CN114015487B - Preparation method of nano ice hydrate - Google Patents
Preparation method of nano ice hydrate Download PDFInfo
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- CN114015487B CN114015487B CN202111324404.2A CN202111324404A CN114015487B CN 114015487 B CN114015487 B CN 114015487B CN 202111324404 A CN202111324404 A CN 202111324404A CN 114015487 B CN114015487 B CN 114015487B
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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Abstract
The invention discloses a preparation method of a nano ice hydrate, belonging to the technical field of natural gas hydrates. The method comprises the following steps: sequentially putting deionized water, nano metal particles and a copper mesh into a reaction kettle, winding a coil of the reaction kettle, cooling in a refrigerating fluid of ethylene glycol, controlling the temperature, introducing gas into the reaction kettle at the temperature of 0.5-5 ℃ and the pressure of 4.6-5MPa, setting alternating current with the voltage of 220V, intermittently adding the deionized water, and irradiating by using an infrared lamp after the deionized water is added to obtain the nano ice hydrate. The method has the advantages of short time for synthesizing the nano ice hydrate, nano-grade obtained ice hydrate, capability of controlling the size of particles, no pollution, capability of detecting various ice hydrate micro-morphologies and structures and wide application range.
Description
Technical Field
The invention belongs to the technical field of natural gas hydrates, and particularly relates to a preparation method of a nano ice hydrate.
Background
In the world, the environmental pollution is serious, the energy crisis is aggravated, and people urgently need to develop new energy to replace the traditional energy. The global natural gas hydrate is widely existed in deep sea or frozen soil, the reserve of the global natural gas hydrate is twice of that of the existing natural gas and petroleum, and the global natural gas hydrate has wide development prospect. The development and utilization of natural gas hydrate are closely concerned and researched in all countries of the world, but the industrialized exploitation needs to be realized, and a long way is needed. The ice hydrate with a large macroscopic scale can be prepared to observe and research the macroscopic morphological characteristics of the ice hydrate. However, the hydrate obtained by the conventional method has large size, and the micro appearance and the structure of the hydrate cannot be observed. Therefore, a method for preparing nano-scale hydrate is urgently needed to observe the micro-morphology and the structure of the ice hydrate.
Disclosure of Invention
The invention aims to provide a preparation method of a nano ice hydrate, which has important significance for exploring generation of the hydrate and development and utilization of a natural gas hydrate.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for preparing nano ice hydrate comprises the following steps:
sequentially putting deionized water, nano metal particles and a copper mesh into a reaction kettle, winding a coil of the reaction kettle, cooling in a refrigerating fluid of ethylene glycol, controlling the temperature, introducing gas into the reaction kettle at the temperature of 0.5-5 ℃ and the pressure of 4.6-5MPa, setting alternating current with the voltage of 220V, intermittently adding the deionized water, and irradiating by using an infrared lamp after the deionized water is added to obtain the nano ice hydrate.
The material of reation kettle is corrosion-resistant stainless steel material, and the winding circular telegram coil produces the magnetic field, and the primary motion is produced to nano-metal particle under gaseous effect, and the nano-metal particle of motion is cutting magnetic induction line motion under the effect in magnetic field, produces the electric current, and final nano-metal particle is random motion on the surface of water, avoids the metal particle reunion, and the sample is more dispersed, is favorable to observing.
Further, the nano metal particles are one of Pd, Pt, Cu, Au, Ag and Cu.
Furthermore, the water bath tank is connected with the constant temperature refrigerator, and the ethylene glycol cooling liquid circularly flows between the constant temperature refrigerator and the water bath tank to keep the temperature of the water bath tank constant; the target temperature (0.5-5 ℃) is the temperature of the cooling liquid in the water bath tank, and the temperature of the refrigerating machine is generally slightly lower than the temperature of the cooling liquid in the water bath tank because heat loss is generated in the circulation process. After the target temperature is reached in the water bath box, the 220V alternating current is conducted to the coil wound on the reaction kettle, the irregular motion of the metal nanoparticles is promoted, and because the ethylene glycol cooling liquid is not conductive, no electric field exists in the water bath box, and the safety coefficient of the device is increased.
Furthermore, the particle size of the nano metal particles is 5-100nm, which can provide nucleation points for the nano ice hydrate and promote the nucleation and growth of the nano ice hydrate.
Further, the diameter of the copper mesh is 3 mm.
Further, the gas is carbon dioxide, methane or ethane.
