A hydrate kinetic promoter and a method for preparing gas hydrates
By using a hydrate kinetic promoter composed of inorganic and organic components, the problem of low gas hydrate formation rate has been solved, and efficient generation of various gas hydrates has been achieved, making it suitable for industrial applications.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SOUTH CHINA UNIV OF TECH
- Filing Date
- 2024-06-07
- Publication Date
- 2026-06-16
AI Technical Summary
Existing gas hydrate preparation processes suffer from low formation rates, long induction times, and low gas storage density, and lack efficient hydrate kinetic promoters suitable for various gas hydrates.
A hydrate kinetic promoter composed of inorganic and organic components, including inorganic components such as boric acid, lithium phosphate, and sodium phosphate, and organic components such as 1-adamantaneamine and geraniol, promotes the formation of gaseous hydrates through low-temperature and high-pressure reactions.
It achieves efficient generation of gas hydrates, is applicable to a variety of gas hydrates, has a large gas storage capacity, is environmentally friendly, low in cost, and is suitable for large-scale industrial applications.
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Figure CN118792011B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of gas hydrate technology, specifically to a hydrate kinetic promoter and a method for preparing gas hydrates. Background Technology
[0002] Gas hydrates, also known as cage hydrates or gas inclusion compounds, are ice-like crystalline compounds formed by encapsulating small guest molecules (such as hydrogen, methane, carbon dioxide, ethane, and propane) within water cages under specific temperature and pressure (generally high pressure). The main water molecules in gas hydrates are interconnected by hydrogen bonds, forming polyhedral cages of different types and proportions, such as type I, type II, and type H structures. Gas hydrates can immobilize guest molecules with specific structures, significantly improving the scale and efficiency of guest molecule storage and transport, and thus possessing immense application value.
[0003] However, existing gas hydrate preparation processes generally suffer from low formation rates, long induction times, and low gas density of the prepared gas hydrates, significantly limiting their industrial application. Currently, methods to promote gas hydrate formation mainly include mechanical methods and chemical additive methods. Mechanical methods involve enhancing mass and heat transfer through stirring, bubbling, etc., thereby promoting gas hydrate formation; however, this method requires sophisticated equipment and its promotion effect is relatively limited. Chemical additive methods involve adding promoters to accelerate gas hydrate formation, offering advantages such as simple operation and low cost; however, there is currently a lack of hydrate kinetic promoters with good promotion effects applicable to various gas hydrates.
[0004] Therefore, it is of great significance to develop a hydrate kinetic promoter that can efficiently promote the formation of gas hydrates and is applicable to a variety of gas hydrates. Summary of the Invention
[0005] The purpose of this invention is to provide a hydrate kinetic promoter and a method for preparing gaseous hydrates.
[0006] The technical solution adopted in this invention is:
[0007] A hydrate kinetics promoter comprises an inorganic component and an organic component; the inorganic component is at least one selected from boric acid, lithium phosphate, sodium phosphate, and lithium tetraborate; the organic component is at least one selected from 1-adamantaneamine, geraniol, cresol red, alizarin red, azurite A, azurite B, melanin, vitamin B1, L-histidine, L-tryptophan, L-arginine, L-methionine, L-cysteine, and sodium dodecyl sulfate.
[0008] Preferably, the inorganic component is boric acid.
[0009] Preferably, the organic component is at least one selected from cresol red, L-histidine, L-tryptophan, L-arginine, and sodium dodecyl sulfate.
[0010] Preferably, the mass ratio of the inorganic component to the organic component is 1:0.1 to 4.
[0011] More preferably, the mass ratio of the inorganic component to the organic component is 1:0.2 to 1.5.
[0012] A method for preparing a hydrate kinetics promoter as described above includes the following steps: mixing inorganic and organic components evenly to obtain the hydrate kinetics promoter.
[0013] A method for preparing gas hydrates includes the following steps: dissolving the above-mentioned hydrate kinetic promoter in water to prepare an inorganic-organic component composite aqueous solution, and then introducing gas to carry out a low-temperature and high-pressure reaction to obtain gas hydrates.
[0014] Preferably, the mass fraction of the inorganic component in the inorganic-organic component composite aqueous solution is 0.1% to 0.5%.
