CN104212428B - It is a kind of to be adapted to high temperature acidified Mannich base corrosion inhibiter preparation method and applications - Google Patents

It is a kind of to be adapted to high temperature acidified Mannich base corrosion inhibiter preparation method and applications Download PDF

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CN104212428B
CN104212428B CN201410400619.1A CN201410400619A CN104212428B CN 104212428 B CN104212428 B CN 104212428B CN 201410400619 A CN201410400619 A CN 201410400619A CN 104212428 B CN104212428 B CN 104212428B
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corrosion inhibiter
mannich base
condensation product
reaction
methyl alcohol
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CN104212428A (en
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韩文礼
李玲杰
解蓓蓓
杨耀辉
徐忠苹
张贻刚
张彦军
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China National Petroleum Corp
CNPC Offshore Engineering Co Ltd
CNPC Engineering Technology Research Institute Co Ltd
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China National Petroleum Corp
CNPC Offshore Engineering Co Ltd
CNPC Engineering Technology Research Institute Co Ltd
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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
    • 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
    • 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
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

It is adapted to high temperature acidified Mannich base corrosion inhibiter preparation method and applications the present invention relates to a kind of, the preparation method is comprised the following steps：Aldehyde ketone amine condensation product is prepared by Mannich base reaction, vacuum distillation purification processes are carried out to aldehyde ketone amine condensation product；During aldehyde ketone amine condensation product after purification added into reaction vessel, then at ambient pressure to adding following reactant in reaction vessel：Triethanolamine, the alcohol of 3 methyl, 1 pentyne 3, paregal O 25, APES OP 10, KI, methyl alcohol, dimethylformamide and bismuth trichloride.The corrosion inhibiter that the preparation method is produced in hydrochloric acid, mud acid and in ethanol solution good dispersion, have that preferable surface-active, coking be few, freezing point is low, can be suitably used for 120 DEG C~140 DEG C deep-wells, 15%~28% concentrated hydrochloric acid or soil acid acidizing well production increment job execution.

Description

It is a kind of to be adapted to high temperature acidified Mannich base corrosion inhibiter preparation method and applications
Technical field
The present invention relates to well production increment operation chemicals technical field, more particularly to it is a kind of be adapted to it is high temperature acidified graceful The uncommon alkali corrosion inhibiter preparation method and applications of Buddhist nun.
Background technology
With deepening continuously for oil field development, new input development block well-digging increases, it is necessary to pass through during oil mining Acidifying improves recovery ratio, and the injection of acid causes the corrosion of oil pipe and underground hardware, causes very big economic loss.Cause In oil well acidation, during especially high temperature deep well and ultradeep well carry out the big acid amount deep-well acidifying of concentrated hydrochloric acid, important task is for this Solve the problems, such as corrosion protection of the high temperature acidified liquid to oil pipe and underground hardware.
In recent years, acidifying progressively develops to high temperature deep well, and in acidifying solution, high temperature is tight to the corrosion inhibiter destruction in acidifying solution Weight, the dramatic decline of corrosion mitigating effect, original corrosion inhibiter can not meet high temperature acidified demand.Conventional high temperature resistance acid domestic at present Change corrosion inhibiter the shortcomings of be not sufficiently stable in the presence of easy coking, layering, dissolution dispersity at high temperature, both do not protected oil pipe with Underground hardware, can cause the injury on stratum again.
The content of the invention
To solve the above problems, the invention provides one kind in hydrochloric acid, mud acid and in ethanol solution good dispersion, have preferably Surface-active, coking are few, freezing point is low, can be suitably used for 120 DEG C~140 DEG C deep-wells, 15%~28% concentrated hydrochloric acid or soil acid acidizings The suitable high temperature acidified Mannich base corrosion inhibiter preparation method and applications of well production increment job execution.
