CN105001850A - Preparation method of dendritic organic amine corrosion inhibitor for acidification and application thereof - Google Patents

Preparation method of dendritic organic amine corrosion inhibitor for acidification and application thereof Download PDF

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Publication number
CN105001850A
CN105001850A CN201510390068.XA CN201510390068A CN105001850A CN 105001850 A CN105001850 A CN 105001850A CN 201510390068 A CN201510390068 A CN 201510390068A CN 105001850 A CN105001850 A CN 105001850A
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China
Prior art keywords
inhibiter
organic amine
preparation
hydrochloric acid
dendritic organic
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CN201510390068.XA
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Chinese (zh)
Inventor
全红平
鲁雪梅
王金玉
胥倩
胥舒惠
蒋定邦
杨凯琪
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Southwest Petroleum University
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Southwest Petroleum University
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/62Compositions for forming crevices or fractures
    • C09K8/72Eroding chemicals, e.g. acids
    • C09K8/74Eroding chemicals, e.g. acids combined with additives added for specific purposes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/54Compositions for in situ inhibition of corrosion in boreholes or wells
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/32Anticorrosion additives

Abstract

The invention relates to a preparation method of a dendritic organic amine corrosion inhibitor for acidification in oil and gas well stimulation operations and an application of the inhibitor. The preparation method is used to solve the problem of corrosion of concentrated acid to equipment during acidification in oil and gas well stimulation. The technical scheme contains the following steps: dissolving diethylenetriamine with the molar ratio of 1 into 15 ml of ethanol, transferring a solution obtained into a 3-mouth flask, introducing nitrogen for protection, and heating to 60-90 DEG C; adding cinnaldehyde with the molar ratio of 0.9-1.2 and a portion of acetophenone to react for 30 min; dropwise adding formaldehyde with the molar ratio of 1-1.1 and the rest acetophenone to react at the temperature of 70-110 DEG C for 7-10 h; and transferring a reaction product into a vacuum rotary evaporator, and conducting reduced pressure distillation at 90 DEG C to prepare the dendritic organic amine corrosion inhibitor. The corrosion inhibitor prepared by the method is added into concentrated hydrochloric acid, and a steel disc is immersed therein for experiments. The product has achieved the standards of second-grade products in the industry. The preparation method has a simple technology and requires no special equipment. The product is used in oil and gas well acidizing operations of concentrated hydrochloric acid or mud acid.

