Disclosure of Invention
The invention provides a method and a device for preparing solid argon by liquid nitrogen, which can prepare the solid argon with low cost and high efficiency, in particular can prepare crude liquid argon containing oxygen and nitrogen with low cost and high efficiency.
The invention is realized by the following technical scheme:
a method for producing solid argon from liquid nitrogen, comprising:
a placing step: placing the heat-conducting container with the liquid nitrogen in argon-containing liquid; and (3) vacuumizing: vacuumizing the liquid nitrogen until the temperature of the liquid nitrogen is reduced to be less than or equal to minus 196 ℃ to form ultra-cold liquid nitrogen; and cooling the argon-containing liquid by the ultra-cold liquid nitrogen to obtain solid argon.
As a preferred embodiment, the argon-containing liquid has a molar percentage of argon greater than 90%.
In a preferred embodiment, the argon-containing liquid further contains one or both of nitrogen and oxygen; preferably, when the argon-containing liquid only contains argon and nitrogen, the mole percentage content of the nitrogen is less than 10%, and more preferably less than 3%; preferably, when the argon-containing liquid only contains argon element and oxygen element, the mole percentage content of the oxygen element is less than 10%, and more preferably less than 3%; preferably, when the argon-containing liquid contains argon element, nitrogen element and oxygen element, the sum of the mole percentages of the nitrogen element and the oxygen element is less than 10%, and more preferably less than 3%.
As a preferred embodiment, during the vacuum-pumping treatment, a nucleating agent is added into the argon-containing liquid; preferably, the nucleating agent is dry ice particles or ice particles; more preferably, the ratio of the number of moles of molecules of the nucleating agent to the number of moles of argon atoms is less than 0.1% when the addition of the nucleating agent is completed.
An apparatus for producing solid argon from liquid nitrogen, comprising: the device comprises an outer cylinder body, an outer cover body, an inner cylinder body and an inner cover body; wherein the content of the first and second substances,
the outer cylinder is used for containing argon-containing liquid and is provided with a heat insulation layer for internal cold insulation; the heat insulation layer is made of a first heat insulation material; the outer cover body is arranged above the opening end of the outer cylinder body and used for sealing the outer cylinder body; the outer cover body is made of a second heat-insulating material; the inner cylinder is arranged inside the outer cylinder and used for containing liquid nitrogen; the inner cylinder body is made of heat conducting materials; the inner cover body is arranged above the opening end of the inner cylinder body and used for sealing the inner cylinder body; the inner cover body is made of a pressure-resistant material; the outer cylinder body and the outer cover body form an argon-containing liquid bin, and the inner cylinder body and the inner cover body form a liquid nitrogen bin.
As a preferred embodiment, the liquid nitrogen bin is provided with a vacuum interface for connecting with a vacuum pump to carry out vacuum-pumping treatment on the liquid nitrogen; preferably, the vacuum port is disposed on the inner cover.
As a preferred embodiment, the liquid nitrogen bin is provided with a liquid nitrogen channel for liquid nitrogen to enter the inner cylinder body; preferably, the liquid nitrogen channel is arranged on the inner cover body; the argon-containing liquid bin is provided with an argon-containing liquid channel for adding argon-containing liquid into the argon-containing liquid bin; preferably, the argon-containing liquid channel is disposed on the outer cylinder.
As a preferred embodiment, the argon-containing liquid bin is provided with a crystal nucleus channel for adding a nucleating agent into the outer cylinder; preferably, the crystal nucleus channel is disposed on the outer cylinder.
As a preferred embodiment, the outer cover body is arranged right above the inner cover body, and a liquid nitrogen channel and/or a vacuum interface are also arranged on the outer cover body; the liquid nitrogen channel arranged on the outer cover body is aligned with the liquid nitrogen channel arranged on the inner cover body; and/or: the vacuum port disposed on the outer cap is aligned with the vacuum port disposed on the inner cap.
