JPS627443A - Gas selective separation material - Google Patents

Abstract

PURPOSE:To especially enhance the separation capacity of oxygen, by forming a gas selective separation material from a contact reaction product of a CO-salt and dipropylenetriamine represented by a specific general formula or a derivative thereof. CONSTITUTION:A compound obtained by contacting a Co-salt with di propylenetriamine represented by formula I or a derivative thereof mainly in the presence of a non-aqueous solvent or adding a solvent to the reaction product of the Co-salt and dipropylenetriamine represented by the formula is used as a gas selective separation material. As the Co-salt, cobalt oxide, cobalt hydroxide, cobalt sulfate and cobalt, etc., are designated. The ratio of the Co-salt and the amine compound represented by the formula I is generally 0.01<amine compound/Co-salt and the contact reaction is pref. performed at 0-200 deg.C under pressure of 0.01-100kg/cm<2>.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a material for selectively separating gases, and particularly to a material for selectively separating gases useful for separating oxygen.

Oxygen is one of the most widely and widely used gases, and its applications include welding and cutting steel materials,
For blowing into blast furnaces, open hearths, converters, etc. #For iron, for refining various metals, for manufacturing petrochemical products in Germany as a chemical raw material, for H'IN in the ceramic industry such as cement, refractories, glass, etc., for urban sewage, etc. The use of oxygen-enriched air is also well known for applications such as activated sludge treatment of general industrial wastewater and medical purposes. The amount of oxygen used in Japan has reached ~10 billion, and most of it is used as a catalyst for the steel industry.

[Conventional technology]

Industrial production of oxygen has been carried out since the beginning of this century by the cryogenic separation method. This method is considered to be the most suitable method when producing large amounts of oxygen (using large-scale equipment), but it requires an extremely large amount of energy.
Furthermore, in the case of on-site use, it is necessary to temporarily fill a pressure-resistant container and transport it, which results in a significant increase in cost. Also, as a method for producing oxygen on a relatively small to medium scale, a method has recently appeared that separates oxygen from air at high concentrations by utilizing the difference in the amount of nitrogen and oxygen adsorbed onto adsorbents such as zeolite, molecular sieves, and carbon. -1 In particular, it is used for various wastewater treatment, various (■ blowing into furnaces, medical purposes, etc.), but the power consumption required to produce oxygen is high, and the production cost of oxygen is high.Others A special method using metal complexes is being researched as a special method for It had the disadvantage of being difficult to use as an economic system because it repeatedly decomposed into darkness.

Starting with research in the US 9th Army around the end of the 7960s,
Research continues to be conducted to improve durability, and relatively durable products such as fluorine and fluorine-substituted products have been discovered. However, in the method using this oxygen complex, the absorption of oxygen is 27 to 3? There was a drawback that the temperature was close to ℃, and the release process had to be carried out at a high temperature of, for example, ♂-℃, and the operation required raising and lowering the temperature.
No. 07 discloses a method for selectively permeating and separating oxygen from air through a membrane in which a solution containing an oxygen complex is held in a porous negative membrane support. In this method, oxygen can be continuously separated using the pressure difference on both sides of the membrane at a constant temperature. In this type of farming, the ratio of oxygen and nitrogen permeation rates is large, and the oxygen permeation rate is large.
This is safe, and for this reason, the high reaction rate between #R complex and the complex, the large diffusion coefficient of the resulting oxygen complex, etc. are considered to be important reasons for safety. However, the above Tokukai Sho! Tar/27
Chemical Revue SF Volume 9 73 cited in Publication No. 07
9, (/97 years), Canadian Journal on Chemistry! Volume 33.24, page (/97/.

) Journal on the American Chemical Society / θ = Volume 3 and! Although many oxygen complexes have been discovered and studied, they are too bulky to stably and reversibly adsorb and desorb oxygen. Ligands were required, and the molecules of oxygen complexes had to be large molecules. With this, a large diffusion coefficient cannot be expected. On the other hand, although various cobalt complexes having relatively small molecular weight ligands have been studied, to date no substance has been found that reversibly adsorbs and deshields rIR elements.

[Purpose of the invention]

We conducted extensive research with the aim of searching for complexes with relatively small ligands that adsorb and desorb oxygen quickly and reversibly. The present invention was achieved by discovering the groundbreaking fact that the obtained complex has the ability to reversibly adsorb and desorb oxygen even though it has a relatively low molecular weight.

That is, the present invention relates to a gas selective separation material comprising a reaction product obtained by contacting (A) a co salt with (ii) diglopyrenetriamine having the formula % or a derivative thereof.

In addition, in order to obtain the above gas selective separation material, contacting of )) and (B) is carried out in the presence of an axial base, or (A)
This invention relates to a gas selective separation material obtained by adding an axial base to the reaction product of (1) and (2).

