JP2007113850A - Object provided with surface having possibility of adherence of nonaqueous matter, treatment method for object surface, and treatment system for object - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent a nonaqueous matter from adhering on an object surface and to increase its sliding characteristic, and at the same time, to provide a rigid object with durability, more suited to an actual operating environment. <P>SOLUTION: A surface treatment film having affinity with a matter different from the nonaqueous matter is formed on a surface of the object having the possibility of adherence of the nonaqueous matter produced by heat exchange with a heat source of zero degrees or more, and placed in an environment having the matter different from the nonaqueous matter. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a technique that makes it difficult to attach a non-aqueous substance to a surface of the object by applying a hydrophilic surface treatment to the surface of the object, thereby facilitating slipping of the non-aqueous substance attached to the surface. Specific examples of non-aqueous substances are clathrate hydrates and other clathrate compounds, but are limited to those produced by heat exchange. A specific example of the hydrophilic surface treatment is formation of an inorganic hydrophilic coating film, and an inorganic hydrophilic coating film having a glass structure is suitable as the inorganic hydrophilic coating film.

Here, in the context of the present invention or in the context of the description thereof, the definitions of the following terms (in brackets) are as set forth below.
(1) “Object” refers to all tangible materials that require prevention of adhesion of non-aqueous substances or increase in slipping properties of clathrate compounds. Specifically, clathrate compounds are produced, transported, contained, etc. This includes any thing that has a part that can come into contact with the clathrate compound during handling or work, and more specifically, the clathrate compound is a heat storage medium (a heat storage medium that flows or flows for the purpose of heat transfer). This includes and includes pipes, valve valves, heat exchangers, storage tanks, heat storage containers, sensor housings of measuring instruments, etc. in thermal energy storage systems and air conditioning systems used as
(2) “Coating” refers to a film disposed on the outer surface of an object and covering the outer surface.
(3) “Object surface”, “Object surface” or “Surface” of an object refers to the outer surface of the object, and when a coating is formed on the outer surface, unless otherwise specified. The outer surface of the coating.
(4) “Paint” refers to a liquid substance that forms a thin film on the surface of the object after application to the surface of the object by evaporation of the solvent or chemical reaction (Iwanami Rikagaku Dictionary 4th Edition).
(5) “Inorganic paint” refers to a paint whose main raw material is inorganic, regardless of whether the solvent is water or non-water, but an organic paint, that is, a paint mainly containing an organic substance Are distinguished.
(6) “Coating film” refers to a film formed by painting, that is, coating and drying / curing or baking.
(7) “Inorganic hydrophilic coating” refers to coating for imparting a hydrophilic function to the surface of an object using an inorganic coating.
(8) “Inorganic hydrophilic coating film” means a hydrophilic coating film formed on the surface of an object by inorganic hydrophilic coating.
(9) “Hydrophilic surface treatment” refers to a treatment for imparting a hydrophilic function to an object surface, and includes inorganic hydrophilic coating.
(10) “Hydrophilic surface treatment film” refers to a film having a hydrophilic function formed on the surface of an object by hydrophilic surface treatment, and includes an inorganic hydrophilic coating film.
(11) “Surface treatment” refers to treatment for imparting some function to the surface of an object, and includes hydrophilic surface treatment.
(12) “Surface treatment film” refers to a film having some function formed on the surface of an object by surface treatment, and includes a hydrophilic surface treatment film.
(13) The “clathrate compound” is a molecule called a host or a host substance or other molecule called a guest substance in a tunnel-like, layer-like, network-like or cage-like structure (inclusion lattice) formed by the compound. Alternatively, it refers to a substance that is formed when a substance enters or is taken in. Examples of the host substance include water, cyclodextrin, and non-water such as the substance disclosed in Patent Document 7. In particular, a clathrate compound in which the host substance is water is called “clathrate hydrate”. Examples of guest materials include alkyl ammonium salts, alkyl phosphonium salts, alkyl sulfonium salts, or a mixture of two or more thereof.

Examples of alkylammonium salts, alkylphosphonium salts, and alkylsulfonium salts include those represented by the general structural formulas (a), (b), and (c), respectively.

In the general structural formulas (a), (b), and (c), R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group having 1 to 5 carbon atoms or hydrogen, at least one of which is a methyl group, An alkyl group such as an ethyl group, a propyl group, a butyl group, or an amyl group. Further, X ^- represents an anion, for example, fluorine ions, chlorine ions, and halogen ions such as bromide ion, nitrate ion, a hydroxyl ion or the like.

  A gas hydrate in which methane or carbon dioxide is incorporated as a guest substance into a cage structure of water molecules is also an inclusion compound (especially an inclusion hydrate).

(14) “Non-aqueous substances” refer to substances other than water and ice. Focusing on the relationship between water molecules, (a) water molecules are essential components but components other than water molecules are also essential. It can be divided into substances other than (a) such as inclusion substances (eg clathrate hydrates) and (a) clathrate compounds other than clathrate hydrates, and the production temperature of non-aqueous substances due to heat exchange In particular, non-aqueous substances can be classified into (c) a substance generated by heat exchange with a refrigerant or a cold heat source having a temperature higher than the solidification temperature of water or zero degrees Celsius, and a substance other than (d) (c).
(15) The “non-aqueous substance generation solution” refers to a solution in which a substance that generates a non-aqueous substance by heat exchange is dissolved in an appropriate solvent. In this case, a non-aqueous substance that is an clathrate compound is referred to as an “clathrate compound generation solution”, and a non-aqueous substance that is an clathrate hydrate is referred to as an “clathrate hydrate generation solution”. A solvent substance that dissolves a substance that generates a non-aqueous substance is different from the non-aqueous substance. More specifically, the solvent substance of the non-aqueous substance generation solution may be a constituent molecule of the non-aqueous substance, but not the non-aqueous substance itself, the solvent substance of the inclusion compound generation solution is the host substance of the inclusion compound. In some cases, it is not the inclusion compound itself. The terms “clathrate compound forming solution” and “clathrate hydrate forming solution” are defined regardless of the difference between the solvent substance and the host substance in each solution.
(16) “Supercooling” in the non-aqueous substance generating solution is a temperature at which the non-aqueous substance is generated in the non-aqueous substance generating solution (hereinafter referred to as “non-aqueous substance generating temperature”. Is called the “clathrate compound formation temperature”, and when the non-aqueous substance is clathrate hydrate, it is called “clathrate hydrate formation temperature”). A phenomenon in which a non-aqueous substance is not immediately generated in a product solution or a state of a non-aqueous substance production solution in which the phenomenon occurs, and “degree of supercooling” means the degree.

For example, an inclusion compound (inclusion hydration) in which the host material is water and the guest material is tetra-n-butylammonium bromide ((C ₄ H ₉ ) ₄ NBr) (hereinafter referred to as “TBAB”), which is a kind of alkylammonium salt Is about 4 degrees when the mass concentration of TBAB in the aqueous solution is 6%, about 6.7 degrees when the mass concentration is 10%, and about 9 degrees when the mass concentration is 20% (both in Celsius). Although it is a product formation temperature, even if it cools below each clathrate hydrate production temperature, if some time does not pass, the clathrate hydrate of TBAB may not be produced | generated in aqueous solution. Such a phenomenon or a state where the phenomenon occurs is supercooling in the aqueous solution.

