Hydrate accelerant, application thereof and gas storage and transportation method

Abstract

The invention relates to the technical field of gas storage and transportation, and discloses a hydrate accelerant, application of the hydrate accelerant and a gas storage and transportation method. The growth promoter is selected from one or more than two of thiobetaine, sodium thiosalicylate, thionicotinamide, thioformamide and thioproline. According to the hydrate accelerant provided by the invention, through the synergistic effect of the growth accelerant and the thermodynamic accelerant, the gas storage capacity of the hydrate in an adsorption-hydration coupling method is effectively improved. According to the gas storage and transportation method provided by the invention, an adsorption method and a hydrate method are innovatively combined for gas storage, firstly, an adsorption material is pretreated suitable for a hydrate coupling method, and then the pretreated adsorption material is coupled with an aqueous solution containing a hydrate accelerant; therefore, the gas storage efficiency and the gas storage capacity of the adsorption material are effectively improved. Through verification, the method can increase the gas storage capacity of the adsorption material by more than one time.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of gas storage and transportation, in particular to a hydrate promoter, application thereof and a gas storage and transportation method. BACKGROUND

[0002] The oilfield associated gas reserves are relatively rich in China, and the oilfield associated gas is mainly composed of small molecules of light hydrocarbons such as methane, ethane and propane. Since it does not reach the economic utilization scale, most of it is directly burned or discharged, which not only causes resource waste, but also pollutes the environment. At present, there is no significant and effective recovery and utilization process for oilfield associated gas at home and abroad. The associated gas is seriously lost in the process of oil and gas production and gathering, and the utilization capacity is relatively weak, which is a great waste. The recovery and utilization of small molecules of light hydrocarbons is an important form to promote clean and efficient use of energy, and efficient and safe recovery technology research is urgently needed.

[0003] In the current traditional light hydrocarbon recovery method, the energy consumption of CNG and LNG is high, and the risk is high; the maturity of adsorption method is high, but it is difficult to store small molecules of light hydrocarbons such as C1-C3. Based on the formation characteristics and physicochemical properties of gas hydrate, hydrate method for storing and transporting natural gas technology, hydrate method for separating technology, hydrate method for cold storage technology and hydrate method for seawater desalination technology are developed. However, due to the slow formation rate of pure gas hydrate and small gas storage capacity, it is not conducive to large-scale industrial application, so the generation of hydrate is the key to solving this problem. However, the current hydrate promoter has limited ability to improve the gas storage capacity of hydrate, which still has the disadvantages of small gas storage capacity of hydrate. Therefore, how to provide a hydrate promoter to improve the gas storage capacity of hydrate is a problem to be solved in the field. SUMMARY

[0004] The purpose of the present application is to overcome the problem of small gas storage capacity of hydrate promoter in the prior art, and to provide a hydrate promoter, application thereof and a gas storage and transportation method.

[0005] In order to achieve the above purpose, the present application provides a hydrate promoter, which contains a thermodynamic promoter and a growth promoter.

[0006] Preferably, the growth promoter is selected from one or more than two of thio betaine, sodium thiosalicylate, thionicotinamide, thioformamide and thio proline.

[0007] Preferably, the thermodynamic promoter is selected from one or more than two of tetrahydrofuran, tetrabutylammonium bromide, cyclopentane and dioxolane.

[0008] Preferably, the mass ratio of the thermodynamic promoter to the growth promoter is 1:0.01-1.1.

[0009] The second aspect of the present application provides an application of the hydrate promoter as described above in the hydrate method for storing and transporting gas.

[0010] The third aspect of the present application provides a method for storing and transporting gas, which comprises:

[0011] (1) pretreating the adsorbent material with an aqueous solution of alkyl sodium sulfate salt;

[0012] (2) coupling the pretreated adsorbent material with an aqueous solution containing a hydrate promoter to obtain a solid-liquid reactant;

[0013] (3) contacting the gas with the solid-liquid reactant;

[0014] wherein the hydrate promoter contains a thermodynamic promoter and a growth promoter;

[0015] The growth promoter is selected from one or more than two of betaine, sodium thiosalicylate, thionicotinamide, thioformamide and thio-proline.

[0016] Preferably, the thermodynamic promoter is selected from one or more than two of tetrahydrofuran, tetrabutylammonium bromide, cyclopentane and dioxolane;

[0017] Preferably, in the hydrate promoter, the mass ratio of the thermodynamic promoter to the growth promoter is 1:0.01-1.1.

[0018] Preferably, in step (1), the alkyl sodium sulfate salt is selected from one or more than two of decyl sodium sulfate, undecyl sodium sulfate, dodecyl sodium sulfate and tridecyl sodium sulfate.

[0019] Preferably, in step (1), the concentration of the aqueous solution of alkyl sodium sulfate salt is 0.01-1.1 mol / L.

[0020] Preferably, in step (1), the adsorbent material is activated carbon and / or metal-organic framework material.

[0021] Preferably, in step (1), the mass ratio of the adsorbent material to the aqueous solution of alkyl sodium sulfate salt is 1:6-15.

[0022] Preferably, in step (1), the pretreatment process comprises:

[0023] immersing the adsorbent material in the aqueous solution of alkyl sodium sulfate salt, and then drying.

[0024] Preferably, the immersion conditions include a time of 20-40 h and a temperature of 30-40℃.

[0025] Preferably, the drying condition comprises: time of 200-500 min, temperature of 100-140℃.

[0026] Preferably, in step (2), the water-soluble hydrate promoter is added in an amount of 0.05-3wt% in the water-soluble hydrate promoter solution.

[0027] Preferably, in step (2), the mass ratio of the pretreated adsorption material to the water-soluble hydrate promoter solution is 1:0.5-1.5.

[0028] Preferably, step (2) specifically comprises: ultrasonic immersion of the pretreated adsorption material in the water-soluble hydrate promoter solution.

[0029] Preferably, the ultrasonic immersion condition comprises: time of 100-200 min, temperature of 20-40℃, and power of 15-25 kHz.

[0030] Preferably, in step (3), the gas is selected from one or more than two of methane, ethane and propane.

[0031] The hydrate promoter provided by the present application effectively improves the gas storage capacity of hydrate in the adsorption-hydrate coupling method through the synergistic effect of growth promoter and thermodynamic promoter.

