WO2014038797A1

WO2014038797A1 - Apparatus and method for separating water and oil in aqueous waste lubricant

Info

Publication number: WO2014038797A1
Application number: PCT/KR2013/007343
Authority: WO
Inventors: 윤승규
Original assignee: 이시영; 박형중
Priority date: 2012-09-04
Filing date: 2013-08-14
Publication date: 2014-03-13
Also published as: KR101283005B1

Abstract

An apparatus and method for separating water and oil in an aqueous waste lubricant are disclosed. Inflowing aqueous waste lubricant from the exterior is stored in a storage bath, and the stored aqueous waste lubricant is moved to a reaction bath. An acid is added to the aqueous waste lubricant moved into the reaction bath and stirred at a certain rate in order to coagulate the oil in the aqueous waste lubricant. The coagulated oil is moved to a separation bath and left standing in order to separate the water and oil. The water separated into the lower layer in the separation bath is moved to a chemical reaction bath, and the oil separated into the upper layer is moved to the storage bath for storage. An alkaline compound is added to the water moved to the chemical reaction bath to control acidity, and stirring is conducted to produce purified water. At room temperature, the water and oil in a non-degradable aqueous waste lubricant may be separated through simple cracking and coagulation reactions. Thus, total normal hexane extracting material (n-H) may be simply and efficiently separated and removed.

Description

【Specification】

[Name of invention]

Oil Separation Apparatus and Method for Water-Soluble Waste Lubricant

Technical Field

The present invention relates to an oil-water separation method and apparatus for hardly decomposable water-soluble waste lubricant oil. More specifically, the present invention relates to an oil-water separation apparatus and method for water-soluble waste lubricant oil which separates the non-degradable water-soluble waste lubricant oil into water and oil by simple operation at room temperature. It is about.

Background Art

Water-soluble waste lubricating oil (oil, oil and oil) is an emulsified emulsion solution, oil-in-water oil type (Οίΐ-in water, type 0 / W) or oil dispersed in oil. It is a water-in oil (W / Ο type). In essence, water and oil are incapable of sustaining a mixed state, so the third component, surfactant, is added to make the emulsion state. In this case, the surface-active substance is called an emulsifier, and the added emulsifier lowers the interfacial free energy by orienting and adsorbing the oil and the water interface, making the emulsification operation easier. As a result, emulsifiers inhibit the phase separation rate of water and oil and maintain the emulsion state.

Therefore, water-soluble waste lubricants must be broken down or neutralized to be separated into water and oil. The conventional method is to add a substance such as acid to decompose the emulsifier. This is the simplest method, but the oil-water separation efficiency is inferior because water-soluble waste lubricants use both strong anionic surfactants and nonionic surfactants simultaneously.

1 is an oil-water separation state diagram of a hardly decomposable water-soluble waste lubricant according to a conventional invention. Referring to Figure 1 간단히 If the pH is adjusted by simply adding an acid to the water-soluble waste lubricating oil, water and oil are not separated, but mixed overall.

In addition, since the oil compartment of the water-soluble waste lubricating oil is 15 μm or more, it is almost 95% separated, but when it is 15 μm or less, only about 90% »is separated. Therefore, oil droplets of 15 μ or less cannot obtain the maximum separation efficiency. have. In addition, when the non-surfactant is used together, a low separation efficiency of less than 90% is obtained.

Conventional techniques for separating the flow of soluble waste lubricating oil include high temperature incineration _and chemical treatment, distillation, ion purification, reduced pressure distillation, and high temperature and high pressure pyrolysis. Among them, the high temperature incineration separates the oil water by raising the temperature from minimum 120 ^° C to maximum 600 ^° C, which entails enormous thermal cost. Son has a big economic loss.

In addition, in recent years, a technique of separating oil and water of the waste metal processing oil using a separator has been used, but there is a problem in that expensive membranes need to be frequently replaced because oil is contaminated in the separator.

[Detailed Description of the Invention]

[Technical problem]

The present invention is to solve the above conventional problems, the object is to simplify the process and economic efficiency by separating the water and oil through a cracking process by cracking and stirring the hardly decomposable water-soluble waste lubricant at room temperature The present invention provides an apparatus and a method for separating oil and water of a hardly decomposable water-soluble waste lubricant.

In addition, the non-degradable water-soluble lubricating oil is made into wastewater which can be treated by a general chemical treatment method, and economically removes more than 99.9% of total normal nucleic acid extracts (oil, n ᅳ H) of less than 0.5w% remaining in the wastewater. The present invention provides an apparatus and a method for separating oil and water of a hardly degradable water-soluble waste lubricant.

In addition, the separated oil is recycled through an appropriate method to prevent water pollution due to difficult-to-decomposable wastewater, and to provide an oil-water separation device and a method for separating oil-degradable water-soluble waste lubricating oil which can secure enormous economics by regenerating oil.

Technical Solution

In order to achieve the above object, there is provided an oil / water separator for water-soluble waste lubricant oil, comprising: a storage tank for storing the water-soluble waste lubricant oil introduced from the outside; A reaction tank for aggregating the oil in the water-soluble waste lubricant oil by stirring the water-soluble waste lubricant oil transferred from the storage tank at a predetermined flow rate; A separation tank receiving the collected oil from the semi-hung tank and stagnating for a predetermined time to separate water and oil; A chemical reaction chamber for receiving the water separated from the separation tank and agitating the transferred water in the state in which the acidity is adjusted by adding alkali; It is characterized in that the oil-water separation device of the water-soluble waste lubricating oil, characterized in that it comprises an oil storage tank for storing the oil flow of the upper portion separated from the separation tank. Preferably, the predetermined flow rate in the reactor is 1 ~ 40cm / s.

Preferably, the semi-aeration tank may be subjected to reaction by receiving the oil separated from the separation tank.

Preferably, the oil and water separation apparatus of the water-soluble waste lubricating oil may be performed ^at 10 ~ 40 ^° C. In addition, the oil-water separation method of the water-soluble waste lubricating oil according to the present invention comprises the steps of: a) storing the water-soluble waste lubricating oil introduced from the outside in a storage tank, and moving the stored water-soluble waste lubricating oil to a reaction tank; b) adding an acid to the water-soluble waste lubricating oil transferred to the semi-aeration tank and agitating at a predetermined flow rate to aggregate the oil in the water-soluble waste lubricating oil; c) separating the water and the oil by moving the condensed oil into a separation tank and stagnation; d) transferring the water of the lower part separated in the separation tank to a chemical reaction tank, and moving the separated upper oil to an oil reservoir for storage; e) adding an alkali to the water moved to the chemical reaction tank to adjust the acidity, and stirring to produce purified water, characterized in that the oil-water separation method of the water-soluble waste lubricating oil comprising the step of producing.

Preferably, the steps _a ) to _e ) are performed at 10-40 ° C.

Preferably, the predetermined flow rate of step b) is 1 ~ 40cm / s.

Preferably, the method may further include adding the oil or the packed oil separated in the step c) to the semi-formation of the step a).

Preferably, the oil or the packed oil separated in step c) is 5-30% of the volume of the water-soluble waste lubricating oil in the semi-aeration tank of step a).

Advantageous Effects

The present invention can separate and remove total normal nucleic acid extract (n-H) simply and very efficiently by separating the flow of hardly decomposable water-soluble waste lubricating oil with simple cracking and coagulation reaction at room temperature.

In addition, when water-in-oil (Water in Oil) having a water content of 5 to 50% in water-soluble waste lubricant is separated from water and oil in the past, high temperature heating is performed, but the present invention can separate water and oil without heating. Available as a pretreatment system.

Therefore, it is economical and energy-saving because it does not use heat, and it can process large capacity, so it can be recycled as raw material of separated oil * alternative energy, and it is also excellent for oil import substitution effect.

[Brief Description of Drawings]

1 is an oil-water separation state diagram of a hardly decomposable water-soluble waste lubricant according to the related art. Figure 2 is a schematic diagram showing the oil and water separation apparatus of the hardly decomposable water-soluble waste lubricating oil according to the present invention.

3 is a flow chart of the oil-water separation method of the hardly decomposable water-soluble waste lubricant according to the present invention. Figure 4a shows the initial state of the physicochemical processing step according to an embodiment of the present invention.

Figure 4b shows an intermediate state of the physicochemical treatment step according to an embodiment of the present invention.

Figure 4c ^'will tanaen or the final state of physical and chemical processing steps in accordance with one embodiment of the present invention.

5 is a state diagram of a separation step according to an embodiment of the present invention.

6 is a state diagram of a chemical treatment step according to an embodiment of the present invention.

[Best form for implementation of the invention]

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings. 2 is a schematic view showing the oil-water separation apparatus 1 of the hardly decomposable water-soluble waste lubricant according to the present invention.

As shown in FIG. 2, a storage tank 2 for storing the water-soluble waste lubricating oil introduced from the outside is provided.

In addition, a reaction tank for supplying a predetermined amount of the water-soluble waste lubricant stored in the storage tank 2 by a transfer pump (not shown) and a transfer pipe (not shown) to stir at a predetermined flow rate to collect the oil in the water-soluble waste lubricant oil (4). ) Is provided.

It is preferable that the predetermined flow rate in the reaction tank is stirred in one direction at 1 to 40 cm / s. If the agitation rate is less than i _cm / _s , the flow rate is too slow to separate the oil and water before the coagulation process takes place, and oil droplets of 15μ or less remain in the water. In addition, when the stirring speed is 40 cm / s or less, the size of the oil seed (Oil Seed) is not larger than 5mm to hinder the coagulation process.

In addition, there is provided a separation tank (6) for separating the water and the oil by stagnating the supplied oil from the semi-aeration tank (4).

The oil separated in the separation tank 6 or the oil in the emulsion state (the oil still in the coagulation stage) is supplied to the semi-aeration tank 4 to accelerate the coagulation. The separated oil or agglomerated oil supplied to the reactor 4 may be added in an amount of 5 to 30¾ »with respect to the volume of the water-soluble waste lubricant.

In addition, there is provided a chemical reaction tank (8) for receiving the water of the lower portion separated from the separation tank (6) to add alkali to adjust to ^ .6 ~ 8 to stir for a certain time to produce purified water.

In addition, the oil of the upper portion separated from the separation tank (6) can be transferred to an oil absorber (not shown). There is provided an oil reservoir 10 for storing.

In addition, the adsorption tower 12 for removing the dissolved organic matter and impurities contained in the water by the activated carbon to the water purified from the chemical reaction tank 8 may be further provided.

3 is a flow chart of the oil-water separation method of the hardly decomposable water-soluble waste lubricant according to the present invention. _.

As shown in FIG. 3, the oil-and-water separation method of the hardly decomposable water-soluble waste lubricant according to the present invention is divided into a physicochemical treatment step, a separation step, a chemical treatment step, and a granular activated carbon treatment step.

The physicochemical treatment step is divided into a pH adjustment step cracking reaction step, and a coagulation step.

The pH adjustment step is adjusted to pH 0-4 by adding acid to the aqueous waste lubricating oil in phase silver, and most preferably to pH 2.5-3. The reason for this is to avoid adding unnecessary excess alkali in the chemical treatment step of the post process.

The pH adjustment step, the cracking reaction step, and the coagulation step using the cohesive force of the oil are performed at about the same time, and the physicochemical treatment step separates the oil and extracts the total normal nucleic acid contained in the aqueous waste lubricating oil. At least 99.5% of the material (n—H) can be removed.

The cracking reaction and the coagulation reaction, which occur almost simultaneously, make oil droplets remaining in water-soluble waste lubricants into over 15μ of coarse oil droplets. Make it float

Thus, oil droplets of 15μ or less rise to the surface and merge with oil droplets of 15μ or more of the minimum surface area and are packed and no longer remain in the water.

The temperature of the cracking process and the coagulation process is 10-40 ^° C. If heated above 60 ^° C, strong acid water will oxidize the oil rapidly. Rapid oxidation causes the problem of dissolving dissolved organics in water, leaving the total normal nucleic acid value above 7,000 mg / L.

In addition, the cra ¾ process and the coagulation process is preferably stirred in one direction at a flow rate of 1 ~ 40 cm / s. If the agitation rate is less than _lcm / _s , the flow rate is too slow to separate the oil and water before the agglomeration process and oil droplets of 15 μ or less remain in the water. In addition, when the stirring speed is 40 cm / s or less, the size of the aggregated oil droplets (Oil Seed) is not larger than 5mm by interfering with the flocculation process. The most desirable agitation rate is 25-35 cm / s, and the oil seed grows most quickly and smoothly.

If the size of the condensed oil drops (Oil Seed) is increased by about 1mm or more, the physicochemical treatment step ends. The size of the oil seed is most preferably about 5mm ~ 1cm. If the oil Seed is moved to the separation stage with the size of less than about 1 隱, oil drops and oil droplets with a minimum surface area of 15μ or less fall back into the water. In addition, when the size of the oil seed is excessively larger than 1 cm and becomes a complete emulsion, there is a problem in that it takes too much time in the separation step.

The next step, the separation step, moves the oil seed of about 5mm ~ lcm size to the separation tank, and it is suspended for 5-9 hours to separate the oil and water. The water-soluble waste lubricating oil transferred to the separation tank is separated into three stages: a pure oil layer, an oil layer in the form of an emulsion (oil fraction still in the coagulation stage) and a water layer.

Referring to FIG. 3, the pure oil or the oil in the emulsion state (oil still in the coagulation stage) separated in the separation stage may be added at the beginning of the physicochemical treatment stage. Separate oil or emulsion oil is added at 5-30% of the volume of the aqueous waste lubricating oil. The most preferred volume ratio is 25%.

Generally, the water-soluble waste lubricant consists of 90 ^ 5 water and 5-10% oil. Since the minimum amount of oil is 5w%, the addition of separated oil or emulsion oil of volume evacuation 2 of water-soluble waste lubricant oil has an oil content of about 30%.

In addition, adding oil in emulsion rather than pure oil speeds up the process.

When the oil obtained in the separation step is added in an amount of 5-30¾ »relative to the volume of the water-soluble waste lubricant, the coagulation proceeds rapidly. In general, very small particles of oil dissolved in water have a particle surface charge (electronegative potential) between very small particles due to frequent contact and reaction. As a result, small charges are attached to large charges.

Accordingly, the phenomenon of coarsening is increased by adding an oil having an opposite charge to the flocculation reaction of the physicochemical treatment step of the present invention. In other words, when the oil is already separated, the polar group acts and is adsorbed to the opposite charge particles, causing the aggregation to rapidly form a large floes (Floes). Therefore, the flotation is maximized, the oil and water separation occurs quickly. . However, if the oil obtained in the separation step is added more than 30% of the volume of the water-soluble waste lubricating oil, but the coarse occurs quickly, the separation time is very slow in the separation step there is a problem that the separation time is long.

The next step, the chemical treatment step, removes the oil remaining in the wastewater through the saponification reaction (331) 110 ^ £ ^ 3 011). The catalyst is neutralized with alkali such as KOH, NaOH, lime water (Ca (0H) ₂ ), and the precipitates are removed.

At this time, the chemical oxygen demand (TC0D) of the wastewater from which the sediment is removed is about 700 mg / L by manganese.

A granular activated carbon treatment step may be further added thereto, and the granular activated carbon treatment step removes dissolved organic matter and impurities in the wastewater by using the adsorption power of the activated carbon.

Hereinafter, the physicochemical processing step will be described in detail with reference to Examples.

Example 1

The water-soluble lubricant is made by distilling at a ratio of 100% of water and 5w。 of the manufacturer's solution of water-soluble lubricant. The total normal nucleic acid extract (n-H) value of the diluted 5w% water soluble lubricant is 38,000.0 mg / L-40,000.0 itig / L. At room temperature, 1,000 ml of aqueous waste lubricating oil was adjusted to pH 2.5-3 by adding acid (HCL, H2S04, etc.), put into a cylindrical CSTR stirrer, and the flow rate (cm / s) was adjusted to 1-40 cm / s. Stir. As a result, the water-soluble lubricating oil begins to collect.

4A to 4C are phase attitudes of the physicochemical processing steps according to an embodiment of the present invention.

Figure 4a is a state diagram according to the initial reaction of the physicochemical treatment step. In the state as shown in Figure 4a, it is preferable to stir vigorously for the first hour. After 1 hour, set the flow rate to l-40cm / s and stir in a constant direction.

Figure 4b is a state diagram according to the mid-term reaction of the physicochemical treatment step. Stirring at room temperature for about 11 hours results in curds as shown in FIG. 4b and starts to produce an oil seed of about 0.1 mm-0.3 mm.

Fig. 4 (: is a state diagram according to the final reaction of the physicochemical treatment step. Further stirring for about 1 hour increases the size of the oil seed to about 1 mm or more, and when further stirring, the aggregated oil seed of 5 mm-lcni is added. As shown in Fig. 4c, when the Oil Seed becomes larger than about 1 mm, the reaction is finished, and the minimum The oil having a surface area of 15μ or less is collected and becomes separable by gravity method.

The total normal nucleic acid extract (n-H) value of the separated wastewater was 86 mg / L, and more than 99.5% of total normal nucleic acid extract (n-H) was removed. Hereinafter, the .separation step will be described in detail with reference to Examples.

Example 2

Figure 5 shows the state of the separation step according to an embodiment of the present invention. Referring to Figure 5, the oil seed of 5mm-lcm formed in the physicochemical treatment step is also stagnated for 7 hours. As shown in FIG. 5, the dark brown top layer is pure oil, which is stored separately or added back to the base oil in the initial stage of the physicochemical treatment of the aqueous waste lubricant.

In addition, the gray thick layer is an oil seed oil in the emulsion state (oil still in the coagulation stage) and may be added to the initial stage of the physicochemical treatment step by mixing with the separated oil.

Also, the transparent yellow bottom layer is separated water and is transferred to the next chemical treatment step. At this time, the total normal nucleic acid extract quality (n-H) value of the separated water is less than 100mg / L. Hereinafter, the chemical treatment step will be described in detail with examples.

Example 3

In 1,000 ml of water separated in the separation step, the catalyst was added with K0H or NaOH or Ca (0H) ₂ to adjust pH to pH 6-8. Initially, the mixture was strongly stirred for 10 minutes, stirred for about 1 hour, and held for about 6 hours. Figure 6 shows the state by the chemical treatment step according to an embodiment of the present invention. As shown in FIG. 6, the transparent yellow upper layer is water from which alkali salts are removed, and the white lower layer is precipitation of alkali salts.

At this time. The total normal nucleic acid extract (n-H) of the sediment-free water was below 8 mg / L, and the biological oxygen demand (TCODmn) was below 700 mg / L. This is where a significant amount of metal is removed from the temperature. Hereinafter, the granular activated carbon treatment step will be described in detail with reference to Examples.

Example 4 The amount of COD of activated carbon (granular charcoal) can adsorb about 20% when the iodine value is 1,000 mg / g, and the maximum saturated adsorption amount is 30-32%. The total normal nucleic acid extract quality (nH) of water treated with granular activated carbon according to an embodiment of the present invention is 8 mg / L or less. In addition, when the water-soluble waste lubricant with a biological oxygen demand (TC0D) of 700 mg / L is passed, activated charcoal (granular coal) treatment results in a TC0D value of 30 mg / L when measured by the TC0D manganese method. When measured by the crop method, a value of 60 mg / L is obtained.

Depending on the regional characteristics of the pressure complex, the discharge criteria for the region can be set for additional activated carbon treatment.

Example 5

Referring to FIG. 3, the oil separated in the separation step or oil in an emulsion state (oil still in the coagulation step) is added at 25% of the volume of the water-soluble waste lubricant at the beginning of the physicochemical treatment step.

By adding oil separated in water-soluble waste lubricating oil or oil in the form of an emulsion dog, the sundries progress rapidly. In about 2 hours of reaction, about 0.1 mm-0.2 mm Oil Seed is generated (see FIG. 4b). After 5 hours of reaction, a 5mm-lcm Oil Seed meets the physicochemical treatment step (see FIG. 4C). The total normal nucleic acid extract quality (n-H) measured at this time is also less than 100itig / L value, it can be seen that more than 99.5% total normal nucleic acid extract quality (n-H) was removed.

Example 6

In the case of water-in-oil in which the water content of the water-soluble waste lubricant is 5w% ~ 50。, add water to adjust the water content to 60-65w%. 1,000 ml of the aqueous waste lubricating oil was adjusted to pH 2.5-3 by adding acid (HCL, H ₂ S0 _4, etc.) at room temperature.

Put in a CSTR stirrer and stir to adjust the flow rate (cm / s) to 1-40 cm / s. As a result, the water-soluble lubricant starts to aggregate.

Within 2 hours of the reaction, an oil Seed (agglomerated oil) of about 0.1 mm-0.3 kPa begins to be produced (see Fig. 4b).

Thereafter, a coarse Oil Seed of 5mm-lcm is formed within 4 hours of the reaction, thereby completing the physicochemical treatment step (see FIG. 4C).

The total normal nucleic acid extract quality (nH) measured at this time is less than 100mg / L value, it can be seen that more than 99.5% total normal nucleic acid extract quality (nH) was removed. Industrial Applicability

As described in detail above, the oil and water separation apparatus and method of the hardly decomposable water-soluble waste lubricant oil at room temperature according to the present invention are simple and highly efficient than the conventional distillation, high temperature incineration distillation under reduced pressure, and pyrolysis. The substance ( _n -H) can be separated and removed. In addition, it is possible to treat the hardly decomposable water-soluble lubricating oil very economically without heating.

Not only does it use less heat, but it also contributes to energy savings, and it can handle large volumes, allowing the separated oil to be recycled as a raw material for alternative energy.

In addition, the oil and water separation device of the hardly decomposable water-soluble waste lubricating oil at room temperature according to the present invention can be large-capacity, and can be applied to the wastewater mixed with more than 3% oil such as food waste water.

Claims

[Range of request]

[Claim 1]

In the oil / water separator of water-soluble waste lubricant,

Storage tank for storing the water-soluble waste lubricant introduced from the outside;

Semi-ung-joong for stirring the oil in the water-soluble waste lubricating oil by stirring the water-soluble waste lubricating oil transferred from the reservoir at a predetermined flow rate;

A separation tank separating the water and the oil by stagnating the conveyed oil from the semi-aeration tank;

A chemical reaction tank receiving the lower water separated from the separation tank and agitating the transferred water in a state in which acidity is adjusted by adding alkali; And

An oil reservoir for storing the oil of the upper portion separated from the separation tank;

It is configured to include,

The reaction tank is oil-water separation device of the water-soluble waste lubricating oil, characterized in that the reaction is transported by the oil separated from the separation tank.

[Claim 2]

The method of claim 1,

Oil-water separator of the water-soluble waste lubricating oil is oil-water separator of the water-soluble waste lubricating oil, characterized in that proceeds ^at 10 ~ 40 ^° C.

[Claim 3]

The method of claim 1,

And a predetermined flow rate in the reactor is: 卜 40 _C m / s.

[Claim 4]

In the oil-water separation method of water-soluble waste lubricant oil,

a) storing the water-soluble waste lubricating oil introduced from the outside in a storage tank, and moving the stored water-soluble waste lubricant to the reaction tank;

b) adding an acid to the water-soluble waste lubricating oil transferred to the semi-aeration tank and agitating at a predetermined flow rate to aggregate the oil in the water-soluble waste lubricating oil;

c) separating the water and the oil by moving the condensed oil into a separation tank and stagnation;

d) transferring the water of the lower part separated in the separation tank to a chemical semi-aperture, and storing the separated upper oil by moving it to an oil reservoir; And e) adding alkali to the water moved to the chemical reaction tank to adjust the acidity, and stirring to generate purified water;

Including;

The oil-separation method of the water-soluble waste lubricating oil further comprising the step of adding the oil separated in the step c) or the coarse oil to the reaction tank of step a). .

[Claim 5]

The method of claim 4,

Step a) to step e) is an oil-water separation method of water-soluble waste lubricating oil, characterized in that proceeds at 1040 ^° C.

[Claim 6]

The method of claim 4,

The predetermined flow rate of step b) is water separation method of water-soluble waste lubricating oil, characterized in that l ~ 40cm / s.

[Claim 7]

The method of claim ⁴ ,

The separated oil or the packed oil in step c) is 5 to 30¾ with respect to the volume of the water-soluble waste lubricant in the semi-aeration tank of step a).

[Claim 8]

The method of claim 4, wherein.

The water separation method of the water-soluble waste lubricating oil, characterized in that further comprising the step of adding water in step a) to make the water content of the water-soluble waste lubricating oil 60 ~ 65 \.