[0015] More preferably, the mass fraction of the inorganic component in the inorganic-organic component composite aqueous solution is 0.2% to 0.4%.
[0016] Preferably, the mass fraction of the organic component in the inorganic-organic composite aqueous solution is 0.02% to 0.4%.
[0017] More preferably, the mass fraction of the organic component in the inorganic-organic component composite aqueous solution is 0.05% to 0.2%.
[0018] Preferably, the gas is at least one selected from methane, carbon dioxide, hydrogen, oxygen, nitrogen, hydrogen sulfide, argon, krypton, xenon, ethane, ethylene, and propane.
[0019] Preferably, the low-temperature high-pressure reaction is carried out at a temperature of 0℃ to 10℃ and a pressure of 2MPa to 5MPa.
[0020] More preferably, the low-temperature high-pressure reaction is carried out at a temperature of 0℃ to 5℃ and a pressure of 3MPa to 4MPa.
[0021] Preferably, the low-temperature high-pressure reaction time is 1 hour to 24 hours.
[0022] The beneficial effects of the present invention are: the hydrate kinetic promoter of the present invention has the advantages of low dosage, high efficiency in promoting the formation of gas hydrates, applicability to a variety of gas hydrates, environmental friendliness, and large gas storage capacity of the prepared gas hydrates. Moreover, its preparation method is simple, the raw materials are widely available and the cost is low, making it suitable for large-scale industrial application.
[0023] Specifically:
[0024] 1) The hydrate kinetic promoter of the present invention can efficiently promote the formation of gas hydrates with only a small amount of dosage, and is applicable to a variety of gas hydrates. The gas hydrates prepared have a large gas storage capacity, and only a small amount of foam or no foam is generated when the gas hydrates are degassed.
[0025] 2) The preparation process of the hydrate kinetic promoter of the present invention is simple, the raw materials are widely available and inexpensive, the production cost is low, and it is suitable for large-scale industrial application. Attached Figure Description
[0026] Figure 1 The figures show the kinetic curves of CO2 absorption in Example 2 and Comparative Example 1.
[0027] Figure 2 The figures show the kinetic curves of CO2 absorption in Examples 2, 4, and 5.
[0028] Figure 3 The diagram shows the dissociation of CO2 hydrates in Examples 2, 4, and 5. Detailed Implementation
[0029] The present invention will be further explained and described below with reference to specific embodiments.
[0030] Example 1:
[0031] A hydrate kinetic promoter is prepared by mixing boric acid and sodium dodecyl sulfate in a mass ratio of 4:1.
[0032] A CO2 hydrate, the preparation method of which is as follows:
[0033] The above-mentioned hydrate kinetic promoter was dissolved in deionized water to prepare an inorganic-organic composite aqueous solution with a boric acid mass fraction of 0.4% and a sodium dodecyl sulfate mass fraction of 0.1%. 10g of the inorganic-organic composite aqueous solution was added to the reactor, and the reactor was purged with CO2 gas three times to remove the air inside the reactor. The reactor was then placed in a circulation tank and cooled to a temperature of 273.2K (about 0℃). CO2 gas was then rapidly introduced into the reactor until the pressure inside the reactor reached 3.3MPa. The reactor was kept at this temperature for 17h (the gas storage of CO2 hydrate obtained after 5min, 15min, 30min, 60min, 120min, 500min and 1000min was recorded. The test results are shown in Table 1). CO2 hydrate was then obtained.
[0034] Example 2:
[0035] A hydrate kinetic promoter is prepared by mixing boric acid and sodium dodecyl sulfate in a mass ratio of 3:2.
[0036] A CO2 hydrate, the preparation method of which is as follows:
[0037] The above-mentioned hydrate kinetic promoter was dissolved in deionized water to prepare an inorganic-organic composite aqueous solution with a boric acid mass fraction of 0.3% and a sodium dodecyl sulfate mass fraction of 0.2%. 10g of the inorganic-organic composite aqueous solution was added to the reactor, and the reactor was purged with CO2 gas three times to remove the air inside the reactor. The reactor was then placed in a circulation tank and cooled to a temperature of 273.2K (about 0℃). CO2 gas was then rapidly introduced into the reactor until the pressure inside the reactor reached 3.3MPa. The reactor was kept at this temperature for 17h (the gas storage of CO2 hydrate obtained after 5min, 15min, 30min, 60min, 120min, 500min and 1000min was recorded. The test results are shown in Table 1). CO2 hydrate was then obtained.
