CN107973417A - The corrosion-proofing and antisludging method and oil production method of composite slow-corrosion scale resistor, oil field water - Google Patents
The corrosion-proofing and antisludging method and oil production method of composite slow-corrosion scale resistor, oil field water Download PDFInfo
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- CN107973417A CN107973417A CN201610933902.XA CN201610933902A CN107973417A CN 107973417 A CN107973417 A CN 107973417A CN 201610933902 A CN201610933902 A CN 201610933902A CN 107973417 A CN107973417 A CN 107973417A
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- water
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- scale resistor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
- C02F5/125—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen combined with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
- C02F5/145—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus combined with inorganic substances
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/20—Displacing by water
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
Abstract
The present invention relates to composite slow-corrosion scale resistor, the corrosion-proofing and antisludging method and oil production method of oil field water.Composite slow-corrosion scale resistor therein, according to the mass fraction, including：5~15 parts of Phos, 7.5~17.5 parts of organic phospho acids, 1~10 part of amine, 4~10 parts of sulfur-containing polymer dirt dispersion agents and optional zinc salt.Inhibition and scale inhibition processing of the composite slow-corrosion scale resistor especially suitable for the oil field water under severe rugged environment.
Description
Technical field
It is more particularly to a kind of the present invention relates to composite slow-corrosion scale resistor, the corrosion-proofing and antisludging method and oil production method of oil field water
Corrosion-proofing and antisludging method available for the oil field water under high temperature, the composite slow-corrosion scale resistor of oxygen environment, a kind of high temperature, oxygen environment
With a kind of deep-well, the oil production method of ultradeep well.
Background technology
The crude oil that oilfield exploitation goes out is with substantial amounts of recovered water.Oil well produced crude oil and recovered water is sent through gathering line
Water-oil separating is carried out to multi-purpose station, the sewage isolated send to deoxidation station and removes in water after sewage disposal system processing is up to standard
Dissolved oxygen, most complete being circulated throughout for oil field extracted water (hereinafter referred to as oil field water) through water-injection station water injection well reinjection into reservoir afterwards
Journey.Water universal salinity in oil field is high, usually dissolved with CO2And H2The corrosive gas such as S, generally in faintly acid (pH 5.5~
7.0), therefore, oil field water has stronger corrosiveness to oil field equipment and gathering line.According to just slightly estimating, corrode and adopted to China
Loss caused by oily industry accounts for the 6% of the industry gross output value, and takes suitable anti-corrosion measure, can retrieve 30%~40% damage
Lose.In a variety of anti-corrosion measures of metal, corrosion inhibiter is most widely used, and the corrosion inhibiter of field use mainly has imidazoles at present
The types such as quinoline, Mannich base, the quaternary ammonium salt of azacyclo-, alkynol, pyridine, quinoline, thiocarbamide, these corrosion inhibiter mechanisms of action are mostly
Absorption film-forming mechanism, i.e. corrosion inhibiter form one layer of continuous or discrete adsorbed film in metal surface, prevent the sun of corrosion process
Pole is reacted or cathode reaction or the progress for preventing two electrode reactions at the same time, reduces corrosion rate.
Above-mentioned corrosion inhibiter respectively has its advantage and disadvantage, such as preferable using most common imidazolines corrosion mitigating effect, but in alkaline ring
Facile hydrolysis in border.Though alkynol class has the advantages that corrosion mitigating effect is preferable, its toxicity is big, additive amount is high, expensive and easily wave
Hair.Similarly there are the problem of the big cost of dosage is higher, compatibility is poor for common Mannich bases and quaternary ammonium salt.Above-mentioned corrosion inhibiter
There are it is common the shortcomings that be that temperature tolerance is not strong, at high temperature easily occur thermal cracking, will be thorough particularly in high temperature, oxygen environment
Bottom is oxidized to CO2And corrosion inhibition is lost, therefore, above-mentioned corrosion inhibiter is only applicable to low temperature, oxygen-free environment in oil field, such as collects defeated
The anti-corrosion of the not high posthole underground equipment of system, sewage disposal system, flood pattern and temperature etc..
Downhole temperature and pressure increase and increase with well depth, in recent years, with deep-well (4500 meters~6000 meters), ultradeep well
A large amount of exploitations of (6000 meters~9000 meters), the temperature tolerance requirement to corrosion inhibiter are also just higher and higher.In order to improve oil recovering
Rate, the oily later stage passing oil well gas injecting mining crude oil of normal open, the positive effect of gas injecting mining are replaced in water filling, but may be brought serious
Downhole corrosion problem.A major reason for causing the problem is to contain certain density oxygen in gas injection, although being replaced with nitrogen
The oxygen content in gas injection has been greatly reduced in air, but restricted nitrogen technical merit limits (film nitrogen), and nitrogen gas purity is only capable of reaching
95.0%~97.5%, wherein can also still cause serious oxygen corrosion containing 2.5%~5.0% oxygen.So far, originally
Field is also difficult to solve the problems, such as this, and reason is：On the one hand, anti-corrosion material is replaced, using high pure nitrogen or using deoxidier
Cost is too high；On the other hand, existing corrosion inhibiting and descaling agent is not suitable for this harsh high temperature, oxygen environment, is used rationally
In the range of amount, the corrosion inhibition rate generally only 20%~30% of these corrosion inhibiting and descaling agents.
