WO2017181393A1 - 一种三元体系流体互溶度测定方法 - Google Patents

一种三元体系流体互溶度测定方法 Download PDF

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WO2017181393A1
WO2017181393A1 PCT/CN2016/079901 CN2016079901W WO2017181393A1 WO 2017181393 A1 WO2017181393 A1 WO 2017181393A1 CN 2016079901 W CN2016079901 W CN 2016079901W WO 2017181393 A1 WO2017181393 A1 WO 2017181393A1
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fluid
pressure
mutual
sampling
tested
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PCT/CN2016/079901
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English (en)
French (fr)
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张丛
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深圳市樊溪电子有限公司
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Priority to PCT/CN2016/079901 priority Critical patent/WO2017181393A1/zh
Priority to PCT/CN2016/080897 priority patent/WO2017181443A1/zh
Publication of WO2017181393A1 publication Critical patent/WO2017181393A1/zh

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/02—Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering

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  • the invention relates to the technical field of dissolution and phase equilibrium in physical chemistry and the technical field of oil and gas exploration and development, in particular to a method for measuring fluid mutual solubility of a ternary system, and further relates to a ternary system fluid mutual solubility measuring system.
  • the cloud point method is to put a pre-configured concentration of solute and solvent into the balance tank, and then gradually change the pressure or temperature until a phase begins to appear or disappears. The pressure, temperature and known solute at this time are observed. The concentration is the solubility at this temperature.
  • the cloud point method is divided into two types: constant temperature method and variable temperature method. Since the cloud point method does not need sampling analysis, it avoids the interference of high pressure sampling on the fluid balance system, but the equipment needs to have a visible window, and the mirror and the kettle body are required. Very high sealing performance, because the temperature that the mirror can withstand is mostly below 200 °C, and the high temperature and high pressure sealing between the sight glass and the kettle body is difficult, so the fluid balance cannot be measured by the cloud point method under high temperature and high pressure conditions. The solubility of the system.
  • the analytical method is to place excess solute in a solvent in the equilibrium tank, and seal it at a constant temperature for continuous or intermittent stirring until it is fully dissolved to form a fluid equilibrium system, and then sample from each phase in the balance tank to the equilibrium kettle.
  • the composition analysis was carried out under normal pressure to obtain the composition of each phase, thereby obtaining the data of the phase equilibrium system.
  • the methods used for component analysis include gas chromatography (GC), high performance liquid chromatography (HPLC), and gravimetric methods.
  • the analytical method can be divided into a dynamic method and a static method depending on the manner in which the dissolution equilibrium is obtained.
  • the dynamic method requires higher equipment and it is more difficult to achieve a dissolution balance.
  • the static method is the most common method for determining fluid solubility.
  • the main problem in the prior art using the static method is the interference of the high temperature and high pressure sampling on the equilibrium state in the reactor, especially the near critical region where the two-phase equilibrium composition is close, the equilibrium time is multiplied, and the measurement error is large.
  • the current general method for determining the equilibrium of dissolution is to determine that the concentration of the two phases remains the same by two or more times, that is, the system can be considered to have reached the equilibrium state of dissolution, but this increases the workload of the measurement.
  • the key to fluid miscibility/solubility determination is how to balance the system as quickly as possible and how to accurately balance the sampling.
  • the fluid mutual solubility/solubility measuring device based on the cloud point method and the analysis method generally only involves the two-phase fluid, the temperature and pressure of the dissolution equilibrium system are low, it is difficult to judge the fluid to be mutually soluble, and the fluid balance system is easily destroyed when sampling. Affects the temperature and pressure of the fluid balance system, resulting in large measurement errors. Therefore, there is an urgent need for an accurate measurement method for measuring the mutual solubility of a ternary system fluid.
  • the present invention proposes a method for determining the mutual solubility of a ternary system fluid. This method of measurement can The ternary system fluid mutual solubility is measured realistically. In addition, the present invention also proposes a ternary system fluid mutual solubility measurement system.
  • a method for determining a mutual solubility of a ternary system fluid comprising the steps of: step 1: injecting a fluid to be tested into a mutual solvent; and step 2, dissolving the fluid to be tested at a constant pressure.
  • step 3 When the pressure and temperature in the mutual solvent are kept substantially unchanged, substantially isothermal isobaric sampling; in step 4, the sampling fluid is collected, and the dissolved amount of the fluid to be tested is separately measured.
  • the sampling can be performed under the condition that the pressure and temperature in the mutual solvent tank remain unchanged, and the temperature of the sampling fluid entering the sampler during sampling is measured.
  • the pressure is basically equivalent to the pressure and temperature in the mutual solvent, so that the sampling solution does not break the dissolved balance of the fluid to be tested in the mutual solvent, so the dissolution characteristics of the sample fluid are equivalent to the dissolution characteristics of the fluid to be tested in the mutual solvent, so that the measurement can be truly determined.
  • the soaking kettle has an operating temperature of up to 400 ° C and a working pressure of up to 100 MPa. Thereby, the versatility of the method for determining the mutual solubility of the ternary system fluid is improved.
  • the mutual solvent is injected in order from the largest to the smallest according to the density of the fluid to be tested. Easy to select the sampling port.
  • step 2 further comprises detecting whether the fluid to be tested in the mutual solvent tank reaches a dissolution equilibrium, and if so, performing step 3, and if not, proceeding to step 2. Thereby, the dissolved equilibrium state of the fluid to be tested in the mutual solvent can be accurately grasped, which is favorable for truly determining the mutual solubility of the fluid to be tested.
  • step 3 further comprises preheating the sampler to a temperature equal to the temperature in the miscible kettle before sampling, increasing the pressure in the sampler to be slightly greater than the pressure in the mutual solvent to open the mutual solvent and the sampler.
  • Sampling valve Since the sampling valve is in fluid communication with the sampling port on the side wall of the mutual solvent tank, the fluid to be tested in the mutual solvent tank does not quickly flow out from the sampling port, which facilitates the retention of the dissolved balance of the fluid to be tested in the mutual solvent.
  • the pressure within the sampler is reduced to slightly less than the pressure within the miscible vessel.
  • the fluid to be tested in the mutual solvent tank slowly flows out from the sampling port until a set amount of the sampling fluid is sampled.
  • the dissolution balance of the fluid to be tested in the mutual dissolution kettle is not broken.
  • a ternary system fluid mutual solubility measuring system comprising: a fluid injection unit comprising a first intermediate container, a second intermediate container and a third intermediate container arranged in parallel; a high-pressure fluid dissolving unit comprising a mutual-dissolving kettle and a dissolving heating furnace, wherein one ends of the first intermediate container, the second intermediate container and the third intermediate container are in fluid communication with the mutual-dissolving tank through a one-way valve, and the dissolving heating furnace is used for maintaining the inside of the mutual melting tank
  • the temperature is constant;
  • the balance sampling unit comprises a pressure balancer, a sampler, a sampling heating furnace and a pressure maintaining device, wherein the pressure balancer is used for maintaining the pressure in the mutual solvent tank substantially unchanged, and the sampler is fluidly connected to the mutual solvent tank through the one-way valve.
  • the sampling furnace maintains the temperature in the sampler equal to the temperature in the mutual solvent, and the pressure maintaining device maintains the pressure in the sampler substantially equal to the pressure in the mutual solvent;
  • the collecting unit It includes a gas-liquid separator that is in fluid communication with the sampler through a one-way valve to collect the sampled fluid.
  • the controller further includes a controller that sends a driving signal to the pressure balancer according to the pressure value in the mutual solvent, the pressure balancer maintains the pressure in the mutual solvent substantially unchanged according to the driving signal, and/or the controller according to
  • the pressure value in the mutual dissolution kettle sends a control signal to the pressure holding device, and the pressure holding device maintains the pressure in the sampler substantially equal to the pressure in the mutual solvent tank according to the control signal.
  • the mutual solvent kettle and the sampler are each connected to a vacuum pump to evacuate the mutual solvent kettle prior to injection and to evacuate the sampler prior to sampling. This improves the accuracy of the mutual solubility measurement.
  • a stirrer is provided in the miscible kettle. Improve the efficiency of mutual dissolution of the fluids to be tested.
  • the invention has the advantages that isothermal isostatic sampling is realized, and the dissolution characteristics of the sampling fluid are equivalent to the dissolution characteristics of the dissolution equilibrium, and the accuracy of the mutual solubility measurement is improved.
  • the working temperature of the mutual solvent kettle can reach 400 ° C, and the working pressure can reach 100 MPa.
  • the versatility of the method for determining the mutual solubility of the ternary system fluid is improved.
  • it also includes detecting whether the fluid to be tested in the mutual solvent tank reaches a dissolution equilibrium, thereby being able to grasp the dissolved equilibrium state of the fluid to be tested in the mutual solvent tank, and improving the accuracy of the mutual solubility measurement.
  • the sampler is preheated prior to sampling to a temperature equal to the temperature in the miscible kettle, and the pressure in the sampler is increased to slightly greater than the pressure in the miscible vessel to open the sampling valve between the mutual solvent kettle and the sampler. It is beneficial to maintain the dissolution balance of the fluid to be tested in the mutual dissolution kettle. After opening the sampling valve, the pressure in the sampler is reduced to slightly less than the pressure in the mutual solvent. Thereby, sampling is performed without breaking the dissolution balance of the fluid to be tested in the mutual solvent.