Further, the intermittent process specifically means injecting 1ml of deionized water every 5min, and repeating the process for 5 times.
The total capacity of the reaction kettle is 10ml, 1ml of deionized water is filled in the reaction kettle before reaction and is used for bearing copper meshes and nano metal particles, a water inlet pipe is provided with 2 channels, a gas channel I is introduced into the reaction kettle and is controlled by a switch to keep a closed state; the air path II is communicated to the atmosphere, and is still controlled by a switch to be kept in an open state; and (4) opening the gas circuit I and closing the gas circuit II at an interval of 5min, keeping the gas circuit for 30S, injecting 1ml of deionized water each time, and repeating for 5 times. The nano-ice hydrate particles and water drops float and converge on the water surface.
The alternating current of 220V generates a magnetic field, so that the nano metal particles move randomly.
The upper end of the reaction kettle is a cover spliced by annular glass and circular stainless steel, the infrared lamp irradiates the reaction kettle through the glass, the nano metal particles are heated and conducted, the size of the nano ice hydrate can be controlled by controlling the intensity, distance and time of the infrared lamp, and the wavelength of the infrared lamp is 850 nm. After the deionized water is injected, the infrared lamp is turned on in the process of generating the nano ice hydrate, the nano metal particles are irradiated to generate micro heat, the hydrate is melted while being formed, the size of the ice hydrate can be controlled, and the size of the prepared nano ice hydrate is about 70nm-10 mu m.
The invention also provides a method for observing the microstructure of the nano ice hydrate, which is to transfer the nano ice hydrate to a sample rod in a liquid nitrogen environment and observe the nano ice hydrate by using a transmission electron microscope.
Compared with the prior art, the invention has the beneficial effects that:
in the traditional method for generating the natural gas hydrate, the obtained hydrate has large size, the size of the hydrate cannot be adjusted, and the obtained hydrate cannot be used for observing the microstructure of the atomic size; the method has the advantages of short time for synthesizing the nano ice hydrate, nano-grade obtained ice hydrate, capability of controlling the size of particles, no pollution, capability of detecting various ice hydrate micro-morphologies and structures and wide application range.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a device for preparing a nano ice hydrate according to the present invention;
FIG. 2 is a schematic structural diagram of a device for observing nano ice hydrate in accordance with the present invention;
FIG. 3 is a transmission electron microscope image of the nano-ice hydrate prepared in example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
FIG. 1 is a diagram of a device for preparing a nano ice hydrate.
FIG. 2 is a diagram of an observation device for nano-ice hydrate in the invention.
Adding 1ml of deionized water (the volume is 10ml) into a reaction kettle, adding nano metal particles such as Pd/Pt/Cu/Au/Ag/Cu and the like, then placing a copper net with the diameter of 3mm into the reaction kettle, winding coils around the closed reaction kettle, placing the reaction kettle in a water bath box, continuously introducing reaction gas into the reaction kettle after the temperature reaches the target temperature (0.5-5 ℃), and keeping the pressure stable (4.6-5 MPa); then, an alternating current of 220V is applied to generate a magnetic field, and the nano metal particles move randomly. The pressure pump (as shown in figure 1) is turned on, the switch on the water injection pipe is closed every 5min, and the pressure is kept closed for 30S, and then high-pressure water enters the reaction kettle through the nozzle (the water injection amount is 1ml each time and lasts for 5 times). The infrared lamp is turned on, the nano metal particles are irradiated to generate micro heat, and the nano ice hydrate is melted while being formed, so that the size of the nano ice hydrate can be controlled.
1ml of deionized water is injected into the reaction kettle in advance, and the copper mesh is placed in the reaction kettle and floats on the water surface.
The gas species is CO2、CH4、C2H6And the like.
The material of reation kettle is corrosion-resistant stainless steel material, and the winding circular telegram coil produces the magnetic field, and the primary motion is produced to nano-metal particle under gaseous effect, and the nano-metal particle of motion is cutting magnetic induction line motion under the effect in magnetic field, produces the electric current, and final nano-metal particle is random motion on the surface of water, avoids the metal particle reunion, and the sample is more dispersed, is favorable to observing.
