CN104212428A - Preparation method and application of Mannich base corrosion inhibitor suitable for high temperature acidification - Google Patents
Preparation method and application of Mannich base corrosion inhibitor suitable for high temperature acidification Download PDFInfo
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- CN104212428A CN104212428A CN201410400619.1A CN201410400619A CN104212428A CN 104212428 A CN104212428 A CN 104212428A CN 201410400619 A CN201410400619 A CN 201410400619A CN 104212428 A CN104212428 A CN 104212428A
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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
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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
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
- C09K8/604—Polymeric surfactants
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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
- C09K8/725—Compositions containing polymers
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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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
Abstract
The invention relates to a preparation method and an application of a Mannich base corrosion inhibitor suitable for high temperature acidification. The preparation method comprises the following steps: preparing an aldehyde-ketone-amine condensate through a Mannich base reaction, and carrying out reduced pressure distillation on the aldehyde-ketone-amine condensate to purify the aldehyde-ketone-amine condensate; and adding the purified aldehyde-ketone-amine condensate into a reaction container, and adding triethanolamine, 3-methyl-1-pentyn-3-ol, peregal O-25, alkylphenol polyoxyethylene OP-10, potassium iodide, methanol, dimethyl formamide and bismuth trichloride into the reaction container under normal pressure. The corrosion inhibitor produced through the preparation method has the advantages of good dispersion in hydrochloric acid, mud acid and ethanol solutions, good surface activity, less coking and low freezing point, and is suitable for yield increase work construction of 120-140DEG C deep wells, 15-28% concentrated hydrochloric acid or mud acid acidification oil and gas wells.
Description
Technical field
The present invention relates to well production increment operation chemical technical field, particularly a kind of applicable high temperature acidified Mannich base inhibiter preparation method and application thereof.
Background technology
Along with deepening continuously of oil-field development, the well-digging of new input development block increases, and in oil mining process, needs to improve recovery ratio by acidifying, and the injection of acid causes the corrosion of oil pipe and down-hole hardware, causes very large financial loss.Therefore in oil well acidation, especially high temperature deep well and ultra deep well carry out in the deep-well acidifying of concentrated hydrochloric acid large acid amount, and important task solves the corrosion prevention problem of high temperature acidified liquid to oil pipe and down-hole hardware.
In recent years, acidifying is progressively to high temperature deep well development, and in acidizing fluid, high temperature destroys serious to the inhibiter in acidizing fluid, and corrosion mitigating effect is extremely acute to decline, and original inhibiter can not meet high temperature acidified demand.At high temperature there is the shortcomings such as easy coking, layering, dissolution dispersity be stable not in current domestic conventional high temperature resistance acidification corrosion inhibitor, had not both protected oil pipe and down-hole hardware, and can cause again the injury on stratum.
Summary of the invention
For solving the problem, the invention provides a kind of in hydrochloric acid, mud acid and ethanolic soln good dispersity, have better surfactivity, coking is few, zero pour is low, can be applicable to 120 DEG C ~ 140 DEG C deep-wells, the applicable high temperature acidified Mannich base inhibiter preparation method of 15% ~ 28% concentrated hydrochloric acid or the job execution of soil acid acidizing well production increment and application thereof.
A kind of applicable high temperature acidified Mannich base inhibiter preparation method provided by the invention, comprises the following steps:
Step 1: prepare aldehyde ketone amine condenses by Mannich base reaction; The moiety of reactant is as follows: with amount of substance than calculating, the methyl phenyl ketone of the rosin Amine D of 1 mol ratio, the paraformaldehyde of 2 ~ 4 mol ratios, 2 ~ 3 mol ratios and 2,4-diacetylmethanes;
Step 2: underpressure distillation purification processes is carried out to described aldehyde ketone amine condenses;
Step 3: the described aldehyde ketone amine condenses after purifying is added in reaction vessel, then adds following reactant at ambient pressure in reaction vessel: trolamine, methylpentynol, peregal O-25, alkylphenol polyoxyethylene OP-10, potassiumiodide, methyl alcohol, dimethyl formamide and Trichlorobismuthine;
Wherein, the massfraction of described reactant is: aldehyde ketone amine condenses: 15% ~ 40%, methylpentynol: 1% ~ 10%, trolamine: 2% ~ 5%, peregal O-25: 5% ~ 15%, alkylphenol polyoxyethylene OP-10:5%, potassiumiodide: 5% ~ 8%, dimethyl formamide: 20% ~ 30%, Trichlorobismuthine: 3% ~ 5%, all the other are methyl alcohol.
