JP2015132011A - Oil content separating method, and oil content separating device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of safely separating oil content with small energy consumption from an oil-containing scale with an average particle diameter of 50 μm or less which contains the oil content, water content or the like and from which it is difficult to separate the oil content.SOLUTION: There is provided a method including: a dispersion step of making a scale dispersion liquid by adding coarse particles to an oil-containing scale of 50 μm or less and immersing it to a dispersion liquid for dispersion; an extraction step of adding a lipophilic organic solvent to the scale dispersion liquid and mixing and stirring it; an organic solvent phase separation step of separating the scale dispersion liquid into an oil-containing lipophilic organic solvent and the scale dispersion liquid; a water phase separation step of separating the scale dispersion liquid into a water phase and a scale phase; a degassing step of volatilizing the lipophilic organic solvent remaining in the scale phase for separation; a coarse particle recovery step of recovering the coarse particles from the scale phase; a distillation step of recovering the lipophilic organic solvent which does not contain oil content from the lipophilic organic solvent separated in the organic solvent phase separation step; an oil content measurement step of measuring the oil content percentage in the oil-containing lipophilic organic solvent after the organic solvent phase separation step; and a deoiling scale recovery step.

Description

  The present invention relates to a method and apparatus for separating oil from scales containing oil and water (hereinafter also referred to as oil-containing scale) that are inevitably generated during industrial production.

For example, in the steel industry, a larger amount of mill scale is generated than the processing equipment such as direct cooling water used for cooling the steel material during the production of the steel material. Such scales are mainly composed of iron oxide (FeO, Fe ₂ O ₃ ) generated from steel, and scales that do not contain oil are useful resources that are reused in steelmaking, steelmaking processes, etc. Become.

  However, since the rolling oil used in the rolling process and the lubricating oil used in the manufacturing machine such as a rolling mill are mixed in the cooling water including scales during the rolling process, the generated scales are often 5 An average of several mass% oil content is contained together with ˜50 mass% water. In addition, oil components may be inevitably mixed during operations such as recombination of rolling rolls, and the oil concentration greatly fluctuates each time such operations are performed. May vary in range.

  Mineral oil, chemically synthesized oil, and animal and vegetable oils are used as rolling oils used in the rolling process and manufacturing machines such as rolling mills. Generally, oils that are liquid at 80 ° C or lower are used. Often to do. These oils include hydrocarbon mineral oils that are relatively weak in polarity, ester animal and vegetable oils and synthetic ester oils that are relatively strong in polarity, and have different physical properties depending on the application. Yes. In many cases, a plurality of oils are used in the rolling process, and therefore, the oil component in the oil-containing scale is often mixed with both a highly polar oil component and a weakly polar oil component.

  When these oil-impregnated scales are used as iron raw materials in a sintering plant, they are heated during the sintering process, causing oil to volatilize, causing clogging of the electrostatic precipitator and bag filter, and causing accidents such as fires. There is.

  In addition, when these oil-impregnated scales are used as iron raw materials in a steelmaking process such as a converter, the scale itself has a fine particle size and increases the amount of dust scattering, which necessitates separate briquetting or pelletization and increases costs. In addition, since it contains oil, it may cause problems such as smoke generation when charged into the converter or steam explosion during pouring.

  For these reasons, various studies have been made on oil-containing scales in order to separate oil and moisture.

  In Patent Document 1, using a co-current type rotary kiln type combustion furnace, the oxygen concentration in the exhaust gas is 0.1 to 5% by volume, and the inner wall surface temperature in the furnace of the oil-impregnated scale inlet is 400 ° C or higher. It has been proposed to burn the oil and cool the scale from which the oil has been removed in a non-oxidizing atmosphere. However, in this method, oil and moisture in the scale can be burned or volatilized and separated from the scale mainly composed of iron oxide, but since the oil concentration in the scale is as low as several mass%, auxiliary oil is required, Running costs are high. Moreover, since it burns in a furnace, the high temperature tolerance of an installation is needed, furnaces, such as a kiln, are needed, and an installation cost becomes high. In addition, the oil contained in the oil-containing scale is burned without being used.

  In Patent Document 2, the oil-impregnated scale accumulated in the crude oil tank is sprayed with crude oil to pulverize the oil-impregnated scale, and a solution containing hydrocarbons is supplied to the pulverized oil-impregnated scale to at least the oil-impregnated scale. There has been proposed a method in which after partly dissolved, a solution containing hydrocarbon oil is further added to stir the oil-containing scale, followed by precipitation separation to separate and recover the liquid component containing the scale and dissolved oil. Although the oil concentration is not described in this method, the oil content in the scale separated by precipitation is considered to exceed 10% by mass, and it is considered impossible to use it directly in the iron making, steel making processes, etc. .

  In Patent Document 3, a liquefied substance that is a gas under normal temperature and normal pressure conditions is brought into contact with an oil-containing substance, and the oil in the oil-containing substance is dissolved in the liquefied substance so that a liquefied substance with a high oil content is reduced. Separating and recovering oil from the oil-containing substance by separating and recovering it from the oil as a gas by vaporizing the gas substance under normal temperature and normal pressure conditions in the oil-rich liquefied product. A method has been proposed. However, in this method, it is necessary to liquefy a substance that is a gas under normal temperature and normal pressure conditions under high pressure, which requires high-pressure equipment and increases equipment costs.

  In Patent Document 4, in order to separate the rolling oil or cutting oil contained in the rolling or cutting sludge, the rolling / cutting sludge is dispersed in water, and the sludge degreasing solvent (organic solvent) is added and mixed and stirred. After standing, after removing the supernatant oil-containing solvent, water is added and mixed, and this is separated into solids and liquids using a centrifuge or squeeze filter to separate the oil in the sludge. Has been. In this document, the whole amount of the separated oil-containing solvent is heated with steam or the like, and the solvent is recovered by distillation.

  However, in this method, no consideration is given to fluctuations in the oil concentration contained in the rolling or cutting sludge. Rolled sludge often fluctuates greatly in oil concentration, but in this method, since the supernatant oil-containing solvent still has a function capable of absorbing oil, a distillation operation is performed, so that the oil-containing solvent in the supernatant is greatly regenerated. I was spending energy.

  In Patent Document 5, an object to be cleaned is immersed in a hydrocarbon solvent that is a cleaning liquid, and oil components adhering to the object to be cleaned are separated into the cleaning liquid. In addition, by measuring the oil concentration in the cleaning liquid in real time with an ultraviolet light absorption photometer or the like, it is possible to maintain the high cleaning performance and reduce the regeneration cost of the cleaning liquid. However, it is not described what the object is to be cleaned. Moreover, although the 1st washing tank which immerses a to-be-washed object in a washing | cleaning liquid mixes the inside of a 1st washing tank with a circulation pump, there is no description about the stirring intensity inside a 1st washing tank. The oil-impregnated scale containing water and oil, which is the subject of the present invention, has a water phase around the oil-containing scale, so simply adding a hydrocarbon solvent as a cleaning agent and simply mixing them. The oil concentration in the oil-impregnated scale cannot be sufficiently reduced.

Japanese Patent Laid-Open No. 10-169957 JP-A-2005-349240 JP 2007-237129 A JP 2000-355718 A JP 2011-32561 A

  As a result of the study by the present inventors, it has been found that it is difficult to separate the oil component in an oil-containing scale having an average particle size (volume basis, hereinafter referred to as volume basis) of 50 μm or less. That is, an oil-containing scale having an average particle size exceeding 50 μm can easily disperse sludge even with weak stirring, and can separate oil components present on the particle surface of the sludge and the particles in the sludge. When the diameter is 50 μm or less, the sludge is not sufficiently dispersed even with strong stirring, and the oil present in the particle group cannot be separated. That is, it has been found that there is a problem that oil from rolling or cutting sludge having an average particle diameter of 50 μm or less cannot be sufficiently separated. Since Patent Document 4 does not recognize the problem, it is considered that the rolling or cutting sludge that is the subject is sludge having an average particle diameter of more than 50 μm.

  The problem of the present invention is that oil-containing scales inevitably generated during industrial production contain oil and water, and the oil concentration varies, and in particular, an average particle size of 50 μm, which has been found to be difficult to separate oil. To provide an oil separation method and apparatus that can safely separate an oil component from the following oil-impregnated scale and can safely obtain a deoiling scale for a low oil component.

In order to solve the above problems, according to one aspect of the present invention,
In an oil separation method for separating the oil from an oil-containing scale containing an oil and moisture and having an average particle size of 50 μm or less,
Adding a coarse particle larger than the average particle diameter of the oil-impregnated scale to the oil-impregnated scale, and immersing and dispersing the oil-impregnated scale and the coarse particle in a dispersion containing water, thereby obtaining a scale dispersion;
An extraction step of adding a lipophilic organic solvent to the scale dispersion, mixing and stirring, and extracting the oil contained in the oil-containing scale into the lipophilic organic solvent;
An organic solvent that separates the mixed liquid of the scale dispersion and the oil-containing lipophilic organic solvent after the extraction step into the oil-containing lipophilic organic solvent and the scale dispersion containing the coarse particles using a difference in specific gravity. A phase separation process;
An aqueous phase separation step for solid-liquid separation of the scale dispersion after the organic solvent phase separation step into a scale phase containing the coarse particles and an aqueous phase due to a specific gravity difference;
A coarse particle recovery step of recovering the coarse particles from the scale phase after the aqueous phase separation step;
A deoiling scale recovery step of recovering the scale phase after the coarse particles are recovered in the coarse particle recovery step as a deoiling scale;
An oil content measurement step for continuously or intermittently measuring the oil content in the oil-containing lipophilic organic solvent separated in the organic solvent phase separation step;
Distilling the oil-containing lipophilic organic solvent separated in the organic solvent phase separation step to regenerate the lipophilic organic solvent not containing oil and recovering the oil,
Including
When the oil content measured in the oil content measurement step is not more than a predetermined value, the oil-containing lipophilic organic solvent separated in the organic solvent phase separation step is returned to the extraction step, and the oil content rate Is greater than the predetermined value, the oil-containing lipophilic organic solvent separated in the organic solvent phase separation step is distilled to lower the oil content to the predetermined value or less, and then to the extraction step. An oil separation method is provided which is characterized by being returned.

  You may make it the particle diameter of the said coarse particle exist in the range of 0.5-3.0 mm, and the addition rate of the said coarse particle with respect to the said oil-containing scale is 1-8 mass%.

  In the extraction step, when the mixed solution composed of the lipophilic organic solvent and the scale dispersion is stirred, the stirring Reynolds number (Re) of the mixed solution may be in the range of 500 to 40,000. .

  In the aqueous phase separation step, solid-liquid separation may be performed using a centrifugal force into a scale phase containing the coarse particles and an aqueous phase. Moreover, when using centrifugal force, you may make it the magnitude | size be 10G or more.

In the extraction step, using a multi-stage countercurrent extraction tank having two or more mixing chambers, the lipophilic organic solvent and the scale dispersion are mixed and stirred,
You may make it contact the said lipophilic organic solvent and the said scale dispersion liquid by a multistage countercurrent type in the said multistage countercurrent type extraction tank.

  In the multi-stage countercurrent extraction tank, the oil content of the oleophilic lipophilic organic solvent in the final-stage mixing chamber where the oil content in the oil-containing scale is the lowest is measured continuously or intermittently, and the oil content is predetermined. The amount of the oleophilic organic solvent that does not contain oil may be controlled in the final-stage mixing chamber so as to be less than the value.

  In the oil content measurement step, in order to measure the oil content in the oil-containing lipophilic organic solvent, the absorbance or viscosity of the oil-containing lipophilic organic solvent is measured, and the oil content is based on the absorbance or the viscosity. May be requested.

  In the extraction step, the lipophilic organic solvent having a mass ratio of 1 time (W / W) to less than 50 times (W / W) with respect to the amount of oil in the oil-containing scale is added to the scale dispersion. May be.

A degassing step of volatile separation of the lipophilic organic solvent remaining in the scale phase after the aqueous phase separation step;
A solid-liquid separation step of separating the scale remaining in the oil-containing lipophilic organic solvent separated in the organic solvent phase separation step;
Further including
In the distillation step, the oil component is included by distilling the lipophilic organic solvent volatilely separated in the degassing step and the oleophilic lipophilic organic solvent after being separated in the solid-liquid separation step. Reclaim no lipophilic organic solvent, and recover the oil
In the oil content measurement step, the oil content in the oil-containing lipophilic organic solvent after being separated in the solid-liquid separation step may be measured continuously or intermittently.

  In the solid-liquid separation step, the scale fraction may be separated from the oleophilic lipophilic organic solvent using filtration or centrifugal force. Moreover, when using a centrifugal force, you may make it the magnitude | size be 500 G or more.

  The lipophilic organic solvent may have a boiling point at normal pressure of less than 100 ° C. and a liquid at normal temperature and normal pressure.

  In the aqueous phase separation step, the aqueous phase separated from the scale phase may be returned to the dispersion step and reused as the dispersion.

