JPS6311504A - Gas separation material - Google Patents

Abstract

PURPOSE:To obtain the title separation material having a high oxygen adsorption and desorption rate and capable of efficiently concentrating oxygen by bringing a composition consisting of a Co salt and an amine compd. having a skeleton shown by a specified formula into contact with a silicon halide compd. CONSTITUTION:A composition consisting of (A) a Co salt (e.g., cobalt thiocyanate) and (B) an amine compd. (e.g., tripropylentetramine and a compd. shown by formula II) having a skeleton expressed by formula I [(n) is 2-10<5> or preferably 2-1,000] is brought into contact with (C) a silicon halide compd. (e.g., silicon tetrafluoride) to obtain the gas separation material. Since the separation performance of the material is high even when the material is used as a gas permselective membrane or as a material for selectively separating gases, oxygen can be highly concentrated. Since the oxygen adsorption and desorption rate of the material is high, oxygen can be concentrated extremely efficiently.

Description

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

Oxygen is the most widely used gas and has been used for many generations, and its fields of use include welding and cutting steel materials, blast furnaces,
Blow into converter, open hearth, etc.! It is known to be used for JA iron, for sharp construction of cement, refractories, and glass in kilns, for activated sludge treatment of urban sewage and general industrial wastewater, and for medical purposes, including the use of oxygen-enriched air. There is. The amount of oxygen used in Japan has reached 0 to 1 billion yen, and most of it is used for the steel industry.

[Conventional technology and its problems]

Industrial production of oxygen has already been carried out since the beginning of this century using cryogenic separation iK.
Therefore, it has been done. This method is.

It is convenient for producing large amounts of oxygen.

It requires an extremely large amount of energy. In addition, when using oxygen on-site, first fill it in a pressure-resistant container [
It is disadvantageous that the gas must be transported, which results in the use of extremely expensive gas.

Recently, as a method for producing oxygen on a relatively small to medium scale, methods of separating and concentrating high-concentration oxygen from air using adsorption particles such as zeolite, molecular sieves, and carbon have been attracting attention recently. However, this method consumes a lot of power (and therefore the production cost of oxygen is high).

Apart from the above method, a specific gold rA that forms an oxygen complex can be used.
Methods have been proposed that utilize complexes in separation techniques. For example, it has been known that a cobalt tones base complex reversibly forms an oxygen complex, but there is a problem with the stability of the complex, making it difficult to use as a one-separation system.

After that, in the late 1940s, four aircraft were used in the United States, and on the other hand, its release (desorption) required a high temperature of around 10 degrees Celsius.
Its adsorption and desorption had the disadvantage of requiring temperature rise and fall.

On the other hand, rf Kaiaki! 9-/2707 discloses a method for selectively separating oxygen from air through a membrane in which a porous support holds a solution containing a complex capable of complexing with oxygen. This method allows continuous separation without changing the temperature by utilizing the difference in partial pressure of oxygen on both sides of the membrane. In such a membrane separation method, it is necessary to have a large permeation rate ratio between oxygen and nitrogen (and a high permeation rate for oxygen, but for this purpose, the reactivity of the complex used with oxygen and the generated oxygen It is considered desirable that the diffusivity of the complex be as high as possible.However,
Tokukai Akira &? -Chemical Review Volume 9/Page 39 (/979) cited in Publication No. 2707, Canadian Journal of Chemistry J! Volume I, 7!1.2
Page (/?7A), Journal of the American Chemical Society Vol. However, research has been conducted on relatively low-molecular cobalt complexes, but the stability of the oxygen complexes is poor and they decompose even at temperatures below freezing. Most of them were things.

[Means for solving problems]

We have a relatively simple and small molecular structure.

In addition, we searched for transition metal complexes that have a high affinity for oxygen and form complexes specifically and quickly, and conducted intensive research with the aim of developing a highly selective separation method for oxygen using these complexes, as described below. The present inventors have discovered that a complex obtained from a ligand having a specific chemical structure, a Co salt, and a halogenated silicon compound is extremely useful, particularly as a highly selective separation method for oxygen, and has thus arrived at the present invention.

That is, the present invention provides (A) Co salt and (B) general formula 4NHCH
The present invention relates to a gas selective separation material formed by contacting (C) a halogenated silicon compound with a composition comprising an amine compound having a skeleton of 2CHICH2+Q (n is the number of B greater than or equal to Q).

Component (A) further primarily in the presence of a non-aqueous solvent.

The present invention relates to a gas selective separation material obtained by contacting (B) and (C), and 5. The present invention relates to a gas selective permeable membrane and a gas selective absorption material containing these gas selective separation materials.

The content of the present invention will be explained in detail below.

As the Co salt of component (A), (B) general formula +NHCH2
Especially if it reacts with an amine compound (hereinafter simply referred to as 1 amine compound 1) or an axial base CD having a skeleton of CH2 (J (2+rl (n is an integer of 2 or more)) to form a complex. Examples include, but are not limited to, the following compounds.

cobalt oxide, cobalt hydroxide, cobalt fluoride, cobalt chloride), cobalt bromide.

Halides such as cobalt iodide and their hydrates, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt cyanide, cobalt thioanate, perfumed cobalt, cobalt periodate, cobalt tetrafluoroborate, oxalic acid Examples include infinite acids and organic acid groups such as cobalt, cobalt tartrate, and cobalt acetate, and their hydrates, double salts such as cobalt alum, and +Q cobalt compounds such as cobaltocene. The valence of cobalt can be arbitrarily selected, but divalent is preferable, and a stepless salt is selected as a suitable cobalt salt.

Component (B) has the general formula -1, NHCH, 0H2CH2+n
It is an amine compound having a skeleton (n is an integer less than or equal to 1).

The range of n is 1 to 100,000, preferably
Col 10,000. More preferably, it is selected from λ~/,000. An amine compound that satisfies the above general formula is
When expressed as +NHCH20H20H2+nY, the following compounds are exemplified. That is, examples of chain polyamine compounds in which X is hydrogen and Y is an amino group include dipropylenetriamine, tripropylenetetramine, and tetraglopylenepentamine.

Examples include heptapropylene hexamine, hexapropylene hexamine, oligopropylene imine, and polypropylene imine.

When X is hydrogen and Y is a compound other than an amino group, as Y -
0027, -0RO, -Q=Q, -0-, -OR.

108B-, ORB, -0==8, -8, -
8R, -0ONHR.

-NHCOR, -ON, -CH=N-, -0=N-
, -IJH-''.

Functional groups such as -NR-, -NR- (where R is hydrogen or an organic group) are selected, and specifically, H+N only CH2CHz CHzsho0H H4NHCH2 (3H20H, +TN(CH3).

H+NHOH, 0H20 horse seven JHR H+NHOH2UH2CH! +rNHOOO1,H,.

H+14HCH2CH, OH2+rNHCH, 0H2C
H,? .

H+NHCH,IjH,OH,+rNHCH,OH,O
H,OH.

H+NHCH,C! H,OH,)y[ICH,OH,C
H,C! H.

Examples include compounds such as H+NHC H, OH, NHOH, OH, (!H/Polystyrene).

Even when X is an organic group, the same functional group as above can be selected as Y, and a specific example is cH3+Nuca, a
H2c Horse Seven NH2゜0sHrG NHOHzOH2C4
hNHz.

C,H7(NHOH,OH,OH2%NH(OH3)
.

CH3+NHC horse (3H, C horseback N (OH3)!01,
H3, (-NHC horse cH, OH, seNH(OH3)01
sH3, +NHOH2C! Horse aH, →r NHCss
Hst polystyrene + NHCH, CH, OH, %NH2
Examples include polyurethane+NHCH, 0R20) T2+TNH+polyurethane), and the like.

can choose (, H3+NHcH, CFi2QH2+T?.

OHs + NHCHzC1120Hz + rCHs.

CH3% NTlOH2 (3H1OH2+rCEl==
A specific example is a compound of OH2. Note that X and Y are not limited to these specific examples, and can be arbitrarily selected as long as they are amine compounds that satisfy the general formula.

Cyclic polyamine compounds represented by the general formula 1 (indicating bifunctional groups such as ffi and polyfunctional organic groups containing them) are also referred to, and specific examples include +NIH, OH C) f25-i .

-+NHC-C Horse CFI, f, , (NIH,C Horse C
Examples include horse racing.

On the other hand, apart from the examples of one or more amine compounds, derivatives thereof are also included in the definition of amine compounds of the present invention. That is, the derivative defined here is the formula +NHOH,OH,OR2+n
In the above, a compound in which part or all of H is substituted with another atom or functional group, or an organic or inorganic polymer or oligomer, etc., and - also refers to an unsaturated compound obtained by elimination of R.

For example, FJ may have a bond as a derivative having a to group other than 'H) is shown as an example, but A may be bonded to either N or C in any form in the derivative. It is sufficient that there are - or more of +NTlcH2(!H20H2+/single 20H2+).Also.

When there are multiple A's, they may be the same or different.

--1 to the north = 111 eyes 4 r 枦 nodimo 1 In addition, A also includes a bifunctional or higher polyfunctional group, but in this case it represents a cyclic compound. In this case, A is the following n == 3
As shown in the example above, it is not necessary to bond within the same unit (also, it is possible to bond between different elements).

-NHC horse CH, CHNI (O/H2 (, HCH, N)
ICH%O horse CH,--A1-NE10H2CH,0FINH(312CH,OH
,NOH,CH20H,-shi-,-”-NT(CHCH,0HNHOH20H20H2NHC
H20H20H, -LA" Furthermore, even if substituent A contains an unsaturated bond, it falls within the scope of the unclaimed invention.

