CN108408725B - Gas hydrate generation promoter and preparation method and application thereof - Google Patents
Gas hydrate generation promoter and preparation method and application thereof Download PDFInfo
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- CN108408725B CN108408725B CN201810159185.9A CN201810159185A CN108408725B CN 108408725 B CN108408725 B CN 108408725B CN 201810159185 A CN201810159185 A CN 201810159185A CN 108408725 B CN108408725 B CN 108408725B
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Abstract
The invention provides a gas hydrate generation accelerant and a preparation method and application thereof. The gas hydrate formation promoter comprises the following components by weight percent (100 wt%): 0.03-1 wt% of nano graphite powder, 0.01-0.06 wt% of alkyl diphenyl ether disulfonate and the balance of water. The gas hydrate generation accelerant provided by the invention uses the nano graphite powder and the alkyl diphenyl ether disulfonate to strengthen the mass and heat transfer process of the hydrate, so that the overall time for generating the hydrate can be shortened, and the synthesis efficiency of the hydrate is improved. The accelerant can be well adapted to the existing hydrate generation system, and has strong adaptability to the temperature and pressure conditions in the hydration reaction. Furthermore, the method is simple. The timely heat conduction can also reduce the working load of a refrigeration system (water bath refrigeration, air cooling and the like), and the operation cost is lower.
Description
Technical Field
The invention belongs to the field of gas hydrate preparation, and particularly relates to a gas hydrate generation accelerant and a preparation method and application thereof.
Background
The gas hydrate is a cage complex formed by gas molecules and water molecules under a certain temperature and pressure condition, at present, a series of novel application technologies with good development prospects in respective fields, including hydrate storage and transportation technology, seawater desalination technology, gas separation technology, cold accumulation technology and the like, are developed based on the physicochemical properties of the hydrate, and the premise of industrial large-scale application of the technologies is how to efficiently and quickly generate the hydrate. At present, the generation strengthening of the hydrate mainly adopts a mechanical strengthening mode, and the realization means mainly comprises bubbling, stirring, spraying and the like. Although the method can accelerate the generation process of the hydrate by increasing gas-liquid disturbance, the method has higher operation cost because of needing external power supply. Chemical strengthening is another means to strengthen the formation of hydrates, which is mainly to change the surface tension of gas-liquid interface, so that the gas is more easily captured, thereby accelerating the formation rate of hydrates. The method has great potential in promoting the generation of hydrate, however, the development of a novel hydrate generation promoter is a problem to be solved by the method at present.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a gas hydrate formation promoter.
Another object of the present invention is to provide a method for producing the above gas hydrate formation promoter.
Still another object of the present invention is to provide the use of the above gas hydrate formation promoter for the preparation of a gas hydrate.
In order to achieve the above object, the present invention provides a gas hydrate formation promoter, wherein the gas hydrate formation promoter comprises the following components, by weight, based on the total weight of 100 wt%: 0.03-1 wt% of nano graphite powder, 0.01-0.06 wt% of alkyl diphenyl ether disulfonate and the balance of water.
In the above gas hydrate formation promoter, preferably, the content of the nano graphite powder is 0.1 wt% to 1 wt%.
In the gas hydrate formation promoter, the purity of the graphite nanoparticles is preferably 95% or more.
In the above gas hydrate formation promoter, preferably, the particle size of the graphite nanoparticles is 20nm to 100 nm; preferably 40nm to 80 mn.
In the above-mentioned gas hydrate formation promoter, preferably, the content of the alkyl diphenyl ether disulfonate is 0.02 wt% to 0.04 wt%.
Among the above-mentioned gas hydrate formation promoters, alkyldiphenyloxide disulfonates are known in the art and may be used as usualPrepared by conventional methods, or commercially available. The alkyl chain length of the alkyl diphenyl ether disulfonate is generally C12-C20In the meantime.
The invention also provides a preparation method of the gas hydrate generation accelerant, wherein the method comprises the following steps:
(1) dissolving alkyl diphenyl ether disulfonate in water to prepare a mother solution A;
(2) adding nano graphite powder into the mother solution A;
(3) and fully dispersing the nano graphite powder in the mother solution A to prepare the gas hydrate generation accelerant.
In the above method for producing a gas hydrate formation promoter, it is preferable that in the step (3), the nano graphite powder is dispersed in the mother liquor a by a combination of stirring and ultrasonic treatment.
In the above method for producing a gas hydrate formation promoter, it is preferable that in the step (3), the graphite nanoparticles are dispersed in the mother liquor a by sequentially performing three-stage operations of the first stirring treatment, the ultrasonic treatment, and the second stirring treatment. Dowfax C6L produced by Dowfax chemistry in the United states is one of alkyl diphenyl ether disulfonate, and experiments show that Dowfax C6L used in the three-stage preparation method has a very good matching effect with nano graphite powder, and a remarkable effect obviously caused by other alkyl diphenyl ether disulfonate can be obtained.
