JPH09323014A - Treatment of gas containing ammonia and amines and treating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To rapidly remove ammonia and amines causing malodor with high removing efficiency by bringing gas containing ammonia and amines into contact with an organic metal complex having a one-dimensional or three-dimensional channel structure to make them adsorbed. SOLUTION: Gas containing ammonia and amines is brought into contact with an organic metal complex having a one-dimensional or three-dimensional channel structure. Then, molecules of ammonia and amines are taken in voids based on the channel structure to be adsorbed, and by combining nitrogen atoms of ammonia and amines with copper ions by coordination in addition to neutralization reaction with carboxylic acid, ammonia and amines are removed. In this way, the removing capacity is large and the removing speed is high.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing ammonia and amines present in a gas, and more particularly to a method for removing ammonia and amines that cause an offensive odor mixed in the air, as well as ammonia and amines. The present invention relates to a treatment material used for removal.

[0002]

2. Description of the Related Art Methods for removing ammonia and amines, which are substances that cause offensive odors, especially from the air, include the removal method using adsorption by activated carbon and the neutralization reaction by acidic substances. A removal method using is known.

[0003]

However, according to the removal method utilizing adsorption by activated carbon, it is difficult to completely remove ammonia and amines and eliminate bad odors.
In addition, in the removal method using the neutralization reaction with an acidic substance, the acidic substance must be attached to the material to be used as a filter, and in order to attach a strong acid with high removal efficiency, select a material that can withstand the strong acidity. It is necessary to give consideration to safety during processing. Since neutralization reaction is an equilibrium reaction in commonly used carboxylic acids, ammonia and amines dissociate after the equilibrium state is reached, and the acid removes ammonia and amines at an equal ratio of 100%. Can't do. The present invention is to provide a method of removing ammonia and amines in a gas by adsorption, complex formation and neutralization with a carboxylic acid, and to provide a treating material used in the removal method.

[0004]

According to the present invention, a gas containing an amine is brought into contact with an organometallic complex having a one-dimensional or three-dimensional channel structure to adsorb and remove the amine on the organometallic complex. The present invention relates to a characteristic method for removing amine in a gas. Since the organometallic complex used in the present invention has a one-dimensional or three-dimensional channel structure, it is adsorbed by accommodating molecules of ammonia and amines in the voids based on this channel structure, and also for neutralization reaction with carboxylic acid. In addition, ammonia and amines are removed by coordinating and bonding the nitrogen atoms of ammonia and amines to copper ions. Therefore, the removal capacity of these compounds is large and the removal rate is fast.

The present invention also provides a method for treating a gas containing ammonia and amines, wherein the gas containing ammonia and amine is brought into contact with an organometallic complex having a one-dimensional or three-dimensional channel structure, A first step of adsorbing and removing ammonia and amine to the organometallic complex to obtain a gas containing no ammonia and amine, and desorbing the amine adsorbed by the organometallic complex in the first step from the organometallic complex. The present invention also relates to a method for treating an amine-containing gas, which includes two steps of the second step of separating and collecting a desorbed gas containing an amine. The amines adsorbed on the organometallic complex of the present invention are desorbed under predetermined conditions. Therefore, by providing the first step of removing amines contained in the gas and the second step of desorbing the amines, the organometallic complex as the adsorbent can be regenerated and repeatedly used,
By concentrating the amine and collecting a gas containing a large amount, it is possible to effectively use the gas or conversely incinerate it. Ammonia has a strong action of forming a complex with an organometallic complex and is difficult to desorb.

The above-mentioned organometallic complex having a one-dimensional or three-dimensional channel structure preferably has a pore diameter of 3 to 20 Å. When it is 3 Å or less, the pore diameter is too small to adsorb molecules of ammonia and amines, and when it is 20 Å or more, the pore diameter is too large and the adsorption rate of ammonia and amines decreases, which is not preferable.

In the present invention, a gas containing ammonia and an amine is passed through a chemical substance adsorbing material in which the organometallic complex having a one-dimensional or three-dimensional channel structure is attached to a substrate having a gas permeable void. It is also a preferable embodiment to use a method of removing ammonia and amine in the gas by performing the above. The organometallic complex having a one-dimensional or three-dimensional channel structure is produced in powder form under normal reaction conditions, and although it can be used as it is, the adsorption device is designed and the organic metal in the adsorption device is used. There are difficulties in exchanging metal complexes. As in the present invention, by adopting a form of a chemical substance adsorbent in which an organometallic complex is attached to a substrate having a gas permeable void, it is extremely easy to design the device and replace the organometallic complex in the device. Can be

In the chemical substance adsorbing material in which the above-mentioned organometallic complex is adhered to a substrate having a gas permeable void, a gas such as a nonwoven fabric or polyurethane foam is added to a reaction solution for producing the organometallic complex. The base material having permeable voids may be dipped and used as a nucleus for crystal formation to be adhered and obtained on the base material.