The solid argon prepared by the method and the device is used as an ultralow temperature cold source.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention obtains the ultra-cold liquid nitrogen (can be as low as 210 ℃ below zero) by vacuumizing the liquid nitrogen, and the ultra-cold liquid nitrogen has higher cold density than the conventional liquid nitrogen and larger temperature difference with the argon-containing liquid, can freeze impure argon-containing liquid and promote the rapid growth of solid argon (argon ice).
2. The argon element mole percentage content of the argon-containing liquid for preparing solid argon can reach more than 90 percent, the argon-containing liquid can adopt not only 99.999 percent of refined argon product, but also crude argon containing oxygen and nitrogen, and the production cost is greatly reduced.
3. The device has simple and reasonable structure and can efficiently prepare the solid argon.
4. The solid argon prepared by the method has larger cold density, compared with liquid nitrogen, the cold density in unit volume is about 80 percent higher, and the solid argon can be effectively used as a cold source for freezing and preserving biological specimens.
5. In the vacuumizing process, the nucleating agent is added into the argon-containing liquid bin, so that the production of solid argon is further accelerated.
6. The method is simple and easy to implement, has low cost, is convenient for industrial production of solid argon, and is suitable for popularization and application.
Detailed Description
In a first aspect, the present invention provides a method for producing solid argon from liquid nitrogen, comprising the steps of:
step one, placing: and placing the cooled heat-conducting container containing the liquid nitrogen into the argon-containing liquid, wherein the liquid nitrogen and the argon-containing liquid are separated by the heat-conducting container.
The argon-containing liquid has an argon element mole percent content of greater than 90% (e.g., can be any of 90.5, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or a range of values therebetween).
The argon-containing liquid can be a refined argon product prepared by an air separation plant, wherein the molar percentage of the argon element is 99.999%.
The argon-containing liquid can also comprise argon element, nitrogen element and oxygen element; wherein, when only argon and nitrogen are contained, the mol percentage content of nitrogen in the argon-containing liquid is less than 10% (for example, it can be any value of 9.5%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1% or a numerical range between any two), and is preferably less than 3%; when only argon and oxygen are contained, the molar percentage of the oxygen in the argon-containing liquid is less than 10% (for example, it may be 9.5%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1% or any value range therebetween), and preferably less than 3%; when argon, nitrogen and oxygen are contained, the sum of the mole percentages of the nitrogen and oxygen in the argon-containing liquid is less than 10% (for example, may be any value of 9.5%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1% or a numerical range therebetween), and is preferably less than 3%. The higher the mole percentage of argon in the argon-containing liquid, the more easily solid argon is formed; if the mole percentage of the oxygen element, the mole percentage of the nitrogen element or the sum of the oxygen element and the nitrogen element is more than or equal to 10 percent, the impurities in the argon-containing liquid are too much, and the argon ice cannot be formed at low temperature.
The argon-containing liquid may be, in particular, crude argon (liquid state) before purification in an air separation plant, which comprises argon in a molar percentage of 97.5% and small amounts of oxygen and nitrogen elements.
Step two, vacuumizing: vacuumizing the liquid nitrogen until the temperature of the liquid nitrogen is reduced to be less than or equal to minus 196 ℃ and is reduced to minus 210 ℃ (for example, the temperature can be any value of minus 196 ℃, minus 197 ℃, minus 198 ℃, minus 199 ℃, minus 200 ℃, minus 201 ℃, minus 202 ℃, minus 203 ℃, minus 204 ℃, minus 205 ℃, minus 206, minus 208 ℃, minus 20 ℃, minus 210 ℃ or a numerical range between any two) to form ultra-cold liquid nitrogen; the ultra-cold liquid nitrogen cools the argon-containing liquid to obtain solid argon.
The super-cold liquid nitrogen has higher cold density than the conventional liquid nitrogen and larger temperature difference with the liquid containing argon, and can promote the rapid growth of argon ice.
In order to increase the generation speed of solid argon and improve the production efficiency, the method further comprises the following steps:
during the vacuum-pumping process, when the temperature of liquid argon is reduced to be less than or equal to minus 189 ℃, a nucleating agent is added into the argon-containing liquid until solid argon begins to be generated.
