阅读说明：本技术 一种sf6混合气体的水合物气体分离装置及方法 (Hydrate gas separation device and method for SF6 mixed gas ) 是由 卞超 甘强 程骏 陈轩 张正东 谭婷月 张晓星 张引 严进 朱正宜 胡隽宇 于 2020-11-27 设计创作，主要内容包括：一种SF6混合气体的水合物气体分离装置,包括：进气单元,结晶器单元,温度控制单元,压强控制单元和出气单元,进气单元与结晶器单元相连接,用于向结晶器单元充入SF6混合气体；结晶器单元用作SF6混合气体的水合物气体分离装置的反应器,形成水合物；温度控制单元用于控制结晶器单元的反应温度；压强控制单元用于控制结晶器单元的反应压强；出气单元包括：气体出口模块和水合物出口模块,分别与结晶器单元相连接,气体出口模块用于测量和收集未形成水合物的气体,水合物出口模块用于测量和收集形成水合物的气体和液体。相较于现有技术中,本发明便于控制,不需要太大的压强,也不需要考虑吸附剂的回收再利用问题,经济成本低廉,极具发展潜力。(A hydrate gas separation device of SF6 mixed gas, comprising: the gas inlet unit is connected with the crystallizer unit and is used for filling SF6 mixed gas into the crystallizer unit; the crystallizer unit is used as a reactor of a hydrate gas separation device of SF6 mixed gas to form hydrate; the temperature control unit is used for controlling the reaction temperature of the crystallizer unit; the pressure control unit is used for controlling the reaction pressure of the crystallizer unit; the air outlet unit comprises: and the gas outlet module and the hydrate outlet module are respectively connected with the crystallizer unit, the gas outlet module is used for measuring and collecting gas which does not form hydrate, and the hydrate outlet module is used for measuring and collecting gas and liquid which form hydrate. Compared with the prior art, the invention is convenient to control, does not need too large pressure intensity, does not need to consider the problem of recycling of the adsorbent, has low economic cost and has great development potential.)

1. A hydrate gas separation device of SF6 mixed gas, comprising: a gas inlet unit, a crystallizer unit, a temperature control unit, a pressure control unit and a gas outlet unit, which are characterized in that,

the gas inlet unit is connected with the crystallizer unit and is used for filling SF6 mixed gas into the crystallizer unit;

the crystallizer unit is used as a reactor of a hydrate gas separation device of SF6 mixed gas to form hydrate;

the temperature control unit is used for controlling the reaction temperature of the crystallizer unit;

the pressure control unit is used for controlling the reaction pressure of the crystallizer unit;

the air outlet unit comprises: and the gas outlet module and the hydrate outlet module are respectively connected with the crystallizer unit, the gas outlet module is used for measuring and collecting gas which does not form hydrate, and the hydrate outlet module is used for measuring and collecting gas and liquid which form hydrate.

2. The hydrate gas separation device of SF6 mixed gas according to claim 1, wherein:

the air intake unit includes: the device comprises a vacuum pump (1), a mixed gas cylinder (2) and a mass flow meter (4); the vacuum pump (1) is used for enabling the whole hydrate gas separation device to be in a vacuum state before an experiment, and the mixed gas cylinder (2) is used for filling mixed gas into the hydrate gas separation device; the first mass flow meter (4) is connected to the crystallizer unit via valves and lines for direct measurement of the feed rate of the feed gas.

3. The hydrate gas separation device of SF6 mixed gas according to claim 2, wherein:

the intake unit further includes: a buffer bottle (3); the vacuum pump (1) is connected with the buffer bottle (3) through a valve and a pipeline, the mixed gas cylinder (2) is connected with the buffer bottle (3) through a pipeline, and the buffer bottle (3) is connected with the first mass flow meter (4) through a valve and a pipeline and used for playing a buffering role.

