WO2023050476A1 - Liquid-phase organic mixture separation method using hydrate phase transition - Google Patents
Liquid-phase organic mixture separation method using hydrate phase transition Download PDFInfo
- Publication number
- WO2023050476A1 WO2023050476A1 PCT/CN2021/123386 CN2021123386W WO2023050476A1 WO 2023050476 A1 WO2023050476 A1 WO 2023050476A1 CN 2021123386 W CN2021123386 W CN 2021123386W WO 2023050476 A1 WO2023050476 A1 WO 2023050476A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid
- hydrate
- organic mixture
- component
- phase
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
Definitions
- the invention belongs to the field of separation science and technology, and relates to a liquid-phase organic mixture separation method utilizing hydrate phase transition.
- the raw materials and products involved in chemical production are usually a mixture of multiple components.
- the mixture needs to be separated into relatively pure substances.
- the most commonly used separation methods are rectification, derivatization, and crystallization. Distillation is the separation of organic mixtures by utilizing the different boiling points of the components.
- the boiling points of the components in the liquid-phase organic mixture are similar, the number of plates required will be very large, and the reflux ratio will be very high, so that the energy input required for the separation process will be large, and the separation cost will be increased.
- the derivatization method is to chemically react the organic mixture to be separated with a certain substance to generate derivative isomers with a large difference in boiling point, and then separate them by rectification and reduction.
- There are problems such as complicated process and low product yield.
- the crystallization method is to lower the liquid-phase organic mixture to a certain temperature so that the substance with a higher melting point is crystallized and separated first.
- the main problem is that the low temperature condition required for the separation process makes the energy consumption huge.
- other methods also have their own shortcomings.
- Hydrate is a non-stoichiometric cage crystal substance formed by water and other small molecule guests, also known as cage hydrate.
- Water molecules are connected by hydrogen bonds to form some polyhedral cages, in which guest molecules of appropriate size can be fixed to form solid hydrates to make them thermodynamically stable, but when the environmental conditions change slightly, the hydrates can be decomposed again into water and guest molecules.
- Organic substances such as cyclopentane and fluorodichloroethane can form hydrates with water under milder conditions, and the process is reversible and controllable, making hydrates have the potential to be applied to the separation of liquid-phase organic mixtures.
- the invention provides a liquid-phase organic mixture separation method utilizing hydrate phase transition to realize effective separation of liquid-phase organic mixtures containing cyclopentane, fluorodichloroethane and the like.
- a liquid-phase organic mixture separation method utilizing hydrate phase transition comprising the following steps:
- step (4) In an environment with a temperature of T, the substance obtained in step (4) is subjected to solid-liquid separation, the obtained solid is the hydrate of component A, and the obtained liquid is component B and unreacted water;
- step (6) Put the hydrate of component A obtained in step (5) under normal pressure at a certain temperature between the phase equilibrium temperature of the hydrate and 25 degrees Celsius to decompose the hydrate into component A and water, The liquid and the liquid obtained in step (5) are separated by a liquid separation method to obtain pure component A, component B and water;
- step (6) The water produced in step (6) is used in step (2) for recycling, and component A and component B obtained in step (6) are put into storage tanks respectively, and samples are taken to analyze their purity.
- Each component in the liquid phase organic mixture is immiscible with water
- the liquid-phase organic mixture must contain a substance capable of forming solid hydrate with water, such as one or two of cyclopentane, fluorodichloroethane and neopentane to be mixed later.
- the solid-liquid separation method includes one or more of vacuum suction filtration, pressure filtration, centrifugal separation and extrusion separation.
- the invention can realize the separation of the components of the liquid-phase organic mixture between zero degrees and 25 degrees Celsius, and the required cooling or heating energy consumption is extremely low; the method uses water as the only reagent without the use of other chemical reagents, and is economical and environmentally friendly , can be recycled; this method can realize the separation of organic mixtures only through the two main processes of hydrate formation and decomposition, and the operation process is simple and easy; this method can simultaneously obtain the components of pure liquid organic mixtures, compared with other The method can only obtain a relatively pure component, and the separation is more efficient; the traditional method requires extremely high energy consumption or the addition of chemical reagents to achieve separation and purification for organic mixture systems with similar boiling points.
- the characteristic of forming hydrates under certain conditions realizes the separation of liquid-phase organic mixtures, so it is more advantageous for liquid-phase organic mixtures with similar boiling points.