[0032] The gas storage and transportation method provided by the present application innovatively combines the adsorption method and the hydrate method to store gas (i.e. the adsorption-hydrate coupling method), first pretreats the adsorption material suitable for the hydrate coupling method, and then couples the pretreated adsorption material with the water-soluble hydrate promoter solution, thereby effectively improving the gas storage efficiency and capacity of the adsorption material. It has been verified that this method can improve the gas storage capacity of the adsorption material by more than one time. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 is a schematic diagram of the performance evaluation device used in the examples and comparative examples of the present application.

[0034] REFERENCE NUMERALS

[0035] 1-gas cylinder; 2-temperature sensor; 3-top valve; 4-pressure sensor; 5-air bath; 6-sapphire reaction kettle; 7-data acquisition system; 8-temperature sensor. DETAILED DESCRIPTION

[0036] The specific embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0037] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0038] The present invention provides a hydrate promoter, which contains a thermodynamic promoter and a growth promoter; wherein the growth promoter is selected from one or more of sulfobetaine, sodium thiosalicylate, thionicotinamide, thioformamide and thioproline.

[0039] The present invention adds a growth promoter on the basis of a thermodynamic promoter, and the two act synergistically to effectively increase the gas storage capacity of hydrates.

[0040] The present invention does not limit the specific selection of the thermodynamic promoter, which can be any conventional thermodynamic promoter in the art. In a specific embodiment, the thermodynamic promoter is selected from one or more of tetrahydrofuran, tetrabutylammonium bromide, cyclopentane, and dioxolane.

[0041] The present invention does not specifically limit the dosage relationship between the thermodynamic promoter and the growth promoter, and can be designed according to the actual application scenario. In a preferred embodiment, the mass ratio of the thermodynamic promoter to the growth promoter is 1:0.01 to 1.1, preferably 1:0.01 to 1. Under the above ratio, the gas storage capacity of the hydrate is higher. Specifically, the mass ratio of the thermodynamic promoter to the growth promoter can be 1:0.01, 1:0.05, 1:0.08, 1:0.1, 1:0.25, 1:0.4, 1:0.5, 1:0.6, 1:0.7 or 1:1,

[0042] The present invention also provides a use of the above-mentioned hydrate promoter in gas storage and transportation by the hydrate method.

[0043] In a specific embodiment, the gas is a light hydrocarbon gas, such as one or more of methane, ethane, and propane. Due to the high gas storage efficiency and capacity of the hydrate promoter, it is particularly effective in recycling light hydrocarbon molecules.

[0044] Among the current traditional light hydrocarbon recovery methods, CNG and LNG have high energy consumption and high risk; the adsorption method and hydrate method have the advantages of mild storage conditions and low gas source requirements, but the former is more difficult to store light hydrocarbon small molecules such as C1-C3, and the latter still has shortcomings in gas storage rate and gas storage capacity.

[0045] In view of this, the present application provides a gas storage and transportation method, aiming to solve the problem of difficult storage and transportation of light hydrocarbon small molecules in oil and gas field non-pipeline gas. In the present application, the gas storage and transportation method comprises:

[0046] (1) The adsorbent material is pretreated with an aqueous solution of alkyl sodium sulfate salt;

[0047] (2) The pretreated adsorbent material is coupled with an aqueous solution containing a hydrate promoter to obtain a solid-liquid reactant;

[0048] (3) The gas is contacted with the solid-liquid reactant;

[0049] Wherein, the hydrate promoter contains a thermodynamic promoter and a growth promoter;

[0050] The growth promoter is selected from one or more than two of betaine, sodium thiosalicylate, thionicotinamide, thioformamide and thio proline.

[0051] The gas storage and transportation method provided by the present application innovatively couples the traditional adsorption method with the hydrate method, improves the gas storage capacity and efficiency of the two methods, and provides a new idea for the recycling of light hydrocarbon small molecules. The method overcomes the shortcomings of short service life of adsorbent material, small adsorption capacity, slow rate of hydrate method, etc. The light hydrocarbon gas is adsorbed by the adsorbent material, and the hydrate is formed in the pore of the adsorbent material, so as to realize the effective recycling of light hydrocarbon small molecules in oilfield associated gas.

[0052] In the method of the present application, the adsorbent material is first pretreated for hydrate coupling, then the hydrate promoter is added to the water for hydrate generation, and then the treated adsorbent material is coupled with the aqueous solution by ultrasonic method, so as to effectively improve the gas storage efficiency and capacity of the adsorbent material. The method can improve the gas storage capacity of the adsorbent material by more than one time, and the main body of the solid-liquid reactant is solid, so the transportation and post-processing process is more convenient, which ensures the safe and efficient recycling of light hydrocarbon small molecules.

[0053] In step (1), the adsorbent material is pretreated with an aqueous solution of alkyl sodium sulfate salt, which makes the adsorbent material more suitable for adsorbing light hydrocarbon small molecules and easier to couple with the hydrate method. The preparation method of the aqueous solution of alkyl sodium sulfate salt comprises mixing alkyl sodium sulfate salt and water.

[0054] In a preferred embodiment, the alkyl sodium sulfate salt is selected from one or more than two of decyl sodium sulfate, undecyl sodium sulfate, dodecyl sodium sulfate and tridecyl sodium sulfate.

[0055] In a preferred embodiment, the concentration of the aqueous solution of alkyl sodium sulfate salt is 0.01-1.1 mol / L, more preferably 0.01-1 mol / L.

[0056] In the method of the present application, the adsorbent material in step (1) can be a conventional adsorbent material in the art. In a preferred embodiment, in step (1), the adsorbent material is activated carbon and / or metal organic framework (MOF).

[0057] In a specific embodiment, the pretreatment process comprises: immersing the adsorbent material in an aqueous solution of alkyl sodium sulfate salt, and then drying.

[0058] In a preferred embodiment, the mass ratio of the adsorbent material to the amount of the aqueous solution of alkyl sodium sulfate salt is 1:6-15.

[0059] In a preferred embodiment, the immersion temperature is 30-40°C.