The water bath tank is connected with the constant temperature refrigerator, and the ethylene glycol cooling liquid circularly flows between the constant temperature refrigerator and the water bath tank to keep the temperature of the water bath tank constant; the target temperature (0.5-5 ℃) is the temperature of the cooling liquid in the water bath tank, and the temperature of the refrigerating machine is generally slightly lower than the temperature of the cooling liquid in the water bath tank because heat loss is generated in the circulation process. After the target temperature is reached in the water bath box, 220V alternating current is conducted to the coil wound on the reaction kettle, irregular movement of the nano metal particles is promoted, and the ethylene glycol cooling liquid is not conductive, so that no electric field exists in the water bath box, and the safety coefficient of the device is increased.
The particle size of the nano metal particles is 5-100nm, and the nano metal particles can provide nucleation points for the nano ice hydrate and promote the nucleation and growth of the nano ice hydrate.
The total capacity of the reaction kettle is 10ml, 1ml of deionized water is filled in the reaction kettle before reaction and is used for bearing copper meshes and nano metal particles, a water inlet pipe is provided with 2 channels, a gas channel I is introduced into the reaction kettle and is controlled by a switch to keep a closed state; the air channel II is communicated to the atmosphere, and is still controlled by a switch to be kept in an open state; and (4) opening the gas circuit I and closing the gas circuit II at an interval of 5min, keeping the gas circuit for 30S, injecting 1ml of deionized water each time, and repeating for 5 times. The water is injected into the reaction kettle through a nozzle and is in a fog shape, and the water can be fully mixed with gas, so that the generation of nano ice hydrate is promoted, and nano ice hydrate particles and water drops float and converge on the water surface.
The upper end of the reaction kettle is a cover spliced by annular glass and circular stainless steel, the infrared lamp irradiates the reaction kettle through the glass, the nano metal particles are heated and conducted, the size of the nano ice hydrate can be controlled by controlling the intensity, distance and time of the infrared lamp, and the wavelength of the infrared lamp is 850 nm. After the deionized water is injected, the infrared lamp is turned on in the process of generating the nano ice hydrate, the nano metal particles are irradiated to generate micro heat, the hydrate is melted while being formed, the size of the ice hydrate can be controlled, and the size of the prepared nano ice hydrate is about 70nm-10 mu m.
The embedded copper mesh is placed on a frozen sample rod, the sample is always soaked in the environment of liquid nitrogen in the sample loading and transferring processes, and then the sample rod is loaded on a sample platform to observe the morphology and structure of the nano ice hydrate by using a transmission electron microscope (the device is shown in figure 2).
Example 1
Adding 1ml of deionized water (the volume is 10ml) into a reaction kettle, adding Pt particles with the diameter of 10nm, then placing a copper net with the diameter of 3mm into the reaction kettle, winding coils around the sealed reaction kettle, placing the reaction kettle in a water bath tank (cooling and controlling the temperature in ethylene glycol refrigerating fluid), continuously introducing reaction gas methane into the reaction kettle when the target temperature reaches 0.5 ℃, and keeping the pressure at 4.6 MPa; then, an alternating current of 220V was applied to generate a magnetic field, and the nano Pt particles moved randomly. The pressure pump is turned on, the switch on the water injection pipe is closed every 5min, and the pressure is kept closed for 30S, and then high-pressure water enters the reaction kettle through the nozzle (the water injection amount is 1ml each time and lasts for 5 times). And (3) turning on an infrared lamp, wherein the wavelength of the infrared lamp is 850nm, the distance between the infrared lamp and the upper end cover of the reaction kettle is 50cm, the irradiation is carried out for 2min, the nano Pt particles are irradiated to generate micro heat, the nano ice hydrate is melted while being formed, and finally, an equilibrium state is achieved. When the total reaction time is 10min, methane hydrate is generated, and the particle size of the methane hydrate is 70-200 nm.
The generated methane hydrate is loaded on a copper net, the embedded copper net is transferred to a sample rod, the sample is always soaked in a liquid nitrogen environment in the transfer process, and a transmission electron microscope is used for observation, so that the result is shown in fig. 3. FIG. 3 shows a high resolution (small graph) of methane hydrate and the corresponding electron diffraction pattern (large graph) in which the interplanar spacing is 2.69 ANGSTROM and the corresponding crystal plane is (102), and the interplanar spacing of the three diffraction rings in the electron diffraction pattern is 1.43 ANGSTROM, 1.64 ANGSTROM and 2.69 ANGSTROM, which correspond to crystal planes (105), (203) and (102), respectively.
The reaction kettle and the temperature sensor are both arranged in a water bath box, the target temperature required in the experiment is 0.5-5 ℃, and the temperature in the reaction kettle is kept above 0 ℃. It is known that water is liquid at temperatures above 0 ℃, CH4、C2H2Waiting for the gas to be gaseous; in the reaction process, small solid particles are generated in the reaction kettle, and further the generation of ice hydrate can be judged.
Example 2
Adding 1ml of deionized water (the volume is 10ml) into a reaction kettle, adding nano Au particles with the particle size of 10nm, putting a copper mesh with the diameter of 3mm into the reaction kettle, winding coils around the closed reaction kettle, putting the reaction kettle into a water bath tank (cooling and controlling the temperature in ethylene glycol refrigerating fluid), continuously introducing reaction gas ethane into the reaction kettle when the target temperature reaches 0.5 ℃, and keeping the pressure at 5 MPa; then, an alternating current of 220V is applied to generate a magnetic field, and the nano Au particles move randomly. The pressure pump is turned on, the switch on the water injection pipe is closed every 5min, and the pressure is kept closed for 30S, and then high-pressure water enters the reaction kettle through the nozzle (the water injection amount is 1ml each time and lasts for 5 times). And (3) turning on an infrared lamp, wherein the wavelength of the infrared lamp is 850nm, the distance between the infrared lamp and a cover at the upper end of the reaction kettle is 50cm, irradiating for 3min, generating micro heat by irradiating the nano Au particles, melting the nano ice hydrate while forming, and generating ethane hydrate when the total reaction time is 15min, wherein the grain diameter of the ethane hydrate is 70-150 nm.
Example 3
The difference from example 1 is that the temperature is 2 ℃.
Example 4
The difference from example 1 is that the temperature is 5 ℃.
Example 5
The difference from example 1 is that the pressure is 3 MPa.
The observation of the methane hydrate obtained in example 3-5 by using a transmission electron microscope revealed that, under the same conditions, the lower the temperature, the higher the pressure, and the more easily the nano-ice hydrate is formed. The nano ice hydrate is prepared at the temperature of 0.5 ℃, so that the interference of water freezing to ice can be eliminated, and the temperature is low, thereby being beneficial to the generation of the ice hydrate. After the temperature exceeds 5 ℃, the pressure required for forming the hydrate is large, the time is long, and the ice hydrate is difficult to generate.
Comparative example 1
The difference from example 1 is that no nano-Pt particles were added.
As a result, it was found that: hydrates agglomerate together and the particle size is not uniform.
Comparative example 2
The difference from example 1 is that no infrared lamp irradiation was performed.
As a result, it was found that: the hydrate particles are dispersed, and the particle size is large and is not uniform.
Comparative example 3
The difference from example 1 is that the deionization was added all continuously.
As a result, it was found that: the time for hydrate formation is prolonged and the gas cannot be sufficiently mixed with deionized water.
Comparative example 4
The difference from example 1 is that the distance between the infrared lamp and the upper end cap of the reaction vessel was 80 cm.
As a result, it was found that: the size of the generated hydrate is large, the particles become thick, and high-resolution imaging cannot be well performed.
Comparative example 5
The difference from example 1 is that the infrared lamp was irradiated for 5 min.
As a result, it was found that: the size of the generated hydrate is large, the particles become thick, and high-resolution imaging cannot be well performed.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A preparation method of a nanometer ice hydrate is characterized by comprising the following steps:
sequentially putting deionized water, nano metal particles and a copper mesh into a reaction kettle, winding a coil of the reaction kettle, cooling in a refrigerating fluid of ethylene glycol, controlling the temperature, introducing gas into the reaction kettle at the temperature of 0.5-5 ℃ and the pressure of 4.6-5MPa, setting alternating current with the voltage of 220V, intermittently adding the deionized water, and irradiating by using an infrared lamp after the deionized water is added to obtain the nano ice hydrate;
the nano metal particles are one of Pd, Pt, Au, Ag and Cu;
the particle size of the nano metal particles is 5-100 nm;
the intermittence specifically means that 1mL of deionized water is injected every 5min and repeated for 5 times.
2. The method of claim 1, wherein the copper mesh has a diameter of 3 mm.
3. The method of claim 1, wherein the gas is carbon dioxide, methane, or ethane.
4. The method of claim 1, wherein the infrared lamp has a wavelength of 850 nm.
5. A method for observing the microstructure of the nano ice hydrate, which is characterized in that the nano ice hydrate prepared by the preparation method of any one of claims 1 to 4 is transferred into a sample rod in a liquid nitrogen environment and observed by using a transmission electron microscope.
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