CN117143332A - Preparation method of corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria - Google Patents
Preparation method of corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria Download PDFInfo
- Publication number
- CN117143332A CN117143332A CN202311403015.8A CN202311403015A CN117143332A CN 117143332 A CN117143332 A CN 117143332A CN 202311403015 A CN202311403015 A CN 202311403015A CN 117143332 A CN117143332 A CN 117143332A
- Authority
- CN
- China
- Prior art keywords
- corrosion inhibitor
- reducing bacteria
- quaternary ammonium
- ammonium salt
- corrosion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000007797 corrosion Effects 0.000 title claims abstract description 82
- 238000005260 corrosion Methods 0.000 title claims abstract description 82
- 239000003112 inhibitor Substances 0.000 title claims abstract description 50
- 241000894006 Bacteria Species 0.000 title claims abstract description 35
- 239000010865 sewage Substances 0.000 title claims abstract description 33
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 18
- 230000002829 reductive effect Effects 0.000 claims description 18
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 239000003208 petroleum Substances 0.000 claims description 13
- FFMBYMANYCDCMK-UHFFFAOYSA-N 2,5-dihydro-1h-imidazole Chemical compound C1NCN=C1 FFMBYMANYCDCMK-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 claims description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- GMIOYJQLNFNGPR-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CN=C(C(O)=O)C=N1 GMIOYJQLNFNGPR-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- -1 5-imidazoline compound Chemical class 0.000 claims description 8
- 150000001348 alkyl chlorides Chemical class 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 abstract description 11
- 230000005764 inhibitory process Effects 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 11
- 239000010959 steel Substances 0.000 abstract description 11
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 8
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 6
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 abstract description 4
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 150000003384 small molecules Chemical class 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 description 40
- 239000000203 mixture Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- 230000001580 bacterial effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000001963 growth medium Substances 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 230000002421 anti-septic effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000009630 liquid culture Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 description 1
- VUQPJRPDRDVQMN-UHFFFAOYSA-N 1-chlorooctadecane Chemical compound CCCCCCCCCCCCCCCCCCCl VUQPJRPDRDVQMN-UHFFFAOYSA-N 0.000 description 1
- RNHWYOLIEJIAMV-UHFFFAOYSA-N 1-chlorotetradecane Chemical compound CCCCCCCCCCCCCCCl RNHWYOLIEJIAMV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002332 oil field water Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/16—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of hydrocarbon radicals substituted by amino or carboxyl groups, e.g. ethylenediamine-tetra-acetic acid, iminodiacetic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- 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
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to the technical field of oilfield chemistry, and discloses a preparation method of a corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria. The corrosion inhibitor contains a large amount of quaternary ammonium salt active functional groups, has excellent antibacterial effect, and can effectively kill sulfate reducing bacteria and polymers of the corrosion inhibitorThe main chain contains quaternary ammonium salt N + The structure of amide bond, imidazoline and pyrazine can form coordination with the original empty metal track on the surface of steel, so that the polymer corrosion inhibitor forms a firm adsorption film on the surface of steel, prevents a corrosion medium from contacting with the steel, reduces the corrosion rate and has excellent corrosion resistance. Meanwhile, compared with small molecules, the polymer corrosion inhibitor provided by the invention has better heat resistance, and still keeps good structural stability and excellent corrosion inhibition rate at high temperature.
Description
Technical Field
The invention relates to the technical field of oilfield chemistry, in particular to a preparation method of a corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria.
Background
In recent years, the water injection amount and the exploitation amount of the oil field in China are increased year by year, and the sewage discharge or sewage reinjection amount is also increased, but the composition of the oil field sewage is complex, the mineralization degree is higher, and the oil field sewage can cause serious corrosion phenomena on oil extraction equipment and pipelines, so that the normal production and the safety of the oil field are affected. Thus solving the problem of corrosion of the oilfield sewage. Development of novel and efficient corrosion inhibitors is an effective method for solving the problem of oilfield wastewater corrosion.
In addition, microorganisms such as sulfate reducing bacteria SRB in the oilfield sewage easily cause microbial corrosion to influence the normal production of the oilfield, and the sulfate reducing bacteria directly corrode equipment to deteriorate the quality of water injection; and corrosion of product metal sulfides can cause blackening of sewage, increase the content of solid suspended matters and influence the quality of oilfield reinjection water. The patent with publication number of CN114085188B discloses that an imidazoline intermediate is formed by acylation and cyclization of organic acid and organic amine, and the corrosion inhibitor is obtained by acrylonitrile reaction, so that the corrosion inhibitor can be applied to the fields of oil extraction, gathering and transportation in oil fields, industrial storage and the like, and can effectively slow down the corrosion of sewage to pipelines, pipe walls, equipment and the like; however, the corrosion inhibitor has no inhibiting and killing effects on sulfate reducing bacteria.
Disclosure of Invention
The invention solves the technical problems that: the corrosion inhibitor can kill sulfate-containing reducing bacteria in oilfield sewage, and has excellent corrosion resistance and inhibition performance.
The technical scheme provided by the invention is as follows:
a preparation method of a corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria comprises the following steps:
s1, adding diethylenetriamine, pyrazine-2, 5-dicarboxylic acid and xylene water-carrying agent into a reaction bottle carrying a water separator, heating to 155-165 ℃, stirring and refluxing to be anhydrous and dripping, heating to 210-225 ℃, stirring and refluxing to be anhydrous and dripping, cooling, filtering, concentrating filtrate under reduced pressure, and recrystallizing and purifying a product by using ethyl acetate to obtain the pyrazine-2, 5-imidazoline intermediate.
S2, placing the reaction bottle in ice bath, adding dimethyl sulfoxide, pyrazine-2, 5-imidazoline compound, N-methyl quaternary ammonium salt diacyl chloride intermediate and N, N-diisopropylethylamine, stirring for 5-10min, removing the ice bath, stirring for reaction, pouring the solution into methanol to precipitate, filtering, washing the filter cake with ethanol, and drying to obtain the corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria.
Further, the proportion of diethylenetriamine, pyrazine-2, 5-dicarboxylic acid and xylene water-carrying agent in S1 is (2.3-2.8) mol to 1mol (80-120) mL.
Further, the reaction in S2 is carried out at a temperature of 20-40℃for 12-36 h.
Further, the ratio of dimethyl sulfoxide, pyrazine-2, 5-imidazoline compound, N-methyl quaternary ammonium salt diacyl chloride intermediate and N, N-diisopropylethylamine in S2 is (3-5) L1 mol (0.8-1.3) mol (2-2.5).
Further, the preparation method of the N-methyl quaternary ammonium salt diacyl chloride intermediate comprises the following steps:
s3, adding acetonitrile, N-methyl iminodiacetic acid and an alkyl chloride compound into a reaction bottle carrying a condensing tube, reacting, cooling, concentrating under reduced pressure, washing a product by petroleum ether, and recrystallizing and purifying in ethanol to obtain an N-methyl quaternary ammonium salt diacetic acid intermediate;
s4, adding thionyl chloride and an N-methyl quaternary ammonium salt diacetic acid intermediate into a reaction bottle carrying a condensing tube, reacting at 65-75 ℃ for 3-6 h, cooling, concentrating under reduced pressure, washing the product with petroleum ether, and drying to obtain the N-methyl quaternary ammonium salt diacyl chloride intermediate.
Further, the ratio of N-methyliminodiacetic acid to the alkyl chloride compound is 1mol (1 to 1.4 mol).
Further, the reaction in S3 is carried out at a temperature of 80-90℃and 36-48 and h.
Further, the alkyl chloride compound has a formula of C n H 2n+1 Cl and n is any integer from 12 to 18.
Further, the ratio of thionyl chloride to N-methyl quaternary ammonium salt diacetic acid intermediate is (1.2-1.8) L to 1mol.