As preferably, the Mannich base reaction process in described step 1 is carried out in enamel reaction still; Reaction vessel in described step 3 is enamel reaction still;
The function that described enamel reaction still has stirring, heats, cools and vacuumize;
Described Mannich base reaction process adds hydrochloric acid as catalyzer;
Rosin Amine D in described step 1 joins in enamel reaction still together with methyl alcohol.
As preferably, the Mannich base reaction process in described step 1 is:
First, the methyl phenyl ketone of the paraformaldehyde of 2 ~ 4 mol ratios, 2 ~ 3 mol ratios and 2,4-diacetylmethane are added enamel reaction still, is slowly warmed up to 100 ~ 110 DEG C, add the catalyzer of hydrochloric acid as reaction, the add-on of described hydrochloric acid is 1% ~ 2% of described rosin Amine D total amount; The pH value of reactant mixed solution is adjusted to 3 by described hydrochloric acid;
Then, the rosin Amine D of 1 mol ratio is joined in described enamel reaction still with methyl alcohol together, react and complete after 14 ~ 18 hours.
As preferably, the underpressure distillation purification processes in described step 2 is carried out in a distillation column.
As preferably, in described step 3, reaction process is:
First, add methyl alcohol, aldehyde ketone amine condenses and other reactants are fully dissolved, stir 30 minutes after being heated to 50 DEG C;
Then, add residue methyl alcohol, make reactant reach desired concn, stir after 30 minutes and stop heating;
Finally, cooled by room temperature, continuous stirring reaction product in process of cooling, when being cooled to normal temperature, the described reaction product obtained is applicable high temperature acidified Mannich base inhibiter.
A kind of applicable high temperature acidified Mannich base inhibiter preparation method provided by the invention can prepare and be applicable to 120 DEG C ~ 140 DEG C high temperature acidified Mannich base inhibiter, is specially adapted to 120 DEG C ~ 140 DEG C deep-wells, 15% ~ 28% concentrated hydrochloric acid or the job execution of soil acid acidizing well production increment.Meanwhile, this preparation method's technique is simple, need not specific installation, reduces production cost.
A kind of applicable high temperature acidified Mannich base inhibiter provided by the invention is produced according to described inhibiter preparation method;
Described inhibiter is applicable to 120 DEG C ~ 140 DEG C deep-wells, 15% ~ 28% concentrated hydrochloric acid or the job execution of soil acid acidizing well production increment.
Applicable high temperature acidified Mannich base inhibiter provided by the invention is the inhibiter produced as stated above, corrosion inhibition rate >=97% of this inhibiter, good dispersity in hydrochloric acid, mud acid and ethanolic soln, there is better surfactivity, coking is few, zero pour is low, makes oil pipe and the erosion rate of down-hole hardware in high temperature acidified liquid lower than the first grade standard of industry.
Accompanying drawing explanation
The process flow sheet of the applicable high temperature acidified Mannich base inhibiter preparation method that Fig. 1 provides for the embodiment of the present invention.
Embodiment
See accompanying drawing 1, a kind of applicable high temperature acidified Mannich base inhibiter preparation method provided by the invention, comprises the following steps:
Step 1: prepare aldehyde ketone amine condenses by Mannich base reaction; The moiety of reactant is as follows: with amount of substance than calculating, the methyl phenyl ketone of the rosin Amine D of 1 mol ratio, the paraformaldehyde of 2 ~ 4 mol ratios, 2 ~ 3 mol ratios and 2,4-diacetylmethanes;
Step 2: underpressure distillation purification processes is carried out to described aldehyde ketone amine condenses;
Step 3: the described aldehyde ketone amine condenses after purifying is added in reaction vessel, then adds following reactant at ambient pressure in reaction vessel: trolamine, methylpentynol, peregal O-25, alkylphenol polyoxyethylene OP-10, potassiumiodide, methyl alcohol, dimethyl formamide and Trichlorobismuthine;
Wherein, the massfraction of reactant is: aldehyde ketone amine condenses: 15% ~ 40%, methylpentynol: 1% ~ 10%, trolamine: 2% ~ 5%, peregal O-25: 5% ~ 15%, alkylphenol polyoxyethylene OP-10:5%, potassiumiodide: 5% ~ 8%, dimethyl formamide: 20% ~ 30%, Trichlorobismuthine: 3% ~ 5%, all the other are methyl alcohol.