Also, the same <K atashi GA to obtain the above gas selective separation material) and (
It relates to a gas selective absorption liquid obtained by contacting B) mainly in the presence of a non-aqueous solvent, or by adding the solvent to the reaction product of (A) and (B).

The present invention also relates to a gas selective permeable membrane containing these gas selective absorption liquids and a gas selective absorption liquid containing these gas selective separation materials.

[#I formation of invention]

Next, the content of the present invention will be explained in detail.

The cobalt salt of (a) is diprobylate I of the present invention.
J 7 MinH2N-cH, -0H2-01[i, -N
H-OH, -OH, -CH2-NH2 or derivatives thereof,
One reason is that any compound may be used as long as it forms a lead body with each axial base to be added, and the following CO compounds are exemplified.

That is, cobalt oxide, cobalt hydroxide, cobalt fluoride, cobalt chloride, cobalt bromide, cobalt iodide, etc.
・Rogenides and their hydrates, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt cyanide, cobalt thiocyanate, cobalt perchlorate, cobalt periodate, cobalt difluoroborate, cobalt sholate, cobalt tartrate, etc. Examples include a-free acids, organic acid salts, and hydrates thereof, double salts such as cobalt alum, and cobalt compounds with cobalt compounds such as cobalt heptane, and the valence of cobalt can be arbitrarily selected.

Among the above cobalt salts, covalent cobalt salts, especially 8A-free
Salt-1tX preferred, Co(SON)2, (3oP, ,
Cool,,0oBr2.00 工2,Co(010,)
t, Co(BII′,),,Co(0OOOH,)t
is exemplified as the most preferred cobalt salt.

The amine compound of CB) required to react with the 00 salt to form a CO complex is dipropylenetriamine H,N-
CH, -CH2-CH2-NH-OH2-Off, -
(H2-NH2 and its derivatives are mentioned. (Hereinafter,
(simply referred to as "amine compound") The derivatives referred to herein are those obtained by replacing all or part of H in formula % and chemically bonding other atoms, functional groups, oligomers, polymers, etc. It also means a compound having an unsaturated bond obtained by partially eliminating hydrogen, and a compound having both a substituent other than the above H and an unsaturated bond.

! There are no particular limitations on how the 8 conductors are connected, but H2muOH,-0H-0)L,,-NH-(J4.-
CM,, -CM, -NH2)12N-OH, -0H2-
CH, ~kJ-CHt-CH, -0K2-NH2ruH, jJ-CH, -OH, -OH, -NH-(H, -C
H2-0H2-Nli-AB-HN-OH2-On, -
0H2-N-CH2-(H, -0H2-NH2B-HN
-OH, -CMH2-CH2-1! JH-f, H, -C
H2-OH, -Nu (-ABA H2N-OH, -CH, -0R2-NH-OH, -an
, -C4-N-A-HN-OH2-OH, -OH, -N
Examples include derivatives such as -OH2-CM, -0H2-IJ, and -Apo (wherein, B represents a functional group obtained by replacing H with , etc.).

It also includes a cyclic body in which two substituted functional groups, oligomers, polymers, etc. are bonded to each other at other ends.

In performing tt substitution or dehydrogenation, there are no limitations on the number of substituents or the number of unsaturated bonds.

Examples of the H-substituted functional groups, oligomers, and polymers in the above general formula include the following.