- Embodiment 1 Taking the liquid-phase organic mixture of cyclopentane and benzene as an example
- phase equilibrium temperature of cyclopentane hydrate under normal pressure is 7 degrees Celsius
- the reactor is placed in an environment with a temperature of 4 degrees Celsius, and the materials in the reactor are fully stirred by mechanical stirring, and the stirring rate is set at 500 r/ min;
- step (4) In an environment with a temperature of 4 degrees Celsius, the substance obtained in step (4) is subjected to suction filtration, and the obtained solid is cyclopentane hydrate, and the obtained liquid is benzene and unreacted water;
- step (6) Decompose the cyclopentane hydrate obtained in step (5) into cyclopentane and water at 20 degrees Celsius under normal pressure, and separate the liquid from the liquid obtained in step (5) by liquid separation to obtain pure Cyclopentane, benzene and water;
- step (7) Use the water produced in step (6) for step (2) and recycle it. Put the cyclopentane and benzene obtained in step (6) into storage tanks respectively, and take samples to analyze their purity.
- the purity of cyclopentane can be The purity of benzene can reach 90%.
- Embodiment 2 Take the liquid phase organic mixture of cyclopentane and neohexane as an example
- phase equilibrium temperature of cyclopentane hydrate under normal pressure is 7 degrees Celsius, and the reactor is placed in an environment with a temperature of 2 degrees Celsius, and the materials in the reactor are fully stirred by magnetic stirring, and the stirring rate is set at 500 r/ min;
- step (4) In an environment with a temperature of 2 degrees Celsius, the substance obtained in step (4) is subjected to suction filtration, and the obtained solid is cyclopentane hydrate, and the obtained liquid is neohexane and unreacted water;
- step (6) Decompose the cyclopentane hydrate obtained in step (5) into cyclopentane and water at 20 degrees Celsius under normal pressure, and separate the liquid from the liquid obtained in step (5) by liquid separation to obtain pure cyclopentane, neohexane and water;
- step (6) The water produced in step (6) is used in step (2) for recycling, and the cyclopentane and neohexane obtained in step (6) are respectively loaded into storage tanks, and the purity of cyclopentane is analyzed by sampling. The purity can reach 99%.
Landscapes
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A liquid-phase organic mixture separation method using hydrate phase transition, relating to the field of separation science and technology. In the method, separation of components of a liquid-phase organic mixture can be achieved at temperatures above zero to 25 degrees Celsius by means of hydrate generation and decomposition, components of a pure liquid-phase organic mixture can be obtained at the same time using water as a unique reagent, without using other chemical reagents, and compared with other separation methods by which only a relatively pure component can be obtained, separation is more efficient; traditional methods require extremely high energy consumption or addition of chemical reagents to achieve separation and purification of organic mixture systems having similar boiling points, in the method, the separation of the liquid-phase organic mixture is achieved only using the property of whether each component can generate a hydrate under operating conditions, and therefore, the method is more advantageous for the liquid-phase organic mixtures having similar boiling points.
Description
本发明属于分离科学与技术领域，涉及一种利用水合物相变的液相有机混合物分离方法。The invention belongs to the field of separation science and technology, and relates to a liquid-phase organic mixture separation method utilizing hydrate phase transition.
化工生产中涉及的原料及产品通常是由多个组分组成的混合物，为了进一步加工利用，需要把混合物分离成比较纯净的物质。对于液相有机混合物，目前最常用的分离方法是精馏法、衍生法和结晶法。精馏法是利用各组分的沸点不同从而实现有机混合物的分离。然而，如果液相有机混合物中的各组分沸点相近，其需要的塔板数将非常大，并且回流比要求十分高，使得分离过程所需的能量输入较大，增加了分离成本。衍生法是将待分离有机混合物与某种物质进行化学反应，生成沸点相差较大的衍生异构体，再通过精馏、还原的方法实现分离，存在过程复杂、产品收率低等问题。结晶法是将液相有机混合物降低至一定温度使熔点较高的物质先结晶分离出来，主要的问题是分离过程需要的低温条件使得能耗巨大。同时，其他方法也存在各自的缺点。The raw materials and products involved in chemical production are usually a mixture of multiple components. For further processing and utilization, the mixture needs to be separated into relatively pure substances. For liquid-phase organic mixtures, the most commonly used separation methods are rectification, derivatization, and crystallization. Distillation is the separation of organic mixtures by utilizing the different boiling points of the components. However, if the boiling points of the components in the liquid-phase organic mixture are similar, the number of plates required will be very large, and the reflux ratio will be very high, so that the energy input required for the separation process will be large, and the separation cost will be increased. The derivatization method is to chemically react the organic mixture to be separated with a certain substance to generate derivative isomers with a large difference in boiling point, and then separate them by rectification and reduction. There are problems such as complicated process and low product yield. The crystallization method is to lower the liquid-phase organic mixture to a certain temperature so that the substance with a higher melting point is crystallized and separated first. The main problem is that the low temperature condition required for the separation process makes the energy consumption huge. At the same time, other methods also have their own shortcomings.
