JP2011144259A - Apparatus for removing phosphoric ester in waste oil and treatment system of waste oil containing pcb - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus for removing a phosphoric ester in waste oil and a treatment system of waste oil containing PCB. <P>SOLUTION: This apparatus includes: a delivery tank 14 which delivers a predetermined amount of waste oil 13 including a phosphoric ester 12; a mixing tank 18 equipped with a stirring means 17 which mixes an alkali agent 16 from an alkali agent delivery tank 15 with the waste oil 13 delivered from the delivery tank 14 through a line L<SB>2</SB>; an analysis part 22 which analyzes phosphorus (P) or phosphoric acid (H<SB>3</SB>PO<SB>4</SB>) in the reaction liquid 19 in which the alkali agent 16 is mixed with the waste oil 13; a circulation line L<SB>4</SB>which returns the reaction liquid 19 to the mixing tank 18; a stationary tank 25 which allows still standing of the reaction liquid 19 according to the result from the analysis part 22 and separates an oil layer 23 from a water layer 24; a filter 26 which removes a solid content in the oil layer 23; a storage tank 28 which stores treated waste oil 27 which was subjected to removal treatment of the phosphoric ester 12 after passed through the filter 26; and a waste water treatment part 29 which removes phosphoric acid in the water layer 24. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an apparatus for removing phosphate ester from waste oil and a treatment system for waste oil containing polychlorinated biphenyl (PCB).

Conventionally, it is known to add organometallic additives, phosphorus compounds, and the like to lubricating oils in order to improve wear resistance. As an organometallic additive, ZnDTP (zinc-dithiophosphate) effective for preventing wear and preventing oxidation is frequently used. TCP (tricresyl phosphate) and the like are known as typical phosphorus compounds (Patent Document 1). This tricresyl phosphate is adsorbed on the metal surface and decomposes to form a phosphate film to prevent wear.
By the way, after its use, it is stored as waste oil in drums.

  Since this tricresyl phosphate is flame retardant, lubricating oil containing tricresyl phosphate cannot be burned and may be stored for a long period of time. If it can be removed automatically, combustion treatment can be carried out, but an efficient removal method has not yet been established.

  Also, PCBs (polychlorinated biphenyls, a general term for polychlorinated biphenyls: chlorinated isomers of biphenyls), which are used as insulating oils in heat media, are strictly stored, but PCB processing facilities are located in various places. (Japan Environmental Safety Corporation (JESCO) has been established as a PCB treatment facility, and PCBs have been installed in several locations throughout the country under the supervision of the country. A waste treatment facility is installed and a treatment business is carried out (Non-Patent Document 1).

  In recent years, various technologies for processing PCBs used for such insulating oils have been proposed (about the evaluation method and the evaluated technology of PCB processing technology in the Industrial Waste Treatment Business Promotion Foundation: Non Patent Document 2).

  The present applicant has previously proposed a hydrothermal oxidative decomposition apparatus as a PCB processing technique, and performs PCB processing for detoxification (Patent Document 2 or 3).

Japanese Patent Laid-Open No. 9-157681 JP-A-9-79531 JP 2003-285041 A

http://www.jesconet.co.jp/business/contents/characteristics/index.html http://www.jesconet.co.jp/business/pcb_technology/pdf/PCB_shori.pdf

  By the way, when the lubricating oil and insulating oil as described above are mixed and stored as waste oil, the phosphoric acid ester has flame retardancy and hygroscopicity. The dechlorination / decomposition treatment method used has the problem that PCB waste oil containing a phosphate ester treatment containing moisture cannot be treated, although PCB can be detoxified by itself.

In addition, although the PCB can be decomposed in the hydrothermal oxidative decomposition apparatus, if a phosphate ester is mixed, apatite (Ca ₅ (PO ₄ ) ₃ (F, Cl, OH)) is generated in the hydrothermal treatment process. From the viewpoint of the soundness of the processing equipment, establishment of an efficient method for removing the phosphate ester is desired as a pretreatment.

  In view of the above problems, the present invention provides a phosphate ester removing device and polychlorinated biphenyl (PCB) in waste oil that can remove phosphate esters in advance when the waste oil is decomposed by a hydrothermal oxidative decomposition device. It is an object to provide a treatment system for contained oil.