The nucleating agent can be added in the following mode: introducing carbon dioxide gas into the argon-containing liquid, and taking dry ice particles solidified by the carbon dioxide gas as a nucleating agent; the volume of the carbon dioxide gas is about the same as the volume of the argon-containing liquid, and the ratio of the number of moles of carbon dioxide molecules to the number of moles of argon atoms is less than 0.1%.
The nucleating agent can be added in the following mode: introducing argon containing water vapor into argon-containing liquid, and using ice particles solidified by the water vapor as a nucleating agent; preferably, the argon gas containing water vapor is argon gas containing saturated water vapor (that is, the argon gas is mixed with water vapor, and the content of water vapor in the argon gas is saturated), and the temperature of the argon gas containing saturated water vapor is normal temperature.
After the addition of the nucleating agent is finished, the ratio of the number of moles of water molecules to the number of moles of argon atoms (i.e., the sum of the number of moles of argon atoms in the argon-containing liquid and the number of moles of argon atoms in the saturated water vapor-containing argon) is less than 0.1% (for example, may be any of 0.08%, 0.05%, 0.03%, 0.01%, 0.005%, or a numerical range therebetween).
Theoretically, liquid nitrogen and argon-containing liquid can form argon ice through heat exchange; however, if no nucleating agent is added, solid argon (argon ice) has a long formation time and a slow growth rate. The method adopts the simplest inorganic nucleating agents, namely dry ice and ice particles, so that the production speed of the argon ice can be accelerated, and other inorganic nucleating agents (such as talcum powder, calcium carbonate, silicon dioxide, alum, titanium dioxide, calcium oxide, magnesium oxide, carbon black, mica and other most developed cheap and practical nucleating agents) can be prevented from becoming impurities in the argon ice, so that harmful residues are not left after the argon ice is melted and evaporated after use.
Taking 1L as an example, the cold requirement for changing liquid argon into solid argon under normal pressure is as follows:
Q=1×1.398×(0.52×(189-186)+29.5)=43.4KJ,
the cold energy of IL liquid nitrogen is: q is 1 × 0.837 × 200 is 167.4KJ,
it can be seen that 1L of liquid nitrogen can prepare 1L of liquid argon into argon ice when the thermal efficiency is about 30%.
As can be seen from the physical properties of the gases in table 1 below, liquid helium can theoretically produce argon ice as well, but at an excessive cost.
In a second aspect, as shown in fig. 1 to 5, the present invention provides an apparatus corresponding to the above method for producing solid argon from liquid nitrogen, comprising:
the outer cylinder body 1 is a container with an opening at one end and is used for containing argon-containing liquid, and a heat insulation layer 11 is arranged for internal cold insulation; the insulation layer 11 is made of a first insulation material. The heat insulation layer 11 may be disposed inside the outer cylinder 1, or the entire outer cylinder 1 may be made of a heat insulating material, and the outer cylinder 1 corresponds to the heat insulation layer 11. The first insulating material may be a polyolefin foam, polyurethane, aerogel, or vacuum interlayer.
And the outer cover body 2 is arranged on the opening end of the outer cylinder body 1 and is used for sealing the outer cylinder body 1 and simultaneously can be connected with the external atmosphere. The outer cover body is made of a second heat-insulating material; the second heat insulating material may be the same as or different from the first heat insulating material, and preferably adopts high-density polyolefin foam material.
The outer cylinder body 1 and the outer cover body 2 jointly form an argon-containing liquid bin. When the inner cylinder body 3 is vacuumized, the interior of the argon-containing liquid bin is kept cold, and air can be prevented from flowing in, so that the situation that oxygen in the air is liquefied in the argon-containing liquid to influence the preparation of solid argon is avoided.
The inner cylinder 3 is a container with an opening at one end, is arranged inside the outer cylinder 1 and is used as a heat conduction container for containing liquid nitrogen; the inner cylinder 2 is made of a heat conductive material (e.g., aluminum alloy) so that heat exchange between the argon-containing liquid and the liquid nitrogen is sufficiently performed.
