JP2009255077A - TREATMENT DEVICE AND TREATMENT METHOD FOR beta LACTAM BASED ANTIBIOTICS-CONTAINING WATER - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treatment device and a treatment method for β lactam based antibiotics-containing water where, first, OH radicals are efficiently produced, thus β lactam based antibiotics can be securely oxidized and decomposed, and secondary, the above operations can be achieved under excellent running cost, posttreatment cost, easiness of control, stability of treatment, initial cost or the like. <P>SOLUTION: In the treatment device 2 and the treatment method, β lactam based antibiotics 1 comprised in treatment water 3 are oxidized and decomposed based on a Fenton process. Then, the treatment device 2 is provided with: a treatment tank 4; and a treatment water feeding means 5, a hydrogen peroxide adding means 6, an iron ion adding means 7 and a pH regulating means 8 attached to the treatment tank 4. Regarding the hydrogen peroxide adding means 6, hydrogen peroxide is added to the treatment water 3 in the treatment tank 4, regarding the iron ion adding means 7, bivalent iron ions are added to the treatment water 3 in the treatment tank 4, and, regarding the pH regulating means 8, the treatment water 3 in the treatment tank 4 is retained to prescribed weak acidity. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a treatment apparatus and treatment method for β-lactam antibiotic-containing water. That is, the present invention relates to a treatment apparatus and a treatment method for oxidizing and decomposing β-lactam antibiotics contained in water to be treated such as waste water based on the Fenton method.

《Technical background》
Recently, in Western countries and Japan, the effects on human bodies and the environment have been pointed out regarding pharmaceuticals remaining and mixed in drinking water and rivers, and the necessity of countermeasures has been discussed.
In particular, antibiotics contained in wastewater have become a major problem, and detection in water purification plants and rivers in metropolitan areas has become a hot topic in MHLW surveys and newspapers.
These will be further described in detail. (1) Drugs such as antibiotics are used in large quantities not only for human medical purposes but also for livestock.
And (2) antibiotics are contained in waste water excreted without being metabolized and biodegraded in the body, waste water applied to the skin and washed away, and waste water from medical institutions such as hospitals.
Therefore (3), antibiotics remain in various water such as river water, water treatment plant intake water, sewage treatment plant inflow water, sewage treatment plant discharge water, ground water, lake water, tap water, drinking water, etc. There is a strong possibility that it has been detected, and its detection and confirmation are in succession.
(4) Although the residual concentration is very small, there is no risk of immediate impact on human health, but there are concerns about adverse effects on the human body, ecosystem, environment, etc. over the long term.

<Conventional technology>
On the other hand, no effective countermeasure technology has been proposed yet. The need for treatment of antibiotics contained in wastewater, for example, treatment needs for β-lactam antibiotics, is expected to increase in the future. Effective treatment technology has not yet been established.
Only the following level can be grasped as this type of prior art.
・ First, conventional water treatment plants and sewage treatment plant facilities can be considered.
・ In hospitals and other medical institutions, contractor processing and incineration are performed as part of industrial waste.
・ Technical proposals include technology to irradiate and oxidize and decompose contaminated water (Patent Document 1), fungi treatment of sludge water and Fenton method (using Fenton reagent of hydrogen peroxide and iron salt) The technique (patent document 2) of oxidizing and decomposing in the generation of OH radicals is only occasionally seen.

《Information on prior art documents》
Patent Document 1 relates to a radiation treatment method, and Patent Document 2 relates to a fungus and a Fenton treatment method.
JP 2004-74119 A JP 2005-526595 A

About the problem
By the way, the following problems have been pointed out for this type of conventional example.
・ First, it was considered difficult to treat antibiotics with large molecular weights using the equipment, capacity, and chemicals used in conventional water treatment plants and sewage treatment plants.
-Regarding the treatment as industrial waste, there is a problem that the cost is extremely high as is well known.
・ Regarding radiation treatment and fungi treatment, problems were pointed out in equipment costs, other initial costs, control complexity, treatment stability, etc.
-Regarding the conventional Fenton method, problems have been pointed out that the processing performance is poor and the running cost (chemical use cost) increases. For example, hydrogen peroxide is easily decomposed into water and oxygen during the treatment, and the generation efficiency of OH radicals is poor, and a large amount of hydrogen peroxide is excessively added to cover this. The post-processing cost by the agent was also increased.

<< About the present invention >>
The treatment apparatus and treatment method for water containing β-lactam antibiotics according to the present invention have been made in order to solve the above-described problems of the conventional examples in view of such circumstances.
According to the present invention, firstly, OH radicals are efficiently generated, so that β-lactam antibiotics can be reliably oxidized and decomposed, and secondly, the running cost, post-treatment cost, It is an object of the present invention to propose a treatment apparatus and treatment method for water containing β-lactam antibiotics, which is realized with excellent controllability, treatment stability, initial cost, and the like.

<About each claim>
The technical means of the present invention for solving such problems, that is, the technical means described in the claims are as follows. First, claim 1 is as follows.
The treatment apparatus for water containing β-lactam antibiotics according to claim 1 oxidizes and decomposes antibiotics contained in the water to be treated based on the Fenton method.
The antibiotic comprises penicillin and other β-lactam organic compounds having a β-lactam structure. The treatment apparatus includes a treatment tank and water to be treated, a hydrogen peroxide addition means, an iron ion addition means, and a pH adjustment means attached to the treatment tank.
The treated water supply means supplies the treated water containing the antibiotic to the treatment tank. The hydrogen peroxide adding means adds hydrogen peroxide to the water to be treated in the treatment tank. The iron ion addition means adds divalent iron ions to the water to be treated in the treatment tank.
The pH adjusting means adds a pH adjusting agent to the treated water supplied to the treated tank from the treated water supply means and the treated water supplied to the treated tank, and the treated water Is maintained at a predetermined weak acidity.

About Claim 2, it is as follows. In the treatment apparatus for water containing β-lactam antibiotics according to claim 2, in claim 1, the hydrogen peroxide adding means adds the entire amount of the aqueous hydrogen peroxide solution at the beginning of the reaction. The iron ion addition means repeats a plurality of cycles intermittently after the addition of hydrogen peroxide, and adds the divalent iron ion solution in portions.
The pH adjusting means is characterized in that an acid pH adjuster is added before the addition of hydrogen peroxide, and an alkaline pH adjuster is added every time an iron ion solution is added after the addition of hydrogen peroxide. And
About Claim 3, it is as follows. In the treatment apparatus for water containing β-lactam antibiotics according to claim 3, in claim 2, the β-lactam antibiotics are penicillin-based, β-lactamase inhibitor-containing penicillin-based, cephem-based, β-lactamase-inhibitor-containing cephem-based. , Carbapenem series, or monobactam series.
The iron ion adding means adds an aqueous solution of ferrous sulfate or ferrous chloride. The pH adjusting means adds sulfuric acid or caustic soda, for example, and maintains the water to be treated in the treatment tank at about pH 4 to suppress decomposition reaction of the added hydrogen peroxide into water and oxygen. It is characterized by.

About Claim 4, it is as follows. The treatment method for water containing β-lactam antibiotics according to claim 4 oxidizes and decomposes the antibiotics contained in the water to be treated based on the treatment process of the Fenton method. The antibiotic comprises penicillin and other β-lactam organic compounds having a β-lactam structure.
Then, hydrogen peroxide, a divalent iron ion solution, and a pH adjuster are added to the water to be treated containing the antibiotic. The total amount of hydrogen peroxide is added at the beginning of the reaction. The divalent iron ion solution is added in portions by repeating a plurality of cycles intermittently after the addition of hydrogen peroxide.
As for the pH adjuster, an acid pH adjuster is added before the addition of hydrogen peroxide, and after the addition of hydrogen peroxide, an alkaline pH adjuster is added for each divided addition of the divalent iron ion solution. The water is maintained at a predetermined weak acidity.

