CN108383740A - A kind of Mannich base quarternary ammonium salt compound and the preparation method and application thereof - Google Patents

A kind of Mannich base quarternary ammonium salt compound and the preparation method and application thereof Download PDF

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Publication number
CN108383740A
CN108383740A CN201810122112.2A CN201810122112A CN108383740A CN 108383740 A CN108383740 A CN 108383740A CN 201810122112 A CN201810122112 A CN 201810122112A CN 108383740 A CN108383740 A CN 108383740A
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mannich base
ammonium salt
quarternary ammonium
salt compound
corrosion
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CN201810122112.2A
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Inventor
李克华
唐甜甜
王任芳
邹华
苏铁军
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Yangtze University
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Yangtze University
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/02Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C225/04Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated
    • C07C225/08Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and containing rings
    • C07C225/12Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and containing rings with doubly-bound oxygen atoms bound to carbon atoms being part of rings
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • 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
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14Nitrogen-containing compounds
    • C23F11/141Amines; Quaternary ammonium compounds
    • C23F11/143Salts of amines
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00Systems containing only non-condensed rings
    • C07C2601/12Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14The ring being saturated
    • 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

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Preventing Corrosion Or Incrustation Of Metals (AREA)
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Abstract

The present invention provides a kind of Mannich base quarternary ammonium salt compounds;The present invention also provides the preparation methods of Mannich base quarternary ammonium salt compound;The present invention also provides application of the Mannich base quarternary ammonium salt compound in oil exploitation in the corrosion and sterilization of steel pipeline.Mannich base quarternary ammonium salt compound of the present invention can reduce a variety of corrosion inhibiter, bactericide compounded inconvenience as disinfecting corrosion inhibitor, corrosion inhibition is excellent and has certain sterilizing ability, and its simple synthetic method, reaction condition is mild, it is at low cost, raw material sources are wide, while can reduce cost to a certain extent.

