CN105973937A - Thermo-physical property measurement system and method of hydrate - Google Patents
Thermo-physical property measurement system and method of hydrate Download PDFInfo
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- 238000005259 measurement Methods 0.000 title claims abstract description 52
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 230000000704 physical effect Effects 0.000 claims abstract description 23
- 238000000748 compression moulding Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000012495 reaction gas Substances 0.000 claims description 32
- 238000001514 detection method Methods 0.000 claims description 27
- 150000004677 hydrates Chemical class 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 18
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- 238000011066 ex-situ storage Methods 0.000 claims description 2
- 238000000691 measurement method Methods 0.000 abstract description 7
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- 238000006703 hydration reaction Methods 0.000 description 1
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Abstract
一种水合物热物性测量系统及其测量方法，热物性测量系统包括高压反应釜、控温装置、压缩成型装置、供气装置、测量装置和数据采集装置。控温装置包括恒温水浴箱，高压反应釜放置在恒温水浴箱内。压缩成型装置包括活塞，活塞后部的高压反应釜内壁上开有进液口，进液口连接有增压泵。测量装置包括热分析仪，热分析仪的探头插入两套筒中间位置。通过上述一种水合物热物性测量系统进行测量时，首先将样品放入套筒内，然后活塞挤压套筒，再然后通过热分析仪测量水合物的热物性。上述一种水合物热物性测量系统及其测量方法，水合物两侧同时受到挤压，探头不会弯折，能减少探头损坏。同时，水合物一致性好，测量精度高。
A hydrate thermophysical property measurement system and a measurement method thereof. The thermophysical property measurement system includes a high-pressure reaction kettle, a temperature control device, a compression molding device, a gas supply device, a measurement device and a data acquisition device. The temperature control device includes a constant temperature water bath box, and the high pressure reaction kettle is placed in the constant temperature water bath box. The compression molding device includes a piston, and a liquid inlet is opened on the inner wall of the high-pressure reaction kettle at the rear of the piston, and the liquid inlet is connected with a booster pump. The measuring device includes a thermal analyzer, and a probe of the thermal analyzer is inserted into the middle of the two sleeves. When measuring by the above-mentioned thermal physical property measurement system of hydrate, the sample is first put into the sleeve, then the piston squeezes the sleeve, and then the thermal physical properties of the hydrate are measured by a thermal analyzer. In the above thermal physical property measurement system of hydrate and its measurement method, both sides of the hydrate are squeezed at the same time, the probe will not be bent, and the damage of the probe can be reduced. At the same time, the hydrate has good consistency and high measurement accuracy.
Description
技术领域technical field
本发明涉及一种热物性测量系统及其测量方法，具体涉及一种测量精度高，探头不易损坏的水合物热物性测量系统及其该水合物热物性测量系统的测量方法。The invention relates to a thermal physical property measurement system and a measurement method thereof, in particular to a hydrate thermal physical property measurement system with high measurement accuracy and a probe that is not easily damaged and the measurement method of the hydrate thermal physical property measurement system.
背景技术Background technique
自从18世纪中期Benjamin Franklin开始对固体的导热能力进行实验研究以来，已研究出多种导热系数的测量方法，导热系数的测量主要分为稳态法和非稳态法两大类。近些年来水合物导热系数的研究取得了一定进展，但由于测量方法和实验手段的差异，测量结果不尽相同。测量过程中，考虑到水合物的亚稳定性，科研人员更倾向于采用非稳态法，如探头法，热线法，瞬变平面热源法等。当使用探头法对水合物的导热系数进行原位测量时，可以径向布置探头，也可以轴向布置探头，当径向布置探头时很难保证对样品进行加压致密时探头形态不改变，且不能有效驱除样品中残余气体；而当轴向布置探头时则不能进行轴向加压。也可采用瞬变平面热源法测量水合物的导热系数，这种方法的优点是测量速度更快，且不受接触热阻的影响，但是探头垂直插入高压反应釜，高压反应釜的盖子安装时探头会旋转，在沉积物介质中探头很容易被损坏，另外，当活塞压实样品时探头易弯曲损坏。Since Benjamin Franklin began to conduct experimental research on the thermal conductivity of solids in the middle of the 18th century, a variety of thermal conductivity measurement methods have been developed. The measurement of thermal conductivity is mainly divided into two categories: steady-state method and unsteady-state method. In recent years, the research on the thermal conductivity of hydrates has made some progress, but due to the differences in measurement methods and experimental means, the measurement results are not the same. In the measurement process, considering the metastability of hydrates, researchers prefer to use non-steady-state methods, such as probe method, hot wire method, transient plane heat source method, etc. When using the probe method to measure the thermal conductivity of hydrates in situ, the probes can be arranged radially or axially. When the probes are arranged radially, it is difficult to ensure that the shape of the probe does not change when the sample is pressurized and compacted. And the residual gas in the sample cannot be effectively expelled; and when the probe is arranged axially, the axial pressure cannot be carried out. The thermal conductivity of hydrates can also be measured by the transient plane heat source method. The advantage of this method is that the measurement speed is faster and it is not affected by the contact thermal resistance. However, the probe is inserted vertically into the high-pressure reactor. The probe will rotate, the probe is easily damaged in the sediment medium, and the probe is easily damaged when the piston compresses the sample.
发明内容Contents of the invention
为了解决现有技术中探头易损坏的问题，本发明提供一种水合物热物性测量系统及其测量方法。In order to solve the problem that the probe is easily damaged in the prior art, the present invention provides a hydrate thermophysical property measurement system and a measurement method thereof.