About Claim 5, it is as follows. In the method for treating β-lactam antibiotic-containing water according to claim 5, in claim 4, the total amount of hydrogen peroxide added is reduced by divalent iron ions dividedly added as a catalyst each time divided addition is performed. OH radicals are generated.
Therefore, the antibiotic contained in the water to be treated is oxidized and decomposed by the OH radicals to be mineralized into a low molecular weight compound.
About Claim 6, it is as follows. The method for treating β-lactam antibiotic-containing water according to claim 6 is the method according to claim 5, wherein the hydroxide ions produced by the reduction reaction of hydrogen peroxide are produced by the oxidation reaction of divalent iron ions. Oxidized with the generated trivalent iron ions, OH radicals are generated.
Therefore, the antibiotic contained in the water to be treated is oxidized and decomposed by the OH radicals to be mineralized into a low molecular weight compound.
About Claim 7, it is as follows. In the method for treating β-lactam antibiotic-containing water according to claim 7, in claim 5 or 6, the generated OH radical further reacts with water such as the water to be treated, so that new OH radical and water The reaction to produce is repeated in a chain.
Therefore, the antibiotic is oxidized and decomposed by OH radicals repeatedly generated in this manner, and is mineralized into a low molecular weight compound.
About Claim 8, it is as follows. In the method for treating β-lactam antibiotic-containing water according to claim 8, in claim 5 or 6, trivalent iron ions produced by oxidation reaction of divalent iron ions react with hydrogen peroxide. Thus, the reaction for generating at least new OH radicals is repeated in a chain manner.
Therefore, the antibiotic is oxidized and decomposed by OH radicals repeatedly generated in this manner, and is mineralized into a low molecular weight compound.

<About the action>
Since the present invention comprises such means, the following is achieved.
(1) Water to be treated containing penicillin and other β-lactam antibiotics is supplied to the treatment apparatus. The β-lactam antibiotic is oxidized and decomposed by a treatment method based on the Fenton method.
(2) This treatment apparatus includes a water to be treated supply means, a treatment tank, a post-treatment tank, and the like. The treatment tank is provided with hydrogen peroxide addition means, iron ion addition means, pH adjustment means, and the like.
(3) And the water to be treated is supplied to the treatment tank, but before that, sulfuric acid or the like is added from the pH adjusting means to make it weakly acidic at about pH 4.
(4) In the treatment tank, first, all the hydrogen peroxide is added from the hydrogen peroxide addition means to the water to be treated.
(5) Then, a divalent iron ion solution is dividedly added from the iron ion adding means, and for each divided addition, caustic soda or the like is added from the pH adjusting means, and the weak acidity of the water to be treated is maintained. .
(6) Now, in the treatment tank, hydrogen peroxide generates OH radicals using divalent iron ions as a catalyst.
In this production reaction, since iron ions are added in portions, there is no possibility of a reaction that wastes OH radicals and iron ions. Further, since the atmosphere is weakly acidic, the catalytic function of iron ions is promoted, so that hydrogen peroxide is not decomposed or wasted into water and oxygen.
(7) OH radicals can also be generated by the reaction of trivalent iron ions and hydroxide ions generated by the above reaction.
(8) The OH radical is further formed by the reaction of the OH radical generated by the above reaction with water such as water to be treated, or the trivalent iron ion and hydrogen peroxide generated by the above reaction. Also by reacting, new products are repeatedly generated in a chain.
(9) In the treatment tank, due to the strong oxidizing power of the OH radicals generated in this way, β-lactam antibiotics contained in the water to be treated are composed of persistent organic compounds having a large molecular weight, It is reliably oxidized and decomposed. Thus, it is mineralized into water, carbon dioxide, and other low-molecular compounds.
(10) Then, the water to be treated is drained outside through the post-treatment tank.
(11) In this processing apparatus and processing method, the addition amount of the Fenton reagent and the like can be easily calculated from the reaction theoretical value, the configuration is relatively simple, and stable processing is possible.
(12) Then, the processing apparatus and the processing method of the present invention exhibit the following effects.

<< First effect >>
First, OH radicals are efficiently generated, so that β-lactam antibiotics can be reliably oxidized and decomposed.
That is, in the processing apparatus and processing method of the present invention, first, a. OH radicals are efficiently generated by maintaining the weak acidity of the water to be treated, adding all of the hydrogen peroxide, split addition of divalent iron ions, and the like.
And b. The OH radical repeats in a chain by the reaction of trivalent iron ions and hydroxide ions, the reaction of the generated OH radicals with water, the reaction of trivalent iron ions with hydrogen peroxide, etc. Produced with high efficiency.
With these a and b, in the present invention, β-lactam antibiotics remaining, mixed and contained in the water to be treated such as waste water are reliably oxidized, decomposed and removed.

<< Second effect >>
Secondly, this is realized with excellent running cost, post-processing cost, ease of control, stability of processing, initial cost, and the like.
That is, in the processing apparatus and processing method of the present invention, first, a. Like the Fenton method of this type, the hydrogen peroxide is not decomposed and wasted into water and oxygen, and it is not necessary to add an excessive amount of hydrogen peroxide. Cost and running cost are reduced.
B. Like this conventional Fenton method, hydrogen peroxide is not added excessively, the water to be treated after treatment has a small residual content of hydrogen peroxide, and the post-treatment cost by the neutralizing agent is also reduced. .
C. The amount of hydrogen peroxide added corresponding to the content of β-lactam antibiotics, the amount of divalent iron ions added corresponding to the amount of hydrogen peroxide added, the amount of pH adjuster added, etc. From the above, the required number of moles can be obtained. Therefore, it is easy to control the addition of an appropriate amount of chemicals without excess and deficiency, and automatic control is possible. For example, there is no situation where divalent iron ions remain or run short, and the processing is stabilized. .
D. Compared with the industrial waste treatment, radiation treatment, fungi treatment, etc. of this kind of conventional example described above, the configuration is relatively simple and easy. From this aspect, the treatment stability is excellent and the initial cost such as equipment cost, etc. These costs are also reduced.
The processing apparatus and the processing method of the present invention open the way to scale-up application to full-scale processing, large-scale processing, large-capacity processing, etc., that is, practical application, from each of a, b, c, d. For example, when the treatment apparatus of the present invention is installed in a facility of a medical institution and the treatment method of the present invention is performed, purification of wastewater containing β-lactam antibiotics can be easily performed.
As described above, the effects exerted by the present invention are remarkably large, such as all the problems existing in this type of conventional example are solved.

《About drawing》
Hereinafter, the treatment apparatus and treatment method for β-lactam antibiotic-containing water according to the present invention will be described in detail based on the best mode for carrying out the invention shown in the drawings.
FIG. 1 is a configuration flowchart for explaining the best mode for carrying out the present invention.

<About β-lactam antibiotic 1>
First, the β-lactam antibiotic 1 that is a processing target of the processing apparatus 2 and the processing method of the present invention will be described.
As is well known, antibiotics are chemical substances produced by microorganisms, and have the ability to prevent, inhibit, alter, and suppress the growth and function of bacteria and other microorganisms, and are widely used as pharmaceuticals. ing. That is, they are used as antibacterial agents, antifungal agents, antiviral agents, antitumor agents and the like.
The present invention is directed to β-lactam antibiotic 1 among such antibiotics. That is, it targets penicillin (PENICILLIN) and other β-lactam organic compounds having a β-lactam structure (β-lactam ring). Specifically, a β-lactam antibiotic 1 comprising a penicillin, β-lactamase inhibitor-containing penicillin, cephem, β-lactamase inhibitor-containing cephem, carbapenem, or monobactam is used.

Such β-lactam antibiotic 1 will be further described in detail.
The β-lactam antibiotic 1 is a general term for cyclic organic compounds containing the atomic group -CONH- in the ring. Representative examples include penicillin (PC), of which penicillin G is the most well known, but penicillin F, penicillin K, penicillin U, Penicillin V, penicillin X and the like.
The specific classification and contents of β-lactam antibiotic 1 are listed as follows (1) to (6).
(1) Penicillin (PC)
・ Penicillin G (PCG)
・ Penicillin F (PCF)
・ Penicillin K (PCK)
・ Penicillin U (PCU)
・ Penicillin V (PCV)
・ Penicillin X (PCX)
・ Methicillin ・ Amoxicillin (AMPC)
・ Ampicillin (ABPC)
・ Cloxacillin (MCIPC)
・ Piperacillin (PIPI)
(2) Penicillin containing β-lactamase inhibitor • Ampicillin / sulbactam (ABPC / SBT)
・ Piperacillin / Tazobactam ((PIPC / TAZ)
(3) Cephem (Ceph)
・ Cefazolin (CEZ)
・ Cefotiam (CTM)
・ Ceftriaxone (CTRX)
・ Ceftazidime (CAZ)
・ Cefpirom (CPR)
・ Cefepime (CEPM)
(4) Cephem series containing β-lactamase inhibitor Cefoperazone / sulbactam (CPZ / SBT)
(5) Carbapenem series ・ Imipenem / cilastatin (IPM / CS)
・ Panipenem / Betamipron (PAPM / BP)
・ Meropenem (MEPM)
(6) Monobactam system ・ Aztreonam (AZT)
-Sulbactam-Tazobactam This invention makes such a beta lactam antibiotic 1 contained in the to-be-treated water 3 such as various wastewaters to be treated.

