JP2014131785A - Alkaline cleaning method of nitrogen-containing organic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To propose an alkaline cleaning method of a nitrogen-containing organic compound, firstly, with which a hardly-decomposable organic compound containing nitrogen such as an amide compound can be cleaned and decomposition treated, and secondly, which is simply, easily, and surely achieved.SOLUTION: In an alkaline cleaning method, an amide compound is cleaned and decomposition treated by imparting high-speed and strong stirring shear force thereto in an alkali aqueous solution, and a surface activating machine 1 is used. The surface activating machine 1 includes a disk-like stirring plate 4 with high-speed rotation installed in a stirring chamber 3 formed in a cylindrical drum 2, and a stirring blade 5 is provided on a plate face of the stirring plate 4 in a protruding condition. The amide compound or the like flows inside the surface activating machine 1 with the alkali aqueous solution and interfacial energy is transiently increased by imparting the stirring shear force. Consequently an addition reaction of a hydroxide ion to a carbonyl group of the amide compound, other addition reactions, a coordination reaction, a chain-transfer reaction and so on are accelerated.

Description

  The present invention relates to an alkali cleaning method for nitrogen-containing organic compounds. That is, the present invention relates to an alkali cleaning method for cleaning and decomposing a hardly decomposable organic compound containing nitrogen.

《Technical background》
Various waste water and sewage often contain various persistent organic compounds, and there are concerns about their adverse effects.
In other words, wastewater and sewage, river water, lake water, groundwater, sewage treatment plant inflow water, sewage treatment plant effluent water, water treatment plant intake water, etc., which have recently been introduced, Detection has been reported one after another.
In particular, in the case of wastewater and sewage from medical institutions such as hospitals, factories and laboratories, and other persistent organic compounds contained in the water environment, such as pharmaceuticals and chemicals remaining in the water environment, There is a growing concern about adverse effects on systems, the environment, etc., which may become social problems, and the need for detoxification treatment is increasing.

<Conventional technology>
On the other hand, an OH radical oxidative decomposition method has been proposed and adopted as an effective treatment technique and purification technique. Typically, the Fenton method has been proposed and adopted.
The Fenton method generates OH radicals, that is, hydroxy radicals (.OH) with hydrogen peroxide and an iron salt, and oxidatively decomposes a hardly decomposable organic compound. The Fenton method is superior in efficiency, certainty, cost, etc. compared to other conventional treatment technologies and purification technologies such as microbial treatment methods, heat treatment methods, and waste disposal methods. , Have gained high reputation.

《Prior art issues》
By the way, the following subject was pointed out about OH radical oxidative decomposition methods, such as the Fenton method.
As is well known, the OH radical is described as the strongest active oxygen, and has a strong oxidizing power, electron scavenging power, decomposing power, and purification power. However, it has been pointed out that organic compounds containing nitrogen are difficult to decompose.
In particular, amide compounds such as residual pharmaceuticals such as carbamazepine and etenzamide, polypeptides (proteins, etc.), residual chemicals such as acetamide, dimethylformamide (DMF), N-methylpyrrolidone have OH radicals such as the Fenton method. However, the decomposition and purification processes are considered difficult.

About the cause
The cause is inferred as follows. The amide compound which is a nitrogen-containing organic compound is a dehydration condensation compound of ammonia or an amine and a carboxylic acid.
In the amide compound, in the carbonyl group derived from carboxylic acid (> C═O), the vacant orbital (counter electron acceptor) lacking the counter-electron of the π molecular orbital of the double bond is a nitrogen atom (N Loan pairs (anti-electron donors) that are non-shared counter-electrons are attracted to each other. The loan pair is interfering with the empty orbit.
As a result, the counter-electrons of the occupied orbitals (packing with electrons) of the same π molecular orbitals are greatly shifted to the oxygen atom (O) side having a high electronegativity. That is, in the case of an amide compound, the π molecular orbital of the carbonyl group is about to be eliminated.
In the case of such an amide compound, the OH radical cannot interfere with the counter-electron of the occupied orbital of the π molecular orbital as in the case of a normal carbonyl group (without bonding with an amine or the like). . The OH radical cannot be attached to the carbon atom (C) side of the occupied orbit in the form of taking one electron of the counter electron.
In the case of a normal carbonyl group, one electron is drawn out from the other two pairs of bonded pair electrons of the carbon atom of the carbonyl group to the other of the remaining counter electrons, and a new carbonyl group is formed as convenient two electrons. Will be played.
However, as described above, the normal cycle of oxidative decomposition by OH radicals, that is, the cycle of generating and annihilating carbonyl groups (> C═O) and carboxyl groups (—COOH) is nitrogen in the case of amide compounds. Being hampered by the presence of a loan pair. Finally, the carbonyl group and its π molecular orbital, which are the basis of this normal cycle, attributed to carbon dioxide (CO ₂ ) and water (H ₂ O) are about to disappear, and oxidative decomposition by OH radicals is prevented.
For amide compounds, it is inferred that purification treatment is difficult with OH radicals for these reasons.

