CN109054790A - A kind of hydrate inhibitor and the preparation method and application thereof - Google Patents
A kind of hydrate inhibitor and the preparation method and application thereof Download PDFInfo
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- CN109054790A CN109054790A CN201811011764.5A CN201811011764A CN109054790A CN 109054790 A CN109054790 A CN 109054790A CN 201811011764 A CN201811011764 A CN 201811011764A CN 109054790 A CN109054790 A CN 109054790A
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- hydrate inhibitor
- terpolymer
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- hydrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
- F17D1/17—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity by mixing with another liquid, i.e. diluting
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/22—Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers
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Abstract
The present invention provides a kind of hydrate inhibitor, by forming following weight percentage components: terpolymer 10-50%, ethers cosolvent 45-85%, dispersing agent 1-30%；Wherein, the terpolymer is vinyl pyrrolidone, caprolactam, isopropyl alkene-Methacrylamide terpolymer；The dispersing agent is at least one of methylcellulose, sodium carboxymethylcellulose, hydroxyethyl cellulose.Meanwhile also providing the preparation method and application of the hydrate inhibitor.Hydrate inhibitor provided by the invention, can be used to inhibiting gas-field exploitation, processing, in transmission process gas hydrates generation, inhibitory effect is obvious, usage amount is few, small to environmental hazard.
Description
Technical field
The invention belongs to oil gas field technical fields, and in particular to a kind of hydrate inhibitor and the preparation method and application thereof.
Background technique
The components such as methane, ethane, carbon dioxide in natural gas act on water under cryogenic high pressure and generate consolidating for ice crystal shape
State hydrate after coalescing, can reduce the circulation area of pipeline, generate throttling, and further speed up the generation of hydrate, from
And block pipeline and equipment in gas-field exploitation, natural gas processing and transmission process, seriously affect gas extraction, conveying and
The safe operation of processing.Therefore, inhibitor is added, forms water in exploitation, processing, transportational process to avoid with prevention natural gas
It is most important to close object blocking pit shaft, processing unit and gas transmission line.
The conventional method for inhibiting gas hydrates to be formed is injection thermodynamic inhibitor, such as electrolyte, methanol, ethylene glycol
Equal substances, avoid and inhibit the formation of hydrate by changing the thermodynamic condition that hydrate generates.But thermodynamics inhibits
Agent has the shortcomings that using concentration high (mass fraction usually account for water phase 20%~60%), consumption is big, at high cost, toxicity is big.With
This is compared, and kinetic inhibitor becomes the hot spot studied both at home and abroad because of the advantages that additive amount is few, at low cost, small toxicity.It
Right aerodynamics inhibitor is by extending the nucleation time of gas hydrates or the growth of gas hydrates being inhibited to reach
Inhibit purpose.The study found that the inhibitory effect of existing single type low dosage kinetic inhibitor is limited, it is not able to satisfy reality
It needs, thus, the rejection of addition auxiliary agent dynamics of contrast enhancement inhibitor becomes focus of attention again.
Summary of the invention
In view of the drawbacks of the prior art, the present invention provides a kind of hydrate inhibitor and preparation method thereof, the hydrate
Inhibitor can effectively inhibit gas-field exploitation, in transmission process gas hydrates generation, inhibit the time long.
A kind of hydrate inhibitor, by forming following weight percentage components: terpolymer 10-50%, ethers hydrotropy
Agent 45-85%, dispersing agent 1-30%；
Wherein, the terpolymer is vinyl pyrrolidone, caprolactam, isopropyl alkene-Methacrylamide system
Standby terpolymer；
The dispersing agent is at least one of methylcellulose, sodium carboxymethylcellulose, hydroxyethyl cellulose.
Preferably, the average molecular weight of the terpolymer is 10000-18000g/mol.
Preferably, the ethers cosolvent is propylene glycol monomethyl ether, propylene-glycol ethyl ether, any one in propandiol butyl ether.
The preparation method of above-mentioned hydrate inhibitor, the method are as follows:
(1) terpolymer is prepared；
(2) then terpolymer, ethers cosolvent, dispersant are stirred.
Preferably, the method that terpolymer is prepared in step (1) is specific as follows: according to molar ratio (1-25): (1-85):
(1-10) adds vinyl pyrrolidone, caprolactam, isopropyl alkene-three kinds of Methacrylamide monomer and initiator
Enter into alcohols solvent, is passed through N2After deoxygenation, it is stirred to react 5-16h at 40-85 DEG C, after being cooled to room temperature, in 40-50 DEG C of baking
2-3h is stood in case, is filtered, and filter residue is washed with water 3 times, is dried in a vacuum drying oven to constant weight；Wherein, described three kinds
The total volume of monomer and the volume ratio of alcohols solvent are 1:(3-5)；The gross mass of three kinds of monomers and the mass ratio of initiator
For 1:(3-5).
Preferably, the alcohols solvent is acetone, methanol, ethyl alcohol, propyl alcohol, n-butanol, at least two in the tert-butyl alcohol.
Preferably, the initiator is hydrogen peroxide, sodium peroxydisulfate, potassium peroxydisulfate or azo-bis-iso-dimethyl.
The hydrate inhibitor is added in Produced Water In Oil-gas Fields, Ngi by the application of above-mentioned hydrate inhibitor, for pressing down
The generation of hydrate processed, the application specifically: by the hydrate inhibitor according to mass concentration at 7.0MPa, 2-4 DEG C
0.1%~1% is added in Produced Water In Oil-gas Fields, Ngi.
Advantages of the present invention:
Hydrate inhibitor provided by the invention, terpolymer therein is as kinetic inhibitor, and ethers cosolvent is not only
The dissolubility of hydrate inhibitor can be enhanced, while also having the function of thermodynamics inhibition, inhibitory effect can be enhanced, and it is current
Most low molecular weight thermodynamic inhibitors are compared, and toxicity is smaller；The hydrate that dispersing agent can be formed effectively in dispersion phase
Particle makes it keep flow regime, and then prevents Hydrate Plugging, collaboration enhancing inhibitory effect.Can be used to inhibiting gas-field exploitation,
The generation of gas hydrates in processing, transmission process, inhibitory effect is obvious, usage amount is few, small to environmental hazard.
Specific embodiment
The evaluation method of inhibitory effect:
Firstly, reaction kettle wash with distilled water, and cleaning solution is discharged.Then, a certain amount of experimental water is pumped into adopt for oil gas field
It is discharged (salinity 52163mg/L), and takes the air in reaction kettle away with vacuum pump；Reaction condition: 3 DEG C of temperature, pressure 7
MPa, being passed through group becomes methane 94.83%, ethane 0.59%, propane 0.11%, N21.90%、CO22.57% experiment gas, will be in kettle
Pressure is adjusted to 7 MPa of experimental pressure, and 1000r/min is stirred to react, and stops experiment after reacting kettle inner pressure mutation, according to
Reacting kettle inner pressure variation and combination temperature situation judge hydrate formation, evaluation inhibitor effect.
Embodiment 1
1. a kind of hydrate inhibitor, by forming following weight percentage components: terpolymer 10%, ethers cosolvent
85%, dispersing agent 5%；
Wherein, the dispersing agent is methylcellulose；The ethers cosolvent is propylene glycol monomethyl ether；
The terpolymer is vinyl pyrrolidone, caprolactam, isopropyl alkene-Methacrylamide ternary are total
Polymers, average molecular weight 10000-18000g/mol；
2. the preparation method of the hydrate inhibitor:
(1) terpolymer is prepared: according to molar ratio 1:1:1 by vinyl pyrrolidone, caprolactam, isopropyl alkene-
Three kinds of monomers of Methacrylamide and initiator are added in alcohols solvent, are passed through N2After deoxygenation, it is stirred to react 5h at 85 DEG C, it is cold
But to after room temperature, 3h is stood in 40 DEG C of baking oven, is filtered, and filter residue is washed with water 3 times, is dried in a vacuum drying oven to perseverance
Weight, obtains vinyl pyrrolidone, caprolactam, isopropyl alkene-Methacrylamide terpolymer；Wherein,
The alcohols solvent is the mixed liquor of acetone and methanol；The initiator is hydrogen peroxide；The total volume of three kinds of monomers with
The volume ratio of alcohols solvent is 1:3；The gross mass of three kinds of monomers and the mass ratio of initiator are 1:3；
(2) by terpolymer, ethers cosolvent, dispersant, stirring.
3. above-mentioned inhibitor, which is configured to the gas field that mass concentration is 0.1%, produces aqueous solution, it is packed into reaction kettle, is being tested
Pressure is 7.0MPa, and experimental temperature starts to be tested under the conditions of being 3 DEG C, and the inhibition time for measuring gas hydrates generation is
4380min。
Embodiment 2
1. a kind of hydrate inhibitor, by forming following weight percentage components: terpolymer 50%, ethers cosolvent
49%, dispersing agent 1%；
Wherein, the dispersing agent is sodium carboxymethylcellulose；The ethers cosolvent is propylene-glycol ethyl ether；
The terpolymer is vinyl pyrrolidone, caprolactam, isopropyl alkene-Methacrylamide preparation three
Membered copolymer, average molecular weight 10000-18000g/mol；
2. the preparation method of the hydrate inhibitor:
(1) terpolymer is prepared: according to molar ratio 1:85:10 by vinyl pyrrolidone, caprolactam, isopropyl
Three kinds of monomers of alkene-Methacrylamide and initiator are added in alcohols solvent, are passed through N2After deoxygenation, it is stirred to react at 40 DEG C
16h after being cooled to room temperature, stands 2h in 50 DEG C of baking oven, and filtering, filter residue is washed with water 3 times, dries in a vacuum drying oven
To constant weight, vinyl pyrrolidone, caprolactam, isopropyl alkene-Methacrylamide terpolymer are obtained；Its
In, the alcohols solvent is the mixed liquor of propyl alcohol, n-butanol；The initiator is potassium peroxydisulfate；The totality of three kinds of monomers
The long-pending volume ratio with alcohols solvent is 1:4；The gross mass of three kinds of monomers and the mass ratio of initiator are 1:4；
(2) by terpolymer, ethers cosolvent, dispersant, stirring.
3. above-mentioned inhibitor, which is configured to the gas field that mass concentration is 1%, produces aqueous solution, it is packed into reaction kettle, is pressed in experiment
Power is 7.0MPa, and experimental temperature starts to be tested under the conditions of being 3 DEG C, and the inhibition time for measuring gas hydrates generation is
4250min。
Embodiment 3
1. a kind of hydrate inhibitor, by forming following weight percentage components: terpolymer 15%, ethers cosolvent
55%, dispersing agent 30%；
Wherein, the dispersing agent is hydroxyethyl cellulose；The ethers cosolvent is propandiol butyl ether；
The terpolymer is vinyl pyrrolidone, caprolactam, isopropyl alkene-Methacrylamide preparation three
Membered copolymer, average molecular weight 10000-18000g/mol；
2. the preparation method of the hydrate inhibitor:
(1) terpolymer is prepared: according to molar ratio 25:85:10 by vinyl pyrrolidone, caprolactam, isopropyl
Three kinds of monomers of alkene-Methacrylamide and initiator are added in alcohols solvent, are passed through N2After deoxygenation, it is stirred to react at 85 DEG C
5h after being cooled to room temperature, stands 3h in 40 DEG C of baking oven, and filtering, filter residue is washed with water 3 times, dries in a vacuum drying oven
To constant weight, vinyl pyrrolidone, caprolactam, isopropyl alkene-Methacrylamide terpolymer are obtained；Its
In, the alcohols solvent is the mixed liquor of acetone and methanol；The initiator is hydrogen peroxide；The total volume of three kinds of monomers
Volume ratio with alcohols solvent is 1:5；The gross mass of three kinds of monomers and the mass ratio of initiator are 1:5；
(2) by terpolymer, ethers cosolvent, dispersant, stirring.
3. above-mentioned inhibitor, which is configured to the gas field that mass concentration is 0.5%, produces aqueous solution, it is packed into reaction kettle, is being tested
Pressure is 7.0MPa, and experimental temperature starts to be tested under the conditions of being 3 DEG C, and the inhibition time for measuring gas hydrates generation is
4580min。
Embodiment 4
1. a kind of hydrate inhibitor, by forming following weight percentage components: terpolymer 20%, ethers cosolvent
55%, dispersing agent 25%；
Wherein, the dispersing agent is the mixture of methylcellulose, sodium carboxymethylcellulose, hydroxyethyl cellulose；The ethers
Cosolvent is propandiol butyl ether；
The terpolymer is the same as embodiment 1.
2. the preparation method is the same as that of Example 1 for the hydrate inhibitor.
3. above-mentioned inhibitor, which is configured to the gas field that mass concentration is 0.3%, produces aqueous solution, it is packed into reaction kettle, is being tested
Pressure is 7.0MPa, and experimental temperature starts to be tested under the conditions of being 3 DEG C, and the inhibition time for measuring gas hydrates generation is
4680min。
Embodiment 5
1. a kind of hydrate inhibitor, by forming following weight percentage components: terpolymer 15%, ethers cosolvent
70%, dispersing agent 15%；
Wherein, the dispersing agent is the mixture of methylcellulose, sodium carboxymethylcellulose, hydroxyethyl cellulose；The ethers
Cosolvent is propandiol butyl ether；
The terpolymer is the same as embodiment 2.
2. the preparation method of the hydrate inhibitor is the same as embodiment 2.
3. above-mentioned inhibitor, which is configured to the gas field that mass concentration is 0.3%, produces aqueous solution, it is packed into reaction kettle, is being tested
Pressure is 7.0MPa, and experimental temperature starts to be tested under the conditions of being 3 DEG C, and the inhibition time for measuring gas hydrates generation is
4720min。
By in embodiment 1-5, remove dispersing agent in ingredient respectively, be correspondingly arranged comparative example 1-5, evaluates its inhibition
Can, it is as a result as follows:
Comparative example 1:2450min.
Comparative example 2:2280min.
Comparative example 3:2540min.
Comparative example 4:2550min.
Comparative example 5:2590min.
Meanwhile blank group as a comparison case 6 is set, thermodynamic inhibitor methanol is comparative example 7 and PVP is comparative example
8, as follows respectively:
Comparative example 6
The gas field recovered water that salinity is 52163mg/L is packed into reaction kettle, is 7.0MPa, experimental temperature 3 in experimental pressure
Start to be tested under the conditions of DEG C, is 40min using the generation time that the above method measures gas hydrates.
Comparative example 7
Methanol is configured to the gas field that mass concentration is 40% and produces aqueous solution, is packed into reaction kettle, is 7.0MPa in experimental pressure,
Experimental temperature starts to be tested under the conditions of being 3 DEG C, and the inhibition time for measuring gas hydrates generation is 160min.
Comparative example 8
PVP is configured to the gas field that mass concentration is 2% and produces aqueous solution, is packed into reaction kettle, is 7.0MPa in experimental pressure, it is real
It tests under the conditions of temperature is 3 DEG C and starts to be tested, the inhibition time for measuring gas hydrates generation is 210min.
Claims (8)
1. a kind of hydrate inhibitor, it is characterised in that: by forming following weight percentage components: terpolymer 10-
50%, ethers cosolvent 45-85%, dispersing agent 1-30%；
Wherein, the terpolymer is vinyl pyrrolidone, caprolactam, isopropyl alkene-Methacrylamide
Terpolymer；
The dispersing agent is at least one of methylcellulose, sodium carboxymethylcellulose, hydroxyethyl cellulose.
