CN117088369A - Continuous preparation, crushing and discharging method and device for carbon dioxide hydrate - Google Patents
Continuous preparation, crushing and discharging method and device for carbon dioxide hydrate Download PDFInfo
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Abstract
本发明涉及二氧化碳水合物连续制取、粉碎排出方法及装置,包括具有内腔的反应器和控温水箱,所述反应器的内腔由水平的隔板分隔为生成腔和粉碎腔,所述生成腔位于粉碎腔的上方,所述隔板连接有驱动隔板移动使得生成腔和粉碎腔连通和封闭的驱动机构;所述粉碎腔的上部连接有进料系统,所述反应器的外壁缠绕设置有控温管线圈,所述控温水箱内设置有循环泵,所述控温管线圈的一端与控温水箱相连,另一端与循环泵相连;所述反应器的顶部设置有搅拌电机,所述搅拌电机连接有搅拌器,所述搅拌器位于生成腔内;所述粉碎腔内设置有粉碎机构,所述粉碎腔的底部设置有排料口。本发明可减少二氧化碳水合物初始生成时间,提高制备效率。
The invention relates to a method and device for the continuous production, crushing and discharge of carbon dioxide hydrate, which includes a reactor with an inner cavity and a temperature-controlled water tank. The inner cavity of the reactor is divided into a generation chamber and a crushing chamber by horizontal partitions. The generation chamber is located above the crushing chamber, and the partition plate is connected to a driving mechanism that drives the partition plate to move so that the generation chamber and the crushing chamber are connected and closed; the upper part of the crushing chamber is connected to a feeding system, and the outer wall of the reactor is wrapped A temperature control pipe coil is provided, and a circulation pump is provided in the temperature control water tank. One end of the temperature control pipe coil is connected to the temperature control water tank, and the other end is connected to the circulation pump; a stirring motor is provided on the top of the reactor, The stirring motor is connected to a stirrer, and the stirrer is located in the generating cavity; a crushing mechanism is provided in the crushing cavity, and a discharge port is provided at the bottom of the crushing cavity. The invention can reduce the initial generation time of carbon dioxide hydrate and improve the preparation efficiency.
Description
技术领域Technical field
本发明属于二氧化碳水合物制备技术领域,尤其是一种二氧化碳水合物连续制取、粉碎排出方法及装置。The invention belongs to the technical field of carbon dioxide hydrate preparation, especially a method and device for continuously preparing, crushing and discharging carbon dioxide hydrate.
背景技术Background technique
工业的发展导致二氧化碳的排放量大幅度增加,二氧化碳加剧了全球温室效应,破坏生态环境,如何解决二氧化碳排放带来的问题,除了减少二氧化碳的排放,或者是严控二氧化碳的排放指标,还可以用另外一种方式:即对二氧化进行捕捉和封存,最终把二氧化碳储存在地下。The development of industry has led to a substantial increase in carbon dioxide emissions. Carbon dioxide has intensified the global greenhouse effect and destroyed the ecological environment. How to solve the problems caused by carbon dioxide emissions, in addition to reducing carbon dioxide emissions or strictly controlling carbon dioxide emission indicators, can also be used Another way is to capture and store carbon dioxide, and ultimately store the carbon dioxide underground.
目前,二氧化碳的封存主要分为陆地上的封存以及海洋的封存,但是出于成本的考虑,大多数学者认为,在废弃油气开采区是二氧化碳封存的最佳场所,其主要原因是相比于其它地质特征不熟悉的地区,在该地区所掌握的地质资料较为丰富,认识也更全面。在海洋上二氧化碳转与碳酸盐等矿物质反应之后,利用海水的高压作用将其进行封存,这也是利用工业废料的有用手段之一。在提高油气采收率上,注入二氧化碳进行驱油也是一种较为普遍的驱油方式。At present, carbon dioxide storage is mainly divided into land storage and ocean storage. However, due to cost considerations, most scholars believe that abandoned oil and gas mining areas are the best places to store carbon dioxide. The main reason is that compared with other In areas where the geological features are unfamiliar, the geological data available in that area is richer and the understanding is more comprehensive. After carbon dioxide reacts with minerals such as carbonates in the ocean, it is stored using the high pressure of seawater. This is also one of the useful methods of utilizing industrial waste. In terms of improving oil and gas recovery, injecting carbon dioxide for oil displacement is also a relatively common oil displacement method.
CN115076594A公开了一种二氧化碳封存方法。通过将灌满高浓度盐水的CO2储存容器置于不小于3000米深度的海水中;将液态CO2输送到封存容器内,利用溢出至储存进液管和排液管中的液态CO2,与海水接触生成CO2水合物封堵储存容器,从而实现封存效果。CN106904616A公开了一种二氧化碳地质封存结构和封存方法,通过对工业生产中产生的二氧化碳进行集中回收,注入到废弃的油田、气田中,使二氧化碳与地下的水生成固态的二氧化碳水合物,达到封存减排的目的。CN211847165U公开了一种二氧化碳地层封存系统,该系统主要是通过水合物反应装置制备二氧化碳水合物,再用管道运输的形式将水合物输送至煤、油气采空区,以水合物的形式进行地层封存。综上,目前最主要的封存系统主要有深海封存、废弃煤层封存等。但现有的这些技术和方法存在的问题是成本高、效率低、安全性较差、装置结构复杂等问题,而且不适宜大型化投入。如何提高制取二氧化碳水合物,并将其封存的效率是一个问题。CN115076594A discloses a carbon dioxide storage method. By placing a CO 2 storage container filled with high-concentration salt water in seawater at a depth of no less than 3,000 meters; transporting liquid CO 2 into the storage container, and utilizing the liquid CO 2 that overflows into the storage inlet and discharge pipes, Contact with seawater generates CO 2 hydrate to seal the storage container, thereby achieving the sealing effect. CN106904616A discloses a carbon dioxide geological storage structure and storage method. By centrally recovering the carbon dioxide produced in industrial production and injecting it into abandoned oil fields and gas fields, the carbon dioxide and underground water form solid carbon dioxide hydrate to achieve storage reduction. The purpose of the platoon. CN211847165U discloses a carbon dioxide formation storage system. The system mainly prepares carbon dioxide hydrate through a hydrate reaction device, and then transports the hydrate to coal, oil and gas goafs in the form of pipeline transportation, and performs formation storage in the form of hydrates. . In summary, the most important storage systems currently include deep sea storage, abandoned coal seam storage, etc. However, these existing technologies and methods have problems such as high cost, low efficiency, poor safety, complex device structure, etc., and are not suitable for large-scale investment. How to improve the efficiency of producing carbon dioxide hydrate and storing it is a problem.
CN104445197A公开了一种二氧化碳水合物制备装置,包括:反应单元,用于容纳水和二氧化碳进行反应;液体循环单元,分别和反应单元顶端的进液口以及底端的出液口连接,用于原料水的供应以及二氧化碳水合物的循环;进气单元,和反应单元顶端的进气口连接,用于二氧化碳原料的供应;破裂单元,设置于反应单元内部,表面带有预定密度的空隙,用于二氧化碳水合物的破裂;以及换热单元,位于破裂单元下方,用于吸收二氧化碳水合物的热量。破裂单元采用带孔的板,难以对水合物进行有效破碎。制备时,二氧化碳水合物初始生长速度慢,效率较低。此外,为了保证设备处于恒温状态,现有的二氧化碳水合物制备装置一般都是设置在恒温箱内部,只适用于小型设备,例如实验室采用的二氧化碳水合物制备装制备,不适用于大型工业化设备。CN104445197A discloses a carbon dioxide hydrate preparation device, which includes: a reaction unit, used to accommodate water and carbon dioxide for reaction; a liquid circulation unit, respectively connected to the liquid inlet at the top and the liquid outlet at the bottom of the reaction unit, for raw material water supply and circulation of carbon dioxide hydrate; the air inlet unit is connected to the air inlet at the top of the reaction unit for the supply of carbon dioxide raw materials; the rupture unit is installed inside the reaction unit with a predetermined density of gaps on the surface for carbon dioxide hydrate rupture; and a heat exchange unit located below the rupture unit for absorbing the heat of carbon dioxide hydrate. The rupture unit uses a plate with holes, which makes it difficult to effectively break hydrates. During preparation, the initial growth rate of carbon dioxide hydrate is slow and the efficiency is low. In addition, in order to ensure that the equipment is at a constant temperature, existing carbon dioxide hydrate preparation devices are generally set up inside a constant temperature box, which is only suitable for small equipment. For example, the carbon dioxide hydrate preparation equipment used in laboratories is not suitable for large industrial equipment. .
发明内容Contents of the invention
本发明所要解决的技术问题是提供一种二氧化碳水合物连续制取、粉碎排出方法及装置,减少二氧化碳水合物初始生成时间,提高制备效率,且可以将反应温度控制在一定的范围内,能够实现工业化应用,并将制得的二氧化碳水合物直接封存在油、气、矿的开采区内。The technical problem to be solved by the present invention is to provide a method and device for the continuous preparation, crushing and discharge of carbon dioxide hydrate, which can reduce the initial generation time of carbon dioxide hydrate, improve the preparation efficiency, and can control the reaction temperature within a certain range, so as to achieve Industrial application, and the produced carbon dioxide hydrate is directly stored in oil, gas and mineral mining areas.
为解决上述问题,本发明采用的技术方案为:二氧化碳水合物连续制取、粉碎排出装置,包括具有内腔的反应器和控温水箱,所述反应器的内腔由水平的隔板分隔为生成腔和粉碎腔,所述生成腔位于粉碎腔的上方,所述隔板连接有驱动隔板移动使得生成腔和粉碎腔连通和封闭的驱动机构;所述粉碎腔的上部连接有进料系统,所述反应器的外壁缠绕设置有控温管线圈,所述控温水箱内设置有循环泵,所述控温管线圈的一端与控温水箱相连,另一端与循环泵相连;所述反应器的顶部设置有搅拌电机,所述搅拌电机连接有搅拌器,所述搅拌器位于生成腔内;所述粉碎腔内设置有粉碎机构,所述粉碎腔的底部设置有排料口。In order to solve the above problems, the technical solution adopted by the present invention is: a device for continuously producing, crushing and discharging carbon dioxide hydrate, including a reactor with an inner cavity and a temperature-controlled water tank. The inner cavity of the reactor is separated by a horizontal partition. A generating chamber and a crushing chamber. The generating chamber is located above the crushing chamber. The partition plate is connected with a driving mechanism that drives the partition plate to move so that the generating chamber and the crushing chamber are connected and closed. The upper part of the crushing chamber is connected with a feeding system. , a temperature control tube coil is wound around the outer wall of the reactor, a circulation pump is provided in the temperature control water tank, one end of the temperature control tube coil is connected to the temperature control water tank, and the other end is connected to the circulation pump; the reaction The top of the device is provided with a stirring motor, the stirring motor is connected to a stirrer, and the stirrer is located in the generating chamber; a crushing mechanism is provided in the crushing chamber, and a discharge port is provided at the bottom of the crushing chamber.
进一步地,所述反应器的顶盖上设置有升降机构,所述升降机构连接有压板,所述压板位于生成腔内。Further, a lifting mechanism is provided on the top cover of the reactor, and the lifting mechanism is connected to a pressure plate, and the pressure plate is located in the generation chamber.
