CN114604828A - Hydrogen concentration device and process by hydrate method - Google Patents

Abstract

The invention provides a hydrate method hydrogen concentration device and a process, the device comprises a hydrate generation part consisting of a hydrogen heat exchanger, a venturi jet mixer, a delay reactor, a hydrate separator and a low temperature circulating pump , and a hydrate decomposition part consisting of a desorption heat exchanger, a desorption heater, and a high-pressure circulating pump; the outlet at the top of the hydrate separator is connected to the shell side inlet of the hydrogen heat exchanger, and the shell side outlet of the hydrogen heat exchanger is used for The purified hydrogen is discharged; the hydrate separator is provided with a hydrate collection device for collecting hydrate, the hydrate collection device is connected to the desorption heat exchanger, and the desorption heat exchanger is connected to the desorption heater, and the shell side of the desorption heater The top outlet is used to discharge desorbed light hydrocarbon gases. The process includes four steps of working fluid preparation, refrigeration system operation, hydrate generation, and hydrate decomposition. The technical solution provided by the invention reduces the hydrogen pressure, and has better technical and economic indicators for the concentration of low-concentration hydrogen.

Description

A kind of hydrate method hydrogen concentration device and process

technical field

The invention relates to the technical field of energy and chemical industry, in particular, to a hydrate method hydrogen concentration device and a process.

Background technique

As an important chemical raw material and energy, hydrogen is widely used in various fields such as chemical industry, synthetic ammonia, and new energy. At the same time, hydrogen is considered to be an ideal clean, high-energy fuel. As a high-energy fuel, liquid hydrogen has been used in aerospace and other fields; as a chemical power source, hydrogen-oxygen fuel cells have been used, such as driving energy for automobiles.

The technologies for the separation of hydrogen-containing gases mainly include PSA pressure swing adsorption, membrane separation, etc. The purification of hydrogen by the hydrate method is an emerging technology. The comparison of various technologies is as follows.

The pressure swing adsorption process (PSA) is widely used in various gas separation occasions. The technology is based on the adsorption of impurity gases under high pressure conditions. Desorption regeneration. Because hydrogen is not easily adsorbed and can pass through directly, and impurity gas molecules such as alkanes are easily adsorbed, thereby improving the purity of hydrogen, the petroleum refining, fertilizer and other industries mainly use pressure swing adsorption technology to purify hydrogen.

The advantage of the pressure swing adsorption process is that its separation effect and concentration effect are excellent. Generally, the purity of hydrogen after PSA separation can reach 99% to 99.99%. Secondly, the process system is mature, the adsorbent can be recycled, and it has good adaptability to the gas to be separated with different impurity contents. Unless the impurity gas content that affects the adsorption process is particularly high, pretreatment is not required. When the hydrogen content is lower, the adsorption separation effect of PSA is more obvious. At the same time, the operating cost of the PSA process is much lower than other hydrogen separation and concentration methods, and is suitable for large and medium-sized petrochemical enterprises.

The disadvantages of pressure swing adsorption are in the following aspects: the one-time investment cost of the first point equipment is too high, the pressure swing adsorption process requires multiple towers to jointly complete the separation process, and the economy is low when the processing scale of the raw gas is small; The total recovery rate of hydrogen at the second point is low, generally only 60% to 80%. The third point is that the pressure swing adsorption adsorbent is easily deactivated, and the raw gas needs to be pretreated to remove the harmful components of the adsorbent. Once the adsorbent is deactivated, it is very time-consuming to replace. The fourth point is that the valve group is frequently opened and closed during the pressure swing adsorption process, and the valve failure rate is high, which affects product quality and production safety.

The membrane separation method uses a selective semi-permeable membrane to have the characteristics of selective permeation and diffusion of specific gas components. The driving force of the separation in this method is the pressure difference existing on both sides of the membrane, and the components on the raw material side selectively permeate the semi-permeable membrane to achieve the purpose of separating and purifying a certain key component. Due to the particularity of the semi-permeable membrane membrane structure, the transfer rates of different components are different. The gas components with fast transfer rate pass through the separation membrane, while the gas components with slower speed can only be retained on the other side of the separation membrane. Among them, hydrogen gas preferentially passes through the semipermeable membrane due to its small molecule and has a faster transmission rate, thereby being separated from the mixed gas.