A kind of suitable high temperature acidified Mannich base corrosion inhibiter preparation method that the present invention is provided, comprises the following steps：
Step 1：Aldehyde ketone amine condensation product is prepared by Mannich base reaction；The constituent of reactant is as follows：With material Amount is than calculating, the rosin amine of 1 mol ratio, the paraformaldehyde of 2~4 mol ratios, the acetophenone of 2~3 mol ratios and 2,4- pentanediones；
Step 2：Vacuum distillation purification processes are carried out to the aldehyde ketone amine condensation product；
Step 3：The aldehyde ketone amine condensation product after by purification is added in reaction vessel, then at ambient pressure to reaction vessel It is middle to add following reactant：Triethanolamine, methylpentynol, peregal O-25, APES OP- 10th, KI, methyl alcohol, dimethylformamide and bismuth trichloride；
Wherein, the mass fraction of the reactant is：Aldehyde ketone amine condensation product：15%~40%, 3- methyl-1-pentenes alkynes -3- Alcohol：1%~10%, triethanolamine：2%~5%, peregal O-25：5%~15%, APES OP-10： 5%th, KI：5%~8%, dimethylformamide：20%~30%, bismuth trichloride：3%~5%, remaining is methyl alcohol.
Preferably, the Mannich base course of reaction in the step 1 is carried out in enamel reaction still；In the step 3 Reaction vessel be enamel reaction still；
The enamel reaction still has the function of stirring, heat, cool down and vacuumize；
The Mannich base course of reaction adds hydrochloric acid as catalyst；
Rosin amine and methyl alcohol in the step 1 are added in enamel reaction still together.
Preferably, the Mannich base course of reaction in the step 1 is：
First, add enamel anti-the paraformaldehyde of 2~4 mol ratios, the acetophenone of 2~3 mol ratios and 2,4- pentanedione Kettle is answered, 100~110 DEG C are slowly warmed up to, adds hydrochloric acid as the catalyst of reaction, the addition of the hydrochloric acid is the rosin The 1%~2% of amine total amount；The hydrochloric acid adjusts to 3 the pH value of reactant mixed liquor；
Then, the rosin amine of 1 mol ratio is added in the enamel reaction still together with methyl alcohol, is reacted 14~18 hours After complete.
Preferably, the vacuum distillation purification processes in the step 2 are carried out in a distillation column.
Preferably, course of reaction is in the step 3：
First, methyl alcohol is added so that aldehyde ketone amine condensation product and other reactants are fully dissolved, and 30 are stirred after being heated to 50 DEG C Minute；
Then, remaining methyl alcohol is added so that reactant reaches required concentration, stirring stops heating after 30 minutes；
Finally, cooled down by room temperature, product is stirred continuously in cooling procedure, when being cooled to normal temperature, the institute for obtaining It is to be adapted to high temperature acidified Mannich base corrosion inhibiter to state product.
A kind of suitable high temperature acidified Mannich base corrosion inhibiter preparation method that the present invention is provided can be prepared and is applied to 120 DEG C~140 DEG C high temperature acidified Mannich base corrosion inhibiter, are particularly well-suited to 120 DEG C~140 DEG C deep-wells, 15%~28% dense salt Acid or soil acid acidizing well production increment job execution.Meanwhile, the preparation method process is simple, without special installation, reduces life Produce cost.
A kind of suitable high temperature acidified Mannich base corrosion inhibiter that the present invention is provided is according to the corrosion inhibiter preparation method Produce；
The corrosion inhibiter is applied to 120 DEG C~140 DEG C deep-wells, 15%~28% concentrated hydrochloric acid or soil acid acidizing well production increments Job execution.
The suitable high temperature acidified Mannich base corrosion inhibiter that the present invention is provided is the corrosion inhibiter produced as stated above, Corrosion inhibition rate >=97% of the corrosion inhibiter, in hydrochloric acid, mud acid and good dispersion in ethanol solution, there is preferable surface-active, and coking is few, Freezing point is low so that primes mark of the corrosion rate of oil pipe and underground hardware in high temperature acidified liquid less than industry It is accurate.
Brief description of the drawings
Fig. 1 is the technological process for being adapted to high temperature acidified Mannich base corrosion inhibiter preparation method provided in an embodiment of the present invention Figure.