About other antibiotics
By the way, the processing apparatus 2 and the processing method of the present invention can be applied to other antibiotics other than the β-lactam antibiotic 1, but are excluded from the current claims. That is, antibiotics having a structure other than β-lactam antibiotic 1 are currently excluded from the scope of claims of this patent application and excluded.
Such other antibiotics are listed as follows (1) to (8).
(1) Aminoglycoside ・ Kanamycin (KM)
・ Streptomycin (SM)
・ Neomycin ・ Gentamicin (GM)
・ Fradiomycin ・ Tobramycin (TOB)
・ Amikacin (AMK)
・ Arbekacin (ABK)
・ Astromycin ・ Isepamicin ・ Bekanamycin ・ Divekacin ・ Micronomycin ・ Netilmycin ・ Paromomycin ・ Ribastomycin ・ Sisomycin (2) Tetracycline ・ Tetracycline ((TC)
・ Doxycycline (DOXY)
・ Minocycline (MINO)
(3) Chloramphenicol system • Chloramphenicol (4) Macrolide system 1) 14-membered ring macrolide • Erythromycin (EM)
・ Clarithromycin (CAM)
・ Roxithromycin (RXM)
2) Nitrogen-containing 15-membered macrolide ・ Azithromycin (AZM)
3) 16-membered macrolide ・ Rokitamicin (RKM)
・ Kitasamycin (LM)
(5) Ketolide system ・ Terithromycin (TEL)
(6) Polyene macrolide system • Nystatin • Amphotericin B (AMPH-B)
(7) Glycopeptide system • Vancomycin (VCM)
・ Teicoplanin (THIC)
(8) Nucleic acid system ・ Fosmidin As described above for other antibiotics.

<< Outline of Processing Apparatus 2 and Processing Method >>
The treatment apparatus 2 and the treatment method of the present invention oxidize and decompose the β-lactam antibiotic 1 contained in the water to be treated 3 based on the improved Fenton treatment process. That is, in the treatment apparatus 2 and the treatment method of the present invention, the water containing the β-lactam antibiotic 1 is treated water 3.
Therefore, the contained β-lactam antibiotic 1 is converted into OH radicals ( ^.OH ) generated by the Fenton main reaction using hydrogen peroxide (H ₂ O ₂ ) and divalent iron ions (Fe ²⁺ ) as a Fenton reagent. ) And oxidized and decomposed by OH radicals generated by the incidental, secondary, and chain reactions of Fenton's main reaction, and mineralized into water, carbon dioxide, and other low-molecular compounds. .
And the processing apparatus 2 and the processing method of this invention are the processing tank 4, the to-be-processed water supply means 5, the hydrogen peroxide addition means 6, the iron ion addition means 7, and the pH adjustment means 8 which were attached to this processing tank 4. And has.
Hereinafter, these will be described in detail.

<< About treated water supply means 5 etc. >>
First, the treated water supply means 5 and the like will be described. The treated water supply means 5 supplies the treated water 3 containing the β-lactam antibiotic 1 to the treatment tank 4 as a treatment target.
That is, in the illustrated example, the treated water 3 is introduced into the raw water tank 9 of the treated water supply means 5, and the treated water 3 is supplied to the treated tank 4 via the raw water tank 9 and the pH adjustment tank 10. Is supplied. The treated water 3 introduced into the raw water tank 9 is subjected to pretreatment such as dust sludge removal and biological treatment in advance as necessary. In the pH adjusting tank 10, a pH adjusting agent is added from the attached pH adjusting means 8.
The pH adjusting means 8 adds a pH adjusting agent to the treated water 3 being supplied from the raw water tank 9 of the treated water supply means 5 to the treated tank 4 so as to reduce the treated water 3 to a predetermined weakness. After adjusting to acidity, it is supplied to the treatment tank 4. That is, the treated water 3 from the raw water tank 9 is often pH 6 or more, for example, so that the pH is adjusted to about pH 5 to about 3, typically about pH 4, so that an acid pH such as sulfuric acid is used as a pH adjuster. A modifier is used.
The reason for adjusting the pH in advance in this way is that, as will be described later, in order to ensure that the OH radical production reaction with hydrogen peroxide and divalent iron ions is performed efficiently as expected. is there.
The pH adjustment tank 10 is used for, for example, large-volume treatment, continuous treatment of the water to be treated 3, treatment of high-concentration β-lactam antibiotic 1, etc. It is possible to carry out the pH adjustment described above instead of using the raw water tank 9 instead of using it.
The treated water supply means 5 and the like are as described above.

<About hydrogen peroxide addition means 6>
Next, the hydrogen peroxide addition means 6 attached to the processing tank 4 will be described. The hydrogen peroxide addition means 6 adds a total amount of an aqueous solution of hydrogen peroxide (H ₂ O ₂ ) to the treated water 3 in the treatment tank 4 as a Fenton reagent at the beginning of the reaction. Hydrogen peroxide is a source of OH radicals.
The amount of hydrogen peroxide added per reaction depends on the specific content and concentration of the β-lactam antibiotic 1 to be treated contained in the water 3 to be treated. The actual required amount (necessary number of moles) calculated as a standard is added all at once at the beginning of the reaction. The next addition is when hydrogen peroxide is exhausted from the water 3 to be treated in the treatment tank 4, that is, at the next reaction, and the whole amount is added in the same manner.
Thus, in this specification, the addition of the total amount means that 100% of the total amount of the drug necessary for the reaction is added all at once.
In this way, the entire amount of hydrogen peroxide is added from the hydrogen peroxide addition means 6.

<< About iron ion addition means 7 >>
Next, the iron ion addition means 7 attached to the processing tank 4 will be described. The iron ion adding means 7 intermittently repeats a plurality of cycles with respect to the water to be treated 3 of the treatment tank 4 after the addition of hydrogen peroxide as described above, thereby supplying a divalent iron ion (Fe ²⁺ ) solution to Fenton. Add in portions as reagents.
That is, substances that generate divalent iron ions in the liquid, such as ferrous sulfate heptahydrate (FeSO ₄ · 7H ₂ O), are typically used as such iron salts, but other anhydrous Salts and hydrated salts such as iron chloride (FeCl ₂ ) and hydrates thereof can also be used. The divalent iron ion functions as a catalyst for the OH radical generation reaction of hydrogen peroxide.
The amount of iron ion added per reaction is calculated based on the theoretical reaction value, but the actual required amount is larger, for example, about 0.5 mole per mole of hydrogen peroxide. .
Moreover, this iron ion is divided and added in multiple times. That is, the necessary amount for one reaction is not added in the whole amount, but is divided into about 3 to 7 times, for example, 5 times, and is added sequentially. As for the addition timing for each time, the next time is added at the stage where the previous addition is gone. Thus, in this specification, divided addition means that the amount of drug necessary for the reaction is added in multiple portions.
The reason why the divalent iron ions are added separately is as follows: a, b, c. First a. If the total amount is added, in the chemical reaction to be described later, the OH radical is wasted at the same time as the intended positive reaction from the original system using hydrogen peroxide as a reactant to the production system using OH radical as a product. Reaction is likely to occur. That is, a reaction in which surplus OH radicals return to water easily occurs, loss occurs, and iron ions used for generating OH radicals are wasted. On the other hand, when the addition is divided, such a reaction is suppressed and the waste of iron ions is eliminated.
B. OH radicals have a very short reaction time due to their intense reaction, and have a very short life. When the total amount is added in a divided manner, OH radicals are generated each time, and the corner of the treated water 3 in the treatment tank 4 is generated. I will come across. As a result, the oxidation and decomposition of β-lactam antibiotic 1 are ensured, made efficient, and accelerated.
C. When the addition is divided, the remaining hydrogen peroxide is smaller than the total addition, and accordingly, the post-treatment cost by the neutralizing agent is reduced accordingly.
In this way, divalent iron ions and the like are dividedly added from the iron ion adding means 7.