The present invention also relates to a treatment material containing an organometallic complex having a one-dimensional or three-dimensional channel structure, which is used in the method for removing the above-mentioned ammonia and amine, and has a substrate having a gas-permeable void. The present invention can be carried out in the form of the chemical substance adsorbing material adhered to, the form accommodated in a non-woven fabric, the form molded with a suitable binder into a suitable form, and the like.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a gas containing ammonia and amine is brought into contact with an organometallic complex having a one-dimensional or three-dimensional channel structure to adsorb and remove the ammonia and amine to the organometallic complex. The present invention relates to a method for removing ammonia and amines in a gas, which is characterized in that Hereinafter, examples of the organometallic complex used in the present invention and an apparatus used for carrying out the removal method will be described.

The organometallic complex having a one-dimensional or three-dimensional channel structure used in the present invention is an organic ligand described in any of the following (A) to (C) and a divalent metal ion, particularly It is preferably obtained by reacting a copper salt. (A) A dicarboxylic acid having two carboxyl groups arranged at point symmetrical positions in the molecule. (B) A bidentate-coordinating organic ligand having atoms capable of coordinating with a metal ion at both ends of a rigid skeleton. (C) A bidentate-coordinating organic ligand having atoms capable of coordinating with a metal ion at both ends of a rigid skeleton, and 2,3-pyrazinedicarboxylic acid. Since these organic ligands form a linear basic skeleton with divalent copper ions, the resulting complex has a one-dimensional or three-dimensional structure.
It has a dimensional channel structure.

The structures of the organometallic complexes (a) to (c) will be specifically described with reference to examples. For example, when copper terephthalate is used as an example of the complex of (a), copper has a plane four-coordination, and two copper ions form 90 molecules of terephthalic acid.
The two oxygen atoms of the carboxyl group are coordinated to different copper ions, respectively. That is, terephthalic acid molecules are arranged in a lattice, and two copper ions exist at the lattice points. And the crystal | crystallization is comprised in the form in which the layer formed from a copper ion and a dicarboxylic acid was laminated | stacked. As a result, the lattices are stacked to form a one-dimensional channel.

As the complex of (b), a complex having a composition of [Ni (bpy) _1.5 (ClO ₄ ) ₂ ] (bpy = 4,4′-bipyridyl) will be described. To 9
At every 0 °, 4,4'-bipyridyl is coordinated by four molecular N atoms, and 4,4'-bipyridyl is coordinated by different N atoms to different Ni ions, respectively, to form a planar lattice,
Crystals are formed by stacking the lattices so that Ni ions are linearly arranged, and the lattices are continuously formed by the stacking to form a one-dimensional channel as in the example of (a). It has been clarified as a result of the analysis that the perchlorate ion in this complex is changed to the nitrate ion to form a crystal having a three-dimensional channel structure.

As the complex of (c), [Cu (bpy) (pyzzdc) ₂ ] (bpy = 4,4′-bipyridyl, pyzdc = 2,3)
-Pyrazinedicarboxylic acid) will be described as an example. 2,3-pyrazinedicarboxylic acid is coordinated with copper ions to form a planar structure, and this plane is coordinated with copper ions. Crystals are formed by laminating 4'-bipyridyl bound to each other, and a channel structure is formed between the layers.

Examples of the dicarboxylic acid having two carboxyl groups arranged at point symmetry positions in the molecule, which are organic ligands constituting the complex (a), include terephthalic acid, fumaric acid, and 1,4- Examples are trans-cyclohexanedicarboxylic acid and 4,4′-biphenyldicarboxylic acid.
In addition, as metal ions, copper ions, chromium ions,
Examples thereof include molybdenum ion, rhodium ion, palladium ion and tungsten ion, and a complex is formed in combination with the dicarboxylic acid.

As the organic ligand constituting the complex of (b), pyrazine, 4,4'-bipyridyl, trans-1,
Those selected from 2-bis (4-pyridyl) ethylene, 1,4-dicyanobenzene, 4,4′-dicyanobiphenyl, 1,2-dicyanoethylene, and 1,4-bis (4-pyridyl) benzene are preferred. , Divalent metal ions are used as the metal ions, specifically, Co, Ni,
It is preferable to use ions of a metal selected from Cu and Zn.