水合物是一种水与其他小分子客体形成的非化学计量性笼状晶体物质，又称为笼型水合物。水分子通过氢键相连形成一些多面体笼子，尺寸合适的客体分子可被固定在其中，形成固体水合物使其具有热力学稳定性，但是当环境条件发生微小的改变之后，水合物又可重新分解为水和客体分子。环戊烷、一氟二氯乙烷等有机物可以在较温和的条件下和水生成水合物，并且该过程可逆可控，使得水合物具有应用于液相有机混合物分离的潜能。Hydrate is a non-stoichiometric cage crystal substance formed by water and other small molecule guests, also known as cage hydrate. Water molecules are connected by hydrogen bonds to form some polyhedral cages, in which guest molecules of appropriate size can be fixed to form solid hydrates to make them thermodynamically stable, but when the environmental conditions change slightly, the hydrates can be decomposed again into water and guest molecules. Organic substances such as cyclopentane and fluorodichloroethane can form hydrates with water under milder conditions, and the process is reversible and controllable, making hydrates have the potential to be applied to the separation of liquid-phase organic mixtures.
本发明提供了一种利用水合物相变的液相有机混合物分离方法，实现含环戊烷、一氟二氯乙烷等液相有机混合物的有效分离。The invention provides a liquid-phase organic mixture separation method utilizing hydrate phase transition to realize effective separation of liquid-phase organic mixtures containing cyclopentane, fluorodichloroethane and the like.
本发明采用的技术方案如下： The technical scheme that the present invention adopts is as follows:
一种利用水合物相变的液相有机混合物分离方法，包括以下步骤：A liquid-phase organic mixture separation method utilizing hydrate phase transition, comprising the following steps:
（1）分析待分离液相有机混合物组分，确定其中所包含的有机物种类及比例，得到该液相有机混合物由质量分数x%的A和y%的B组成，其中组分A能够和水生成水合物；(1) Analyze the components of the liquid-phase organic mixture to be separated, determine the types and proportions of organic substances contained therein, and obtain that the liquid-phase organic mixture is composed of mass fraction x% of A and y% of B, wherein component A can be mixed with water Formation of hydrates;
（2）将液相有机混合物装入反应器中，根据组分A的水合物生成反应式，按照组分A和水的摩尔比以及组分A的含量，计算需要的水量为m，向反应器中加入1.5m的水，使得液相有机混合物中的组分A能够完全生成固体水合物；(2) Put the liquid-phase organic mixture into the reactor, according to the hydrate formation reaction formula of component A, according to the molar ratio of component A to water and the content of component A, calculate the required amount of water as m, to the reaction Add 1.5m of water into the tank, so that component A in the liquid phase organic mixture can completely generate solid hydrate;
（3）将反应器置于零度以上和常压下水合物相平衡温度以下的温度范围内，记为T，利用机械搅拌或磁力搅拌等充分搅拌反应器内的物质，搅拌速率控制在200 r/min-1000 r/min;(3) Put the reactor in the temperature range above zero and below the hydrate phase equilibrium temperature under normal pressure, denoted as T, fully stir the material in the reactor by mechanical stirring or magnetic stirring, and control the stirring rate at 200 r /min-1000 r/min;
（4）利用温度传感器实时监测反应器内的温度变化，温度传感器顶端没入液相有机混合物中，由于水合物生成是放热反应会导致反应器内温度上升，直至反应器内温度上升后又降低至T并保持不变4小时以上，则水合物完全生成；(4) Use the temperature sensor to monitor the temperature change in the reactor in real time. The top of the temperature sensor is submerged in the liquid-phase organic mixture. Since the hydrate formation is an exothermic reaction, the temperature in the reactor will rise until the temperature in the reactor rises and then decreases. to T and remain unchanged for more than 4 hours, the hydrate is completely formed;
（5）在温度为T的环境中，将步骤（4）所得物质进行固液分离，所得固体为组分A的水合物，所得液体为组分B和未反应的水；(5) In an environment with a temperature of T, the substance obtained in step (4) is subjected to solid-liquid separation, the obtained solid is the hydrate of component A, and the obtained liquid is component B and unreacted water;
（6）将步骤（5）所得的组分A的水合物在常压下置于水合物相平衡温度和25摄氏度之间的某一温度条件下，使水合物分解为组分A和水，将该液体和步骤（5）所得液体分别利用分液法进行分离，得到纯净的组分A、组分B和水；(6) Put the hydrate of component A obtained in step (5) under normal pressure at a certain temperature between the phase equilibrium temperature of the hydrate and 25 degrees Celsius to decompose the hydrate into component A and water, The liquid and the liquid obtained in step (5) are separated by a liquid separation method to obtain pure component A, component B and water;
（7）将步骤（6）所产生的水用于步骤（2），循环使用，将步骤（6）所得组分A和组分B分别装入储罐，并取样分析其纯度。(7) The water produced in step (6) is used in step (2) for recycling, and component A and component B obtained in step (6) are put into storage tanks respectively, and samples are taken to analyze their purity.