Examples of functional groups include halogen atoms such as P, Cl, Br, and carboxyl groups or metal salts thereof (-000H, -CO
OM ), Su/I/ Honyl 4 (-BOsH), Su/
L/ finyl group (-8o2H), m anhydride (-Co-
(J-co-), oxycarbonyl group (-00OR),
Haloformyl group (-COX), carbamoyl group (-a
oNH2), hydrazinocarbonyl group (-0ONHNH
2), imide, i group (-00-NH-CO-), amidi/ group (-c, N
li, ), nitrile group (-ON), incyano group (
-No ), formyl group (-0HO), carbonyl group (
C=0), water #1 group (-okl), alkoxy (-
OR), phenoxy group (-0-@), mercapto group (
-Sa ), hydroperoxy group (-0-OH), amino group (-NH2), imino group (=NH), hydrazino group (-NHNH2), sulfide group (-8R), peroxy group (-0-0- R), diazo group (=Nt), azide group (-Ns), nitroso group (-No), nitro group (
-NO2) and an organic group. The a-group mentioned here includes all the groups of organic compounds and organometallic compounds that are normally considered, and is not particularly limited. For example, methyl group, ethyl group, propyl group, fluor group, hentyl group, heyacyl group, hegetyl group, octyl group, nonyl group, decyl group,
1N-chain or branched saturated aliphatic hydrocarbon groups such as undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, hegetadecyl group, octadecyl group, nonadecyl group, ethynyl group, allyl group, vinyl group, etc. P) "unsaturated aliphatic hydrocarbon group,
Cyclopropyl, j cyclobutyl, cyclopentyl, cyclohexy, 71! /, F0 cyclo to f tyl, cyclooctyl, cyclodecyl, etc. W; Fa alicyclic hydrocarbon water wood group, full pen to buta full pen,
Unsaturated alicyclic hydrocarbon groups such as annulene; aromatic hydrocarbon groups such as phenyl, tolyl, cumyl, styryl, xylyl, sinane, and mesityl; fused polycyclic hydrocarbon groups such as indene, naphthalene, and azulene; pyrrolidinyl, 3-isoxasilyl, 3-morpholyl, cofuryl, cobiridyl, coquinolyl, goupiperidyl, imidazoyl, biradiyl, triazoyl, tetrazoyl,
Heterocyclic compounds such as piperidino, morpholino, furfuryl, -tenyl, virol, thiazole, aliphatic hydrocarbon groups having an aromatic ring such as benzyl, derivatives of these polar hydrocarbon groups, tridecyl group IJ /I, triethyl A silicon-containing functional group such as silyl or the above organic group having a silicon-containing functional group, a fluorine-containing functional group such as perfluoromethyl or perfluoroethyl, or the above-mentioned organic group having a fluorine-containing functional group An example is &4.

In addition, in the case of direct conversion, it may be an oligomer molecule or a polymer molecule, and this is a molecule in which 7 or more units of formula % are substituted with H in the oligomer molecule or polymer molecule. IJ w- or a compound that binds to an oligomer.

For example, H2N -CH, -CH2-CH, -NH-OH2-C
H2-OH2-MB2-oligo7-(or polymer) H,N-OH,-0112-OH,-N-01(2-O
H,C! H2-Nl (2 oligomer (or polymer) H,N-CH2-0H-OH2-N)i-OH2-OH
, -OH, -NH.

Oligomer (or polymer) (H2N-CH, -0H2-OH2-NH-C1(2-
It is expressed as a compound such as OH, -0H2-IJH nine polymers (n is an integer of 2 or more).

The oligomer used here is the molecule it 100-3
θ, θQ0, α-olefin, higher alcohol,
polyethylene glycol, crown ether, polysulfide, polyethyleneimine, fluorine-containing oligomer,
Low molecular weight polyethylene, low molecular weight polypropylene, polypropylene gellicol, polyglycerin, oligoester, acrylate, sodium polyacrylate, adiponitrile, low molecular weight polybutene, polyisobutylene, liquid bottle, su7lydiene, liquid chloride:・9゛Examples include liquid polypentadiene, synthetic chile 1, neugomer, polyisocyanate oligomer, phenol resin, amine resin, xylene resin, ketone resin, oligopeptide, and lipid.

Also, the polymer used here has a molecular weight /, θ0θ~/, 0
0θ, θ0θ, but not limited to, natural rubber, neoprene, polybutadiene, polybutylene, polyisoprene, polybutene, polyethylene, polyimbutylene,
Polymethylene, bolider methylbentene/, polypropylene, polyacrylic acid, polybutyl acrylate,
Polyethylene acrylate, polyisobutyl acrylate, polymethyl acrylate, polybutyl acrylate, polyacrylamide, polybutyl methacrylate, polyethyl methacrylate, polymethyl methacrylate,
Polymethacrylic acid, polyethyl methacrylate, polytrimethylsilyl methacrylate, polymethacrylamide, polyvinyl ether, polyvinyl thioether, polyvinyl alcohol, polyvinyl ketone, polyvinyl chloride, polyvinylidene chloride, polydifluoroethylene, polytriple oleoethylene, polymethacrylonitrile, polyvinyl Fluoride, polyvinylidene fluoride, polyvinyl ester, polyvinyl acetate, polyvinyl formate, polystyrene, poly-α-methylstyrene, polydivinylbenzene, polyvinylcarbazole, polyvinylpyridine, polyvinylpyrrolidone, polyphenylene, polyoxide, polyoxymethylene, polycarbonate , polyethylene adiphate, polyethylene terephthalate, polyester, polyurethane, polysulfone, elevated trosopolymer, polyamideimide, polysiloxane, polysulfide, polythioether, polysulfonamide, polyamide, polyimide, polyurea, polyphosphazene, polysilane, polysilazane, polyfuran, holibenzo Oxazole, polyoxadiazole, polybenzothiazole, polypyromellitimide, polyquinoxaline, polybenzimidazole, polydioquine isoindoline, polyoquine indoline, phoritriazine, bolihi 0 ridazine, polybi 2
gin, polypyridine, polypiperidine, polypyrazole, polypyrrolidine, polycarborane, polybicyclononane, polydibenzofuran, polyacetal, acetylene polymer, and random copolymers, graft copolymers, block copolymers of each of these polymers, and Chemically modified 1 combination of them, boron polymer, silicon polymer,
germanium polymer, nitrogen polymer, oxygen polymer,
Inorganic homopolymers such as sulfur polymer, selenium polymer, phosphorus polymer, beryllium hydride polymer, magnesium hydride polymer, boron hydride polymer, aluminum hydride polymer, gallium hydride polymer, indium hydride polymer, boron nitride polymer, nitride Inorganic heteropolymers such as aluminum polymers, silicon nitride polymers, silicon polymers, nitrided IJ polymers, phosphoric acid polymers, phosphorus-containing polymers, sulfur nitride polymers,
Organic derivatives of these inorganic polymers, various coordination polymers, organometallic polymers, carborane polymers, ionic polymers, polyion complexes, silicates, phosphates, inorganic glasses, activated carbon, molecular sieves, ceramics, Inorganic polymers such as carbon polymers and silicon carbide polymers, homoglycans such as cellulose, starch, pullulan, glycogen, dextran, mannan, galactan, fructan, laminaran, lichenan, nigeran, bentosan, glucomannoglycan, galactomannoglycan, heteroglycans such as arabinogalactoglycan, arabinoxyloglycan, vegetable gum, and seaweed polysaccharide; polyurethane such as pectin, alginic acid, and bacterial polysaccharide; hyaluronic acid;
:5701 minic acid, chondroitin sulfate, deru rJ7 acid, heparin, heparan sulfate, keratan sulfate, l,
917%.

