WO2023169553A1 - 一种双效水合物抑制剂的微观和宏观评价方法 - Google Patents

一种双效水合物抑制剂的微观和宏观评价方法 Download PDF

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WO2023169553A1
WO2023169553A1 PCT/CN2023/080736 CN2023080736W WO2023169553A1 WO 2023169553 A1 WO2023169553 A1 WO 2023169553A1 CN 2023080736 W CN2023080736 W CN 2023080736W WO 2023169553 A1 WO2023169553 A1 WO 2023169553A1
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pressure
hydrate
pipeline
experimental
temperature
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PCT/CN2023/080736
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English (en)
French (fr)
Inventor
王志远
裴继昊
孙宝江
单正锋
陈龙桥
张剑波
童仕坤
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中国石油大学(华东)
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Publication of WO2023169553A1 publication Critical patent/WO2023169553A1/zh

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N19/00—Investigating materials by mechanical methods
    • G01N19/04—Measuring adhesive force between materials, e.g. of sealing tape, of coating

Definitions

  • the invention relates to a microscopic and macroscopic evaluation method of a dual-effect hydrate inhibitor and belongs to the technical field of performance evaluation of hydrate inhibitors.
  • the current evaluation methods for dual-effect hydrate inhibitors are mainly divided into two aspects: macroscopic and microscopic.
  • equipment such as flow loops, high-pressure stirring kettles, and swing kettles are generally used to evaluate the performance of hydrate inhibitors.
  • Temperature and pressure changes, torque changes, and ball movement time are used to evaluate the performance of the inhibitor.
  • the circulation pump will continuously destroy the formed hydrate aggregates, and the static reactor cannot achieve dual-stage hydrate control under flow conditions.
  • Performance evaluation of effective inhibitors; microscopic evaluation generally uses a micromechanical force experimental device (MMF) to measure the adhesion between hydrate particles and between particles and walls.
  • MMF micromechanical force experimental device
  • the present invention provides a microscopic and macroscopic evaluation method of dual-effect hydrate inhibitors. This method is also suitable for the performance evaluation of traditional thermodynamic inhibitors and kinetic inhibitors.
  • the present invention is aimed at dual-effect inhibitors. Comprehensive evaluation is carried out from both micro and macro perspectives, so as to screen out dual-effect inhibitors with excellent performance more intuitively and efficiently.
  • a microscopic and macroscopic evaluation method for dual-effect hydrate inhibitors are comprehensively evaluated from microscopic and macroscopic perspectives through a microscopic evaluation device and a macroscopic evaluation device, respectively, and dual-effect inhibitors with excellent performance are screened out. agent.
  • the inhibitor solution includes single agent or compound agent.
  • Single agent such as thermodynamic inhibitor: ethylene glycol, kinetic inhibitor: PVP, PVCap, polyIPMA, antipolymerization agent: quaternary ammonium salts, etc.
  • the compound agent is a combination of the above single agents. .
  • the microscopic evaluation device includes an MMF measurement module, a constant temperature water bath module, a gas injection module A, and a data acquisition module A.
  • the MMF measurement module includes a high-pressure chamber, a three-dimensional shifting connecting rod, and a three-dimensional moving stage.
  • the three-dimensional moving stage It is installed in the high-pressure chamber and connected to the three-dimensional shift link. The position of the three-dimensional moving stage can be adjusted through the three-dimensional shift link.
  • the high-pressure chamber includes 4 sealing rings, and the 4 sealing rings are respectively distributed at the high-pressure chamber cover.
  • the connection between the three-dimensional shift connecting rod and the high-pressure cavity can withstand a pressure of 25MPa, and high-pressure hydrate particle MMF experiments can be carried out through glass fiber in the high-pressure cavity;
  • the ice particles can generate hydrate particles through the ice particle induction method, which can be used to evaluate hydrate particles and hydrate particles, hydrate particles and liquid droplets, or hydrate particles and wetted carbon steel surfaces.
  • the constant temperature water bath module includes a circulating water bath system.
  • the high-pressure chamber is placed in a constant temperature environment to reach the temperature required for the experiment.
  • the circulation pump and the sealing chamber are connected through a hose, and the outside of the hose is insulated by insulation materials;
  • the gas injection module A includes a high-pressure gas source A.
  • the pipeline of the high-pressure gas source A is connected to the high-pressure cavity through a pressure reducing valve A and an air inlet valve A. Gas is introduced into the high-pressure cavity through the high-pressure gas source A through a cooling device.
  • the ice particle induction method is used to produce hydrate particles.
  • the pipeline of high-pressure gas source A is provided with a pressure gauge A, and the high-pressure chamber is also provided with a vent valve A;
  • the data acquisition module A includes a microscopic imaging system, a data acquisition system A, a temperature sensor A and a pressure sensor A.
  • the high-pressure cavity is equipped with a visual window, and the microscopic imaging system is aligned with the visual window for real-time observation.
  • the temperature sensor A and the pressure sensor A are both connected to the high-pressure cavity and used to measure the pressure and temperature in the high-pressure cavity in real time.
  • the microscopic imaging system, the temperature sensor A and the pressure sensor A are all Connected to the signal of data acquisition system A, the temperature and pressure changes during the experiment are collected, monitored and recorded in real time through data acquisition module A, and the microscopic morphology of hydrate particles is observed in real time through the microscopic imaging system. Dynamic table testing of micromechanical forces between hydrate particles.
  • the high-pressure gas source A is hydrocarbon gas, such as methane gas, propane gas or a mixture of the two, and cannot be acidic gases such as carbon dioxide.
  • the above-mentioned dual-effect hydrate inhibitor performance microscopic evaluation system is used to conduct experiments.
  • the experimental process includes four stages: experimental preparation stage, hydrate particle induction generation stage, hydrate shell annealing, and pull-off test.
  • Experimental steps of the microscopic evaluation device include:
  • the experimental temperature referred to in the present invention needs to be specifically judged based on the degree of subcooling.
  • the degree of subcooling the phase equilibrium temperature of hydrate formation - the ambient temperature.
  • the phase equilibrium temperature in turn depends on the pressure conditions. Therefore, it is necessary to first determine the degree of subcooling required for the test, then determine the test pressure (phase equilibrium temperature), and finally determine the experimental temperature.
  • the experimental temperature is 1°C - room temperature.
  • the maximum pressure of the equipment is 10MPa, the phase equilibrium temperature cannot be increased indefinitely. If you want to achieve high supercooling conditions, you can only lower the experimental temperature as much as possible.
  • the experimental temperature can be 1 -3°C.
  • the moving end is allowed to continue to move to compress the fixed end and displace by 0.3mm.
  • the two measuring objects remain in contact for 10 seconds, and then slowly pull apart at a constant speed until the two measuring objects are completely separated;
  • the two measurement objects are the hydrate particles generated by the ice particle induction method in step 2) and the hydrate mentioned in step 1).
  • the center of the measurement object should be kept on the same horizontal line during testing;
  • Hooke's law is used to calculate the micromechanical force between two measurement objects, and one experiment is repeated 40 times;
  • step 1) the process of measuring the elastic coefficient of glass fiber is preferably:
  • the displacement on the image can be converted into actual displacement using calibration paper, or processed using ImageJ software.
  • step 4 when using Hooke's law to calculate the micromechanical force between two objects, in order to eliminate the influence of particle size on the measurement, the particle size needs to be normalized, and then the micromechanical force between the two objects can be obtained.
  • F is the measured value of the micromechanical force between the two measuring objects, N; F * is the correction value of the micromechanical force between the two measuring objects, N; k is the elastic coefficient of the glass fiber, N/m; ⁇ is the actual displacement of the fixed end, m; R 1 and R 2 are the curvature radii of the two measurement objects, m; R * is the harmonic mean radius, m.