In order to solve the above problem, according to another aspect of the present invention,
In an oil separation device that separates the oil from an oil-containing scale containing an oil and moisture and having an average particle size of 50 μm or less,
A scale dispersion generating device for generating a scale dispersion by mixing the oil-containing scale, coarse particles larger than the average particle diameter of the oil-containing scale, and a dispersion containing water;
In the mixing chamber, the lipophilic organic solvent and the scale dispersion are mixed and stirred, and the oil contained in the oil-containing scale is extracted into the lipophilic organic solvent, and the mixture of the scale dispersion and the oil-containing lipophilic organic solvent. An extraction tank that separates the oil-containing lipophilic organic solvent and the scale dispersion containing the coarse particles using a specific gravity difference;
An aqueous phase separation device for solid-liquid separation of the scale dispersion discharged from the extraction tank into a scale phase containing the coarse particles and an aqueous phase;
A recovery device for recovering the coarse particles from the scale phase discharged from the aqueous phase separator, and recovering the scale phase after the coarse particles are recovered as a deoiling scale;
A first oil content measuring device for measuring the oil content in the oil-containing lipophilic organic solvent separated by the extraction tank;
A distillation apparatus for regenerating the lipophilic organic solvent not containing oil and recovering the oil by distilling the oil-containing lipophilic organic solvent separated by the extraction tank;
With
When the oil content rate measured by the first oil content measuring device is below a predetermined value, the oil-containing lipophilic organic solvent separated by the extraction tank is returned to the mixing chamber of the extraction tank, When the oil content is larger than the predetermined value, the oil-containing lipophilic organic solvent separated by the extraction tank is distilled by the distillation apparatus, thereby reducing the oil content to the predetermined value or less. An oil separator is provided, which is returned to the mixing chamber of the extraction tank.

  You may make it the particle diameter of the said coarse particle exist in the range of 0.5-3.0 mm, and the addition rate of the said coarse particle with respect to the said oil-containing scale is 1-8 mass%.

  You may make it the said extraction tank stir the said liquid mixture so that the stirring Reynolds number (Re) of the liquid mixture which consists of the said lipophilic organic solvent and the said scale dispersion may be in the range of 500-40000.

  As the aqueous phase separation device, a precipitation tank that solid-liquid separates the scale dispersion liquid into a scale phase containing coarse particles and an aqueous phase due to a difference in specific gravity may be used.

  The aqueous phase separation device may be a cyclone or a centrifugal separator that separates the scale dispersion into a scale phase containing the coarse particles and an aqueous phase using a centrifugal force. Moreover, when using centrifugal force, it is preferable that the magnitude | size is 10 G or more.

The extraction tank is a multistage countercurrent extraction tank having a mixing chamber of two or more stages,
You may make it contact the said lipophilic organic solvent and the said scale dispersion liquid by a multistage countercurrent type in the said multistage countercurrent type extraction tank.

The apparatus further comprises a second oil content measuring device that continuously or intermittently measures the oil content of the oil-containing lipophilic organic solvent in the final-stage mixing chamber in which the oil content in the oil-containing scale is lowest in the multi-stage countercurrent extraction tank. ,
The amount of the oleophilic organic solvent that does not contain oil in the mixing chamber at the final stage may be controlled so that the oil content measured by the second oil content measuring device is a predetermined value or less. Good.

  The first oil content measuring device measures the absorbance or viscosity of the oil-containing lipophilic organic solvent in order to measure the oil content in the oil-containing lipophilic organic solvent, and based on the absorbance or the viscosity, The oil content may be obtained.

  In the extraction tank, the lipophilic organic solvent having a mass ratio of 1 time (W / W) to less than 50 times (W / W) relative to the amount of oil in the oil-containing scale is added to the scale dispersion. May be.

A deaeration device that volatilizes and separates the lipophilic organic solvent remaining in the scale phase discharged from the aqueous phase separator;
A solid-liquid separator that separates the scale remaining in the oil-containing lipophilic organic solvent separated by the extraction tank;
Further including
The oleophilic organic solvent volatilely separated by the degassing device and the oleophilic oleophilic organic solvent separated by the solid-liquid separation device are distilled by the distillation device, so that the oleophilicity does not contain the oil component. Regenerate the organic solvent and recover the oil,
The first oil content measuring device may continuously or intermittently measure the oil content in the oil-containing lipophilic organic solvent separated by the solid-liquid separator.

  A filtration device or a centrifuge device may be used as the solid-liquid separation device. The centrifugal separator separates the scale from the oil-containing lipophilic organic solvent using centrifugal force, and the magnitude of the centrifugal force is preferably 500 G or more.

  The lipophilic organic solvent may have a boiling point at normal pressure of less than 100 ° C. and a liquid at normal temperature and normal pressure.

  The aqueous phase separated from the scale phase by the aqueous phase separation device may be returned to the scale dispersion producing device and reused as the dispersion.

According to the present invention, it is possible to easily separate oil from oil-containing scales inevitably generated in the production process of steel products and oil-containing scales, particularly oil-containing scales having an average particle diameter of 50 μm or less, which is difficult to separate oil. In addition, since a lipophilic organic solvent can be used efficiently, it is possible to provide a safe oil separation method that consumes less energy and does not generate smoke or steam explosion. Furthermore, the solid material mainly composed of iron oxide (FeO, Fe ₂ O ₃ ) separated from the oil-impregnated scale can be reused as it is in the iron making, steel making processes and the like.

FIG. 1 is a schematic diagram showing the presence of oil and moisture in an oil-containing scale. FIG. 2 is a flowchart illustrating an oil separation method according to an embodiment of the present invention. FIG. 3 is a diagram showing the scale dispersion that has been allowed to stand in the standing (separation) step, and is a schematic diagram showing the relationship between the oleophilic lipophilic organic solvent phase, the aqueous phase, and the precipitation scale phase. FIG. 4 is a graph showing the relationship between the stirring Reynolds number in the extraction tank and the oil distribution ratio. FIG. 5 is a graph showing the relationship between the stirring Reynolds number and the oil removal rate in a single-stage extraction tank. FIG. 6 is a graph showing the relationship between the input amount of the lipophilic organic solvent relative to the oil content and the oil removal rate in the oil-containing scale. FIG. 7 is a graph showing the relationship between the oil content concentration and the absorbance of the filtrate of the supernatant oil-containing lipophilic organic solvent when n-hexane is used as the lipophilic organic solvent. FIG. 8 is a graph showing the relationship between the oil concentration and the viscosity of the filtrate of the supernatant oil-containing lipophilic organic solvent when n-hexane is used as the lipophilic organic solvent. FIG. 9 is a graph showing the relationship between the oil concentration in the oil-containing lipophilic organic solvent phase and the oil removal rate from the oil-containing scale when n-hexane is used as the lipophilic organic solvent. FIG. 10 is a schematic view showing an oil separation device using the multistage countercurrent extraction tank according to the first embodiment of the present invention. FIG. 11 shows an example of an apparatus used for the dispersion step ST1. FIG. 12 shows an example of an apparatus used for the deaeration process ST5. FIG. 13 is a graph showing the influence of the coarse particle addition rate into the oil-containing scale on the oil removal rate. FIG. 14 is a supplementary diagram for explaining a calculation formula (Formula 1) of the stirring Reynolds number. FIG. 15 is a diagram showing the relationship between centrifugal force and oil distribution ratio. FIG. 16 is a diagram showing the relationship between centrifugal force and emulsion phase rate. FIG. 17 is a supplementary diagram for explaining the calculation formula (Formula 2) of the emulsion phase ratio. FIG. 18 is a schematic diagram showing an example of an oil separation device using a multistage countercurrent extraction device (two-stage) process according to the second embodiment of the present invention. FIG. 19 is a schematic view showing an oil separator using a single-stage oil extractor system according to the third embodiment of the present invention.

  Hereinafter, an oil separation method from an oil-containing scale according to an embodiment of the present invention will be described with reference to the drawings.

  The oil-containing scale that is an object of the oil separation method according to the present embodiment is a scale that contains oil and moisture, for example, an oil-containing scale that is generated in a rolling process, and is sometimes referred to as oil-containing sludge. In particular, it is difficult to separate oil from an oil-containing scale having an average particle size of 50 μm or less. The particle diameter is measured by a laser diffraction / scattering method, and the average particle diameter is expressed on a volume basis.

  First, the presence form of oil and moisture in the oil-containing scale will be described. As shown in FIG. 1, the moisture and oil content in the oil-containing scale are present as oil moisture in the bulk, oil moisture in the gap, oil moisture in the capillary, oil moisture adsorbed on particles such as the scale. . Oil moisture refers to a state where oil and moisture are mixed.

  The oil moisture in the bulk is moisture and oil present around the scale particle group. The oil moisture in the gap is moisture and oil surrounded by a gap formed by agglomeration of large and small solid particles such as scale. Furthermore, oil moisture in the capillary is moisture and oil that are combined by capillary pressure in the capillary on the scale surface. Furthermore, the oil moisture adsorbed on the particles such as the scale is the moisture and oil chemically adsorbed on the scale.

  Oil and moisture in the bulk are moisture and oil that have almost no binding force with particles such as scales and can be easily separated by applying external pressure. Mechanical force such as a pressure dehydrator or centrifugal dehydration Separation can be carried out by operations such as dehydration / deoiling by a machine or natural dehydration / deoiling by standing.

  In addition, since the oil and water in the gap is surrounded by solid particles such as scales, it cannot be separated by operations such as dehydration / deoiling by mechanical force or dehydration / deoiling by standing. .

  Furthermore, oil moisture in the capillary is moisture or oil held inside the capillary on the particle surface such as scale by capillary force, and, like oil moisture in the gap, dehydration / deoiling or static by mechanical force. It cannot be separated by operations such as dehydration and deoiling.

  Furthermore, the oil and water adsorbed on the particles such as scale is the water and oil that is chemically bonded to the particle surface and inside, and the water and oil that can be separated only by volatilization due to temperature rise or chemical reaction. It is. In other words, oil moisture in the gap, oil moisture in the capillaries, and adsorbed oil moisture can be removed by normal dehydration and deoiling operations (mechanical dehydration and deoiling operations using a centrifugal dehydrator or filter press, or standing still. Natural dehydration / deoiling etc.) cannot be separated.

  When the lipophilic organic solvent is added to the scale containing oil and moisture and then stirred to extract the oil in the oil-containing scale, the oil in the bulk easily comes into contact with the organic solvent and is thus easily extracted. However, since the oil in the gap and the oil in the capillary are surrounded by the scale, and moisture exists in the gap between the scale particles or in the capillary at the same time as the oil, the oil in the gap or in the capillary is Moisture is blocked by the scale, and the lipophilic organic solvent cannot easily come into contact with oil in the gap or oil in the capillary. In particular, when the average particle size of the scale is small, in the oil-containing aggregates containing oil and moisture in the gaps or capillaries, the oil content in the gaps or the capillaries is highly viscous, and the dispersibility of the aggregates by stirring alone is high. In many cases, the oil content in the oil-impregnated scale is difficult to extract and is difficult to decrease.

  The inventor of the present invention is oleophilic, which easily evaporates oil in the gap and oil in the capillary, among oil in the gap, oil in the capillary and adsorbed oil that cannot be separated by normal dehydration / deoiling operation. After substituting with an organic solvent, the present inventors have found that the oil content in the oil-impregnated scale can be reduced by volatilizing the lipophilic organic solvent in the gaps and capillaries.

  In addition, by selecting an organic solvent that has a boiling point of less than 100 ° C. at normal pressure and is liquid at normal temperature and pressure as an oleophilic organic solvent, water evaporation is suppressed and the organic solvent is mainly volatilized. It has also been found that hot wastewater generated in factories and the like can be used as a heat source for volatilization.

  Moreover, if the dispersibility of an oil-impregnated scale improves by adding a lipophilic organic solvent, the oil content in an oil-impregnated scale will fall easily. In the extraction step, the stirring Reynolds number (Re) of the mixed liquid composed of the lipophilic organic solvent and the oil-containing scale is preferably 500 or more. As a result, it was found that the oil-impregnated scale can be further dispersed, so that it can be further deoiled. Furthermore, it has been found that by adding water containing a hydrophilic organic solvent, the dispersibility of the oil-containing scale is further improved and the deoiling efficiency is improved.

  Furthermore, the oil-impregnated scale having a small particle diameter of 50 μm or less and coarse particles (preferably coarse particles having a particle diameter of 0.5 to 3.0 mm) are mixed and stirred before adding the lipophilic organic solvent. It is preferable to keep it. As a result, the coarse particles collide with the oil-impregnated scale in the form of aggregates, and the aggregates are temporarily dispersed, so that the lipophilic organic solvent is forcibly brought into contact with the oil in the gaps and in the capillaries. Therefore, it was found that the oil removal rate can be increased even with an oil-containing scale having a small particle size.

  As the coarse particles, the true specific gravity of the scale is about 5 to 5.5, but those having the same true specific gravity and difficult to be pulverized by stirring are preferable. Specifically, scales having a particle diameter of 0.5 to 3.0 mm, sand, slag, iron ore, sintered iron oxide, or metal powder can be used as the coarse particles.

  Furthermore, after adding the lipophilic organic solvent to the slurry in which the oil-impregnated scale is dispersed in the dispersion containing water and extracting the oil component into the solvent by vigorous stirring, the mixture is allowed to stand, as shown in FIG. In addition, the scale is precipitated at the bottom, the aqueous phase is at the top, and the lipophilic organic solvent containing oil is present at the top. There is a gap in the lowermost scale phase, and a part of the lipophilic organic solvent containing oil remains in the gap together with moisture. By applying centrifugal force, the lipophilic organic solvent containing moisture and oil remaining in the gap in the scale phase can be pushed out from the gap in the scale phase, so the oil removal rate can be increased. it can. Specifically, by applying a centrifugal force of 10 G or more, more preferably a centrifugal force of 50 G or more, the amount of the oleophilic lipophilic organic solvent in the scale phase precipitated at the bottom is reduced, thereby removing oil. I found that the rate can be increased.