所述液相有机混合物中各组分均和水不互溶；Each component in the liquid phase organic mixture is immiscible with water;
所述液相有机混合物中必须包含一种能够和水生成固体水合物的物质，如环戊烷、一氟二氯乙烷、新戊烷中的一种或二种以后混合。The liquid-phase organic mixture must contain a substance capable of forming solid hydrate with water, such as one or two of cyclopentane, fluorodichloroethane and neopentane to be mixed later.
所述的固液分离方法包括真空抽滤，加压过滤，离心分离，挤压分离中的一种或几种。The solid-liquid separation method includes one or more of vacuum suction filtration, pressure filtration, centrifugal separation and extrusion separation.
本发明能够在零度以上至25摄氏度之间实现液相有机混合物的各组分分离，所需制冷或加热的能耗极低；该方法以水作为唯一试剂，无需其他化学试剂的使用，经济环保，可循环利用；该方法仅通过水合物生成和分解两个主要过程即可实现有机混合物分离，操作过程简便易行；该方法能够同时得到纯净的液相有机混合物各组分，相比较于其他方法只能得到一种较纯净组分，分离更高效；传统方法对于沸点相近的有机混合物体系需要极高的能耗或者化学试剂添加才能实现分离提纯，该方法仅仅利用各组分是否能够在操作条件下生成水合物这一特性实现液相有机混合物分离，因此，对于沸点相近的液相有机混合物更具有优势。The invention can realize the separation of the components of the liquid-phase organic mixture between zero degrees and 25 degrees Celsius, and the required cooling or heating energy consumption is extremely low; the method uses water as the only reagent without the use of other chemical reagents, and is economical and environmentally friendly , can be recycled; this method can realize the separation of organic mixtures only through the two main processes of hydrate formation and decomposition, and the operation process is simple and easy; this method can simultaneously obtain the components of pure liquid organic mixtures, compared with other The method can only obtain a relatively pure component, and the separation is more efficient; the traditional method requires extremely high energy consumption or the addition of chemical reagents to achieve separation and purification for organic mixture systems with similar boiling points. The characteristic of forming hydrates under certain conditions realizes the separation of liquid-phase organic mixtures, so it is more advantageous for liquid-phase organic mixtures with similar boiling points.
以下技术方案，进一步说明本发明的具体实施方式。The following technical schemes further illustrate the specific embodiments of the present invention.
实施例1：以环戊烷和苯的液相有机混合物为例Embodiment 1: Taking the liquid-phase organic mixture of cyclopentane and benzene as an example
（1）利用气相色谱-质谱联用分析环戊烷和苯液相有机混合物，确定其中所包含的有机物种类及比例，得到该液相有机混合物由质量分数40%的环戊烷和60%的苯组成，其中组分环戊烷可以和水生成水合物；(1) Use gas chromatography-mass spectrometry to analyze the liquid phase organic mixture of cyclopentane and benzene, determine the type and proportion of organic matter contained therein, and obtain the liquid phase organic mixture with a mass fraction of 40% cyclopentane and 60% Composed of benzene, the component cyclopentane can form hydrate with water;
（2）将100 g的环戊烷和苯的液相有机混合物装入反应器中，因此加入反应器的环戊烷为40 g（0.57摩尔），1摩尔环戊烷可以和17摩尔水生成环戊烷水合物，因此理论需水量为174.42 g（9.69摩尔），向反应器中加入261.63 g的水，使得液相有机混合物中的环戊烷能够完全生成固体水合物；(2) Put 100 g of the liquid-phase organic mixture of cyclopentane and benzene into the reactor, so the amount of cyclopentane added to the reactor is 40 g (0.57 moles), and 1 mole of cyclopentane can be produced with 17 moles of water Cyclopentane hydrate, so the theoretical water requirement is 174.42 g (9.69 moles), and 261.63 g of water is added to the reactor, so that the cyclopentane in the liquid phase organic mixture can completely generate solid hydrate;
（3）常压下环戊烷水合物的相平衡温度为7摄氏度，将反应器置于温度为4摄氏度的环境中，利用机械搅拌充分搅拌反应器内的物质，搅拌速率设置为500 r/min;(3) The phase equilibrium temperature of cyclopentane hydrate under normal pressure is 7 degrees Celsius, the reactor is placed in an environment with a temperature of 4 degrees Celsius, and the materials in the reactor are fully stirred by mechanical stirring, and the stirring rate is set at 500 r/ min;
