KR101486238B1 - Manufacturing method of metal impregnated active carbon fiber for target solvent voc killing - Google Patents

Abstract

The present invention relates to an active metal impregnating active material capable of selectively adsorbing and catalytically decomposing a specific solvent such as acetone, benzene, and ethylene glycol used in a diffusion process or a cleaning process in a semiconductor or LCD manufacturing process by attaching an active metal to activated carbon fiber And a method for producing carbon fiber.

Description

TECHNICAL FIELD [0001] The present invention relates to a method of manufacturing a specific solvent-target activated metal impregnated activated carbon fiber,

The present invention relates to an active metal impregnated active material capable of selectively adsorbing and catalytically decomposing an organic solvent such as acetone, benzene, and ethylene glycol used in a diffusion process or a cleaning process in a semiconductor or LCD manufacturing process by attaching an active metal to activated carbon fiber And a method for producing carbon fiber.

At present, in the case of granular activated carbon or powder activated carbon, which is used for removing environmental pollutants in various kinds of ship water and water treatment fields, most of the reaction mechanisms are physically adsorbed, which restricts adsorption and does not adsorb satisfactorily.

In addition, there is a disadvantage that the amount of filling must be large in order to obtain a relatively high efficiency, and therefore, it is limitedly applied only to the use of a mobile facility or a local exhaust device.

Activated carbon fiber is a fibrous active material composed of polycrystalline structured fiber polymer. It is a new material produced by a kind of advanced science and technology. It is highly efficient and stable in performance. Therefore, it can be applied to various applications. All.

This is because the adsorption efficiency is more than 10 times higher than that of activated carbon in granular state, and the activated carbon fiber (ACF) is not restricted in length, has good selectivity, uniform quality and stability, high adsorption capacity and high strength, It does not pollute tea pollution and has advantages of acid, alkali resistance, high temperature, nontoxic, tasteless, adsorption, desorption speed, long service life, various forms and convenient processing.

Activated metal impregnated activated carbon fiber is a new material material which has a specific metal salt impregnated on existing activated carbon fiber and greatly improved the chemical adsorption performance by adding catalytic performance by metal salt to the adsorption power of existing activated carbon fiber.

Particularly, the active metal impregnated activated carbon fibers have the advantage of being able to produce target activated carbon fibers exhibiting superior performance in adsorption of specific substances by adhering specific components.

 The present invention reveals limitations in terms of selectivity and efficiency in completely targeting and capturing not only benzene, which is a hazardous chemical used in the semiconductor diffusion process and the cleaning process but also specific materials such as ethylene glycol, acetone, n-butyl acetate and n-hexane have. Accordingly, it is an object of the present invention to provide a specific solvent-targeted active metal impregnated activated carbon fiber capable of targeting and adsorbing such a specific material and a method for producing the same.

The present invention is to develop a porous target adsorbent for removing various solvents and solvent components discharged in various processes, and it is intended to provide an adsorbent having improved adsorption performance and ability to adsorb specific substances to existing adsorbents.

In order to further improve the high pores and excellent adsorption performance of existing activated carbon fibers (ACFs), the present invention may be used for adsorbing a screened active metal to increase adsorption performance for a specific solvent, , Impregnation time, and temperature, it is possible to supply impregnated activated carbon fibers of target activated metal which completely improves the problem that the conventional physical adsorption method does not catch or the adsorption efficiency deteriorates.

 The present invention can be applied to industrial sites where harmful organic solvents and the like are used to completely remove harmful substances from human bodies. In particular, in the case of a target-type adsorbent, it can exhibit superior performance in adsorbing toxic substances, And so on.

In addition, it is applied to various industrial fields and exhibits excellent adsorption performance and selectivity even in a small volume, so that the size of the air pollution prevention facility can be reduced and the facility can be efficiently operated.

In addition, when impregnated activated carbon fibers or ion-exchange activated carbon fibers, which have already been applied to the water treatment field, are selectively applied, it is possible to smoothly apply the present invention to the fields of selectively adsorbing specific substances and improving water pollution.

FIG. 1 shows the adsorption performance of acetone according to the impregnated active metal. The SV value at this time is 3,000 hr ^-1 , the impregnation temperature is 100 ° C, and the impregnation time is 5 hr.

The present invention relates to the production of impregnated activated carbon fibers.