  Furthermore, when a part of the lipophilic organic solvent is vaporized, it adheres as a foam on the surface of the scale, so that a part of the scale may float in the supernatant phase (lipophilic organic solvent phase). Also, by forming an emulsion with lipophilic organic solvent and water, and the scale component stays at the interface, the emulsion becomes metastable, the emulsion phase cannot be destroyed (cannot be demilked), part of the scale May float in the supernatant phase (lipophilic organic solvent phase). If the supernatant phase is distilled without removing the scale, it is necessary to discharge the scale from the distillation apparatus, which is often an obstacle in operation. In addition, regarding the amount of water added to disperse the rolling / cutting scale, if the amount of water is insufficient, an interface between the water phase and the supernatant phase exists in the scale phase that precipitates. When separating the supernatant phase from the phase, the oil remains on the scale and the oil removal rate cannot be improved. Regarding scale recovery, the recovery phase is obtained by separating (dehydrating) the aqueous phase part by centrifugation or squeezing filtration, but water and solvent remain in the gap in the recovery scale. Therefore, the odor caused by organic solvents is remarkably harmful to health. Further, when the scale is put into a drying apparatus to dry the recovered scale, the handling property is deteriorated because the scale is cake-like. In addition, butyl acetate, toluene, and xylene are also included as solvents used in the prior art. These solvents have a boiling point of 100 ° C. or higher at normal pressure, and a heat source of 100 ° C. or higher is required for distillation. It becomes.

  Based on the above knowledge, the oil component separation method according to the present embodiment, in which the oil component is separated from the oil-containing scale using a lipophilic organic solvent, will be described with reference to FIG. FIG. 2 is a flowchart showing an oil separation method according to this embodiment. First, the role of each process from ST1 to ST10 will be described.

  As shown in FIG. 2, the oil separation method according to the present embodiment includes a dispersion step ST1, an extraction step ST2, an organic solvent phase separation step ST3, an aqueous phase separation step ST4, a degassing step ST5, and coarse particles. A recovery step ST8, a deoiling scale recovery step ST9, a solid-liquid separation step ST6, a distillation step ST7, and an oil content measurement step ST10 are included.

(1) In the dispersion step ST1, an oil-impregnated scale and a dispersion-promoting agent are added to a dispersion liquid containing water (for example, water itself or a liquid obtained by adding a hydrophilic solvent to water, hereinafter also simply referred to as “dispersion liquid”). A scale dispersion is obtained by dispersing coarse particles.
(2) In the extraction step ST2, a lipophilic organic solvent is added to a scale dispersion containing coarse particles and mixed and stirred to extract oil from the oil-containing scale in the lipophilic organic solvent.
Here, the oil-impregnated scale is often a mud semi-solid, and even if a lipophilic organic solvent is added to the oil-impregnated scale from the beginning and stirred, the dispersibility is poor. If a solvent is present, it is necessary to form a sealed structure for safety measures. Therefore, it is preferable to first add water or the like to stir and disperse the oil-containing scale, and then add and add the lipophilic organic solvent. That is, it is preferable not to perform ST1 and ST2 at the same time, but to perform ST2 in order after ST1.
(3) In the organic solvent phase separation step ST3, the mixture of the scale dispersion containing coarse particles after the extraction step ST2 and the oleophilic lipophilic organic solvent is allowed to stand, and then becomes a supernatant on the upper portion of the scale dispersion by specific gravity separation. The oil-containing oleophilic organic solvent present is removed by draining and separated from the remainder (scale dispersion containing coarse particles) from which the supernatant oil-containing oleophilic organic solvent has been removed. Specific gravity separation can use natural sedimentation by gravity, for example. Here, the oil-containing lipophilic organic solvent is a lipophilic organic solvent containing an oil extracted from the oil-containing scale.

(4) In the aqueous phase separation step ST4, the scale dispersion containing the coarse particles separated in the organic solvent phase separation step ST3 is subjected to specific gravity separation, so that the solid phase is separated into an aqueous phase composed of excess water and a scale phase containing coarse particles. To separate. As a specific gravity separation method, it is possible to naturally settle the scale by gravity using the difference in specific gravity between water and scale, but at this time, if a separation method (centrifugal separation method) that applies centrifugal force is performed, Since the oil component can be further separated by pushing out the lipophilic organic agent containing the oil component from within the scale phase having a large specific gravity, the oil component in the oil-containing scale is further reduced, which is preferable. The magnitude of the centrifugal force is preferably 10 G or more, more preferably 50 G or more. Furthermore, the water phase part which consists of excess water | moisture content is returned to the said dispersion | distribution process ST1, and the water of the said water phase is reused as a dispersion liquid.
(5) A small amount of scale dispersion remains on the solid side (scale phase containing coarse particles) after solid-liquid separation in the aqueous phase separation step ST4, and a slight amount of lipophilic organic solvent remains in the scale dispersion. doing. Therefore, in the deaeration step ST5, the lipophilic organic solvent is subjected to reduced pressure and / or heating to volatilize and separate.
(6) In the coarse particle recovery step ST8, the coarse particles mixed in the dispersion step ST1 are separated and separated from the scale phase containing the coarse particles after the oleophilic organic solvent is volatilized and separated in the degassing step ST5. Collect and separate into coarse particles and deoiling scale. Further, the coarse particles recovered in this step ST8 are returned to the dispersion step ST1, added to the oil-containing scale, and reused.

(7) In the deoiling scale recovery step ST9, the scale phase after the coarse particles are recovered in ST8 is finally recovered as a deoiling scale. There is a small amount of excess water in the deoiling scale, which is removed separately.
(8) In the solid-liquid separation step ST6, the supernatant oil-containing oleophilic organic solvent separated in the organic solvent phase separation step ST3 is filtered, or centrifugal force is applied to make a small amount or a large amount in the supernatant oil-containing oleophilic organic solvent. The fine scale remaining in is separated into solid and liquid. This step ST6 can be omitted when almost no scale remains in the separated oil-containing lipophilic organic solvent. When a small amount of scale is contained in the separated oleophilic lipophilic organic solvent, the scale can be separated by filtration, but when it is contained in a large amount, it is better to separate by applying centrifugal force.
(9) In the distillation step ST7, the oil-free oleophilic organic solvent obtained in the solid-liquid separation step ST6 and the oleophilic organic solvent volatilized and separated in the deaeration step ST5 are subjected to distillation operation to contain no oil. Regenerate the oily organic solvent and recover the oil.

  (10) In the oil content measurement step ST10, the oil content in the oil-containing lipophilic organic solvent obtained in the solid-liquid separation step ST6 is continuously or intermittently measured by the oil content measurement device. In this oil content measurement step ST10, the oil content in the oil-containing lipophilic organic solvent after the solid-liquid separation step ST6 is measured continuously or intermittently, but as the oil extraction process proceeds in the extraction step, the oil content is It rises over time. Therefore, the oil-containing lipophilic organic solvent is returned to the extraction step ST2 until the oil content reaches a predetermined value. Thereafter, when the oil content reaches a predetermined value, the oil-containing oleophilic organic solvent is distilled in the distillation step ST7 by either heating to a boiling point or higher or reducing the pressure. After reducing the oil content to the predetermined value or less and regenerating the lipophilic organic solvent not containing the oil, the lipophilic organic solvent having the oil content of the predetermined value or less is returned to the extraction step ST2.

  Hereinafter, each process of ST1-ST10 is demonstrated sequentially including the apparatus to be used.

(Dispersion step ST1)
A dispersion liquid containing water (only water is acceptable) is added to the oil-impregnated scale to disperse the oil-impregnated scale and form a slurry so that it can be pumped. An example of an apparatus used for the dispersion step ST1 is shown in FIG. An oil-impregnated scale 55 and coarse particles 57 to be added to promote dispersion are introduced into a slurrying tank 53 charged with water 56 as a dispersing agent by a belt conveyor 51, and the inside of the slurrying tank 53 is stirred by an agitator 52. Then, a mixture of water 56, oil-containing scale 55 and coarse particles 57 is slurried. The slurried oil-impregnated scale is fed by the pump 54 to the extraction step ST2 which is the next step.

  If the coarse particles to be added have a particle size larger than the average particle size of the oil-impregnated scale, a dispersion promoting effect can be obtained, but particles having a particle size of 0.5 to 3.0 mm are preferable. If the particle diameter is less than 0.5 mm, the oil-impregnated scale is not sufficiently dispersed even under strong stirring, and the oil removal rate may not be improved. If the particle diameter is more than 3.0 mm, coarse particles are likely to precipitate, which is likely to cause clogging in the extraction step ST2.

The specific gravity of the coarse particles to be added is preferably particles larger than the specific gravity of water, more preferably coarse particles having a specific gravity comparable to that of the oil-containing scale.
Moreover, the addition rate of coarse particles is preferably 1 to 8% by mass with respect to the total mass of the oil-containing scale (after draining, 20 to 40% by mass of the total of oil and moisture is included, but there is little fluctuation). Outer number: percentage of [mass of coarse particles / mass of oil-impregnated scale]. The reason will be described in Example 1.

  Further, the amount of water used in the dispersion step ST1 is also an important condition when separating the oil from the oil-containing scale. The amount of the dispersion added is preferably 1.5 to 10 times (W / W) by mass ratio with respect to the solid content of the oil-containing scale.

  In FIG. 3, water (dispersion) is added to the oil-impregnated scale, and a lipophilic organic solvent for extracting the oil component is further added. After stirring with an impeller and the like, the state after standing is schematically shown. Show. After standing, the scale is precipitated at the bottom, the aqueous phase is at the top, and the lipophilic organic solvent containing oil is present at the top.

  If the amount of water added as a dispersion is small, the precipitated scale will not be completely immersed in the dispersion, and the supernatant oil-containing oleophilic organic solvent phase containing oil will come into contact with the scale portion. In other words, the interface between the aqueous phase and the supernatant oleophilic lipophilic organic solvent phase is present in the scale phase. In such a case, even if the supernatant oil-impregnated lipophilic organic solvent phase is separated, even the oil-impregnated lipophilic organic solvent in contact with the precipitated scale may not be separated, and the oil content reduction rate from the oil-impregnated scale is reduced. There is.

  Therefore, it is important that the amount of water added as a dispersion in the dispersion step ST1 is equal to or greater than the amount in which the oil-containing scale can be immersed in the dispersion. Specifically, the addition amount of the water is preferably 1.5 times (W / W) or more by mass ratio with respect to the solid content of the oil-containing scale. On the other hand, if the amount of water added as a dispersion is large in the dispersion step ST1, the contact probability between the oil-containing scale containing coarse particles and the lipophilic organic solvent decreases in the extraction step ST2. It is necessary to lengthen the time or increase the stirring strength. Therefore, the amount of the dispersion added in the dispersion step ST1 is preferably 10 times (W / W) or less in terms of mass ratio with respect to the solid content of the oil-containing scale.

(Extraction step ST2)
Next, in the extraction step ST2, a lipophilic organic solvent is added to the scale dispersion containing coarse particles and stirred and mixed. Thereby, the oil component in the oil-containing scale is extracted into the lipophilic organic solvent. The stirring / mixing time is almost steady in a short time, but is preferably 1 minute or more and less than 30 minutes. When the scale dispersion after stirring and mixing is allowed to stand, as shown in FIG. 3, it is separated from the top into a scale phase containing a supernatant oil-containing lipophilic organic solvent phase, an aqueous phase, and precipitated coarse particles.

  The lipophilic organic solvent is preferably a solvent having a boiling point of less than 100 ° C. at normal pressure and a liquid at normal temperature and normal pressure. Further, as shown in FIG. 3, the specific gravity of the lipophilic organic solvent is preferably smaller than the specific gravity of water (dispersion) in order to separate the lipophilic organic solvent phase and the aqueous phase by utilizing the specific gravity difference. The supernatant oil-containing lipophilic organic solvent separated in the organic solvent phase separation step ST3 contains oil from the supernatant oil-containing lipophilic organic solvent by distillation operation in the distillation step ST7 after solid-liquid separation in the solid-liquid separation step ST6. No oleophilic organic solvent is recovered and recovered. Further, in a degassing step ST5 described later, the lipophilic organic solvent is volatilized and separated from the scale phase containing coarse particles. From the viewpoint of reducing heating energy when evaporating these lipophilic organic solvents, the lipophilic organic solvent is preferably a liquid having a relatively low boiling point, specifically, diethyl ether, pentane, hexane, ethyl formate, acetic acid. One or more selected from ethyl and benzene are preferable, and pentane or hexane is more preferable.

  The oil content in the oil-impregnated scale is mineral oil, chemically synthesized oil, or animal and vegetable oil. Since the boiling point generally exceeds 100 ° C, it is separated from these lipophilic organic solvents using the difference in boiling point. can do.

  In a single stage extraction tank, 5 g of coarse particles (particle size: 0.5 to 3.0 mm) having an oil content of 0% by mass are mixed with 95 g of an oil-containing scale having an oil content of 10% by mass and an average particle size of 21 μm, and water is added thereto. FIG. 4 shows the relationship between the stirring Reynolds number (Re) indicating the stirring strength of the mixed solution and the oil distribution ratio when 200 g is added and an arbitrary amount of hexane is added as a lipophilic organic solvent and stirred for 30 minutes. It is. The oil distribution ratio is the ratio of the oil concentration in the oil-impregnated scale after deoiling to the oil concentration in the lipophilic organic solvent after deoiling (oil distribution ratio = oil content in the oil-containing scale after deoiling). Concentration / oil concentration in the lipophilic organic solvent after deoiling).

