CN114806528B - Low-dosage PKO-containing compound double-effect hydrate inhibitor and preparation method and application thereof - Google Patents

Low-dosage PKO-containing compound double-effect hydrate inhibitor and preparation method and application thereof Download PDF

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CN114806528B
CN114806528B CN202210515041.9A CN202210515041A CN114806528B CN 114806528 B CN114806528 B CN 114806528B CN 202210515041 A CN202210515041 A CN 202210515041A CN 114806528 B CN114806528 B CN 114806528B
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王志远
裴继昊
孙宝江
孙金声
钟杰
童仕坤
李鹏飞
张剑波
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China University of Petroleum East China
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
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    • C09K2208/22—Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers

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Abstract

The invention relates to the technical field of natural gas hydrates, in particular to a compound double-effect hydrate inhibitor containing low-dose PKO, and a preparation method and application thereof. The preparation raw materials of the compound double-effect hydrate inhibitor containing low-dose PKO comprise ethylene glycol (MEG), PKO auxiliary agent and CDEA solvent, wherein the mass ratio of the ethylene glycol to the PKO auxiliary agent to the CDEA solvent is (10-30): 0.05 to 0.1:2.5 to 5. After the common MEG is compounded with the low-dose PKO, the inhibition performance of the MEG can be obviously improved, so that the thermodynamic inhibition effect of the traditional MEG is exerted, and the polymerization inhibition effect of the PKO is also exerted; meanwhile, after compounding, the injection concentration of MEG is greatly reduced (the maximum injection concentration can be reduced by 50-60%), and the inhibitor cost is reduced.