本发明提供的一种水合物热物性测量系统，包括高压反应釜、控温装置、压缩成型装置、供气装置、测量装置和数据采集装置。所述高压反应釜下部设置有底座支架，底座支架上设置有两个套筒，两个套筒对称分布，各套筒沿横向轴线壁面上的中心位置开有加料孔；高压反应釜内还设置有压力传感器和第一温度传感器，第一温度传感器通过加料孔伸入套筒内。所述控温装置包括恒温水浴箱，高压反应釜放置在恒温水浴箱内，恒温水浴箱内设置有盘管，所述盘管内有制冷剂循环流动。恒温水浴箱内还设置有第二温度传感器和搅拌器；恒温水浴箱连接有温度控制器。所述压缩成型装置包括两个分别设置在两个套筒后部的活塞，两个活塞后部的高压反应釜内壁上还分别开有进液口，两个进液口分别连接有第一液压支管和第二液压支管，第一液压支管和第二液压支管均连通液压主管，所述液压主管连通增压泵；所述液压主管上还设置有液压主阀。供气装置包括检漏通道、抽真空通道、反应气体供气通道和放空通道；检漏通道、抽真空通道、反应气体供气通道和放空通道均与高压反应釜相连通；所述抽真空通道还连接有真空泵；反应气体供气通道连通反应气体气瓶；放空通道上设置有安全阀和放气阀。所述测量装置包括热分析仪，热分析仪的探头上设置有由聚甲基丙烯酸甲酯制成的保护膜；两个套筒上设置有相对分布的凹槽，当两个套筒扣合在一起时，两个凹槽形成探头安装孔，所述探头通过探头安装孔插入两套筒中间位置。所述数据采集器连接有热分析仪、压力传感器、第一温度传感器，数据采集器还通过数据输出信号线连接有计算机。A hydrate thermophysical property measurement system provided by the present invention includes a high-pressure reaction kettle, a temperature control device, a compression molding device, a gas supply device, a measurement device and a data acquisition device. The lower part of the high-pressure reaction kettle is provided with a base bracket, and two sleeves are arranged on the base bracket. The two sleeves are symmetrically distributed, and each sleeve has a feeding hole at the center of the wall surface along the transverse axis; There are a pressure sensor and a first temperature sensor, and the first temperature sensor extends into the sleeve through the feeding hole. The temperature control device includes a constant temperature water bath box, and the high-pressure reaction kettle is placed in the constant temperature water bath box, and a coil is arranged in the constant temperature water bath box, and a refrigerant circulates in the coil tube. The constant temperature water bath box is also provided with a second temperature sensor and a stirrer; the constant temperature water bath box is connected with a temperature controller. The compression molding device includes two pistons respectively arranged at the rear of the two sleeves, liquid inlets are respectively opened on the inner wall of the high-pressure reactor at the rear of the two pistons, and the two liquid inlets are respectively connected to the first hydraulic pressure The branch pipe and the second hydraulic branch pipe, the first hydraulic branch pipe and the second hydraulic branch pipe are all connected to the hydraulic main pipe, and the hydraulic main pipe is connected to the booster pump; the hydraulic main pipe is also provided with a hydraulic main valve. The gas supply device includes a leak detection channel, a vacuuming channel, a reaction gas supply channel and a venting channel; the leak detection channel, the vacuuming channel, the reaction gas supply channel and the venting channel are all connected with the high-pressure reactor; the vacuuming channel A vacuum pump is also connected; the reaction gas supply channel is connected with the reaction gas cylinder; a safety valve and an air release valve are arranged on the venting channel. The measuring device includes a thermal analyzer, the probe of the thermal analyzer is provided with a protective film made of polymethyl methacrylate; the two sleeves are provided with relatively distributed grooves, when the two sleeves are fastened together When they are together, the two grooves form a probe mounting hole through which the probe is inserted into the middle of the two sleeves. The data collector is connected with a thermal analyzer, a pressure sensor, and a first temperature sensor, and the data collector is also connected with a computer through a data output signal line.
优选的，所述压缩成型装置还包括压力控制组件，压力控制组件包括用于测量套筒与活塞距离的测距仪，所述测距仪连接有液压控制器，所述液压控制器连接有第一电动液压阀和第二电动液压阀，所述第一电动液压阀和第二电动液压阀分别安装在第一液压支管和第二液压支管上。通过测距仪测量活塞与套筒之间距离，测距仪将信号输送至液压控制器，液压控制器判断两活塞分别距离相对应套筒距离，并通过调节第一电动液压阀和第二电动液压阀调节活塞运动速度，使两个活塞同时分别抵接两套筒并进行压缩，保证在压缩过程中探头不被破坏。Preferably, the compression molding device further includes a pressure control assembly, the pressure control assembly includes a range finder for measuring the distance between the sleeve and the piston, the range finder is connected to a hydraulic controller, and the hydraulic controller is connected to a second An electro-hydraulic valve and a second electro-hydraulic valve, the first electro-hydraulic valve and the second electro-hydraulic valve are installed on the first hydraulic branch pipe and the second hydraulic branch pipe respectively. The distance between the piston and the sleeve is measured by the range finder, and the range finder sends the signal to the hydraulic controller. The hydraulic controller judges the distance between the two pistons and the corresponding sleeve, and adjusts the first electro-hydraulic valve and the second electro-hydraulic valve. The hydraulic valve adjusts the movement speed of the piston, so that the two pistons contact the two sleeves at the same time and compress it, so as to ensure that the probe is not damaged during the compression process.
再优选的，所述测距仪包括两个红外信号组件，所述红外信号组件包括红外发射器和红外接收器，所述两个红外信号组件分别固定在套筒的后部凹槽内。通过红外信号组件测量套筒和活塞距离，测量精度高。Still preferably, the range finder includes two infrared signal assemblies, the infrared signal assemblies include an infrared emitter and an infrared receiver, and the two infrared signal assemblies are respectively fixed in the rear grooves of the sleeve. The distance between the sleeve and the piston is measured by the infrared signal component, and the measurement accuracy is high.
优选的，活塞与高压反应釜内壁接触处设置有密封垫圈。在活塞与高压反应釜内壁接触处设置密封垫圈，可以防止活塞后部液体泄漏进入两活塞之间的高压反应釜空腔。Preferably, a gasket is provided at the contact between the piston and the inner wall of the autoclave. A sealing gasket is arranged at the contact between the piston and the inner wall of the high-pressure reactor, which can prevent the liquid at the rear of the piston from leaking into the cavity of the high-pressure reactor between the two pistons.
优选的，所述高压反应釜内部还通过铰接件设置有至少两个支撑杆，探头固定在支撑杆的上端，铰接件通过螺纹连接在反应釜内壁上。当需要取出或放入套筒时，只需旋转支撑杆即可即可，支撑杆的设置不会影响套筒的取出与放入。当套筒过大时，还可以将螺纹连接的铰接件拆卸，然后取下支撑杆，最后取出或放入套筒，所述支撑杆的设置可以固定探头，同时，也不影响套筒的取出或放入。Preferably, at least two support rods are provided inside the high-pressure reactor through a hinge, the probe is fixed on the upper end of the support rod, and the hinge is connected to the inner wall of the reactor through threads. When it is necessary to take out or put in the sleeve, it is only necessary to rotate the support rod, and the setting of the support rod will not affect the taking out and putting in of the sleeve. When the sleeve is too large, the threaded hinge can be disassembled, then the support rod can be removed, and finally the sleeve can be taken out or put in. The setting of the support rod can fix the probe, and at the same time, it does not affect the removal of the sleeve or put in.
本发明提供的一种水合物热物性测量系统，与现有技术相比，具有以下有益效果：Compared with the prior art, a hydrate thermophysical property measurement system provided by the present invention has the following beneficial effects:
上述一种水合物热物性测量系统，可以使沉积物与溶液原位高压合成水合物，可以原位测量热物性参数，也可以非原位测量水合物热物性参数，能够减少探头损坏，提高实验测量精度。The above-mentioned thermophysical property measurement system of hydrate can make sediment and solution synthesize hydrate in situ under high pressure, and can measure thermophysical parameters in situ, and can also measure thermophysical parameters of hydrate in situ, which can reduce probe damage and improve experimental performance. measurement accuracy.
所述套筒可以将样品压缩成标准柱状体，保证样品的一致性，减小样品对测量结果的影响。套筒的设置防止水合物被挤压到上部高压反应釜筒状盖中；也可以最大限度减少沉积物或水合物散落在高压反应釜内壁上，从而减少活塞运动阻力，尽可能减少了活塞两侧压差。套筒上开有加料孔，加料孔可以用来加入松散的干的沉积物，也可以方便插入第一温度传感器。The sleeve can compress the sample into a standard column to ensure the consistency of the sample and reduce the influence of the sample on the measurement result. The setting of the sleeve prevents the hydrate from being extruded into the cylindrical cover of the upper autoclave; it can also minimize the sediment or hydrate scattered on the inner wall of the autoclave, thereby reducing the movement resistance of the piston and reducing the two-way pressure of the piston as much as possible. side differential. A feeding hole is provided on the sleeve, and the feeding hole can be used to add loose dry deposits, and can also be used for conveniently inserting the first temperature sensor.