(17) “Adhesion” of a substance means that the substance does not adhere to the object surface. For example, this is the case where an object surface at a temperature below the clathrate compound formation temperature is in contact with the clathrate compound formation solution and the clathrate compound produced as a result of heat exchange remains attached to the object surface. .
(18) “Adhesiveness” of a substance refers to a property in which an inclusion compound or other non-aqueous substance does not adhere to the surface of the object, or is difficult to leave, or a non-aqueous substance adheres to the object surface. It refers to the likelihood of the adhesion or the degree of the likelihood of the adhesion. In the case where the non-aqueous substance is reattached after being detached from the surface of the object, the ease of the reattachment or the degree of the ease of the reattachment is included. The adhesion of the non-aqueous material is defined regardless of the likelihood of the nucleation of the non-aqueous material on the surface of the object or the degree of the probability of the nucleation.
(19) “Preventing adhesion” or “preventing adhesion” of a substance refers to suppressing, avoiding or preventing the adhesion of the substance to the surface of an object.
(20) “Sliding” of a substance means that the substance attached to the surface of the object is released from the state of slipping, peeling off, or being removed from the surface, and “sliding” of the substance is The property that the substance attached to the surface of the object slips off from the surface, or the property that the substance attached to the surface of the object slips easily. Say degree. Inclusion compounds and other non-aqueous substances can be easily slipped off, and the amount of non-aqueous substances can be reduced or easily reduced. Also, non-aqueous substances can hardly be slipped off and the amount of non-aqueous substances can be increased or decreased. There is a qualitative tendency to make it easier.
(21) “Forced force”, particularly “forced force” that promotes slipping of an object attached to the surface of an object refers to a force acting so that the inclusion compound attached to the object surface is likely to slip. The forcing force is (A) a force created artificially for the purpose of slipping off the substance and (B) a force that does not fall under (A). It can be categorized as one that exhibits the effect of slipping off the compound. The latter (B) can be divided into (B-1) that corresponds to artificially generated force and (B-2) that does not correspond to artificially generated force. For example, when slipping between the surface of an object and a non-aqueous material attached thereto is a problem, since gravity acting on the non-aqueous material is not an artificially generated force (A) and (B It does not fall under -1) and directly corresponds to the force that exerts the effect of slipping off non-aqueous substances, so it does not fall under (B-2), and therefore does not fall under forcing. However, after the non-aqueous material slips off due to natural force, it collides with another non-aqueous material adhering to another place on the surface of the object, and the other non-aqueous material slips off due to the impact at that time Although the impact force does not correspond to (A), it corresponds to (B-2), and thus corresponds to the forcing force. In addition, when the non-aqueous material is generated in the container by exchanging heat between the non-aqueous material generating solution in the container and the refrigerant outside the container using the container wall as the heat exchange surface, the container wall in the container is scraped off. The scraping force (shearing force) when sliding off non-aqueous substances and the vibration force when urging the container wall surface to urge sliding off non-aqueous substances fall under (A) and rotate or move within the container. Viscosity of non-aqueous substance generation solution (including slipped non-aqueous substance particles or the slurry when the particles are dispersed and slurried in non-aqueous substance generation solution), turbulent flow generated near the container wall (container wall Adhered to or generated on the wall of the container due to collisions with non-aqueous substances after sliding, including turbulent flow that occurs in the vicinity, turbulent flow that occurs downstream of deformed parts of the surface, and turbulent flow that occurs due to temporary increase or decrease of liquid Or grown non-aqueous substances Force acting on the non-aqueous material when slipping occurs corresponds to (B-1).
(22) “Hydrophilic” refers to “a property of a substance having a large interaction with water and a high affinity” (Iwanami Dictionary of Physical and Chemical Dictionary, 5th edition). The term “superhydrophilic” may be defined according to the degree of wettability of the coating (especially the contact angle) or because it also has special properties such as a photocatalytic effect, which are also included in hydrophilicity. .
(23) “Hydrophilization” means giving or having a hydrophilic function.
(24) “Heat source” means a supply source of heat energy necessary for generating a substance. When a non-aqueous substance or an inclusion compound is generated by heat exchange with a refrigerant or a cold heat source, the refrigerant or the cold heat source is Included in the heat source.

  For the purpose of preventing adhesion of substances on the surface of an object, it is one of the conventional means to perform surface treatment on the surface of the object in advance. For example, when the substance is ice, snow and ice are prevented from adhering by forming a water-repellent coating film on the object surface (Patent Document 1), and by forming a water-repellent region and a hydrophilic region on the object surface, van der The difference of the Waals force is made up, thereby promoting the slipping of the ice on the surface (Patent Document 2). Further, when ice is produced by heat exchange with the object surface, the heat exchange surface is coated with a water-repellent paint to promote slipping of ice from the heat exchange surface (Patent Document 3). Furthermore, the generation | occurrence | production of the water droplet adhering to the surface of a fin and a heat exchanger tube is prevented by performing the hydrophilic treatment to the fin and heat exchanger tube of a heat exchanger (patent document 4, patent document 8).

  However, none of these conventional techniques is used to treat the surface of an object for the purpose of preventing adhesion of inclusion compounds and other non-aqueous substances, but non-aqueous systems that are generated by heat exchange with a heat source of zero degrees Celsius or higher. The surface of the object is not subjected to surface treatment for the purpose of preventing adhesion of substances. In addition, none of these conventional techniques are used for surface treatment of the object surface for the purpose of preventing adhesion of non-aqueous substances generated by heat exchange with a heat source of zero degrees Celsius or higher. In addition, a hydrophilic film is not formed on the object surface, particularly on the heat exchange surface.

  When a clathrate compound is produced using a heat exchanger and used as a heat storage medium, the heat exchange surface of the heat exchanger, the inner wall surface of the piping or heat storage container, the valve valve body surface, or the sensor housing of the measuring device The clathrate compound adheres, causing clogging, sometimes resulting in thermal resistance, causing fluctuations in production over time, and hindering stable production. Problems caused by the inclusion of such clathrate compounds are not limited to the case where clathrate compounds are used as a heat storage medium, regardless of the purpose of use, and the operation, performance, and operating status of the devices and systems that produce clathrate compounds. For example, when a gas mixture is concentrated and separated by utilizing the characteristics of the clathrate compound (see Patent Literature 5 and Patent Literature 6), the clathrate compound When a technology that utilizes the characteristics of the above is put into practical use, it becomes manifest as a technical obstacle. However, the technology that prevents the inclusion of the clathrate compound on the surface of the object has not received much attention in the past because of the fact that the technology that utilizes the characteristics of the clathrate compound has not been put into practical use. Was not progressing.

  When an inclusion compound or other non-aqueous substance adheres to the surface of the object and this becomes a technical obstacle, it is necessary to remove the non-aqueous substance. When removing the non-aqueous material, a forcing force may be applied to the surface of the object to which it is attached. For example, this applies to a case where non-aqueous substances attached to the surface of an object are scraped with a brush or brush, a mechanical impact is applied by hitting with a hammer, or a mechanical vibration is applied by operating an ultrasonic vibrator. However, it is not necessary to intentionally apply a forcing force for the purpose of removing deposits, and there are many cases where a certain forcing force acts on the object in an environment where the object is actually used. Therefore, when a coating is formed by applying a surface treatment to the surface of an object, thereby preventing the adhesion of non-aqueous substances, the coating must be strong and durable enough to resist forcing. Become. When a film with insufficient strength and durability is formed on the surface, the application of the object is naturally narrow.

  The present invention has been made in view of the above points, and is generated by heat exchange with a non-aqueous substance or heat source that is placed in an environment where water molecules exist and is generated by heat exchange with a heat source of zero degrees Celsius or higher. By making the surface of the object on which the inclusion compound may adhere hydrophilic, it is possible to prevent the adhesion of these substances to the surface of the object, and to maintain the effect over a long period of time, and use the object for a wide range of purposes. It aims at providing the technology which enables it to be used.

  In particular, the present invention relates to a heat exchange surface, a pipe, and a heat exchanger of a heat exchanger constituting an apparatus and system for producing a clathrate compound by heat exchange in a technical field utilizing the characteristics of the clathrate compound, for example, an air conditioning field or a heat storage field. Prevents the inclusion compound from adhering to the surface of the object where the inclusion compound can adhere, such as the inner wall surface of the heat storage container, the valve valve surface, and the sensor housing of the measuring device, and the operation, performance, and operation of the device and system The purpose is to provide technology that can improve and maintain the stability and soundness of the situation.

JP 2000-26844 A JP 2002-88347 A JP 62-500043 A JP-A-1-249863 Japanese Patent Application No. 2004-308355 Japanese Patent Application No. 2005-016863 JP 2005-36197 A JP-A-10-253195

  In the first aspect of the object according to the present invention, there is a possibility that a non-aqueous substance generated by heat exchange with a heat source of zero degrees Celsius or higher may adhere, and the object is placed in an environment where a substance different from the non-aqueous substance exists, It has a surface on which a surface treatment film having affinity for a non-aqueous substance and a different substance is formed. In the second aspect of the object according to the present invention, there is a possibility that an inclusion compound produced by heat exchange with a heat source adheres, and the inclusion compound is placed in an environment where a substance different from the inclusion compound exists, and the inclusion compound. And a surface on which a surface treatment film having an affinity with a different substance is formed. According to a third aspect of the object of the present invention, in the first or second aspect of the object, the surface treatment film is an inorganic hydrophilic coating film. According to a fourth aspect of the object of the present invention, in the third aspect of the object, the inorganic hydrophilic coating film is an inorganic hydrophilic coating film having a glass structure. The inorganic hydrophilic coating film preferably has a glass structure containing boron ions. According to a fifth aspect of the object of the present invention, in the third or fourth aspect of the object, the object is installed in an environment in which a forcing force that promotes slipping of the non-aqueous substance attached to the surface of the object acts. is there.

  In the first aspect of the object surface treatment method according to the present invention, there is a possibility that a non-aqueous substance generated by heat exchange with a heat source of zero degrees Celsius or higher may adhere, and there is a substance different from the non-aqueous substance. The surface of an object placed in the environment is subjected in advance to a surface treatment that gives an affinity between the non-aqueous substance and a different substance. In the second aspect of the processing method according to the present invention, there is a possibility that a clathrate compound produced by heat exchange with a heat source may adhere, and an object placed in an environment where a substance different from the clathrate compound exists. A surface treatment for giving affinity to a substance different from the inclusion compound is applied to the surface in advance. A third aspect of the processing method according to the present invention is the first or second aspect of the processing method, wherein the surface treatment is an inorganic hydrophilic coating. According to a fourth aspect of the processing method of the present invention, in the third aspect of the processing method, the coating formed by the inorganic hydrophilic coating is an inorganic hydrophilic coating film having a glass structure. . The inorganic hydrophilic coating film preferably has a glass structure containing boron ions. According to a fifth aspect of the processing method of the present invention, in the third or fourth aspect of the processing method, the object acts in an environment in which a forcing force that promotes slipping of the non-aqueous substance attached to the surface acts. It will be installed.

  The object processing system according to the present invention is a compulsory that acts to promote slipping of the inclusion compound attached to the surface of the object according to any one of the first to fourth aspects of the object according to the present invention. Forcing force generating means for generating force. With this processing system, the fifth aspect of the object and object surface processing method according to the present invention is realized.

  According to the present invention, by forming a hydrophilic surface treatment film on the surface of an object placed in an environment where water molecules exist, heat with a non-aqueous substance or heat source generated by heat exchange with a heat source of zero degrees Celsius or more is obtained. The effect of preventing adhesion of clathrate compounds produced by exchange and improving slipperiness can be obtained. In particular, when the hydrophilic surface-treated film is an inorganic hydrophilic coating film, it becomes a film having higher strength and durability, so that the object can be used in a wide range of applications while maintaining such effects. Further, when the inorganic hydrophilic coating film has a glass structure, the strength and durability are further increased.

  When a forcible force that promotes the slipping of clathrate compounds and other non-aqueous substances attached to the surface of the object acts, the slipping of the non-aqueous substances attached to the object surface is promoted and reattachment is prevented. The effect of preventing the adhesion of water-based substances is enhanced, and the slipperiness is also improved. In this case, since a forcing force acts on the surface of the object, there are concerns about the strength and durability of the coating. However, such a concern is eliminated if it is an inorganic hydrophilic coating film, particularly a film having a glass structure.

  Examples according to the present invention will be described below. Examples of the hydrophilic surface treatment applied to the surface of the object include, for example, a composition obtained by adding borate to (a) alkali metal silicate and mixing fine scaly transparent silica as an inorganic filler (Japanese Patent Laid-Open No. 2005-15728). And (ii) a composition in which calcium silicate or zinc phosphate is added to an alkali metal silicate, and natural glass mainly composed of colemanite or urexite as an inorganic filler is mixed in the form of fine scales (Japanese Patent Laid-Open No. 6-329949). No. 6, JP-A-6-329950, etc.) and an inorganic hydrophilic coating is preferred. In any of the compositions (a) and (ii), trace substances may be further blended.

