TWI409220B - Preparation of Aniline - based Solid - Fixing Silica Solid Absorbents - Google Patents
Preparation of Aniline - based Solid - Fixing Silica Solid Absorbents Download PDFInfo
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本發明係有關於一種苯胺基官能基固著矽膠固體吸收劑之製備方法，尤其是一種以矽膠為基體並於矽膠表面進行胺基化處理，繼而於苯胺聚合物形成過程中，予以固著製備成矽膠固著苯胺聚合物吸收劑。The invention relates to a method for preparing an anilino functional solid-fixed silica solid absorbent, in particular to a gelatin-based substrate and amination treatment on the surface of the tannin extract, followed by solidification in the formation of the aniline polymer. The aniline polymer absorbent is fixed by the ruthenium.
對於現有火力電廠排放煙氣中二氧化碳的捕捉方式，則隸屬燃燒後的捕捉技術，其中可應用進行二氧化碳捕捉的技術，主要有化學吸收法、物理吸附法、薄膜分離法和冷凍分離法等(請參照藍啟仁，「二氧化碳攫取和儲存報告」出國會議，2005)。基於現有火力電廠所排放煙氣中的二氧化碳濃度仍屬偏低程度因素考量，在進行煙氣中二氧化碳的捕捉應用上，化學吸收方法為常被優先考慮的技術。綜合現行可應用以進行電廠排放煙氣中二氧化碳捕捉的商業化操作程序資料(請參照D. Chapel,J. Ernest,and C. Mariz,“Recovery of CO2 from flue gases: commercial trends,”Canadian Society of Chemical Engineers annual Meeting,Canada,1999；M.T. Sander,C.L. Mariz,Energy Conve vol. 33,p. 341,1992.；T. Mimura.H. Simayos Energy Conversion and Management,vol. 38,p. S57,1997.；以及T. Suda,T. Mimura,and M. Iijima,Energy and Resource vol. 23,p. 307,2002.)，可得知於30%乙醇胺(Monoethanolamine,MEA)溶液中添加適當的安定劑和腐蝕劑，屬目前最廣泛採用以進行煙氣中二氧化碳捕捉的化學吸收劑；唯由於該操作程序仍需面臨化學吸收劑使用的劣化耗損，化學吸收劑傳輸程序所需能源消耗，以及二氧化碳吸附/脫附程序的能源消耗等問題，致使其操作費用成本仍屬偏高的程度，誠屬美中不足之處。For the capture method of carbon dioxide in flue gas from existing thermal power plants, it is a post-combustion capture technology, in which carbon dioxide capture technology can be applied, mainly chemical absorption method, physical adsorption method, membrane separation method and freezing separation method. Refer to Lan Qiren, “Carbon Dioxide Capture and Storage Report”, National Conference, 2005). Based on the fact that the concentration of carbon dioxide in the flue gas emitted by existing thermal power plants is still a low degree factor, chemical absorption methods are often preferred techniques for capturing carbon dioxide in flue gas. Integrate current commercial operating procedures that can be applied to capture carbon dioxide in power plant emissions (see D. Chapel, J. Ernest, and C. Mariz, “Recovery of CO 2 from flue gases: commercial trends,” Canadian Society Of Chemical Engineers annual Meeting, Canada, 1999; MT Sander, CL Mariz, Energy Conve vol. 33, p. 341, 1992.; T. Mimura. H. Simayos Energy Conversion and Management, vol. 38, p. S57, 1997 And T. Suda, T. Mimura, and M. Iijima, Energy and Resource vol. 23, p. 307, 2002.), it is known that a suitable stabilizer is added to a solution of 30% ethanolamine (MEA). And corrosive agents, which are the most widely used chemical absorbents for carbon dioxide capture in flue gas; only because of the operational procedures still need to face the deterioration of the use of chemical absorbents, the energy consumption required for the chemical absorbent transport process, and carbon dioxide adsorption / The problem of energy consumption in the desorption process has caused the cost of operating costs to remain high, which is a drawback.