  As shown in FIG. 4, when the stirring Reynolds number is large, the oil distribution ratio becomes small. That is, the oil concentration in the oil-impregnated scale after deoiling is reduced, and the oil removal rate can be increased. Moreover, if the usage-amount of a lipophilic organic solvent is increased, the oil concentration in a lipophilic organic solvent will fall, the oil concentration in the oil-containing scale after deoiling will also fall, and an oil removal rate can be enlarged. Further, from FIG. 4, if the stirring Reynolds number is set, the oil content distribution ratio, which is the ratio of the oil concentration in the oil-impregnated scale after deoiling to the oil concentration in the lipophilic organic solvent, is determined. The oil content in the oil-containing scale after deoiling can be estimated by continuously or intermittently measuring the oil content concentration. In other words, by increasing the amount of organic solvent renewed or regenerated by distillation, the oil content in the scale after deoiling is controlled by controlling the oil concentration in the lipophilic organic solvent to be below a certain value. Can be controlled below a certain value.

  In a single-stage extraction tank, 5 g of coarse particles (particle size: 0.5 to 3.0 mm) having an oil content of 0% by mass and 200 g of water are added to 95 g of an oil-containing scale having an oil content of 10% by mass and an average particle size of 21 μm. FIG. 5 shows the relationship between the stirring Reynolds number and the oil removal rate when 20 g of hexane was added as an oily organic solvent and stirred for 30 minutes. From FIG. 5, it can be seen that when the stirring Reynolds number is in the range of 500 to 40,000, the dispersion of the oil-impregnated scale sufficiently proceeds and the oil content can be separated by 40% by mass or more.

  If the stirring Reynolds number is less than 500, the oil removal in the single-stage extraction tank is as low as less than 40% by mass. Therefore, in order to obtain a high oil removal rate, a multistage extraction tank having a very large number of stages is required. Due to the structure of the extraction tank, it becomes difficult to manufacture and it is not realistic. When the stirring Reynolds number is 10,000 or more, the increase in the oil removal rate gradually decreases, and when the stirring Reynolds number is 40000 or more, no significant improvement in the oil removal rate is observed.

The rotation speed of the stirrer is n [s ⁻¹ ], the geometric shape of the stirrer is the tank diameter D [m], the liquid depth H [m], the stirring blade diameter d [m], and the blade width b [ m] (see FIG. 14), the stirring Reynolds number (Re) is expressed as shown in equation (1).

Stirring Reynolds number (Re) = (n × d ² × ρ) / μ (1)
Where ρ: density of the liquid mixture (kg / m ³ ), μ: viscosity of the liquid mixture (Pa · s)

  The amount of the oleophilic organic solvent added may be adjusted as appropriate so as to obtain the required oil removal rate, but is preferably 1 time (W / W) or more by mass ratio with respect to the amount of oil in the oil-containing scale. Less than 50 times (W / W) is good. FIG. 6 shows the oil removal rate in the oil-impregnated scale with respect to the ratio between the amount of added lipophilic organic solvent (pentane) and the amount of oil in the oil-containing scale. As shown in FIG. 6, when the amount of the oleophilic organic solvent added is too small relative to the amount of oil in the oil-containing scale, the oil removal rate in the oil-containing scale is reduced, which is not preferable. Further, if the amount of the oleophilic organic solvent added is too large, the oil removal rate is saturated, so that excessive addition is not necessary.

  Moreover, although demonstrated in Example 1, the dispersion | distribution of an oil-impregnated scale further improves by adding one or more types of hydrophilic organic solvents chosen from acetone, methanol, ethanol, propanol, and ethyl acetate with a lipophilic organic solvent. And the oil removal rate is improved. When adding a hydrophilic organic solvent, it is preferable to add together with the lipophilic organic solvent described in FIG. 2 in the extraction step ST2.

(Organic solvent phase separation step ST3)
In the organic solvent phase separation step ST3, the lipophilic organic solvent having the smallest specific gravity is separated from the mixture of the lipophilic organic solvent, the dispersion liquid (water, etc.), and the scale discharged from the extraction step ST2 using the difference in specific gravity. And discharge the lipophilic organic solvent. Specific gravity separation methods include, for example, centrifugal separation using a centrifugal force by a cyclone or a centrifugal separator, or natural separation using gravity.
As an example of an apparatus used in the organic solvent phase separation step ST3, a lipophilic organic solvent temporary storage tank (reference numeral in FIG. 10) located in the upper stage of a multistage countercurrent extraction tank (extraction process ST2) described later which is a continuous processing method. 32). Although the shaft of the stirring device 41 passes through the temporary lipophilic organic solvent storage tank 32, the temporary storage of the lipophilic organic solvent storage tank 32 is hardly stirred. Therefore, since the specific gravity of the lipophilic organic solvent is smaller than the specific gravity of water or scale, the lipophilic organic solvent rises and is temporarily stored in the lipophilic organic solvent temporary storage tank 32.

(Aqueous phase separation step ST4)
In the aqueous phase separation step ST4, the mixture of water and scale (scale dispersion) after separation from the lipophilic organic solvent in the organic solvent phase separation step ST3 is separated by specific gravity using an aqueous phase separation device, Solid-liquid separation into a scale phase containing coarse particles. Specific gravity separation methods include centrifugal separation using a centrifugal force by a cyclone or a centrifugal separator, or natural separation using gravity. As an example of the water phase separation apparatus used in the water phase separation step ST4, a closed type precipitation tank (reference numeral in FIG. 10), which is a continuous treatment method, is installed at the subsequent stage of a multistage countercurrent extraction tank described later. 37). This is a natural separation method using gravity. The lower part of the settling tank 37 is cone-shaped, and has a structure in which scales containing precipitated coarse particles tend to gather. Thereby, the scale dispersion is separated into an aqueous phase and a scale phase containing coarse particles. The aqueous phase is returned to the dispersion step ST1 and reused as a dispersion. The scale phase containing the precipitated coarse particles is sent to the next degassing step ST5. By recovering the scale phase containing the separated coarse particles, the oil content in the scale decreases. The scale phase containing the coarse particles separated and recovered is sent to the next deaeration step ST5.

  Due to the specific gravity separation, the scale, dispersion liquid (water), and lipophilic organic solvent are phase-separated in descending order of specific gravity. Since there is a gap between the scale particles in the scale phase, the dispersion liquid (water) and a small amount of A lipophilic organic solvent remains. Since this lipophilic organic solvent contains the oil extracted from the oil-impregnated scale in the extraction step ST2, if the residual amount of the lipophilic organic solvent is large, the oil concentration in the deoiled scale finally obtained is reduced. Enlarge.

  Therefore, instead of the natural separation method using gravity by the sedimentation tank 37 shown in FIG. 10, a centrifugal separation method is adopted, and a centrifugal force is applied to the oil-impregnated scale, so that the scale phase is consolidated, The particle gap is also reduced, and the amount of the oleophilic organic solvent remaining in the scale phase is pushed out together with water and reduced. That is, the oil concentration in the deoiling scale finally obtained can be reduced by applying a centrifugal force. FIG. 15 shows the influence of centrifugal force on the oil distribution ratio. From FIG. 15, in natural sedimentation (1G), the oil distribution ratio was 0.11, but when the centrifugal force is applied, the oil distribution ratio decreases. When the centrifugal force is 5G or more, the oil distribution ratio is 0.07 or less, and when the centrifugal force is 40G or more, the oil distribution ratio is about 0.05, which is almost constant. Therefore, it can be said that the centrifugal force is preferably 10 G or more, and more preferably 50 G or more. Examples of equipment for applying centrifugal force include a liquid cyclone or a centrifuge.

(Deaeration process ST5)
In the deaeration step ST5, the scale containing the coarse particles on the solid side after the solid-liquid separation in the aqueous phase separation step ST4 is heated and / or depressurized, whereby the parent adhered to the scale containing the coarse particles. The oily organic solvent is evaporated and separated from the scale containing coarse particles. An example of the deaeration device used in the deaeration process ST5 is shown in FIG. The scale 65 separated in the aqueous phase separation step ST4 is heated in a heating jacket 62 and placed in a degassing tank 61 that can be sealed, and mixed with an agitator 66 to such an extent that scales containing coarse particles do not precipitate. While reducing the atmospheric pressure in the deaeration tank 61 with the vacuum pump 63, steam or hot water is introduced into the heating jacket 62 to heat the scale containing coarse particles. The lipophilic organic solvent in the scale 65 containing coarse particles evaporates and is discharged from the vacuum pump 63. The evaporated lipophilic organic solvent is liquefied and regenerated in a distillation step ST7 described later.

  The lipophilic organic solvent to be used has a boiling point of less than 100 ° C. at normal pressure, and specifically, one or more kinds selected from diethyl ether, pentane, hexane, ethyl formate, and ethyl acetate are preferable, and pentane or hexane is more preferable. preferable. The boiling point of these organic solvents is 34 ° C to 77 ° C at normal pressure. Therefore, at normal pressure, the heating temperature may be set to a temperature 5 to 20 ° C. higher than the boiling point of the organic solvent, the heating temperature is less than 100 ° C., and the lipophilic organic solvent volatilizes preferentially over water. When the atmospheric pressure (internal pressure) in the deaeration tank 61 is reduced by a vacuum pump, the temperature is set to 5 to 20 ° C. higher than the boiling point at the internal pressure.

(Solid-liquid separation step ST6)
The supernatant oleophilic lipophilic organic solvent phase separated in the organic solvent phase separation step ST3 may contain a part of the floated scale. In particular, since the lipophilic organic solvent used in the present embodiment has a boiling point of less than 100 ° C., fine bubbles are likely to be generated during stirring, and the fine bubbles are attached to the scale. There are things to do. Alternatively, when an emulsion is formed with a lipophilic organic solvent and water and the scale component stays at the interface, the emulsion becomes metastable, the emulsion phase cannot be broken (cannot be demilked), and part of the scale May float in the supernatant phase (organic solvent phase).

  In this case, the supernatant oil-containing lipophilic organic solvent phase is separated into a supernatant and a scale by filtration or centrifugation. When the amount of scale in the supernatant oil-containing lipophilic organic solvent is small, the scale can be sufficiently separated by filtration, but when the amount of scale is large, it is preferable to separate the scale by centrifugation. By using such centrifugation, the scale floating from the lower aqueous phase to the upper organic solvent phase can be suppressed, and the thickness C (see FIG. 17) of the scale phase in the organic solvent phase can be reduced.

  This criterion cannot be determined unconditionally, and it is better to confirm it by experiments. However, it is possible to use filtration or centrifugation separately with a scale concentration of about 30-50 g / L in the supernatant as the boundary. good. Despite the fact that there is more scale than the boundary, when filtration is performed, the filtration resistance is large and it takes a long time to separate the scale.

Next, FIG. 16 shows the volume ratio of the scale in the supernatant oil-containing lipophilic organic solvent when the centrifugal force is applied to the supernatant oil-containing lipophilic organic solvent in which the scale component is floating. It is. The vertical axis in FIG. 16, “emulsion phase ratio”, uses A and C in FIG.
Emulsion phase rate = C / A (2)
This is the value expressed. From FIG. 16, the emulsion phase rate is slightly improved at 210 G to 86%, but at 500 G, the emulsion phase rate is greatly improved to 28%. Therefore, the magnitude of the centrifugal force is preferably 500 G or more, more preferably 1000 G or more. When it is less than 500 G, the scale contained in the supernatant often does not precipitate sufficiently. In addition, when a scale is not contained in a supernatant liquid, you may abbreviate | omit solid-liquid separation process ST6.

  Although the scale is contained, if the supernatant oil-containing lipophilic organic solvent is distilled in the distillation step ST7 which is the next step without solid-liquid separation of the supernatant oil-containing lipophilic organic solvent, troubles such as blockage due to scale increase. . Therefore, it is preferable to solve these problems by filtering or centrifuging the supernatant oil-containing lipophilic organic solvent in advance and separating the scale in the supernatant oil-containing lipophilic organic solvent.

(Measurement step ST10 of oil content and distillation step ST7)
Next, the oil content (hereinafter referred to as oil content) in the supernatant oil-containing lipophilic organic solvent phase is measured continuously or intermittently, and the organic solvent phase separation step is performed until the oil content does not reach a predetermined value. The supernatant oil-containing lipophilic organic solvent separated in ST3 is returned to the extraction step ST2.

  On the other hand, when the oil content reaches a predetermined value, the supernatant oil-containing oleophilic organic solvent is purified by distillation in whole by heating and / or depressurizing above the boiling point (distillation step ST7) and regenerating. The obtained lipophilic organic solvent is returned to the extraction step ST2. In addition, when the supernatant oil-containing lipophilic organic solvent is returned to the extraction step ST2 and reused, the shortage of the lipophilic organic solvent is supplemented from outside the system.

(Coarse particle recovery step ST8)
In the degassing step ST5, the lipophilic organic solvent in the scale containing the coarse particles is evaporated, and then the coarse particles mixed in the dispersion step ST1 are collected in the coarse particle collection step ST8. As the coarse particles for promoting the dispersion effect, coarse particles having a particle size of 0.5 to 3.0 mm are preferable, and since the particle size is sufficiently large, separation and collection can be easily performed by a separation operation using a sieve. Can do. The coarse particles separated and collected by sieving are mixed again with the oil-containing scale in the dispersion step ST1.