  Here, a paint in which the composition (ii) was uniformly dispersed in water was used, and this was applied to the object surface to form a hydrophilic surface treatment film. A cross section of the surface of the object thus obtained is schematically shown in FIG. In this figure, the material of the object 1 can be selected from inorganic materials such as those capable of forming a coating film and not causing any actual damage even when exposed to the baking temperature of the paint, such as stainless steel, aluminum, and copper. The hydrophilic surface treatment film 2 is an inorganic hydrophilic coating film, particularly a coating film having a glass structure containing borate ions, and generally has a higher baking temperature and a very high strength as compared with organic coatings. According to the pencil hardness test (conforming to JIS / K7125), it is “9H” or more, and according to the abrasion resistance test (see JIS / K7125), it is about “no scratches are recognized”. Note that paints that use non-volatile water as a solvent instead of volatile solvents are generally used when a volatile solvent is used. This is because the strength and durability of the coating film tend to be relatively lowered.

  An inclusion compound, particularly an inclusion hydrate, was used as the non-aqueous substance, and an inclusion compound formation solution, particularly an inclusion hydrate formation solution, was used as the non-aqueous substance formation solution. This clathrate hydrate forming solution was a TBAB 10 wt% aqueous solution in which the host material and the guest material were water and TBAB, respectively. As described above, this clathrate hydrate formation solution has a clathrate hydrate formation temperature of zero degrees Celsius or higher. Therefore, it corresponds to a non-aqueous substance production solution that produces a non-aqueous substance by heat exchange with a heat source of zero degrees Celsius or higher.

(Simple wetting test of clathrate hydrate formation solution)
An inorganic hydrophilic coating film is applied by coating a surface of an aluminum flat plate with a side of 50 centimeters and a thickness of 5 millimeters in which the above composition (i) is uniformly dispersed in water at a thickness of 30 microns and baking. Formed. A flat plate on which this inorganic hydrophilic coating film was formed was placed on a flat pedestal, and the same amount of distilled water and clathrate hydrate forming solution were dropped from the same height from the same height onto the flat plate. The area and the minimum width of the droplets that spread out were measured. As a result, it was found that the clathrate hydrate forming solution had an area equivalent to or larger than distilled water. Based on the minimum width, the clathrate hydrate forming solution was 1.1 to 1.2 times distilled water. By the way, this result shows that the concentration of the TBAB aqueous solution is in the range of 4 to 30% by weight (the concentration range of the clathrate hydrate production solution set when the clathrate hydrate is actually used as a heat storage medium). There was no big difference even if it was changed. Therefore, it can be said that the clathrate hydrate forming solution has the same degree of affinity as or higher than water for the inorganic hydrophilic coating film.

(Solvent wettability simple experiment)
A set of aluminum flat plates each having a side of 50 centimeters and a thickness of 5 millimeters was prepared, and a paint in which the above composition (i) was uniformly dispersed in water was applied to one surface of one flat plate at a thickness of 30 microns. An inorganic hydrophilic coating film was formed by baking. The other flat plate was used as a control and was left solid without forming a paint film. Next, the same amount of methanol, ethanol, acetone, and benzene was dropped from the same height from the same height onto the flat plate on which the inorganic hydrophilic coating film was formed and the control flat plate, and the droplets spread on each flat plate. The area and minimum width were measured. As a result, it was found that the area of the droplet formed on the flat plate on which the coating film was formed was larger than that formed on the control flat plate with any organic solvent. Based on the minimum width, it was 1.8 times or more for methanol and ethanol, 1.3 to 1.4 times for acetone, and 1.2 to 1.3 times for benzene. Therefore, it can be said that the above-mentioned inorganic hydrophilic coating film does not have affinity (hydrophilicity) only for water but also has affinity for typical organic solvents such as methanol, ethanol, acetone, and benzene.

(Drip experiment of substances different from non-aqueous substances)
A set of aluminum flat plates each having a side of 50 centimeters and a thickness of 5 millimeters was prepared, and a paint in which the above composition (i) was uniformly dispersed in water was applied to one surface of one flat plate at a thickness of 30 microns. An inorganic hydrophilic coating film was formed by baking. The other flat plate was used for control, and was left solid without forming a coating film on the bottom surface. A flat plate with an inorganic hydrophilic coating film and a flat plate for control are placed on a horizontal pedestal, and the same amount of clathrate hydrate formation solution is dropped from the same height from the vertical direction into the freezer. Clathrate hydrate was formed. Then, it installed in the horizontal base, the same amount clathrate hydrate production | generation solution was dripped little by little from the perpendicular direction from fixed height, and the progress of peeling of clathrate hydrate was investigated. As a result, the clathrate hydrate adhered earlier on the flat plate on which the inorganic hydrophilic coating film was formed, and more clathrate hydrates slipped as a lump at a time.

  In the above drop experiment, the result was the same even when a clathrate hydrate formation solution was not dropped but a substance having affinity for distilled water, methanol, ethanol, acetone, and benzene was dropped. .

(Sliding shear test)
In each case, a stainless steel plate (SUS304) and an aluminum plate (commercially available) with a thickness of 0.8 mm are prepared, and a coating obtained by uniformly dispersing the composition (ii) in water on the substrate surface cut out from the plate is 30 to 40. Apply and bake at a thickness of about a micrometer. A droplet of clathrate hydrate forming solution is dropped on the coating film formed in this way to form a liquid aggregate (liquid reservoir) having a diameter of about 30 mm, and cooled to form a solid form of clathrate hydrate. (Hereinafter, this solid mass is called “solid mass” and the clathrate hydrate forming solution is cooled to produce the clathrate hydrate solid mass. Called "solidification"). When the substrate having the solid mass on the surface was taken out of the cooling environment and slowly tilted without giving an impact, the solid mass slipped out of several substrates by its own weight. In addition, when a droplet of the clathrate hydrate forming solution is dropped on a solid mass (particularly at the boundary with the substrate surface at the outer edge of the solid mass), part or all of the solid mass slipped on the surface of all the substrates. .

  Further, a square flat plate having a side of 100 mm is cut out as a test piece from the above stainless steel plate and aluminum plate, and a set of test pieces is used for coating film formation and for comparison, and a considerable number of sets are prepared. A paint in which the above composition (ii) is uniformly dispersed in water is applied to a test piece for forming a coating film at a thickness of about 30 to 40 μm and baked. Next, the cylindrical ring is cut out from a hard polyvinyl chloride pipe for water supply (commercially available product having an outer diameter of about 38 mm and an inner diameter of 31 mm), and polished smoothly so that there is no gap when both ends of the cylindrical ring are placed on a horizontal plane, Keep the height the same. Further, a member 13 (described later) with which an end of a stainless steel wire 9 (described later) can be engaged is attached at the same height. Next, a test piece (hereinafter referred to as “coating film test piece”) on which an inorganic hydrophilic coating film is formed and a control test piece are arranged on a horizontal plane, and a cylindrical ring is arranged at the center of each surface. At this time, the cylindrical ring is arranged so that the end face of the cylindrical ring faces and closely contacts the surface of the test piece (in the case of the coated film test piece, the side on which the coated film is formed), and the test piece and the cylindrical ring Pour the same amount of clathrate hydrate formation solution into the cylindrical ring while applying pressure so as not to separate the coating film test piece and the control test piece as the cooling temperature, cooling rate, supercooling degree, etc. Cool with the same cooling conditions, or change the cooling conditions to cool another set of test pieces in the same way, cool the clathrate hydrate formation solution in the cylindrical ring on the test piece surface, and solidify To do.