Mecopolysaccharides such as Mun, blood type polysaccharides, ethylcellulose, carboxymethylcellulose, acetylcellulose,
Examples include derivatives of the above polysaccharides such as triacetate and ethyl amylose, polyamino acids and their derivatives, polypeptides and their conductors, lipids and their derivatives, sepharose, ion exchange resin hydrogels, proteins and their derivatives, and nucleic acids and their derivatives. .

When reacting the CO salt with the amine compound or its derivative, the oxygen separation ability of the resulting separation material can be improved by further carrying out the reaction in the presence of an axial base or by adding an axial base to the reaction product. can be further improved. This axial base does not necessarily mean that the coordination direction in the reaction product lead body in the present invention is the axial direction. -/2
Examples include Lewis bases such as imidazole, ketone, amine, amide, ester, lactone, sulfoxide, and pyridine, as described in 7θ2. Specific examples of such compounds include /-methylimidazole, 2-methylimidazole, /, 2-dimethylimidazole, imidazoles such as benzimidazole, dimethyl sulfoxide, N, N/-diethylethylenediamine, cudimethylamine pyridine, and Aminepyridine, Shimazuka-bipyridine, y-methoxypyridine, goomethylaminopyridine, 3. Curtidine, 3. ! - Pyridines such as lutidine, pyridine, co-methylpyridine, Goussian pyridine, pyrazine, davirollidinoviridine, N-methylpyrazinium halide, picoline, r-
Lactones such as butyrolactone, esters such as ethyl benzoate and ethyl acetate, phosphoric acid amides such as hexamethylphosphoric triamide, amides such as dimethylacetamide, preferably /-methylimidazole, comethylimidazole, Guaminopyridine, γ-butyrolactone are used.

As mentioned above, the reaction between the Co salt and the amino compound can be carried out in the presence or absence of an axial base, or by reacting the former in advance and then adding the axial base. It is done. A solvent is not necessarily required for the reaction, but when a solvent is used, the following compounds are exemplified. Namely, examples thereof include r-butyrolactone, dimethyl sulfoxide, propylene carbonate, diethyl sulfoxide, N-methylpyrrolidone, dimethylacetamide, r-valerolactone, dimethylformamide, formamide, ε-caprolactone, tributyl phosphate, diethylene glycol dimethyl ether, benzonitrile, and the like. Also included are some of the above axial bases. However, the solvent is not necessarily limited to these solvents.

The above-mentioned Co salt, dipropylene triamine or its derivative, axial base, and solvent may each be used in combination of seven or more types. It can also be used in combination with compounds outside the scope of the above definition.

During the reaction between Co salt and amine compound, the amine compound and C
The ratio of O salt varies depending on the type of Co salt used, but is generally 0.0/(amine compound/Co salt (molar ratio)
is required, preferably Q, /<amine compound/Co
100θ (molar ratio), particularly preferably selected from /amine compound/Co salt=θ (molar ratio).

Co salt is C00I□, coBr,, Co (0cOC1
i3) 2(2) if 1≦amine compound/Co
(molar ratio) gives the most favorable results.

