JP2013017930A - Method for improving voc recovery rate in low-temperature liquefied voc recovery method by moisture removal and cold heat recovery using adsorbent - Google Patents
Method for improving voc recovery rate in low-temperature liquefied voc recovery method by moisture removal and cold heat recovery using adsorbent Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 81
- 238000011084 recovery Methods 0.000 title claims abstract description 45
- 238000001179 sorption measurement Methods 0.000 claims abstract description 150
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000008929 regeneration Effects 0.000 claims abstract description 23
- 238000011069 regeneration method Methods 0.000 claims abstract description 23
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010457 zeolite Substances 0.000 claims abstract description 17
- 238000010926 purge Methods 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012855 volatile organic compound Substances 0.000 claims description 249
- 238000003795 desorption Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 31
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 9
- 238000005338 heat storage Methods 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007084 catalytic combustion reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000036962 time dependent Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
Description
本発明は、吸着剤を利用した、揮発性有機化合物（以下ＶＯＣ）と水分を含む排ガス中の水分除去、ＶＯＣを低温液化回収する方法に関し、特に塗料、インキ、接着剤などを取扱う施設から排出される排ガス中に含まれるＶＯＣの分離・回収方法に関するものである。 The present invention relates to a method for removing moisture from exhaust gas containing volatile organic compounds (VOC) and moisture using an adsorbent, and a method for liquefying and recovering VOC at low temperature, and in particular discharged from facilities handling paints, inks, adhesives, etc. The present invention relates to a method for separating and recovering VOC contained in exhaust gas.
ＶＯＣを含有する排ガス処理に於いて最も頻繁に採用されている方法は、排ガスに含まれるＶＯＣを高シリカゼオライトが充填された吸着塔に供給してＶＯＣを吸着除去し、ＶＯＣを吸着した高シリカゼオライト吸着塔に高温熱風を供給してＶＯＣを高温脱着させ、減容濃縮して、脱着されたＶＯＣを触媒燃焼で酸化分解する（ＴＳＡ−ＶＯＣ＋触媒燃焼）方法である。 The most frequently used method in the treatment of 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 absorb VOC. This is a method in which hot hot air is supplied to the zeolite adsorption tower to desorb VOC at a high temperature, reduce the volume and concentrate, and oxidatively decompose the desorbed VOC by catalytic combustion (TSA-VOC + catalytic combustion).
又今後普及が予想されるものとしては米国環境保護局（ＥＰＡ）が提案している強誘電体（チタン酸バリウム等）の充填塔において強誘電体表面で延命放電を行い、ここにＶＯＣ含有ガスを供給して酸化分解する充填塔プラズマ（Ｐａｃｋｅｄ Ｂｅｄ Ｐｌａｓｍａ）処理法がある。 Also expected to be widely used in the future is a life extension discharge on the surface of a ferroelectric (barium titanate, etc.) packed by the US Environmental Protection Agency (EPA). There is a packed tower plasma treatment method in which oxidative decomposition is carried out by supplying a methane.
しかしながら、上記の方法はＶＯＣの処理に対し一定の性能を示しているが、（ＴＳＡ−ＶＯＣ＋触媒燃焼）では装置の複雑さと操作の煩雑さによるコスト低減の限界があり、充填塔プラズマ処理では処理可能な対象ＶＯＣ及びＶＯＣ除去率に限界があり今後のＶＯＣ排出規制に対応できない懸念がある。 However, although the above method shows a certain performance for VOC processing, (TSA-VOC + catalytic combustion) has a limit of cost reduction due to complexity of the apparatus and complicated operation. There is a limit to the possible target VOC and VOC removal rate, and there is a concern that it will not be able to meet future VOC emission regulations.
ＶＯＣ含有ガスにオゾンを加えてＶＯＣの均一気相反応による酸化分解をすることも考えられるが、低濃度ＶＯＣに対するオゾン酸化反応が遅いこと、未反応オゾンの処理が煩雑なこと、酸化剤として使用するオゾンの製造コストが高価なことから実用化には至っていない。又オゾン酸化反応の反応効率の向上のためＶＯＣを高シリカゼオライトに吸着して除去した後、ＶＯＣを吸着した高シリカゼオライトにオゾンを添加してゼオライト中で共吸着したＶＯＣとオゾンの酸化反応の高効率化を計ることが提案されている。この方法においてオゾン反応の高効率化は実現するが、オゾンの製造コストが高価な点については依然未解決である。 Ozone can be added to the VOC-containing gas for oxidative decomposition 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 oxidizing agent 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 in this method, the cost of manufacturing ozone is still unsolved.
以上のような状況を踏まえて本発明者は、上記特許文献１に提案したように、水分選択型吸着剤を用いてＶＯＣと水分を含有する気体から水分のみを吸着除去した後、ＶＯＣを低温液化して回収し、ＶＯＣ回収後の低温空気から蓄熱式熱交換器もしくはプレートフィン式熱交換器を使用して冷熱を回収し、連続的な水分除去・ＶＯＣ回収に成功した。しかしながら、上記冷熱回収方法を用いたＶＯＣ液化回収方法において、水分選択型吸着剤吸着塔において、吸着剤に水分吸着と同時に、ＶＯＣが共吸着し、低温液化凝縮器に供給されることがなく、再生工程で水分が脱着する時に、ＶＯＣも脱着して、系外に排出され、ＶＯＣ回収率を低下する要因となっていることが確認された。 Based on the above situation, the present inventor, as proposed in the above-mentioned Patent Document 1, adsorbs and removes only moisture from a VOC and moisture-containing gas using a moisture-selective adsorbent, and then lowers the VOC at a low temperature. Liquefied and recovered, cold energy was recovered from the low-temperature air after VOC recovery using a regenerative heat exchanger or plate fin heat exchanger, and succeeded in continuous water removal and VOC recovery. However, in the VOC liquefaction recovery method using the cold recovery method described above, in the moisture selective adsorbent adsorption tower, VOC is co-adsorbed simultaneously with moisture adsorption on the adsorbent, and is not supplied to the low temperature liquefaction condenser. It was confirmed that when moisture was desorbed in the regeneration process, VOC was also desorbed and discharged out of the system, which was a factor in reducing the VOC recovery rate.
上記特許文献１に提案したように、本発明者等は、水分選択型吸着剤を充填した水分吸着塔を二つ設けて、交互に吸脱着操作を行い、加えて水分吸着塔の出口に蓄熱材充填塔を設け、一方の水分吸着塔に於いて、ＶＯＣ及び水分を含有する空気を加圧して水分吸着塔に導入して吸着剤と接触させて水分を吸着剤に吸着させてＶＯＣと分離し、続いて流過する低水分濃度のＶＯＣ含有ガスを低温に冷却された蓄熱材充填塔に導入して蓄熱材と接触させて冷却し、さらに最寒冷温度になるように冷却器で冷却してＶＯＣを液化回収し、流過する低温、低ＶＯＣ濃度、低水分濃度の空気を蓄熱材充填塔に導入し蓄熱材と接触させて冷熱を回収して昇温し、続いて室温に昇温した低ＶＯＣ濃度、低水分濃度の空気を減圧して他方の水分吸着塔に導入して吸着剤と接触させて水分を吸着剤から脱着させて水分吸着剤を再生する方法において、吸着工程に水分が破過する前に塔を切り替えて吸着工程と脱着工程を繰り返し行い、水分除去、冷熱回収を行うことにより連続的なＶＯＣの低温液化回収方法の成立することを既に見いだしているが、この方法では、図１に示すように、水分選択型吸着剤吸着塔において水分除去時にＶＯＣが水分とともに共吸着して、ＶＯＣ回収のための低温凝縮器に回収されず、水分選択型吸着剤吸着塔の再生時に水分とともにＶＯＣが脱着し、高度なＶＯＣ回収の障害になっていることが判明した。本発明に使用している水分吸着剤が分子篩型吸着剤であることから、ＶＯＣが吸着剤の結晶表面に吸着されているものと思われた。このため発明者らは図１に示すように、１塔が吸着工程、他塔が再生工程にある水分選択型吸着剤吸着塔の入口、出口、再生工程のＶＯＣ濃度の経時変化を計測した結果、ＶＯＣは再生直後の比較的短い時間に高濃度に脱着することが確認された。このため発明者らは、脱着工程出口にＶＯＣ吸着塔を設置し、高濃度ＶＯＣが流過する時間帯だけ、ＶＯＣ吸着塔によりＶＯＣを吸着除去して処理ガスを系外に放出し、吸着したＶＯＣは残りの時間を使って、外部気体(通常は空気)をＶＯＣ吸着塔に向流に供給しＶＯＣを脱着させ、脱着したＶＯＣを吸着工程の水分選択型吸着剤吸着塔の入口に循環してＶＯＣを回収することで、外部へのＶＯＣの放出を最小とするＶＯＣの液化回収方法を考案するに至った。 As proposed in Patent Document 1 above, the present inventors provided two moisture adsorption towers filled with a moisture-selective adsorbent, alternately performed adsorption / desorption operations, and additionally stored heat at the outlet of the moisture adsorption tower. A material packed tower is provided, and in one moisture adsorption tower, air containing VOC and moisture is pressurized and introduced into the moisture adsorption tower and brought into contact with the adsorbent to adsorb moisture to the adsorbent and separate from the VOC. Then, the low-concentration VOC-containing gas flowing through is introduced into the heat storage material packed tower cooled to a low temperature, brought into contact with the heat storage material, cooled, and further cooled by a cooler so as to reach the coldest temperature. VOC is liquefied and recovered, and air flowing through low temperature, low VOC concentration and low moisture concentration is introduced into the heat storage material packed tower and brought into contact with the heat storage material to recover the cold temperature and then increase the temperature to room temperature. The low VOC concentration and low moisture concentration air is decompressed and introduced into the other moisture adsorption tower. In the method of regenerating the moisture adsorbent by contacting the adsorbent with water and desorbing the moisture from the adsorbent, the adsorption process and the desorption process are repeated by switching the tower before the moisture breaks through the adsorption process. It has already been found that a continuous low-temperature liquefaction recovery method for VOCs can be established by performing recovery, but in this method, as shown in FIG. It was found that VOC was desorbed along with moisture during regeneration of the moisture-selective adsorbent adsorption tower and became an obstacle to advanced VOC recovery. . Since the water adsorbent used in the present invention is a molecular sieve type adsorbent, it was considered that VOC was adsorbed on the crystal surface of the adsorbent. For this reason, as shown in FIG. 1, the inventors measured the time-dependent changes in the VOC concentration at the entrance and exit of the moisture-selective adsorbent adsorption tower, where one tower is in the adsorption process and the other tower is in the regeneration process. It was confirmed that VOC was desorbed at a high concentration in a relatively short time immediately after regeneration. For this reason, the inventors installed a VOC adsorption tower at the exit of the desorption process, and during the time zone during which high-concentration VOC flows, the VOC was adsorbed and removed by the VOC adsorption tower, and the processing gas was discharged out of the system and adsorbed. The VOC uses the remaining time to supply an external gas (usually air) to the VOC adsorption tower in countercurrent, desorb the VOC, and circulate the desorbed VOC to the inlet of the moisture selective adsorbent adsorption tower in the adsorption process. By recovering the VOC, a VOC liquefaction recovery method that minimizes the release of the VOC to the outside has been devised.
かくして、本発明によれば、下記の１〜４の発明を提供する：
１．少なくとも２塔式の水分吸着塔の１塔に於いて、ＶＯＣ及び水分を含有する空気を加圧して水分選択型吸着剤を充填した吸着塔に導入して吸着剤と接触させて水分を吸着剤に吸着させてＶＯＣと分離し、続いて最寒冷温度になるように流過する低水分濃度のＶＯＣ含有空気を冷却器で冷却してＶＯＣを液化回収し、流過する低ＶＯＣ濃度、低水分濃度の空気を減圧して、他方の水分吸着塔に導入して吸着剤と接触させて、先に吸着された水分を吸着剤から脱着させて水分吸着剤を再生し、吸着工程に水分が破過する前に塔を切り替えて吸着工程と脱着工程を繰り返し行う、連続的に水分除去とＶＯＣ低温液化回収方法において、ＶＯＣ吸着剤を充填したＶＯＣ吸着塔を水分脱着工程出口に設置して、水分脱着工程開始後の一定時間内に水分吸着剤から水分とともに脱離するＶＯＣを含む脱着ガスをＶＯＣ吸着塔に通過させ共存するＶＯＣを吸着除去し、それ以外の時間にＶＯＣ吸着塔に外部気体を向流に流過して吸着したＶＯＣを脱着し、脱着ＶＯＣ含有気体を吸着工程の水分吸着塔の入口に戻して外部へのＶＯＣの放出を最小とするＶＯＣの液化回収方法。(請求項１)
２．請求項１において、水分選択型吸着剤吸着塔の再生工程に水分とともに流過するＶＯＣの吸着剤として、ゼオライト窓径がＶＯＣ分子直径よりも大きく且つ、ＳｉＯ２／Ａｌ２Ｏ３比が２０以上の高シリカゼオライト、ミクロ孔がＶＯＣ分子直径よりも大きな活性炭、ミクロ孔がＶＯＣ分子直径よりも大きく且つ、ＳｉＯ２／Ａｌ２Ｏ３比が２０以上のメソポーラスシリカを単独または併用してなるＶＯＣ吸着剤を使用して、上記吸着剤を充填したＶＯＣ吸着塔を水分脱着工程の出口に設置し、水分脱着工程開始後の一定時間内に脱着ガスをＶＯＣ吸着塔に通過させて共存するＶＯＣを吸着除去し、それ以外の時間にＶＯＣ吸着塔に外部気体を向流に流過して吸着したＶＯＣを脱着し、脱着したＶＯＣ含有気体を吸着工程の水分選択型吸着剤吸着塔の入口に戻して外部へのＶＯＣの放出を最小とするＶＯＣの液化回収方法。（請求項２）
３．前記の方法において、ＶＯＣ吸着塔に使用するＶＯＣ吸着剤が、ハニカムに成型さることを特徴とする請求項１及び２のいずれかに記載のＶＯＣ低温液化回収方法。（請求項３）
４．前記のＶＯＣ吸着工程と再生工程において、ＶＯＣ吸着工程に於ける１サイクルの処理ガス量のうちのＶＯＣ吸着塔を流過するガス量Ｇ１ＶＯＣ(ｍ３N/サイクル)、吸着圧力をＰａ（ｋＰａ）、吸着したＶＯＣを外部気体で脱着して水分選択型吸着剤吸着塔に還流するＶＯＣ再生工程に於ける塔内圧力をＰｄ（ｋＰａ）として、ＶＯＣを除去して還流するのに必要な一サイクルのパージ空気量をＧｐ(ｍ３N/サイクル)において、Ｇｐ ＝ Ｋ×Ｐｄ／Ｐａ×Ｇ１ＶＯＣとして、係数Ｋを１．１以上とする請求項１および２、３のいずれかに記載のＶＯＣ液化回収方法。（請求項４）
Thus, according to the present invention, the following inventions 1 to 4 are provided:
1. In at least one of the two-column type moisture adsorption towers, air containing VOC and moisture is pressurized and introduced into an adsorption tower filled with a moisture-selective adsorbent and brought into contact with the adsorbent to absorb the moisture. The VOC-containing air having a low water concentration that is allowed to adsorb to the VOC and separated from the VOC and then cooled to cool to the coldest temperature is cooled by a cooler to liquefy and recover the VOC. Reduce the concentration of air, introduce it into the other moisture adsorption tower and bring it into contact with the adsorbent, desorb the previously adsorbed moisture from the adsorbent, regenerate the moisture adsorbent, and break the moisture into the adsorption process. In the continuous moisture removal and VOC low-temperature liquefaction recovery method, the adsorption process and the desorption process are repeated by switching the tower before passing, and a VOC adsorption tower filled with the VOC adsorbent is installed at the outlet of the moisture desorption process. Moisture absorption within a certain time after the start of the desorption process The desorbed gas containing VOC desorbed together with the moisture from the agent is passed through the VOC adsorption tower to adsorb and remove the coexisting VOC. At other times, the VOC adsorbed by passing the external gas through the countercurrent to the VOC adsorption tower. A method for liquefying and recovering VOCs that desorbs and returns the desorbed VOC-containing gas to the entrance of the moisture adsorption tower in the adsorption step to minimize the release of VOCs to the outside. (Claim 1)
2. In Claim 1, as a VOC adsorbent that flows together with moisture in the regeneration step of the moisture selective adsorbent adsorption tower, the zeolite window diameter is larger than the VOC molecular diameter, and the SiO 2 / Al 2 O 3 ratio is 20 or more. VOC adsorption consisting of high silica zeolite, activated carbon with micropores larger than VOC molecular diameter, mesoporous silica with micropores larger than VOC molecular diameter and SiO 2 / Al 2 O 3 ratio of 20 or more, alone or in combination A VOC adsorption tower filled with the above adsorbent is installed at the outlet of the moisture desorption process using an adsorbent, and the coexisting VOC is adsorbed by allowing the desorption gas to pass through the VOC adsorption tower within a certain time after the start of the moisture desorption process. At other times, external gas is passed through the VOC adsorption tower countercurrently to desorb the adsorbed VOC, and the desorbed VOC-containing gas is subjected to moisture selection in the adsorption process. A method for liquefying and recovering VOC that returns to the inlet of the adsorbent adsorption tower and minimizes the release of VOC to the outside. (Claim 2)
3. 3. The VOC low-temperature liquefaction recovery method according to claim 1, wherein the VOC adsorbent used in the VOC adsorption tower is formed into a honeycomb. (Claim 3)
4). In the VOC adsorption step and the regeneration step, the gas amount G1 VOC (m 3 N / cycle) flowing through the VOC adsorption tower out of the processing gas amount in one cycle in the VOC adsorption step, and the adsorption pressure is Pa (kPa). ), The pressure inside the tower in the VOC regeneration step in which the adsorbed VOC is desorbed with an external gas and refluxed to the moisture-selective adsorbent adsorption tower is Pd (kPa). The purge air amount of the cycle is Gp (m 3 N / cycle), and Gp = K × Pd / Pa × G1 VOC , and the coefficient K is 1.1 or more. VOC liquefaction recovery method. (Claim 4)
本発明によれば、水分選択型吸着剤吸着塔を用いたＶＯＣ回収法においては、水分の吸着除去工程、脱着工程に続いて、水分とともに共吸着したＶＯＣが水分脱着工程に水分とともに脱着し、ＶＯＣ回収のための低温凝縮器に回収されず、高度なＶＯＣ回収の障害になっていることを考慮し、脱着工程出口にＶＯＣ吸着塔を設置し、高濃度ＶＯＣが流過する時間帯だけ、ＶＯＣを吸着除去して処理ガスを系外に放出し、吸着したＶＯＣは残りの時間を使って、外部気体(通常は空気)を使用して向流に供給し、脱着したＶＯＣは吸着工程の水分選択型吸着剤吸着塔の入口に循環してＶＯＣを回収することで、外部へのＶＯＣの放出を最小とし、少なくとも供給したＶＯＣの９０％以上を液化回収する方法を提供することができる。 According to the present invention, in the VOC recovery method using a moisture-selective adsorbent adsorption tower, following the moisture adsorption removal step and desorption step, the VOC co-adsorbed with moisture is desorbed together with moisture in the moisture desorption step, Considering that it is not recovered by the low-temperature condenser for VOC recovery and is an obstacle to advanced VOC recovery, a VOC adsorption tower is installed at the desorption process outlet, and only during the time zone when high concentration VOC flows, VOC is adsorbed and removed, and the processing gas is released out of the system. The adsorbed VOC is supplied to the counterflow using an external gas (usually air) using the remaining time, and the desorbed VOC is absorbed in the adsorption process. By circulating VOCs at the inlet of the moisture-selective adsorbent adsorption tower and recovering VOCs, it is possible to provide a method of liquefying and recovering at least 90% or more of the supplied VOCs by minimizing the release of VOCs to the outside.
以下、本発明の水分吸着、ＶＯＣ液化回収方法について図面を用いて具体的に説明する。 Hereinafter, the water adsorption and VOC liquefaction recovery method of the present invention will be specifically described with reference to the drawings.
本発明において用いるＶＯＣ吸着剤は、ゼオライト窓径がＶＯＣ分子直径よりも大きく且つ、ＳｉＯ２／Ａｌ２Ｏ３比が２０以上の高シリカゼオライト、ミクロ孔がＶＯＣ分子直径よりも大きな活性炭、ミクロ孔がＶＯＣ分子直径よりも大きく且つ、ＳｉＯ２／Ａｌ２Ｏ３比が２０以上のメソポーラスシリカを単独または併用してなるＶＯＣ吸着剤であり、発明者らは、非特許文献１に記述している。 The VOC adsorbent used in the present invention is a high silica zeolite having a zeolite window diameter larger than the VOC molecular diameter and a SiO 2 / Al 2 O 3 ratio of 20 or more, activated carbon having a micropore larger than the VOC molecular diameter, micropore Is a VOC adsorbent formed by using mesoporous silica having a larger VOC molecular diameter and a SiO 2 / Al 2 O 3 ratio of 20 or more alone or in combination, and the inventors describe it in Non-Patent Document 1. .
図２は、本発明の方法におけるＶＯＣ回収工程の概略図である。また図２の方法を実施するシーケンステーブルを表１に示す。 FIG. 2 is a schematic view of the VOC recovery step in the method of the present invention. A sequence table for implementing the method of FIG. 2 is shown in Table 1.
表１に示すように、本発明方法のＶＯＣ回収工程は、４ステップから構成される。 As shown in Table 1, the VOC recovery process of the method of the present invention is composed of four steps.
ＶＯＣの液化回収に於ける第１ステップの操作法を、図２を使用して説明する。
第１ステップ（水分吸着ａ塔‐吸着工程、水分吸着ｂ塔―向流パージ工程、ＶＯＣ吸着塔―ＶＯＣ吸着工程）
ＶＯＣ、水分を含有する空気が流路１、ブロワー２からバルブ３ａを通じて水分／ＶＯＣ選択性の高い水分吸着剤５の充填された水分吸着塔４ａに、吸着圧力約１１０〜１５０ｋＰａで供給されると、水分のみが選択的に吸着されてＶＯＣを含有する室温、超乾燥状態の空気が塔後方から流過する。この時の塔４ａの前方には水分吸着帯６が形成され、塔後方には共吸着したＶＯＣの吸着帯７が形成され、水分吸着塔４ａから流出した気体がバルブ８ａを通じてプレートフィン熱交換器９に供給される。この時、プレートフィン熱交換器９の高温側では、水分吸着塔の４ａから温度２５℃、水分濃度１００ｐｐｍ、ＶＯＣとして５，０００ｐｐｍのイソプロビルアルコール（ＩＰＡ）を含有する気体が５ｍ３Ｎ／ｈの流量で供給され、一方低温側では温度−６０℃、水分濃度１００ｐｐｍ、ＶＯＣとしてのＩＰＡが１００ｐｐｍまでに除去された低温空気が供給され、この低温空気の冷熱が回収されることから、上記室温のＶＯＣ含有乾燥空気と熱交換して、ＶＯＣ含有乾燥空気は冷却される。流路１０から流過した低温、ＶＯＣ含有乾燥空気はチラーユニット１１で最寒冷に冷却されて、流路１２からＶＯＣが液化回収される。ＶＯＣが液化回収により除去された低温、超乾燥空気は流路１３からプレートフィン熱交換器９に供給され、乾燥空気は昇温する。昇温した乾燥空気はバルブ８ｂを通じて水分吸着剤５の充填された水分吸着塔４ｂに向流に供給される。ここで吸着塔４ｂは、バルブ３ｂを通じて真空ポンプ１４で排気されるため、再生圧力約５０〜８０ｋＰａの低圧で吸着された水分は脱着して水分吸着剤が再生される。このとき、脱着工程の初期に高濃度のＶＯＣが流過することが、回収ＶＯＣ損失の要因となっている。このため、本発明では、第１ステップでは、水分吸着塔４ｂから流過するＶＯＣを流路１５、バルブ１６を通じて、ＶＯＣ吸着剤１７を充填したＶＯＣ吸着塔１８に供給して、ＶＯＣを吸着除去して処理後の空気は流路２０から系外に放出される。なおＶＯＣ吸着剤１７のＶＯＣ吸着帯１９が形成され前方から後方に移動する。なお水分を主成分として含有する流路は点線で、ＶＯＣを主成分として含有する流路は実線で、空気のみの流路は１点鎖線で、ＶＯＣ、水分とも含有する流路は２点鎖線で表す。
The operation method of the 1st step in the liquefaction collection | recovery of VOC is demonstrated using FIG.
First step (moisture adsorption a tower-adsorption process, moisture adsorption b tower-countercurrent purge process, VOC adsorption tower-VOC adsorption process)
When air containing VOC and water is supplied from the flow path 1 and the blower 2 through the valve 3a to the water adsorption tower 4a filled with the moisture adsorbent 5 having high moisture / VOC selectivity at an adsorption pressure of about 110 to 150 kPa. Only the moisture is selectively adsorbed and room temperature and ultra-dry air containing VOC flows from the rear of the tower. At this time, a moisture adsorption zone 6 is formed in front of the tower 4a, a co-adsorbed VOC adsorption zone 7 is formed in the rear of the tower, and the gas flowing out from the moisture adsorption tower 4a passes through a valve 8a through a plate fin heat exchanger. 9 is supplied. At this time, on the high temperature side of the plate fin heat exchanger 9, a gas containing isopropyl chloride alcohol (IPA) of 5,000 ppm as a VOC at a temperature of 25 ° C., a water concentration of 100 ppm, and a VOC of 5 m 3 N / h On the other hand, on the low temperature side, low temperature air from which temperature is −60 ° C., moisture concentration is 100 ppm, and IPA as VOC is removed up to 100 ppm is supplied, and the cold air of this low temperature air is recovered, so that the room temperature The VOC-containing dry air is cooled by heat exchange with the VOC-containing dry air. The low-temperature, VOC-containing dry air flowing from the flow path 10 is cooled to the coldest temperature by the chiller unit 11, and VOC is liquefied and recovered from the flow path 12. The low temperature and ultra dry air from which the VOC has been removed by liquefaction recovery is supplied from the flow path 13 to the plate fin heat exchanger 9, and the dry air is heated. The dried air whose temperature has been raised is supplied countercurrently to the moisture adsorption tower 4b filled with the moisture adsorbent 5 through the valve 8b. Here, since the adsorption tower 4b is exhausted by the vacuum pump 14 through the valve 3b, the moisture adsorbed at a regeneration pressure of about 50 to 80 kPa is desorbed to regenerate the moisture adsorbent. At this time, the high concentration of VOC flowing through at the initial stage of the desorption process is a factor of the recovery VOC loss. Therefore, in the present invention, in the first step, the VOC flowing from the moisture adsorption tower 4b is supplied to the VOC adsorption tower 18 filled with the VOC adsorbent 17 through the flow path 15 and the valve 16, and the VOC is removed by adsorption. Thus, the treated air is discharged from the flow path 20 to the outside of the system. A VOC adsorption band 19 of the VOC adsorbent 17 is formed and moves from the front to the rear. The flow path containing water as a main component is a dotted line, the flow path containing VOC as a main component is a solid line, the flow path containing only air is a one-dot chain line, and the flow path containing both VOC and water is a two-dot chain line. Represented by
第２ステップ（水分吸着ａ塔−吸着工程、水分吸着ｂ塔−向流パージ工程、ＶＯＣ吸着塔向流再生ＶＯＣ循環）
第２ステップの操作方法を図３で表す。水分吸着ａ塔−吸着工程、プレートフィン熱交による冷熱回収、水分吸着ｂ塔−向流パージ工程は、ステップ１と同様である。しかし水分吸着塔４ｂから流過するＶＯＣ濃度は１，０００ｐｐｍ以下に低下するのでＶＯＣ吸着塔１８でのＶＯＣ吸着は停止し、水分吸着塔から流過する処理ガスは、図３に示すように流路１５、バルブ２１から低濃度ＶＯＣ含有気体として系外に放出される。ＶＯＣが吸着されたＶＯＣ吸着塔１８のＶＯＣ吸着剤１７は、バルブ２２を開くことで流路２０からパージ空気が取り込まれ、ＶＯＣ吸着帯１９は塔後方から前方に移動し脱着したＶＯＣは循環流路２３からブロワー１の入口に循環して再度ＶＯＣ低温液化処理に供されることとなる。
Second step (moisture adsorption a tower-adsorption process, moisture adsorption b tower-countercurrent purge process, VOC adsorption tower countercurrent regeneration VOC circulation)
The operation method of the second step is shown in FIG. The moisture adsorption a tower-adsorption process, cold heat recovery by plate fin heat exchange, and the moisture adsorption b tower-countercurrent purge process are the same as in step 1. However, since the VOC concentration flowing from the moisture adsorption tower 4b decreases to 1,000 ppm or less, the VOC adsorption in the VOC adsorption tower 18 is stopped, and the processing gas flowing from the moisture adsorption tower flows as shown in FIG. It is discharged out of the system as a low-concentration VOC-containing gas from the passage 15 and the valve 21. The VOC adsorbent 17 of the VOC adsorption tower 18 to which VOC has been adsorbed takes in purge air from the flow path 20 by opening the valve 22, and the VOC adsorption zone 19 moves forward from the rear of the tower and desorbs the VOC that circulates. It circulates from the path 23 to the inlet of the blower 1 and is again subjected to the VOC low temperature liquefaction treatment.
第３〜４ステップでは、第１〜２ステップと同じ操作をａ塔とｂ塔を変更して実施する。第１〜４ステップで構成されるＶＯＣ回収率の向上を図った、本ＰＳＡ−ＶＯＣのシーケンス表を表１に示す。 In the third to fourth steps, the same operation as in the first and second steps is performed by changing the tower a and the tower b. Table 1 shows a sequence table of this PSA-VOC in which the VOC recovery rate composed of the first to fourth steps is improved.
以下、実施例により本発明をさらに具体的に説明する。
第１ステップ（水分吸着ａ塔−吸着工程、水分吸着ｂ塔−向流パージ工程、ＶＯＣ吸着塔‐ＶＯＣ吸着工程）
図２に於いてＩＰＡ５，０００ｐｐｍ、水分２．５ｖｏｌ％を含有する空気を流路１、ブロワー２からバルブ３ａを通じて水分／ＩＰＡ選択性の高い水分吸着剤５の充填された水分吸着塔４ａに、吸着圧力約１１０〜１５０ｋＰａで供給されると水分のみが選択的に吸着されてＩＰＡを含有する室温（２５℃）、超乾燥状態（水分濃度１０ｐｐｍ以下、Ｄ．Ｐ．−６０℃以下）の空気が塔後方から流過し、バルブ８ａを通じてプレートフィン式熱交換器９流路１０を通じて供給される。水分吸着剤は候補吸着剤粉末を担持したハニカム（嵩密度０．４ｇ／ｃｍ３，プレート間ピッチ２ｍｍ、プレート厚０．２ｍｍ）である。この時、プレートフィン式熱交換器９高温側から供給されたＩＰＡ５，０００ｐｐｍ含有、２５℃の乾燥空気は、プレートフィン式熱交換器９の低温側からのＩＰＡ除去後の−６０℃の低温乾燥空気と熱交換して、高温側は２５℃から−５０℃に冷却され、低温側は−６０℃から２０℃に昇温する。流路１０から流過した−５０℃、ＩＰＡ５，０００ｐｐｍ含有乾燥空気はチラーユニット１１で最寒冷の−６５℃に冷却されて、流路１２から回収率８０％程度で液化回収される。未回収のＶＯＣ１，０００ｐｐｍを含有する温度−６５℃、水分濃度１０ｐｐｍ以下（Ｄ．Ｐ．−６０℃以下）の超乾燥空気は流路１３からプレートフィン式熱交換器９にバルブ８ｂを通じて供給され、乾燥空気は２０℃に昇温する。昇温した乾燥空気はバルブ８ｂを通じて水分吸着剤５の充填された水分吸着塔４ｂに向流に供給される。ここで吸着塔４ｂは、バルブ３ｂを通じて真空ポンプ１４で排気されるため、再生圧力約５０〜８０ｋＰａの低圧で吸着された水分は脱着して再生される。
Hereinafter, the present invention will be described more specifically with reference to examples.
First step (moisture adsorption a tower-adsorption process, moisture adsorption b tower-countercurrent purge process, VOC adsorption tower-VOC adsorption process)
In FIG. 2, air containing IPA of 5,000 ppm and water of 2.5 vol% is supplied to the water adsorption tower 4a filled with the water adsorbent 5 having high moisture / IPA selectivity from the flow path 1 and the blower 2 through the valve 3a. When supplied at an adsorption pressure of about 110 to 150 kPa, only moisture is selectively adsorbed and contains IPA at room temperature (25 ° C.) and in an ultra-dry state (moisture concentration of 10 ppm or less, DP-60 ° C. or less). Flows from behind the tower and is supplied through the plate fin type heat exchanger 9 flow path 10 through the valve 8a. The moisture adsorbent is a honeycomb (bulk density 0.4 g / cm 3 , pitch between plates 2 mm, plate thickness 0.2 mm) carrying candidate adsorbent powder. At this time, the dry air at 25 ° C. containing IPA of 5,000 ppm supplied from the high temperature side of the plate fin heat exchanger 9 is subjected to low temperature drying at −60 ° C. after removing the IPA from the low temperature side of the plate fin heat exchanger 9. By exchanging heat with air, the high temperature side is cooled from 25 ° C. to −50 ° C., and the low temperature side is heated from −60 ° C. to 20 ° C. The dry air containing −50 ° C. and 5,000 ppm of IPA flowing from the flow path 10 is cooled by the chiller unit 11 to the coldest −65 ° C., and is liquefied and recovered from the flow path 12 at a recovery rate of about 80%. Ultra-dry air containing unrecovered VOC of 1,000 ppm at a temperature of −65 ° C. and a water concentration of 10 ppm or less (DP-60 ° C. or less) is supplied from the flow path 13 to the plate fin heat exchanger 9 through the valve 8b. The dry air is heated to 20 ° C. The dried air whose temperature has been raised is supplied countercurrently to the moisture adsorption tower 4b filled with the moisture adsorbent 5 through the valve 8b. Here, since the adsorption tower 4b is evacuated by the vacuum pump 14 through the valve 3b, the moisture adsorbed at a low pressure of about 50 to 80 kPa is desorbed and regenerated.
減圧条件下、乾燥空気を向流に流すことで吸着剤を再生する操作を向流パージと呼ぶ。吸着圧力をＰａ（ｋＰａ）、再生圧力をＰｄ（ｋＰａ）として向流パージ率Ｋは、Ｋ ＝ Ｐａ／Ｐｄで定義される。本実験結果によるとＫは少なくとも１．１以上でないと出口水分濃度を１０ｐｐｍ以下に保つことは難しい。 The operation of regenerating the adsorbent by flowing dry air in countercurrent under reduced pressure is called countercurrent purge. The countercurrent purge rate K is defined as K = Pa / Pd, where the adsorption pressure is Pa (kPa) and the regeneration pressure is Pd (kPa). According to the results of this experiment, it is difficult to keep the outlet moisture concentration at 10 ppm or less unless K is at least 1.1 or more.
ここでＩＰＡのような親水性のＶＯＣの吸着では図１の従来法で示したように、ＶＯＣが水分吸着剤５に共吸着して、脱着工程の初期に水分とともに脱着し、ＶＯＣ回収率低下の要因となっている。このため、本発明では、第１ステップでは、水分吸着塔４ｂから流過するＶＯＣを２００秒間、流路１５、バルブ１６を通じて、ＶＯＣ吸着剤１７を充填したＶＯＣ吸着塔１８に供給して、ＶＯＣを吸着除去して処理後の空気は流路２０から系外に放出される。なおＶＯＣ吸着剤１７のＶＯＣ吸着帯１９が形成され前方から後方に移動する。このときの水分吸着工程の入口ＩＰＡ濃度、出口ＩＰＡ濃度、チラーユニット出口のＩＰＡ濃度、脱着工程の水分吸着塔出口濃度の経時変化を図４に示す。図１と比較することにより、脱着工程で流過したＶＯＣはＶＯＣ吸着剤１７により除去されるため、処理後のガスは流路２０から系外に放出してかまわない。 Here, in the adsorption of hydrophilic VOC such as IPA, as shown in the conventional method of FIG. 1, VOC co-adsorbs to the moisture adsorbent 5 and desorbs with moisture at the beginning of the desorption process, resulting in a decrease in the VOC recovery rate. It is a factor of. For this reason, in the present invention, in the first step, the VOC flowing from the moisture adsorption tower 4b is supplied to the VOC adsorption tower 18 filled with the VOC adsorbent 17 through the flow path 15 and the valve 16 for 200 seconds to obtain the VOC. Is removed by adsorption from the flow path 20. A VOC adsorption band 19 of the VOC adsorbent 17 is formed and moves from the front to the rear. FIG. 4 shows changes over time in the inlet IPA concentration, outlet IPA concentration, chiller unit outlet IPA concentration, and moisture adsorption tower outlet concentration in the desorption step at this time. By comparing with FIG. 1, the VOC flowed through in the desorption process is removed by the VOC adsorbent 17, so that the treated gas may be discharged out of the system from the flow path 20.
第２ステップ（水分吸着ａ塔−吸着工程、水分吸着ｂ塔−向流パージ工程、ＶＯＣ吸着塔−向流再生ＶＯＣ循環）
水分吸着塔４ａの水分吸着剤５の水分吸着、プレートフィン式熱交換器での高温、高濃度ＩＰＡ含有空気と低温、低濃度ＩＰＡ含有空気の熱交換、チラーユニットでのＩＰＡの液化回収、水分吸着塔４ｂの水分吸着剤５の再生は、ステップ１と同一である。ここで水分吸着剤４ｂからの共吸着ＩＰＡの脱着が終了しているため、ＩＰＡが吸着されたＶＯＣ吸着塔１８のＶＯＣ吸着剤１７は、バルブ２２を開くことで流路２０からパージ空気が取り込まれ、ＶＯＣ吸着帯１９は塔後方から前方に移動し脱着したＩＰＡは、流路２１から流過し、循環流路２３からブロワー１の入口に循環して再度ＩＰＡ低温液化処理に供されることとなる。このため、ステップ１で吸着されたＩＰＡは１，６００秒間、ＩＰＡを含有しない外部空気を使用して向流にパージされて除去され、水分吸着塔入口に還流される。
Second step (moisture adsorption a tower-adsorption process, moisture adsorption b tower-countercurrent purge process, VOC adsorption tower-countercurrent regeneration VOC circulation)
Moisture adsorption of the moisture adsorbent 5 in the moisture adsorption tower 4a, high temperature in the plate fin type heat exchanger, heat exchange between air containing high concentration IPA and low temperature, air containing low concentration IPA, liquefaction recovery of IPA in the chiller unit, moisture The regeneration of the moisture adsorbent 5 in the adsorption tower 4b is the same as in Step 1. Here, since the desorption of the co-adsorbed IPA from the moisture adsorbent 4b has been completed, the VOC adsorbent 17 of the VOC adsorption tower 18 to which the IPA has been adsorbed takes in purge air from the flow path 20 by opening the valve 22. Then, the VOC adsorption zone 19 moves from the rear of the tower to the front and is desorbed. The IPA flows from the flow path 21, circulates from the circulation flow path 23 to the inlet of the blower 1, and is again subjected to the IPA low temperature liquefaction treatment. It becomes. For this reason, the IPA adsorbed in Step 1 is purged and removed countercurrently using external air that does not contain IPA for 1,600 seconds, and then refluxed to the moisture adsorption tower inlet.
ここで第１〜２ステップと同じ操作をａ塔とｂ塔を変更して、第３〜４ステップで実施する。 Here, the same operation as the first and second steps is performed in the third to fourth steps by changing the tower a and the tower b.
水分吸着剤として最も性能の高いゼオライトＫ−Ａをハニカムに成型して用いて、ＶＯＣ吸着塔にＶＯＣ吸着剤としてＵＳＹハニカム吸着剤（ＳｉＯ２／Ａｌ２Ｏ３比１００のパウダーをライナー間ピッチ２ｍｍ、ライナー厚み０．１ｍｍ、山−山間ピッチ１．６ｍｍ、嵩密度０．４５ｇ／ｃｍ３）を使用し、水分吸着剤再生工程の初期で水分吸着塔から流過するＶＯＣをＶＯＣ吸着塔で除去する時のＶＯＣ処理ガス量と再生パージガス量、ＶＯＣ吸着塔の再生圧力変更時のＩＰＡ回収率の関係を調べた。結果を表２−１と表２−２に示す。 The best performance of zeolite K-A as a moisture adsorbent used by molding into a honeycomb, USY honeycomb adsorbent (SiO 2 / Al 2 O 3 between 100 to powder ratio liner pitch 2mm as VOC adsorbent VOC adsorption tower , Liner thickness 0.1 mm, mountain-mountain pitch 1.6 mm, bulk density 0.45 g / cm 3 ), and VOC flowing from the moisture adsorption tower at the initial stage of the moisture adsorbent regeneration process is removed by the VOC adsorption tower. The relationship between the amount of VOC treatment gas and the amount of regeneration purge gas at the time of regeneration, and the IPA recovery rate when changing the regeneration pressure of the VOC adsorption tower was examined. The results are shown in Table 2-1 and Table 2-2.
ＶＯＣ吸着塔を設置しない場合のＩＰＡ回収率は８４％にとどまるが、ＶＯＣ吸着塔の設置によってＩＰＡの回収率は９５％以上に達成している。ただし吸着したＶＯＣの脱着が定常的に維持されるためには、再生パージ用空気量Ｇｐと、ＶＯＣ処理のためにＶＯＣ吸着塔を流過するガス量Ｇ１ＶＯＣとして、Ｇｐ ＝ Ｋ×Ｐｄ／Ｐａ×Ｇ１ＶＯＣとして、の式における係数Ｋが１．１を超えることが必要なことがわかる。このため再生パージ用空気量の増大とＶＯＣ吸着塔の真空減圧脱着が有効なことがわかる。 When the VOC adsorption tower is not installed, the IPA recovery rate is only 84%. However, the installation of the VOC adsorption tower achieves an IPA recovery rate of 95% or more. However, in order to constantly maintain the desorption of the adsorbed VOC, the regenerating purge air amount Gp and the gas amount G1 VOC flowing through the VOC adsorption tower for VOC treatment are expressed as Gp = K × Pd / Pa It can be seen that the coefficient K in the equation is required to exceed 1.1 as xG1 VOC . For this reason, it can be seen that an increase in the amount of air for regeneration purge and vacuum vacuum desorption of the VOC adsorption tower are effective.
次に、水分吸着剤として最も性能の高いゼオライトＫ−Ａをハニカムに成型して用いて、ＶＯＣ吸着塔にＶＯＣ吸着剤として（１）ＵＳＹ(超安定Ｙ型ゼオライト)、ＳｉＯ２／Ａｌ２Ｏ３比１００、（２）シリカライト、ＳｉＯ２／Ａｌ２Ｏ３比２００、（３）ＵＳＭ(超安定モルデナイト) 、ＳｉＯ２／Ａｌ２Ｏ３比１００、（４）β、ＳｉＯ２／Ａｌ２Ｏ３比１００、（５）メソポーラスシリカ、ＳｉＯ２／Ａｌ２Ｏ３比∞について、各原料のパウダーをライナー間ピッチ２ｍｍ、ライナー厚み０．１ｍｍ、山−山間ピッチ１．６ｍｍ、かさ密度０．４５ｇ／ｃｍ３のハニカムに成型し、実施例１のＲＵＮ１と同一条件でＶＯＣ回収及びＶＯＣ循環を行った時の回収ＶＯＣの種類とＶＯＣ吸着剤の関係を調べた。結果を表３に示す。 Next, the zeolite KA having the highest performance as a moisture adsorbent is molded into a honeycomb and used as a VOC adsorber in a VOC adsorbent (1) USY (ultra stable Y zeolite), SiO 2 / Al 2 O 3 ratio 100, (2) silicalite, SiO 2 / Al 2 O 3 ratio 200, (3) USM (ultra stable mordenite), SiO 2 / Al 2 O 3 ratio 100, (4) β, SiO 2 / Al 2 For O 3 ratio 100, (5) mesoporous silica, and SiO 2 / Al 2 O 3 ratio ∞, each raw material powder is 2 mm in liner pitch, 0.1 mm in liner thickness, 1.6 mm in mountain-mountain pitch, and a bulk density of 0. It was molded into a 45 g / cm 3 honeycomb, and the relationship between the type of recovered VOC and the VOC adsorbent when VOC recovery and VOC circulation were performed under the same conditions as RUN 1 of Example 1 was examined. The results are shown in Table 3.
分子直径の小さなＩＰＡではシリカライトを用いる場合に最も高いＶＯＣ回収率が得られる。ゼオライト系の吸着剤はすべて良好な性能を示すが、メソポーラスシリカの一種であるＭＣＭ−４１では、吸着剤窓径が大きすぎるためか、かえってＩＰＡの回収率は低下している。分子直径が０．５ｎｍに近いトルエンでは、シリカライトによる吸着量が低下し、それ以外の窓径が０．６ｎｍを超える吸着剤ではＭＣＭ−４１を含めて良好な性能を示す。ヘプタコサフルオロトリブチルアミンは分子直径が１ｎｍを超えており、ゼオライト系はすべて吸着性能を示さず、メソポーラスシリカに属するＭＣＭ−４１のみが良好な性能を示す。 With IPA having a small molecular diameter, the highest VOC recovery is obtained when silicalite is used. Zeolite-based adsorbents all exhibit good performance. However, in MCM-41, which is a kind of mesoporous silica, the recovery rate of IPA is lowered because the adsorbent window diameter is too large. Toluene having a molecular diameter close to 0.5 nm reduces the adsorption amount by silicalite, and other adsorbents having a window diameter exceeding 0.6 nm show good performance including MCM-41. Heptacosafluorotributylamine has a molecular diameter of more than 1 nm, and all zeolite systems do not show adsorption performance, and only MCM-41 belonging to mesoporous silica shows good performance.
このように、ＶＯＣガスを含む各種排気ガスから水分を吸着除去しＶＯＣを回収することができ、水分吸着塔再生工程に流過するＶＯＣを塔後方部に設置したＶＯＣ吸着塔で吸着し、水分吸着塔入口へ再循環することで外部に排出するＶＯＣを最小に抑制する。また、回収されたＶＯＣは殆ど劣化しておらず、ＶＯＣを低コスト、高効率に回収し、完全再利用することができる。ＶＯＣを取扱い広範な産業分野に利用できる。 Thus, VOC can be recovered by adsorbing and removing moisture from various exhaust gases including VOC gas, and VOC flowing through the moisture adsorption tower regeneration process is adsorbed by the VOC adsorption tower installed at the rear of the tower, By recirculating to the adsorption tower inlet, VOC discharged to the outside is minimized. Further, the recovered VOC is hardly deteriorated, and the VOC can be recovered with low cost and high efficiency and can be completely reused. It handles VOCs and can be used in a wide range of industrial fields.
流路 １、１０、１２、１５
ブロワー ２、
バルブ ３ａ、３ｂ、８ａ、８ｂ、１６
水分吸着塔 ４ａ、４ｂ
水分吸着剤 ５
水分吸着帯 ６
ＶＯＣ吸着帯 ７
プレートフィン式熱交換器 ９
チラーユニット １１
真空ポンプ １４
ＶＯＣ吸着剤 １７、
ＶＯＣ吸着塔 １８、
ＶＯＣ吸着帯 １９、
流路 ２０
Flow path 1, 10, 12, 15
Blower 2,
Valve 3a, 3b, 8a, 8b, 16
Moisture adsorption tower 4a, 4b
Moisture absorbent 5
Moisture absorption zone 6
VOC adsorption zone 7
Plate fin heat exchanger 9
Chiller unit 11
Vacuum pump 14
VOC adsorbent 17,
VOC adsorption tower 18,
VOC adsorption zone 19,
Channel 20
図３の付番は、図２と同一番号は同一のものを示す。
流路 ２１、
バルブ ２２、
循環流路 ２３
In FIG. 3, the same reference numerals as those in FIG.
Flow path 21,
Valve 22,
Circulation channel 23
Claims (4)
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