<About pH adjusting means 8>
Next, the pH adjusting means 8 attached to the processing tank 4 will be described. The pH adjusting means 8 adjusts the pH of the water to be treated 3 before being supplied from the water to be treated supplying means 5 to the treatment tank 4 and the water to be treated 3 after being supplied to the treatment tank 4 as described above. An agent is added to maintain the water to be treated 3 at a weak acidity of about pH 4, for example.
That is, the pH adjusting means 8 adds an acid pH adjuster such as sulfuric acid (H ₂ SO ₄ ) before the addition of hydrogen peroxide, and after the addition of hydrogen peroxide, An alkaline pH adjuster such as caustic soda (NaOH) is added.
The reasons for maintaining the water to be treated 3 at about pH 3 to about pH 5 typically about pH 4 are as follows: a, b, c.
First a. As will be described later, it functions to suppress a wasteful decomposition reaction of hydrogen peroxide into water and oxygen that inhibits the intended reaction. With this, b. It functions to promote electron donation of divalent iron ions to hydrogen peroxide. C. It functions to promote and ensure the incidental, secondary, and chain-repeated OH radical generation reactions described below. With these a, b, and c, generation of OH radicals proceeds efficiently.
On the other hand, first, the treated water 3 from the raw water tank 9 of the treated water supply means 5 is often, for example, pH 6 or higher, so that, as described above, in the pH adjusting tank 10, for example, from the pH adjusting means 8 Sulfuric acid is added to adjust the pH to about 4, for example.
Then, after the fact, when divalent iron ions are added in the treatment tank 4, the pH of the water to be treated 3 is lowered to, for example, about 2.8 and the acidity is excessively increased. For each divided addition, for example, caustic soda is added to adjust the pH of the water to be treated 3 to about pH 4, for example.
The pH adjusting means 8 is as described above.

<< Reaction in Treatment Tank 4 (OH Radical Generation: Part 1) >>
Next, the chemical reaction (generation of OH radicals: part 1) in the treatment tank 4 will be described.
In the treatment apparatus 2 and treatment method, first, in the treatment tank 4, the water 3 to be treated is stirred and flowed down, and the added hydrogen peroxide is added as a catalyst to the divalent iron ion. To generate OH radicals.
The generation of such OH radicals will be further described in detail. In the treatment tank 4, OH radicals are generated based on the following chemical formulas 1 and 2 (chemical formula 3). This is the Fenton main reaction.

These will be further described in detail. In this Fenton main reaction, the divalent iron ions (Fe ²⁺ ) sequentially added from the iron ion addition means 7 in the reaction formula of the above chemical formula 1 maintain the treated water 3 in a weakly acidic atmosphere having a pH of about 4, for example. Therefore, as a catalyst, electrons (e ⁻ ) are sequentially donated to the hydrogen peroxide (H ₂ O ₂ ) of the above reaction formula 2 as a catalyst, and the self oxidizes to trivalent iron ions ( Fe ³⁺ ).
Therefore, in the reaction formula of Chemical Formula 2, all of the hydrogen peroxide initially added from the hydrogen peroxide addition means 6 is sequentially supplied with electrons based on the chemical formula of Chemical Formula 1, and in each case, OH radical (.OH) And hydroxide ions (OH ⁻ ) are produced. When the reaction formulas of Chemical Formula 1 and Chemical Formula 2 are synthesized together, the reaction formula of Chemical Formula 3 is obtained.
By the way, in such a reaction, since the to-be-processed water 3 is maintained in the weakly acidic atmosphere as mentioned above, it is suppressed that hydrogen peroxide is decomposed | disassembled into water and oxygen, and wasted. On the other hand, if it is not maintained in a weakly acidic atmosphere, hydrogen peroxide becomes water molecules (H ₂ O) while generating oxygen (O) in the nascent stage according to the following reaction formula 4; The reaction formula of Chemical Formula 2 (Chemical Formula 3) is wasted without generating OH radicals. It should be noted that oxygen in this nascent stage is out of the system as oxygen molecules (O ₂ ) when there is no oxidation target.
In the treatment tank 4, first, OH radicals are generated by such a Fenton main reaction.

<< Reaction in treatment tank 4 (generation of OH radicals: 2) >>
Next, the chemical reaction (generation of OH radical: part 2) in the treatment tank 4 will be described. Secondly, in the treatment tank 4, OH radicals (.OH) can be generated also by the following reaction formulas 5 and 6.
That is, in the treatment tank 4, first of all, OH radicals are generated by the Fenton main reaction in the reaction formula of the chemical formula 3 (Chemical formula 1, Chemical formula 2). OH radicals can also be generated incidentally, secondaryly, or chained by the reaction formula of ## STR5 ##

This will be further described in detail. In the treatment tank 4, the hydroxide ions (OH ⁻ ) generated by the reduction reaction of hydrogen peroxide are converted into trivalent iron ions (Fe ³⁺ ) generated by the oxidation reaction of divalent iron ions. Oxidized to generate OH radicals (.OH).
That is, the trivalent iron ion generated by the chemical formula 1 is converted into an electron (e ⁻ ) from the hydroxide ion generated by the chemical formula 2 according to the chemical formula 5 and chemical formula 6 above. OH radicals are generated, and they are reduced to divalent iron ions and returned.
In this way, when not only the reaction formula of Chemical Formula 3 (Chemical Formula 1, Chemical Formula 2) but also the chemical formulas of Chemical Formula 5 and Chemical Formula 6 occur in a chain-balanced manner, OH radicals are generated more efficiently. The
Secondly, in the treatment tank 4, OH radicals can be generated by such a reaction.

<< Reaction in Treatment Tank 4 (Generation of OH radical: Part 3) >>
Next, the chemical reaction (generation of OH radicals: part 3) in the treatment tank 4 will be described. In the treatment tank 4, in addition to the first and second described above, new OH radicals are generated incidentally, secondary, and chained by the third reaction.
That is, the OH radicals generated in the reaction formulas of Chemical Formula 3 (Chemical Formula 1, Chemical Formula 2) and Chemical Formula 5 and Chemical Formula 6 react with water such as the water to be treated 3 to generate new OH radicals and water. The reaction to generate is repeated in a chained manner according to the following reaction formulas 7 and 8.

These will be further described in detail. First, in a neutral to alkaline atmosphere, OH radicals extract hydrogen atoms from water molecules and oxidize them to generate oxygen molecules, and are themselves reduced to water molecules.
On the other hand, in an acidic atmosphere, the OH radical (.OH) withdraws electrons (e ⁻ ) from water molecules (H ₂ O) according to the above reaction formula (7) and converts itself into hydroxide ions (OH ⁻ ). However, this abstraction reaction radically splits and activates water molecules to generate new OH radicals (.OH) and protons (H ⁺ ). The generated hydroxide ions and protons disappear by generating new water (H ₂ O) in the reaction formula of the above formula 8.
Since the water 3 to be treated in the treatment tank 4 is maintained in a weakly acidic atmosphere, new OH radicals are generated in this way. Further, based on the OH radicals thus generated, A series of reactions like this occur in a chain, and the subsequent process is repeated in a chain.
That is, once OH radicals are generated by the reaction formulas such as Chemical Formula 3, etc., OH radicals are obtained semipermanently by a chain reaction afterwards using this as an initiation reaction and reaction initiator. The OH radical excluding the amount consumed in the oxidation and decomposition processes of the β-lactam antibiotic 1 repeats generation / extinction coexisting with chain generation / extinction of protons. Considering that the OH radical has a very short lifetime, the significance of such repeated generation is great.
Thirdly, in the treatment tank 4, OH radicals are also generated by such a reaction.

