JP5298292B2 - A temperature swing method VOC concentration and a low-temperature liquefied VOC recovery method in which moisture is removed using an adsorbent and cold energy is recovered. - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a VOC recovering method by low temperature VOC condensation following the removal of moisture after performing volume reduction/concentration on a treated gas in a temperature swinging VOC absorption apparatus. <P>SOLUTION: VOC is adsorbed at a low temperature by the temperature swinging VOC adsorption apparatus; nitrogen is desorbed as a purge gas at a high temperature; after volume reduction/concentration is performed on the treated gas, nitrogen containing VOC and moisture is pressurized and is introduced into a moisture selective-type adsorbent adsorption towers 15a, 15b to remove the moisture. Liquefaction recovery is performed on VOC at a low temperature; cold is recovered from dry nitrogen after the recovery; then the adsorption tower after the moisture is adsorbed is decompressed to adsorb and remove the moisture and a heat retentive cold recovery is performed using the dry nitrogen as a countercurrent purge gas; and after the moisture is removed from nitrogen that is allowed to flow for filtration, the nitrogen is reflux-recycled as a purge gas. As a VOC selective-type adsorbent 5, one kind or more are selected from the group consisting of silica lite, USM, &beta;, USY, MSP, and, as a moisture selective-type adsorbent 16, one kind or more are selected from the group consisting of K-A, Na-A, Na-K-A and Ca-A. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention is a temperature swing method VOC concentration / low temperature liquefied VOC recovery method in which moisture is removed using an adsorbent and cold energy is recovered.

  The most frequently used method for treating exhaust gas containing VOC is to supply VOC contained in the exhaust gas to an adsorption tower packed with high silica zeolite to adsorb and remove VOC, and to adsorb VOC. This is TSA-VOC + catalytic combustion in which high temperature hot air is supplied to the adsorption tower to desorb VOC at high temperature, and the VOC desorbed by volume reduction and concentration is oxidized and decomposed by catalytic combustion.

  Also expected to be widely used in the future is a life-extinguishing discharge on the surface of a ferroelectric (barium titanate, etc.) packed by the US Environmental Protection Agency (EPA), which contains VOC-containing gas. There is a packed tower plasma treatment that oxidizes and decomposes by supplying (Paked Bed Plasma). Although these methods show a certain level of performance for VOC processing, TSA-VOC + catalytic combustion has the limitations of cost reduction due to the complexity of the equipment and the complexity of operation. In packed tower plasma processing, the target VOC and VOC are removed. There is a concern that the rate will be limited and future VOC emission regulations will not be met.

  It may be possible to add ozone to the VOC-containing gas and oxidatively decompose it by homogeneous gas phase reaction of VOC, but the ozone oxidation reaction to low concentration VOC is slow, the treatment of unreacted ozone is complicated, and it is used as an oxidant Since the production cost of ozone is high, it has not been put into practical use. In order to improve the reaction efficiency of the ozone oxidation reaction, VOC is adsorbed on high silica zeolite and removed, then ozone is added to the high silica zeolite adsorbed with VOC to co-adsorb the VOC and ozone in the zeolite. It has been proposed to improve efficiency. Although the efficiency of the ozone reaction can be improved by this method, the cost of manufacturing ozone is still unsolved.

Oxygen Selectivity on Partially K Exchanged Na-A Type Zeolite at Low Temperature, IZUMI J, SUZUKI M, ADSORPTION, VOL. 7, PAGE. 27-39, (2001).

  In the above-described prior art, a method for recovering the VOC without degrading it with high efficiency has not been put into practical use. In particular, using cold storage air heat storage heat exchanger as a cold recovery method, using a heat storage heat exchanger, using VOC recovery as a moisture adsorbent, using dry air after cold recovery, continuous cold recovery, moisture The use of removal methods is not known.

  The present inventors introduced air containing volatile organic compounds (hereinafter referred to as VOC) and moisture into a VOC selective adsorbent adsorption tower at a relatively low temperature in at least one of the two tower type adsorption towers. The VOC is adsorbed by the adsorbent to release the air out of the system, the adsorbed VOC is desorbed using nitrogen at a relatively high temperature, the VOC treatment gas is reduced in volume, and the volume is reduced. Concentrated VOC gas is adsorbed by adsorbing air containing volatile organic compounds (hereinafter referred to as VOC) and moisture into a moisture-selective adsorbent adsorption tower in at least one of the two tower type adsorption towers. The water is adsorbed to the adsorbent and separated from the VOC, and then introduced into the heat storage material packed tower cooled to a low temperature, brought into contact with the heat storage material, cooled, and cooled to the coldest temperature. Liquefaction and recovery of VOC by cooling in a vessel, low temperature, low VOC flowing through Reduce the pressure of air with a low moisture concentration, introduce it into another heat storage material packed tower, bring it into contact with the heat storage material, recover the cold, raise the temperature, reduce the air, and introduce it into another moisture selective adsorbent adsorption tower The adsorbent to desorb moisture from the adsorbent, regenerate the moisture adsorbent, switch the tower before moisture breaks through, remove moisture, collect cold, and remove moisture from the flowing nitrogen. After the removal, it was found that the VOC recovery method under the low temperature liquefaction condition was established continuously by using it for the high temperature regeneration of the VOC selective adsorbent.