<< About the present invention >>
The alkali cleaning method (alkaline bath method) of the nitrogen-containing organic compound of the present invention has been made in order to solve the above-mentioned problems of the prior art in view of such circumstances.
In the present invention, firstly, it is possible to wash and decompose a hard-to-decompose organic compound containing nitrogen such as an amide compound, and secondly, this is simply and easily realized with certainty. The object is to propose an alkali cleaning method for organic compounds.

<About each claim>
The technical means of the present invention for solving such a problem is as follows, as described in the claims.
First, claim 1 is as follows.
The alkali cleaning method for a nitrogen-containing organic compound according to claim 1 is characterized in that the nitrogen-containing hard-to-decompose organic compound is washed and decomposed by applying a high-speed and strong stirring shear force in an alkaline aqueous solution. .
About Claim 2, it is as follows.
In the alkali cleaning method of the nitrogen-containing organic compound according to claim 2, the surface active machine according to claim 1 is used.
In the surface-active machine, a disc-shaped stirring plate that rotates at high speed and powerful is provided in a stirring chamber formed in a cylindrical drum, and stirring blades are provided on the plate surface of the stirring plate. Then, the alkaline aqueous solution of the organic compound flows in the surface active machine from the inlet to the outlet.
About Claim 3, it is as follows.
In the alkali cleaning method for a nitrogen-containing organic compound according to claim 3, in claim 2, the organic compound comprises an amide compound.
It is characterized by being selected from acetamide, dimethylformamide (DMF), carbamazepine, formamide, benzamide, etenzamide, N-methylpyrrolidone, and polypeptide.

About Claim 4, it is as follows.
In the alkali cleaning method for a nitrogen-containing organic compound according to claim 4, the surface-active machine according to claim 3 is a method in which the aqueous solution of the organic compound to be heated is first subjected to high-speed and powerful rotation of the stirring plate. It exerts a function of applying a stirring shear force sufficient to increase energy transiently. Thus, the organic compound exhibits a function of promoting the addition of a hydroxide ion (OH ⁻ ) to a carbonyl group (> C═O) of the organic compound.
About Claim 5, it is as follows.
In the alkali cleaning method for a nitrogen-containing organic compound according to claim 5, the carbon atom (C) side of a vacant orbital lacking a counter electron in the π molecular orbital of the carbonyl group (> C = O) of the organic compound according to claim 4 Reaction with addition of hydroxide ion (OH ⁻ ) and reaction of hydrogen ion (H ⁺ ) in the ionized water region to the loan pair side which is the unshared electron pair of nitrogen atom (N) of the organic compound And a reaction in which a hydroxide ion (OH ⁻ ) is added to a carbon atom of the organic compound converted to a carbocation (C ⁺ ) at least proceeds.
About Claim 6, it is as follows.
The method for alkaline cleaning of a nitrogen-containing organic compound according to claim 6 is characterized in that, in claim 5, the aqueous alkaline solution is an aqueous sodium hydroxide (NaOH) solution.
About Claim 7, it is as follows.
In the alkali cleaning method for a nitrogen-containing organic compound according to claim 7, in claim 6, the organic compound passes through regeneration of a carbonyl group after liberating an amine moiety such as ammonia (NH ₃ ). And finally, it is characterized by being at least converted to sodium bicarbonate (NaHCO ₃ ).

About Claim 8, it is as follows.
In the alkali cleaning method for a nitrogen-containing organic compound according to claim 8, the alkali cleaning method according to claim 3 is performed as a pretreatment of the oxidative decomposition method.
And the obstructive factor of this oxidative decomposition method is eliminated about this organic compound. Therefore, the subsequent oxidative decomposition method is characterized in that the residue of the organic compound is oxidatively decomposed.
About Claim 9, it is as follows.
In the alkali cleaning method for a nitrogen-containing organic compound according to claim 9, the oxidative decomposition method according to claim 8 comprises a Fenton method.
Then, hydrogen peroxide, divalent iron ions, and a pH adjuster are added to the water to be treated containing the residue of the organic compound, and OH radicals (.OH) are generated. Thus, the OH radical is characterized by oxidative decomposition of the residue.

<About the action>
Since the present invention comprises such means, the following is achieved.
(1) An alkaline aqueous solution of a nitrogen-containing organic compound, specifically, an aqueous sodium hydroxide solution of an amide compound is charged into a surface active machine.
(2) The surface active machine imparts a strong stirring shear force at high speed, and the nitrogen-containing organic compound has a transient increase in interfacial energy.
(3) Accordingly, the cleaning and decomposition treatment is performed, and the reaction described below proceeds, so that the interfacial energy is sedated and stabilized.
(4) That is, the following reaction proceeds in order for the amide compound. A reaction in which a hydroxide ion is added to an empty orbit of the π molecular orbital of a carbonyl group. A reaction in which hydrogen ions in the ionized water region coordinate with a loan pair, which is an unshared electron pair of nitrogen atoms (the amine part is liberated). Reaction in which a hydroxide ion is added to the carbocationized carbon atom of the main body residue after free cleavage.
(5) In the amide compound, such a reaction becomes a pillar, and a reaction linked to these is added, and after passing through regeneration of the carbonyl group, finally, at least sodium hydrogencarbonate is formed.
(6) By the way, the alkali cleaning method of the present invention is often implemented as a pretreatment of the OH radical oxidative decomposition method. That is, in many cases, the OH radical oxidative decomposition method is applied to the final residue to be subjected to oxidative decomposition after the amide structure that has been an inhibiting factor is destroyed and eliminated by the alkali cleaning method.
(7) For example, the final residue of an amide compound such as carbamazepine, ethenamide, N-methylpyrrole, polypeptide, and the like corresponds to this. A representative example of the OH radical oxidative decomposition method is the Fenton method.
(8) The present invention exhibits the following effects.

