阅读说明：本技术 一种用于酸化压裂用中高温缓蚀剂及其制备方法 (Medium-high temperature corrosion inhibitor for acid fracturing and preparation method thereof ) 是由 张科良 于 2021-01-18 设计创作，主要内容包括：一种用于酸化压裂用中高温缓蚀剂及其制备方法,由和组成,制备方法为：在三口烧瓶中先加入芳基酮、小分子C-1-C-3醇或N,N-二甲基甲酰胺、催化剂,搅拌分散均匀,加热至45-60℃,分三-四次加入多聚甲醛粉末,后升温至60℃-100℃反应0.5-6h；再通过恒压滴液漏斗滴加有机胺,搅拌混合均匀,滴加浓盐酸调节反应混合物的pH＝1-6,再加入芳基酮或脂肪酮,反应温度为60-100℃,搅拌下继续曼尼希碱反应4-10小时,冷却,得到酸化缓蚀剂产品；本发明具有用量少,抗腐蚀强、与其它油气田添加剂配伍良好等特点,可应用于原油常规开采酸化压裂领域。(A middle-high temperature corrosion inhibitor for acid fracturing and its preparing process are disclosed And the preparation method comprises the following steps: firstly adding aryl ketone and micromolecule C into a three-neck flask 1 ‑C 3 Alcohol or N, N-dimethylformamide and a catalyst are stirred and dispersed uniformly, heated to 45-60 ℃, added with paraformaldehyde powder in three-four times, heated to 60-100 ℃ and reacted for 0.5-6 h; then, dropping organic amine through a constant-pressure dropping funnel, stirring and mixing uniformly, dropping concentrated hydrochloric acid to adjust the pH value of the reaction mixture to 1-6, adding aryl ketone or aliphatic ketone, reacting at the temperature of 60-100 ℃, continuing the Mannich base reaction for 4-10 hours under stirring, and cooling to obtain an acidified corrosion inhibitor product; the invention has the advantages of low consumption, strong corrosion resistance and the addition of other oil and gas field additivesThe method has the characteristics of good compatibility and the like, and can be applied to the field of acid fracturing in conventional crude oil exploitation.)

1. A medium-high temperature corrosion inhibitor for acidizing and fracturing is characterized by comprising substances shown in a general formula 1 and a general formula 2, wherein the relative contents of the substances are randomly prepared, and the compound shown in the formula 1 accounts for 15-40% of the total mass:

wherein: r ═ phenyl, naphthyl, anthryl, phenanthryl, benzylidene, p-phenoxyphenyl, and the like; r₁，R₂Cyclohexyl, phenyl, benzyl, longer carbon chain (C)₄-C₁₈) Alkyl, polyene polyamine.

2. The medium-high temperature corrosion inhibitor for acid fracturing as claimed in claim 1, wherein the compound of formula 1 is most preferably 25-35% by mass of the total mass.

3. The preparation method of the medium-high temperature corrosion inhibitor for acid fracturing based on the claim 1 or 2 is characterized by comprising the following steps:

firstly adding 15-22g of aryl ketone and 35-75mL of micromolecule C into a three-neck flask₁-C₃Alcohols or N, N-dimethylformamide0.1-0.5g of catalyst, stirring and dispersing uniformly, heating to 45-60 ℃, adding 5-11g of paraformaldehyde powder in three-four times, heating to 60-100 ℃ and reacting for 0.5-6 h; and then 9-18g of organic amine is dripped through a constant pressure dropping funnel, the mixture is stirred and mixed evenly, concentrated hydrochloric acid is dripped to adjust the pH value of the reaction mixture to 1-6, then 0-10g of aryl ketone or aliphatic ketone is added, the reaction temperature is 60-100 ℃, the Mannich base reaction is continued for 4-10 hours under stirring, and the product of the acidizing corrosion inhibitor is obtained after cooling.

4. The method for preparing the medium-high temperature corrosion inhibitor for acid fracturing as claimed in claim 3, wherein the aryl ketone comprises: acetophenone, anthraethanone, phenacetone, p-phenoxyacetophenone, benzylidene acetone, or alkyl substitution of the above methyl ketones.

5. The preparation method of the medium-high temperature corrosion inhibitor for acid fracturing as claimed in claim 3, wherein the catalyst comprises: anhydrous potassium carbonate, anhydrous sodium carbonate or a mixture of the two.

6. The method for preparing the medium-high temperature corrosion inhibitor for acid fracturing as claimed in claim 3, wherein the organic amine comprises: cyclohexylamine, aniline, benzylamine, longer carbon chain C₄-C₁₈The aliphatic primary amine is combined with one or more of secondary amine, salicyloyl hydrazine, benzoyl hydrazine, ethanolamine, diethanolamine, ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylenehexamine and polyene polyamine in any proportion.