In order to produce impregnated activated carbon, impregnated active carbon fiber was pretreated first, and impregnated active carbon fiber was prepared and final impregnated activated carbon was produced through impregnation with final impregnated active carbon fiber.

Of activated carbon fiber  Pretreatment

The activated carbon fiber absorbs and absorbs a considerable amount of water and organic matter from the atmosphere even before the impregnated material is adhered due to its high specific surface area and adsorption characteristic. Therefore, it is necessary to remove these foreign materials in order to smoothly and optimally impregnate the active metal. Therefore, the activated carbon fiber is slowly heated (10 ³ torr) under vacuum (105 ° C) and heated and desorbed for 24 hours or more .

Activated carbon fiber Additive solution  Produce

Copper, Cu, platinum, Pt, chromium, Cr, palladium, and Pd were selected as active metals for screening. A wearing solution was prepared. The amount of distilled water used to dissolve the impregnated metal was determined in consideration of the specific surface area of the activated carbon fiber used in the present invention. The amount of distilled water was determined so that the active metal could be sufficiently dispersed and impregnated on a wide surface. The results are shown in Table 1. In the basic experiment, it was confirmed that when the impregnated metal loading exceeded 0.5 wt.%, The impregnated properties were deteriorated and the metal loading was maintained at 0.20 to 0.25 wt.%.

Conditions for impregnated metal solution preparation Impregnated metal Impregnated metal loading (g) Amount of distilled water (g) Cu 0.25 wt% / ACF g ACF per gram, 20ml Cr Cr, Pt Cr, Pd Cr, Pt, Pd Cu, Cr, Pt, Pd

As a precursor of impregnated metal, Cr (NO ₃ ) ₃ (Chromium (III) nitrate solution 40%) for chromium, CuSO ₄ (Copper (II) sulfate 97.5%) for copper, Pd ₃ ) ₂ (Palladium nitrate 10%) and H ₂ PtCl ₆ · nH ₂ O (Chloroplatinic acid hydrate 10%) were used.

In the present invention, impregnated activated carbon fiber manufacturing process is based on the most simple and widely used impregnation method. In this method, activated carbon is dipped in a metal salt solution to impregnate deeply into the pores, followed by activation through post treatment.

In general, when impregnated activated carbon is produced, impregnated metal is impregnated in an ionic state and in a saturated state in order to secure activity on a surface of activated carbon fiber to be adsorbed gas, so that impregnated activated carbon fiber having excellent adsorbability can be produced.

Activated carbon fiber  Active metal solution Affix

The prepared activated carbon fibers were impregnated into the prepared active metal solution through the above screening and manufacturing process, and active metal impregnated activated carbon fibers were prepared. Activated metal impregnated activated carbon fibers were prepared by selecting the type of impregnated metal solution, the reaction temperature at impregnation, and the change of impression time.

Conditions and conditions for impregnation of the metal solution applied in the present invention are shown in Table 2.

Conditions of metal impregnation according to manufacturing variables Manufacturing variable Attachment condition Activated carbon fiber 5 g Impregnated metal Cu, Cr, Cr-Pt, Cr-Pd, Cr-Pt-Pd, Impingement time 1, 3, 5 hr Impingement temperature 25 ° C, 100 ° C

Impregnated activated carbon fiber  Drying and Activation

The impregnated activated carbon fibers prepared under the above impregnation conditions are dried to remove the solvent and to leave only the impurities on the surface of the pores. Since the porous material such as activated carbon fiber takes a long time to completely dry even the solvent in deep micro pores, it is necessary to remove the moisture of the solution and remove moisture in a short time, After removing moisture from the vacuum chamber using an evaporator and drying, the drying was finally performed in the oven. The drying conditions are shown in Table 3.

Impregnated activated carbon fiber drying conditions division Drying conditions Aspirator / Rotary Evaporator 80 ℃ 40 min Dry oven 110 ° C 24 hr

After the above drying process, the metal salt is dried at 150 ° C. for about 3 hours under a nitrogen atmosphere to activate the metal salt. Nitrogen injected was filtered through an air filter to remove water and the flow rate was controlled by an MFC controller. The heating temperature was raised in two steps, initially adjusted to 90 ° C for 1 hour and then activated at 150 ° C for 3 hours. Table 4 shows the activation conditions.

Impregnated activated carbon fiber activation conditions division Drying conditions N2 gas 12 to 15 ml / min - ACF g Time 3 hr Temperature 150 ℃

Impregnated activated carbon fiber  Reaction activity test

As a representative experimental material of the chain structure organic compound for the impregnated activated carbon fiber prepared by the method applied to the present invention, acetone was selected as a substance to be abated and an abatement efficiency measurement experiment was conducted. The acetone removal efficiency was analyzed using a GreenLine 9000 gas analyzer from Eurotron, the first type approved by the Ministry of Environment. The acetone gas introduced into the reactor was a 0.01% concentration gas manufactured by Seonggang Specialty Gas Co., and the gas flow rate was controlled by SMTEK MFC and DFC-5000. The acetone gas used in the experiment was CH ₃ COCH ₃ 0.1% (N ₂ balance). The reaction activity test conditions used in the present invention are shown in Table 5.

Experimental conditions of impregnated activated carbon fiber reaction activity division Condition Gas Acetone, benzene Concentration (ppm) 300 Space velocity (hr-1) 3,000, 6,000, 12,000 Time (min) 0 to 120 (15 min interval) Temperature (℃) 25, 100

Removal of acetone from activated carbon fiber impregnated with copper as active metal

Adsorption performance test for acetone on activated carbon impregnated activated carbon fibers, which were prepared by using copper as an active metal and different preparation times of copper for 1hr, 3hr and 5hr as manufacturing variables, were performed. On the other hand, SV was tested at 3,000, 6,000, and 12,000 hr ^-1 , respectively, by changing the impregnation temperature of copper.

The acetone removal efficiency of activated carbon fiber with copper as active metal (loading time 5 hr) time
(min) SV-3,000 SV-6,000 SV-12,000 Existing ACF 25 ℃ 100 ℃ Existing ACF 25 ℃ 100 ℃ Existing ACF 25 ℃ 100 ℃ 0 100 100 100 100 100 100 69 72 75 15 100 100 100 80 100 100 59 70 72 30 100 100 100 70 100 100 48 58 65 45 78 100 100 61 82 100 43 52 58 60 75 100 100 56 80 78 40 43 50 75 74 80 100 54 73 75 37 39 42 90 74 78 80 54 71 71 33 38 34 105 71 76 78 49 64 67 30 27 29 120 71 72 74 49 57 59 27 25 26

It was confirmed that the activated carbon fiber impregnated with copper had a 100% increase in adsorption retention time more than twice as compared with the existing simple activated carbon fiber.

On the other hand, the impregnated activated carbon fibers produced at higher temperatures exhibited a 100% adsorption performance duration of 25% than the activated carbon fibers impregnated with copper at 125% and 25, respectively, rather than the activated carbon fibers. As a result, it was confirmed that the impregnation of metal at high temperature was effective for increasing the adsorption performance of activated carbon fiber. It was confirmed that activation energy above a certain temperature during the manufacturing process contributes to the impregnation of the metal and hence the adsorption performance.

Removal of acetone from activated carbon fiber impregnated with chromium as active metal

The acetone adsorption performance of activated carbon fiber impregnated with chromium as an active metal was tested. As in the case of copper, chromium migration time of 1hr, 3hr, and 5hr were prepared as manufacturing variables. The reaction parameters were changed to 3,000, 6,000, and 12,000 hr ^-1 , respectively.

The acetone removal efficiency of activated carbon fiber with chromium impregnated with active metal (loading time 5 hr) Time
(min) SV-3,000 SV-6,000 SV-12,000 Existing ACF 25 ℃ 100 ℃ Existing ACF 25 ℃ 100 ℃ Existing ACF 25 ℃ 100 ℃ 0 100 0 100 100 100 100 100 69 71 71 15 100 100 100 80 100 100 59 68 71 30 100 100 100 70 100 100 48 60 67 45 78 100 100 61 82 100 43 54 59 60 75 100 100 56 79 80 40 48 51 75 74 79 100 54 74 75 37 41 42 90 74 78 100 54 71 71 33 38 31 105 71 76 75 49 63 67 30 34 29 120 71 74 72 49 58 61 27 26 26

The overall adsorption performance was found to be excellent when adsorbed at high temperatures as in the case of copper. However, in the case of activated carbon fiber impregnated with chromium, the better the adsorption performance was, the longer the adsorption time was.

Remove activated carbon fiber acetone impregnated with chromium, platinum and palladium mixture

Since chromium exhibited the best adsorption performance, adsorption performance evaluation was carried out by impregnating platinum and palladium with impregnated metal, which had good oxidation activity and good adsorptivity. Since it was confirmed that the activated carbon fibers prepared at a high temperature of 100 had a better adsorption performance, the impregnated activated carbon fibers were not prepared and impregnation was performed for 5 hours at a time so that the impregnation time was maximized .

As a result of the adsorption performance measurement, the adsorption performance was improved by the low SV, and the adsorption performance was about 8 ~ 10% higher than the activated carbon fiber of the chromium impregnation, 100 production, and SV = 3,000 hr ^-1, It can be confirmed that it is improved.

In addition, when the platinum and palladium precious metals were impregnated, the effect was good even under the condition of SV of 6,000 hr ^{-1. As} a result, it was confirmed that the adsorption performance can be guaranteed even at a relatively high SV when mixed with various metals.

Removal of acetone from the activated carbon fiber impregnated with a mixture of chromium, platinum and palladium as an active metal (carrying time: 5 hr) time
(min) SV-3,000 SV-6,000 SV-12,000 Existing ACF 100 ℃ Existing ACF 100 ℃ Existing ACF 100 ℃ 0 100 100 100 100 69 100 15 100 100 80 100 59 73 30 100 100 70 100 48 68 45 78 100 61 100 43 64 60 75 100 56 100 40 57 75 74 100 54 100 37 49 90 74 100 54 76 33 39 105 71 100 49 71 30 30 120 71 78 49 62 27 25

Removal of acetone from activated carbon fiber impregnated with a mixture of copper, chromium, platinum and palladium

As a result of the above acetone removal efficiency test, the removal efficiency of chromium and platinum palladium metal materials was highest when they were carried at 100 ° C for 5 hours. Therefore, the adsorption performance test was carried out by adding copper to chromium and platinum palladium metal materials with high removal efficiency.

Removal of acetone from the activated carbon fiber impregnated with a mixture of copper, chromium, platinum and palladium as the active metal (carrying time 5 hr) time
(min) SV-3,000 SV-6,000 SV-12,000 Existing ACF 100 ℃ Existing ACF 100 ℃ Existing ACF 100 ℃ 0 100 100 100 100 69 100 15 100 100 80 100 59 70 30 100 100 70 100 48 62 45 78 100 61 100 43 58 60 75 100 56 100 40 52 75 74 100 54 100 37 47 90 74 100 54 100 33 41 105 71 100 49 76 30 36 120 71 100 49 65 27 31

As a result of the performance test, it was confirmed that the activated carbon fiber impregnated with the impregnated metal copper-chromium-platinum-palladium mixture completely maintained the adsorption performance of 100% at SV of 3,000 hr ^-1 there was.

SV: SPACE VELOCITY
ACF: Activated carbon fiber (ACTIVE CARBON FIBER)
MFC: Mass flow controller (MASS FLOW CONTROLLER)

Claims (3)

The present invention relates to a process for producing an active metal impregnated activated carbon fiber exhibiting excellent adsorption ability to a specific solvent,
(S1) heating the activated carbon fibers under a vacuum (10 ³ torr) to gradually heat and desorb moisture and foreign matter at 105 ° C for at least 24 hours;
(S2) a step of preparing an impregnation solution of copper, platinum, chromium and palladium, which are selected candidates of impregnated metal through screening;
(S3) attaching the activated carbon fiber prepared in the step (S1) and the additive liquid prepared in the step (S2) to the activated carbon fiber using an impregnation method;
The impregnated activated carbon fibers prepared in the step (S3) are dried in a vacuum oven using a vacuum dryer aspirator and a rotary evaporator, followed by drying in a dry oven (S4);
(S5) activating the impregnated activated carbon fibers dried in step (S4) at 90 DEG C for 1 hour and then for 3 hours at 150 DEG C in a nitrogen atmosphere, Method of manufacturing fiber The method according to claim 1, characterized in that the amount of metal supported is maintained at 0.20 to 0.25 wt% in adhering at least one metal selected from the group consisting of copper, chromium, platinum, palladium and mixtures thereof as the active metal Method for producing active metal impregnated activated carbon fiber A process for producing an active metal impregnated activated carbon fiber according to claim 1, which exhibits an adsorption capacity of 5 to 100% higher than that of the existing activated carbon fiber in acetone, benzene, ethylene glycol, n-butyl acetate and n-hexane,

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