Therefore, as long as the above conditions are satisfied, it goes without saying that even if diluted with an amine compound other than the invention 1/A, it falls within the scope of the invention, and the ratio of the A0 axial base to the Co salt is not particularly limited. is 0.00/(Axial salt M10O salt (mole ratio) is good, preferably 0.0/
(Axial base/Co salt (1000 (molar ratio), most preferably 0.l<Axial base/Co salt!0
(molar ratio) is selected.

On the other hand, it is not always necessary to use a solvent, but it may be effective in improving the performance of the resulting separation material. In that case, it is preferable to use a solvent (solvent/CO salt (10000
(molar ratio) is selected. In this case, the ratio of the amine compound and the axial base is selected in the same manner as above. When reacting each of the amine compound and the axial base in the presence or absence of a solvent, is not particularly limited. Further, the axial base may be added either by cooling or not, but when the axial base is added, the resulting separation material has excellent oxygen separation performance, so it is desirable to add the axial base.

The reaction temperature and pressure are not particularly limited, but are generally 0 to 2.
It is desirable to carry out at 00°C, θ, 07 to 700 and 9/d. In addition, prior to the reaction, pretreatment such as heat treatment and reduced pressure treatment of raw materials,
Although purification such as dehydration and deoxidation is preferably performed, conditions such as reaction temperature and reaction pressure may be changed during the reaction. The reaction time is not particularly limited, but is selected from 0.7 to 700 hours, preferably o, r to /Q hours.

The reaction product obtained by the reaction of the cobalt salt, the amine compound, and the axial base may be taken out as a solid component by a method such as depressurization or precipitation, and then dissolved again in a soluble solvent.

Next, a method for selectively separating a specific gas, particularly oxygen, using the gas selective separation phase obtained by the reaction of a CO salt, an amine compound, and an axial base of the present invention will be described.

First, the gas selective permeation membrane containing the gas selective separation material of the present invention will be explained. As a method for using it as a gas selective permeation membrane, the gas selective separation material of the present invention (hereinafter referred to as "separation material") is bonded to a base membrane formed into a membrane, and the separation material bonded to a polymer or oligomer is used alone or in combination with other polymers. A method of forming a film by mixing, a monomolecular film with a separating material alone or together with other molecules,
Possible methods include a method of forming a bilayer film, a cumulative film, an interlayer exchange, etc., a method of impregnating or retaining a separation material alone or a solution thereof as a liquid film in the porous P&, and the like. A membrane in which a separation material is bonded to the membrane or a separation material is formed alone or mixed with other polymers, a membrane that holds the above-mentioned monomolecular film, etc., and a support used for the purpose of holding the above-mentioned liquid film. The type of material for the body membrane is not particularly limited, but may include regenerated cellulose, cellulose ester, polycarpo 4-), polyester, Teflon, nylon, acetyl cellulose, polyacrylonitrile, polyvinyl alcohol, polymethyl methacrylate, polysulfone, polyethylene, polypropylene, Polyvinylpyridine, polyphenylene oxide, polyphenylene oxide sulfonic acid, polybenzimidazole, polyimidazopyrrolone, polypiperazine amide, polystyrene, polyamino acid, polyurethane, polyamino acid polyurethane comonomer, polysiloxane, polysiloxane polycarbonate copolymer, polytrimethylvinylsilane , organic polymers such as collagen, polyion complexes, polyurea, polyamide, polyimide, polyamideimide, polyvinyl chloride, and sulfonated polyfurfuryl alcohol, and inorganic substances such as glass, aluminum, silica, silica alumina, carbon, and gold nuggets. It will be done.

The shape of these supports may be flat, tubular, spiral, or hollow fiber.

These supports may be entirely porous, an anisotropic film with a dense layer only on the surface, or a homogeneous film.
. Alternatively, the surface may be coated with a thin film of another material by a method such as vapor deposition, coating, polymerization, or plasma coating. Although the overall thickness is not particularly limited, /Q~1
A range of 000μ is preferred. Such a support can also be used by being superimposed on a support made of another material.

Next, to explain the current state of separation membranes in general, various polymer membranes have been known as separation membranes for gas mixtures, but these membranes have relatively small gas permeation coefficients, and High quality materials are desired. When the membrane is in a liquid state, the gas solubility coefficient and diffusion coefficient are generally large, and therefore the permeation coefficient can be increased. Furthermore, when such a liquid membrane contains a substance that selectively and reversibly interacts only with a certain gas, it is important to further increase the permeability of that gas. On the other hand, the selective performance of a membrane is given by the difference in bath decomposition temperature between gases to the membrane and the difference in the diffusion rate of gases in the membrane, so it is possible to selectively reversibly interact only with the above-mentioned specific gases. When the film contains a substance that has a gas, the degree of solubility of only that gas increases, and the selectivity can be greatly increased.