7. The preparation method of the medium-high temperature corrosion inhibitor for acid fracturing as claimed in claim 3, wherein the optimal mass ratio of aryl ketone, paraformaldehyde and catalyst is 16-20:6-10: 0.2-0.4; adding paraformaldehyde powder, heating to 65-95 deg.C, and reacting for 1.5-4.5 h.

8. The preparation method of the medium-high temperature corrosion inhibitor for acid fracturing as claimed in claim 3, wherein the aryl ketone is further added, and the best mass ratio is aryl ketone to organic amine is 2-8: 10-16; the optimal reaction temperature is 65-100 ℃, the optimal reaction time of the Mannich base is 6-10 hours, and the optimal reaction pH is 2-5.

Technical Field

The invention relates to the technical field of oilfield chemical agents, in particular to a medium-high temperature corrosion inhibitor for acid fracturing and a preparation method thereof.

Background

Acidification is one of effective technical measures for increasing the yield of an oil-gas well and increasing the injection of a water injection well in the process of carbonate reservoir development. However, in production practice, due to the severe corrosion of oil well metal tubing by acid liquor, the acidizing stimulation technology has not been widely applied and developed until after the acidizing corrosion inhibitor is released in the 30 th 20 th century. The acidizing corrosion inhibitor is popular with people because of the advantages of small dosage, simple construction process, no need of special additional equipment (such as electrochemical protection) and the like. In the process of acidizing construction, the acidizing corrosion inhibitor is added into the acid liquor to inhibit the corrosion of the acid liquor to the underground pipe column and equipment.

At present, although there are thousands of acidizing corrosion inhibitors in use in various oil fields at home, the types of acidizing corrosion inhibitors are few in terms of chemical composition. These are mainly: heterocyclic quaternary ammonium salt, imidazoline, organic amine, Mannich base, unsaturated aldehyde and other corrosion inhibitors, and various corrosion inhibitors of different types, organic corrosion inhibitors, inorganic corrosion inhibitors and synergists. At present, corrosion inhibitors for industrial application obtained on site are basically compounded products. It should be noted that the corrosion resistance of the corrosion inhibitor is related to parameters such as the molecular structure of the corrosion inhibitor, the spatial distribution of functional groups, the film forming capability of the metal surface, the relative dissolution amount and the like, and is also related to factors such as the composition and content of an acidification medium, the type of metal, the use temperature and the like.

U.S. Pat. No. 5,5096618 discloses that alpha-benzoyl-allyl alcohol (BAA) is an effective acidification corrosion inhibitor. The high-temperature high-efficiency corrosion inhibitor can be obtained by compounding the quaternary ammonium salt with quinoline. Van hongbo et al (Van hongbo, Pengxuang, Zheng Jia 291302-benzoyl-3-hydroxy-1-propene (alpha-arylformyl-allyl alcohol) -a novel hydrochloric acid corrosion inhibitor [ J ]. MATERIALS PROTECTION,1997,30(6):8-10) found that BAA and propiolic alcohol have better corrosion resistance than propiolic alcohol under the same conditions, no matter whether the BAA and the propiolic alcohol are singly compared or after being compounded, and simultaneously, the BAA and the propiolic alcohol have good synergistic action with organic nitride. Liuxiang et al (Juchao, Liuxiang, 2-benzoyl-3-hydroxy-1-propylene and Mannich base corrosion inhibition synergy [ J ]. Sian Petroleum university (Nature science edition) 2015,30(3):82-86) find that BAA and Mannich base have good corrosion inhibition performance on N80 steel sheets in hydrochloric acid medium; under the conditions of certain addition of the corrosion inhibitor and no change of other conditions, after the BAA and the Mannich base are compounded according to a certain proportion, the corrosion rate of an N80 steel sheet in a hydrochloric acid medium is obviously lower than that of the BAA or the Mannich base which is used alone, the polarization resistance is increased, the BAA and the Mannich base show good synergistic effect, and the composite corrosion inhibitor plays a role in inhibiting corrosion through a geometric coverage effect. Gaojiacun et al (Gaojiacun, von Lily, Wen Yongji, et al. research on synergistic effect of Mannich base type corrosion inhibitors [ J ]. Sinkiang Petroleum gas, 2007,3(3):86-88) synthesize XY-3 corrosion inhibitors from selected ketones, aldehydes, and amines through a multi-step reaction mainly involving Mannich reaction. And separating the self-made corrosion inhibitor product XY-3; and (3) performing performance evaluation on the separated Mannich reaction crystal, mother liquor and XY-3 corrosion inhibitor by using the petroleum industry standard. The experimental results show that: although the pure Mannich base crystal has good corrosion inhibition performance, the Mannich base crystal has a large difference from a corrosion inhibitor XY-3 with a plurality of components, and the high-concentration corrosion rate of the Mannich base crystal is 10.1 times of that of XY-3; the observation shows that the surface of the test piece of the corrosion inhibitor XY-3 is bright, and the corrosion inhibitor has a uniform adsorption layer on the surface of the test piece, which indicates that a plurality of components compete for adsorption to form a compact adsorption film on the surface of the test piece, thereby having good protection effect on steel. However, this document does not have the process conditions for preparing the corrosion inhibitor, and the parameters such as the material type, the reaction ratio, the catalyst and the amount thereof, the reaction time, the reaction temperature, etc. cannot be known.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a medium-high temperature corrosion inhibitor for acid fracturing and a preparation method thereof, which couple the preparation of alpha-arylformyl-allyl alcohol (called BAA when aryl is a benzene ring) and the preparation of Mannich base, and provides an effective method for preparing a multi-component compound type acid corrosion inhibitor, so that complex compounding work is avoided, expensive synergists such as propiolic alcohol and the like can be omitted, the multi-component high-temperature high-efficiency acid corrosion inhibitor containing the alpha-arylformyl-allyl alcohol and the Mannich base can be conveniently obtained, and the relative content of the alpha-arylformyl-allyl alcohol and the Mannich base can be flexibly adjusted.