The invention has the technical effects that: the invention carries out quaternization and acyl chlorination reaction on N-methyl iminodiacetic acid, alkyl chloride compound and thionyl chloride to obtain a novel N-methyl quaternary ammonium salt diacyl chloride intermediate; the diethylenetriamine and pyrazine-2, 5-dicarboxylic acid undergo dehydration and cyclization reactions to obtain a novel pyrazine-2, 5-imidazoline intermediate; finally, in a system of N, N-diisopropylethylamine, the two are polymerized to obtain the novel corrosion inhibitor which is used for sulfate-containing reducing bacteria oilfield sewage treatment.
The polymer main chain of the corrosion inhibitor prepared by the invention contains hydrophilic amide bond and quaternary ammonium salt structure, and the water solubility and dispersion stability of the corrosion inhibitor are obviously improved.
The corrosion inhibitor prepared by the invention contains a large number of quaternary ammonium salt active functional groups, has excellent antibacterial effect, can effectively kill sulfate reducing bacteria, and has a Minimum Inhibitory Concentration (MIC) of only 15.63-7.81 ug/mL for the sulfate reducing bacteria. The biological corrosion of sulfate reducing bacteria to equipment can be effectively prevented, and the deterioration of water quality of water injection is avoided; meanwhile, the formation of metal sulfides which are corrosion products of sulfate reducing bacteria is reduced, the content of solid suspended matters in sewage is reduced, and the quality of oilfield reinjection water is improved.
The polymer main chain of the corrosion inhibitor contains quaternary ammonium salt N + The structure of amide bond, imidazoline and pyrazine can form coordination with the original empty metal track on the surface of steel, so that the polymer corrosion inhibitor forms a firm adsorption film on the surface of steel, prevents a corrosion medium from contacting with the steel, reduces the corrosion rate and has excellent corrosion resistance. Meanwhile, compared with small molecules, the polymer corrosion inhibitor of the invention has heat resistanceBetter performance, good structural stability and excellent corrosion inhibition rate at high temperature.
Drawings
FIG. 1 is a reaction scheme for the preparation of pyrazine-2, 5-imidazoline intermediates;
FIG. 2 is a reaction scheme for the preparation of an N-methyl quaternary ammonium salt diacid chloride intermediate;
FIG. 3 is a reaction scheme for preparing corrosion inhibitors for sulfate-reducing bacteria-containing oilfield sewage.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
(1) Acetonitrile, 0.1mol of N-methyl iminodiacetic acid and 0.1mol of 1-chlorododecane are added into a reaction bottle carrying a condensation tube, the mixture is reacted at a temperature of 90 ℃ for 36 h, cooled and concentrated under reduced pressure, and the product is recrystallized and purified in ethanol after being washed by petroleum ether, thus obtaining the N-methyl quaternary ammonium salt diacetic acid intermediate.
(2) 150mL of thionyl chloride and 0.1mol of N-methyl quaternary ammonium salt diacetic acid intermediate are added into a reaction bottle carrying a condensation tube, the mixture is reacted at the temperature of 70 ℃ for 6 h, the mixture is cooled, decompressed and concentrated, and the product is washed by petroleum ether and dried to obtain the N-methyl quaternary ammonium salt diacyl chloride intermediate.
(3) Adding 0.28mol of diethylenetriamine, 0.1mol of pyrazine-2, 5-dicarboxylic acid and 12 mL xylene water-carrying agent into a reaction bottle carrying a water separator, heating to 165 ℃, stirring and refluxing until no water drops, heating to 210 ℃, stirring and refluxing until no water drops, cooling, filtering, concentrating the filtrate under reduced pressure, and recrystallizing and purifying the product by using ethyl acetate to obtain the pyrazine-2, 5-imidazoline intermediate.
(4) Placing the reaction bottle in ice bath, adding 300 mL dimethyl sulfoxide, 0.1mol pyrazine-2, 5-imidazoline compound, 0.08mol N-methyl quaternary ammonium salt diacyl chloride intermediate and 0.2mol N, N-diisopropylethylamine, stirring for 10min, removing ice bath, stirring at 20 ℃ to react for 24 h, pouring the solution into methanol to precipitate, filtering, washing the filter cake with ethanol, and drying to obtain the corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria.