CN 103030216A disclose a kind of high temperature resistant scaling inhibitor with emulsification and preparation method thereof.Press
Weight fraction meter, calgon 2%~9%, zinc sulfate 13%~20%, polyoxyethylene nonylphenol ether -15 1%~3%, amino front three
Pitch phosphonic acids 10%~18%, 2- phosphonic acids -1,2,4- butane tricarboxylates 8%~16% and sodium sulfite 4%~6%.The agent is 85
DEG C, effect is preferable under hypoxia condition.
CN102911651A discloses a kind of oil field composite corrosion inhibitor.The mass percent of each component is：Sodium molybdate
5%~10%, sodium phosphate 10%~20%, AA-AMPS copolymers 0.5%~1%, aminotrimethylenephosphonic acid 1%~2%, hydroxyl
Base ethylidene diphosphonic acid 1%~2%.Corrosion inhibiter effect under 70 DEG C, hypoxia condition is preferable.
CN104233310A discloses a kind of compound Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor and preparation method thereof, the matter of each component
Measuring percentage is：Alkyl acid imidazoline quaternary ammonium salt 30%~35%, nitrogenous organic multicomponent phosphate 8%~10%, amphoteric surface
Activating agent 1%~2%, dispersant 0.5%~1%, cosolvent 1%~2%.Corrosion inhibiter effect under 50 DEG C, hypoxia condition
Preferably.
So far, in aqueous medium corrosion-resistant field, there are no the corrosion inhibiter of high temperature resistant (100 DEG C of ＞), more there are no it is both resistance to
High temperature and the corrosion inhibiter of resistance to oxidation.
The content of the invention
The main object of the present invention is to provide a kind of composite slow-corrosion scale resistor, a kind of corrosion-proofing and antisludging method and one of oil field water
Kind oil production method, solves the problems, such as the oil field aqueous corrosion of high temperature, aerobic environment.
The main contents of the present invention are as follows：
1. a kind of composite slow-corrosion scale resistor, according to the mass fraction, including：5~15 parts of Phos, 7.5~17.5 parts it is organic
Phosphonic acids, 1~10 part of amine, 4~10 parts of sulfur-containing polymer dirt dispersion agents and optional zinc salt.
2. according to the composite slow-corrosion scale resistor described in 1, it is characterised in that the Phos is selected from sodium phosphate, biphosphate
Sodium, disodium hydrogen phosphate, potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid,
At least one of sodium tripolyphosphate, potassium tripolyphosphate, calgon and hexa metaphosphoric acid potassium.
3. according to foregoing any composite slow-corrosion scale resistor, it is characterised in that the organic phospho acid is selected from hydroxy ethylidene two
Phosphonic acids (HEDP), 2- hydroxyphosphonoacetic acid (HPAA), 2- phosphonobutanes -1,2,4- tricarboxylic acids (PBTCA) and polyalcohol phosphoric acid
At least one of ester (PAPE)；Preferably 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) and/or 2- hydroxyphosphonoacetic acid (HPAA).
4. according to foregoing any composite slow-corrosion scale resistor, it is characterised in that the amine is selected from hydroxyl and substitutes or non-take
The substituted or non-substituted saturation nitrogen oxa- ring of the substituted or non-substituted saturation nitrogen heterocyclic of fatty amine, the hydroxyl in generation, hydroxyl
At least one of compound and polyethylene polyamine；It is preferably selected from monomethyl amine, dimethylamine, trimethylamine, monoethyl amine, diethylamine, three
Ethamine, ethylenediamine, a propylamine, di-n-propylamine, tripropyl amine (TPA), isopropylamine, diisopropylamine, 1,2- dimethyl propylamines, 1,2- propane diamine, 2-
Allylamine, cyclopropylamine, n-butylamine, di-n-butylamine, isobutyl amine, sec-butylamine, 1,4- butanediamine, tert-butylamine, di-iso-butylmanice, hexylamine,
2 ethyl hexylamine, hexamethylene diamine, monoethanolamine, diethanol amine, triethanolamine, 3- Propanolamines, monoisopropanolamine, diisopropanolamine (DIPA),
Triisopropanolamine, N, N methyldiethanol amine, N, N- diethyl ethylene diamines, triethylenediamine, diethylenetriamines, six methylenes
At least one of urotropine, hexamethylene imine, triethylenediamine, cyclic ethylene imines, morpholine, piperazine and cyclohexylamine.
5. according to foregoing any composite slow-corrosion scale resistor, it is characterised in that the sulfur-containing polymer dirt dispersion agent choosing
From acrylic acid and bipolymer (AA-AMPS), maleic anhydride and the 2- acryloyls of 2- acrylamido -2- methyl-propanesulfonic acids
The binary of the bipolymers (MA-AMPS) of amido -2- methyl-propanesulfonic acids, acrylic acid and allyl polyethenoxy ether ammonium sulfate
Bipolymer (MA-APES), the acrylic acid of copolymer (AA-APES), maleic anhydride and allyl polyethenoxy ether ammonium sulfate
With terpolymer (AA-MA-AMPS), acrylic acid and the Malaysia of maleic anhydride and 2- acrylamido -2- methyl-propanesulfonic acids
At least one of terpolymer of acid anhydrides and allyl polyethenoxy ether ammonium sulfate (AA-MA-APES).