In the above method for producing a gas hydrate formation promoter, the conditions of the first stirring treatment are preferably: stirring at 800rpm of 300-; preferably 500 and 700rpm for 30-40 min. Preferably, the ultrasonic treatment conditions are: performing ultrasonic treatment for 15-20 min. Preferably, the conditions of the second stirring treatment are: stirring at 600-; preferably 750 and 850rpm for 30-40 min.
The invention also provides the application of the gas hydrate generation accelerant in preparing the gas hydrate. Preferably, the conditions for preparing the gas hydrate are: the temperature is 0-15 ℃, and the pressure is 0-15 MPa. Under the condition, the induction time for generating the hydrate is 1-5 min.
The scheme provided by the invention has the following beneficial effects:
(1) the gas hydrate generation accelerant provided by the invention uses the nano graphite powder and the alkyl diphenyl ether disulfonate to strengthen the mass and heat transfer process of the hydrate, so that the overall time for generating the hydrate can be shortened, and the synthesis efficiency of the hydrate is improved.
(2) Compared with the traditional hydrate generation accelerant (comprising SDS, SDBS and the like) with a single carbon chain, the gemini surfactant has better compatibilization effect, the using amount is greatly reduced, and the nano graphite powder can flow out along with liquid water after the hydrate is decomposed, so that the gemini surfactant can be repeatedly utilized, and the cost is greatly saved.
(3) The gas hydrate generation accelerant not only can reduce the surface tension of a gas-liquid interface to promote the generation of a hydrate, but also can lead out heat in the reaction process of the hydrate in time, so that the temperature in a reaction kettle is more stable, and on the other hand, the generation process of the hydrate is greatly strengthened.
(4) The gas hydrate generation accelerant can be well adapted to the existing hydrate generation system, and has strong adaptability to the temperature and pressure conditions in the hydration reaction. Furthermore, the method is simple. The timely heat conduction can also reduce the work load of a refrigeration system (water bath refrigeration, air cooling and the like) and reduce the operation cost.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a gas hydrate generation accelerant, which comprises the following preparation processes:
(1) in the total amount of 1000g, nano graphite powder, alkyl diphenyl ether disulfonate (Dowfax C6L) and distilled water are respectively weighed according to the proportion of 0.03%, 0.01% and 99.96% by using an electronic balance, Dowfax C6L is added into the distilled water, and the mother liquor A is obtained by fully stirring.
(2) Adding nano graphite particles into the mother solution A;
(3) stirring at 600rpm for 40min by using a magnetic stirrer, dispersing the stirred liquid by using ultrasonic waves for 18min, stirring the dispersed liquid at 800rpm again, and controlling the stirring time to be about 38min to obtain the gas hydrate generation accelerant. And packaging the prepared solution for later use.
Application experiments:
the application experiment is carried out in a reaction kettle with the volume of 500mL, the gas selected by a laboratory is carbon dioxide, 250mL of the prepared gas hydrate generation accelerant is added into the reaction kettle through a liquid inlet system, the water bath temperature is controlled at 4 ℃ through a water circulation refrigeration system, gas is introduced through a gas inlet system until the pressure in the kettle reaches 3.5MPa, the volume is fixed under the condition that the rotating speed is 300rpm to generate hydrate, and the appearance of hydrate crystal nuclei in a window is observed after 157 s.
Example 2
The embodiment provides a gas hydrate generation accelerant, which comprises the following preparation processes:
(1) weighing nano graphite powder, alkyl diphenyl ether disulfonate (Dowfax C6L) and distilled water respectively by using an electronic balance according to the proportion of 1%, 0.06% and 98.94% in the total amount of 1000g, adding Dowfax C6L into the distilled water, and fully stirring to obtain mother liquor A;
(2) adding nano graphite particles into the mother solution A;
(3) stirring with a magnetic stirrer at 600rpm for 40min, dispersing the stirred liquid with ultrasonic wave for 18min, stirring again at 800rpm for about 38min, packaging the prepared solution, and standing.
Application experiments:
the application experiment is carried out in a reaction kettle with the volume of 500mL, the gas selected by a laboratory is carbon dioxide, 250mL of the prepared gas hydrate generation accelerant is added into the reaction kettle through a liquid inlet system, the water bath temperature is controlled at 4 ℃ through a water circulation refrigeration system, gas is introduced through a gas inlet system until the pressure in the kettle reaches 4MPa, the volume is fixed under the condition that the rotating speed is 300rpm to generate hydrate, and the appearance of hydrate crystal nuclei in a window is observed after 62 s.
Example 3
The embodiment provides a gas hydrate generation accelerant, which comprises the following preparation processes:
(1) in the total amount of 1000g, nano graphite powder, alkyl diphenyl oxide disulfonate (Dowfax C6L) and distilled water are respectively weighed according to the proportion of 0.12%, 0.02% and 99.86% by using an electronic balance, Dowfax C6L is added into the distilled water, and the mother liquor A is obtained by fully stirring.
(2) Adding nano graphite particles into the mother solution A;
(3) stirring at 600rpm for 40min by using a magnetic stirrer, dispersing the stirred liquid by using ultrasonic waves for 18min, stirring the dispersed liquid at 800rpm again, and controlling the stirring time to be about 38min to obtain the gas hydrate generation accelerant. And packaging the prepared solution for later use.