An inner cover body 4 arranged on the opening end of the inner cylinder body 3 and used for sealing the inner cylinder body 3 so as to be vacuumized; the inner lid 4 is made of a pressure-resistant material, preferably an aluminum alloy.
The inner cylinder 3 and the inner cover 4 jointly form a liquid nitrogen bin for hermetically containing liquid nitrogen.
The liquid nitrogen bin is provided with a vacuum interface 5 which is used for being connected with a vacuum pump to vacuumize liquid nitrogen; preferably, the vacuum port 5 is provided on the inner lid 4.
The liquid nitrogen bin is also provided with a liquid nitrogen channel 6 for allowing liquid nitrogen to enter the inner cylinder 3 and supplementing the liquid nitrogen consumed in the inner cylinder; the liquid nitrogen channel 6 is preferably arranged on the inner cap 4.
The liquid nitrogen bin and the argon-containing liquid bin are both provided with temperature measuring equipment (such as a thermometer or a temperature sensor; not shown), are preferably arranged on the outer cover body 2 and the inner cover body 4, and can also be arranged on the outer cylinder body 1;
the liquid nitrogen bin is provided with a safety valve (not shown) for air release; the safety valve is used for adjusting the internal pressure of the liquid nitrogen bin to be maintained at an atmospheric pressure.
As a preferred embodiment, as shown in fig. 1 to 5, the outer lid 2 is disposed immediately above the inner lid 4, so that the structure is more compact; thus, the outer cover body 2 is also correspondingly provided with a vacuum interface 5 and/or a liquid nitrogen channel 6; the liquid nitrogen channel arranged on the outer cover body 2 is aligned with the liquid nitrogen channel arranged on the inner cover body 4, so that the pipeline inserted into the liquid nitrogen channel smoothly enters the inner cylinder body 3, and/or: the vacuum ports provided on the outer cap 2 are aligned with the vacuum ports provided on the inner cap 4 so that the lines inserted into the vacuum ports can be smoothly introduced into the inner cylinder 3.
As a preferred embodiment, as shown in fig. 3, the argon-containing liquid bin is further provided with an argon-containing liquid channel 7 for allowing the argon-containing liquid to enter the outer cylinder 1 so as to supplement or add the argon-containing liquid into the outer cylinder 1. An argon-containing liquid passage 7 is preferably provided in the outer cylinder 1.
In the process of preparing solid argon by the device, corresponding pipelines are inserted into the vacuum interface 5 and the liquid nitrogen channel 6, and corresponding equipment is connected (as shown in fig. 5); after the device finishes preparing the solid argon, the outer cover body 2 with the pipeline can be removed; then the pipeline is removed from the inner cover body 4, and the redundant liquid nitrogen is removed from the inner cylinder body 3; a new outer cap 2 without a passage is then fitted over the open end of the outer cylinder 1, so that the device becomes a container for use in the storage and transport of biological samples. When the outer cylinder 1 of the above apparatus is further provided with the crystal nucleus channel 8 and/or the argon-containing liquid channel 7, it is also necessary to close the channel provided in the outer cylinder 1 with a vent plug (e.g., a sponge plug) after the outer cap 2 with the piping is removed.
In a preferred embodiment, when the method for preparing solid argon from liquid nitrogen is also carried out by adding a nucleating agent into the argon-containing liquid, the structure of the device is correspondingly improved:
the argon-containing liquid bin is also provided with a crystal nucleus channel 8 for allowing a nucleating agent to enter the outer cylinder body 1 so as to accelerate the generation speed of solid argon; the crystal nucleus channel 8 is provided on the outer cylinder 1 (as shown in fig. 4).
In a third aspect, the solid argon produced by the method or apparatus is used as an ultra-low temperature cold source, particularly for preserving biological samples.
Compared with liquid nitrogen, the cold energy density in unit volume of the solid argon is higher by about 80 percent; referring to the table one, the first step is shown,
the cold density is calculated as follows: the cold energy of liquid nitrogen A is 200 multiplied by 0.837 is 167.4, and the cold energy of solid argon B is (162.3+29.5) multiplied by 1.616 is 309.9; (A-B)/A is 85.1%.