  Subsequently, by using the test apparatus shown in FIG. 2, a sliding shear force (shearing force necessary for sliding the clathrate hydrate attached to the test piece) with respect to the set of the coating film test piece 31 and the control test piece 32. Was measured. This test apparatus includes a horizontal pedestal 4 for horizontally loading the test piece 3 (31, 32), a fixing jig 5 and 6 for fixing the test piece 3 and hindering its horizontal movement, and a cylinder on the test piece 3. An upper limiting member 7 that is arranged in a non-contact and horizontal manner in the vicinity of the pole at the upper end of the ring 11 and obstructs the vertical movement of the cylindrical ring 11, a vertical base 8 that horizontally supports the upper limiting member 7, and a cylinder on the test piece 3 A stainless steel wire 9 that applies a tensile force in the horizontal direction to the member 13 of the ring 11 and a horizontal support base 10 that supports horizontal movement of the stainless steel wire 9 by pulleys 101 and 102 are provided. The vertical position of the upper restricting member 7 can be adjusted by a coordinate adjusting means (not shown), and the vertical position of the pulleys 101 and 102, and hence the vertical position of the stainless steel wire 9, is also another coordinate adjusting means ( (Not shown) can be adjusted. A load cell (not shown) connected to the end of the wire 9 opposite to the member 13 by installing the test piece 3 in this apparatus and pulling it at a constant speed in the direction H parallel to the surface of the test piece 3 using the stainless steel wire 9. Read the load change. A solid inclusion clathrate hydrate 12 exists on the surface of the test piece 3 inside the cylindrical ring 11 on the test piece 3. When the cylindrical ring 11 is pulled with the wire 9, a certain tension is reached. The solid mass slips off from the surface of the test piece 3. The maximum load read by the load cell at the time of sliding is defined as the sliding shear force. When measuring the sliding shear force with this test device, after removing the test piece from the cooling atmosphere, immediately install it on the horizontal pedestal and apply the pressure so that the test piece and the cylindrical ring are not separated from each other. And cancel the measurement.

  FIG. 3 shows the results obtained by measuring the sliding shear force of the set of the coating film test piece and the control test piece and calculating the ratio of the measured values in each set. Three cooling conditions were set, 6 points were measured for each cooling condition, and the remaining 4 points excluding the maximum and minimum values were evaluated. As a result, the inorganic hydrophilic coating film was not formed. It was found that the sliding shear force was reduced by 50% (maximum 63%, minimum 30%) on average. The maximum value and the minimum value excluding 6 points were both less than 1.0.

  When the pressure applied so that the test piece and the cylindrical ring are not separated when the sliding shear force is measured using the test apparatus shown in FIG. 2, the test piece is slightly accelerated in the horizontal direction ( Or about 32% of the coating film test piece, the clathrate compound that should have adhered to the surface slipped from the initial installation position together with the cylindrical ring. Also from this, the slipping property of clathrate hydrate by the inorganic hydrophilic coating film formed on the coating film test piece is considerably high, and the effect of preventing or suppressing the clathrate hydrate adhesion is remarkable. I understand.

  With the cooling conditions fixed, 6 point measurements were performed on the same coating film test piece (SUS304) and control test piece set, and the evaluation performed on the remaining 4 points excluding the maximum and minimum values was repeated 10 times. FIG. 4 shows a summary of the ratio of the sliding shear force. From this figure, when the sliding shear force is 0.45 to 0.50, the frequency of occurrence is the highest, and the average is 0.48, and a decrease of more than 50% in the sliding shear force can be confirmed.

  Next, a description will be given of an experiment on the adhesion and sliding properties of clathrate hydrate in an environment in which a forcing force acts and the results thereof.

(Agitation swirl test)
Using the stirrer shown in FIG. 5, the effect of the forcing force that acts directly or indirectly by the turning of the stirring means was examined. This stirrer is composed of a container 16 having refrigerant inlets and outlets 161 and 162 and a container 17 disposed on the inside thereof, and a target temperature (zero degrees Celsius) is set in a space between both containers (at least a space between the bottom surfaces of both containers). The clathrate hydrate forming solution contained in the container 17 is cooled by the refrigerant with the wall surface of the container 17 as a heat exchange surface, and has a rotating surface parallel to the bottom surface of the container 17. Stirring is performed by a single stirring blade 18. The stirring blade 18 is connected to a motor 19 outside the container 16 via a rotary shaft 20 and rotates at a position close to the bottom surface of the container 17 that is not in contact (a position separated from the bottom surface by 1 mm to several mm). The rotational speed and rotational torque of the motor 19 are variable, and the rotational shaft 20 is disposed so as to penetrate near the center of the upper lid 21 of the container 16. The upper lid 21 is provided with a transparent plate-lined observation window (not shown). The containers 16 and 17 and the stirring blade 18 are made of stainless steel, and the bottom surfaces of the containers 16 and 17 have a substantially mirror-like shape so that the face of the observer appears unclear.

  A clathrate hydrate forming solution is used as the object to be cooled, and a set of containers 17 (171, 172) of the same size and the same material is prepared. The dispersed paint was applied at a thickness of 30 μm and baked to form an inorganic hydrophilic coating film. The other container was for control purposes and was left solid without forming a paint film on the bottom. First, the clathrate generation solution is placed in the control container 172, placed in the container 16, the stirring blade 18 is placed in the container 17, and stirring by the high-speed rotation of the blade 18 is started and refrigerant flow is started. did. After a while, abnormal noise suddenly started to be mixed with the turning sound of the stirring blade 18. The clathrate hydrate formation solution in the container 17 gradually became cloudy, and the generation and increase of clathrate hydrate particles were confirmed, and a slurry state was obtained. Stirring is stopped before the rotation is stopped, the upper lid 21 is quickly removed, the clathrate hydrate particles and the remaining clathrate hydrate forming solution are removed from the container 17, and the bottom is observed. The clathrate hydrate was formed in a group and was thicker than the case of the container 171 described later. When stirring was continued for a long time, concentric rubbing (not shown) was confirmed at the bottom of the container 17. Since the stirring blade 18 was rotating in a non-contact manner with the bottom of the container 17, clathrate hydrate caught between the rotating surface of the stirring blade 18 and the bottom surface of the container 17 (inclusion water generated on the bottom surface). It is considered that the cause of scuffing is the inclusion and growth of clathrate hydrate generated and grown in Japanese and offshore clathrate hydrate formation solutions.