（4）利用温度传感器实时监测反应器内的温度变化，温度传感器顶端没入液相有机混合物中，由于环戊烷水合物生成是放热反应会导致反应器内温度上升，直至反应器内温度先上升至7摄氏度，然后又逐步降低至4摄氏度并保持6小时不变，则环戊烷水合物完全生成；(4) Use the temperature sensor to monitor the temperature change in the reactor in real time. The top of the temperature sensor is submerged in the liquid-phase organic mixture. Since the formation of cyclopentane hydrate is an exothermic reaction, the temperature in the reactor will rise until the temperature in the reactor first Rise to 7 degrees Celsius, then gradually decrease to 4 degrees Celsius and keep it unchanged for 6 hours, then cyclopentane hydrate is completely formed;
（5）在温度为4摄氏度的环境中，将步骤（4）所得物质进行抽滤，所得固体为环戊烷水合物，所得液体为苯和未反应的水；(5) In an environment with a temperature of 4 degrees Celsius, the substance obtained in step (4) is subjected to suction filtration, and the obtained solid is cyclopentane hydrate, and the obtained liquid is benzene and unreacted water;
（6）将步骤（5）所得的环戊烷水合物在常压下20摄氏度分解为环戊烷和水，将该液体和步骤（5）所得液体分别利用分液法进行分离，得到纯净的环戊烷、苯和水；(6) Decompose the cyclopentane hydrate obtained in step (5) into cyclopentane and water at 20 degrees Celsius under normal pressure, and separate the liquid from the liquid obtained in step (5) by liquid separation to obtain pure Cyclopentane, benzene and water;
（7）将步骤（6）所产生的水用于步骤（2），循环使用，将步骤（6）所得环戊烷和苯分别装入储罐，并取样分析其纯度，环戊烷纯度可达90%，苯的纯度可达到95%。(7) Use the water produced in step (6) for step (2) and recycle it. Put the cyclopentane and benzene obtained in step (6) into storage tanks respectively, and take samples to analyze their purity. The purity of cyclopentane can be The purity of benzene can reach 90%.
实施例2：以环戊烷和新己烷的液相有机混合物为例Embodiment 2: Take the liquid phase organic mixture of cyclopentane and neohexane as an example
（1）利用气相色谱-质谱联用分析环戊烷和新己烷液相有机混合物，确定其中所包含的有机物种类及比例，得到该液相有机混合物由质量分数85%的环戊烷和15%的新己烷组成，其中组分环戊烷可以和水生成水合物；组分新己烷在常压下不可生成水合物；(1) Use gas chromatography-mass spectrometry to analyze the liquid phase organic mixture of cyclopentane and neohexane, determine the type and proportion of organic matter contained therein, and obtain the liquid phase organic mixture consisting of 85% cyclopentane and 15% by mass fraction % neohexane, wherein the component cyclopentane can form hydrates with water; the component neohexane cannot form hydrates under normal pressure;
（2）将环戊烷和新己烷的液相有机混合物装入反应器中，因此加入反应器的环戊烷为7.5 g（0.17摩尔），1摩尔环戊烷可以和17摩尔水生成环戊烷水合物，因此理论需水量为32.7 g（1.82摩尔），向反应器中加入49.05 g的水，使得液相有机混合物中的环戊烷能够完全生成固体水合物；(2) Put the liquid-phase organic mixture of cyclopentane and neohexane into the reactor, so the amount of cyclopentane added to the reactor is 7.5 g (0.17 moles), and 1 mole of cyclopentane can form a cyclopentane with 17 moles of water Pentane hydrate, so the theoretical water requirement is 32.7 g (1.82 moles), and 49.05 g of water is added to the reactor, so that the cyclopentane in the liquid phase organic mixture can completely generate solid hydrate;
（3）常压下环戊烷水合物的相平衡温度为7摄氏度，将反应器置于温度为2摄氏度的环境中，利用磁力搅拌充分搅拌反应器内的物质，搅拌速率设置为500 r/min;(3) The phase equilibrium temperature of cyclopentane hydrate under normal pressure is 7 degrees Celsius, and the reactor is placed in an environment with a temperature of 2 degrees Celsius, and the materials in the reactor are fully stirred by magnetic stirring, and the stirring rate is set at 500 r/ min;
（4）利用温度传感器实时监测反应器内的温度变化，温度传感器顶端没入液相有机混合物中，由于环戊烷水合物生成是放热反应会导致反应器内温度上升，直至反应器内温度先上升至7摄氏度，然后又逐步降低至2摄氏度并保持6小时不变，则环戊烷水合物完全生成；(4) Use the temperature sensor to monitor the temperature change in the reactor in real time. The top of the temperature sensor is submerged in the liquid-phase organic mixture. Since the formation of cyclopentane hydrate is an exothermic reaction, the temperature in the reactor will rise until the temperature in the reactor first Rise to 7 degrees Celsius, then gradually decrease to 2 degrees Celsius and keep it unchanged for 6 hours, then cyclopentane hydrate is completely formed;