6. according to foregoing any composite slow-corrosion scale resistor, it is characterised in that the sulfur-containing polymer dirt dispersion agent choosing
From bipolymer (AA-APES), maleic anhydride and the pi-allyl polyoxy second of acrylic acid and allyl polyethenoxy ether ammonium sulfate
Bipolymer (MA-APES), acrylic acid and the maleic anhydride of alkene ether ammonium sulfate and allyl polyethenoxy ether ammonium sulfate
At least one of terpolymer (AA-MA-APES).
7. according to foregoing any composite slow-corrosion scale resistor, it is characterised in that the zinc salt be selected from zinc chloride, zinc nitrate and
At least one of zinc sulfate.
8. according to foregoing any composite slow-corrosion scale resistor, it is characterised in that according to the mass fraction, the compound slow corrosion resistance
Dirty agent is also containing 45.5~82.5 parts of water.
9. according to foregoing any composite slow-corrosion scale resistor, it is characterised in that the composite slow-corrosion scale resistor is by inorganic
Phosphorus, organic phospho acid, amine, sulfur-containing polymer dirt dispersion agent, optional zinc salt and water composition.
10. a kind of preparation method of composite slow-corrosion scale resistor, according to the mass fraction, by 5~15 parts of Phos, 7.5~
17.5 parts of organic phospho acids, 1~10 part of amine, 4~10 parts of sulfur-containing polymer dirt dispersion agents and optional zinc salt are mixed with water, to obtain the final product
The composite slow-corrosion scale resistor.
11. according to the preparation method described in 10, it is characterised in that according to the mass fraction, the dosage of water is 45.5~82.5
Part.
12. according to the preparation method described in 10 or 11, it is characterised in that the Phos is selected from sodium phosphate, biphosphate
Sodium, disodium hydrogen phosphate, potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid,
At least one of sodium tripolyphosphate, potassium tripolyphosphate, calgon and hexa metaphosphoric acid potassium.
13. according to 10~12 any preparation methods, it is characterised in that the organic phospho acid is selected from hydroxy ethylidene two
Phosphonic acids (HEDP), 2- hydroxyphosphonoacetic acid (HPAA), 2- phosphonobutanes -1,2,4- tricarboxylic acids (PBTCA) and polyalcohol phosphoric acid
At least one of ester (PAPE)；Preferably 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) and/or 2- hydroxyphosphonoacetic acid (HPAA).
14. according to 10~13 any preparation methods, it is characterised in that the amine is selected from hydroxyl and substitutes or non-take
The substituted or non-substituted saturation nitrogen oxa- ring of the substituted or non-substituted saturation nitrogen heterocyclic of fatty amine, the hydroxyl in generation, hydroxyl
At least one of compound and polyethylene polyamine；It is preferably selected from monomethyl amine, dimethylamine, trimethylamine, monoethyl amine, diethylamine, three
Ethamine, ethylenediamine, a propylamine, di-n-propylamine, tripropyl amine (TPA), isopropylamine, diisopropylamine, 1,2- dimethyl propylamines, 1,2- propane diamine, 2-
Allylamine, cyclopropylamine, n-butylamine, di-n-butylamine, isobutyl amine, sec-butylamine, 1,4- butanediamine, tert-butylamine, di-iso-butylmanice, hexylamine,
2 ethyl hexylamine, hexamethylene diamine, monoethanolamine, diethanol amine, triethanolamine, 3- Propanolamines, monoisopropanolamine, diisopropanolamine (DIPA),
Triisopropanolamine, N, N methyldiethanol amine, N, N- diethyl ethylene diamines, triethylenediamine, diethylenetriamines, six methylenes
At least one of urotropine, hexamethylene imine, triethylenediamine, cyclic ethylene imines, morpholine, piperazine and cyclohexylamine.
15. according to 10~14 any preparation methods, it is characterised in that the sulfur-containing polymer dirt dispersion agent choosing
From acrylic acid and bipolymer (AA-AMPS), maleic anhydride and the 2- acryloyls of 2- acrylamido -2- methyl-propanesulfonic acids
The binary of the bipolymers (MA-AMPS) of amido -2- methyl-propanesulfonic acids, acrylic acid and allyl polyethenoxy ether ammonium sulfate
Bipolymer (MA-APES), the acrylic acid of copolymer (AA-APES), maleic anhydride and allyl polyethenoxy ether ammonium sulfate
With terpolymer (AA-MA-AMPS), acrylic acid and the Malaysia of maleic anhydride and 2- acrylamido -2- methyl-propanesulfonic acids
At least one of terpolymer of acid anhydrides and allyl polyethenoxy ether ammonium sulfate (AA-MA-APES).
16. according to 10~15 any preparation methods, it is characterised in that the sulfur-containing polymer dirt dispersion agent choosing
From bipolymer (AA-APES), maleic anhydride and the pi-allyl polyoxy second of acrylic acid and allyl polyethenoxy ether ammonium sulfate
Bipolymer (MA-APES), acrylic acid and the maleic anhydride of alkene ether ammonium sulfate and allyl polyethenoxy ether ammonium sulfate
At least one of terpolymer (AA-MA-APES).
17 according to 10~16 any preparation methods, it is characterised in that the zinc salt be selected from zinc chloride, zinc nitrate and
At least one of zinc sulfate.