Specific embodiment
Referring to accompanying drawing 1, a kind of suitable high temperature acidified Mannich base corrosion inhibiter preparation method that the present invention is provided, including with Lower step：
Step 1：Aldehyde ketone amine condensation product is prepared by Mannich base reaction；The constituent of reactant is as follows：With material Amount is than calculating, the rosin amine of 1 mol ratio, the paraformaldehyde of 2~4 mol ratios, the acetophenone of 2~3 mol ratios and 2,4- pentanediones；
Step 2：Vacuum distillation purification processes are carried out to the aldehyde ketone amine condensation product；
Step 3：The aldehyde ketone amine condensation product after by purification is added in reaction vessel, then at ambient pressure to reaction vessel It is middle to add following reactant：Triethanolamine, methylpentynol, peregal O-25, APES OP- 10th, KI, methyl alcohol, dimethylformamide and bismuth trichloride；
Wherein, the mass fraction of reactant is：Aldehyde ketone amine condensation product：15%~40%, methylpentynol： 1%~10%, triethanolamine：2%~5%, peregal O-25：5%~15%, APES OP-10：5%th, iodine Change potassium：5%~8%, dimethylformamide：20%~30%, bismuth trichloride：3%~5%, remaining is methyl alcohol.
Preferably, the Mannich base course of reaction in step 1 is carried out in enamel reaction still；Reaction in step 3 is held Device is enamel reaction still；Enamel reaction still has the function of stirring, heat, cool down and vacuumize；Mannich base course of reaction adds Enter hydrochloric acid as catalyst；Rosin amine and methyl alcohol in step 1 are added in enamel reaction still together.
Preferably, the Mannich base course of reaction in step 1 is：First, by the paraformaldehyde of 2~4 mol ratios, 2~3 The acetophenone and 2,4- pentanedione of mol ratio add enamel reaction still, are slowly warmed up to 100~110 DEG C, add hydrochloric acid as anti- The catalyst answered, the addition of hydrochloric acid is the 1%~2% of rosin amine total amount；Hydrochloric acid arrives the pH value regulation of reactant mixed liquor 3；Then, the rosin amine of 1 mol ratio is added in enamel reaction still together with methyl alcohol, reaction is completed after 14~18 hours.
Preferably, the vacuum distillation purification processes in step 2 are carried out in a distillation column.
Preferably, course of reaction is in step 3：First, adding needs the methyl alcohol of addition half so that aldehyde ketone amine is condensed Thing and other reactants fully dissolve, and are stirred 30 minutes after being heated to 50 DEG C；Then, adding needs the first of addition residue half Alcohol so that reactant reaches required concentration, stirring stops heating after 30 minutes；Finally, cooled down by room temperature, in cooling procedure Product is stirred continuously, when being cooled to normal temperature, the product for obtaining is to be adapted to high temperature acidified Mannich base corrosion inhibiter.
A kind of suitable high temperature acidified Mannich base corrosion inhibiter that the present invention is provided is produced according to corrosion inhibiter preparation method Out；The corrosion inhibiter is applied to 120 DEG C~140 DEG C deep-wells, 15%~28% concentrated hydrochloric acid or soil acid acidizing well production increment and makees Industry is constructed；Corrosion inhibition rate >=97% of corrosion inhibiter.
Embodiment 1
By the amount of material than calculating, by the paraformaldehyde of 2 mol ratios, the acetophenone of 2 mol ratios and 2,4- pentanediones are added Enamel reaction still, is slowly warmed up to 100 DEG C, adds hydrochloric acid as the catalyst of reaction, and hydrochloric acid is by the pH value of reactant mixed liquor Adjust to 3；Then, the rosin amine of 1 mol ratio is added in enamel reaction still together with methyl alcohol, reaction generates aldehyde after 16 hours Ketoamine condensation product.Then the aldehyde ketone amine condensation product of generation is added in destilling tower carries out vacuum distillation purification processes.
Aldehyde ketone amine condensation product after purification is added in enamel reaction still, it is normal to control the pressure in enamel reaction still Pressure, then to adding following reactant in enamel reaction still：Triethanolamine, methylpentynol, peregal O-25, alkyl Phenol polyethenoxy ether OP-10, KI, methyl alcohol, dimethylformamide and bismuth trichloride.Wherein, the quality hundred of each reactant Point ratio is：Aldehyde ketone amine condensation product：25%th, methylpentynol：5%th, triethanolamine：2%th, APES OP-10：5%th, peregal O-25：5%th, dimethylformamide：30%th, KI：5%th, bismuth trichloride：3%th, methyl alcohol： 20%.During addition reactant, first adding needs the methyl alcohol of addition half, while other reactants are added into enamel reaction still In so that aldehyde ketone amine condensation product and other reactants fully dissolve, and are stirred 30 minutes after being heated to 50 DEG C；Then, addition need to add Enter the methyl alcohol of amount residue half so that reactant reaches required concentration, stirring stops heating after 30 minutes；Finally, by room temperature Cooling, is stirred continuously product in cooling procedure, and when being cooled to normal temperature, the product for obtaining is high suitable for 120 DEG C The Mannich base corrosion inhibiter of temperature acidifying.