高压反应釜置入恒温水浴箱内，制冷剂在盘管内循环流动实现控温，恒温水浴箱内温度由温度控制器进行调控，对水浴温度可进行程序降温和升温，即通过温度振荡法使高压反应釜内物质快速反应；恒温水浴设置第一温度传感器、第二温度传感器和搅拌器，第一温度传感器用以测量套筒内温度，第二温度传感器用于测量恒温水浴箱内水浴实时温度，搅拌器使恒温水浴箱内各处温度均匀。The high-pressure reaction kettle is placed in a constant temperature water bath box, and the refrigerant circulates in the coil to realize temperature control. The material in the reaction kettle reacts quickly; the constant temperature water bath is equipped with a first temperature sensor, a second temperature sensor and a stirrer, the first temperature sensor is used to measure the temperature in the sleeve, and the second temperature sensor is used to measure the real-time temperature of the water bath in the constant temperature water bath box, The stirrer makes the temperature uniform throughout the constant temperature water bath.
压缩成型装置包括增压泵和高压反应釜两端受液压驱动的活塞，当判断水合物反应结束后，通过增压泵加压，高压反应釜两端的活塞向套筒方向运动，活塞挤压套筒，完成对样品的压缩成型，由于探头固定于高压反应釜中心位置，采用双侧挤压可保证探头不会因为挤压而发生位移，可有效保护探头，使探头不被破坏。The compression molding device includes a booster pump and pistons driven by hydraulic pressure at both ends of the high-pressure reactor. When it is judged that the hydrate reaction is over, the booster pump pressurizes, and the pistons at both ends of the high-pressure reactor move toward the sleeve, and the piston squeezes the sleeve. Cylinder to complete the compression molding of the sample. Since the probe is fixed at the center of the autoclave, double-sided extrusion can ensure that the probe will not be displaced due to extrusion, which can effectively protect the probe and prevent the probe from being damaged.
高压反应釜内由于活塞的挤压，必导致釜内压力升高，为保证釜内压力在安全压力下，防空通道上设置安全阀，压力设置稍高于高压反应釜内水合物生成压力。当活塞挤压造成高压反应釜内压力超过安全阀设定压力时，安全阀打开，释放压力，当高压反应釜内压力达到安全阀设定压力时，安全阀关闭，以此保证高压反应釜在安全压力下工作，使高压反应釜内压力保持恒定，减少因压力变化对水合物样品产生的影响。Due to the extrusion of the piston in the high-pressure reaction kettle, the pressure inside the kettle will inevitably increase. In order to ensure that the pressure in the kettle is under a safe pressure, a safety valve is installed on the air defense passage, and the pressure setting is slightly higher than the hydrate formation pressure in the high-pressure reaction kettle. When the pressure in the high-pressure reactor exceeds the set pressure of the safety valve due to the extrusion of the piston, the safety valve opens to release the pressure. When the pressure in the high-pressure reactor reaches the set pressure of the safety valve, the safety valve closes to ensure that the high-pressure reactor remains Work under safe pressure to keep the pressure inside the autoclave constant and reduce the impact of pressure changes on hydrate samples.
本发明还提供一种水合物热物性测量方法，所述测量方法需使用上述一种水合物热物性测量系统，具体测量步骤如下：The present invention also provides a method for measuring thermal physical properties of hydrates. The measuring method needs to use the above-mentioned thermal physical properties measuring system for hydrates. The specific measurement steps are as follows:
第一步，将探头的保护膜卡在两个套筒的凹槽内，然后将两个扣合在一起的套筒放到横置的高压反应釜中。In the first step, the protective film of the probe is stuck in the groove of the two sleeves, and then the two sleeves snapped together are placed in the horizontal high-pressure reactor.
第二步，安装好高压反应釜的筒状盖，通过检漏通道进行系统检漏，保证高压反应釜没有漏点。The second step is to install the cylindrical cover of the autoclave, and conduct system leak detection through the leak detection channel to ensure that there are no leaks in the autoclave.
然后关闭检漏通道上的检漏阀门，打开抽真空阀门，启动真空泵，将高压反应釜抽真空，抽真空完毕后，关闭抽真空阀门并把高压反应釜放到恒温水浴箱中；根据实验要求，调整恒温水浴箱内温度。Then close the leak detection valve on the leak detection channel, open the vacuum valve, start the vacuum pump, and evacuate the high-pressure reactor. After the vacuum is completed, close the vacuum valve and put the high-pressure reactor into a constant temperature water bath; , adjust the temperature inside the constant temperature water bath.
第三步，打开反应气体气瓶，打开反应气体供气通道的供气阀门，向高压反应釜中通入反应气体至实验要求压力，静置一段时间后调节水浴温度至实验要求温度，进行水合物生成反应。The third step is to open the reaction gas cylinder, open the gas supply valve of the reaction gas supply channel, feed the reaction gas into the high-pressure reactor to the pressure required by the experiment, and after standing for a period of time, adjust the temperature of the water bath to the temperature required by the experiment for hydration product formation reaction.
第四步，采用温度振荡法使水合物反应完全，工作人员可通过计算水合物反应所需反应气体量、加入反应气体量和高压反应釜内气体压力确认是否反应完全。反应完全后，打开液压主阀，启动手动增压泵加压，待压力达到所需压力时，活塞对两个套筒两侧同时挤压获得压缩后的水合物样品。The fourth step is to use the temperature oscillation method to make the hydrate reaction complete. The staff can confirm whether the reaction is complete by calculating the amount of reaction gas required for the hydrate reaction, the amount of reaction gas added, and the gas pressure in the high-pressure reactor. After the reaction is complete, open the hydraulic main valve and start the manual booster pump to pressurize. When the pressure reaches the required pressure, the piston squeezes both sides of the two sleeves simultaneously to obtain the compressed hydrate sample.
第五步，待样品压缩完毕后，启动热分析仪进行水合物热物性的测量，热分析仪通过探头对样品进行加热,同时记录温度随时间升高的阻值并将其反馈回热分析仪，在由热分析仪将测量信息传递给数据采集器进行实时数据采集，最终由计算机计算得出水合物样品的热物性参数。Step 5: After the sample is compressed, start the thermal analyzer to measure the thermal properties of the hydrate. The thermal analyzer heats the sample through the probe, and at the same time records the resistance value of the temperature rising with time and feeds it back to the thermal analyzer , the thermal analyzer transmits the measurement information to the data collector for real-time data collection, and finally the computer calculates the thermal physical parameters of the hydrate sample.
优选的，当水合物样品原位生成时，首先称量一定比例的沉积物和溶液填充在两个套筒内，压实抹平表面，然后将两个套筒扣合在一起。Preferably, when the hydrate sample is generated in situ, a certain proportion of sediment and solution is firstly weighed and filled in the two sleeves, the surface is compacted and smoothed, and then the two sleeves are fastened together.
优选的，当水合物样品原位生成且样品为松散颗粒状时，首先将安装有探头的两个套筒安放到横置的高压反应釜中，然后将沉积物和溶液从套筒上的加料孔中慢慢注入。Preferably, when the hydrate sample is generated in situ and the sample is in the form of loose particles, first place the two sleeves with probes installed in a horizontal high-pressure reactor, and then feed the sediment and solution from the sleeves Inject slowly into the hole.