18. a kind of corrosion-proofing and antisludging method of oil field water, before oil field water is injected stratum, 1~9 is added into oil field water
Composite slow-corrosion scale resistor described in one.
19. according to the corrosion-proofing and antisludging method described in 18, it is characterised in that the use environment of the oil field water, temperature ＞ 100
DEG C, partial pressure of oxygen >=0.05Mpa.
20. according to the corrosion-proofing and antisludging method described in 18 or 19, it is characterised in that the use environment of the oil field water, temperature
125~160 DEG C, 0.05~3.5Mpa of partial pressure of oxygen.
21. according to 18~20 any corrosion-proofing and antisludging methods, it is characterised in that the salinity of the oil field water is
100000~300000mg/L.
22. according to 18~21 any corrosion-proofing and antisludging methods, it is characterised in that compound slow in terms of every liter of oil field water
The dosage for losing antisludging agent is 450~550mg.
23. according to 18~22 any corrosion-proofing and antisludging methods, it is characterised in that before oil field water is injected stratum,
The pH value that oil field water is adjusted with inorganic acid and/or inorganic base is 4.5~6.0.
A kind of 24. oil production method, by the way of water and gas mixed water injection, it is characterised in that in the water, add 1
~9 any composite slow-corrosion scale resistors；In the gas, with volume fraction, oxygen content ＞ 2%.
25. according to the method described in 24, it is characterised in that in terms of every liter of water, the Phos of addition, organic phospho acid, amine, contain
The total amount of sulphur polymeric scale inhibitor dispersant and optional zinc salt is 70~300mg, is preferably 130~220mg.
26. according to the method described in 24 or 25, it is characterised in that the salinity of the water is 100000~300000mg/
L。
27. according to 24~26 any methods, it is characterised in that water and gas mixed water injection are deep-well or ultradeep well.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
Technical term in the present invention, the present invention provide definition from its definition, do not provide definition then by this area
Common meaning understands.
In the context of the present specification, in addition to the content clearly stated, any matters or item do not mentioned are equal
Directly it is applicable in the existing knowledge of this area.
Existing document shows that existing corrosion inhibiting and descaling agent is not suitable for high temperature, oxygen containing environment, in conventional practice
In, the corrosion inhibition rate generally only 20%~30% of existing corrosion inhibiting and descaling agent.The research of the present invention finds, downhole temperature and pressure with
The increase of well depth and increase, if containing certain oxygen in environment, be close to or up to wet oxidation operating condition (125~
320 DEG C, 0.5~20MPa) when, the common organic inhibitor in oil field, such as imidazoline, Mannich base, quaternary ammonium salt, alkynol, pyrrole
Pyridine, quinoline, thiocarbamide etc., can be decomposed and lose corrosion inhibition.The research of the present invention is found, although in high temperature, oxygen containing environment
Under, organic phospho acid can be decomposed, but its catabolite has corrosion inhibition；Although amine does not have corrosion inhibition, it decomposes production
Thing is conducive to protect the stability of deposition film.The research of the present invention also found, although under high temperature, oxygen-containing environment, individually make
It is limited with the effect of inorganic inhibitor, but its corrosion mitigating effect is more stable.
Based on above-mentioned cognition and a large number of experiments, the present invention is ultimately formed, particular content is as follows.
First, composite slow-corrosion scale resistor
The present invention provides a kind of composite slow-corrosion scale resistor, according to the mass fraction, including：5~15 parts of Phos, 7.5~
17.5 parts of organic phospho acids, 1~10 part of amine, 4~10 parts of sulfur-containing polymer dirt dispersion agents and optional zinc salt.
In the case of preferable, according to the mass fraction, the composite slow-corrosion scale resistor includes：7.5~12.5 parts of Phos,
10~15 parts of organic phospho acids, 2~8 parts of amine, 4~10 parts of sulfur-containing polymer dirt dispersion agents and 0~2 part of zinc salt.
In the case of preferred, according to the mass fraction, the composite slow-corrosion scale resistor includes：7.5~12.5 parts inorganic
Phosphorus, 10~15 parts of organic phospho acids, 2~8 parts of amine, 5~8 parts of sulfur-containing polymer dirt dispersion agents and 0.5~1.5 part of zinc salt.
According to the present invention, the Phos is had no particular limits, can is that this area is used as deposition membranous type inhibition
The various Phos of agent, it is either phosphate and/or phosphoric acid acid salt or polymeric phosphate, preferably phosphate
And/or phosphoric acid acid salt.The research of the present invention is found, if do not lost largely because of precipitation, Phos can be in high temperature, oxygen-containing
In the environment of, play certain corrosion inhibition；Also, in main inorganic inhibitor, such as chromate, bichromate, nitrous
Hydrochlorate, silicate, borate, molybdate, Phos, zinc salt etc., there are cooperative effect between Phos and amine, in high temperature, contain
In the environment of oxygen, the two cooperation can reach more satisfactory corrosion mitigating effect.
According to the present invention, the Phos may be selected from Phos and be selected from sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, phosphorus
Sour potassium, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, sodium tripolyphosphate, trimerization
At least one of potassium phosphate, calgon and hexa metaphosphoric acid potassium.
According to the present invention, the Phos be preferably selected from Phos be selected from sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate,
At least one of potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphoric acid.
