JPH0379282B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an oxygen selective separation material useful for oxygen separation and concentration. Oxygen is the gas most widely used and in large quantities, and its fields of use include welding and cutting steel materials, blowing into blast furnaces, converters, and open hearths, and other steelmaking applications, as well as cement, refractories, and glass in the ceramic industry. It is known for its uses, including the use of oxygen-enriched air, for the production of water, for activated sludge treatment of urban sewage and general industrial wastewater, and for medical purposes. The amount of oxygen used in Japan is 90~
10 billion ^m3 , most of which is used for the steel industry. [Prior art and its problems] Industrial production of oxygen has been carried out already since the beginning of this century by cryogenic separation methods. Although this method is convenient for producing large amounts of oxygen, it requires an extremely large amount of energy. Furthermore, when oxygen is used on-site, it is necessary to first fill it in a pressure-resistant container and transport it, which is disadvantageous because it results in the use of extremely expensive gas. Furthermore, as a method for producing oxygen on a relatively small to medium scale, a method of separating and concentrating highly concentrated oxygen from air using adsorbents such as zeolite, molecular sieves, and carbon has recently attracted attention. However, this method consumes a lot of power and therefore the production cost of oxygen is high. Apart from the above methods, a method has been proposed in which a specific metal complex that forms an oxygen complex is used in the separation method. For example, it was known that a cobalt-Schiff base complex reversibly forms an oxygen complex, but the stability of the complex was problematic, making it difficult to use as a separation system. after that
In the late 1960s, the United States Air Force and others conducted research to improve the stability and durability of complexes, and long-lived complexes such as fluorine derivative fluorine were discovered. However, although this complex absorbs oxygen at room temperature (27-38℃), its release (desorption) is
Since it requires a high temperature of around 80°C, its adsorption and desorption has the disadvantage of requiring temperature elevation and cooling. On the other hand, JP-A-59-12707 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. There is. 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 membrane separation methods, it is necessary to have a large permeation rate ratio between oxygen and nitrogen and a high permeation rate of oxygen, but for this purpose, the reactivity of the complex used with oxygen and the diffusivity of the generated oxygen complex are required. It is considered desirable that the value be as high as possible. However, Chemical Revue, Vol. 79, p. 139 (1979), Canadian Journal of Chemistry, Vol. 54, p. 342 (1976), and Journal of the American Chemical Society, Vol. 102, cited in the above-mentioned JP-A-59-12707. As can be seen on page 3285 (1980), the oxygen complexes that have been discovered and studied so far require large ligands and therefore have very unsatisfactory diffusivity. On the other hand, research has also been carried out on relatively low-molecular cobalt complexes, but most of the oxygen complexes have poor stability and decompose even at sub-zero temperatures. [Means for solving the problem] We searched for transition metal complexes that have a relatively simple and small molecular structure, have a high affinity for oxygen, and form complexes specifically and rapidly. As a result of intensive research aimed at developing a method for highly selective separation of oxygen using The present invention was achieved by discovering that it is extremely useful as a separation material. That is, the present invention provides (A) Co salt and (B) general formula -(
The present invention relates to an oxygen selective separation material formed by contacting a halogenated silicon compound (C) with a composition comprising an amine compound having a skeleton of NHCH ₂ CH ₂ CH ₂ ) _-o (n is an integer of 2 or more). Further mainly in the presence of a non-aqueous solvent, component (A),
This invention relates to an oxygen selective separation material obtained by contacting (B) and (C). The present invention also relates to a gas selective permeable membrane and a gas selective absorption material containing these oxygen selective separation materials. The content of the present invention will be explained in detail below. The Co salt of component (A) has the general formula (B) - (
NHCH ₂ CH ₂ CH ₂ )- _o (n is an integer of 2 or more) which reacts with an amine compound (hereinafter simply referred to as "amine compound") or an axial base (D) to form a certain type of complex. Although there are no particular limitations, the following compounds can be exemplified. That is, cobalt oxide, cobalt hydroxide, halides such as cobalt fluoride, cobalt chloride, cobalt bromide, cobalt iodide and their hydrates, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt cyanide, Inorganic and organic acid salts such as cobalt thiocyanate, cobalt perchlorate, cobalt periodate, cobalt tetrafluoroborate, cobalt oxalate, cobalt tartrate, and cobalt acetate, and their hydrates, as well as double salts such as cobalt alum. and organic cobalt compounds such as cobaltocene. These cobalt valences can be arbitrarily selected, but divalent ones are preferred, and inorganic salts are selected as suitable cobalt salts. Component (B) has the general formula -(NHCH ₂ CH ₂ CH ₂ ) - _o (n is 2
It is an amine compound having a skeleton of (an integer greater than or equal to). The range of n is 2 to 100000, preferably 2
-10,000, more preferably 2-1,000.
An amine compound that satisfies the above general formula is
NHCH ₂ CH ₂ CH ₂ )- _o When represented by Y, 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, tetrapropylenepentamine, heptapropylenehexamine, hexapropyleneheptamine,
Examples include oligopropylene imine and polypropylene imine. When X is hydrogen and Y is a compound other than an amino group, Y
as −CO ₂ ⁻ , −CRO,