本发明与现有技术相比，具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
上述一种水合物热物性测量方法，只需将水合物或沉积物与溶液放置在套筒内，两个活塞分别从两侧挤压两个套筒，水合物两侧同时受到挤压，探头不会移动，也不会弯折，能够减少探头损坏。同时，两侧挤压后的水合物一致性好，实验测量精度高。样品添加到套筒内，可以防止样品掉落并粘附到高压反应釜的内壁上。The above method for measuring the thermal physical properties of hydrates only needs to place hydrates or sediments and solutions in the sleeve, and the two pistons squeeze the two sleeves from both sides respectively, and both sides of the hydrate are squeezed at the same time, and the probe Will not move or bend, reducing probe damage. At the same time, the consistency of the hydrate after extrusion on both sides is good, and the experimental measurement accuracy is high. The sample is added to the sleeve, which prevents the sample from falling and sticking to the inner wall of the autoclave.
高压反应釜置入恒温水浴箱内，恒温水浴箱内温度由温度控制器进行调控，通过温度振荡法，使温度不断变动，可以加快水合物的生成反应。The high-pressure reaction kettle is placed in a constant temperature water bath box, and the temperature in the constant temperature water bath box is regulated by a temperature controller. Through the temperature oscillation method, the temperature is continuously changed, which can speed up the formation reaction of hydrates.
附图说明Description of drawings
图1是一种水合物热物性测量系统的结构示意图。Fig. 1 is a schematic structural diagram of a hydrate thermophysical property measurement system.
图2是两个套筒的剖面图。Figure 2 is a cross-sectional view of two sleeves.
图3是高压反应釜的侧剖面图。Fig. 3 is a side sectional view of the autoclave.
1、高压反应釜；2套筒；3活塞；4探头；5筒状盖；6手动增压泵；7、8反应气体气瓶；9真空泵；10气体流量计；11、12气体减压阀；13压力传感器；14第一温度传感器；15安全阀；16放气阀；17a第一电动液压阀；17b第二电动液压阀；18液压主阀；19、20第一压力表；21、22供气阀门、23抽真空阀门；24液压控制器；25第二温度传感器；26搅拌器；27密封垫圈；28底座支架；29盘管；30恒温水浴箱；31测距仪；32计算机；33数据采集器；34热分析仪；35信号电缆；36加料孔；37红外信号组件；38支撑杆；39探头电缆；40第二压力表。1. High pressure reactor; 2 sleeve; 3 piston; 4 probe; 5 cylindrical cover; 6 manual booster pump; 7, 8 reaction gas cylinder; 9 vacuum pump; 10 gas flow meter; ; 13 pressure sensor; 14 first temperature sensor; 15 safety valve; 16 air release valve; 17a first electro-hydraulic valve; 17b second electro-hydraulic valve; Air supply valve, 23 vacuum valve; 24 hydraulic controller; 25 second temperature sensor; 26 agitator; 27 sealing gasket; 28 base bracket; 34 thermal analyzer; 35 signal cable; 36 feeding hole; 37 infrared signal component; 38 support rod; 39 probe cable; 40 second pressure gauge.
具体实施方式detailed description
实施例1Example 1
一种水合物热物性测量系统，包括高压反应釜1、控温装置、压缩成型装置、供气装置、测量装置和数据采集装置。所述高压反应釜1下部设置有底座支架28，底座支架28上设置有两个套筒2，两个套筒2对称分布，各套筒2沿横向轴线壁面上的中心位置开有加料孔36；高压反应釜1内还设置有压力传感器13和第一温度传感器14，第一温度传感器14通过加料孔36插入套筒2内。A hydrate thermophysical property measurement system includes a high-pressure reaction kettle 1, a temperature control device, a compression molding device, a gas supply device, a measurement device and a data acquisition device. The lower part of the high-pressure reactor 1 is provided with a base bracket 28, and the base bracket 28 is provided with two sleeves 2, and the two sleeves 2 are symmetrically distributed, and each sleeve 2 has a feeding hole 36 at the center of the wall surface along the transverse axis A pressure sensor 13 and a first temperature sensor 14 are also provided in the high pressure reactor 1, and the first temperature sensor 14 is inserted into the sleeve 2 through the feeding hole 36.
所述控温装置包括恒温水浴箱30，高压反应釜1放置在恒温水浴箱30内，恒温水浴箱30内设置有盘管29，所述盘管29内有制冷剂循环流动。恒温水浴箱30内还设置有第二温度传感器25和搅拌器26，恒温水浴箱30连接有温度控制器。The temperature control device includes a constant temperature water bath box 30, and the high pressure reaction kettle 1 is placed in the constant temperature water bath box 30, and the constant temperature water bath box 30 is provided with a coil 29, and a refrigerant circulates in the coil 29. A second temperature sensor 25 and an agitator 26 are also arranged in the constant temperature water bath box 30 , and the constant temperature water bath box 30 is connected with a temperature controller.
所述压缩成型装置包括两个分别设置在两个套筒2后部的活塞3，活塞3与高压反应釜1内壁接触处设置有密封垫圈27。两个活塞3后部的高压反应釜1内壁上还分别开有进液口，两个进液口分别连接有第一液压支管和第二液压支管，第一液压支管和第二液压支管均连通液压主管，所述液压主管连通增压泵，所述增压泵可以是手动增压泵6；所述液压主管上还设置有液压主阀18。压缩成型装置还包括压力控制组件，压力控制组件包括用于测量套筒2与活塞3距离的测距仪31，测距仪31包括两个红外信号组件37，所述红外信号组件37包括红外发射器和红外接收器，所述两个红外信号组件37分别固定在套筒2的后部凹槽内。通过红外信号组件37测量套筒2和活塞3距离，测量精度高。测距仪31还连接有液压控制器24，所述液压控制器24连接有第一电动液压阀17a和第二电动液压阀17b，第一电动液压阀17a和第二电动液压阀17b分别安装在第一液压支管和第二液压支管上。通过测距仪31测量活塞3与套筒2之间距离，测距仪31将信号输送至液压控制器24，液压控制器24判断两活塞3分别距离套筒2距离，并通过调节第一电动液压阀17a和第二电动液压阀17b调节活塞3运动速度，使两个活塞3同时分别抵接两套筒2；在活塞3抵接套筒2后，测距仪31测距得距离为零，此时将距离信号传递给液压控制器24，液压控制器24控制第一电动液压阀17a和第二电动液压阀17b使其开启程度相同，保证两活塞3挤压力基本相同，以保证在压缩过程中探头4不被破坏。The compression molding device includes two pistons 3 respectively arranged at the rear of the two sleeves 2 , and a sealing gasket 27 is arranged at the contact between the piston 3 and the inner wall of the autoclave 1 . There are also liquid inlets on the inner wall of the high-pressure reactor 1 at the rear of the two pistons 3. The two liquid inlets are respectively connected to the first hydraulic branch pipe and the second hydraulic branch pipe. The first hydraulic branch pipe and the second hydraulic branch pipe are connected. A hydraulic main pipe, the hydraulic main pipe communicates with a booster pump, and the booster pump may be a manual booster pump 6; a hydraulic main valve 18 is also arranged on the hydraulic main pipe. The compression molding device also includes a pressure control assembly. The pressure control assembly includes a distance meter 31 for measuring the distance between the sleeve 2 and the piston 3. The distance meter 31 includes two infrared signal assemblies 37. The infrared signal assembly 37 includes an infrared transmitter The two infrared signal components 37 are respectively fixed in the rear groove of the sleeve 2. The distance between the sleeve 2 and the piston 3 is measured by the infrared signal component 37, and the measurement accuracy is high. The range finder 31 is also connected with a hydraulic controller 24, and the hydraulic controller 24 is connected with a first electrohydraulic valve 17a and a second electrohydraulic valve 17b, and the first electrohydraulic valve 17a and the second electrohydraulic valve 17b are respectively installed on On the first hydraulic branch pipe and the second hydraulic branch pipe. The distance between the piston 3 and the sleeve 2 is measured by the range finder 31, and the range finder 31 sends the signal to the hydraulic controller 24. The hydraulic controller 24 judges the distance between the two pistons 3 and the sleeve 2 respectively, and adjusts the distance between the two pistons 3 and the sleeve 2 by adjusting the first motor The hydraulic valve 17a and the second electro-hydraulic valve 17b adjust the moving speed of the piston 3, so that the two pistons 3 respectively abut the two sleeves 2 at the same time; after the piston 3 abuts the sleeve 2, the distance measured by the range finder 31 is zero At this time, the distance signal is transmitted to the hydraulic controller 24, and the hydraulic controller 24 controls the first electro-hydraulic valve 17a and the second electro-hydraulic valve 17b to make the opening degree the same, so as to ensure that the extrusion force of the two pistons 3 is basically the same, so as to ensure that The probe 4 is not damaged during the compression process.