In the present invention, the organic phospho acid is had no particular limits, it can be that water treatment agent field is conventional use of
Various organic phospho acids, both can be nitrogenous organic phosphoric acid, or nitrogen-free organic phosphoric acid, preferably nitrogen-free organic phosphoric acid.It is preferred that
In the case of, the organic phospho acid is selected from 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP), 2- hydroxyphosphonoacetic acid (HPAA), 2- phosphonic acids fourths
At least one of alkane -1,2,4- tricarboxylic acids (PBTCA), Polyol Phosphate (PAPE).In the case of more preferably, the organic phosphine
Acid is selected from 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) and/or 2- hydroxyphosphonoacetic acid (HPAA).The research discovery of the present invention, in spite of
Machine phosphonic acid can be decomposed under high temperature, oxygen-containing environment, but its catabolite has certain corrosion inhibition；Also, although amine
Without corrosion inhibition, but its catabolite under high temperature, aerobic environment has promotion to foregoing corrosion inhibition.
According to the present invention, the carbon number of the amine is preferably 1~10, and more preferably 1~6.
According to the present invention, the amine is selected from substituted or non-substituted full of the substituted or non-substituted fatty amine of hydroxyl, hydroxyl
With at least one of nitrogen heterocyclic and polyethylene polyamine.The research of the present invention is found, although amine does not have corrosion inhibition,
But catabolite of the amine under high temperature, aerobic environment is conducive to protect the stability of deposition film, under high temperature, oxygen-containing environment,
Amine coordinates with Phos and organic phospho acid can reach more satisfactory corrosion mitigating effect.
According to the present invention, the amine may be selected from monomethyl amine, dimethylamine, trimethylamine, monoethyl amine, diethylamine, triethylamine, second
Diamines, a propylamine, di-n-propylamine, tripropyl amine (TPA), isopropylamine, diisopropylamine, 1,2- dimethyl propylamines, 1,2- propane diamine, 2- allylamines,
Cyclopropylamine, n-butylamine, di-n-butylamine, isobutyl amine, sec-butylamine, 1,4- butanediamine, tert-butylamine, di-iso-butylmanice, hexylamine, 2- ethyl hexyls
Amine, hexamethylene diamine, monoethanolamine, diethanol amine, triethanolamine, 3- Propanolamines, monoisopropanolamine, diisopropanolamine (DIPA), three isopropanols
Amine, N, N methyldiethanol amine, N, N- diethyl ethylene diamines, triethylenediamine, diethylenetriamines, hexa,
At least one of hexamethylene imine, triethylenediamine, cyclic ethylene imines, morpholine, piperazine and cyclohexylamine.
According to the present invention, the amine is preferably selected from least one of hexa, monoethanolamine, ethylenediamine
In the present invention, the sulfur-containing polymer dirt dispersion agent is had no particular limits, it can be that water treatment agent is led
The conventional use of various sulfur-containing polymer dirt dispersion agents in domain.
According to the present invention, the sulfur-containing polymer dirt dispersion agent may be selected from acrylic acid and 2- acrylamido -2- methyl -
The bipolymer of the bipolymer (AA-AMPS) of propane sulfonic acid, maleic anhydride and 2- acrylamido -2- methyl-propanesulfonic acids
(MA-AMPS), the bipolymer of acrylic acid and allyl polyethenoxy ether ammonium sulfate (AA-APES), maleic anhydride and allyl
Bipolymer (MA-APES), acrylic acid and the maleic anhydride and 2- acrylamido -2- first of base polyoxyethylene ether ammonium sulfate
Terpolymer (AA-MA-AMPS), acrylic acid and the maleic anhydride and allyl polyethenoxy ether ammonium sulfate of base-propane sulfonic acid
At least one of terpolymer (AA-MA-APES).
According to the present invention, the sulfur-containing polymer dirt dispersion agent is preferably selected from acrylic acid and allyl polyethenoxy ether sulphur
Bipolymer (the MA- of the bipolymer (AA-APES) of sour ammonium, maleic anhydride and allyl polyethenoxy ether ammonium sulfate
APES), in the terpolymer of acrylic acid and maleic anhydride and allyl polyethenoxy ether ammonium sulfate (AA-MA-APES)
It is at least one.
According to the present invention, zinc salt is had no particular limits, can is conventional use of various zinc in water treatment agent field
Salt, is preferably at least one of zinc chloride, zinc nitrate and zinc sulfate.It should be appreciated that during selection zinc salt, at least to ensure institute
The zinc salt under expense can be completely soluble in water.
According to the present invention, the amount of the zinc salt can be 0~5 part, generally 0~2 part.
According to the present invention, according to the mass fraction, the composite slow-corrosion scale resistor is containing 45.5~82.5 parts of water, preferably
Water containing 52.5~76.5 parts of water, further preferably 55~75 parts.
According to the present invention, the composite slow-corrosion scale resistor is by Phos, organic phospho acid, amine, sulfur-containing polymer scale inhibition point
Powder, optional zinc salt and water composition.In the case of preferable, the composite slow-corrosion scale resistor is by Phos, nitrogen-free organic phosphine
Acid, amine, sulfur-containing polymer dirt dispersion agent, optionally containing nitrogen organic phosphonic acid, optional zinc salt and water composition.