Description

A kind of acidifying preparation method of dendritic organic amine inhibiter and application thereof
Technical field
The present invention relates to a kind of preparation method for the dendritic organic amine inhibiter of acidifying in well production increment operation and application thereof.
Background technology
In order to improve oil well crude oil recovery ratio and oil-gas field volume increase usually employing acidifying measure in the oil reservoir development process of petroleum industry field.But while acid stimulation, the acid solution of acidifying for oil pipe and down-hole metal equipment corrosion very serious, also likely cause breaking of tubing, cause very large financial loss.
Along with the exploitation of profound level infiltration oil reservoir, concentrated acid acidifying usage quantity constantly increases, and solves the corrosion of concentrated acid to pipe-line equipment in acidization and remains one of problem needing research.There are some problems in the concentrated acid acidification corrosion inhibitor of current use, the corrosion inhibition rate of inhibiter compared with low, addition large, easily precipitate coking in high-temperature high concentration acid solution, environment is had to pollution and other is poor by agent compatibleness.In order to make up the some shortcomings of existing acidification corrosion inhibitor, develop can be used for high concentrated acid, environmental pollution is little, corrosion mitigating effect is good inhibiter is of great importance to oil reservoir development.
Summary of the invention
The object of the invention is: during in order to solve acidifying in well production increment, acid solution is to the corrosion of underground equipment, poorly soluble for the acidification corrosion inhibitor used at present, environmental pollution is large, addition is large, easily precipitate in concentrated acid, the problems such as corrosion mitigating effect difference, special go out a kind of acidifying preparation method of dendritic organic amine inhibiter and application thereof.
For solving the problem, the present invention by the following technical solutions: the preparation method of dendritic organic amine inhibiter comprises the following steps in a kind of acidifying: the amount of substance mol ratio preparing this inhibiter raw materials used is: formaldehyde: methyl phenyl ketone: diethylenetriamine: phenylacrolein=1 ~ 1.1: 2 ~ 2.2: 1: 0.9 ~ 1.2; By mol ratio be first 1 diethylenetriamine be dissolved in 15ml ethanol, move in there-necked flask and pass into nitrogen protection, be warming up to 70 ~ 100 DEG C; Then adding mol ratio is the phenylacrolein of 0.9 ~ 1.2 and the methyl phenyl ketone reaction 30min of partial amount; Finally dripping mol ratio is the formaldehyde of 1 ~ 1.1 and the methyl phenyl ketone of residual content, at temperature is 70 ~ 100 DEG C, react 7 ~ 10h; Reacted product is moved in vacuum rotary evaporator, at 90 DEG C, carries out underpressure distillation obtain dendritic organic amine inhibiter.
The application of dendritic organic amine inhibiter in acid solution inhibition prepared by above-mentioned preparation method, it is the dendritic organic amine inhibiter of 0.6% of acid solution total amount by quality, joining mass percentage concentration is in the concentrated hydrochloric acid of 20%, being hung by Q235 steel disc immerses in above-mentioned hydrochloric acid soln, at temperature is 90 DEG C, soaks 4h, then takes out, cleaning, dry, weigh; Through experiment detection display, the corrosion speed of Q235 steel disc is 4.75 ~ 6.23g/ (m 2h), corrosion inhibition rate is 99.88% ~ 99.91%; According to standard SY/T5405-1996 require regulation, at 90 DEG C 20% concentrated hydrochloric acid in corrosion speed be 3 ~ 5g/ (m 2h) be first grade, 5 ~ 10g/ (m 2h) be seconds.Prove that this inhibiter has reached seconds required standard by experiment.
The present invention compared with the prior art, specifically has following beneficial effect: (1) this preparation method is simple, without the need to other specific installation, reduces production cost; (2) inhibiter that obtains of this preparation method, corrosion mitigating effect is good, and corrosion inhibition rate can reach more than 99.88%, and it is very well dispersed in hydrochloric acid and mud acid solution, have good surfactivity, completely without coking, in acidizing fluid, erosion rate reaches the secondary standard of the industry; (3) this dendritic organic amine inhibiter Applicable temperature is at 90 DEG C, concentration be 15% ~ 20% concentrated hydrochloric acid or mud acid well production increment construction operation in.
Embodiment
Embodiment 1
First will take 4.12g diethylenetriamine is dissolved in 15ml alcohol solvent, moves in there-necked flask and passes into nitrogen protection, be warming up to 80 DEG C; Then 5.29g phenylacrolein and 4.80g methyl phenyl ketone reaction 30min is dripped; Finally drip formaldehyde solution and 4.81g methyl phenyl ketone that 3.57g concentration is 37%, at temperature is 80 DEG C, reacts 8h; Reacted product is moved in vacuum rotary evaporator, at 90 DEG C, carries out underpressure distillation obtain dendritic organic amine inhibiter.
Corrosion inhibition evaluation is carried out by the aldehyde ketone amine condenses inhibiter of static weight loss method to synthesis, it is in the concentrated hydrochloric acid of 20% that this inhibiter of 4.5g is added mass percentage concentration, being hung by Q235 steel disc immerses in above-mentioned hydrochloric acid soln, 4h is soaked at temperature is 90 DEG C, then take out, cleaning, dries, weighs; Through experiment detection display, the corrosion speed of Q235 steel disc is 6.23g/ (m 2h), corrosion inhibition rate is 99.88%; According to standard SY/T 5405-1996 seconds require regulation, at 90 DEG C 20% concentrated hydrochloric acid in corrosion speed be 5 ~ 10g/ (m 2h).Prove that this inhibiter has reached seconds required standard by experiment.