As preferably, the Mannich base reaction process in step 1 is carried out in enamel reaction still; Reaction vessel in step 3 is enamel reaction still; The function that enamel reaction still has stirring, heats, cools and vacuumize; Mannich base reaction process adds hydrochloric acid as catalyzer; Rosin Amine D in step 1 joins in enamel reaction still together with methyl alcohol.
As preferably, Mannich base reaction process in step 1 is: first, by the methyl phenyl ketone and 2 of the paraformaldehyde of 2 ~ 4 mol ratios, 2 ~ 3 mol ratios, 4-diacetylmethane adds enamel reaction still, slowly be warmed up to 100 ~ 110 DEG C, add the catalyzer of hydrochloric acid as reaction, the add-on of hydrochloric acid is 1% ~ 2% of rosin Amine D total amount; The pH value of reactant mixed solution is adjusted to 3 by hydrochloric acid; Then, the rosin Amine D of 1 mol ratio is joined in enamel reaction still together with methyl alcohol, react and complete after 14 ~ 18 hours.
As preferably, the underpressure distillation purification processes in step 2 is carried out in a distillation column.
As preferably, in step 3, reaction process is: first, adds the methyl alcohol needing add-on half, and aldehyde ketone amine condenses and other reactants are fully dissolved, and stirs 30 minutes after being heated to 50 DEG C; Then, add the methyl alcohol needing add-on to remain half, make reactant reach desired concn, stir after 30 minutes and stop heating; Finally, cooled by room temperature, continuous stirring reaction product in process of cooling, when being cooled to normal temperature, the reaction product obtained is applicable high temperature acidified Mannich base inhibiter.
A kind of applicable high temperature acidified Mannich base inhibiter provided by the invention is produced according to inhibiter preparation method; This inhibiter is applicable to 120 DEG C ~ 140 DEG C deep-wells, 15% ~ 28% concentrated hydrochloric acid or the job execution of soil acid acidizing well production increment; Corrosion inhibition rate >=97% of inhibiter.
embodiment 1
By amount of substance than calculating, the methyl phenyl ketone of the paraformaldehyde of 2 mol ratios, 2 mol ratios and 2,4-diacetylmethanes being added enamel reaction still, being slowly warmed up to 100 DEG C, add the catalyzer of hydrochloric acid as reaction, the pH value of reactant mixed solution is adjusted to 3 by hydrochloric acid; Then, the rosin Amine D of 1 mol ratio is joined in enamel reaction still together with methyl alcohol, react and generate aldehyde ketone amine condenses after 16 hours.Then the aldehyde ketone amine condenses of generation is joined in distillation tower and carry out underpressure distillation purification processes.
Aldehyde ketone amine condenses after purifying is joined in enamel reaction still, the pressure controlled in enamel reaction still is normal pressure, then adds following reactant in enamel reaction still: trolamine, methylpentynol, peregal O-25, alkylphenol polyoxyethylene OP-10, potassiumiodide, methyl alcohol, dimethyl formamide and Trichlorobismuthine.5%, Trichlorobismuthine wherein, the mass percent of each reactant is: aldehyde ketone amine condenses: 25%, methylpentynol: 5%, trolamine: 2%, alkylphenol polyoxyethylene OP-10:5%, peregal O-25: 5%, dimethyl formamide: 30%, potassiumiodide:: 3%, methyl alcohol: 20%.When adding reactant, first add the methyl alcohol needing add-on half, other reactants are joined in enamel reaction still simultaneously, aldehyde ketone amine condenses and other reactants are fully dissolved, stir 30 minutes after being heated to 50 DEG C; Then, add the methyl alcohol needing add-on to remain half, make reactant reach desired concn, stir after 30 minutes and stop heating; Finally, cooled by room temperature, continuous stirring reaction product in process of cooling, when being cooled to normal temperature, the reaction product obtained is be applicable to 120 DEG C of high temperature acidified Mannich base inhibiter.