进一步地,所述进料系统包括二氧化碳收集罐、加压装置、第一预冷装置、水箱和第二预冷装置,所述生成腔的侧壁设置有进水口和进气口,所述二氧化碳收集罐、加压装置、第一预冷装置和进气口依次连接,所述水箱、第二预冷装置与进水口依次相连。Further, the feeding system includes a carbon dioxide collection tank, a pressurizing device, a first pre-cooling device, a water tank and a second pre-cooling device. The side wall of the generation chamber is provided with a water inlet and an air inlet. The carbon dioxide The collection tank, the pressurizing device, the first precooling device and the air inlet are connected in sequence, and the water tank, the second precooling device and the water inlet are connected in sequence.
进一步地,所述粉碎机构包括粉碎电机,所述粉碎电机连接有转轴,所述转轴上设置有粉碎刀片。Further, the crushing mechanism includes a crushing motor, the crushing motor is connected to a rotating shaft, and a crushing blade is provided on the rotating shaft.
进一步地,所述生成腔内设置有温度传感器和压力传感器。Further, a temperature sensor and a pressure sensor are provided in the generation chamber.
进一步地,所述反应器的外壁设置有用于将反应器固定在井筒内壁的定位机构。将上述二氧化碳水合物连续制取、粉碎排出装置的反应器安装在油、气或者矿开采井的底部;Further, the outer wall of the reactor is provided with a positioning mechanism for fixing the reactor to the inner wall of the wellbore. Install the reactor of the above-mentioned carbon dioxide hydrate continuous production, crushing and discharge device at the bottom of an oil, gas or mineral mining well;
二氧化碳水合物连续制取、粉碎排除方法包括:Methods for continuous production, crushing and removal of carbon dioxide hydrate include:
对生成腔进行抽真空,将控温水箱中的水循环通入控温管线圈,使得生成腔内的温度达到工艺要求;Evacuate the generation chamber and circulate the water in the temperature-controlled water tank into the temperature-control tube coil so that the temperature in the generation chamber reaches the process requirements;
将二氧化碳加压、预冷后通入生成腔,同时将水预冷后通入生成腔;The carbon dioxide is pressurized, pre-cooled and then introduced into the generation chamber, while water is pre-cooled and then introduced into the generation chamber;
搅拌器对水和二氧化碳进行搅拌,水与二氧化碳反应生成二氧化碳水合物;The stirrer stirs water and carbon dioxide, and water reacts with carbon dioxide to form carbon dioxide hydrate;
反应完成后,驱动机构驱动隔板移动,生成腔与粉碎腔连通,生成腔中的二氧化碳水合物落入粉碎腔,利用粉碎机构将二氧化碳水合物进行破碎,破碎后的二氧化碳水合物通过排料口落入油、气或者矿的开采区,二氧化碳水合物在地层压力下保持稳定;After the reaction is completed, the driving mechanism drives the partition to move, and the generation cavity is connected with the crushing cavity. The carbon dioxide hydrate in the generation cavity falls into the crushing cavity. The crushing mechanism is used to crush the carbon dioxide hydrate, and the crushed carbon dioxide hydrate passes through the discharge port. Falling into oil, gas or mineral mining areas, carbon dioxide hydrate remains stable under formation pressure;
生成腔中的二氧化碳水合物全部排出后,驱动机构驱动隔板复位,使隔板将生成腔与粉碎腔相互独立,再次向生成腔中通入水和二氧化碳,搅拌器上残留的二氧化碳水合物在离心力的作用下进入水和二氧化碳,残留的二氧化碳水合物即可作为晶核,二氧化碳水合物可以直接在该晶核上进行生长,从而省略了成核阶段,提高制备效率。After all the carbon dioxide hydrate in the generation chamber is discharged, the driving mechanism drives the partition to reset, so that the partition separates the generation chamber and the crushing chamber from each other. Water and carbon dioxide are again introduced into the generation chamber, and the remaining carbon dioxide hydrate on the agitator is released by the centrifugal force. When water and carbon dioxide enter into the process, the remaining carbon dioxide hydrate can be used as a crystal nucleus, and the carbon dioxide hydrate can grow directly on the crystal nucleus, thereby omitting the nucleation stage and improving the preparation efficiency.
进一步地,将二氧化碳加压至1.27至4.6MPa,预冷至275至295开尔文后通入生成腔,将水预冷至275至283开尔文后通入生成腔。Further, the carbon dioxide is pressurized to 1.27 to 4.6 MPa, precooled to 275 to 295 Kelvin and then introduced into the generation chamber, and the water is precooled to 275 to 283 Kelvin and then introduced into the generation chamber.
进一步地,生成腔内的压强大于或等于7.2MPa,温度为270至280开尔文。Further, the pressure in the generation cavity is greater than or equal to 7.2MPa, and the temperature is 270 to 280 Kelvin.
进一步地,控温水箱和进料系统设置在地面上。Further, the temperature-controlled water tank and feeding system are set on the ground.
本发明的有益效果是:1、本发明通过在反应器的外壁缠绕设置控温管线圈,工作时,控温水箱将其内部的水控制在恒定的温度范围内,并将控温水箱中的水通入控温管线圈,使控温水箱中的水循环流动,从而对反应器进行控温,防止反应器内的温度过高或者过低,使得反应器内部的温度保持稳定,有利于水合物的稳定生长。这种保温方式结构简单,保温效果好,适用于各种大小的反应器,有利于实现工业化应用。The beneficial effects of the present invention are: 1. The present invention winds and sets a temperature control pipe coil on the outer wall of the reactor. When working, the temperature control water tank controls the water inside it within a constant temperature range, and controls the water in the temperature control water tank. Water flows into the temperature control tube coil to circulate the water in the temperature control water tank, thereby controlling the temperature of the reactor to prevent the temperature in the reactor from being too high or too low, so that the temperature inside the reactor remains stable, which is beneficial to hydrates stable growth. This insulation method has a simple structure and good insulation effect. It is suitable for reactors of various sizes and is conducive to industrial application.