Thus, according to the present invention, the following inventions 1 to 8 are provided:
1. In one of at least two towers, an air containing a volatile organic compound (hereinafter referred to as VOC) and water is introduced into the VOC adsorption tower at a relatively low temperature and brought into contact with the VOC selective adsorbent. VOC is adsorbed by an adsorbent, air is released to the outside of the system, and the adsorbed VOC is desorbed using nitrogen at a relatively high temperature to reduce and concentrate the VOC processing gas, and to reduce at least the reduced and concentrated VOC gas. in 1 column of the adsorption tower of the double column, a volatile organic compound Mono及 beauty a nitrogen containing water pressurized by introducing into water adsorption tower water selective adsorbent adsorbent moisture in contact with Adsorption and separation from VOC, followed by cooling with a cooler to reach the coldest temperature, liquefying and collecting VOC, reducing low VOC and low moisture concentration nitrogen flowing through, adsorbing other moisture It is introduced into a moisture-selective adsorbent adsorption tower and brought into contact with the adsorbent to remove moisture. The temperature used to regenerate the moisture adsorbent by desorbing from the adsorbent, switching the tower to remove the moisture before the moisture breaks through, removing the nitrogen that has passed through, and then regenerating the VOC selective adsorbent at a high temperature Swing method VOC concentration, low temperature liquefied VOC recovery method.
2. In the above SL 1, the VOC adsorption towers instead filled at least two tower of VOC selective adsorbent, using VOC adsorption tower of the rotor type having a low temperature adsorption zone and high temperature zone, the purge gas of the hot regeneration zone A temperature swing method VOC concentration and low temperature liquefied VOC recovery method, in which nitrogen is used to liquefy and recover VOC in a low temperature liquefaction condenser, and then the nitrogen that has passed is removed from the water, and then used for high temperature regeneration of the VOC selective adsorbent.
3. In the above SL 1 Similarly, the VOC adsorption towers instead filled at least two tower of VOC selective adsorbent, using VOC adsorption tower of the rotor type having a low temperature adsorption zone and high temperature zone, a purge gas of the hot regeneration zone Temperature swing method VOC concentration in which high-temperature air is used for liquefaction and VOC is liquefied and collected in a low-temperature liquefaction condenser, and then air containing non-condensed VOC and water that has passed through is returned to the low-temperature adsorption zone of the VOC selective adsorbent. Low temperature liquefied VOC recovery method.
4 . The VOC selective adsorbent is at least one selected from the group consisting of silicalite, USM, β, USY, MPS, VOC according to 1 above , temperature swing method VOC concentration after removing moisture from moisture-containing air, low temperature Liquefied VOC recovery method .
5 . Moisture selective adsorbent, K-A, is Na-A, one or more selected from the group consisting of Na-K-A and Ca-A, according to the above item 1, wherein VOC, after removal of water from moisture-laden air Low temperature liquefied VOC recovery method .
6 . One or more kinds of moisture-selective adsorbents selected from the group consisting of KA, Na-A, Na-KA and Ca-A whose surfaces are in a liquid phase and silica-coated with a hydrolysis product of an organosilicon compound in it, the one wherein the VOC, low-temperature liquefied VOC recovery method after removal of water from the moisture-containing air.
7 . One or more kinds of moisture-selective adsorbents selected from the group consisting of KA, Na-A, Na-KA and Ca-A whose surfaces are in the gas phase and silica-coated with hydrolysis products of organosilicon compounds in it, the one wherein the VOC, low-temperature liquefied VOC recovery method after removal of water from the moisture-containing air.
8 . 8. A low-temperature liquefied VOC recovery method in which a moisture-selective adsorbent is formed in a honeycomb and performs water removal and cold recovery as described in any one of 1 to 7 above .

In this method, a raw material gas containing VOC and moisture is adsorbed by a VOC selective adsorbent at a relatively low temperature near room temperature, detoxified air is released out of the system, and the adsorbed VOC is released at a relatively high temperature. Since VOC is desorbed using nitrogen and the volume is reduced to about 4 to 12 times, the downstream low-temperature liquefied VOC recovery device can be miniaturized , and nitrogen is used as the purge gas. Deterioration, VOC adsorbent deterioration, and ignition, explosion, etc. during VOC recovery can be avoided. Recovery of volume-reduced and concentrated VOC near atmospheric pressure is performed in an adsorption tower filled with a moisture adsorbent that hardly adsorbs VOC, and the nitrogen from which VOC has been removed is used to regenerate the VOC adsorbent in the previous stage. Therefore, in this method, VOC in the VOC-containing nitrogen can be liquefied and recovered at a low temperature below room temperature. Therefore, the recovery process is safe because it is performed in a nitrogen atmosphere, and VOC is recovered without deterioration, and the VOC adsorbent is not deteriorated. By adopting this method, it is possible to provide a VOC recovery apparatus that is compact, safe and operated in a nitrogen atmosphere, and that saves energy and does not deteriorate the recovered solvent and adsorbent.

