reaction was stopped. After the solution was cooled to room temperature, it was transferred to an acetone solution, stirred and filtered, and freeze-dried to obtain a white powder solid, which was N-(octadecylamidopropyl)-N,N - tertiary dimethylamine.

[0066] (2) Add the obtained N-(octadecylamidopropyl)-N,N-dimethyl tertiary amine into a 500mL round bottom flask, add 100mL tetrahydrofuran to dissolve, cool down to 5°C after complete dissolution, and gradually LiAlH was added dropwise 4 THF solution, wherein the molar ratio of N-(octadecylamidopropyl)-N,N-dimethyl tertiary amine to metal hydride is 1:2, after the dropwise addition is completed, the temperature is raised to 65°C for 36 hours, After the reaction, add deionized water, 1...

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Abstract

The invention discloses a viscoelastic surfactant for high-temperature self-steering acid. Its structural formula is as follows: wherein, n is a saturated alkane with 2 to 8 carbon atoms, R 1 is a saturated or unsaturated alkane with 18 to 28 carbon atoms, R 2 , R 3 are independently methyl, ethyl, hydrogen atoms, R 2 , R 3 Can be the same or different, X ‑ for Cl ‑ 、Br ‑ , F ‑ , CO 3 2‑ , SO 4 2‑ 、HCOO ‑ 、CH 3 COO ‑ any of the. The preparation method of the surfactant is as follows: it generates an intermediate product through acid amine condensation reaction between fatty acid and organic amine, then reacts with metal hydride to generate fatty amine, and then adds acid solution to protonate it to obtain super long-chain viscose Elastic cationic surfactant. The invention also provides the application of the surfactant as a thickening diverting agent for self-steering acid. The surfactant of the present invention can be used as a self-steering acid of a thickening diverting agent at a high temperature of 150° C., and has the advantages of stable structure, thickening of acid solution, uniform acidification, automatic diversion, and the like.

Description

technical field [0001] The invention relates to the field of oil and gas exploitation, in particular to a viscoelastic surfactant for high-temperature self-steering acid, a preparation method and application. Background technique [0002] In order to restore and increase the production of low-permeability oil and gas wells, acid liquid (usually 20% concentration of hydrochloric acid) is often injected into the reservoir, through which the acid liquid acts on rock cement (cement mostly contains carbonates and clay) or formation pores, Dissolution and corrosion of blockages in fractures, restore reservoir permeability, and expand oil and gas seepage channels (K.M.Bartko, F.F.Chang, L.A.Behrmann, I.C.Walton. Effective matrix acidizing in carbonate reservoir-Does perforating matter? Paper presented at SPE Middle East Oil and Gas Show and Conference, MEOS, Proceedings, Bahrain, 250-259, 2007). But for a long time, there have been two problems in the conventional acid system: (1)...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01F17/18C09K23/18
CPCC09K8/602C09K8/74C09K2208/30C07C231/02C07C209/50C07C233/09C07C211/22C07C209/44
Inventor 冯玉军王骥殷鸿尧
Owner SICHUAN UNIV
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