The advantages of membrane separation technology are that the process is simple and feasible, the process complexity is low, and the equipment investment and energy costs are easy to control, so it has become a hot spot in research fields and applications. However, the membrane separation method itself also has inevitable shortcomings:

(1) The separation membrane has higher requirements on the raw material gas, and is easily destroyed and deactivated by impurity gas. Therefore, before membrane separation, it is necessary to pretreat the feed gas to remove impurity gases that damage the membrane, and to regularly clean, inspect and replace the separation membrane, resulting in higher operating costs in the later stage.

(2) The processing capacity of the separation membrane is low, and the separation membrane itself is contradictory in terms of permeation flux and permeation selectivity, which directly leads to the contradiction between the hydrogen yield and concentration, that is, the increase of the permeation flux of the porous membrane and the permeation selectivity The property will inevitably decrease, resulting in a decrease in H2 concentration after separation. Under the premise of not reducing the concentration of H2 recovery, only by increasing the area of the separation membrane and additional investment, the gas processing capacity can be increased.

In the hydrate method, small gas molecules and water form a cage-like hydrated lattice under certain pressure and temperature conditions, and the small gas molecules are adsorbed into the cage-like hydrated lattice as guest molecules. When the guest gas small molecules fill the lattice, they tend to be stable. Different gas molecules will form cage-like lattices with different structures due to their different structures and sizes, so different gases have different degrees of difficulty in forming hydrates. The gas that is easy to generate hydrate will be preferentially generated into the hydrate phase, so as to realize the separation of the gas mixture. Because the H molecule is too small, it is difficult to form stable hydrates under normal conditions, while gas molecules such as alkanes and alkenes and impurity gases such as _hydrogen sulfide can be enveloped by cage structures to form stable hydrates, so the hydrate separation method is particularly It is suitable for the separation of hydrogen and other impurity gases.

Compared with traditional mixed gas separation methods, hydrate separation gas has many advantages, such as low process complexity, relatively mild operating conditions and wide application range. The hydrate separation technology does not require pretreatment of raw materials, and the heavy components in the tail gas can promote the formation of hydrates. In particular the hydrogen sulfide component is an excellent thermodynamic accelerator for hydrates. In addition, the working fluid in the separation process is mainly water, and general substances do not have toxic effects on water, so the working fluid does not have the problem of failure. Finally, since the hydration reaction is concentrated under high pressure, the pressure drop of hydrogen after concentration is small and can be ignored.

Hydrogen plays an increasingly important role in the future new energy structure, and the hydrate method, as an emerging hydrogen purification technology, is bound to be more and more applied.

SUMMARY OF THE INVENTION

According to the above-mentioned problems such as high investment, large area and complicated process flow of the hydrogen concentration device, a hydrate method hydrogen concentration device and process are provided.

The technical means adopted in the present invention are as follows:

A hydrate method hydrogen concentration device, comprising a hydrate generation part consisting of a hydrogen heat exchanger, a venturi jet mixer, a time delay reactor, a hydrate separator, a low temperature circulating pump, and a desorption heat exchanger, Hydrate decomposition part composed of desorption heater and high pressure circulating pump;

The delay reactor is a multi-tube heat exchanger, the tube side of the delay reactor is used for circulating the hydrogen-water mixture, and the shell side of the delay reactor is used for circulating the refrigerant; the hydrate separation A synergistic nozzle is arranged in the device; the tube side of the hydrogen heat exchanger is communicated with the bypass inlet of the venturi jet mixer, and the straight inlet of the venturi jet mixer is communicated with the low temperature circulating pump. outlet, the straight outlet of the venturi jet mixer is connected to the tube side inlet of the time delay reactor, and the tube side outlet of the time delay reactor is connected to the synergistic nozzle; the top of the hydrate separator The outlet of the hydrogen heat exchanger is connected to the shell side inlet of the hydrogen heat exchanger, and the shell side outlet of the hydrogen heat exchanger is used to discharge the purified hydrogen; the outlet at the bottom of the hydrate separator is connected to the low temperature circulating pump. Entrance;