<< First effect >>
First, it is possible to wash and decompose a hard-to-decompose organic compound containing nitrogen such as an amide compound.
In the alkaline washing method of the nitrogen-containing compound of the present invention, for an amide compound, addition of a hydroxide ion to a carbonyl group, addition of a hydroxide ion to a carbocationized carbon atom, distribution of a hydrogen ion to a loan pair of nitrogen atoms. And other reactions proceed.
As a result, the amide structure is disintegrated, eliminated, and externalized, and, for example, an amine moiety such as ammonia (→ ammonium ion) is liberated and decomposed into sodium bicarbonate (bicarbonate) and the like. The amine portion can be easily treated by an adsorption fiber method, a crystal crystallization separation method, or the like, and sodium hydrogen carbonate can be easily treated as an inorganic substance by a membrane separation method, a crystal crystallization method, or the like.
In addition, when a residue exists, it decomposes | disassembles into a carbon dioxide, water, etc. by OH radical oxidative decomposition methods, such as the Fenton method (in this case, this invention becomes pre-processing of an oxidative decomposition method).
As described above, nitrogen-containing organic compounds such as amide compounds, which have been difficult to decompose and difficult to decompose in this kind of conventional technology, are cleaned and decomposed by the alkali cleaning method of the present invention.

<< Second effect >>
Secondly, this is simple, easy and reliable. The alkali cleaning method of the nitrogen-containing organic compound of the present invention uses a surface active machine to transiently increase the interfacial energy by applying a high-speed and strong stirring shear force, thereby allowing hydroxide ions to carbonyl groups of the amide compound. In addition to addition reactions, addition reactions and coordination reactions are promoted and advanced as expected.
The alkali cleaning method of the present invention employs a surface-active machine, so that it is more reliable and efficient than the above-described conventional technology, and is excellent in cost, while being nitrogen such as a hardly decomposable amide compound. A cleaning decomposition treatment of the organic compound contained is realized.
As described above, the effects exerted by the present invention are remarkably large, such as all the problems existing in this type of prior art are solved.

The alkali cleaning method of the nitrogen-containing organic compound according to the present invention will be described for explaining the mode for carrying out the invention, and a surface active machine will be shown. And (1) figure is side explanatory drawing which notched a part, (2) figure is a sectional view taken along the line XX of (1) figure, (3) figure is (1) figure It is arrow sectional drawing along the YY line. It is used for description of the form for implementing this invention, and is a block diagram (the 1) of a reaction process. It is used for description of the form for implementing this invention, and is a block diagram (the 2) of a reaction process.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
About amide compounds
In the alkali cleaning method of the present invention, a hard-to-decompose organic compound containing nitrogen is subjected to a cleaning and decomposition treatment. First, an amide compound that is a typical example of a nitrogen-containing organic compound will be described.
The amide compound is a dehydration condensation product of ammonia (NH ₃ ) or amine (tertiary amine, ≡N) (secondary amine,> NH) (primary amine, —NH ₂ ) and carboxylic acid (—COOH). It becomes more.
For example, acetamide (CH ₃ CONH ₂ ), dimethylformamide (DMF, HCON (CH ₃ ) ₂ ), formamide (HCONH ₂ ), benzamide (C ₆ H ₅ CONH ₂ ), carbamazepine, etenzamid, N-methylpyrrolidone, polypeptide , Other peptides and the like are exemplified as the subject of the present invention.
Polypeptide is a dehydration condensation polymer of α-amino acid, and protein is a typical example. Polyamide-based synthetic fibers such as polyamide, for example, 6,6 nylon fibers, are also an object of the present invention.
Carbamazepine, etenzamide, etc. are known as water environment residues and persistent pharmaceuticals. Acetamide, dimethylformamide (DMF), and N-methylpyrrolidone are known as chemicals that remain in the water environment and are hardly decomposable.
The amide compound is as described above.

<< Surface-active machine 1 >>
Next, the surface active machine 1 will be described with reference to FIG. In the alkali cleaning treatment method of the present invention, an amide compound, which is a hardly decomposable nitrogen-containing organic compound, is washed and decomposed by applying a high-speed and strong stirring shear force in an alkaline aqueous solution.
First, the surface active machine 1 will be described. In the surface active machine 1, a disc-shaped stirring plate 4 capable of high-speed and powerful rotation is provided in a stirring chamber 3 formed in a cylindrical drum 2, and stirring blades 5 are provided on the plate surface of the stirring plate 4. Has been. Then, the nitrogen-containing organic compound as the solute to be treated flows from the inlet 6 to the outlet 7 of the surface active machine 1 together with the alkaline aqueous solution of the solvent.