Example 2
(1) Acetonitrile, 0.1mol of N-methyl iminodiacetic acid and 0.12mol of 1-chlorotetradecane are added into a reaction bottle carrying a condensation tube, the mixture is reacted at the temperature of 85 ℃ for 36 h, cooled and concentrated under reduced pressure, and the product is recrystallized and purified in ethanol after being washed by petroleum ether, thus obtaining the N-methyl quaternary ammonium salt diacetic acid intermediate.
(2) 180mL of thionyl chloride and 0.1mol of N-methyl quaternary ammonium salt diacetic acid intermediate are added into a reaction bottle carrying a condensation tube, the mixture is reacted at the temperature of 75 ℃ for 3 h, the mixture is cooled, decompressed and concentrated, and the product is washed by petroleum ether and dried to obtain the N-methyl quaternary ammonium salt diacyl chloride intermediate.
(3) Adding 0.28mol of diethylenetriamine, 0.1mol of pyrazine-2, 5-dicarboxylic acid and 12 mL xylene water-carrying agent into a reaction bottle carrying a water separator, heating to 160 ℃, stirring and refluxing until no water drops, heating to 225 ℃, stirring and refluxing until no water drops, cooling, filtering, concentrating the filtrate under reduced pressure, and recrystallizing and purifying the product by using ethyl acetate to obtain the pyrazine-2, 5-imidazoline intermediate.
(4) Placing the reaction bottle in ice bath, adding 350 mL dimethyl sulfoxide, 0.1mol pyrazine-2, 5-imidazoline compound, 0.01mol N-methyl quaternary ammonium salt diacyl chloride intermediate and 0.22mol N, N-diisopropylethylamine, stirring for 5min, removing ice bath, stirring at 20 ℃ to react for 36 h, pouring the solution into methanol to precipitate, filtering, washing the filter cake with ethanol, and drying to obtain the corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria.
Example 3
(1) Acetonitrile, 0.1mol of N-methyl iminodiacetic acid and 0.13mol of 1-chlorohexadecane are added into a reaction bottle carrying a condensation tube, 48 h is reacted at the temperature of 80 ℃, the mixture is cooled and concentrated under reduced pressure, and the product is recrystallized and purified in ethanol after being washed by petroleum ether, thus obtaining the N-methyl quaternary ammonium salt diacetic acid intermediate.
(2) 120mL of thionyl chloride and 0.1mol of N-methyl quaternary ammonium salt diacetic acid intermediate are added into a reaction bottle carrying a condensation tube, the mixture is reacted at the temperature of 70 ℃ for 4 h, the mixture is cooled, decompressed and concentrated, and the product is washed by petroleum ether and dried to obtain the N-methyl quaternary ammonium salt diacyl chloride intermediate.
(3) Adding 0.25mol of diethylenetriamine, 0.1mol of pyrazine-2, 5-dicarboxylic acid and 12 mL xylene water-carrying agent into a reaction bottle carrying a water separator, heating to 155 ℃, stirring and refluxing until no water drops, heating to 220 ℃, stirring and refluxing until no water drops, cooling, filtering, concentrating the filtrate under reduced pressure, and recrystallizing and purifying the product by using ethyl acetate to obtain the pyrazine-2, 5-imidazoline intermediate.
(4) Placing the reaction bottle in ice bath, adding 420 mL dimethyl sulfoxide, 0.1mol pyrazine-2, 5-imidazoline compound, 0.011mol N-methyl quaternary ammonium salt diacyl chloride intermediate and 0.25mol N, N-diisopropylethylamine, stirring for 8min, removing ice bath, stirring at 30 ℃ to react for 24 h, pouring the solution into methanol to precipitate, filtering, washing the filter cake with ethanol, and drying to obtain the corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria.
