Separation membrane and its preparation

[Detailed Description of the Invention]

(Field of the Invention) The present invention begins gas separation and relates to part 1iIII! used for extensive uses, such as precision filtration and marginal filtration and a reverse osmosis method, and its manufacturing method. (PRIOR ART) In fields, such as gas separation which separates specific gas from mixed gas by a gaseous diffusion process, the demarcation membrane with the fine pores of 100 aperture several 10~Losing far smaller than the average free path of a gas molecule is used. Although the organic polymer film is usually used as this conventional kind of a demarcation membrane, it cannot be used at the temperature more than 100 degreeC, and also is inferior to chemical resistance and endurance, and various problems are left behind on practical use. Although the method of, sintering metallic powder and the end of ceramic powder on the other hand in order to raise heat resistance, and manufacturing a porous demarcation membrane is also known, It is difficult to make the demarcation membrane by this method into the film thickness of 1 or less fi from the problem of intensity, and there was a field which lacks in practicality too as a demarcation membrane for gas separation expected to make film thickness thin as much as possible, and to raise separation efficiency. Then, as shown in JP,59-59223,A, a porous object like a ceramic sintered compact is impregnated with barrier membrane formation ingredients, such as solution-like aluminum Arco lard or aluminum chelate, Although the trial which obtains the barrier membrane which dries, calcinates and becomes from a multilayer porous body after hydrolysis is also conducted, By this method, when moisture and the organic binder in solution dispersed, even if it was easy to leave a crack and air bubbles into barrier membrane and controlled the fine pores in barrier membrane to 100 aperture several 10~Losing, a great portion of gas was spread through the tens of micro penetration hole by a crack, and there was a fault it is hard to make desirable gas separation perform. (Problem which an invention tends to solve) The present invention solves such a conventional problem, It excels in heat resistance, chemical resistance, and endurance, and also when film thickness is made very thin, an aperture without a possibility of producing a crack etc. is completed for the purpose of the demarcation membrane provided with a majority of 5~2000 persons' fine pores, and its manufacturing method. (Means for solving a problem) The present invention covered the surface of the base material consisting of the ceramic porous object which has the continuous aperture produced by calcinating a powder object with the thin film generated from the gaseous phase with the fine pores of a majority of 5~2000 apertures. The base material (1) consisting of the ceramic porous object used in the present invention has 0.5~30 micro in the aperture produced by calcinating the powder object (2) of ceramic prizes, such as alumina, silica, mullite, and a cordylite, preferably about 0*5~1micro continuous fine pores (3). Gas diffusion resistance becomes that a pole diameter is less than 0.5micro with size, and if 30 micro is exceeded conversely, it will become difficult to form a thin film in the surface. Base material 11 consisting of a ceramic porous object is a central layer with a comparatively coarse particle size like illustration (4 As). It is preferred that a particle size shall consist of a fine surface coat (5) also with a pole diameter and small surface coarseness, A way performing the surface treatment for making the surface smooth surface coarseness to less than 1micro covers a ceramic particle minute as the method of zero desirable surface treatment, It is il film (61 is formed.) of metallic or the quality of ceramics by a gaseous phase method to the surface of the base material (1) which did in this way and was 1micro or less preferably 30micro or less about surface coarseness which can take arbitrary means, such as a method of Glazed(ing) glaze, and the method of carrying out surface polish. Applied heat or quantity of motion to the substance which consists of a substance in which you are going to make it form a thin film, or its raw material, and it decomposed into the atom, the molecule, or the aggregate, and also a gaseous phase method is defined as a method of making it combine or condense on the base of somewhere else, and is divided roughly into a chemical reaction method (CVD method) and a physical vapor deposition method (the PVD method). Although a chemical reaction method is further classified into a chemical reaction method in a narrow sense, a chemical transport method, substrate reaction method, the spraying method, etc., after changing all into the compound which is easy to evaporate the material used as a thin film and carrying through the gaseous phase, it is the method of making a chemical reaction perform in a substrate face, and forming a film. In a vacuum like a vacuum evaporation method, an ion plating method, the sputtering method, and a plasma process, the physical vapor deposition method added physical energy to the material, and evaporated it, and also it is the method of making it vapor-deposit to up to a substrate, and forming a film. The base material with which the thin film (6) generated on a substrate by these gaseous phase methods serves as a substrate (if it processes controlling temperature, atmosphere pressure, etc. of 11 to a suitable value) It becomes thin film+6+ which has a porous pillar-shaped structure and has almost uniform fine pores of 5~2000 persons' aperture according to the nuclear growth or the self-shade-and-shadow effect in a generation process. Since the fall of the separation performance of gas will arise if the penetration speed of gas becomes it small that an aperture is less than five persons, practicality is lost and 2000 persons are exceeded, it shall control so that an aperture will be 5~2000 persons. 