2、搅拌器不仅仅起到对水和二氧化碳进行搅拌的作用,还起到了保留少量二氧化碳水合物的作用,二氧化碳水合物制备过程中,搅拌器上不可避免会附着一些水合物,这些水合物不会落入粉碎腔,而是停留在搅拌器上,下一次制备二氧化碳水合物时,搅拌器转动产生离心力,搅拌器上残留的二氧化碳水合物在离心力的作用下快速、均匀地进入水和二氧化碳中,这些残留的二氧化碳水合物作为晶核,新的二氧化碳水合物可以直接在晶核上生长,节省了成核过程,节省了成核时间,因此制备效率得到提升。2. The stirrer not only plays the role of stirring water and carbon dioxide, but also plays the role of retaining a small amount of carbon dioxide hydrate. During the preparation process of carbon dioxide hydrate, some hydrates will inevitably adhere to the stirrer, and these hydrates will not will fall into the crushing chamber, but stay on the agitator. When preparing carbon dioxide hydrate next time, the rotation of the agitator will generate centrifugal force. The remaining carbon dioxide hydrate on the agitator will quickly and evenly enter the water and carbon dioxide under the action of centrifugal force. , these residual carbon dioxide hydrates serve as crystal nuclei, and new carbon dioxide hydrates can grow directly on the crystal nuclei, saving the nucleation process and nucleation time, so the preparation efficiency is improved.
3、本发明的反应器结构简单,直接安装在油、气或者矿开采井内,制备的二氧化碳水合物直接填充、封存在油、气或者矿的开采区内,实现二氧化碳的封存。3. The reactor of the present invention has a simple structure and is directly installed in an oil, gas or mineral mining well. The prepared carbon dioxide hydrate is directly filled and sealed in the oil, gas or mineral mining area to achieve carbon dioxide storage.
4、通过对二氧化碳水合物进行粉碎,避免了二氧化碳水合物堵塞排出通道,同时促使二氧化碳水合物充满油、气或者矿开采区内的空间,减小填充间隙,提高单位体积内的填充量。4. By pulverizing the carbon dioxide hydrate, the carbon dioxide hydrate is prevented from clogging the discharge channel, and at the same time, the carbon dioxide hydrate is forced to fill the space in the oil, gas or mining area, reducing the filling gap and increasing the filling amount per unit volume.
附图说明Description of the drawings
图1是本发明的示意图;Figure 1 is a schematic diagram of the present invention;
附图标记:1—反应器;2—隔板;3—生成腔;4—粉碎腔;5—控温水箱;6—控温管线圈;7—循环泵;8—搅拌电机;9—搅拌器;10—排料口;11—升降机构;12—压板;13—二氧化碳收集罐;14—加压装置;15—第一预冷装置;16—水箱;17—进水口;18—进气口;19—粉碎电;20—粉碎刀片;21—温度传感器;22—压力传感器;23—定位机构;24—第二预冷装置;100—井筒。Reference signs: 1—Reactor; 2—Partition; 3—Generation chamber; 4—Pulverizing chamber; 5—Temperature control water tank; 6—Temperature control tube coil; 7—Circulation pump; 8—Stirring motor; 9—Stirring 10—discharge port; 11—lifting mechanism; 12—pressure plate; 13—carbon dioxide collection tank; 14—pressurizing device; 15—first precooling device; 16—water tank; 17—water inlet; 18—air inlet port; 19—crushing electricity; 20—crushing blade; 21—temperature sensor; 22—pressure sensor; 23—positioning mechanism; 24—second precooling device; 100—wellbore.
具体实施方式Detailed ways
下面结合附图和实施例对本发明进一步说明。The present invention will be further described below in conjunction with the accompanying drawings and examples.
本发明的二氧化碳水合物连续制取、粉碎排出装置,如图1所示,包括具有内腔的反应器1和控温水箱5,反应器1的内腔由水平的隔板2分隔为生成腔3和粉碎腔4,生成腔3位于粉碎腔4的上方,隔板2连接有驱动隔板2移动使得生成腔3和粉碎腔4连通和封闭的驱动机构;粉碎腔4的上部连接有进料系统,反应器1的外壁缠绕设置有控温管线圈6,控温水箱5内设置有循环泵7,控温管线圈6的一端与控温水箱5相连,另一端与循环泵7相连;反应器1的顶部设置有搅拌电机8,搅拌电机8连接有搅拌器9,搅拌器9位于生成腔3内;粉碎腔4内设置有粉碎机构,粉碎腔4的底部设置有排料口10。The carbon dioxide hydrate continuous production, crushing and discharge device of the present invention, as shown in Figure 1, includes a reactor 1 with an inner cavity and a temperature-controlled water tank 5. The inner cavity of the reactor 1 is divided into a generation chamber by a horizontal partition 2 3 and crushing chamber 4. The generating chamber 3 is located above the crushing chamber 4. The partition plate 2 is connected with a driving mechanism that drives the partition plate 2 to move so that the generating chamber 3 and the crushing chamber 4 are connected and closed; the upper part of the crushing chamber 4 is connected with a feed System, the outer wall of the reactor 1 is wrapped with a temperature control pipe coil 6, and a circulation pump 7 is installed in the temperature control water tank 5. One end of the temperature control pipe coil 6 is connected to the temperature control water tank 5, and the other end is connected to the circulation pump 7; reaction The top of the device 1 is provided with a stirring motor 8, which is connected to a stirrer 9. The stirrer 9 is located in the generating chamber 3; a crushing mechanism is provided in the crushing chamber 4, and a discharge port 10 is provided at the bottom of the crushing chamber 4.