（5）在温度为2摄氏度的环境中，将步骤（4）所得物质进行抽滤，所得固体为环戊烷水合物，所得液体为新己烷和未反应的水；(5) In an environment with a temperature of 2 degrees Celsius, the substance obtained in step (4) is subjected to suction filtration, and the obtained solid is cyclopentane hydrate, and the obtained liquid is neohexane and unreacted water;
（6）将步骤（5）所得的环戊烷水合物在常压下20摄氏度分解为环戊烷和水，将该液体和步骤（5）所得液体分别利用分液法进行分离，得到纯净的环戊烷、新己烷和水；(6) Decompose the cyclopentane hydrate obtained in step (5) into cyclopentane and water at 20 degrees Celsius under normal pressure, and separate the liquid from the liquid obtained in step (5) by liquid separation to obtain pure cyclopentane, neohexane and water;
（7）将步骤（6）所产生的水用于步骤（2），循环使用，将步骤（6）所得环戊烷和新己烷分别装入储罐，并取样分析其纯度，环戊烷的纯度可达99%。(7) The water produced in step (6) is used in step (2) for recycling, and the cyclopentane and neohexane obtained in step (6) are respectively loaded into storage tanks, and the purity of cyclopentane is analyzed by sampling. The purity can reach 99%.
Claims (6)
- 一种利用水合物相变的液相有机混合物分离方法，其特征包括以下步骤：A liquid-phase organic mixture separation method utilizing hydrate phase transition, characterized in comprising the following steps:（1）分析待分离液相有机混合物组分，确定其中所包含的有机物种类及比例，得到该液相有机混合物由质量分数x%的A和y%的B组成，其中组分A能够和水生成水合物；(1) Analyze the components of the liquid-phase organic mixture to be separated, determine the types and proportions of organic substances contained therein, and obtain that the liquid-phase organic mixture is composed of mass fraction x% of A and y% of B, wherein component A can be mixed with water Formation of hydrates;（2）将液相有机混合物装入反应器中，根据组分A的水合物生成反应式，按照组分A和水的摩尔比以及组分A的含量，计算需要的水量为m，向反应器中加入1.5m的水，使得液相有机混合物中的组分A能够完全生成固体水合物；(2) Put the liquid-phase organic mixture into the reactor, according to the hydrate formation reaction formula of component A, according to the molar ratio of component A to water and the content of component A, calculate the required amount of water as m, to the reaction Add 1.5m of water into the tank, so that component A in the liquid phase organic mixture can completely generate solid hydrate;（3）将反应器置于零度以上和常压下水合物相平衡温度以下的温度范围内，记为T，利用机械搅拌或磁力搅拌等充分搅拌反应器内的物质，搅拌速率控制在200 r/min-1000 r/min;(3) Put the reactor in the temperature range above zero and below the hydrate phase equilibrium temperature under normal pressure, denoted as T, fully stir the material in the reactor by mechanical stirring or magnetic stirring, and control the stirring rate at 200 r /min-1000 r/min;（4）利用温度传感器实时监测反应器内的温度变化，温度传感器顶端没入液相有机混合物中，由于水合物生成是放热反应会导致反应器内温度上升，直至反应器内温度上升后又降低至T并保持不变4小时以上，则水合物完全生成；(4) Use the temperature sensor to monitor the temperature change in the reactor in real time. The top of the temperature sensor is submerged in the liquid-phase organic mixture. Since the hydrate formation is an exothermic reaction, the temperature in the reactor will rise until the temperature in the reactor rises and then decreases. to T and remain unchanged for more than 4 hours, the hydrate is completely formed;（5）在温度为T的环境中，将步骤（4）所得物质进行固液分离，所得固体为组分A的水合物，所得液体为组分B和未反应的水；(5) In an environment with a temperature of T, the substance obtained in step (4) is subjected to solid-liquid separation, the obtained solid is the hydrate of component A, and the obtained liquid is component B and unreacted water;（6）将步骤（5）所得的组分A的水合物在常压下置于水合物相平衡温度和25摄氏度之间的某一温度条件下，使水合物分解为组分A和水，将该液体和步骤（5）所得液体分别利用分液法进行分离，得到纯净的组分A、组分B和水；(6) Put the hydrate of component A obtained in step (5) under normal pressure at a certain temperature between the phase equilibrium temperature of the hydrate and 25 degrees Celsius to decompose the hydrate into component A and water, The liquid and the liquid obtained in step (5) are separated by a liquid separation method to obtain pure component A, component B and water;（7）将步骤（6）所产生的水用于步骤（2），循环使用，将步骤（6）所得组分A和组分B分别装入储罐，并取样分析其纯度。(7) The water produced in step (6) is used in step (2) for recycling, and component A and component B obtained in step (6) are put into storage tanks respectively, and samples are taken to analyze their purity.