  Next, the same kind and the same amount of clathrate hydrate forming solution is put in the container 171 and installed in the container 16, the stirring blade 18 is installed in the container 17, high-speed stirring is started, and in the case of the container 172 The refrigerant flow was started to achieve the same cooling conditions. After a while, abnormal noise suddenly started to be mixed with the turning sound of the stirring blade 18, but the sounding frequency or volume was much lower than that of the container 172. As in the case of the container 172, the clathrate hydrate formation solution in the container 17 gradually became cloudy during the cooling process, and the generation and increase of clathrate hydrate particles were confirmed. After the stirring is stopped, the upper lid 21 is immediately removed, the clathrate hydrate particles and the remaining clathrate hydrate forming solution are removed from the container 17, and the bottom surface of the container 17 is observed. The Japanese hydrate is not formed or the clathrate hydrate is formed in a group form locally on the bottom surface. Even in the latter case, the clathrate hydrate adheres more than in the case of the container 172. The amount was much less. Even if stirring was continued for a long time, no rubbing could be confirmed at the bottom of the container 17.

  In addition, when observing the bottom of the container 17 after the rotation of the blade 18 is stopped, vibration and acceleration are not applied as much as possible during the operation of removing the clathrate hydrate particles and the remaining clathrate hydrate forming solution from the container 17. Thus, even when the container 17 was handled, a considerable amount of the clathrate hydrate particles adhering to the bottom part slipped off. It is thought that the clathrate hydrate particles slip off due to their own weight.

  In the apparatus shown in FIG. 5, the forcing force that allows the clathrate hydrate attached to the bottom surface of the container 17 to slide off is mainly the forcing force of the above (B), more specifically, the rotating surface of the stirring blade 18 and the container 17. Clathrate hydrate formation solution or clathrate hydrate entrained between the bottom and the clathrate hydrate generated or grown in the clathrate hydrate generated on the bottom and offshore clathrate hydrate formation solution It can be inferred that this is a shearing force or impact force due to contact with the hydrate. In this case, the means for generating the forcing force is the stirring blade 18 in a narrow sense, and the blade 18, the motor 19, and the rotating shaft 20 in a broader sense.

(Scraping turning test)
Using the scraping device shown in FIG. 6, the effect of a forcing force that works directly or indirectly by turning of the scraping means was examined. Since this scraping device has basically the same configuration as the stirring device shown in FIG. 5, the same reference numerals as those in FIG. 5 are assigned to the same parts in FIG. Description is omitted. On the other hand, what is unique in FIG. 6 is a scraping blade 22, which corresponds to a structure in which an acrylic resin member 221 is fixed over substantially the entire tip of the stirring blade 18 shown in FIG. 5. The acrylic resin member 221 contacts the bottom surface of the container 17 with a certain pressure. For this reason, when the scraping blade 22 connected to the motor 19 outside the container 16 via the rotating shaft 20 rotates, the bottom surface of the container 17 receives friction that is scraped by the acrylic resin member 221 and adheres to the bottom surface of the container 17. A shearing force that separates the clathrate hydrate and the bottom surface, that is, a forcing force (mainly the forcing force (A) described above) causing the clathrate hydrate to slide off is generated. Needless to say, the means for generating the forcing force is the scraping blade 22, particularly the acrylic resin member 221 at the tip thereof, and the blade 22, the motor 19, and the rotating shaft 20 in a broad sense.

  A clathrate hydrate forming solution is used as the object to be cooled, and a set of containers 17 (171, 172) of the same size and the same material is prepared. The dispersed paint was applied at a thickness of 30 μm and baked to form an inorganic hydrophilic coating film. The other container was for control purposes and was left solid without forming a paint film on the bottom. First, the clathrate hydrate production solution was placed in the control container 172, placed in the container 16, the raking blade 22 was placed in the container 17, and scraping was started and the refrigerant flow was started. The blades 22 were rotated at a lower speed and higher torque than the case of the stirring blades 18. After a while, an unusual noise begins to occur suddenly mixed with the swirling sound of the scraping blade 22 (including the friction sound between the acrylic resin member 221 and the bottom surface of the container 17), the volume increases with time, and the sound continues. It became. During the scraping process, the clathrate hydrate forming solution in the container 17 gradually became cloudy, and the generation and increase of clathrate hydrate particles were confirmed, and a slurry state was obtained. After the scraping is stopped, the upper lid 21 is quickly removed, the clathrate hydrate particles and the remaining clathrate hydrate forming solution are removed from the container 17, and the bottom is observed. As a result, the clathrate hydrate is found at the bottom of the container 17. It was formed in groups. In most cases of scraping for a long time, a concentric or concentric arc-shaped rubbing (not shown) was confirmed at the bottom of the container 17. This rubbing occurred much earlier than with the stirring blade 18. The clathrate hydrate particles generated on the bottom surface of the container 17 and the large clathrate hydrate particles generated and grown in the offshore clathrate hydrate formation solution are entrained by the scraping blade 22. It is thought that it was the cause of the abrasion that the forcing force was added.

  Next, the same kind and the same amount of clathrate hydrate forming solution is put in the container 171, installed in the container 16, the raking blade 22 is installed in the container 17, stirring is started, and in the case of the container 172 The refrigerant flow was started to achieve the same cooling conditions. The frequency of occurrence of abnormal noise mixed with the swirling sound of the scraping blade 22 is considerably low, and even when it occurs, the volume is much lower than in the case of the container 172. However, as in the case of the container 172, the clathrate hydrate forming solution in the container 17 gradually became cloudy during the cooling process, and generation and increase of clathrate hydrate particles were confirmed. After the scraping is stopped, the upper lid 21 is quickly removed, the clathrate hydrate particles and the remaining clathrate hydrate forming solution are removed from the container 17, and the bottom is observed. As a result, clathrate hydrate is completely formed. There wasn't. Even if stirring was continued for a long time, no rubbing could be confirmed at the bottom of the container 17.

  In addition, when observing the bottom of the container 17 after the rotation of the blades 22 is stopped, vibration and acceleration are not applied as much as possible during the operation of removing the clathrate hydrate particles and the remaining clathrate hydrate forming solution from the container 17. Thus, even when the container 17 was handled, a considerable amount of the clathrate hydrate particles adhering to the bottom part slipped off. It is thought that the clathrate hydrate particles slip off due to their own weight.

(Summary of test results)
From the above, the following can be understood.
(A) If the surface of an object on which an inorganic hydrophilic coating film is formed is placed in an environment where water or an organic solvent having an affinity for the coating film is present, the slipping property of clathrate hydrate increases. Adhesion of clathrate hydrate is prevented. In other words, when the surface of an object on which a non-aqueous substance generated by heat exchange with a heat source may adhere is placed in an environment where water, an organic solvent, or other substances different from the non-aqueous substance exist, This means that if a surface treatment film having an affinity with water, an organic solvent or other substances different from non-aqueous substances is formed, adhesion of non-aqueous substances can be prevented. More specifically, a clathrate hydrate such as a heat exchanger for producing a clathrate hydrate, a pipe line for transporting the clathrate slurry, a wall surface of a tank for storing the clathrate hydrate, etc. There is a possibility that clathrate hydrates generated by heat exchange will be deposited in an environment that comes into contact with the product solution or its solvent. It can be said that the formation of a conductive coating film is effective.
(B) By the formation of the inorganic hydrophilic coating film, the slipping property of the clathrate hydrate is increased, the adhesion of the clathrate hydrate is suppressed or prevented, and the clathrate hydrate forming solution is sheared. Even if force, impact force resulting from clathrate hydrate particle collision, shear force resulting from contact with acrylic resin member, frictional force or other stress, that is, forced force, strength and durability at the bottom of container 17 Is secured.