Tested by performance test and the Mannich base corrosion inhibiter for generating is tested, be the 2% of acid solution weight by total amount Mannich base corrosion inhibiter be added in the concentrated hydrochloric acid that 120 DEG C of mass fraction is 20%, N80 steel pipes are then placed in above-mentioned salt In acid, testing result is shown as, and the corrosion rate of steel pipe is 16.51g/m2* h, corrosion inhibition rate is 99.18%.According to standard SY/ The regulation of T5405 primes requirement, the corrosion rate in 120 DEG C of high temperature acid solutions is：20~30g/m2* h, therefore the corrosion inhibiter reaches To primes requirement.
Embodiment 2
By the amount of material than calculating, by the paraformaldehyde of 4 mol ratios, the acetophenone of 3 mol ratios and 2,4- pentanediones are added Enamel reaction still, is slowly warmed up to 110 DEG C, adds hydrochloric acid as the catalyst of reaction, and hydrochloric acid is by the pH value of reactant mixed liquor Adjust to 3；Then, the rosin amine of 1 mol ratio is added in enamel reaction still together with methyl alcohol, reaction generates aldehyde after 16 hours Ketoamine condensation product.Then the aldehyde ketone amine condensation product of generation is added in destilling tower carries out vacuum distillation purification processes.
Aldehyde ketone amine condensation product after purification is added in enamel reaction still, it is normal to control the pressure in enamel reaction still Pressure, then to adding following reactant in enamel reaction still：Triethanolamine, methylpentynol, peregal O-25, alkyl Phenol polyethenoxy ether OP-10, KI, methyl alcohol, dimethylformamide and bismuth trichloride.Wherein, the quality hundred of each reactant Point ratio is：Aldehyde ketone amine condensation product：35%th, methylpentynol：5%th, triethanolamine：2%th, APES OP-10：5%th, peregal O-25：5%th, dimethylformamide：30%th, KI：5%th, bismuth trichloride：3%th, methyl alcohol：10%. During addition reactant, first adding needs the methyl alcohol of addition half, while other reactants are added in enamel reaction still so that Aldehyde ketone amine condensation product and other reactants fully dissolve, and are stirred 30 minutes after being heated to 50 DEG C；Then, adding needs addition remaining The methyl alcohol of half so that reactant reaches required concentration, stirring stops heating after 30 minutes；Finally, cooled down by room temperature, cold But product is stirred continuously during, when being cooled to normal temperature, the product for obtaining is high temperature acidified graceful suitable for 120 DEG C The uncommon alkali corrosion inhibiter of Buddhist nun.
Tested by performance test and the Mannich base corrosion inhibiter for generating is tested, be the 2% of acid solution weight by total amount Mannich base corrosion inhibiter be added in the concentrated hydrochloric acid that 120 DEG C of mass fraction is 20%, N80 steel pipes are then placed in above-mentioned salt In acid, testing result is shown as, and the corrosion rate of steel pipe is 15.43g/m2* h, corrosion inhibition rate is 99.24%.According to standard SY/ The regulation of T5405 primes requirement, the corrosion rate in 120 DEG C of high temperature acid solutions is：20~30g/m2* h, therefore the corrosion inhibiter reaches To primes requirement.
Embodiment 3
By the amount of material than calculating, by the paraformaldehyde of 4 mol ratios, the acetophenone of 3 mol ratios and 2,4- pentanediones are added Enamel reaction still, is slowly warmed up to 110 DEG C, adds hydrochloric acid as the catalyst of reaction, and hydrochloric acid is by the pH value of reactant mixed liquor Adjust to 3；Then, the rosin amine of 1 mol ratio is added in enamel reaction still together with methyl alcohol, reaction generates aldehyde after 17 hours Ketoamine condensation product.Then the aldehyde ketone amine condensation product of generation is added in destilling tower carries out vacuum distillation purification processes.