Description

A kind of Mannich base quarternary ammonium salt compound and the preparation method and application thereof
Technical field
The present invention relates to metal corrosion and protection field more particularly to a kind of Mannich base quarternary ammonium salt compound and its preparations Method and application.
Background technology
The problem of with the continuous exploitation in oil field, water content constantly rises, bacteria breed and corrosion becomes increasingly conspicuous, every year all It can cause huge economic loss.The crude oil produced in oil field operation environment still can be containing there are salt (chlorine through dehydration Change sodium, magnesium chloride, calcium chloride and sulfate) oil field water, the presence of these chlorides makes there are a large amount of Cl- in medium, right Oil equipment constitutes great threat;There is also various micropopulations in oil field development system, they are to oil Loss is very huge caused by field equipment and pipeline corrosion, and one of the most common bacterium is sulfate reducing bacteria (SRB), it Corrosion of metal process can be participated under given conditions, be to the maximum microorganism of oil field Influence of production.
Therefore, addition fungicide and corrosion inhibiter not only can achieve the purpose that effectively but also economically anti-corrosion and bacterial control, because This, filling fungicide and corrosion inhibiter is at must row process together with domestic many oil gas fields.Under normal conditions, oilfield technology personnel Processing method for oil pipeline antisepsis and sterilization is injected into water flooding after compounding corrosion inhibiter and fungicide.
However the deficiency of the above method is that corrosion inhibiter, the type of fungicide are various, screening process is complicated, and compound proportion is difficult To be optimal effect.
Invention content
It is an object of the invention to overcome the deficiencies of existing technologies, provide a kind of Mannich base quarternary ammonium salt compound and its Preparation method and application, it is multiple which as disinfecting corrosion inhibitor can reduce a variety of corrosion inhibiter, fungicide The inconvenience matched, corrosion inhibition is excellent and has certain sterilizing ability, and its simple synthetic method, and reaction condition is mild, cost Low, raw material sources are wide, while can reduce cost to a certain extent.
The invention is realized in this way:
The present invention provides a kind of Mannich base quarternary ammonium salt compound, chemical structural formula is as follows:
The present invention also provides a kind of disinfecting corrosion inhibitors, including the Mannich base quarternary ammonium salt compound.
The present invention also provides the preparation methods of the Mannich base quarternary ammonium salt compound, include the following steps:
Step 1, by cyclohexanone and hydrazine hydrate with molar ratio for 0.9:1.0 are added in ethyl alcohol, based on mass fraction, control Solvent total amount is the 35% of material quantity and hereinafter, glutaraldehyde is added, and the molar ratio of the glutaraldehyde and the cyclohexanone is 1: 1, hydrochloric acid regulation system pH value in 4~5 ranges, control the reaction time within the scope of 2~2.5h, controlling reaction temperature be 35 ± 1℃;
Benzyl chloride is added in step 2, after completion of the reaction, and the molar ratio of the benzyl chloride and the cyclohexanone is 8:9, it will Temperature rises to 40 ± 1 DEG C, and for salt acid for adjusting pH value in 2~3 ranges, the control reaction time is 1h, finally that gained compound is cold But to room temperature, Mannich base quarternary ammonium salt compound as described in claim 1.
The present invention also provides a kind of application of disinfecting corrosion inhibitor in oil exploitation in the corrosion and sterilization of steel pipeline.
The invention has the advantages that:
1, the main component category quaternary ammonium salt of disinfecting corrosion inhibitor provided by the invention is a kind of typical absorbent-type inhibition Agent can form adsorbed film in A3 steel surfaces and slow down corrosion rate of the brine media to it, same preventing Cl- from corroding steel When, corrosion of the sulfate reducing bacteria (SRB) to steel can be also prevented to a certain extent, further slow down the corrosion feelings of steel Condition, the anti-corrosion of steel pipeline and sterilization suitable for oil exploitation reduce a variety of corrosion inhibiter, bactericide compounded inconvenience, together When reduce cost to a certain extent, had practical application value in oil field operation environment.
2, the reaction principle of disinfecting corrosion inhibitor of the invention is reliable, reaction raw materials are economical and easily available, simple production process, reaction Mild condition, property stabilization, good water solubility, convenient for promoting.
Description of the drawings
Fig. 1 be the disinfecting corrosion inhibitor that provides of experimental example 3 of the present invention in 3% (mass percent) saline solution to A3 steel Polarization curve;
Fig. 2 be the disinfecting corrosion inhibitor that provides of experimental example 4 of the present invention in 3% (mass percent) saline solution to A3 steel AC impedance figure;
Fig. 3 is the sterilizing ability test chart for the disinfecting corrosion inhibitor that experimental example 5 of the present invention provides.
Specific implementation mode
The preparation embodiment of 1 disinfecting corrosion inhibitor of embodiment
Step 1, the cyclohexanone (C by 88.2g6H10O, relative molecular mass 98) and the mass fraction of 96.90ml be (relative density is 20 DEG C of 1.032g/mL at, N to 50% hydrazine hydrate2H4·H2O, relative molecular mass 50) it is added to 7ml 95% ethyl alcohol (density 0.78g/mL) in (molar ratio of cyclohexanone and hydrazine hydrate be 0.9:1.0),
Solvent total amount is controlled as the 35% of raw material total amount (total amount of cyclohexanone and hydrazine hydrate solute) (with mass fraction Meter) hereinafter, the glutaraldehyde of 0.9mol is added while stirring, hydrochloric acid regulation system pH value controls the reaction time in 4~5 ranges Within the scope of 2~2.5h, controlling reaction temperature is 35 ± 1 DEG C;