- 根据权利要求1所述的一种利用水合物相变的液相有机混合物分离方法，其特征在于，所述液相有机混合物中各组分均和水不互溶。A liquid-phase organic mixture separation method utilizing hydrate phase transition according to claim 1, characterized in that each component in the liquid-phase organic mixture is immiscible with water.
- 根据权利要求1或2所述的一种利用水合物相变的液相有机混合物分离方法，其特征在于，所述液相有机混合物中必须包含一种能够和水生成固体水合物的物质。A method for separating a liquid-phase organic mixture using a hydrate phase transition according to claim 1 or 2, wherein the liquid-phase organic mixture must contain a substance capable of forming a solid hydrate with water.
- 根据权利要求3所述的一种利用水合物相变的液相有机混合物分离方法，其特征在于，所述液相有机混合物是指环戊烷、一氟二氯乙烷、新戊烷中的一种或二种以上混合。A method for separating a liquid-phase organic mixture utilizing a hydrate phase transition according to claim 3, wherein the liquid-phase organic mixture refers to one of cyclopentane, fluorodichloroethane, and neopentane. A mixture of two or more types.
- 根据权利要求1、2或4所述的一种利用水合物相变的液相有机混合物分离方法，其特征在于，所述的固液分离方法为真空抽滤、加压过滤、离心分离、挤压分离。A liquid-phase organic mixture separation method utilizing hydrate phase transition according to claim 1, 2 or 4, characterized in that, the solid-liquid separation method is vacuum filtration, pressure filtration, centrifugal separation, extrusion Press to separate.
- 根据权利要求3所述的一种利用水合物相变的液相有机混合物分离方法，其特征在于，所述的固液分离方法为真空抽滤、加压过滤、离心分离、挤压分离。A liquid-phase organic mixture separation method using hydrate phase transition according to claim 3, characterized in that, the solid-liquid separation method is vacuum filtration, pressure filtration, centrifugal separation, extrusion separation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111157376.X | 2021-09-30 | ||
| CN202111157376.XA CN113941173A (en) | 2021-09-30 | 2021-09-30 | Liquid phase organic mixture separation method by utilizing phase change of hydrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023050476A1 true WO2023050476A1 (en) | 2023-04-06 |
Family
ID=79329059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2021/123386 WO2023050476A1 (en) | 2021-09-30 | 2021-10-13 | Liquid-phase organic mixture separation method using hydrate phase transition |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113941173A (en) |
| WO (1) | WO2023050476A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016037494A1 (en) * | 2014-09-12 | 2016-03-17 | 中国科学院广州能源研究所 | Method for separating mixed gas by hydrate process |
| WO2016152890A1 (en) * | 2015-03-26 | 2016-09-29 | 日本ゼオン株式会社 | Method for separating polymer solution and water |
| CN107185275A (en) * | 2017-07-07 | 2017-09-22 | 大连理工大学 | A kind of oil water mixture separation method based on hydrate principle |
| CN113104923A (en) * | 2021-03-26 | 2021-07-13 | 大连理工大学 | Method for desalting high-salinity wastewater based on liquid-solid phase change method |
| CN114133311A (en) * | 2020-09-03 | 2022-03-04 | 中国科学院大连化学物理研究所 | Low-carbon naphthenic gas enrichment and recovery method through gas-solid-liquid phase change of gas hydrate |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258391C (en) * | 2003-04-14 | 2006-06-07 | 中国石油化工股份有限公司 | Method for separating low boiling point gas mixture using hydrate method and its system |
| AU2014410146B2 (en) * | 2014-10-31 | 2018-07-12 | Exxonmobil Upstream Research Company | A multiphase separation system |
| CN105859506B (en) * | 2015-01-21 | 2018-07-13 | 中国石油天然气股份有限公司 | A method of utilizing extraction rectification technique isolating cyclopentane and neohexane |
| CN109824106B (en) * | 2019-03-18 | 2021-10-15 | 大连理工大学 | Normal-pressure continuous seawater desalination system based on hydrate method and application method thereof |