  In addition, it is needless to say that the above result is applied to the non-aqueous substance generated by heat exchange with the heat source, and accordingly, the clathrate compound generated by heat exchange is also applied. The above results are new findings regarding non-aqueous substances produced by heat exchange with a heat source of zero degrees Celsius or higher.

(Application example of test results)
FIG. 7 is a front half-cutaway perspective view showing a heat exchange drum and scraper blades according to the main part of the clathrate hydrate production apparatus. The heat exchange drum is suspended in a tank (not shown) by a suspension member (not shown), and the clathrate hydrate particles or slurry are cooled by cooling the clathrate hydrate forming solution in the tank. A cylindrical drum 717, a rotary shaft 720 installed at the center of the drum 717 and driven to rotate by a motor 719 (not shown), and a swirling blade-like member attached to the rotary shaft 720 718 and a large number of refrigerant pipes 760 provided on the peripheral surface material constituting the drum 717. The refrigerant flowing through the refrigerant pipe 760 enters the pipe 760 from the refrigerant forward pipe 761 (not shown) at zero degrees Celsius, and goes out of the pipe 760 from the refrigerant return pipe 762 (not shown). Therefore, the inner surface 717S is cooled to a temperature of zero degrees Celsius or higher, and the clathrate hydrate forming solution existing inside the drum 717 is cooled, and clathrate hydrate is generated. The clathrate hydrate produced by such heat exchange adheres to the inner surface 717S and accumulates there. The vertically set rotating shaft 720 is loosely fitted by two upper and lower couplings 730, and the relative distance between the rotating shaft 720 and the drum 717 is kept constant by the coupling 730 and the support rod 740 extending from the coupling 730. . The swirling blade-like member 718 orbits around the rotating shaft 720 with a slight clearance from the inner surface 717S of the drum, thereby scraping off the clathrate hydrate adhering to the inner surface 717S of the drum, and its inner surface 717S. Separate from the water to the offshore solution and float in the solution.

  Here, a hydrophilic surface treatment film, desirably an inorganic hydrophilic coating film, having a glass structure (more desirably having a glass structure containing borate ions) is formed on the inner surface 717S in advance. This improves the slipping property of the clathrate hydrate from the inner surface 717S, facilitates the scraping by the swirling blade-like member 718, and improves the strength and durability of the inner surface 717S. Therefore, it becomes possible to produce clathrate hydrate stably for a long time.

  Note that the drum 717 and its inner surface 717S correspond to the container 17 and its bottom surface, and the refrigerant pipe 760 and the space through which the refrigerant flows are between the container 16 and the container 17 (particularly in the region of the bottom surface of the container 17). The rotating shaft 720 corresponds to the rotating shaft 20, and the swirling blade-shaped member 718 corresponds to the stirring blade 18 (forced force generating means in a narrow sense). Further, the inner surface 717S of the drum 717 has a hydrophilic surface treatment film, preferably an inorganic hydrophilic coating film, which has a glass structure (more preferably a glass structure containing borate ions), or Each structure incorporating them corresponds to an object according to the present invention, and forming a hydrophilic surface treatment film on the drum inner surface 717S corresponds to the object surface treatment method according to the present invention. Furthermore, the clathrate hydrate production apparatus shown in FIG. 7 is provided with a hydrophilic surface treatment film applied to the inner surface 717S of the drum 717, or a facility that exhibits a function planned by incorporating it. Facilities, mechanisms, and the like correspond to the object processing system according to the present invention.

  8 and 9 are diagrams showing a schematic configuration and a longitudinal section of the clathrate hydrate production apparatus, respectively. This production apparatus is an apparatus for producing a solution containing a solid mass of clathrate hydrate or a slurry of the solid mass by cooling the clathrate hydrate production solution to solidify it. An inner pipe 817 through which the product-generating solution flows, an outer pipe 816 through which a cooling medium for cooling the solution to zero degrees Celsius (or a controlled temperature higher), and an inner pipe 817 are provided. A rotating body 820 having a plurality of blades 830 each having a cutting edge 831 that elastically contacts the inner surface 817S of the inner surface 817S, and a motor 819 that drives the rotating body 820 around the rotation shaft 821. Since the inner surface 817S of the inner tube is cooled by the cooling medium, the clathrate hydrate producing solution in the vicinity thereof is cooled, and clathrate hydrate is produced. The clathrate hydrate generated by such heat exchange adheres to the inner surface 817S of the inner tube and accumulates there. The rotating body 820 is loaded into the blade 830, a blade guide 870 that enables movement of the blade 830 along the radial direction of the inner tube 817, and the blade guide 870, and the blade tip 831 included in each blade 830 includes an inner tube. Since the spring 880 that urges the inner surface 817S to contact with the inner surface 817S at all times with a uniform pressing force is provided, even if the axis of the rotary shaft 821 is eccentric with respect to the inner tube 817, the blade 830 is always stable, The clathrate hydrate adhering to the inner surface 817S can be scraped off.

  Here, a hydrophilic surface treatment film, preferably an inorganic hydrophilic coating film, having a glass structure (more preferably having a glass structure containing borate ions) is formed in advance on the inner surface 817S of the inner tube. As a result, the slipping property of the clathrate hydrate from the inner surface 817S is improved, the scraping by the blade 830 is facilitated, and the strength and durability of the inner surface 817S are improved. Therefore, it becomes possible to produce clathrate hydrate stably for a long time.

  The rotating shaft 821 of the rotating body 820 corresponds to the rotating shaft 22, and the outer tube 816, the inner tube 817 and the cooling medium correspond to the refrigerant flowing through the container 16, the container 17, and the space between the two containers, respectively. The state in which the blade 830 and its blade edge 831 respectively correspond to the scraping blade 22 and the acrylic resin member 221 and the blade edge 831 of each blade is elastically in contact with the inner surface 817S of the inner tube is made of acrylic resin although it is hard. This corresponds to the state in which the member 221 is in contact with the bottom surface of the container 17. The blade 830, particularly the cutting edge 831 constituting its tip, corresponds to a forcible force generating means (in a narrow sense), but in a broader sense, a rotating body 820, a blade guide 870, a spring 880, and the like may be included therein. . Further, a hydrophilic surface-treated film, preferably an inorganic hydrophilic coating film, having a glass structure (more preferably having a glass structure containing borate ions) on the inner surface 817S of the inner tube, or those Each of the structures in which is incorporated corresponds to the object according to the present invention, and forming the hydrophilic surface treatment film on the inner tube inner surface 817S corresponds to the object surface treatment method according to the present invention. Furthermore, the clathrate hydrate manufacturing apparatus shown in FIGS. 8 and 9 is provided with a hydrophilic surface treatment film on the inner surface 817S of the inner tube, or exhibits a function planned by incorporating it. Equipment, facilities, mechanisms, and the like correspond to the object processing system according to the present invention. Furthermore, the apparatus shown in FIGS. 7 to 9 has been described as an apparatus for generating an clathrate hydrate from an clathrate hydrate formation solution by heat exchange with the heat source. It is not limited. That is, in FIG. 7 to FIG. 9, in order to generate non-aqueous substances other than clathrate hydrate (including clathrate compounds other than clathrate hydrate) by heat exchange with the heat source, the clathrate compound generation solution However, if you select other non-aqueous substance production solutions and adjust the heat source to a cooling temperature suitable for the desired non-aqueous substance, the devices depicted in these drawings will be widely used in non-aqueous substance production. It becomes a device.