(Deoiling scale recovery step ST9)
The scale separated and recovered by sieving is recovered as a deoiling scale from which oil has been removed. Since excess water is present in the deoiling scale, it is dehydrated using a mechanical dehydrator such as a centrifuge, a filter press, or a vacuum dehydrator, or the scale is stacked in a yard and dehydrated by gravity.

  The present inventor can continuously or intermittently measure the absorbance or viscosity in the supernatant oil-containing lipophilic organic solvent after oil extraction in the measurement step ST10 even when the oil concentration of the oil-containing scale varies greatly. The oil concentration in the lipophilic organic solvent (corresponding to the above oil content) can be quantified, and based on the quantified value, the supernatant oil-impregnated organic solvent has the capacity to absorb the oil in the oil-impregnated scale. I found out that I can judge. As a result, the amount of oil extracted from the lipophilic organic solvent can always be maximized, and the distillation amount of the supernatant oil-impregnated lipophilic organic solvent can be minimized, so that the distillation apparatus can be reduced and the amount of heat required for distillation can be reduced. become.

  On the other hand, as described above, by controlling the oil concentration in the lipophilic organic solvent to a predetermined value or less, the oil content in the scale after deoiling can be controlled to a certain value or less. In this case, when the oil concentration in the lipophilic organic solvent becomes equal to or higher than a predetermined value, the oil is removed from the lipophilic organic solvent containing the oil in the distillation step ST7, and the lipophilic organic solvent returned to the extraction step ST2 is regenerated. To do.

  In the filtrate of the supernatant oil-containing lipophilic organic solvent when n-hexane is used as the lipophilic organic solvent and power oil 460 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., paraffinic hydrocarbon) is used as the lipophilic organic solvent in FIG. The relationship between oil concentration and absorbance (cell width: 10 mm) is shown. FIG. 8 shows the relationship between the oil concentration and the viscosity in the filtrate of the supernatant oil-containing oleophilic organic solvent.

  As shown in FIGS. 7 and 8, it can be seen that both the absorbance and the viscosity increase as the oil concentration in the supernatant oleophilic lipophilic organic solvent increases. The relationship between the oil concentration and the absorbance or viscosity varies depending on the type of oil and the type of lipophilic organic solvent to be used.

  Usually, since the oil is yellowish, the absorption wavelength when measuring the absorbance of the filtrate of the oleophilic lipophilic organic solvent may be around 350 to 500 nm. Moreover, it is also possible to measure the oil concentration in the supernatant oil-containing lipophilic organic solvent by gas chromatography measurement, liquid chromatography measurement, infrared absorption spectrum measurement, or fluorescence spectrum measurement.

  And it is preferable to perform distillation only when the oil content in the lipophilic organic solvent reaches a predetermined oil concentration. In FIG. 9, as an example, n-hexane is used as a lipophilic organic solvent, and n- when an oil component is separated from an oil-containing scale (containing 6.2% by mass of power oil 460 as an oil component). The relationship between the oil concentration contained in hexane (lipophilic organic solvent) and the oil removal rate is shown. As shown in FIG. 9, when the oil content concentration in n-hexane is 0.1 W / W or less by mass ratio, the oil removal rate shows a constant value of 80 to 85%, but in n-hexane more than this When the oil concentration is reached, the oil removal rate decreases. When it is desired to maintain the oil removal rate at 80% by mass or more, when the oil concentration in the n-hexane phase is 0.1 W / W or more by mass ratio, the supernatant oil-containing lipophilic organic solvent is distilled. . As shown in FIG. 7, this point is a point where the absorbance is 0.85 at an absorption wavelength of 400 nm and an absorption cell width of 10 mm, and the viscosity is a point of 1 mPa · s as shown in FIG.

  In the distillation step ST7, the oleophilic organic solvent can be distilled by heating and / or reducing the pressure of the supernatant oil-containing lipophilic organic solvent to the boiling point or higher. Since the boiling point of the oleophilic organic solvent is less than 100 ° C. at normal pressure, warm waste water (40 to 80 ° C.) generated in the factory can be used. The boiling point of the oleophilic organic solvent can be reduced to 80 ° C. or less by reducing the pressure, and by using the warm waste water, the oleophilic organic solvent can be recovered while reducing energy consumption. After distillation, although the oil component initially contained in the oil-containing scale and a small amount of water remain, it can be recovered as an oil component and used as fuel oil or regenerated oil.

  In the extraction step ST2, a multistage countercurrent type extraction tank in which the extraction tank is multistage and the scale dispersion containing the lipophilic organic solvent and coarse particles is a countercurrent type can be used.

  FIG. 10 is a schematic diagram showing a schematic configuration of an oil separation device 30 using the multistage countercurrent extraction tank according to the present embodiment. As shown in FIG. 10, the oil separation device 30 includes a multi-stage countercurrent extraction tank 31 (extraction tank), a slurrying facility 33 (scale dispersion generation device), and an oil content measurement device 35 (first oil content measurement device). ), A solid-liquid separation device (not shown), a distillation device 36, a settling tank 37 (water phase separation device), a deaeration device 38, and an oil content measurement device 40 (second oil content measurement device). And a coarse particle recovery device 42 (recovery device). The multistage countercurrent extraction tank 31 includes a lipophilic organic solvent temporary storage tank 32, a slurry zone 34, and a stirring device 41.

  For example, in the multistage counter-flow type extraction tank 31 shown in FIG. 10 (four stages in FIG. 10 and the first, second, third and fourth stages from the bottom), the single-stage extraction tank (mixing chamber) is in the vertical direction. It is a structure arranged side by side. The mixing chambers of each stage of the multistage counter-flow type extraction tank 31 are connected to a part of the upper surface and the lower surface, and the mixture is stirred in the mixing chamber for each stage by the stirring device 41. The shaft of the stirrer 41 passes through the opening connecting the mixing chambers of each stage in the vertical direction, passes through the gap between the opening and the shaft, and contains a lipophilic organic solvent and coarse particles in the mixing chamber. Can move gradually. If the gap between the opening and the shaft is too large, the agitation of each stage will affect each other, and the oleophilic organic solvent, oil-impregnated scale, and water in the mixing chamber of each stage will be in contact with the parent in the mixing chamber of another stage. Since it is easily mixed with the oily organic solvent, the oil-containing scale, and water, the oil concentration in the lipophilic organic solvent at each stage or the gradient of the oil concentration in the oil-containing scale is difficult to follow. Therefore, the gap between the opening and the shaft may be a gap that is not blocked by the oil-containing scale, the lipophilic organic solvent, and water.

  The oleophilic organic solvent is put into the first mixing chamber at the bottom of the multistage counter-current extraction tank 31, and since the specific gravity of the oleophilic organic solvent is smaller than that of water, the oleophilic organic solvent floats up, and the uppermost fourth stage. Are temporarily stored in the lipophilic organic solvent temporary storage tank 32 above the mixing chamber. On the other hand, the oil-impregnated scale is slurried with a mixing device in the slurrying device 33 and then put into the uppermost fourth mixing chamber of the multi-stage countercurrent extraction tank 31 to be mixed with the oleophilic organic solvent. The oil content in the oil-impregnated scale is extracted into the oleophilic organic solvent, and the oil-impregnated scale gradually moves to the first mixing chamber at the bottom and is mixed with the oleophilic organic solvent that does not contain oil. The oil component is extracted and finally reaches the slurry zone 34 at the bottom of the first-stage mixing chamber. Thus, in the multistage countercurrent extraction tank 31, the oleophilic organic solvent heading from below to above and the oil-containing scale (scale dispersion) heading from above to below contact in a multistage countercurrent manner. The multistage countercurrent extraction tank 31 can increase the oil removal rate as compared to the single-stage extraction tank.

  In order to measure the oil concentration in the oleophilic organic solvent containing oil accumulated in the oleophilic organic solvent temporary storage tank 32, a solid-liquid separator (not shown) is attached to the oleophilic organic solvent temporary storage tank 32. )), And an oil content measuring device 35 is provided. The solid-liquid separator separates the oleophilic lipophilic organic solvent separated by the multistage countercurrent extraction tank 31 and stored in the temporary storage tank 32 of the oleophilic organic solvent, and remains in the oleophilic oleophilic organic solvent. Solid scale is separated from the scale. As the solid-liquid separation device, for example, a filtration device that separates the scale component by filtering the oil-containing lipophilic organic solvent or a centrifugal separation device that separates the scale component by centrifuging the oil-containing lipophilic organic solvent is used. be able to. In addition, when a scale is hardly contained in the oleophilic lipophilic organic solvent, the solid-liquid separation device may be saved.

  The oil content measuring device 35 collects a part of the oil-containing lipophilic organic solvent from the temporary lipophilic organic solvent storage tank 32 and measures the absorbance or viscosity of the oil-containing lipophilic organic solvent continuously or intermittently. Based on the absorbance or viscosity thus measured, the oil concentration (oil content) of the oleophilic lipophilic organic solvent is obtained using the correlation obtained in advance by experiments (see FIGS. 7 and 8). Is possible.

  When the oil concentration of the oleophilic lipophilic organic solvent measured by the oil content measuring device 35 exceeds a predetermined value, the oleophilic oleophilic organic solvent is charged into the distillation device 36 until the oil concentration becomes less than the predetermined value. By operation, it is separated into a lipophilic organic solvent and an oil component.

  When the oil concentration of the oleophilic oleophilic organic solvent measured by the oleophilic measuring device 35 is not more than a predetermined value, the oleophilic oleophilic organic solvent in the oleophilic organic solvent temporary storage tank 32 is mixed in the uppermost fourth stage. Return to the chamber and extract the oil in the oil-containing scale into a lipophilic organic solvent. When returning to the lowermost first-stage mixing chamber, the oil concentration in the lipophilic organic solvent in the first-stage mixing chamber increases, and accordingly, the oil concentration in the scale after deoiling increases. As a result, it is difficult to stably reduce the oil concentration in the deoiling scale below a predetermined value.

  In addition, a pipe with a diameter of about 10 to 30 mm is connected to the lowermost first-stage mixing chamber, and a small amount of oil-containing oleophilic organic solvent collected in the upper part of the first-stage mixing chamber is sampled from the upper part of the inclined pipe. Then, the oil concentration in the oil-containing lipophilic organic solvent is continuously or intermittently measured by the oil content measuring device 40 capable of measuring the absorbance or the viscosity. Regarding the oil concentration in the organic solvent in the lowermost mixing chamber at the bottom and the oil concentration in the deoiling scale accumulated in the slurry zone 34, as described above, when the stirring Reynolds number is constant, the oil distribution ratio (= Oil concentration in the oil-impregnated scale after deoiling / oil concentration in the lipophilic organic solvent after deoiling) is almost constant. Therefore, if the oil concentration in the organic solvent increases, the oil content in the deoiling scale The concentration also increases. That is, by adjusting the amount of the oleophilic organic solvent regenerated by the distillation apparatus 36 that is introduced into the lowermost first-stage mixing chamber, the oil concentration in the lowermost first-stage oleophilic lipophilic organic solvent is adjusted. The oil concentration in the deoiling scale can be substantially controlled below the predetermined value. In order to reduce the oil concentration in the first-stage oil-impregnated lipophilic organic solvent in the lowermost part to a predetermined value or less, the lipophilic organic solvent regenerated by the distillation apparatus 36 put in the lowermost first-stage mixing chamber For example, the amount of charging can be controlled.

  The oil concentration in the oil-impregnated scale charged into the uppermost fourth-stage mixing chamber varies in the range of 1 to 10 several mass%. By suppressing the oil content concentration in the oil-containing lipophilic organic solvent in the lipophilic organic solvent temporary storage tank 32 that is upward from the uppermost fourth-stage mixing chamber, the uppermost fourth-stage mixing chamber The fluctuation of the oil concentration in the oil-impregnated scale charged into the mixing chamber is suppressed, and the oil-impregnated scale having an oil concentration of a predetermined value or less can be sent to the lower third mixing chamber.

  The water accumulated in the slurry zone 34 and the deoiling scale are transferred to a closed precipitation tank 37 and left in the precipitation tank 37 to be separated into supernatant water and precipitated deoiling scale. The supernatant water is sent to the slurrying equipment 33 and used for slurrying the oil-containing scale. On the other hand, the precipitated deoiling scale contains a slight amount of lipophilic organic solvent. Therefore, the precipitated deoiling scale is put into the degassing device 38, and decompressed or heated, and the oleophilic organic solvent remaining in the deoiling scale is volatilized and separated. Remove remaining organic solvent. The oleophilic organic solvent volatilized by the deaeration device 38 is put into the distillation device 36 and regenerated.

  When using a multistage counter-flow type extraction tank as a single-stage extraction tank, the first to third mixing chambers and the oil content measuring device 40 in the four-stage multi-stage countercurrent extraction tank of FIG. It can be used as a single-stage extraction tank.

  FIG. 18 illustrates an oil separation apparatus using a multistage countercurrent extraction tank (multistage countercurrent extraction apparatus (two stages) 100) having two or more mixing chambers according to the second embodiment of the present invention. It is a schematic diagram to do. FIG. 18 shows a case where the liquid cyclone (103, 105) and the centrifuge 108 are used in the organic solvent phase separation step (ST3) and the aqueous phase separation step (ST4).