  • the microscopic evaluation method of the dual-effect hydrate inhibitor of the present invention is mainly reflected in the adhesion between hydrate particles and hydrate particles, hydrate particles and liquid droplets, and hydrate particles and the wetted carbon steel surface in the high-pressure system.
  • different experimental materials are placed at the tip of the glass fiber, and the adhesion force between the two objects is measured.
  • the smaller the adhesion force value represents the aggregation ability between hydrate particles and between hydrate particles-droplets-hydrate particles.
  • the macroscopic evaluation device includes an experimental module, a water injection module, an air injection module B and a data acquisition module B.
  • the experimental module includes a constant temperature water bath and a fully transparent PVC pipe located in the constant temperature water bath.
  • the fully transparent PVC pipe is preferred.
  • the inner diameter is 12mm, the total length is 1.0m, and it can withstand a pressure of 10MPa.
  • the hydrate generation, deposition, and clogging processes all occur in a fully transparent PVC pipe.
  • the constant temperature water bath is connected to the refrigeration cycle machine through the pipeline to keep the temperature of the constant temperature water bath constant.
  • Both ends of the fully transparent PVC pipe are equipped with a temperature sensor B and a pressure sensor B.
  • the data acquisition module collects and monitors the temperature and pressure changes during the experiment in real time;
  • the gas injection module includes a high-pressure gas source B.
  • the pipeline of high-pressure gas source B is connected through the pressure reducing valve B, the gas flow meter, the air inlet valve B, the cooling tube plate and the inlet of the fully transparent PVC pipe.
  • the outlet of the fully transparent PVC pipe is also connected to a pipeline outlet valve.
  • the pipeline outlet valve is connected to the atmosphere.
  • the experimental pressure is controlled by controlling the outlet valve.
  • the high-pressure gas passes through the gas flow meter and the test solution from the pipeline inlet. Before entering the experimental pipeline, the high-pressure gas must pass through a coil placed in a cold water bath for cooling to reach the experimental temperature;
  • the water injection module includes a container for holding the test solution.
  • the test solution enters from the inlet of the fully transparent PVC pipe through a liquid plunger pump and a water inlet valve.
  • a vent valve B is provided on the pipe of the test solution.
  • the liquid plunger The pump can control the water injection rate by adjusting the pump frequency.
  • the test solution is an inhibitor solution. Which type of inhibitor needs to be tested needs to be prepared into a test solution with the required concentration according to the test needs, such as ethylene glycol solution, etc.;
  • the data acquisition module B includes a data acquisition system B and a DV camera.
  • the DV camera is used to capture the blocking process in the fully transparent PVC pipe in real time, that is, the hydrate migration and deposition blocking state, a gas flow meter, and temperature sensors at both ends of the fully transparent PVC pipe.
  • Both B and pressure sensor B are connected to data acquisition system B.
  • Temperature sensor B and pressure sensor B monitor the temperature and pressure changes of the inlet and outlet in real time and transmit them to data acquisition system B together with the gas flow meter.
  • the outlet pipe of the fully transparent PVC pipe is bent and placed in a 100°C insulation barrel. Due to the small diameter of the pipe outlet, there is a serious throttling effect, which makes the temperature at the outlet low and it is easy to generate hydrates, which will not be used in experiments. section is blocked, so use an insulated barrel to heat the pipe outlet to prevent the outlet from being clogged.
  • the experimental steps of the macroscopic evaluation device include:
  • the experimental gas such as hydrocarbon gas
  • the experimental gas such as hydrocarbon gas
  • S3 record the initial amount of test solution, start the liquid plunger pump, inject the test solution into the fully transparent PVC pipe at a constant rate (the rate depends on the required pipe flow pattern distribution and gas injection speed), and record the time when the injection starts , as the starting moment of the experiment;
  • the pipeline inlet pressure was maintained stable by controlling the pressure reducing valve B.
  • the pipeline outlet pressure and gas flow rate were reduced to 0 (i.e., the pressure sensor B at the outlet end of the fully transparent PVC pipe, and the gas flow meter When the value is 0), it means that the experiment is over. Turn off the liquid plunger pump and record the remaining test solution volume and time. This time is used as the end time of the experiment. Slowly open the pipe outlet valve to reduce the pressure in the pipe, promote the decomposition of hydrate, and weigh the hydrate. The weight of water decomposed by the substance is used to back-calculate the amount of hydrate deposited.
  • the air inlet valve B Opens the air inlet valve B to continuously ventilate the pipe, and place a collector at the outlet of the pipe to collect the decomposed water of hydrate in the pipe, thereby obtaining the weight of the decomposed water of hydrate.
  • the amount of hydrate can be inferred from the type of hydrate generated and the amount of decomposed water.
  • the ideal molecular formula of type I hydrate is 8M ⁇ 46H 2 O, so 5.75 water molecules are needed to generate one hydrate molecule
  • type II The molecular formula of hydrate is 24M ⁇ 136H 2 O. It takes 5.67 water molecules to generate one hydrate. Therefore, the amount of hydrate generated can be deduced by decomposing the amount of water.
  • the macroscopic evaluation method of the dual-effect hydrate inhibitor of the present invention is mainly reflected in three aspects: the experimental pipeline blockage time, the pipeline inlet and outlet pressure difference, and the temperature drop amplitude caused by the throttling effect after the pipeline is completely blocked.
  • the dual-effect inhibitor can be compared in terms of "preventing the aggregation of hydrate particles” and "inhibiting the accumulation of hydrate particles in the pipeline”.
  • the effect of double-effect inhibitors can also be compared by comparing the magnitude of the outlet temperature drop when the pipeline is completely blocked, the smaller the temperature drop. , which means that the looser the hydrate aggregates formed, the better the inhibition effect is.
  • the present invention can not only explain the mechanism of action of dual-effect inhibitors from a microscopic perspective, accurately evaluate the effects of inhibitors on particle aggregation and particle adhesion, and provide a theoretical basis for the screening of dual-effect inhibitors; it can also From a macro perspective, a flow evaluation device close to on-site working conditions was used to verify the selected inhibitors, and the effects of the double-action inhibitors under different production parameters were obtained, achieving an all-round and multi-angle performance evaluation of the double-action inhibitors.
  • Figure 1 is a schematic structural diagram of the microscopic evaluation device of the present invention.
  • Figure 2 is a schematic diagram of the positional relationship between the two glass fibers in Figure 1;
  • Figure 3 is a schematic structural diagram of the macroscopic evaluation device of the present invention.
  • Figure 4(a) shows the pressure change curve at the inlet and outlet of the flow pipeline
  • Figure 4(b) shows the temperature change curve of the inlet and outlet of the flow pipeline
  • Figure 5 shows the change curve of gas flow rate in the flow pipeline
  • 1-high-pressure air source A 2-pressure gauge A, 3-microscopic imaging system, 4-temperature sensor A, 5-pressure sensor A, 6-data acquisition system A, 7-sealing ring, 8-circulating water bath System, 9-high pressure chamber, 10-three-dimensional shifting connecting rod, 11-three-dimensional moving stage, 12-glass fiber, 13-fixed support, 14-constant temperature water bath, 15-fully transparent PVC pipe, 16-refrigeration cycle Machine, 17-temperature sensor B, 18-pressure sensor B, 19-high pressure gas source B, 20-gas flow meter, 21-cooling tube plate, 22-pressure gauge B, 23-test solution, 24-liquid plunger pump , 25-data acquisition system B, 26-DV camera, 27-magnetic stirrer, V1-pressure reducing valve A, V2-air inlet valve A, V3-vent valve A, V4-pressure reducing valve B, V5-air inlet Valve B, V6-pipe outlet valve, V7-water inlet valve, V8-vent valve B.
  • a micro- and macro-evaluation method for dual-effect hydrate inhibitors uses a micro-evaluation device and a macro-evaluation device to comprehensively evaluate and screen dual-effect hydrate inhibitors from both micro and macro perspectives.
  • a dual-effect inhibitor with excellent performance was developed.