The principle is as follows: because the temperature difference between liquid argon (-186 ℃) and solid argon (-189 ℃) is narrow under the atmospheric condition, the limited surface of the argon ice is slowly and uniformly melted and volatilized, but not completely and rapidly liquefied and gasified, so that the argon ice is convenient to store and transport in the air and is more suitable to be used as an ultralow temperature cold source.
Watch 1
Note 1: the density of solid argon at the triple point obtained by measuring solid and liquid argon by PVT is 1.616 + -0.004 g/cm3. See https:// www.sciencedirect.com/science/article/abs/pii/0375960167906561.
Note 2: the density of nitrogen at 0 ℃ (32 ° f) and 1 atmosphere was 1.251 g/l, and the density of ultra pure nitrogen at 0 ℃ and 101,325kPa was: 1,251g/L, and a density at 15 ℃ of 1,185 g/L.
Note 3: http:// www.r744.com/files/pdf _088. pdf.
Note 4 https:// www.engineeringtoolbox.com/carbon-dioxide-d _974. html.
Example 1
Example 1 solid argon was prepared using the apparatus of fig. 1 by a method comprising:
(1) filling liquid nitrogen into the inner cylinder 3, covering the inner cover body 4 after the liquid nitrogen surface is stable, and adding a semen argon product into the outer cylinder 1; as shown in fig. 4 for liquid argon level 7 and liquid nitrogen level 8.
(2) The outer cover body 2 is covered at the opening end of the outer cylinder body 1, each pipeline is connected, liquid nitrogen in the inner cylinder body 3 is vacuumized, the vacuum degree in the inner cylinder body 3 is lower than 0.1 standard atmospheric pressure, the temperature of the liquid nitrogen is reduced to 210 ℃ below zero to form ultra-cold liquid nitrogen, and solid argon is generated and grown.
The preparation method of this example compares the following prior art: placing the test tube filled with the semen argon product into a beaker filled with liquid nitrogen, and cooling the semen argon product in the test tube to obtain solid argon; the same weight of solid argon was prepared and the time taken for this example was only less than one third of the prior art.
Example 2
Example 1 solid argon was prepared using the apparatus of fig. 1 by a method comprising:
(1) liquid nitrogen is filled into the inner cylinder 3, after the liquid nitrogen surface is stable, the inner cover body 4 is covered, and then the refined liquid argon product is added into the outer cylinder 1.
(2) And then adding liquid oxygen and liquid nitrogen into the outer cylinder body 1, and uniformly mixing to form argon-containing liquid in the outer cylinder body 1, wherein the molar percentage of oxygen elements is 5%, and the molar percentage of nitrogen elements is 3%.
(3) The outer cover body 2 is covered at the opening end of the outer cylinder body 1, each pipeline is connected, liquid nitrogen in the inner cylinder body 3 is vacuumized, the vacuum degree in the inner cylinder body 3 is lower than 0.1 standard atmospheric pressure, the temperature of the liquid nitrogen is reduced to 210 ℃ below zero to form ultra-cold liquid nitrogen, and solid argon is generated and grown.
The preparation method of the embodiment compares with the following prior art: placing a test tube filled with argon-containing liquid (wherein the mol percent of oxygen element is 5 percent, and the mol percent of nitrogen element is 3 percent) into a beaker filled with liquid nitrogen, and cooling an argon-containing liquid product in the test tube; because the liquid containing argon also contains nitrogen and oxygen elements, solid argon can not be obtained by adopting the prior art.
Example 3
Example 1 solid argon was prepared using the apparatus of fig. 1 by a method comprising:
(1) liquid nitrogen is filled into the inner cylinder 3, after the liquid nitrogen surface is stable, the inner cover body 4 is covered, and crude argon (liquid argon before refining in an air separation plant) is added into the outer cylinder 1 to be used as argon-containing liquid, wherein the argon comprises 97.5% of argon in molar percentage, and a small amount of oxygen and nitrogen.