  A first invention of the present invention for solving the above-described problems is a supply tank for supplying a predetermined amount of waste oil containing a phosphate ester, and supplying an alkaline agent to the waste oil supplied from the supply tank, thereby allowing a saponification reaction. A mixing tank equipped with a stirring means for proceeding, an analysis unit for analyzing the phosphoric acid ratio in the reaction solution, a circulation line for returning the reaction solution to the mixing tank, and the reaction solution being allowed to stand based on the result of the analysis unit And a stationary tank that separates into an oil layer and an aqueous layer, a filter that removes solids in the oil layer, a storage tank that stores treated waste oil from which the phosphate ester that has passed through the filter has been removed, and An apparatus for removing phosphate esters in waste oil, comprising a wastewater treatment unit for removing phosphoric acid from an aqueous layer.

  According to a second aspect of the present invention, there is provided the apparatus for removing a phosphate ester from waste oil according to the first aspect, wherein the addition amount of the saponifying agent is 10% by weight or less.

  The third invention is characterized in that in the waste oil characterized in that in the first or second invention, the waste oil is characterized by comprising an emulsifying means using waste oil mixed with water as an emulsified liquid, and a heating part for heating the emulsifying means. In the phosphate ester removal apparatus.

  According to a fourth aspect of the present invention, there is provided the apparatus for removing a phosphate ester from waste oil according to the third aspect of the invention, wherein the heating temperature of the heating section is 80 to 100 ° C.

  According to a fifth invention, in any one of the first to fourth inventions, when the analysis unit analyzes and the phosphoric acid concentration in water or the phosphoric acid ester concentration in oil reaches a predetermined concentration, It is in the phosphate ester removal apparatus in waste oil characterized by having the determination part which performs operation which switches to a storage tank.

  6th invention has an inorganic filling tank with which the waste-water-treatment part filled with the solid adsorbent which contains at least any one of Ca, Mg, Na, and Al in any one invention of 1st thru | or 5. In the apparatus for removing phosphate ester from waste oil, phosphoric acid is fixed with a metal salt.

  A seventh invention is the phosphate ester removing apparatus in the waste oil according to any one of the first to sixth inventions, wherein the waste oil contains polychlorinated biphenyl (PCB).

  The eighth invention comprises a phosphoric acid ester removing device in the seventh waste oil, and a hydrothermal oxidative decomposition device that decomposes polychlorinated biphenyl (PCB) in the waste oil from which the phosphoric acid ester has been removed. A waste oil treatment system containing polychlorinated biphenyl (PCB) is featured.

According to the present invention, the phosphoric acid ester in waste oil can be brought into contact with metallic iron, the extreme pressure reaction can be advanced, and phosphoric acid can be made mineralized efficiently, and the subsequent waste oil treatment can be performed. It becomes simple.
In addition, when decomposing PCB in waste oil with hydrothermal oxidative decomposition equipment, phosphate ester is removed in advance, so that apatite of phosphate ester does not occur, so hydrothermal decomposition of insulating oil and lubricating oil The reaction can be performed efficiently.

FIG. 1 is a schematic view of an apparatus for removing a phosphate ester from waste oil according to a first embodiment. FIG. 2 is a schematic view of an apparatus for removing a phosphate ester from other waste oil according to the first embodiment. FIG. 3 is a schematic diagram of a waste oil treatment system including a phosphate ester removing device in waste oil according to the second embodiment.

  Hereinafter, the present invention will be described in detail with reference to the drawings. Note that the present invention is not limited to the embodiments. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art or those that are substantially the same.