  • the microscopic evaluation device includes an MMF measurement module, a constant temperature water bath module, a gas injection module A and a data acquisition module.
  • the MMF measurement module includes a high-pressure chamber 9, a three-dimensional shift connecting rod 10 and a three-dimensional moving stage 11.
  • the three-dimensional moving stage 11 is set on
  • the high-pressure cavity 9 is connected to the three-dimensional shift link 10.
  • the three-dimensional shift link 10 can adjust the position of the three-dimensional moving stage 11.
  • the high-pressure cavity 9 includes four sealing rings 7, and the four sealing rings are respectively distributed.
  • the high-pressure chamber cover and the connection between the three-dimensional shift connecting rod and the high-pressure chamber can withstand a pressure of 25MPa.
  • High-pressure hydrate particle MMF experiments can be carried out through glass fiber in the high-pressure chamber;
  • Two glass fibers 12 are provided inside the high-pressure chamber 9.
  • One end of one glass fiber is fixed on the inner wall of the high-pressure chamber 9 through a fixed support 13, the other end is used to place ice particles, and one end of the other glass fiber passes through a fixed support 13. It is fixed on the three-dimensional moving stage 11, and the other end is used to place ice particles/liquid droplets/carbon steel.
  • the ice particles are made into hydrate particles through the ice particle induction method, and then the hydrate particles and hydrate particles, hydrate particles and The adhesion force between liquid droplets or hydrate particles and the wetted carbon steel surface;
  • the constant temperature water bath module includes a circulating water bath system 8.
  • the high-pressure chamber 9 is placed in a constant temperature environment to reach the temperature required for the experiment. In order to increase the service life of the circulating pump built in the water bath, it is preferred to place the circulating water bath system and the high-pressure sealed cabin on the same level. , the circulation pump and the sealing chamber are connected through a hose, and the outside of the hose is insulated by insulation material;
  • the gas injection module A includes a high-pressure gas source A1.
  • the pipeline of the high-pressure gas source A1 is connected to the high-pressure cavity 9 through the pressure reducing valve AV1 and the air inlet valve AV2. Gas is introduced into the high-pressure cavity through the high-pressure gas source A1 through the cooling device.
  • the ice particle induction method is used to produce hydrate particles.
  • the pipeline of high-pressure gas source A1 is equipped with a pressure gauge A2, and the high-pressure chamber 9 is also equipped with a vent valve AV3;
  • the data acquisition module A includes a microscopic imaging system 3, a data acquisition system A6, a temperature sensor A4 and a pressure sensor A5.
  • the high-pressure chamber 9 is equipped with a visual window, and the microscopic imaging system 3 is aligned with the visual window to observe the high pressure in real time.
  • the microscopic morphology inside the cavity, the temperature sensor A4 and the pressure sensor A5 are both connected to the high-pressure cavity 9 for real-time measurement of the pressure and temperature in the high-pressure cavity.
  • the microscopic imaging system 3, the temperature sensor A4 and the pressure sensor A5 are all connected to the data collection System A6 signal connection, real-time acquisition, monitoring and recording of temperature and pressure changes during the experiment through data acquisition module A, real-time observation of the microscopic morphology of hydrate particles through the microscopic imaging system, and testing of the micromechanics between hydrate particles by controlling the three-dimensional moving stage force.
  • High-pressure gas source A1 is hydrocarbon gas.
  • the experimental process includes the experimental preparation stage, hydration
  • the experimental steps of the microscopic evaluation device include four stages: particle induction generation stage, hydrate shell annealing, and pull-off test.
  • the prepared ice particles are quickly put into the high-pressure cavity.
  • the ice particles are placed together with the glass fibers in the high-pressure cavity.
  • One glass fiber is fixed on the three-dimensional moving stage 11 through the fixed bracket 13 as the moving end, and the other glass fiber passes through the fixed bracket. 13 is fixed on the inner wall of the high-pressure chamber as a fixed end.
  • the ice particle induction method is an existing mature technology and will not be described here). This moment is recorded as the initial moment of the experiment.
  • t 0 the hydrate particles are formed from the inhibitor solution;
  • the two measurement objects are the hydrate particles generated by the ice particle induction method in step 2) and the hydrate particles (ice particle formation)/carbon steel/liquid droplets mentioned in step 1). During the test, the center of the measurement object should be kept on the same horizontal line;
  • step 1) the process of measuring the elastic coefficient of glass fiber is preferably:
  • step 4 when using Hooke's law to calculate the micromechanical force between two objects, in order to eliminate the influence of particle size on the measurement, the particle size needs to be normalized, and then the corrected value of the micromechanical force between the two objects can be obtained.
  • F is the measured value of the micromechanical force between the two measuring objects, N; F * is the correction value of the micromechanical force between the two measuring objects, N; k is the elastic coefficient of the glass fiber, N/m; ⁇ is the actual displacement of the fixed end, m; R 1 and R 2 are the curvature radii of the two measurement objects, m; R * is the harmonic mean radius, m.
  • the macroscopic evaluation device includes an experimental module, a water injection module, a gas injection module B and a data collection Module B
  • the experimental module includes a constant temperature water bath 14 and a fully transparent PVC pipe 15 located in the constant temperature water bath 14.
  • the fully transparent PVC pipe 15 has an inner diameter of 12mm, a total length of 1.0m, a pressure resistance of 10MPa, and hydrate generation, deposition, The clogging process occurs in the fully transparent PVC pipe 15.
  • the constant temperature water bath 14 is connected to the refrigeration cycle machine 16 through a pipeline to keep the temperature of the constant temperature water bath 14 constant.
  • Both ends of the fully transparent PVC pipe 15 are provided with a temperature sensor B17 and a pressure sensor. B18, collect and monitor temperature and pressure changes during the experiment in real time through the data acquisition module;
  • the gas injection module includes a high-pressure gas source B19.
  • the pipeline of the high-pressure gas source B19 is connected through the pressure reducing valve BV4, the gas flow meter 20, the air inlet valve BV5, the cooling tube plate 21 and the inlet of the fully transparent PVC pipe 15.
  • the high-pressure gas source B19 A pressure gauge B22 is provided on the pipeline, and the outlet of the fully transparent PVC pipe 15 is also connected to a pipeline outlet valve V6.
  • the pipeline outlet valve V6 is connected to the atmosphere, and the experimental pressure is controlled by controlling the outlet valve; the high-pressure gas passes through the gas flow meter 20 and is tested The solution enters from the entrance of the pipeline. Before entering the experimental pipeline, the high-pressure gas must be cooled through a coil placed in a cold water bath to reach the experimental temperature;
  • the water injection module includes a container for holding the test solution 23.
  • the test solution 23 enters from the inlet of the fully transparent PVC pipe 15 through the liquid plunger pump 24 and the water inlet valve V7.
  • the pipe of the test solution 23 is provided with a vent valve BV8.
  • the plunger pump 24 can control the water injection rate by adjusting the pump frequency.
  • the test solution is an inhibitor solution. Which type needs to be tested? Inhibitors need to be prepared into a test solution with the required concentration according to the test needs, such as ethylene glycol solution, etc.;
  • the data acquisition module B includes a data acquisition system B25 and a DV camera 26.
  • the DV camera 26 is used to capture the clogging process in the fully transparent PVC pipe 15 in real time, that is, the hydrate migration, deposition and clogging state.
  • the gas flow meter 20 and the fully transparent PVC pipe both The temperature sensor B17 and pressure sensor B18 at the end are both connected to the data acquisition system B25.
  • the temperature sensor B17 and the pressure sensor B18 monitor the temperature and pressure changes of the inlet and outlet in real time and transmit them to the data acquisition system B together with the gas flow meter.
  • the outlet pipe of the fully transparent PVC pipe 15 is bent and placed in a 100°C insulation barrel. Due to the small diameter of the pipe outlet, there is a serious throttling effect, which makes the temperature at the outlet low and it is easy to generate hydrates, blocking the non-experimental section. , so use an insulated barrel to heat the pipe outlet to prevent clogging at the outlet.
  • the pressure reducing valve BV4 was controlled to maintain the stability of the pipeline inlet pressure.
  • the pipeline outlet pressure and gas flow decreased to 0 (that is, the pressure sensor B at the outlet end of the fully transparent PVC pipe, to and the value of the gas flow meter is 0), which means the experiment is over.

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Abstract

一种双效水合物抑制剂的微观和宏观评价方法，属于水合物抑制剂性能评价技术领域，该方法同样适用于传统热力学抑制剂与动力学抑制剂性能评价。通过微观评价装置和宏观评价装置对双效水合物抑制剂分别从微观和宏观两个角度综合评价，从而更直观高效地筛选出性能优良的双效抑制剂。该方法既能从微观角度解释双效抑制剂的作用机理，精准地评价抑制剂在颗粒聚集、颗粒附着两个方面的效果，为双效抑制剂的筛选提供了理论依据；又能从宏观角度利用接近现场工况的流动评价装置对所筛选出的抑制剂进行验证，得到不同生产参数下双效抑制剂的作用效果，实现了对双效抑制剂全方位、多角度的性能评价。

Description

一种双效水合物抑制剂的微观和宏观评价方法 技术领域
本发明涉及一种双效水合物抑制剂的微观和宏观评价方法，属于水合物抑制剂性能评价技术领域。
背景技术
在深水油气钻采与水合物开发过程中，泥线附近温度低、压力高，地层产出的气体与水极易在该环境下生成天然气水合物，沉积附着在管壁上，造成井筒流动面积减小，甚至堵塞生产管柱，严重威胁工作人员的生命安全。目前常用的水合物防治思路为添加过量热力学抑制剂以完全杜绝井筒中水合物的生成，但是抑制剂用量大、成本高、环境不友好。水合物动态防治策略是近年来提出的水合物防治新思路，该技术允许水合物的生成，但使形成的水合物保持流动性并沿管道流动，避免形成的水合物颗粒聚集和在管道沉积。目前水合物抑制剂也在朝着“允许水合物生成、防止颗粒聚集、抑制颗粒附着”的双效抑制剂方向发展。但是目前的双效抑制剂评价手段比较单一，不能高效且全面的评价一种双效抑制剂的性能。
当前针对双效水合物抑制剂的评价手段主要分为宏观与微观两个方面，宏观上一般采用流动环路、高压搅拌釜、摇摆釜等设备对水合物抑制剂进行性能评价，通过监测体系中的温压变化、扭矩变化、小球运动时间来评价抑制剂的性能，但是在流动环路中，循环泵会不断破坏形成的水合物聚集体，而静态反应釜无法实现在流动状态下对双效抑制剂的性能评价；微观评价一般采用微机械力实验装置(MMF)测量水合物颗粒间、颗粒与壁面间的粘附力，但是该方法一般在常压下进行，无法准确表征现实生产中的抑制效果。
发明内容
为了解决现有技术的不足，本发明提供一种双效水合物抑制剂的微观和宏观评价方法，该方法同样适用于传统热力学抑制剂与动力学抑制剂性能评价，本发明针对双效抑制剂从微观和宏观两个角度进行综合评价，从而更直观高效地筛选出性能优良的双效抑制剂。
本发明采用以下技术方案：
一种双效水合物抑制剂的微观和宏观评价方法，通过微观评价装置和宏观评价装置对双效水合物抑制剂分别从微观和宏观两个角度综合评价，筛选出性能优良的双效抑制 剂。
首先利用微观评价装置测量所需测试抑制剂溶液形成的水合物颗粒与水合物颗粒、液滴、碳钢表面的粘附力大小，该值越小说明抑制剂性能越优；然后利用宏观评价装置开展宏观堵塞实验，得到注入不同抑制剂溶液条件下管道堵塞时间，该值越大说明抑制剂性能越优，从而从宏观流动状态下对微观实验进行验证。
抑制剂溶液包括单剂或复合剂，单剂如热力学抑制剂：乙二醇，动力学抑制剂：PVP、PVCap、polyIPMA，防聚剂：季铵盐类等，复合剂为上述单剂复配。
优选的，所述微观评价装置包括MMF测量模块、恒温水浴模块、注气模块A和数据采集模块A，所述MMF测量模块包括高压腔体、三维移轴连杆和三维移动台，三维移动台设置于高压腔体内，且与三维移轴连杆连接，通过三维移轴连杆能够调节三维移动台的位置，高压腔体内包括4个密封圈，4个密封圈分别分布在高压腔体盖处和三维移轴连杆与高压腔体的连接处，可耐压25MPa，可以在该高压腔体内通过玻璃纤维进行高压水合物颗粒MMF实验；
所述高压腔体内部设置有两个玻璃纤维，一个玻璃纤维一端固定在高压腔体内壁上，另一端用于放置冰颗粒，另一个玻璃纤维的一端固定在三维移动台上，另一端用于放置冰颗粒/液滴/碳钢，冰颗粒可通过冰粒诱导法生成水合物颗粒，可用于评价水合物颗粒与水合物颗粒、水合物颗粒与液滴或者水合物颗粒与润湿碳钢表面的粘附力大小；
所述恒温水浴模块包括一循环水浴系统，高压腔体置于恒温环境下以达到实验所需温度，为提高水浴内置的循环泵的使用寿命，优选将循环水浴系统与高压密封舱置于同一水平线，循环泵与密封腔通过软管连接，软管外通过保温材料保温；
所述注气模块A包括高压气源A，高压气源A的管道经减压阀A、进气阀A与高压腔体连接，通过高压气源A经过冷却装置向高压腔体内通入气体，利用冰粒诱导法生产水合物颗粒，高压气源A的管道上设置有压力表A，所述高压腔体上还设置有放空阀A；
所述数据采集模块A包括显微成像系统、数据采集系统A、温度传感器A和压力传感器A，所述高压腔体安装有可视窗口，显微成像系统对准可视窗口设置，以实时观测高压腔体内部的微观形态，所述温度传感器A和压力传感器A均与高压腔体连接，用于实时测量高压腔体内压力和温度，所述显微成像系统、温度传感器A和压力传感器A均与数据采集系统A信号连接，通过数据采集模块A实时采集、监测实验过程中的温压变化并记录，通过显微成像系统实时观测水合物颗粒的微观形态，通过控制三维移 动台测试水合物颗粒间微机械力。
优选的，所述高压气源A为烃类气体，如甲烷气体、丙烷气体或两者的混合气体等，不能为二氧化碳等酸性气体。