Through performance test experiments is tested the Mannich base inhibiter generated, be the massfraction that the Mannich base inhibiter of 2% of acid solution weight joins 120 DEG C by total amount be in the concentrated hydrochloric acid of 20%, then N80 steel pipe is placed in above-mentioned hydrochloric acid, detected result is shown as, and the corrosion speed of steel pipe is 16.51g/m
2* h, corrosion inhibition rate is 99.18%.According to the regulation that standard SY/T5405 first grade requires, the corrosion speed in 120 DEG C of high temperature acid solutions is: 20 ~ 30g/m
2* h, therefore this inhibiter reaches first grade requirement.
embodiment 2
By amount of substance than calculating, the methyl phenyl ketone of the paraformaldehyde of 4 mol ratios, 3 mol ratios and 2,4-diacetylmethanes being added enamel reaction still, being slowly warmed up to 110 DEG C, add the catalyzer of hydrochloric acid as reaction, the pH value of reactant mixed solution is adjusted to 3 by hydrochloric acid; Then, the rosin Amine D of 1 mol ratio is joined in enamel reaction still together with methyl alcohol, react and generate aldehyde ketone amine condenses after 16 hours.Then the aldehyde ketone amine condenses of generation is joined in distillation tower and carry out underpressure distillation purification processes.
Aldehyde ketone amine condenses after purifying is joined in enamel reaction still, the pressure controlled in enamel reaction still is normal pressure, then adds following reactant in enamel reaction still: trolamine, methylpentynol, peregal O-25, alkylphenol polyoxyethylene OP-10, potassiumiodide, methyl alcohol, dimethyl formamide and Trichlorobismuthine.Wherein, the mass percent of each reactant is: aldehyde ketone amine condenses: 35%, methylpentynol: 5%, trolamine: 2%, alkylphenol polyoxyethylene OP-10:5%, peregal O-25: 5%, dimethyl formamide: 30%, potassiumiodide: 5%, Trichlorobismuthine: 3%, methyl alcohol: 10%.When adding reactant, first add the methyl alcohol needing add-on half, other reactants are joined in enamel reaction still simultaneously, aldehyde ketone amine condenses and other reactants are fully dissolved, stir 30 minutes after being heated to 50 DEG C; Then, add the methyl alcohol needing add-on to remain half, make reactant reach desired concn, stir after 30 minutes and stop heating; Finally, cooled by room temperature, continuous stirring reaction product in process of cooling, when being cooled to normal temperature, the reaction product obtained is be applicable to 120 DEG C of high temperature acidified Mannich base inhibiter.
Through performance test experiments is tested the Mannich base inhibiter generated, be the massfraction that the Mannich base inhibiter of 2% of acid solution weight joins 120 DEG C by total amount be in the concentrated hydrochloric acid of 20%, then N80 steel pipe is placed in above-mentioned hydrochloric acid, detected result is shown as, and the corrosion speed of steel pipe is 15.43g/m
2* h, corrosion inhibition rate is 99.24%.According to the regulation that standard SY/T5405 first grade requires, the corrosion speed in 120 DEG C of high temperature acid solutions is: 20 ~ 30g/m
2* h, therefore this inhibiter reaches first grade requirement.
embodiment 3
By amount of substance than calculating, the methyl phenyl ketone of the paraformaldehyde of 4 mol ratios, 3 mol ratios and 2,4-diacetylmethanes being added enamel reaction still, being slowly warmed up to 110 DEG C, add the catalyzer of hydrochloric acid as reaction, the pH value of reactant mixed solution is adjusted to 3 by hydrochloric acid; Then, the rosin Amine D of 1 mol ratio is joined in enamel reaction still together with methyl alcohol, react and generate aldehyde ketone amine condenses after 17 hours.Then the aldehyde ketone amine condenses of generation is joined in distillation tower and carry out underpressure distillation purification processes.