According to the present invention, the composite slow-corrosion scale resistor is suitable for 20~160 DEG C of temperature, 1~70Mpa of stagnation pressure, oxygen
Press 0.05~3.5Mpa under, pH 4.5~7.5,100000~300000mg/L of salinity oil field water inhibition and scale inhibition at
Reason.
2nd, the preparation method of composite slow-corrosion scale resistor
It is according to the mass fraction, inorganic by 5~15 parts the present invention provides a kind of preparation method of composite slow-corrosion scale resistor
Phosphorus, 7.5~17.5 parts of organic phospho acids, 1~10 part of amine, 4~10 parts of sulfur-containing polymer dirt dispersion agents and optional zinc salt and water
Mixing, up to the composite slow-corrosion scale resistor.
According to the present invention, according to the mass fraction, the dosage of water is 45.5~82.5 parts.
In the case of preferable, according to the mass fraction, by 7.5~12.5 parts of Phos, 10~15 parts of organic phospho acids, 2~8 parts
Amine, 4~10 parts of sulfur-containing polymer dirt dispersion agents, 0~2 part of zinc salt are mixed with 52.5~76.5 parts of water.
In the case of preferred, according to the mass fraction, by 7.5~12.5 parts of Phos, 10~15 parts of organic phospho acids, 2~8
Part amine, 5~8 parts of sulfur-containing polymer dirt dispersion agents, 0.5~1.5 part of zinc salt are mixed with 55~75 parts of water.
Phos, organic phospho acid, amine, sulfur-containing polymer dirt dispersion agent and the zinc salt and their dosage are with before
It is identical to state the content of corresponding part, the present invention repeats no more this.
3rd, the corrosion-proofing and antisludging method of oil field water
The present invention provides a kind of corrosion-proofing and antisludging method of oil field water, before oil field water is injected stratum, into oil field water
Add foregoing any composite slow-corrosion scale resistor.
According to the present invention, the use environment of the oil field water under a subterranean formation, 100 DEG C of temperature ＞, partial pressure of oxygen >=0.05Mpa.
According to the present invention, the use environment of the oil field water under a subterranean formation, 125~160 DEG C of temperature, partial pressure of oxygen 0.05~
3.5Mpa。
According to the present invention, the salinity of the oil field water is 100000~300000mg/L.
According to the present invention, in terms of every liter of oil field water, the dosage of composite slow-corrosion scale resistor is generally between 450~550mg.
, according to the invention it is preferred to before oil field water is injected stratum, the pH of oil field water is adjusted with inorganic acid and/or inorganic base
It is worth for 4.5~6.0.
Phos, organic phospho acid, amine, sulfur-containing polymer dirt dispersion agent and the zinc salt and their dosage are with before
It is identical to state the content of corresponding part, the present invention repeats no more this.
4th, oil production method
The present invention provides a kind of oil production method, by the way of water and gas mixed water injection, it is characterised in that the water
In, add foregoing any composite slow-corrosion scale resistor；In the gas, with volume fraction, oxygen content ＞ 2%.
According to the present invention, in terms of every liter of water, the Phos of addition, organic phospho acid, amine, sulfur-containing polymer dirt dispersion agent and
The total amount of optional zinc salt is 70~300mg, is preferably 130~220mg.
According to the present invention, the salinity of the water is 100000~300000mg/L.
According to the present invention, water and gas mixed water injection is deep-well or ultradeep well.
According to the present invention, the gas is nitrogen；Wherein, with volume fraction, oxygen content is 2.5%~5%.
Phos, organic phospho acid, amine, sulfur-containing polymer dirt dispersion agent and the zinc salt and their dosage are with before
It is identical to state the content of corresponding part, the present invention repeats no more this.
All features disclosed in this invention can in any combination, these combinations should be understood presently disclosed or note
The content of load, unless those skilled in the art think that the combination is substantially unreasonable.Numerical point disclosed in this specification, is not only wrapped
Include specifically disclosed numerical point, further include the endpoint of each number range, the scope that these numerical points are combined all should by regarding
For the present invention it is disclosed or record scope, no matter whether separately disclosing these numerical value pair herein.
Further illustrate the present invention by the following examples.In embodiment and comparative example, various raw materials can be by commercially available
Obtain or be made by known method.
In embodiment and comparative example, 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP), 2- hydroxyphosphonoacetic acid (HPAA), 2- phosphonic acids fourths
Alkane -1,2,4- tricarboxylic acids (PBTCA), Polyol Phosphate (PAPE) are purchased from the calm and peaceful limited public affairs of water process science and technology share in Shandong
Department.
In embodiment and comparative example, the bipolymer (AA- of acrylic acid and 2- acrylamido -2- methyl-propanesulfonic acids
AMPS), the bipolymer of acrylic acid and allyl polyethenoxy ether ammonium sulfate (AA-APES), maleic anhydride and pi-allyl gather
Bipolymer (MA-APES), acrylic acid and the maleic anhydride and allyl polyethenoxy ether sulfuric acid of ethylene oxide ether ammonium sulfate
Terpolymer (AA-MA-APES), acrylic acid and the maleic anhydride of ammonium and the three of 2- acrylamido -2- methyl-propanesulfonic acids
Membered copolymer (AA-MA-AMPS) is purchased from Beijing Lin Hua water quality stabilizers factory.
Embodiment 1~6
Embodiment 1~6 is used to illustrate composite slow-corrosion scale resistor provided by the invention and preparation method thereof.