Specific examples of the above rrLIA group A other than H are as follows: oxycarbonyl group (-cooR), haloformyl group (-0
0X), carbamoyl group (-0ONH2), H)
” 5 dinocarbonyl group (-C0kJHNH2),
imido group (-CO-NH-CO-), amidino group (-C
=NH), diazo group NH2 (-ON), isodiazo group (-NC), formyl group (-
cqo), carbonyl group (,Q=Q), hydroxyl group (-
OR), alkoxy group (-OR), phenoxy group (-〇ph3 mercapto group (-8H), hydroperoxy group (-00H), amino group (-NH,), imino group (:
NH), hydrazino group (-NHN horse), sulfide group (-8R), 'peroxy group (-00R), diazo group (
Nz), azide group (N3), nido Oso group (-No).

Examples include a nitro group (N02) and an organic group.

The organic group here includes all organic compounds and organometallic compound groups that are normally considered, and is not particularly limited. For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hequinyl group.

Heptyl group, octyl/L/ group, nonyl group, denyl group.

Straight chain or branched saturated aliphatic hydrocarbon groups such as undecyl group, dodecyl group, tridenyl group, unsaturated aliphatic hydrocarbon groups such as ethynyl group, allyl group, vinyl group, cyclopropyl, cyclobutyl.

Alicyclic saturated hydrocarbon groups such as cyclopentyl, cyclohexyl, cyclooctyl, and cyclodecyl; alicyclic unsaturated hydrocarbon groups such as fulpene, heptaflupene, and annulene;
Phenyl, toluyl.

Aromatic hydrocarbon groups such as cumyl, styryl, xylyl, sinane, mesityl, indene, naphthalene, etc. 0, quaphoryl, 2-furyl, copyridyl, coquinolyl, 41-piperidyl, imidazoyl, biradiyl, triazoyl, tetrazoyl,
Piperidino, Morpholino, Furfuryl, Cochinil.

Heterocyclic compounds such as virol and thiazole, aliphatic hydrocarbon groups having an aromatic ring such as benzyl, derivatives of these various hydrocarbon groups, silicon-containing functional groups such as trimethylsilyl and triethylsilyl, or the above-mentioned silicon-containing functional groups, Examples include fluorine-containing functional groups such as perfluoromethyl and perfluoroethyl, and the above-mentioned fluorine-containing groups.

As the substituent for the parent, H, oligomer or polygu molecules can also be used. The oligomers used here have molecules of xioo to J0.000 and include α-olefins, higher alcohols, polyethylene glycols, crown ethers, polysulfides, and polyethyleneimines.

Fluorine-containing oligomers, polyethylene, polypropylene,
Polypropylene glycol, polyglycerin, oligoester acrylate, sodium polyacrylate, adiponitrile, polybutene, polyisobutylene, cyfmidodecatriene, liquid polybutadiene, liquid polychloroprene, liquid polypentadiene, synthetic terpenoids.

Examples include polystyrene, petroleum resin, human oil, silicone oligomer, polyisocyanate oligomer, phenol resin, amino resin, xylylene resin, ketone resin, oligopeptide, and lipid.

Father, the polymer used here has a molecular weight of t, oo.

-/, 00θ9000, but not particularly limited to, natural rubber, neoprene, polybutadiene, polybutylene, polyinoprene, polybutene, polyethylene, polyinobutylene, polymethylpentene/, polypropylene, polyacrylic acid.

Polybutyl acrylate, polyisobutyl acrylate, polymethyl acrylate, polysodium acrylate, polyacrylamide, polybutyl methacrylate, polyethyl methacrylate, polymethyl methacrylate,
Polymethacrylic acid, polysodium methacrylate, polytrimethylsilyl methacrylate, polymethacrylamide, polyvinyl ether, polyvinyl thioether, polyvinyl alcohol, polyvinyl ketone, polyvinyl chloride, polyvinylidene chloride, polydifluoroethylene, polytrifluoroethylene, polymethacrylonitrile.

Polyvinyl fluoride, polyvinylidene fluoride, polyvinyl ester, polyvinyl acetate, 2% ribinyl formate, polystine.

Polyα-methylstyrene, polydivinylbenzene, polyvinylcarbazole, polyvinylpyridine, polyvinylpyrrolidone, polyphenylene.

Polyphenylene oxide, polyoxymethylene.

Polycarbonate, polyethylene adipate.

Polyethylene terephthalate, polyester.

Polyurethane, polysulfone, nitrosopolymer, polyamideimide, polysiloxane, polysulfide,
Polythioether, polysulfonamide, polyamide, polyimide, polyurethane, polyphosphazene, polysilane, polysilazane, polyfuran, polybenzoxazole, polyoxadiazole, polybenzothiazo-/
L/, polypyromellitimide, polyquinoxaline, polybenzimidazole, polyoxoindoline, polytriazine, polypyridazine.

Polypiperazine, polypyridine, polypiperidine, polypyrazole, polypyrrolidine, polycarborane, polyfluorescein, polybicyclononane, polydibenzofuran, polyphthalide.