In order to achieve the purpose, the technical scheme of the invention is realized as follows:

a medium-high temperature corrosion inhibitor for acidizing and fracturing comprises substances shown in general formulas 1 and 2, wherein the relative contents of the substances are randomly prepared, the compound shown in the general formula 1 accounts for 15-40% of the total mass, and the optimal content is 25-35%:

wherein: r ═ phenyl, naphthyl, anthryl, phenanthryl, benzylidene, p-phenoxyphenyl, and the like; r₁，R₂Cyclohexyl, phenyl, benzyl, longer carbon chain (C)₄-C₁₈) Alkyl, polyene polyamine.

A preparation method of a medium-high temperature corrosion inhibitor for acid fracturing comprises the following steps:

firstly adding 15-22g of aryl ketone and 35-75mL of micromolecule C into a three-neck flask₁-C₃Alcohol or N, N-dimethylformamide and 0.1-0.5g of catalyst are stirred and dispersed evenly, heated to 45-60 ℃, added with 5-11g of paraformaldehyde powder in three-four times, heated to 60-100 ℃ and reacted for 0.5-6 h; and then 9-18g of organic amine is dripped through a constant pressure dropping funnel, the mixture is stirred and mixed evenly, concentrated hydrochloric acid is dripped to adjust the pH value of the reaction mixture to 2-6, then 0-10g of aryl ketone or aliphatic ketone is added, the reaction temperature is 60-100 ℃, the Mannich base continues to react for 4-10 hours under stirring, and the product of the acidizing corrosion inhibitor is obtained after cooling.

The aryl ketone comprises: acetophenone, anthraethanone, phenacetone, p-phenoxyacetophenone, benzylidene acetone, or alkyl substitution of the above methyl ketones.

The catalyst comprises: anhydrous potassium carbonate, anhydrous sodium carbonate or a mixture of the two.

The organic amine comprises: cyclohexylamine, aniline, benzylamine, longer carbon chain C₄-C₁₈The aliphatic primary amine is combined with one or more of secondary amine, salicyloyl hydrazine, benzoyl hydrazine, ethanolamine, diethanolamine, ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylenehexamine and polyene polyamine in any proportion.

The optimal mass ratio of the aryl ketone to the paraformaldehyde to the catalyst is 16-20:6-10: 0.2-0.4; adding paraformaldehyde powder, heating to 65-95 deg.C, and reacting for 1.5-4.5 h.

The best mass ratio of aryl ketone to organic amine is 2-8: 10-16; the optimal reaction temperature is 65-100 ℃, the optimal reaction time of the Mannich base is 6-10 hours, and the optimal reaction pH is 2-5.

The invention has the advantages that:

1. the complex compounding work can be avoided by adopting a one-pot preparation process; generally speaking, under the set conditions, acetophenone and paraformaldehyde react under the alkaline condition to generate a certain amount of 2-benzoyl-3-hydroxy-1-propylene; adding organic amine, adjusting the pH of the medium, and performing condensation reaction between ketone-aldehyde amine to generate an aminomethylated product-Mannich base;

2. the molecular structure and relative composition of the composite acidizing corrosion inhibitor can be designed according to the composition of an acidizing medium and the temperature of the medium.