[0060] The present application does not limit the specific time of the immersion, which can be designed according to the immersion temperature and the concentration of the aqueous solution of alkyl sodium sulfate salt. In a preferred embodiment, the immersion time is more than 20h, so that the immersion effect is good. In consideration of the immersion effect and time saving, more preferably, the immersion time is 20-40h.

[0061] In a preferred embodiment, the drying time is more than 200min, and the drying temperature is 100-140°C. More preferably, the drying time is 350-400min, so that the drying effect is good and time saving.

[0062] In a specific embodiment, the thermodynamic promoter is selected from one or more than two of tetrahydrofuran, tetrabutylammonium bromide, cyclopentane and dioxolane.

[0063] In a preferred embodiment, in the hydrate promoter, the mass ratio of the thermodynamic promoter to the growth promoter is 1:0.01-1.1, preferably 1:0.01-1. Under the above amount range, the gas storage capacity of the hydrate is higher. Specifically, the mass ratio of the thermodynamic promoter to the growth promoter can be 1:0.01, 1:0.05, 1:0.08, 1:0.1, 1:0.25, 1:0.4, 1:0.5, 1:0.6, 1:0.7 or 1:1.

[0064] In step (2) of the present application, the coupling of the pretreated adsorbent material with the aqueous solution containing the hydrate promoter. In a specific implementation, the coupling process adopts ultrasonic immersion method.

[0065] In a specific embodiment, step (2) specifically comprises: ultrasonic immersion of the pretreated adsorbent material with the aqueous solution containing the hydrate promoter.

[0066] In a preferred embodiment, the amount of hydrate promoter added in the aqueous solution of hydrate promoter is 0.05-3wt%.

[0067] In a preferred embodiment, the mass ratio of the pretreated adsorbent material to the aqueous solution of hydrate promoter is 1:0.5-1.5, so that the impregnation effect is better.

[0068] In a preferred embodiment, the ultrasonic impregnation time is more than 100min.

[0069] Further preferably, the ultrasonic impregnation conditions include: time of 100-200min, temperature of 20-40℃, and power of 15-25kHz.

[0070] In the method of the present application, the gas in step (3) is a light hydrocarbon small molecule gas.

[0071] Preferably, in step (3), the gas is selected from one or more than two of methane, ethane and propane.

[0072] In a specific embodiment, step (3) specifically includes: placing the solid-liquid reactant into a reaction kettle, vacuumizing the system and introducing the reaction gas for replacement for 3 times, adjusting the temperature in the air bath to the experimental temperature, waiting for the temperature in the reaction kettle to be stable for 60min, introducing the gas into the reaction kettle to the experimental pressure, and the reaction time is 120min. After the reaction in the reaction kettle is completed, the air bath temperature is adjusted to 25℃, so that the hydrate in the reaction kettle is completely decomposed.

[0073] Further, the experimental temperature is 0-10℃ (i.e. 273.15-283.15K), and the experimental pressure is 0-10MPa.

[0074] In the method of the present application, the adsorbent material treated with the aqueous solution of hydrate promoter can be reused.

[0075] The present application will be described in detail below by way of examples, but the scope of protection of the present application is not limited thereto.

[0076] In the following examples and comparative examples, experiments are carried out using a performance evaluation device as shown in Figure 1 The working volume of the device is 50cm3, the maximum working pressure is 15MPa, and the working temperature range is 183K-423K.

[0077] Referring to Figure 1 , the performance evaluation device includes: a gas cylinder 1, a first temperature sensor 2, a top valve 3, a pressure sensor 4, a high-low temperature experiment box 5, a sapphire reaction kettle 6, a data acquisition system 7 and a second temperature sensor 8.

[0078] The gas cylinder 1 is connected with the sapphire reaction kettle 6 through a pipeline, and is responsible for providing light hydrocarbon small molecule gases such as methane and ethane; the first temperature sensor 2 is connected with the top of the sapphire reaction kettle 6, and is used for monitoring the temperature in the kettle in real time; the pressure sensor 4 is connected with the top of the sapphire reaction kettle 6, and is used for monitoring the pressure in the kettle in real time; the top valve 3 is responsible for controlling the entry and discharge of the gas in the kettle; the sapphire reaction kettle 6 is a fully transparent sapphire reaction kettle, and is arranged in the high-low temperature experiment box 5; the second temperature sensor 8 is connected with the high-low temperature experiment box 5, and is used for monitoring the temperature in the high-low temperature experiment box 5; and the data acquisition system 7 is a computer data automatic acquisition system, and is used for recording the system temperature, pressure and reaction time.

[0079] The specific steps of the performance evaluation experiment by using the performance evaluation device are as follows:

[0080] (1) Wash the reaction kettle, add solid-liquid reactants, install the reaction kettle, vacuumize the system, and introduce experimental gas for replacement for 3 times;

[0081] (2) Set the system temperature to the experimental temperature, when the temperature in the reaction kettle reaches the preset value and is stable for 1 hour, introduce experimental gas to the experimental pressure, and the computer data automatic acquisition system records the change of the system temperature and pressure, and records the system pressure at the 30th minute and the 120th minute of the reaction.

[0082] (3) After 120 minutes, the system pressure is basically stable, the adsorption process and the hydrate generation process are completed, the experimental temperature is adjusted to 25 DEG C, and the hydrate is decomposed.

[0083] The gas storage capacity of the solid-liquid system is calculated as follows:

[0084] After the gas is introduced into the reaction kettle, the molar molecular weight of the gas phase in the kettle is obtained by the actual gas state equation:

[0085]

[0086] The molar molecular weight of the gas in the system at the end of the reaction stage is obtained by the actual gas state equation:

[0087]

[0088] In the formula, n0 and n e are the molar numbers of the gas phase molecules in the initial system and the system after the reaction is completed; P0 and P e are the pressures at the initial moment of the system and at the end of the generation stage, Pa; V g is the volume of the gas phase in the reaction kettle, m 3 ; Z0 and Z eThe gas compressibility coefficient of the system at the initial and end time of the hydrate formation stage is calculated by the Peng-Robinson equation; R is the gas constant, J / (mol*K); T is the set temperature of the experiment, K.

[0089] The gas consumption of the gas-phase molecules during the reaction process is:

[0090] Δn = n0 - n e

[0091] The gas storage capacity of the system is:

[0092]

[0093] wherein, m c is the mass of the adsorbent material.