Polyacetal, acetylene polymers, random copolymers, block copolymers, graft copolymers of these polymers, chemically modified copolymers thereof, boron-containing polymers, silicon-containing polymers, germanium-containing borya, nitrogen-containing Inorganic heteropolymers such as nitride polymers, silicon nitride polymers, nitride polymers, phosphorus polymers, phosphorus-containing polymers, and sulfur nitride polymers.

1': 1゜j Otsu! Organic derivatives of these inorganic polymers, various coordination polymers, various organic gold IF4 polymers, ionic polymers, polyion complexes, K! Salts, llinates, inorganic glasses, activated carbon, molecular sieves, ceramics, carbon polymers, inorganic polymers such as silicon carbide polymers, and cellulose.

Heteroglycans such as starch, glycogen, dextran, mannan, galactan, fructan, vegetable rubber, seaweed polysaccharides, polysaccharides and their derivatives such as algin, chitin, ethyl cellulose, polyamino acids, polypeptides, Lipids and their derivatives, Sepharose.

Examples include ion exchange resin hydrogels, proteins and their derivatives, and nucleic acids and their derivatives.

Also, as for derivatives having unsaturated bonds, as in A above, the amine compound should have 7 or more unsaturated bonds in any form (it does not matter if they are branched unsaturated bonds). As part of specific examples, the following example can be given for the case where n=3.

-aHca2an, an-=Nc horse C horse OH, IJHC
-○H,C bird--NHOH,OH,C horse NHO horse 0H=
=OHNHO horse OH, CH, --icH, CaH2NH
c4cm, an2Nuca, c horse 011. --NT10
H, C, H = OH2NHOH2CH 20 horses NHC horses ○ =
OR (B represents an atom or functional group with a covalence or higher) component (C
) is a halogenated silicon compound containing one or more halogen-
It means any compound having a silicon bond, and it does not matter whether it is a mixture or a polymer as long as it satisfies the above conditions.

For example, silicon tetrafluoride, silicon tetrachloride, silica tetrabromide, silicon tetraiodide, bromotrichlorosilane, dichlorodibromosilane, dichlorodifluoronane, trichloridesilane, trichlorosilane, dichlorosilane, chlorosilane, triiodosilane , hexafluorodisilane.

Hexachlorodisilane, hexabromodinelan, hexaiododisilane, hexachlorodisiloxane, hexadiomodisiloxane, hexaiododisiloxane and perchloropolysiloxane.

Inorganic silicon compounds such as perhalogenated siloxane monomers such as perbromopolysiloxane and bayodopolysiloxane, and mixtures thereof, trimethylfluorosilane, trimethylchlorosilane, trimethylbromosilane,
Trimethyliodosilane, methyldichlorosilane, chloromethyldichlorosilane, dimethyldichlorosilane.

Methyltrichlorosilane, methyltribromosilane, methyltriiodosilane, dimethyldibromosilane, dimethylshortsilane, i,3-short octamethyltrisilane, vinyltrichlorane, allyltrichlora
Nran, vinyldimethylchloronane, allyldimethylchlorosilane, /,/-cycloO-/-nracyclohexane*j-n, /,/-')7fromo/-silaneclohexane, /,/-short-/-silacyclohexane , /, /-cycloro/-silanecrobutane, /, /
Cyclic and chain aliphatic silicon compounds such as -cycloCj-/-nracyclopentane, phenyltrichlorosilane,
Diphenyldichlorosilane.

Trimethylchlorosilane, phenyltriiotonane, phenyltriiotonane, diphenyljotonane, triphenyliodosilane, α-naphthyltrichlorosilane, α-naphthyltriiotonane, p-methquine phenyltriiodosilane, benzyltriodosilane Examples of inorganic and organic polymers substituted with halogen-containing groups such as iodosilane, enylmethyldichlororane, fluorine methyldichlorane, and halogenated organic polymers of the present invention include polystyrene and the like. Further examples include inorganic and organosilicon polymers whose skeletons include the above-mentioned nests having halogen-silicon bonds.

Reaction products or mixtures of the above halogenated silicon compounds and other compounds also fall within the scope of the present invention, and compounds that result in a halogen-silicon bond are also included in the halogenated silicon compounds of the present invention. For example, a silicon compound having an aryl group such as a phenyl group or a hydrogen group reacts with a halogen such as chlorine, odor, or iodine to produce a halogenated silicon compound.

In addition, one of the halogenated silicon compounds of the present invention is the above-mentioned specific fl.
(Also, they can be used by mixing or reacting with halogens such as fluorine, chlorine, bromine, iodine, or other halogenated compounds.)