Each group distribution ratio in the composite slow-corrosion scale resistor of embodiment 1~6 is shown in Table 1.
The formula and preparation method of 1 composite slow-corrosion scale resistor of table
Comparative example 1~5
Each group distribution ratio in the composite slow-corrosion scale resistor of comparative example 1~5 is shown in Table 2.
Table 2 is used for the formula and preparation method of the composite slow-corrosion scale resistor contrasted
Embodiment 7
The present embodiment is used for the effect for illustrating the composite slow-corrosion scale resistor in previous embodiment and comparative example.
With reference to People's Republic of China (PRC) oil and gas industry standard SY/T 7025-2014《Acid-soluble oil gas field corrosion inhibiter
Performance test room evaluation method》In high pressure dynamic corrosion test；Embodiment 1~6 and comparative example 1~5 are obtained compound slow
Lose antisludging agent and carry out benchmark test.In terms of every liter of oil field mock water, the dosage of composite slow-corrosion scale resistor is 500mg；Experiment
In 13, after adding agent, the pH value for adjusting oil field mock water is 7；In remaining experiment, after adding agent, the pH value for adjusting oil field mock water is
5；140 DEG C, partial pressure of oxygen 2.6Mpa of test temperature, when experiment 6 is small.
GB/T 16632-2008 are pressed respectively《The measure tosca method of water treatment agent scale-inhibiting properties》With GBT 22626-
2008《The measure calcium phosphate deposition method of water treatment agent scale-inhibiting properties》In method, the front and rear calcium of analysis experiment firmly and total phosphorus, meter
Calculate resistance calcium carbonate scale rate, total phosphorus coefficient of stabilization.
Experiment water is simulation oil water in field, water quality such as table 3.
3 oil field mock water water quality of table
| Ion | mg/L |
| Cl- | 133658 |
| SO4 2- | 150 |
| HCO3 - | 33.8 |
| Na+ | 71634.4 |
| Ca2+ | 11272.5 |
| Mg2+ | 1161.8 |
| Br- | 180 |
| I- | 10 |
| It is total | 218100.6 |
The test effect of composite slow-corrosion scale resistor prepared by embodiment 1~6 and comparative example 1~5 is shown in Table 4.After the test,
The pH value of oil field mock water is detected, tests the pH value of 8~10 (comparative examples 2~4) between 2.5~4.0, (the contrast of experiment 7,11
Example 1 and comparative example 5-1) pH value between 7.0~8.0, experiment 13 (embodiments 1) pH value be 8.2, remaining experiment pH value
Between 5.5~6.5.
4 anticorrosion-antiscaling effect of table
| Test number | Composite slow-corrosion scale resistor source | Corrosion inhibition rate/% | Hinder calcium carbonate scale rate/% | Total phosphorus coefficient of stabilization/% |
| 1 | Embodiment 1 | 84.5 | 85.2 | 74.3 |
| 2 | Embodiment 2 | 86.2 | 83.4 | 76.1 |
| 3 | Embodiment 3 | 88.8 | 86.7 | 82.2 |
| 4 | Embodiment 4 | 78.0 | 89.8 | 75.4 |
| 5 | Embodiment 5 | 75.1 | 80.3 | 78.9 |
| 6 | Embodiment 6 | 66.5 | 82.1 | 80.4 |
| 7 | Comparative example 1 | -14.7 | 82.0 | - |
| 8 | Comparative example 2 | 40.6 | 86.3 | 86.4 |
| 9 | Comparative example 3 | 25.3 | 87.6 | 88.3 |
| 10 | Comparative example 4 | 30.2 | 92.3 | 80.2 |
| 11 | Comparative example 5-1 | -18.3 | 84.6 | - |
| 12 | Comparative example 5-2 | 71.7 | 80.0 | 43.0 |
| 13 | Embodiment 1 | 72.5 | 80.2 | 64.1 |
Claims (23)
1. a kind of composite slow-corrosion scale resistor, according to the mass fraction, including：5~15 parts of Phos, 7.5~17.5 parts of organic phospho acids,
1~10 part of amine, 4~10 parts of sulfur-containing polymer dirt dispersion agents and optional zinc salt.
2. composite slow-corrosion scale resistor described in accordance with the claim 1, it is characterised in that the Phos is selected from sodium phosphate, phosphoric acid
Sodium dihydrogen, disodium hydrogen phosphate, potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate,
At least one of phosphoric acid, sodium tripolyphosphate, potassium tripolyphosphate, calgon and hexa metaphosphoric acid potassium.
3. composite slow-corrosion scale resistor described in accordance with the claim 1, it is characterised in that the organic phospho acid is selected from hydroxy ethylidene
Di 2 ethylhexyl phosphonic acid, 2- hydroxyphosphonoacetic acid, 2- phosphonobutanes -1,2, at least one of 4- tricarboxylic acids and Polyol Phosphate.
4. composite slow-corrosion scale resistor described in accordance with the claim 1, it is characterised in that the amine is selected from hydroxyl and substitutes or non-take
The substituted or non-substituted saturation nitrogen oxa- ring of the substituted or non-substituted saturation nitrogen heterocyclic of fatty amine, the hydroxyl in generation, hydroxyl
At least one of compound and polyethylene polyamine.