1 shows a first embodiment of the present invention. 2 shows a second embodiment of the present invention. Example 4 3 shows a third embodiment of the present invention. (Example 5)

The VOC selective adsorbent used in the present invention is at least one selected from the group consisting of silicalite, USM, β, USY, MPS, and the moisture selective adsorbent used in the present invention is KA, Na. It is 1 or more types chosen from the group which consists of -A, Na-KA and Ca-A. Here, Na-K-A is obtained by reducing a window diameter by exchanging a part of Na of Na-A-type zeolite with K and performing a heat treatment. This preparation method is described in Non-Patent Document 1. ing.
The VOC selective adsorbent is judged to have a high VOC / moisture separation coefficient in the VOC-water binary system, and the moisture selective adsorbent has a high water / VOC separation coefficient in the VOC-water binary system. To be judged.

  As the moisture selective adsorbent, from the group consisting of KA, Na-A, Na-KA and Ca-A whose surfaces are silica-coated with a hydrolysis product of an organosilicon compound in the liquid phase or gas phase. It is preferably one or more selected. Moisture selectivity is enhanced by silica-coating the surface of the adsorbent crystal in the gas phase or liquid phase with the hydrolysis product of the organosilicon compound.

The moisture-selective adsorbent having a silica coat on the crystal surface used in the present invention is obtained by suspending zeolite powder in a slurry form in a solvent such as methyl alcohol, and a template such as tetraethoxyorthosilicate (TEOS) on the crystal surface. When an amount corresponding to the necessary thickness is added, and water is added thereto at a H ₂ O / TEOS ratio of about 5 to 20, silica is precipitated.

  After coating is completed, silica sol is added to prepare a slurry of zeolite: silica sol: deionized water = 5 to 30: 1 to 10: 100, and the slurry is immersed and supported on the honeycomb substrate, and the temperature is about 90 to 150. Remove the surface moisture at about 0.5-3 hours at ℃, heat up at about 30-80 ℃ / h and hold at about 250-450 ℃ for about 0.5-3 hours to complete dehydration of silicic acid Thus, the Si—O—Si network on the zeolite crystal surface is completed and the activation by dehydration is completed. Under this coating condition, a silica thin film of 0.05 to 0.1 μm is formed on the crystal surface.

  Similarly, when ammonia vapor containing TEOS (tetra-ethyl-ortho-silicate) or TMOS (tetra-methyl-ortho-silicate) is adsorbed on the A-type zeolite powder, the surface of the A-type zeolite crystal is hydrolyzed by TEOS and TMOS. In addition, a Si-O-Si network is formed to produce a silica thin film.

  Silica-coated KA, Na-A, Na-KA, and Ca-A zeolite may be used in combination of two or more thereof.

If the adsorbent having a silica coat on the crystal surface used in the present invention is a honeycomb-formed adsorbent, it is desirable because the pressure loss when passing through the adsorbent adsorption tower is reduced. As a method for preparing the honeycomb, the zeolite is supported by dipping in a mixed slurry of the zeolite and an inorganic binder such as silica sol on an aluminosilicate substrate and drying it. When the soaking and drying are repeated several times, a predetermined loading amount is reached. (Bulk density of 0.3 or more, zeolite loading of 0.1 g / ml or more) When this is calcined at 350 ° C. or more for 1 hour, fixation and activation of the zeolite to the base material are achieved.
Another method is to prepare a paper containing zeolite with aluminosilicate fiber, the zeolite, inorganic binder, and cellulose (making paper), forming a part of it into a corrugated shape using a corrugating machine, and laminating flat plates and corrugated plates alternately. Then, the honeycomb is formed. When this is calcined at 350 ° C. or higher for 1 hour, fixation and activation of the zeolite to the base material are achieved.

[VOC adsorption tower]
First step (A tower-adsorption process, B tower-regeneration process)
In FIG. 1, VOC and moisture containing air are passed from a flow path 1 and a blower 2 to a VOC adsorption tower 4a filled with a VOC / moisture selective VOC adsorbent 5 through a valve 3a. When supplied at 50 ° C., only the VOC is selectively adsorbed and the air from which the VOC has been removed flows from the rear of the tower and is discharged out of the system through the valve 6 a and the flow path 7. At this time, the VOC adsorption tower 4b holds the VOC that has been adsorbed in the previous adsorption process, and the nitrogen that has been refluxed from the liquefaction recovery process and heated by the heater 29 comes into contact with the VOC adsorbent 5 and decreases. It is concentrated and desorbed. The volume-reduced and concentrated VOC-containing nitrogen flowing from the flow path 12 is supplied to the blower 13 of the low-temperature liquefaction recovery unit.