Such a surface active machine 1 will be further described in detail. In the cylindrical drum 2 provided with the inlet 6 and the outlet 7 of the surface active machine 1, a plurality of disk-shaped baffle partition plates 8 are arranged in a row at equal intervals in the horizontal axis direction. In addition, the intervals divided by the partition plates 8 are the stirring chambers 3 respectively.
A shaft 10 is provided in the axial direction through the central communication hole 9 of each partition plate 8. A disc-ring shaped stirring plate 4 with a shaft hole is fitted into and attached to the shaft 10 for each stirring chamber 3, and substantially arc-shaped and strip-shaped stirring blades 5 are provided on both front and rear surfaces of each stirring plate 4. Are convex. The shaft 10 is connected to a speed reducer 11 and a motor 12.
Accordingly, the alkaline aqueous solution of the amide compound that flows from the upstream stirring chamber 3 to the downstream stirring chamber 3 is rotated at high speed by the motor 12 by rotating each stirring plate 4 and stirring blade 5 at high speed. Agitation shearing force is applied.
In the illustrated surface active machine 1, a plurality of stirring chambers 3 are separately formed in the cylindrical drum 2, but regardless of this, the stirring chamber 4 in the cylindrical drum 2 and the stirring plate 4 with the stirring blades 5 are provided. However, a batch type surface active machine 1 provided with only one set is of course possible.

Surfactants machine 1 relates agitating plate 4 and stirring blades 5, at a stirring speed of the extent or ~900rpm less 300 rpm, per weight solution unit 50 kW / ^{m 3} or more ~150kW / ^{m 3} or less of the stirring shear (unit power ) Is stirred so that Thus, a strong stirring shear force is applied to the alkaline aqueous solution of the amide compound at high speed.
The above figures are as follows. In each case, when the value is less than the lower limit, the amide compound is uncertainly washed and decomposed (the transient increase in the interfacial energy described below is insufficient). On the other hand, when the above upper limit is exceeded, the power loss becomes excessive, the running cost increases, and a problem arises in the mechanical performance resistance.
Typically, a stirring rotational speed of the extent or ~800rpm less 700 rpm, carried out at 80 kW / ^{m 3} or more ~90kW / ^{m 3} or less extent stirring shearing force (unit power).

As the alkaline aqueous solution, a sodium hydroxide (NaOH) aqueous solution having a concentration of about 3% is typically added.
And an amide compound is thrown in and supplied to the surface active machine 1 so that it may become a density | concentration (weight%) of 5% or more and 30% or less with respect to alkaline aqueous solution. Usually, the alkaline aqueous solution is charged first, and the amide compound is charged later.
The concentration conditions are as follows. When the value is less than the lower limit, the amide compound is uncertainly washed and decomposed (the transient increase in interfacial energy is insufficient). On the other hand, when the upper limit value is exceeded, a problem arises in the mechanical performance strength, and the rotation of the stirring plate 4, the stirring blade 5, the motor 12 and the like is hindered. Typically, the concentration is about 10% by weight.
In the figure, reference numeral 13 denotes a heating means using, for example, steam. This heating means 13 is provided outside so as to cover the outer surface of the cylindrical drum 2, and the internal stirring chamber 3 is heated and maintained under a temperature condition of 80 ° C. or higher and 95 ° C. or lower. Typically, the heat is maintained at about 85 ° C. to 90 ° C. Thus, thermal energy is applied, and the cleaning and decomposition treatment, which is an endothermic reaction, is promoted. The cleaning / decomposing time is, for example, about 5 minutes to 10 minutes.
The configuration of the surface active machine 1 is as described above.

<< Function of surface-active machine 1 (transient improvement of interfacial energy) >>
Next, the function of the surface active machine 1 will be described with reference to FIG. In the alkali cleaning method of the present invention, the surface active machine 1 first exhibits the following functions.
That is, the surface-active machine 1 has a function of imparting a stirring shear force sufficient to transiently increase the interfacial energy of the alkaline aqueous solution of the amide compound, which is a nitrogen-containing organic compound to be heated, by the high-speed and powerful rotation of the stirring plate 4. Demonstrate.

The function of such a surface-active machine 1 will be further described in detail. In the surface-active machine 1, the stirring plate 4 with the stirring blade 5 rotates at high speed and force. Therefore, the amide compound and the aqueous alkaline solution are forced to contact and collide with the stirring plate 4, the stirring blade 5, the inner surface of the cylindrical drum 2, the partition plate 8, etc., and a high-speed and powerful stirring shear force field generated instantaneously. Exposed to.
Therefore, first, an amide compound composed of a crystalline solid or liquid as a solute is sufficiently mixed and dissolved in an alkaline aqueous solution composed of warm water that is accompanied by an excess of hydroxide ions (OH ⁻ ) and hydrogen ions (H ⁺ ) as solvents. It is done.
At the same time, the interfacial energy is improved. At the interface between the amide compound and the aqueous alkali solution, the interfacial energy is transiently improved as the shear surface, active surface, and friction energy are formed, expanded, and increased. Thus, the surface-active machine 1 first exhibits a high-speed and powerful stirring shear force imparting function sufficient to transiently improve the interfacial energy.
The amide compound which is a dehydration condensate is more suitable for thermodynamic natural nature, and dehydration condensation requires energy from the external system for hydrolysis and alkali washing decomposition, which are the reverse reactions. The improvement of the interfacial energy described above and the application of thermal energy by the heating means 13 described above are part of that.
The function of the surface active machine 1 (transient improvement of the interfacial energy) is as described above.

