KR101576079B1 - Treating Apparatus of Waste Insulating Oil with Polychlorinated Biphenyls - Google Patents

Treating Apparatus of Waste Insulating Oil with Polychlorinated Biphenyls Download PDF

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KR101576079B1
KR101576079B1 KR1020140025455A KR20140025455A KR101576079B1 KR 101576079 B1 KR101576079 B1 KR 101576079B1 KR 1020140025455 A KR1020140025455 A KR 1020140025455A KR 20140025455 A KR20140025455 A KR 20140025455A KR 101576079 B1 KR101576079 B1 KR 101576079B1
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reactor
insulating oil
catalyst
waste
biphenyl
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KR20150103871A (en
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신영호
손석진
류완호
전재욱
이성우
서지영
이태범
권혜림
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주식회사 제이에스엘코리아
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Abstract

The present invention relates to an apparatus for treating polychlorinated biphenyl of waste insulating oil, comprising: a pump for transferring and supplying waste insulating oil containing polychlorinated biphenyl; A reactor filled with a waste heat insulating oil containing polybrominated biphenyl, which is supplied by the pump, and a catalyst for decomposing polybrominated biphenyl by inducing oxidation-reduction reaction from the supplied oxygen; A heating unit for heating and heating the reactor to form an atmosphere for activation of the catalyst filled in the reactor; An air supply unit for supplying oxygen required for the redox reaction in the reactor to the reactor side; And a receiving tank for collecting the waste insulating oil and the decomposed chlorine molecules and gas after the reaction in the reactor is completed. The polyphenylene chloride in the waste insulating oil can be decomposed and treated at a high treating rate, The present invention relates to an apparatus for treating polychlorinated biphenyl of waste insulating oil capable of performing treatment at a high concentration at a relatively low cost.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an apparatus for treating polychlorinated biphenyl

The present invention relates to a treatment apparatus for decomposing polybrominated biphenyls in a waste insulating oil such as a transformer containing polychlorinated biphenyls (PCBs) to decompose and detoxify the waste, and more particularly, To an apparatus for treating a waste insulating oil containing polychlorinated biphenyl, which detoxifies polychlorinated biphenyls.

Generally, polychlorinated biphenyls (PCBs) have a structure in which hydrogen bonded to ten hydrogen atoms at the biphenyl (C 6 H 5 -C 6 H 5 ) skeleton connecting two benzene rings is substituted with 1 to 10 As chlorine (Cl) atom-substituted compounds, there are 209 isomers theoretically, but about 100 species are actually used.

These polychlorinated biphenyls (PCBs) are used for versatile purposes such as insulation oil, heat medium, lubricant, and plasticizer because they are free from the risk of thermal deformation and excellent in insulation or electrical properties and chemically stable. Insoluble in water and excellent in electrical insulation, it has been used as insulating oil for electrical products such as transformers and capacitors.

However, polychlorinated biphenyls (PCBs) are one of the endocrine disruptors despite their many useful advantages. They are environmental hormone harmful substances that cause diseases such as ecosystem, degradation of human reproductive function, malformation, growth disorder, It is classified as Persistant Organic Pollutants (POPs) and is being managed.

Currently, polychlorinated biphenyls (PCBs) are prohibited from use, but they have been used in the past and are a problem when disposing of waste insulating oil. Therefore, measures and measures are required for efficient treatment.

Conventional processing techniques for such polychlorinated biphenyls (PCBs) can be divided into thermal processing, chemical processing, and other processing techniques.

The thermal treatment technology is mainly used at a high temperature incineration method. Advantages include high processing speed and low volume of treated waste. However, disadvantage is the generation of aromatic hydrocarbons such as dioxins, limitations on application of liquid or gas medium, Is relatively high.

The chemical treatment technology has the advantage of being able to process various media with a high processing speed and of being able to reuse the insulating oil after the treatment unlike the thermal treatment technique. The metal sodium dispersion method, the alkali catalytic decomposition method, the dechlorination decomposition method using the noble metal catalyst However, there is a disadvantage in that the configuration of the apparatus is complicated and the processing time is not constant. In particular, there is a problem in that the treatment efficiency is low or the reaction time is very long when a high concentration (1,000 ppm or more) of polychlorinated biphenyl is used , There is a problem that high cost is incurred in the case of noble metal catalyst, and some catalysts are not reusable, and metal sodium dispersion method has a problem that explosion is dangerous and very careful handling is required in handling.

