CN107868157B - A kind of novel hydrates kinetic inhibitor and preparation method thereof - Google Patents

A kind of novel hydrates kinetic inhibitor and preparation method thereof Download PDF

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CN107868157B
CN107868157B CN201610861454.7A CN201610861454A CN107868157B CN 107868157 B CN107868157 B CN 107868157B CN 201610861454 A CN201610861454 A CN 201610861454A CN 107868157 B CN107868157 B CN 107868157B
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CN107868157A (en
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梁德青
张倩
史伶俐
龙臻
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Guangzhou Institute of Energy Conversion of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F126/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F126/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F126/10—N-Vinyl-pyrrolidone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
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    • 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
    • C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
    • 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 invention discloses a kind of structural formula hydrate dynamic inhibitors as shown in formula I, it is of the invention water-soluble fine, inhibitory activity is high, good inhibitory effect can be obtained, and dosage is few, cost reduces, with low dosage, efficiently, the advantages that applicability is wide, it can be under low dosage concentration (0.1~10wt%), effectively delay hydrate nucleation time in high supercooling degree environment, reduce hydrate generating rate, suitable for oil gas water three phase or grease or air water two-phase coexistent system, applied to oil-gas mining, inhibit the generation of hydrate in processing and transmission process, it is not restricted by degree of supercooling and application, prospect with wide application.Wherein R is * (CH2) m*, m=1~5；N=10~10000.

Description

A kind of novel hydrates kinetic inhibitor and preparation method thereof
Technical field:
The present invention relates to chemical technology fields, and in particular to a kind of novel hydrates kinetic inhibitor and its preparation side Method.
Background technique:
Gas hydrates are the solids like ice formed under high pressure, cryogenic conditions by water and natural gas.Hydrate Generation is exactly that oil & gas industry needs to avoid the problem that all the time, because of hydrate energy obstructed flow line, valve, well head and pipe Road etc. causes heavy losses to production.
The conventional method for preventing hydrate from generating has voltage drop method, temperature-raising method and except three kind of water law.Research and practice have shown that this Three kinds of methods have certain inhibitory effect, but since its is at high cost, application limitation is big, therefore physical method application range relatively has Limit is generally used to do the rescue method after auxiliary rejection condition and pipeline obstruction.Thermodynamic inhibitor includes methanol, ethyl alcohol, second The solubility such as glycol alcohols, inorganic salts etc. are also once widely used in oil & gas industry, but because its usage amount is big (in aqueous solution It is 20%~50% can just have ideal inhibitory effect that concentration, which will reach mass fraction), at high cost and pollution environment, just gradually by It eliminates.
The 1970s, the engineer Kuliev of Russia prevented the generation of hydrate by adding surfactant, This is the earliest record for preventing hydrate from generating by using low dosage hydrate inhibitor (LDHIs).Because it pollutes low suppression Effect processed is good, dosage is few (as long as concentration in aqueous solution, which reaches mass fraction, has ideal inhibition for 0.1%~1.0% Effect) to receive extensive attention.LDHIs has been increasingly becoming with development by continuous innovation and has been expected to replace the heating power such as ethyl alcohol Common inhibitor learning inhibitor, being widely used in oil gas field.In commercial field, LDHIs can be subdivided into dynamics suppression again Preparation (KHIs) and polymerization inhibitor (AAs).KHIs is usually dissolved in the high molecular polymer of water, it can postpone hydrate growth and Nucleation, to prevent it from blocking oil-gas pipeline.Although AAs cannot postpone the growth nucleation of hydrate, can be mutually mixed in oil It is adsorbed to the surface of hydrate particle together, is dispersed in suspension within hydrate crystal grain in condensation phase, prevents the aggregation of hydrate It is blocking, to guarantee the proper flow of oil-gas pipeline.The nucleation time of hydrate, which is also known as induction time, to be measured in practical application One important references factor of KHIs quality.The induction time length of hydrate depends on degree of supercooling: degree of supercooling is bigger, when induction Between it is shorter；Degree of supercooling is smaller, and induction time is longer.In addition, absolute pressure is also the key factor for influencing hydrate and generating.