The organic ligand constituting the complex (c) is
One of the organic ligands used in (b) and pyrazinedicarboxylic acid are used in combination, and the same metal ion as in (b) is used.

The production of these organometallic complexes is carried out by preparing a solution of an organic ligand and a solution of a metal salt as a raw material, mixing these and reacting them. The solvent used is not particularly limited as long as it does not react with an organic ligand or a metal ion or form a complex. The counter ion of the metal ion is not particularly limited as long as it does not inhibit the solubility of the metal salt in the solvent and the formation of the one-dimensional channel structure of the resulting complex. In the production of the complex (a), it is preferable to add an organic acid to the solution of dicarboxylic acid to adjust the pH, and formic acid, acetic acid, trifluoroacetic acid, propionic acid or the like can be used.

An example of a gas treating apparatus used for carrying out the method for treating a gas containing ammonia and amines according to the present invention will be described with reference to FIG. The gas treatment device 1 includes an adsorbent storage chamber 3 for storing the adsorbent 2 and the adsorbent storage chamber 3
The first recovery passage 5 and the second recovery passage 6 that selectively guide the gas discharged from the adsorbent storage chamber 3 and the treated gas supply passage 4 that can supply or stop the supply of the gas to be treated. Is equipped with.

The processing target gas supply passage 4 is connected to the adsorbent storage chamber 3, and a supply side switching valve 7 for freely switching the supply state and the supply stopped state is provided in the middle of the adsorbent storage chamber 3. . Further, the first recovery passage 5 and the second recovery passage 6 are also connected to the adsorbent storage chamber 3, and a first switching valve 8 and a second switching valve 9 are provided respectively. In the example of FIG. 1, the first and second recovery paths 5 and 6 are branched from one connection path connected to the adsorbent storage chamber 3, but they may be connected separately. It may be connected by a three-way switching valve rather than one connection path. The above-mentioned connection of the processing target gas supply path 4, the adsorbent storage chamber 3, the first recovery path 5, and the second recovery path 6 is used as follows, for example. The ammonia- and amine-containing gas to be treated is guided to the adsorbent storage chamber 3 through the treatment target gas supply passage 4. In this case, the supply-side switching valve 7 is in the open state, the first switching valve 8 is opened, the second switching valve 9 is closed, and the processing is performed through the first recovery passage 5.
The gas from which ammonia and amine have been removed is discharged. When the adsorption capacity of the organometallic complex as the adsorbent stored in the adsorbent storage chamber 3 reaches the limit, the first switching valve 8 is closed and the second switching valve 8 is closed.
The switching valve 9 is opened, and the adsorbent storage chamber 3 is further desorbed with ammonia and amines adsorbed by the organometallic complex, for example, in a heated state to desorb ammonia and amines.
A gas containing high concentrations of ammonia and amine is discharged through the second recovery passage 6. At this time, the supply-side switching valve 7 may be in an open state or a closed state. For example, when heating the adsorbent storage chamber 3 as described above, the supply-side switching valve 7 is opened to contain untreated ammonia and amine. A gas may be used as a carrier to discharge desorbed ammonia and amine. Further, when desorbing ammonia and amine under vacuum conditions in the adsorbent storage chamber 3, the supply side switching valve 7 is closed. The vacuum pump connected to the second recovery passage 6 is operated.

As the amines to be treated by the present invention, any of aliphatic, alicyclic and aromatic monoamines and polyamines can be treated, but particularly malodorous substances such as methylamine, dimethylamine and trimethylamine. It is effective in removing lower aliphatic amines such as ethyl amine.

[0022]

[Synthesis of organometallic complex]

(Synthesis example 1) Methanol 100 cm ³ , formic acid 14 cm ³
2.53 g of 1,4-trans-cyclohexanedicarboxylic acid is dissolved in the mixed solvent of and cooled to room temperature. To the obtained 1,4-trans-cyclohexanedicarboxylic acid solution, 3.3 g of copper formate was added with stirring to 100 cm of methanol.
^The solution dissolved in ³ was added dropwise and allowed to stand for 1 day. The formed precipitate was suction filtered, washed and then dried at 120 ° C. for 4 hours. The resulting precipitate weighed 1.71 g and was analyzed to be copper 1,4-trans-cyclohexanedicarboxylate. This organometallic complex has a specific surface area of 480 m ² / g,
The pore size was 4.7Å.