An apparatus for removing phosphate ester from waste oil according to Embodiment 1 of the present invention will be described with reference to the drawings. FIG. 1 is a schematic view of an apparatus for removing a phosphate ester from waste oil according to a first embodiment.
As shown in FIG. 1, phosphate esters removing apparatus 10A in the waste oil, and storage tank 11 for storing the waste oil 13 containing phosphoric acid ester 12, phosphoric acid ester, which is fed by the line L ₁ from-holding tube tank 11 A supply tank 14 for supplying a predetermined amount of waste oil 13 containing 12 and a stirring means 17 for mixing the alkaline agent 16 from the alkaline agent supply tank 15 with the waste oil 13 fed from the supply tank 14 via the line L ₂ . A mixing tank 18, an analysis unit 22 for analyzing phosphorus (P) or phosphoric acid (H ₃ PO ₄ ) in a reaction solution 19 in which the alkaline agent 16 is mixed with the waste oil 13, and the reaction solution 19 is mixed with the mixing tank 18. a circulation line L ₄ back to, allowed to stand the reaction mixture 19 based on the result of the analysis unit 22, a stationary tank 25 that is separated into a oil layer 23 and water layer 24, the solids in the oil layer 23 A filter 26 to be removed, a storage tank 28 for storing treated waste oil 27 from which the phosphate ester 12 that has passed through the filter 26 has been removed, and a wastewater treatment unit 29 for removing phosphoric acid from the aqueous layer 24. Is.
In FIG. 1, reference numerals V ₁ and V ₂ denote switching valves, P _{1 to} P ₃ denote feed pumps, and lines L ₃ and L _{5 to} L ₈ denote feed lines, respectively.

The alkaline agent 16 supplied from the alkaline agent supply tank 15 is supplied in order to saponify and decompose the phosphate ester 12 and is added to the waste oil 13 by about 10% by weight.
In addition, when there is little content of the phosphate ester 12, it is trying to reduce the addition amount.
Here, as the alkaline agent 16, for example, sodium hydroxide (NaOH) or sodium carbonate (NaCO ₃ ) can be used.

In the mixing tank 18 to which the alkaline agent 16 is supplied, the saponification reaction is advanced by stirring by the stirring means 17 to form phosphoric acid.
The mixing tank 18 is provided with a heater (heating to about 80 ° C.) H as a heating means so that the saponification reaction proceeds.

In the following [Chemical Formula 1], TCP (tricresyl phosphate) is taken as an example of the phosphate ester. As shown in the reaction formula, TCP (tricresyl phosphate) is saponified and decomposed by sodium hydroxide (NaOH) by oxidative decomposition to mineralize P as sodium phosphate (Na ₃ PO ₄ ).

The reaction solution 19 is monitored for its saponification decomposition state by an analysis unit 22 that chemically analyzes the ratio of phosphoric acid (H ₃ PO ₄ ) in water or phosphorus (P) in oil.
While the saponification decomposition does not proceed, the circulation line L ₄ is used to return to the mixing tank 18 and the saponification decomposition processing by the stirring means 17 of the mixing tank 18 is repeated again.

The analysis result in the analysis unit 22 is sent to the determination unit 30, where saponification decomposition is completed when the ratio of phosphoric acid (H ₃ PO ₄ ) or phosphorus (P) reaches a predetermined concentration. The switching valve V ₁ is switched and fed to the stationary tank 25 via the line L ₅ .
Here, as the predetermined concentration, for example, when 10% or less of a phosphate ester is contained in the lubricating oil, when determining the ratio of phosphoric acid (H ₃ PO ₄ ) in the water of the reaction liquid 19, When phosphoric acid becomes about 20% or more, it is determined that saponification decomposition proceeds and the transition from the oil layer to the water layer is completed.
On the other hand, when judging the ratio of phosphorus (P) in the oil, when it becomes about 10 to 100 ppm, it is judged that the oxidative decomposition proceeds and the transfer from the oil layer to the water layer is completed.
This determination may be performed both or one of them.
The oil tank 23 and the water layer 24 are separated by being allowed to stand for a predetermined time in the stationary tank 25.

  The determination of completion is made by comparing the concentration of phosphorus (P) in the aqueous layer 24 with the target concentration. For example, if the target value is <100 ppm, it is determined that the concentration is less than that. The determination may be performed by a determination method based on a combination with an analysis method, a determination method based on a combination of a bomb combustion decomposition method and a chemical analysis (such as an absorptiometry), or the like.

Thereafter, the oil layer 23 is fed to the filter 26 through the line L ₆ and the line L ₇ , where the solid content in the oil is removed. Thereafter, the treated waste oil 27 from which the phosphate ester 12 has been removed is stored in a storage tank 28.
Here, as the filter 26, in order to efficiently remove a small amount of phosphate ester remaining in the oil layer 23, phosphorus is attached to the metal (iron) using a metal filter (for example, an iron-based mesh filter). Try to remove.

  Thereafter, the treated waste oil 27 is treated by a predetermined waste oil treatment device (combustion treatment, hydrothermal decomposition treatment, etc.).

  According to the present invention, the phosphate ester in the waste oil can be efficiently treated by hydrolysis, and the subsequent waste oil (lubricating oil) becomes incombustible and combustion treatment is possible.

Further, after the processing of the oil layer 23 is completed, the switching valve V ₂ is switched, and the water layer 24 is fed to the waste water treatment unit 29 through the line L ₈ to fix the phosphoric acid.
The wastewater treatment unit 29 for fixing phosphoric acid has an inorganic filling tank filled with a solid adsorbent containing at least one of Ca, Mg, Na, and Al, for example, and phosphoric acid is fixed with a metal salt. (For example, apatite (Ca ₅ (PO ₄ ) ₃ (F, Cl, OH)) is generated). Thereafter, the pH is adjusted in a pH adjusting tank and then discharged to the outside.

  Further, even when the waste oil is processed by the hydrothermal oxidative decomposition apparatus 120, since the phosphate ester is removed in advance, the apatite formation due to the phosphate ester does not occur in the hydrothermal oxidative decomposition process. Hydrothermal decomposition reaction of insulating oil and lubricating oil can be performed efficiently.

FIG. 2 is a schematic view of an apparatus for removing a phosphate ester from other waste oil according to the first embodiment.
As shown in FIG. 2, the phosphate ester removing device 10 </ b> B in the waste oil is provided with an emulsifying means 20 for emulsifying the hydrogen peroxide water and the waste oil on the downstream side of the mixing tank 18.
Here, the emulsifying means 20 for emulsifying the reaction liquid 19 may be any means as long as it is a finely mixed state of oil and water, but it is particularly preferable to use a line mixer.
This line mixer can be a finely emulsified reaction liquid 19 in order to efficiently treat the hydrolysis.
The emulsifying means 20 other than the line mixer may be any stirring means that can give a high share to the fluid, and examples thereof include a rotary mill, a blade rotation type, and an ultrasonic vibration type. it can.

  The emulsifying means 20 is provided with a heating unit 21 such as a heater for heating to about 80 to 100 ° C. as necessary in order to promote saponification decomposition as shown in [Chemical Formula 1].

  According to the present invention, the phosphate ester in the waste oil can be efficiently processed by saponification decomposition, and the subsequent waste oil (lubricating oil) becomes non-flammable and can be burned.

  In addition, even when waste oil is treated with a hydrothermal oxidative decomposition apparatus, the phosphate ester is removed in advance, so that apatite formation due to the phosphate ester does not occur during the hydrothermal oxidative decomposition treatment. The hydrothermal decomposition reaction of oil and lubricating oil can be performed efficiently.

A waste oil processing system including a phosphate ester removing device in waste oil according to an embodiment of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view of a waste oil treatment system containing polychlorinated biphenyl (PCB) equipped with a phosphate ester removing device in waste oil according to Example 3.
As shown in FIG. 3, a waste oil treatment system 100 including a phosphate ester removal device in waste oil includes a phosphate ester removal device 10A (10B, 10C) in waste oil according to Example 1 or Example 2, and It includes a hydrothermal oxidative decomposition apparatus 120 that hydrolyzes and decomposes PCBs.
Here, the schematic structure of the hydrothermal oxidative decomposition apparatus 120 is as follows: the treated waste oil 27 from which the phosphate ester has been removed, oil (for reaction promotion) 31, sodium hydroxide (NaOH) 32, pure water 33, and oxygen (O ₂ ). 34 is provided with a cylindrical primary reaction tower 101 for charging 34, a secondary reaction tower 107 for completing the decomposition treatment reaction, a cooler 108, and a pressure reducing valve 109 for the reactor. A gas-liquid separator 110 that separates waste water (H ₂ O, NaCl) 114 and exhaust gas (CO ₂ ) 112 is disposed downstream of the pressure reducing valve 109. The secondary reactor 107 can be omitted as necessary.

In the hydrothermal oxidative decomposition apparatus 120, the pressure in the primary reaction tower 101 is increased to, for example, about 26 MPa by pressurization with a pressure pump. The heat exchanger 121 preheats H ₂ O to about 300 ° C. Further, oxygen 34 from the high-pressure oxygen supply equipment 117 is jetted into the primary reaction tower 101, and the temperature is raised to 350 ° C. to 400 ° C. (preferably up to 370 ° C.) by the internal reaction heat. By this stage, an oxidative decomposition reaction has occurred in the primary reaction tower 101, and the PCB contained in the treated waste oil 27 has been decomposed into CO ₂ and H ₂ O. Next, in the cooler 108, the fluid from the secondary reaction tower 107 is cooled to about 100 ° C. and the pressure is reduced to atmospheric pressure by the pressure reducing valve 109 at the subsequent stage. Then, CO ₂ and water vapor and the treatment liquid are separated by the gas-liquid separator 110, and the CO ₂ and water vapor are exhausted from the chimney 113 into the environment as the exhaust gas 112 through the activated carbon layer 111. The drainage 114 is treated to a predetermined standard and temporarily stored in the discharge tank 115. 120a to 120d are storage tanks, 121 is a heat exchanger, 122a to 122d are pumps, and 123 is a mixer.

  Thus, according to the present embodiment, even when waste oil is processed by the hydrothermal oxidative decomposition apparatus 120, the phosphate ester is previously removed by the phosphate ester removing apparatus 10A (10B, 10C) in the waste oil. In the hydrothermal decomposition treatment in the hydrothermal oxidative decomposition treatment apparatus 120, apatite formation caused by the phosphate ester does not occur, and the hydrothermal decomposition reaction of the waste oil (insulating oil or lubricating oil) 13 is stably performed. Can do.

  As mentioned above, according to the phosphate ester removal apparatus in waste oil which concerns on this invention, the phosphate ester in waste oil can be processed efficiently by hydrolysis, and subsequent waste oil processing becomes easy.

DESCRIPTION OF SYMBOLS 10A, 10B Phosphate ester removal apparatus in waste oil 12 Phosphate ester 13 Waste oil 16 Alkaline agent 18 Mixing tank 19 Reaction liquid 20 Emulsifying means 21 Warming part 22 Analytical part 23 Oil layer 24 Water layer 25 Standing tank 26 Filter 27 Treatment waste oil 29 Wastewater treatment unit 30 Judgment unit H Heater

Claims (8)

A supply tank for supplying a predetermined amount of waste oil containing phosphate ester;
A mixing tank provided with a stirring means for supplying an alkaline agent to the waste oil supplied from the supply tank and causing a saponification reaction to proceed;
An analysis unit for analyzing the proportion of phosphoric acid in the reaction solution;
A circulation line for returning the reaction liquid to the mixing tank;
Based on the result of the analysis unit, the reaction solution is allowed to stand, and a stationary tank that separates the oil layer and the water layer;
A filter for removing solids in the oil layer;
A storage tank for storing treated waste oil from which the phosphate ester that has passed through the filter has been removed;
An apparatus for removing phosphate esters in waste oil, comprising: a wastewater treatment section for removing phosphoric acid in the aqueous layer. In claim 1,
An apparatus for removing a phosphate ester from waste oil, wherein the addition amount of the saponifying agent is 10% by weight or less. In claim 1 or 2,
Emulsification means using waste oil mixed with water as an emulsion,
An apparatus for removing a phosphate ester from waste oil, comprising a heating unit for heating the emulsifying means. In claim 3,
The apparatus for removing a phosphate ester in waste oil, wherein the heating temperature of the heating section is 80 to 100 ° C. In any one of Claims 1 thru | or 4,
In the waste oil characterized by having a determination unit that performs an operation of switching to a stationary tank when the concentration of phosphoric acid in water or the concentration of phosphate ester in oil reaches a predetermined concentration Phosphate ester removal equipment. In any one of Claims 1 thru | or 5,
In the waste oil characterized in that the waste water treatment unit has an inorganic filling tank filled with a solid adsorbent containing at least one of Ca, Mg, Na, and Al, and fixes phosphoric acid with a metal salt. Phosphate ester removal equipment. In any one of Claims 1 thru | or 6,
The apparatus for removing a phosphate ester from waste oil, wherein the waste oil contains polychlorinated biphenyl (PCB). An apparatus for removing phosphate ester from waste oil according to claim 7;
A waste oil treatment system containing polychlorinated biphenyl (PCB), comprising a hydrothermal oxidative decomposition apparatus for decomposing polychlorinated biphenyl (PCB) in the waste oil from which the phosphate ester has been removed.

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