本發明之一目的係提供一種苯胺基官能基固著矽膠固體吸收劑之製備方法，其係以矽膠為基體並於矽膠表面進行胺基化處理，繼而於苯胺聚合物形成過程中，予以固著製備成矽膠固著苯胺聚合物吸收劑。An object of the present invention is to provide a method for preparing an anilino functional solid-fixed silica solid absorbent, which is based on a silicone resin and subjected to amination treatment on the surface of the tannin extract, and then fixed in the formation of the aniline polymer. The aniline polymer absorbent is prepared as a tannin adhesive.
本發明之另一目的係提供一種苯胺基官能基固著矽膠固體吸收劑之製備方法，其具備相對於乙醇胺之低二氧化碳脫附程序的能源消耗。Another object of the present invention is to provide a process for the preparation of an anilino functional solid-fixing silicone solid absorbent having an energy consumption relative to a low carbon dioxide desorption procedure of ethanolamine.
本發明之另一目的係提供一種苯胺基官能基固著矽膠固體吸收劑之製備方法，其而建立固體吸收劑的合成製備技術，並應用於捕捉二氧化碳及儲存。Another object of the present invention is to provide a method for preparing an anilino functional solid-fixed silica solid absorbent, which is a synthetic preparation technique for a solid absorbent, which is used for capturing carbon dioxide and storing.
為達上述之目的，本發明之一種苯胺基官能基固著矽膠固體吸收劑之製備方法，其包括下列步驟：將矽膠以酸溶液進行純化前處理；將矽膠進行胺基化處理；與苯胺聚合物進行反應；以及將矽膠固著於該苯胺聚合物上。In order to achieve the above object, a method for preparing an anilino functional solid-fixing solid absorbent according to the present invention comprises the following steps: pre-purifying the tannin extract with an acid solution; aminating the tannin; and polymerizing with an aniline The reaction is carried out; and the tannin is fixed to the aniline polymer.
其中，該酸溶液為鹽酸、硝酸或硫酸。Wherein, the acid solution is hydrochloric acid, nitric acid or sulfuric acid.
其中，於該將矽膠以酸溶劑進行純化前處理之步驟中，係將矽膠置於1：1鹽酸、硝酸或硫酸溶液中浸泡二天後，再以過濾方式將矽膠與鹽酸、硝酸或硫酸溶液加以分離，經鹽酸、硝酸或硫酸溶液浸泡處理後的矽膠，再以二次蒸餾水來反覆清洗，最後靜置於乾燥器中加以乾燥。Wherein, in the step of pretreating the tannin extract in an acid solvent, the tannin extract is immersed in a 1:1 hydrochloric acid, nitric acid or sulfuric acid solution for two days, and then the tannin extract and the hydrochloric acid, nitric acid or sulfuric acid solution are filtered. Separation, the gelatin after being soaked in hydrochloric acid, nitric acid or sulfuric acid solution, and then repeatedly washed with double distilled water, and finally placed in a desiccator and dried.
其中，於該進行胺基化處理之步驟中，係稱取20克重經清洗且乾燥過的矽膠，放置於100毫升10% 3-丙胺基三乙氧基矽烷化合物的丙酮溶液中，於45℃的溫度條件下連續攪拌反應4小時，待合成反應完成後，將固著於矽膠表面上的3-丙胺基三乙氧基矽烷產品以過濾方式加以分離，並以丙酮清洗數次後靜置乾燥，所得成品將與苯胺聚合物進行後續固著合成之用。Wherein, in the step of performing the amination treatment, 20 g of the washed and dried tannin extract is weighed and placed in 100 ml of an acetone solution of 10% 3-propylaminotriethoxydecane compound at 45 The reaction was continuously stirred at a temperature of ° C for 4 hours. After the completion of the synthesis reaction, the 3-propylaminotriethoxydecane product immobilized on the surface of the silicone was separated by filtration, and washed several times with acetone and then allowed to stand. After drying, the resulting product will be subjected to subsequent fixation synthesis with the aniline polymer.