  • FIG. 1 is a flow chart of a ternary system fluid mutual solubility determination method in accordance with a preferred embodiment of the present invention
  • FIG. 2 is a schematic illustration of a ternary system fluid mutual solubility determination system in accordance with a preferred embodiment of the present invention.
  • a ternary system fluid mutual solubility measurement method and a ternary system fluid mutual solubility measurement system are proposed.
  • the assay method will be described in detail below in connection with the assay system.
  • the ternary system refers to three kinds of pure substance fluids or mixed substance fluids which are insoluble or have low solubility at normal temperature and pressure.
  • Mixed material ternary system fluid such as formation water (water in which inorganic minerals are dissolved) is a one-way system, crude oil (complex organic matter mixture) is a binary system, natural gas (mixed hydrocarbon gas) is a ternary system; pure substance three Yuan System fluids, such as pure water, are monobasic systems, toluene is a binary system, and methane is a ternary system.
  • the present invention is applicable not only to the measurement of the mutual solubility of the ternary system fluid, but also to the measurement of the mutual solubility of the binary system fluid.
  • the assay system includes a fluid injection unit, a high temperature and high pressure fluid dissolution unit, and a balance sampling unit.
  • the assay system of the present invention and its various units are described in detail below.
  • the fluid injection unit includes a first intermediate container 14, a second intermediate container 15, and a third intermediate container 16 which are disposed in parallel.
  • the fluid to be tested may be injected into the mutual solvent tank 7 through the first intermediate container 14, the second intermediate container 15, and the third intermediate container 16, respectively.
  • one end of the first intermediate container 14, the second intermediate container 15, and the third intermediate container 16 are in fluid communication with the miscible tank 7 through a one-way valve, the first intermediate container 14, the second intermediate container 15, and the third intermediate portion.
  • the other end of the container 16 is connected to the high pressure pump 1, whereby the high pressure pump 1 can pressurize the fluid to be tested in the first intermediate container 14, the second intermediate container 15, and the third intermediate container 16, so that the fluid to be tested is pressurized It is injected into the mutual solvent tank 7 to facilitate mutual dissolution of the fluid to be tested.
  • the high temperature and high pressure fluid dissolution unit includes a mutual dissolution kettle 7 and a dissolution heating furnace 6.
  • the dissolution heating furnace 6 is disposed on the outer periphery of the mutual solvent tank 7 for maintaining the temperature in the mutual solvent tank 7 constant.
  • the balance sampling unit includes a pressure balancer, a sampler 10, a sampling furnace 11 and a pressure maintaining device 12, and the pressure balancer is connected to the mutual solvent tank 7 for maintaining the pressure in the mutual solvent tank 7 substantially constant.
  • the sampler 10 is in fluid communication with the miscible kettle 7 through a one-way valve.
  • the sampling furnace 11 maintains the temperature in the sampler 10 equal to the temperature in the miscible vessel 7, and the pressure maintaining device 12 maintains the pressure in the sampler 10 substantially equal to the mutual solvent.
  • the sampler 10 can be configured as a cylindrical barrel, the rodless end of the sampler 10 being in fluid communication with the miscible vessel 7 via a one-way valve, and the pressure holding device 12 can be a sampling high pressure pump.
  • the pressure balancer includes a piston barrel 5 disposed at an end of the mutual solvent tank 7 (which may be a bottom end as shown) and a piston rod movement of the constant pressure constant speed high pressure pump 4 driving the piston barrel 5 to change the mutual dissolution tank 7 The volume, thereby adjusting the pressure in the mutual dissolution kettle 7.
  • the mutual solvent kettle shown in the drawing is a barrel shape placed vertically, and the present invention is not limited thereto, and may be horizontally placed.
  • the sampler 10 is not limited to being located at the upper portion of the mutual solvent tank 7 in the drawing, and a sampling port connected to the sampler 10 may be provided at any height position on the side surface of the mutual solvent tank 7 as needed.
  • the collection unit includes a gas-liquid separator 13 that is in fluid communication with the sampler 10 through a one-way valve to collect the sampled fluid.
  • the measuring system further includes a controller, and the controller sends a driving signal to the pressure balancer according to the pressure value in the mutual solvent tank 7, and the constant pressure constant speed high pressure pump 4 moves the piston cylinder 5 according to the driving signal to change the mutual melting kettle.
  • the volume of 7 is such that the pressure in the mutually dissolved kettle 7 remains substantially unchanged.
  • the controller transmits a control signal to the pressure holding device 12 based on the pressure value in the mutual solvent tank 7, and the pressure holding device 12 changes the volume of the sampler 10 according to the control signal so that the pressure in the sampler 10 is substantially equal to the pressure in the mutual solvent tank 7. .