(2) The outer cover body 2 is covered at the opening end of the outer cylinder body 1, each pipeline is connected, liquid nitrogen in the inner cylinder body 3 is vacuumized, the vacuum degree in the inner cylinder body 3 is lower than 0.1 standard atmospheric pressure, the temperature of the liquid nitrogen is reduced to 210 ℃ below zero to form ultra-cold liquid nitrogen, and solid argon is generated and grown.
The preparation method of the embodiment compares with the following prior art: placing a test tube filled with argon-containing liquid (wherein the mol percent of oxygen element is 5 percent, and the mol percent of nitrogen element is 3 percent) into a beaker filled with liquid nitrogen, and cooling an argon-containing liquid product in the test tube; because the liquid containing argon also contains nitrogen and oxygen elements, solid argon can not be obtained by adopting the prior art.
Example 4
This example used the apparatus of fig. 4 to produce solid argon by a process comprising:
(1) liquid nitrogen is filled into the inner cylinder 3, after the liquid nitrogen surface is stable, the inner cover body 4 is covered, and then the refined liquid argon product is added into the outer cylinder 1.
(2) Covering the outer cylinder body 1 with the outer cover body 2, connecting pipelines, and vacuumizing liquid nitrogen in the inner cylinder body 3; in the process of vacuumizing, when the temperature of the argon-containing liquid is reduced to be lower than minus 189 ℃, a small amount of carbon dioxide gas (the carbon dioxide gas forms dry ice particles as a nucleating agent) is introduced into the outer cylinder 1 until solid argon begins to be generated in the outer cylinder 1. The amount of carbon dioxide gas required is approximately equal to the volume of the argon-containing liquid, and the ratio of the number of moles of carbon dioxide molecules to the number of moles of argon atoms is less than 0.1%.
(3) The vacuum degree in the inner cylinder 3 is lower than 0.1 standard atmospheric pressure, the temperature of the liquid nitrogen is reduced to 210 ℃ below zero to form ultra-cold liquid nitrogen, and the solid argon is continuously generated and grown.
The preparation method of this example compares the following prior art: placing the test tube filled with the semen argon product into a beaker filled with liquid nitrogen, and cooling the semen argon product in the test tube to obtain solid argon; the same weight of solid argon was prepared and the time taken for this example was only less than one third of the prior art and only one half of that of example 1.
Example 5
This example used the apparatus of fig. 4 to produce solid argon by a process comprising:
(1) liquid nitrogen is filled into the inner cylinder 3, after the liquid nitrogen surface is stable, the inner cover body 4 is covered, and then the refined liquid argon product is added into the outer cylinder 1.
(2) Covering the outer cover body 2 at the opening end of the outer cylinder body 1, connecting pipelines, and vacuumizing liquid nitrogen in the inner cylinder body 3; in the process of vacuumizing, when the temperature of the argon-containing liquid is reduced to be lower than minus 189 ℃, a small amount of argon gas containing saturated water vapor (the water vapor forms ice particles to be used as a nucleating agent) is introduced into the outer cylinder body 1 until solid argon begins to be generated in the outer cylinder body 1. The amount of argon containing saturated water vapor is desirably about the volume of the argon-containing liquid, and the ratio of the number of moles of water molecules to the number of moles of argon atoms (i.e., the sum of the number of moles of argon atoms in the argon-containing liquid and the number of moles of argon atoms in the argon-containing saturated water vapor after the addition of the crystal nuclei is completed) is less than 0.1%.
(3) The vacuum degree in the inner cylinder 3 is lower than 0.1 standard atmospheric pressure, the temperature of the liquid nitrogen is reduced to 210 ℃ below zero to form ultra-cold liquid nitrogen, and the solid argon is continuously generated and grown.
The preparation method of this example compares the following prior art: placing the test tube filled with the semen argon product into a beaker filled with liquid nitrogen, and cooling the semen argon product in the test tube to obtain solid argon; the same weight of solid argon was prepared and the time taken for this example was only less than one third of the prior art and only one half of that of example 1.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.