4. The hydrate gas separation device of SF6 mixed gas according to any of claims 1 to 3, wherein:

the crystallizer unit comprises: a piston (11), a stirrer (12) and a crystallizer tank (13); the piston (11) is arranged at the mouth of the crystallizer tank (13) and is used for sealing the crystallizer tank (13); the stirrer (12) is arranged inside the crystallizer tank (13) and is used for operating at a set speed and stirring gas and liquid inside the reactor; a crystallizer tank (13) is used as a reactor for the hydrate gas separation device.

5. The hydrate gas separation device of SF6 mixed gas according to any of claims 1 to 3, wherein:

the temperature control unit includes: a temperature control coolant circulation shell (9) and a platinum wire resistance thermometer (17); a coolant is arranged in the temperature control coolant circulating shell (9), and the crystallizer tank (13) is arranged in the coolant; a platinum wire resistance thermometer (17) is inserted into the crystallizer tank (13) through the crystallizer tank (13) body and the temperature control coolant circulating shell (9) to measure the temperature of the interior of the crystallizer tank (13) during reaction.

6. The hydrate gas separation device of SF6 mixed gas according to any of claims 1 to 3, wherein:

the pressure control unit includes: a pressure gauge (14) and a manual pressure gauge (15); the pressure gauge is connected with a manual pressure intensity device (15), and the manual pressure intensity device (15) is connected with the crystallizer tank (13) through a piston (11).

7. The hydrate gas separation device of SF6 mixed gas according to any of claims 1 to 3, wherein:

the gas outlet module comprises: a third flow meter (16) and an unvulcanized gas tank (18); the third flow meter (16) is connected with the crystallizer unit (16) through a valve and a pipeline, and the non-liquefied gas tank (18) is connected with the third flow meter (16) through a pipeline; gas which does not form hydrate in the crystallizer unit enters an unvulcanized gas tank (18) through a third flow meter (16), and the third flow meter (16) obtains the flow rate of the gas which does not form hydrate.

8. The hydrate gas separation device of SF6 mixed gas according to any of claims 1 to 3, wherein:

the hydrate outlet module comprises: a liquefied gas tank (5), a second flowmeter (6), a decomposer (7) and a liquid outlet/inlet valve (8) which are connected in sequence through pipelines; hydrate liquid formed by gas and liquid in the crystallizer unit enters a decomposer (7) through a liquid outlet/inlet valve (8), SF6 hydrate is decomposed by changing the temperature and the pressure of the decomposer (7), the decomposed SF6 gas enters a liquefied gas tank (5) through a second flowmeter (6), and the second flowmeter (6) obtains the flow rate of the gas forming the hydrate.

9. A hydrate gas separation method of SF6 mixed gas using the hydrate gas separation device according to any one of claims 1 to 8, comprising the steps of:

step 1, setting experimental conditions, including: vacuumizing the hydrate gas separation device and setting a set reaction temperature;

step 2, introducing raw material gas, namely SF6 mixed gas into the hydrate gas separation device, and continuously supplying the raw material gas to the crystallizer unit through a first mass flow meter (4);

step 3, adjusting the pressure control unit to enable the crystallizer unit to reach the set reaction pressure;

step 4, when the gas pressure reaches the experimental value, opening a hydrate outlet module, releasing unreacted gas after hydration in the crystallizer unit, simultaneously recording the reaction time, and measuring the total volume of the unreacted gas;

and 5, opening a hydrate outlet module to decompose SF6 hydrate, and synchronously collecting unreacted gas and dissociated gas samples in the continuous separation process.

10. The hydrate gas separation method of SF6 mixed gas according to claim 9, wherein:

the step 1 specifically comprises the following steps:

step 1.1, adding a proper surfactant into a crystallizer tank (13);

step 1.2, opening a temperature control unit to keep the coolant liquid at a constant experimental temperature;

step 1.3, opening a vacuum pump (1) and vacuumizing a hydrate gas separation device;

and step 1.4, opening a stirrer (12) of the crystallizer tank (13) to enable the crystallizer tank to run at a set speed.

Technical Field

The invention belongs to the technical field of electrical equipment recovery, and particularly relates to a hydrate gas separation device for SF6 mixed gas.