反应器1采用金属罐体,生成腔3的断面呈圆形或者矩形,粉碎腔4呈半球形,反应器1的顶部通过顶盖封口。隔板2采用金属板,可以由多块金属板拼接成圆形板,每一块金属板的两端设置销轴,销轴与反应器1侧壁转动配合,驱动机构可以是多个翻转电机,每个翻转电机与一块金属板的销轴相连。需要使生成腔3和粉碎腔4连通时,翻转电机带动每一块金属板转动90度,使得金属块处于竖直状态;当需要使生成腔3和粉碎腔4隔开时,翻转电机带动每一块金属板转动至水平状态,各个金属板即可拼接成隔板2。此外,隔板2也可以水平插接于反应器1,驱动机构采用直线电机、气缸或者液压缸等,可以推动隔板2水平移动,需要使生成腔3和粉碎腔4连通时,直线电机、气缸或者液压缸拉动隔板2向外移动至反应器1之外,需要使生成腔3和粉碎腔4隔开时,直线电机、气缸或者液压缸推动隔板2向内运动至反应器1内部。The reactor 1 adopts a metal tank, the cross section of the generation chamber 3 is circular or rectangular, the crushing chamber 4 is hemispherical, and the top of the reactor 1 is sealed by a top cover. The partition 2 is made of a metal plate, which can be spliced into a circular plate by multiple metal plates. Pins are provided at both ends of each metal plate. The pins rotate and cooperate with the side walls of the reactor 1. The driving mechanism can be multiple flip motors. Each flip motor is connected to a pin on a metal plate. When it is necessary to connect the generating chamber 3 and the crushing chamber 4, the flipping motor drives each metal plate to rotate 90 degrees so that the metal block is in a vertical state; when it is necessary to separate the generating chamber 3 and the crushing chamber 4, the flipping motor drives each metal plate. The metal plates are rotated to a horizontal state, and each metal plate can be spliced into a partition 2. In addition, the partition 2 can also be horizontally plugged into the reactor 1. The driving mechanism adopts a linear motor, a pneumatic cylinder or a hydraulic cylinder, etc., which can push the partition 2 to move horizontally. When it is necessary to connect the generation chamber 3 and the crushing chamber 4, the linear motor, The air cylinder or hydraulic cylinder pulls the partition 2 to move outward to the outside of the reactor 1. When it is necessary to separate the generation chamber 3 and the crushing chamber 4, the linear motor, air cylinder or hydraulic cylinder pushes the partition 2 to move inward to the inside of the reactor 1. .
控温水箱5中存储有控温水,控温水箱5具有调节水温的功能,具体的水温调节方式采用现有技术即可,使控温水的温度始终处于一定的范围内。控温管线圈6采用管道,缠绕设置在反应器1外壁,相邻两圈管道之间密接触,不留间隙,从而将反应器1的外壁覆盖,能够更加有效地控制反应器1的温度。循环泵7驱动控温水进入控温管线圈6,控温水流经控温管线圈6后回到控温水箱5,循环流动,可以有效控制反应器1的温度。采用这种控温方式,适用于各种尺寸的反应器1,有利于实现工业化应用。Temperature-controlled water is stored in the temperature-controlled water tank 5. The temperature-controlled water tank 5 has the function of adjusting the water temperature. The specific water temperature adjustment method can adopt existing technology, so that the temperature of the temperature-controlled water is always within a certain range. The temperature control tube coil 6 adopts a pipe and is wound around the outer wall of the reactor 1. Two adjacent circles of pipes are in close contact without leaving any gaps, thereby covering the outer wall of the reactor 1 and controlling the temperature of the reactor 1 more effectively. The circulating pump 7 drives the temperature-controlled water to enter the temperature-controlled pipe coil 6. The temperature-controlled water flows through the temperature-controlled pipe coil 6 and then returns to the temperature-controlled water tank 5. The circulating flow can effectively control the temperature of the reactor 1. This temperature control method is suitable for reactors 1 of various sizes and is conducive to industrial application.
为了促使水和二氧化碳均匀接触,生成腔3内设置了搅拌器9。搅拌电机8用于带动搅拌器9转动,搅拌电机8可以安装在顶盖的上表面。在二氧化碳水合物生长过程中,部分二氧化碳水合物会附着在搅拌器9上,粉碎时,这些水合物不会落入粉碎腔4,而是停留在搅拌器9上,下一次制备二氧化碳水合物时,搅拌器9转动产生离心力,搅拌器9上残留的二氧化碳水合物在离心力的作用下快速、均匀地进入水和二氧化碳中,这些残留的二氧化碳水合物作为晶核,新的二氧化碳水合物可以直接在晶核上生长,节省了成核过程,节省了成核时间,因此制备效率得到提升。In order to promote uniform contact between water and carbon dioxide, a stirrer 9 is provided in the generation chamber 3 . The stirring motor 8 is used to drive the stirrer 9 to rotate, and the stirring motor 8 can be installed on the upper surface of the top cover. During the growth process of carbon dioxide hydrate, part of the carbon dioxide hydrate will adhere to the agitator 9. During crushing, these hydrates will not fall into the crushing chamber 4, but stay on the agitator 9. The next time carbon dioxide hydrate is prepared, , the rotation of the stirrer 9 generates centrifugal force, and the residual carbon dioxide hydrate on the stirrer 9 quickly and evenly enters the water and carbon dioxide under the action of centrifugal force. These residual carbon dioxide hydrates serve as crystal nuclei, and the new carbon dioxide hydrate can be directly added to the water and carbon dioxide. Growth on crystal nuclei saves the nucleation process and nucleation time, so the preparation efficiency is improved.