[0094] Example 1

[0095] (1) A sodium decyl sulfate aqueous solution with a concentration of 0.02 mol / L is prepared; then 3 g of activated carbon is immersed in 20 g of the sodium decyl sulfate aqueous solution, the immersion time is 24 h, and the immersion temperature is 30°C; after the immersion is completed, the activated carbon is placed in a vacuum drying oven for drying, the drying time is 360 min, and the drying temperature is 120°C.

[0096] (2) Tetrahydrofuran and thio-proline are mixed according to a mass ratio of 1:0.2 to obtain a hydrate promoter; the hydrate promoter is mixed with water, wherein the addition amount of the hydrate promoter is 0.1 wt%, to obtain a water solution containing the hydrate promoter.

[0097] (3) 2 g of the water solution containing the hydrate promoter in step (2) is coupled with the pretreated activated carbon in step (1) by using an ultrasonic immersion method, the immersion temperature is 25°C, the immersion time is 120 min, and the power is 20 kHz, to obtain a solid-liquid reactant.

[0098] In this example, the performance evaluation device described above is used for performance evaluation, the solid-liquid reactant in step (3) is added into a reaction kettle, the temperature of the reaction kettle is adjusted, and after the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, ethane gas is introduced into the reaction kettle until the pressure reaches 1.5 MPa. The system pressure is 629 kPa and 507 kPa at the 30th min and the 120th min after the gas is introduced, respectively, and the calculated ethane adsorption amount is 8.78 mmol / g and 9.93 mmol / g, respectively.

[0099] Example 2

[0100] (1) Preparation of a 0.05 mol / L aqueous solution of sodium undecyl sulfate; then 3 g of activated carbon is immersed in 20 g of the aqueous solution of sodium undecyl sulfate, the immersion time is 24 h, and the immersion temperature is 30°C; after the immersion is completed, the activated carbon is placed in a vacuum drying oven for drying, the drying time is 360 min, and the drying temperature is 120°C.

[0101] (2) A hydrate promoter is prepared by mixing tetrahydrofuran, tetrabutylammonium bromide and thio betaine according to a mass ratio of 1:1:0.5; the hydrate promoter is mixed with water, wherein the addition amount of the hydrate promoter is 0.3 wt%, to obtain an aqueous solution containing the hydrate promoter.

[0102] (3) 2 g of the aqueous solution containing the hydrate promoter in step (2) is coupled with the activated carbon pretreated in step (1) by using an ultrasonic immersion method, the immersion temperature is 25°C, the immersion time is 120 min, and the power is 20 kHz, to obtain a solid-liquid reactant.

[0103] In this embodiment, the performance evaluation device is used for performance evaluation, the solid-liquid reactant in step (3) is added into a reaction kettle, the temperature of the reaction kettle is adjusted, and after the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, ethane gas is introduced into the reaction kettle until the pressure reaches 1.5 MPa. The system pressure is 606 kPa and 479 kPa at the 30th min and the 120th min after the gas is introduced, respectively, and the calculated ethane adsorption amounts are 9.00 mmol / g and 10.14 mmol / g, respectively.

[0104] Example 3

[0105] (1) Preparation of a 0.2 mol / L aqueous solution of sodium dodecyl sulfate; then 3 g of activated carbon is immersed in 25 g of the aqueous solution of sodium dodecyl sulfate, the immersion time is 24 h, and the immersion temperature is 30°C. After the immersion is completed, the activated carbon is placed in a vacuum drying oven for drying, the drying time is 360 min, and the drying temperature is 120°C.

[0106] (2) A hydrate promoter is prepared by mixing cyclopentane and sodium thiosalicylate according to a mass ratio of 1:0.5; the hydrate promoter is mixed with water, wherein the addition amount of the hydrate promoter is 0.5 wt%, to obtain an aqueous solution containing the hydrate promoter.

[0107] (3) 3 g of the aqueous solution containing the hydrate promoter in step (2) is coupled with the activated carbon pretreated in step (1) by using an ultrasonic immersion method, the immersion temperature is 30°C, the immersion time is 120 min, and the power is 20 kHz, to obtain a solid-liquid reactant.

[0108] The performance evaluation device is used for performance evaluation. The solid-liquid reactant in step (3) is added into the reaction kettle. The temperature of the reaction kettle is adjusted. After the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, ethane gas is introduced into the reaction kettle until the pressure reaches 1.5 MPa. The system pressure is 563 kPa and 442 kPa at the 30th minute and the 120th minute after the introduction of the gas, respectively. The calculated ethane adsorption amount is 9.39 mmol / g and 10.47 mmol / g, respectively.

[0109] Example 4

[0110] (1) A sodium tridecyl sulfate aqueous solution with a concentration of 0.5 mol / L is prepared. 3 g of activated carbon is immersed in 30 g of the sodium tridecyl sulfate aqueous solution. The immersion time is 24 h, and the immersion temperature is 30°C. After the immersion is completed, the activated carbon is placed in a vacuum drying box for drying. The drying time is 360 min, and the drying temperature is 120°C.

[0111] (2) The dioxolane and thionicotinamide are mixed according to a mass ratio of 1:0.7 to obtain a hydrate promoter. The hydrate promoter is mixed with water. The addition amount of the hydrate promoter is 1.0 wt%, and a water solution containing the hydrate promoter is obtained.

[0112] (3) 4 g of the water solution containing the hydrate promoter in step (2) is coupled with the pretreated activated carbon in step (1) by using an ultrasonic immersion method. The immersion temperature is 30°C, the immersion time is 120 min, and the power is 20 kHz. A solid-liquid reactant is obtained.

[0113] The performance evaluation device is used for performance evaluation. The solid-liquid reactant in step (3) is added into the reaction kettle. The temperature of the reaction kettle is adjusted. After the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, ethane gas is introduced into the reaction kettle until the pressure reaches 1.5 MPa. The system pressure is 563 kPa and 442 kPa at the 30th minute and the 120th minute after the introduction of the gas, respectively. The calculated ethane adsorption amount is 9.39 mmol / g and 10.47 mmol / g, respectively.