[0038] Example 3:
[0039] A hydrate kinetic promoter is prepared by mixing boric acid and sodium dodecyl sulfate in a mass ratio of 2:3.
[0040] A CO2 hydrate, the preparation method of which is as follows:
[0041] The above-mentioned hydrate kinetic promoter was dissolved in deionized water to prepare an inorganic-organic composite aqueous solution with a boric acid mass fraction of 0.2% and a sodium dodecyl sulfate mass fraction of 0.3%. 10g of the inorganic-organic composite aqueous solution was added to the reactor, and the reactor was continuously purged with CO2 gas three times to remove the air inside the reactor. The reactor was then placed in a circulation tank and cooled to a temperature of 273.2K (about 0℃). CO2 gas was then rapidly introduced into the reactor until the pressure inside the reactor reached 3.3MPa. The reactor was kept at this temperature for 17h (the gas storage of CO2 hydrate obtained after 5min, 15min, 30min, 60min, 120min, 500min and 1000min was recorded. The test results are shown in Table 1). CO2 hydrate was then obtained.
[0042] Example 4:
[0043] A hydrate kinetic promoter is prepared by mixing boric acid and L-histidine in a mass ratio of 4:1.
[0044] A CO2 hydrate, the preparation method of which is as follows:
[0045] The above-mentioned hydrate kinetic promoter was dissolved in deionized water to prepare an inorganic-organic component composite aqueous solution with a boric acid mass fraction of 0.4% and an L-histidine mass fraction of 0.1%. 10g of the inorganic-organic component composite aqueous solution was then added to the reactor. The reactor was then purged three times with CO2 gas to remove the air inside. The reactor was then placed in a circulation tank and cooled to a temperature of 273.2K (about 0℃). CO2 gas was then rapidly introduced into the reactor until the pressure inside the reactor reached 3.3MPa. The reactor was kept at this temperature for 17h (the gas storage capacity of CO2 hydrate obtained after 5min, 15min, 30min, 60min, 120min, 500min and 1000min of reaction was recorded. The test results are shown in Table 1). CO2 hydrate was then obtained.
[0046] Example 5:
[0047] A hydrate kinetic promoter is prepared by mixing boric acid and L-arginine in a mass ratio of 4:1.
[0048] A CO2 hydrate, the preparation method of which is as follows:
[0049] The above-mentioned hydrate kinetic promoter was dissolved in deionized water to prepare an inorganic-organic composite aqueous solution with a boric acid mass fraction of 0.4% and an L-arginine mass fraction of 0.1%. 10g of the inorganic-organic composite aqueous solution was added to the reactor, and the reactor was purged with CO2 gas three times to remove the air inside the reactor. The reactor was then placed in a circulation tank and cooled to a temperature of 273.2K (about 0℃). CO2 gas was then rapidly introduced into the reactor until the pressure inside the reactor reached 3.3MPa. The reactor was kept at this temperature for 17h (the gas storage of CO2 hydrate obtained after 5min, 15min, 30min, 60min, 120min, 500min and 1000min was recorded. The test results are shown in Table 1). CO2 hydrate was then obtained.
[0050] Example 6:
[0051] A hydrate kinetic promoter is prepared by mixing boric acid and L-tryptophan in a mass ratio of 4:1.
[0052] A CO2 hydrate, the preparation method of which is as follows:
[0053] The above-mentioned hydrate kinetic promoter was dissolved in deionized water to prepare an inorganic-organic composite aqueous solution with a boric acid mass fraction of 0.4% and an L-tryptophan mass fraction of 0.1%. 10g of the inorganic-organic composite aqueous solution was added to the reactor, and the reactor was continuously purged with CO2 gas three times to remove the air inside the reactor. The reactor was then placed in a circulation tank and cooled to a temperature of 273.2K (about 0℃). CO2 gas was then rapidly introduced into the reactor until the pressure inside the reactor reached 3.3MPa. The reactor was kept at this temperature for 17h (the gas storage of CO2 hydrate obtained after 5min, 15min, 30min, 60min, 120min, 500min and 1000min was recorded. The test results are shown in Table 1). CO2 hydrate was then obtained.