优选的，利用上述双效水合物抑制剂性能微观评价系统开展实验，实验流程包括实验准备阶段、水合物颗粒诱导生成阶段、水合物壳退火、拉脱测试四个阶段，微观评价装置的实验步骤，包括：
1)实验准备阶段：
采用循环水浴系统将恒温环境降温至(-7)～(-10)℃，并测量实验所需的玻璃纤维的弹性系数，取两个玻璃纤维，在一个玻璃纤维上尖端放置所需的测试液液滴，并通过液氮制备冰颗粒，在另一个玻璃纤维尖端根据需要放置冰颗粒、碳钢或液滴；
2)水合物颗粒诱导生成阶段：
将制得的冰颗粒迅速放入高压腔体，打开放空阀A，通过高压气源A向高压腔体循环通气，保证高压腔体内部气体纯净，关闭放空阀A，加压至实验所需压力，水合物颗粒经过冰粒诱导生成(需要水合物生成的温度和压力必须达到相平衡条件，冰粒诱导法为现有成熟技术，此处不再赘述)，该时刻记为实验初始时刻，该水合物颗粒为抑制剂溶液形成；
3)水合物颗粒退火阶段：
将恒温环境的温度升至实验温度并保持稳定2h，即退火2h，以确保水合物颗粒的外壳足够坚硬；
值得注意的是，本发明所指的实验温度需要具体根据过冷度来判断，过冷度＝水合物生成的相平衡温度-环境温度，相平衡温度又取决于压力条件。因此首先需确定测试所需的过冷度，然后确定测试压力(相平衡温度)，最后可以确定实验温度。理想条件下该实验温度为1℃-室温，但由于设备承压最高为10MPa，相平衡温度不能无限升高，若想达到高过冷条件，只能尽可能降低实验温度，实验温度可为1-3℃。
4)粘附力测试阶段：
通过三维移轴连杆调整三维移动台，使得两测量对象保持在同一水平线，然后控制三维移动台使其上的玻璃纤维尖端缓慢匀速靠近另一个玻璃纤维的尖端，即移动端逐渐靠近固定端，两测量对象接触后，使移动端继续运动压迫固定端并位移0.3mm，两测量对象保持接触10s，再缓慢匀速拉开，直至两测量对象完全分开；
两测量对象分别为步骤2)冰粒诱导法生成的水合物颗粒及步骤1)提及的水合物 颗粒(冰颗粒形成)/碳钢/液滴，测试时应保持测量对象中心保持同一水平线；
利用显微成像系统拍摄两测量对象分开时的图像，并测量所拍摄图像中固定端的位移，然后转化为固定端的实际位移；
利用胡克定律计算两测量对象间的微机械力，一次实验重复40次；
5)实验结束，通过放空阀A缓慢泄压。
优选的，步骤1)中，测量玻璃纤维弹性系数的过程优选为：
在电子天平上放置一个支架，然后将玻璃纤维压迫支架顶端，记录玻璃纤维底端位移及天平示数，根据胡克定律计算弹性系数；
优选的，步骤4)中，测量所拍摄图像中固定端的位移后，可利用标定纸将图像上的位移转化为实际位移，或者采用ImageJ软件处理得到。
优选的，步骤4)中，利用胡克定律计算两个对象间微机械力时，为消除颗粒尺寸对测量的影响，需要对颗粒尺寸进行归一化处理，进而可得到两对象间微机械力的修正值，具体的，两测量对象间的微机械力计算过程为：
F＝k·δ  (1)

其中，F为两测量对象间微机械力测量值，N；F*为两测量对象间微机械力修正值，N；k为玻璃纤维的弹性系数，N/m；δ为固定端的实际位移，m；R1、R2为两测量对象的曲率半径，m；R*为调和平均半径，m。
本发明的双效水合物抑制剂的微观评价方法主要体现在高压体系内水合物颗粒与水合物颗粒、水合物颗粒与液滴、水合物颗粒与润湿碳钢表面的粘附力大小。根据测试需求在玻璃纤维尖端处放置不同实验材料，测量两个对象间的粘附力大小，粘附力值越小，代表水合物颗粒间、水合物颗粒-液滴-水合物颗粒间聚集能力越差，代表水合物颗粒在管壁附着能力越差，证明双效抑制剂“防止颗粒聚集、抑制颗粒附着”效果越好。
优选的，所述宏观评价装置包括实验模块、注水模块、注气模块B和数据采集模块B，所述实验模块包括恒温水浴槽和位于恒温水浴槽内的全透明PVC管，全透明PVC管优选内径为12mm，总长度为1.0m，可耐压10MPa，水合物生成、沉积、堵塞过程均发生在全透明PVC管中，恒温水浴槽通过管道连接制冷循环机用于保持恒温水浴槽温度恒定，全透明PVC管的两端均设置有一温度传感器B和压力传感器B，通过数据采集模块实时采集并监测实验过程中的温压变化；
所述注气模块包括一高压气源B，高压气源B的管道经减压阀B、气体流量计、进气阀B、冷却管盘与全透明PVC管的进口连接，高压气源B的管道上设置有压力表B，全透明PVC管的出口还连接有管道出口阀门，管道出口阀门与大气相连通，通过控制出口阀控制实验压力；高压气体经过气体流量计与测试溶液从管道入口处进入，其中高压气体进入实验管道前需经过放置于冷水浴中的盘管进行降温冷却，以达到实验温度；
所述注水模块包括用于盛放测试溶液的容器，测试溶液经液体柱塞泵、进水阀从全透明PVC管的进口进入，所述测试溶液的管道上设置有放空阀B，液体柱塞泵可通过调整泵频来控制注水速率，测试溶液为抑制剂溶液，需要测试哪种类型抑制剂，需根据测试需要配制成所需浓度的测试溶液，如乙二醇溶液等；
所述数据采集模块B包括数据采集系统B和DV摄像机，DV摄像机用于实时拍摄全透明PVC管内的堵塞过程，即水合物运移沉积堵塞状态，气体流量计、全透明PVC管两端的温度传感器B和压力传感器B均与数据采集系统B连接，温度传感器B和压力传感器B实时监测进出口温压变化并随气体流量计共同传入数据采集系统B中。
优选的，全透明PVC管的出口管道弯曲放置在100℃保温桶中，管道出口的管线由于管径较小，存在严重的节流效应，使得出口处温度较低易生成水合物，将非实验段堵塞，因此利用保温桶对管道出口加热，防止出口处堵塞。
优选的，宏观评价装置的实验步骤，包括：
S1，实验准备阶段：
向全透明PVC管通入实验气体(如烃类气体)，排出管内残余空气和液体水，确保管内气体纯净，将恒温水浴槽温度降至实验温度，将测试溶液降温至实验温度(溶液配制好后可在冰箱中降至实验温度，然后实验过程中通过冰块保持低温)并通过磁力搅拌器使其混合均匀；
S2，开启数据采集系统B采集数据，打开进气阀使实验气体进入实验管路，控制管道出口阀门以改变全透明PVC管的压力，当全透明PVC管内压力达到实验压力后(根据设备安全要求，实验压力安全区间为0-10MPa)，保持管道出口阀门开度稳定；
S3，记录测试溶液初始量，启动液体柱塞泵，以恒定速率向全透明PVC管注入测试溶液(该速率取决于所需的管流流型分布及气体注入速度)，并记录开始注入的时间，以此作为实验开始时刻；
S4，通过温度传感器B、压力传感器B及气体流量计实时采集数据，通过DV摄像机实时拍摄全透明PVC管内水合物生成沉积堵塞过程；
S5，实验中通过控制减压阀B维持管道入口压力稳定，当观察到水合物堵塞的发生、管道出口压力及气体流量降低为0(即全透明PVC管出口端的压力传感器B，以及气体流量计的值为0时)，意味着实验结束，关闭液体柱塞泵并记录剩余测试溶液量及时间，该时间作为实验终止时间，缓慢打开管道出口阀门降低管内压力，促进水合物分解，称量水合物分解水的重量并以此反算沉积的水合物量。
管内压力降低后，水合物会全部分解，打开进气阀B持续向管内通气，并在管路出口处放置一个收集器来收集管中水合物分解水，从而得到水合物分解水的重量。水合物的量可由生成的水合物的类型和分解水的量进行反推，如：I型水合物理想分子式为8M·46H2O，因此若生成一个水合物分子需要5.75个水分子；II型水合物分子式为24M·136H2O，生成一个水合物需要5.67个水分子，因此通过分解水的量可以反推出生成的水合物的量。