Background

Due to the strong insulating property and arc extinguishing capability, the SF6 is widely applied to gas insulation equipment, such as gas insulation closed combined electrical appliances, gas-filled cabinets, gas insulation circuit breakers, gas insulation pipeline buses and the like, wherein the gas consumption of high-voltage switch equipment accounts for more than 80% of that of SF6, and the gas consumption of medium-voltage switch equipment accounts for about 10%.

With the rapid increase of the usage amount of the development of the power industry, the debugging and the maintenance of the SF6 gas insulation equipment and the leakage and the recovery of gas can make the SF6 enter the atmospheric environment. However, sulfur hexafluoride (SF6) is one of the six emission reduction target gases specified by the kyoto protocol, namely carbon dioxide (CO2), methane (CH4), nitrous oxide (N2O), perfluorinated carbon compounds (HFCs), perfluorinated carbon compounds (PFCs), and sulfur hexafluoride (SF 6).

The SF6 gas is recognized as a greenhouse gas with greater harm to the atmospheric environment, has a potential value 23900 times that of CO2 in greenhouse effect, and has a life of 3400 years in the atmosphere. Therefore, it is very slow to prevent SF6 from being released into the atmosphere and recover and reuse SF6 gas.

In the prior art, since the SF6+ N2 gas mixture is used for various industrial purposes, while SF6 is generally mixed with air during the recycling of electrical equipment, SF6 should be separated from the gas mixture for recycling and reuse. Several methods such as liquefaction, adsorption and membrane separation have been used for the separation of SF 6.

Several methods currently used have more or less some limitations, the liquefaction method: the boiling point of SF6 gas is-50 ℃, so SF6 gas is easy to liquefy, usually pure SF6 liquid liquefies at room temperature (20 ℃) and gas pressure of 2.0MPa, but if the content of SF6 gas in the mixed gas is low, the partial pressure of SF6 is low, so that the required pressure is high for liquefying the mixed gas at room temperature, the requirement on a pressure container is high, and the mixed gas is not economical, so that the low-content SF6 mixed gas is difficult to separate by a liquefying method; adsorbent method: the amount of SF6 retired adsorbent generated and buried in an electric power system every year is huge, the buried SF6 retired adsorbent not only causes huge waste, but also carries toxic substances which cause great harm to the environment; polymer film method: at different temperatures, the permeation R of different gases through the polymeric membrane is different, and the gas with high permeability penetrates through the polymeric membrane faster. However, the membrane separation technology has the disadvantages that the membrane itself needs to be inspected and cleaned regularly, and the cost is high in the later period.

Disclosure of Invention

In order to solve the defects in the prior art, the invention aims to provide a hydrate gas separation device and method for SF6 mixed gas, which are convenient to control, do not need too large pressure and have low economic cost.

The invention adopts the following technical scheme. A hydrate gas separation device of SF6 mixed gas, comprising: the gas inlet unit is connected with the crystallizer unit and is used for filling SF6 mixed gas into the crystallizer unit;

the crystallizer unit is used as a reactor of a hydrate gas separation device of SF6 mixed gas to form hydrate;

the temperature control unit is used for controlling the reaction temperature of the crystallizer unit;

the pressure control unit is used for controlling the reaction pressure of the crystallizer unit;

the air outlet unit comprises: and the gas outlet module and the hydrate outlet module are respectively connected with the crystallizer unit, the gas outlet module is used for measuring and collecting gas which does not form hydrate, and the hydrate outlet module is used for measuring and collecting gas and liquid which form hydrate.

Preferably, the air intake unit includes: a vacuum pump, a mixed gas cylinder and a mass flowmeter; the vacuum pump is used for enabling the whole hydrate gas separation device to be in a vacuum state before an experiment, and the mixed gas cylinder is used for filling mixed gas into the hydrate gas separation device; the first mass flow meter is connected to the crystallizer unit via valves and lines for direct measurement of the feed gas supply.

Preferably, the air intake unit further includes: a buffer bottle; the vacuum pump is connected with the buffer bottle through a valve and a pipeline, the mixed gas cylinder is connected with the buffer bottle through a pipeline, and the buffer bottle is connected with the first mass flow meter through a valve and a pipeline and used for playing a role in buffering.