Other processing technologies include biological treatment methods using microorganisms and methods of removing electron beams by irradiation, but there is a possibility that the treatment cost is high or the undissolved polychlorinated biphenyls (PCBs) And there is a limitation in application to a mobile processing device because of the large size of the device.

On the other hand, Korean Patent No. 10-0969548 and Korean Patent Laid-open No. 10-2010-0024143 disclose a configuration for desalination using metal sodium, and Korean Patent Laid-Open No. 10-2007-0066727 Discloses a method of detoxifying polybrominated biphenyls by using a metal catalyst and an alkali, and Korean Patent No. 10-0899800 discloses a method of pyrolysis and melting treatment using plasma, -2010-0055642 discloses a structure for decomposing polychlorinated biphenyls by using an electron beam, which corresponds to the prior art having the above-mentioned conventional problems.

Korean Registered Patent No. 10-0969548 (issued on July 12, 2010) Korean Patent Publication No. 10-2010-0024143 (published on March 15, 2010) Korean Patent Registration No. 10-0899800 (Bulletin of May 28, 2009) Korean Patent Publication No. 10-2010-0055642 (published on May 27, 2010)

Disclosure of the Invention The present invention has been made in view of the above-mentioned problems, and it is an object of the present invention to provide an apparatus for treating waste insulating oil containing polychlorinated biphenyl, which is capable of detoxifying polychlorinated biphenyls through desalting using an oxidation- The purpose is to provide.

The present invention can decompose and remove the polychlorinated biphenyls in the waste insulating oil by inducing the oxidation and reduction reaction through the supply of oxygen and the reaction with the catalyst, and by using the low-cost transition metal catalyst, The present invention has another object to provide an apparatus for treating a waste insulating oil containing polychlorinated biphenyl.

The present invention relates to a treatment device for a waste insulating oil containing polychlorinated biphenyl, which enables continuous treatment, enables a mobile treatment to be carried out with a small scale of the apparatus, There is another purpose in providing.

The present invention provides an apparatus for treating a waste insulating oil containing polychlorinated biphenyl, which is capable of separating and removing decomposition materials more easily by bringing about layer separation of the decomposed material after chemical treatment by oxidation-reduction reaction There is a purpose.

In order to accomplish the above object, the present invention relates to an apparatus for treating an insulating oil containing polychlorinated biphenyl for detoxifying a waste insulating oil containing polychlorinated biphenyl, the waste oil containing polychlorinated biphenyl is transferred A pump for feeding; A reactor filled with a catalyst for inducing a redox reaction from the waste insulation oil containing polybrominated biphenyl fed by the pump and decomposing polybrominated biphenyls; A heating unit for heating and heating the reactor to form an atmosphere for activation of the catalyst filled in the reactor; An air supply unit for supplying oxygen required for the redox reaction in the reactor to the reactor side; And a receiving tank for collecting the waste heat insulating oil and the decomposed chlorine (Cl) molecules and gas after the reaction in the reactor is completed.

(H 2 O) and sodium hydroxide (NaOH) are filled in the receiving tank to remove the decomposed chlorine (Cl) molecules in the form of hydrogen chloride (HCl) or sodium chloride (NaCl), and a catalyst Is formed of a transition metal in the form of supporting chromium on a titania support.

In the heating unit, the inside of the reactor is heated to a temperature of 100 to 900 ° C to raise the temperature. In the air supply unit, oxygen is supplied at a rate of 0.1 mole or more to the molar ratio of chromium content to the weight of the catalyst.

The apparatus for treating the waste insulating oil containing polychlorinated biphenyls can be installed in a vehicle and configured to be movable.

According to the present invention, it is possible to decompose and remove the polychlorinated biphenyls in the waste insulating oil by introducing the waste insulating oil having polychlorinated biphenyl directly into the reactor filled with the catalyst to induce the oxidation-reduction reaction, And it is possible to perform a continuous treatment and also to produce a treatment capable of treatment at a high concentration.

In addition, the present invention can be configured at relatively low cost and can be configured as a large-scale apparatus, so that it can be configured as a portable processing device capable of transporting by truck, It is possible to meet the requirements of environmental pollution prevention.

Further, the present invention is able to separate the decomposed material after passing through the chemical treatment in the reactor by passing the decomposed material through the aqueous solution of sodium hydroxide, so that the decomposition material can be more easily separated and removed.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a view showing a conceptual constitution of a polychlorinated biphenyl treatment apparatus in a waste insulating oil of the present invention. FIG.
2 is a schematic diagram of an apparatus for treating polychlorinated biphenyls in waste heat insulating oil of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. The present invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.

1 and 2, the apparatus 100 for treating a polychlorinated biphenyl according to an embodiment of the present invention includes a pump 110, a reactor 120 filled with a catalyst 101, a heating unit 130 An air supply unit 140, and a receive tank 150. [

The pump 110 pumps the waste insulating oil from the waste insulating oil storage tank 10 in which waste oil containing polychlorinated biphenyls (PCBs) is stored, and transfers the waste oil to the reactor 120 where the catalyst is filled. And supplies the waste insulation oil at a constant flow rate and flow rate.

At this time, the waste insulating oil storage tank 10 stores waste insulating oil containing polychlorinated biphenyls (PCBs) used in other industrial fields including a transformer and a condenser.

The reactor 120 is filled with the catalyst 101 and induces a redox reaction through the catalyst from the polychlorinated biphenyl-containing waste insulating oil transferred and supplied by the pump 110, .

As the catalyst 101, a low-cost transition metal is used so as to have a relatively low processing cost and induce a quick reaction with polybrominated biphenyls and increase the decomposition efficiency. In the transition metal of the transition metal supported on the titania support, .

More specifically, the catalyst 101 is prepared by dissolving chromium in a predetermined amount of distilled water to form a chromium solution to contain 0.1 to 10% by weight of chromium relative to the weight of titania, and a step of preparing a chromium solution having a specific surface area of 40 to 400 m 2 / g, The titania surface of the anatase crystal structure was modified to a TiO 2 / SO 4 type support by adding 10 times sulfuric acid to the weight of the titania in the filter paper, drying it in the air and calcining it at a temperature of 400 ° C or higher for about 1 hour And the surface-modified TiO 2 / SO 4 was added to the chromium solution prepared in the previous step together with the distilled water. The mixture was stirred for 12 to 24 hours and sufficiently mixed. The mixture was then concentrated under reduced pressure by rotary evaporation at 70 ° C., ≪ / RTI > and evaporating.

The heating unit 130 heats the reactor 120 to raise an atmosphere for activating the transition metal catalyst 101 filled in the reactor 120.

The heating unit 130 has a configuration in the form of a roof for uniform heating and includes a reactor 120 and a temperature controller 131 for controlling the heating temperature, The interior of the reactor 120 is heated to a temperature of 100 to 900 DEG C in order to form an oxidation atmosphere by the catalyst 101 filled in the reactor 120 and to activate the atmosphere.

If the heating temperature is lower than 100 ° C., the removal reaction of the PCBs to be injected does not occur and the reaction for decomposing the polychlorinated biphenyl may not be induced properly. If the heating is conducted at a temperature exceeding 900 ° C., The phase transition of the titania from the anatase to the rutile phase causes the reduction of the specific surface area of the catalyst and the decrease of the catalytic activity.

That is, maintaining the inside of the reactor 120 at a temperature in the range of 100 to 900 ° C can activate the catalyst while preventing the phase transition of the catalyst and form an oxidizing atmosphere for inducing the redox reaction, It can be shown to be useful for the decomposition treatment of biphenyl chloride.

The air supply unit 140 supplies the oxygen necessary for the oxidation-reduction reaction in the reactor 120 filled with the catalyst 101 into the reactor 120, and it is preferable to use the air compressor.

Since the amount of air supplied through the air supply unit 140 varies depending on the content of chromium (Cr) contained in the catalyst, oxygen is supplied at a rate of 0.1 mol or more per minute to the molar ratio of the chromium content, So that the amount of air supplied can be adjusted.

For example, when 400 g of the catalyst 101 is placed in the reactor, the weight of chromium in the catalyst is 0.4 g to 40 g, and the amount of chromium in the catalyst is 52 The molar ratio of chromium to 0.1 wt.% To 10 wt.% Of chromium is 0.4 / 52 to 40/52 = 0.00769 mol to 0.769 mol. 0.008 mol to 0.8 mol based on the mass / 0.0179 L = 17.9 ml = 17.9 cc, and oxygen in the air is 21%, so that the amount of air supplied per minute is 17.9 cc / min ÷ 0.21 = 85.23 cc / min, so that 85 cc / min to 85,000 cc / min are supplied It is controlled by the weight of the catalyst.

As an example of the treatment of the waste insulating oil, when the waste insulating oil having a concentration of polychlorinated biphenyls (PCBs) (1184 ppm) is treated, waste heat insulating oil is injected into the reactor 120 and the reactor is heated at 100 ° C to 900 ° C When supplied at 85cc / min, the concentration of polychlorinated biphenyls (PCBs) as shown in the table below is detected.

Heating temperature
(° C) 100 150 200 300 400 600 700 800 900 Detection concentration
(ppm) 53 30 Less than 0.5 Less than 0.5 Less than 0.5 Less than 0.5 Less than 0.5 8 25

At this time, when air is supplied in excess of 85 cc / min while heating the reactor at a temperature in the range of 100 ° C to 900 ° C, the polychlorinated biphenyl concentration below the detected concentration at each of the temperatures in Table 1 is detected. However, the permissible concentration of polychlorinated biphenyls which can be transported after the field detoxification treatment of domestic polychlorinated biphenyls is specified to be less than 2 ppm or less than 50 ppm.

Therefore, it is possible to perform the continuous process operation by easily controlling the temperature of the heating part without supplying excess air, and it is possible to induce the reaction with the polybrominated biphenyls without reducing the activity of the catalyst, The catalyst is heated at a heating temperature in the range of 100 ° C. to 900 ° C. so that the concentration of polychlorinated biphenyl is detected to be 53 ppm to 25 ppm after the reduction treatment so that the concentration of chromium contained in the catalyst is 0.1 mol Or more of oxygen is supplied per minute.

That is, when 400 g of the catalyst is charged into the reactor as in the embodiment, the air supplied to the reactor is supplied to the reactor as if supplying air of 85 cc / min or more, which corresponds to 0.1 mol or more of the molar ratio of chromium to the reactor, The amount of air corresponding to 0.1 mol or more of the molar ratio of the chromium content to the catalyst is changed depending on the weight of the catalyst.

The receiving tank 150 collects the waste heat insulating oil and the decomposed chlorine (Cl) molecules and gas after the oxidation-reduction reaction by the catalyst in the reactor 120. The receiving tank 150 is made of chlorine (NaOH) solution to remove water in the form of sodium chloride (NaCl) or to pass water (H 2 O) in order to desalt and remove the hydrogen chloride (HCl)

In addition, the reactor 120 and the receiving tank 150 are connected to each other through a pipe, and after the oxidation-reduction reaction by the catalyst in the reactor 120 is completed, the waste heat insulating oil and decomposed chlorine (Cl) Gas is formed so as to be transferred to the receiving tank 150.

The operation of the apparatus 100 for treating polychlorinated biphenyl of the waste insulating oil according to the embodiment of the present invention having the above-described structure will be described below.

The pump 110 is operated to pump the waste insulating oil from the waste insulating oil storage tank 10 storing the waste insulating oil containing polychlorinated biphenyls (PCBs) and transfer it to the reactor 120 side filled with the catalyst 101 .

The reactor 120 induces a redox reaction through the catalyst 101 with respect to the polychlorinated biphenyl-containing waste insulating oil fed and fed by the pump 110 to decompose the polychlorinated biphenyl.

At this time, in the air supply unit 140, oxygen necessary for the reaction in the reactor 120 filled with the catalyst 101 is supplied into the reactor 120, so that the oxygen supply necessary for the reaction is performed according to the concentration of the polychlorinated biphenyl Depending on the weight of the catalyst to be fed into the reactor, oxygen corresponding to 0.1 mol or more of the molar ratio of chromium is supplied.

In the heating unit 130, the reactor 120 is heated to heat and maintain the internal temperature at 100 ° C. to 900 ° C., thereby forming and activating an oxidizing atmosphere by the catalyst 101 filled in the reactor 120.

In the reactor 120, the catalyst 101 in which chromium is supported on the titania support under such an atmosphere induces activation and redox reaction. In the present invention, the waste insulating oil containing polychlorinated biphenyl is introduced into the reactor 120, To perform the decomposition treatment of the polychlorinated biphenyl in the waste insulating oil.

In addition, the catalyst 101 having chromium carried on the titania support reacts with lattice oxygen by adsorbing biphenyl chlorides in the waste insulating oil to the active point chromium (VI), and the chromium (VI) consuming the lattice oxygen is chromium (III) and then reacts with oxygen in the air supplied from the air supply unit 140 to supplement the lattice oxygen. After completion of the reaction at the reaction active site, desorption is performed to circulate one cycle of the reaction. .

That is, in the reactor 120 filled with the catalyst 101, decomposition and removal of the polychlorinated biphenyl are performed by the oxidation-reduction reaction by the catalyst 101 as shown in the following chemical formula (1).

[Chemical Formula 1]

Figure 112014021214896-pat00001
+ O 2 → CnHx (hydrocarbons) + Cl 2 + CO 2

As described above, the decomposed material is chemically treated in the reactor 120 filled with the catalyst 101 by the direct injection of waste insulating oil containing polychlorinated biphenyl, and then transported and supplied to the receiving tank 150.

Since the water (H 2 O) is filled in the receiving tank 150, the decomposed chlorine (Cl) molecules are removed in the form of hydrogen chloride (HCl) and subjected to desalting treatment. As shown in the following chemical formula 2, The process of removing the decomposed chlorine (Cl) molecule in the form of sodium chloride (NaCl) and desalting it when the aqueous solution of sodium hydroxide (NaOH) is filled is shown in Chemical Formula (3).

(2)

CnHx + Cl 2 + CO 2 + H 2 O → CnHx + 2HCl + CO 2 + H 2 O

(2)

CnHx + Cl 2 + CO 2 + 2 NaOH (aq) + H 2 O → CnHx + 2NaCl + CO 2 + H 2 O

Here, by passing the chemically decomposed material through the receiver tank 150 through the aqueous solution of sodium hydroxide (NaOH) in the reactor 120, it is possible to derive the layer separation as shown in FIG. 2, Lt; / RTI >

Therefore, the present invention can provide an apparatus which can realize a high processing speed while allowing continuous processing.

In addition, the polybrominated biphenyls (PCBs) have to be transported after being detoxified in the field when the concentration is 50 ppm or more. Since the scale of the device is not so large, As a result, the PCBs can be immediately treated in the field, and can be moved to less than 50 ppm in accordance with the regulations.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, And will be within the technical scope of the present invention.

101: catalyst 110: pump
120: reactor 130: heating section
140: air supply unit 150:

Claims (5)

An apparatus for treating an insulating oil containing polychlorinated biphenyl for detoxifying a waste insulating oil containing polychlorinated biphenyl,
A pump for transferring and supplying a waste insulating oil containing polychlorinated biphenyl;
A reactor filled with a waste heat insulating oil containing polybrominated biphenyl fed by the pump and a catalyst for inducing an oxidation-reduction reaction from the supplied oxygen to decompose the polybrominated biphenyl;
A heating unit for heating and heating the reactor to form an atmosphere for activation of the catalyst filled in the reactor;
An air supply unit for supplying oxygen required for the redox reaction in the reactor to the reactor side;
And a receiving tank for collecting the waste insulating oil and the decomposed chlorine (Cl) molecules and gas after the reaction is finished in the reactor,
Wherein the catalyst to be filled in the reactor is formed of a transition metal in the form of supporting chromium on a titania support. The method according to claim 1,
Characterized in that the receiving tank is filled with water (H 2 O) and sodium hydroxide (NaOH) aqueous solution to remove the decomposed chlorine (Cl) molecules in the form of hydrogen chloride (HCl) or sodium chloride (NaCl) Apparatus for treating biphenyl chlorides. delete The method according to claim 1,
Wherein the heating unit heats the inside of the reactor to a temperature of 100 to 900 degrees to raise the temperature, and in the air supply unit, 0.1 mole or more of oxygen is supplied to the reactor in relation to the molar ratio of the chromium content to the weight of the catalyst per minute, Apparatus for treating biphenyl chlorides. The method according to claim 1,
Wherein the apparatus for treating the waste insulation oil containing polychlorinated biphenyl is installed in a vehicle and configured to be movable.
KR1020140025455A 2014-03-04 2014-03-04 Treating Apparatus of Waste Insulating Oil with Polychlorinated Biphenyls KR101576079B1 (en)

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JP2005139440A (en) * 2003-10-17 2005-06-02 Hitoshi Mizuguchi Method for decomposing compound
WO2013089222A1 (en) 2011-12-15 2013-06-20 堺化学工業株式会社 Granular body of titanium oxide having transition metal and/or transition metal oxide supported thereon, and method for decomposing waste plastic/organic material using said granular body

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005139440A (en) * 2003-10-17 2005-06-02 Hitoshi Mizuguchi Method for decomposing compound
WO2013089222A1 (en) 2011-12-15 2013-06-20 堺化学工業株式会社 Granular body of titanium oxide having transition metal and/or transition metal oxide supported thereon, and method for decomposing waste plastic/organic material using said granular body

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