Aldehyde ketone amine condenses after purifying is joined in enamel reaction still, the pressure controlled in enamel reaction still is normal pressure, then adds following reactant in enamel reaction still: trolamine, methylpentynol, peregal O-25, alkylphenol polyoxyethylene OP-10, potassiumiodide, methyl alcohol, dimethyl formamide and Trichlorobismuthine.Wherein, the mass percent of each reactant is: aldehyde ketone amine condenses: 35%, methylpentynol: 5%, trolamine: 2%, alkylphenol polyoxyethylene OP-10:5%, peregal O-25: 5%, dimethyl formamide: 20%, potassiumiodide: 5%, Trichlorobismuthine: 3%, methyl alcohol: 20%.When adding reactant, first add the methyl alcohol needing add-on half, other reactants are joined in enamel reaction still simultaneously, aldehyde ketone amine condenses and other reactants are fully dissolved, stir 30 minutes after being heated to 50 DEG C; Then, add the methyl alcohol needing add-on to remain half, make reactant reach desired concn, stir after 30 minutes and stop heating; Finally, cooled by room temperature, continuous stirring reaction product in process of cooling, when being cooled to normal temperature, the reaction product obtained is be applicable to 130 DEG C of high temperature acidified Mannich base inhibiter.
Through performance test experiments is tested the Mannich base inhibiter generated, be the massfraction that the Mannich base inhibiter of 2% of acid solution weight joins 130 DEG C by total amount be in the concentrated hydrochloric acid of 20%, then N80 steel pipe is placed in above-mentioned hydrochloric acid, detected result is shown as, and the corrosion speed of steel pipe is 28.57g/m
2* h, corrosion inhibition rate is 98.59%.According to the regulation that standard SY/T5405 first grade requires, the corrosion speed in 130 DEG C of high temperature acid solutions is: 20 ~ 30g/m
2* h, therefore this inhibiter reaches first grade requirement.
embodiment 4
By amount of substance than calculating, the methyl phenyl ketone of the paraformaldehyde of 2 mol ratios, 2 mol ratios and 2,4-diacetylmethanes being added enamel reaction still, being slowly warmed up to 100 DEG C, add the catalyzer of hydrochloric acid as reaction, the pH value of reactant mixed solution is adjusted to 3 by hydrochloric acid; Then, the rosin Amine D of 1 mol ratio is joined in enamel reaction still together with methyl alcohol, react and generate aldehyde ketone amine condenses after 15 hours.Then the aldehyde ketone amine condenses of generation is joined in distillation tower and carry out underpressure distillation purification processes.
Aldehyde ketone amine condenses after purifying is joined in enamel reaction still, the pressure controlled in enamel reaction still is normal pressure, then adds following reactant in enamel reaction still: trolamine, methylpentynol, peregal O-25, alkylphenol polyoxyethylene OP-10, potassiumiodide, methyl alcohol, dimethyl formamide and Trichlorobismuthine.Wherein, the mass percent of each reactant is: aldehyde ketone amine condenses: 40%, methylpentynol: 5%, trolamine: 2%, alkylphenol polyoxyethylene OP-10:5%, peregal O-25: 5%, dimethyl formamide: 20%, potassiumiodide: 5%, Trichlorobismuthine: 3%, methyl alcohol: 15%.When adding reactant, first add the methyl alcohol needing add-on half, other reactants are joined in enamel reaction still simultaneously, aldehyde ketone amine condenses and other reactants are fully dissolved, stir 30 minutes after being heated to 50 DEG C; Then, add the methyl alcohol needing add-on to remain half, make reactant reach desired concn, stir after 30 minutes and stop heating; Finally, cooled by room temperature, continuous stirring reaction product in process of cooling, when being cooled to normal temperature, the reaction product obtained is be applicable to 140 DEG C of high temperature acidified Mannich base inhibiter.
Through performance test experiments is tested the Mannich base inhibiter generated, be the massfraction that the Mannich base inhibiter of 2% of acid solution weight joins 140 DEG C by total amount be in the concentrated hydrochloric acid of 20%, then N80 steel pipe is placed in above-mentioned hydrochloric acid, detected result is shown as, and the corrosion speed of steel pipe is 49.91g/m
2* h, corrosion inhibition rate is 97.72%.According to the regulation that standard SY/T5405 first grade requires, the corrosion speed in 140 DEG C of high temperature acid solutions is: 40 ~ 50g/m
2* h, therefore this inhibiter reaches first grade requirement.
embodiment 5
By amount of substance than calculating, the methyl phenyl ketone of the paraformaldehyde of 2 mol ratios, 2 mol ratios and 2,4-diacetylmethanes being added enamel reaction still, being slowly warmed up to 100 DEG C, add the catalyzer of hydrochloric acid as reaction, the pH value of reactant mixed solution is adjusted to 3 by hydrochloric acid; Then, the rosin Amine D of 1 mol ratio is joined in enamel reaction still together with methyl alcohol, react and generate aldehyde ketone amine condenses after 15 hours.Then the aldehyde ketone amine condenses of generation is joined in distillation tower and carry out underpressure distillation purification processes.