<< Function of surface-active machine 1 (cleaning and decomposing process) >>
Next, cleaning and decomposing treatment of the amide compound that is a nitrogen-containing organic compound based on the function of the surface active machine 1 will be described.
As described above, the surface-active machine 1 first transiently improves the interfacial energy based on the stirring shear force imparting function. Then, it promotes a predetermined addition reaction, coordination reaction, chain reaction and the like.
Therefore, between the amide compound and sodium hydroxide (NaOH), which is an alkaline aqueous solution, the following predetermined addition reaction, coordination reaction, chain reaction, etc. are promoted in line with the thermodynamic natural tendency and thus increased as described above. The interfacial energy that has been sedated is stabilized and stabilized.
The amide compound is finally converted to at least sodium bicarbonate after liberating the amine moiety.

The outline of the reaction of such alkali cleaning and decomposition treatment is as follows (details of the reaction will be described in the examples described later).
In the surface active machine 1, first, as an important reaction for starting the reaction, the π molecular orbital of the carbonyl group (> C═O) of the amide compound has a water atom on the carbon atom (C) side of the vacant orbital lacking a counter electron. Hydroxide ion (OH ⁻ ) in an aqueous sodium oxide (NaOH) solution is added.
Then, as the next reaction, the hydrogen ion (H ⁺ ) in the ionized water region is coordinated to the loan pair side, which is the unshared electron pair of the nitrogen atom (N) of the amide compound, and thus, for example, ammonia (NH ₃ ), dimethyl Amine moieties such as amine ((CH ₃ ) ₂ NH), methylamine (NH ₂ CH ₃ ), or ammonium hydroxide (anhydrous, NH ₄ OH) are liberated.
Then, a hydroxide ion (OH ⁻ ) is added to the carbocation (C ⁺ ) -converted carbon atom as a reaction for the free and cleaved main body residue.
In the amide compound, such an electron neutralization reaction becomes a pillar, and cleavage, liberation, diffusion, and other various chain reactions are added to these reactions, and finally, at least sodium bicarbonate (NaHCO ₃ ). To be decomposed.
On the way, it goes through a carbonyl group regeneration reaction. In addition, as a reaction to the counter electron accompanying the final cleavage residue side, a reaction in which hydrogen ions (H ⁺ ) in the ionized water region coordinate is often added.
The function of the surface active machine 1 (alkali cleaning decomposition treatment) is as described above.

《Action etc.》
The alkali cleaning method of the nitrogen-containing organic compound of the present invention is configured as described above. Therefore, it becomes as follows.
(1) An alkaline aqueous solution of a nitrogen-containing organic compound is put into the surface active machine 1 with the heating means 13.
Specifically, an aqueous solution of sodium hydroxide (NaOH) of an amide compound such as acetamide, dimethylformamide (DMF), formamide, benzamide, carbamazepine, etenzamide, N-methylpyrrolidone, or a polypeptide (protein, etc.) is a surface active machine. 1

(2) The surface active machine 1 can apply a strong stirring shear force at high speed, and exhibits a stirring shear force applying function sufficient to transiently increase the interfacial energy.
Therefore, the interface between the amide compound and the alkaline aqueous solution is activated and the interface energy is transiently improved. At the same time, thermal energy is also applied by the heating means 13.

  (3) Thus, the surface-active machine 1 is subjected to alkali cleaning decomposition treatment, and the desired addition reaction, coordination reaction, reaction linked to these, etc. described in the following (4) and (5) proceed in order. Thus, the increased interfacial energy is sedated and stabilized.

(4) That is, in the surface active machine 1, the following reaction proceeds for the amide compound. First, a hydroxide ion (OH ⁻ ) is added to the vacant orbit of the π molecular orbital of the carbonyl group (> C═O).
Next, hydrogen ions (H ⁺ ) in the ionized water region are coordinated to loan pairs that are unshared electron pairs of nitrogen atoms (N). Thus, for example, an amine moiety such as ammonia (NH ₃ ), dimethylamine ((CH ₃ ) ₂ NH), methylamine (NH ₂ CH ₃ ), or ammonium hydroxide (anhydrous, NH ₄ OH) is liberated (note that These can be oxidatively decomposed by the OH radical oxidative decomposition method).
Then, as a reaction to the main body residue after free cleavage, a hydroxide ion (OH ⁻ ) is added to the carbocation (C ⁺ ) -converted carbon atom.