供气装置包括检漏通道、抽真空通道、反应气体供气通道和放空通道；检漏通道、抽真空通道、反应气体供气通道和放空通道均与高压反应釜1相连通。所述抽真空通道还连接有真空泵9；所述反应气体供气通道连通反应气体气瓶7、8；所述放空通道上设置有安全阀15和放气阀16。The gas supply device includes a leak detection channel, a vacuuming channel, a reaction gas supply channel and a venting channel; The vacuum pumping channel is also connected to a vacuum pump 9; the reaction gas supply channel is connected to the reaction gas cylinders 7 and 8; a safety valve 15 and a gas release valve 16 are arranged on the venting channel.
所述测量装置包括热分析仪34，所述热分析仪34可以是Hot Disk热常数分析仪，热分析仪34的探头4上设置有由聚甲基丙烯酸甲酯制成的保护膜；两个套筒2上设置有相对分布的凹槽，当两个套筒2扣合在一起时，两个凹槽形成探头4安装孔，所述探头4通过探头4安装孔插入两套筒2中间位置。Described measuring device comprises thermal analyzer 34, and described thermal analyzer 34 can be Hot Disk thermal constant analyzer, and the probe 4 of thermal analyzer 34 is provided with the protective film that is made by polymethyl methacrylate; Two The sleeve 2 is provided with relatively distributed grooves. When the two sleeves 2 are fastened together, the two grooves form the installation hole of the probe 4, and the probe 4 is inserted into the middle position of the two sleeves 2 through the installation hole of the probe 4. .
所述数据采集器33连接有热分析仪34、压力传感器13、第一温度传感器14，数据采集器33还通过数据输出信号线连接有计算机32；其中，数据采集器33可以使用安捷伦数据采集仪。Described data collector 33 is connected with thermal analyzer 34, pressure sensor 13, first temperature sensor 14, and data collector 33 is also connected with computer 32 by data output signal line; Wherein, data collector 33 can use Agilent data collector .
进一步的，所述高压反应釜1内部还通过铰接件设置有至少两个支撑杆38，探头4固定在支撑杆38的上端，铰接件通过螺纹连接在反应釜内壁上。当需要取出或放入套筒2时，只需旋转支撑杆38即可即可，支撑杆38的设置不会影响套筒2的取出与放入。当套筒2过大时，还可以将螺纹连接的铰接件拆卸，然后取下支撑杆38，最后取出或放入套筒2，所述支撑杆38的设置可以固定探头4，同时，也不影响套筒2的取出或放入。Further, at least two support rods 38 are provided inside the autoclave 1 through hinges, the probe 4 is fixed on the upper end of the support rods 38, and the hinges are connected to the inner wall of the reactor through threads. When it is necessary to take out or put in the sleeve 2, it is only necessary to rotate the support rod 38, and the setting of the support rod 38 will not affect the taking out and putting in of the sleeve 2. When the sleeve 2 is too large, the threaded joint can also be disassembled, then the support rod 38 can be removed, and finally the sleeve 2 can be taken out or put into the sleeve 2. The setting of the support rod 38 can fix the probe 4, and at the same time, the Affect the taking out or putting in of sleeve 2.
上述一种水合物热物性测量系统，可以使沉积物与溶液原位高压合成水合物，可以原位测量热物性参数，也可以进行非原位测量热物性参数，能够减少探头4损坏，提高实验测量精度。The above-mentioned hydrate thermophysical property measurement system can make hydrates synthesized from sediments and solutions at high pressure in situ, can measure thermophysical parameters in situ, and can also measure thermophysical parameters in situ, which can reduce the damage of probe 4 and improve the experimental efficiency. measurement accuracy.
所述套筒2可以将样品压缩成标准柱状体，保证样品的一致性，减小样品对实验测量结果的影响。套筒2的设置防止水合物样品被挤压到上部高压反应釜1筒状盖5中；也可以最大限度减少沉积物样品散落在高压反应釜1内壁上，从而减少活塞3运动阻力，尽可能减少了活塞3两侧压差。套筒2上开有加料孔36，加料孔36可以用来加入松散的干的沉积物，也可方便插入第一温度传感器14。The sleeve 2 can compress the sample into a standard column to ensure the consistency of the sample and reduce the influence of the sample on the experimental measurement results. The setting of the sleeve 2 prevents the hydrate sample from being squeezed into the cylindrical cover 5 of the upper autoclave 1; it can also minimize the sediment sample from being scattered on the inner wall of the autoclave 1, thereby reducing the movement resistance of the piston 3, and as far as possible The pressure difference on both sides of the piston 3 is reduced. A feeding hole 36 is opened on the sleeve 2, and the feeding hole 36 can be used to add loose dry deposits, and can also be used to insert the first temperature sensor 14 conveniently.
高压反应釜1置入恒温水浴箱30内，制冷剂在盘管29内循环实现控温，恒温水浴箱30内温度由温度控制器进行调控，对水浴温度可进行程序降温和升温，高压反应釜1内设置第一温度传感器14，恒温水浴设置第二温度传感器25和搅拌器26，第一温度传感器14用以测量套筒2内温度，第二温度传感器25用于测量恒温水浴箱30内水浴实时温度，搅拌器26使恒温水浴箱30内各处温度均匀。The high-pressure reaction kettle 1 is placed in the constant temperature water bath box 30, and the refrigerant circulates in the coil 29 to realize temperature control. 1 is provided with a first temperature sensor 14, and the constant temperature water bath is provided with a second temperature sensor 25 and an agitator 26. The first temperature sensor 14 is used to measure the temperature in the sleeve 2, and the second temperature sensor 25 is used to measure the temperature of the water bath in the constant temperature water bath box 30. Real-time temperature, stirrer 26 makes temperature everywhere in constant temperature water bath box 30 uniform.