  • the controller obtains the pressure value and the temperature value in the mutual solvent tank 7 It is obtained by a pressure sensor and a temperature sensor provided on the mutual solvent tank 7.
  • the sampler 10 is also provided with a pressure sensor and a temperature sensor for controlling the sampling heating furnace 11 and the pressure maintaining device 12, and the controller receives the monitoring signals of the pressure sensor and the temperature sensor at different positions to realize the fluid to be tested in the mutual solvent tank 7, respectively. Constant temperature and constant pressure mutual dissolution and isothermal isobaric sampling.
  • the mutual solvent tank 7 and the sampler 10 are respectively connected with a vacuum pump 9, and the mutual solvent tank 7 and the sampler 10 are respectively connected to the vacuum pump 9 through a one-way valve as shown in the drawing, before the fluid to be tested is injected.
  • the mutual solvent kettle 7 was evacuated.
  • the sampler 10 is evacuated by a vacuum pump 9 before sampling. Improve the accuracy of mutual solubility determination.
  • a stirrer 8 is provided in the mutual solvent kettle 7.
  • it may be a retractable magnetic stirrer provided on the top of the mutual solvent kettle 7.
  • the agitator is agitated with the fluid to be sufficiently dissolved. After stirring for a certain period of time, let stand for a period of time to allow the fluid to be tested to reach a dissolved equilibrium state.
  • the measuring method comprises the step 1: injecting the fluid to be tested into the mutual solvent tank 7 (see Fig. 1).
  • the fluid to be tested can be directly injected into the mutual solvent tank 7.
  • the fluid at normal temperature can be directly added, and the semi-fluid sample, such as a semi-fluid crude oil sample at normal temperature, can be preheated to a fluid state and then added, and the gas sample passes through the gas.
  • the pressurization system is pressurized to a certain pressure and injected into the mutual solvent kettle 7.
  • the interior of the miscible tank 7 is evacuated prior to injecting the fluid so as not to affect the determination of the mutual solubility.
  • the mutual injection tank 7 is sequentially injected from the largest to the smallest, and a plurality of sampling ports are disposed on the side wall of the mutual solvent tank 7, thereby facilitating the selection of the sampling port at the time of sampling.
  • the order of adding and adding the fluid is determined according to the density of the three fluids to be tested, and the higher density is added first, and the density is small, such as formation water, normal crude oil and high pressure.
  • the density of natural gas is reduced in turn, first adding formation water, then adding crude oil, and finally injecting natural gas.
  • the operating temperature of the mutually soluble kettle 7 may be any set temperature, preferably, the highest temperature is up to 400 ° C and the working pressure is up to 100 MPa.
  • Step 2 Constant pressure constant temperature dissolves the fluid to be tested.
  • the start-up dissolution heating furnace 6 starts to raise the temperature to a set temperature at a certain heating rate, and the increase of the temperature causes an increase in the pressure in the mutual solvent tank 7.
  • the constant pressure constant-speed high-pressure pump 4 can be passed down.
  • step 2 further comprises detecting whether the fluid to be tested in the mutual solvent tank 7 reaches a dissolution equilibrium, and if so, performing step 3, and if not, proceeding to step 2.
  • the mutual dissolution kettle 7 is provided with a dissolution balance monitoring unit 3 for determining whether or not the fluid to be tested has reached a dissolution equilibrium.
  • the dissolution balance monitoring unit 3 is composed of a resistivity measuring device, which is based on the fact that the resistivity of the fluid to be tested changes after the fluid of any one of the fluids to be tested is dissolved, and the resistivity of the fluid to be tested is reached when the equilibrium state is reached. Then no change, according to which it can be judged whether the ternary system fluid has reached the dissolution equilibrium at the set temperature and the set pressure.
  • the dissolution balance monitoring unit 3 may be disposed at different positions of the mutual solvent kettle 7 as needed.
  • Step 3 When the pressure and temperature in the mutual solvent tank 7 are kept substantially unchanged, the isothermal isostatic sampling is performed. Before sampling Preheating the sampler 10 to a temperature substantially equal to the temperature in the miscible tank 7, increasing the pressure in the sampler 10 to a pressure slightly greater than that in the miscible tank 7, generally not exceeding 5%, to open the mutual solvent kettle 7 and the sampler 10. Sampling valve between. Since the sampling valve is in fluid communication with the sampling port on the side wall of the mutual solvent tank 7, the fluid to be tested in the mutual solvent tank 7 does not rapidly flow out from the sampling port, which facilitates the maintenance of the dissolution balance of the fluid to be tested in the mutual solvent tank 7.
  • the pressure in the sampler 10 is reduced to a pressure slightly less than that in the miscible tank 7, typically no more than 5%.