Before, during, or after the contact reaction between the Co salt and the amine compound or the silicon halide compound, the oxygen separation ability of the separation material obtained by further adding an axial base and reacting is determined as described in the additional publication. (Lewis bases such as imidazole, ketone, amine, amide, ester, lactone, sulfoxide, and pyridine can be mentioned. Specific examples of such compounds include l-methylimidazole 1.2-methylimidazole, /, -Imidazole such as dimethylimidazole, benzimidazole, etc./L/a, dimethylsulfokind, N,N'-diethylethylenediamine, gauge methylaminopyridine, l
l-aminopyridine, lI, p'-piperidine, dermetquinpyridine, dermethylaminopyridine, 3. y-
Lutidine, 3. ! -A/Tidine, pyridine, dermethylpyridine, lI-cyanopyridine, piperazine.

Derpyrrolidinoviridine, N-methylpyrazinium halide, pyridines such as picoline, lactones such as γ-butyrolactone, and ethyl benzoate.

There are esters such as ethyl acetate, and l-methylimidazole, lI-dimethylaminopyridine, and benzoethyl benzoate are preferably used. Also.

A polymer having the above skeleton and polyvinyl vicritone,
Polymers such as polyvinylpyridine, polymethyl methacrylate or copolymers thereof can also be used as axial bases.

As mentioned above, by further adding an axial base and reacting it before, during or after the contact reaction between the CO salt and the amine compound or the /'t O-genide silicon compound, a separation material with even higher selectivity can be obtained. be able to. When reacting.

A solvent is not necessarily required, but if a solvent is used conveniently, 1
The following compounds are exemplified. Namely, r-butyrolactone, dimethyl sulfoxide, propylene carbonate, diethyl sulfoxide.

N-methylpyrrolidone, dimethylacetamide.

r-valerolactone, dimethylformamide.

Formamide, C-caprolactone, 11-butyl phosphate, diethylene glycol dimethyl ether,
Examples include benzonitrile.

Further, some of the above-mentioned axial bases can also be mentioned.

However, the solvent is not necessarily limited to these solvents.

The above-mentioned CO salts, amine compounds, halogenated silicon compounds, axial bases, and solvents may be used in combination of 7 types or λ or more types. It can also be conveniently used by mixing it with compounds outside the scope of the above definition.

When a halogenated silicon compound is catalytically reacted with a composition consisting of a CO salt and an amine compound, the following methods (a) to (d) can be exemplified, but the method is not limited to these methods. You may perform it by combining suitably.

(a) A method in which a CO salt and an amine compound are catalytically reacted with a halogenated silicon compound during or after the reaction.

(b) A method in which an amine compound is reacted after contacting a CO salt and a halogenated silicon compound, or a method in which a CO salt is reacted after contacting an amine compound and a halogenated silicon compound, 3. (c) Coexistence of a halogenated silicon compound A method of catalytically reacting a CO salt and an amine compound as described below.

(d) A method in which a gas selective separation material is prepared by the methods of (a) to (c) or by an appropriate method from a QO salt and an amine compound, and then a halogenated silicon compound is brought into contact with the gas in the presence of the gas to be separated. .

The reactions in (a) to (c) above can be carried out using the solvents already exemplified, but the solvents can be used at any stage before, during, or after the catalytic reactions in (a) to () and). It can be selected arbitrarily. Also, top 5. The method of contacting or adding the axial base at that time is not particularly limited and can be arbitrarily selected. Therefore.

When contacting each of the CO salt, amine compound, and halogenated silicon compound by the methods (a) to (d) above,
The axial base may be added at any reaction stage, and a mixture or reactant of the axial base and the silicon halide compound may be added.

Ingredients (A), (B), (C) and CD) mentioned above
In the catalytic reaction, the amount of each component used is not particularly limited, but it is preferable to use each component in the following ratios.

That is, the ratio of amine compound to CO salt, amine compound/
The OO salt (molar ratio) is preferably θ,oi or more, more preferably 0. /～/ 000. Most preferably 0.3-
Selected from a range of 20. Therefore, as long as these conditions are satisfied, it goes without saying that even if the composition is diluted with an amine compound other than that of the present invention, it is within the scope of the present invention.

Ratio (mole ratio) of axial base and CO salt: Akinyal base/Co salt should be used so that it is 0.00/or more, but preferably the amount of halogenated silicon compound is θ, 0/~'. When expressed as a ratio (sol ratio) to the amine compound, the silicon halide compound/amine compound is 0.
．． 07 or more, but preferably θ, θ-10
00, more preferably θ, is selected from the range of / to 0.

On the other hand, when using a solvent, solvent/CO salt/θ, 000
(molar ratio). In this case, the ratio of amine compound, silicon halide compound, and axial base to CO salt is selected from the above-mentioned ranges.

The reaction temperature and pressure are not particularly limited, but the yield is θ~2
It is preferable to carry out the reaction at 0θ°C and 0.0/−/θo klil//ctd. Further, prior to one reaction, it is preferable to perform pretreatment such as heat treatment and reduced pressure treatment, and purification such as dehydration and deoxidation of the raw materials, but during the reaction, the reaction temperature may vary.

Conditions such as reaction pressure may be changed. The reaction time is not particularly limited, but is 0.7 to 100 hours, preferably 0.7 to 7 hours.
0 hours is selected.

When using a gas-selective separation material as a bath liquid, a bioisolated product obtained by reacting an amine compound, a halogenated silicon compound, and an axial base in the presence or absence of a non-aqueous solvent is used. It is also possible to dissolve it in a medium that can be dissolved again later.

Next, a method for selectively separating a gas at a constant trt, especially oxygen, using the gas selective separation material obtained by the CO salt, amine compound, halogenated silicon compound, and akinyal R group') EZ reaction of the present invention will be explained. The membrane 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 1 separation material) is bonded to a base membrane formed into a membrane. Method 1: Forming a film into a stacked film, an interlayer film, etc. 1 Methods include impregnating or retaining the separating material alone or its solution as a liquid film in a porous film, an anisotropic film, or a composite film. Will the separation material be bonded to the membrane?

A membrane formed by using a separation material alone or mixed with other polymers, or a base film that holds the above-mentioned monomolecular film, etc., and the above-mentioned ''
g! The type of material of the membrane of the support used for the purpose of holding the membrane is not particularly limited, but m-cellulose, cellulose
-ester, polycarbonate, polyester, Teflon, nylon, acetylcellulose, polyacrylonitrile, polyvinyl alcohol, polymethyl methacrylate, polysulfone, polyethylene.

Polypropylene, polyvinylpyridine, polyphenylene oxide, polyphenylene oxide sulfonic acid, polybenzimidazole, polyimidazopyrrone a, polypiperazinamide, polystyrene, polyamino acid, polyurethane, polyamino acid polyurethane copolymer, polysiloxane, polysiloxane polycarbonate copolymer Polymer.

Polytrimethylvinylsilane, Kolaken, polyion complex, polyurea, polyamide, polyimide, polyamideimide, polyvinyl chloride.

Ift polymers such as sulfonated polyfurfuryl alcohol 4 and non-functional substances such as glass, alumina, silica, silica alumina, carbon, and metals may be mentioned.

These supports are flat, tubular, and spiral.

It can be used in any hollow fiber form. Further, these supports may be entirely porous, may be an anisotropic film having a dense layer on only one surface, or may be a homogeneous film. of other materials by vapor deposition, coating, polymerization, plasma polymerization, etc.
The membrane may have been subjected to 4 rp. The overall thickness is not particularly limited, but is preferably in the range of 10 to 1000 microns.

Such a support can also be used in nine layers with other materials.

Next, I will explain the general characteristics of separation membranes. Child membranes are known, but these membranes have a relatively small trace coefficient, and materials with higher permeability coefficients are desired. ing. If the membrane is liquid.

In general, the solubility coefficient and diffusion coefficient of gases become larger, and therefore the permeability coefficient becomes thicker.Furthermore, in such a liquid film, there is a substance that selectively and reversibly interacts only with a certain gas. If it is included, the permeability of the gas can be further increased.On the other hand, the selective performance of the membrane is given by the difference in solubility of gases in the membrane and the difference in the rate of diffusion of gases in the membrane. When a membrane contains a substance that selectively and reversibly interacts only with a specific gas as described above, the solubility of only that gas increases and the selectivity improves dramatically.

Of course, the selective separation performance of the membrane is also improved if the solid membrane contains a substance that selectively and reversibly interacts only with a specific gas on its surface or inside.

In general, when a specific substance is contained in a liquid membrane, the selective separation performance of the membrane becomes stronger (improved). Numerous examples are known of membranes containing substances that do this.

For example, A, ;', 7/Zadako Publication), separation of nitric oxide using a formamide solution of ferrous chloride (A, 1.Ch, E, Jo
Urnal.

701/6. AJ, 4'0! r (/970), )
, Schiff 7 base etc. as a ligand and the separation of oxygen using a CO complex bath liquid (Japanese Patent Application Laid-Open No. 19-19-/Core 07), and these liquid membranes are used by being held on a membrane that serves as a support. be done.

Although the method is not particularly limited in the present invention, when the gas selective separation material or its solution is used as a liquid membrane, it is used while being in contact with or held on a membrane serving as a support. In this case, the layer thickness of the gas selective separation material or its solution can be used as long as it is several angstroms or more, and is not particularly limited. When these liquid membranes are used without stirring, it is preferable that the thickness is smaller because a higher permeation rate can be obtained. however.

If the thickness is too small, the permeation rate of gases other than those intended for separation will increase, resulting in a decrease in selective separation performance, which is not preferable. The most suitable film thickness varies depending on the bonding and dissociation η rate constants, equilibrium constants, and other conditions between the gas and these reaction products. It is preferable that the film thickness is approximately the same as that in the case without stirring.

When separating gases, a membrane holding the separation material or its solution on a support can be used, or a method can be used to separate the gases between the two sides of the membrane, as in the case of ordinary gas separation using polymer membranes. Used by creating a partial pressure difference between the gases to be separated.