Second step (A tower-regeneration process, B tower-adsorption process)
Here, the same operation as the first step is performed in the second step by changing the A tower and the B tower.

[PSA-VOC low temperature liquefaction recovery]
First step (A tower-adsorption process, B tower-countercurrent purge process)
In FIG. 1, the adsorption pressure of about 110 is applied to the moisture adsorption tower 15a filled with the moisture adsorbent 16 having a high moisture / VOC selectivity from the flow path 12 and the blower 13 through the valve 14a. When supplied at ˜150 kPA, only moisture is selectively adsorbed and room temperature and ultra-dry nitrogen containing VOC flows from the rear of the tower, and the heat storage material 20 is filled with the heat storage material 20 through the pressure reducing valve 17a and the valve 18a. It is supplied to the material packed tower 19a. At this time, the tower 19a is cooled by the cold heat collected in the previous regeneration step, and comes into contact with dry nitrogen at room temperature containing VOC, so that the heat storage material 20 is heated and the dry nitrogen is cooled. The low-temperature, VOC-containing dry nitrogen flowing from the flow path 22 is cooled to the coldest in the chiller unit 23, and the VOC is liquefied and recovered from the flow path 25. The low-temperature and ultra-dry nitrogen containing unrecovered VOC is supplied from the flow path 24 to the heat storage material packed tower 19b filled with the heat storage material 20, the heat storage material 20 is cooled, and the dry nitrogen is heated. The heated dry nitrogen is supplied countercurrently to the moisture adsorption tower 15b filled with the moisture adsorbent 16 through the valve 18b and the pressure reducing valve 17b. Here, since the adsorption tower 15b is exhausted by the vacuum pump 26 through the valve 21b, the moisture adsorbed at a low pressure of about 50 to 80 kPa is desorbed and regenerated. Here, the heat storage material is composed of metal balls such as iron or aluminum having a diameter of 0.5 to 10 mm. The water-containing nitrogen that has passed through is cooled by the chiller unit 27 to remove the water from the flow path 28 and return to the heater 29 as a purge gas.

Second step (A tower-adsorption process, B tower-pressurization process)
When the regeneration of the moisture adsorbent 16 in the moisture adsorption tower 15b is completed and the valve 14b is closed immediately before the moisture adsorption zone of the moisture adsorption tower 15a reaches the rear of the tower, the pressure in the heat storage material packed tower 19b and the moisture adsorption tower 15b is increased. Is increased to a pressure substantially equal to the adsorption pressure, and the second step is completed.

Here, the same operation as the first and second steps is performed in the third to fourth steps by changing the A tower and the B tower. Table 1 shows the sequence of a low-temperature liquefied VOC recovery method that performs temperature swing method VOC concentration, moisture adsorption removal, and regenerative cold recovery by this apparatus.
Hereinafter, the present invention will be described more specifically with reference to examples.

[TSA-VOC volume reduction concentration process]
In FIG. 1, 150 m ³ N / h of air containing 1,800 ppm of acetone and 2.5 vol% of water is filled with acetone adsorbent 5 having high acetone / water selectivity through the flow path 1 and the blower 2 through the valve 3a. When acetone is supplied to the acetone adsorption tower 4a at an adsorption temperature of about 25 ° C., only acetone is selectively adsorbed, and air with an acetone concentration of 180 ppm and a low acetone concentration flows from the rear of the tower 4a. 7 is released out of the system. At this time, the acetone adsorption tower 4b holds the acetone adsorbed in the previous adsorption step, and the nitrogen heated by the heater 29 refluxed from the liquefaction recovery step comes into contact with the acetone adsorbent 5 and decreases. It is concentrated and desorbed. A purge gas having an acetone concentration of 13,500 ppm and a flow rate of 20 m ³ N / h flowing from the flow path 12 is supplied to the blower 13 of the low temperature liquefaction recovery unit.

[PSA-VOC low temperature liquefaction recovery]
Subsequently, in FIG. 1, acetone and nitrogen containing water are adsorbed from the flow path 12 and the blower 13 through the valve 14a to the water adsorption tower 15a filled with the moisture adsorbent 16 having high moisture / acetone selectivity. When supplied at a pressure of about 110 to 150 kPA, only moisture is selectively adsorbed, and acetone containing 25 ° C. and dew point −68 ° C. ultra-dry nitrogen flows from the rear of the column, and the pressure reducing valve 17a and valve 18a And supplied to the heat storage material filling tower 19a filled with the heat storage material 20. At this time, the column 19a is -55 by cold recovered in the last regeneration step - 60 ° C. and cooled to, in contact with the acetone containing dry nitrogen, the heat storage material 20 is heated, dry nitrogen is -55 Cool to ° C. The low-temperature, acetone-containing dry nitrogen flowing through the flow path 22 is cooled to −60 ° C. by the chiller unit 23, and acetone is liquefied and recovered from the flow path 25. Low-temperature, ultra-dry nitrogen containing unrecovered acetone with an acetone concentration of 1,400 ppm is supplied from the flow path 24 to the heat storage material packed tower 19b filled with the heat storage material 20, the heat storage material 20 is cooled, and the dry nitrogen is 20 ° C. The temperature rises to The heated dry nitrogen is supplied countercurrently to the moisture adsorption tower 15b filled with the moisture adsorbent 16 through the valve 18b and the pressure reducing valve 17b. Here, since the adsorption tower 15b is exhausted by the vacuum pump 26 through the valve 21b, the adsorbed moisture is desorbed and regenerated at a regeneration pressure of about 50 to 80 kPa. Here, the heat storage material is composed of metal balls such as iron or aluminum having a diameter of 0.5 to 10 mm. The water-containing nitrogen flowing from the vacuum pump 26 is cooled to 5 ° C. by the chiller unit 27, the water is liquefied and removed from the flow path 28, and the dry nitrogen returns to the heater 29 as a regeneration purge gas.

  When this step is completed, the same operation as the first and second steps is performed in the third and fourth steps by changing the tower A and the tower B.

A) Various zeolite-based moisture adsorbents as moisture-selective adsorbents according to moisture-selective adsorbent samples 1-1 to 1-12, Comparative Examples 13 and 14, and VOC-selective adsorbent samples 2-1 to 2-5 B) Evaluation of performance on the left, and c) Performance evaluation of various zeolite-based VOC adsorbents as VOC selective adsorbents.
In order to confirm the effectiveness of the present invention, a honeycomb of silicalite, USM, β, USY, MPS was prepared as the VOC selective adsorbent honeycomb 5 of the packed towers 4a, 4b, the inlet gas amount was 80m3N / h, the inlet gas composition The performance of a VOC recovery apparatus composed of a TSA-VOC volume reduction concentration unit and a PSA-VOC low-temperature liquefaction recovery unit was evaluated under the following conditions: acetone 1,800 ppm, moisture 2.5 vol%, and residual gas air conditions.

  Here, as the moisture selective adsorbent honeycomb 16 of the packed towers 15a and 15b, KA, Na-A, Na-KA, KA (10 nm), Na-A (10 nm), Na-K- A (10 nm), KA (50 nm), Na-A (50 nm), Na-KA (50 nm), KA (100 nm), Na-A (100 nm), Na-KA (100 nm) A comparative evaluation was conducted.

Here, the values in parentheses in KA, Na-A, and Na-KA are the thin film thickness of the silica coat. Here, for thin film growth on zeolite crystals by silica coating of KA, Na-A, and Na-KA, zeolite powder is suspended in a slurry in methyl alcohol, and tetraethoxy orthosilicate (TEOS) is suspended in this. Is added to the crystal surface in an amount corresponding to the required thickness, and when water is added thereto at a H ₂ O / TEOS molar ratio of about 10, silica is precipitated. (This time, adjustment was made so that 10 to 20 nm of silica was deposited by one coating, and this time, adjustment was made to be 50 nm by 3 times and 100 nm by 5 times.)

  After coating is completed, it is immersed in a honeycomb substrate and supported at a bulk specific gravity of about 0.4. After removing surface moisture at 110 ° C. for 1 hour, the temperature is raised to 50 ° C./h to 350 ° C., and 350 ° C. For 1 hour to complete the dehydration of silicic acid to complete the Si—O—Si network on the zeolite crystal surface, and the activation by dehydration is completed.

  TSA-VOC volume reduction concentration unit and PSA-VOC low temperature using moisture selective adsorbent SAMPLE # 1-1 to 1-12, Comparative Examples 13 and 14 and VOC selective adsorbent SAMPLE # 2-1 to 2-5 Table 2 shows the performance of the VOC recovery device composed of the liquefaction recovery unit. (SAMPLE # 14 and 15 are comparative reference products)

In any case, the acetone recovery rate is 90% or more, and the dew point at the outlet of the moisture adsorption tower is below −60 ° C., indicating the effectiveness of the present invention. As VOC selective adsorbents, any high SiO ₂ / Al ₂ O ₃ ratio zeolite and mesoporous silica showed high acetone adsorption performance, and silicalite, β and USY showed particularly high acetone adsorption performance. As the moisture selective adsorbent, KA, Na-KA, Na-A, and these silica-coated products showed high moisture adsorption performance showing molecular sieve effect on acetone. In particular, KA (10 nm) showed high moisture removal performance. This seems to be because the window diameter (the crystal gas passage) has a relatively high moisture adsorption rate and a molecular sieving effect on acetone.

  Next, silicalite with the highest performance as the acetone selective adsorbent of the TSA-VOC volume reduction and concentration unit, and KA (10 nm) with the highest performance as the moisture adsorbent of the PSA-VOC low temperature liquefaction recovery unit are used as the honeycomb. The results of acetone recovery are shown in Table 3.

Similarly, the material balance is shown in Table 4.

Since the outlet acetone concentration was set to 180 ppm at a raw material flow rate of 150 m ³ N / h and acetone of 1,800 ppm, the acetone recovery rate was 90%. The adsorbed acetone was desorbed at 20 m ³ N / h nitrogen and a temperature of 120 ° C., so the desorbed acetone was concentrated 7.5 times and the acetone concentration reached 14,000 ppm. After dehydration, this was liquefied and collected at -60 ° C., so that the non-condensable gas concentration was 1,200 ppm, and 90% of the supplied acetone was recovered. The non-coagulated gas was recycled and used as purge nitrogen after dehydration. Since the recovery rate of nitrogen was 99% and nitrogen was used as the purge gas, the thermal decomposition of acetone on the surface of the adsorbent was suppressed, and the deterioration of the adsorbent was also suppressed.

  Next, silicalite, which has the highest performance as an ethyl acetate selective adsorbent in the TSA-VOC volume reduction concentration unit, and KA (10 nm), which has the highest performance as a moisture adsorbent in the PSA-VOC low-temperature liquefaction recovery unit, are used as a honeycomb. The results of ethyl acetate recovery used are shown in Table 5.

Similarly, the mass balance is shown in Table 6.

Since the outlet ethyl acetate concentration was set to 200 ppm at a raw material flow rate of 150 m ³ N / h and ethyl acetate of 3,500 ppm, the ethyl acetate recovery rate was 94%. The adsorbed ethyl acetate was desorbed at 20 m ³ N / h nitrogen and a temperature of 120 ° C., so the desorbed ethyl acetate was concentrated 7.5 times and the ethyl acetate concentration reached 26,000 ppm. After dehydration, this was liquefied and collected at -60 ° C., so the non-condensable gas concentration was 1,200 ppm, and 95% of the supplied ethyl acetate was recovered. The non-coagulated gas was recycled and used as purge nitrogen after dehydration. Since the recovery rate of nitrogen was 99% and nitrogen was used as the purge gas, the thermal decomposition of ethyl acetate on the surface of the adsorbent was suppressed, and the deterioration of the adsorbent was also suppressed.

Next, FIG. 2 shows a flow sheet of a method of using a recently popular honeycomb rotor and reducing and concentrating the volume of VOC and then liquefying and recovering with PSA-VOC. 150 m 3 N / h of air containing a toluene concentration of 5,000 ppm as VOC is supplied from the flow path 31 to the honeycomb rotor 33 filled with the USY honeycomb 34 and removed so as to have an outlet toluene concentration of 100 ppm in the adsorption zone 33a. 32, discharged from the blower 35 to the outside of the system. In the desorption zone 33b, the adsorbed toluene is supplied from the heater 29 and desorbed using high-temperature nitrogen at a temperature of 120 ° C. and a flow rate of 20 m 3 N / h as a purge gas in the desorption process, and is discharged from the blower 11 and the flow path 12 to the PSA-VOC. It is supplied at a flow rate of 20 m3 N / h and a toluene concentration of 30,000 ppm. As the moisture selective adsorbent 16, KA (10 nm) having the highest performance was used as a honeycomb. In the PSA-VOC liquefaction recovery unit, the non-condensed gas concentration is removed to 50 ppm, the moisture-containing nitrogen is cooled to a dew point of 5 ° C. by the chiller unit 27, and the moisture is removed from the flow path 28 to the outside of the system. Degradation of recovered toluene and USY was avoided because nitrogen was used as the purge gas. Since about 5% of the flow rate leaked in the honeycomb rotor, nitrogen was supplemented at about 1 m3 N / h.

Similarly, FIG. 3 shows a flow sheet of a method of liquefying and recovering with PSA-VOC after reducing and concentrating VOC in a conventional method of using a honeycomb rotor that has recently been spread. 150 m ³ N / h of air containing a toluene concentration of 500 ppm as VOC is supplied from the flow path 31 to the honeycomb rotor 33 filled with the USY honeycomb 34 and removed so as to have an outlet toluene concentration of 50 ppm in the adsorption zone 33a. 32, discharged from the blower 35 to the outside of the system. In the desorption zone 33b, the adsorbed toluene is desorbed by using a high temperature air at a temperature of 120 ° C. and a flow rate of 20 m ³ N / h as a purge gas in the desorption process, and is supplied from the heater 36 and desorbed from the blower 11 and the flow path 12. Are supplied at a flow rate of 20 m ³ N / h and a toluene concentration of 3,000 ppm. As the moisture selective adsorbent 16, KA (10 nm) having the highest performance was used as the honeycomb. In the PSA-VOC liquefaction recovery unit, the non-condensed gas concentration is removed to 50 ppm, and the gas is refluxed from the flow path 37 to the flow path 31 to be recovered at the maximum toluene recovery rate. Since recovered air and USY deteriorate by about 5% / year because air is used as the purge gas, it is not necessary to use nitrogen as the purge gas, and the non-condensed gas released from the PSA-VOC is dehumidified. Therefore, the apparatus configuration can be simplified.

  VOC can be recovered from various exhaust gases including VOC gas and is not discharged to the outside. Further, the recovered VOC is hardly deteriorated, and the VOC can be recovered with low cost and high efficiency and can be completely reused. Since the volume reduction concentration can be 4 to 12 times in the pretreatment system, an inexpensive and compact VOC recovery unit can be provided.

[TSA-VOC volume reduction unit (2 tower type)]
-7,12 flow path 2,11 blower 3a, 3b. 6a, 6b, 8a, 8b, 9a, 9b Automatic valve 4a, 4b VOC adsorption tower 5 VOC selection type adsorbent 18 Pressure reducing valve [TSA-VOC volume reduction concentration unit (honeycomb rotor)]
31, 32, 37 Flow path 35 Blower 33 Honeycomb rotor 33a Adsorption zone 33b Heating regeneration zone
36 Heater [PSA-VOC liquefaction recovery unit]
12, 22, 24, 28 Flow path 13 Blower 14a, 14b. 18a, 18b, 21a, 21b Automatic valve 15a, 15b Moisture adsorption tower 16 Moisture selective adsorbent 17a, 17b Pressure reducing valve 19a, 19b Heat storage material filling tower 20 Heat storage material 23, 27 Chiller unit 26 Vacuum pump

Claims (5)

Volatile organic compounds (hereinafter referred to as VOC) and air containing moisture is introduced from the tower forward 1 tower VOC adsorption tower of at least a double column packed with VOC selective adsorbent in a relative low temperature VOC Contact with the selective adsorbent to adsorb VOC to the adsorbent and release air from the rear of the tower to the outside of the system,
The V OC process gas volume reduction concentrated desorbed VOC nitrogen that is heated to VOC adsorption tower adsorbs VOC introduced from the tower behind,
Volume reduction concentrated by the VOC gas is introduced from the tower forward 1 tower water adsorption tower filled with at least two tower water selective adsorbent is contacted with moisture-selective adsorbent is adsorbed by the adsorbent of moisture Separating from VOC- containing nitrogen ,
Subsequently, the VOC-containing dry nitrogen coming out from the rear of the moisture adsorption tower is introduced from the front of the tower into the heat storage material packed tower filled with the heat storage material, and the temperature of the heat storage material cooled by the cold energy recovered in the regeneration process is raised, and the VOC Contain dry nitrogen,
Cooling the low-temperature, VOC-containing dry nitrogen flowing from the rear of the tower with a chiller unit, liquefying and recovering VOC,
Low temperature and ultra dry nitrogen containing unrecovered VOC flowing through is introduced into the other heat storage material packed tower from the rear of the tower to cool the heat storage material, and the temperature of the low temperature and ultra dry nitrogen containing unrecovered VOC is raised. ,
Subsequently, ultra dry nitrogen containing unrecovered unrecovered VOC that has flowed from the front of the heat storage material packed tower is introduced into the moisture adsorption tower that has adsorbed other moisture from the rear of the tower to desorb moisture from the moisture adsorbent. Regenerate moisture adsorbent,
Contains unrecovered VOC that has flowed from the front of the moisture adsorption tower , cools the nitrogen containing moisture with a chiller unit to condense the moisture, and removes the moisture.
Then containing unrecovered VOC, a dry nitrogen to remove water by refluxing as a purge gas from the tower behind the VOC adsorption tower ended adsorption was heated by the heater to the high temperature of the VOC-selective adsorbent,
When regenerating the moisture adsorption tower, before the moisture breaks through the moisture adsorption tower, the tower is switched to remove the moisture,
A temperature swing method VOC concentration and low temperature liquefied VOC recovery method that repeats the above steps,
VOC selective adsorbents are silicalite, dealuminated mordenite (hereinafter USM), beta (hereafter β), dealuminated Y-type zeolite (hereafter USY), high SiO ₂ / Al ₂ O ₃ ratio mesoporous silica (hereinafter MPS). ) Or more selected from the group consisting of
Moisture selective adsorbent is K-A, Na-A, Na-K-A, Ca-A, or K- having a surface coated with silica in the liquid phase or gas phase with a hydrolysis product of an organosilicon compound. A temperature swing method VOC concentration, a low-temperature liquefied VOC recovery method, which is at least one selected from the group consisting of A, Na-A, Na-KA and Ca-A. Instead of a VOC adsorption tower filled with at least two towers of VOC selective adsorbent, a rotor type VOC adsorption tower having a low temperature adsorption zone and a high temperature regeneration zone is used, and nitrogen is used as a purge gas in the high temperature regeneration zone. 2. The temperature swing method VOC concentration and the low temperature liquefied VOC recovery method according to claim 1, wherein the VOC is liquefied and recovered by a low temperature liquefaction condenser, and then the nitrogen that has passed is removed from the water and then used for high temperature regeneration of the VOC selective adsorbent. . A breathable adsorption rotor filled with an adsorbent is provided, and a low-temperature adsorption zone and a high-temperature regeneration zone are partitioned in the rotation direction in the rotation region of the adsorption rotor, and the rotation direction of the adsorption rotor is determined by the rotation of the adsorption rotor. In such a configuration that the low-temperature adsorption zone and the high-temperature regeneration zone are repeatedly passed in order,
In the low temperature adsorption zone, air containing a volatile organic compound (hereinafter referred to as VOC) and moisture is supplied to the rotor portion passing through the zone at a relatively low temperature, and is brought into contact with the VOC selective adsorbent to generate VOC gas. Is adsorbed by the adsorbent and air is released outside the system.
In the high temperature regeneration zone, the air is heated by a heater to raise the temperature, and the heated air is supplied to the rotor part in the zone passing process, and the VOC adsorbed by the adsorbent in the low temperature adsorption zone of the rotor part Desorbing the gas to regenerate the adsorbent at a high temperature and allowing the VOC-containing air to flow out of the zone,
The heated VOC-containing air that has passed through the high temperature regeneration zone is introduced from the front of the tower into one of the moisture adsorption towers filled with at least two towers of moisture-selective adsorbent and brought into contact with the moisture-selective adsorbent. Water is adsorbed on the adsorbent and separated from the VOC-containing air,
Subsequently, the heated VOC-containing dry air that has come out from the rear of the moisture adsorption tower is introduced from the front of the tower into the heat storage material packed tower filled with the heat storage material, and the heat storage material cooled by the cold energy recovered in the regeneration process is increased. Cool the heated VOC-containing dry air,
The VOC is liquefied and recovered by further cooling the low-temperature, VOC-containing dry air flowing from the back of the moisture adsorption tower with a chiller unit,
Low-temperature, ultra-dry air containing unrecovered VOC flowing through the chiller unit is introduced into the other heat storage material packed tower from the rear of the tower to cool the heat storage material, and low-temperature, ultra-dry air containing unrecovered VOC is supplied. Raise the temperature,
Subsequently, super dry air containing heated unrecovered VOC flowing from the front of the heat storage material packed tower is introduced from the rear of the tower into the moisture adsorption tower that has adsorbed moisture, and moisture is desorbed from the moisture adsorbent to absorb moisture. Regenerate the agent,
Contains unrecovered VOC that has flowed from the front of the moisture adsorption tower, and recirculates the moisture-containing air to the VOC and moisture-containing air in the rotor portion that is passing through the low-temperature adsorption zone;
When regenerating the moisture adsorption tower, before the moisture breaks through the moisture adsorption tower, the tower is switched to remove the moisture,
A temperature swing method VOC concentration and low temperature liquefied VOC recovery method that repeats the above steps,
VOC selective adsorbents are silicalite, dealuminated mordenite (hereinafter USM), beta (hereafter β), dealuminated Y-type zeolite (hereafter USY), high SiO ₂ / Al ₂ O ₃ One or more selected from the group consisting of specific mesoporous silica (hereinafter MPS),
Moisture selective adsorbent is K-A, Na-A, Na-K-A, Ca-A, or K- having a surface coated with silica in the liquid phase or gas phase with a hydrolysis product of an organosilicon compound. One or more selected from the group consisting of A, Na-A, Na-KA and Ca-A,
Temperature swing method VOC concentration, low temperature liquefied VOC recovery method. VOC selective adsorbent and the moisture-selective adsorbent, which is a honeycomb formed, water removal according to any one of claims 1 to 3, performs the recovery of cold, temperature swing method VOC concentration, low-temperature liquefied VOC recovery method . Moisture adsorption by introducing ultra-dry nitrogen containing unrecovered unrecovered VOC that has flowed up from the front of the heat storage material packed tower into the moisture adsorption tower that has adsorbed other moisture from the tower rear to desorb moisture from the moisture adsorbent. When the agent is regenerated, ultra-dry nitrogen containing unrecovered VOC is supplied to the moisture adsorption tower counter-currently through the pressure reducing valve, exhausted by a vacuum pump from the front of the adsorption tower, and adsorbed at a low pressure of about 50-80 kPa. The temperature swing method VOC concentration and the low-temperature liquefied VOC recovery method for performing water removal and cold recovery according to any one of claims 1 to 3, wherein the moisture adsorbent is regenerated by desorbing the moisture.