Currently, cyclic lactames quasi polymer and hyperbranched polyester amide quasi polymer are oil gas field fields using more Kinetic inhibitor.These polymer are in Britain, and the South Sea, the Gulf of Mexico, South America, the area such as Middle East, which is all successfully used to, to prevent The generation of pipeline-like hydrate.Polyvinyl pyrrole network alkanone is a kind of cyclic lactames quasi polymer and a kind of more common Hydrate inhibitor.But due to it there are poorly water-soluble, inhibitory effect it is not ideal enough or even under conditions of compared with high supercooling degree The defects of (degree of supercooling is greater than 6 DEG C) loses inhibitory effect, so that its application range is restricted.This just promotes researcher not It is disconnected to explore, make every effort to develop good inhibitory effect, applied widely, high financial profit and environmental-friendly novel hydrates inhibition Agent.
Summary of the invention:
The object of the present invention is to provide a kind of novel hydrates kinetic inhibitor and preparation method thereof, which can be Under low dosage concentration (0.1~2wt%), in high supercooling degree environment, effectively delay the nucleation of hydrate, reduces hydrate and generate speed Rate has many advantages, such as that inhibitory effect is good, dosage is few, applicability is wide.
The present invention is achieved by the following technical programs:
A kind of structural formula hydrate dynamic inhibitor as shown in formula I, the hydrate dynamic inhibitor are carboxyl The poly N-vinyl pyrrole network alkanone of change is formed by mercaptan carboxylic acid and N- vinylpyridine network alkanone monomer polymerization；
Wherein R is * (CH2) m*, m=1~5；N=10~10000.
The volume ratio of the mercaptan carboxylic acid and N- vinylpyridine network alkanone monomer is 1:30~5:1.
Average molecular weight Mw=1000~1000000 of the hydrate dynamic inhibitor.
The mercaptan carboxylic acid is the mercaptan carboxylic acid of the C2~C6 such as thioacetic acid or 3- mercaptopropionic acid.
The preparation method of the hydrate dynamic inhibitor, comprising the following steps: weigh two isobutyl of chain initiator azo N- vinylpyridine network alkanone monomer, mercaptan carboxylic acid and N, N- dimethyl is successively slowly added dropwise in nitrile in reaction flask, under nitrogen atmosphere Formamide solvent is reacted 2~20 hours at a temperature of 60~140 DEG C in nitrogen atmosphere；After obtained head product is cooled to room temperature It recrystallized, filtered, dried, obtain target product；The initiator amount accounts for 0.5wt%~2wt% of solvent usage；Solvent Dosage is 1-20 times of N- vinylpyridine network alkanone monomer volume；The volume ratio of mercaptan carboxylic acid and N- vinylpyridine network alkanone monomer For 1:30~5:1.
The reagent of recrystallization is cold ethyl acetate.
The present invention also protects the application of the hydrate dynamic inhibitor, and the hydrate inhibitor is applied to oil gas water The generation of hydrate in three-phase system, grease or air water two-phase system, relative to the dense of water when the hydrate inhibitor uses Degree is 0.1wt%~20wt%, and being applicable in pressure is 1~25MPa, and temperature is -25~25 DEG C.
Concentration when the hydrate inhibitor use relative to water is preferably 0.1wt%~10wt%.
Beneficial effects of the present invention are as follows:
(1) present invention is used as kinetic inhibitor polymer, adds carboxyl on poly N-vinyl pyrrole network alkanone polymeric chain, Therefore the polymeric water-soluble is fine, has wide applicability, is suitable for oil gas water three phase or grease or air water two-phase coexistent System, applied to the generation for inhibiting hydrate in oil-gas mining, processing and transmission process.
(2) inhibitory activity of the present invention is high, and dosage is few, and cost reduces: because the lactam polymer of five-membered cyclic is inherently It is hydrate inhibitor, along with carboxyl is preferable hydrophilic radical, the oxygen atom on carboxyl can form hydrogen bond with hydrone, To prevent guest molecule to contact with hydrone, its inhibitory effect is further improved, the additional amount of such inhibitor is much Less than conventional heat inhibitor, run-of-the-mill concentration is about 0.1~10wt%, and reagent cost substantially reduces.
In short, the present invention is water-soluble very well, inhibitory activity is high, can obtain good inhibitory effect, and dosage is few, cost drop It is low, have many advantages, such as that low dosage, efficient, applicability is wide, can be under low dosage concentration (0.1~10wt%), high supercooling degree environment In effectively delay hydrate nucleation time, reduce hydrate generating rate, be suitable for oil gas water three phase or grease or air water two-phase System coexists, applied to the generation for inhibiting hydrate in oil-gas mining, processing and transmission process, not by degree of supercooling and application It restricts, the prospect with wide application.