The hydrate separator is provided with a hydrate collection device for collecting hydrate, the hydrate collection device is connected to the bottom inlet of the shell side of the desorption heat exchanger, and the top two of the shell side of the desorption heat exchanger are two. Each outlet is connected to the shell side of the desorption heater, the shell side top outlet of the desorption heater is used to discharge desorbed light hydrocarbon gas, and the shell side bottom outlet of the desorption heater is connected to the desorption heat exchanger. The tube side inlet, the tube side outlet of the desorption heat exchanger is connected to the inlet of the high-pressure circulating pump through a filter, and the outlet of the high-pressure circulating pump is connected to the straight-through inlet of the venturi jet mixer.

Further, the Venturi jet mixer is a liquid-band-gas mixer; the delay reactor is a U-tube heat exchanger with 4-6 tube passes.

Further, the hydrate collection device includes a tooth weir structure.

Further, the desorption heat exchanger is a U-shaped tube heat exchanger with a liquid bag; the desorption heater is a kettle-type U-shaped tube heat exchanger with a baffle plate, and the top of the desorption heater is provided with an air bag , and a de-foaming net is arranged in the air bag.

The present invention also provides a hydrate method hydrogen concentration process, which adopts the above-mentioned hydrate method hydrogen concentration device, and specifically includes the following steps:

Step 1): working solution preparation: add solvent T and active agent S to the factory softened water, the concentration of solvent T is 20-30%wt, the concentration of active agent S is 100-1000mg/L, and the prepared working solution is passed into the venturi jet mixer;

Step 2): refrigerating system operation: start the refrigerating unit to freeze and cool down the shell side of the delay reactor, for removing the heat of reaction when the hydration reaction occurs in the delay reactor, and the freezing liquid is ammonia cold or frozen brine;

Step 3): Hydrate generation: Hydrogen containing impurities such as light hydrocarbons passes through the tube side of the hydrogen heat exchanger through the Venturi jet mixer, and after mixing with the working liquid, it is passed into the tube side of the delay reactor for hydration reaction, and then The hydrate separator is passed through the synergistic nozzle. In the hydrate separator, the light hydrocarbons are combined with the working fluid to form hydrate. The hydrate is slightly lighter than the working fluid. The hydrate floating on the water surface is collected by the hydrate collector, and then Entering the shell side of the desorption heat exchanger in the hydrate decomposition section, the working fluid is passed through the outlet at the bottom of the hydrate separator into the low temperature circulating pump and returned to the venturi jet mixer for the next cycle, and the hydrogen passes through the outlet at the top of the hydrate separator. Entering the hydrogen heat exchanger, it is discharged from the shell side outlet of the hydrogen heat exchanger;

Step 4): Hydrate Decomposition: Hydrate enters the shell side of the desorption heater through the shell side of the desorption heat exchanger, and is heated and decomposed under low pressure conditions to release light hydrocarbon gas, and the light hydrocarbon is discharged from the top outlet of the shell side of the desorption heater. , the working fluid returns to the tube side of the desorption heat exchanger through the bottom outlet of the shell side of the desorption heater, flows out from the tube side outlet of the desorption heat exchanger, and then returns to the Venturi jet mixer through the filter and the high-pressure circulating pump in turn to enter the next round cycle.

Further, in step 1), the temperature of the working solution is maintained at 40°C to 60°C, and the suspended matter is less than 20 mg/L.

Further, the venturi jet mixer pressurizes the hydrogen by 0.5kPa-5kPa, so that the hydrogen pressure reaches 2.0MPaG-20.0MPaG.

Further, the reaction time of the delay reactor is 20s～300s, the reaction temperature is 3-10℃, and the temperature of the freezing liquid is 0～5℃; the head of the low temperature circulating pump is 15m～50m, and the circulating liquid-gas ratio is 1:50～200; the tube side of the desorption heater is heated by circulating hot water at 35～40℃; the shell side pressure of the desorption heater is controlled at 0.3MPag～2.2MPag, and the temperature is controlled at 15-22℃; The lift of the high-pressure circulating pump is 150m-2000m, and the circulating liquid-gas ratio is 1:50-200.