压缩成型装置包括增压泵和高压反应釜1两端受液压驱动的活塞3，当判断水合物反应结束后，通过增压泵加压，高压反应釜1两端的活塞3向套筒2方向运动，活塞3挤压套筒2，完成对样品的压缩成型，采用双侧挤压可保证探头4不会因为挤压而发生位移，可有效保护探头4不被破坏。The compression molding device includes a booster pump and a hydraulically driven piston 3 at both ends of the high-pressure reactor 1. When it is judged that the hydrate reaction is over, the booster pump pressurizes and the piston 3 at both ends of the high-pressure reactor 1 moves toward the sleeve 2. , the piston 3 squeezes the sleeve 2 to complete the compression molding of the sample, and the double-sided extrusion can ensure that the probe 4 will not be displaced due to extrusion, which can effectively protect the probe 4 from being damaged.
高压反应釜1内由于活塞3的挤压，必导致釜内压力升高，为保证釜内压力在安全压力下，防空通道上设置安全阀15，压力设置稍高于高压反应釜1内水合物生成压力，当活塞3挤压造成高压反应釜1内压力超过安全阀15设定压力时，安全阀15打开，释放压力，当高压反应釜1内压力达到安全阀15设定压力时，安全阀15关闭，以此保证高压反应釜1在安全压力下工作，使高压反应釜1内压力保持恒定，减少因压力变化对水合物样品产生的影响。Due to the extrusion of the piston 3 in the high-pressure reactor 1, the pressure inside the kettle will inevitably rise. In order to ensure that the pressure in the kettle is under a safe pressure, a safety valve 15 is set on the air defense passage, and the pressure setting is slightly higher than that of the hydrate in the high-pressure reactor 1. Generate pressure. When the pressure in the high pressure reactor 1 exceeds the set pressure of the safety valve 15 due to the extrusion of the piston 3, the safety valve 15 is opened to release the pressure. When the pressure in the high pressure reactor 1 reaches the set pressure of the safety valve 15, the safety valve 15 is closed, so as to ensure that the high-pressure reactor 1 works under a safe pressure, keep the pressure inside the high-pressure reactor 1 constant, and reduce the influence of the pressure change on the hydrate sample.
实施例2Example 2
一种水合物热物性测量方法，所述测量方法需使用实施例1所述的一种水合物热物性测量系统，具体测量步骤如下：A method for measuring thermal physical properties of hydrates, the measuring method needs to use the system for measuring thermal physical properties of hydrates described in Example 1, and the specific measurement steps are as follows:
第一步，称量一定比例的沉积物和溶液填充在两个套筒2内，压实抹平表面，然后将两个套筒2扣合在一起。将带有保护膜的探头4卡在两个套筒2的凹槽内，然后将两个扣合在一起的套筒2放到横置的高压反应釜1中。In the first step, a certain proportion of sediment and solution is weighed and filled in the two sleeves 2, and the surface is compacted and smoothed, and then the two sleeves 2 are fastened together. The probe 4 with the protective film is clamped in the grooves of the two sleeves 2, and then the two sleeves 2 snapped together are placed in the horizontal autoclave 1.
第二步，安装好高压反应釜1的筒状盖5，通过检漏通道连通氮气瓶和高压反应釜1，打开检漏通道上的检漏阀门，充入氮气进行系统检漏，保证高压反应釜1没有漏点。The second step is to install the cylindrical cover 5 of the high-pressure reactor 1, connect the nitrogen cylinder and the high-pressure reactor 1 through the leak detection channel, open the leak detection valve on the leak detection channel, and fill in nitrogen for system leak detection to ensure high-pressure reaction Kettle 1 has no leaks.
然后关闭检漏阀门，打开抽真空阀门23，启动真空泵9，将高压反应釜1抽真空，抽真空完毕后，关闭抽真空阀门23并把高压反应釜1放到恒温水浴箱30中；根据实验要求，调整恒温水浴箱30内温度。Then close the leak detection valve, open the vacuum valve 23, start the vacuum pump 9, and the autoclave 1 is vacuumized, after the vacuuming is finished, close the vacuum valve 23 and put the autoclave 1 into the constant temperature water bath box 30; according to the experiment Requirements, adjust the temperature in the constant temperature water bath box 30.
第三步，打开反应气体气瓶7、8，打开反应气体供气通道的供气阀门21、22，向高压反应釜1中通入反应气体至实验要求压力，静置一段时间后调节水浴温度至实验要求温度，进行水合物生成反应。The third step is to open the reaction gas cylinders 7 and 8, open the gas supply valves 21 and 22 of the reaction gas supply channel, and feed the reaction gas into the high pressure reactor 1 to the pressure required by the experiment, and adjust the temperature of the water bath after standing for a period of time To the temperature required by the experiment, the hydrate formation reaction is carried out.
第四步，采用温度振荡法使水合物反应完全，工作人员可通过计算水合物反应所需反应气体量、加入反应气体量和高压反应釜1内气体压力确认是否反应完全。打开液压主阀18，启动手动增压泵6加压，待压力达到所需压力时，活塞3对两个套筒2两侧同时挤压获得压缩后的水合物样品。The fourth step is to use the temperature oscillation method to complete the hydrate reaction. The staff can confirm whether the reaction is complete by calculating the amount of reaction gas required for the hydrate reaction, the amount of reaction gas added, and the gas pressure in the high-pressure reactor 1. Open the hydraulic main valve 18, start the manual booster pump 6 to pressurize, and when the pressure reaches the required pressure, the piston 3 simultaneously squeezes both sides of the two sleeves 2 to obtain a compressed hydrate sample.
第五步，待样品压缩完毕后，启动热分析仪34开始水合物热物性的测量，热分析仪34通过探头4对样品进行加热,同时记录温度随时间升高的阻值并将测量信号反馈回热分析仪34，在由热分析仪34将测量信号传递给数据采集器33进行实时数据采集，最终由计算机32计算得出水合物样品的热物性参数。In the fifth step, after the compression of the sample is completed, start the thermal analyzer 34 to start the measurement of the thermal properties of the hydrate. The thermal analyzer 34 heats the sample through the probe 4, and at the same time records the resistance value of the temperature rising with time and feeds back the measurement signal The heat recovery analyzer 34 transmits the measurement signal from the heat analyzer 34 to the data collector 33 for real-time data collection, and finally the computer 32 calculates the thermophysical parameters of the hydrate sample.
实施例3Example 3
一种水合物热物性测量方法，所述测量方法需使用实施例1所述的一种水合物热物性测量系统，具体测量步骤如下：A method for measuring thermal physical properties of hydrates, the measuring method needs to use the system for measuring thermal physical properties of hydrates described in Example 1, and the specific measurement steps are as follows:
第一步，当水合物样品原位生成且样品为松散颗粒状时，首先将安装有探头4的两个套筒2安放到横置的高压反应釜1中，然后将沉积物和溶液从套筒2上的加料孔36中慢慢注入。In the first step, when the hydrate sample is generated in situ and the sample is in the form of loose particles, first place the two sleeves 2 equipped with probes 4 into the horizontal high-pressure reactor 1, and then remove the sediment and solution from the sleeves. Slowly inject in the feeding hole 36 on the cylinder 2.
第二步，安装好高压反应釜1的筒状盖5，通过检漏通道连通氮气瓶和高压反应釜1，打开检漏通道上的检漏阀门，充入氮气进行系统检漏，保证高压反应釜1没有漏点。The second step is to install the cylindrical cover 5 of the high-pressure reactor 1, connect the nitrogen cylinder and the high-pressure reactor 1 through the leak detection channel, open the leak detection valve on the leak detection channel, and fill in nitrogen for system leak detection to ensure high-pressure reaction Kettle 1 has no leaks.