(Synthesis Example 2) Dimethylformamide (DM
F) 0.25 g of biphenyldicarboxylic acid was dissolved in a mixed solvent of 90 cm ³ and formic acid 0.5 cm ³ . A solution prepared by dissolving 0.5 g of copper formate in 25 cm ³ of methanol was added dropwise to this solution at room temperature with stirring, and the mixture was left standing at room temperature.
After 1 day, the precipitate formed was suction filtered, washed and
It was dried at 00 ° C. for 4 hours. The obtained precipitate is 0.24
It was g, and as a result of the analysis, it was copper biphenyldicarboxylate. This organometallic complex has a specific surface area of 1200 m ² /
g, and the pore size was 7.8Å.

[Measurement of Ammonia Adsorption Amount] With respect to the organometallic complexes obtained in (Synthesis Example 1) and (Synthesis Example 2), the ammonia adsorption amount was measured by the following method. The organometallic complex was pretreated at a pressure of 10 ^-2 torr and a temperature of 110 ° C for 1 hour, and then the temperature was kept at 25 ° C to introduce ammonia stepwise, and the weight change of the complex at each step was converted to quartz. It was measured by a gravimetric method using a spring. The same measurement was performed using fibrous activated carbon as a comparison. The results are shown in FIGS. 2 to 5, respectively. From this result, the organometallic complex
It can be seen that the adsorption capacity is superior to the fibrous activated carbon, and the adsorption amount per unit volume is larger than the adsorption amount per unit weight. This shows that the adsorption device has an advantage that it can be designed more compactly than when activated carbon is used as the adsorbent.

(Treatment of Amine-Containing Gas) The organometallic complex obtained in (Synthesis example 1) was put in a non-woven fabric and stored in the adsorbent storage chamber shown in FIG.
Air containing m is introduced into the adsorbent storage chamber 3 through the gas supply passage 4 to be treated, the supply side switching valve 7 is opened, the second switching valve 9 is closed, and the treatment is performed from the first recovery passage 5. The gas that has been discharged is discharged. When the treatment effect was evaluated by a sensory test by 5 monitors, all 5 monitors felt a strong odor of trimethylamine in the air before the treatment, but all of the air discharged from the first recovery route was completely I didn't feel any odor. A similar experiment was conducted using the organometallic complex obtained in (Synthesis example 2) instead of the one obtained in (Synthesis example 1), but the effect was the same.

[Brief description of drawings]

FIG. 1 is a schematic diagram of the configuration of a gas treatment device containing ammonia and amines.

FIG. 2 is a graph showing the adsorption amount of ammonia per unit weight by copper 1,4-trans-cyclohexanedicarboxylate.

FIG. 3 is a graph showing the amount of adsorption of ammonia per unit volume by copper 1,4-trans-cyclohexanedicarboxylate.

FIG. 4 is a graph showing the amount of ammonia adsorbed by copper biphenyldicarboxylate per unit weight.

FIG. 5 is a graph showing the adsorption amount of ammonia per unit volume by copper biphenyldicarboxylate.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Gas treatment device 2 Adsorbent (organic metal complex) 3 Adsorbent storage chamber 4 Treatment target gas supply path 5 First recovery path 6 Second recovery path 7 Supply side switching valve 8 First switching valve 9 Second switching valve 10 Vacuum pump

Claims (6)

[Claims] 1. A gas containing ammonia and amines is brought into contact with an organometallic complex having a one-dimensional or three-dimensional channel structure, and the ammonia and amines are adsorbed to and separated from the organometallic complex. A method for treating gas containing ammonia and amines. 2. A method of treating a gas containing ammonia and amines, wherein the gas containing ammonia and amines is brought into contact with an organometallic complex having a one-dimensional or three-dimensional channel structure, Of the compounds adsorbed to and removed from the organometallic complex in the first step of obtaining a gas containing no ammonia or amines, and the amines adsorbed by the organometallic complex in the first step are removed from the organometallic complex. A method for treating a gas containing ammonia and amines, comprising the two steps of the second step of separating and collecting the desorbed gas containing amines. 3. The organometallic complex having a one-dimensional or three-dimensional channel structure is brought into contact by passing through a chemical substance adsorbing material attached to a base material having a gas permeable void. The method for treating a gas containing ammonia and amines according to claim 1 or 2. 4. The method for treating a gas containing ammonia and amines according to claim 1, wherein the organometallic complex having a one-dimensional or three-dimensional channel structure has a pore size of 3 to 20 Å. 5. A treatment material for a gas containing ammonia and amines, which contains an organometallic complex having a one-dimensional or three-dimensional channel structure. 6. The treatment material for ammonia- and amine-containing gas according to claim 5, wherein the organometallic complex having a one-dimensional or three-dimensional channel structure has a pore size of 3 to 20 Å.