  • the fluid to be tested in the mutual solvent tank 7 slowly flows out from the sampling port until a set amount of the sampling fluid is sampled.
  • Step 4 Collect the sampling fluid and measure the dissolved amount of the fluid to be tested.
  • the sampling valve is opened to drive the sampling fluid in the sampler 10 to the gas-liquid separator 13.
  • the dissolved amount of different phase fluids in the ternary system was measured.
  • the oil and water in the water phase can be collected into a conical flask, and the sampler and the pipeline are washed with chloroform multiple times, and the oil can be dissolved in chloroform at normal temperature and pressure, thereby being pure
  • the aqueous phase was separated, the organic phase and the aqueous phase were separated by a separating funnel, the volume of water was quantified by a measuring cylinder, and the organic phase (chloroform phase) was concentrated by a rotary evaporator, and then filtered into a small beaker of constant weight to be evaporated to dry chloroform. After constant weight, the amount of crude oil dissolved in the aqueous phase can be

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Abstract

一种三元体系流体互溶度测定方法，包括以下步骤：步骤1，将待测流体分别注入互溶釜中；步骤2，恒压恒温溶解所述待测流体；步骤3，保持所述互溶釜内压力和温度基本不变的情况下，大体等温等压取样；步骤4，收集取样流体，分别测得所述待测流体的溶解量。使用这种测定方法，能够真实地测定三元体系流体互溶度。

Description

一种三元体系流体互溶度测定方法 技术领域
本发明涉及物理化学中溶解与相平衡技术领域和油气勘探与开发技术领域，具体涉及一种三元体系流体互溶度测定方法，此外，还涉及一种三元体系流体互溶度测定系统。
背景技术
目前，测定流体互溶度/溶解度主要采用浊点法和分析法。浊点法是将预先配置好的一定浓度的溶质与溶剂放入平衡釜内，然后逐渐改变压力或温度，直至观察到某一相开始出现或消失，此时的压力、温度以及已知的溶质浓度即该温度压力下的溶解度。
浊点法又分为恒温法和变温法两种，由于浊点法无需取样分析，因而避免了高压取样对流体平衡体系的干扰，但是需要设备带有可视窗口，对视镜和釜体要求非常高的密封性，由于视镜所能承受的温度大多在200℃以下，并且视镜和釜体之间的高温高压密封比较困难，因此在高温高压条件下，不能采用浊点法测定流体平衡体系的溶解度。
分析法是将过量的溶质置于平衡釜内的溶剂中，密封在恒温下进行连续或者间断的搅拌，直到充分溶解形成流体平衡体系，再通过从平衡釜内的每一相中取样至平衡釜外，在常压下进行组成分析，得到各相组成，以此求得相平衡体系的数据。组分分析采用的方法有气相色谱法(GC)、高效液相色谱法(HPLC)、重量法等各种测试方法。依据获得溶解平衡的方式可以将分析法分为动态法和静态法。动态法对设备要求较高，较难以达到溶解平衡。相比较而言，静态法是测定流体溶解度最为常用的方法。现有技术中采用静态法存在的主要问题是高温高压取样对反应釜内平衡状态的干扰，尤其是两相平衡组成接近的近临界区，平衡时间成倍增加，测定误差较大。目前判断溶解平衡的通用方法是通过两次以上测定两相的浓度保持不变，即可以认为该体系达到了溶解平衡状态，但这样增加了测定的工作量。