Alternatively, a method may be used in which a container containing the separation material of the present invention or its solution is placed separately from the membrane cell, and a pump is used to guide the liquid from there to the surface of the supporting membrane (primary side of the membrane) of the membrane cell for circulation. You can also do it. In this case, for example, oxygen is absorbed into the optical liquid in the reservoir container, and the dissolved or combined gas is continuously dissociated and desorbed by reducing the pressure on the secondary side of the membrane in the membrane cell, and the secondary side of the membrane is continuously dissociated and desorbed. It is also possible to use a method of highly selectively and continuously removing oxygen by continuously carrying out an operation in which the oxygen-depleted liquid is returned to the reservoir and dissolved again. In this case, if the temperature of the membrane cell and the reservoir are set independently, oxygen can be extracted easily.・I can do it. Although the temperature of the membrane cell portion is not particularly limited, it can be used within the range of, for example, O-100°C.

Next, a gas selective absorbent containing the separation material of the present invention will be explained. Organic polymer is used as a separation material for gas selective absorption.

4) Possible methods include a method in which the separation material is supported on a porous carrier such as a material, a method in which a liquid separation material is used alone or as a solution thereof, and the like. When supporting the separation material on a porous carrier made of an organic polymer or an inorganic material, the materials that can be used as the carrier include the above-mentioned polymers exemplified in the section of the explanation of amine compound derivatives or materials for the support membrane of the present separation material. Can you give me an example? In addition, when using one separation material as an absorbent,
The liquid separation material can be used alone or as a solution in another M medium.

In this case, the solvent used during the production of this separation material is
It may be used as it is, or a solvent such as W'rtanike may be used. Oxygen can selectively be dissolved in a larger amount in the solution of the separation material than other gases. In this case, the pressure and oxygen partial pressure of the mixed gas containing the #R element in contact with the separation material solution are not particularly limited, but the pressure of the mixed gas is usually 0. /~100 Yu shoulder,
The oxygen partial pressure is θ, oi~/θkl? Used with /i. The partial pressure of the enzyme in contact with fG' of this separation material is even more than that of oxygen! Oxygen absorption occurs between θ°C and IOθ°C.

Another method of increasing the oxygen absorption rate is to increase the surface area of the gas-liquid interface, and it is desirable to blow gas into the separation material bath liquid or to stir the solution. When the solution of the separation material which has alternatively absorbed a larger amount of the 8 elements is reduced in pressure, an oxygen-rich gas is released. There is no particular limit to the pressure and temperature, but it is usually 0 to 1 kg, 7 cups,
It is carried out at 0-200°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 carry out the desorption while stirring the solution because the release rate can be increased.

Although the apparatus for using the separation material of the present invention as a gas selective permeation A membrane is not particularly limited, the following method can be used, for example. That is, a membrane holding a separation material is mounted on a module, an inlet for a supply gas and a persillary are provided on the primary side of the membrane, and an outlet for a product stream is provided on the secondary side of the membrane. An empty pump is installed at the product stream outlet Kn to take out the product stream that has permeated through the membrane under reduced pressure. If necessary, connect to the module and provide a pressure regulator flow rate side. Using such a device, for example, air is supplied to the primary side of the membrane J/ Feeder C1 mainly permeates oxygen through the membrane and enriched with nitrogen, 1 Air is supplied to the primary side of the membrane IJ1! From the persillo of i, the oxygen-enriched scavenging gas -1;j body is taken out from the secondary side of the membrane. The 9-enriched air or oxygen-enriched gas discharged from the module can also be returned to the supply side and recycled for use. Alternatively, instead of supplying gas to the primary side of the membrane, a separation material or a solution thereof in which the supplied gas is dissolved is supplied, and oxygen #! is supplied from the secondary side of the membrane.
At the same time, the condensed gas is taken out, and the separation material liquid whose amount of acid collected in the bath has decreased is taken out from the persilo on the primary side of the membrane.

The separation material liquid with reduced dissolved oxygen is returned to the supply tank, where it is sufficiently absorbed with air, etc., and then supplied to the membrane module. Of course, instead of removing the permeate gas by pumping the membrane's secondary fill 'l It is also possible to operate with a partial pressure lower than that on the supply side.

Next, when the separation material of the present invention is supported on a porous solid and used as an absorbent material, it is sufficient to fill a column or the like with 9 non-separable particles. A feed gas containing oxygen is introduced through the gas inlet of the column and the absorption of each column is carried out in the main i (92) as practiced in the absorption method.

It is also possible to take out the accumulated cotton gas continuously by shifting the desorption time in stages (1).The above method is one example, and the method is not limited to this method.