Description

Low-dosage PKO-containing compound double-effect hydrate inhibitor and preparation method and application thereof
Technical Field
The invention relates to the technical field of natural gas hydrates, in particular to a compound double-effect hydrate inhibitor containing low-dose PKO, and a preparation method and application thereof.
Background
In the exploitation process of natural gas hydrate in sea area, a low-temperature high-pressure environment exists near a submarine mud line, the supercooling degree can reach 10-15 ℃ at the highest, and hydrate decomposed gas and water are easy to regenerate hydrate in the exploitation pipeline under the condition. Once the secondary hydrate is formed, the yield is reduced by light weight, and serious production accidents are caused by heavy weight. At present, the hydrate test exploitation usually adopts a thermodynamic inhibitor to prevent the risk of secondary hydrate, but the method has the defects of high inhibitor dosage (generally more than 50 weight percent), high cost and harm to the environment caused by partial chemical agents.
Numerous studies have shown that low doses of hydrate inhibitors can achieve inhibition at low concentrations (0.1 to 2.0 wt.%) including kinetic inhibitors (KHI) and inhibitors (AAs). The KHI has low dosage, but is easy to lose efficacy under the condition of high supercooling degree (more than 10 ℃), and cannot meet the environmental requirement of high supercooling degree in the sea area hydrate exploitation process. AAs are generally polymers or surfactants that allow hydrate formation, prevent hydrate aggregation, and allow it to form a stable hydrate slurry. Most AAs need to be used in oil-water emulsion, and cannot meet the conditions of a high-water system in a hydrate production pipeline; and AAs are used as a surfactant, have the effect of promoting the generation of hydrate, and are not ideal in control effect when being independently applied to the hydrate.
Therefore, how to provide a hydrate inhibitor with high efficiency, low cost, low toxicity, easy preparation and easy recovery is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a compound double-effect hydrate inhibitor containing low-dose PKO, and a preparation method and application thereof, so as to solve the problem that the existing hydrate inhibitor cannot meet the flow guarantee under the sea natural gas hydrate exploitation condition (high supercooling degree and high water content). The compound inhibitor has the effect of a traditional thermodynamic inhibitor, and can change the phase balance condition of the hydrate, so that the generation condition of the hydrate moves to a low-temperature high-pressure area; meanwhile, the polymerization inhibitor has the effect of enabling the generated hydrate particles to form hydrate slurry and flow in the pipeline along with the fluid without agglomerating or depositing on the pipe wall. Meanwhile, the compound inhibitor has the advantages of high efficiency, low cost, low toxicity, easy preparation, easy recovery and the like.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a low-dose PKO-containing compound double-effect hydrate inhibitor, which comprises the following raw materials of ethylene glycol, PKO auxiliary agent and CDEA solvent in a mass ratio of 10-30: 0.05 to 0.1:2.5 to 5.
Preferably, the PKO aid is cocamidopropyldimethylamine with a molecular formula of C 17 H 20 N 4 O 2 The structural formula is as follows:
Figure BDA0003641129940000021
preferably, the CDEA solvent is coconut diethanolamide with the formula RCON (CH 2 CH 2 OH) 2 Wherein R is cocoyl.
The invention also provides a preparation method of the compound double-effect hydrate inhibitor containing low-dose PKO, which comprises the following steps: and mixing ethylene glycol, PKO auxiliary agent and CDEA solvent to obtain the compound double-effect hydrate inhibitor containing low-dose PKO.
Preferably, the mixing is performed by mixing the PKO aid and the CDEA solvent and then mixing with ethylene glycol.
The invention also provides application of the low-dose PKO-containing compound double-effect hydrate inhibitor, wherein the low-dose PKO-containing compound double-effect hydrate inhibitor is mixed with water for use, and the mass ratio of the low-dose PKO-containing compound double-effect hydrate inhibitor to the water is 1:1.8 to 6.
The technical principle of the invention is as follows: the traditional thermodynamic inhibitor is used as a main agent, a PKO polymerization inhibitor capable of playing an anti-polymerization role under the condition of high water content is used as an auxiliary agent, and Coconut Diethanolamide (CDEA) which is easy to dissolve in water and low in cost is used as a solvent of PKO to form the compound hydrate inhibitor with synergistic interaction among all components.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) High performance: the compound double-effect hydrate inhibitor can play a role in inhibiting hydrate in a severe environment with high supercooling degree and high water content (up to 100 percent) in the exploitation process of natural gas hydrate in sea areas, and has double-effect inhibition performance of a thermodynamic inhibitor and a polymerization inhibitor;
(2) The cost is low: the application concentration of the traditional thermodynamic inhibitor in the conventional deep water oil gas development can reach 60%, and aiming at the working condition of sea natural gas hydrate exploitation, the mud line accessory pressure is higher, the temperature is lower, the consumption of the thermodynamic inhibitor is also increased, and the consumption of MEG can be reduced by about 50-60% by adding a small amount of PKO dissolved in CDEA solvent in MEG, so that the inhibitor cost is greatly reduced;
(3) Low toxicity: the MEG is the simplest dihydric alcohol, is commonly used as an antifreezing agent or a raw material for synthesizing terylene, and is currently becoming the most commonly used thermodynamic inhibitor; PKO and CDEA are used as nonionic surfactants and are prepared from coconut oil serving as raw materials, and the nonionic surfactants and the coconut oil are widely applied to daily chemical industry, textile industry and other industries, so that the raw materials of the hydrate inhibitor have low toxicity;
(4) Easy preparation: the invention innovatively adopts CDEA as a solvent, and utilizes the similar principle of miscibility to dissolve solid PKO which is difficult to dissolve in water; meanwhile, the solvent and MEG are easy to dissolve in water, so that three medicaments are easily compounded by a conventional mixing means to form the high-efficiency hydrate inhibitor.
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FIG. 1 is a flow chart of a test of a dual effect hydrate inhibitor of the present invention.
Detailed Description
The invention provides a low-dose PKO-containing compound double-effect hydrate inhibitor, which comprises the following raw materials of ethylene glycol, PKO auxiliary agent and CDEA solvent in a mass ratio of 10-30: 0.05 to 0.1:2.5 to 5, preferably 24 to 30:0.05 to 0.1:2.5 to 5.
In the invention, the PKO auxiliary agent is cocamidopropyldimethylamine with a molecular formula of C 17 H 20 N 4 O 2 The structural formula is as follows:
Figure BDA0003641129940000041
in the invention, the CDEA solvent is coconut diethanolamide with a molecular formula of RCON (CH) 2 CH 2 OH) 2 Wherein R is cocoyl.
The invention also provides a preparation method of the compound double-effect hydrate inhibitor containing low-dose PKO, which comprises the following steps: and mixing ethylene glycol, PKO auxiliary agent and CDEA solvent to obtain the compound double-effect hydrate inhibitor containing low-dose PKO.
In the invention, the mixing is mixing the PKO auxiliary agent and the CDEA solvent and then mixing the PKO auxiliary agent and the CDEA solvent with the ethylene glycol, preferably mixing the PKO auxiliary agent and the CDEA solvent, stirring to completely dissolve the PKO auxiliary agent, and then adding the ethylene glycol and uniformly mixing.
The invention also provides application of the low-dose PKO-containing compound double-effect hydrate inhibitor, wherein the low-dose PKO-containing compound double-effect hydrate inhibitor is mixed with water for use, and the mass ratio of the low-dose PKO-containing compound double-effect hydrate inhibitor to the water is 1:1.8 to 6, preferably 1:1.8 to 2.2.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention. The equipment and instrumentation used in the present invention are conventional products in the art, unless specifically indicated.