粉碎机构用于将二氧化碳水合物破碎成小颗粒,以便于排出和封存二氧化碳水合物,防止二氧化碳水合物堵塞排出通道,同时促使二氧化碳水合物充满油、气或者矿开采区内的空间,减小填充间隙,提高单位体积内的填充量。粉碎机构具体包括粉碎电机19,粉碎电机19连接有转轴,转轴上设置有粉碎刀片20。The crushing mechanism is used to break carbon dioxide hydrate into small particles to facilitate the discharge and storage of carbon dioxide hydrate, prevent carbon dioxide hydrate from blocking the discharge channel, and at the same time promote carbon dioxide hydrate to fill the space in oil, gas or mining areas, reducing filling gap to increase the filling volume per unit volume. The crushing mechanism specifically includes a crushing motor 19. The crushing motor 19 is connected to a rotating shaft, and a crushing blade 20 is provided on the rotating shaft.
二氧化碳水合物为固体,可能会稳定停留在反应器1内壁与搅拌器9之间,难以依靠自身的重力掉落至粉碎腔4中,因此,本发明在反应器1的顶盖上设置有升降机构11,升降机构11连接有压板12,压板12位于生成腔3内。具体地,反应器1的顶盖上设置有多个向下凹陷的凹槽,每个凹槽中设置一个升降机构11,升降机构11位于顶盖的上表面,并通过一根连接杆与压板12相连。为了提高密封性,顶盖的上表面设置有密封垫。升降机构11可以是直线电机、液压缸等设备。压板12可以是多个,每个压板12通过竖直的连接杆与升降机构11相连,且压板12与搅拌器9之间适当的间距,防止运行时两者相互碰撞而损坏。此外,压板12也可以是圆环形,水平设置,搅拌器9位于压板12的内孔中。二氧化碳水合物制备完成后,打开隔板2,然后利用升降机构11驱动压板12向下移动,从而将生成腔3中的二氧化碳水合物压至粉碎腔4内。Carbon dioxide hydrate is a solid and may stay stably between the inner wall of the reactor 1 and the stirrer 9, making it difficult to fall into the crushing chamber 4 by its own gravity. Therefore, in the present invention, a lifting device is provided on the top cover of the reactor 1. Mechanism 11, the lifting mechanism 11 is connected to a pressure plate 12, and the pressure plate 12 is located in the generation chamber 3. Specifically, the top cover of the reactor 1 is provided with a plurality of downwardly concave grooves, and a lifting mechanism 11 is provided in each groove. The lifting mechanism 11 is located on the upper surface of the top cover and is connected to the pressure plate through a connecting rod. 12 connected. In order to improve the sealing performance, a sealing gasket is provided on the upper surface of the top cover. The lifting mechanism 11 may be a linear motor, a hydraulic cylinder or other equipment. There may be multiple pressure plates 12, and each pressure plate 12 is connected to the lifting mechanism 11 through a vertical connecting rod, and there is an appropriate distance between the pressure plate 12 and the agitator 9 to prevent the two from colliding with each other and causing damage during operation. In addition, the pressure plate 12 can also be annular and arranged horizontally, with the stirrer 9 located in the inner hole of the pressure plate 12 . After the preparation of carbon dioxide hydrate is completed, the partition plate 2 is opened, and then the lifting mechanism 11 is used to drive the pressing plate 12 to move downward, thereby pressing the carbon dioxide hydrate in the generation chamber 3 into the crushing chamber 4 .
进料系统用于通入水和二氧化碳,包括水供应系统和二氧化碳供应系统,二氧化碳供应系统包括二氧化碳收集罐13、加压装置14、第一预冷装置15,水供应系统包括水箱16和第二预冷装置24,二氧化碳收集罐13用于存储收集的二氧化碳,加压装置14用于对二氧化碳进行加压,使得二氧化碳的压力满足水合物生成条件。第一预冷装置15用于对二氧化碳进行冷却,使得二氧化碳的温度满足水合物生成条件。水箱16用于存储反应用水,第二预冷装置24用于对反应用书进行预冷。生成腔3的侧壁设置有进水口17和进气口18,二氧化碳收集罐13、加压装置14、第一预冷装置15和进气口18依次连接,水箱16、第二预冷装置24与进水口17依次相连。为了便于将反应用水输送至生成腔3,第二预冷装置24与进水口17之间可以设置水泵。为了控制流量,可以在进水口17和进气口18设置流量计以及电磁阀。The feed system is used to introduce water and carbon dioxide, including a water supply system and a carbon dioxide supply system. The carbon dioxide supply system includes a carbon dioxide collection tank 13, a pressurizing device 14, and a first precooling device 15. The water supply system includes a water tank 16 and a second precooling device. The cooling device 24 and the carbon dioxide collection tank 13 are used to store the collected carbon dioxide, and the pressurizing device 14 is used to pressurize the carbon dioxide so that the pressure of the carbon dioxide meets the hydrate formation conditions. The first precooling device 15 is used to cool the carbon dioxide so that the temperature of the carbon dioxide meets the hydrate formation conditions. The water tank 16 is used to store reaction water, and the second precooling device 24 is used to precool the reaction water. The side wall of the generation chamber 3 is provided with a water inlet 17 and an air inlet 18. The carbon dioxide collection tank 13, the pressurizing device 14, the first precooling device 15 and the air inlet 18 are connected in sequence. The water tank 16 and the second precooling device 24 Connected to the water inlet 17 in sequence. In order to facilitate the delivery of reaction water to the generation chamber 3 , a water pump may be provided between the second precooling device 24 and the water inlet 17 . In order to control the flow, flow meters and solenoid valves can be installed at the water inlet 17 and the air inlet 18 .
为了实时监测生成腔3内的温度和压力,生成腔3内设置有温度传感器21和压力传感器22。温度传感器21和压力传感器22检测生成腔3内的温度和压力,根据检测结果调节控温水的温度以及加压装置14加压大小,确保生成腔3内的温度和压力始终处于工艺要求的范围内。In order to monitor the temperature and pressure in the generating chamber 3 in real time, a temperature sensor 21 and a pressure sensor 22 are provided in the generating chamber 3 . The temperature sensor 21 and the pressure sensor 22 detect the temperature and pressure in the generation chamber 3, and adjust the temperature of the temperature-controlled water and the pressure of the pressurizing device 14 according to the detection results to ensure that the temperature and pressure in the generation chamber 3 are always within the range required by the process. Inside.