Of course, the selective separation performance is improved when a substance that selectively and reversibly interacts only with the gas on the surface and inside the solid membrane is present, but in general, when a certain gas is present in the liquid membrane, the selective separation performance is improved. The selective separation performance of the membrane is greater when it contains a substance that selectively and reversibly interacts only with the membrane.

Many examples are known of such membranes containing substances that selectively and reversibly interact only with certain gases. Data//7t), separation of olefins using a silver water bath (Tokukosho!!-J'/♂4t2)
, Separation of nitric oxide by a formamide solution of ferrous chloride (A, Engineering Ch E Journal vol /6
Aj 410t page/97θ year), oxygen content by CO complex bath liquid with Schiff base etc. as a ligand = h, etc. These liquid groups are used while being retained on a membrane serving as a support.

In the present invention, the method of incorporating the gas selective separation material described in the claims into the gas selective permeation membrane is not particularly limited, but when used as a liquid membrane, the gas selective separation material or its solution may be incorporated into the gas selective separation material or its solution. It is used in contact with or holding a membrane that serves as a support.

The thickness of the gas selective separation material or its solution can be used at a thickness of several angstroms or more, and is not particularly limited. However, when the liquid film of these reaction products is used without stirring, it is preferable to make the film thinner in order to obtain a higher permeation rate. In addition, when the thickness is reduced by 90%, the permeation rate of gases other than those for the purpose of separation is also unfavorably reduced. The most suitable film thickness varies depending on the rate constants of binding and dissociation between gas and these reaction products, equilibrium constants, and other conditions, but is approximately 0.0/~roooo
It is used at a film thickness of μ, more preferably θ, /~10,000 μ. Further, when the liquid film is used under stirring, there is no problem even if the film is thick, but it is preferable that the substantial film thickness existing as a diffusion layer on the surface of the support film be as thin as possible.

A good method can be considered to separate gases using a gas-selective separation material or a membrane holding its bath liquid on a support. It is used by creating a partial pressure difference between the gases to be separated on both sides.

In addition, a container containing the gas selective separation material of the present invention or its solution is placed separately from the membrane cell, and a pump is used to guide this liquid to the surface of the support membrane (the primary side of the membrane) of the membrane cell for circulation. You can also use In this case, for example, oxygen is sufficiently absorbed into the liquid in the reservoir container, and then the gas is dissolved in the membrane cell by reducing the pressure on the secondary side of the membrane to continuously dissociate the bound gas. Desorbed and guided to the secondary side of the membrane,
It is also possible to use a method in which chlorine is extracted continuously and highly selectively by continuously carrying out an operation in which the oxygen-depleted liquid is introduced into a reservoir and the oxygen is dissolved again. In this case, the temperature of the membrane cell and the reservoir can be made different to facilitate the extraction of oxygen. Although the temperature of the membrane cell portion is not particularly limited, it can be used, for example, in the range of 0 to 200°C.

Next, a gas selective absorbent containing the gas selective separation material of the present invention will be explained. As a method of use as a gas selective absorbent, a method of supporting the gas selective separation material of the present invention (referred to as "separation material") on a porous carrier such as an organic polymer or an inorganic material;
Possible methods include using the liquid component [8] alone or as a solution. When supporting the separation material on a porous carrier of organic polymer or inorganic material, the charge used as the carrier is the above-mentioned polymer exemplified in the explanation section of the amine compound derivative or the support when holding the separation material on the membrane. The materials mentioned above as examples of materials that can be used as body membranes can be cited as examples of carrier materials that can be used as they are. In addition, when this separation material is used as an absorption liquid, the liquid separation material can be used alone or as a bath liquid dissolved in a solvent. In this case, the solvent used in the production of the separation material may be used as is, or another solvent may be used. Oxygen is selectively dissolved in the solution of this separation material in a higher amount than other gases. In this case a bath of separating material! There are no particular restrictions on the pressure of the mixed gas containing oxygen in contact with the gas and the oxygen pressure, but the pressure of the mixed gas flowing through is 9/clA at θ, / ~ / 00, and the oxygen partial pressure is 0.0 / ~ /Okg/-
used in The higher the oxygen partial pressure in contact with the solution of this separation material, the more e! The absorption rate of the cord is greatly advantageous. Also, lower temperatures are advantageous because the amount of absorption is larger, but usually -! θ℃~/
Oxygen absorption takes place at Qθ°C. Another method for increasing the oxygen absorption rate is to increase the area of the gas-liquid interface, and it is desirable to bubble gas into the separation material solution or stir the solution. The solution of the separation material that has selectively absorbed a larger proportion of oxygen is then reduced in pressure, releasing an oxygen-rich gas.

