JP3471155B2 - Water treatment method and water treatment agent - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the continuous or continuous removal of organic substances contained therein from water continuously or discontinuously generated, particularly water containing a surfactant, continuously or continuously and efficiently. The present invention relates to a water treatment agent and a water treatment method which are effective for the treatment. More specifically, a compound containing an organic substance having a specific function is used as a water treatment agent, and it is brought into contact with the water to be treated to rapidly transfer the organic substance in the water to be treated into the water treatment agent, and then water and water after the treatment. Separated from treatment agent,
The separated water treatment agent is reused as a water treatment agent in the contact process repeatedly or circulated to the limit of its capacity, and the purified water is reused as rinse water or discharged as waste water to the outside of the water treatment system. The present invention relates to a water treatment method and a water treatment agent effective for the water treatment method, characterized in that the operation is continuously or intermittently carried out. Also,
The present invention relates to a rinsing method for rinsing while utilizing the water treatment method.

[0002]

2. Description of the Related Art Wastewater containing organic substances has been conventionally treated by various methods. The technical contents of conventional water treatment agents and water treatment methods and their problems are described below, taking rinsing waste water containing a surfactant generated from the rinsing step in washing as an example.

The cleaning process using a water-based cleaning agent is a cleaning process for removing stains on parts with the cleaning agent, and then a rinsing process for removing the cleaning agent containing dirt components adhering to the parts with water after the cleaning process ( Rinsing step), and a drying step of drying the rinsed part.

Surfactants are generally added to water-based cleaning agents for the purpose of removing liquid or solid organic contaminants such as processing oil and wax adhering to parts and inorganic powder such as polishing powder. . Surfactants are generally compounds having both a lipophilic group such as a hydrocarbon having an affinity for oil and a hydrophilic group having an affinity for water in the molecule.

The surfactant incorporated in the detergent is adsorbed on all substances existing in water, such as oily stains and the surface of parts, and greatly changes the physical properties of the surface to accelerate the removal of dirt or stains on parts. To prevent redeposition.

These surfactants are excellent in solubility in water and also excellent in the ability to emulsify and disperse removed organic stains such as oily stains in water and stabilize them. For this reason, when the parts are continuously washed, organic substances such as surfactants and oily stains in the cleaning process adhere to the parts and are brought into the rinsing process,
This results in an increase in the organic matter concentration in the waste rinse water.
As a result, these rinse effluents cannot be drained without wastewater treatment, and strict water treatment is required for drainage.

Further, even if rinsing water is circulated for reducing the amount of waste water, the concentration of organic substances in the rinsing water gradually increases, and the function as rinsing water that requires cleanliness is lost. For this reason, it is essential to remove the organic matter even when the rinse water is reused.

As described above, in the rinse water generated in the rinsing step, a large amount of "cleaning agent containing dirt components adhering to the parts and taken out from the cleaning step" is mixed as an organic matter, so that a treatment for removing these organic matters is performed. Without it, it cannot be discharged into the sea or rivers and reused as the final rinse water that requires high cleanliness.

Conventionally, these organic substances in wastewater are treated by methods such as biodegradation treatment with activated sludge and the like, adsorption treatment with activated carbon and the like, separation treatment such as coagulation sedimentation by using organic or inorganic coagulant or pressure floating. Has been processed.

[0010] However, these treatment methods have various problems such as the treatment method, the treatment capacity or the type of dirt existing in water, and the like. is necessary.

For example, although the biodegradation treatment method using activated sludge has the advantage that a large amount of wastewater can be treated, in order to make the activated sludge work efficiently, the concentration of organic matter in the wastewater must be below a certain concentration (below a limit concentration). ) Must be diluted with water, and the biodegradation of organic matter requires a treatment time of one day or one week, depending on the type of organic matter. Therefore, there is a problem that the processing equipment becomes large and the processing time is long.

On the other hand, the adsorption treatment method using activated carbon or the like is a method of adsorbing and removing organic substances on the surface of activated carbon whose adsorbed area is increased by forming pores and the like. Therefore, it has an advantage that organic matter in water can be efficiently removed to a low concentration. However, the adsorption area of activated carbon is limited, and even low-molecular organic substances that are easily adsorbed can adsorb only about 3/10 of the weight of activated carbon. Further, a certain adsorption time is required for the organic matter to be adsorbed on the surface of the activated carbon, and in order to increase the adsorption efficiency, the flow rate of the treatment liquid must be controlled to be low or the activated carbon capacity must be increased. For these reasons, activated carbon treatment costs are high, and the treatment speed is difficult to increase. Furthermore, there is a problem that the inorganic substances in the activated carbon are eluted and contaminated in water as ions, which makes it difficult to reuse the treated water as rinse water.

The use of an organic or inorganic coagulant is effective for treating organic substances that show ionicity in water to some extent, but treatment of water that contains oils and nonionic surfactants that do not show ionicity. It is not suitable for use, and the type of stain must be selected for its use, or the ions or organic substances derived from the used treatment agent itself will dissolve and contaminate the treated water to contaminate the treated water and re-use the water after treatment. There is also a problem that it hinders its use and that it takes a long time to agglomerate or settle dirt, resulting in a long processing time and enormous processing equipment.

Various water treatment methods have been proposed to solve these problems. For example, JP-A-54-149330
In the gazette, "Oil-containing degreasing liquid containing a surfactant has a cloud point of 40
A method for regenerating a cleaning liquid is disclosed, which comprises adding a nonionic surfactant having a temperature of not higher than 0 ° C or insoluble in water, heating to 40 ° C or higher to separate oil / water, and then removing an oil layer portion. Further, in Japanese Patent Laid-Open No. 59-4881, a technique relating to "a cleaning apparatus including a step of introducing a coagulant into rinsing water and stirring the mixture to coagulate an organic substance dissolved in the rinsing liquid and remove the coagulated product with a filter" Is disclosed.