[0114] Example 5

[0115] (1) A sodium dodecyl sulfate aqueous solution with a concentration of 0.7 mol / L is prepared. Then, 3 g of activated carbon is immersed in 30 g of the sodium dodecyl sulfate aqueous solution. The immersion time is 24 h, and the immersion temperature is 30°C. After the immersion is completed, the activated carbon is placed in a vacuum drying box for drying. The drying time is 360 min, and the drying temperature is 120°C.

[0116] (2) Mix the dioxolan with the thionicotinamide according to a mass ratio of 1:1 to obtain a hydrate promoter; mix the hydrate promoter with water, wherein the addition amount of the hydrate promoter is 1.5 wt%, to obtain an aqueous solution containing the hydrate promoter.

[0117] (3) Take 3 g of the aqueous solution containing the hydrate promoter in step (2) and couple with the pretreated activated carbon in step (1), and the coupling process adopts the ultrasonic immersion method, the immersion temperature is 30°C, the immersion time is 120 min, and the power is 20 kHz, to obtain a solid-liquid reactant.

[0118] In this embodiment, the performance evaluation device is used for performance evaluation, the solid-liquid reactant in step (3) is added into the reaction kettle, the temperature of the reaction kettle is adjusted, and after the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, ethane gas is introduced into the reaction kettle to 1.5 MPa. After the gas is introduced, the system pressure is 523 kPa and 396 kPa at the 30th min and the 120th min, respectively, and the calculated ethane adsorption amount is 9.75 mmol / g and 10.87 mmol / g, respectively.

[0119] Example 6

[0120] (1) Prepare a sodium decyl sulfate aqueous solution with a concentration of 1.0 mol / L; then immerse 3 g of activated carbon in 35 g of the sodium decyl sulfate aqueous solution, the immersion time is 24 h, and the immersion temperature is 30°C; after the immersion is completed, place it in a vacuum drying box for drying, the drying time is 360 min, and the drying temperature is 120°C.

[0121] (2) Mix the tetrahydrofuran with the thioformamide according to a mass ratio of 1:1 to obtain a hydrate promoter; mix the hydrate promoter with water, wherein the addition amount of the hydrate promoter is 2.0 wt%, to obtain an aqueous solution containing the hydrate promoter.

[0122] (3) Take 2 g of the aqueous solution containing the hydrate promoter in step (2) and couple with the pretreated activated carbon in step (1), and the coupling process adopts the ultrasonic immersion method, the immersion temperature is 30°C, the immersion time is 120 min, and the power is 20 kHz, to obtain a solid-liquid reactant.

[0123] In this embodiment, the performance evaluation device is used for performance evaluation, the solid-liquid reactant in step (3) is added into the reaction kettle, the temperature of the reaction kettle is adjusted, and after the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, ethane gas is introduced into the reaction kettle to 1.5 MPa. After the gas is introduced, the system pressure is 511 kPa and 403 kPa at the 30th min and the 120th min, respectively, and the calculated ethane adsorption amount is 9.86 mmol / g and 10.81 mmol / g, respectively.

[0124] Example 7

[0125] (1) Preparation of a 0.8 mol / L aqueous solution of sodium undecyl sulfate; then 3 g of activated carbon is immersed in 20 g of the aqueous solution of sodium undecyl sulfate, the immersion time is 24 h, and the immersion temperature is 40°C; after the immersion is completed, the activated carbon is placed in a vacuum drying oven for drying, the drying time is 360 min, and the drying temperature is 120°C.

[0126] (2) The tetrabutylammonium bromide and thioproline are mixed according to a mass ratio of 1:1 to obtain a hydrate promoter; the hydrate promoter is mixed with water, wherein the addition amount of the hydrate promoter is 2.0 wt%, to obtain an aqueous solution containing the hydrate promoter.

[0127] (3) 3 g of the aqueous solution containing the hydrate promoter in step (2) is coupled with the activated carbon pretreated in step (1) by using an ultrasonic immersion method, the immersion temperature is 40°C, the immersion time is 120 min, and the power is 20 kHz, to obtain a solid-liquid reactant.

[0128] In this example, the performance evaluation device is used for performance evaluation, the solid-liquid reactant in step (3) is added to a reaction kettle, the temperature of the reaction kettle is adjusted, and after the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, ethane gas is introduced into the reaction kettle to 1.5 MPa. The system pressure is 531 kPa and 409 kPa at the 30th min and the 120th min after the gas is introduced, respectively, and the calculated ethane adsorption amount is 9.68 mmol / g and 10.76 mmol / g, respectively.

[0129] Example 8

[0130] (1) Preparation of a 0.6 mol / L aqueous solution of sodium tridecyl sulfate; then 3 g of activated carbon is immersed in 45 g of the aqueous solution of sodium tridecyl sulfate, the immersion time is 24 h, and the immersion temperature is 40°C; after the immersion is completed, the activated carbon is placed in a vacuum drying oven for drying, the drying time is 360 min, and the drying temperature is 120°C.

[0131] (2) The dioxolane and thioproline are mixed according to a mass ratio of 1:1 to obtain a hydrate promoter; the hydrate promoter is mixed with water, wherein the addition amount of the hydrate promoter is 2.0 wt%, to obtain an aqueous solution containing the hydrate promoter.

[0132] (3) 3 g of the aqueous solution containing the hydrate promoter in step (2) is coupled with the activated carbon pretreated in step (1) by using an ultrasonic immersion method, the immersion temperature is 40°C, the immersion time is 120 min, and the power is 20 kHz, to obtain a solid-liquid reactant.

[0133] The performance evaluation device is used for performance evaluation. The solid-liquid reactant in step (3) is added into the reaction kettle. The temperature of the reaction kettle is adjusted. After the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, ethane gas is introduced into the reaction kettle until the pressure reaches 1.5 MPa. The system pressure is 547 kPa and 422 kPa at the 30th minute and the 120th minute after the introduction of the gas, respectively. The calculated ethane adsorption amount is 9.53 mmol / g and 10.65 mmol / g, respectively.

[0134] Example 9

[0135] (1) A sodium dodecyl sulfate aqueous solution with a concentration of 0.1 mol / L is prepared. Then, 3 g of activated carbon is immersed in 18 g of the sodium dodecyl sulfate aqueous solution. The immersion time is 24 h, and the immersion temperature is 40°C. After the immersion is completed, the activated carbon is placed in a vacuum drying box for drying. The drying time is 360 min, and the drying temperature is 120°C.