本发明的双效水合物抑制剂的宏观评价方法主要体现在实验管道堵塞时间、管道进出口压力差、管道发生完全堵塞后节流效应导致的温降幅度三个方面。通过对比实验开始时刻到管道发生完全堵塞所需时间长短、管道进出口压差值达到最大所需时间长短，可对比双效抑制剂在“防止水合物颗粒聚集”、“抑制水合物颗粒在管壁附着”两方面的效果，该时间越长，证明该类型抑制剂效果越好；也可通过对比管道发生完全堵塞时出口温降幅度大小来对比双效抑制剂的效果，温降幅度越小，代表形成的水合物聚集体越疏松，证明抑制效果越好。
本发明未详尽之处，均可参见现有技术。
本发明的有益效果为：
1、本发明的双效水合物抑制剂的微观和宏观评价方法，在微观评价方面，该评价方法解决了传统MMF测量无法在高压条件下进行的问题，并提出了通过测量水合物颗粒与水合物颗粒、液滴、润湿壁面间的粘附力来评价双效抑制剂性能的方法；在宏观评价方面，该评价方法解决了传统流动环路中因循环泵对水合物聚集体破坏而无法实时监测水合物聚集形态的问题，创新性地利用流动压差与节流温降曲线表征抑制剂对水合物沉积堵塞的影响。
2、本发明既能从微观角度解释双效抑制剂的作用机理，精准地评价抑制剂在颗粒聚集、颗粒附着两个方面的效果，为双效抑制剂的筛选提供了理论依据；又能从宏观角度利用接近现场工况的流动评价装置对所筛选出的抑制剂进行验证，得到不同生产参数下双效抑制剂的作用效果，实现了对双效抑制剂全方位、多角度的性能评价。
附图说明
图1为本发明的微观评价装置结构示意图；
图2为图1中两玻璃纤维的位置关系示意图；
图3为本发明的宏观评价装置结构示意图；
图4(a)为流动管路进出口压力变化曲线；
图4(b)为流动管路进出口温度变化曲线；
图5为流动管路气体流速变化曲线；
其中，1-高压气源A，2-压力表A，3-显微成像系统，4-温度传感器A，5-压力传感器A，6-数据采集系统A，7-密封圈，8-循环水浴系统，9-高压腔体，10-三维移轴连杆，11-三维移动台，12-玻璃纤维，13-固定支座，14-恒温水浴槽，15-全透明PVC管，16-制冷循环机，17-温度传感器B，18-压力传感器B，19-高压气源B，20-气体流量计，21-冷却管盘，22-压力表B，23-测试溶液，24-液体柱塞泵，25-数据采集系统B，26-DV摄像机，27-磁力搅拌器，V1-减压阀A，V2-进气阀A，V3-放空阀A，V4-减压阀B，V5-进气阀B，V6-管道出口阀门，V7-进水阀，V8-放空阀B。
具体实施方式：
为了使本技术领域的人员更好的理解本说明书中的技术方案，下面结合本说明书实施中的附图，对本发明书实施例中的技术方案进行清楚、完整的描述，但不仅限于此，本发明未详尽说明的，均按本领域常规技术。
实施例1：
一种双效水合物抑制剂的微观和宏观评价方法，如图1-5所示，通过微观评价装置和宏观评价装置对双效水合物抑制剂分别从微观和宏观两个角度综合评价，筛选出性能优良的双效抑制剂。
首先利用微观评价装置测量所需测试抑制剂溶液形成的水合物颗粒与水合物颗粒、液滴、碳钢表面的粘附力大小，该值越小说明抑制剂性能越优；然后利用宏观评价装置开展宏观堵塞实验，得到注入不同抑制剂溶液条件下管道堵塞时间，该值越大说明抑制剂性能越优，从而从宏观流动状态下对微观实验进行验证。
实施例2：
一种双效水合物抑制剂的微观和宏观评价方法，如实施例1所述，所不同的是，如图1，微观评价装置包括MMF测量模块、恒温水浴模块、注气模块A和数据采集模块A，MMF测量模块包括高压腔体9、三维移轴连杆10和三维移动台11，三维移动台11设置于 高压腔体9内，且与三维移轴连杆10连接，通过三维移轴连杆10能够调节三维移动台11的位置，高压腔体9内包括4个密封圈7，4个密封圈分别分布在高压腔体盖处和三维移轴连杆与高压腔体的连接处，可耐压25MPa，可以在该高压腔体内通过玻璃纤维进行高压水合物颗粒MMF实验；
高压腔体9内部设置有两个玻璃纤维12，一个玻璃纤维一端通过固定支座13固定在高压腔体9内壁上，另一端用于放置冰颗粒，另一个玻璃纤维的一端通过固定支座13固定在三维移动台11上，另一端用于放置冰颗粒/液滴/碳钢，通过冰粒诱导法将冰颗粒制成水合物颗粒，进而评价水合物颗粒与水合物颗粒、水合物颗粒与液滴或者水合物颗粒与润湿碳钢表面的粘附力大小；
恒温水浴模块包括一循环水浴系统8，高压腔体9置于恒温环境下以达到实验所需温度，为提高水浴内置的循环泵的使用寿命，优选将循环水浴系统与高压密封舱置于同一水平线，循环泵与密封腔通过软管连接，软管外通过保温材料保温；
注气模块A包括高压气源A1，高压气源A1的管道经减压阀AV1、进气阀AV2与高压腔体9连接，通过高压气源A1经过冷却装置向高压腔体内通入气体，利用冰粒诱导法生产水合物颗粒，高压气源A1的管道上设置有压力表A2，高压腔体9上还设置有放空阀AV3；
数据采集模块A包括显微成像系统3、数据采集系统A6、温度传感器A4和压力传感器A5，高压腔体9安装有可视窗口，显微成像系统3对准可视窗口设置，以实时观测高压腔体内部的微观形态，温度传感器A4和压力传感器A5均与高压腔体9连接，用于实时测量高压腔体内压力和温度，显微成像系统3、温度传感器A4和压力传感器A5均与数据采集系统A6信号连接，通过数据采集模块A实时采集、监测实验过程中的温压变化并记录，通过显微成像系统实时观测水合物颗粒的微观形态，通过控制三维移动台测试水合物颗粒间微机械力。
高压气源A1为烃类气体。
实施例3：
一种双效水合物抑制剂的微观和宏观评价方法，如实施例2所述，所不同的是，利用上述双效水合物抑制剂性能微观评价系统开展实验，实验流程包括实验准备阶段、水合物颗粒诱导生成阶段、水合物壳退火、拉脱测试四个阶段，微观评价装置的实验步骤，包括：
1)实验准备阶段：
采用循环水浴系统8将恒温环境降温至-7℃(循环水浴系统中的液体为防冻液，最低可达到(-50)℃，降到该温度是为了保持冰颗粒不融化)，取两根实验所需玻璃纤维，并测量玻璃纤维的弹性系数，如图2所示，在一个玻璃纤维12上尖端x1放置所需的测试液液滴，并通过液氮制备冰颗粒，根据实验要求在另一个玻璃纤维尖端x2根据需要放置冰颗粒/碳钢/液滴(冰颗粒与液滴均由抑制剂溶液生成)；
2)水合物颗粒诱导生成阶段：
将制得的冰颗粒迅速放入高压腔体，同时冰颗粒连同玻璃纤维一起放置高压腔体内，使一个玻璃纤维通过固定支架13固定在三维移动台11作为移动端，另一个玻璃纤维通过固定支架13固定在高压腔体内壁面作为固定端，打开放空阀AV3，通过高压气源A1向高压腔体9循环通气5min以上，保证高压腔体9内部气体纯净，关闭放空阀AV3，加压至实验所需压力，水合物颗粒经过冰粒诱导生成(需要水合物生成的温度和压力必须达到相平衡条件，冰粒诱导法为现有成熟技术，此处不再赘述)，该时刻记为实验初始时刻t0，该水合物颗粒为抑制剂溶液形成；
3)水合物颗粒退火阶段：
将恒温环境的温度升至实验温度并保持稳定2h，即退火2h，以确保水合物颗粒的外壳足够坚硬；
4)粘附力测试阶段：