However, these techniques are for "continuously or continuously, rapidly and efficiently removing contained organic substances" from water continuously or discontinuously generated, particularly water containing a surfactant. No mention is made of effective water treatment agents and techniques relating to water treatment agents and, of course, implementation in such processes is not possible. Technically required performance such as water treatment method and water treatment agent for rapidly or continuously removing organic substances from a large amount of wastewater generated in a rinsing process, or a method for reusing water treated by these water treatment methods. Could not be achieved by these conventional techniques at all.

As described above, each of the existing water treatment methods has its own problems, and it is necessary to secure a place for water treatment, invest in facilities, or utilize utilities such as activated carbon or coagulant to operate these facilities. A huge amount of capital investment and running costs such as cost or number of processes were required. In particular, in an aqueous solution containing a surfactant, decomposition due to biodegradation inhibition by surfactants or adsorption of activated carbon, premature deterioration of separation membranes, aggregation inhibition by flocculants such as nonionic surfactants, etc. Alternatively, the separation processing speed is not always sufficient, which causes the size of the processing equipment to increase.

[0017]

Under the circumstances described above, organic substances such as surfactants and organic stains contained in water can be treated continuously or continuously promptly and with good durability regardless of the type. As a result, it has been desired to develop a treatment agent and a water treatment method that are compact and that can be closed by reusing used water and that can realize water treatment with a small number of steps and running costs.

In view of the above situation, an object of the present invention is to select the type of organic matter contained therein from water continuously or discontinuously generated, especially water containing a surfactant, continuous or A water treatment method and water treatment agent that are effective for continuous, rapid, and efficient removal, and as a result, water with a small facility that can be recycled by reuse of used water and that has fewer process steps and running costs. It is an object of the present invention to provide a water treatment method and a water treatment agent that can realize the treatment, and a rinsing method that is performed using the water treatment method.

[0019]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that the water treatment method, water treatment agent and rinsing method described below satisfy the target performance. The present invention has been completed.

That is, the gist of the present invention is (1) a water treatment method in which water to be treated containing at least an organic substance is brought into contact with a water treatment agent which is compatible with the organic substance and hardly soluble or insoluble in water. After the contact step of contacting the water treatment agent with the water to be treated, a separation step of separating the water treatment agent from the mixed liquid after contact is provided, and the water treatment agent separated in this separation step is contacted again. A water treatment method characterized by continuously or intermittently performing water treatment while circulatingly using the water to be treated in the cleaning step.
Rinsing water generated in a rinsing step performed later,
The water treatment agent is liquid at the temperature for water treatment and
Solubility in water at temperatures of 0.0001 to 2.0 weight
The organic substance is contained in the amount of
Water treatment method containing one or both of B, A: branched or straight chain saturated or unsaturated having 8 to 20 carbon atoms
Higher alcohol having alkyl group, B: branched or straight chain saturated or unsaturated having 4 to 20 carbon atoms
Alkylphenol or alkyl having an alkyl group
Runafutoru, or their formalin condensates, (2) a method rinsing with a rinsing step with water, the (1) Symbol placement of the water treatment method, water rinsing the treated water obtained by treating the rinse water A rinsing method, characterized in that the rinsing step is carried out while cyclically using the rinsing method, ( 3 ) The rinsing method according to ( 2 ) above, wherein the rinsing step is carried out in a facility capable of storing water to be treated, ( 4 ) rinsing step However, the rinsing method according to ( 2 ) or ( 3 ) above, which is provided after the washing step with the oil-water separator or the pre-rinsing step with the oil-water separator, ( 5 ) The rinsing water has an organic matter concentration of 10 When the detergent mixture prepared to have a weight percentage is left at 60 ° C. for 30 minutes,
Separation rate of organic substances from the detergent mixture is 50% by weight
The above ( 2 ), which contains the above-mentioned detergent,
(4) The method of rinsing according to any one relates to.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION First, the water treatment method of the present invention will be described. The water treatment method of the present invention is a water treatment method in which water to be treated containing at least an organic substance (water to be treated) is brought into contact with a water treatment agent that is compatible with the organic substance and hardly soluble or insoluble in water. After the contact step of contacting the water treatment agent with the water to be treated, a separation step of separating the water treatment agent from the mixed liquid after contact is provided, and the water treatment agent separated in this separation step is contacted again. The water treatment is characterized by continuous or intermittent water treatment while being recycled.

When the water treatment method of the present invention is used, the water to be treated can be continuously treated while the water treatment agent is completely closed and reused. Therefore, the number of steps required for water treatment and the size of water treatment equipment can be reduced. The labor cost and capital investment cost can be significantly reduced. In addition, the working environment can be kept clean. Further, when the cleaning method and the cleaning agent of the present invention are used for the treatment of rinse water in the cleaning step, it is not necessary to stop the operation of the rinse step as in the case of batch type water treatment, which can greatly contribute to the improvement of productivity. Since the treated water can be reused as rinsing water, etc., a closed system that does not generate any drainage can be constructed, which not only helps save labor costs, equipment investment costs and running costs such as water used, but also helps protect the environment.

Here, by providing an equipment capable of storing the treated water outside the contacting step and the separating step and supplying the treated water from the equipment, the water treatment efficiency is improved, and the water treatment equipment can be downsized. It is preferable in that the water can be treated without stopping the operation of the facility for generating the water to be treated and the productivity is improved (especially when the treated water is circulated). Further, the water to be treated to be brought into contact with the water treatment agent is introduced from the outside of the system of the contact step and the separation step, and the treated water from which the water treatment agent is separated is discharged out of the system of the contact step and the separation step. Is preferable for the same reason as above.