(5) In the amide compound, such a reaction becomes a pillar, and a chain reaction is added to these reactions. After passing through a carbonyl group regeneration reaction, at least the amide compound is finally carbonated. It will be converted to sodium hydride (NaHCO ₃ ).
In addition, as a reaction to the counter electron accompanying the final cleaved residue, a reaction in which hydrogen ions (H ⁺ ) in the ionized water region are coordinated is often added.

(6) By the way, the alkali cleaning method of the present invention is often implemented as a pretreatment of the OH radical oxidative decomposition method.
In other words, the amide structure is collapsed and externalized by the alkali washing method described above, and the amine part is separated and liberated. Therefore, the OH radical oxidative decomposition method is a factor that inhibits the OH radical oxidative decomposition method. Reference) is resolved.
Therefore, even after the alkali cleaning method is performed, if the final residue to be oxidatively decomposed remains, such a final residue is oxidatively decomposed by the OH radical oxidative decomposition method.

  (7) For example, the final residue (second amine linked to the aromatic ring) in the case of amide compound carbamazepine, the final residue (free benzene ring, specifically phenylmethyl ether) in the case of ethenamide, N-methylpyrrolidone This corresponds to the final residue (propyl alcohol) in the case of, the final residue (alcohol) in the case of a polypeptide, and the like.

(8) As the OH radical oxidative decomposition method, there are a photocatalytic method and an ozone photooxidation method, but the Fenton method is typical. In the Fenton method, hydrogen peroxide, divalent iron ions, and a pH adjuster are added to the water to be treated containing the final residue to generate OH radicals (.OH), and the generated OH A radical oxidatively degrades the final residue.
The operation of the present invention is as described above.

Examples of the alkali cleaning method for nitrogen-containing organic compounds according to the present invention will be described below with reference to FIGS.
In this example, the process steps of the alkaline wash reaction are logically verified for the amide compound dimethylformamide (DMF).
The following chemical formula 1 is a schematic diagram of the structural formula of dimethylformamide. Chemical formula 2 is a schematic diagram of a structural formula for explaining steps (1) to (4).

First, the process steps of Chemical Formula 2 will be described. First, with respect to dimethylformamide shown in Chemical Formula 1, as shown in Chemical Formula 2 and Step (1) in FIG. 2, a hydroxide ion is added to the vacant orbit of the π molecular orbital of the carbonyl group.
That is, the amide structure of dimethylformamide is formed by covalently connecting a tertiary amine to a carbon atom of a carbonyl group.
Then, in the π molecular orbital of the double bond of the carbonyl group (> C═O), a sodium hydroxide (NaOH) aqueous solution that is an alkaline aqueous solution is substantially free from a vacant orbital (counter electron acceptor) that is a Lewis acid. , A large amount and excess of hydroxide ions (OH ⁻ ) are added to the ionized water region as a Lewis base (counter-electron donor). It is added to the carbon atom (C) side having a high contribution rate to the orbit.

Then, as shown in the above chemical formula 2 and step (2) in FIG. 2, in the carbonyl group, the counter-electron of the occupied orbit of the π molecular orbital moves, and the oxygen atom end becomes anionized.
That is, due to the addition of hydroxide ions in step (1) described above, in the carbonyl group of dimethylformamide, the counter electrons on the occupied orbitals (paired electrons) of the π molecular orbitals that disappear together with the empty orbitals are instantaneously covered. In order to eliminate the occupied orbit, the oxygen atom (O) end moves to the end of the oxygen atom (O) having a high contribution rate to the orbit, and the oxygen atom (O) end is anionized.
In this way, the π molecular orbitals of the carbonyl group dissolve and disappear together with not only the empty orbitals but also the chemical structure.
Then, as shown in the chemical formula 2 and step (3) in FIG. 2, the oxygen atom (O) end anionized as described above attracts sodium ions (Na ⁺ ). That is, the anionized oxygen atom end of the carbonyl group of dimethylformamide attracts sodium ions that are cations in the aqueous sodium hydroxide solution.

At the same time, as shown in the above chemical formula 2 and step (4) in FIG. 2, hydrogen ions in the ionized water region coordinate to a loan pair of amine nitrogen atoms. Since the carbonyl group disappears and disappears in the above steps (1) and (2), the loan pair is not delocalized and is normally localized and has recovered its independence, and hydrogen ions can be coordinated. .
That is, in a sodium hydroxide (NaOH) aqueous solution that is a strong alkaline aqueous solution, hydrogen ions (protons, H ⁺ ) are accompanied and caused by a large amount of hydroxide ions (OH ⁻ ) and ionization of water molecules as a pair. Supplied.
In the case of dimethylformamide in the illustrated example, the hydrogen ion is attached and coordinate-bonded to a loan pair (unshared electron pair) of a nitrogen atom of a tertiary amine (-N <).