[0054] Example 7:
[0055] A hydrate kinetic promoter is prepared by mixing boric acid and cresol red in a mass ratio of 10:1.
[0056] A CO2 hydrate, the preparation method of which is as follows:
[0057] The above-mentioned hydrate kinetic promoter was dissolved in deionized water to prepare an inorganic-organic component composite aqueous solution with a boric acid mass fraction of 0.2% and a cresol red mass fraction of 0.02%. 10g of the inorganic-organic component composite aqueous solution was added to the reactor, and the reactor was continuously purged with CO2 gas three times to remove the air inside the reactor. The reactor was then placed in a circulation tank and cooled to a temperature of 273.2K (about 0℃). CO2 gas was then rapidly introduced into the reactor until the pressure inside the reactor reached 3.3MPa. The reactor was kept at this temperature for 17h (the gas storage of CO2 hydrate obtained after 5min, 15min, 30min, 60min, 120min, 500min and 1000min was recorded. The test results are shown in Table 1). CO2 hydrate was then obtained.
[0058] Example 8:
[0059] A hydrate kinetic promoter is prepared by mixing sodium phosphate and sodium dodecyl sulfate in a mass ratio of 4:1.
[0060] A CO2 hydrate, the preparation method of which is as follows:
[0061] The above-mentioned hydrate kinetic promoter was dissolved in deionized water to prepare an inorganic-organic component composite aqueous solution with a sodium phosphate mass fraction of 0.4% and a sodium dodecyl sulfate mass fraction of 0.1%. 10g of the inorganic-organic component composite aqueous solution was then added to the reactor. The reactor was then purged with CO2 gas three times to remove the air inside the reactor. The reactor was then placed in a circulation tank and cooled to a temperature of 273.2K (about 0℃). CO2 gas was then rapidly introduced into the reactor until the pressure inside the reactor reached 3.3MPa. The reactor was kept at this temperature for 17h (the gas storage of CO2 hydrate obtained after 5min, 15min, 30min, 60min, 120min, 500min and 1000min was recorded. The test results are shown in Table 1). CO2 hydrate was then obtained.
[0062] Comparative Example 1:
[0063] A CO2 hydrate, the preparation method of which is as follows:
[0064] Add 10g of deionized water to the reactor, then purge the reactor three times with CO2 gas to remove the air inside. Place the reactor in a circulation tank and cool it to a temperature of 273.2K (about 0℃). Then, rapidly charge the reactor with CO2 gas until the pressure inside the reactor reaches 3.3MPa. Keep it at this temperature for 17h (the gas storage capacity of CO2 hydrate obtained after 5min, 15min, 30min, 60min, 120min, 500min and 1000min of reaction is recorded. The test results are shown in Table 1). CO2 hydrate is then obtained.
[0065] Comparative Example 2:
[0066] A CO2 hydrate, the preparation method of which is as follows:
[0067] Boric acid was dissolved in deionized water to prepare a 0.5% boric acid solution. 10g of the boric acid solution was then added to the reaction vessel. The reaction vessel was then purged three times with CO2 gas to remove the air inside. The reaction vessel was then placed in a circulation tank and cooled to a temperature of 273.2K (approximately 0℃). CO2 gas was then rapidly introduced into the reaction vessel until the pressure inside the vessel reached 3.3MPa. The reaction was maintained at this temperature for 17h (the gas storage capacity of CO2 hydrate obtained after 5min, 15min, 30min, 60min, 120min, 500min and 1000min of reaction was recorded. The test results are shown in Table 1). CO2 hydrate was then obtained.
[0068] Comparative Example 3:
[0069] A CO2 hydrate, the preparation method of which is as follows:
[0070] Sodium dodecyl sulfate was dissolved in deionized water to prepare a 0.5% sodium dodecyl sulfate solution. 10g of the sodium dodecyl sulfate solution was then added to a reaction vessel. The reaction vessel was then purged three times with CO2 gas to remove the air inside. The reaction vessel was then placed in a circulation tank and cooled to a temperature of 273.2K (approximately 0℃). CO2 gas was then rapidly introduced into the reaction vessel until the pressure inside the vessel reached 3.3MPa. The reaction was maintained at this temperature for 17h (the gas storage capacity of CO2 hydrate obtained after 5min, 15min, 30min, 60min, 120min, 500min and 1000min of reaction was recorded. The test results are shown in Table 1). CO2 hydrate was then obtained.