[0136] (2) Tetrabutylammonium bromide, tetrahydrofuran, and thiourea are mixed according to a mass ratio of 1:1:0.5 to obtain a hydrate promoter. The hydrate promoter is mixed with water. The addition amount of the hydrate promoter is 3 wt%, and a water solution containing the hydrate promoter is obtained.

[0137] (3) 2 g of the water solution containing the hydrate promoter in step (2) is coupled with the pretreated activated carbon in step (1) by using an ultrasonic immersion method. The immersion temperature is 40°C, the immersion time is 120 min, and the power is 20 kHz. A solid-liquid reactant is obtained.

[0138] The performance evaluation device is used for performance evaluation. The solid-liquid reactant in step (3) is added into the reaction kettle. The temperature of the reaction kettle is adjusted. After the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, ethane gas is introduced into the reaction kettle until the pressure reaches 1.5 MPa. The system pressure is 634 ka and 520 kPa at the 30th minute and the 120th minute after the introduction of the gas, respectively. The calculated ethane adsorption amount is 8.74 mmol / g and 9.77 mmol / g, respectively.

[0139] Example 10

[0140] (1) A sodium dodecyl sulfate aqueous solution with a concentration of 0.1 mol / L is prepared. Then, 3 g of activated carbon is immersed in 18 g of the sodium dodecyl sulfate aqueous solution. The immersion time is 24 h, and the immersion temperature is 40°C. After the immersion is completed, the activated carbon is placed in a vacuum drying box for drying. The drying time is 360 min, and the drying temperature is 120°C.

[0141] (2) Mix cyclopentane and thionicotinamide according to a mass ratio of 1:0.2 to obtain a hydrate promoter; mix the hydrate promoter with water, wherein the hydrate promoter is added in an amount of 2.8 wt% to obtain a water solution containing the hydrate promoter.

[0142] (3) Take 2.5 g of the water solution containing the hydrate promoter in step (2) and couple with the activated carbon pretreated in step (1) by using an ultrasonic immersion method, wherein the immersion temperature is 40°C, the immersion time is 120 min, and the power is 20 kHz to obtain a solid-liquid reactant.

[0143] In this embodiment, the performance evaluation device is used to evaluate the performance, the solid-liquid reactant in step (3) is added into the reaction kettle, the temperature of the reaction kettle is adjusted, and after the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, ethane gas is introduced into the reaction kettle to 1.5 MPa. After the gas is introduced, the system pressure is 603 ka and 496 kPa at the 30th min and the 120th min, respectively, and the calculated ethane adsorption amount is 9.02 mmol / g and 9.98 mmol / g, respectively.

[0144] Example 11

[0145] (1) Prepare a 0.4 mol / L sodium tridecyl sulfate aqueous solution; immerse 3 g of activated carbon in 25 g of the above-mentioned sodium tridecyl sulfate aqueous solution, and the immersion time is 30 h and the immersion temperature is 30°C; after the immersion is completed, place it in a vacuum drying box for drying, and the drying time is 360 min and the drying temperature is 120°C.

[0146] (2) Mix dioxolane, tetrahydrofuran and sodium thiosalicylate according to a mass ratio of 1:2:0.3 to obtain a hydrate promoter; mix the hydrate promoter with water, wherein the hydrate promoter is added in an amount of 2.5 wt% to obtain a water solution containing the hydrate promoter.

[0147] (3) Take 2.5 g of the water solution containing the hydrate promoter in step (2) and couple with the activated carbon pretreated in step (1) by using an ultrasonic immersion method, wherein the immersion temperature is 40°C, the immersion time is 120 min, and the power is 20 kHz to obtain a solid-liquid reactant.

[0148] In this embodiment, the performance evaluation device is used to evaluate the performance, the solid-liquid reactant in step (3) is added into the reaction kettle, the temperature of the reaction kettle is adjusted, and after the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, ethane gas is introduced into the reaction kettle to 1.5 MPa. After the gas is introduced, the system pressure is 611 ka and 489 kPa at the 30th min and the 120th min, respectively, and the calculated ethane adsorption amount is 8.95 mmol / g and 10.05 mmol / g, respectively.

[0149] Example 12

[0150] (1) A sodium tridecyl sulfate aqueous solution with a concentration of 0.5 mol / L was prepared; 3 g of activated carbon was immersed in 30 g of the sodium tridecyl sulfate aqueous solution, the immersion time was 30 h, and the immersion temperature was 35 °C; after the immersion was completed, the activated carbon was placed in a vacuum drying oven for drying, the drying time was 360 min, and the drying temperature was 120 °C.

[0151] (2) The dioxolane and the thio-proline were mixed at a mass ratio of 1:0.7 to obtain a hydrate promoter; the hydrate promoter was mixed with water, wherein the hydrate promoter was added in an amount of 2.0 wt%, to obtain a hydrate promoter-containing aqueous solution.

[0152] (3) 3.5 g of the hydrate promoter-containing aqueous solution in step (2) was coupled with the activated carbon pretreated in step (1) by using an ultrasonic immersion method, the immersion temperature was 40 °C, the immersion time was 120 min, and the power was 20 kHz, to obtain a solid-liquid reactant.

[0153] In this example, the performance evaluation device described above was used for performance evaluation; the solid-liquid reactant in step (3) was added to a reaction kettle, the temperature of the reaction kettle was adjusted, and after the temperature of the reaction kettle was reduced to 273.25 K and stabilized for 1 h, ethane gas was introduced into the reaction kettle until the pressure reached 1.5 MPa. The system pressure was 579 kPa and 437 kPa at the 30th min and the 120th min after the gas was introduced, respectively, and the calculated ethane adsorption amounts were 9.24 mmol / g and 10.51 mmol / g, respectively.

[0154] Example 13

[0155] (1) A sodium tridecyl sulfate aqueous solution with a concentration of 0.7 mol / L was prepared; 3 g of activated carbon was immersed in 40 g of the sodium tridecyl sulfate aqueous solution, the immersion time was 35 h, and the immersion temperature was 40 °C; after the immersion was completed, the activated carbon was placed in a vacuum drying oven for drying, the drying time was 360 min, and the drying temperature was 120 °C.