[Formula] -O ^- , -OR, -CSS ^- , CRS,

[Formula] -S ^- , -SR, -CONHR, -NHCOR, -CN, -CH=N-,

[Formula] Functional groups such as -NH ^- , -NR ^- , -NR ₂ (where R is hydrogen or an organic group) are selected, specifically H-(NHCH ₂ CH ₂ CH ₂ ) - ₃ OH H -(NHCH ₂ CH ₂ CH ₂ )- ₃ N(CH ₃ ) ₂ H- (NHCH ₂ CH ₂ CH ₂ )- ₃ NHR H-(NHCH ₂ CH ₂ CH ₂ )- ₃ NHCOC ₁₇ H ₃₅ and other compounds I can give an example. In addition to the above functional groups, Y may also include F, Cl,
Br, I, and R (where R is an organic group) can also be mentioned. Specifically, H-(NHCH ₂ CH ₂ CH ₂ )- ₂ NHCH ₂ CH ₂ CH ₂ F, H-(NHCH ₂ CH ₂ CH ₂ )- ₂ NHCH ₂ CH ₂ CH ₂ OH, H-(NHCH ₂ CH _Examples include _{compounds such as 2CH2 ) -2NHCH2CH2CH2CH3 , H-(NHCH2CH2CH2 ) -2NHCH2CH2CH2- ( polystyrene )} . Even when X is an organic group, the same functional group as _mentioned above can be selected as Y, and specific examples include _CH3- ( _{NHCH2CH2CH2 ) -2NH2 , C6H5- (} NHCH ₂ CH ₂ CH ₂ ) − ₂ NH ₂ , C ₃ H ₇ − (NHCH ₂ CH ₂ CH ₂ ) − ₂ NH (CH ₃ ), CH ₃ − (NHCH ₂ CH ₂ CH ₂ ) − ₂ N (CH ₃ ) ₂ C ₁₇ H ₃₅ −((NHCH ₂ CH ₂ CH ₂ ) − ₂ NH(CH ₃ ) C ₁₅ H ₃₁ −(NHCH ₂ CH ₂ CH ₂ )− ₂ NHC ₁₅ H ₃₁ Polystyrene − (NHCH ₂ CH ₂ CH ₂ ) _{-2NH2polyurethane-} ( _NHCH2CH2CH2 ) _-2NH- ( _polyurethane ), etc.Furthermore, when n is an integer of 3 or more, _Y can be F _, Fl, Br, I, R. _{( However , R is an organic group ) can be selected . _ 2} ) - ₃ CH=CH ₂ compounds can be mentioned as a specific example. Note that the above 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. In addition, the general formula

[Formula] and

Also included are cyclic polyamine compounds represented by the formula (where R represents a bifunctional group such as CO, NR', S, O, or a polyfunctional organic group containing these), and specific examples include -(
NHCH ₂ CH ₂ CH ₂ ) − ₃ , −(NHCH ₂ CH ₂ CH ₂ ) − ₄ , −(
Examples include NHCH ₂ CH ₂ CH ₂ ) _-5 . On the other hand, in addition to the above examples of amine compounds, derivatives thereof are also included in the definition of amine compounds of the present invention. That is, the derivative defined here has the formula −(
Compounds in which part or all of H in NHCH ₂ CH ₂ CH ₂ ) _-o is substituted with other atoms or functional groups, or organic or inorganic polymers and oligomers, and further unsaturated compounds obtained by elimination of H. It also means For example, as a derivative having a substituent other than H

[Formula] (A is a substituent other than H and may have an unsaturated bond) is shown as an example, but A is N in any form in the derivative.
or C No matter which element it is bonded to, it is sufficient that one or more exists, and therefore it is not necessarily -(
NHCH ₂ CH ₂ CH ₂ )-1 or more need not exist in one unit. Furthermore, when there are multiple A's, they may be the same or different. A also includes a difunctional or higher polyfunctional group, in which case it represents a cyclic compound. In this case, A does not need to be bonded within the same unit, or may be bonded between different elements, as shown in the example of n=3 below. Further, even if substituent A contains an unsaturated bond, it is within the scope of the present invention. Specific examples of the above substituent A other than H include the following functional groups, oligomers, and polymers. Functional groups include halogen atoms such as F, Cl, Br, and I, carboxyl groups, or metal salts thereof (-COOH,
-COO), sulfonyl group (-SO ₃ H), sulfinyl group (-SO ₂ H), acid anhydride (-CO-O-CO
-), oxycarbonyl group (-COOR), haloformyl group (-COX), carbamoyl group (-
CONH ₂ ), hydrazinocarbonyl group (-
CONHNH ₂ ), imide group (-CO-NH-CO-),
Amidino group

〔Example〕

Hereinafter, the content of the present invention will be explained with reference to Examples. In the Examples of the present application, the gas permeation rate was measured as follows. That is, a flat membrane made of polytrimethylvinylsilane is attached as a base membrane to a cylindrical glass cell with an outer diameter of 45 mm, and after a solution containing the selective separation material to be tested is injected onto the top of the membrane, a permeation test gas is passed through it while stirring. I let it happen. On the other hand, the permeation rate Q was determined by reducing the pressure below the base membrane (secondary side) and analyzing the amount of gas permeated within a certain period of time using gas chromatography. Note that Q in this example is a value measured at 30°C unless otherwise specified, and its unit is
cc(STP)/ ^cm2・sec・cmHg. Further, α represents the velocity ratio of oxygen to nitrogen (QO ₂ /QN ₂ ). Example 1 (a) Preparation of separation material 2 ml of trimethylsilyl iodide in a 50 ml flask
ml, and 2 ml of 1-methylimidazole was gradually added dropwise while stirring under a nitrogen atmosphere, causing a reaction with intense heat generation to produce a solid. After 30 minutes, add 0.88 cobalt thiocyanate anhydride to the reaction mixture.
A solution separately prepared from 2.6 ml of tripropylenetetramine and 10 ml of dimethyl sulfoxide was added and stirred to obtain a dark reddish-brown slurry of separation material. (b) Measurement of gas permeation rate 10 ml of the separation material prepared in (a) was placed in a cell for measuring gas permeation, and air was passed over the separation material stirred at a rate of 0.5 min. Next, the pressure on the 2 o'clock side was adjusted to 2 mmHg, and the measurement temperature was adjusted to 30°C.
Then, pour 2 ml of 1- into the separation material from the top of the cell.
When methylimidazole was added and the permeated gas was analyzed by gas chromatography, it was found that
The oxygen concentration was found to be 90.9%. This corresponds to α being 37.4 and QO ₂
was 1.3×10 ^-6 . This separation material showed high selective separation properties over a long period of time. Example 2 (a) Synthesis of Co-polyamine complex After 2.6 g of cobalt thiocyanate anhydride was placed in a 100 ml flask and thoroughly degassed and dried, 8.6 ml of tripropylenetetramine was gradually added dropwise with stirring under purified nitrogen. . An exothermic reaction occurred and a dark reddish-brown homogeneous solution was obtained. While stirring at room temperature, 21.4 ml of degassed and purified dimethyl sulfoxide was added to the reaction mixture, and the reaction was continued to obtain the desired complex. (b) Contact with silicon halide 0.9 ml of degassed and dried hydrogen-substituted silicone oil (KF-99 manufactured by Shin-Etsu Chemical Co., Ltd.) in a 50 ml flask
was collected, and 1.3 g of iodine was added to react under purified nitrogen. Next, 2 ml of 1-methylimidazole was added, and a white solid was obtained with intense heat generation. After adding 10 ml of the complex solution obtained in (a) to the obtained solid, the mixture was heated to 100°C and reacted to obtain a separation material. (c) Measurement of gas permeation rate When the separation material prepared in (b) was subjected to a gas permeation test in the same manner as in (b) of Example 1, it was found that the oxygen concentration of the permeated gas was 78.1%. This is α
corresponds to 13.4, and QO ₂ is
It was 5.1×10 ^-7 . It can be seen that halogenated silicon polymers also have an effect on selective separation. [Effects of the Invention] When the separation material of the present invention is used, oxygen can be concentrated to a high concentration because of its high separation performance both as a gas selective permeation membrane and as a gas selective absorption material. Since the rate of adsorption and desorption of oxygen is much faster than that of conventionally known oxygen complexes, oxygen can be concentrated very efficiently. For example, nearly 100% oxygen can be efficiently extracted from air in one or two steps. On the other hand, when the supplied gas is air, the remaining gas from which oxygen has been separated contains a high concentration of nitrogen, making it 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 using the oxygen selective separation material of the present invention. Oxygen is a gas widely used in all industries, especially for welding and cutting steel materials.
The separation material of the present invention can be used in the fields of oxygen blowing into electric furnaces, glass melting, pulp bleaching, wastewater treatment, metal processing, paper manufacturing, aviation, space, pollution prevention, medical care, electronic industry, chemical industry, marine development, etc. It can be usefully used. 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.

Claims (1)

[Claims] 1 (A) Co salt and (B) general formula -(NHCH ₂ CH ₂ CH ₂ ) - _o
An oxygen separation material formed by contacting a composition comprising an amine compound having a skeleton (n is an integer of 2 or more) with (C) a halogenated silicon compound. 2. In the separation material described in claim 1, components (A), (B), and (C) are brought into contact in the presence of (D) an axial base, or component (D) is brought into contact with component (A). , (B) and (C) are added after contact.