[0071] Performance testing:
[0072] The kinetic curves of CO2 absorption in Example 2 and Comparative Example 1 are as follows: Figure 1 As shown.
[0073] The kinetic curves of CO2 absorption in Examples 2, 4, and 5 are as follows: Figure 2 As shown.
[0074] The dissociation of CO2 hydrate in Examples 2, 4, and 5 (preliminary dissociation at room temperature and atmospheric pressure) is shown in the figure below. Figure 3 As shown.
[0075] The gas storage capacity test results of CO2 hydrates obtained from different reaction times in Examples 1-8 and Comparative Examples 1-3 are shown in the table below:
[0076] Table 1 shows the gas storage capacity test results of CO2 hydrates obtained at different reaction times in Examples 1-8 and Comparative Examples 1-3.
[0077]
[0078]
[0079] Depend on Figures 1-3 As shown in Table 1:
[0080] 1) The hydrate kinetic promoter in Example 2 showed the best effect, with a CO2 hydrate storage capacity of 323.5 mg / g obtained after 1000 min of reaction. 90 The time required to reach 90% of the gas storage capacity is approximately 77.5 minutes. The gas storage capacity of CO2 hydrate is much higher than that of CO2 hydrate in Comparative Examples 1-3.
[0081] 2) The gas storage capacity of CO2 hydrate in Examples 4 and 5 is basically the same as that of CO2 hydrate in Example 2, except for t 90 The process takes a little longer, and the CO2 hydrate produced does not generate foam during dissociation, so it will not harm the environment.
[0082] Furthermore, tests revealed that using the hydrate kinetic promoters from Examples 1-8 to prepare methane hydrate, hydrogen hydrate, oxygen hydrate, nitrogen hydrate, hydrogen sulfide hydrate, argon hydrate, krypton hydrate, xenon hydrate, ethane hydrate, ethylene hydrate, and propane hydrate also efficiently promoted the formation of gaseous hydrates.
[0083] In summary, the hydrate kinetic promoter of the present invention has the advantages of requiring less dosage, being able to efficiently promote the formation of gas hydrates, being applicable to a variety of gas hydrates, being environmentally friendly, and producing gas hydrates with large gas storage capacity. Furthermore, its preparation method is simple, the raw materials are widely available and the cost is low, making it suitable for large-scale industrial application.
[0084] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.
Claims
1. A hydrate kinetics promoter, characterized in that, The composition includes inorganic components and organic components; the inorganic component is boric acid; the organic component is at least one of cresol red, L-histidine, L-tryptophan, L-arginine, and sodium dodecyl sulfate; the mass ratio of the inorganic component to the organic component is 1:0.1 to 4.
2. The hydrate kinetics promoter according to claim 1, characterized in that: The mass ratio of the inorganic component to the organic component is 1:0.2 to 1.
5.
3. A method for preparing a hydrate kinetics promoter as described in claim 1 or 2, characterized in that, The process includes the following steps: mixing inorganic and organic components evenly to obtain a hydrate kinetic promoter.
4. A method for preparing gas hydrates, characterized in that, The process includes the following steps: dissolving the hydrate kinetic promoter described in claim 1 or 2 in water to prepare an inorganic-organic component composite aqueous solution, and then introducing carbon dioxide to carry out a low-temperature and high-pressure reaction to obtain a gaseous hydrate.
5. The method for preparing gas hydrates according to claim 4, characterized in that: The inorganic component in the inorganic-organic composite aqueous solution has a mass fraction of 0.1% to 0.5%.
6. The method for preparing gas hydrates according to claim 4 or 5, characterized in that: The mass fraction of the organic component in the inorganic-organic composite aqueous solution is 0.02% to 0.4%.
7. The method for preparing gas hydrates according to claim 4 or 5, characterized in that: The low-temperature high-pressure reaction is carried out under conditions of 0℃~10℃ and 2MPa~5MPa.
8. The method for preparing gas hydrates according to claim 4 or 5, characterized in that: The low-temperature high-pressure reaction time is 1 hour to 24 hours.