Preferably, the crystallizer unit comprises: a piston, a stirrer and a crystallizer tank; the piston is arranged at the mouth of the crystallizer tank and is used for sealing the crystallizer tank; the stirrer is arranged in the crystallizer tank and is used for running at a set speed and stirring gas and liquid in the reactor; the crystallizer tank serves as a reactor for the hydrate gas separation device.

Preferably, the temperature control unit includes: a temperature control coolant circulation housing and a platinum wire resistance thermometer; a coolant is arranged in the temperature control coolant circulating shell, and the crystallizer tank is arranged in the coolant; the platinum wire resistance thermometer is inserted into the crystallizer tank through the crystallizer tank body and the temperature control coolant circulating shell, and the temperature of the internal reaction of the crystallizer tank is measured.

Preferably, the pressure control unit includes: pressure gauges and manual pressure gauges; the pressure gauge is connected with a manual pressure intensity device, and the manual pressure intensity device is connected with the crystallizer tank through a piston.

Preferably, the gas outlet module comprises: a third flow meter and an unvulcanized gas tank; the third flow meter is connected with the crystallizer unit through a valve and a pipeline, and the non-liquefied gas tank is connected with the third flow meter through a pipeline; and the gas which does not form the hydrate in the crystallizer unit enters the non-liquefied gas tank through a third flow meter, and the third flow meter obtains the flow of the gas which does not form the hydrate.

Preferably, the hydrate outlet module comprises: the liquefied gas tank, the second flowmeter, the decomposer and the liquid outlet/inlet valve are connected in sequence through pipelines; hydrate liquid formed by gas and liquid in the crystallizer unit enters the decomposer through the liquid outlet/inlet valve, SF6 hydrate is decomposed by changing the temperature and the pressure of the decomposer, the decomposed SF6 gas enters the liquefied gas tank through the second flowmeter, and the second flowmeter obtains the flow rate of the gas forming the hydrate.

The invention also provides a hydrate gas separation method of SF6 mixed gas by using the hydrate gas separation device, which comprises the following steps:

step 1, setting experimental conditions, including: vacuumizing the hydrate gas separation device and setting a set reaction temperature;

step 2, introducing raw material gas, namely SF6 mixed gas into the hydrate gas separation device, and continuously supplying the raw material gas to the crystallizer unit through a first mass flow meter;

step 3, adjusting the pressure control unit to enable the crystallizer unit to reach the set reaction pressure;

step 4, when the gas pressure reaches the experimental value, opening a hydrate outlet module, releasing unreacted gas after hydration in the crystallizer unit, simultaneously recording the reaction time, and measuring the total volume of the unreacted gas;

and 5, opening a hydrate outlet module to decompose SF6 hydrate, and synchronously collecting unreacted gas and dissociated gas samples in the continuous separation process.

Preferably, step 1 specifically comprises:

step 1.1, adding a proper surfactant into a crystallizer tank;

step 1.2, opening a temperature control unit to keep the coolant liquid at a constant experimental temperature;

step 1.3, opening a vacuum pump, and vacuumizing a hydrate gas separation device;

and step 1.4, opening a stirrer of the crystallizer tank to enable the stirrer to run at a set speed.

Compared with the prior art, the hydrate gas separation device for SF6 mixed gas has the advantages that the hydrate gas separation technology is convenient to control, the pressure intensity does not need to be too high, the problem of recycling of the adsorbent does not need to be considered, the economic cost is not high, and the development potential is very high.

Drawings

Fig. 1 is a schematic diagram of a hydrate gas separation device for SF6 mixed gas provided by the invention;

fig. 2 is a flow chart of a hydrate gas separation method of SF6 mixed gas provided by the invention.

In the figure:

1-a vacuum pump;

2-mixed gas cylinder;

3-a buffer tank;

4-mass flow meter;

5-liquefied gas tank;

6-a second flow meter;

7-decomposer;

8-liquid outlet/inlet;

9-a temperature controlled coolant circulation housing;

10-a visible window;

11-a piston;

12-a stirrer;

13-a crystallizer tank;

14-a pressure gauge;

15-a manual pressure gauge;

16-a third flow meter;

17-platinum wire resistance thermometer;

18-tank of non-liquefied gas.