Compared with the prior art, the present invention has the following advantages:

The hydrogen concentration device and process provided by the present invention adopt the low temperature and high pressure conditions, light hydrocarbons and water to form hydrates, and the hydrates are decomposed under high temperature and low pressure conditions, and have the following beneficial effects:

(1) Low investment, small footprint, and reduced hydrogen pressure;

(2) It has the ability to remove various impurities such as light hydrocarbons and hydrogen sulfide;

(3) It is suitable for various raw materials and does not require raw material pretreatment.

Based on the above reasons, the present invention can be widely promoted in the field of energy and chemical industry.

Description of drawings

In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description These are some embodiments of the present invention, and for those of ordinary skill in the art, other drawings can also be obtained from these drawings without any creative effort.

Fig. 1 is the schematic diagram of the hydrogen concentration device of the hydrate method according to the present invention.

In the figure: 1. Hydrogen heat exchanger; 2. Venturi jet mixer; 3. Delay reactor; 4. Hydrate separator; 5. Efficiency nozzle; 6. Hydrate collection device; 7. Cryogenic circulating pump ; 8, desorption heat exchanger; 9, desorption heater; 11, shell side top outlet; 12, filter; 13, high pressure circulating pump.

Detailed ways

It should be noted that the embodiments of the present invention and the features of the embodiments may be combined with each other under the condition of no conflict. The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.

In order to make the purposes, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments It is only a part of the embodiments of the present invention, but not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

It should be noted that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly dictates otherwise, the singular is intended to include the plural as well, furthermore, it is to be understood that when the terms "comprising" and/or "including" are used in this specification, it indicates that There are features, steps, operations, devices, components and/or combinations thereof.

The relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the invention unless specifically stated otherwise. Meanwhile, it should be understood that, for convenience of description, the dimensions of various parts shown in the accompanying drawings are not drawn in an actual proportional relationship. Techniques, methods, and devices known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, such techniques, methods, and devices should be considered part of the authorized specification. In all examples shown and discussed herein, any specific values should be construed as illustrative only and not limiting. Accordingly, other examples of exemplary embodiments may have different values. It should be noted that like numerals and letters refer to like items in the following figures, so once an item is defined in one figure, it does not require further discussion in subsequent figures.

In the description of the present invention, it should be understood that the orientations indicated by orientation words such as "front, rear, top, bottom, left, right", "horizontal, vertical, vertical, horizontal" and "top, bottom" etc. Or the positional relationship is usually based on the orientation or positional relationship shown in the drawings, which is only for the convenience of describing the present invention and simplifying the description, and these orientation words do not indicate or imply the indicated device or element unless otherwise stated. It must have a specific orientation or be constructed and operated in a specific orientation, so it should not be construed as a limitation on the scope of protection of the present invention: the orientation words "inside and outside" refer to the inside and outside relative to the contour of each component itself.

For ease of description, spatially relative terms, such as "on", "over", "on the surface", "above", etc., may be used herein to describe what is shown in the figures. The spatial positional relationship of one device or feature shown to other devices or features. It should be understood that spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as "above" or "over" other devices or features would then be oriented "below" or "over" the other devices or features under its device or structure". Thus, the exemplary term "above" can encompass both an orientation of "above" and "below." The device may also be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptions used herein interpreted accordingly.

In addition, it should be noted that the use of words such as "first" and "second" to define components is only for the convenience of distinguishing corresponding components. Unless otherwise stated, the above words have no special meaning and therefore cannot be understood to limit the scope of protection of the present invention.