流体互溶度/溶解度测定的关键是如何使体系尽快达到平衡，如何准确平衡取样。目前，基于浊点法和分析法的流体互溶度/溶解度测定装置一般仅涉及到两相流体，溶解平衡体系温度和压力都较低，判断流体达到互溶状态困难，而且取样时容易破坏流体平衡体系，影响流体平衡体系的温度和压力，造成测量误差大。因此，急需一种测量准确的三元体系流体互溶度测定方法。
发明内容
针对上述的问题，本发明提出了一种三元体系流体互溶度测定方法。这种测定方法能够 真实地测定三元体系流体互溶度。此外，本发明还提出了一种三元体系流体互溶度测定系统。
根据本发明的第一方面，提出了一种三元体系流体互溶度测定方法，包括以下步骤：步骤1，将待测流体分别注入互溶釜中；步骤2，恒压恒温溶解所述待测流体；步骤3，保持互溶釜内压力和温度基本不变的情况下，大体等温等压取样；步骤4，收集取样流体，分别测得所述待测流体的溶解量。
采用本发明提供的三元体系流体互溶度测定方法进行互溶度测定时，能够在互溶釜内的压力和温度保持不变的情况下进行取样，而且取样时进入到取样器中的取样流体的温度和压力基本等同于互溶釜内压力和温度，由此取样时没有打破互溶釜内待测流体溶解平衡，因此取样流体的溶解特征等同于互溶釜内待测流体的溶解特征，从而能够真实地测定该温度和压力条件下的流体互溶度。
在一个实施例中，互溶釜的工作温度可达400℃，工作压力可达100MPa。由此提高该三元体系流体互溶度测定方法的通用性。
在一个实施例中，根据待测流体的密度按由大到小依次注入互溶釜中。便于取样端口的选择。
在一个实施例中，步骤2还包括检测互溶釜中的待测流体是否达到溶解平衡，若是，执行步骤3，如不是，继续执行步骤2。由此能够准确掌握互溶釜内待测流体的溶解平衡状态，利于真实地测定待测流体的互溶度。
在一个实施例中，步骤3还包括取样之前预热取样器至等温于互溶釜内的温度，将取样器内的压力增加至略大于互溶釜内的压力，以打开互溶釜和取样器之间的取样阀。由于取样阀流体连通于互溶釜侧壁上的取样端口，由此使得互溶釜内待测流体不会从取样端口迅速涌出，利于互溶釜内待测流体溶解平衡的保持。
在一个实施例中，打开取样阀之后，将取样器内的压力降至略小于互溶釜内的压力。由此互溶釜内的待测流体从取样端口缓慢流出，直至取样设定量的取样流体为止。从而没有打破互溶釜内待测流体的溶解平衡。
根据本发明的第二方面，还提出了一种三元体系流体互溶度测定系统，其包括：流体注入单元，其包括并联设置的第一中间容器、第二中间容器和第三中间容器；高温高压流体溶解单元，其包括互溶釜和溶解加热炉，第一中间容器、第二中间容器和第三中间容器的一端通过单向阀流体连通于互溶釜，溶解加热炉用于保持互溶釜内的温度不变；平衡取样单元，包括压力平衡器、取样器、取样加热炉和压力保持装置，压力平衡器用于保持互溶釜内的压力大体不变，取样器通过单向阀流体连通于互溶釜，取样加热炉保持取样器内的温度等同于互溶釜内的温度，压力保持装置保持取样器内的压力大体等同于互溶釜内的压力；收集单元， 其包括气液分离器，气液分离器通过单向阀流体连通于取样器，以收集取样流体。
采用本发明提供的三元体系流体互溶度测定系统进行互溶度测定时，能够实现等温等压取样，而且取样时流体的溶解特征没有发生变化，提高互溶度测定的准确性。
在一个实施例中，其还包括控制器，控制器根据互溶釜内压力值向压力平衡器发送驱动信号，压力平衡器根据驱动信号保持互溶釜内的压力大体不变，和/或控制器根据互溶釜内压力值向压力保持装置发送控制信号，压力保持装置根据控制信号保持取样器内的压力大体等同于互溶釜内的压力。由此能够实时地控制互溶釜内的压力保持恒定，以及实时地控制取样器内的压力大体等同于互溶釜内的压力。
在一个实施例中，互溶釜和取样器分别连接有真空泵，以在注入之前将互溶釜抽真空，并且在取样之前将取样器抽真空。由此提高互溶度测定的准确性。
在一个实施例中，互溶釜中设置有搅拌器。提高待测流体相互溶解的效率。
与现有技术相比，本发明的优点在于，实现了等温等压取样，而且取样流体的溶解特征等同于溶解平衡的溶解特征，提高了互溶度测定的准确性。优选地，互溶釜的工作温度可达400℃，工作压力可达100MPa。由此提高该三元体系流体互溶度测定方法的通用性。另外，还包括检测互溶釜中的待测流体是否达到溶解平衡，由此能够掌握互溶釜内待测流体的溶解平衡状态，提高互溶度测定的准确性。取样之前预热取样器至等温于互溶釜内的温度，将取样器内的压力增加至略大于互溶釜内的压力，以打开互溶釜和取样器之间的取样阀。利于互溶釜内待测流体溶解平衡的保持。打开取样阀之后，将取样器内的压力降至略小于互溶釜内的压力。由此在不打破互溶釜内待测流体的溶解平衡的状态下进行取样。