The pressure and temperature are not particularly limited, but the reaction is usually carried out at a pressure of θ to 7 to 9/-, and at a temperature of - to θ°C to ioo°C.

The lower the pressure and the higher the temperature, the more advantageous it is to release oxygen. In this case as well, it is advantageous to perform the desorption while stirring the solution because the release rate can be accelerated.

Although the apparatus for using the gas selective separation material of the present invention as a gas selective permeation membrane is not particularly limited, the following method can be used, for example. That is, a module is equipped with a membrane containing a separation material, an inlet for a supply gas and a persilo are provided on the seventh side of the membrane, and an outlet for a product stream is provided on the secondary side of the membrane. A vacuum pump is installed at the output of the product stream to extract the product stream that has passed through the membrane under reduced pressure. If necessary, connect to the module and provide a pressure regulator flow meter. Using such a device, for example, air is supplied to the 7th side of the membrane, mainly oxygen permeates through the membrane, nitrogen-enriched air is passed through the membrane on the 7th side of the membrane, and oxygen and condensed gas are passed through the membrane. From the next 1141J, je starts. The housework-enriched air or oxygen-enriched gas discharged from the module can be returned to the supply side again for circulation and use. Alternatively, instead of supplying gas to the seventh side of the membrane, a separation material or its solution in which the supplied gas is dissolved is supplied. The liquid corresponding to the decrease in the amount of oxygen in the bath is removed from the Persillo on the 7th side of the tank. The separation material liquid with a reduced amount of dissolved oxygen is returned to the supply tank, where it is sufficiently absorbed with air, etc., and then supplied to the arm module again. Of course, instead of evacuating the secondary side of the membrane with a vacuum pump to remove the permeated gas, another gas that can be separated from oxygen is supplied to the secondary side of the gland, and the partial pressure of oxygen in the permeated gas is increased. It is also possible to operate at a lower state than that on the feed side. When the gas selective separation material of the present invention is supported on a porous solid and used as an absorbent, the separation material can be used in a tower, etc. Fill it. A feed gas containing oxygen is introduced through the gas inlet of the column, mainly absorbs oxygen, and the oxygen-depleted gas is released from the persillo. Next, the tower is depressurized to desorb oxygen from the separation material and extract oxygen-enriched gas. In this case, one or more columns filled with absorbent are installed, and p, s.

As carried out in Method A, the time for attaching and detaching each tower is shifted in stages to IM! It is also possible to carry out the process of removing and removing horse mackerel continuously. The 1st floor of the first floor contains seven examples, and is not limited to this method.

Next, when the gas selective separation material of the present invention or its solution is used as an absorption liquid, the liquid of the separation material is filled into an absorption tower as an absorption liquid. Next, the oxygen-depleted supply gas is introduced into the absorption tower, and the absorption liquid absorbs oxygen. The oxygen-depleted gas is released from Persilo. Next, the absorption liquid that has absorbed oxygen is sent to a stripper tower. Under reduced pressure or heating, the absorbed oxygen-enriched gas is released from the absorption liquid and taken out. On the other hand, the absorption liquid from which oxygen has been released is returned to the absorption tower, and air or the like is introduced again to absorb oxygen. Repeat this operation continuously. A pressure machine, a blower, a fan vacuum pump, a pressure regulator, a flow meter, and a circulation pump can be connected to the absorption tower and the stripper tower as necessary. The above method is just seven examples) and is not limited to this method.

The gas-selective separation material of the present invention has high separation performance regardless of whether it is used as a gas-selective permeable membrane, a gas-selective absorbent, or in other cases, so oxygen can be removed with high efficiency. Can be concentrated. In addition, since the rate of adsorption and desorption of @ elements is much faster than that of known oxygen complexes, it is possible to coarsen oxygen very efficiently. For example, nearly 100 units of oxygen can be efficiently extracted from air in seven or two stages. On the other hand, when the supplied gas is air, the residual gas after decomposing oxygen is a gas containing a high concentration of nitrogen, and is therefore valuable as a method for producing high concentration nitrogen. Apart from this, it is also useful as a method for removing oxygen from a gas containing a trace amount of oxygen.

Oxygen can be separated from air using the gas selective separation material of the present invention. Oxygen is a gas widely used in all industries, especially in welding and cutting steel materials, and in electric furnaces. 1
Plain blowing, glass melting, pulp bleaching, wastewater treatment, metal processing, paper manufacturing, aviation, space, pollution prevention, medical care, electronics industry,
The gas selective separation material of the present invention can be usefully used in fields such as chemical industry and marine development. On the other hand, if nitrogen is separated from the remaining gas after removing oxygen from air, it becomes an inert gas that is useful in a wide range of fields such as the electronic industry, food industry, steel metallurgy industry, chemical industry, and medical use.