Step 2, after completion of the reaction, is added the benzyl chloride of 0.8mol, temperature is risen to 40 ± 1 DEG C, salt acid for adjusting pH value is 2 In~3 ranges, the control reaction time is 1h, is finally cooled to room temperature gained compound;
Mannich base quarternary ammonium salt compound is dissolved in organic solvent, and is mixed with distilled water by step 3 in proportion, stirs It mixes uniformly.
Here why Mannich base quarternary ammonium salt compound is dissolved in organic solvent, what wherein organic solvent played is The effect of solubilising, solubilising refer to insoluble drug under the action of surfactant, increase solubility in a solvent and are formed molten The process of liquid.The dosage of solubilizer:One timing of temperature, the solubilizer of sufficient amount is added into drug can be made clear solution, i.e., Make to remain to after dilution keep clarification, if but proportioning it is improper, clear solution cannot be obtained or solution can be become by clarification in dilution It obtains muddy.
Preferably, in the step 3, the mass percent of each component is:Inhibition host agent:30~35%;It is organic molten Agent:15~20%;Distilled water:Surplus.
2 disinfecting corrosion inhibitor corrosion inhibition of embodiment is tested
Since oil field pipe is mainly N80 steel, therefore the present invention is examined to carry come simulated experiment using different N80 steel The corrosion inhibition of the disinfecting corrosion inhibitor of confession.Test condition is as follows:Under normal pressure, 35 DEG C of constant temperatures, made using 3%NaCl solution For corrosive medium, N80 steel discs are suspended in 3%NaCl solution using static steel weight-loss method, 65 DEG C of water bath with thermostatic control, place 6h Afterwards, when measuring the disinfecting corrosion inhibitor of addition embodiment 1 and disinfecting corrosion inhibitor not being added, the mass change of steel disc simultaneously calculates inhibition Rate, wherein slowly increasing the concentration of disinfecting corrosion inhibitor, experimental result is as follows:
Table 1 is the disinfecting corrosion inhibitor static evaluation test result in the embodiment 1 under various concentration.
As shown in Table 1, when disinfecting corrosion inhibitor it is a concentration of 0 when, i.e., when corrosion inhibiter not being added, corrosion rate 0.0793mm/ A, carbon steel surface corrosion are extremely serious;And after corrosion inhibiter is added, carbon steel surface corrosion rate is obviously slack-off, and with sterilization inhibition The increase of the concentration of agent, corrosion rate is slower and slower, illustrates that the disinfecting corrosion inhibitor in the application has excellent corrosion mitigating effect.
2 disinfecting corrosion inhibitor electrochemical tests of embodiment are tested
Electro-chemical test uses occasion China CHI660E electrochemical workstations, and N80 steel discs (working electrode) are embedded in epoxy resin In the polytetrafluoroethylene (PTFE) set of polyamide sealing, test area 0.3cm2, auxiliary electrode is using platinum electrode, reference electrode Using saturated calomel electrode (SEC, saturation KCl solution), experiment test temperature is room temperature.Method of polarization curve dynamic potential scanning is by sun Pole is carried out to cathode, sweep speed 0.5mv/s, and scanning range is opposite open circuit potential -200mv to -700mv.
The results are shown in Figure 1:The disinfecting corrosion inhibitor post-etching current density of the application has been added to have significantly compared with blank solution It reduces, the positive and negative pole Tafel slope of polarization curve is all increased compared with blank, and corrosion potential is moved to negative sense, shows this Corrosion inhibiter is the corrosion inhibiter based on inhibition cathodic process.
3 disinfecting corrosion inhibitor electrochemical AC impedance of embodiment is tested
Electro-chemical test uses occasion China CHI660E electrochemical workstations, and N80 steel discs (working electrode) are embedded in epoxy resin In the polytetrafluoroethylene (PTFE) set of polyamide sealing, test area 0.3cm2, auxiliary electrode is using platinum electrode, reference electrode Using saturated calomel electrode (SEC, saturation KCl solution), experiment test temperature is room temperature.AC impedence method is adopted from high frequency to low frequency With log scan, range of scanned frequencies 0.1Hz~1000kHz, data analysis uses ZView softwares.
The results are shown in Figure 2, and in 3% saline solution, with the increase of disinfecting corrosion inhibitor concentration, the semicircle of capacitive reactance arc is straight Diameter gradually increases, this shows that disinfecting corrosion inhibitor forms protective film in A3 strips, effectively inhibits test piece in brine Corrosion.
The bactericidal property of 4 disinfecting corrosion inhibitor of embodiment is tested
The disinfecting corrosion inhibitor of the application tests the bactericidal property of sulfate reducing bacteria, test method reference standard SY/ T5329-1994 is evaluated and tested using dilution-to-extinction method, and is imitated with fungicide SJ-66 with market fungicide 1227 and oil field Fruit compares.Experimental result is as shown in figure 3, and be summarized as follows table 2.
Table 2 is that the bactericidal property of the fungicide of various concentration evaluates and tests test result
Various concentration mg/L 1227 sterilizing rates (%) SJ-66 sterilizing rates (%) Corrosion inhibiter sterilizing rate %
10 99.91 97.83 58.33
30 99.9 95.83 90
50 100 99.78 90
70 100 99.85 95.83
100 100 100 95.83
By upper table 2 it is found that the sterilizing rate of the disinfecting corrosion inhibitor of the application almost reaches market fungicide 1227 and oil The germicidal efficiency of field fungicide SJ-66;In summary, disinfecting corrosion inhibitor of the present invention itself has the same of excellent corrosion mitigating effect When, there is a degree of killing effect to SRB bacteriums, further slows down the corrosion condition of steel.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.