Then, the cleaning and decomposition process proceeds from the chemical step 2 to the chemical step 3. Chemical formula 3 is a schematic diagram of a structural formula for explaining steps (5) to (7).
First, as shown in the above chemical formula 3 and step (5) in FIG. 2, the amine part is liberated based on the trivalent nitrogen atom.
That is, in dimethylformamide, the coordinate bond to the nitrogen atom of the hydrogen ion described above in step (4) is covalently bonded. In order to satisfy and maintain the trivalence that is the valence of the nitrogen atom, the nitrogen atom breaks the bond with the adjacent carbon atom and holds the bond pair electron in the self (the loan lost in the step (4)). A new loan pair (instead of a pair). As such, it liberates as dimethylamine ((CH ₃ ) ₂ NH).
In the case of other amide compounds other than the dimethylformamide of the examples, for example, they are liberated as ammonia (NH ₃ ), methylamine (NH ₂ CH ₃ ), ammonium hydroxide (anhydrous, NH ₄ OH), etc. In any case, the amine part is liberated from the carbon atom side of the main body part.

In this way, the C—N bond is broken as shown in the above chemical formula 3 and step (6) in FIG. The bond between the carbon and nitrogen atoms of dimethylformamide is broken.
Therefore, as shown in the above chemical formula 3 and step (7) in FIG. 2, the carbon atom is converted to a carbocation (C ⁺ ) with the above cutting.
That is, the carbon atom (C) side of the dimethylformamide main body portion is bonded to electrons with the liberation and cleavage of the amine portion such as dimethylamine ((CH ₃ ) ₂ NH) in the above steps (5) and (6). Deprived of the nitrogen atom (N) on the amine side. Thus, the carbon atom is converted to a carbocation (C ⁺ ).

Then, the washing and separation process proceeds from the process step of Chemical Formula 3 to the process step of Chemical Formula 4 above. Chemical formula 4 is a schematic diagram of a structural formula for explaining steps (8) to (10).
First, as shown in Chemical Formula 4 and step (8) in FIG. 2, a hydroxide ion (OH ⁻ ) is added to the carbocation (C ⁺ ).
That is, on the main body part side where the amine part is liberated, the anion hydroxide ion (OH ⁻⁾ present in a large amount in the alkaline aqueous solution, that is, the sodium hydroxide aqueous solution, is converted into the carbocation (C ⁺ ) carbon atom formed in the step (7). ) Is added.
As a result, on the main body side, the hydroxyl group (—OH) attached to the carbon atom (C) becomes 2 equivalents. In addition to 1 mole added in step (1), the addition in step (8) results in a total of 2 moles.

Therefore, the process proceeds to the above chemical formula 4 or step (9) in FIG. 2, and in the main body, 1 mol of water molecules is liberated from 2 equivalents of hydroxyl groups of carbon atoms. That is, 2 mol of hydroxyl group is attached to the same carbon atom, and 1 mol of water molecule is liberated based on the thermodynamic natural tendency.
As a result, a carbonyl group (> C═O) is generated as shown in the above chemical formula 4 and step (10) in FIG. A new carbonyl group has been regenerated.

Thereafter, the cleaning / decomposing process proceeds from the chemical step 4 to the chemical step 5. Chemical formula 5 is a schematic diagram of a structural formula for explaining steps (11) to (13).
First, as shown in the above chemical formula 5 and step (11) in FIG. 3, a hydroxide ion is present in the vacant orbit of the π molecule of the new carbonyl group (> C═O) generated in the step (10). (OH ⁻ ) is added. Since the addition reaction in step (11) is the same as that described in step (1), the description thereof is omitted.
Then, as shown in the above chemical formula 5 and step (12) in FIG. 3, in the new carbonyl group, the counter electrons of the occupied orbitals (paired electrons) of the π molecular orbitals move, and oxygen atoms (O ) The end is anionized. Since the electron transfer in step (12) is the same as that described in step (2), the description thereof is omitted.
Then, as shown in the chemical formula 5 and step (13) in FIG. 3, the oxygen atom (O) end anionized as described above attracts sodium ions (Na ⁺ ). The pulling reaction in step (13) is the same as that described in step (3), and will not be described.

Then, the cleaning and decomposition process proceeds from the chemical step 5 to the chemical step 6 described above. Chemical formula 6 is a schematic diagram of a structural formula for explaining steps (14) and (15).
The first, as shown in step (14) in the chemical formula 6 in and 3, one of the ^"-O - + Na ^+" in the "Na ^+" is diffused. That is, as a result of the step (13), two equivalents of “—O ⁻ + Na ⁺ ” that are transiently linked to the carbon atom (C) can be formed, and interfere (resonate) around the carbon atom. Therefore, one sodium ion is released and diffused for stability.

Then, as shown in the above chemical formula 6 or step (15) in FIG. 3, the carbonyl group (> C═O) is regenerated by eliminating the anionized oxygen atom (O ⁻ ).
That is, in the step (14), the oxygen atom (O ⁻ ) of the anion that has liberated and diffused the cation sodium ion (Na ⁺ ) has been moved by an electron to eliminate the anion, and the carbon atom (C) A double bond is intended. Thus, a new carbonyl group is regenerated.