Example 1

As shown in Figure 1, the present invention provides a hydrate method hydrogen concentration device, including a hydrogen heat exchanger 1, a venturi jet mixer 2, a delay reactor 3, a hydrate separator 4, and a low temperature circulating pump The hydrate generation part composed of 7, and the hydrate decomposition part composed of a desorption heat exchanger 8, a desorption heater 9, and a high-pressure circulating pump 13;

The delay reactor 3 is a multi-tube heat exchanger, the tube side of the delay reactor 3 is used to circulate the hydrogen-water mixture, and the shell side of the delay reactor 3 is used to circulate the frozen liquid; the The hydrate separator 4 is provided with a booster nozzle 5; the tube side of the hydrogen heat exchanger 1 is communicated with the bypass inlet of the venturi jet mixer 2, and the straight inlet of the venturi jet mixer 2 Be connected to the outlet of the low temperature circulating pump 7, the straight outlet of the venturi jet mixer 2 is connected to the tube side inlet of the time delay reactor 3, and the tube side outlet of the time delay reactor 3 is connected to the the booster nozzle 5; the outlet at the top of the hydrate separator 4 is connected to the shell side inlet of the hydrogen heat exchanger 1, and the shell side outlet of the hydrogen heat exchanger 1 is used to discharge purified hydrogen; The outlet at the bottom of the hydrate separator 4 is connected to the inlet of the low-temperature circulating pump 7;

The hydrate separator 4 is provided with a hydrate collection device 6 for collecting hydrate, and the hydrate collection device 6 is connected to the bottom inlet of the shell side of the desorption heat exchanger 8. The desorption heat exchanger 8 The top two outlets of the shell side are connected to the shell side of the desorption heater 9, the shell side top outlet of the desorption heater 9 is used to discharge the desorption light hydrocarbon gas, and the shell side bottom outlet of the desorption heater 9 is communicated To the tube side inlet of the desorption heat exchanger 8, the tube side outlet of the desorption heat exchanger 8 is connected to the inlet of the high pressure circulating pump 13 through the filter 12, and the outlet of the high pressure circulating pump 13 is connected to the Thru inlet for Venturi jet mixer 2.

Further, the venturi jet mixer 2 is a liquid-band gas mixer; the delay reactor 3 is a U-shaped tube heat exchanger with 4-6 tube passes.

Further, the hydrate collection device 6 includes a tooth weir structure.

Further, the desorption heat exchanger 8 is a U-shaped tube heat exchanger with a liquid bag; the desorption heater 9 is a U-shaped tube heat exchanger with a clapboard in a kettle type, and the top of the desorption heater 9 is An air bag is provided, and a defoaming net is arranged in the air bag.

The present invention also provides a hydrate concentration process for hydrogen concentration, which adopts the low temperature and high pressure conditions to form hydrates between light hydrocarbons and water, and the principle of hydrate decomposition under high temperature and low pressure conditions to realize the separation of light hydrocarbons and hydrogen. The hydrate method hydrogen concentration device specifically includes the following steps:

Step 1): working solution preparation: add solvent T and active agent S to the factory softened water, the concentration of solvent T is 20-30%wt, the concentration of active agent S is 100-1000mg/L, and the prepared working solution is passed into the venturi Jet mixer 2;

Step 2): refrigerating system operation: start the refrigerating unit to freeze and lower the temperature on the shell side of the delay reactor 3, for removing the reaction heat when the hydration reaction occurs in the delay reactor 3, the freezing liquid CWS is ammonia cold or frozen brine ;

Step 3): Hydrate generation: Hydrogen containing impurities such as light hydrocarbons passes through the tube side of the hydrogen heat exchanger 1 to the Venturi jet mixer 2, and after mixing with the working liquid, it is passed into the tube side of the delay reactor 3 for hydration After the reaction, it is passed to the hydrate separator 4 through the synergistic nozzle 5. In the hydrate separator 4, the light hydrocarbons combine with the working fluid to form hydrates. The hydrates are slightly lighter than the working fluids, and the hydrates floating on the water surface pass through The material is collected by the collector 6, and then enters the shell side of the desorption heat exchanger 8 in the hydrate decomposition section. The working fluid is passed through the outlet at the bottom of the hydrate separator into the low temperature circulating pump 7 and returned to the venturi jet mixer 2 to enter the next cycle. , the hydrogen enters the hydrogen heat exchanger 1 through the outlet at the top of the hydrate separator 4, and is discharged from the shell side outlet of the hydrogen heat exchanger 1;