  When it is necessary to transport a supercooled non-aqueous substance generating solution by piping, if the supercooling state is canceled during transport, the non-aqueous substance will solidify in a short time and adhere to the inner surface of the pipe, hindering transport. cause. Therefore, a surface treatment film having affinity with a substance different from the non-aqueous substance is formed on the inner surface of the pipe, and the substance different from the non-aqueous substance is used as a solvent to form a non-aqueous substance generation solution, or a non-aqueous substance generation solution. Carry in after being mixed. Then, even if the supercooled state is canceled during the conveyance and the non-aqueous substance adheres to the inner surface of the pipe, the adhesion is lowered, and the shearing force by the solution is received, so that the non-aqueous substance is easily slipped off. Therefore, it is possible to transport the supercooled non-aqueous substance generating solution over a long distance.

  In addition, when the supercooled non-aqueous substance generating solution is allowed to flow, deformed pipes that easily form turbulent flow, the inner surface of the valve device, and the supercooled nonaqueous substance generating solution collide with the supercooled state. The surface of the impingement plate for releasing, the surface of a rotating propeller that releases cavitation by generating cavitation in the supercooled non-aqueous substance generating solution, and the like are also suitable as the application target of the present invention. Since these objects are subjected to shearing force and impact force due to the movement of the non-aqueous substance generating solution, a surface treatment film having affinity with a substance different from the non-aqueous substance is previously formed on the surface. By using a substance different from the non-aqueous substance as a solvent to make a non-aqueous substance-generating solution, or mixing it in the non-aqueous substance-generating solution, the effect of preventing or suppressing the adhesion of the non-aqueous substance becomes more prominent. Become.

  In addition, in the case of the above-described irregularly-shaped pipes and valve devices, it can be said that the internal structure itself functions as a force generation means. Further, a means (for example, a pump device) for applying a force sufficient to collide with the collision plate to the supercooled non-aqueous substance generating solution, and the rotary propeller for generating cavitation in the supercooled nonaqueous substance generating solution. Corresponds to the force generation means in each case.

  According to the present invention, there is a possibility that a non-aqueous substance generated by heat exchange with a heat source of zero degrees Celsius or higher may adhere, and the non-aqueous substance is placed on the surface of an object placed in an environment where a substance different from the non-aqueous substance exists. By forming a surface treatment film that has an affinity with a substance different from an aqueous substance, there is a possibility that an inclusion compound produced by heat exchange with a heat source may be attached, and the inclusion compound has a different substance. By forming a surface treatment film on the surface of an object placed in an environment that has an affinity for a substance different from the inclusion compound, it is possible to prevent adhesion of non-aqueous substances on the surface of the object and increase slipperiness. Since the strength and durability of the surface can be improved, it is possible to provide an object, an object surface processing method, and an object processing system that are more suitable in a realistic environment.

It is explanatory drawing which shows the principal part of the cross section of the object which concerns on this invention. It is explanatory drawing which shows schematic structure of the test apparatus of sliding shear force. It is explanatory drawing which collects and shows the test result (sliding shear force ratio) of sliding shear force according to a raw material and cooling conditions. It is explanatory drawing which summarizes and shows the test result (sliding shear force ratio) of sliding shear force paying attention to generation frequency. It is explanatory drawing which shows schematic structure of the test apparatus (scraping apparatus) of the adhesion property or sliding property of a clathrate compound when a forcing force acts. It is explanatory drawing which shows schematic structure of the test apparatus (pressure welding apparatus) of the adhesion property or slipperiness | attachment property of a clathrate compound when a forced force acts. It is a front-half body cutout perspective view for demonstrating the drum and scraper blade part which concern on the principal part of the clathrate hydrate manufacturing apparatus which concerns on this invention. It is explanatory drawing which shows schematic structure of the clathrate hydrate manufacturing apparatus which concerns on this invention. It is a longitudinal cross-sectional view of the clathrate hydrate manufacturing apparatus which concerns on this invention.

Explanation of symbols

1 object
2 Surface treatment membrane
3 Test pieces
4 horizontal pedestals
9 Stainless steel wire 11 Cylindrical ring 17 Container 18 Stirring blade 19 Motor 20 Rotating shaft 22 Scraping blade 221 Acrylic resin member

Claims (11)

  There is a possibility that a non-aqueous substance generated by heat exchange with a heat source of zero degrees Celsius or higher is attached, and it is placed in an environment where a substance different from the non-aqueous substance exists, and has an affinity for a substance different from the non-aqueous substance. An object comprising a surface on which a surface treatment film is formed.   There is a possibility that the clathrate compound generated by heat exchange with the heat source may be attached, and the clathrate compound is placed in an environment where a different substance exists, and has a affinity for a substance different from the clathrate compound. An object comprising a surface on which is formed.   The object according to claim 1, wherein the surface treatment film is an inorganic hydrophilic coating film.   The object according to claim 3, wherein the inorganic hydrophilic coating film is an inorganic hydrophilic coating film having a glass structure.   5. The object according to claim 3, wherein the object is installed in an environment in which a forcing force that promotes slipping of the non-aqueous substance attached to the surface acts.   There is a possibility that a non-aqueous substance generated by heat exchange with a heat source of zero degrees Celsius or higher may adhere to the surface of an object placed in an environment where a substance different from the non-aqueous substance exists, and a substance different from the non-aqueous substance A method for treating the surface of an object, characterized in that a surface treatment is applied in advance to give an affinity for.   There is a possibility that the clathrate compound produced by heat exchange with the heat source adheres to the surface of an object placed in an environment where a substance different from the clathrate compound is present. A method for treating an object surface, wherein surface treatment for imparting properties is performed in advance.   The method for treating an object surface according to claim 6 or 7, wherein the surface treatment is an inorganic hydrophilic coating.   9. The method for treating an object surface according to claim 8, wherein the coating film formed by the inorganic hydrophilic coating is an inorganic hydrophilic coating film having a glass structure.   The method for treating an object surface according to claim 8 or 9, wherein the object is placed in an environment in which a forcing force that promotes slipping of the clathrate compound adhering to the surface acts.   An object according to any one of claims 1 to 4, and a forcing force generating means for generating a forcing force that acts to promote slipping of the clathrate compound adhering to the surface of the object. Object processing system.

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