Example 4
(1) Acetonitrile, 0.1mol of N-methyl iminodiacetic acid and 0.014mol of 1-chlorooctadecane are added into a reaction bottle carrying a condensation tube, the mixture is reacted at the temperature of 90 ℃ for 36 h, cooled, decompressed and concentrated, and the product is subjected to petroleum ether washing and then recrystallized and purified in ethanol to obtain the N-methyl quaternary ammonium salt diacetic acid intermediate.
(2) 150mL of thionyl chloride and 0.1mol of N-methyl quaternary ammonium salt diacetic acid intermediate are added into a reaction bottle carrying a condensation tube, the mixture is reacted at the temperature of 65 ℃ for 6 h, the mixture is cooled, concentrated under reduced pressure, and the product is washed by petroleum ether and dried to obtain the N-methyl quaternary ammonium salt diacyl chloride intermediate.
(3) Adding 0.23mol of diethylenetriamine, 0.1mol of pyrazine-2, 5-dicarboxylic acid and 12 mL xylene water-carrying agent into a reaction bottle carrying a water separator, heating to 160 ℃, stirring and refluxing until no water drops, heating to 225 ℃, stirring and refluxing until no water drops, cooling, filtering, concentrating the filtrate under reduced pressure, and recrystallizing and purifying the product by using ethyl acetate to obtain the pyrazine-2, 5-imidazoline intermediate.
(4) Placing the reaction bottle in ice bath, adding 500 mL dimethyl sulfoxide, 0.1mol pyrazine-2, 5-imidazoline compound, 0.13mol N-methyl quaternary ammonium salt diacyl chloride intermediate and 0.25mol N, N-diisopropylethylamine, stirring for 5min, removing ice bath, stirring at 20 ℃ to react for 36 h, pouring the solution into methanol to precipitate, filtering, washing the filter cake with ethanol, and drying to obtain the corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria.
Comparative example 1
Acetonitrile, 0.1mol of N-methyl iminodiacetic acid and 0.1mol of 1-chlorododecane are added into a reaction bottle carrying a condensation tube, the mixture is reacted at a temperature of 90 ℃ for 36 h, cooled and concentrated under reduced pressure, and the product is recrystallized and purified in ethanol after being washed by petroleum ether, thus obtaining the N-methyl quaternary ammonium salt diacetic acid intermediate.
Comparative example 2
Adding 0.28mol of diethylenetriamine, 0.1mol of pyrazine-2, 5-dicarboxylic acid and 12 mL xylene water-carrying agent into a reaction bottle carrying a water separator, heating to 165 ℃, stirring and refluxing until no water drops, heating to 210 ℃, stirring and refluxing until no water drops, cooling, filtering, concentrating the filtrate under reduced pressure, and recrystallizing and purifying the product by using ethyl acetate to obtain the pyrazine-2, 5-imidazoline intermediate.
Water solubility test:
adding the corrosion inhibitor into distilled water to prepare 10g/L solution, fully stirring for 10min at 25 ℃, standing for different times, and observing the state of the solution.
Table 1 water solubility test
The polymer main chain of the corrosion inhibitor contains hydrophilic amide bond and quaternary ammonium salt structure, so that the water solubility and dispersion stability of the corrosion inhibitor are obviously improved.
Antibacterial performance test:
the corrosion inhibitor, the N-methyl quaternary ammonium salt diacetic acid intermediate (comparative example 1) and the pyrazine-2, 5-imidazoline intermediate (comparative example 2) are respectively used as antibacterial agents, and sulfate reducing bacteria SRB are used as test strains.
Activation of SRB bacterial powder: adding 0.5mL of sterilized water and SBR bacterial powder into a sterilized test tube, stirring and dispersing, then transferring and taking 0.1mL of bacterial suspension, dripping the bacterial suspension into the middle of an agar plate culture medium, and culturing the bacterial suspension in a constant temperature incubator at 37 ℃ for 5 days to obtain SRB bacterial liquid.