| CN110566300B (en) * | 2019-09-12 | 2022-04-29 | 天津大学 | Component-adjustable organic Rankine cycle system based on hydrate separation characteristic |
-
2021
- 2021-09-30 CN CN202111157376.XA patent/CN113941173A/en not_active Withdrawn
- 2021-10-13 WO PCT/CN2021/123386 patent/WO2023050476A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016037494A1 (en) * | 2014-09-12 | 2016-03-17 | 中国科学院广州能源研究所 | Method for separating mixed gas by hydrate process |
| WO2016152890A1 (en) * | 2015-03-26 | 2016-09-29 | 日本ゼオン株式会社 | Method for separating polymer solution and water |
| CN107185275A (en) * | 2017-07-07 | 2017-09-22 | 大连理工大学 | A kind of oil water mixture separation method based on hydrate principle |
| CN114133311A (en) * | 2020-09-03 | 2022-03-04 | 中国科学院大连化学物理研究所 | Low-carbon naphthenic gas enrichment and recovery method through gas-solid-liquid phase change of gas hydrate |
| CN113104923A (en) * | 2021-03-26 | 2021-07-13 | 大连理工大学 | Method for desalting high-salinity wastewater based on liquid-solid phase change method |
Non-Patent Citations (2)
| Title |
|---|
| SUN, ZHIGAO ET AL.: "Experimental Study on the Formation Process of Cyclopentane Hydrate", CHINESE JOURNAL OF REFRIGERATION TECHNOLOGY, vol. 32, no. 2, 30 June 2012 (2012-06-30), pages 23 - 25, XP009544827 * |
| WEI, ZHONGCHENG: "Fiber Optic Material Preparation Technology", BEIJING UNIVERSITY OF POSTS AND TELECOMMUNICATIONS PRESS, 30 September 2016 (2016-09-30) * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113941173A (en) | 2022-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101245026A (en) | Process for producing 1,4-(2,4-diaminophenyloxy)-2,5-di-t-butyl benzene | |
| WO2019196132A1 (en) | Pentanediamine sebacate salt and crystal thereof | |
| US4644076A (en) | Continuous process for the synthesis of hexamethyldisilazane | |
| JPS60172945A (en) | Manufacture of phthalic acid esters | |
| CN113582874B (en) | Synthesis method of bromoacetonitrile | |
| WO2023050476A1 (en) | Liquid-phase organic mixture separation method using hydrate phase transition | |
| CN103396292B (en) | Method for industrially producing A,A'-dihydroxy-1,3-diisobutylbenzene | |
| CN107382886B (en) | Method for constructing N-2-aryl substituted-1, 2, 3-triazole | |
| CN1847223A (en) | Production process of tetrabromobispheno S bis (2,3-dibromopropyl) ether | |
| CN117843435A (en) | Crude oil azeotrope separation method based on cage compound phase change method | |
| CN113024411B (en) | Preparation method of tralkoxydim | |
| CN1037890A (en) | The manufacture method of dihydroxyphenyl propane | |
| CN1314648C (en) | Method for preparing butanedione | |
| US9604895B2 (en) | Lactate production process | |
| CN104910004B (en) | A kind of method of PTA waste residue resource | |
| CN108484353B (en) | Synthetic method of 2, 4-dichloro-5-fluoro (trichloromethyl) benzene | |
| RU2767422C1 (en) | Method of producing styrene by liquid-phase dehydration of methylphenylcarbinol-containing raw material | |
| US3031500A (en) | Conversion of ammonium salts | |
| CN117050011B (en) | Method for synthesizing 2-methylquinoline by using vinyl acetate as raw material | |
| CN114735687B (en) | Synthesis method of graphene | |
| CN115368217B (en) | Synthesis method of 3,4, 5-trimethoxytoluene | |
| CN111704599B (en) | Preparation method of xanthene compound | |
| CN109553553B (en) | Method for preparing isopropyl phenylimino ester | |
| CN110003046B (en) | Synthesis method of (Z) -4-imine arylmethyl-1, 2-naphthalenedione compound | |
| CN109651261B (en) | Method for synthesizing 4-amino-2, 5-dimethoxypyrimidine by one-pot method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21959040 Country of ref document: EP Kind code of ref document: A1 |