2. hydrate inhibitor according to claim 1, it is characterised in that: the average molecular weight of the terpolymer is
10000-18000g/mol。
3. hydrate inhibitor according to claim 1, it is characterised in that: the ethers cosolvent is propylene glycol monomethyl ether, third
Any one in glycol ether, propandiol butyl ether.
4. the preparation method of hydrate inhibitor described in claim 1, it is characterised in that: the method are as follows:
(1) terpolymer is prepared；
(2) then terpolymer, ethers cosolvent, dispersant are stirred.
5. the preparation method of hydrate inhibitor according to claim 4, it is characterised in that: preparation ternary is total in step (1)
The method of polymers is specific as follows: according to molar ratio (1-25): (1-85): (1-10) is by vinyl pyrrolidone, vinyl in oneself
Amide, isopropyl alkene-three kinds of Methacrylamide monomer and initiator are added in alcohols solvent, are passed through N2After deoxygenation, in 40-
85 DEG C are stirred to react 5-16h, and after being cooled to room temperature, 2-3h is stood in 40-50 DEG C of baking oven, and filtering, filter residue is washed with water 3
It is secondary, it is dried in a vacuum drying oven to constant weight；Wherein, the volume ratio of the total volume of three kinds of monomers and alcohols solvent
For 1:(3-5)；The gross mass of three kinds of monomers and the mass ratio of initiator are 1:(3-5).
6. the preparation method of the hydrate inhibitor according to claim 5, it is characterised in that: the alcohols solvent is third
Ketone, methanol, ethyl alcohol, propyl alcohol, n-butanol, at least two in the tert-butyl alcohol.
7. the preparation method of the hydrate inhibitor according to claim 5, it is characterised in that: the initiator is peroxide
Change hydrogen, sodium peroxydisulfate, potassium peroxydisulfate or azo-bis-iso-dimethyl.
8. the application of hydrate inhibitor described in claim 1, it is characterised in that: the application are as follows: at 7.0MPa, 2-4 DEG C
The hydrate inhibitor is added in Produced Water In Oil-gas Fields, Ngi according to mass concentration 0.1%~1%.
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Cited By (5)
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|---|---|---|---|---|
| CN113214811A (en) * | 2021-04-09 | 2021-08-06 | 华南理工大学 | Efficient natural gas hydrate low-dose compound inhibitor and application thereof |
| CN113817443A (en) * | 2020-06-18 | 2021-12-21 | 中国石油化工股份有限公司 | Hydrate decomposition inhibiting composition, coupling enhanced solid hydrate and method for enhancing storage and transportation stability of solid hydrate |
| CN114230716A (en) * | 2021-12-30 | 2022-03-25 | 清华大学深圳国际研究生院 | Preparation method and application of terpolymer |
| CN114316136A (en) * | 2022-01-13 | 2022-04-12 | 西华师范大学 | Hydrogen bond enhanced hydrate inhibitor and preparation method thereof |
| CN116396429A (en) * | 2023-04-14 | 2023-07-07 | 西南石油大学 | A kind of natural gas hydrate kinetic inhibitor and its preparation method |
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| CN114316136A (en) * | 2022-01-13 | 2022-04-12 | 西华师范大学 | Hydrogen bond enhanced hydrate inhibitor and preparation method thereof |
| CN114316136B (en) * | 2022-01-13 | 2023-01-31 | 西华师范大学 | A kind of hydrogen bond enhanced hydrate inhibitor and preparation method thereof |
| CN116396429A (en) * | 2023-04-14 | 2023-07-07 | 西南石油大学 | A kind of natural gas hydrate kinetic inhibitor and its preparation method |
| CN116396429B (en) * | 2023-04-14 | 2023-10-13 | 西南石油大学 | A kind of natural gas hydrate kinetic inhibitor and preparation method thereof |
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