Detailed Description

The present invention will be described in detail with reference to examples.

A preparation method of a medium-high temperature corrosion inhibitor for acid fracturing comprises the following steps:

adding 15-22g aryl ketone and 35-75mL micromolecule C into a 100mL three-neck flask₁-C₃Alcohol or N, N-dimethylformamide and 0.1-0.5g of catalyst are stirred and dispersed evenly, heated to 45-60 ℃, added with 5-11g of paraformaldehyde powder in three-four times, heated to 60-100 ℃ and reacted for 0.5-6 h; the reaction formula is as follows:

wherein: r ═ phenyl, naphthyl, anthryl, phenanthryl, benzylidene, p-phenoxyphenyl;

and then 9-18g of organic amine is dripped through a constant-pressure dropping funnel, the mixture is stirred and mixed uniformly, concentrated hydrochloric acid is dripped to adjust the pH value of the reaction mixture to be 2-6, 0-10g of aryl ketone is added, the reaction temperature is 60-100 ℃, the Mannich base continues to react for 4-10 hours under stirring, and the product of the acidified corrosion inhibitor is obtained after cooling, wherein the reaction formula is as follows:

R₁，R₂cyclohexyl, phenyl, benzyl, longerCarbon chain (C)₄-C₁₈) Alkyl, polyene polyamine.

The first embodiment is as follows:

the preparation of this example comprises the following steps:

firstly adding 12.01g of acetophenone, 40mL of methanol and 0.15g of anhydrous potassium carbonate into a 100mL three-neck flask, stirring and heating to uniformly disperse, adding 6g of paraformaldehyde powder for three times, heating to 65 ℃, and carrying out reflux reaction for 1.5 h; 6.6g of cyclohexylamine is dripped through a constant-pressure dropping funnel, after the mixture is stirred and mixed uniformly, concentrated hydrochloric acid is used for adjusting the pH value of the reaction mixture to be 4, 3.9g of aliphatic ketone acetone is dripped, the reaction is continued for 8 hours under the stirring, and the high-efficiency corrosion inhibitor product 1 can be obtained after cooling.

Example two:

the preparation of this example comprises the following steps:

adding 12g of acetophenone, 35mL of absolute ethanol and 0.2g of anhydrous potassium carbonate into a 100mL three-neck flask, adding 6g of paraformaldehyde powder into the flask in four times while stirring and heating, heating the mixture to 78 ℃, and carrying out reflux reaction for 1.5 hours; and (3 g) dropwise adding ethylenediamine into the reaction mixture through a constant-pressure dropping funnel, uniformly stirring and mixing, adjusting the pH value of the reaction mixture to be 4 by using concentrated hydrochloric acid, continuously reacting for 7 hours under stirring, and cooling to obtain a high-efficiency corrosion inhibitor product 2.

Example three:

the preparation of this example comprises the following steps:

adding 12g of acetophenone, 60mL of N, N-dimethylformamide and 0.25g of anhydrous potassium carbonate into a 100mL three-neck flask, stirring and heating, adding 6g of paraformaldehyde powder for three times, heating to 90-95 ℃, carrying out reflux reaction for 1.5h, adding 2.7g of ethylenediamine through a constant-pressure dropping funnel, uniformly stirring and mixing, adjusting the pH value of a reaction mixture to 3 by using concentrated hydrochloric acid, and continuously reacting for 6h under stirring. Cooling to obtain the high-efficiency corrosion inhibitor product 3.

Example four:

the preparation of this example comprises the following steps:

adding 12g of acetophenone, 40mL of isopropanol solvent and 0.32g of anhydrous potassium carbonate as a metered catalyst into a 100mL three-neck flask, adding 6g of paraformaldehyde powder for 4 times under stirring and heating, and heating to 70-85 ℃ for reflux reaction for 4.5 hours; adding 14.88g of cyclohexylamine through a constant-pressure dropping funnel, stirring and mixing uniformly, adjusting the pH value of the reaction mixture to 3 by using concentrated hydrochloric acid, dropwise adding 8.9g of aliphatic ketone acetone, continuously reacting for 12 hours under stirring, and cooling to obtain a high-efficiency corrosion inhibitor product 4.

TABLE 1 results of evaluation of acidizing corrosion inhibitors for four examples

Evaluation conditions of the acidizing corrosion inhibitor: the addition amount of the acidizing corrosion inhibitor is 1 percent, and N80 coupon is corroded for 4 hours at 90 ℃ by 15 percent hydrochloric acid.