<< Reaction in Treatment Tank 4 (OH Radical Generation: Part 4) >>
Next, the chemical reaction (generation of OH radical: part 4) in the treatment tank 4 will be described. In the treatment tank 4, in addition to the first, second, and third described above, OH radicals are newly generated incidentally, subsidiaryly, and continuously by the following reaction.
That is, the reaction in which trivalent iron ions generated by the oxidation reaction of divalent iron ions react with hydrogen peroxide to newly generate OH radicals or the like is represented by the following chemical formulas 9 and 10. The reaction formula (reaction formula of Formula 11) is repeated in a chain.

These will be further described in detail. The trivalent iron ion (Fe ³⁺ ) generated by the reaction formula of Chemical Formula 3 (Chemical Formula 1) reacts with hydrogen peroxide (H ₂ O ₂ ) by the reaction formula of Chemical Formula 9 above. The iron ion is reduced to a divalent iron ion (Fe ²⁺ ), and a superoxide anion (.O ₂ ⁻ ), which is an ion generated by combining oxygen molecules with electrons, is generated.
Then, according to the reaction formula of the above chemical formula 10, this radical superoxide anion can react with hydrogen peroxide to generate an OH radical (.OH). When the reaction formulas of the chemical formulas 9 and 10 are synthesized together, the chemical formula of the chemical formula 11 is obtained.
Thus, as long as hydrogen peroxide that was the source of OH radical generation in the reaction formula of Chemical Formula 3 (Chemical Formula 2) remains, (in the process of oxidation and decomposition of β-lactam antibiotic 1, OH Even if radicals are consumed and exhausted, as long as surplus hydrogen peroxide remains, new OH radicals are chained semipermanently based on the hydrogen peroxide) It will continue to be generated. Considering that the OH radical has an extremely short lifetime, the significance of such generation continuation is great.
However, in order to ensure that the reaction formula of Chemical Formula 11 (Chemical Formula 9, Chemical Formula 10) occurs, even a weakly acidic atmosphere that does not decompose hydrogen peroxide into water and dissolved oxygen (see the chemical formula of Chemical Formula 4), A pH operation is required, such as adding caustic soda or the like to the water to be treated 3 of the treatment tank 4 by the pH adjusting means 8, and it is necessary to move the pH value to the alkali side.
Furthermore, although the divalent iron ion generated by the reaction formula of Chemical Formula 11 (Chemical Formula 9) lowers the pH, the necessary pH operation is performed in order to coexist with hydrogen peroxide that is stably present in the weakly acidic atmosphere as described above. If carried out, the generation of OH radicals can be expected by the Fenton main reaction of the reaction formula such as Chemical Formula 3 above.
In the treatment tank 3, fourthly, OH radicals are also generated by such a reaction.

<< Reaction in Treatment Tank 4 (Oxidation and Decomposition of β-Lactam Antibiotic 1) >>
Next, oxidation, decomposition, and mineralization of β-lactam antibiotic 1 by OH radical will be described.
In this treatment apparatus 2 and treatment method, in the treatment tank 4, the β-lactam antibiotic 1 contained in the water to be treated 3 is oxidized by the OH radicals generated in the Fenton main reaction and others in this way. , Decomposed and mineralized.
These will be described in more detail. The OH radical, that is, the hydroxy radical (.OH) has a strong oxidizing power as is well known. That is, it has an extremely strong electron (e ⁻ ) deprivation ability, oxidation ability, that is, activation ability and decomposition ability, which is unparalleled as an active oxygen species, and is highly reactive with radicals. In addition, since the reaction is intense, its existence time is a very short-lived chemical species.
Now, the OH radical dispersed in the aqueous phase oxidizes the β-lactam antibiotic 1 contained in the water 3 to be treated, and eventually decomposes. In other words, OH radicals follow the chain process of oxidation and addition of the organic structure of β-lactam antibiotic 1 and the intermediate structure of its degradation process, thereby sequentially breaking the carbon chain, organic bond, and molecular bond. , Decomposed and divided, and finally oxidized, decomposed and mineralized into inorganic low molecular weight compounds.
Most of β-lactam antibiotic 1 is oxidized, decomposed, and mineralized into water and carbon dioxide. The remaining small portion is oxidized, decomposed, and mineralized by a very small amount of other low-molecular compounds.
In the treatment tank 4, the β-lactam antibiotic 1 is thus oxidized, decomposed and mineralized.

<< About the post-treatment tank 11 >>
Next, the post-treatment tank 11 will be described. A post-treatment tank 11 is attached to the treatment tank 4 described above. And the to-be-processed water 3 after (beta) lactam antibiotic 1 is oxidized and decomposed | disassembled by the above-mentioned to this post-processing tank 11 is discharged | emitted from the processing tank 4, a required process is performed, and it drains outside.
Such a post-treatment tank 11 will be further described in detail. The illustrated post-treatment tank 11 includes a neutralization tank 12, a precipitation tank 13, a coagulation sedimentation tank 14, a filtration tank 15, a pH adjustment tank 16, a treatment water tank 17, and the like in order toward the downstream.
First, the water 3 to be treated after the oxidation and decomposition treatment of the β-lactam antibiotic 1 is discharged from the treatment tank 4 to the neutralization tank 12 of the post-treatment tank 11. In the neutralization tank 12, a pH adjuster such as caustic soda is added to the water 3 to be treated, and the pH is adjusted to the optimum value for the inorganic flocculant. When hydrogen peroxide remains even in the treated water 3, a neutralizing agent such as catalase is added in order to avoid water pollution.
Next, in the sedimentation tank 13, the colloidal complex with iron contained as a residue in the water to be treated 3 flowing in from the neutralization layer 12 is solid-liquid separated and precipitated and removed in the lower part.
In the next coagulation sedimentation tank 14, for example, polyaluminum chloride (PAC, Al ₂ (OH) _n Cl _6-n ) or chloride chloride is used as the inorganic coagulant for the treated water 3 flowing from the upper part of the sedimentation tank 13. Diiron (FeCl ₃ ) is added and stirred. Thus, the colloidal complex remaining in the water to be treated 3 without being precipitated in the settling tank 13 is agglomerated and solid-liquid separated to be precipitated and removed.
In addition, when the residual amount of trivalent iron ions (Fe ³⁺ ) generated by the Fenton method in the water to be treated 3 is large, the iron ions (Fe ³⁺ ) function as an inorganic flocculant. The addition of is unnecessary. If necessary, a storage sedimentation tank is provided next to the aggregation sedimentation tank 14, and for example, an anion is added as a polymer flocculant so that the colloidal complex is further agglomerated, blocked, and solid-liquid separated. , And precipitation and removal may be attempted.
Then, the water to be treated 3 sequentially passes through the filtration tank 15, the pH adjustment tank 16, and the treated water tank 17. Thus, the treated water 3 is further purified, adjusted to a pH value suitable for external drainage, and then drained from the treated water tank 17 to be discharged.
The post-treatment tank 11 is as described above.

《Action etc.》
The treatment apparatus 2 and treatment method for water containing β-lactam antibiotic 1 according to the present invention are configured as described above. Therefore, it becomes as follows.
(1) Penicillin-based, β-lactamase inhibitor-containing penicillin-based, cephem-based, β-lactamase-inhibitor-containing cephem-based, carbapenem-based, or monobactam-based waste water containing β-lactam antibiotic 1 having a β-lactam structure, etc. The treated water 3 is supplied to the treatment device 2.
The treatment device 2 purifies the treated water 3 by oxidizing and decomposing the remaining and mixed β-lactam antibiotic 1 by a treatment method based on the treatment process of the Fenton method.

(2) And this processing apparatus 2 is equipped with the raw | natural water tank 9, the pH adjustment tank 10, the processing tank 4, the post-processing tank 11, etc. of the to-be-processed water supply means 5 in order.
A pH adjusting means 8 is attached to the pH adjusting tank 10. The treatment tank 4 is provided with hydrogen peroxide adding means 6, iron ion adding means 7, pH adjusting means 8, and the like.

  (3) The treated water 3 is supplied from the raw water tank 9 of the treated water supply means 5 to the treatment tank 4. In addition, before the water 3 to be treated is supplied to the treatment tank 4, in the illustrated example, in the pH adjustment tank 10, an acid pH adjuster such as sulfuric acid is added from the pH adjustment means 8, so that the pH is about 3 to about 5 such as about pH 4. It is considered to be slightly acidic.