Weighing 1.5. 1.5 g beef extract peptone culture medium, adding into 100mL sterilized water, stirring to obtain liquid culture medium, transferring 3. 3 mL liquid culture medium, adding into sterilized test tube, adding antiseptic, stirring for dispersion, controlling antiseptic concentration to 1000 ug/mL-3.91 ug/L by double dilution method, adding no antiseptic solution as blank group, and finally dripping 0.1mL concentration to 1×10 6 CFU/mL SRB bacterial liquid, the test tube is cultivated at a constant temperature at 37 ℃, and the minimum inhibitory concentration of MIC is determined by observing the growth condition of bacteria.
Table 2 antibacterial property test:
the corrosion inhibitors prepared in examples 1-4 contain a large number of quaternary ammonium salt active functional groups, have excellent antibacterial effect, and have a Minimum Inhibitory Concentration (MIC) of only 15.63-7.81 ug/mL for sulfate reducing bacteria. The pyrazine-2, 5-imidazoline intermediate prepared in comparative example 2 had no antibacterial effect on sulfate-reducing bacteria.
And (3) testing corrosion resistance and inhibition performance:
corrosion inhibition effect evaluation is carried out according to the standard GB10124-1988, SY/5273-1991, oil field water injection corrosion inhibitor evaluation method, SYJ26-28, water corrosiveness test method and normal pressure static hanging piece weightlessness method. Corrosion testing procedure and corrosion rate were tested in accordance with standard SY/T5273-2014.
And (3) taking the steel sheet as a corrosion inhibition matrix, washing with acetone and ethanol in sequence, wiping, drying and weighing. The corrosive medium is field simulated oilfield sewage, the pH is 7, and the test temperature is 25 ℃.
The corrosion inhibitor, N-methyl quaternary ammonium salt diacetic acid intermediate (comparative example 1), pyrazine-2, 5-imidazoline intermediate (comparative example 2) were added to distilled water to prepare 20mg/L solutions as corrosion inhibitor solutions, and the test results were shown in the following table.
Table 3 corrosion rate and corrosion inhibition performance test of the corrosion inhibitors:
corrosion inhibitors prepared in examples 1-4, which contain quaternary ammonium salt N in the polymer backbone + The structure of amide bond, imidazoline and pyrazine can form coordination with the original empty metal track on the surface of steel, so that the polymer corrosion inhibitor forms a firm adsorption film on the surface of steel, prevents a corrosion medium from contacting with the steel, reduces the corrosion rate and has excellent corrosion resistance.
The corrosion inhibition performance of the corrosion inhibitor on the steel sheet is tested at different temperatures:
table 4 high temperature corrosion inhibition performance test of corrosion inhibitors:
the corrosion inhibitors of examples 1-4 are polymers, which have better heat resistance than small molecules, and still maintain good structural stability at high temperature, so that excellent corrosion inhibition rate can be maintained, and the corrosion inhibition rate still reaches 90.2-93.0% at 75 ℃.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (9)
1. The preparation method of the corrosion inhibitor for sulfate-reducing bacteria-containing oilfield sewage is characterized by comprising the following steps of:
s1, adding diethylenetriamine, pyrazine-2, 5-dicarboxylic acid and xylene water-carrying agent into a reaction bottle carrying a water knockout drum, heating to 155-165 ℃, stirring and refluxing to be anhydrous and dripping, heating to 210-225 ℃, stirring and refluxing to be anhydrous and dripping, cooling, filtering, concentrating filtrate under reduced pressure, and recrystallizing and purifying a product by using ethyl acetate to obtain a pyrazine-2, 5-imidazoline intermediate;
s2, placing the reaction bottle in ice bath, adding dimethyl sulfoxide, pyrazine-2, 5-imidazoline compound, N-methyl quaternary ammonium salt diacyl chloride intermediate and N, N-diisopropylethylamine, stirring for 5-10min, removing the ice bath, stirring for reaction, pouring the solution into methanol to precipitate, filtering, washing the filter cake with ethanol, and drying to obtain the corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria.