Detailed Description

The present application is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present application is not limited thereby.

As shown in fig. 1, the present invention provides a hydrate gas separation device of SF6 mixed gas, comprising: the device comprises an air inlet unit, a crystallizer unit, a temperature control unit, a pressure control unit and an air outlet unit.

The air intake unit includes: vacuum pump 1, gas mixture bottle 2, buffer cylinder 3 and mass flow meter 4.

Vacuum pump 1 is connected with buffer bottle 3 through valve and pipeline for make whole hydrate gas separation device be vacuum state before the experiment, prevent the interference of residual gas to the experiment in the device.

The mixed gas cylinder 2 is connected with the buffer cylinder 3 through a pipeline and is used for filling mixed gas into the hydrate gas separation device to play a role of gas inlet.

Buffer bottle 3 is connected with first mass flow meter 4 through valve and pipeline for play the cushioning effect, prevent to give vent to anger too fast, the control of being convenient for.

The first mass flow meter 4 is connected to the crystallizer unit via valves and lines for direct measurement of the mass flow of the medium through the meter, via which the feed of feed gas is measured.

The crystallizer unit comprises: a piston 11, a stirrer 12 and a crystallizer tank 13.

The piston 11 is arranged at the mouth of the crystallizer tank 13 and is used for sealing the crystallizer tank 13.

An agitator 12 is provided inside the crystallizer tank 13 for operating at a set speed to agitate the gas and liquid inside the reactor to bring them into more intimate contact to increase the driving force for hydrate formation while avoiding freezing.

The crystallizer tank 13 is a reactor of the hydrate gas separation device, and a preferable but non-limiting embodiment is that stainless steel is used as the material. The reactor is surrounded by a temperature controlled coolant circulation housing 9, through which the temperature controlled coolant circulation housing 9 is passed, a preferred but non-limiting embodiment being to use an aqueous glycol solution, i.e. to control the temperature required for the reaction by means of the temperature controlled coolant circulation housing 9.

Both the crystallizer tank 13 and the temperature control coolant circulation housing 9 have two viewing windows 10 through which the conditions inside the reactor can be observed.

The principle of separating the mixed gas by the hydrate method is that the gas molecules which enter the cage firstly, namely the gas molecules which are easy to generate the hydration reaction are gathered in the hydrate phase under the condition of low pressure by utilizing the difference of the temperature and the pressure of the hydrate formed by different gas molecules, and the gas molecules which do not form the hydrate phase temporarily are gathered in the gas phase and then are discharged, so that a plurality of gases can be separated.

The temperature control unit includes: a temperature control coolant circulation case 9 and a platinum wire resistance thermometer 17.

The temperature control coolant circulation housing 9 is provided with a coolant inside, and a crystallizer tank 13 is provided in the coolant.

A platinum wire resistance thermometer 17 is inserted into the crystallizer tank 13 through the body of the crystallizer tank 13 and the temperature control coolant circulation housing 9 to measure the temperature of the interior of the crystallizer tank 13 during reaction.

The pressure control unit includes: a pressure gauge 14 and a manual pressure gauge 15.

The pressure gauge is connected to a manual pressure gauge 15, and the manual pressure gauge 15 is connected to the crystallizer tank 13 through a piston 11. The manual pressure gauge 15 is used for supplying an experimental operator to control the pressure inside the crystallizer tank 13, and the experimental operator can adjust the pressure through the reading of the pressure gauge 14, so that the pressure during the reaction can reach the requirement.

The air outlet unit comprises: a gas outlet module and a hydrate outlet module. Wherein the gas outlet module comprises: a third flow meter 16 and an unvented gas tank 18. The third flow meter 16 is connected to the crystallizer unit 16 via valves and lines, and the non-liquefied gas tank 18 is connected to the third flow meter 16 via lines. The gas in the crystallizer unit that does not form hydrates enters the non-liquefied gas tank 18 through the third flow meter 16, and the third flow meter 16 obtains the flow rate of the gas that does not form hydrates.