附图说明
在下文中将基于实施例并参考附图来对本发明进行更详细的描述。其中：
图1是根据本发明的一个优选实施例的三元体系流体互溶度测定方法的流程图；
图2是根据本发明的一个优选实施例的三元体系流体互溶度测定系统的示意图。
在图中，相同的构件由相同的附图标记标示。附图并未按照实际的比例绘制。
具体实施方式
下面将结合附图对本发明做进一步说明。
如图1和图2所示，根据本发明提出三元体系流体互溶度测定方法和三元体系流体互溶度测定系统。下面将结合所述测定系统详细地说明所述测定方法。
需要说明的是，三元体系是指三种在常温常压下不溶或溶解度很低的纯物质流体或者混合物质流体。混合物质三元体系流体，如地层水(溶解有无机矿物质的水)为一元体系，原油(复杂的有机质混合物)为二元体系，天然气(混合烃类气体)为三元体系；纯物质三元 体系流体，如纯水为一元体系，甲苯为二元体系，甲烷为三元体系。
需要说明的是，本发明不仅适用于三元体系流体互溶度的测定，也适用于二元体系流体互溶度的测定。
所述测定系统包括包括流体注入单元、高温高压流体溶解单元和平衡取样单元。下面详细地描述本发明的测定系统及其各单元。
如图2所示，流体注入单元包括并联设置的第一中间容器14、第二中间容器15和第三中间容器16。待测流体可以分别通过第一中间容器14、第二中间容器15和第三中间容器16注入到互溶釜7内。如图所示，第一中间容器14、第二中间容器15和第三中间容器16的一端通过单向阀与互溶釜7流体连通，第一中间容器14、第二中间容器15和第三中间容器16的另一端连接于高压泵1，由此高压泵1可以加压第一中间容器14、第二中间容器15和第三中间容器16中的待测流体，从而待测流体被加压后注入到互溶釜7内，利于待测流体的相互溶解。
如图2所示，高温高压流体溶解单元包括互溶釜7和溶解加热炉6。溶解加热炉6设置于互溶釜7的外周，用于保持互溶釜7内的温度不变。
如图2所示，平衡取样单元包括压力平衡器、取样器10、取样加热炉11和压力保持装置12，压力平衡器连接于互溶釜7，用于保持互溶釜7内的压力大体不变。取样器10通过单向阀流体连通于互溶釜7，取样加热炉11保持取样器10内的温度等同于互溶釜7内的温度，压力保持装置12保持取样器10内的压力大体等同于互溶釜7内的压力。如图所示取样器10可以构造为活塞筒状，取样器10的无杆端通过单向阀流体连通于互溶釜7，压力保持装置12可以是取样高压泵。例如压力平衡器包括设置于互溶釜7的端部(如图所示可以是底端)的活塞筒5和恒压恒速高压泵4驱动活塞筒5的活塞杆移动，以改变互溶釜7的容积，从而调节互溶釜7内的压力。需要说明的是，图中示出的互溶釜为竖直放置的桶状，本发明并不局限于此，也可以是水平放置。另外，取样器10不限于在附图中位于互溶釜7的上部，互溶釜7侧面任一高度位置均可按照需要设置有与取样器10连接的取样端口。
如图2所示，收集单元包括气液分离器13，气液分离器13通过单向阀流体连通于取样器10，以收集取样流体。
作为优选的实施例，所述测定系统还包括控制器，控制器根据互溶釜7内压力值向压力平衡器发送驱动信号，恒压恒速高压泵4根据驱动信号移动活塞筒5来改变互溶釜7的容积，从而保持互溶釜7内的压力大体不变。另外，控制器根据互溶釜7内压力值向压力保持装置12发送控制信号，压力保持装置12根据控制信号改变取样器10的容积，使得取样器10内的压力大体等同于互溶釜7内的压力。另外，控制器获取互溶釜7内的压力值和温度值可以 通过设置于互溶釜7上的压力传感器和温度传感器获取。此外取样器10上也设置有压力传感器和温度传感器控制取样加热炉11和压力保持装置12，控制器接收上述不同位置的压力传感器和温度传感器的监测信号分别实现互溶釜7内的待测流体的恒温恒压互溶以及等温等压取样。
优选地，如图2所示，互溶釜7和取样器10分别连接有真空泵9，如图所示互溶釜7和取样器10分别通过单向阀连通于真空泵9，在待测流体注入之前将互溶釜7抽真空。另外，取样之前通过真空泵9将取样器10抽真空。提高了互溶度测定的准确性。
此外，互溶釜7中设置有搅拌器8。例如可以是设置在互溶釜7的顶部的可伸缩磁力搅拌器。搅拌器对待测流体进行搅拌，以能够相互充分溶解。搅拌一定时间之后再静置一段时间让待测流体达到溶解平衡状态。