  The dispersion step (ST1) is a slurrying tank 101, the extraction step (ST2) is a first stage extraction tank 102 and a second stage extraction tank 104, and the deaeration step (ST5) is a deaerator 106, coarse particle recovery step ( ST8) is executed by the coarse particle recovery device 112, the solid-liquid separation step (ST6) is executed by the centrifugal separator 108, the distillation step (ST7) is executed by the distillation device 109, and the oil content measurement step (ST10) is executed by the oil content measurement device 110. An apparatus for executing the recovery step (ST9) is not shown.

  As shown in FIG. 18, a multistage countercurrent extraction device (two stages) 100 includes a slurrying tank 101, a first stage extraction tank 102, a second stage extraction tank 104, a first stage hydrocyclone 103, A second-stage liquid cyclone 105, an oil separator 107, a centrifuge 108, a distillation device 109, a deaeration device 106, an oil content measurement device (110, 111), and a coarse particle recovery device 112 are provided.

  In the first stage extraction tank 102 and the second stage extraction tank 104, the object to be processed is vigorously stirred by the stirrer so that the stirring Reynolds number becomes 500 or more. In the first-stage liquid cyclone 103 and the second-stage liquid cyclone 105, the object to be processed is put into the liquid cyclone so that the object to be processed is subjected to a centrifugal force of 10 G or more, more preferably a centrifugal force of 50 G or more. . In the centrifuge 108, the centrifuge is selected so that a centrifugal force of 500G or more, more preferably 1000G or more is applied to the object to be processed.

  The oil-impregnated scale 120, water (dispersion liquid) 121, and coarse particles 133 are put into the slurrying tank 101 and mixed to form a slurry. The slurried oil-impregnated scale is put into the first stage extraction tank 102 and vigorously stirred with a stirrer to extract the oil content in the oil-impregnated scale into a lipophilic organic solvent. Thereafter, the oil-containing scale and the lipophilic organic solvent discharged from the first-stage extraction tank 102 are charged into the first-stage liquid cyclone 103, the overflow 122 containing the fine scale, the oil-containing lipophilic organic solvent and water, and coarse particles And underflow 123 containing scale. The overflow 122 is separated into water and an oleophilic organic solvent containing a fine scale by using the specific gravity difference in the oil separator 107. The water (dispersion liquid) 125 separated by the oil separator 107 and the underflow 123 separated by the first-stage liquid cyclone 103 are fed to the second-stage extraction tank 104 and regenerated by the distillation apparatus 109. It is mixed with the oily organic solvent 130 and vigorously stirred with a stirrer to further extract the oil in the oil-containing scale.

  Thereafter, the oil-impregnated scale and the lipophilic organic solvent discharged from the second-stage extraction tank 104 are charged into the second-stage liquid cyclone 105, and an overflow 129 containing fine scale, a lipophilic organic solvent and water, coarse particles, It isolate | separates into the underflow 128 containing a scale. The oil concentration in the lipophilic organic solvent phase in the overflow 129 is measured by the oil content measuring device 111. If the oil concentration is less than the predetermined value, the overflow 129 is returned to the second stage extraction tank 104 and the second stage. In the extraction tank 104, it is used to extract oil. On the other hand, if the oil concentration in the lipophilic organic solvent phase is equal to or higher than a predetermined value, the oil is returned to the first stage extraction tank 102 and used to extract the oil in the first stage extraction tank 102.

  Further, the underflow 128 separated by the second-stage liquid cyclone 105 contains a slight lipophilic organic solvent. Therefore, the underflow 128 including the deoiling scale is put into the degassing device 106, depressurized or heated, and the oleophilic organic solvent remaining in the deoiling scale is volatilized and separated, thereby removing the oil. Remove the lipophilic organic solvent remaining in the scale. The lipophilic organic solvent volatilized in the deaeration device 106 is input to the distillation device 109 and regenerated.

  In addition, the deoiling scale discharged from the deaerator 106 includes coarse particles 133 mixed in the slurrying tank 101. The coarse particles are collected by the coarse particle collecting apparatus 112, and again the slurrying tank. 101. The deoiling scale separated by the coarse particle collecting device 112 is discharged out of the system and collected together with the water (dispersed liquid) 121 mixed in the slurrying tank 101. The recovered deoiling scale is easy to dehydrate and can be dehydrated using a mechanical dehydration apparatus. Usually, water (dispersion liquid) is separated in a yard or a sedimentation tank.

  The oil concentration in the lipophilic organic solvent containing the fine scale separated by the oil separator 107 is measured by the oil content measuring device 110. If the oil content concentration is less than the predetermined value, the oil content is returned to the first extraction tank 102, If it is a predetermined value or more, it is sent to the centrifuge 108 and centrifuged with a centrifugal force of 500 G or more, more preferably 1000 G or more, to precipitate the fine scale and water floating in the lipophilic organic solvent. The precipitated fine scale and water (dispersion) 126 are returned to the first stage extraction tank 102.

  The oil-containing oleophilic organic solvent separated by the centrifugal separator 108 is sent to the distillation apparatus 109, where it is separated into the oleophilic organic solvent and the oil, and the oleophilic organic solvent is regenerated. The regenerated lipophilic organic solvent is put into the second-stage extraction tank 104 and used again to extract oil. The oil separated by the distillation device 109 is discharged out of the system and collected.

  FIG. 19 is a schematic view illustrating an oil separation device using a single-stage oil extraction device (single-stage oil separation device 150) having one mixing chamber according to the third embodiment of the present invention. In FIG. 19, in the organic solvent phase separation step (ST3) and the aqueous phase separation step (ST4), the first-stage liquid cyclone (153) and the second-stage liquid cyclone (154) are used, and the solid-liquid separation step (ST6). Shows a case where a third-stage liquid cyclone (155) is used.

  The dispersion step (ST1) is a slurrying tank 151, the extraction step (ST2) is an extraction tank 152, the deaeration step (ST5) is a deaeration device 156, the coarse particle recovery step (ST8) is a coarse particle recovery device 160, and a distillation. The step (ST7) is executed by the distillation device 158, the oil content measurement step (ST10) is executed by the oil content measurement device 157, and the device for executing the oil removal scale recovery step (ST9) is not shown.

  As shown in FIG. 19, the single-stage oil separation device 150 includes a slurrying tank 151, an extraction tank 152, a first-stage liquid cyclone 153, a second-stage liquid cyclone 154, a third-stage liquid cyclone 155, A distillation device 158, a deaeration device 156, an oil content measurement device 157, and a coarse particle recovery device 160 are provided.

  In the extraction tank 152, the object to be treated is vigorously stirred by the stirrer so that the stirring Reynolds number becomes 500 or more. In the first-stage liquid cyclone 153 and the second-stage liquid cyclone 154, the object to be processed is charged into the liquid cyclone so that a centrifugal force of 10 G or more, more preferably 50 G or more is applied to the object to be processed. In the third-stage liquid cyclone 155, the object to be processed is put into the liquid cyclone so that a centrifugal force of 500G or more, more preferably, 1000G or more is applied to the object to be processed.

  The oil-impregnated scale 171, water (dispersed liquid) 183, and coarse particles 181 are put into a slurrying tank 151, mixed, and slurried. The slurried oil-containing scale is put into the extraction tank 152 and strongly stirred by a stirrer to extract the oil content in the oil-containing scale into a lipophilic organic solvent. Thereafter, the oil-impregnated scale and the lipophilic organic solvent discharged from the extraction tank 152 are charged into the first-stage liquid cyclone 153, the overflow 173 containing the fine scale, the lipophilic organic solvent, and water (dispersion), and coarse particles And underflow 172 containing scale. The overflow 173 is put into the second-stage liquid cyclone 154 and separated into an overflow 175 containing a fine scale, a lipophilic organic solvent and water (dispersion), and an underflow 174 containing water (dispersion). The overflow 175 is charged into the third-stage hydrocyclone 155 and separated into an underflow 176 containing a fine scale and water (dispersed liquid) and an overflow 177 containing an oil-containing lipophilic organic solvent. The underflow 174 containing water (dispersion) from the second-stage liquid cyclone 154 and the underflow 176 containing fine scale and water (dispersion) from the third-stage liquid cyclone 155 are returned to the extraction tank 152. Is done.

  The oil concentration in the oil-containing lipophilic organic solvent phase in the overflow 177 containing the oil-containing lipophilic organic solvent from the third-stage liquid cyclone 155 is measured by the oil content measuring device 157, and if the oil content concentration is less than a predetermined value The overflow 177 is returned to the extraction tank 152, and if the oil concentration in the oil-containing oleophilic organic solvent phase is not less than a predetermined value, it is introduced into the distillation device 158 and separated into the oleophilic organic solvent and the oil component. Regenerate the organic solvent. The regenerated lipophilic organic solvent 178 is put into the extraction tank 152 and used again to extract oil. The oil separated by the distillation device 158 is discharged out of the system and collected.

  The underflow 172 separated by the first-stage liquid cyclone 153 contains a slight lipophilic organic solvent. Therefore, the underflow 172 including the deoiling scale is introduced into the degassing device 156, and the deoiling scale 156 is depressurized or heated to volatilize and separate the oleophilic organic solvent remaining in the deoiling scale. The organic solvent remaining in the scale is removed. The lipophilic organic solvent volatilized by the degassing device 156 is input to the distillation device 158 and regenerated.

  Further, the deoiling scale discharged from the deaeration device 156 contains coarse particles 181 mixed in the slurrying tank 151, and the coarse particles are collected by the coarse particle collecting device 160, and again the slurrying tank 151. In The deoiling scale separated by the coarse particle collecting device 160 is discharged out of the system and collected together with the water (dispersed liquid) 183 mixed in the slurrying tank 151. The recovered deoiling scale is easy to dehydrate and usually separates water in a yard or settling tank.

  Next, examples of the present invention will be described. In addition, the following Examples are only the example conditions adopted in order to confirm the feasibility and effects of the present invention, and the present invention is not limited to the conditions of the following Examples.

Example 1
The oil-impregnated scale used in Example 1 is an oil-impregnated scale obtained by dehydrating the oil-impregnated scale generated in the rolling process of the steel mill at the steel mill with a centrifuge, and having different average particle diameters (volume basis). A sample was used.

  Oil-impregnated scale containing oil-impregnated scale (15 g as a solid) and coarse particles (scale) with a particle size of 0.5 to 2.5 mm and no oil contained in 300 mL glass container that can be sealed and stirred inside with a stirrer Was added at an addition rate of 0 to 8% by mass with respect to the mass (total mass including oil and moisture). Next, pure water was added, and then acetone (which may not be added) as a hydrophilic organic solvent and n-pentane as a lipophilic organic solvent were sealed and sealed, and then stirred with a stirrer for 30 minutes. At that time, the stirring Reynolds number was 550 (see Table 1). After stirring, the mixture was allowed to stand for 60 minutes, and then the stopper was temporarily opened, the glass container was tilted obliquely, and almost all of the supernatant oil-containing lipophilic organic solvent phase was recovered. After separation of the supernatant oil-containing lipophilic organic solvent phase, the aqueous phase remaining in the container and the precipitated scale were subjected to suction filtration using filter paper 5C, and separated into an aqueous phase portion and a scale portion. The scale portion was dried at 105 ° C. for 2 hours, and the oil concentration was measured. The oil content was measured by extracting the oil content from the scale by a Soxhlet extraction method using n-hexane as the extraction solvent, and quantifying the oil content by the gravimetric method. In addition, the compounding conditions of pure water, acetone, and n-pentane are shown in Table 1. Table 1 shows the oil concentration and the oil removal rate in the deoiling scale.

1) Influence of Coarse Particle Addition From Comparative Examples 1-5 and Examples 1-1 to 1-4, the influence of the coarse particle addition ratio into the oil-containing scale on the oil removal rate will be described. When the addition rate of coarse particles is increased, the oil removal rate is increased. Even when 5% by mass or more of coarse particles are added, the improvement in oil removal rate is small, and the addition rate of coarse particles is preferably 1 to 8% by mass. It is considered that by adding coarse particles to the oil-containing aggregates containing the oil in the gaps between the particles, the coarse particles have increased the chance of contact between the oil in the aggregates and n-pentane, and the oil has been extracted.

  Moreover, in Comparative Example 1-1 to Comparative Example 1-6, Comparative Example 1-8, and Comparative Example 1-9 in which coarse particles are not added, the oil removal rate increases as the average particle size of the oil-containing scale increases. Yes. It is also considered that the oil removal rate has increased for the same reason as when coarse particles are added.

  In the present invention, an oil-impregnated scale having an average particle diameter of 50 μm or less is targeted. In Comparative Example 1-1 to Comparative Example 1-3, since the average particle diameter of the oil-containing scale is more than 50 μm, which is outside the scope of the present invention, an oil removal rate of 25% by mass or more is obtained. On the other hand, in Comparative Example 1-4 to Comparative Example 1-6, Comparative Example 1-8, and Comparative Example 1-9, the average particle size of the oil-impregnated scale is 50 μm or less, which is the object of the present invention, but coarse particles are used. Since it is not added, oil removal cannot be suitably performed, and only a low oil removal rate of 11.6% by mass or less is obtained.

  On the other hand, in Example 1-1 to Example 1-4 and Example 1-6 to Example 1-19 of the present invention, the average particle size of the oil-impregnated scale is 50 μm or less, which is the subject of the present invention. However, despite the sufficiently low value of 21 μm, the dispersibility of the oil-containing scale can be improved by adding coarse particles, so that an oil content removal rate of 13.7% by mass or more is obtained.