  (4) First, an aqueous solution of hydrogen peroxide is added from the hydrogen peroxide adding means 6 to the water to be treated 3 supplied to the treatment tank 4. The total amount of hydrogen peroxide is added at the beginning of the reaction.

(5) In the treatment tank 4, after the hydrogen peroxide is added in this way, a divalent iron ion solution is added from the iron ion addition means 7 to the water to be treated 3. This addition is performed by repeating a plurality of cycles intermittently divided into a plurality of times by divided addition during the reaction after the addition of hydrogen peroxide.
Further, for each divided addition of iron ions, an alkaline pH adjusting agent such as caustic soda is added from the pH adjusting means 8 so that the water to be treated 3 always maintains a weak acidity of about pH 4, for example. That is, the water to be treated 3 is adjusted to an optimum pH for generating OH radicals.

(6) Now, in the treatment tank 4, OH radicals are generated based on the following first, second, third and fourth reactions.
First, the total amount of hydrogen peroxide added as described above is reduced by divalent iron ions added in portions as a catalyst, and OH radicals are generated each time the addition is performed.
That is, by the Fenton main reaction in the reaction formula of Chemical Formula 3 (Chemical Formula 1, Chemical Formula 2), the divalent iron ion donated an electron to hydrogen peroxide to become a trivalent iron ion, and the electron was donated. Hydrogen peroxide generates OH radicals.
The generation of OH radicals is carried out efficiently without waste, since there is no risk of wasteful reaction of OH radicals and divalent iron ions because divalent iron ions are added in portions. Is done.
In addition to this, the generation of OH radicals is more efficiently and reliably performed by being maintained in a weakly acidic atmosphere having a pH of about 4. That is, under the weak acid atmosphere, first, electron donation of divalent iron ions is promoted, and further, hydrogen peroxide is decomposed into water and oxygen by the reaction formula (4) and is wasted. Suppressed and avoided, generating full-capacity OH radicals.

(7) Second, OH radicals are hydroxylated by a reduction reaction of hydrogen peroxide with trivalent iron ions generated by an oxidation reaction of divalent iron ions in the treatment tank 4. Ions can also be generated by oxidation.
That is, OH radicals can be generated by the reaction formulas of Chemical Formula 5 and Chemical Formula 6 based on the trivalent iron ions and hydroxide ions generated by the reaction formula of Chemical Formula 3 (Chemical Formula 1, Chemical Formula 2). From this aspect, OH radicals are efficiently generated. The OH radicals are also generated in a chain every time iron ions are dividedly added.

(8) OH radicals are also generated by the following third and fourth. That is, other than the Fenton main reaction of (6) above, it continues to be efficiently generated by incidental, secondary, and chain reactions.
Thirdly, OH radicals generated by the reaction formula of the chemical formula 3 react with water such as the water to be treated 3 by the reaction formulas of the chemical formulas 7 and 8 to form new OH radicals in a chain. Generated repeatedly.
Fourthly, the trivalent iron ion generated by the reaction formula of Chemical Formula 3 (Chemical Formula 1) and hydrogen peroxide react by the reaction formula of Chemical Formula 11 (Chemical Formula 9 and Chemical Formula 10). New OH radicals are repeatedly generated in a chain.
Note that the generation of the first, second, third, and fourth OH radicals ends when the hydrogen peroxide of the Fenton reagent is exhausted in the processing tank 4.

(9) Now, the OH radicals thus generated have a very strong oxidizing power. Therefore, in the treatment tank 4, the β-lactam antibiotic 1 contained in the water to be treated 3 is oxidized and decomposed by the OH radicals, and thus becomes mineralized to a low molecular weight compound.
Penicillin and other β-lactam antibiotics 1 are extremely high molecular weight and difficult-to-separate organic compounds, but by chain addition of OH radicals and oxidation reactions, low molecular compounds such as water and carbon dioxide are obtained. It becomes mineralized.

(10) The β-lactam antibiotic 1 contained in the water to be treated 3 is thus mineralized into water, carbon dioxide and the like, and is discharged from the treatment tank 4 to the post-treatment tank 11. The illustrated post-treatment tank 11 includes a neutralization tank 12, a sedimentation tank 13, a coagulation sedimentation tank 14, a filtration tank 15, a pH adjustment tank 16, a treated water tank 17, and the like.
Since hydrogen peroxide is effectively used without waste for the generation of OH radicals as described above, the remaining amount after the treatment is small, and the use of the neutralizing agent in the neutralization tank 12 is negligible or absent. .
And the to-be-processed water 3 is adjusted to the state which can be drained by passing through the post-treatment tank 11, and is drained outside.

(11) In this treatment apparatus 2 and treatment method, as described above, the β-lactam antibiotic 1 contained in the water to be treated 3 is mineralized based on the treatment process of the Fenton method, etc. To be realized.
That is, the amount of chemicals added such as hydrogen peroxide, divalent iron ions, and Fenton's reagent such as a pH adjuster is easily calculated from the theoretical reaction value, and is the same as or larger than the theoretical reaction value. Several times as much as the actual required amount is added, and thus the addition amount is optimized.
The treatment apparatus 2 is provided with a raw water tank 9 and a post-treatment tank 11 with a treatment tank 4 as the center, and a hydrogen peroxide addition means 6, an iron ion addition means 7, a pH adjustment means 8 and the like. It consists of the structure which was made. That is, in this processing method, the processing device 2 having a relatively simple configuration is used, and stable processing is possible.
The operation of the present invention is as described above.

Hereinafter, an example of the oxidation and decomposition processes will be described in detail with respect to the processing apparatus 2 and the processing method according to the present invention.
That is, in Example 1, with respect to the place described above as the reaction in the treatment tank 4 (oxidation and decomposition of β-lactam antibiotic 1), for penicillin G, which is a representative example of β-lactam antibiotic 1, An example of the oxidation and decomposition process is theoretically verified.
Penicillin G (PCG) contained in the water to be treated 3 includes the organic structure of an unstable intermediate of its oxidation and decomposition process, and the chain process of the reaction formulas shown in the following chemical formulas 13 to 18 ( By following 1) to (32), the OH radicals (.OH) are sequentially oxidized. Then, water _(H 2 O), carbon dioxide _(CO 2), and to the other low molecular compounds, decomposition, thus mineralized.
First, the molecular formula (empirical formula) of penicillin G is C ₁₆ H ₁₈ N ₂ O ₄ S, and the structural formula (schematic formula) is as shown in the following chemical formula 12.

First, penicillin G, which is a starting material, first follows the chain processes (1) to (6) of the following reaction formulas 13 and 14, and is sequentially oxidized and added by OH radicals.
Therefore, the decomposition of the cyclic structure proceeds, and aldehyde formation, carboxyl oxidation, alcoholation, etc. are sequentially performed, and carbon dioxide (CO ₂ ) and water (H ₂ O) are derived, generated, and liberated along the way. The
Note that methanol (CH ₃ OH) generated in the process (5) -1 in the reaction formula of Chemical Formula 14 is oxidized and separated into carbon dioxide and water by OH radicals in the process (5) -2. The residue of process (5) -1 proceeds to process (6).

Next, the chain processes (7) to (18) of the reaction formulas of the following chemical formulas 15 and 16 will be described next to the chain processes (1) to (6) of the chemical formulas and chemical formulas 14 described above. ), Oxidation and addition by OH radicals are sequentially performed for each residue. As the decomposition proceeds, carbon dioxide and water are derived, generated and liberated along the way.
These will be further described in detail. First, the process (6) of the chemical formula 14 described above passes through the processes (7), (8), and (9) of the chemical formula 15 and then reaches the process (10).
Then, the residue body on the right side of the process (10) proceeds to the process (11) of Chemical formula 16, and then in the process (12), the residue body is moved to the process (27) and below described in detail later. Will proceed. Note that the process (12) produced in the -N (= O), the process (13), leads to the process (15) via (14), nitrate ions ^- the (NO _3).
On the other hand, the residue body on the left side of the process (10) proceeds to the process (16) and then reaches the processes (17) and (18).