然后关闭检漏阀门，打开抽真空阀门23，启动真空泵9，将高压反应釜1抽真空，抽真空完毕后，关闭抽真空阀门23并把高压反应釜1放到恒温水浴箱30中；根据实验要求，调整恒温水浴箱30内温度。Then close the leak detection valve, open the vacuum valve 23, start the vacuum pump 9, and the autoclave 1 is vacuumized, after the vacuuming is finished, close the vacuum valve 23 and put the autoclave 1 into the constant temperature water bath box 30; according to the experiment Requirements, adjust the temperature in the constant temperature water bath box 30.
第三步，打开反应气体气瓶7、8，打开反应气体供气通道的供气阀门21、22，向高压反应釜1中通入反应气体至实验要求压力，静置一段时间后调节水浴温度至实验要求温度，进行水合物反应。The third step is to open the reaction gas cylinders 7 and 8, open the gas supply valves 21 and 22 of the reaction gas supply channel, and feed the reaction gas into the high pressure reactor 1 to the pressure required by the experiment, and adjust the temperature of the water bath after standing for a period of time To the temperature required by the experiment, the hydrate reaction is carried out.
第四步，采用温度振荡法使水合物反应完全，工作人员可通过计算水合物反应所需反应气体量、加入反应气体量和高压反应釜1内气体压力确认是否反应完全。打开液压主阀18，启动手动增压泵6加压，待压力达到所需压力时，活塞3对两个套筒2两侧同时挤压获得压缩后的水合物样品。The fourth step is to use the temperature oscillation method to complete the hydrate reaction. The staff can confirm whether the reaction is complete by calculating the amount of reaction gas required for the hydrate reaction, the amount of reaction gas added, and the gas pressure in the high-pressure reactor 1. Open the hydraulic main valve 18, start the manual booster pump 6 to pressurize, and when the pressure reaches the required pressure, the piston 3 simultaneously squeezes both sides of the two sleeves 2 to obtain a compressed hydrate sample.
第五步，待样品压缩完毕后，启动热分析仪34开始水合物热物性的测量，热分析仪34通过探头4对样品进行加热,同时记录温度随时间升高的阻值并将测量信号反馈回热分析仪34，在由热分析仪34将测量信号传递给数据采集器33进行实时数据采集，最终由计算机32计算得出水合物样品的热物性参数。In the fifth step, after the compression of the sample is completed, start the thermal analyzer 34 to start the measurement of the thermal properties of the hydrate. The thermal analyzer 34 heats the sample through the probe 4, and at the same time records the resistance value of the temperature rising with time and feeds back the measurement signal The heat recovery analyzer 34 transmits the measurement signal from the heat analyzer 34 to the data collector 33 for real-time data collection, and finally the computer 32 calculates the thermophysical parameters of the hydrate sample.
实施例4Example 4
一种水合物热物性测量方法，所述测量方法需使用实施例1所述的一种非原位水合物热物性测量系统，具体测量步骤如下：A method for measuring thermal physical properties of hydrates, the measuring method needs to use the ex-situ hydrate thermal physical properties measurement system described in Example 1, and the specific measurement steps are as follows:
第一步，首先将采集到的水合物样品压制成两块同样规格的样品，使其能放进套筒2中，与探头4接触面磨平。然后将两个套筒2扣合在一起。将带有保护膜的探头4卡在两个套筒2的凹槽内，再然后将两个扣合在一起的套筒2放到横置的高压反应釜1中。In the first step, the collected hydrate samples are compressed into two samples of the same specification so that they can be put into the sleeve 2 and the contact surface with the probe 4 is ground flat. Then snap the two sleeves 2 together. The probe 4 with the protective film is clamped in the grooves of the two sleeves 2, and then the two sleeves 2 snapped together are placed in the horizontal high-pressure reactor 1.
第二步，安装好高压反应釜1的筒状盖5，通过检漏通道连通氮气瓶和高压反应釜1，打开检漏通道上的检漏阀门，充入氮气进行系统检漏，保证高压反应釜1没有漏点。The second step is to install the cylindrical cover 5 of the high-pressure reactor 1, connect the nitrogen cylinder and the high-pressure reactor 1 through the leak detection channel, open the leak detection valve on the leak detection channel, and fill in nitrogen for system leak detection to ensure high-pressure reaction Kettle 1 has no leaks.
然后关闭检漏阀门，打开抽真空阀门23，启动真空泵9，将高压反应釜1抽真空，抽真空完毕后，关闭抽真空阀门23并把高压反应釜1放到恒温水浴箱30中；根据实验要求，调整恒温水浴箱30内温度。Then close the leak detection valve, open the vacuum valve 23, start the vacuum pump 9, and the autoclave 1 is vacuumized, after the vacuuming is finished, close the vacuum valve 23 and put the autoclave 1 into the constant temperature water bath box 30; according to the experiment Requirements, adjust the temperature in the constant temperature water bath box 30.
第三步，打开反应气体气瓶7、8，打开反应气体供气通道的供气阀门21、22，向高压反应釜1中通入所需反应气体至实验要求压力，静置一段时间后调节水浴温度至实验要求温度，进行水合物反应。The third step is to open the reaction gas cylinders 7 and 8, open the gas supply valves 21 and 22 of the reaction gas supply channels, and feed the required reaction gas into the high pressure reactor 1 to the required pressure of the experiment, and adjust it after standing for a period of time. The temperature of the water bath reaches the temperature required by the experiment, and the hydrate reaction is carried out.
第四步，打开液压主阀18，启动手动增压泵6加压，待压力达到所需压力时，活塞3对两个套筒2两侧同时挤压获得压缩后的水合物样品。The fourth step is to open the hydraulic main valve 18 and start the manual booster pump 6 to pressurize. When the pressure reaches the required pressure, the piston 3 simultaneously squeezes both sides of the two sleeves 2 to obtain a compressed hydrate sample.
第五步，待样品压缩完毕后，启动热分析仪34开始水合物热物性的测量，热分析仪34通过探头4对样品进行加热,同时记录温度随时间升高的阻值并将其反馈回热分析仪34，在由其传递给数据采集器33进行实时数据采集，最终由计算机32计算得出水合物样品的热物性参数。In the fifth step, after the compression of the sample is completed, start the thermal analyzer 34 to start the measurement of the thermal properties of the hydrate. The thermal analyzer 34 heats the sample through the probe 4, and simultaneously records the resistance value of the temperature rising with time and feeds it back to The thermal analyzer 34 transmits it to the data collector 33 for real-time data collection, and finally the computer 32 calculates the thermal physical parameters of the hydrate sample.
上述实施例2至实施例4所述的一种水合物热物性测量方法，只需将水合物或沉积物与溶液放置在套筒2内，两个活塞3分别从两侧挤压两个套筒2，水合物两侧同时受到挤压，探头4不会移动，也不会弯折，能够减少探头4损坏。同时，两侧挤压后的水合物一致性好，实验测量精度高。样品添加到套筒2内，可以防止样品掉落并粘附到高压反应釜1的内壁上。A method for measuring the thermal physical properties of hydrates described in the above-mentioned Examples 2 to 4, only needs to place the hydrate or sediment and the solution in the sleeve 2, and the two pistons 3 squeeze the two sleeves from both sides respectively. In the cylinder 2, both sides of the hydrate are squeezed at the same time, and the probe 4 will not move or bend, which can reduce the damage of the probe 4. At the same time, the consistency of the hydrate after extrusion on both sides is good, and the experimental measurement accuracy is high. The sample is added into the sleeve 2, which can prevent the sample from falling and sticking to the inner wall of the autoclave 1.