Aldehyde ketone amine condensation product after purification is added in enamel reaction still, it is normal to control the pressure in enamel reaction still Pressure, then to adding following reactant in enamel reaction still：Triethanolamine, methylpentynol, peregal O-25, alkyl Phenol polyethenoxy ether OP-10, KI, methyl alcohol, dimethylformamide and bismuth trichloride.Wherein, the quality hundred of each reactant Point ratio is：Aldehyde ketone amine condensation product：35%th, methylpentynol：5%th, triethanolamine：2%th, APES OP-10：5%th, peregal O-25：5%th, dimethylformamide：20%th, KI：5%th, bismuth trichloride：3%th, methyl alcohol：20%. During addition reactant, first adding needs the methyl alcohol of addition half, while other reactants are added in enamel reaction still so that Aldehyde ketone amine condensation product and other reactants fully dissolve, and are stirred 30 minutes after being heated to 50 DEG C；Then, adding needs addition remaining The methyl alcohol of half so that reactant reaches required concentration, stirring stops heating after 30 minutes；Finally, cooled down by room temperature, cold But product is stirred continuously during, when being cooled to normal temperature, the product for obtaining is high temperature acidified graceful suitable for 130 DEG C The uncommon alkali corrosion inhibiter of Buddhist nun.
Tested by performance test and the Mannich base corrosion inhibiter for generating is tested, be the 2% of acid solution weight by total amount Mannich base corrosion inhibiter be added in the concentrated hydrochloric acid that 130 DEG C of mass fraction is 20%, N80 steel pipes are then placed in above-mentioned salt In acid, testing result is shown as, and the corrosion rate of steel pipe is 28.57g/m2* h, corrosion inhibition rate is 98.59%.According to standard SY/ The regulation of T5405 primes requirement, the corrosion rate in 130 DEG C of high temperature acid solutions is：20~30g/m2* h, therefore the corrosion inhibiter reaches To primes requirement.
Embodiment 4
By the amount of material than calculating, by the paraformaldehyde of 2 mol ratios, the acetophenone of 2 mol ratios and 2,4- pentanediones are added Enamel reaction still, is slowly warmed up to 100 DEG C, adds hydrochloric acid as the catalyst of reaction, and hydrochloric acid is by the pH value of reactant mixed liquor Adjust to 3；Then, the rosin amine of 1 mol ratio is added in enamel reaction still together with methyl alcohol, reaction generates aldehyde after 15 hours Ketoamine condensation product.Then the aldehyde ketone amine condensation product of generation is added in destilling tower carries out vacuum distillation purification processes.
Aldehyde ketone amine condensation product after purification is added in enamel reaction still, it is normal to control the pressure in enamel reaction still Pressure, then to adding following reactant in enamel reaction still：Triethanolamine, methylpentynol, peregal O-25, alkyl Phenol polyethenoxy ether OP-10, KI, methyl alcohol, dimethylformamide and bismuth trichloride.Wherein, the quality hundred of each reactant Point ratio is：Aldehyde ketone amine condensation product：40%th, methylpentynol：5%th, triethanolamine：2%th, APES OP-10：5%th, peregal O-25：5%th, dimethylformamide：20%th, KI：5%th, bismuth trichloride：3%th, methyl alcohol：15%. During addition reactant, first adding needs the methyl alcohol of addition half, while other reactants are added in enamel reaction still so that Aldehyde ketone amine condensation product and other reactants fully dissolve, and are stirred 30 minutes after being heated to 50 DEG C；Then, adding needs addition remaining The methyl alcohol of half so that reactant reaches required concentration, stirring stops heating after 30 minutes；Finally, cooled down by room temperature, cold But product is stirred continuously during, when being cooled to normal temperature, the product for obtaining is high temperature acidified graceful suitable for 140 DEG C The uncommon alkali corrosion inhibiter of Buddhist nun.