Application experiments:
the application experiment is carried out in a reaction kettle with the volume of 500mL, the gas selected by a laboratory is carbon dioxide, 250mL of the prepared gas hydrate generation accelerant is added into the reaction kettle through a liquid inlet system, the water bath temperature is controlled at 4 ℃ through a water circulation refrigeration system, gas is introduced through a gas inlet system until the pressure in the kettle reaches 3MPa, the volume is fixed under the condition that the rotating speed is 300rpm to generate hydrate, and the appearance of hydrate crystal nuclei in a window is observed after 87 s.
Example 4
The embodiment provides a gas hydrate generation accelerant, which comprises the following preparation processes:
(1) in a total amount of 1000g, nano graphite powder, alkyl diphenyl oxide disulfonate (Dowfax C6L) and distilled water were weighed out by an electronic balance at a ratio of 0.6%, 0.04% and 99.36%, respectively, Dowfax C6L was added to the distilled water, and the mixture was stirred sufficiently to obtain a mother liquor A.
(2) Adding nano graphite particles into the mother solution A;
(3) stirring at 600rpm for 40min by using a magnetic stirrer, dispersing the stirred liquid by using ultrasonic waves for 18min, stirring the dispersed liquid at 800rpm again, and controlling the stirring time to be about 38min to obtain the gas hydrate generation accelerant. And packaging the prepared solution for later use.
Application experiments:
the application experiment is carried out in a reaction kettle with the volume of 500mL, the gas selected by a laboratory is carbon dioxide, 250mL of the prepared gas hydrate generation accelerant is added into the reaction kettle through a liquid inlet system, the water bath temperature is controlled at 4 ℃ through a water circulation refrigeration system, gas is introduced through a gas inlet system until the pressure in the kettle reaches 2.5MPa, the volume is fixed under the condition that the rotating speed is 300rpm to generate the hydrate, and the appearance of hydrate crystal nuclei in a window is observed after 2 min.
Claims (11)
1. A gas hydrate formation promoter, wherein the gas hydrate formation promoter comprises the following components, by weight, based on the total weight of 100 wt%:
0.03-1 wt% of nano graphite powder, 0.01-0.06 wt% of alkyl diphenyl ether disulfonate and the balance of water; the particle size of the nano graphite powder is 20nm-100 nm.
2. A gas hydrate formation promoter according to claim 1, wherein the nano graphite powder is contained in an amount of 0.1 to 1 wt%.
3. A gas hydrate formation promoter according to claim 1, wherein the purity of the graphite nanoparticles is 95% or more.
4. A gas hydrate formation promoter according to claim 1, wherein the nano graphite powder has a particle size of 40nm to 80 mn.
5. A gas hydrate formation promoter according to claim 1, wherein the content of the alkyl diphenyl oxide disulfonate is 0.02 wt% to 0.04 wt%.
6. A method for producing a gas hydrate formation promoter as claimed in any one of claims 1 to 5, wherein the method comprises the steps of:
(1) dissolving alkyl diphenyl ether disulfonate in water to prepare a mother solution A;
(2) adding nano graphite powder into the mother solution A;
(3) and fully dispersing the nano graphite powder in the mother solution A to prepare the gas hydrate generation accelerant.
7. The preparation method according to claim 6, wherein in the step (3), the nano graphite powder is dispersed in the mother liquor A by using a combination of stirring and ultrasonic treatment.
8. The preparation method according to claim 6, wherein in the step (3), the nano graphite powder is dispersed in the mother liquor A by sequentially adopting three-stage operation of the first stirring treatment, the ultrasonic treatment and the second stirring treatment.
9. The production method according to claim 8, wherein the conditions of the first agitation treatment are: stirring at 800rpm of 300-; the ultrasonic treatment conditions are as follows: performing ultrasonic treatment for 15-20 min; the conditions of the second stirring treatment are as follows: stirring at 600-.
10. Use of a gas hydrate formation promoter according to any one of claims 1 to 5 in the preparation of a gas hydrate.
11. Use according to claim 10, wherein the conditions for preparing the gas hydrate are: the temperature is 0-15 ℃, and the pressure is 0-15 MPa.
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| CN201810159185.9A CN108408725B (en) | 2018-02-26 | 2018-02-26 | Gas hydrate generation promoter and preparation method and application thereof |
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| WO2012030181A2 (en) * | 2010-09-01 | 2012-03-08 | 한국화학연구원 | Accelerator for preparation of natural gas hydrate |
| CN103663451B (en) * | 2013-11-18 | 2016-04-13 | 常州大学 | A kind of gas hydrate promoter for generation and preparation method thereof |
| CN103962078B (en) * | 2014-04-25 | 2016-05-04 | 常州大学 | A kind of gas hydrate promoter for generation |
| CN104437290B (en) * | 2014-11-24 | 2017-01-11 | 常州大学 | Compound gas hydrate generation accelerant and preparation method thereof |
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