高压反应釜1置入恒温水浴箱30内，恒温水浴箱30内温度由温度控制器进行调控，通过温度振荡法，使温度不断变动，可以加快水合物的生成反应。The high-pressure reaction kettle 1 is placed in a constant temperature water bath box 30, and the temperature inside the constant temperature water bath box 30 is regulated by a temperature controller. The temperature is continuously changed through the temperature oscillation method, which can accelerate the formation reaction of hydrates.
当然，上述说明并非是对本发明的限制，本发明也并不仅限于上述举例，本技术领域的技术人员在本发明的实质范围内所做出的变化、改型、添加或替换，也应属于本发明的保护范围。Of course, the above descriptions are not intended to limit the present invention, and the present invention is not limited to the above examples. Changes, modifications, additions or replacements made by those skilled in the art within the scope of the present invention shall also belong to the present invention. protection scope of the invention.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107930566A (en) * | 2017-12-27 | 2018-04-20 | 盐城工学院 | A kind of multifunctional magnetic-force stirring Hydrothermal Synthesiss device and reaction system |
| CN108169448A (en) * | 2017-12-06 | 2018-06-15 | 中国科学院广州能源研究所 | A kind of hydrate fabricated in situ and its comprehensive physical property testing device |
| CN108458910A (en) * | 2018-05-15 | 2018-08-28 | 青岛海洋地质研究所 | Separation hydrate and it is compacted into blocking device and method in a kind of solution |
| CN111487678A (en) * | 2020-04-20 | 2020-08-04 | 青岛海洋地质研究所 | Analysis method for determining high-resolution small multichannel seismic minimum offset distance and system delay |
| CN112362690A (en) * | 2020-11-06 | 2021-02-12 | 西南石油大学 | Hydrate generation induction time measuring device |
| CN112546962A (en) * | 2020-12-01 | 2021-03-26 | 中国科学院广州能源研究所 | Device and method for quickly preparing gas hydrate cylinder |
| CN112577991A (en) * | 2020-06-24 | 2021-03-30 | 山东科技大学 | Device and method for measuring heat conductivity coefficient of hydrate by means of ex-situ pressure maintaining and fidelity |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1700446A1 (en) * | 1988-12-14 | 1991-12-23 | Институт Физико-Технических Проблем Севера Якутского Филиала Со Ан Ссср | Plant for gas hydrate study |
| CN1588022A (en) * | 2004-10-12 | 2005-03-02 | 中国科学院广州能源研究所 | Method and device for in-site measuring gas hydrate and deposit sediment heat stability containing hydrate |
| CN101718730A (en) * | 2009-12-04 | 2010-06-02 | 中国科学院广州能源研究所 | Method and device for measuring the resistivity of gas hydrate and hydrate-containing sediment in situ |
| CN101718725A (en) * | 2009-12-08 | 2010-06-02 | 中国科学院广州能源研究所 | Device for measuring sample thermo-physical property in situ |
| CN102042995A (en) * | 2010-07-01 | 2011-05-04 | 青岛海洋地质研究所 | Gas hydrate thermophysical property simulation experiment device |
| CN104215499A (en) * | 2014-09-22 | 2014-12-17 | 青岛海洋地质研究所 | Multifunctional triaxial compression testing device containing natural gas hydrate sediment and testing method thereof |
| CN104833582A (en) * | 2015-05-21 | 2015-08-12 | 大连理工大学 | Natural gas hydrate sediment triaxial test device |
| CN205826576U (en) * | 2016-07-18 | 2016-12-21 | 山东科技大学 | A kind of hydrate thermophysical property measurement system |
-
2016
- 2016-07-18 CN CN201610566181.3A patent/CN105973937B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1700446A1 (en) * | 1988-12-14 | 1991-12-23 | Институт Физико-Технических Проблем Севера Якутского Филиала Со Ан Ссср | Plant for gas hydrate study |
| CN1588022A (en) * | 2004-10-12 | 2005-03-02 | 中国科学院广州能源研究所 | Method and device for in-site measuring gas hydrate and deposit sediment heat stability containing hydrate |
| CN101718730A (en) * | 2009-12-04 | 2010-06-02 | 中国科学院广州能源研究所 | Method and device for measuring the resistivity of gas hydrate and hydrate-containing sediment in situ |
| CN101718725A (en) * | 2009-12-08 | 2010-06-02 | 中国科学院广州能源研究所 | Device for measuring sample thermo-physical property in situ |
| CN102042995A (en) * | 2010-07-01 | 2011-05-04 | 青岛海洋地质研究所 | Gas hydrate thermophysical property simulation experiment device |
| CN104215499A (en) * | 2014-09-22 | 2014-12-17 | 青岛海洋地质研究所 | Multifunctional triaxial compression testing device containing natural gas hydrate sediment and testing method thereof |
| CN104833582A (en) * | 2015-05-21 | 2015-08-12 | 大连理工大学 | Natural gas hydrate sediment triaxial test device |
| CN205826576U (en) * | 2016-07-18 | 2016-12-21 | 山东科技大学 | A kind of hydrate thermophysical property measurement system |
Non-Patent Citations (2)
| Title |
|---|
| 刘昌岭 等: "不同体系下天然气水合物 P-T 稳定条件及其影响因素的实验研究", 《中国科学：地球科学》 * |
| 黄犊子 等: "水合物合成及导热系数测定", 《地球物理学报》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108169448A (en) * | 2017-12-06 | 2018-06-15 | 中国科学院广州能源研究所 | A kind of hydrate fabricated in situ and its comprehensive physical property testing device |
| CN108169448B (en) * | 2017-12-06 | 2020-06-12 | 中国科学院广州能源研究所 | A kind of hydrate in situ synthesis and its comprehensive physical property testing device |
| CN107930566A (en) * | 2017-12-27 | 2018-04-20 | 盐城工学院 | A kind of multifunctional magnetic-force stirring Hydrothermal Synthesiss device and reaction system |
| CN108458910A (en) * | 2018-05-15 | 2018-08-28 | 青岛海洋地质研究所 | Separation hydrate and it is compacted into blocking device and method in a kind of solution |
| CN111487678A (en) * | 2020-04-20 | 2020-08-04 | 青岛海洋地质研究所 | Analysis method for determining high-resolution small multichannel seismic minimum offset distance and system delay |
| CN112577991A (en) * | 2020-06-24 | 2021-03-30 | 山东科技大学 | Device and method for measuring heat conductivity coefficient of hydrate by means of ex-situ pressure maintaining and fidelity |
| CN112577991B (en) * | 2020-06-24 | 2023-03-14 | 山东科技大学 | Device and method for ex-situ pressure-maintaining fidelity measurement of heat conductivity coefficient of hydrate |
| CN112362690A (en) * | 2020-11-06 | 2021-02-12 | 西南石油大学 | Hydrate generation induction time measuring device |
| CN112546962A (en) * | 2020-12-01 | 2021-03-26 | 中国科学院广州能源研究所 | Device and method for quickly preparing gas hydrate cylinder |
| WO2021208509A1 (en) * | 2020-12-01 | 2021-10-21 | 中国科学院广州能源研究所 | Apparatus and method for rapid preparation of gas hydrate column |
| CN112546962B (en) * | 2020-12-01 | 2022-02-18 | 中国科学院广州能源研究所 | Device and method for rapid preparation of gas hydrate column |
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