10A~100micro is suitable for the film thickness, and it can also use metal besides an oxide, carbide, and a nitriding thing, and an intermetallic compound as the quality of the material. Thus, the demarcation membrane covered with the thin film (6) which generated the surface of the base material (1) consisting of a ceramic porous object from the gaseous phase is obtained. (OPERATION) Since the demarcation membrane of the present invention constituted in this way covers the surface of the base material (1) consisting of the ceramic porous object excellent in mechanical strength with the thin film (6) generated from the gaseous phase with the fine pores of a majority of 5~2000 apertures, A thin film (6) can be made thin to the IOA~100micro optimal thickness for gas separation, and moreover, since the thin film (6) is firmly supported by the surface of base material il+ which consists of a ceramic porous object excellent in gas permeability, gas separation can be made to perform efficiently. Unlike the conventional organic polymer film, since the demarcation membrane of the present invention consists of the quality of glass, quality of ceramics, or metallic, it is excellent in heat resistance, chemical resistance, and endurance. According to the method of the present invention, unlike the method of impregnating the conventional ceramic sintered compact etc. with aluminum Arco lard etc., drying and calcinating after hydrolysis, and obtaining a demarcation membrane, a crank is not produced in a film and the optimal demarcation membrane for making gas separation perform efficiently can be manufactured easily. (EXAMPLE) Example 1 The granular object of the quality of mullite is calcinated, and it has continuous fine pores with an average pole diameter of 25 micro, and formed the plate-like base material consisting of 20 micro of surface coarseness, and the nature of mullite porous object of thickness 1fi. The thin film of 30 micro of film thickness with the fine pores of 200 average pole diameters which process this by a gaseous phase chemical reaction method in a reaction pipe, and consist of quality of AlzOs on the surface of a base material was formed. Material gas is AlCl3 and H!O and carrier gas set reaction temperature to 900 degreeC by Ar and 0!. Example 2 The surface of the base material consisting of the same nature of mullite porous object as Example 1 was ground, and surface coarseness was 1 micro, and also it formed mll* by the gaseous phase chemical reaction method like Example 1. Example 3 It is alpha-A l about the surface of the base material consisting of the same nature of mullite porous object as Example 1! It covered with Os, and surface coarseness and an average pole diameter were 1 micro, and also it formed the thin film like Example 1. Example 4 The plate-like base material which calcinates the granular object of the quality of alumina and consists of the average pole diameter of l micro, surface coarseness of 2 micro, and a nature of alumina porous object on thickness the 1st was formed, and the thin film of the quality of Altos of 2 micro of film thickness which has fine pores of 50 average pole diameters for this in the surface by a vacuum evaporation method in a reaction pipe was formed. As for the evaporation source, Ot and pressure are 10-'torr(s) and A.I. Artificial Intelligence and atmosphere kept the temperature of the base material at 400 degrees. Example 5 The porous plate-like base material which consists of the quality of porcelain of the average pole diameter of l micro and 1micro of surface coarseness thickness 0.5fi was created, and the thin film of film thickness [ which has fine pores of 100 average pole diameters for this in the surface of a porous base material by the sputtering method in a reaction pipe / O61 micro ] AIN was formed. Negative pole material is A1 and is Ar5XI Q-3torrb Nt. It was made to discharge as monotonous temperature 200degreeC under the atmosphere of 2X10-'Lorr. In addition, only the base material of the quality of mullite, the quality of alumina, and the quality of porcelain used in Example 1.4.5 as a comparative example was prepared, and the separation test of H, 50(volume)%, and Nt50% of - mixed gas was done using the circulation type gas separating apparatus. As a result of testing the supply side pressure of 5.0 kg on condition of /a!, outflow lateral pressure 1 kg/c+J, and temperature C of 300 degrees, the result as the following table was obtained. (EFFECT OF THE INVENTION) On the surface of the base material where the present invention consists of a ceramic porous object excellent in mechanical strength and gas permeability so that clearly also from the above explanation, Since a thin film with fine pores suitable for gas separation is covered, it is a thing to which gas separation can be made to perform efficiently, and also it excels also in the homogeneity of fine pores, heat resistance, chemical resistance, and endurance. According to the present invention method, crank generating of such a demarcation membrane is also afraid (it is stabilized, and it can manufacture and also can also manufacture the thing of arbitrary film thickness or a pole diameter freely.). Thus, it is although the present invention is useful in the field of gas separation, such as Ht recovery from the subraw gas of an iron mill, mixture ratio adjustment of the synthesis gas (C0Hi) in C1 chemistry, and concentration of helium from natural gas, In addition, the demarcation membranes of the present invention are filtration of solution or an organic solvent, and filtration of yeast or mold, Bacteria, the field of precision filtration like filtration of a virus, and proteinic concentration, It can use effective also in the field of reverse osmosis methods, such as manufacture of freshening of sea water, salt water, etc. besides the field of marginal filtration, such as concentration of physiologically active substances, such as recovery, refining, vaccines, enzyme, a virus, and nucleic acid, recovery, and refining, pure water, and aseptic water. Therefore, as what swept away the problem of this kind of the former [ present invention ] of demarcation membrane, the place which contributes to development of industry is size very much.

[Brief Description of the Drawings]

A drawing is a partial expanded sectional view showing the demarcation membrane of the present invention typically. (l): A base material, (3): Fine pores, (5): A surface coat, (6): Thin film l : Up 2↓1 Ito