  Further, when Comparative Example 1-8 and Example 1-5 were compared, or when Comparative Example 1-9 and Example 1-6 were compared, both were the same except for the presence or absence of addition of coarse particles. It is a condition. Here, the oil removal rate of 6.7% by mass in Example 1-5 is approximately three times the oil removal rate of 2.2% by mass of Comparative Example 1-8. Further, the oil removal rate of 13.7% by mass in Example 1-6 is approximately twice the oil removal rate of 6.7% by mass in Comparative Example 1-9. As can be seen from these comparison results, it can be said that the addition of coarse particles has proved that the oil removal rate can be improved by a factor of 2 or more.

  In Examples 1-5, 1-6, Comparative Examples 1-8, and Comparative Examples 1-9, the ratio of the amount of n-pentane (lipophilic organic solvent) added to the scale oil (pentane / oil ratio) ) Is very low as 0.4 or 1.0, and the amount of lipophilic organic solvent added is significantly less than in Comparative Examples 1-4 and 1-5, so scale oil is extracted into the lipophilic organic solvent. This is a very severe condition. Even under such conditions, in Examples 1-5 and 1-6, oil removal rates of 6.7% by mass and 13.7% by mass were obtained, and the difference in the amount of lipophilic organic solvent added was Considering it, it can be said that a superior oil removing effect was obtained even when compared with Comparative Examples 1-4 and 1-5.

2) Influence of the addition amount of n-pentane on the oil content in the oil-containing scale From Comparative Example 1-7, Example 1-3, Example 1-5, and Example 1-6 to Example 1-12 The effect of the ratio of n-pentane addition amount (lipophilic organic solvent) (also referred to as pentane / oil content ratio) to the amount of oil in the oil-containing scale will be described. It can be said that the oil content in the oil-impregnated scale is reduced by adding n-pentane so that the pentane / oil content ratio is 1 (W / W) or more. When the pentane / oil ratio increases, the oil removal rate increases. When the pentane / oil ratio exceeds 5 (W / W), the oil removal rate improves to 50% by mass, and the oil separation effect from the oil-containing scale Can be said to be high. From this, it can be said that the pentane / oil content ratio is preferably 1 (W / W) or more, and more preferably 5 (W / W) or more, for oil separation from the oil-containing scale. Therefore, it is preferable to add a lipophilic organic solvent having a mass ratio of 1 time (W / W) or more, more preferably 5 times (W / W) or more, to the scale dispersion with respect to the amount of oil in the oil-containing scale. It can be said.

  Further, from Examples 1-8 to 1-12, it can be seen that even when the pentane / oil ratio is 50 (W / W) or more, the oil removal rate is saturated and does not increase so much. Therefore, from the viewpoint of efficient use of the oleophilic organic solvent, the oleophilic organic solvent / oil content ratio is less than 50 (W / W), that is, 50 times the mass ratio of the oil content in the oil-containing scale (W It can be said that it is preferable to add a lipophilic organic solvent of less than / W) to the scale dispersion.

3) Effect of addition amount of acetone on solid content of oil-impregnated scale According to Example 1-3 and Examples 1-33 to Example 1-15, acetone (hydrophilic organic solvent) with respect to the solid content in the oil-impregnated scale ) Of the added amount (also referred to as acetone / solids ratio). As the acetone / solid ratio increases, the dispersibility of the oil-impregnated scale improves and the oil removal rate increases. In the case of this oil-impregnated scale, when the acetone / solid ratio exceeds 0.2 (W / W), the oil removal rate exceeds 70% by mass.

4) Effect of water addition amount on solid content of oil-impregnated scale According to Example 1-3, Example 1-16 to Example 1-19, and Reference Example 1-20, the amount of solid matter in the oil-impregnated scale is The influence of the ratio of the amount of water added (also referred to as water / solid ratio) will be described. Here, the added amount of water refers to the sum of the added amount of water and the added amount of hydrophilic solvent (acetone) shown in Table 1. When the water / solid ratio is less than 1.5 (W / W), the volume of the aqueous phase portion becomes small at the time of standing, and the aqueous phase is hidden (duplicated) in the precipitation scale phase, The oil-impregnated lipophilic organic solvent phase was present in contact with the upper part of the precipitation scale phase.

  On the other hand, when the water / solid ratio exceeds 1.5 (W / W), the volume of the water phase portion becomes large at the time of standing, and the water phase and the supernatant oil-impregnated lipophilic organic solvent above the precipitation scale phase. There will be an interface with the phase. As a result, the supernatant oil-impregnated lipophilic organic solvent phase can be easily separated, the oil-impregnated lipophilic organic solvent phase does not remain in the precipitation scale phase, and the oil removal rate of the oil-impregnated scale is improved. From the above, it can be said that a water / solid ratio of 1.5 (W / W) or more is optimal for oil separation from an oil-containing scale.

(Example 2)
In Example 2, the oil content separation operation of the oil-impregnated scale was performed using the multistage countercurrent extraction tank 31 (four stages, 0.4 L × 4 stages) shown in FIG. The stirring Reynolds number in the mixing chamber of each stage was 3200. In the experiment, 5% by mass (W / W) of coarse particles (scale) having a particle diameter of 0.5 to 2.5 mm with respect to the solid content of the oil-impregnated scale was added to the oil-impregnated scale (Table 2) previously slurried. Were mixed and continuously charged into the multistage countercurrent extraction tank 31 at 280 ml / min. The residence time of the oil-impregnated scale in the multistage countercurrent extraction tank 31 was about 4 minutes. N-Hexane was used as a lipophilic organic solvent. Oil concentration in n-hexane in the first mixing chamber at the bottom of the multi-stage countercurrent extraction tank 31 (also referred to as first-stage oil concentration) and n-hexane in the uppermost lipophilic organic solvent zone The oil concentration in the inside (also referred to as the fourth-stage oil concentration) was continuously measured with an absorptiometer. The target value of the oil concentration in the deoiling scale after the treatment was 0.4% by mass. In order to reduce the oil concentration in the scale to 0.4% by mass or less, it is necessary to maintain the first stage oil concentration at 3.3% by mass or less from a preliminary experiment, and this predetermined value (3.3% by mass) ) The flow rate was adjusted so that the amount of n-hexane not containing oil contained in the first-stage mixing chamber was within the range of 10 to 20 ml / min so that the following could be maintained. In addition, when the predetermined value (33% by mass) or more is reached so that the concentration of the fourth-stage oil can be maintained at 33% by mass or less, the fourth-stage mixing is performed from the uppermost lipophilic organic solvent temporary storage tank 32. The return to the chamber was stopped, the system was discharged out of the system, and the distillation operation was performed by the distillation device 36 to separate into n-hexane and oil. The deoiled scale accumulated in the slurry zone 34 was transferred to a closed settling tank 37, left in the settling tank 37, separated into supernatant water and deoiled scale, and the supernatant water was discarded. On the other hand, the precipitated deoiling scale was put into a deaeration device 38, and the pressure was reduced to 200 mmHg, and n-hexane remaining in the deoiling scale was volatilized to obtain a slurry-like deoiling scale. The oil content in the deoiling scale was measured, and the oil separation performance from the oil-containing scale was evaluated.

  As a result, the oil content concentration in the deoiling scale was an average of 0.39% by mass (0.26 to 0.5% by mass), and the target value of 0.4% by mass could be achieved.

  Moreover, the slurry-like deoiling scale was wet-sieved with a sieve having an opening of 0.5 mm, and 96% of the coarse particles to which 0.5 mm or more of coarse particles were initially added could be easily recovered.

Example 3
In Example 3, the oil content separation operation of the oil-impregnated scale was performed using a multistage countercurrent extraction device (two stages) 100 (100 L × two stages) shown in FIG. The stirring Reynolds number in the first extraction tank 102 and the second extraction tank 104 was about 3200. The hydrocyclone size was selected so that the centrifugal force in the first-stage hydrocyclone 103 and the second-stage hydrocyclone 105 was about 250G. Moreover, the centrifugal force in the centrifuge 108 was 3000G.

  In the experiment, 5% by mass (W / W) of coarse particles (scale) having a particle diameter of 0.5 to 2.5 mm with respect to the solid content of the oil-impregnated scale was mixed with the oil-impregnated scale (Table 3) that had been slurried in advance. The multistage countercurrent extraction device (two stages) 100 was continuously charged at about 13 L / min.

  The oil-impregnated scale used in Example 3 has an average particle size smaller than that of the oil-impregnated scale used in Example 2 and contains 5% of particles of 1 μm or less that are considered to float easily in the hexane phase. The scale is likely to surface. The residence time of the oil-impregnated scale in the first stage extraction tank 102 and the second stage extraction tank 104 was about 3 min. N-Hexane was used as a lipophilic organic solvent. Oil concentration in n-hexane discharged from the first-stage extraction tank 102 (also referred to as first-stage oil concentration) and oil concentration in n-hexane discharged from the second-stage extraction tank 104 (second-stage oil content) Concentration) was continuously measured with oil content measuring devices 110 and 111 (absorptiometers). The target value of the oil concentration in the deoiling scale after the treatment was 0.4% by mass. In order to reduce the oil concentration in the scale to 0.4% by mass or less, it is necessary to maintain the second-stage oil concentration at 3.3% by mass or less from a preliminary experiment. This predetermined value (3.3% by mass) ) The flow rate was adjusted within the range of 0.2 to 0.8 L / min of the input amount of n-hexane not containing oil to the second stage extraction tank 104 so that it could be maintained below.

  Further, in order to maintain the first-stage oil concentration at 33% by mass or less, when the value exceeds the predetermined value (33% by mass), the return to the first-stage extraction tank 102 is stopped and the centrifuge 108 is stopped. The fine scale floating in the n-hexane phase is precipitated by centrifugal force, the precipitated fine scale is put into the first extraction tank 102, and the oil-containing n-hexane excluding the fine scale is Then, the solution was sent to the distillation apparatus 109 and subjected to distillation operation to separate into n-hexane and oil.

  The recovered n-hexane was again charged into the second extraction tank 104 while adjusting the flow rate as described above. The deoiling scale discharged from the second-stage liquid cyclone 105 with the underflow 128 is depressurized to 200 mmHg by the degassing device 106 (dehexane device), the remaining hexane is evaporated, and then the slurry-like deoiling scale is obtained. 132 was recovered. The oil content in the deoiling scale 132 was measured, and the oil separation performance from the oil-containing scale was evaluated.

  As a result, the oil concentration in the deoiling scale 132 was an average of 0.39 mass% (0.27 to 0.53 mass%), and the target value of 0.4 mass% could be achieved. Further, the slurry-like deoiling scale 132 was wet-sieved with a sieve having an opening of 0.5 mm, and 97% of the coarse particles having 0.5 mm or more of the coarse particles initially added could be easily recovered. . Moreover, the emulsion phase rate of the oil-containing n-hexane containing fine scale charged into the centrifuge 108 was 95 to 100%, but the emulsion phase rate after the treatment with the centrifuge 108 was 8 to 12%. Yes, the emulsion phase rate could be reduced sufficiently.

The n-hexane containing the oil component on which the fine scale floats is put into the centrifuge 108 in FIG. 18, and the pressure is ² kgf / cm ^{2 with} a pressure filtration device (filtration area 100 cm ² ). When it was filtered under pressure, it took 165 minutes to filter 1 L. From this value, when pressure filtration is performed at 2 kgf / cm ² in Example 3, a filtration device requiring a filtration area of 43 m ² is required, and a large device is required. Therefore, when a large amount of scale floats in the hexane phase, it can be said that a scale separation method using centrifugal force is preferable to filtration.

Example 4
In Example 4, the oil content separation operation of the oil-impregnated scale was performed using the single-stage type oil content separation device 150 (97 L × 1 stage) shown in FIG. The stirring Reynolds number in the extraction tank 152 was about 3200. The hydrocyclone size was selected so that the centrifugal forces in the first to third stage hydrocyclones (153, 154, 155) were about 250 G, about 250 G, and about 3000 G, respectively.

  In the experiment, 5% by mass (W / W) of coarse particles (scale) having a particle diameter of 0.5 to 2.5 mm with respect to the solid content of the oil-impregnated scale was mixed with the oil-impregnated scale (Table 3) that had been slurried in advance. The single-stage extraction tank 150 was continuously charged at about 13 L / min.

  The oil-impregnated scale used in Example 4 has an average particle size smaller than that of the oil-impregnated scale used in Example 2 and contains 5% of particles having a size of 1 μm or less which is considered to easily float on the hexane phase. It was assumed that the scale was likely to surface. The residence time of the oil-containing scale in the extraction tank 152 was about 3 minutes. N-Hexane was used as a lipophilic organic solvent. The oil concentration in n-hexane discharged from the extraction tank 152 was continuously measured with an oil content measuring device 157 (absorptiometer). The target value of the oil concentration in the deoiling scale 179 after the treatment was 0.4% by mass. In order to reduce the oil concentration in the scale to 0.4% by mass or less, from a preliminary experiment, the predetermined value (3.3% by mass) is set so that the oil concentration in n-hexane can be maintained at 3.3% by mass or less. ) In the case of the above, the return to the extraction tank 152 was stopped, the solution was sent to the distillation apparatus 158, and the distillation operation was performed to separate n-hexane and oil.

  The collected n-hexane was put into the extraction tank 152 again. The deoiling scale discharged from the first-stage liquid cyclone 153 in the underflow 172 is depressurized to 200 mmHg by a degassing device 156 (dehexane device), and the remaining hexane is evaporated, and then a slurry-like deoiling scale is obtained. 179 was recovered. The oil content in the oil removal scale 179 was measured, and the oil separation performance from the oil-containing scale was evaluated.