Embodiment 2
First will take 4.12g diethylenetriamine is dissolved in 15ml alcohol solvent, moves in there-necked flask and passes into nitrogen protection, be warming up to 90 DEG C; Then 5.29g phenylacrolein and 5.09g methyl phenyl ketone reaction 30min is dripped; Finally drip formaldehyde solution and 5.00g methyl phenyl ketone that 3.25g concentration is 37%, at temperature is 90 DEG C, reacts 7h; Reacted product is moved in vacuum rotary evaporator, at 90 DEG C, carries out underpressure distillation obtain dendritic organic amine inhibiter.
Corrosion inhibition evaluation is carried out by the aldehyde ketone amine condenses inhibiter of static weight loss method to synthesis, it is in the concentrated hydrochloric acid of 20% that this inhibiter of 4.5g is added mass percentage concentration, being hung by Q235 steel disc immerses in above-mentioned hydrochloric acid soln, 4h is soaked at temperature is 90 DEG C, then take out, cleaning, dries, weighs; Through experiment detection display, the corrosion speed of Q235 steel disc is 4.99g/ (m 2h), corrosion inhibition rate is 99.90%; According to standard SY/T 5405-1996 first grade require regulation, at 90 DEG C 20% concentrated hydrochloric acid in corrosion speed be 3 ~ 5g/ (m 2h).Prove that this inhibiter has reached first grade required standard by experiment.
Embodiment 3
First will take 4.12g diethylenetriamine is dissolved in 15ml alcohol solvent, moves in there-necked flask and passes into nitrogen protection, be warming up to 70 DEG C; Then 4.76g phenylacrolein and 5.28g methyl phenyl ketone reaction 30min is dripped; Finally drip formaldehyde solution and 5.29g methyl phenyl ketone that 3.25g concentration is 37%, at temperature is 70 DEG C, reacts 9h; Reacted product is moved in vacuum rotary evaporator, at 90 DEG C, carries out underpressure distillation obtain dendritic organic amine inhibiter.
Corrosion inhibition evaluation is carried out by the aldehyde ketone amine condenses inhibiter of static weight loss method to synthesis, it is in the concentrated hydrochloric acid of 20% that this inhibiter of 4.5g is added mass percentage concentration, being hung by Q235 steel disc immerses in above-mentioned hydrochloric acid soln, 4h is soaked at temperature is 90 DEG C, then take out, cleaning, dries, weighs; Through experiment detection display, the corrosion speed of Q235 steel disc is 5.02g/ (m 2h), corrosion inhibition rate is 99.90%; According to standard SY/T 5405-1996 seconds require regulation, at 90 DEG C 20% concentrated hydrochloric acid in corrosion speed be 5 ~ 10g/ (m 2h).Prove that this inhibiter has reached seconds required standard by experiment.
Embodiment 4
First will take 4.12g diethylenetriamine is dissolved in 15ml alcohol solvent, moves in there-necked flask and passes into nitrogen protection, be warming up to 80 DEG C; Then 5.29g phenylacrolein and 5.87g methyl phenyl ketone reaction 30min is dripped; Finally drip formaldehyde solution and 5.89g methyl phenyl ketone that 3.25g concentration is 37%, at temperature is 80 DEG C, reacts 10h; Reacted product is moved in vacuum rotary evaporator, at 90 DEG C, carries out underpressure distillation obtain dendritic organic amine inhibiter.
Corrosion inhibition evaluation is carried out by the aldehyde ketone amine condenses inhibiter of static weight loss method to synthesis, it is in the concentrated hydrochloric acid of 20% that this inhibiter of 4.5g is added mass percentage concentration, being hung by Q235 steel disc immerses in above-mentioned hydrochloric acid soln, 4h is soaked at temperature is 90 DEG C, then take out, cleaning, dries, weighs; Through experiment detection display, the corrosion speed of Q235 steel disc is 5.62g/ (m 2h), corrosion inhibition rate is 99.89%; According to standard SY/T 5405-1996 seconds require regulation, at 90 DEG C 20% concentrated hydrochloric acid in corrosion speed be 5 ~ 10g/ (m 2h).Prove that this inhibiter has reached seconds required standard by experiment.
Embodiment 5
First will take 4.12g diethylenetriamine is dissolved in 15ml alcohol solvent, moves in there-necked flask and passes into nitrogen protection, be warming up to 100 DEG C; Then 4.76g phenylacrolein and 5.09g methyl phenyl ketone reaction 30min is dripped; Finally drip formaldehyde solution and 5.00g methyl phenyl ketone that 3.25g concentration is 37%, at temperature is 100 DEG C, reacts 7h; Reacted product is moved in vacuum rotary evaporator, at 90 DEG C, carries out underpressure distillation obtain dendritic organic amine inhibiter.
Corrosion inhibition evaluation is carried out by the aldehyde ketone amine condenses inhibiter of static weight loss method to synthesis, it is in the concentrated hydrochloric acid of 20% that this inhibiter of 4.5g is added mass percentage concentration, being hung by Q235 steel disc immerses in above-mentioned hydrochloric acid soln, 4h is soaked at temperature is 90 DEG C, then take out, cleaning, dries, weighs; Through experiment detection display, the corrosion speed of Q235 steel disc is 4.75g/ (m 2h), corrosion inhibition rate is 99.91%; According to standard SY/T 5405-1996 first grade require regulation, at 90 DEG C 20% concentrated hydrochloric acid in corrosion speed be 3 ~ 5g/ (m 2h).Prove that this inhibiter has reached first grade required standard by experiment.
Can be drawn by above embodiment, preparation method's technique of this aldehyde ketone amine condenses inhibiter is simple, without the need to specific installation; At being applicable to 90 DEG C in 15% ~ 20% concentrated hydrochloric acid or the job execution of soil acid acidizing well production increment, corrosion inhibition rate >99.88%.