Next, when the separation material of the present invention or its solution is used as an absorption liquid, the liquid of the separation material 1 is filled into an absorption tower or the like as an absorption liquid. Next, a feed gas containing oxygen is introduced into the absorption tower, and the absorption liquid is made to absorb oxygen. The oxygen-depleted gas is released from Persilo. Next, the absorption liquid that has absorbed oxygen is sent to a stripper tower and the absorbed oxygen-enriched gas is released from the absorption liquid and taken out under reduced pressure or heating. On the other hand, the absorption liquid that has released the RE is returned to the absorption tower, and air or the like is introduced again to absorb oxygen. Repeat this operation continuously. Absorption towers and S) IJ tube towers are equipped with compressors, blowers,
You can connect a fan, Makabe pump, pressure regulator, flow meter, and circulation pump. The above method is one example, and the method is not limited to this method.

〔Example〕

A flat membrane made of polytrimethylvinylsilane was installed as a base membrane in a cylindrical glass cell, and after a solution containing the selective separation material to be tested was injected onto the top of the membrane, a permeation test gas was passed through the cell while stirring continuously. On the other hand, reduce the pressure below the base membrane (secondary side),
The permeation rate Q was determined by analyzing the amount of gas permeated within a certain period of time using gas chromatography. In addition.

Q in this example is a value measured at 30°C unless otherwise specified, and its unit is cc (8, T, P, )/(yJ
-seanu・C7rLHg. Also, I is oxygen relative to nitrogen, 0
Eliminate the 1 degree ratio (Q, 02/Q, N2).

Example/ (a) Preparation of separation material Add trimester lyluiodine to some flasks.
After 30 minutes, 2 ml of go-methylimidazole was slowly added dropwise while stirring under a nitrogen atmosphere. After 30 minutes, cobalt thioneanate anhydride, 1 ml of tripropylene were added to the reaction mixture. /Ntetramine2. Arnl and dimethyl sulfoxide 10
When a separate solution of PI3 was added to m1 and stirred, a dark reddish-brown slurry-like separation material was obtained. J41))
Measurement of gas permeation rate Separation material 10 prepared in (a) was placed in a cell for gas permeation measurement.
Aliquot the rttl and add air to 0. j It was passed over a separation material stirred at M degree of 137 minutes. Next, the pressure on the secondary side was adjusted to COXTM Hg, and the measurement temperature was adjusted to 30°C. Next, 2 rnl of i-methylimidazole was added into the separation material from the top of the cell.

, 7" through the gaff that passed through the plate; P", and Q02 was 7 x 10-6. This separation material has a long and high selective separation property. Shown over time.

Example λ (a) Synthesis of co-polyamine complex 10011LI flask was charged with cobalt thionate anhydride I, degassed and dried in the main valve, and then tripropylenetetramine f was added with stirring under tfA nitrogen.
, A R/ was gradually added dropwise.

An exothermic reaction occurred and a dark reddish-brown homogeneous solution was obtained. While stirring at room temperature, degassed and purified dimethyl sulfoxide λ/, rnl was added to the reaction mixture, and the reaction was continued to obtain the target complex.

(1)) Degassed and dried hydrogen-substituted silicone oil (
0.9 ml of Shin-Etsu Chemical Co., Ltd. jffKF-99) was collected, and iodine/3jj was added thereto under purified nitrogen for reaction.

Next, l-methyl/'p was added, and the mixture was heated to 100'C for 770 minutes to react, thereby obtaining a separation material.

(C) Measurement of gas permeation rate When a gas permeation test was carried out on the separation material classified as 'rJ14 in (1)) in the same manner as in (b) of Example 1, the oxygen concentration of the permeated gas was found to be L/%. It turns out.

This corresponds to α being /3.11, and Qo2 is! , /×10-'. If the separation material of the present invention is used for selective separation of halogenated silicon polymers, it can be used as a gas selective permeation membrane or as a gas selective absorption material with high separation injection ability, allowing oxygen to be concentrated at high concentrations. You can do it. Because the rate of adsorption and desorption of oxygen is much faster than that of conventionally known oxygen complexes, it is extremely efficient at absorbing oxygen.
) can be served. For example, nearly 700% of acid can be efficiently extracted from air in one or two steps. On the other hand, if the charged gas is air, ri! The gas remaining after the separation of the gas contains a high concentration of nitrogen, and is also useful as a method for producing nitrogen. In addition, 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 by using the gas selective separation material of the present invention, but oxygen is a gas that is widely used in all industries, and is particularly harmful to steel materials.

Cutting into the electric furnace! Repeated penetration and glass melting.

The separation material of the present invention can be usefully used in fields such as pulp treatment, wastewater treatment, metal processing, paper manufacturing, aviation, space, pollution prevention, medical care, electronic industry, 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, Kaei industry, and medical use.

Claims (2)

[Claims] (1) (A) Co salt and (B) general formula -(NHCH_2O
A gas separation material formed by contacting (C) a halogenated silicon compound with a composition consisting of an amine compound having a skeleton of H_2CH_2)-_n (n is an integer of 2 or more). (2) In the separation material according to claim 1, the components (A), (B), and (C) are brought into contact in the presence of (D) an axial base, or the component (D) is brought into contact with the component (D). A), (
A gas separation material added after contacting B) and (C).