其中，於該與苯胺聚合物進行反應之步驟中，係將該表面胺基化處理過的矽膠，放置於含有1毫升苯胺和100毫升1M鹽酸、硝酸或硫酸溶液中，並於磁攪拌器上進行均勻攪拌，繼而將2.44克(NH4 )S2 O8 溶於50毫升1M鹽酸、硝酸或硫酸溶液添加於混合均勻的前述溶液中，經至少24小時的聚合反應，以過濾方式加以分離，即可獲得矽膠固著苯胺聚合物吸收劑。Wherein, in the step of reacting with the aniline polymer, the surface aminated gelatin is placed in a solution containing 1 ml of aniline and 100 ml of 1 M hydrochloric acid, nitric acid or sulfuric acid, and placed on a magnetic stirrer. Stirring was carried out, and then 2.44 g of (NH 4 )S 2 O 8 was dissolved in 50 ml of 1 M hydrochloric acid, nitric acid or sulfuric acid solution, and the mixture was uniformly mixed in the above solution, and separated by filtration for at least 24 hours. A silicone-fixed aniline polymer absorbent can be obtained.
其中，於該將矽膠固著於該苯胺聚合物上之步驟中，係將所得合成產品續須依1M鹽酸、硝酸或硫酸溶液和二次蒸餾水等步驟加以清洗，最後將洗淨的矽膠固著苯胺聚合物吸收劑放置於乾燥器內(60℃)靜置乾燥。Wherein, in the step of fixing the tannin to the aniline polymer, the obtained synthetic product is continuously washed according to the steps of 1M hydrochloric acid, nitric acid or sulfuric acid solution and double distilled water, and finally the washed tannin is fixed. The aniline polymer absorbent was placed in a desiccator (60 ° C) and allowed to stand for drying.
為使 貴審查委員能進一步瞭解本發明之結構、特徵及其目的，茲附以圖式及較佳具體實施例之詳細說明如后。The detailed description of the drawings and the preferred embodiments are set forth in the accompanying drawings.
請一併參照圖1～圖2，其中圖1繪示本發明一較佳實施例之苯胺基官能基固著矽膠固體吸收劑之製備方法之流程示意圖；圖2繪示本發明一較佳實施例之具苯胺基官能基固體吸收劑之分子結合示意圖。如圖所示，本發明之苯胺基官能基固著矽膠固體吸收劑之製備方法，其包括下列步驟：將矽膠以酸溶液進行純化前處理(步驟1)；將矽膠進行胺基化處理(步驟2)；與苯胺聚合物進行反應(步驟3)；以及將矽膠固著於該苯胺聚合物上(步驟4)。1 to FIG. 2, FIG. 1 is a schematic flow chart of a method for preparing an anilino functional solid-fixed solid absorbent according to a preferred embodiment of the present invention; FIG. 2 is a view showing a preferred embodiment of the present invention; A schematic diagram of the molecular binding of an anilino functional solid absorbent. As shown in the figure, the preparation method of the anilino functional group-fixed silicone solid absorbent of the present invention comprises the following steps: pre-purifying the tannin extract with an acid solution (step 1); and subjecting the tannin to amination treatment (step) 2); reacting with the aniline polymer (step 3); and fixing the tannin to the aniline polymer (step 4).
於該步驟1中，將矽膠以酸溶液進行純化前處理；其中，該酸溶液例如但不限於為鹽酸、硝酸或硫酸，且其係將矽膠置於1：1鹽酸、硝酸或硫酸溶液中浸泡二天後，再以過濾方式將矽膠與鹽酸、硝酸或硫酸溶液加以分離，經鹽酸、硝酸或硫酸溶液浸泡處理後的矽膠，再以二次蒸餾水來反覆清洗，最後靜置於乾燥器中加以乾燥。In the step 1, the tannin extract is pre-purified with an acid solution; wherein the acid solution is, for example but not limited to, hydrochloric acid, nitric acid or sulfuric acid, and the gum is soaked in a 1:1 hydrochloric acid, nitric acid or sulfuric acid solution. After two days, the tannin extract is separated from the hydrochloric acid, nitric acid or sulfuric acid solution by filtration, and the tanned rubber is soaked in hydrochloric acid, nitric acid or sulfuric acid solution, and then repeatedly washed with double distilled water, and finally placed in a desiccator to be dried. .
於該步驟2中，將矽膠進行胺基化處理；其中，係稱取20克重經清洗且乾燥過的矽膠，放置於100毫升10%3-丙胺基三乙氧基矽烷化合物的丙酮溶液中，於45℃的溫度條件下連續攪拌反應4小時，待合成反應完成後，將固著於矽膠表面上的3-丙胺基三乙氧基矽烷產品以過濾方式加以分離，並以丙酮清洗數次後靜置乾燥，所得成品將與苯胺聚合物進行後續固著合成之用。In the step 2, the tannin extract is subjected to amination treatment; wherein, 20 g of the washed and dried tannin extract is weighed and placed in 100 ml of a 10% 3-propylaminotriethoxydecane compound in acetone. The reaction was continuously stirred at a temperature of 45 ° C for 4 hours. After the completion of the synthesis reaction, the 3-propylaminotriethoxydecane product immobilized on the surface of the silicone was separated by filtration and washed several times with acetone. After standing to dry, the resulting product will be used for subsequent fixation synthesis with the aniline polymer.
於該步驟3中，與苯胺聚合物進行反應；其中，係將該表面胺基化處理過的矽膠，放置於含有1毫升苯胺和100毫升1M鹽酸、硝酸或硫酸溶液中，並於磁攪拌器上進行均勻攪拌，繼而將2.44克(NH4 )S2 O8 溶於50毫升1M鹽酸、硝酸或硫酸溶液添加於混合均勻的前述溶液中，經至少24小時的聚合反應，以過濾方式加以分離，即可獲得矽膠固著苯胺聚合物吸收劑。In the step 3, reacting with the aniline polymer; wherein, the surface aminated gelatin is placed in a solution containing 1 ml of aniline and 100 ml of 1 M hydrochloric acid, nitric acid or sulfuric acid, and magnetic stirrer Stirring uniformly, then 2.44 g of (NH 4 )S 2 O 8 was dissolved in 50 ml of 1 M hydrochloric acid, nitric acid or sulfuric acid solution and added to the above mixed solution, and separated by filtration for at least 24 hours. , the silicone adhesive aniline polymer absorbent can be obtained.
於該步驟4中，將矽膠固著於該苯胺聚合物上；其係將所得合成產品續須依1M鹽酸、硝酸或硫酸溶液和二次蒸餾水等步驟加以清洗，最後將洗淨的矽膠固著苯胺聚合物吸收劑放置於乾燥器內(60℃)靜置乾燥。In the step 4, the tannin is fixed on the aniline polymer; the obtained synthetic product is continuously washed according to the steps of 1M hydrochloric acid, nitric acid or sulfuric acid solution and double distilled water, and finally the washed tannin is fixed. The aniline polymer absorbent was placed in a desiccator (60 ° C) and allowed to stand for drying.
如圖2所示，本發明之具苯胺基官能基固體吸收劑於製作過程中，首先將矽膠表面之OH分子經由鹽酸、硝酸或硫酸溶液進行純化前處理，再將矽膠進行胺基化處理，其中胺基之化學式為NH2 (CH2 )3 Si(OCH3 )3 ，使矽膠表面之具有矽膠固著胺基(NH2 -Si)分子，接著將矽膠固著於該苯胺聚合物上，使聚苯胺之化學式與該NH2 分子連結，如此即成為一具苯胺基官能基固體吸收劑。As shown in FIG. 2, in the preparation process, the aniline functional solid absorbent of the present invention firstly purifies the OH molecule on the surface of the tannin by hydrochloric acid, nitric acid or sulfuric acid solution, and then performs the amination treatment of the tannin extract. The chemical formula of the amine group is NH 2 (CH 2 ) 3 Si(OCH 3 ) 3 , so that the surface of the tannin has a ruthenium-fixed amine (NH 2 -Si) molecule, and then the tannin is fixed on the aniline polymer. The chemical formula of polyaniline is bonded to the NH 2 molecule, thus becoming an anilino functional solid absorbent.
請一併參照圖3a～圖4，其中圖3a繪示以FTIR光譜儀量測得矽膠樣品所得之紅外光譜之特徵峰示意圖；圖3b繪示以FTIR光譜儀量測得矽膠固著胺基(NH2 -Si)樣品所得之紅外光譜之特徵峰示意圖；圖3c繪示以FTIR光譜儀量測得矽膠固著苯胺聚合物(PANI-Si)樣品所得之紅外光譜之特徵峰示意圖；圖4繪示以FTIR光譜儀量測得掺雜及未掺雜聚苯胺化合物樣品所得之紅外光譜之特徵峰示意圖。如圖所示，經由矽膠固著苯胺聚合物(PANI-Si)的紅外光譜圖譜與矽膠固著胺基(NH2 -Si)紅外光譜圖譜之比對(參見圖4所示)，可得知在1580和1479 cm-1 分別為Imino-1,4-phenylene和quinine dimine之伸縮訊號；而1200~1400 cm-1 來自於苯胺環上C－N之不同伸縮模式；而苯環之C－C與C=C依其振動波峰可標示出855 cm-1 。根據上述各特徵峰，可證明所合成為矽膠固著苯胺聚合物。Please refer to FIG. 3a to FIG. 4 together, wherein FIG. 3a is a schematic diagram showing the characteristic peaks of the infrared spectrum obtained by measuring the tannin sample by the FTIR spectrometer; and FIG. 3b is a graph showing the immobilized amine group (NH 2 by the FTIR spectrometer). -Si) The characteristic peak of the infrared spectrum obtained by the sample; FIG. 3c is a schematic diagram showing the characteristic peaks of the infrared spectrum obtained by measuring the aniline-fixed aniline polymer (PANI-Si) sample by FTIR spectrometer; FIG. 4 shows FTIR A characteristic peak of the infrared spectrum obtained by measuring the doped and undoped polyaniline samples by a spectrometer. As shown in the figure, the infrared spectrum of the aniline-fixed aniline polymer (PANI-Si) is compared with the infrared spectrum of the cerium-fixed amine group (NH 2 -Si) (see Figure 4). In 1580 and 1479 cm -1 are the stretching signals of Imino-1,4-phenylene and quinine dimine respectively; and 1200~1400 cm -1 are derived from different stretching modes of C-N on the aniline ring; and C-C of benzene ring With C=C, the vibration peak can be marked 855 cm -1 . According to the above characteristic peaks, it was confirmed that the aniline polymer was synthesized as a tannin.
請一併參照圖5a～圖5c，其中圖5a繪示以拉曼(Raman)光譜儀量測得矽膠樣品所得之拉曼光譜圖之特徵峰示意圖；圖5b繪示以拉曼光譜儀量測得矽膠固著胺基(NH2 -Si)樣品所得之拉曼光譜圖之特徵峰示意圖；圖5c繪示以拉曼光譜儀量測得矽膠固著苯胺聚合物(PANI-Si)樣品所得之拉曼光譜圖之特徵峰示意圖。由該圖中可得知矽膠固著苯胺聚合物(PANI-Si)拉曼(Raman)光圖譜與矽膠固著胺基(NH2 -Si)拉曼光圖譜，亦呈現明顯不同的官能基特徵峰。Please refer to FIG. 5a to FIG. 5c together, wherein FIG. 5a shows a characteristic peak of a Raman spectrum obtained by measuring a tannin sample by a Raman spectrometer; FIG. 5b shows a tantalum measured by a Raman spectrometer. Schematic diagram of the characteristic peak of the Raman spectrum obtained by immobilizing the amine-based (NH 2 -Si) sample; Figure 5c shows the Raman spectrum obtained by measuring the aniline-fixed aniline polymer (PANI-Si) sample by Raman spectrometer A schematic diagram of the characteristic peaks of the figure. From the figure, it can be seen that the aniline-fixed aniline polymer (PANI-Si) Raman spectrum and the ruthenium-fixed amine (NH 2 -Si) Raman spectrum also show distinct functional characteristics. peak.
根據本發明之苯胺基官能基固著矽膠固體吸收劑之製備方法所製備之具苯胺基官能基固體吸收劑可以利用熱重分析儀中來進行矽膠固著苯胺聚合物應用於二氧化碳吸附/脫附可行性，首先於室溫條件下，通入二氧化碳氣流，進行矽膠固著苯胺聚合物吸附二氧化碳反應；繼而於不同脫附溫度(80℃、70℃和60℃)設定條件下，並通入氮氣氣流，以進行矽膠固著苯胺聚合物脫附二氧化碳反應。請參照圖6，其繪示在不同脫附溫度(80℃、70℃和60℃)設定條件下，本發明之矽膠固著苯胺聚合物應用於二氧化碳吸附/脫附特性之示意圖。如圖所示，於室溫條件下，通入二氧化碳氣流，則矽膠固著苯胺聚合物將吸附二氧化碳而呈現重量增加繼而到達最大值(約100%程度)，然後改通入氮氣氣流並在不同脫附溫度(80℃、70℃和60℃)設定條件下，則矽膠固著苯胺聚合物所吸附二氧化碳將被脫附，繼而呈現重量減低現象並可到達最小值(約98%程度)。基於60℃脫附溫度設定條件下，於15分鐘的實驗操作，並無法有效將吸附二氧化碳予以脫附，因此，80℃和70℃脫附溫度設定條件應較為適當。The aniline functional solid absorbent prepared by the method for preparing an anilino functional solid-fixed solid absorbent according to the present invention can be used in a thermogravimetric analyzer for gutta-fixing an aniline polymer for carbon dioxide adsorption/desorption Feasibility, firstly, under the condition of room temperature, a carbon dioxide gas stream is passed to carry out the adsorption reaction of the aniline polymer to adsorb carbon dioxide; then, under different desorption temperatures (80 ° C, 70 ° C and 60 ° C), nitrogen is introduced. The gas stream is used to carry out the desorption of carbon dioxide by the aniline polymer. Please refer to FIG. 6 , which is a schematic diagram showing the application of the phthalocyanine-fixed aniline polymer of the present invention to carbon dioxide adsorption/desorption characteristics under different desorption temperatures (80° C., 70° C., and 60° C.). As shown in the figure, at room temperature, a carbon dioxide gas stream is passed, and the styrene-fixed aniline polymer adsorbs carbon dioxide and exhibits a weight increase and then reaches a maximum value (about 100%), and then is diverted into a nitrogen gas stream and is different. Under the conditions of desorption temperature (80 ° C, 70 ° C and 60 ° C), the carbon dioxide adsorbed by the phthalocyanine-fixed aniline polymer will be desorbed, which will then exhibit a weight reduction phenomenon and reach a minimum (about 98%). Based on the 60 °C desorption temperature setting condition, the adsorption of carbon dioxide could not be effectively desorbed in the experimental operation for 15 minutes. Therefore, the setting conditions of the desorption temperature of 80 ° C and 70 ° C should be appropriate.
為進一步探討覆蓋於矽膠表層固著苯胺聚合物的含量，本發明將氧氣氣流通入熱重分析儀中，並將最高加熱溫度設定為900℃，請參照圖7，其繪示覆蓋於本發明之矽膠表層固著苯胺聚合物重量估算之示意圖。如圖所示，覆蓋於本發明之矽膠表層固著苯胺聚合物將完全被燃燒，繼而可獲得穩定的最低重量值(為80.44%程度)。假若將圖6所獲得二氧化碳吸附，除以圖7所獲得苯胺聚合物固著量，則初步可估算出矽膠固著苯胺聚合物上固著苯胺聚合物的二氧化碳吸附容量約為10%(Kg CO2 /Kg)的程度，在此圖中，約有80%的矽膠被留下。In order to further investigate the content of the aniline polymer coated on the surface layer of the silicone rubber, the present invention passes the oxygen gas flow into the thermogravimetric analyzer, and sets the maximum heating temperature to 900 ° C. Please refer to FIG. 7 , which is shown to cover the present invention. A schematic diagram of the weight estimation of the aniline polymer in the surface layer of the rubber. As shown, the aniline polymer coated on the silicone surface layer of the present invention will be completely burned, and a stable minimum weight value (to the extent of 80.44%) can be obtained. If the carbon dioxide adsorption obtained in Fig. 6 is removed, the aniline polymer immobilized on the aniline polymer can be estimated to have a carbon dioxide adsorption capacity of about 10% (Kg CO). The extent of 2 / Kg), in this figure, about 80% of the silicone is left behind.
另利用熱重量分析儀方法針對聚苯胺測試樣品，進行連續5次循環吸脫附的行為評估。請參照圖8，其繪示本發明之聚苯胺測試樣品進行連續5次循環吸脫附的行為評估之測試示意圖。如圖所示，依據聚苯胺測試樣品每一次二氧化碳吸附循環的實驗結果，可估算其每公斤二氧化碳的捕捉容量變化情形，參見表1所示，其顯示聚苯胺測試樣品每一次二氧化碳吸附循環實驗，所估算其每公斤二氧化碳的捕捉容量變化情形係介於0.085-0.098 Kg CO2 /Kg容量範圍。In addition, the polyaniline test sample was subjected to a thermal gravimetric method for the behavior evaluation of five consecutive cycles of adsorption and desorption. Please refer to FIG. 8 , which is a schematic diagram showing the test of the behavioral evaluation of the polyaniline test sample of the present invention for 5 consecutive cycles of adsorption and desorption. As shown in the figure, according to the experimental results of each carbon dioxide adsorption cycle of the polyaniline test sample, the change of the capture capacity per kg of carbon dioxide can be estimated, as shown in Table 1, which shows the carbon dioxide adsorption cycle test of the polyaniline test sample. The estimated change in capture capacity per kg of carbon dioxide is in the range of 0.085-0.098 Kg CO 2 /Kg.
因此，本案之一種苯胺基官能基固著矽膠固體吸收劑之製備方法確實較習知技術具新穎性及進步性。Therefore, the preparation method of an anilino functional solid-fixed solid absorbent in the present case is indeed novel and advanced compared with the prior art.
綜上所述，藉由本創作之苯胺基官能基固著矽膠固體吸收劑之製備方法之實施，其具有：1其係以矽膠為基體並於矽膠表面進行胺基化處理，繼而於苯胺聚合物形成過程中，予以固著製備成矽膠固著苯胺聚合物吸收劑；2.其具備相對於乙醇胺之低二氧化碳脫附程序的能源消耗；以及3.其而建立固體吸收劑的合成製備技術，並應用於捕捉二氧化碳及儲存等優點。因此，本發明之苯胺基官能基固著矽膠固體吸收劑之製備方法確實較習知技術具有進步性。In summary, the preparation method of the anilino functional solid-fixed solid absorbent according to the present invention has the following steps: 1. The base is made of tannin and subjected to amination treatment on the surface of the tannin, followed by the aniline polymer. During the formation process, it is prepared to fix the aniline polymer absorbent by bismuth; 2. it has the energy consumption of the low carbon dioxide desorption procedure relative to ethanolamine; and 3. the synthetic preparation technology for establishing the solid absorbent, and Used to capture carbon dioxide and storage. Therefore, the preparation method of the anilino functional group-fixed silicone solid absorbent of the present invention is indeed more advanced than the prior art.
本案所揭示者，乃較佳實施例，舉凡局部之變更或修飾而源於本案之技術思想而為熟習該項技藝之人所易於推知者，俱不脫本案之專利權範疇。The disclosure of the present invention is a preferred embodiment. Any change or modification of the present invention originating from the technical idea of the present invention and being easily inferred by those skilled in the art will not deviate from the scope of patent rights of the present invention.
綜上所陳，本案無論就目的、手段與功效，在在顯示其迥異於習知之技術特徵，且其首先發明合於實用，亦在在符合發明之專利要件，懇請 貴審查委員明察，並祈早日賜予專利，俾嘉惠社會，實感德便。In summary, this case, regardless of its purpose, means and efficacy, is showing its technical characteristics that are different from the conventional ones, and its first invention is practical and practical, and it is also in compliance with the patent requirements of the invention. I will be granted a patent at an early date.
步驟1：將矽膠以酸溶液進行純化前處理；Step 1: pretreating the tannin extract with an acid solution;
步驟2：將矽膠進行胺基化處理；Step 2: subjecting the tannin to amination treatment;
步驟3：與苯胺聚合物進行反應；以及Step 3: reacting with the aniline polymer;
步驟4：將矽膠固著於該苯胺聚合物上。Step 4: Fix the tannin on the aniline polymer.
圖1為一示意圖，其繪示本發明一較佳實施例之苯胺基官能基固著矽膠固體吸收劑之製備方法之流程示意圖。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the flow of a method for preparing an anilino functional solid-fixing solid absorbent according to a preferred embodiment of the present invention.
圖2為一示意圖，其繪示本發明一較佳實施例之具苯胺基官能基固體吸收劑之分子結合示意圖。2 is a schematic view showing the molecular bonding diagram of an anilino functional solid absorbent according to a preferred embodiment of the present invention.
圖3a為一示意圖，其繪示以FTIR光譜儀量測得矽膠樣品所得之紅外光譜之特徵峰示意圖。Fig. 3a is a schematic view showing a characteristic peak of an infrared spectrum obtained by measuring a tannin sample by an FTIR spectrometer.
圖3b為一示意圖，其繪示以FTIR光譜儀量測得矽膠固著胺基(NH2 -Si)樣品所得之紅外光譜之特徵峰示意圖。Fig. 3b is a schematic view showing a characteristic peak of an infrared spectrum obtained by measuring a sample of a ruthenium-fixed amine (NH 2 -Si) by an FTIR spectrometer.
圖3c為一示意圖，其繪示以FTIR光譜儀量測得矽膠固著苯胺聚合物(PANI-Si)樣品所得之紅外光譜之特徵峰示意圖。Fig. 3c is a schematic view showing the characteristic peaks of the infrared spectrum obtained by measuring the aniline-fixed aniline polymer (PANI-Si) sample by FTIR spectrometer.
圖4為一示意圖，其繪示以FTIR光譜儀量測得掺雜及未掺雜聚苯胺化合物樣品所得之紅外光譜之特徵峰示意圖。4 is a schematic view showing a characteristic peak of an infrared spectrum obtained by measuring a sample of a doped and undoped polyaniline compound by an FTIR spectrometer.
圖5a為一示意圖，其繪示以拉曼(Raman)光譜儀量測得矽膠樣品所得之拉曼光譜圖之特徵峰示意圖。FIG. 5a is a schematic diagram showing a characteristic peak of a Raman spectrum obtained by measuring a tannin sample by a Raman spectrometer.
圖5b為一示意圖，其繪示以拉曼光譜儀量測得矽膠固著胺基(NH2 -Si)樣品所得之拉曼光譜圖之特徵峰示意圖。Fig. 5b is a schematic view showing a characteristic peak of a Raman spectrum obtained by measuring a ruthenium-fixed amine (NH 2 -Si) sample by a Raman spectrometer.
圖5c為一示意圖，其繪示以拉曼光譜儀量測得矽膠固著苯胺聚合物(PANI-Si)樣品所得之拉曼光譜圖之特徵峰示意圖。Fig. 5c is a schematic view showing the characteristic peaks of the Raman spectrum obtained by measuring the aniline-fixed aniline polymer (PANI-Si) sample by Raman spectroscopy.
圖6為一示意圖，其繪示在不同脫附溫度(80℃、70℃和60℃)設定條件下，本發明之矽膠固著苯胺聚合物應用於二氧化碳吸附/脫附特性之示意圖。Fig. 6 is a schematic view showing the application of the aniline-fixed aniline polymer of the present invention to carbon dioxide adsorption/desorption characteristics under different desorption temperatures (80 ° C, 70 ° C and 60 ° C).
圖7為一示意圖，其繪示覆蓋於本發明之矽膠表層固著苯胺聚合物重量估算之示意圖。Fig. 7 is a schematic view showing the weight estimation of the aniline polymer adhered to the surface layer of the silicone of the present invention.
圖8為一示意圖，其繪示本發明之聚苯胺測試樣品進行連續5次循環吸脫附的行為評估之測試示意圖。Fig. 8 is a schematic view showing the test of the behavior evaluation of the polyaniline test sample of the present invention for 5 consecutive cycles of adsorption and desorption.
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