[0156] (2) Cyclopentane and thionicotinamide were mixed at a mass ratio of 1:0.8 to obtain a hydrate promoter; the hydrate promoter was mixed with water, wherein the hydrate promoter was added in an amount of 1.5 wt%, to obtain a hydrate promoter-containing aqueous solution.

[0157] (3) 3 g of the hydrate promoter-containing aqueous solution in step (2) was coupled with the activated carbon pretreated in step (1) by using an ultrasonic immersion method, the immersion temperature was 40 °C, the immersion time was 120 min, and the power was 20 kHz, to obtain a solid-liquid reactant.

[0158] The performance evaluation device is used for performance evaluation. The solid-liquid reactant in step (3) is added into the reaction kettle. The temperature of the reaction kettle is adjusted. After the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, ethane gas is introduced into the reaction kettle until the pressure reaches 1.5 MPa. After the gas is introduced, the system pressure is 577 ka and 454 kPa at the 30th minute and the 120th minute, respectively. The calculated ethane adsorption amount is 9.26 mmol / g and 10.34 mmol / g, respectively.

[0159] Example 14

[0160] (1) A sodium tridecyl sulfate aqueous solution with a concentration of 0.8 mol / L is prepared. 3 g of activated carbon is immersed in 40 g of the sodium tridecyl sulfate aqueous solution. The immersion time is 30 h, and the immersion temperature is 40°C. After the immersion is completed, the activated carbon is placed in a vacuum drying box for drying. The drying time is 360 min, and the drying temperature is 120°C.

[0161] (2) Tetrahydrofuran and thioformamide are mixed in a mass ratio of 1:0.8 to obtain a hydrate promoter. The hydrate promoter is mixed with water. The addition amount of the hydrate promoter is 1.0 wt%, and a water solution containing the hydrate promoter is obtained.

[0162] (3) 3 g of the water solution containing the hydrate promoter in step (2) is coupled with the pretreated activated carbon in step (1) by using an ultrasonic immersion method. The immersion temperature is 40°C, the immersion time is 120 min, and the power is 20 kHz. A solid-liquid reactant is obtained.

[0163] The performance evaluation device is used for performance evaluation. The solid-liquid reactant in step (3) is added into the reaction kettle. The temperature of the reaction kettle is adjusted. After the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, ethane gas is introduced into the reaction kettle until the pressure reaches 1.5 MPa. After the gas is introduced, the system pressure is 577 ka and 454 kPa at the 30th minute and the 120th minute, respectively. The calculated ethane adsorption amount is 9.26 mmol / g and 10.34 mmol / g, respectively.

[0164] Example 15

[0165] (1) A sodium tridecyl sulfate aqueous solution with a concentration of 1.0 mol / L is prepared. 3 g of activated carbon is immersed in 20 g of the sodium tridecyl sulfate aqueous solution. The immersion time is 24 h, and the immersion temperature is 35°C. After the immersion is completed, the activated carbon is placed in a vacuum drying box for drying. The drying time is 360 min, and the drying temperature is 120°C.

[0166] (2) mixing cyclopentane and thiocyanate according to a mass ratio of 1:1 to obtain a hydrate promoter; mixing the hydrate promoter with water, wherein the hydrate promoter is added in an amount of 0.5wt%, to obtain an aqueous solution containing the hydrate promoter.

[0167] (3) coupling 3.5g of the aqueous solution containing the hydrate promoter in step (2) with the activated carbon pretreated in step (1), wherein the coupling is performed by using an ultrasonic immersion method, the immersion temperature is 40℃, the immersion time is 120min, and the power is 20kHz, to obtain a solid-liquid reactant.

[0168] The performance evaluation device is used to evaluate the performance of the solid-liquid reactant in step (3), and the solid-liquid reactant is added into the reaction kettle. The temperature of the reaction kettle is adjusted, and ethane gas is introduced into the reaction kettle until the pressure reaches 1.5MPa after the temperature of the reaction kettle is reduced to 273.25K and stabilized for 1h. The system pressure is 628kPa and 514kPa at the 30th minute and the 120th minute after the gas is introduced, respectively. The calculated ethane adsorption amount is 8.79mmol / g and 9.82mmol / g, respectively.

[0169] Comparative Example 1

[0170] The activated carbon used in this comparative example is not treated.

[0171] The performance evaluation device is used to evaluate the performance of the solid-liquid reactant in step (3), and the solid-liquid reactant is added into the reaction kettle. The temperature of the reaction kettle is adjusted, and ethane gas is introduced into the reaction kettle until the pressure reaches 1.5MPa after the temperature of the reaction kettle is reduced to 273.25K and stabilized for 1h. The system pressure is 628kPa and 514kPa at the 30th minute and the 120th minute after the gas is introduced, respectively. The calculated ethane adsorption amount is 8.79mmol / g and 9.82mmol / g, respectively.

[0172] Comparative Example 2

[0173] The activated carbon used in this comparative example is pretreated.

[0174] Specifically, the following steps are included: 3g of untreated activated carbon is added into a beaker, and 20g of 0.5mol / L sodium decyl sulfate aqueous solution is added for immersion at 35℃ for 24h. After the immersion is completed, the sample is dried in a vacuum drying oven for 360min at a drying temperature of 120℃.

[0175] The performance evaluation device is used to evaluate the performance of the above-mentioned performance evaluation device. The pretreated activated carbon is added into the reaction kettle. After the system is vacuumed and the reaction gas is replaced for three times, the temperature of the reaction kettle is adjusted. When the temperature of the reaction kettle is reduced to 273.25K and stabilized for 1h, ethane gas is introduced into the reaction kettle to 1.5MPa. The system pressure is 1102kPa and 1076kPa at 30min and 120min after the gas is introduced, respectively, and the ethane adsorption amount is 4.22mmol / g and 4.48mmol / g, respectively.

[0176] Comparative Example 3

[0177] The comparative example is untreated activated carbon + hydration.

[0178] Specifically, the following steps are included: 3g of untreated activated carbon is added into a beaker, and 3g of H2O is added. The two are ultrasonically immersed for 120min at 30℃. After the immersion is completed, a solid-liquid mixture is obtained.