Step 4): Hydrate Decomposition: Hydrate enters the shell side of the desorption heater 9 through the shell side of the desorption heat exchanger 8, and is heated and decomposed under low pressure conditions to release light hydrocarbon gas, and the light hydrocarbons are released from the top of the shell side of the desorption heater 9 The outlet discharge device, the working fluid returns to the tube side of the desorption heat exchanger 8 through the bottom outlet of the shell side of the desorption heater 9, flows out from the tube side outlet of the desorption heat exchanger 8, and then returns to the venturi through the filter 12 and the high-pressure circulating pump 13 in turn Jet mixer 2 enters the next cycle.

Further, in step 1), the temperature of the working solution is maintained at 40°C to 60°C, and the suspended matter is less than 20 mg/L.

Further, the Venturi jet mixer 2 is used to realize uniform mixing of hydrogen and working fluid, and pressurize the hydrogen by 0.5 kPa to 5 kPa, so that the hydrogen pressure reaches 2.0 MPaG to 20.0 MPaG.

Further, the reaction time of the delay reactor 3 is 20s～300s, the reaction temperature is 3-10°C, and the temperature of the freezing liquid is 0～5°C; the head of the low temperature circulating pump 7 is 15m～50m, and the circulating liquid gas The ratio is 1:50～200; the tube side of the desorption heater 9 is heated by circulating hot water at 35～40℃; the shell side pressure of the desorption heater 9 is controlled at 0.3MPag～2.2MPag, and the temperature is controlled at 15- 22°C; the lift of the high-pressure circulating pump 13 is 150m-2000m, and the circulating liquid-gas ratio is 1:50-200.

Taking the 5000Nm ³ /h hydrogen concentration device as an example, the device and process of the present invention and the PSA technology are used for hydrogen purification respectively. The technical and economic indicators of the two processes are compared in Table 1.

Table 1 The present invention is compared with PSA technical and economic indicators

It can be seen from Table 1 that the device and process provided by the present invention have the advantages of low investment, small footprint, reduced hydrogen pressure, and good technical and economic indicators for the concentration of low-concentration hydrogen.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that it can still be Modifications are made to the technical solutions described in the foregoing embodiments, or some or all of the technical features thereof are equivalently replaced; these modifications or replacements do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (8)