Claims (6)

1. a kind of Mannich base quarternary ammonium salt compound, chemical structural formula are as follows:
2. a kind of disinfecting corrosion inhibitor, which is characterized in that including Mannich base quarternary ammonium salt compound described in claim 1.
3. disinfecting corrosion inhibitor as claimed in claim 2, which is characterized in that Mannich base quaternization described in claim 1 It is molten in organic solvent to close object.
4. a kind of preparation method of Mannich base quarternary ammonium salt compound described in claim 1, which is characterized in that including walking as follows Suddenly:
Step 1, by cyclohexanone and hydrazine hydrate with molar ratio for 0.9:1.0 are added in ethyl alcohol, based on mass fraction, control solvent Total amount is the 35% of material quantity and hereinafter, glutaraldehyde is added, and the molar ratio of the glutaraldehyde and the cyclohexanone is 1:1, salt Sour regulation system pH value is in 4~5 ranges, and the control reaction time, controlling reaction temperature was 35 ± 1 DEG C within the scope of 2~2.5h;
Benzyl chloride is added in step 2, after completion of the reaction, and the molar ratio of the benzyl chloride and the cyclohexanone is 8:9, by temperature 40 ± 1 DEG C are risen to, for salt acid for adjusting pH value in 2~3 ranges, the control reaction time is 1h, is finally cooled to gained compound Room temperature, Mannich base quarternary ammonium salt compound as described in claim 1.
5. the preparation method of Mannich base quarternary ammonium salt compound as described in claim 1, which is characterized in that in the step 1 It is to be added while stirring when glutaraldehyde is added.
6. a kind of corrosion and sterilization of Mannich base quarternary ammonium salt compound described in claim 1 steel pipeline in oil exploitation In application.
CN201810122112.2A 2018-02-07 2018-02-07 A kind of Mannich base quarternary ammonium salt compound and the preparation method and application thereof Pending CN108383740A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109233776A (en) * 2018-08-29 2019-01-18 江苏师范大学 A kind of preparation method of novel Mannich base quaternary ammonium salt corrosion inhibitor

Citations (3)

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Publication number Priority date Publication date Assignee Title
CN104560005A (en) * 2015-01-21 2015-04-29 长江大学 Mannich base type acidizing corrosion inhibitor and preparation method thereof
CN104831286A (en) * 2015-04-13 2015-08-12 长江大学 Schiff base type acidification corrosion inhibitor, preparation method and applications thereof
CN105838345A (en) * 2016-04-25 2016-08-10 长江大学 Corrosion inhibitor for oilfield flooding and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104560005A (en) * 2015-01-21 2015-04-29 长江大学 Mannich base type acidizing corrosion inhibitor and preparation method thereof
CN104831286A (en) * 2015-04-13 2015-08-12 长江大学 Schiff base type acidification corrosion inhibitor, preparation method and applications thereof
CN105838345A (en) * 2016-04-25 2016-08-10 长江大学 Corrosion inhibitor for oilfield flooding and preparation method thereof

Non-Patent Citations (2)

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VIJAY K. DAS ET AL.: "Protection and deprotection chemistry catalyzed by zirconium oxychloride octahydrate (ZrOCl2·8H2O)", 《GREEN CHEMISTRY LETTERS AND REVIEWS》 *
唐甜甜 等: "两种曼尼希碱缓蚀剂的缓蚀性能", 《腐蚀与防护》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109233776A (en) * 2018-08-29 2019-01-18 江苏师范大学 A kind of preparation method of novel Mannich base quaternary ammonium salt corrosion inhibitor

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Application publication date: 20180810