In the water treatment method of the present invention, first, it is necessary to have a contact step in which the water to be treated and the water treatment agent come into contact with each other. In this contacting step, since the organic matter contained in the water to be treated is removed, the water to be treated and the water treatment agent are effectively contacted with each other, and the organic matter in the water to be treated is effectively transferred into the water treatment agent.

In order to effectively transfer the organic substances in the water to be treated to the water treatment agent, it is necessary to increase the frequency of contact between the water to be treated and the water treatment agent. In order to increase the contact frequency, it is effective to increase the contact area between the water to be treated and the water treatment agent and keep the contact time long. In order to secure the contact area more effectively, it is effective to refine either or both of the treated water and the water treatment agent and increase the surface area and contact frequency of each by refining. It is desirable to have a shearing force applying means for applying a shearing force to the liquid. Examples include pipeline mixers, gear pumps, mixing pumps, homomixers,
Although there is an ultrasonic wave generator or the like, any machine or equipment that applies a shearing force to each other may be used.

Other than the above, the following equipment can be cited as effective equipment in the contact step. A: The water to be treated and the treatment agent are brought into contact with each other while passing through a granular filler such as a columnar shape or a layered shape or a mesh-like substance. Examples of the granular substance include inorganic substances such as glass grains, ceramic grains, metal grains, and sand grains, and organic substances such as plastic grains. Further, as the reticulated substance, a fibrous substance such as glass fiber, synthetic fiber, natural fiber, inorganic fiber, steel fiber or the like may be used, and they may be used as they are,
Alternatively, it may be woven, made into a non-woven fabric, or may be heated to be partially melted and sintered to be used in a tubular shape or a cloth shape. A punching board having a plurality of holes formed in a plate made of metal, ceramics, a plastic plate, or the like may be used. B: Either the water treatment agent or the water to be treated may be atomized, and the contacting step may be performed while pouring, jetting or spraying the water treatment agent or water to be treated or the water treatment agent or water to be treated which is not atomized. . C: You may perform a contact process, stirring a water treatment agent and to-be-processed water by air bubbling. These equipments may be configured by using one or more, and may be used in parallel or in series. By introducing these facilities, the contact process can be made smaller and more efficient. The contact time is not particularly limited, but generally longer is more effective. It may be arbitrarily determined according to the degree of treatment required for the treated water.

In the water treatment method of the present invention, it is more preferable to have a contact step in which the water to be treated and the water treatment agent are brought into contact with each other outside the container containing the water to be treated. For example, in the case where the effluent in the container containing the water to be treated is circulated and reused while treating the liquid in the container containing the water to be treated, as in the case where the rinse wastewater is reused as rinse water, the conventional method By directly pouring the water treatment agent into the container, the water to be treated is contaminated with the water treatment agent, and it is necessary to stop using the liquid until the water treatment is completed. '' If there is a contact step of contacting the water to be treated with the water treatment agent outside the plant, such contamination by the introduction of the water treatment agent can be avoided, and the treatment liquid can be used while performing the water treatment. That is, the use of the liquid or the container is stopped until the treated water is contaminated with the treated water treatment agent by the introduction of the water treatment agent into the container containing the water to be treated and the water treatment is completed. This is preferable because it is possible to prevent a decrease in productivity and loss of opportunity caused by stopping the operation of the washing machine or the like.

In the water treatment method of the present invention, this "contact step"
Next, a "separation step" for separating the treated water and the water treatment agent is provided. More strictly, in this step, "water in the water to be treated" and "a water treatment agent in which an organic substance to be removed in the water to be treated is transferred into the liquid" are separated. Since the water treatment agent of the present invention is relatively sparingly water-soluble or insoluble, it is easily separated from water.

The following are examples of equipment effective in the separation step. A: The water to be treated and the treatment agent are separated while passing through a granular filler such as a columnar shape or a layered shape or a mesh material. Examples of the granular substance include inorganic substances such as glass grains, ceramic grains, metal grains, and sand grains, and organic substances such as plastic grains. Further, as the reticulated substance, a fibrous substance such as glass fiber, synthetic fiber, natural fiber, inorganic fiber, steel fiber, etc. may be used, or they may be used as they are, or may be woven or made into a non-woven fabric, or by applying heat. A part thereof may be melted and sintered, or used in a tubular shape or a cloth shape. A punching board having a plurality of holes formed in a plate made of metal, ceramics, a plastic plate, or the like may be used. However, in order to carry out the separation more efficiently, resulting in downsizing of the equipment and improvement of treatment efficiency, baffle plates, coagulation membranes (coalescer membranes),
In addition to a separation membrane such as an RO membrane or a centrifuge, equipment for promoting separation such as electric utilization separation for imparting a charge to droplets is effective, and it is more preferable to use one or more of these. B: A mixed solution of the water treatment agent and the water to be treated formed in the contacting step is injected, jetted or sprayed into the liquid in which the water treatment agent forms a continuous phase, or by spraying or spraying the water treatment agent and the treated water. It is preferable to use a separation method that promotes the separation because the separation efficiency is good.

In this contacting step, "water to be treated" may be added to "water treatment agent", or "water treatment agent" may be added to "water to be treated". The contacting step and the separating step may be performed in the same processing apparatus (in the container),
It may be performed in separate devices (containers). Further, the contacting step and the separating step may be performed using an apparatus (container) that can be simultaneously or in parallel in the same processing apparatus (container).

There is no particular limitation on the mixing ratio of the water to be treated and the water treatment agent in the contacting step, but the frequency of contact with each other is more effectively obtained, the water treatment efficiency is increased, and the equipment load is reduced. Mixing ratio of water treatment agent to water is 1/99
A ratio in the range of 99 to 99/1 is preferable, and 5/95 to 97 /
A ratio of 3 is particularly preferred. In order to improve the contact efficiency and the separation efficiency in the contact step and the separation step, the water treatment liquid may be heated or cooled for treatment.

Separation of "water in water to be treated" from the liquid sent from the contacting step to "separation step" and "a water treatment agent in which organic substances to be removed from the water to be treated are transferred into the liquid" Can be carried out continuously or intermittently. Here, the "separated water treatment agent" is sent to the contact process again due to the pipeline, overflow, etc. used. On the other hand, since the treated water is sufficiently purified, it may be discharged out of the system as waste water, or may be reused as rinse water or the like. The method of reusing as rinse water leads to reduction of the cost of water to be used without drainage to the outside of the system, and is most preferable from the viewpoint of environment or cost.

In the water treatment method of the present invention, the equipment capable of storing the water to be treated, the apparatus used in the contact step, and the apparatus used in the separation step are connected by the liquid transportation facility, and the water treatment agent is used. It is preferable that the separated treated water is continuously introduced again into a facility capable of storing the water to be treated again. Specifically, for example, the "treatment is attempted" such as a storage tank for rinsing liquid, etc. "Container containing water" and "contact process", "contact process" and "separation process", and further "separation process" and "container containing water to be treated" are liquid transportation facilities such as pipelines and overflows. It is preferable that they are connected continuously. By doing so, the water to be treated can be continuously treated without requiring human power, and the used treating agent can be automatically separated and collected and sent to the contacting process again, and can be recycled and used as a treating agent to the limit of its capacity. The treated water can be sent as a rinse water to a container containing the water to be treated, and a compact and closed water treatment system or a treated water reuse system can be constructed.

The present water treatment method can effectively exhibit the above characteristics when it is used in a series of steps of continuously cleaning various parts with a water-based or semi-water-based cleaning agent while using a large amount of water. It is valid. Especially when used in the rinsing step, the effect becomes remarkable. That is, the effect of the present invention is remarkable when the water to be treated is rinse water generated in the rinse step performed after the washing step.

The effect of the water treatment method of the present invention becomes remarkable when the water to be treated contains a surfactant, including the rinse water generated in the above rinsing step. This is because, as described above, the treatment of water containing a nonionic surfactant is particularly difficult as compared with the case of containing other organic substances.

In the water treatment method of the present invention, the water treatment agent separated in the separation step is preferably added to the treated water at a place other than the final treated water itself or a facility capable of storing the treated water. . For example, when used for washing, especially for rinsing, it is preferable that the water treatment agent and the water to be treated are brought into contact with each other at any place before the step of contacting outside the container containing the water to be treated. When the water treatment agent is put into the container containing the water to be treated, the water treatment agent itself temporarily contaminates the liquid in the container containing the water to be treated, for example, the cleaning agent or rinsing water. This is because there is a risk of damage. This tendency is particularly noticeable in rinse water that is circulated and used because it is difficult to mix organic substances. In this case, the liquid in the container containing the water to be treated must be treated with water to clean it to a level where the cleanability and rinseability can be ensured, and it is necessary to stop the component washing during this period.

If the water treatment agent and the water to be treated are brought into contact with each other at any part before the final treatment water itself or outside the container containing the treatment water, including the contact step, such cleaning can be performed. There is no problem of stopping, and the production efficiency of washing is significantly improved, which is preferable.

Therefore, the rinsing method of the present invention is a rinsing method having a rinsing step using water, wherein the treated water obtained by treating the rinsing water by the above-mentioned water treatment method is circulated and used as rinsing water. In addition, the rinsing step is performed. In this case, it is preferable that the rinsing step is performed in a facility capable of storing the water to be treated.

In order to increase the water treatment efficiency in the rinsing step, downsize the water treatment equipment, and increase the durability of the water treating agent, the amount of detergents and organic substances derived from organic contaminants brought into the rinsing step can be significantly reduced. It is preferable to use the water treatment method of the present invention in the rinsing step subsequent to the washing step in which the oil / water separator is installed or the pre-rinsing step in which the oil / water separator is installed.

As a cleaning agent used in the cleaning step, an aqueous cleaning agent solution prepared to have an organic matter concentration of 10% by weight is used.
When a detergent characterized by having a separation rate of organic substances from the detergent aqueous solution of 50% by weight or more when left standing for 30 minutes at 0 ° C. Removal of organic substances by a water treatment method The treatment efficiency of water is improved, which is preferable. When the rinsing step is performed by a plurality of rinsing devices, the water treatment method or the water treatment agent of the present invention may be used by installing one in each of the rinsing devices.
Rinsing wastewater generated from a plurality of rinsing devices may be treated by one water treatment device.

Next, the water treatment agent of the present invention will be described. The water treatment agent of the present invention is preferably used in the water treatment method of the present invention, but such a water treatment agent exhibits a liquid state at a temperature at which the water treatment is performed and has a solubility in water of 0.0001 to It is required to contain 2.0% by weight of organic matter. If it is not liquid at the temperature at which the water treatment is performed, it is not preferable because the atomization in the contact step or the atomized particles in the separation step cannot be rapidly coalesced and separated, resulting in a reduction in water treatment efficiency.

When the solubility is less than 0.0001% by weight, the polarity of the water treatment agent is too low, and it is difficult to obtain the effect of water treatment especially on the polar organic substance. On the other hand, if the solubility exceeds 2.0% by weight, the water treatment agent itself is highly soluble in water, and as a result, the effect of removing organic substances from water is difficult to obtain. From such a viewpoint, the solubility of the water treatment agent at the water treatment temperature is 0.0001 to
It is preferably 1% by weight, particularly preferably 0.0005 to 0.5% by weight.

In the water treatment method of the present invention, the water treatment agent which is particularly preferably used is liquid at the temperature for water treatment and has a solubility in water of 0.000 at that temperature.
1% by weight or more and less than 0.02% by weight of organic matter, 0.02
It is preferable that the composition contains at least one organic compound in an amount of 0.5% by weight or more and 0.5% by weight or less, and that the solubility of the compound in water at the temperature for water treatment is 0.0001 to 0.4% by weight. .

Organic substances in the range of 0.0001 to less than 0.02% by weight have an affinity for small polar organic substances such as mineral oil and are effective in removing them, and organic substances in the range of 0.02% to 0.5% by weight are effective. It has an affinity with polar organic substances and is effective in its removal, and when both of them coexist, it is effective and preferable for treating water to be treated containing organic substances having a wide range of characteristics compared to the case where each of them is used alone.

From the viewpoint of safety, the boiling point of the water treatment agent is preferably higher than the water treatment temperature. Further, the water treatment agent of the present invention, when a mixed solution of water and a water treatment agent prepared to have an organic matter concentration of 10% by weight is left standing at 60 ° C. for 30 minutes, the separation rate of the organic matter in the mixed solution Is more preferably 98% by weight or more. When the separation rate is 98% by weight or more, the separation rate of the water treatment agent and water in the separation step is increased, the treatment amount per unit time is increased, and as a result, the equipment can be downsized, which is preferable.

Regarding the separation rate in the separation step, it is preferable that there is a difference in specific gravity between water and the water treatment agent, so that the separation rate is increased, and the separation rate is 30 ° C.
Specific gravity of the water treatment agent in 0.95 or less or 1.0
5 or more is more preferable. Further, the viscosity of the water treatment agent is preferably such that the lower the viscosity of the water treatment agent, the more easily it is made into fine particles by the shearing force in the contacting step, and particularly preferably 100 cst or less.

Further, the boiling point at 1 atm is 150 to 3
A water treatment agent having a temperature of 50 ° C. is particularly preferable when used in a water treatment method in which treated water is reused as rinse water. Even if the water treatment agent dissolves or mixes in the treated water and is reused as rinse water, it is rinsed with the rinse water, and even if the rinse water adheres to the parts, the water treatment that exists in the rinse water This is because the agent is less likely to volatilize and remain in the next drying step and does not adversely affect the washability. If the boiling point is below 150 ° C, there is a risk of fire.
At 0 ° C or higher, it tends to remain slightly.

Examples of the organic substances having the above properties contained in the water treatment agent are hydrocarbon compounds, which are linear or branched chain hydrocarbons having saturated or unsaturated bonds. Hydrocarbons containing one or more aromatic rings or aliphatic rings or both in the molecule. A hydrocarbon containing one or more aromatic rings or aliphatic rings having a linear or branched chain hydrocarbon having a saturated or unsaturated bond, or both of them. Compound having a functional group-OH group, -SH group, a primary to quaternary amino group, an ether bond, an ester bond, or a carboxyl group or a carbonyl group at any part of the molecule of the above hydrocarbon compound A compound having one or more of one or more groups. Examples thereof include, but are not limited to, a compound having one or more kinds of functional groups of halogen element and Si element in any part of the molecule of the above hydrocarbon compound.

Although partially overlapping with the above-mentioned items (a) to (d), examples of the water treatment agent of the present invention include a water treatment agent containing one or both of the following A and B, and any of the following A and B. One or both, and a water treatment agent containing one or both of the following C and D, a water treatment agent containing 20% by weight or more of one or both of the following A and B, or the following A , B, and either or both of the following C and D, in an amount of 70% by weight or more. A: A higher alcohol having a branched or straight-chain saturated or unsaturated alkyl group having 8 to 20 carbon atoms. B: Alkylphenol or alkylnaphthol having a branched or straight-chain saturated or unsaturated alkyl group having 4 to 20 carbon atoms, or a formalin condensate thereof. C: A compound of any of hydrocarbons having 8 to 40 carbon atoms which may have a cyclic structure of an aromatic ring or an aliphatic ring in the molecule. D: 1 in a hydrocarbon molecule which may have a cyclic structure of an aromatic ring or an aliphatic ring in a molecule having 8 to 40 carbon atoms
A compound having 3 ether bonds, ester bonds, and carbonyl groups.

As a specific compound, in the cleaning method of the present invention, water treatment containing one or both of the compounds represented by the following formula 1 or formula 2 is preferable because it shows good water treatability. Formula 1; {(R1) (X1) b} a (R2) Formula 2; {(R1) (X1) (Z1) (X2)} a (R2) R1 and R2 are hydrogen or 1 to 20 carbon atoms. It is a hydrocarbon group which may have a cyclic structure of an aromatic ring or an aliphatic ring in the molecule and may be a heterohydrocarbon, which controls the solubility or specific gravity of the water treatment agent in water. 1 to 20 carbon atoms
Is preferable, and 3 to 10 is particularly preferable. When the carbon number is 21 or more, the viscosity of the water treatment agent becomes high and the water treatment property deteriorates. X1 and X2 are -O-, -COO-, -OCOO-,
It represents either -N <, -CONH-, or -CO-, and having these functional groups is preferable because the affinity for polar organic substances is increased and the water treatment efficiency for these stains is improved. In particular, -OH groups such as higher alcohols and alkylphenols, -O- such as dialkyl ethers.
A group and a compound containing a -CO- group such as a dialkylketone as a functional group are preferable because they are less susceptible to deterioration such as hydrolysis in water.

Z1 represents an alkylene (C2-4) oxide adduct having an average addition mole number of 1 to 50. The alkylene oxide adduct has a good affinity with a nonionic surfactant often used in detergents, and is particularly effective and preferable for treating wastewater mixed with a nonionic surfactant. A compound in which the average number of moles of alkylene oxide added is 1 to 10 is preferable because it has appropriate water solubility and is excellent in the effect of removing the nonionic surfactant. When it exceeds 50, the water solubility increases and the aqueous solution tends to thicken. a represents any number from 1 to 6. 1 to 3 is preferable in order to obtain a proper viscosity. b represents a number of 0 or 1.

As the compounds represented by the formulas 1 and 2, one or more compounds of the formula 1 or 2 may be used, and one or more compounds of the formulas 1 and 2 may be blended. You may use it. The compound of the formula 1 shows good water-treatability against stains such as hydrocarbons such as mineral oil and paraffin having a low polarity and a relatively low polarity, or long chain dialkyl esters, and the compound of the formula 2 has a relatively large polarity. Since the nonionic surfactant exhibits good water-treatability with respect to highly polar organic substances, the compound of the formula 1 and the compound of the formula 2 are used in combination, so that even a wide range of water such as rinsing waste water can be treated. It is preferable because it can be processed even if it contains organic substances of various kinds.

In the present invention, when the total content of the compounds represented by the formulas 1 and / or 2 is 50% by weight or more, the compounding effect of the compounds becomes remarkable, and 70% by weight or more is more preferable.

The content of the inorganic compound in the water treatment agent used in the water treatment method of the present invention is preferably 1% by weight or less. In particular, when the water treatment method and the water treatment agent of the present invention are used at the time of washing, especially at the time of rinsing, if the water treatment agent contains an inorganic substance, the inorganic substance tends to be mixed in the treated water used as the rinse water. Inorganic substances mixed in the treated water, that is, the rinse water, tend to remain on the cleaned parts after rinsing and deteriorate the cleanability. As described above, in the case where the treatment liquid does not like to be mixed with the inorganic substance, the smaller content of the inorganic substance is preferable. It is particularly preferably 0.1% by weight or less.

The water treatment agent of the present invention as described above can be suitably used in both the water treatment method and the rinsing method of the present invention.

In the water treatment, a plurality of water treatment methods of the present invention may be provided, if necessary, and may be combined with a conventionally used water treatment method such as activated carbon or ion exchange resin. The water treatment method or water treatment agent of the present invention,
It is effective in any industrial field or application as long as the purpose is to remove organic matter from water containing organic matter.

As an example thereof, in addition to precision parts described later, treatment of water generated during refining and dyeing in the textile industry, treatment of water generated in the cleaning industry for clothes and bedding, family restaurants and hotels, etc. Water treatment in the kitchen, etc. generated in the service industry, water treatment in the food industry such as edible meat and meat, processing oil used for cutting, grinding and rolling, or processing oil attached to metal parts after processing Electrical equipment such as the treatment of removing liquids, the treatment of water generated in the machinery industry, the treatment of water generated by the oleochemical industry, plastics, rubber, and industry, the treatment of water generated in silicon wafers and semiconductor-related industries, or domestic wastewater, etc. However, it is not limited to these.

The preferred fields of use are surfactants,
In particular, in the field of precision parts cleaning, metal processing parts cleaning, which generates a large amount of water to be treated containing nonionic surfactants,
It is an industrial field such as the primary treatment of wastewater in the oil and fat chemistry, food, petrochemical industries and the like.

In the present invention, precision parts refer to, for example, electronic parts, electrical parts, precision machine parts, resin processed parts, optical parts and the like. Here, as the electronic component, for example, a printed wiring board used in a computer and its peripheral devices, home appliances, communication devices, OA devices, other electronic application devices, etc .; I
C hoop agents used for contact members such as lead frames, resistors, capacitors, relays; liquid crystal displays used for office automation equipment, watches, computer equipment, toys, home appliances, etc.
Magnetic recording components used for acoustic recording / reproducing components and related components; semiconductor materials such as silicon and ceramic wafers; electrostrictive components such as crystal oscillators; used for CDs, PDs, copying machines, optical recording machines, etc. Photoelectric conversion components that can be used. Examples of electrical parts include electric motor parts such as brushes, rotors, stators, housings, etc., ticket issuing parts used in vending machines and various devices, and currency inspection parts used in vending machines, cash dispensers and the like.
The precision machine parts include, for example, bearings used in precision drive equipment, video recorders, etc .; machining parts such as carbide chips. Examples of resin-processed parts include precision resin-processed parts used in cameras, automobiles, and the like. Furthermore, examples of optical components include cameras, glasses, and lenses used in optical devices.
Other parts include eyeglass frames, watch cases, watch belts, and the like.

[0060]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, Examples 1, 5
Is a reference example.

(1) Water for Test Treatment Assuming rinsing drainage generated in the rinsing step of metal processed parts, water for treatment containing 3% by weight of the cleaning agent and organic matter derived from oily stain shown in Table 1 below was prepared. did.

[0062]

[Table 1]

The organic substances 1 to 4 are assumed to be compounds derived from detergents, and the organic substances 4 to 6 are assumed to be compounds derived from oily stains such as processing oil. Here, the organic substance 4 is assumed to be one in which the higher fatty acid used as the oiliness agent is saponified by the alkali in the detergent.

(2) Test Method and Results The test water having an organic substance concentration of 3% by weight shown in Table 1 was placed in the treated water storage tank 1 (50 L) of the apparatus shown in FIG. 1 and kept at 50 ° C. It was 20 liters of the oil / water separator 3 was charged with 5 liters of the water treatment agent shown in Table 2.

[0065]

[Table 2]

The water to be treated is supplied to the mixing apparatus 2 at a rate of 10 liters / minute and 5 liters / minute, while the water treatment agent separated by the oil / water separator 3 is supplied to the mixing apparatus 2 at a rate of 1 liter / minute. Supplied. The water treatment agent thus mixed and separated by the oil-water separation device was sent to the mixing device 2 and circulated for use. The treated water was returned to the treated water storage tank 1. Water was sampled from the treated water storage tank outlet side sampling position 5, the oil / water separator outlet side sampling position 6 and the treated water storage tank inside sampling position 4 of this water treatment device, and the amount of organic substances contained therein was measured. The water treatability was investigated by changing the type of treatment agent and treatment conditions. The organic matter concentration in the treated water and the treated water was determined by measuring the TOC.

Water treatment rate (%) = [(TOC of the treated water sampled from the outlet side of the treated water storage tank)-
(TOC of the treated water sampled from the outlet side of the oil / water separator)] × 100 ÷ (TOC of the treated water sampled from the outlet side of the treated water storage tank) Here, the higher the water treatment rate, the better the water treatability. Indicates that.

(3) Composition before Water Treatment and Water Treatability In the water treatment apparatus of FIG. 1, the water treatment agents shown in Table 2 (Examples 1 to 1) were used.
6, the water treatability (water treatment rate) of Comparative Examples 1 to 3) was measured. At this time, a gear pump was used as the mixing device, and a separator equipped with a coalescer membrane was used as the oil / water separator, and the test was performed at a treated water flow rate of 10 liters / minute.
The results are shown in Table 3.

[0069]

[Table 3]

A water treatment agent having a solubility of 0.4% by weight or less in a formulation prepared by blending a compound having a solubility of 0.02% by weight or more and a compound having a solubility of less than 0.02% by weight (Example 6). Showed a good water treatment rate. Further, a water treatment agent containing dodecylphenol (Examples 2, 3,
4, 6) showed a good water treatment rate. On the other hand, Comparative Example 1
Has a high water solubility and deteriorates water treatment.

(4) Water Treatment Conditions and Water Treatability In the water treatment apparatus of FIG. 1, the water treatment agent shown in Table 2 (Example 6) was used as the water treatment agent, and a shearing force was applied using a gear pump in the mixing apparatus. Water treatment performance when applied and when treated without using a gear pump, water treatment performance when a coalescer membrane is used in the oil-water separator and when only a "baffle plate" is attached, and the flow rate of treated water The water treatability was evaluated when the value was changed to 10 liters / minute and 5 liters / minute. The results are shown in Tables 4 and 5.

[0072]

[Table 4]

[0073]

[Table 5]

From these evaluations, a gear pump or the like was introduced to enhance the shearing force, or the flow rate of the water to be treated was reduced to double the mixing ratio of the water to be treated and the water treating agent to the water to be treated. It was found that the water treatability was improved by increasing the contact frequency of. Further, as an oil / water separator, an oil / water separator using a coalescer membrane showed better water treatment than an oil / water separator equipped with a simple “baffle plate”. It has been previously confirmed that the coalescer membrane is superior in oil-water separation ability per unit time, and this difference in oil-water separation ability is reflected in the water treatability.

(5) Comparison with non-continuous water treatment method In the water treatment method of the present invention, the water to be treated introduced into these steps is continuously circulated while circulating the water treatment agent between the contact step and the separation step. Although it is characterized by treating, in order to compare with the conventional water treatment method that the treated water cannot be treated continuously,
The evaluation was performed using the water treatment device shown in FIG.

In the water treatment apparatus shown in FIGS. 1 and 2, the organic substance composition Nos. The organic matter content of water in the tank after water treatment was 6 in which the treated water for test having an organic matter concentration of 3% by weight was placed and treated with water in each device.
The time to reach weight% was measured. The water treatment condition in the water treatment apparatus of FIG. 1 is the water treatment method described in (4) above, using the water treatment agent of Example 6 of Table 2 as the water treatment agent, and the flow rate of the water to be treated is 10 liters / minute. Using a gear pump as the mixing device and a separator having a coalescer membrane as the oil / water separator, the treated water separated by the oil / water separator was treated while being returned to the treated water storage tank. As a result, the amount of organic substances in the treated water storage tank became 0.1% by weight 20 minutes after the start of water treatment.

On the other hand, the water treatment device (50 L) shown in FIG.
The same amount of 5 liters of the same water treatment agent used in the water treatment apparatus of FIG. 1 was added to the above, and the mixture was stirred at a temperature of 50 ° C. for a certain period of time and allowed to stand still. The sample was sampled and the amount of contained organic matter was measured. The stirring was performed by rotating a stirring blade having two blades having a length of 5 cm at 100 rotations / minute to stir the water to be treated and the water treatment agent. Under such conditions, the water to be treated and the water treatment agent could not be mixed well, and even if the mixture was stirred for 3 hours or longer, it did not reach 0.1 wt%.

The number of revolutions was set to 2000 rpm, the mixture was stirred for 30 minutes and then left standing for 45 minutes, whereby the organic substance content in the aqueous layers sampled from the upper and lower layers reached 0.1% by weight. It took about 10 minutes to remove the water treatment agent floating on the upper layer, and skimming was performed so that the water treatment agent was not mixed in the treated water. As a result, the organic matter concentration of the lower layer portion in the aqueous phase was maintained at 0.1% by weight, but the organic matter concentration of the upper layer portion in the aqueous phase increased to 0.3% by weight.

From these results, the water treatment in the water treatment apparatus shown in FIG. 2 requires three times or more the time required for the water treatment as compared with the water treatment method using the water treatment apparatus shown in FIG. Considering the mixing of the water treatment agent into the treated water when removing the treatment agent, it cannot be said that the upper layer portion could be treated, and only 80 to 90% of the water to be treated could be treated.

When the treated water storage tank is used as a tank for storing or rinsing rinsing drainage generated in the rinsing step of washing, and this rinsing drainage is treated with water and reused, if it is treated by the water treatment method of the present invention, While it is possible to operate the washing machine without stopping it, the processing method of FIG. 2 has to stop the operation for several hours until the processing is completed, which is not practical at all. In order to operate the washing machine without stopping with the treatment method of Fig. 2, a water treatment tank with a capacity three times that of the treatment water storage tank is separately provided outside the treatment water storage tank, and the treatment water is treated while being treated there. The method of returning to the treated water storage tank must be taken. From these, it has been clarified that the water treatment method of the present invention has an advantage that the water treatment efficiency can be improved with very small equipment and the washing machine can be operated without stopping. In order to obtain such advantages, it is clear that the treated water storage tank, the contacting step, and the separating step are continuous in a liquid transportation facility such as a pipeline.

When a cleaning agent aqueous solution prepared to have an organic matter concentration of 10% by weight was allowed to stand at 60 ° C. for 30 minutes, the rate of separation of the organic matter from the cleaning agent aqueous solution was 80% by weight [C ₁₂ paraffin]. / C ₁₃ O (EO) ₇ H / C ₆ O (E
O) ₂ H = 50/15/35 blend (where _n in C n is the average number of carbon atoms, (EO) _m is the average m of ethylene oxide)
Molar adduct)] or separation rate 0% by weight (C ₁₃ O
After the cleaning step of cleaning with the (EO) ₂₀ H) cleaning agent, the pre-rinsing step in which an oil / water separator is installed is followed by rough rinsing, and then the water treatment method of the present invention is performed in the rinsing step. The durability of the water treatment agent was extended by about 30 times when the cleaning agent having the separation rate of 80% by weight was used as compared with the case of using the cleaning agent of 0% by weight (C ₁₃ O (EO) ₂₀ H). .
This indicates that the water treatment method of the present invention is particularly effective when the water to be treated contains a detergent having a high separation rate of organic substances from the detergent mixture.

[0082]

EFFECTS OF THE INVENTION By using the water treatment method and the water treatment agent of the present invention, the water to be treated can be collected in a very compact facility in a completely closed state while collecting, recycling and reusing the water without human labor. Since continuous treatment is possible, the number of processes required for water treatment can be reduced and the water treatment equipment can be downsized, and labor costs and equipment investment costs can be significantly reduced. Further, the rinsing method of the present invention uses the cleaning method and the cleaning agent of the present invention in the treatment of rinsing water in the washing step, and it is not necessary to stop the operation of the rinsing step as in the case of batch type water treatment,
It can greatly contribute to the improvement of productivity. Since the treated water can be reused as rinse water, etc., a closed system that does not generate any wastewater can be constructed, which not only reduces personnel expenses and facility investment costs, but also helps protect the environment.

[Brief description of drawings]

FIG. 1 is a schematic view of an example of an apparatus that can be used in the water treatment method of the present invention.

FIG. 2 is a schematic view of an example of an apparatus used in a batch-type water treatment method.

[Explanation of symbols]

1 Treated water storage tank 2 mixing equipment 3 Oil-water separator 4 Tank sampling position 5 Tank outlet side sampling position 6 Oil-water separator outlet sampling position 7 treated water 8 Water treatment agent 10 Treated water storage tank 11 stirrer 12 Treated water 13 Upper layer sampling position 14 Lower layer sampling position

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C02F 9/00 C02F 9/00 502Z 504 504B 504D (56) Reference JP-A-62-97690 (JP, A) JP-A-53 -30164 (JP, A) JP 53-21858 (JP, A) JP 50-80265 (JP, A) JP 49-99601 (JP, A) JP 49-32465 (JP, A) ) JP-A-7-195065 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C02F 1 / 58,1 / 26 B01D 11/04

Claims (5)

(57) [Claims] 1. A water treatment method in which water to be treated containing at least an organic substance (hereinafter referred to as "water to be treated") is contacted with a water treatment agent which is compatible with the organic substance and hardly soluble or insoluble in water. Therefore, next to the contacting step of contacting the water treatment agent with the water to be treated, a separation step of separating the water treatment agent from the mixed liquid after the contact is provided, and the water treatment agent separated in this separation step is reused. A water treatment method characterized by continuously or intermittently performing water treatment while circulatingly using it in a contact step.
The rinsing in which the water to be treated is carried out after the washing step
Rinse water generated in the process, the water treatment agent
Liquid at the temperature of operation and into water at that temperature
Of organic matter having a solubility of 0.0001 to 2.0% by weight
Either of the following A or B as the organic substance, or
Is a water treatment method containing both. A: C8-20 branched or straight-chain saturated or unsaturated
Higher alcohol having an alkyl group. B: C4-C20 branched or straight-chain saturated or unsaturated
Alkylphenol or alkyl having an alkyl group
Lunaphthol or formalin condensate thereof. 2. A method rinsing with a rinsing step using water, wherein the water treatment method of claim 1 Symbol placement, while recycling the rinse water treated water obtained by treating the rinsing water, a rinsing step A rinsing method characterized by performing. 3. The rinsing method according to claim 2 , wherein the rinsing step is performed in a facility capable of storing the water to be treated. 4. A rinsing step, the washing step or oil-water separator installation the pre-rinse process rinsing according to claim 2, wherein is provided the next step has established the oil-water separator. 5. When the detergent mixture prepared by rinsing water so that the concentration of organic matter is 10% by weight is left at 60 ° C. for 30 minutes, the separation rate of organic matter from the detergent mixture is 50.
Those containing detergent is wt% or more claim 2
~ The rinsing method according to any one of 4 above.