Test method
The performance of the compound double-effect hydrate inhibitor is evaluated by adopting a high-pressure flow loop, wherein the high-pressure flow loop comprises an air injection module, an experiment module and a data acquisition module. The experimental module comprises a constant-temperature water bath tank and a full-transparent PVC pipe, wherein the constant-temperature environment of 0-20 ℃ can be maintained in the water bath through a refrigerating system, the inner diameter of the full-transparent PVC pipe is 12mm, the pressure can be bearing 0-10 MPa, and the full-transparent PVC pipe is an experimental pipe section for forming hydrate by gas and water contact and flowing; the data acquisition module consists of a temperature sensor multiplied by 2, a pressure sensor multiplied by 2, a gas flowmeter, an acquisition system and a DV camera, wherein the two temperature and pressure sensors are respectively connected to the inlet and outlet positions of the full-transparent PVC pipe; the liquid injection module comprises a container for containing inhibitor solution, the inhibitor solution enters the fully transparent PVC pipe through the plunger pump and the liquid inlet valve, and the inhibitor solution is stirred by the magnetic stirrer in the whole course in the experimental process; the gas injection module comprises a high-pressure gas source, and the gas enters the pipeline through a pressure stabilizing valve and a gas flowmeter, and the pressure stabilizing valve is used for stably controlling the pressure in the experimental pipeline section. The hydrate generation and pipeline blockage processes can be judged by temperature, pressure and gas flow curves in the experimental process, and can also be directly observed through the full transparent PVC pipe.
The inhibition effect of the compound double-effect hydrate inhibitor designed by the invention can be judged according to the generation induction time of the hydrate (the time for the crystallization and nucleation of a large amount of the hydrate), the generation amount of the hydrate and the pipeline blockage time, and the longer the generation induction time of the hydrate is, the smaller the generation amount of the hydrate is, the better the thermodynamic inhibition effect of the inhibitor is proved, and the longer the pipeline blockage time is, the better the double-effect inhibition effect of the inhibitor is proved.
The specific implementation process comprises the following steps:
before the experiment starts, preparing inhibitor solution to be tested according to the requirement, cooling to about 1 ℃, and uniformly mixing by using a magnetic stirrer; reducing the water bath temperature to 1 ℃ by using a circulating refrigerator and keeping the water bath temperature stable; the inside of the experimental apparatus was repeatedly rinsed with deionized water, and then purged to dryness with methane gas (the gas in each of examples and comparative examples was 99.99% pure methane gas). And (3) starting a data acquisition system to acquire data, opening an air inlet valve to enable methane to enter an experimental pipeline, controlling an outlet valve of a pipeline to change the pressure of the experimental pipeline section, keeping the outlet valve stable after the pressure reaches the required pressure (5-10 MPa), and keeping the pressure in the pipeline stable by controlling an inlet pressure stabilizing valve. The liquid plunger pump was started, a test solution was introduced into the tube at a constant rate (0.2 g/s), and the time at which the injection started was recorded as the start time. The temperature and pressure data and the gas flow data in the pipeline are acquired in real time through the temperature and pressure sensor and the gas flowmeter, the process of generating, depositing and blocking the hydrate in the pipeline is shot through the DV camera in the whole process, when the outlet pressure and the gas flow are reduced to 0, the pipeline is completely blocked, the test is finished, and the time is the experiment termination time. After the experiment is finished, the pipeline outlet valve is slowly opened to reduce the pressure in the pipeline, the hydrate is decomposed, the ventilation is continuously carried out in the pipeline, and a collector is arranged at the pipeline outlet to collect the water decomposed by the hydrate, so that the weight of the water decomposed by the hydrate is obtained, and the generation amount of the hydrate in the pipeline can be reversely pushed. The test procedure is shown in fig. 1.
Deionized water (serial number 1), MEG single agents (serial numbers 2 and 3), PKO aqueous solutions (serial numbers 4 and 5) and the low-dose PKO-containing compound double-effect hydrate inhibitors (serial numbers 6 to 10) of the invention are subjected to test experiments according to the proportion and the concentration in table 1, the test equipment adopts the high-pressure flow loop, and the performance of different inhibitors is evaluated by utilizing a plurality of parameters such as hydrate generation induction time, hydrate generation amount, pipeline blocking time and the like, and the results are shown in table 1. Wherein, the numbers 1 to 5 are comparative examples and the numbers 6 to 10 are examples.
TABLE 1 evaluation results of Performance of different types of hydrate inhibitors
Figure BDA0003641129940000061
Figure BDA0003641129940000071
As can be seen from the test data in table 1, under the test conditions, 60% by mass of MEG can completely inhibit the formation of hydrate, and when the MEG mass fraction is reduced to 30%, the pipe blockage occurs in a short time although there is some inhibition of the formation of hydrate; although the low-dose PKO single agent can prevent particles from aggregating and adhering, the generation induction time of the hydrate is greatly shortened, the generation of the hydrate is promoted, and the effect of prolonging the blocking time of a pipeline is not obvious in a comprehensive view.
Compared with MEG single agents and PKO single agents, the compound double-effect hydrate inhibitor containing low-dose PKO has certain advantages in the aspect of prolonging the pipeline blocking time: when the MEG concentration is lower (10 percent, sequence number 6), the thermodynamic inhibition effect is not obvious, but is still better than the inhibition effect under single dose; when the MEG concentration reaches 20% (sequence numbers 7 and 9), the inhibitor simultaneously shows the double-effect performance of a thermodynamic inhibitor and a polymerization inhibitor, so that the hydrate generation induction time is prolonged, the aggregation adhesion among particles is weakened, and the pipeline blocking time is obviously prolonged (the hydrate generation induction time under the MEG concentration is smaller than that of a single MEG agent with the concentration of 30%, but the blocking time is longer than that of the single MEG agent with the concentration of 30%, and the polymerization inhibition effect of the compound inhibitor is proved; the smaller the PKO concentration is, the more excellent the performance is, which shows that the low-dose PKO can meet the polymerization inhibition function, and the growth promotion effect is more obvious under the high-dose PKO condition, but is not beneficial to the hydrate inhibition effect; after 30% of MEG (serial number 8) by mass fraction is compounded with low-dose PKO, although hydrate is still generated after a period of time, hydrate slurry with fluidity is formed under the polymerization inhibition effect of PKO, and no pipeline blockage occurs within the test time (30 min), and the inhibition effect is the same as that of 60% of MEG by mass fraction.
Therefore, after the MEG is compounded with the low-dose PKO, the inhibition performance of the MEG can be obviously improved, the traditional thermodynamic inhibition effect of the MEG is exerted, and the polymerization inhibition effect of the PKO is also exerted; meanwhile, after compounding, the injection concentration of MEG is greatly reduced (up to 50-60%), and the inhibitor cost is reduced.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (5)