Further, following the chain processes (7) to (18) of the reaction formulas of the chemical formulas 15 and 16 described above, the chain processes (19) to (24) of the chemical formula of the following chemical formula 17 are followed. For each residue, decomposition further proceeds by oxidation and addition of OH radicals, and carbon dioxide and water are derived and released in the middle.
These will be further described in detail. First, the residue main body (HO-NHO) on the right side of the process (18) of the chemical formula 16 described above proceeds to the process (19) -1 of the chemical formula 17 and then 1 generated in the process (19) -2. / 2O ₂ results in nitric acid (HNO ₃ ) in process (19) -3.
In contrast, the residue main body (carboxylic acid) on the left side of the process (18) of Chemical Formula 16 proceeds from the process (20) to the process (21). The formaldehyde (HCHO) produced in the process (21) reaches the process (22) and is oxidized and decomposed into carbon dioxide and water.
On the other hand, the phenol (C ₆ H ₅ OH) produced in the process (21) goes to the next processes (23) and (24).

Finally, following the chain processes (19) to (24) of the chemical formula of the chemical formula 17, following the chain processes (25) to (32) of the chemical formula of the chemical formula 18 described above, further oxidation of OH radicals and The decomposition proceeds with the addition. In addition, carbon dioxide and water are derived, generated and liberated along the way, and finally the residues themselves are all returned to carbon dioxide and water.
These will be further described in detail. First, the phenol (C ₆ H ₅ OH) produced in the process (21) of the chemical formula 17 passes through the processes (23) and (24) as described above, and then the process (25)- Formaldehyde (HCHO) is produced in the process (25) -2 by the hydrogen radical (H ⁺ + e ⁻ ) produced in 1 and then returned to carbon dioxide and water in the process (26).
Further, the residue main body of the process (12) of the chemical formula 16 described above leads from the process (27) of the chemical formula 18 to the processes (28) and (29).
Then, O = S− produced in the process (29) is attributed to water and sulfate ions (SO ₄ ²⁻ ) in the process (30). The —CO—CH ₃ produced in the process (29) produces acetic acid (CH ₃ —COOH) in the process (31), and then returns to carbon dioxide and water in the process (32).

For example, in this way, penicillin G (PCG), which is an example of β-lactam antibiotic 1, is theoretically all by following the chain processes (1) to (32) of the chemical formulas 13 to 18. It will be oxidized, decomposed and mineralized.
That is, most of them are oxidized, decomposed and mineralized by carbon dioxide (CO ₂ ) and water (H ₂ O), and oxidized, decomposed and mineralized by very few other low molecular compounds. .
By the way, when the place explained above is summarized (that is, when the respective reaction formulas are added up), the following general reaction formula of the chemical formula 19 is obtained.

In the general reaction formula of Chemical Formula 19, 1 mol of penicillin G is theoretically converted to 70 mol of water and 16 mol of carbon dioxide, 9 mol of oxygen, 2 mol of nitric acid, 1 mol by 126 mol of OH radical. Mineralized to sulfuric acid.
In this example, OH radicals may be prepared in advance in an amount of 126 mol as a theoretical reaction value, but the actual required amount is prepared several times, for example, several times. Of course, the same applies to hydrogen peroxide, divalent iron ions, and the like, which are OH radical products.
About Example 1, as above

Next, a second embodiment of the present invention will be described.
In Example 2, other examples of oxidation and decomposition processes of penicillin G (PCG, benzylpenicillin), which is a representative example of β-lactam antibiotic 1, are theoretically verified. The example of the second embodiment conforms to the above-described example of the first embodiment, but it follows a considerably different oxidation / decomposition process.
Also in this Example 2, penicillin G contained in the water to be treated 3 is shown in the following chemical formulas 20 to 37 including the organic structure of an intermediate product that is unstable in its oxidation and decomposition processes. The reaction formulas of the chain process formulas 1 to 42 are traced.
In turn, OH radicals (.OH) are involved, and oxidation and addition reactions proceed. At the same time, water, carbon dioxide, oxygen, and other low-molecular compounds are derived, generated, liberated, and decomposed and mineralized. End up.

These will be further described in detail. The starting material penicillin G (see the chemical formula 12 for its structural formula and chemical formula) first follows Formula 1 to Formula 5 of the chain process shown in Chemical Formula 20 to Chemical Formula 24 below, and sequentially OH Oxidation and addition by radicals are performed.
Then, from the generation side of Expression 5, the process is divided into the following chain processes a, b, and c. That is, a. The left-side residue on the side of Formula 5 proceeds to the chain process of Formula 6 below in Formula 25 below; b. The central residue on the side of Formula 5 proceeds to the chain process of Formula 14 below in Chemical Formula 27 below, c. The right-hand residue on the side of Formula 5 proceeds to the chain process of Formula 21 below in Chemical Formula 29 below.
And first a. In formulas 6 to 13 of the chain processes of the following chemical formula 25 to chemical formula 26, oxidation and addition by OH radicals are sequentially performed, and finally formed formaldehyde (HCHO) is converted into carbon dioxide, oxygen and water in formula 13. And decomposed.
B. In formulas 14 to 20 of the chain processes of the following chemical formulas 27 to 28, oxidation and addition by OH radicals are sequentially performed, and finally, nitric acid (HNO ₃ ) is generated by the formula 20.
C. After passing through the formula 21 and formula 22 of the chain process of the following chemical formula 29, the SO produced by the formula 22 proceeds to the formula 23 to formula 27 of the chain process of the chemical formula 30 to chemical formula 31 below, and oxidation with OH radicals Addition proceeds, and finally, sulfuric acid (H ₂ SO ₄ ) is generated according to Formula 27. At the same time, the residue main body on the side of Formula 22 proceeds to Formula 28 to Formula 42 of the chain process of Formula 32 to Formula 37 below, and oxidation and addition by OH radicals proceed, finally in Formula 42 Nitric acid (HNO ₃ ) is produced.
First, of course, in the reaction formula of each process, water, carbon dioxide, oxygen and the like are derived, generated and liberated, respectively.
Secondly, in Formula 12, Formula 20, Formula 27, and Formula 42, first, hydrogen radicals (H ⁺ + e ⁻ ), which are hydrogen atoms in the nascent stage, are generated together with oxygen molecules by oxidative decomposition of water molecules by OH radicals. (This formation reaction is described only by the chemical formula, not the structural formula.) Thus, the reduction reaction of the target residue (intermediate product) proceeds by this hydrogen radical.
Thirdly, regarding the description of the reaction formula of each process, in principle, the chemical formula is shown in the upper part, and the structural formula is shown in the lower part.

The above chemical formula 38 is a general reaction formula of the reaction formulas of the chain processes shown in the chemical formulas 20 to 37.
As shown in the general reaction formula of this chemical formula 38, theoretically, 1 mol of penicillin G is converted into 16 mol carbon dioxide, 12 mol oxygen, 2 mol nitric acid by 137 mol OH radical. It is oxidized, decomposed and mineralized by 1 mol of sulfuric acid and 75 mol of water.
In addition, although 137 mol should just prepare OH radical as a theoretical reaction value, about several times as many as it is prepared as actually required amount. The same applies to hydrogen peroxide, divalent iron ions, and the like, which are OH radical products.
About Example 2, it is as above.

Next, a third embodiment of the present invention will be described.
That is, the experimental result of Example 3 is demonstrated regarding the processing apparatus 2 and the processing method of this invention.
In this experiment, treated water 3 (concentration 10 mg / L) containing benzylpenicillin potassium (C ₁₆ H ₁₇ KN ₂ O ₄ S), which is an example of penicillin G, is first used as sample 1-1 (raw water). It supplied to the processing tank 4 under normal temperature. And each chemical | medical agent was added in predetermined order, changing the addition amount suitably for every sample 1-2, 1-3, 1-4, and 1-5.
On the other hand, to-be-treated water 3 (concentration 50 mg / L) in which the concentration of benzylpenicillin potassium was changed was supplied as sample 2-1 (raw water) to treatment tank 4 at room temperature. And each chemical | medical agent was added in the predetermined order by changing the addition amount with sample 2-2, 2-3.
Sample 2-2 is a reference example in which only hydrogen peroxide is added, and Samples 1-2, 1-3, 1-4, 1-5, and 2-3 are Fenton methods of the present invention. It is the Example processed by.
・ The experimental procedure is as follows. That is, first, the treated water 3 is treated by the Fenton method or the like, and then the complex is aggregated, precipitated and removed by addition of PAC, and solid-liquid separation is performed (see the above-mentioned place regarding the post-treatment tank 11). The treated water 3 in the form of filtrate was used as an analysis object of the experiment and an evaluation object of the experiment result.
・ Test conditions are as follows. That is, the amount of each chemical added, such as hydrogen peroxide as a source of generation of OH radicals in the Fenton method, ferrous sulfate as a catalyst, sulfuric acid or caustic soda for pH adjustment, PAC for aggregation, etc. is shown in Table 1 below. , As shown in Table 2.