[0179] The performance evaluation device is used to evaluate the performance of the above-mentioned performance evaluation device. The pretreated activated carbon is added into the reaction kettle. After the system is vacuumed and the reaction gas is replaced for three times, the temperature of the reaction kettle is adjusted. When the temperature of the reaction kettle is reduced to 273.25K and stabilized for 1h, ethane gas is introduced into the reaction kettle to 1.5MPa. The system pressure is 1102kPa and 1076kPa at 30min and 120min after the gas is introduced, respectively, and the ethane adsorption amount is 4.22mmol / g and 4.48mmol / g, respectively.

[0180] Comparative Example 4

[0181] The method described in Example 6 is used for implementation, except that no hydration promoter containing compound is added (i.e. the comparative example uses pretreated activated carbon + hydration). Specifically, the following steps are included:

[0182] (1) A sodium decyl sulfate aqueous solution with a concentration of 1.0mol / L is prepared. Then 3g of activated carbon is immersed in 35g of the above-mentioned sodium decyl sulfate aqueous solution, the immersion time is 24h, and the immersion temperature is 30℃. After the immersion is completed, it is placed in a vacuum drying oven for drying, the drying time is 360min, and the drying temperature is 120℃.

[0183] (2) Take 2 g of pure water and couple with the activated carbon pretreated in step (1), and the coupling process uses ultrasonic immersion method, the immersion temperature is 30°C, the immersion time is 120 min, and the power is 20 kHz, to obtain a solid-liquid reactant. The performance evaluation device is used for performance evaluation, the solid-liquid reactant is added into the reaction kettle, the system is vacuumized and the reaction gas is introduced for replacement for 3 times, then the temperature of the reaction kettle is adjusted, the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, and then ethane gas is introduced into the reaction kettle to 1.5 MPa. After the gas is introduced, the system pressure is 836 kPa and 759 kPa at the 30th min and the 120th min, respectively, and the ethane adsorption amount is 6.84 mmol / g and 7.57 mmol / g, respectively.

[0184] Comparative Example 5

[0185] The method of Example 6 is followed, except that the hydrate promoter does not contain a growth promoter (thiocarbamide).

[0186] The performance evaluation device is used for performance evaluation, the solid-liquid reactant is added into the reaction kettle, the system is vacuumized and the reaction gas is introduced for replacement for 3 times, then the temperature of the reaction kettle is adjusted, the temperature of the reaction kettle is reduced to 273.25 K and stabilized for 1 h, and then ethane gas is introduced into the reaction kettle to 1.5 MPa. After the gas is introduced, the system pressure is 836 kPa and 759 kPa at the 30th min and the 120th min, respectively, and the ethane adsorption amount is 6.84 mmol / g and 7.57 mmol / g, respectively.

[0187] The above describes the preferred embodiments of the present application in detail, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A hydrate accelerator, characterized in that: The hydrate promoter contains a thermodynamic promoter and a growth promoter; Wherein, the growth promoter is selected from one or more of thiobetaine, sodium thiosalicylate, thionicotinamide, thioformamide and thioproline.

2. The hydrate promoter according to claim 1, characterized in that The thermodynamic promoter is selected from one or more of tetrahydrofuran, tetrabutylammonium bromide, cyclopentane and dioxolane.

3. The hydrate promoter according to claim 1 or 2, characterized in that The mass ratio of the thermodynamic promoter to the growth promoter is 1:0.01-1.

1.

4. Use of the hydrate promoter according to any one of claims 1 to 3 in gas storage and transportation by the hydrate method.

5. The use according to claim 4, characterized in that The gas is selected from one or more of methane, ethane and propane.

6. A gas storage and transportation method, characterized in that: The method includes: (1) pretreating the adsorption material with an aqueous solution of sodium alkyl sulfate; (2) coupling the pretreated adsorption material with an aqueous solution containing a hydrate promoter to obtain a solid-liquid reactant; (3) contacting the gas with the solid-liquid reactant; Wherein, the hydrate promoter contains a thermodynamic promoter and a growth promoter; The growth promoter is selected from one or more of thiobetaine, sodium thiosalicylate, thionicotinamide, thioformamide and thioproline.

7. The method according to claim 6, characterized in that The thermodynamic promoter is selected from one or more of tetrahydrofuran, tetrabutylammonium bromide, cyclopentane and dioxolane; Preferably, in the hydrate promoter, the mass ratio of the thermodynamic promoter to the growth promoter is 1:0.01 to 1.

1.

8. The method according to claim 6, characterized in that In step (1), the alkyl sulfate sodium salt is selected from one or more of decyl sodium sulfate, undecyl sodium sulfate, dodecyl sodium sulfate, and tridecyl sodium sulfate; Preferably, in step (1), the concentration of the alkyl sulfate sodium salt aqueous solution is 0.01 to 1.1 mol / L; Preferably, in step (1), the adsorption material is activated carbon and / or metal organic framework material; Preferably, in step (1), the mass ratio of the adsorption material to the alkyl sulfate sodium salt aqueous solution is 1:6-15.

9. The method according to claim 6 or 8, characterized in that In step (1), the pretreatment process includes: The adsorbent material is impregnated in an aqueous solution of sodium alkyl sulfate and then dried.

10. The method according to claim 9, characterized in that The immersion conditions include: a time of 20 to 40 hours and a temperature of 30 to 40°C; Preferably, the drying conditions include: a drying time of 200 to 500 minutes and a temperature of 100 to 140°C.

11. The method according to claim 6, characterized in that In step (2), the amount of the hydrate promoter added to the aqueous solution containing the hydrate promoter is 0.05 to 3 wt%; Preferably, in step (2), the mass ratio of the pretreated adsorption material to the aqueous solution containing the hydrate promoter is 1:0.5-1.

5.

12. The method according to claim 6 or 11, characterized in that Step (2) specifically comprises: ultrasonically impregnating the pretreated adsorption material with an aqueous solution containing a hydrate promoter; Preferably, the ultrasonic immersion conditions include: time of 100 to 200 minutes, temperature of 20 to 40° C., and power of 15 to 25 kHz.

13. The method according to claim 6, characterized in that In step (3), the gas is selected from one or more of methane, ethane and propane.

Images