本发明的反应器1可以直接将制得的二氧化碳水合物填充至油、气、矿的开采区内,为了便于固定反应器1,反应器1的外壁设置有用于将反应器1固定在井筒100内壁的定位机构23。井筒100即油井、气井或者矿井等开采井,定位机构23可以是将反应器1悬挂在井筒100内壁的悬挂机构,悬挂机构设置为多个,保证悬挂的稳定性。破碎的二氧化碳水合物从粉碎腔4底部的排料口10排出后,落入油、气或者矿的开采区内,二氧化碳水合物填充已经开采的空间,可以提高地层的稳定性,降低塌方风险,并且在地层的压力下,二氧化碳水合物可以保持稳定,不易分解,因此可以实现二氧化碳水合物的封存。The reactor 1 of the present invention can directly fill the produced carbon dioxide hydrate into the oil, gas, ore mining area. In order to facilitate the fixation of the reactor 1, the outer wall of the reactor 1 is provided with a structure for fixing the reactor 1 to the wellbore 100. Positioning mechanism 23 on the inner wall. The wellbore 100 is a production well such as an oil well, a gas well, or a mine. The positioning mechanism 23 may be a suspension mechanism that hangs the reactor 1 on the inner wall of the wellbore 100. Multiple suspension mechanisms are provided to ensure the stability of the suspension. After the broken carbon dioxide hydrate is discharged from the discharge port 10 at the bottom of the crushing chamber 4, it falls into the oil, gas or mineral mining area. The carbon dioxide hydrate fills the already mined space, which can improve the stability of the formation and reduce the risk of landslides. And under the pressure of the formation, carbon dioxide hydrate can remain stable and difficult to decompose, so carbon dioxide hydrate can be stored.
二氧化碳水合物连续制取、粉碎排出方法,包括:Methods for continuously producing, crushing and discharging carbon dioxide hydrate include:
将图1所示的二氧化碳水合物连续制取、粉碎排出装置的反应器1安装在油、气或者矿开采井的底部,制得的二氧化碳水合物可以直接排放至油、气或者矿开采井的底部,然后将二氧化碳水合物推入已开采区域,无需管道输送二氧化碳水合物,二氧化碳水合物的封存效率更高,避免了管道堵塞的风险。The reactor 1 of the carbon dioxide hydrate continuous production, crushing and discharge device shown in Figure 1 is installed at the bottom of an oil, gas or mining well, and the produced carbon dioxide hydrate can be directly discharged to the oil, gas or mining well. At the bottom, the carbon dioxide hydrate is then pushed into the mined area, eliminating the need for pipelines to transport carbon dioxide hydrate. The carbon dioxide hydrate is more efficiently stored and avoids the risk of pipeline blockage.
由于井下空间有限,因此将控温水箱5和进料系统设置在地面上,控温水箱5通过柔性的管道连接控温管线圈6即可,进料系统通过柔性的管道连接进水口17和进气口18即可。将控温水箱5和进料系统设置在地面上,还可以更加方便地将收集的二氧化碳存储在二氧化碳收集罐13中,同时便于控制、调节控温水箱5内的水温。Since the underground space is limited, the temperature-controlled water tank 5 and the feeding system are set on the ground. The temperature-controlled water tank 5 is connected to the temperature-control pipe coil 6 through a flexible pipe. The feeding system is connected to the water inlet 17 and the inlet through a flexible pipe. Air port 18 is enough. Placing the temperature-controlled water tank 5 and the feeding system on the ground can also more conveniently store the collected carbon dioxide in the carbon dioxide collection tank 13, and at the same time facilitate the control and adjustment of the water temperature in the temperature-controlled water tank 5.
对生成腔3进行抽真空,避免空气等杂质气体影响水合物的生成。将控温水箱5中的水循环通入控温管线圈6,使得生成腔3内的温度达到工艺要求,具体地,生成腔3内的温度控制在270至280开尔文。The generation chamber 3 is evacuated to prevent impurity gases such as air from affecting the generation of hydrate. The water in the temperature-controlled water tank 5 is circulated into the temperature-controlled tube coil 6 so that the temperature in the generation chamber 3 reaches the process requirements. Specifically, the temperature in the generation chamber 3 is controlled at 270 to 280 Kelvin.
将二氧化碳加压、预冷后通入生成腔3,同时将水预冷后通入生成腔3。具体地,将二氧化碳加压至1.27至4.6MPa,预冷至275至295开尔文后通入生成腔3,将水预冷至275至283开尔文后通入生成腔3。生成腔3内的压强大于或等于7.2MPa,可利用气泵将二氧化碳输送至生成腔3。The carbon dioxide is pressurized and pre-cooled and then introduced into the generation chamber 3. At the same time, the water is pre-cooled and then introduced into the generation chamber 3. Specifically, carbon dioxide is pressurized to 1.27 to 4.6 MPa, precooled to 275 to 295 Kelvin and then introduced into the generation chamber 3. Water is precooled to 275 to 283 Kelvin and then introduced into the generation chamber 3. The pressure in the generation chamber 3 is greater than or equal to 7.2MPa, and an air pump can be used to transport carbon dioxide to the generation chamber 3.