Claims (2)

1. an acidifying preparation method for dendritic organic amine inhibiter, is characterized in that: the amount of substance mol ratio preparing this inhibiter raw materials used is: formaldehyde: methyl phenyl ketone: diethylenetriamine: phenylacrolein=1 ~ 1.1: 2 ~ 2.2: 1: 0.9 ~ 1.2; By mol ratio be first 1 diethylenetriamine be dissolved in 15ml ethanol, move in there-necked flask and pass into nitrogen protection, be warming up to 70 ~ 100 DEG C; Then adding mol ratio is successively the phenylacrolein of 0.9 ~ 1.2 and the methyl phenyl ketone reaction 30min of partial amount; Dripping mol ratio is again the formaldehyde of 1 ~ 1.1 and the methyl phenyl ketone of residual content, at temperature is 70 ~ 100 DEG C, react 7 ~ 10h; Finally product is moved in vacuum rotary evaporator, at 90 DEG C, carry out underpressure distillation obtain dendritic organic amine inhibiter.
2. inhibiter preparation method according to claim 1, it is characterized in that: the application of dendritic organic amine in acid solution inhibition that this preparation method obtains, it is the above-mentioned obtained dendritic organic amine inhibiter of 0.6% of acid solution total amount by quality, joining mass percentage concentration is in the hydrochloric acid of 20%, is hung by Q235 steel disc and immerses in above-mentioned hydrochloric acid soln, at temperature is 90 DEG C, soaks 4h, then take out, cleaning, dries, weighs; Through experiment detection display, the corrosion speed of Q235 steel disc is 4.75 ~ 6.23g/ (m 2h), corrosion inhibition rate is 99.88% ~ 99.91%; According to standard SY/T 5405-1996 require regulation, at 90 DEG C 20% concentrated hydrochloric acid in corrosion speed be 3 ~ 5g/ (m 2h) be first grade, 5 ~ 10g/ (m 2h) be seconds.Prove that this inhibiter has reached seconds required standard by experiment.
CN201510390068.XA 2015-07-03 2015-07-03 Preparation method of dendritic organic amine corrosion inhibitor for acidification and application thereof Pending CN105001850A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110577829A (en) * 2018-06-08 2019-12-17 中国石油天然气股份有限公司 Cinnamaldehyde Schiff base acidizing corrosion inhibitor, preparation and use method

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CA2841020A1 (en) * 2011-08-19 2013-02-28 Petrochina Company Limited A multi-branched mannich base corrosion inhibitor and preparation method thereof
CN102953064A (en) * 2011-08-19 2013-03-06 中国石油天然气股份有限公司 Mannich base corrosion-retarding neutralizer and preparation method thereof
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110577829A (en) * 2018-06-08 2019-12-17 中国石油天然气股份有限公司 Cinnamaldehyde Schiff base acidizing corrosion inhibitor, preparation and use method

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Application publication date: 20151028