  As a result, the oil concentration in the deoiling scale was an average of 0.4% by mass (0.23 to 0.55% by mass), and the target value of 0.4% by mass could be achieved. Moreover, the slurry-like deoiling scale was wet-sieved with a sieve having an opening of 0.5 mm, and 96% of the coarse particles to which 0.5 mm or more of coarse particles were initially added could be easily recovered.

  The emulsion phase ratio of the oil-containing n-hexane containing fine scale charged into the third-stage liquid cyclone 155 was 93 to 100%, but the emulsion phase ratio after the treatment with the third-stage liquid cyclone 155 was 7%. It was ˜11%, and the emulsion phase rate could be sufficiently reduced.

  In Example 4, only the liquid cyclone was used. However, as in Example 3, a centrifuge can be used, and the same deoiling effect can be obtained.

  The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious that a person having ordinary knowledge in the technical field to which the present invention pertains can come up with various changes or modifications within the scope of the technical idea described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.

30: Oil separator 31: Multistage countercurrent extraction tank 32: Temporary storage tank for lipophilic organic solvent 33: Slurry equipment 34: Slurry zone 35: Oil content measuring device 36: Distillation device 37: Precipitation tank 38: Deaeration device 40 : Oil content measuring device 41: Stirring device 42: Coarse particle recovery device (sieving)
51: Belt conveyor 52: Stirrer 53: Slurry tank 54: Pump 55: Oil-impregnated scale 56: Water 57: Coarse particles 61: Degassing tank 62: Warming jacket 63: Vacuum pump 64: Pump 65: Scale 66: Stirrer 100: Multistage counter-current type extraction device (2 stages)
101: Slurry tank 102: First stage extraction tank 103: First stage liquid cyclone 104: Second stage extraction cyclone 105: Second stage liquid cyclone 106: Deaerator 107: Oil separator 108: Centrifuge 109: Distillation Device 110: Oil content measuring device 111: Oil content measuring device 112: Switching valve 113: Switching valve 120: Oil-containing scale 121: Water (dispersed liquid)
122: Overflow 123: Underflow 125: Water (dispersion)
126: Water and fine scale 127: Oil-containing lipophilic organic solvent 128: Underflow 129: Overflow 130: Recycled lipophilic organic solvent 131: Oil content 132: Deoiled scale and water 133: Coarse particles 134: Coarse particles 135: Fine scale Oil-containing lipophilic organic solvent 150: Single stage oil extraction device 151: Slurry tank 152: Extraction tank 153: First stage liquid cyclone 154: Second stage liquid cyclone 155: Third stage liquid cyclone 156: Deaerator 157 : Oil content measuring device 158: Distillation device 159: Switching valve 160: Coarse particle recovery device 161: Oil-containing lipophilic organic solvent 171: Oil-containing scale 172: Underflow 173: Overflow 174: Underflow 175: Overflow 176: Underflow 177: Overflow 78: Play oleophilic organic solvent 179: de-oiling Scale 180: Oil 181: coarse particles 182: coarse particles 183: water (dispersion)

Claims (29)

In an oil separation method for separating the oil from an oil-containing scale containing an oil and moisture and having an average particle size of 50 μm or less,
Adding a coarse particle larger than the average particle diameter of the oil-impregnated scale to the oil-impregnated scale, and immersing and dispersing the oil-impregnated scale and the coarse particle in a dispersion containing water, thereby obtaining a scale dispersion;
An extraction step of adding a lipophilic organic solvent to the scale dispersion, mixing and stirring, and extracting the oil contained in the oil-containing scale into the lipophilic organic solvent;
An organic solvent that separates the mixed liquid of the scale dispersion and the oil-containing lipophilic organic solvent after the extraction step into the oil-containing lipophilic organic solvent and the scale dispersion containing the coarse particles using a difference in specific gravity. A phase separation process;
An aqueous phase separation step for solid-liquid separation of the scale dispersion after the organic solvent phase separation step into a scale phase containing the coarse particles and an aqueous phase due to a specific gravity difference;
A coarse particle recovery step of recovering the coarse particles from the scale phase after the aqueous phase separation step;
A deoiling scale recovery step of recovering the scale phase after the coarse particles are recovered in the coarse particle recovery step as a deoiling scale;
An oil content measurement step for continuously or intermittently measuring the oil content in the oil-containing lipophilic organic solvent separated in the organic solvent phase separation step;
Distilling the oil-containing lipophilic organic solvent separated in the organic solvent phase separation step to regenerate the lipophilic organic solvent not containing oil and recovering the oil,
Including
When the oil content measured in the oil content measurement step is not more than a predetermined value, the oil-containing lipophilic organic solvent separated in the organic solvent phase separation step is returned to the extraction step, and the oil content rate Is greater than the predetermined value, the oil-containing lipophilic organic solvent separated in the organic solvent phase separation step is distilled to lower the oil content to the predetermined value or less, and then to the extraction step. An oil separation method characterized by returning the oil.   The particle diameter of the coarse particles is in a range of 0.5 to 3.0 mm, and the addition ratio of the coarse particles to the oil-impregnated scale is 1 to 8% by mass. The oil separation method as described.   In the extraction step, when the mixed liquid composed of the lipophilic organic solvent and the scale dispersion is stirred, the stirring Reynolds number (Re) of the mixed liquid is in the range of 500 to 40,000. The oil-separating method according to claim 1 or 2.   4. The oil component separation according to claim 1, wherein in the water phase separation step, solid-liquid separation is performed using a centrifugal force into a scale phase containing the coarse particles and an aqueous phase. Method.   The oil separation method according to claim 4, wherein the centrifugal force is 10 G or more. In the extraction step, using a multi-stage countercurrent extraction tank having two or more mixing chambers, the lipophilic organic solvent and the scale dispersion are mixed and stirred,
6. The oil separation according to claim 1, wherein the lipophilic organic solvent and the scale dispersion are brought into contact in a multistage countercurrent manner in the multistage countercurrent extraction tank. Method.
In the multi-stage countercurrent extraction tank, the oil content of the oleophilic lipophilic organic solvent in the final-stage mixing chamber where the oil content in the oil-containing scale is the lowest is measured continuously or intermittently, and the oil content is predetermined. The oil separation method according to claim 6, wherein an input amount of the lipophilic organic solvent not containing oil to the mixing chamber at the final stage is controlled so as to be equal to or less than the value.   In the oil content measurement step, in order to measure the oil content in the oil-containing lipophilic organic solvent, the absorbance or viscosity of the oil-containing lipophilic organic solvent is measured, and the oil content is based on the absorbance or the viscosity. The oil separation method according to any one of claims 1 to 7, wherein the oil content separation method is obtained.   In the extraction step, the lipophilic organic solvent having a mass ratio of 1 time (W / W) to less than 50 times (W / W) with respect to the amount of oil in the oil-containing scale is added to the scale dispersion. The oil separation method according to any one of claims 1 to 8, wherein the oil separation method is characterized. A degassing step of volatile separation of the lipophilic organic solvent remaining in the scale phase after the aqueous phase separation step;
A solid-liquid separation step of separating the scale remaining in the oil-containing lipophilic organic solvent separated in the organic solvent phase separation step;
Further including
In the distillation step, the oil component is included by distilling the lipophilic organic solvent volatilely separated in the degassing step and the oleophilic lipophilic organic solvent after being separated in the solid-liquid separation step. Reclaim no lipophilic organic solvent, and recover the oil
The oil content measurement step is characterized by continuously or intermittently measuring the oil content in the oil-containing lipophilic organic solvent after being separated in the solid-liquid separation step. 2. The oil separation method according to claim 1.   The oil component separation method according to claim 10, wherein in the solid-liquid separation step, the scale component is separated from the oil-containing lipophilic organic solvent using filtration or centrifugal force.   The oil separation method according to claim 11, wherein the centrifugal force is 500 G or more.   The oil-separating method according to any one of claims 1 to 12, wherein the lipophilic organic solvent has a boiling point at normal pressure of less than 100 ° C and is liquid at normal temperature and pressure.   14. The water phase separation process according to claim 1, wherein the water phase separated from the scale phase is returned to the dispersion process and reused as the dispersion. Oil separation method. In an oil separation device that separates the oil from an oil-containing scale containing an oil and moisture and having an average particle size of 50 μm or less,
A scale dispersion generating device for generating a scale dispersion by mixing the oil-containing scale, coarse particles larger than the average particle diameter of the oil-containing scale, and a dispersion containing water;
In the mixing chamber, the lipophilic organic solvent and the scale dispersion are mixed and stirred, and the oil contained in the oil-containing scale is extracted into the lipophilic organic solvent, and the mixture of the scale dispersion and the oil-containing lipophilic organic solvent. An extraction tank that separates the oil-containing lipophilic organic solvent and the scale dispersion containing the coarse particles using a specific gravity difference;
An aqueous phase separation device for solid-liquid separation of the scale dispersion discharged from the extraction tank into a scale phase containing the coarse particles and an aqueous phase;
A recovery device for recovering the coarse particles from the scale phase discharged from the aqueous phase separator, and recovering the scale phase after the coarse particles are recovered as a deoiling scale;
A first oil content measuring device for measuring the oil content in the oil-containing lipophilic organic solvent separated by the extraction tank;
A distillation apparatus for regenerating the lipophilic organic solvent not containing oil and recovering the oil by distilling the oil-containing lipophilic organic solvent separated by the extraction tank;
With
When the oil content rate measured by the first oil content measuring device is below a predetermined value, the oil-containing lipophilic organic solvent separated by the extraction tank is returned to the mixing chamber of the extraction tank, When the oil content is larger than the predetermined value, the oil-containing lipophilic organic solvent separated by the extraction tank is distilled by the distillation apparatus, thereby reducing the oil content to the predetermined value or less. An oil content separation device, which is returned to the mixing chamber of the extraction tank.   The particle diameter of the coarse particles is in a range of 0.5 to 3.0 mm, and the addition ratio of the coarse particles with respect to the oil-impregnated scale is 1 to 8% by mass. The oil content separation apparatus as described.   The extraction tank stirs the mixed solution so that a stirring Reynolds number (Re) of the mixed solution composed of the lipophilic organic solvent and the scale dispersion is in a range of 500 to 40,000. The oil separator according to claim 15 or 16.   The said water phase separation apparatus is a precipitation tank which solid-liquid separates the said scale dispersion liquid into the scale phase and water phase containing the said coarse particle by specific gravity difference, The any one of Claims 15-17 characterized by the above-mentioned. The oil separator according to claim 1.   The water phase separation device is a cyclone or a centrifugal separator that uses a centrifugal force to solid-liquid separate the scale dispersion into a scale phase containing the coarse particles and an aqueous phase. The oil separator according to any one of 15 to 18.   The oil separation device according to claim 19, wherein the centrifugal force is 10G or more. The extraction tank is a multistage countercurrent extraction tank having a mixing chamber of two or more stages,
The oil separation according to any one of claims 15 to 20, wherein the lipophilic organic solvent and the scale dispersion are brought into contact with each other in a multistage countercurrent type in the multistage countercurrent extraction tank. apparatus. The apparatus further comprises a second oil content measuring device that continuously or intermittently measures the oil content of the oil-containing lipophilic organic solvent in the final-stage mixing chamber in which the oil content in the oil-containing scale is lowest in the multi-stage countercurrent extraction tank. ,
The amount of the oleophilic organic solvent not containing oil is controlled with respect to the final-stage mixing chamber so that the oil content measured by the second oil content measuring device is a predetermined value or less. The oil separator according to claim 21.   The first oil content measuring device measures the absorbance or viscosity of the oil-containing lipophilic organic solvent in order to measure the oil content in the oil-containing lipophilic organic solvent, and based on the absorbance or the viscosity, The oil content separation device according to any one of claims 15 to 22, wherein an oil content rate is obtained.   In the extraction tank, the lipophilic organic solvent having a mass ratio of 1 time (W / W) to less than 50 times (W / W) with respect to the amount of oil in the oil-containing scale is added to the scale dispersion. The oil separator according to any one of claims 15 to 23, characterized in that it is characterized in that: A deaeration device that volatilizes and separates the lipophilic organic solvent remaining in the scale phase discharged from the aqueous phase separator;
A solid-liquid separator that separates the scale remaining in the oil-containing lipophilic organic solvent separated by the extraction tank;
Further including
The oleophilic organic solvent volatilely separated by the degassing device and the oleophilic oleophilic organic solvent separated by the solid-liquid separation device are distilled by the distillation device, so that the oleophilicity does not contain the oil component. Regenerate the organic solvent and recover the oil,
The first oil content measuring device continuously or intermittently measures the oil content in the oil-containing lipophilic organic solvent separated by the solid-liquid separation device. The oil content separation apparatus of any one of Claims.   26. The oil separation method according to claim 25, wherein the solid-liquid separation device is a filtration device or a centrifugal separation device.   27. The centrifugal separator according to claim 26, wherein the centrifugal separation device separates the scale component from the oleophilic lipophilic organic solvent using a centrifugal force, and the centrifugal force has a magnitude of 500G or more. Oil separator.   The oil-separating apparatus according to any one of claims 15 to 27, wherein the lipophilic organic solvent has a boiling point at normal pressure of less than 100 ° C and is liquid at normal temperature and pressure. 29. The water phase separated from the scale phase by the water phase separator is returned to the scale dispersion generator and reused as the dispersion. The oil-separation device described in 1.