搅拌器9对水和二氧化碳进行搅拌,水与二氧化碳反应生成二氧化碳水合物。利用温度传感器21和压力传感器22实时检测生成腔3内的温度和压强,温度过高或者过低时,通过调节控温水的水温来调节生成腔3内的温度。当生成腔3内压强过低时,再次通入二氧化碳以提高压强。The stirrer 9 stirs water and carbon dioxide, and water and carbon dioxide react to form carbon dioxide hydrate. The temperature sensor 21 and the pressure sensor 22 are used to detect the temperature and pressure in the generation chamber 3 in real time. When the temperature is too high or too low, the temperature in the generation chamber 3 is adjusted by adjusting the temperature of the temperature-controlled water. When the pressure in the generation chamber 3 is too low, carbon dioxide is introduced again to increase the pressure.
反应完成后,搅拌器9停止转动。驱动机构驱动隔板2移动,生成腔3与粉碎腔4连通,生成腔3中的二氧化碳水合物落入粉碎腔4,可采用升降机构11推动压板12向下移动,推动二氧化碳水合物快速落入粉碎腔4。利用粉碎机构将二氧化碳水合物进行破碎,破碎后的二氧化碳水合物通过排料口10落入油、气或者矿的开采区,二氧化碳水合物在地层压力下保持稳定。After the reaction is completed, the stirrer 9 stops rotating. The driving mechanism drives the partition 2 to move, and the generation chamber 3 is connected with the crushing chamber 4. The carbon dioxide hydrate in the generation chamber 3 falls into the crushing chamber 4. The lifting mechanism 11 can be used to push the pressure plate 12 to move downward, pushing the carbon dioxide hydrate to fall quickly. Crushing chamber 4. The carbon dioxide hydrate is crushed by a crushing mechanism, and the broken carbon dioxide hydrate falls into the oil, gas or mineral mining area through the discharge port 10, and the carbon dioxide hydrate remains stable under the formation pressure.
生成腔3中的二氧化碳水合物全部排出后,驱动机构驱动隔板2复位,使隔板2将生成腔3与粉碎腔4隔开,再次向生成腔3中通入水和二氧化碳,再次启动搅拌器9,搅拌器9上残留的二氧化碳水合物在离心力的作用下进入水和二氧化碳,残留的二氧化碳水合物即可作为晶核,二氧化碳水合物可以直接在该晶核上进行生长,从而省略了成核阶段,提高制备效率。After all the carbon dioxide hydrate in the generation chamber 3 is discharged, the driving mechanism drives the partition 2 to reset so that the partition 2 separates the generation chamber 3 from the crushing chamber 4. Water and carbon dioxide are introduced into the generation chamber 3 again, and the mixer is started again. 9. The remaining carbon dioxide hydrate on the stirrer 9 enters the water and carbon dioxide under the action of centrifugal force. The remaining carbon dioxide hydrate can be used as a crystal nucleus, and the carbon dioxide hydrate can grow directly on the crystal nucleus, thereby omitting nucleation. stage to improve preparation efficiency.
公知的,水合物产生包括成核和生长两个阶段,成核是指形成具有临界尺寸的、稳定的水合物晶核的过程,生长是指新的水合物以晶核作为骨架,不断附着在骨架上,使得水合物体积逐渐增大。本发明中,通过将搅拌器9上残留的二氧化碳水合物作为下一次制备二氧化碳水合物的晶核,新的二氧化碳水合物可以直接在晶核基础上生长,省去了成核过程,因此可以更加快速地得到二氧化碳水合物,提高制备效率。It is known that hydrate generation includes two stages: nucleation and growth. Nucleation refers to the process of forming stable hydrate crystal nuclei with critical size. Growth refers to the process of new hydrates using the crystal nuclei as the skeleton and constantly attaching to the hydrate. On the skeleton, the volume of hydrate gradually increases. In the present invention, by using the remaining carbon dioxide hydrate on the stirrer 9 as the crystal nucleus for the next preparation of carbon dioxide hydrate, new carbon dioxide hydrate can grow directly on the basis of the crystal nucleus, eliminating the nucleation process, so it can be more Quickly obtain carbon dioxide hydrate and improve preparation efficiency.
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.
Claims (10)
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CN108117076A (en) * | 2017-12-15 | 2018-06-05 | 浙江海洋大学 | A kind of carbon dioxide hydrate reaction unit and the method for improving its generation effect |
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CN111333435A (en) * | 2020-04-10 | 2020-06-26 | 青岛海洋地质研究所 | Preparation device and preparation method of carbon dioxide hydrate micro-fertilizer |
CN112473572A (en) * | 2020-11-16 | 2021-03-12 | 中国石油大学(华东) | Hydration reaction device |
KR20220089176A (en) * | 2020-12-21 | 2022-06-28 | 울산과학기술원 | Apparatus for CO2 hydrate generating and storing and Method for same the using |
US20220411290A1 (en) * | 2019-11-28 | 2022-12-29 | Korea Institute Of Industrial Technology | Pellet manufacturing apparatus and water treatment method using same |
CN116040138A (en) * | 2023-01-06 | 2023-05-02 | 重庆大学 | A method for ocean storage of carbon dioxide hydrate |
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CN108117076A (en) * | 2017-12-15 | 2018-06-05 | 浙江海洋大学 | A kind of carbon dioxide hydrate reaction unit and the method for improving its generation effect |
US20220411290A1 (en) * | 2019-11-28 | 2022-12-29 | Korea Institute Of Industrial Technology | Pellet manufacturing apparatus and water treatment method using same |
CN111285374A (en) * | 2020-03-24 | 2020-06-16 | 兰州理工大学 | A kind of carbon dioxide formation storage method and system |
CN111333435A (en) * | 2020-04-10 | 2020-06-26 | 青岛海洋地质研究所 | Preparation device and preparation method of carbon dioxide hydrate micro-fertilizer |
CN112473572A (en) * | 2020-11-16 | 2021-03-12 | 中国石油大学(华东) | Hydration reaction device |
KR20220089176A (en) * | 2020-12-21 | 2022-06-28 | 울산과학기술원 | Apparatus for CO2 hydrate generating and storing and Method for same the using |
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