通过三维移轴连杆10调整三维移动台11，使得两测量对象保持在同一水平线，如图2所示，x1上下运动至与x2在同一个水平线上，然后控制三维移动台11使其上的玻璃纤维尖端x1缓慢匀速靠近另一个玻璃纤维的尖端x2，即移动端逐渐靠近固定端，两测量对象接触后，使移动端继续运动压迫固定端并位移0.3mm，两测量对象保持接触10s，再缓慢匀速拉开，直至两测量对象完全分开；
因为玻璃纤维本身具有弹性，当x1移动到与x2接触时，x1继续移动会压迫x2端朝x1原本位移的方向继续移动；
两测量对象分别为步骤2)冰粒诱导法生成的水合物颗粒及步骤1)提及的水合物颗粒(冰颗粒形成)/碳钢/液滴，测试时应保持测量对象中心保持同一水平线；
利用显微成像系统拍摄两测量对象分开时的图像，通过ImageJ软件测得分开时刻x2端颗粒位移，转化为固定端的实际位移，利用胡克定律计算两个对象间微机械力，一次实验重复40次，所需测试抑制剂溶液形成的水合物颗粒与水合物颗粒/液滴/碳钢间粘附力越小，证明抑制剂性能越优越；
5)实验结束，通过放空阀AV3缓慢泄压。
步骤1)中，测量玻璃纤维弹性系数的过程优选为：
在电子天平上放置一个支架，然后将玻璃纤维压迫支架顶端，记录玻璃纤维底端位移及天平示数，根据胡克定律计算弹性系数；
步骤4)中，利用胡克定律计算两个对象间微机械力时，为消除颗粒尺寸对测量的影响，需要对颗粒尺寸进行归一化处理，进而可得到两对象间微机械力的修正值，具体的，两测量对象间的微机械力计算过程为：
F＝k·δ   (1)

其中，F为两测量对象间微机械力测量值，N；F*为两测量对象间微机械力修正值，N；k为玻璃纤维的弹性系数，N/m；δ为固定端的实际位移，m；R1、R2为两测量对象的曲率半径，m；R*为调和平均半径，m。
实施例4：
一种双效水合物抑制剂的微观和宏观评价方法，如实施例1所述，所不同的是，如图3所示，宏观评价装置包括实验模块、注水模块、注气模块B和数据采集模块B，实验模块包括恒温水浴槽14和位于恒温水浴槽14内的全透明PVC管15，全透明PVC管15内径为12mm，总长度为1.0m，可耐压10MPa，水合物生成、沉积、堵塞过程均发生在全透明PVC管15中，恒温水浴槽14通过管道连接制冷循环机16用于保持恒温水浴槽14温度恒定，全透明PVC管15的两端均设置有一温度传感器B17和压力传感器B18，通过数据采集模块实时采集并监测实验过程中的温压变化；
注气模块包括一高压气源B19，高压气源B19的管道经减压阀BV4、气体流量计20、进气阀BV5、冷却管盘21与全透明PVC管15的进口连接，高压气源B19的管道上设置有压力表B22，全透明PVC管15的出口还连接有管道出口阀门V6，管道出口阀门V6与大气相连通，通过控制出口阀控制实验压力；高压气体经过气体流量计20与测试溶液从管道入口处进入，其中高压气体进入实验管道前需经过放置于冷水浴中的盘管进行降温冷却，以达到实验温度；
注水模块包括用于盛放测试溶液23的容器，测试溶液23经液体柱塞泵24、进水阀V7从全透明PVC管15的进口进入，测试溶液23的管道上设置有放空阀BV8，液体柱塞泵24可通过调整泵频来控制注水速率，测试溶液为抑制剂溶液，需要测试哪种类型 抑制剂，需根据测试需要配制成所需浓度的测试溶液，如乙二醇溶液等；
数据采集模块B包括数据采集系统B25和DV摄像机26，DV摄像机26用于实时拍摄全透明PVC管15内的堵塞过程，即水合物运移沉积堵塞状态，气体流量计20、全透明PVC管两端的温度传感器B17和压力传感器B18均与数据采集系统B25连接，温度传感器B17和压力传感器B18实时监测进出口温压变化并随气体流量计共同传入数据采集系统B中。
全透明PVC管15的出口管道弯曲放置在100℃保温桶中，管道出口的管线由于管径较小，存在严重的节流效应，使得出口处温度较低易生成水合物，将非实验段堵塞，因此利用保温桶对管道出口加热，防止出口处堵塞。
实施例5：
一种双效水合物抑制剂的微观和宏观评价方法，如实施例4所述，所不同的是，宏观评价装置的实验步骤，包括：
S1，实验准备阶段：
依次打开减压阀V4、进气阀V5、管道出口阀门V6，向全透明PVC管15通入实验气体，排出管内残余空气和液体水，确保管内气体纯净，然后将阀门全部关闭，利用制冷循环机16将恒温水浴槽14温度降至实验温度，将测试溶液降温至实验温度并通过磁力搅拌器27使其混合均匀；
S2，开启数据采集系统B25采集数据，温度传感器B17采集进出口温度变化，压力传感器B18采集进出口压力变化，气体流量计20采集气体流速变化，打开减压阀BV4、进气阀BV5使实验气体进入实验管路，压力表B22数值为气源剩余压力和气源出口压力，控制管道出口阀门V6以改变全透明PVC管的压力，当全透明PVC管内压力达到实验压力后，保持管道出口阀门V6开度稳定；
S3，记录测试溶液初始重量m0，启动液体柱塞泵24，保持进水阀V7关闭，打开放空阀BV8排掉管线中的残余水与空气，关闭放空阀BV8，打开进水阀V7以恒定速率向全透明PVC管15注入测试溶液23，并记录开始注入的时间t0，以此作为实验开始时刻；
S4，通过温度传感器B17、压力传感器B18及气体流量计20实时采集数据，通过DV摄像机26实时拍摄全透明PVC管内水合物生成沉积堵塞过程；
S5，实验中通过控制减压阀BV4维持管道入口压力稳定，当观察到水合物堵塞的发生、管道出口压力及气体流量降低为0(即全透明PVC管出口端的压力传感器B，以 及气体流量计的值为0时)，意味着实验结束，关闭液体柱塞泵24并记录剩余测试溶液量及时间t，该时间作为实验终止时间，缓慢打开管道出口阀门V6降低管内压力，促进水合物分解，称量水合物分解水的重量并以此反算沉积的水合物量。
实施例6：
一种双效水合物抑制剂的微观和宏观评价方法，如实施例3所述，所不同的是：
(1)准备待评价的水合物抑制剂A、B并制备不同浓度的抑制剂溶液，其中A为单一型抑制剂，B为复配型抑制剂，如表1所示。在两个玻璃纤维尖端放置该抑制剂溶液液滴并通过液氮制备冰颗粒(以测量水合物颗粒与颗粒间的粘附力为例)，并迅速放入腔体内，通入甲烷气体并加压至实验压力，水合物颗粒生成；
(2)将水浴温度升至实验温度并退火2h，调整三维移轴连杆使两水合物颗粒缓慢匀速靠近并接触位移0.3mm，保持两颗粒接触10s再缓慢拉开，然后通过胡克定律计算两颗粒间微机械力，一次实验重复40次，根据微机械力测量结果表征抑制剂抑制颗粒聚集效果(评价抑制剂抑制颗粒在管壁附着的效果可将其中一个颗粒换为碳钢)，如表1所示：
表1：双效水合物抑制剂在微观评价装置中的性能评价结果
(3)利用与(1)相同的水合物抑制剂溶液利用宏观评价装置开展流动状态下水合物沉积堵塞实验，利用恒温水浴槽将管道降温至实验温度，向管道内通入甲烷气体并加压至实验压力保持稳定，然后通入配制降温后的抑制剂溶液，注入过程中始终通过磁力搅拌器搅拌；
(4)利用温度传感器B17和压力传感器B18及气体流量计20实时采集数据，如图4(a)、4(b)、5所示，当管道出口压力及流量降为0且管道发生明显堵塞时，实验结束，缓慢释放管内压力，根据实验堵塞时间对微观实验结果进行验证及宏观评价，如表2所示：
表2：双效水合物抑制剂在流动管路中的性能评价结果