When an experiment was conducted under the test conditions shown in Tables 1 and 2, the experimental results shown in Table 3 below were obtained.
That is, the content of potassium benzylpenicillin contained in the water to be analyzed 3 to be analyzed, and other analysis items are the samples 1-1 and 2-1 (raw water) before the Fenton treatment and the sample 2-2 (reference) Example) and the results of measurement for samples 1-2, 1-3, 1-4, 1-5, and 2-3 (Examples of the present invention) after Fenton treatment, and the experimental results in Table 3 below was gotten.
The measurement and analysis methods for each analysis item are as follows.
Water temperature: JIS K0102.12 (by glass rod thermometer)
COD-Mn (oxygen consumption by potassium permanganate at 100 ° C)
: JIS K0102.17 (potassium permanganate titration method at 100 ° C.)
(Oxygen conversion)
・ COD-Cr (Oxygen consumption by potassium dichromate)
: JIS K0102.20 (potassium dichromate oxidation method) (oxygen conversion)
・ TOC (total organic carbon)
: JIS K0102.22.1 (combustion oxidation-infrared TOC analysis method) (C conversion)
-Benzylpenicillin potassium: High performance liquid chromatograph mass spectrometry-Electrical conductivity: JIS K0102.13.1 (electrode method)

From the experimental results shown in Table 3, the following points were confirmed in terms of data. That is, according to Examples of Samples 1-2, 1-3, 1-4, 1-5, and 2-3 treated by the Fenton method of the present invention, penicillin G, which is a representative example of β-lactam antibiotic 1, The data confirms that benzylpenicillin potassium has been oxidized, decomposed, and mineralized into carbon dioxide, oxygen, water, nitric acid, etc. by OH radicals, and almost no longer exists in treated water 3. Evaluated.
This was supported by a decrease in data values such as COD-Mn, COD-Cr, and TOC, and an increase in data values of electrical conductivity.
In addition, benzylpenicillin potassium is measured at 1.5 mg / L in sample 1-1 (raw water), while sample concentration is 10 mg / L, and sample concentration is 50 mg / L. In 2-1 (raw water), it is measured as 5.5 mg / L, which is due to the fact that the measurement residue exists as ions. That is, benzylpenicillin potassium seems to be ionized in an aqueous solution, and according to the high performance liquid chromatograph mass spectrometry adopted as an analysis method this time, the mass existing as benzylpenicillin potassium was measured, and the above value was obtained.
About Example 3, it is as above.

BRIEF DESCRIPTION OF THE DRAWINGS It is used for description of the best form for implementing invention about the processing apparatus and processing method of beta lactam antibiotics containing water concerning the present invention, and is the composition flow figure.

DESCRIPTION OF SYMBOLS 1 (beta) lactam antibiotics 2 Processing apparatus 3 To-be-processed water 4 Processing tank 5 To-be-processed water supply means 6 Hydrogen peroxide addition means 7 Iron ion addition means 8 pH adjustment means 9 Raw water tank 10 pH adjustment tank 11 Post-treatment tank 12 In Japanese tank 13 Precipitation tank 14 Coagulation sedimentation tank 15 Filtration tank 16 pH adjustment tank 17 Treated water tank

Claims (8)

A treatment device that oxidizes and decomposes antibiotics contained in water to be treated based on the Fenton method,
The antibiotic comprises a penicillin or other β-lactam organic compound having a β-lactam structure, and the treatment apparatus includes a treatment tank, a water to be treated supply means attached to the treatment tank, and a hydrogen peroxide addition means. , Iron ion addition means, pH adjustment means,
The treated water supply means supplies the treated water containing the antibiotic to the treatment tank, and the hydrogen peroxide addition means adds hydrogen peroxide to the treated water in the treatment tank, The iron ion addition means adds divalent iron ions to the water to be treated in the treatment tank,
The pH adjusting means adds a pH adjusting agent to the treated water supplied to the treated tank from the treated water supply means and the treated water supplied to the treated tank, and the treated water Is maintained at a predetermined weak acidity, a treatment apparatus for water containing β-lactam antibiotics. 2. The treatment apparatus for water containing β-lactam antibiotics according to claim 1, wherein the hydrogen peroxide addition means adds a total amount of an aqueous solution of hydrogen peroxide at the beginning of the reaction, and the iron ion addition means contains hydrogen peroxide. After the addition, intermittently repeat multiple cycles to add the divalent iron ion solution in portions,
The pH adjusting means is characterized in that an acid pH adjuster is added before the addition of hydrogen peroxide, and an alkaline pH adjuster is added every time an iron ion solution is added after the addition of hydrogen peroxide. An apparatus for treating water containing β-lactam antibiotics. The treatment apparatus for water containing β-lactam antibiotics according to claim 2, wherein the β-lactam antibiotics are penicillin, β-lactamase inhibitor-containing penicillin, cephem, β-lactamase inhibitor-containing cephem, carbapenem Or monobactam series,
The iron ion adding means adds an aqueous solution of ferrous sulfate or ferrous chloride, and the pH adjusting means adds, for example, sulfuric acid or caustic soda, so that the water to be treated in the treatment tank is brought to about pH 4. A treatment apparatus for water containing β-lactam antibiotics, characterized by maintaining and suppressing decomposition reaction of added hydrogen peroxide into water and oxygen. A treatment method that oxidizes and decomposes antibiotics contained in water to be treated based on the Fenton treatment process,
The antibiotic comprises a penicillin or other β-lactam organic compound having a β-lactam structure,
Hydrogen peroxide, a divalent iron ion solution, and a pH adjuster are added to the water to be treated containing the antibiotic, and hydrogen peroxide is added in its entirety at the beginning of the reaction. The ionic solution is divided and added in multiple cycles intermittently after the addition of hydrogen peroxide,
As for the pH adjuster, an acid pH adjuster is added before the addition of hydrogen peroxide, and after the addition of hydrogen peroxide, an alkaline pH adjuster is added for each divided addition of the divalent iron ion solution. A method for treating β-lactam antibiotic-containing water, characterized by maintaining water at a predetermined weak acidity. 5. The method for treating β-lactam antibiotic-containing water according to claim 4, wherein the total amount of hydrogen peroxide added is reduced by divalent iron ions added in portions as a catalyst, and OH radicals are added. Is generated,
Thus, treatment of water containing β-lactam antibiotics, wherein the antibiotic contained in the water to be treated is oxidized and decomposed by the OH radicals to be mineralized into low molecular weight compounds. Method. 6. The method for treating β-lactam antibiotic-containing water according to claim 5, wherein the hydroxide ions produced by the reduction reaction of hydrogen peroxide are further produced by the oxidation reaction of divalent iron ions. Oxidized with valent iron ions to generate OH radicals,
Thus, treatment of water containing β-lactam antibiotics, wherein the antibiotic contained in the water to be treated is oxidized and decomposed by the OH radicals to be mineralized into low molecular weight compounds. Method. The method for treating β-lactam antibiotic-containing water according to claim 5 or 6, wherein the generated OH radical further reacts with water such as the water to be treated to generate new OH radical and water. The reaction is repeated in a chain,
Thus, the treatment method for water containing β-lactam antibiotics, characterized in that the antibiotics are oxidized and decomposed by the OH radicals that are repeatedly generated in this way and are mineralized into low molecular weight compounds. . The method for treating β-lactam antibiotic-containing water according to claim 5 or 6, wherein trivalent iron ions produced by oxidation reaction of divalent iron ions react with hydrogen peroxide, so that at least The reaction to generate new OH radicals is repeated in a chain,
Thus, the treatment method for water containing β-lactam antibiotics, characterized in that the antibiotics are oxidized and decomposed by the OH radicals that are repeatedly generated in this way and are mineralized into low molecular weight compounds. .

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