Aldehyde ketone amine condenses after purifying is joined in enamel reaction still, the pressure controlled in enamel reaction still is normal pressure, then adds following reactant in enamel reaction still: trolamine, methylpentynol, peregal O-25, alkylphenol polyoxyethylene OP-10, potassiumiodide, methyl alcohol, dimethyl formamide and Trichlorobismuthine.Wherein, the mass percent of each reactant is: aldehyde ketone amine condenses: 40%, methylpentynol: 5%, trolamine: 2%, alkylphenol polyoxyethylene OP-10:5%, peregal O-25: 5%, dimethyl formamide: 25%, potassiumiodide: 5%, Trichlorobismuthine: 3%, methyl alcohol: 10%.When adding reactant, first add the methyl alcohol needing add-on half, other reactants are joined in enamel reaction still simultaneously, aldehyde ketone amine condenses and other reactants are fully dissolved, stir 30 minutes after being heated to 50 DEG C; Then, add the methyl alcohol needing add-on to remain half, make reactant reach desired concn, stir after 30 minutes and stop heating; Finally, cooled by room temperature, continuous stirring reaction product in process of cooling, when being cooled to normal temperature, the reaction product obtained is be applicable to 140 DEG C of high temperature acidified Mannich base inhibiter.
Through performance test experiments is tested the Mannich base inhibiter generated, be the massfraction that the Mannich base inhibiter of 2% of acid solution weight joins 140 DEG C by total amount be in the concentrated hydrochloric acid of 20%, then N80 steel pipe is placed in above-mentioned hydrochloric acid, detected result is shown as, and the corrosion speed of steel pipe is 48.14g/m
2* h, corrosion inhibition rate is 97.62%.According to the regulation that standard SY/T5405 first grade requires, the corrosion speed in 140 DEG C of high temperature acid solutions is: 40 ~ 50g/m
2* h, therefore this inhibiter reaches first grade requirement.
Can be known by above embodiment, a kind of applicable high temperature acidified Mannich base inhibiter preparation method provided by the invention can prepare and be applicable to 120 DEG C ~ 140 DEG C high temperature acidified Mannich base inhibiter, is specially adapted to 120 DEG C ~ 140 DEG C deep-wells, 15% ~ 28% concentrated hydrochloric acid or the job execution of soil acid acidizing well production increment.Meanwhile, this preparation method's technique is simple, need not specific installation, reduces production cost.
Applicable high temperature acidified Mannich base inhibiter provided by the invention is the inhibiter produced as stated above; corrosion inhibition rate >=97% of this inhibiter; good dispersity in hydrochloric acid, mud acid and ethanolic soln; there is better surfactivity; coking is few, and zero pour is low, makes oil pipe and the erosion rate of down-hole hardware in high temperature acidified liquid lower than the first grade standard of industry; effectively protect oil pipe and down-hole hardware, can not formation damage again simultaneously.
Above-described embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only the specific embodiment of the present invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. be applicable to a high temperature acidified Mannich base inhibiter preparation method, it is characterized in that, comprise the following steps:
Step 1: prepare aldehyde ketone amine condenses by Mannich base reaction; The moiety of reactant is as follows: with amount of substance than calculating, the methyl phenyl ketone of the rosin Amine D of 1 mol ratio, the paraformaldehyde of 2 ~ 4 mol ratios, 2 ~ 3 mol ratios and 2,4-diacetylmethanes;
Step 2: underpressure distillation purification processes is carried out to described aldehyde ketone amine condenses;
Step 3: the described aldehyde ketone amine condenses after purifying is added in reaction vessel, then adds following reactant at ambient pressure in reaction vessel: trolamine, methylpentynol, peregal O-25, alkylphenol polyoxyethylene OP-10, potassiumiodide, methyl alcohol, dimethyl formamide and Trichlorobismuthine;
Wherein, the massfraction of described reactant is: aldehyde ketone amine condenses: 15% ~ 40%, methylpentynol: 1% ~ 10%, trolamine: 2% ~ 5%, peregal O-25: 5% ~ 15%, alkylphenol polyoxyethylene OP-10:5%, potassiumiodide: 5% ~ 8%, dimethyl formamide: 20% ~ 30%, Trichlorobismuthine: 3% ~ 5%, all the other are methyl alcohol.
2. inhibiter preparation method according to claim 1, is characterized in that:
Mannich base reaction process in described step 1 is carried out in enamel reaction still; Reaction vessel in described step 3 is enamel reaction still;
The function that described enamel reaction still has stirring, heats, cools and vacuumize;
Described Mannich base reaction process adds hydrochloric acid as catalyzer;
Rosin Amine D in described step 1 joins in enamel reaction still together with methyl alcohol.
3. inhibiter preparation method according to claim 1, is characterized in that:
Mannich base reaction process in described step 1 is:
First, the methyl phenyl ketone of the paraformaldehyde of 2 ~ 4 mol ratios, 2 ~ 3 mol ratios and 2,4-diacetylmethane are added enamel reaction still, is slowly warmed up to 100 ~ 110 DEG C, add the catalyzer of hydrochloric acid as reaction, the add-on of described hydrochloric acid is 1% ~ 2% of described rosin Amine D total amount; The pH value of reactant mixed solution is adjusted to 3 by described hydrochloric acid;
Then, the rosin Amine D of 1 mol ratio is joined in described enamel reaction still with methyl alcohol together, react and complete after 14 ~ 18 hours.
4. inhibiter preparation method according to claim 1, is characterized in that:
Underpressure distillation purification processes in described step 2 is carried out in a distillation column.
5. inhibiter preparation method according to claim 1, is characterized in that:
In described step 3, reaction process is:
First, add methyl alcohol, aldehyde ketone amine condenses and other reactants are fully dissolved, stir 30 minutes after being heated to 50 DEG C;
Then, add residue methyl alcohol, make reactant reach desired concn, stir after 30 minutes and stop heating;
Finally, cooled by room temperature, continuous stirring reaction product in process of cooling, when being cooled to normal temperature, the described reaction product obtained is applicable high temperature acidified Mannich base inhibiter.
6. be applicable to an application for high temperature acidified Mannich base inhibiter, it is characterized in that:
Described inhibiter produces according to the inhibiter preparation method described in any one of Claims 1 to 5;
Described inhibiter is applicable to 120 DEG C ~ 140 DEG C deep-wells, 15% ~ 28% concentrated hydrochloric acid or the job execution of soil acid acidizing well production increment.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104745175A (en) * | 2015-03-06 | 2015-07-01 | 中国石油集团渤海钻探工程有限公司 | Propynylamine high-temperature acidizing corrosion inhibitor and preparation method thereof |
| CN107162226A (en) * | 2017-05-27 | 2017-09-15 | 徐文忠 | A kind of anti-incrustation corrosion inhibitor, its preparation method and application |
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| CN107987822A (en) * | 2017-12-06 | 2018-05-04 | 唐山市金沙工贸有限公司 | High-temperature acidification corrosion inhibitor and preparation method thereof and application |
| CN110283581A (en) * | 2018-03-19 | 2019-09-27 | 中国石油天然气股份有限公司 | Acidification corrosion inhibitor suitable for 160 DEG C or more high temperature |
| CN110283581B (en) * | 2018-03-19 | 2021-08-03 | 中国石油天然气股份有限公司 | Acidizing corrosion inhibitor suitable for high temperature of above 160 DEG C |
| CN110982508A (en) * | 2019-12-26 | 2020-04-10 | 西南石油大学 | Mannich base acidizing corrosion inhibitor and preparation method thereof |
| CN110982508B (en) * | 2019-12-26 | 2022-03-08 | 西南石油大学 | Mannich base acidizing corrosion inhibitor and preparation method thereof |
| CN114437694A (en) * | 2021-12-31 | 2022-05-06 | 中国石油天然气集团有限公司 | Corrosion inhibitor for acid liquor and preparation and application thereof |
| CN114437694B (en) * | 2021-12-31 | 2023-06-23 | 中国石油天然气集团有限公司 | Corrosion inhibitor for acid liquor and preparation and application thereof |
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