由表1、2测试结果可以得出，双效水合物抑制剂的加入可以有效降低水合物颗粒间的粘附力，使得生成的水合物颗粒很难聚集成团，从而保持一定的流动性，水合物即使生成也能随管流排出管外，避免块状水合物聚集体的形成及管壁附着沉积，从而延缓了水合物堵塞管道的时间。同时根据测试结果可以看出，对于水合物抑制剂单剂A，浓度越高性能越优；而由单剂A、B复配得到的复配型抑制剂性能远远优于单剂效果。
以上所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明所述原理的前提下，还可以作出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (2)

  1. 一种双效水合物抑制剂的微观和宏观评价方法，其特征在于，通过微观评价装置和宏观评价装置对双效水合物抑制剂分别从微观和宏观两个角度综合评价，筛选出性能优良的双效水合物抑制剂；
    所述微观评价装置包括MMF测量模块、恒温水浴模块、注气模块A和数据采集模块A，所述MMF测量模块包括高压腔体、三维移轴连杆和三维移动台，三维移动台设置于高压腔体内，且与三维移轴连杆连接，通过三维移轴连杆能够调节三维移动台的位置；
    所述高压腔体内部设置有两个玻璃纤维，一个玻璃纤维一端固定在高压腔体内壁上，另一端用于放置冰颗粒，另一个玻璃纤维的一端固定在三维移动台上，另一端用于放置冰颗粒或液滴或碳钢；
    所述恒温水浴模块包括一循环水浴系统，高压腔体置于恒温环境下以达到实验所需温度；
    所述注气模块A包括高压气源A，高压气源A的管道经减压阀A、进气阀A与高压腔体连接，高压气源A的管道上设置有压力表A，所述高压腔体上还设置有放空阀A；
    所述数据采集模块A包括显微成像系统、数据采集系统A、温度传感器A和压力传感器A，所述高压腔体安装有可视窗口，显微成像系统对准可视窗口设置，以实时观测高压腔体内部的微观形态，所述温度传感器A和压力传感器A均与高压腔体连接，用于实时测量压力和温度，所述显微成像系统、温度传感器A和压力传感器A均与数据采集系统A信号连接；
    微观评价装置的实验步骤，包括：
    1)实验准备阶段：
    采用循环水浴系统将恒温环境降温至-7～-10℃，并测量实验所需的玻璃纤维的弹性系数，取两个玻璃纤维，在一个玻璃纤维上尖端放置所需的测试液液滴，并通过液氮制备冰颗粒，在另一个玻璃纤维尖端根据需要放置冰颗粒或碳钢或液滴；
    2)水合物颗粒诱导生成阶段：
    将制得的冰颗粒迅速放入高压腔体，打开放空阀A，通过高压气源A向高压腔体循环通气，保证高压腔体内部气体纯净，关闭放空阀A，加压至实验所需压力，水合物颗粒经过冰粒诱导生成，该时刻记为实验初始时刻；
    3)水合物颗粒退火阶段：
    将恒温环境的温度升至实验温度并保持稳定2h，以确保水合物颗粒的外壳足够坚硬；
    4)粘附力测试阶段：
    通过三维移轴连杆调整三维移动台，使得两测量对象保持在同一水平线，然后控制三维移动台使其上的玻璃纤维尖端缓慢匀速靠近另一个玻璃纤维的尖端，即移动端逐渐靠近固定端，两测量对象接触后，使移动端继续运动压迫固定端并位移0.3mm，两测量对象保持接触10s，再缓慢匀速拉开，直至两测量对象完全分开；
    利用显微成像系统拍摄两测量对象分开时的图像，并测量所拍摄图像中固定端的位移，然后转化为固定端的实际位移；
    利用胡克定律计算两测量对象间的微机械力，一次实验重复40次；
    5)实验结束，通过放空阀A缓慢泄压；
    步骤1)中，测量玻璃纤维弹性系数的过程为：
    在电子天平上放置一个支架，然后将玻璃纤维压迫支架顶端，记录玻璃纤维底端位移及天平示数，根据胡克定律计算弹性系数；
    步骤4)中，测量所拍摄图像中固定端的位移后，利用标定纸将图像上的位移转化为实际位移，或者采用ImageJ软件处理得到；
    步骤4)中，两测量对象间的微机械力计算过程为：
    F＝k·δ  (1)

    其中，F为两测量对象间微机械力测量值，N；F*为两测量对象间微机械力修正值，N；k为玻璃纤维的弹性系数，N/m；δ为固定端的实际位移，m；R1、R2为两测量对象的曲率半径，m；R*为调和平均半径，m；
    所述宏观评价装置包括实验模块、注水模块、注气模块B和数据采集模块B，所述实验模块包括恒温水浴槽和位于恒温水浴槽内的全透明PVC管，恒温水浴槽通过管道连接制冷循环机用于保持恒温水浴槽温度恒定，全透明PVC管的两端均设置有一温度传感器B和压力传感器B；
    所述注气模块B包括一高压气源B，高压气源B的管道经减压阀B、气体流量计、进气阀B、冷却管盘与全透明PVC管的进口连接，高压气源B的管道上设置有压力表B，全透明PVC管的出口还连接有管道出口阀门；
    所述注水模块包括用于盛放测试溶液的容器，测试溶液经液体柱塞泵、进水阀从全 透明PVC管的进口进入，所述测试溶液的管道上设置有放空阀B；
    所述数据采集模块B包括数据采集系统B和DV摄像机，DV摄像机用于实时拍摄全透明PVC管内的堵塞过程，气体流量计、全透明PVC管两端的温度传感器B和压力传感器B均与数据采集系统B连接；
    全透明PVC管的出口管道弯曲放置在100℃保温桶中；
    宏观评价装置的实验步骤，包括：
    S1，实验准备阶段：
    向全透明PVC管通入实验气体，排出管内残余空气和液体水，确保管内气体纯净，将恒温水浴槽温度降至实验温度，将测试溶液降温至实验温度并通过磁力搅拌器使其混合均匀；
    S2，开启数据采集系统B采集数据，打开进气阀使实验气体进入实验管路，控制管道出口阀门以改变全透明PVC管的压力，当全透明PVC管内压力达到实验压力后，保持管道出口阀门开度稳定；
    S3，记录测试溶液初始量，启动液体柱塞泵，以恒定速率向全透明PVC管注入测试溶液，并记录开始注入的时间，以此作为实验开始时刻；
    S4，通过温度传感器B、压力传感器B及气体流量计实时采集数据，通过DV摄像机实时拍摄全透明PVC管内水合物生成沉积堵塞过程；
    S5，实验中通过控制减压阀B维持管道入口压力稳定，当观察到水合物堵塞的发生、管道出口压力及气体流量降低为0，意味着实验结束，关闭液体柱塞泵并记录剩余测试溶液量及时间，该时间作为实验终止时间，缓慢打开管道出口阀门降低管内压力，促进水合物分解，称量水合物分解水的重量并以此反算沉积的水合物量；
    宏观评价装置的实验方法体现在实验管道堵塞时间、管道进出口压力差、管道发生完全堵塞后节流效应导致的温降幅度三个方面；通过对比实验开始时刻到管道发生完全堵塞所需时间长短、管道进出口压差值达到最大所需时间长短，对比双效水合物抑制剂在“防止水合物颗粒聚集”、“抑制水合物颗粒在管壁附着”两方面的效果，时间越长，证明抑制剂效果越好；或者通过对比管道发生完全堵塞时出口温降幅度大小来对比双效水合物抑制剂的效果，温降幅度越小，代表形成的水合物聚集体越疏松，证明抑制效果越好。
  2. 根据权利要求1所述的双效水合物抑制剂的微观和宏观评价方法，其特征在于，所述高压气源A为烃类气体。
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