〔Example〕

The present invention will be explained in detail below with reference to Examples.

In the Examples of the present application, the gas permeation rate was measured as follows. That is, the outer diameter is 4t! A flat membrane made of polytrimethylvinylsilane is installed as a base membrane in a cylindrical glass cell, and after injecting the dispersion or slurry containing the selective parking material to be tested, the permeation test gas is introduced under stirring. It was distributed. On the other hand, the υ permeation rate Q was determined by reducing the pressure on one side (secondary side) of the base membrane and analyzing the amount of gas permeated within a certain period of time by gas chromatography. Note that Q in this example is a value measured at 30° C. (unless otherwise specified), and its unit is CC/−·5eC−cInHI. In addition, the amount of gas absorbed by α was measured as follows. That is, a fixed amount of the selective separation material KPJ'r or its solution was poured into a glass container with a known volume, and then the inside of the container was depressurized and degassed. After sufficient degassing, a bending gas was introduced while the container was maintained at 23° C., and the amount absorbed was measured using a gas buret. To measure the amount of gas absorbed in a solution state, the amount of absorption of the used Futsuka Monokino was measured as a blank, and this was subtracted to determine the amount of absorption of the separating agent.

Examples/(a) Preparation of separation material 2.3-dipropylene triamine and thiocyanate (coba/l/), θ, y r F were charged into a JONt hook and stirred under nitrogen, causing a reaction with slight heat generation. /
After the evening, dimethyl sulfoxide (hereinafter simply referred to as DMSO) was added, and the mixture was heated to 60° C. and reacted for several hours to obtain a deep red homogeneous solution.

(1)) Measurement of gas permeation rate Separation agent 10-
was fractionated, and air was passed through it at a rate of θ, j l/min. Next, the secondary side pressure was adjusted to 2 Dragon HP and the measurement temperature was increased to 3
When the temperature was adjusted to 0°C and the permeated gas was analyzed by gas chromatography, it was found that the oxygen concentration was 2.3%. Also, at this time, the raw transmission speed W QOt is Da, O×/
It's θ-6, α is! It was 0.2.

Example (a) Preparation of separating agent Dipropylenetriamine, 3- and copal thiocyanate) 0.9 j
After reacting #/-methylimidazoleco, 2r
After adding nl and reacting for 70 minutes, DMSO7- was added and stirred at to°C for 2 hours to obtain a deep red homogeneous solution.

(1)) Measurement of gas permeation rate When an air gas permeation test was conducted in the same manner as in (1)), the oxygen concentration of the permeated gas was ? It was Yuchi. Also, QO2 at this time is J', 7 X /θ-6, and α is! , Nidemeta. It can be seen that α increases when /-methylimidazole is used as the axial base.

(C) Measurement of gas absorption amount 2! Separating agent jd prepared in (a) was placed in a glass container (a), and after sufficient degassing, the amount of oxygen absorbed was measured using a gas buret. The amount of oxygen absorbed at the center was determined by subtracting the amount of oxygen absorbed from the DMSO-/-methylimidazole mixture. As a result, the oxygen absorption ratio was 2-2, which corresponded to 0.74 molecules of oxygen per cobalt atom.

The separation agent was degassed under reduced pressure and the amount of oxygen absorbed was measured again? It was Go. This indicates that the separating agent reabsorbs oxygen.

Example 3 A separating agent was prepared in exactly the same manner as in Example 2(a) except that cobalt acetate was used instead of cobalt thiocyanate, and a dark reddish-brown homogeneous solution was obtained. Using this solution, we traced the gas permeation performance in the same manner as in Example/(b), and found that the cumulative concentration of # in the permeated gas was 3♂
,! H, Q02 was 8 x/θ-6 and α was 2.3.

Example 2 A separating agent was prepared in the same manner as in Example /(b), except that in (a), cobalt bromide) /,, 21/ was used as a substitute for cobalt thiocyanate. When gas permeation performance was measured using
．． 6. [Effects of the Invention] The gas selective separation material according to the present invention has particularly excellent oxygen separation ability, so it is useful in a wide range of industrial fields.

Claims (3)

[Claims] (1) (A) Co salt and (B) formula H_2N-CH_2-CH_2-CH_2-NH-CH
A gas selective separation material comprising a reaction product obtained by contacting dipropylene triamine or a derivative thereof represented by _2-CH_2-CH_2-NH_2. (2) In the separation material according to claim 1, (
A gas selective separation material obtained by bringing A) and (B) into contact in the presence of an axial base, or by adding an axial base to the reaction product of (A) and (B). (3) In the separation material according to claim 1 or 2, (A) and (B) are brought into contact mainly in the presence of a non-aqueous solvent, or (A) and ( A gas selective separation material obtained by adding the solvent to the reaction product with B).