2. The method for preparing the corrosion inhibitor for sulfate-reducing bacteria-containing oilfield sewage according to claim 1, wherein the proportion of diethylenetriamine, pyrazine-2, 5-dicarboxylic acid and xylene water-carrying agent in S1 is (2.3-2.8) mol to 1mol (80-120) mL.
3. The method for preparing a corrosion inhibitor for sulfate-reducing bacteria-containing oilfield sewage according to claim 1, wherein the reaction in S2 is performed at a temperature of 20-40 ℃ of 12-36 h.
4. The method for preparing a corrosion inhibitor for sulfate-reducing bacteria-containing oilfield sewage according to claim 1, wherein the ratio of dimethyl sulfoxide, pyrazine-2, 5-imidazoline compound, N-methyl quaternary ammonium salt diacid chloride intermediate and N, N-diisopropylethylamine in S2 is (3-5) L to 1mol (0.8-1.3) mol (2-2.5).
5. The method for preparing a corrosion inhibitor for sulfate-reducing bacteria-containing oilfield sewage according to claim 4, wherein the method for preparing the N-methyl quaternary ammonium salt diacid chloride intermediate comprises the following steps:
s3, adding acetonitrile, N-methyl iminodiacetic acid and an alkyl chloride compound into a reaction bottle carrying a condensing tube, reacting, cooling, concentrating under reduced pressure, washing a product by petroleum ether, and recrystallizing and purifying in ethanol to obtain an N-methyl quaternary ammonium salt diacetic acid intermediate;
s4, adding thionyl chloride and an N-methyl quaternary ammonium salt diacetic acid intermediate into a reaction bottle carrying a condensing tube, reacting at 65-75 ℃ for 3-6 h, cooling, concentrating under reduced pressure, washing the product with petroleum ether, and drying to obtain the N-methyl quaternary ammonium salt diacyl chloride intermediate.
6. The method for preparing a corrosion inhibitor for sulfate-reducing bacteria-containing oilfield sewage according to claim 5, wherein the ratio of the N-methyliminodiacetic acid to the alkyl chloride compound is 1mol (1-1.4 mol).
7. The method for preparing a corrosion inhibitor for sulfate-reducing bacteria-containing oilfield sewage according to claim 5, wherein the reaction in S3 is performed at a temperature of 80-90 ℃ of 36-48 h.
8. The method for preparing a corrosion inhibitor for sulfate-reducing bacteria-containing oilfield sewage as defined in claim 5, wherein the alkyl chloride compound has a molecular formula of C n H 2n+1 Cl and n is any integer from 12 to 18.
9. The method for preparing a corrosion inhibitor for sulfate-reducing bacteria-containing oilfield sewage according to claim 5, wherein the ratio of thionyl chloride to N-methyl quaternary ammonium salt diacetic acid intermediate in S4 is (1.2-1.8) L to 1mol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311403015.8A CN117143332B (en) | 2023-10-27 | 2023-10-27 | Preparation method of corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311403015.8A CN117143332B (en) | 2023-10-27 | 2023-10-27 | Preparation method of corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117143332A true CN117143332A (en) | 2023-12-01 |
| CN117143332B CN117143332B (en) | 2024-01-02 |
Family
ID=88910376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311403015.8A Active CN117143332B (en) | 2023-10-27 | 2023-10-27 | Preparation method of corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117143332B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103898515A (en) * | 2012-12-28 | 2014-07-02 | 中国石油天然气集团公司 | Corrosion inhibitor for gas field and preparation method thereof |
| US20180148632A1 (en) * | 2016-11-30 | 2018-05-31 | Ecolab Usa Inc. | Composition for remediating iron sulfide in oilfield production systems |
| CN110157402A (en) * | 2018-03-27 | 2019-08-23 | 德蓝水技术股份有限公司 | A kind of antibacterial anti-H of salt tolerant2S/CO2Corrosion inhibiter and preparation method thereof |