5. according to the composite slow-corrosion scale resistor described in claim 4, it is characterised in that the amine be selected from monomethyl amine, dimethylamine,
Trimethylamine, monoethyl amine, diethylamine, triethylamine, ethylenediamine, a propylamine, di-n-propylamine, tripropyl amine (TPA), isopropylamine, diisopropylamine, 1,2-
Dimethyl propylamine, 1,2- propane diamine, 2- allylamines, cyclopropylamine, n-butylamine, di-n-butylamine, isobutyl amine, sec-butylamine, 1,4- fourths two
Amine, tert-butylamine, di-iso-butylmanice, hexylamine, 2 ethyl hexylamine, hexamethylene diamine, monoethanolamine, diethanol amine, triethanolamine, 3- propyl alcohol
Amine, monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, N, N methyldiethanol amine, N, N- diethyl ethylene diamines, Sanya second
Base diamines, diethylenetriamines, hexa, hexamethylene imine, triethylenediamine, cyclic ethylene imines, morpholine, piperazine
At least one of piperazine and cyclohexylamine.
6. composite slow-corrosion scale resistor described in accordance with the claim 1, it is characterised in that the sulfur-containing polymer dirt dispersion agent choosing
From bipolymer, maleic anhydride and the 2- acrylamido -2- first of acrylic acid and 2- acrylamido -2- methyl-propanesulfonic acids
The bipolymer of base-propane sulfonic acid, the bipolymer of acrylic acid and allyl polyethenoxy ether ammonium sulfate, maleic anhydride and alkene
Bipolymer, acrylic acid and the maleic anhydride and 2- acrylamido -2- the-the third sulphurs of methyl of propyl group polyoxyethylene ether ammonium sulfate
In terpolymer, acrylic acid and the maleic anhydride of acid and the terpolymer of allyl polyethenoxy ether ammonium sulfate at least
It is a kind of.
7. according to the composite slow-corrosion scale resistor described in claim 6, it is characterised in that the sulfur-containing polymer dirt dispersion agent choosing
From acrylic acid and bipolymer, maleic anhydride and the allyl polyethenoxy ether ammonium sulfate of allyl polyethenoxy ether ammonium sulfate
Bipolymer, acrylic acid and maleic anhydride and allyl polyethenoxy ether ammonium sulfate terpolymer at least one
Kind.
8. composite slow-corrosion scale resistor described in accordance with the claim 1, it is characterised in that the zinc salt is selected from zinc chloride, zinc nitrate
At least one of with zinc sulfate.
9. composite slow-corrosion scale resistor described in accordance with the claim 1, it is characterised in that according to the mass fraction, the compound slow corrosion
Antisludging agent contains 45.5~82.5 parts of water.
10. composite slow-corrosion scale resistor described in accordance with the claim 1, it is characterised in that the composite slow-corrosion scale resistor is by nothing
Machine phosphorus, organic phospho acid, sulfur-containing polymer dirt dispersion agent, optional zinc salt and water composition.
11. a kind of preparation method of composite slow-corrosion scale resistor, according to the mass fraction, by 5~15 parts of Phos, 7.5~17.5 parts
Organic phospho acid, 1~10 part of amine, 4~10 parts of sulfur-containing polymer dirt dispersion agents and optional zinc salt are mixed with water, up to described
Composite slow-corrosion scale resistor.
12. according to the preparation method described in claim 10, it is characterised in that according to the mass fraction, the dosage of water for 45.5~
82.5 parts.
13. according to the preparation method described in claim 11 or 12, it is characterised in that the dosage of zinc salt is 0~2 part.
14. a kind of corrosion-proofing and antisludging method of oil field water, before oil field water is injected stratum, claim 1 is added into oil field water
~10 any composite slow-corrosion scale resistors.
15. according to the corrosion-proofing and antisludging method described in claim 14, it is characterised in that the use environment of the oil field water, temperature
100 DEG C of ＞, partial pressure of oxygen >=0.05Mpa.
16. according to the corrosion-proofing and antisludging method described in claim 15, it is characterised in that the use environment of the oil field water, temperature
125~160 DEG C, 0.05~3.5Mpa of partial pressure of oxygen.
17. according to the corrosion-proofing and antisludging method described in claim 14, it is characterised in that the salinity of the oil field water is 100000
~300000mg/L.
18. according to the corrosion-proofing and antisludging method described in claim 14, it is characterised in that in terms of every liter of oil field water, compound slow corrosion resistance
The dosage of dirty agent is 450~550mg.
19. according to the corrosion-proofing and antisludging method described in claim 14, it is characterised in that before oil field water is injected stratum, with nothing
The pH value that machine acid and/or inorganic base adjust oil field water is 4.5~6.0.
20. a kind of oil production method, by the way of water and gas mixed water injection, it is characterised in that in the water, adding right will
Seek 1~10 any composite slow-corrosion scale resistor；In the gas, with volume fraction, oxygen content ＞ 2%.
21. in accordance with the method for claim 20, it is characterised in that in terms of every liter of water, the Phos of addition, organic phospho acid,
The total amount of amine, sulfur-containing polymer dirt dispersion agent and optional zinc salt is 70~300mg.
22. in accordance with the method for claim 20, it is characterised in that the salinity of the water is 100000~300000mg/
L。
23. in accordance with the method for claim 20, it is characterised in that water and gas mixed water injection are deep-well or ultradeep well.
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