1. a hydrate method hydrogen concentration device, is characterized in that, comprises the hydrate generation part that is made up of hydrogen heat exchanger, venturi jet mixer, time delay reactor, hydrate separator, cryogenic circulation pump, and Hydrate decomposition part consisting of desorption heat exchanger, desorption heater and high pressure circulating pump; The delay reactor is a multi-tube heat exchanger, the tube side of the delay reactor is used for circulating the hydrogen-water mixture, and the shell side of the delay reactor is used for circulating the refrigerant; the hydrate separation A synergistic nozzle is arranged in the device; the tube side of the hydrogen heat exchanger is communicated with the bypass inlet of the venturi jet mixer, and the straight inlet of the venturi jet mixer is communicated with the low temperature circulating pump. outlet, the straight outlet of the venturi jet mixer is connected to the tube side inlet of the time delay reactor, and the tube side outlet of the time delay reactor is connected to the synergistic nozzle; the top of the hydrate separator The outlet of the hydrogen heat exchanger is connected to the shell side inlet of the hydrogen heat exchanger, and the shell side outlet of the hydrogen heat exchanger is used to discharge the purified hydrogen; the outlet at the bottom of the hydrate separator is connected to the low temperature circulating pump. Entrance; The hydrate separator is provided with a hydrate collection device for collecting hydrate, the hydrate collection device is connected to the bottom inlet of the shell side of the desorption heat exchanger, and the top two of the shell side of the desorption heat exchanger are two. Each outlet is connected to the shell side of the desorption heater, the shell side top outlet of the desorption heater is used to discharge desorbed light hydrocarbon gas, and the shell side bottom outlet of the desorption heater is connected to the desorption heat exchanger. The tube side inlet, the tube side outlet of the desorption heat exchanger is connected to the inlet of the high-pressure circulating pump through a filter, and the outlet of the high-pressure circulating pump is connected to the straight-through inlet of the venturi jet mixer. 2. The hydrate method hydrogen concentration device according to claim 1, wherein the venturi jet mixer is a liquid-band gas type mixer; the time delay reactor is a U of 4 to 6 tubes Type tube heat exchanger. 3 . The hydrogen concentration device for a hydrate method according to claim 1 , wherein the hydrate collection device comprises a tooth weir structure. 4 . 4. The hydrate method hydrogen concentration device according to claim 1, wherein the desorption heat exchanger is a U-shaped tube heat exchanger with a liquid bag; the desorption heater is a kettle-type inner spacer A U-shaped tube heat exchanger with a plate, an air bag is arranged on the top of the desorption heater, and a de-foaming net is arranged in the air bag. 5. a hydrate method hydrogen concentration process, is characterized in that, adopts the hydrate method hydrogen concentration device of claim 1, specifically comprises the following steps: Step 1): working solution preparation: add solvent T and active agent S to the factory softened water, the concentration of solvent T is 20-30%wt, the concentration of active agent S is 100-1000mg/L, and the prepared working solution is passed into the venturi jet mixer; Step 2): refrigerating system operation: start the refrigerating unit to freeze and cool down the shell side of the delay reactor, for removing the heat of reaction when the hydration reaction occurs in the delay reactor, and the freezing liquid is ammonia cold or frozen brine; Step 3): Hydrate generation: Hydrogen containing impurities such as light hydrocarbons passes through the tube side of the hydrogen heat exchanger through the Venturi jet mixer, and after mixing with the working liquid, it is passed into the tube side of the delay reactor for hydration reaction, and then The hydrate separator is passed through the synergistic nozzle. In the hydrate separator, the light hydrocarbons are combined with the working fluid to form hydrate. The hydrate is slightly lighter than the working fluid. The hydrate floating on the water surface is collected by the hydrate collector, and then Entering the shell side of the desorption heat exchanger in the hydrate decomposition section, the working fluid is passed through the outlet at the bottom of the hydrate separator into the low temperature circulating pump and returned to the venturi jet mixer for the next cycle, and the hydrogen passes through the outlet at the top of the hydrate separator. Entering the hydrogen heat exchanger, it is discharged from the shell side outlet of the hydrogen heat exchanger; Step 4): Hydrate Decomposition: Hydrate enters the shell side of the desorption heater through the shell side of the desorption heat exchanger, and is heated and decomposed under low pressure conditions to release light hydrocarbon gas, and the light hydrocarbon is discharged from the top outlet of the shell side of the desorption heater. , the working fluid returns to the tube side of the desorption heat exchanger through the bottom outlet of the shell side of the desorption heater, flows out from the tube side outlet of the desorption heat exchanger, and then returns to the Venturi jet mixer through the filter and the high-pressure circulating pump in turn to enter the next round cycle. 6 . The hydrate method hydrogen concentration process according to claim 5 , wherein, in step 1), the temperature of the working solution is maintained at 40° C. to 60° C., and the suspended matter is less than 20 mg/L. 7 . 7 . The hydrogen enrichment process of the hydrate method according to claim 5 , wherein the Venturi jet mixer pressurizes the hydrogen by 0.5 kPa to 5 kPa, so that the hydrogen pressure reaches 2.0 MPaG to 20.0 MPaG. 8 . 8 . The hydrate method hydrogen concentration process according to claim 5 , wherein the reaction time of the delay reactor is 20s～300s, the reaction temperature is 3-10°C, and the temperature of the freezing liquid is 0～5 . ℃; the head of the low temperature circulating pump is 15m～50m, and the ratio of circulating liquid to gas is 1:50～200; the tube side of the desorption heater is heated by circulating hot water at 35～40°C; the shell side of the desorption heater The pressure is controlled at 0.3MPag-2.2MPag, and the temperature is controlled at 15-22°C; the lift of the high-pressure circulating pump is 150m-2000m, and the circulating liquid-gas ratio is 1:50-200.

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