| CN114456148A (en) * | 2022-01-11 | 2022-05-10 | 中海油天津化工研究设计院有限公司 | Oil field corrosion inhibitor with good compatibility and preparation method thereof |
| CN114591224A (en) * | 2020-12-03 | 2022-06-07 | 中国石油天然气股份有限公司 | Corrosion inhibitor with hydrate inhibition function and preparation method and application thereof |
-
2023
- 2023-10-27 CN CN202311403015.8A patent/CN117143332B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103898515A (en) * | 2012-12-28 | 2014-07-02 | 中国石油天然气集团公司 | Corrosion inhibitor for gas field and preparation method thereof |
| US20180148632A1 (en) * | 2016-11-30 | 2018-05-31 | Ecolab Usa Inc. | Composition for remediating iron sulfide in oilfield production systems |
| CN110157402A (en) * | 2018-03-27 | 2019-08-23 | 德蓝水技术股份有限公司 | A kind of antibacterial anti-H of salt tolerant2S/CO2Corrosion inhibiter and preparation method thereof |
| CN114591224A (en) * | 2020-12-03 | 2022-06-07 | 中国石油天然气股份有限公司 | Corrosion inhibitor with hydrate inhibition function and preparation method and application thereof |
| CN114456148A (en) * | 2022-01-11 | 2022-05-10 | 中海油天津化工研究设计院有限公司 | Oil field corrosion inhibitor with good compatibility and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117143332B (en) | 2024-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2006034101A1 (en) | Polymeric quaternary ammonium salts useful as corrosion inhibitors and biocides | |
| CN108840803B (en) | Method for synthesizing asymmetric biquaternary ammonium salt bactericide | |
| CN111020599B (en) | Corrosion inhibitor for soft water circulating heating/cooling system and preparation method thereof | |
| CN117143332B (en) | Preparation method of corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria | |
| CN111321412B (en) | High-salt-content weak-acid oil field water quality corrosion inhibitor with chloride ion content of more than 5 ten thousand ppm | |
| RU2573385C2 (en) | Stable aqueous acrylamide solution | |
| CN111153933B (en) | Bactericide for polymer-containing sewage in oil field and preparation method thereof | |
| CN108373536B (en) | Synthesis method and application of modified polyaspartic acid with Schiff base structure | |
| CN116081787A (en) | Quaternary phosphonium salt type sterilizing water treatment agent and preparation method thereof | |
| CN114907403B (en) | Double quaternary phosphonium salt bactericide and synthetic method thereof | |
| CN111109265A (en) | Corrosion inhibition bactericide, preparation method and application in CO2Corrosion inhibition bactericide for driving and producing well | |
| CN114158560B (en) | Bactericide for industrial cooling water | |
| US4217329A (en) | Sulfone containing quaternary ammonium derivatives of 1,4-thiazines | |
| CN103260409B (en) | For the shielded Antimicrobe compound of high temperature application | |
| CN109987723B (en) | Non-phosphorus scale and corrosion inhibitor and preparation method and application thereof | |
| CN114456148A (en) | Oil field corrosion inhibitor with good compatibility and preparation method thereof | |
| US4336156A (en) | Quaternary ammonium salts of α-1,4-thiazine alkanephosphonic acids | |
| JPS604107A (en) | Preservation of aqueous solution, emulsion and dispersion | |
| CN103260404A (en) | Protected antimicrobial compounds for high temperature applications | |
| CN111471444B (en) | Polyamino bactericidal surfactant and preparation method and application thereof | |
| CN109705059B (en) | Asymmetric gemini acidizing corrosion inhibitor and preparation method thereof | |
| CN116770314A (en) | Sterilization corrosion inhibitor for oil field mixed transportation sea pipe and preparation method thereof | |
| US4200634A (en) | Sulfone containing quaternary ammonium derivatives of 1,4-thiazines as microbiocides | |
| CN111690936A (en) | Compound corrosion inhibitor suitable for AZ91D magnesium alloy in neutral saline water medium and preparation method thereof | |
| US2310789A (en) | Linear polymeric amidine salts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |