TWI477320B - A modified sulfur dioxide adsorbent - Google Patents
A modified sulfur dioxide adsorbent Download PDFInfo
- Publication number
- TWI477320B TWI477320B TW101143905A TW101143905A TWI477320B TW I477320 B TWI477320 B TW I477320B TW 101143905 A TW101143905 A TW 101143905A TW 101143905 A TW101143905 A TW 101143905A TW I477320 B TWI477320 B TW I477320B
- Authority
- TW
- Taiwan
- Prior art keywords
- sulfur dioxide
- adsorption
- adsorbent
- modified
- gas
- Prior art date
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
Description
本發明係關於一種二氧化硫吸附劑，特別是關於一種可再生之經改質二氧化硫吸附劑，其係可以經由160~250℃之脫附溫度處理，或進一步結合氮氣進行脫附再生，使該經改質二氧化硫吸附劑脫附所吸附的二氧化硫，而再生後之二氧化硫吸附劑可以重覆進行二氧化硫之吸附作用，以有效進行二氧化硫之淨化作業。The invention relates to a sulfur dioxide adsorbent, in particular to a renewable modified sulfur dioxide adsorbent, which can be treated by desorption temperature of 160-250 ° C or further combined with nitrogen for desorption regeneration. The sulfur dioxide adsorbent desorbs the adsorbed sulfur dioxide, and the regenerated sulfur dioxide adsorbent can repeatedly carry out the adsorption of sulfur dioxide to effectively carry out the sulfur dioxide purification operation.
一般工廠廢氣可分為有機廢氣與無機廢氣，該無機廢氣又可分為酸性氣體與鹼性氣體，該無機廢氣中主要的酸性氣體有HCN、SO2 、Cl2 及HCl；習知用於去除氣體中酸性氣體大概可分為乾式吸附及濕式吸收/反應兩種方式，在乾式吸附方法中往往使用改質活性碳來吸附酸性氣體，而改質活性碳則需要浸漬下列二種物質來進行改質：(1)氧化劑：如鉻鹽、銅鹽及鋅鹽等過渡金屬；(2)鹼性物質：如氨水、碳酸鉀、氫氧化鈉及氫氧化鉀等。The general factory exhaust gas can be divided into organic waste gas and inorganic waste gas, and the inorganic waste gas can be further divided into an acid gas and an alkaline gas. The main acid gases in the inorganic waste gas are HCN, SO 2 , Cl 2 and HCl; The acid gas in the gas can be divided into dry adsorption and wet absorption/reaction. In the dry adsorption method, the modified activated carbon is often used to adsorb the acid gas, and the modified activated carbon needs to be impregnated with the following two substances. Modification: (1) oxidant: transition metals such as chromium salts, copper salts and zinc salts; (2) alkaline substances: such as ammonia water, potassium carbonate, sodium hydroxide and potassium hydroxide.
上述改質活性碳主要是利用過渡金屬鹽將酸性氣體氧化，再利用鹼性物質將酸性物質吸附住，經由吸附酸性物質之功效以達到去除氣體中酸性氣體之目的。The modified activated carbon is mainly obtained by oxidizing an acid gas by using a transition metal salt, and then adsorbing the acidic substance by using an alkaline substance, thereby removing the acid gas in the gas by the effect of adsorbing the acidic substance.
此外，於二氧化硫之淨化方面，先將二氧化硫與氧化物反應成三氧化硫，再將三氧化硫與水結合後反應成硫 酸，以將二氧化硫進行淨化，其反應式下所示：SO2(gas) → SO2(ads) In addition, in the purification of sulfur dioxide, the sulfur dioxide and the oxide are first reacted into sulfur trioxide, and then the sulfur trioxide is combined with water to be converted into sulfuric acid to purify the sulfur dioxide, and the reaction formula is as follows: SO 2 (gas ) → SO 2(ads)
SO2(ads) +O(ads) → SO3(ads) SO 2(ads) +O (ads) → SO 3(ads)
SO3(ads) +H2 O → H2 SO4(ads) SO 3(ads) +H 2 O → H 2 SO 4(ads)
SO4(ads) +H2 O → H2 SO4(aq) SO 4(ads) +H 2 O → H 2 SO 4(aq)
習知技術中利用改質活性碳來去除酸性氣體之專利如US 4075282、US 4677096、US 5063196、US 5113856、US 5492882及US 5496785等，皆是以活性碳浸漬鉻鹽、銅鹽、鋅鹽等過渡金屬來去除氣體中的二氧化硫分子，但上述以吸附方法去除二氧化硫的改質活性吸附劑皆無法進行再生，此乃因為上述專利中所提供之吸附劑於吸附二氧化硫後無法再生使用，且上述吸附劑大都含有金屬離子及硫化物，長期下來該等無法再生之二氧化硫吸附劑之廢棄累積反而造成環境的危害。The use of modified activated carbon to remove acid gases in the prior art, such as US Pat. No. 4,075, 282, US Pat. No. 4,677,096, US Pat. No. 5,063,196, US Pat. No. 5,113,856, US Pat. No. 5,492,882, and US Pat. No. 5,496, 785, etc., all impregnating chromium salts, copper salts, zinc salts, etc. with activated carbon. The transition metal is used to remove the sulfur dioxide molecules in the gas, but the above-mentioned modified active adsorbent for removing sulfur dioxide by the adsorption method cannot be regenerated because the adsorbent provided in the above patent cannot be regenerated after adsorbing sulfur dioxide, and the above adsorption Most of the agents contain metal ions and sulfides, and the long-term accumulation of these non-renewable sulfur dioxide adsorbents will cause environmental hazards.
而習知於煙道廢氣處理中常使用濕式吸收/反應的方式來去除二氧化硫，主要是因為煙道廢氣中的二氧化硫濃度較高，通常高達數千甚至數萬ppm(百萬分之一)，故以液相濕式洗滌搭配吸附劑或反應劑可將煙道廢氣中之二氧化硫有效去除；如中華民國專利358038中使用含KOH的鹼性洗滌液去除二氧化硫；中華民國專利377305使用洗滌之方式去除二氧化硫，將洗滌液與碳酸鈣、氫氧化鈣及氫氧化鎂相接觸，形成亞硫酸鹽或硫酸鹽；中華民國專利238260使用Mg4 V2 O9 為活性組成並以氧化鋁、氧化鈰、二氧化鈦或氧化矽為載體，構成去除二氧化硫之催化劑； 此外，亦有將二氧化硫處理分成吸收處理及再生處理兩階段，例如中國專利公告號CN 1345621 A中使用(NH4 )2 CO3 或氨水或(NH4 )2 SO3 作為吸收劑吸收廢氣中之二氧化硫，再將吸收液導入鈣化再生桶(石灰桶)中進行再生，產生NH3 及CO2 ；再者，於中國專利公告號CN 101920159 A中揭示將含有二氧化硫吸收劑之溶液以濕式法吸收二氧化硫後，再將溶液通入含有有機胺鹽之溶液中進行再生；此外，於在美國專利5695727中揭示使用含鈣、鎂化合物之水溶液進行二氧化硫之吸收並以含鐵螯合物去除氮氧化物，並於高溫(800~1000℃)下與鐵進行還原而再生。However, it is customary to use a wet absorption/reaction method to remove sulfur dioxide in flue gas treatment, mainly because the concentration of sulfur dioxide in the flue gas is high, usually up to thousands or even tens of thousands of ppm (parts per million). Therefore, the liquid phase wet scrubbing with the adsorbent or the reactant can effectively remove the sulfur dioxide in the flue gas; for example, the KOH-containing alkaline washing liquid removes the sulfur dioxide in the Republic of China Patent 358038; the Republic of China patent 377305 uses the washing method to remove Sulfur dioxide, the washing liquid is contacted with calcium carbonate, calcium hydroxide and magnesium hydroxide to form sulfite or sulfate; Republic of China patent 238260 uses Mg 4 V 2 O 9 as active composition and is made of alumina, cerium oxide, titanium dioxide Or cerium oxide as a carrier to form a catalyst for removing sulfur dioxide; in addition, sulfur dioxide treatment is also divided into two stages of absorption treatment and regeneration treatment, for example, (NH 4 ) 2 CO 3 or ammonia water or (NH) used in Chinese Patent Publication No. CN 1345621 A 4 ) 2 SO 3 is used as an absorbent to absorb sulfur dioxide in the exhaust gas, and then the absorption liquid is introduced into a calcification regeneration tank (lime barrel) for regeneration. Producing NH 3 and CO 2 ; further, in Chinese Patent Publication No. CN 101920159 A, it is disclosed that the solution containing the sulfur dioxide absorbent is wet-absorbed by sulfur dioxide, and then the solution is passed into a solution containing an organic amine salt for regeneration; Further, in U.S. Patent No. 5,695,727, the use of an aqueous solution containing a calcium or magnesium compound for the absorption of sulfur dioxide and the removal of nitrogen oxides by an iron-containing chelate is carried out, and is regenerated by reduction with iron at a high temperature (800 to 1000 ° C).
除了以活性碳作為吸附二氧化硫之吸附劑外，以氧化鋁作為二氧化硫吸附劑亦持續被研究(JOURNAL OF CATALYSIS 21,270-281(1971)Applied Catalysis,74(1991)53-64；Applied Catalysis,55(1989)193-213；Applied Catalysis B：Environmental 65(2006)249-260)，A.V.deo等人以FTIR的變化研究氧化鋁與二氧化硫的吸附機制，發現氧化鋁主要是以表面的氫氧基與二氧化硫相結合並形成彎曲的O-S-O化學鍵結，此一鍵結於加熱到高溫400℃後就會逐漸被破壞，氧化鋁表面又回到原先的OH型態。亦有文獻提到以氧化鋁作為載體表面以氧化金屬(Separation and Purification Technology 13(1998)65-77)或金屬離子(Applied Catalysis,43(1988)167-176)進行改質，以促進對二氧化硫之吸附或氧化能力，但其進行再生時需要相當高的反應溫度及添加部份還原性氣體，就二氧化硫之淨化而 言是相當不利的。最近在少數的期刊方面有揭示可循環吸附去除二氧化硫吸附劑的文獻，係使用氮氣在120℃對吸附二氧化硫之改質氧化鋁進行再生程序(Fuel 93(2012)385-390,Bioresource Technology 102(2011)524-528)，可將吸附於吸附劑之二氧化硫脫除，雖可達成循環吸脫附的目的，但其測試條件以煙道氣體為主，進氣組成中二氧化硫濃度高達0.5~2.0 wt%且氧氣濃度低，吸附劑的飽和吸附容量約為30到60mg/g，穿出吸附量(breakthrough capacity)則約為10~20 mg/g，對於二氧化硫之吸附量較低，且無法適用於一般低濃度(100ppm以下)二氧化硫廢氣之處理條件，故提供一種適用於低濃度(100ppm以下)二氧化硫廢氣之可再生二氧化硫吸附劑，係為二氧化硫淨化之一重要問題。In addition to using activated carbon as an adsorbent for adsorbing sulfur dioxide, the use of alumina as a sulfur dioxide adsorbent has also been continuously studied (JOURNAL OF CATALYSIS 21, 270-281 (1971) Applied Catalysis, 74 (1991) 53-64; Applied Catalysis, 55 (1989). 193-213; Applied Catalysis B: Environmental 65 (2006) 249-260), AVdeo et al. studied the adsorption mechanism of alumina and sulfur dioxide by the change of FTIR, and found that alumina is mainly composed of surface hydroxyl groups and sulfur dioxide. Bonding and forming a curved OSO chemical bond, the bond is gradually destroyed after heating to a high temperature of 400 ° C, and the alumina surface returns to the original OH form. It has also been mentioned in the literature that alumina is used as a carrier surface to be modified with oxidized metal (Separation and Purification Technology 13 (1998) 65-77) or metal ion (Applied Catalysis, 43 (1988) 167-176) to promote the sulphur dioxide. The adsorption or oxidizing ability, but it requires a relatively high reaction temperature and a part of reducing gas for regeneration, and the purification of sulfur dioxide The words are quite unfavorable. Recently, in a few journals, there is a literature on the recyclable adsorption of sulfur dioxide adsorbents. The regeneration process of modified alumina adsorbing sulfur dioxide at 120 ° C is used (Fuel 93 (2012) 385-390, Bioresource Technology 102 (2011). 524-528), the sulfur dioxide adsorbed on the adsorbent can be removed, although the purpose of cyclic adsorption and desorption can be achieved, but the test conditions are mainly flue gas, the concentration of sulfur dioxide in the intake composition is as high as 0.5~2.0 wt% The oxygen concentration is low, the saturated adsorption capacity of the adsorbent is about 30 to 60 mg/g, and the breakthrough capacity is about 10-20 mg/g. The adsorption amount of sulfur dioxide is low, and it is not suitable for general use. Low-concentration (100ppm or less) sulfur dioxide waste gas treatment conditions, so provide a renewable sulfur dioxide adsorbent suitable for low concentration (less than 100ppm) sulfur dioxide waste gas, which is an important issue in the purification of sulfur dioxide.
為了改善上述習知技術所面臨之問題，本發明之目的係提供一種經改質之二氧化硫吸附劑，其係包含：一擔體，該擔體係為氧化鋁；一改質劑，該改質劑係為2.5~10 wt%之鈉離子胺鹽；其特徵在於該經改質之二氧化硫吸附劑係可重覆再生，並其再生條件為以160~250℃進行二氧化硫之脫附。In order to improve the problems faced by the above-mentioned prior art, the object of the present invention is to provide a modified sulfur dioxide adsorbent comprising: a support, the support system is alumina; a modifier, the modifier It is a sodium ion amine salt of 2.5 to 10 wt%; characterized in that the modified sulfur dioxide adsorbent can be regenerated repeatedly, and the regeneration condition is desulfurization of sulfur dioxide at 160-250 °C.
又如上所述經改質之二氧化硫吸附劑，其中該改質鈉離子較佳為5 wt%；而再生條件較佳為200~220℃，且係可進一步結合氮氣或濕空氣進行脫附再生，並該二氧化硫處 理濃度為100ppm以下。Further, as described above, the modified sulfur dioxide adsorbent, wherein the modified sodium ion is preferably 5 wt%; and the regeneration condition is preferably 200 to 220 ° C, and may be further combined with nitrogen or humid air for desorption regeneration. And the sulfur dioxide The concentration is 100 ppm or less.
藉由上述所提供經改質之二氧化硫吸附劑，該經改質之二氧化硫吸附劑無須於高達400℃的溫度下進行再生，亦可進一步結合氮氣或濕空氣進行再生，且再生後之二氧化硫吸附劑具有穩定之二氧化硫飽和及穿出吸附量，於高濃度二氧化硫條件下，相較於習知之改質氧化鋁具有較高之二氧化硫吸附效能，亦能於低濃度二氧化硫100ppm以下條件進行再生脫附，係為淨化二氧化硫廢氣產業中有效再生之一吸附劑。By the modified sulfur dioxide adsorbent provided above, the modified sulfur dioxide adsorbent does not need to be regenerated at a temperature of up to 400 ° C, and may be further combined with nitrogen or humid air for regeneration, and the sulfur dioxide adsorbent after regeneration It has stable sulfur dioxide saturation and permeation adsorption capacity. Under the condition of high concentration of sulfur dioxide, it has higher sulfur dioxide adsorption efficiency than the modified alumina, and can also be regenerated and desorbed under the condition of low concentration of sulfur dioxide below 100ppm. An adsorbent for efficient regeneration in the purification of sulfur dioxide waste gas industry.
為使充分瞭解本發明之目的、特徵及功效，茲藉由下述具體之實施例，並配合所附之圖式，對本發明做一詳細說明，說明如後：In order to fully understand the objects, features and advantages of the present invention, the present invention will be described in detail by the following specific embodiments and the accompanying drawings.
使用商業化氧化鋁球(2~3 mm)加以破碎後過篩取16-30 mesh顆粒，取10克氧化鋁顆粒，再依化學計量取一定量的鈉離子胺鹽溶解於去離子水中，倒入裝有氧化鋁顆粒之梨形瓶中略微攪拌後，以旋轉揮發儀將水分移除在移至烘箱中以120℃進行乾燥後備用。分別合成2.5、5、10、20及30 wt%改質劑含量之二氧化硫吸附劑。After crushing with commercial alumina balls (2~3 mm), 16-30 mesh particles are sieved, 10 g of alumina particles are taken, and a certain amount of sodium ion amine salt is dissolved in deionized water by stoichiometry. After slightly stirring into a pear-shaped flask containing alumina granules, the water was removed by a rotary volatizer and moved to an oven to dry at 120 ° C for use. A sulfur dioxide adsorbent having a modifier content of 2.5, 5, 10, 20 and 30 wt% was synthesized, respectively.
二氧化硫吸附測試使用內徑為10 mm之一玻璃固定床反應器，吸附劑使用量2.0克。分別進行高濃度(無水)及低 濃度二氧化硫吸附測試，前者主要測試吸附劑之最大二氧化硫穿出吸附量及飽和吸附量，後者主要測試吸附劑在一般外氣環境下之二氧化硫穿出吸附量。高濃度二氧化硫吸附之測試氣體之二氧化硫濃度4000 ppm/N2 ，測試氣體流量為105 ml/min，溫度25~28℃，尾氣通入8.8L/min稀釋進行後分析。低濃度二氧化硫吸附測試氣體之二氧化硫濃度以4000 ppm/N2 之標準氣體與大量空氣進行配製到二氧化硫濃度為50 ppm，測試氣體流量為3L/min，溫度25~28℃，相對溼度65~70%。二氧化硫分析儀器使用Industrial Scientific公司的ATX-612多功能偵測器，其偵測方式為電化學式，偵測濃度最高為99.9 ppm。吸附測試及容量分為穿出及飽和兩種，穿出吸附量測試之停止時機為C/C0=5%，而飽和吸附量測試之停止時機為C/C0>95%，兩者之吸附量依吸附時間及流量和濃度加以計算。The sulfur dioxide adsorption test uses a glass fixed bed reactor with an inner diameter of 10 mm and an adsorbent usage of 2.0 g. High-concentration (anhydrous) and low-concentration sulfur dioxide adsorption tests were carried out separately. The former mainly tests the maximum sulfur dioxide permeation adsorption amount and saturated adsorption amount of the adsorbent, and the latter mainly tests the sulfur dioxide permeation adsorption amount of the adsorbent in a general external gas environment. The sulfur dioxide concentration of the test gas adsorbed by high concentration sulfur dioxide is 4000 ppm/N 2 , the test gas flow rate is 105 ml/min, the temperature is 25-28 ° C, and the tail gas is diluted to 8.8 L/min for analysis. The concentration of sulfur dioxide in the low-concentration sulfur dioxide adsorption test gas is prepared with a standard gas of 4000 ppm/N 2 and a large amount of air to a sulfur dioxide concentration of 50 ppm, a test gas flow rate of 3 L/min, a temperature of 25 to 28 ° C, and a relative humidity of 65 to 70%. . The sulfur dioxide analyzer uses Industrial Scientific's ATX-612 multi-function detector, which is electrochemical and has a detection concentration of up to 99.9 ppm. The adsorption test and capacity are divided into two types: breakthrough and saturation. The stop timing of the adsorption adsorption test is C/C0=5%, and the stop timing of the saturated adsorption test is C/C0>95%. Calculated based on adsorption time and flow rate and concentration.
吸附劑的脫附使用一外層包覆加熱及保溫材料之內徑10 mm之玻璃固定床反應器，脫附溫度及加熱速率由溫控器控制，溫度最高可達300℃，加熱速率可達20℃/min。脫附氣體流量為3L/min，氣體可為空氣或氮氣，並可藉由加裝氣泡瓶來增加脫附氣體之溼度。The desorption of the adsorbent uses a glass fixed bed reactor with an outer cover of heating and insulating material with an inner diameter of 10 mm. The desorption temperature and heating rate are controlled by a thermostat, the temperature can be up to 300 ° C, and the heating rate can reach 20 °C/min. The desorption gas flow rate is 3 L/min, the gas may be air or nitrogen, and the humidity of the desorption gas may be increased by adding a bubble bottle.
吸附劑之比表面積以Micromeritics Model ASAP 2000儀器在液態氮溫度下進行恆溫吸脫附並以runauer-Emmett-Teller(BET)方程式計算所得。The specific surface area of the adsorbent was subjected to constant temperature adsorption desorption at a liquid nitrogen temperature using a Micromeritics Model ASAP 2000 instrument and calculated by the runauer-Emmett-Teller (BET) equation.
以不同吸附亦進行二氧化硫吸附效能之測試，其結果如第1圖所示，第1圖即為不同吸附劑吸附二氧化硫之吸附穿出曲線，第1圖中之曲線可明顯看出不同結構的沸石包括Y、X及A形沸石，對二氧化硫之吸附能力皆低，其中吸附能力較好的是13X沸石。在相同結構之A形沸時中4A及5A沸石對二氧化硫之吸附能力相近，而3A沸石之吸附能力較差。The adsorption performance of sulfur dioxide was also tested by different adsorptions. The results are shown in Fig. 1. The first figure shows the adsorption breakthrough curves of sulfur dioxide adsorbed by different adsorbents. The curve in Fig. 1 clearly shows the zeolites with different structures. Including Y, X and A zeolites, the adsorption capacity for sulfur dioxide is low, and the 13X zeolite is preferred. In the A-boiling of the same structure, the adsorption capacities of the 4A and 5A zeolites for sulfur dioxide are similar, while the adsorption capacity of the 3A zeolite is poor.
相較於沸石對二氧化硫之吸附能力，活性氧化鋁對二氧化硫之吸附能力較佳，穿出吸附量約為90 mg/g。活性氧化鋁對二氧化硫之吸附機制已被詳細研究過，氧化鋁主要是以表面的氫氧基與二氧化硫相結合並形成彎曲的O-S-O化學鍵結[JOURNAL OF CATALYSIS 21,270-281(1971)]，此一較強的化學鍵最後會形成亞硫酸鋁，並且在下次吸附時無法再次吸附二氧化硫。所以活性氧化鋁吸附二氧化硫的量與其表面OH官能基之數量相關，一但所有OH官能基都被佔滿，且形成亞硫酸鋁，則此氧化鋁就無法再吸附二氧化硫。Compared with the adsorption capacity of zeolite on sulfur dioxide, activated alumina has better adsorption capacity for sulfur dioxide, and the adsorption capacity is about 90 mg/g. The adsorption mechanism of activated alumina to sulfur dioxide has been studied in detail. Alumina is mainly composed of surface hydroxyl groups combined with sulfur dioxide and forms a curved OSO chemical bond [JOURNAL OF CATALYSIS 21, 270-281 (1971)]. Strong chemical bonds eventually form aluminum sulfite and cannot adsorb sulfur dioxide again during the next adsorption. Therefore, the amount of sulfur dioxide adsorbed by the activated alumina is related to the amount of OH functional groups on the surface. Once all the OH functional groups are occupied and aluminum sulfite is formed, the alumina can no longer adsorb sulfur dioxide.
由於氧化鋁對二氧化硫具有較佳之吸附容量，故以氧化鋁作為擔體進行改質，將含有不同改質劑含量經改質之二氧化硫吸附劑進行孔洞特性分析，結果如下表1所示：表1、不同含量改質劑之經改質二氧化硫吸附劑孔洞特性
由上表1可知，未進行改質之氧化鋁比表面積為301 m2 /g，隨著改質劑量增加，比表面積與孔洞體積逐漸下降，表示改質劑會覆蓋或充填氧化鋁表面孔洞。當改質劑含量為5 wt%時比表面積下降37 m2 /g，10 wt%時比表面積下降67 m2 /g，而20 wt%時比表面積大幅下降159 m2 /g。It can be seen from the above Table 1 that the specific surface area of the alumina which has not been modified is 301 m 2 /g, and the specific surface area and the pore volume gradually decrease as the amount of the modified substance increases, indicating that the modifier covers or fills the pores of the alumina surface. When the modifier content is 5 wt%, the specific surface area decreases by 37 m 2 /g, the specific surface area decreases by 67 m 2 /g at 10 wt%, and the specific surface area decreases by 159 m 2 /g at 20 wt%.
將具有不同含量改質劑之經改質二氧化硫吸附劑進行二氧化硫吸附測試，其穿出曲線如第2圖所示，其中未改質氧化鋁的尾氣約在25分鐘時逐漸有二氧化硫穿出，含有2.5wt%、5 wt%及10 wt%經改質之二氧化硫吸附劑的尾氣則約在35及40分鐘時逐漸有二氧化硫穿出。當改質劑含量提高到20 wt%及30 wt%時，經改質之二氧化硫吸附劑對二氧化硫之吸附能力反而下降，其中30 wt%經改質之二氧化硫吸附劑吸附能力的變化更為明顯，約在3分鐘時尾氣就有二氧化硫穿出。並含量為2.5wt%、5 wt%及10 wt%經改質之二氧化硫吸附劑的穿出吸附量皆較未改質氧化鋁來得高。The modified sulfur dioxide adsorbent with different content of modifier is subjected to sulfur dioxide adsorption test, and the breakthrough curve is shown in Fig. 2, wherein the tail gas of the unmodified alumina gradually passes through sulfur dioxide at about 25 minutes, containing The tail gas of the modified sulphur dioxide adsorbent at 2.5 wt%, 5 wt%, and 10 wt% gradually bleeds out at about 35 and 40 minutes. When the content of modifier is increased to 20 wt% and 30 wt%, the adsorption capacity of the modified sulfur dioxide adsorbent on sulfur dioxide is decreased, and the change of adsorption capacity of 30 wt% of the modified sulfur dioxide adsorbent is more obvious. At about 3 minutes, there is sulfur dioxide out of the exhaust. The amount of the adsorbed sulfur dioxide adsorbent having a content of 2.5 wt%, 5 wt% and 10 wt% was higher than that of the unmodified alumina.
由於氧化鋁吸附劑本身即可吸附二氧化硫，再加上改 質劑之加成效果，會增加對二氧化硫之吸附量，但就2表1的孔洞數據及第2圖之穿出曲線圖，可以發現當改質劑含量在10 wt%以下時，改質劑可有效增加對二氧化硫的吸附容量，但當改質劑量高達20、30 wt%時，由於改質劑大量覆蓋氧化鋁表面或形成堆疊，使得氧化鋁表面無法吸附二氧化硫，導致二氧化硫穿出時間較未改質氧化鋁為短。Since the alumina adsorbent itself can adsorb sulfur dioxide, plus The addition effect of the granule will increase the adsorption amount of sulfur dioxide. However, with respect to the hole data of Table 1 and the breakthrough curve of Fig. 2, it can be found that when the modifier content is below 10 wt%, the modifier It can effectively increase the adsorption capacity of sulfur dioxide, but when the modification dosage is as high as 20 or 30 wt%, the surface of the alumina can not adsorb sulfur dioxide due to the large amount of modifier covering the surface of alumina or forming a stack, resulting in less sulfur dioxide outbreak time. The modified alumina is short.
將經5 wt%改質劑改質之二氧化硫吸附劑進行二氧化硫飽和吸附後在不同的溫度下進行脫附，脫附氣體為氮氣且通過含水之氣泡瓶以增加脫附氣體之溼度，脫附時間為120分鐘，脫附後之樣品再進行二氧化硫吸附，結果如第3圖所示。在第3圖中可以明顯看出當以較高溫度進行脫附之再生效果較好，新鮮的經5 wt%改質劑改質之二氧化硫吸附劑對二氧化硫之飽和吸附量約為250 mg/g，120、160及200℃再生後樣品之飽和吸附量分別為66、124及153 mg/g，顯示提高脫附溫度有助於樣品的再生效率，同時，經不同溫度測試結果，當溫度提高至250℃亦具有良好之再生效率。The sulphur dioxide adsorbent modified by 5 wt% modifier is subjected to sulfur dioxide saturation adsorption and desorbed at different temperatures. The desorbed gas is nitrogen and passes through a water-containing bubble bottle to increase the humidity of the desorbed gas, and the desorption time For 120 minutes, the desorbed sample was further subjected to sulfur dioxide adsorption, and the results are shown in Fig. 3. It can be clearly seen in Fig. 3 that when the desorption is carried out at a higher temperature, the regeneration effect is better, and the saturated adsorption capacity of the fresh sulfur dioxide adsorbent modified by the 5 wt% modifier is about 250 mg/g. The saturated adsorption capacities of the samples after regeneration at 120, 160 and 200 °C were 66, 124 and 153 mg/g, respectively. It showed that increasing the desorption temperature contributed to the regeneration efficiency of the sample. At the same time, the temperature was increased to the temperature test results. 250 ° C also has good regeneration efficiency.
以經10 wt%改質劑改質之二氧化硫吸附劑進行高濃度二氧化硫吸附測試，其結果為飽和吸附量為43 mg/g，穿出吸附量為27 mg/g，其中相對於Fuel(2012)所揭示之改質氧化鋁於相同條件測試結果之飽和吸附量為28.5mg/g，即本發明所得之經10 wt%改質劑改質之二氧化硫吸附劑之飽和 吸附量係為習知的1.5倍(43/28.5)以上，即可得知本發明中之經改質之二氧化硫吸附劑相較於習知之改質氧化鋁有較高的吸附能力。The high-concentration sulfur dioxide adsorption test was carried out with a sulfur dioxide adsorbent modified with 10 wt% modifier, and the saturated adsorption amount was 43 mg/g, and the breakthrough adsorption amount was 27 mg/g, which is relative to Fuel (2012). The saturated adsorption amount of the modified alumina disclosed in the same condition test result is 28.5 mg/g, that is, the saturation of the sulfur dioxide adsorbent modified by the 10 wt% modifier modified by the present invention. The adsorption amount is 1.5 times (43/28.5) or more as known, and it can be known that the modified sulfur dioxide adsorbent in the present invention has a higher adsorption capacity than the conventional modified alumina.
將經5 wt%改質劑改質之二氧化硫吸附劑及未改質之氧化鋁進行低濃度二氧化硫吸脫附測試(吸附條件：二氧化硫濃度為50 ppm，測試氣體流量為3L/min，溫度25~28C，相對溼度65~70%，到達尾氣二氧化硫濃度為入口濃度的5%(C/C0=5%)時停止吸附程序，再進行脫附程序，室溫飽和溼度之氣體加熱到脫附溫度230~250℃，氣體流量為3L/min，脫附氣體：空氣)，結果如第4圖所示，由第4圖顯示經5 wt%改質劑改質之二氧化硫吸附劑對二氧化硫之穿出吸附量較改質前高出1倍以上，且經5 wt%改質劑改質之二氧化硫吸附劑可循環再生之穿出吸附量如下表2所示：
如上表2所示，經5 wt%改質劑改質之二氧化硫吸附劑經10次循環再生仍具有5.2 mg/g以上之穿出吸附量，且於10次循環再生後，該穿出吸附量即維持穩定值，相較於 未改質之氧化鋁吸附劑，經3次循環再生其穿出吸附量即降低至2 mg/g，即可得知本發明中之經改質之二氧化硫吸附劑具有良好的循環再生之吸附效能。As shown in Table 2 above, the sulfur dioxide adsorbent modified by the 5 wt% modifier has a permeation adsorption amount of 5.2 mg/g or more after 10 cycles of regeneration, and after 10 cycles of regeneration, the permeation adsorption amount That is, maintaining a stable value compared to The unmodified alumina adsorbent can be reduced to 2 mg/g after 3 cycles of regeneration, and it can be known that the modified sulfur dioxide adsorbent of the present invention has good adsorption performance for recycling. .
另外進行經5 wt%改質劑改質之二氧化硫吸附劑之飽和吸附及使用氮氣進行脫附(吸附條件：二氧化硫濃度為50 ppm，測試氣體流量為3L/min，溫度25~28℃，相對溼度65~70%，到達尾氣二氧化硫濃度為入口濃度的95%(C/C0=95%)以上時停止吸附程序，再進行脫附程序，室溫飽和溼度之氣體加熱到脫附溫度220℃，氣體流量為3L/min，脫附氣體：氮氣，)，進行10次吸脫附程序結果如第5圖所示，由第5圖結果可知，經5 wt%改質劑改質之二氧化硫吸附劑於使用氮氣進行脫附再生時，不論是飽和吸附量及穿出吸附量於第2次再生後即維持一穩定狀態，即表示以氮氣及220℃進行脫附再生即為該經5 wt%改質劑改質之二氧化硫吸附劑之良好再生條件。In addition, the saturated adsorption of sulfur dioxide adsorbent modified by 5 wt% modifier is carried out and desorption is carried out using nitrogen gas (adsorption conditions: sulfur dioxide concentration is 50 ppm, test gas flow rate is 3 L/min, temperature is 25-28 ° C, relative humidity 65~70%, stop the adsorption process when the concentration of sulfur dioxide in the exhaust gas is above 95% (C/C0=95%) of the inlet concentration, and then carry out the desorption procedure. The gas at room temperature saturation temperature is heated to the desorption temperature of 220 °C. The flow rate is 3L/min, desorption gas: nitrogen,), and the results of 10 adsorption and desorption procedures are shown in Fig. 5. From the results in Fig. 5, it is known that the sulfur dioxide adsorbent modified by 5 wt% of the modifier is When desorption regeneration is carried out using nitrogen gas, both the saturated adsorption amount and the permeation adsorption amount are maintained in a stable state after the second regeneration, that is, the desorption regeneration by nitrogen gas and 220 ° C means that the 5 wt% modification is performed. Good regeneration conditions of the sulfur dioxide adsorbent modified by the agent.
經由上述實驗結果得知，本發明所提供經改質之二氧化硫吸附劑，該經改質之二氧化硫吸附劑無須於高達400℃的溫度下進行再生，亦可進一步結合氮氣或濕空氣進行再生，且再生後之二氧化硫吸附劑具有穩定之二氧化硫飽和及穿出吸附量，於高濃度二氧化硫條件下，相較於習知之改質氧化鋁亦具有較高之二氧化硫吸附效能，亦能於低濃度二氧化硫100ppm以下條件進行再生吸附，係為淨化二氧化硫廢氣產業中有效再生之一吸附劑。According to the above experimental results, the modified sulfur dioxide adsorbent provided by the present invention does not need to be regenerated at a temperature of up to 400 ° C, and can be further combined with nitrogen or humid air for regeneration. The regenerated sulphur dioxide adsorbent has stable sulfur dioxide saturation and permeation adsorption capacity. Under the condition of high concentration of sulfur dioxide, it has higher sulfur dioxide adsorption efficiency than the conventional modified alumina, and can also be used at low concentration of sulfur dioxide below 100ppm. The condition for regenerative adsorption is to purify one of the effective regeneration agents in the sulfur dioxide waste gas industry.
第1圖係為不同吸附劑對二氧化硫之吸附穿出曲線圖。Figure 1 is a graph showing the adsorption and bleed out of different adsorbents for sulfur dioxide.
第2圖係為不同含量改質劑之經改質二氧化硫吸附劑之穿出曲線圖。Figure 2 is a cross-sectional view of the modified sulfur dioxide adsorbent with different contents of the modifier.
第3圖係為不同再生溫度對經改質二氧化硫吸附劑之吸附曲線圖。Figure 3 is a graph showing the adsorption curves of different regeneration temperatures for modified sulfur dioxide adsorbents.
第4圖係為低濃度無氮氣脫附之二氧化硫吸附劑再生吸附曲線圖。Figure 4 is a regenerative adsorption curve of a sulfur dioxide adsorbent with a low concentration and no nitrogen desorption.
第5圖係為低濃度氮氣脫附之經改質二氧化硫吸附劑再生吸附曲線圖。Figure 5 is a regenerative adsorption curve of a modified sulfur dioxide adsorbent for low concentration nitrogen desorption.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW101143905A TWI477320B (en) | 2012-11-23 | 2012-11-23 | A modified sulfur dioxide adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW101143905A TWI477320B (en) | 2012-11-23 | 2012-11-23 | A modified sulfur dioxide adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201420180A TW201420180A (en) | 2014-06-01 |
| TWI477320B true TWI477320B (en) | 2015-03-21 |
Family
ID=51393106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW101143905A TWI477320B (en) | 2012-11-23 | 2012-11-23 | A modified sulfur dioxide adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI477320B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3075434A1 (en) * | 2015-04-02 | 2016-10-05 | Bayer Technology Services GmbH | Continuous method for the purification of gases containing so2 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4325926A (en) * | 1977-12-16 | 1982-04-20 | Chevron Research Company | Process for removing sulfur dioxide from a gas |
| US4894179A (en) * | 1987-10-13 | 1990-01-16 | Exxon Research And Engineering Company | Absorbent composition containing a tertiary amino azabicyclic alcohol and an amine salt |
-
2012
- 2012-11-23 TW TW101143905A patent/TWI477320B/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4325926A (en) * | 1977-12-16 | 1982-04-20 | Chevron Research Company | Process for removing sulfur dioxide from a gas |
| US4894179A (en) * | 1987-10-13 | 1990-01-16 | Exxon Research And Engineering Company | Absorbent composition containing a tertiary amino azabicyclic alcohol and an amine salt |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201420180A (en) | 2014-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hanif et al. | Sulfur dioxide removal: An overview of regenerative flue gas desulfurization and factors affecting desulfurization capacity and sorbent regeneration | |
| Yang et al. | Removal of elemental mercury from flue gas using red mud impregnated by KBr and KI reagent | |
| Choo et al. | Hydrogen sulfide adsorption by alkaline impregnated coconut shell activated carbon | |
| Gao et al. | Physicochemical properties of metal-doped activated carbons and relationship with their performance in the removal of SO2 and NO | |
| Tan et al. | Preparation and characterization of Fe2O3–SiO2 composite and its effect on elemental mercury removal | |
| Huang et al. | Effect of moisture on H2S adsorption by copper impregnated activated carbon | |
| Fang et al. | Selective oxidation of hydrogen sulfide to sulfur over activated carbon-supported metal oxides | |
| Elsayed et al. | Desulfurization of air at high and low H2S concentrations | |
| CN105233806B (en) | It is a kind of at the same purify hydrogen sulfide, hydrogen phosphide, arsenic hydride adsorbent preparation method | |
| Xu et al. | Removal of SO2 from O2-containing flue gas by activated carbon fiber (ACF) impregnated with NH3 | |
| Wu et al. | Efficient removal of mercury from flue gases by regenerable cerium-doped functional activated carbon derived from resin made by in situ ion exchange method | |
| CN103801387A (en) | Carbocoal-based photo-catalytic oxidation fuel gas desulfurization and denitration agent and preparation method thereof | |
| CN102099115A (en) | Deodorizing catalyst, deodorizing method using same and method for regenerating the catalyst | |
| Kapica-Kozar et al. | Alkali-treated titanium dioxide as adsorbent for CO2 capture from air | |
| Ling et al. | An experimental and DFT study on enhanced elemental mercury removal performance via cerium chloride modified carbon aerogel: A synergistic effect between chemical adsorption and thermal catalysis | |
| CN110144250A (en) | The preparation method of organic sulfur compound scavenger in a kind of fuel | |
| TWI477320B (en) | A modified sulfur dioxide adsorbent | |
| CN105854541A (en) | Method for reducing and removing nitrogen oxide by adsorption-oxidation and liquid phase absorption | |
| CN109593583A (en) | A kind of the removing system and sulfur method of hydrogen sulfide | |
| Wang et al. | Effect of activated carbon support on CS2 removal over coupling catalysts | |
| KR101502238B1 (en) | Carbon dioxide absorbent and carbon dioxide capture process thereof | |
| Wang et al. | Treating waste with waste: Facile KHCO3-modified calcium carbide slag for simultaneous removal of NO and SO2 | |
| Lim et al. | Surface impregnation of glycine to activated carbon adsorbents for dry capture of carbon dioxide | |
| Shelyapina et al. | Materials for CO 2, SO x, and NO x Emission Reduction | |
| CN111375274A (en) | Containing SO2Gas treatment method and apparatus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |