KR20010099069A - Adsorbent for volatile organic compounds and filter using the same - Google Patents

Abstract

The present invention relates to a volatile organic substance adsorbent and a filter using the same. More specifically, the adsorbent is a styrene-butadiene-styrene rubber in an adsorbent for removing VOCs discharged from the vent portion of an oil and organic solvent storage tank. And / or 10 to 300 parts by weight of one or more natural materials selected from the group consisting of 100 parts by weight of styrene-isoprene rubber, 0.1 to 10 parts by weight of surfactant, and activated carbon, cane, charcoal, scrubber (rice name) and rice husk as bulking agents. And a body having an inlet and an outlet through which VOCs discharged from the vent of the oil and organic solvent storage tank are introduced. The inlet and outlet are connected in series or in parallel to the connecting pipe for connecting a plurality of the body, the body is filled with the adsorbent. The filter of the present invention can be used for adsorption and removal of volatile organic compounds discharged from storage tanks containing not only organic solvents and oils (gasoline, diesel, kerosene, naphtha, crude oil, etc.) but also all hydrocarbon-based compounds. It can be used and applied to pretreatment device of VOCs removal device such as biofilter, adsorption removal pretreatment device of VOCs discharged from coating facility.

Description

Adsorbent for volatile organic compounds and filter using the same}

The present invention relates to a volatile organic substance adsorbent and a filter using the same, more specifically, organic solvents and oils (gasoline, diesel, kerosene, naphtha, crude oil, etc.) as well as discharged from the storage tank in which all hydrocarbon-based compounds are stored Adsorption and removal of volatile organic compounds, volatile organic substances adsorbents and filters using them for pretreatment of VOCs removal equipment such as activated carbon adsorption, biofilters, adsorption removal pretreatment of VOCs discharged from coating facilities It is about.

VOCs is the abbreviation of VOCs (Volatile Organic Compounds) and is a major air pollutant generated during industrial activities. In particular, VOCs, together with SOx and NOx in combustion exhaust gases, receive sunlight from the atmosphere as the main factor of air pollution. It has been identified as the main substance that causes photochemical reactions to produce ground level ozone and also causes the greenhouse effect.

As shown in FIG. 1, VOCs removal technologies are roughly classified into physical treatment technologies such as adsorption, chemical treatment technologies such as incineration, and biological treatment technologies such as biofilters. It is optionally used depending on the circumstances.

As a material technology, Korean Utility Model Application No. 2000-027730 discloses a odor removing tower, which is a structure of a predetermined size, in a device for removing odorous substances and organic odorous substances including volatile organic compounds generated at industrial sites. ; A blower for transferring a malodorous substance into the inside of the malodor removing tower; An activated carbon fiber filter installed in the malodor removing tower to adsorb the malodorous substance introduced from the blower; And it is disclosed a malodorous substance removal device using activated carbon fibers including a regeneration means for spraying a high-pressure steam into the odor removal tower to remove the malodorous substances adsorbed on the activated carbon fibers to restore the adsorption power of the activated carbon fibers , Korean Patent Laid-Open No. 2001-035502 discloses a 6: 1 to 8: 1 ratio inside a lattice case formed of a medium filter formed of a bottom filter, a support and a nonwoven fabric, and a stainless steel wire mesh in an exhaust gas suction / desorption device for a paint booth. Disclosed is a VOCs adsorption and desorption apparatus for a coating booth composed of a VOCs combustion device equipped with an activated carbon filter and granular activated carbon and a natural zeolite filled with a blower blower.

As a chemical treatment method, Korean Patent Laid-Open Publication No. 2000-06882 discloses KMnO ₄ 10,000 to 80,000 mg / l, NaOCl 1,000 to 50,000 mg / l, Ca (OH) ₂ 100 to 5,000 mg / l, and Na ₂ CO ₃ 100 to Volatile organic compounds comprising one or more components selected from the group consisting of 10,000 mg / l, FeSO ₄ 10,000-200,000 mg / l and CuSO ₄ 10,000-200,000 mg / l and industrial deodorants for treating odors and methods of using the same Korean Patent Laid-Open No. 2001-035478 discloses volatile organic compounds and odor removal including 10,000 to _30,000 mg / l starch, 30,000 to 80,000 mg / l Na ₂ CO _{3 and} 1,000 to 15,000 mg / l CaCO _3. The deodorant composition for the present invention and a method of using the deodorant composition for reacting for 3 seconds to 10 minutes by mixing or spraying 100 to 5,000 mg / l to the malodor source or volatile organic compounds.

In addition, as a biological technology, Korean Patent Laid-Open Publication No. 2000-012740 discloses a device for removing odors and VOC substances contained in air, wherein a contaminant gas passage hole is provided on a lower surface or a lower side, or a lower and lower side. A case having an upper surface or an upper side, or another pollutant gas passage formed on the upper side and the upper side; A support shelf positioned on an inner lower surface of the case; A microbial carrier layer loaded on the support shelf to the height of the exhaust port; Disclosed is a biofilter for deodorizing and decomposing VOC substances, including; a spray tube installed in a form intersecting an empty space between an upper surface of the carrier layer and an upper surface of the case to spray a microbial culture solution onto the carrier layer.

Among these, biodeodorization technology has the technical advantage that it can be operated at room temperature and atmospheric pressure without generating much harmful substances to humans or cause secondary pollution, as well as economic advantages over other treatment technologies. Therefore, in recent years, a number of research cases on the development of various odorous substances and VOCs removal technology using biofilters are increasing rapidly, and in practice, many biofilters are introduced and utilized in the field. However, biofilters can be applied only in situations where the amount and concentration of VOCs are kept constant, and oils and solvents (Benzene, Toluene, Xylene; BTX), etc., are momentarily high and discontinuously when they enter and leave the storage facility. It is not applicable when high concentrations of VOCs are generated. In addition, when treating complex VOCs such as gasoline, a sharp decrease in efficiency occurs, so the development of a pretreatment device thereof should be prioritized.

Accordingly, an object of the present invention is to provide an adsorbent that can drastically reduce the amount of VOCs discharged from storage tanks of all organic hydrocarbon compounds including oils such as gasoline and organic solvents such as benzene, toluene, and xylene. .

Another object of the present invention is to provide a filter filled with the adsorbent so as to maintain the efficiency of the adsorbent optimally.

Adsorbent of the present invention for achieving the above object in the adsorbent for removing VOCs discharged from the vent of the oil and organic solvent storage tank, 100 parts by weight of styrene-butadiene-styrene rubber and / or styrene-isoprene rubber, interface 0.1 to 10 parts by weight of the active agent, and 10 to 300 parts by weight of one or more natural substances selected from the group consisting of activated carbon, sorghum can, charcoal, loofah (plant name) and rice husk as bulking agents.

To achieve another object of the present invention, the filter includes a body having an inlet and an outlet through which VOCs discharged from the vent of the oil and organic solvent storage tank are introduced; The inlet and outlet are connected in series or in parallel to the connecting pipe for connecting a plurality of the body, the body is filled with the adsorbent.

1 is a diagram showing a conventional method of treating VOCs and their problems.

2 is a view schematically showing a first stage form of a filter including an adsorbent according to the present invention.

3 is a view schematically showing a series of three stages of the filter according to the present invention.

Figure 4 is a graph showing the results of evaluating the removal performance for benzene (Benzene) using a filter (Example 1) according to the present invention.

5 is a graph showing the results of evaluating the removal performance of toluene using a filter (Example 2) according to the present invention.

Figure 6 is a graph showing the results of evaluating the removal performance for xylene (Xylene) using a filter according to the present invention (Example 3).

Looking at the present invention in more detail as follows.

First, the VOCs adsorbent used in the present invention uses the oil solidifying agent used in the diffusion prevention and separation of the effluent oil and organic hazardous chemical solution disclosed in Korea Patent Publication No. 2000-61544.

The solidifying agent is a block copolymer prepared by polymerizing butadiene and styrene in an organic solvent under an organic catalyst and a block copolymer prepared by polymerizing styrene and isoprene under an organic catalyst in an organic solvent. Each of these is prepared alone or blended through a physical bonding process with a nonionic surfactant. For example, styrene-butadiene-styrene rubber is prepared by copolymerizing 30 to 55% by weight of 1,3-butadiene and 45 to 70% by weight of styrene in an n-hexane solvent under an alkyl-lithium catalyst. This method copolymerizes styrene and isoprene to form styrene-isoprene rubber. Polyoxyethylene alkyl ether type nonionic surfactant (HLB10 or less), polyoxyethylene oxypropylene glycol compound, sorbitan ester type surfactant, sorbitan ester using methanol as a solvent as a solvent using these as sole or blend It is prepared by physically binding a certain time in a solution of 0.1 to 10% by weight of a surfactant such as an ethoxy compound and / or a fatty acid ester compound.

The oil solidifying agent solidifies the spilled oil in a short time to prevent diffusion and can be easily removed and can be used for the treatment of harmful chemicals, so that it can be widely applied in the field of environmental pollution prevention, especially in marine oil spills. In the event of a large amount of oil being released at the time of an accident or confining oil with an oil fence, it can be solidified instantaneously and floated on the water surface to remove it, thereby maximizing the prevention effect without preventing the spread of spilled oil and causing secondary pollution. It is a big advantage.

However, when the VOCs are removed by filling the solidifying agent with the filter, the solidifying agent is solidified as VOCs are adsorbed to the solidifying agent, thereby causing the filter to be clogged. This clogging occurs from the bottom of the filled solidifying agent, which is the inlet of VOCs, and thus the VOCs do not diffuse throughout the packed bed, resulting in reduced treatment efficiency and pressure loss. That is, the removal of volatile organic compounds emitted from the storage tank in which not only organic solvents and oils (gasoline, diesel, kerosene, naphtha, crude oil, etc.) but also all hydrocarbon-based compounds are stored using the solidifying agent is due to solidification of the overall filler. Not desirable

Therefore, in the present invention, the solidifying agent mixes a certain amount of various natural substances selected from the group consisting of activated carbon, sorghum can, charcoal, scrubber (plant name) and rice husk as bulking agents according to the inflow concentration of VOCs. Use it. As such, by adding the bulking agent to the solidifying agent, the particles exist as independent particles before the adsorption of VOCs, but after the adsorption, the solidification is performed around the bulking agent to prevent clogging of the filter. This increases and the elapsed processing operation time, that is, the replacement time of the filler, becomes long.

According to the present invention, the mixing ratio of the solidifying agent and the bulking agent can be changed according to the amount and concentration of VOCs generated, and can also be changed according to the final required concentration by connecting a plurality of cylindrical filters in series or in parallel as shown in FIG. have. Preferably, the mixing weight ratio of the bulking agent to the solidifying agent decreases later. For example, when three filters are connected in series as shown in FIG. 3, the solidifying agent: bulking agent is filled in a weight ratio of 3: 7, 2: 5 in the 2nd stage, and 7: 3 in the 3rd stage. Pressure loss and short circuit can be minimized.

The filter according to the present invention is designed in the form as shown in Figure 3, the material was made of SUS-304. That is, the filter includes a body having an inlet and an outlet through which VOCs discharged from the vent of the oil and organic solvent storage tank are introduced; It consists of a connecting pipe connecting the inlet and the outlet in series or in parallel, the inside of the body is filled with the adsorbent of the present invention. In addition, the body is connected to the plurality by the connecting tube can minimize the pressure loss and short circuit phenomenon.

Such a filter of the present invention may be used and applied to a pretreatment apparatus of a VOCs removal apparatus such as activated carbon adsorption or a biofilter, or an adsorption removal pretreatment apparatus of VOCs discharged from a painting facility.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to the following Examples.

Preparation Example 1

50% by weight of styrene-butadiene-styrene rubber (SBS) and styrene-isoprene rubber (SI) were each blended into methanol solution containing each surfactant (0.1 to 10% by weight), and then stirred for a predetermined time. Complete the physical bond, separate it and dry it.

[Composition of Solidifying Agent]

SBS & SI 100 parts by weight

5 parts by weight of polyoxyethylene alkyl ether non-ionic surfactant

3 parts by weight of polyoxyethylene oxypropylene glycol compound

30 parts by weight of methanol

-----------

138 parts by weight

The solidification time and the degree of solidification were measured when the solidifying agent prepared in this process was added with 1 to 2 g of the solidifying agent with respect to 10 g of each organic solution, and the results are shown in Table 1 below. Experimental conditions were carried out at room temperature to put 10g of each experimental solution in 0.4L saline solution (2wt% salt).

Solution type Addition amount (%) Solidification time (minutes) Solidification Via 10 3 Good Machine oil 20 3 Good A heavy oil 10 3 Good B heavy oil 20 10 Good Organic solvent 10 3 Good

Preparation Example 2

The filter used in this production example was designed in the form as shown in Figure 3, the material was made of SUS-304, the size of the VOCs inlet was 80mm. The VOCs adsorbent used in the filter was a natural material mixed with activated carbon and charcoal in a ratio of 1: 1 as the solidifying agent and bulking agent of Preparation Example 1. The mixing weight ratio of the solidifying agent and the bulking agent was changed to 3: 7 in the first stage and 5: 5 in the second stage, and 7: 3 in the third stage.

Comparative Example 1-2 and Example 1-6

This example is to measure the service life of the adsorbent, the apparatus used is designed in the form as shown in Figure 2, the material is made of glass. The experiment was carried out by filling the lower Erlenmeyer flask with 500 ml of gasoline and toluene, respectively, and adjusting the air flow rate to 5 L / min with manometa. The VOCs adsorbents used in the upper filter used 100 g of the solidifying agents of Preparation Example 1 and Preparation Example 2, respectively. When the air flow rate of the manometa was reduced to 4.5 L / min or less, the experiment was stopped when the pressure loss occurred, and the remaining amount of the Erlenmeyer flask was measured. The results are shown in Table 2. As shown in Table 2, the amount of VOCs adsorbed per unit adsorbent was 3 to 5 times higher when mixed with the bulking agent as in Preparation Example 2 than when only the solidifying agent of Preparation Example 1 was used, and the pressure loss occurrence time was longer. The lifetime of the adsorbent is considered to be long.

Test subject VOCs Adsorbent (1) Pressure loss occurrence time (hr) Residual volume (ml) VOC concentration in ppm (1) Processing efficiency (%) Adsorption removal amount (g VOCs / g adsorbent) Inlet Outlet Gasoline Comparative Example 1 (Manufacturing Example 1) 1.8 437 114,000 66,500 41.7 0.26 Example 1 (3: 7) * 5.7 295 98,500 22,400 77.3 1.58 Example 2 (5: 5) 4.9 332 94,600 15,600 83.5 1.40 Example 3 (7: 3) 3.6 365 105,000 21,800 79.2 1.07 toluene Comparative Example 2 5.2 367 86,500 42,800 50.5 0.67 Example 4 (3: 7) 11.8 195 87,200 11,200 87.2 2.66 Example 5 (5: 5) 9.4 258 85,900 9,300 89.2 2.16 Example 6 (7: 3) 7.8 304 86,600 10,500 87.9 1.72

* The ratio is the mixed weight ratio of the solidifying agent and bulking agent of Preparation Example 1.

Example 7

The temperature of the benzene storage tank was maintained at 50 ° C. to evaluate the removal performance of benzene using the filter prepared in Preparation Example 2, and the experiment was carried out with the filling height and the capacity of the adsorbent as 20 cm and 3 L. As a result of using gas chromatography (Model: HP 5890, Column: FID) as shown in Figure 4 was obtained.

As can be seen in Figure 4, the average removal efficiency during the driving time 55hr was about 85% was very high. In order to determine the accuracy of the removal, the measurement was performed using a gas chromatography-quantitative analyzer (HP 5973N). As a result, as a result of analyzing the samples collected at the operation time of 24 hr, the removal concentration of 454 ppm was measured at the inflow concentration of 12,340 ppm and the removal efficiency was about 96%.

Example 8

To evaluate the removal performance of toluene using the filter prepared in Preparation Example 2, the temperature of the toluene storage tank was maintained at 30, 40, and 50 ° C., and the filling height and capacity of the adsorbent were 20 cm and 3 L. While performing the experiment, the average removal efficiency measured using gas chromatography was measured, and the results as shown in FIG. 5 were obtained.

As shown in FIG. 5, the removal efficiency tended to decrease slightly as the experiment temperature was increased, but the removal efficiency was higher than about 95%.

Table 3 below shows the results obtained by using a gas chromatography-quantitative analyzer after taking a sample at an experimental elapsed time of 24 hr. Regardless of temperature change, the removal efficiency was over 99%.

Temperature (℃) Inflow concentration (ppm) Runoff concentration (ppm) Removal efficiency (%) 30 5,340 20 99.63 40 11,570 60 99.48 50 11,540 70 99.39

Example 9

The temperature of the xylene storage tank was maintained at 50 ° C. to evaluate the removal performance of xylene using the filter prepared in Preparation Example 2, and the experiment was carried out using a packing height and a capacity of 20 cm and 3 L of the adsorbent. As a result of measuring xylene removal efficiency of up to 60 hr of elapsed time using gas chromatography, the results as shown in FIG. 6 were obtained. As shown in FIG. 6, the average removal efficiency during the driving time of 60 hr was very high, about 97%.

On the other hand, as measured by a gas chromatography-quantitative analyzer for a sample taken at 24 hours of elapsed operating time, the flow rate was not measured at an inflow concentration of 8,750 ppm. In addition, both ethylbenzene and xylene were removable.

As described above, as a result of measuring the adsorption removal efficiency of the adsorbents for BTX according to the present invention all shows a high removal efficiency of more than 90%, it is possible to effectively increase the amount of VOCs discharged from the BTX storage tank to effectively reduce the air pollution by VOCs It is expected to be considerably reduced. In addition, as shown in FIG. 3, when the filter of the present invention is installed in multiple stages or when the biofilter is installed as a high treatment process after the adsorption pretreatment of the adsorbent according to the present invention, it is determined that the emission standard concentration or less can be sufficiently satisfied.

Example 10

The temperature of the storage tank was maintained at 35 ° C. to evaluate the removal performance of gasoline, diesel and indoor kerosene using the filter prepared in Preparation Example 2, and the filling height and capacity of the adsorbent according to the present invention were 30 cm and 4.5. While performing the experiment with ℓ using a sample of gas chromatography and gas chromatography-quantitative analyzer in the elapsed operating time 48 hr sample was analyzed and the results were obtained as shown in Table 4.

sample Operating temperature (℃) Driving elapsed time (hrs) Inflow concentration (ppm) Runoff concentration (ppm) Removal efficiency (%) Remarks Gasoline 35 ℃ 48 24,511 1,519 93.8 GC / MS Via 12,250 453 96.3 GC, FID Indoor kerosene 13,470 512 96.2 GC, FID

As shown in Table 4, gasoline with a very low boiling point exhibited very high removal efficiencies of 90% or more, even though the experimental temperature was tested at 35 ° C under very bad conditions. Considering that the holding temperature is 30 ° C. or less, it is judged that the practicality of the filter according to the present invention is very large. In addition, in the case of diesel oil and indoor kerosene, the removal rate is very high, about 96% or more, and it is determined that the adsorbent of the present invention can effectively reduce the air pollution weighting problem caused by VOCs.

As described above, the present invention can be used for adsorption and removal of organic solvents and oils (gasoline, diesel, kerosene, naphtha, crude oil, etc.) as well as volatile organic compounds discharged from a storage tank in which all hydrocarbon-based compounds are stored. It can be used and applied to the pretreatment device of VOCs removal device such as activated carbon adsorption, biofilter, the adsorption removal pretreatment device of VOCs discharged from coating facilities.

Claims (6)

In the adsorbent for removing VOCs discharged from the vent of the oil and organic solvent storage tank, 100 parts by weight of styrene-butadiene-styrene rubber and / or styrene-isoprene rubber, 0.1 to 10 parts by weight of surfactant, and bulking agent selected from one or more selected from the group consisting of activated carbon, sorghum, charcoal, scrubber (plant name) and rice husk Volatile organic material adsorbent comprising 10 to 300 parts by weight of natural materials. The method of claim 1, wherein the surfactant is a polyoxyethylene alkyl ether type nonionic surfactant (HLB 10 or less), polyoxyethylene oxypropylene glycol compound, sorbitan ester type surfactant, sorbitan ester ethoxy compound and fatty acid ester At least one adsorbent selected from the group consisting of compound compounds. A body having an inlet and an outlet through which VOCs discharged from a vent of the oil and organic solvent storage tank are introduced; Consists of a connecting pipe connecting the inlet and outlet in series or parallel to the body, The inside of the body is filled with the adsorbent according to claim 1 or 2, characterized in that the adsorption filter volatile organic material. The volatile organic material adsorption filter according to claim 3, wherein the mixing weight ratio of the bulking agent to the solidifying agent in the adsorbent filled in the body decreases toward the rear end. The method according to claim 4, wherein when the three bodies are connected, the solidifying agent: bulking agent in the first stage is filled in a weight ratio of 3: 7, the second stage is 5: 5, and the third stage is filled with 7: 3. Volatile organic material adsorption filter. The method of claim 3, wherein the filter is used as a pretreatment device for activated carbon adsorption VOCs removal device, a pretreatment device for biofilter VOCs removal device, or an adsorption removal pretreatment device for VOCs discharged from a painting facility. filter.