1. The compound double-effect hydrate inhibitor containing low-dose PKO is characterized in that the preparation raw materials comprise ethylene glycol, PKO auxiliary agent and CDEA solvent, and the mass ratio of the ethylene glycol to the PKO auxiliary agent to the CDEA solvent is (10-30): 0.05 to 0.1:2.5 to 5;
the PKO auxiliary agent is cocamidopropyl dimethylamine with a molecular formula of C 17 H 20 N 4 O 2 The structural formula is as follows:
Figure FDA0004230897880000011
2. the low dose PKO-containing dual active hydrate inhibitor of claim 1, wherein the CDEA solvent is coconut diethanolamide having the formula RCON (CH 2 CH 2 OH) 2 Wherein R is cocoyl.
3. A method of preparing a low dose PKO-containing dual active hydrate inhibitor according to any one of claims 1 to 2, comprising the steps of: and mixing ethylene glycol, PKO auxiliary agent and CDEA solvent to obtain the compound double-effect hydrate inhibitor containing low-dose PKO.
4. The method of preparing a dual effect hydrate inhibitor containing a low dose of PKO according to claim 3, wherein the mixing is mixing the PKO aid and the CDEA solvent followed by mixing with ethylene glycol.
5. The use of a low-dose PKO-containing dual-effect hydrate inhibitor according to any one of claims 1 to 2, characterized in that the low-dose PKO-containing dual-effect hydrate inhibitor is mixed with water for use, and the mass ratio of the low-dose PKO-containing dual-effect hydrate inhibitor to water is 1:1.8 to 6.
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FR2625548B1 (en) * 1987-12-30 1990-06-22 Inst Francais Du Petrole PROCESS FOR DELAYING FORMATION AND / OR REDUCING THE TENDENCY TO AGGLOMERATION OF HYDRATES
BRPI0708852B1 (en) * 2006-03-21 2017-11-28 Akzo Nobel N .V. METHODS FOR INHIBITING AGGLOMERATION OF GAS HYDRATES, AND COMPOSITION CONTAINING AN ANTIAGLOMERANT GAS HYDRATE AND A CORROSION INHIBITOR
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