Tested by performance test and the Mannich base corrosion inhibiter for generating is tested, be the 2% of acid solution weight by total amount Mannich base corrosion inhibiter be added in the concentrated hydrochloric acid that 140 DEG C of mass fraction is 20%, N80 steel pipes are then placed in above-mentioned salt In acid, testing result is shown as, and the corrosion rate of steel pipe is 49.91g/m2* h, corrosion inhibition rate is 97.72%.According to standard SY/ The regulation of T5405 primes requirement, the corrosion rate in 140 DEG C of high temperature acid solutions is：40~50g/m2* h, therefore the corrosion inhibiter reaches To primes requirement.
Embodiment 5
By the amount of material than calculating, by the paraformaldehyde of 2 mol ratios, the acetophenone of 2 mol ratios and 2,4- pentanediones are added Enamel reaction still, is slowly warmed up to 100 DEG C, adds hydrochloric acid as the catalyst of reaction, and hydrochloric acid is by the pH value of reactant mixed liquor Adjust to 3；Then, the rosin amine of 1 mol ratio is added in enamel reaction still together with methyl alcohol, reaction generates aldehyde after 15 hours Ketoamine condensation product.Then the aldehyde ketone amine condensation product of generation is added in destilling tower carries out vacuum distillation purification processes.
Aldehyde ketone amine condensation product after purification is added in enamel reaction still, it is normal to control the pressure in enamel reaction still Pressure, then to adding following reactant in enamel reaction still：Triethanolamine, methylpentynol, peregal O-25, alkyl Phenol polyethenoxy ether OP-10, KI, methyl alcohol, dimethylformamide and bismuth trichloride.Wherein, the quality hundred of each reactant Point ratio is：Aldehyde ketone amine condensation product：40%th, methylpentynol：5%th, triethanolamine：2%th, APES OP-10：5%th, peregal O-25：5%th, dimethylformamide：25%th, KI：5%th, bismuth trichloride：3%th, methyl alcohol：10%. During addition reactant, first adding needs the methyl alcohol of addition half, while other reactants are added in enamel reaction still so that Aldehyde ketone amine condensation product and other reactants fully dissolve, and are stirred 30 minutes after being heated to 50 DEG C；Then, adding needs addition remaining The methyl alcohol of half so that reactant reaches required concentration, stirring stops heating after 30 minutes；Finally, cooled down by room temperature, cold But product is stirred continuously during, when being cooled to normal temperature, the product for obtaining is high temperature acidified graceful suitable for 140 DEG C The uncommon alkali corrosion inhibiter of Buddhist nun.
Tested by performance test and the Mannich base corrosion inhibiter for generating is tested, be the 2% of acid solution weight by total amount Mannich base corrosion inhibiter be added in the concentrated hydrochloric acid that 140 DEG C of mass fraction is 20%, N80 steel pipes are then placed in above-mentioned salt In acid, testing result is shown as, and the corrosion rate of steel pipe is 48.14g/m2* h, corrosion inhibition rate is 97.62%.According to standard SY/ The regulation of T5405 primes requirement, the corrosion rate in 140 DEG C of high temperature acid solutions is：40~50g/m2* h, therefore the corrosion inhibiter reaches To primes requirement.
By above example it is recognised that a kind of of present invention offer is adapted to high temperature acidified Mannich base corrosion inhibiter system Preparation Method can be prepared suitable for 120 DEG C~140 DEG C high temperature acidified Mannich base corrosion inhibiter, be particularly well-suited to 120 DEG C~140 DEG C deep-well, 15%~28% concentrated hydrochloric acid or soil acid acidizing well production increment job execution.Meanwhile, the preparation method process is simple, Without special installation, production cost is reduced.
The suitable high temperature acidified Mannich base corrosion inhibiter that the present invention is provided is the corrosion inhibiter produced as stated above, Corrosion inhibition rate >=97% of the corrosion inhibiter, in hydrochloric acid, mud acid and good dispersion in ethanol solution, there is preferable surface-active, and coking is few, Freezing point is low so that primes mark of the corrosion rate of oil pipe and underground hardware in high temperature acidified liquid less than industry Standard, is effectively protected oil pipe and underground hardware, while will not be damaged to stratum again.
Above-described specific embodiment, has been carried out further to the purpose of the present invention, technical scheme and beneficial effect Describe in detail, should be understood that and the foregoing is only specific embodiment of the invention, be not limited to this hair Bright, all any modification, equivalent substitution and improvements within the spirit and principles in the present invention, done etc. should be included in the present invention Protection domain within.

Claims (5)

1. it is a kind of to be adapted to high temperature acidified Mannich base corrosion inhibiter preparation method, it is characterised in that to comprise the following steps：
Step 1：Aldehyde ketone amine condensation product is prepared by Mannich base reaction；The constituent of reactant is as follows：With the amount ratio of material Calculate, the rosin amine of 1 mol ratio, the paraformaldehyde of 2~4 mol ratios, the acetophenone of 2~3 mol ratios and 2,4- pentanedione；It is described Mannich base course of reaction in step 1 is carried out in enamel reaction still；The Mannich base course of reaction is：First, by 2~ The paraformaldehyde of 4 mol ratios, the acetophenone of 2~3 mol ratios and 2,4- pentanedione add the enamel reaction still, are slowly warmed up to 100~110 DEG C, add hydrochloric acid as the catalyst of reaction, the addition of the hydrochloric acid be the rosin amine total amount 1%~ 2%；The hydrochloric acid adjusts to 3 the pH values of reactant mixed liquor；Then, the rosin amine of 1 mol ratio is added together with methyl alcohol To in the enamel reaction still, reaction is completed after 14~18 hours；
Step 2：Vacuum distillation purification processes are carried out to the aldehyde ketone amine condensation product；
Step 3：The aldehyde ketone amine condensation product after by purification is added in reaction vessel, is then added in reaction vessel at ambient pressure Enter following reactant：Triethanolamine, methylpentynol, peregal O-25, APES OP-10, iodine Change potassium, methyl alcohol, dimethylformamide and bismuth trichloride；
Wherein, the mass fraction of the reactant is：Aldehyde ketone amine condensation product：15%~40%, methylpentynol： 1%~10%, triethanolamine：2%~5%, peregal O-25：5%~15%, APES OP-10：5%th, iodine Change potassium：5%~8%, dimethylformamide：20%~30%, bismuth trichloride：3%~5%, remaining is methyl alcohol.
2. corrosion inhibiter preparation method according to claim 1, it is characterised in that：
Reaction vessel in the step 3 is enamel reaction still；
The enamel reaction still has the function of stirring, heat, cool down and vacuumize；
The Mannich base course of reaction adds hydrochloric acid as catalyst；
Rosin amine and methyl alcohol in the step 1 are added in enamel reaction still together.
3. corrosion inhibiter preparation method according to claim 1, it is characterised in that：
Vacuum distillation purification processes in the step 2 are carried out in a distillation column.
4. corrosion inhibiter preparation method according to claim 1, it is characterised in that：
Course of reaction is in the step 3：
First, add methyl alcohol so that aldehyde ketone amine condensation product and other reactants fully dissolve, 30 points are stirred after being heated to 50 DEG C Clock；
Then, remaining methyl alcohol is added so that reactant reaches required concentration, stirring stops heating after 30 minutes；
Finally, cooled down by room temperature, product is stirred continuously in cooling procedure, when being cooled to normal temperature, what is obtained is described anti- It is to be adapted to high temperature acidified Mannich base corrosion inhibiter to answer product.
5. a kind of application for being adapted to high temperature acidified Mannich base corrosion inhibiter, it is characterised in that：
The corrosion inhibiter is produced according to the corrosion inhibiter preparation method described in any one of Claims 1 to 4；
The corrosion inhibiter is applied to 120 DEG C~140 DEG C deep-wells, 15%~28% concentrated hydrochloric acid or soil acid acidizing well production increment operations Construction.
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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
CN106645137A (en) * 2016-12-29 2017-05-10 中国石油天然气股份有限公司 Method for testing chelating capacity of chelating acid to metal calcium ions
CN107162226A (en) * 2017-05-27 2017-09-15 徐文忠 A kind of anti-incrustation corrosion inhibitor, its preparation method and application
CN107573914A (en) * 2017-08-29 2018-01-12 中国石油集团渤海钻探工程有限公司 A kind of compound acidification corrosion inhibitor based on Mannich base and BAA
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
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
CN110982508B (en) * 2019-12-26 2022-03-08 西南石油大学 Mannich base acidizing corrosion inhibitor and preparation method 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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