Then, the cleaning / decomposing process proceeds from the chemical step 6 to the chemical step 7. Chemical formula 7 is a schematic diagram of a structural formula for explaining Steps (16) to (20).
First, as shown in the chemical formula 7 and step (16) in FIG. 3, sodium hydrogen carbonate (NaHCO ₃ ) is generated.
That is, in step (15), a new carbonyl group (CO) is generated as the anion of the anionized oxygen atom (O ⁻ ) is eliminated. As a result, the carbon atom (C) is disconnected from the hydrogen atom (H) having a relatively weak bonding force in order to satisfy and maintain the tetravalence of its own valence.
As a result, the main body is entirely converted to sodium bicarbonate. Sodium ion (Na ⁺ ) + bicarbonate ion (HCO ₃ ⁻ ) → sodium bicarbonate (NaHCO ₃ ).

On the other hand, as shown in the above chemical formula 7 and step (17) in FIG. 3, the final residue on the side cleaved based on the tetravalence which is the valence of the carbon atom includes the chemical residues in chemical formula 7 and FIG. As shown in step (18) of FIG. In the case of the dimethylformamide of the examples, the final residue on the cleaved bond side is composed of a hydrogen atom (H), and this hydrogen atom is accompanied by a bond pair electron with a carbon atom.
Then, in the case of the example, as shown in the chemical formula 7 or step (19) in FIG. 3, the hydrogen atom thus cut and carrying the counter electron is transferred to the hydrogen in the ionized water region. Ions (H ⁺ ) are coordinated. Then, as shown in Chemical Formula 7 and step (20) in FIG. 3, the final residue is hydrogenated (H ₂ ).
In the case of other amide compounds that are not dimethylformamide in the examples, the final residue side may be converted to, for example, methane (CH ₄ ) by coordination of hydrogen ions. In addition, there are cases where the final residue is formed into an alcohol, a free benzene ring, or the like, which can be an object of the OH radical oxidative decomposition method.
About an Example, it is as above.

DESCRIPTION OF SYMBOLS 1 Surface active machine 2 Cylindrical drum 3 Stirring chamber 4 Stirring plate 5 Stirring blade 6 Inlet 7 Outlet 8 Partition plate 9 Central communication hole 10 Shaft 11 Reducer 12 Motor 13 Heating means

Claims (9)

  An alkali cleaning method for a nitrogen-containing organic compound, characterized in that a nitrogen-containing hard-to-decompose organic compound is washed and decomposed by applying a high-speed and strong stirring shear force in an alkaline aqueous solution. In claim 1, a surface active machine is used, and the surface active machine is provided with a disk-shaped stir plate rotating at high speed and powerful in a stir chamber formed in a cylindrical drum. A stirring blade is projected on the plate surface,
An alkali cleaning method for a nitrogen-containing organic compound, characterized in that an aqueous alkali solution of the organic compound flows in the surface active machine from an inlet to an outlet.   3. The organic compound according to claim 2, wherein the organic compound is an amide compound, and is selected from acetamide, dimethylformamide (DMF), formamide, benzamide, carbamazepine, etenzamide, N-methylpyrrolidone, and a polypeptide. , Alkaline cleaning method for nitrogen-containing organic compounds. The surface active machine according to claim 3, wherein the organic compound to be heated and maintained is subjected to high-speed and powerful rotation of the stirring plate for the alkaline aqueous solution of the organic compound.
First, it exerts a function of imparting a stirring shear force sufficient to transiently increase the interfacial energy, and thus has a function of promoting the addition of hydroxide ions (OH ⁻ ) to the carbonyl group (> C═O) of the organic compound. An alkaline cleaning method for nitrogen-containing organic compounds, characterized by 5. The reaction of adding a hydroxide ion (OH ⁻ ) to the carbon atom (C) side of a vacant orbital lacking a counter electron with respect to the π molecular orbital of the carbonyl group (> C═O) of the organic compound according to claim 4. ,
A reaction in which a hydrogen ion (H ⁺ ) in an ionized water region is coordinated to a loan pair side that is an unshared electron pair of a nitrogen atom (N) of the organic compound;
An alkali cleaning method for a nitrogen-containing organic compound, characterized in that at least a reaction in which a hydroxide ion (OH ⁻ ) is added to a carbocation (C ⁺ ) carbon atom of the organic compound proceeds.   6. The alkali cleaning method for nitrogen-containing organic compounds according to claim 5, wherein the aqueous alkali solution comprises an aqueous sodium hydroxide (NaOH) solution. The organic compound according to claim 6, wherein the organic compound liberates an amine moiety such as ammonia (NH ₃ ) and then regenerates the carbonyl group.
An alkali cleaning method for a nitrogen-containing organic compound, characterized in that it is finally converted to at least sodium hydrogen carbonate (NaHCO ₃ ). In claim 3, the alkali cleaning method is carried out as a pretreatment of the oxidative decomposition method, and the inhibiting factor of the oxidative decomposition method is eliminated for the organic compound,
Thus, in the subsequent oxidative decomposition method, a residue of the organic compound is oxidatively decomposed, and the alkali cleaning method for a nitrogen-containing organic compound is characterized. 9. The oxidative decomposition method according to claim 8, comprising a Fenton method, wherein hydrogen peroxide, divalent iron ions, and a pH adjuster are added to water to be treated containing the residue of the organic compound, and OH Radical (.OH) is generated,
A method for alkali cleaning a nitrogen-containing organic compound, wherein the OH radical oxidatively decomposes the residue.

Images