Detailed description of the invention:
Fig. 1 is the carbon-13 nmr spectra figure of the product of embodiment 1；
Fig. 2 is the infrared spectrogram of the product of embodiment 1；
Fig. 3 is that reaction kettle hydration is added by mass concentration for 2.0wt% aqueous solution in the hydrate inhibitor that embodiment 1 obtains Time-temperature in object generating process, when m- pressure curve exemplary diagram；
Fig. 4 is the carbon-13 nmr spectra figure of the product of embodiment 2；
Fig. 5 is the FTIR spectrum figure of the product of embodiment 2.
Specific embodiment:
It is to further explanation of the invention, rather than limiting the invention below.
Embodiment 1: structural formula hydrate dynamic inhibitor as shown in formula II (abbreviation PVPSCH2COOH synthesis)
Wherein, the average value of n is 478.
Synthetic method is the following steps are included: weigh chain initiator azodiisobutyronitrile 352mg (2mmol) in 250mL eggplant shape Reaction flask vacuumizes after being sealed with rubber stopper-leads to nitrogen 3 times；N- vinylpyridine network alkanone monomer 20mL is successively slowly added dropwise (206mmol), thioacetic acid 0.56mL (about 5mmol) and n,N-Dimethylformamide solvent 100mL, with liquid nitrogen frozen-pumping- Ramp cycle 3 times；It is reacted 7 hours at a temperature of 80 DEG C in nitrogen atmosphere；Obtained head product is slowly dropped into after being cooled to room temperature After 1000mL cold ethyl acetate recrystallized, filtered, obtained solid is 48 hours dry under the conditions of 45 DEG C in a vacuum drying oven It is 1 hour dry under the conditions of 105 DEG C, obtain target product.Weight average molecular weight (Mw) is 53124,13CNMR spectrogram (D2O makees molten Agent) as shown in Figure 1, chemical shift δ be located at 13.32ppm, 17.60ppm, 20.67ppm, 31.18ppm, 32.74ppm, The carbon original positioned at 2,4,1,3,5,8,6,9,7 is respectively corresponded at 42.43ppm, 61.46ppm, 174.87ppm, 178.72ppm Sub- absorption peak shows that the substance of synthesis is PVPSCH2COOH.Infrared (FTIR) spectrogram of its Fourier is as shown in Fig. 2, FTIR is composed Wave number is~1680cm in figure-1It is C=O absorption peak, wave number is~1300cm-1It is-C-N absorption peak, wave number is~3500cm-1、 ~3000cm-1,~1680cm-1,~1250cm-1It is carboxyl characteristic absorption peak.The substance for further demonstrating that synthesis is PVPSCH2COOH.Its gel permeation chromatography (GPC) data is as shown in table 1:
Table 1
Embodiment 2: structural formula hydrate dynamic inhibitor (PVPSCH as shown in formula III2CH2COOH synthesis)
Wherein, the average value of n is 1665.
Synthetic method is the following steps are included: weigh chain initiator azodiisobutyronitrile 176mg (1mmol) in 100mL eggplant shape Reaction flask vacuumizes after being sealed with rubber stopper-leads to nitrogen 3 times；N- vinylpyridine network alkanone monomer 11mL, 3- is successively slowly added dropwise Mercaptopropionic acid 0.28mL (about 2.5mmol) and n,N-Dimethylformamide solvent 50mL, with liquid nitrogen frozen-pumping-ramp cycle 3 It is secondary；It is reacted 12 hours at a temperature of 80 DEG C in nitrogen atmosphere；Obtained head product is slowly dropped into the cold second of 400mL after being cooled to room temperature Then at 105 DEG C of items after acetoacetic ester recrystallized, filtered, obtained solid is 48 hours dry under the conditions of 45 DEG C in a vacuum drying oven It is 1 hour dry under part, obtain target product.Weight average molecular weight (Mw) is 184908,13CNMR spectrogram (D2O makees solvent) such as Fig. 4 institute Show, Fourier is infrared, and (FTIR) spectrogram is as shown in Figure 5.
Embodiment 3: inhibitory effect evaluation
The method of inhibitory effect evaluation of the present invention is as follows:
Experimental facilities is visualization high-pressure stirring experimental rig, which includes sapphire highpressure reaction Kettle, magnetic stirring apparatus, Cryogenic air bath, temperature and pressure transmitter, vacuum pump, camera, high pressure gas cylinder and data collecting instrument etc.. The sapphire highpressure reaction kettle maximum working pressure 11MPa, operating temperature range -30~80 DEG C.The sapphire highpressure is anti- Answer pressure in kettle kettle that can freely adjust by air valve.Cryogenic air bath can provide -30~80 for sapphire highpressure reacting kettle jacketing DEG C steady temperature.Data collection system acquires and stores in real time the parameters such as pressure, temperature and revolving speed in reaction kettle kettle.Hydrate Temperature or pressure change of the formation when can pass through reaction carry out judgement or camera is directly observed.After reaction starts, in kettle It is the starting point that hydrate generates that point drops in the point that pressure drop, that is, pressure downward trend deviates original trend, corresponding to this point Temperature is the minimum temperature that solution can bear.Constant stirring rate is opened when sapphire highpressure reactor temperature is constant Beginning is passed through methane gas object, closes intake valve when reacting kettle inner pressure is setting value.Then, with constant rate of temperature fall When (such as 1 DEG C/h) makes the temperature in reaction kettle drop to the pressure below the generation temperature of hydrate.Solution can bear most Low temperature thus during hydrate generation temperature.The function and effect of new inhibitor can be according to being added to the molten of the inhibitor Minimum temperature that liquid can bear quantifies.The generation temperature of hydrate is lower, and inhibitory effect is better.
Specific implementation process:
It before experiment operation, is first cleaned repeatedly with deionized water reaction kettle three to five times, then purges reaction kettle and reality with nitrogen Test pipe-line system, it is ensured that system is dry.Reaction kettle is vacuumized, the hydrate of the deionized water or preparation that suck 12.0mL inhibits Agent solution is first passed through the methane gas of 1MPa purity 99.99%, then vacuumizes again to exclude air in kettle, and repeatedly 3 Secondary, constant stirring rate 800rpm starts to be passed through methane gas object, directly when sapphire highpressure reactor temperature is 20 DEG C To reacting kettle inner pressure it is constant be 8.0MPa when close intake valve.Then, the temperature in reaction kettle is made with the rate of temperature fall of 1 DEG C/h - 10 DEG C are dropped to from 20 DEG C.Camera observation and temperature, pressure change curve method are used simultaneously, judge whether hydrate gives birth to At.
Pure water is added in reaction kettle and is tested, the results showed that, the generation temperature of the hydrate under the system is 7.5 ℃。
It is 3.6 × 10 by weight average molecular weight5, mass concentration is respectively 0.1%, 1%, 2% poly N-vinyl pyrrole network alkane Ketone (abbreviation PVP K90) aqueous solution is added in reaction kettle and is tested, and the results are shown in Table 2.
Hydrate dynamic inhibitor (the abbreviation PVPSCH that the weight average molecular weight that embodiment 1 is obtained is 531242COOH) Aqueous solution is respectively to be tested in 0.1%, 1%, 2% addition reaction kettle by mass concentration, and the results are shown in Table 2.
The hydrate dynamic inhibitor that the weight average molecular weight that embodiment 2 is obtained is 184908 is (referred to as PVPSCH2CH2COOH) aqueous solution is respectively to be tested in 0.1%, 1%, 2% addition reaction kettle by mass concentration, as a result such as Shown in table 2.
Table 2
As shown in Table 1, the present invention can use in high supercooling degree environment, can have under low dosage concentration (0.1~10wt%) Effect delays hydrate nucleation time, reduces hydrate generating rate, have many advantages, such as low dosage, efficiently, applicability it is wide, with compared with Good inhibitory effect.

Claims (3)

1. a kind of application of structural formula hydrate dynamic inhibitor as shown in formula I, which is characterized in that the hydrate inhibits Generation of the agent applied to hydrate in oil gas water three phase system, grease or air water two-phase system, the hydrate inhibitor use When relative to water concentration be 0.1wt%~20wt%, be applicable in pressure be 1~25MPa, temperature be -25~25 DEG C；The hydration Object kinetic inhibitor is the poly N-vinyl pyrrole network alkanone of carboxylated, is gathered by mercaptan carboxylic acid and N- vinylpyridine network alkanone monomer It closes；
Wherein R is * (CH2) m*, m=1~5；N=10~10000.
2. the application of hydrate dynamic inhibitor according to claim 1, which is characterized in that the mercaptan carboxylic acid and N- The volume ratio of vinylpyridine network alkanone monomer is 1:30~5:1.
3. the application of hydrate dynamic inhibitor according to claim 1, which is characterized in that the hydrate inhibitor When use relative to the concentration of water be 0.1wt%~10wt%.
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