该测定方法包括的步骤1：将待测流体分别注入互溶釜7(参见图1)中。待测流体可以直接注入互溶釜7内，作为优选地，常温下为流体的样品可以直接加入，半流体样品如常温下为半流体的原油样品可以预热至流体状态后加入，气体样品通过气体增压系统增压至一定压力后注入到互溶釜7内。作为优选地，注入流体前将互溶釜7内抽真空，以免影响互溶度的测定。进一步地，根据待测流体的密度按由大到小依次注入互溶釜7中，由于互溶釜7的侧壁上设置有多个取样端口，以此便于取样时取样端口的选择。具体地，以三元体系流体为例，依据三种待测流体的密度大小确定流体的加入顺序与加入量，密度较高的先加入，密度小的后加入，例如地层水、正常原油与高压天然气的密度依次变小，先加地层水，再加入原油，最后注入天然气。由于常温状态下待测流体不相互溶解或者互溶度极低，所以注入到互溶釜7内的待测流体的量要远大于待测流体的互溶度。互溶釜7的工作温度可以是任意的设定温度，优选地，最高温度可达400℃，工作压力可达100MPa。
步骤2：恒压恒温溶解所述待测流体。启动溶解加热炉6按一定升温速率开始升温至设定温度，由于温度的升高会导致互溶釜7内压力的增加，当压力超过设定压力之后，可以通过恒压恒速高压泵4向下移动活塞筒5，将压力调节至设定值。优选地，步骤2还包括检测互溶釜7中的待测流体是否达到溶解平衡，若是，执行步骤3，如不是，继续执行步骤2。如图2所示，互溶釜7上设置有用于测定待测流体是否达到溶解平衡的溶解平衡监测单元3。溶解平衡监测单元3由电阻率测定装置组成，这是基于待测流体中的任一元体系流体在溶解了之后，待测流体的电阻率会发生改变，而当达到溶解平衡状态时，其电阻率则不再变化，据此可判断三元体系流体在设定温度和设定压力下是否已经达到溶解平衡。另外，溶解平衡监测单元3可以根据需要设置于互溶釜7的不同位置处。
步骤3：保持互溶釜7内压力和温度基本不变的情况下，大体等温等压取样。取样之前 预热取样器10至大体等温于互溶釜7内的温度，将取样器10内的压力增加至略大于互溶釜7内的压力，一般不超过5％，以打开互溶釜7和取样器10之间的取样阀。由于取样阀流体连通于互溶釜7侧壁上的取样端口，互溶釜7内的待测流体不会从取样端口迅速涌出，利于互溶釜7内待测流体溶解平衡的保持。优选地，打开取样阀之后，将取样器10内的压力降至略小于互溶釜7内的压力，一般不超过5％。由此互溶釜7内的待测流体从取样端口缓慢流出，直至取样设定量的取样流体为止。
步骤4：收集取样流体，分别测得所述待测流体的溶解量。打开取样阀门，将取样器10内的取样流体驱至气液分离器13中。分别测出三元体系中不同相态流体的溶解量。以油气水三元体系流体互溶试验为例，可将水相中的油水收集到三角烧瓶中，并用氯仿多次洗涤取样器与管线，油在常温常压下能够溶解在氯仿中，从而与纯水相分层，用分液漏斗分离有机相与水相，用量筒定量水的体积，有机相(氯仿相)用旋转蒸发器浓缩之后，过滤到已恒重的小烧杯中，待挥发干氯仿之后再恒重，即可以得到水相中溶解的原油量。油相含水率采用“GB/T260-88“原油含水量测定法(蒸馏法)”进行测定。
虽然已经参考优选实施例对本发明进行了描述，但在不脱离本发明的范围的情况下，可以对其进行各种改进并且可以用等效物替换其中的部件。本发明并不局限于文中公开的特定实施例，而是包括落入权利要求的范围内的所有技术方案。

Claims (6)

  1. 一种三元体系流体互溶度测定方法，其特征在于，包括以下步骤：
    步骤1，将待测流体分别注入互溶釜中；
    步骤2，恒压恒温溶解所述待测流体；
    步骤3，保持所述互溶釜内压力和温度基本不变的情况下，大体等温等压取样；
    步骤4，收集取样流体，分别测得所述待测流体的溶解量。
  2. 根据权利要求1所述的三元体系流体互溶度测定方法，其特征在于，所述互溶釜的工作温度可达400℃，工作压力可达100MPa。
  3. 根据权利要求1或2所述的三元体系流体互溶度测定方法，其特征在于，根据所述待测流体的密度按由大到小依次注入所述互溶釜中。
  4. 根据权利要求1所述的三元体系流体互溶度测定方法，其特征在于，所述步骤2还包括检测所述互溶釜中的所述待测流体是否达到溶解平衡，若是，执行所述步骤3，如不是，继续执行所述步骤2。
  5. 根据权利要求1所述的三元体系流体互溶度测定方法，其特征在于，所述步骤3还包括取样之前预热取样器至等温于所述互溶釜内的温度，将所述取样器内的压力增加至略大于所述互溶釜内的压力，以打开所述互溶釜和所述取样器之间的取样阀。
  6. 根据权利要求5所述的三元体系流体互溶度测定方法，其特征在于，打开所述取样阀之后，将所述取样器内的压力降至略小于所述互溶釜内的压力。
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