The hydrate outlet module comprises: a liquefied gas tank 5, a second flowmeter 6, a decomposer 7 and a liquid outlet/inlet valve 8 which are connected in sequence through pipelines. Hydrate liquid formed by gas and liquid in the crystallizer unit enters the decomposer 7 through the liquid outlet/inlet valve 8, SF6 hydrate is decomposed by changing the temperature and pressure of the decomposer 7, the decomposed SF6 gas enters the liquefied gas tank 5 through the second flow meter 6, and the second flow meter 6 obtains the flow rate of the gas forming the hydrate.

As shown in fig. 2, the present invention provides a hydrate gas separation method of SF6 mixed gas using the gas separation apparatus, comprising the steps of:

step 1, setting various experimental conditions, including: vacuumizing the hydrate gas separation device and setting a set reaction temperature; the method specifically comprises the following steps:

step 1.1, adding a proper surfactant into a crystallizing tank, wherein the surfactant is a dynamic promoter for hydrate formation and is used for overcoming the problem of low forming speed of SF6 hydrate. It will be appreciated that the skilled person can arbitrarily select a surfactant suitable for the experiment, and a preferred but non-limiting embodiment is to use SDS (sodium dodecyl sulfate) as the surfactant.

Step 1.2, the temperature control unit is turned on to maintain the coolant liquid at a constant experimental temperature for further ensuring the temperature of the reaction vessel, i.e. the crystallizer tank 13. It is understood that the experimental temperature can be arbitrarily set by those skilled in the art for the purpose of experiment, and a preferred but non-limiting embodiment is to set the experimental temperature at 6 ℃ to 7 ℃.

And step 1.3, opening the vacuum pump 1, and performing a vacuum-pumping experiment on the experimental device to prevent residual gas in the device from interfering with the experiment.

Step 1.4, the agitator 12 is turned on and operated at a set speed to increase the driving force for hydrate formation while avoiding freezing. It will be appreciated that the speed of rotation of the stirrer 12 may be set arbitrarily by the person skilled in the art for experimental purposes, a preferred but non-limiting embodiment being between 3 and 6 m/s.

And 2, introducing a raw material gas, namely SF6 mixed gas into the hydrate gas separation device, and continuously supplying the raw material gas to the crystallizer tank 13 through the first mass flow meter 4.

And 3, adjusting the manual pressure intensity device 15, and observing the reading of the pressure intensity meter to enable the pressure intensity of the gas in the reactor to reach an experimental value. It will be understood that the pressure of the gas in the reactor can be set arbitrarily by the person skilled in the art for experimental purposes, a preferred but non-limiting embodiment being 1 MPa.

And 4, when the gas pressure reaches an experimental value, opening a gas release valve above the crystallizer tank 13, releasing unreacted gas after hydration, and recording the reaction time. The total volume of unreacted gas was measured with the third flow meter 16.

And 5, keeping the temperature and the gas pressure in the crystallizer tank 13 constant in the whole reaction process. The liquid outlet release valve 8 is opened and the hydrate formed in the crystallizer is brought by the liquid into the decomposer 7, SF6 hydrate is decomposed by controlling the pressure and temperature of the decomposer 7, and the volume of the cracked gas is measured by the second flow meter 6. In the continuous separation process, the unreacted gas and the dissociated gas samples are synchronously collected.

Compared with the prior art, the hydrate gas separation device for SF6 mixed gas has the advantages that the hydrate gas separation technology is convenient to control, the pressure intensity does not need to be too high, the problem of recycling of the adsorbent does not need to be considered, the economic cost is not high, and the development potential is very high.

The present applicant has described and illustrated embodiments of the present invention in detail with reference to the accompanying drawings, but it should be understood by those skilled in the art that the above embodiments are merely preferred embodiments of the present invention, and the detailed description is only for the purpose of helping the reader to better understand the spirit of the present invention, and not for limiting the scope of the present invention, and on the contrary, any improvement or modification made based on the spirit of the present invention should fall within the scope of the present invention.